PHENYL-SUBSTITUTED BICYCLOOCTANE-1,3-DIONE DERIVATIVES

DERIVES DE BICYCLOOCTANE-1,3-DIONE A SUBSTITUTION PHENYLE

English Abstract

The invention relates to novel compounds of the formula (I)
(see formula I)
in which X, Y, Z, A, B and G have the meanings given above,
to a plurality of processes and intermediates for their preparation and to
their use as pesticides and/or
herbicides.
Moreover, the invention relates to selective herbicidal compositions
comprising, firstly, the
phenyl-substituted bicyclooctane-1,3-dione derivates and, secondly, a crop
plant compatibility-
improving compound.
The present invention furthermore relates to increasing the activity of crop
protection
compositions comprising in particular phenyl-substituted bicyclooctane-1,3-
dione derivates by
adding ammonium salts or phosphonium salts and, if appropriate, penetrants, to
the corresponding
compositions, to processes for their preparation and to their use in crop
protection as insecticides
and/or acaricides and/or for preventing unwanted plant growth.

French Abstract

La présente invention concerne de nouveaux composés de formule (I) dans laquelle X, Y, Z, A, B et G possèdent la signification figurant ci-dessus, plusieurs procédés et produits intermédiaires pour leur production, et leur utilisation en tant qu'agents anti-parasitaires et/ou herbicides. L'invention concerne en outre des agents herbicides sélectifs qui contiennent les dérivés de bicyclooctane-1,3-dione à substitution phényle d'une part et un composé améliorant la compatibilité avec les plantes cultivées d'autre part. Elle concerne encore le renforcement de l'action d'agents phytosanitaires contenant en particulier des dérivés de bicyclooctane-1,3-dione à substitution phényle par l'ajout de sels d'ammonium ou de phosphonium et éventuellement d'agents favorisant la pénétration, les produits correspondants, des procédés de production desdits agents et leur utilisation dans le domaine phytosanitaire en tant qu'insecticides et/ou acaricides et/ou pour empêcher la croissance de plantes adventices.

Claims

-189-
Claims
1. Compounds of the formula (I)
<IMG>
in which
X represents alkyl, cycloalkyl or alkoxy,
Y represents hydrogen, alkyl or alkoxy,
Z represents hydrogen, alkyl or cycloalkyl,
where
A and B together with the carbon atom to which they are attached represent a
saturated or
unsaturated unsubstituted or substituted cycle which optionally contains at
least
one heteroatom,
or
A and B together with the carbon atom to which they are attached represent a
carbonyl
group, a C1-C4-alkylene group or a =N-OR9 group,
G represents hydrogen (a) or represents one of the groups
<IMG>
in which

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E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R1 represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl,
alkylthioalkyl, polyalkoxyalkyl or optionally halogen-, alkyl- or alkoxy-
substituted
cycloalkyl which may be interrupted at least one heteroatom, in each case
optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or
hetaryloxy-
alkyl,
R2 represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl,
polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl,
phenyl or benzyl,
R3, R4 and R5 independently of one another represent in each case optionally
halogen-
substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio,
cycloalkylthio or represent in each case optionally substituted phenyl,
benzyl,
phenoxy or phenylthio,
R6 and R7 independently of one another represent hydrogen, in each case
optionally
halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent
optionally substituted phenyl, represent optionally substituted benzyl, or
together
with the nitrogen atom to which they are attached represent a cycle which is
optionally interrupted by oxygen or sulphur,
R9 represents hydrogen, represents in each case optionally substituted alkyl,
cycloalkyl, CH2-cycloalkyl, alkenyl, alkinyl, arylalkyl or hetarylalkyl.
2. Compounds of the formula (I) according to Claim 1 in which
X represents C1-C4-alkyl, C3-C6-cycloalkyl or C1-C4-alkoxy,
Y represents hydrogen, C1-C4-alkyl or C1-C4-alkoxy,
Z represents hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl,
A, B and the carbon atom to which they are attached represent C3-C8-cycloalkyl
or C5-

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C8-cycloalkenyl, in which optionally one or two ring members are replaced by
oxygen and/or sulphur and which are optionally mono- to tetrasubstituted by C1-
C8-alkyl, C1-C8-alkenyl, C1-C4-alkylene, C1-C8-halogenalkyl, C1-C6-alkoxy-C1-
C4-
alkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, hydroxyl, hydroxy-C1-C4-alkyl or
benzyloxy, or a further fused-on C3-C8-cycloalkyl ring in which optionally one
or
two ring members are replaced by oxygen or sulphur, or which is optionally
mono-
or disubstituted by C1-C8-alkyl, or
A, B and the carbon atom to which they are attached represent a carbonyl
group,
represent a C1-C4-alkylene group or represent a =N-OR9 group,
G represents hydrogen (a) or represents one of the groups
<IMG>
in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur, and
M represents oxygen or sulphur,
R1 represents in each case optionally halogen-substituted C1-C20-alkyl, C2-C20-
alkenyl, C1-C8-alkoxy-C1-C3-alkyl, C1-C8-alkylthio-C1-C8-alkyl, poly-C1-
C8-alkoxy-C1-C8-alkyl or optionally halogen-, C1-C6-alkyl- or C1-C6-
alkoxy-substituted C3-C8-cycloalkyl in which optionally one or more not
directly adjacent ring members are replaced by oxygen and/or sulphur,
represents optionally halogen-, cyano-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-,
C1-C6-halogenalkyl-, C1-C6-halogenalkoxy-, C1-C6-alkylthio- or C1-C6-
alkylsulphonyl-substituted phenyl,
represents optionally halogen-, nitro-, cyano-, C1-C6-alkyl-, C1-C6-alkoxy-,

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C1-C6-halogenalkyl- or C1-C6-halogenalkoxy-substituted phenyl-C1-C6-
alkyl,
represents optionally halogen- or C1-C6-alkyl-substituted 5- or 6-membered
hetaryl,
represents optionally halogen- or C1-C6-alkyl-substituted phenoxy-C1-C6-
alkyl or
represents optionally halogen-, amino- or C1-C6-alkyl-substituted 5- or 6-
membered hetaryloxy-C1-C6-alkyl,
R2 represents in each case optionally halogen-substituted C1-C20-alkyl, C2-C20-
alkenyl, C1-C8-alkoxy-C2-C8-alkyl, poly-C1-C8-alkoxy-C2-C8-alkyl,
represents optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted
C3-C8-cycloalkyl or
represents in each case optionally halogen-, cyano-, nitro-, C1-C6-alkyl-,
C1-C6-alkoxy-, C1-C6-halogenalkyl- or C1-C6-halogenalkoxy-substituted
phenyl or benzyl,
R3 represents optionally halogen-substituted C1-C8-alkyl or represents in each
case optionally halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-halogenalkyl-,
C1-C4-halogenalkoxy-, cyano- or nitro-substituted phenyl or benzyl,
R4 and R5 independently of one another represent in each case optionally
halogen-
substituted C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylamino, Di-(C1-C8-
alkyl)amino,
C1-C8-alkylthio, C2-C8-alkenylthio, C3-C7-Cycloalkylthio or represent in each
case
optionally halogen-, nitro-, cyano-, C1-C4-alkoxy-, C1-C4-halogenalkoxy-, C1-
C4-
alkylthio-, C1-C4-halogenalkylthio-, C1-C4-alkyl- or C1-C4-halogenalkyl-
substituted
phenyl, phenoxy or phenylthio,
R6 and R7 independently of one another represent hydrogen, represent in each
case
optionally halogen-substituted C1-C8-alkyl, C3-C8-cycloalkyl, C1-C8-alkoxy, C3-
C8-
alkenyl, C1-C8-alkoxy-C1-C8-alkyl, represent optionally halogen-, C1-C8-
halogen-
alkyl-, C1-C8-alkyl- or C1-C8-alkoxy-substituted phenyl, optionally halogen-,
C1-C8-
alkyl-, C1-C8-halogenalkyl- or C1-C8-alkoxy-substituted benzyl or together

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represent an optionally C1-C4-alkyl-substituted C3-C6-alkylene radical in
which
optionally one carbon atom is replaced by oxygen or sulphur,
R9 represents hydrogen, represents C1-C6-alkyl, C3-C6 cycloalkyl, CH2C3-C6-
cycloalkyl, C3-C6-alkenyl, C3-C6-alkinyl, each of which is optionally
mono- to pentasubstituted by halogen, or represents phenyl-C1-C2-alkyl or
hetaryl-C1-C2-alkyl, each of which is optionally mono- to trisubstituted by
alkyl, halogen, alkoxy, halogenalkyl or halogenalkoxy.
3. Compounds of the formula (I) according to Claim 1 in which
X represents methyl, ethyl, cyclopropyl, methoxy or ethoxy,
Y represents hydrogen, methyl or ethyl.
Z represents hydrogen, methyl, ethyl or cyclopropyl,
A, B and the carbon atom to which they are attached represent C3-C8-cycloalkyl
or C5-
C8-cycloalkenyl in which optionally one or two ring members are replaced by
oxygen and/or sulphur and which is optionally mono- to tetrasubstituted by C1-
C4-
alkyl, C1-C4-alkenyl, a =CH, group, trifluoromethyl, C1-C4-alkoxy, C1-C4-
alkoxy-
C1-C2-alkyl or by one of the groups
<IMG>
or
A, B and the carbon atom to which they are attached represent a carbonyl
group,
represent a C1-C4-alkylene group or represent a =N-OR9 group,
G represents hydrogen (a) or represents one of the groups
<IMG>

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in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 represents C1-C8-alkyl, C2-C8-alkenyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-
alkylthio-C1-C2-alkyl, each of which is optionally mono- to trisubstituted
by fluorine or chlorine, or represents C3-C6-cycloalkyl which is optionally
mono- or disubstituted by fluorine, chlorine, C1-C2-alkyl or C1-C2-alkoxy
and in which optionally one or two not directly adjacent ring members are
replaced by oxygen,
represents phenyl which is optionally mono- or disubstituted by fluorine,
chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl
or C1-C2-haloalkoxy,
R2 represents C1-C8-alkyl, C2-C8-alkenyl or C1-C4-alkoxy-C2-C4-alkyl, each of
which is optionally mono- to trisubstituted by fluorine,
represents C3-C6-cycloalkyl which is optionally monosubstituted by C1-C2-
alkyl or C1-C2-alkoxy or
represents phenyl or benzyl, each of which is optionally mono- or
disubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-
C3-alkoxy, trifluoromethyl or trifluoromethoxy,
R3 represents C1-C6-alkyl which is optionally mono- to trisubstituted by
fluorine or represents phenyl which is optionally monosubstituted by
fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl,
trifluoromethoxy, cyano or nitro,
R4 represents C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylamino, Di-(C1-C6-
alkyl)amino, C1-C6-alkylthio, C3-C4-alkenylthio, C3-C6-cycloalkylthio, each
of which is optionally mono- to trisubstituted by fluorine or chlorine, or
represents phenyl, phenoxy or phenylthio, each of which is optionally
monosubstituted by fluorine, chlorine, bromine, nitro, cyano, C1-C3-

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alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio, C1-C3-
alkyl or trifluoromethyl,
R5 represents C1-C6-alkylthio or C1-C6-alkoxy which is optionally
monosubstituted by chlorine,
R6 represents hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-
alkenyl, C1-C6-alkoxy-C1-C4-alkyl, represents phenyl which is optionally
monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, C1-C4-
alkyl or C1-C4-alkoxy, represents benzyl which is optionally
monosubstituted by fluorine, chlorine, bromine, C1-C4-alkyl,
trifluoromethyl or C1-C4-alkoxy,
R7 represents C1-C6-alkyl, C3-C6-alkenyl or C1-C6-alkoxy-C1-C4-alkyl,
R6 and R7 together represent an optionally methyl- or ethyl-substituted C4-C5-
alky-
lene radical in which optionally one methylene group is replaced by oxygen or
sulphur,
R9 represents hydrogen, represents C1-C4-alkyl, C3-C6-cycloalkyl, CH2-C3-C6-
cycloalkyl, C3-C4-alkenyl, C3-C4-alkinyl, each of which is optionally
mono- to trisubstituted by fluorine or chlorine, represents benzyl or
pyridinylmethyl, each of which is optionally mono- or disubstituted by C1-
C2-alkyl, C1-C2-alkoxy, fluorine, chlorine, bromine, trifluoromethyl or
trifluoromethoxy.
4. Compounds of the formula (I) according to Claim 1 in which
X represents methyl, ethyl, cyclopropyl, methoxy or ethoxy,
Y represents hydrogen, methyl or ethyl,
Z represents hydrogen, methyl, ethyl or cyclopropyl,
A, B and the carbon atom to which they are attached represent C3-C7-cycloalkyl
or C5-
C7-cycloalkenyl in which optionally one or two ring members are replaced by
oxygen and/or sulphur and which is optionally mono-, di-, tri- or
tetrasubstituted
by methyl, in each case monosubstituted by ethyl, a =CH2 group, methoxy or
ethoxy,

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A, B and the carbon atom to which they are attached represent a carbonyl
group,
represent a=CH2 group, represent a=CH2-CH3 group, represent a=CH2-C2H5
group or represent a=N-OR9 group,
G represents hydrogen (a) or represents one of the groups
<IMG>
in which
E represents a metal ion equivalent (Na+ or K+),
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 represents C1-C6-alkyl, C2-C6-alkenyl, C1-C2-alkoxy-C1-alkyl, C1-C2-
alkylthio-C1-
alkyl or C3-C6-cyclopropyl which is optionally monosubstituted by fluorine,
chlorine, methyl or methoxy or represents C1-C4-alkyl which is monosubstituted
by
chlorine,
represents phenyl which is optionally monosubstituted by fluorine, chlorine,
bromine, cyano, nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
R2 represents C1-C8-alkyl, C2-C6-alkenyl or C1-C4-alkoxy-C2-C3-alkyl, each of
which
is optionally mono- to trisubstituted by fluorine, represents phenyl or
benzyl,
R3 represents C1-C6-alkyl or represents phenyl which is optionally
monosubstituted by
chlorine or C1-C4-alkyl,
R9 represents hydrogen, represents in each case optionally fluorine-
substituted
methyl, ethyl, propyl, n-butyl, isobutyl, s-butyl or tert-butyl, represents
allyl,
chloroallyl, propinyl, butinyl, chlorobenzyl, chloropyridylmethyl, CH(CH3)-
C.ident.CH, cyclopropyl, cyclobutyl, cyclopentyl, CH2-cyclopropyl, CH2-
cyclobutyl or
CH2-cyclopentyl.
5. Compounds of the formula (I) according to Claim 1 in which

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x represents methyl, ethyl or methoxy,
Y represents methyl or ethyl,
Z represents hydrogen, methyl or ethyl,
A, B and the carbon atom to which they are attached represent C5-C7-cycloalkyl
or C7-
cycloalkenyl which optionally two ring members are replaced by oxygen and/or
sulphur and which is optionally mono-, di- or tetrasubstituted by methyl, in
each
case monosubstituted by ethyl, a=CH2 group, methoxy, ethoxy or benzyloxy,
A, B and the carbon atom to which they are attached represent a carbonyl
group,
represent a=CH2 group or represent a=N-OR9 group,
G represents hydrogen (a) or represents one of the groups
<IMG>
in which
E represents a metal ion equivalent,
L represents oxygen and
M represents oxygen,
R1 represents C1-C6-alkyl or C1-C2-alkoxy-C1-alkyl or C1-C4-alkyl which is
monosubstituted by chlorine.
represents phenyl which is optionally monosubstituted by chlorine, methyl
or methoxy,
R2 represents C1-C8-alkyl,
R3 represents methyl, phenyl or p-methylphenyl,
R9 represents hydrogen, methyl, isopropyl, isobutyl, tert-butyl, CH2CF3,
propinyl (CH2-C.ident.CH), CH(CH3)-C.ident.CH, cyclopropyl, cyclopentyl, CH2)-
cyclopropyl, CH2-cyclopentyl.

- 198-
6. Process for preparing compounds of formula (I) according to Claim 1,
characterized in
that, to obtain
(A) Compounds of the formula (I-a)
<IMG>
in which
A, B, X, Y and Z have the meaning given above,
ketocarboxylic esters of the formula (II)
<IMG>
in which
A, B, X, Y and Z have the meaning given above, and
R8 represents alkyl,
are cyclised intramolecularly, if appropriate in the presence of a diluent and
in the
presence of a base,
(B) Compounds of the formula (I-b) shown above in which A, B, R1, X, Y and Z
have
the meanings given above, compounds of the formula (I-a) shown above in which
A, B, X, Y and Z have the meanings given above are in each case reacted

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(.alpha.) with acid halides of the formula (III)
(III)
in which
R1 has the meaning given above and
Hal represents halogen
or
(.beta.) with carboxylic anhydrides of the formula (IV)
R1-CO-O-CO-R1 (IV)
in which
R1 has the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder;
(C) Compounds of the formula (I-c) shown above in which A, B, R2, M, X, Y and
Z
have the meanings given above and L represents oxygen, compounds of the
formula (I-a) shown above in which A, B, X, Y and Z have the meanings given
above are in each case reacted
with chloroformic esters or chloroformic thio esters of the formula (V)
R2-M-CO-C1 (V)
in which
R2 and M have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder;
(D) Compounds of the formula (I-c) shown above in which A, B, R2, M, X, Y and
Z

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have the meanings given above and L represents sulphur, compounds of the
formula (I-a) shown above in which A, B, X, Y and Z have the meanings given
above are in each case reacted
with chloromonothioformic esters or chlorodithioformic esters of the formula
(VI)
<IMG>
in which
M and R2 have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder;
(E) Compounds of the formula (I-d) shown above in which A, B, R3, X, Y and Z
have
the meanings given above, compounds of the formula (I-a) shown above in which
A, B, X, Y and Z have the meanings given above are in each case reacted,
with sulphonyl chlorides of the formula (VII)
R3-SO2-C1 (VII)
in which
R3 has the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder,
(F) Compounds of the formula (I-e) shown above in which A, B, L, R4, R5, X, Y
and Z
have the meanings given above, compounds of the formula (I-a) shown above in
which A, B, X, Y and Z have the meanings given above are in each case reacted
with phosphorus compounds of the formula (VIII)

-201 -
<IMG>
in which
L, R4 and R5 have the meanings given above and
Hal represents halogen,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder,
(G) Compounds of the formula (I-f) shown above in which A, B, E, X, Y and Z
have
the meanings given above, compounds of the formula (I-a) in which A, B, X, Y
and Z have the meanings given above are in each case reacted
with metal compounds or amines of the formulae (IX) and (X) respectively,
Me(OR10)t (IX) <IMG>
in which
Me represents a mono- or divalent metal,
t represents the number 1 or 2 and
R10, R11, R12 independently of one another represent hydrogen or alkyl,
if appropriate in the presence of a diluent,
(H) Compounds of the formula (I-g) shown above in which A, B, L, R6, R7, X, Y
and Z
have the meanings given above, compounds of the formula (I-a) shown above in
which A,
B, X, Y and Z have the meanings given above are in each case reacted
(.alpha.) with isocyanates or isothiocyanates of the formula (XI)
R6-N=C=L (XI)

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in which
R6 and L have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of a catalyst,
or
(.beta.) with carbamoyl chlorides or thiocarbamoyl chlorides of the formula
(XII)
<IMG>
in which
L, R6 and R7 have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder.
7. Compositions for controlling pests and/or unwanted vegetation,
characterized in that they
comprise at least one compound of the formula (I) according to Claim 1.
8. Method for controlling animal pests and/or unwanted vegetation,
characterized in that
compounds of the formula (I) according to Claim 1 are allowed to act on pests,
unwanted
vegetation and/or their habitat.
9. Use of compounds of the formula (I) according to Claim 1 for controlling
animal pests
and/or unwanted vegetation.
10. Process for preparing compositions for controlling pests and/or unwanted
vegetation,
characterized in that compounds of the formula (I) according to Claim 1 are
mixed with
extenders and/or surfactants.
11. Use of compounds of the formula (I) according to Claim 1 for preparing
compositions for
controlling pests and/or unwanted vegetation.
12. Compositions, comprising an effective amount of an active compound
combination
comprising, as components,

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(a') at least one compound of the formula (1) in which A, B, G, X, Y and Z
have the
meaning given above
and
(b') at least one crop plant compatibility-improving compound from the
following
group of compounds: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14.
13. Compositions according to Claim 12 in which the crop plant compatibility-
improving
compound is cloquintocet-mexyl.
14. Compositions according to Claim 12 in which the crop plant compatibility-
improving
compound is mefenpyr-diethyl.
15. Compositions according to Claim 12 in which the crop plant compatibility-
improving
compound is cyprosulfamide.
16. Method for controlling unwanted vegetation, characterized in that a
composition according
to Claim 12 is allowed to act on the plants or their surroundings.
17. Use of a composition according to Claim 12 for controlling unwanted
vegetation.
18. Method for controlling unwanted vegetation, characterized in that a
compound of the formula
(I) according to Claim 1 and the crop plant compatibility-improving compound
according to
Claim 12 are allowed to act separately in close temporal succession on the
plants or their
surroundings.
19. Compounds of the formula (II)
<IMG>
in which
A, B, X, Y, Z and R8 have the meanings given above.

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20. Compounds of the formula (XIII)
<IMG>
in which
A, B, X, Y, and Z have the meanings given above.
21. Compounds of the formula (XIV)
<IMG>
in which
A, B, X, Y, Z, R8 and R8 have the meanings given above.
22. Compounds of the formula (XIX)
<IMG>
in which
X, Y, Z and Hal have the meanings given in the table
Hal x Y Z
Cl C2H5 CH3 CH3

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Cl OCH3 CH3 C2H5
Cl cyclopropyl CH3 C2H5
Br cyclopropyl CH3 C2H5
23. Composition, comprising
- at least one compound of the formula (I) according to Claim 1 or a
composition
according to Claim 12 and
- at least one salt of the formula (III')
<IMG>
in which
D represents nitrogen or phosphorus,
R26, R27, R28 and R29 independently of one another represent hydrogen or in
each case
optionally substituted C1-C8-alkyl or mono- or polyunsaturated, optionally
substituted C1-C8-alkylene, the substituents being selectable from halogen,
nitro
and cyano,
n represents 1, 2, 3 or 4,
R30 represents an inorganic or organic anion.
24. Composition according to Claim 23, characterized in that it comprises at
least one
penetrant.
25. Method for increasing the activity of pesticides and/or herbicides
comprising an active
compound of the formula (I) according to Claim 1 or a composition according to
Claim 12,

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characterized in that the ready-to-use composition (spray liquor) is prepared
using a salt of
the formula (III') according to Claim 23.
26. Method according to Claim 25, characterized in that the spray liquor is
prepared using a
penetrant.

Description

CA 02739870 2011-04-07
BCS 08-3052-Foreign countries Gam/Gr 2009-09-10
-1-
Phenyl-substituted bicycllooctane-1,3-dione derivatives
The present invention relates to novel phenyl-substituted bicyclooctane-l,3-
dione derivatives, to a
plurality of processes for their preparation and to their use as pesticides
and/or herbicides.
Moreover, the invention relates to novel selective herbicidal active compound
combinations
comprising, firstly, phenyl-substituted bicyclooctane-l,3-dione derivates and,
secondly, at least
one crop plant compatibility-improving compound, which combinations can be
used with
particularly good results for the selective control of weeds and various crops
of useful plants.
The present invention furthermore relates to increasing the activity of crop
protection
compositions comprising in particular phenyl-substituted bicyclooctane-1,3-
dione derivates by
adding ammonium salts or phosphonium salts and, if appropriate, penetrants, to
the corresponding
compositions, to processes for their preparation and to their use in crop
protection as insecticides
and/or for preventing unwanted plant growth.
It is known that certain substituted 2-arylcyclopentanediones have herbicidal,
insecticidal and
acaricidal properties (cf., for example, US-4 283 348; 4 338 122; 4 436 666; 4
526 723; 4 551 547;
4 632 698; WO 96/01 798; WO 96/03 366, WO 97/14 667 and also WO 98/39281, WO
99/43649,
WO99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO 03/062244, WO 04/080962,
WO04/111042, WO05/092897, WO06/029799, WO07/080066, WO07/096058, WO 09/019005
and W009/019015). Also known are compounds which are substituted in a similar
way:
3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-l-one from the publication
Micklefield et. al.,
Tetrahedron, (1992), 7519-26 and the natural product Involution (-)-cis-5-(3,4-
dihydroxyphenyl)-
3,4-dihydroxy-2-(4-hydroxyphenyl)-cyclopent-2-enone from the publication
Edwards et al.,
J. Chem. Soc. S, (1967), 405-9. An insecticidal or acaricidal action is not
described. Moreover,
2-(2,4,6-trimethylphenyl)-1,3-indanedione is known from the publication J.
Economic
Entomology, 66 (1973), 584 and the laid-open publication DE-A 2 361 084, with
herbicidal and
acaricidal actions being stated.
However, in particular at low application rates and concentrations, the
activity and activity
spectrum of these compounds is not always fully satisfactory. Furthermore, the
compatibility of
these compounds with plants is not always sufficient.

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This invention now provides novel compounds of the formula (I)
O
X
A X:j
Y
(1)
B
z
O
in which
X represents alkyl, cycloalkyl or alkoxy,
Y represents hydrogen, alkyl or alkoxy,
Z represents hydrogen, alkyl or cycloalkyl,
where
A and B together with the carbon atom to which they are attached represent a
saturated or
unsaturated unsubstituted or substituted cycle which optionally contains at
least one
heteroatom,
or
A and B together with the carbon atom to which they are attached represent a
carbonyl group, a C,-
C4-alkylene group or a =N-OR9 group,
G represents hydrogen (a) or represents one of the groups
O L R4
2 3
R, (b), M R (c) SO2 R (d), /~ R5 (e),
L
R6
E (fl or N (g),
L R
in which
E represents a metal ion equivalent or an ammonium ion,

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L represents oxygen or sulphur,
M represents oxygen or sulphur,
R` represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl,
alkylthioalkyl, polyalkoxyalkyl or optionally halogen-, alkyl- or alkoxy-
substituted
cycloalkyl which may be interrupted by at least one heteroatom, in each case
optionally
substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
R2 represents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl,
polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl,
phenyl or
benzyl,
R3, R4 and R5 independently of one another represent in each case optionally
halogen-substituted
alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio,
cycloalkylthio or represent
in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio,
R6 and R7 independently of one another represent hydrogen, in each case
optionally halogen-
substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent
optionally substituted
phenyl, represent optionally substituted benzyl, or together with the nitrogen
atom to
which they are attached represent a cycle which is optionally interrupted by
oxygen or
sulphur,
R9 represents hydrogen, represents in each case optionally substituted alkyl,
cycloalkyl, CH7
cycloalkyl, alkenyl, alkinyl, arylalkyl or hetarylalkyl.
Depending inter alia on the nature of the substituents, the compounds of the
formula (I) may be
present as geometric and/or optical isomers or isomer mixtures of varying
composition which, if
appropriate, may be separated in a customary manner. The present invention
provides both the
pure isomers and the isomer mixtures, their preparation and use and
compositions comprising
them. However, for the sake of simplicity, hereinbelow only compounds of the
formula (I) are
referred to, although what is meant is both the pure compounds and, if
appropriate, mixtures
having various proportions of isomeric compounds.
Depending on the position of the substituent G, the compounds of the formula
(I) can be present in
the two isomeric forms of the formulae (I-A) and (I-B)

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G\ O X
O X A
A Y
B
B
O Z
Z G/
(I-A) (I-B)
which is meant to be indicated by the broken line in formula (I).
The compounds of the formulae (I-A) and (I-B) can be present both as mixtures
and in the form of
their pure isomers. If appropriate, mixtures of the compounds of the formulae
(I-A) and (I-B) can
be separated by physical methods, for example by way of chromatographic
methods.
For reasons of clarity, hereinbelow only one of the possible isomers is shown
in each case. This
does not exclude that, if appropriate, the compounds may be present in the
form of the isomer
mixtures or in the respective other isomeric form.
Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group
G, the following
principle structures (I-a) to (I-g) result:
(I-a): (I-b):
OH X O
A Y R 1
O X
B A
O Z
BX
0 Z

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(I-c): (I-d):
L
11 C 3
-M-R2 SO2-R
O O X
X
A A
Y
B Y B X:1 _
O Z O Z
(I-e): (I-f):
4
L'\ /R 5 E
P-R O X
O X A 0 Y
A Y B
B O Z
O Z
(I-g):
R7
N-R6
L---~
O X
A
XD B Y
O Z
in which
A, B, E, L, M, X, Y, Z, R', R2, R3, R4, R5, R6 and R7 have the meanings given
above.
A further form of stereoisomerism results from the cis-attachment of the two
carbacyclic five-
membered rings, namely in the case where specifically the two substituents A
and B in formula
(la) are not identical.

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H X
H O
Y
anti p
A Z
B
syn
(Ia)
Hereinbelow, the isomers encountered in this case are referred to as "syn" and
"anti", respectively,
depending on whether the substituent A or B to be prioritized according to the
Cahn-Ingold-Prelog
rules is in the anti- or syn-position to the cyclopentanedione ring. Two
examples of such forms of
isomerism in the compounds of the formula (I-a) are mentioned below:
H X H X
H O - H O
Y
Y
O
Z S O Z
us U10
syn-isomer anti-isomer
H X H X
H O H O
Y Y
O O
Z O Z
O` O
/X\ O
syn-isomer anti-isomer
Furthermore, it has been found that the novel compounds of the formula (I) are
obtained by one of
the processes described below:
(A) Compounds of the formula (1-a)

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OH X
A
B Y (I-a)
O Z
in which
A, B, X, Y and Z have the meaning given above
are obtained when
ketocarboxylic esters of the formula (II)
A C02R8
B O
X (II)
Z Y
in which
A, B, X, Y and Z have the meaning given above and
R8 represents alkyl (in particular C,-C8-alkyl)
are cyclized intramolecularly, if appropriate in the presence of a diluent and
in the
presence of a base.
Moreover, it has been found
(B) that the compounds of the formula (I-b) shown above in which A, B, R', X,
Y and Z have
the meanings given above are obtained when compounds of the formula (I-a)
shown above
in which A, B, X, Y and Z have the meanings given above are in each case
reacted

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(u) with acid halides of the formula (III)
Hal 'Y R'
(III)
0
in which
R' has the meaning given above and
Hal represents halogen (in particular chlorine or bromine)
or
(13) with carboxylic anhydrides of the formula (IV)
R'-CO-O-CO-R' (IV)
in which
R' has the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder;
(C) that the compounds of the formula (I-c) shown above in which A, B, R2, M,
X, Y and Z
have the meanings given above and L represents oxygen are obtained when the
compounds
of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings
given
above are in each case reacted
with chloroformic esters or chloroformic thio esters of the formula (V)
R2-M-CO-Cl (V)
in which
R2 and M have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder;
(D) that compounds of the formula (I-c) shown above in which A, B, R2, M, X, Y
and Z have

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the meanings given above and L represents sulphur are obtained when compounds
of the
formula (I-a) shown above in which A, B, X, Y and Z have the meanings given
above are
in each case reacted
with chloromonothioformic esters or chlordithioformic esters of the formula
(VI)
CI "Y M-R2
(VI)
I
in which
M and R2 have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder;
(E) that compounds of the formula (I-d) shown above in which A, B, R3, X, Y
and Z have the
meanings given above are obtained when compounds of the formula (I-a) shown
above in
which A, B, X, Y and Z have the meanings given above are in each case reacted
with sulphonyl chlorides of the formula (VII)
R3-S02-Cl (VII)
in which
R3 has the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder,
(F) that compounds of the formula (I-e) shown above in which A, B, L, R4, R5,
X, Y and Z
have the meanings given above are obtained when compounds of the formula (I-a)
shown
above in which A, B, X, Y and Z have the meanings given above are in each case
reacted
with phosphorus compounds of the formula (VIII)

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R4
Hal - P (VIII)
11\ 5
L R
in which
L, R4 and R5 have the meanings given above and
Hal represents halogen (in particular chlorine or bromine),
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder,
(G) that compounds of the formula (I-f) shown above in which A, B, E, X, Y and
Z have the
meanings given above are obtained when compounds of the formula (1-a) in which
A, B,
X, Y and Z have the meanings given above are in each case reacted
with metal compounds or amines of the formulae (IX) or (X), respectively
R10 NR 11
Me(OR10)t (IX) 412 (X)
in which
Me represents a mono- or divalent metal (preferably an alkali metal or
alkaline earth
metal, such as lithium, sodium, potassium, magnesium or calcium),
t represents the number I or 2 and
R10 R", Rig independently of one another represent hydrogen or alkyl
(preferably C,-C8-
alkyl),
if appropriate in the presence of a diluent,
(H) that compounds of the formula (I-g) shown above in which A, B, L, R6, R',
X, Y and Z
have the meanings given above are obtained
when compounds of the formula (I-a) shown above in which A, B, X, Y and Z have
the
meanings given above are in each case reacted

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(a) with isocyanates or isothiocyanates of the formula (XI)
R6-N=C=L (XI)
in which
R6 and L have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of a catalyst,
or
(B) with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (X11)
ILI
R~NACI (XII)
R7,-
in which
L, R6 and R' have the meanings given above,
if appropriate in the presence of a diluent and if appropriate in the presence
of an acid
binder.
Furthermore, it has been found that the novel compounds of the formula (I) are
very effective as
pesticides, preferably as insecticides, acaricides and herbicides.
Surprisingly, it has now also been found that certain substituted cyclic
ketoenoles, when used
together with the crop plant compatibility-improving compounds
(safener/antidotes) described
below, efficiently prevent damage to the crop plants and can be used in a
particularly advantageous
manner as broad-spectrum combination preparations for the selective control of
unwanted plants in
crops of useful plants, such as, for example, in cereals, but also in maize,
potatoes, soya beans and
rice.
The invention also provides selective herbicidal compositions comprising an
effective amount of
an active compound combination comprising, as components,
a') at least one compound of the formula (I), in which A, B, G, X, Y and Z
have the meaning
given above

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and
(b') at least one crop plant compatibility-improving compound (safener).
The safeners are preferably selected from the group consisting of.
COI
(RA1)fA / 2 (Si)
WA RA
S1) Compounds of the formula (S1)
where the symbols and indices have the following meanings:
nA is a natural number from 0 to 5, preferably from 0 to 3;
RA' is halogen, (C,-C4)-alkyl, (C,-C4)-alkoxy, nitro or (CI-C4)-haloalkyl;
WA is an unsubstituted or substituted divalent heterocyclic radical from the
group
consisting of partially unsaturated or aromatic five-membered heterocycles
having
I to 3 hetero ring atoms from the group consisting of N and 0, where at least
one
nitrogen atom and at most one oxygen atom is present in the ring, preferably a
radical from the group consisting of (WAS) to (WA4),
NN NN -(CH2)MA
\N \ \ \ \ \~ \i~~
N
RAs R RA6 RA7 RA8 O-N
A g
(WA') (WA2) (WA3) (WA4)
mA is 0 or 1;
RA2 is ORA3, SRA3 or NRA3RA4 or a saturated or unsaturated 3- to 7-membered
heterocycle having at least one nitrogen atom and up to 3 heteroatoms,
preferably
from the group consisting of 0 and S, which is attached via the nitrogen atom
to
the carbonyl group in (Si) and which is unsubstituted or substituted by
radicals
from the group consisting of (C,-C4)-alkyl, (C,-C4)-alkoxy and optionally
substituted phenyl, preferably a radical of the formula ORA3, NT-IRA q or
N(CH3)1, in
particular of the formula ORA3;

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RA3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon
radical having
preferably a total of l to 18 carbon atoms;
RA4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted
henyl;
RAs is H, (C1-C8)-alkyl, (CI-C8)-haloalkyl, (C1-C4)-alkoxy-(CI-C8)-alkyl,
cyano or
COORA9 where RA9 is hydrogen, (CI-C8)-alkyl, (CI-C8)-haloalkyl, (C1-C4)-alkoxy-
(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C12)-cycloalkyl or tri-(CI-C4)-
alkylsilyl;
RA6, RA', RA8 are identical or different and are hydrogen, (CI-C8)-alkyl, (CI-
C8)-haloalkyl,
(C3-C12)-cycloalkyl or substituted or unsubstituted phenyl;
preferably:
a) compounds of the type of the dichlorophenylpyrazoline-3-carboxylic acid (S
1a),
preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-
5-methyl-2-pyrazoline-3-carboxylic acid, ethyl
1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate
(S1-1) ("mefenpyr-diethyl"), and related compounds, as described in
WO-A-91/07874;
b) derivatives of dichlorophenylpyrazolecarboxylic acid (S1b), preferably
compounds
such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2),
ethyl
1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl
1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4) and
related compounds, as described in EP-A-333 131 and EP-A-269 806;
c) derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1 ), preferably
compounds
such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5),
methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related
compounds, as described, for example, in EP-A-268554;
d) compounds of the type of the triazolecarboxylic acids (S1 d), preferably
compounds
such as fenchlorazole(-ethyl), i.e. ethyl
1-(2,4-dichlorophenyl)-5-trichloromethyl-(1 H)-1,2,4-triazole-3-carboxylate
(S1-7),
and related compounds, as described in EP-A-174 562 and EP-A-346 620;
e) compounds of the type of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-
carboxylic
acid or the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (Sle), preferably

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compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate
(S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related
compounds, as described in WO-A-91/08202, or 5,5-diphenyl-2-
isoxazolinecarboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-
isoxazolinecarboxylate
(51-11) ("isoxadifen-ethyl") or n-propyl 5,5 -diphenyl-2-isoxazol inecarboxy
late
(S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-
13),
as described in the patent application WO-A-95/07897.
S2) Quinoline derivatives of the formula (S2)
rN O (S2)
O
~T R 2
B B
where the symbols and indices have the following meanings:
RBI is halogen, (C,-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C,-C4)-haloalkyl;
nB is a natural number from 0 to 5, preferably from 0 to 3;
RB2 is ORBS, SRBS or NRBSRBq or a saturated
or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom
and
up to 3 heteroatoms, preferably from the group consisting of 0 and S, which is
attached via the nitrogen atom to the carbonyl group in (S2) and which is
unsubstituted or substituted by radicals from the group consisting of (C,-C4)-
alkyl,
(C,-C4)-alkoxy and optionally substituted phenyl, preferably a radical of the
formula ORBS, NHRB4 or N(CH3)2, in particular of the formula ORB3;
RB3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon
radical having
preferably a total of I to 18 carbon atoms;
RB4 is hydrogen, (C,-C6)-alkyl, (C,-C6)-alkoxy or substituted or unsubstituted
phenyl;
TB is a (Cl- or C2)-alkanediyl chain which is unsubstituted or substituted by
one or

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two (C,-C4)-alkyl radicals or by [(C,-C3)-alkoxy]carbonyl;
preferably:
a) compounds of the type of the 8-quinolinoxyacetic acid (S2a), preferably
1-methylhexyl (5-chloro-8-quinolinoxy)acetate ("cloquintocet-mexyl") (S2-1),
1,3-dimethyl-but-l-yl (5-chloro-8-quinolinoxy)acetate (S2-2),
4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (S2-3),
1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (S2-4),
ethyl (5-chloro-8-quinolinoxy)acetate (S2-5),
methyl (5-chloro-8-quinolinoxy)acetate (S2-6),
allyl (5-chloro-8-quinolinoxy)acetate (S2-7),
2-(2-propylideneiminoxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxo-
prop-1-yl (5-chloro-8-quinolinoxy)acetate (S2-9) and related compounds, as
described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366,
and also (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and salts,
for
example its lithium, sodium, potassium, calcium, magnesium, aluminium, iron,
ammonium, quaternary ammonium, sulphonium or phosphonium salts, as
described in WO-A-2002/34048;
b) compounds of the type of the (5-chloro-8-quinolinoxy)malonic acid (S2b),
preferably compounds such as diethyl (5-chloro-8-quinolinoxy)malonate, diallyl
(5-chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8-
quinolinoxy)malonate
and related compounds, as described in EP-A-0 582 198.
S3) Compounds of the formula (S3)
O
RCS N C (S3)
3
RC
where the symbols and indices have the following meanings:
RC` is (C,-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl,
(C3-C7)-
cycloalkyl, preferably dichloromethyl;
Rc2, RC3 are identical or different and are hydrogen, (C,-C4)-alkyl, (C2-C4)-
alkenyl, (C2-

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C4)-alkynyl, (C,-C4)-haloalkyl, (C-C4)-haloalkenyl, (C,-C4)-alkylcarbamoyl-
(CI-C4)-alkyl, (C7-C4)-alkenylcarbamoyl-(C,-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-
alkyl, dioxolanyl (C, C4) alkyl, thiazolyl, furyl, furylalkyl, thienyl,
piperidyl,
substituted or unsubstituted phenyl, or RC2 and Rc3 together form a
substituted or
unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine,
piperidine,
morpholine, hexahydropyrimidine or benzoxazine ring;
preferably:
active compounds of the type of the dichloroacetamides which are frequently
used
as pre-emergence safeners (soil-acting safeners), such as, for example,
"dichlormid" (N,N-diallyl-2,2-dichloroacetamide) (S3-1),
"R-29148" (3-dichloroacetyl-2,2,5-trimethyl-l,')-oxazolidine) from Stauffer
(S3-2),
"R-28725" (3-dichloroacetyl-2,2-dimethyl-l,')-oxazolidine) from Stauffer (S3-
3),
"benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),
"PPG-1292" (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG
Industries (S3-5),
"DKA-24" (N-ally]-N-[(allylaminocarbonyl)methyl]dichloroacetamide) from
Sagro-Chem (S3-6),
"AD-67" or "MON 4660" (3-dichloroacetyl-l-oxa-3-azaspiro[4,5]decane) from
Nitrokemia or Monsanto (S3-7),
"TI-35" (1-dichloroacetylazepane) from TRI-Chemical RT (S3-8)
"diclonon" (dicyclonon) or "BAS145138" or "LAB145138" (S3-9) (3-
dichloroacetyl-2,5,5-trimethyl-1,3-diazabicyclo[4.3.0]nonane) from BASF,
"furilazole" or "MON 13900" ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-
dimethyloxazolidine) (S3-10) and also its (R)-isomer (S3-11).
S4) N-Acylsulphonamides of the formula (S4) and their salts
RD 3 (RD4)D
RDA O O
S (S4)
O XD
(RD2)nD
where the symbols and indices have the following meanings:

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XD is CH or N;
RD' is CO-NRDSRD6 or NHCO-RD7;
RD2 is halogen, (C,-C4)-haloalkyl, (C,-C4)-haloalkoxy, nitro, (C-C4)-alkyl,
(C,-C4)-
alkoxy, (C-C4)-alkylsulphonyl, (C,-C4)-alkoxycarbonyl or (C,-C4)-
alkylcarbonyl;
RD3 is hydrogen, (CI-C4)-alkyl, (C7-C4)-alkenyl or (C-C4)-alkynyl;
RD4 is halogen, nitro, (C,-C4)-alkyl, (C,-C4)-haloalkyl, (C,-C4)-haloalkoxy,
(C3-C6)-
cycloalkyl, phenyl, (C,-C4)-alkoxy, cyano, (C,-C4)-alkylthio, (C1-C4)-alkyl-
sulphinyl, (C,-C4)-alkylsulphonyl, (C,-C4)-alkoxycarbonyl or (Ct-C4)-
alkylcarbonyl;
RD5 is hydrogen, (C,-C6)-alkyl, (C3-C6)-cycloalkyl, (C-C6)-alkenyl, (C2-C6)-
alkynyl,
(C5-C6)-cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl which contains
VD
heteroatoms from the group consisting of nitrogen, oxygen and sulphur, where
the
seven last-mentioned radicals are substituted by VD substituents from the
group
consisting of halogen, (C-C6)-alkoxy, (C,-C6)-haloalkoxy, (CI-C,)-
alkylsulphinyl,
(C,-C,)-alkylsulphonyl, (C3-C6)-cycloalkyl, (C,-C4)-alkoxycarbonyl, (CI-C4)-
alkylcarbonyl and phenyl and, in the case of cyclic radicals, also (CI-C4)-
alkyl and
(C1-C4)-haloalkyl;
RD6 is hydrogen, (C,-C6)-alkyl, (C-C6)-alkenyl or (C-C6)-alkynyl, where the
three last-
mentioned radicals are substituted by VD radicals from the group consisting of
halogen, hydroxy, (C,-C4)-alkyl, (C,-C4)-alkoxy and (C,-C4)-alkylthio, or
RD5 and R 6 together with the nitrogen atom carrying them form a pyrrolidinyl
or
piperidinyl radical;
RD7 is hydrogen, (C-C4)-alkylamino, di-(C-C4)-alkylamino, (C,-C6)-alkyl, (C3-
C6)-
cycloalkyl, where the 2 last-mentioned radicals are substituted by VD
substituents
from the group consisting of halogen, (C,-C4)-alkoxy, halo-(C,-C6)-alkoxy and
(Cl_C4)-alkylthio and, in the case of cyclic radicals, also (C,-C4)-alkyl and
(C,-C4)-
haloalkyl;
nD is 0, 1 or 2;
MD is 1 or 2;

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VD is 0, 1, 2 or 3;
from among these, preference is given to compounds of the type of the N-
acylsulphonamides,
for example of the formula (S4a) below, which are known, for example, from WO-
A-
97/4subchamberl6
O O O 4
(RD )MD
~
~N S-N (S4a)
RD H O H
in which
RD7 is (C,-C6)-alkyl, (C3-C6)-cycloalkyl, where the 2 last-mentioned radicals
are
substituted by VD substituents from the group consisting of halogen, (C,-C4)-
alkoxy, halo-(C,-C6)-alkoxy and (C,-C4)-alkylthio and, in the case of cyclic
radicals, also (C,-C4)-alkyl and (C,-C4)-haloalkyl;
RD4 is halogen, (C,-C4)-alkyl, (C,-C4)-alkoxy, CF3,
MD 1 or 2;
VD is 0, 1, 2 or 3;
and also
acylsulphamoylbenzamides, for example of the formula (S4b) below, which are
known, for
example, from WO-A-99/16744,
R5
ND O O
H' Y-C~- ISN (RD )MD (S4b)
O O H
for example those in which
RD' = cyclopropyl and (RD4) = 2-OMe ("cyprosulfamide", S4-1),
RD' = cyclopropyl and (RD4) = 5-C1-2-OMe (S4-2),
RD' = ethyl and (RD4) = 2-OMe (S4-3),

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RD' = isopropyl and (RD4) = 5-C1-2-OMe (S4-4) and
RD' = isopropyl and (RD) = 2-OMe (S4-5)
and also
compounds of the type of the N-acylsulphamoylphenylureas of the formula (S4 ),
which
are known, for example, from EP-A-365484,
s
a
D O O (R
N D )mD
~ (S4c)
R 9/ H II1 1
D
in which
RD8 and RD9 independently of one another are hydrogen, (C,-C8)-alkyl, (C3-C8)-
cycloalkyl,
(C3-C6)-alkenyl, (C3-C6)-alkynyl,
RD4 is halogen, (C1-C4)-alkyl, (C,-C4)-alkoxy, CF3,
MD is l or 2;
for example
1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea,
1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea,
1-[4-(N-4,5-dimethylbenzoylsulphamoyl)phenyl]-3-methylurea.
S5) Active compounds from the class of the hydroxyaromatics and aromatic-
aliphatic
carboxylic acid derivatives (S5), for example ethyl 3,4,5-triacetoxybenzoate,
3,5-
dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic
acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 1,2-dihydro-2-oxo-6-
trifluoromethylpyridine-3-carboxamide, 2,4-dichlorocinnamic acid, as described
in
WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
S6) Active compounds from the class of the 1,2-dihydroquinoxalin-2-ones (S6),
for
example 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-
thienyl)-1,2-dihydroquinoxaline-2-thione, l-(2-aminoethyl)-3-(2-thienyl)-1,2-
dihydroquinoxalin-2-one hydrochloride, 1-[2-(diethylamino)ethyl]-6,7-dimethyl-
3-

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thiophen-2-ylquinoxalin-2(1H)-one, 1-(2-methylsulphonylaminoethyl)-3-(2-
thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.
S7) Compounds of the formula (S7), as described in WO-A-1998/38856,
H2I,AE
(j)nE1
\ H \ (S7)
(RE1)nE / I / (RE2)E3
where the symbols and indices have the following meanings:
RE1, RE2 independently of one another are halogen, (C,-C4)-alkyl, (C,-C4)-
alkoxy, (C,-C4)-
haloalkyl, (C,-C4)-alkylamino, di-(C,-C4)-alkylamino, nitro;
AE is COORE3 or COSRE4
RE3, RE4 independently of one another are hydrogen, (C,-C4)-alkyl, (C2-C6)-
alkenyl, (C2-
C4)-alkynyl, cyanoalkyl, (C,-C4)-haloalkyl, phenyl, nitrophenyl, benzyl,
halobenzyl, pyridinylalkyl or alkylammonium,
nEI is0or1;
nE2, nE3 independently of one another are 0, 1 or 2,
preferably:
diphenylmethoxyacetic acid,
ethyl diphenylmethoxyacetate,
methyl diphenylmethoxyacetate (CAS Reg. No.: 41858-19-9) (S7-1).
S8) Compounds of the formula (S8), as described in WO-A-98/27049,
RF2 O
O
(S8)
(RF1)nF F I
XF RF3
in which

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XF is CH or N,
nF is, if XF=N, an integer from 0 to 4 and
is, if XF=CH, an integer from 0 to 5,
RF' is halogen, (C1-C4)-alkyl, (C,-C4)-haloalkyl, (C,-C4)-alkoxy, (C,-C4)-
haloalkoxy,
nitro, (C,-C4)-alkylthio, (C,-C4)-alkylsulphonyl, (C,-C4)-alkoxycarbonyl,
optionally substituted phenyl, optionally substituted phenoxy,
RF2 is hydrogen or (C,-C4)-alkyl,
RF3 is hydrogen, (C,-C8)-alkyl, (C2-C4)-alkenyl, (C'--C4)-alkynyl or aryl,
where each of
the carbon-containing radicals mentioned above is unsubstituted or substituted
by
one or more, preferably by up to three, identical or different radicals from
the
group consisting of halogen and alkoxy; or salts thereof,
preferably compounds in which
XF is CH,
nF is an integer from 0 to 2,
RF' is halogen, (C,-C4)-alkyl, (C,-C4)-haloalkyl, (C,-C4)-alkoxy, (CI-C4)-
haloalkoxy,
RF2 is hydrogen or (C,-C4)-alkyl,
RF3 is hydrogen, (C,-C8)-alkyl, (C7-C4)-alkenyl, (C2-C4)-alkynyl or aryl,
where each of
the carbon-containing radicals mentioned above is unsubstituted or substituted
by
one or more, preferably by up to three, identical or different radicals from
the
group consisting of halogen and alkoxy;
or salts thereof,
S9) Active compounds from the class of the 3-(5-tetrazolylcarbonyl)-2-
quinolones
(S9), for example
1,2-dihydro-4-hydroxy-l-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg.
No.: 219479-18-2), 1,2-dihydro-4-hydroxy-l-methyl-3-(5-tetrazolylcarbonyl)-2-
quinolone (CAS Reg. No.: 95855-00-8), as described in WO-A-1999/000020.
S 10) Compounds of the formula (S 10a) or (S 10b)

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as described in WO-A-2007/023719 and WO-A-2007/023764
O Z- RG3
11 _ 2 \
(RG1)nc S N YG RG (RG1)nG ~_ 2
'
0 SH YG RG
0 O
(S1 Oa) (S1 Ob)
in which
RG' is halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3
YG, ZG independently of one another are 0 or S,
nG is an integer from 0 to 4,
RG2 is (C1-C16)-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl; benzyl,
halobenzyl,
RGS is hydrogen or (C1-C6)-alkyl.
Sl l) Active compounds of the type of the oxyimino compounds (S11), which are
known
as seed dressings, such as, for example, "oxabetrinil" ((Z)-1,3-dioxolan-2-
ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as seed dressing
safener for millet against metolachlor damage,
"fluxofenim" (1-(4-chlorophenyl)-2,2,2-trifluoro-l-ethanone 0-(1,3-dioxolan-2-
ylmethyl)oxime) (S11-2), which is known as seed dressing safener for millet
against metolachlor damage, and
"cyometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile)
(S 11-3)), which is known as seed dressing safener for millet against
metolachlor
damage.
S12) Active compounds from the class of the isothiochromanones (S12), such as,
for
example, methyl [(3-oxo-1 H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate
(CAS Reg. No.: 205121-04-6) (S12-1) and related compounds from
WO-A-1998/13361.

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S13) One or more compounds from group (S 13):
"naphthalic anhydride" (1.8-naphthalenedicarboxylic anhydride) (S13-1), which
is
known as seed dressing safener for corn against thiocarbamate herbicide
damage,
"fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S 13-2), which is known as
safener
for pretilachlor in sown rice,
"flurazole" (benzyl 2-chloro-4-trifluoromethyl-l,3-thiazole-5-carboxylate)
(S13-3),
which is known as seed dressing safener for millet against alachlor and
metolachior damage,
"CL-304415" (CAS Reg. No.: 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-
benzopyran-4-acetic acid) (S13-4) from American Cyanamid, which is known as
safener for corn against imidazolinone damage,
"MG-191" (CAS Reg. No.: 96420-72-3) (2-di chloromethyl-2-methyl-1,3-
dioxolane) (S 13-5) from Nitrokemia, which is known as safener for corn,
"MG-838" (CAS Reg. No.: 133993-74-5) (2-propenyl 1-oxa-4-
azaspiro[4.5]decane-4-carbodithioate) (S 13-6) from Nitrokemia,
"disulfoton" (0,0-diethyl S-2-ethylthioethyl phosphorodithioate) (S 13-7),
"dietholate" (0,0-diethyl O-phenyl phosphorothioate) (S 13-8),
"mephenate" (4-chlorophenyl methylcarbamate) (S 13-9).
S14) Active compounds which, besides a herbicidal effect against harmful
plants, also
have a safener effect on crop plants such as rice, such as, for example,
"dimepiperate" or "MY-93" (S-1-methyl-l-phenylethyl piperidine-l-
carbothioate),
which is known as safener for rice against molinate herbicide damage,
"daimuron" or "SK 23" (1-(1-methyl-l-phenylethyl)-3-p-tolylurea), which is
known as safener for rice against imazosulphuron herbicide damage,
"cumyluron" _ "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-l-phenyl-
ethyl)urea, see JP-A-60087254), which is known as safener for rice against
some
herbicide damage,

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"methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone), which
is known as safener for rice against some herbicide damage,
"CSB" (1-bromo-4-(chloromethylsulphonyl)benzene) from Kumiai, (CAS Reg.
No. 54091-06-4), which is known as safener against some herbicide damage in
rice.
S15) Active compounds which are primarily used as herbicides, but also have
safener
effect on crop plants, for example
(2,4-dichlorophenoxy)acetic acid (2,4-D),
(4-chlorophenoxy)acetic acid,
(R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
(4-chloro-o-tolyloxy)acetic acid (MCPA),
4-(4-chloro-o-tolyloxy)butyric acid,
4-(4-chlorophenoxy)butyric acid,
3,6-dichloro-2-methoxybenzoic acid (dicamba),
1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor-ethyl).
Most preferred crop plant compatibility-improving compounds [component (b')]
are cloquintocet-
mexyl, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim,
cumyluron, S4-1 and S4-5,
and particular emphasis is given to cloquintocet-mexyl and mefenpyr-diethyl.
Emphasis is also given
to cyprosulphamide (S4-1).
Examples of the selective herbicidal combinations according to the invention
comprising in each case
one active compound of the formula (1) and in each case one of the safeners
defined above are listed
below:

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Active compound of Safener Active compound of Safener
the formula the formula
I-a-1 cloquintocet-mexyl I-a-7 fenchlorazole-ethyl
I-a-1 fenchlorazole-ethyl I-a-7 isoxadifen-ethyl
I-a-l isoxadifen-ethyl I-a-7 mefenpyr-diethyl
I-a-1 mefenpyr-diethyl I-a-7 fenclorim
I-a-1 fenclorim I-a-7 cum luron
1-a-I cum luron I-a-7 S4-1
I-a-I S4-1 I-a-7 S4-5
I-a-1 S4-5 1-a-8 clo uintocet-mexyl
I-a-2 clo uintocet-mex l I-a-8 fenchlorazole-ethyl
I-a-2 fenchlorazole-ethyl I-a-8 isoxadifen-ethyl
I-a-2 isoxadifen-ethyl I-a-8 mefenpyr-diethyl
I-a-2 mefen yr-diethyl I-a-8 fenclorim
I-a-2 fenclorim I-a-8 cum luron
I-a-2 cumyluron I-a-8 S4-1
I-a-2 S4-1 I-a-8 S4-5
I-a-2 S4-5 I-a-9 clo uintocet-mex l
I-a-3 clo uintocet-mexyl I-a-9 fenchlorazole-ethyl
I-a-3 fenchlorazole-ethyl I-a-9 isoxadifen-ethyl
I-a-3 isoxadifen-ethyl 1-a-9 mefenpyr-diethyl
I-a-3 mefen r-dieth l I-a-9 fenclorim
I-a-3 fenclorim I-a-9 cumyluron
I-a-3 cumyluron I-a-9 S4-1
I-a-3 S4-1 I-a-9 S4-5
I-a-3 S4-5 I-a-10 clo uintocet-mex 1
I-a-4 clo uintocet-mex l I-a-10 fenchlorazole-ethyl
I-a-4 fenchlorazole-ethyl I-a-10 isoxadifen-ethyl
1-a-4 isoxadifen-ethyl I-a-l0 mefenpy -diethyl
I-a-4 mefenpyr-diethyl I-a- 10 fenclorim
I-a-4 fenclorim I-a-10 cumyluron
I-a-4 cum luron I-a-10 S4-1
I-a-4 S4-1 I-a-10 S4-5
I-a-4 S4-5 I-a-11 clo uintocet-mexyl
I-a-S cloquintocet-mexyl I-a-11 fenchlorazole-ethyl
I-a-S fenchlorazole-eth l I-a-11 isoxadifen-ethyl
I-a-S isoxadifen-ethyl 1-a-11 mefenpyr-diethyl
I-a-5 mefenpyr-diethyl I-a- II fens lori m
I-a-S fenclorim I-a-I1 cumyluron
I-a-5 cumyluron I-a-I1 S4-1
I-a-S S4-1 I-a-11 S4-5
I-a-S S4-5 I-a-12 cloquintocet-mexyl
I-a-6 clo uintocet-mexyl I-a-l2 fenchlorazole-ethyl
I-a-6 fenchlorazole-ethyl I-a- 12 isoxadifen-ethyl
I-a-6 isoxadifen-ethyl I-a-12 mefen yr-diethyl
I-a-6 mefen yr-diethyl I-a-12 fenclorim
I-a-6 fenclorim I-a-12 cum luron
I-a-6 cumyluron I-a-12 S4-1
I-a-6 S4-l I-a-12 S4-5
I-a-6 S4-5 I-a- 13 clog uintocet-mexyl
I-a-7 clo uintocet-mex l I-a-13 fenchlorazole-ethyl

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Active compound of Safener Active compound of Safener
the formula the formula
I-a-13 isoxadifen-ethyl I-a- 19 mefenpyr-diethyl
I-a-13 mefenpyr-diethyl I-a-19 fenclorim
I-a-13 fenclorim I-a-19 cumyluron
I-a-13 cumyluron I-a-19 S4-1
I-a-13 S4-1 I-a-19 S4-5
I-a-13 S4-5 I-a-20 clo uintocet-mex l
I-a-14 clo uintocet-mex l I-a-20 fenchlorazole-ethyl
I-a-14 fenchlorazole-ethyl I-a-20 isoxadifen-ethyl
I-a-14 isoxadifen-ethyl I-a-20 mefen yr-diethyl
I-a-14 mefen yr-dieth l I-a-20 fenclorim
I-a- 14 fenclorim I-a-20 cumyluron
I-a-14 cumyluron I-a-20 S4-1
I-a-14 S4-1 I-a-20 S4-5
I-a-14 S4-5 I-a-21 clo uintocet mex l
I-a- 15 clo uintocet-mex l I-a-21 fenchlorazole-ethyl
I-a-15 fenchlorazole-ethyl I-a-21 isoxadifen-ethyl
I-a-15 isoxadifen-ethyl I-a-21 mefenpyr-diethyl
I-a-15 mefen r-dieth l I-a-21 fenclorim
I-a-15 fenclorim I-a-21 cumyluron
I-a-15 cumyluron I-a-21 S4-1
I-a-15 S4-1 I-a-21 S4-5
I-a-15 S4-5 I-a-22 clo uintocet-mex l
1-a-16 cloquintocet-mexyl I-a-22 fenchlorazole-ethyl
I-a-16 fenchlorazole-ethyl I-a-22 isoxadifen-ethyl
I-a-16 isoxadifen-ethyl I-a-22 mefenpyr-d ethyl
I-a- 16 mefen yr-diethyl I-a-22 fenclorim
I-a-16 fenclorim I-a-22 cumyluron
I-a-16 cumyluron I-a-22 S4-1
I-a-16 S4-1 I-a-22 S4-5
I-a-16 S4-5 I-a-23 clo uintocet mexyl
I-a-17 clo uintocet-mexyl I-a-23 fenchlorazole-ethyl
I-a-17 fenchlorazole-ethyl I-a-23 isoxadifen-ethyl
I-a- 17 isoxadifen-ethyl I-a-23 mefen r-dieth l
I-a-17 mefenpyr-diethyl I-a-23 fenclorim
I-a- 17 fenclorim I-a-23 cumyluron
I-a-17 cumyluron I-a-23 S4-1
I-a-17 S4-1 I-a-23 S4-5
I-a-17 S4-5 I-a-24 clo uintocet-mexyl
I-a- 18 clo uintocet-mexyl I-a-24 fenchlorazole-ethyl
I-a- 18 fenchlorazole-ethyl I-a-24 isoxadifen-ethyl
I-a- 18 isoxadifen-ethyl I-a-24 mete thyl
I-a- 18 mefenpyr-diethyl I-a-24 fenclorim
I-a-18 fenclorim I-a-24 cumyluron
I-a-18 cum luron I-a-24 S4-1
I-a- 18 S4-1 I-a-24 S4-5
I-a-18 S4-5 I-a-25 clo uintocet mex l
I-a-19 clo uintocet-mex l I-a-25 fenchlorazole-ethyl
I-a-19 fenchlorazole-ethyl I-a-25 isoxadifen-ethyl
I-a-19 isoxadifen-ethyl I-a-25 mefen r-dieth l

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Active compound of Safener Active compound of Safener
the formula the formula
1-a-25 fenclorim I-a-3 I cumyluron
I-a-25 cumyluron I-a-31 S4-1
I-a-25 S4-1 I-a-3 I S4-5
I-a-25 S4-5 I-a-32 clo uintocet-mex l
I-a-26 clo uintocet-mex 1 I-a 32 fenchlorazole-ethyl
I-a-26 fenchlorazole-ethyl I-a-32 isoxadifen-ethyl
I-a-26 isoxadifen-ethyl I-a-32 mefen r-dieth l
I-a-26 mefen r-dieth 1 I-a-32 fenclorim
I-a-26 fenclorim I-a-32 cumyluron
I-a-26 cumyluron I-a-32 S4-1
I-a-26 S4-1 I-a-32 S4-5
I-a-26 S4-5 [-a-33 cloquintocet-mexyl
I-a-27 clo uintocet mexyl I-a-33 fenchiorazole-ethyl
I-a-27 fenchlorazole-ethyl I-a-33 isoxadifen-eth 1
I-a-27 isoxadifen-eth 1 I-a-33 mefenpyr-diethyl
I-a-27 mefen yr-dieth 1 I-a-33 fenclorim
I-a-27 fenclorim I-a-33 cumyluron
I-a-27 cumyluron I-a-33 S4-1
I-a-27 S4-1 I-a-33 S4-5
I-a-27 S4-5 I-a-34 cloquintocet-mexyl
I-a-28 cloquintocet-mexyl I-a-34 fenchlorazole-ethyl
I-a-28 fenchlorazole-ethyl I-a-34 isoxadifen-eth l
I-a-28 isoxadifen-ethyl I-a-34 mefenpyr-diethyl
I-a-28 mefenpyr-diethyl I-a-34 fenclorim
I-a-28 fenclorim I-a-34 cumyluron
I-a-28 cum luron I-a-34 S4-1
I-a-28 S4-1 I-a-34 S4-5
I-a-28 S4-5 I-a-35 cloquintocet-mexyl
I-a-29 clog uintocet-mex l I-a-35 fenchlorazole-ethyl
1-a-29 fenchlorazole-ethyl I-a-35 isoxadifen-ethyl
I-a-29 isoxadifen-ethyl I-a-35 mefen r-dieth l
I-a-29 mefen r-dieth 1 I-a-35 fenclorim
I-a-29 fenclorim I-a-35 cumyluron
1-a-29 cumyluron I-a-35 S4-1
I-a-29 S4-1 I-a-35 S4-5
I-a-29 S4-5 I-a-36 clo uintocet-mex l
I-a-30 clo uintocet-mex 1 I-a-36 fenchlorazole-ethyl
I-a-30 fenchlorazole-ethyl I-a-36 isoxadifen-ethyl
1-a-30 isoxadifen-ethyl [-a-36 mefen r-dieth l
1-a-30 mefen r-dieth 1 I-a-36 fenclorim
I-a-30 fenclorim I-a-36 cumyluron
I-a-30 cumyluron I-a-36 S4-1
I-a-30 S4-1 I-a-36 S4-5
I-a-30 S4-5 I-a-37 clo uintocet-mexyl
I-a-31 cloquintocet-mexyl I-a-37 fenchlorazole-ethyl
I-a-31 fenchlorazole-ethyl I-a-37 isoxadifen-ethyl
I-a-31 isoxadifen-ethyl I-a-37 mefen r-dieth l
I-a-31 mefenpyr-diethyl I-a-37 fenclorim
I-a-31 fenclorim I-a-37 cumyluron

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Active compound of Safener Active compound of Safener
the formula the formula
I-a-37 S4-1 I-a-43 S4-5
I-a-37 S4-5 I-a-44 cloquintocet-mexyl
I-a-38 cloquintocet-mexyl I-a-44 fenchiorazole-ethyl
I-a-38 fenchlorazole-ethyl I-a-44 isoxadifen-eth
I-a-38 isoxadifen-ethyl I-a-44 mefen yr-dieth l
I-a-38 mefenpyr-diethyl I-a-44 fenclorim
I-a-38 fenclorim I-a-44 cumyluron
I-a-38 cum luron I-a-44 S4-1
I-a-38 S4-1 I-a-44 S4-5
I-a-38 S4-5 I-a-45 cloquintocet-mexyl
I-a-39 clo uintocet-mex l I-a-45 fenchiorazole-ethyl
I-a-39 fenchlorazole-ethyl I-a-45 isoxadifen-ethyl
I-a-39 isoxadifen-ethyl I-a-45 mefenpyr-diethyl
I-a-39 mefen r-dieth l I-a-45 fenclorim
I-a-39 fenclorim I-a-45 cum luron
I-a-39 cumyluron I-a-45 S4-1
I-a-39 S4-1 I-a-45 S4-5
I-a-39 S4-5 I-a-46 clo uintocet-mex l
I-a-40 cloquintocet-mexyl I-a-46 fenchlorazole-ethyl
I-a-40 fenchlorazole-ethyl I-a-46 isoxadifen-ethyl
I-a-40 isoxadifen-ethyl I-a-46 mefen yr-diethyl
I-a-40 mefen r-dieth l I-a-46 fenclorim
I-a-40 fenclorim I-a-46 cumyluron
I-a-40 cumyluron I-a-46 S4-1
I-a-40 S4-1 I-a-46 S4-5
I-a-40 S4-5 I-a-47 clo uintocet-mexyl
I-a-41 cloquintocet-mexyl I-a-47 fenchlorazole-ethyl
I-a-41 fenchlorazole-ethyl I-a-47 isoxadifen-ethyl
I-a-41 isoxadifen-ethyl I-a-47 mefen vr-diethyl
I-a-41 mefenpyr-diethyl I-a-47 fenclorim
I-a-41 fenclorim I-a-47 cumyluron
I-a-41 cum luron I-a-47 S4-1
I-a-41 S4-1 I-a-47 S4-5
1-a-41 S4-5 I-a-48 cloquintocet-mexyl
I-a-42 cloquintocet-mexyl I-a-48 fenchlorazole-ethyl
I-a-42 fenchlorazole-ethyl 1-a-48 isoxadifen-ethyl
I-a-42 isoxadifen-ethyl I-a-48 mefen r-diethyl
I-a-42 mefen yr-diethyl I-a-48 fenclorim
I-a-42 fenclorim I-a-48 cum luron
I-a-42 cumyluron I-a-48 S4-1
I-a-42 S4-1 I-a-48 S4-5
I-a-42 S4-5 I-a-49 clo uintocet-mex l
I-a-43 clo uintocet-mex l I-a-49 fenchlorazole-ethyl
I-a-43 fenchlorazole-ethyl I-a-49 isoxadifen-ethyl
I-a-43 isoxadifen-ethyl I-a-49 mefen yr-di eth l
I-a-43 mefen yr-diethyl I-a-49 fenclorim
I-a-43 fenclorim I-a-49 cumyluron
I-a-43 cumyluron I-a-49 S4-1
I-a-43 S4-1 I-a-49 S4-5

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Active compound of Safener Active compound of Safener
the formula the formula
I-a-50 cloquintocet-mexyl I-a-56 fenchlorazole-ethyl
I-a-50 fenchlorazole-ethyl I-a-56 isoxadifen-ethyl
I-a-50 isoxadifen-ethyl I-a-56 mefen r-diethyl
I-a-50 mefen r-diethyl I-a-56 fenclorim
I-a-50 fenclorim I-a-56 cumyluron
I-a-50 cumyluron I-a-56 S4-1
I-a-50 S4-1 I-a-56 S4-5
I-a-50 S4-5 I-a-57 clo uintocet-mex l
I-a-51 clog uintocet-mexyl I-a-57 fenchlorazole-ethyl
I-a-51 fenchlorazole-ethyl I-a-57 isoxadifen-ethyl
1-a-51 isoxadifen-ethyl I-a-57 mefen r-dieth l
I-a-51 mefen yr-diethyl I-a-57 fenclorim
I-a-51 fenclorim I-a-57 cumyluron
I-a-51 cum luron I-a-57 S4-1
I-a-51 S4-1 I-a-57 S4-5
I-a-51 S4-5 I-a-58 cloquintocet-mexyl
I-a-52 clo uintocet-mexyl I-a-58 fenchlorazole-ethyl
I-a-52 fenchlorazole-ethyl I-a-58 isoxadifen-ethyl
I-a-52 isoxadifen-ethyl I-a-58 mefen yr-diethyl
I-a-52 mefenpyr-diethyl I-a-58 fenclorim
I-a-52 fenclorim I-a-58 cumyluron
I-a-52 cumyluron I-a-58 S4-1
I-a-52 S4-1 I-a-58 S4-5
I-a-52 S4-5 I-a-59 cloquintocet-mexyl
I-a-53 clog uintocet-mex l I-a-59 fenchlorazole-ethyl
I-a-53 fenchlorazole-eth l I-a-59 isoxadifen-ethyl
I-a-53 isoxadifen-ethyl I-a-59 mefenpyr-diethyl
I-a-53 mefenpyr-diethyl I-a-59 fenclorim
I-a-53 fenclorim I-a-59 cumyluron
1-a-53 cumyluron I-a-59 S4-1
I-a-53 S4-1 I-a-59 S4-5
I-a-53 S4-5 I-a-60 clo uintocet-mex l
I-a-54 cloquintocet-mexyl I-a-60 fenchlorazole-ethyl
I-a-54 fenchlorazole-ethyl I-a-60 isoxadifen-ethyl
I-a-54 isoxadifen-ethyl I-a-60 mete thyl
I-a-54 mefen r-dieth l 1-a-60 fenclorim
I-a-54 fenclorim I-a-60 cumyluron
I-a-54 cumyluron I-a-60 S4-1
I-a-54 S4-1 I-a-60 S4-5
I-a-54 S4-5 I-a-61 clo uintocet mex l
I-a-55 cloquintocet-mexyl I-a-61 fenchlorazole-ethyl
I-a-55 fenchlorazole-ethyl I-a-61 isoxadifen-ethyl
I-a-55 isoxadifen-ethyl I-a-61 mefen r-dieth l
I-a-55 mefen yr-diethyl I-a-61 fenclorim
I-a-55 fenclorim I-a-61 cumyluron
I-a-55 cumyluron I-a-61 S4-1
I-a-55 S4-1 I-a-61 S4-5
I-a-55 S4-5 I-a-62 clo uintocet-mex l
I-a-56 cloquintocet-mexyl I-a-62 fenchlorazole-ethyl

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Active compound of Safener Active compound of Safener
the formula the formula
I-a-62 isoxadifen-ethyl I-a-68 mefenpyr-diethyl
I-a-62 mefenpyr-diethyl I-a-68 fenclorim
I-a-62 fenclorim I-a-68 cumyluron
I-a-62 cum luron I-a-68 S4-1
I-a-62 S4-1 I-a-68 S4-5
I-a-62 S4-5 I-a-69 cloquintocet-mexyl
I-a-63 clog uintocet-mex l I-a-69 fenchlorazole-ethyl
I-a-63 fenchlorazole-ethyl I-a-69 isoxadifen-ethyl
I-a-63 isoxadifen-ethyl I-a-69 mefen yr-diethyl
I-a-63 mefenpyr-diethyl I-a-69 fenclorim
I-a-63 fenclorim I-a-69 cumyluron
1-a-63 cumyluron I-a-69 S4-1
I-a-63 S4-1 I-a-69 S4-5
I-a-63 S4-5 I-a-70 clo uintocet-mex l
I-a-64 clo uintocet-mex l I-a-70 fenchlorazole-ethyl
I-a-64 fenchlorazole-ethyl I-a-70 isoxadifen-ethyl
I-a-64 isoxadifen-ethyl I-a-70 mefenpyr-diethyl
1-a-64 mefen r-dieth l I-a-70 fenclorim
I-a-64 fenclorim I-a-70 cumyluron
I-a-64 cumyluron I-a-70 S4-1
I-a-64 S4-1 I-a-70 S4-5
I-a-64 S4-5 I-a-71 clo uintocet-mex l
I-a-65 cloquintocet-mexyl I-a-71 fenchlorazole-ethyl
I-a-65 fenchlorazole-ethyl I-a-71 isoxadifen-ethyl
I-a-65 isoxadifen-ethyl I-a-71 mefen r-di eth l
I-a-65 mefen vr-diethyl 1-a-71 fenclorim
I-a-65 fenclorim I-a-71 cumyluron
I-a-65 cumyluron I-a-71 S4-1
I-a-65 S4-1 I-a-71 S4-5
I-a-65 S4-5 I-a-72 cloquintocet-mexyl
I-a-66 cloquintocet-mexyl I-a-72 fenchlorazole-ethyl
1-a-66 fenchlorazole-ethyl I-a-72 isoxadifen-ethyl
I-a-66 isoxadifen-ethyl I-a-72 mefen r-dieth l
I-a-66 mefen yr-diethyl I-a-72 fenclorim
I-a-66 fenclorim I-a-72 cumyluron
I-a-66 cumyluron I-a-72 S4-1
I-a-66 S4-1 I-a-72 S4-5
I-a-66 S4-5 I-a-73 cloquintocet-mexyl
1-a-67 clo uintocet-mex l I-a-73 fenchlorazole-ethyl
I-a-67 fenchlorazole-ethyl I-a-73 isoxadifen-ethyl
I-a-67 isoxadifen-ethyl I-a-73 mefenpyr-d ethyl
I-a-67 mefenpyr-diethyl I-a-73 fenclorim
I-a-67 fenclorim 1-a-73 cumyluron
I-a-67 cumyluron I-a-73 S4-1
I-a-67 S4-1 I-a-73 S4-5
I-a-67 S4-5 I-a-74 clo uintocet-mexyl
I-a-68 clo uintocet-mex l I-a-74 fenchlorazole-ethyl
I-a-68 fenchlorazole-ethyl I-a-74 isoxadifen-ethyl
I-a-68 isoxadifen-ethyl I-a-74 mefen yr-diethyl

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Active compound of Safener Active compound of Safener
the formula the formula
I-a-74 fenclorim I-b-5 cumyluron
I-a-74 cumyluron I-b-S S4-1
I-a-74 S4-1 I-b-5 S4-5
I-a-74 S4-5 I-b-6 clo uintocet-mex 1
I-a-75 clo uintocet-mexyl I-b-6 fenchlorazole-ethyl
I-a-75 fenchlorazole-ethyl I-b-6 isoxadifen-ethyl
I-a-75 isoxadifen-ethyl I-b-6 mefen r-diethyl
I-a-75 mefen r-dieth 1 I-b-6 fenclorim
I-a-75 fenclorim I-b-6 cumyluron
I-a-75 cumyluron I-b-6 S4-1
1-a-75 S4-1 I-b-6 S4-5
I-a-75 S4-5 I-b-7 cloquintocet-mex l
I-b-1 cloquintocet-mexyl I-b-7 fenchlorazole-ethyl
I-b-1 fenchlorazole-ethyl I-b-7 isoxadifen-ethyl
I-b-1 isoxadifen-ethyl I-b-7 mefen r-dieth l
I-b-1 mefenyr-diethyl I-b-7 fenclorim
I-b-I fenclorim I-b-7 cumyluron
I-b-1 cum luron 1-b-7 S4-1
I-b-1 S4-1 I-b-7 S4-5
I-b-1 S4-5 I-b-8 clo uintocet-mexyl
I-b-2 cloquintocet-mexyl I-b-8 fenchlorazole-ethyl
I-b-2 fenchlorazole-ethyl I-b-8 isoxadifen-ethyl
I-b-2 isoxadifen-ethyl I-b-8 mefen yr-diethyl
I-b-2 mefenpyr-diethyl I-b-8 fenclorim
I-b-2 fenclorim I-b-8 cumyluron
I-b-2 cumyluron I-b-8 S4-1
I-b-2 S4-1 I-b-8 S4-5
I-b-2 S4-5 I-b-9 cloquintocet-mexyl
I-b-3 clo uintocet-mex l I-b-9 fenchlorazole-ethyl
I-b-3 fenchlorazole-ethyl I-b-9 isoxadifen-ethyl
I-b-3 isoxadifen-ethyl I-b-9 mefenpyr-diethyl
I-b-3 mefen r-dieth l I-b-9 fenclorim
I-b-3 fenclorim I-b-9 cumyluron
I-b-3 cumyluron I-b-9 S4-1
I-b-3 S4-1 I-b-9 S4-5
I-b-3 S4-5 I-b-10 clo uintocet mex l
I-b-4 clo uintocet-mexyl I-b-10 fenchlorazole-ethyl
1-b-4 fenchlorazole-ethyl I-b- 10 isoxadifen-ethyl
I-b-4 isoxadifen-ethyl I-b- 10 mefen r-dieth l
I-b-4 mefen r-dieth l I-b- 10 fenclorim
I-b-4 fenclorim I-b- 10 cumyluron
I-b-4 cumyluron I-b-10 S4-1
I-b-4 S4-1 I-b-10 S4-5
I-b-4 S4-5 I-b-11 clo uintocet-mexyl
I-b-5 cloquintocet-mexyl I-b- Il fenchlorazole-ethyl
I-b-S fenchlorazole-ethyl I-b-11 isoxadifen-ethyl
I-b-S isoxadifen-ethyl I-b-11 mefen r-dieth l
I-b-5 mefenpyr-diethyl I-b-11 fenclorim
I-b-S fenclorim I-b-11 cumyluron

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Active compound of Safener Active compound of Safener
the formula the formula
I-b-11 S4-1 I-b- 17 S4-5
I-b-11 S4-5 I-b-18 c loquintocet-mexyl
I-b- 12 clog uintocet-mexyl I-b-18 fenchlorazole-ethyl
I-b- 12 fenchlorazole-ethyl I-b-18 isoxadifen-ethyl
I-b- 12 isoxadifen-ethyl I-b- 18 mefen yr-diethyl
I-b-12 mefenpyr-diethyl I-b- 18 fenclorim
1-b-12 fenclorim I-b-18 cumyluron
I-b-12 cumvluron I-b-18 S4-1
I-b-12 S4-1 I-b- 18 S4-5
1-b-12 S4-5 I-b-19 cloquintocet-mexyl
I-b-13 clo uintocet-mex l I-b- 19 fenchlorazole-ethyl
I-b-13 fenchlorazole-ethyl I-b- 19 isoxadifen-ethyl
I-b-13 isoxadifen-ethyl I-b-19 mefenyr-diethyl
I-b-13 mefen r-dieth l I-b-19 fenclorim
I-b-13 fenclorim I-b-19 cumyluron
I-b-13 cum luron I-b-19 S4-1
I-b-13 S4-1 I-b-19 S4-5
I-b-13 S4-5 I-b-20 clo uintocet mex l
I-b- 14 clog uintocet-mexyl I-b-20 fenchlorazole-ethyl
I-b- 14 fenchlorazole-ethyl I-b-20 isoxadifen-ethyl
I-b- 14 isoxadifen-ethyl I-b-20 mefenpyr-diethyl
I-b-14 mefen r-diethyl I-b-20 fenclorim
I-b-14 fenclorim I-b-20 cumyluron
I-b-14 cumyluron I-b-20 S4-1
I-b-14 S4-1 I-b-20 S4-5
I-b-14 S4-5 I-b-21 cloquintocet-mexyl
I-b-15 cloquintocet-mexyl I-b-21 fenchlorazole-ethyl
I-b-15 fenchlorazole-ethyl I-b-21 isoxadifen-ethyl
I-b-15 isoxadifen-ethyl I-b-21 mefen r-dieth l
I-b-15 mefen yr-diethyl I-b-21 fenclorim
I-b-15 fenclorim I-b-21 cumyluron
I-b-15 cumyluron I-b-21 S4-1
I-b-15 S4-1 I-b-21 S4-5
I-b-15 S4-5 I-b-22 clo uintocet mexyl
I-b- 16 clog uintocet-mexyl I-b-22 fenchlorazole-ethyl
I-b-16 fenchlorazole-ethyl I-b-22 isoxadifen-eth l
I-b- 16 isoxadifen-ethyl I-b-22 mefen yr-diethyl
I-b- 16 mefenpyr-diethyl I-b-22 fenclorim
I-b- 16 fenclorim I-b-22 cumyluron
I-b-16 cumvluron I-b-22 S4-1
I-b- 16 S4-1 I-b-22 S4-5
I-b- 16 S4-5 I-b-23 cloquintocet-mexvl
I-b-17 clo uintocet-mex l I-b-23 fenchlorazole-ethyl
I-b-17 fenchlorazole-ethyl I-b-23 isoxadifen-ethyl
I-b-17 isoxadifen-ethyl I-b-23 mefenpyr-diethyl
I-b- 17 mefen yr-diethyl I-b-23 fenclorim
I-b-17 fenclorim I-b-23 cum luron
I-b-17 cumvluron I-b-23 S4-1
I-b-17 S4-1 I-b-23 S4-5

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Active compound of Safener Active compound of Safener
the formula the formula
I-b-24 clo uintocet-mexyl -1-b-3 )0 fenchlorazole-ethyl
I-b-24 fenchlorazole-ethyl I-b-30 isoxadifen-ethyl
1-b-24 isoxadifen-ethyl 1-b-30 mefenpyr-diethyl
1-b-24 mefen r-dieth l I-b-30 fenclorim
I-b-24 fenclorim I-b-30 cumyluron
I-b-24 cumyluron 1-b-30 S4-1
I-b-24 S4-1 1-b-30 S4-5
I-b-24 S4-5 I-b-3I clo uintocet-mex l
I-b-25 cloquintocet-mexyl I-b-31 fenchlorazole-ethyl
I-b-25 fenchlorazole-ethyl I-b-31 isoxadifen-ethyl
I-b-25 isoxadifen-ethyl I-b-31 mefen r-dieth l
I-b-25 mefenpyr-diethyl I-b-3I fenclorim
I-b-25 fenclorim I-b-31 cumyluron
I-b-25 cumyluron I-b-3I S4-1
I-b-25 S4-1 I-b-31 S4-5
I-b-25 S4-5 1-b-3 32 clo uintocet mexyl
I-b-26 clo uintocet-mexyl I-b-32 fenchlorazole-ethyl
I-b-26 fenchlorazole-ethyl I-b-32 isoxadifen-ethyl
1-b-26 isoxadifen-ethyl I-b-32 mefenpyr-diethyl
I-b-26 mefenpyr-diethyl I-b-32 fenclorim
I-b-26 fenclorim I-b-32 cumyluron
I-b-26 cumyluron I-b-32 S4-1
I-b-26 S4-1 I-b-32 S4-5
I-b-26 S4-5 I-b-33 clo uintocet-mexyl
I-b-27 clo uintocet-mex l I-b-33 fenchlorazole-ethyl
I-b-27 fenchlorazole-ethyl -t-b-3 )3 isoxadifen-ethyl
I-b-27 isoxadifen-ethyl I-b-33 mefenpyr-diethyl
I-b-27 mefenpyr-diethyl I-b-33 fenclorim
I-b-27 fenclorim I-b-33 cumyluron
I-b-27 cumyluron I-b-33 S4-1
I-b-27 S4-1 -1-b-3 )3 S4-5
I-b-27 S4-5 I-b-34 clo uintocet-mex l
I-b-28 clo uintocet-mex l I-b-34 fenchlorazole-ethyl
I-b-28 fenchlorazole-ethyl I-b-34 isoxadifen-ethyl
I-b-28 isoxadifen-ethyl I-b-34 mefenpyr-diethyl
I-b-28 mefen yr-diethyl 1-b-34 fenclorim
I-b-28 fenclorim I-b-34 cumyluron
I-b-28 cumyluron I-b-34 S4-1
I-b-28 S4-1 1-b-34 S4-5
I-b-28 S4-5 I-b-35 clo uintocet-mex 1
I-b-29 cloquintocet-mexyl I-b-35 fenchlorazole-ethyl
I-b-29 fenchlorazole-ethyl 1-b-35 isoxadifen-ethyl
I-b-29 isoxadifen-ethyl I-b-35 mefen r-dieth l
I-b-29 mefenpyr-diethyl I-b-35 fenclorim
I-b-29 fenclorim I-b-35 cumyluron
I-b-29 cumyluron I-b-35 S4-1
I-b-29 S4-1 I-b-35 S4-5
I-b-29 S4-5 I-b-36 clo uintocet-mexyl
I-b-30 clo uintocet-mex l I-b-36 fenchlorazole-ethyl

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Active compound of Safener Active compound of Safener
the formula the formula
I-b-36 isoxadifen-ethyl I-b-42 mefen yr-diethyl
1-b-36 mefen yr-diethyl I-b-42 fenclorim
I-b-36 fenclorim I-b-42 cumyluron
I-b-36 cum luron I-b-42 S4-1
1-b-36 S4-1 I-b-42 S4-5
I-b-36 S4-5 I-b-43 clo uintocet-mex l
I-b-37 clo uintocet-mex l I-b-43 fenchlorazole-ethyl
I-b-37 fenchlorazole-ethyl I-b-43 isoxadifen-ethyl
I-b-37 isoxadifen-ethyl I-b-43 mefen yr-dieth 1
1-b-37 mefen yr-diethyl I-b-43 fenclorim
I-b-37 fenclorim I-b-43 cumyluron
1-b-37 cumyluron I-b-43 S4-1
I-b-37 S4-1 I-b-43 S4-5
I-b-37 S4-5 I-b-44 clo uintocet-mex 1
I-b-38 clo uintocet-mex 1 I-b-44 fenchlorazole-ethyl
I-b-38 fenchlorazole eth 1 I-b-44 isoxadifen-ethyl
I-b-38 isoxadifen-ethyl I-b-44 mefenpyr-diethyl
I-b-38 mefen r-dieth 1 I-b-44 fenclorim
I-b-38 fenclorim I-b-44 cumyluron
I-b-38 cumyluron I-b-44 S4-1
I-b-3 8 S4-1 1-b-44 S4-5
I-b-38 S4-5 I-b-45 clo uintocet-mex l
1-b-39 clo uintocet-mex l I-b-45 fenchlorazole-ethyl
I-b-39 fenchlorazole-eth 1 I-b-45 isoxadifen-ethyl
I-b-39 isoxadifen-ethyl I-b-45 mefen yr-diethyl
I-b-39 mefen yr diethyl I-b-45 fenclorim
I-b-39 fenclorim I-b-45 cumyluron
I-b-39 cumyluron I-b-45 S4-1
I-b-39 S4-1 1-b-45 S4-5
1-b-3)9 S4-5 I-b-46 clo uintocet-mexyl
I-b-40 clo uintocet-mexyl I-b-46 fenchlorazole-ethyl
I-b-40 fenchlorazole-ethyl i-b-46 isoxadifen-ethyl
I-b-40 isoxadifen-eth t I-b-46 mefen r-ieth 1
I-b-40 mefen yr-diethyl I-b-46 fenclorim
I-b-40 fenclorim I-b-46 cumyluron
1-b-40 cum luron 1-b-46 S4-1
I-b-40 S4-1 I-b-46 S4-5
I-b-40 S4-5 I-b-47 cloquintocet-mexyl
I-b-41 clo uintocet-mex l 1-b-47 fenchlorazole-ethyl
1-b-41 fenchlorazole-ethyl I-b-47 isoxadifen-ethyl
I-b-41 isoxadifen-ethyl I-b-47 mefen pyr-diethyl
I-b-41 mefenpyr-diethyl I-b-47 fenclorim
I-b-41 fenclorim I-b-47 cumyluron
I-b-41 cumyluron I-b-47 S4-1
I-b-41 S4-1 I-b-47 S4-5
I-b-41 S4-5 I-b-48 clo uintocet-mex 1
I-b-42 clo uintocet-mex l 1-b-48 fenchlorazole-ethyl
I-b-42 fenchlorazole-ethyl I-b-48 isoxadifen-ethyl
I-b-42 isoxadifen-ethyl I-b-48 mefen vr-diethyl

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Active compound of Safener Active compound of Safener
the formula the formula
I-b-48 fenclorim I-b-54 cumyluron
I-b-48 cumyluron I-b-54 S4-1
I-b-48 S4-1 I-b-54 S4-5
I-b-48 S4-5 I-b-55 clo uintocet-mex l
1-b-49 cloquintocet-mexyl I-b-55 fenchlorazole-ethyl
1-b-49 fenchlorazole-ethyl I-b-55 isoxadifen-ethyl
I-b-49 isoxadifen-ethyl I-b-55 mefen r-diethyl
I-b-49 mefen r-dieth l I-b-55 fenclorim
I-b-49 fenclorim I-b-55 cumyluron
I-b-49 cumyluron I-b-55 S4-1
I-b-49 S4-1 I-b-55 S4-5
I-b-49 S4-5 I-b-56 clo uintocet-mexyl
I-b-50 cloquintocet-mexyl I-b-56 fenchlorazole-ethyl
1-b-50 fenchlorazole-ethyl I-b-56 isoxadifen-ethyl
I-b-50 isoxadifen-ethyl I-b-56 mefen r-dieth 1
I-b-50 mefenpyr-diethyl I-b-56 fenclorim
I-b-50 fenclorim 1-b-56 cumyluron
I-b-50 cum luron I-b-56 S4-1
I-b-50 S4-1 I-b-56 S4-5
I-b-50 S4-5 I-b-57 clo uintocet-mexyl
I-b-51 cloquintocet-mexyl I-b-57 fenchlorazole-ethyl
I-b-SI fenchlorazole-ethyl I-b-57 isoxadifen-ethyl
I-b-51 isoxadifen-ethyl I-b-57 mefen yr-diethyl
I-b-51 mefenpyr-diethyl I-b-57 fenclorim
I-b-51 fenclorim I-b-57 cum luron
I-b-51 cumyluron I-b-57 S4-1
I-b-51 S4-1 I-b-57 S4-5
I-b-51 S4-5 I-b-58 clo uintocet-mexyl
I-b-52 clo uintocet-mex l I-b-58 fenchlorazole-ethyl
I-b-52 fenchlorazole-ethyl I-b-58 isoxadifen-ethyl
1-b-52 isoxadifen-ethyl I-b-58 mefen yr-diethyl
I-b-52 mefen r-dieth l I-b-58 fenclorim
I-b-52 fenclorim I-b-58 cumyluron
I-b-52 cumyluron I-b-58 S4-1
I-b-52 S4-1 I-b-58 S4-5
I-b-52 S4-5 I-b-59 clo uintocet-mexvl
I-b-53 clo uintocet-mex l I-b-59 fenchlorazole-ethyl
1-b-53 fenchlorazole-ethyl I-b-59 isoxadifen-ethyl
I-b-53 isoxadifen-ethyl I-b-59 mefen r-dieth l
I-b-53 mefen r-dieth l I-b-59 fenclorim
1-b-53 fenclorim I-b-59 cumyluron
I-b-53 cumyluron I-b-59 S4-1
I-b-53 S4-1 I-b-59 S4-5
I-b-53 S4-5 I-b-60 clo uintocet-mexyl
I-b-54 cloquintocet-mexyl I-b-60 fenchlorazole-ethyl
I-b-54 fenchlorazole-ethyl I-b-60 isoxadifen-ethyl
1-b-54 isoxadifen-ethyl I-b-60 mefen r-dieth l
I-b-54 mefen r-dieth l I-b-60 fenclorim
I-b-54 fenclorim 1-b-60 cumyluron

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36
Active compound of Safener Active compound of Safener
the formula the formula
I-b-60 54-1 I-b-66 S4-5
I-b-60 54-5 I-b-67 clo uintocet-mexyl
I-b-61 clo uintocet-mex l I-b-67 fenchlorazole-ethyl
I-b-61 fenchlorazole-ethyl I-b-67 isoxadifen-ethyl
I-b-61 isoxadifen-ethyl I-b-67 mefen yr-diethyl
I-b-61 mefen r-diethyl I-b-67 fenclorim
I-b-61 fenclorim I-b-67 cum luron
I-b-61 cumvluron I-b-67 S4-1
I-b-61 S4-1 I -b-67 S4-5
1-b-61 S4-5 I-b-68 clo uintocet-mex l
I-b-62 clo uintocet-mex 1 I-b-68 fenchlorazole-ethyl
1-b-62 fenchlorazole-eth 1 I-b-68 isoxadifen-ethyl
I-b-62 isoxadifen-ethyl I-b-68 mefenpyr-diethyl
1-b-62 mefen pr-dieth 1 I-b-68 fenclorim
I-b-62 fenclorim I-b-68 cum luron
1-b-62 cum luron I-b-68 54-1
I-b-62 S4-1 I-b-68 S4-5
I-b-62 54-5 I-b-69 clo uintocet mex 1
I-b-63 clo uintocet-mex l I-b-69 fenchlorazole-ethyl
I-b-63 fenchlorazole-ethyl I-b-69 isoxadifen-ethyl
I-b-63 isoxadifen-ethyl I-b-69 mefen yr-diethyl
1-b-63 mefen r-dieth l I-b-69 fenclorim
I-b-63 fenclorim I-b-69 cum luron
1-b-63 cumyluron I-b-69 54-1
I-b-63 S4-1 I-b-69 S4-5
1-b-63 S4-5 I-b-70 clo uintocet mexyl
I-b-64 cloquintocet-mexyl I-b-70 fenchlorazole-ethyl
1-b-64 fenchlorazole-ethyl I-b-70 isoxadifen-ethyl
1-b-64 isoxadifen-ethyl I-b-70 mefen r-dieth 1
I-b-64 mefen yr diethyl I-b-70 fenclorim
1-b-64 fenclorim 1-b-70 cum luron
I-b-64 cum luron 1-b-70 S4-1
I-b-64 54-1 I-b-70 S4-5
1-b-64 S4-5 I-b-7l clo uintocet-mex l
t-b-65 cloquintocet-mexyl I-b-71 fenchlorazole-ethyl
I-b-65 fenchlorazole-ethyl I-b-71 isoxadifen-ethyl
I-b-65 isoxadifen-ethyl I-b-71 mefen yr-diethyl
1-b-65 mefen r-diethyl I -b-71 fenclorim
I-b-65 fenclorim 1-b-71 cum luron
I-b-65 cumyluron 1-b-71 54-1
I-b-65 S4-1 I-b-71 S4-5
I-b-65 54-5 I-b-72 clo uintocet-mexyl
I-b-66 clo uintocet-mexyl I-b-72 fenchlorazole-eth 1
I-b-66 fenchlorazole eth l I-b-72 isoxadifen-ethyl
I-b-66 isoxadifen-ethyl I-b-72 mefenpyr-diethyl
I-b-66 mefen yr-diethyl 1-b-72 fenclorim
1-b-66 fenclorim I-b-72 cum luron
1-b-66 cum luron I-b-72 S4-1
I-b-66 S4-1 I-b-72 S4-5

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Active compound of Safener Active compound of Safener
the formula the formula
I-b-73 clo uintocet-mexyl I-b-79 fenchlorazole-ethyl
I-b-73 fenchlorazole-ethyl I-b-79 isoxadifen-ethyl
I-b-73 isoxadifen-ethyl I-b-79 mefenp r-diethyl
I-b-73 mefenpyr-diethyl I-b-79 fenclorim
I-b-73 fenclorim I-b-79 cumyluron
I-b-73 cumyluron I-b-79 S4-1
I-b-73 54-1 I-b-79 S4-5
1-b-73 S4-5 I-c-I clo uintocet-mex l
I-b-74 clo uintocet-mexyl 1-c-I fenchlorazole-ethyl
I-b-74 fenchlorazole-ethyl I-c-1 isoxadifen-ethyl
I-b-74 isoxadifen-eth 1 I-c-I mefen r-dieth l
I-b-74 mefen yr-diethyl I-c-I fenclorim
I-b-74 fenclorim I-c-I cumyluron
I-b-74 cum luron I-c-I S4-1
I-b-74 S4-1 I-c-I S4-5
I-b-74 54-5 I-c-2 clo uintocet-mexyl
I-b-75 clog uintocet-mexyl I-c-2 fenchlorazole-ethyl
I-b-75 fenchlorazole-ethyl I-c-2 isoxadifen-ethyl
I-b-75 isoxadifen-ethyl I-c-2 mefenpyr-diethyl
I-b-75 mefenpyr-diethyl I-c-2 fenclorim
I-b-75 fenclorim 1-c-2 cumyluron
I-b-75 cum luron I-c-2 S4-1
I-b-75 S4-1 I-c-2 S4-5
I-b-75 S4-5 I-c-3 clo uintocet-mexyl
I-b-76 clo uintocet-mex 1 I-c-3 fenchlorazole-ethyl
I-b-76 fenchlorazole-ethyl I-c-3 isoxadifen-ethyl
I-b-76 isoxadifen-ethyl I-c-3 mefen yr-diethyl
I-b-76 mefen yr-dieth 1 I-c 3 fenclorim
I-b-76 fenclorim I-c-3 cum luron
I-b-76 cumyluron 1-c-3 54-1
I-b-76 S4-1 I-c 3 S4-5
I-b-76 S4-5 I-c-4 clo uintocet-mexvl
1-b-77 clo uintocet-mex l I-c-4 fenchlorazole-ethyl
I-b-77 fenchlorazole-ethyl I-c-4 isoxadifen-ethyl
I-b-77 isoxadifen-ethyl I-c-4 mefen yr-diethyl
I-b-77 mefen r-dieth l I-c-4 fenclorim
I-b-77 fenclorim 1-c-4 cum luron
1-b-77 cumyluron I-c-4 54-1
I-b-77 S4-1 I-c-4 S4-5
I-b-77 S4-5 I-c-S clo uintocet mex l
I-b-78 clo uintocet-mexyl I-c-5 fenchlorazole-ethyl
I-b-78 fenchlorazole-ethyl I-c-5 isoxadifen-ethyl
I-b-78 isoxadifen-ethyl I-c-S mefen r-dieth l
I-b-78 mefen r-diethyl I-c-S fenclorim
I-b-78 fenclorim I-c-S cumyluron
I-b-78 cumyluron I-c-S S4-1
I-b-78 S4-1 1-c-S S4-5
I-b-78 S4-5 I-c-6 cloquintocet-mexyl
I-b-79 clo uintocet-mexyl I-c-6 fenchlorazole-ethyl

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-38-
Active compound of Safener Active compound of Safener
the formula the formula
1-c-6 isoxadifen-ethyl I-c-12 mefen yr-diethyl
I-c-6 mefenpyr-diethyl I-c-12 fenclorim
I-c-6 fenclorim I-c-12 cumyluron
I-c-6 cumyluron I-c-12 S4-1
I-c-6 S4-1 I-c-12 S4-5
1-c-6 S4-5 I-c-13 clo uintocet-mexyl
I-c-7 cto uintocet-mex l I-c-13 fenchlorazole-ethyl
I-c-7 fenchlorazole-ethyl I-c-13 isoxadifen-ethyl
I-c-7 isoxadifen-ethyl I-c-13 mefenpyr-d ethyl
I-c-7 mefenpyr-diethyl I-c-13 fenclorim
I-c-7 fenclorim I-c-13 cumyluron
I-c-7 cumyl uron I-c-13 S4-1
I-c-7 S4-1 I-c-13 S4-5
I-c-7 S4-5 I-c-14 clo uintocet-mex l
1-c-8 clo uintocet-mex l I-c-14 fenchlorazole-ethyl
I-c-8 fenchlorazole-ethyl I-c-14 isoxadifen-ethyl
1-c-8 isoxadifen-ethyl I-c- 14 mefenpyr-diethyl
I-c-8 mefen r-dieth l I-c- 14 fenclorim
I-c-8 fenclorim I-c-14 cumyluron
I-c-8 cumyluron I-c-14 S4-1
I-c-8 S4-1 I-c-14 S4-5
I-c-8 S4-5 I-c-15 clo uintocet mex l
I-c-9 clo uintocet-mexyl I-c-15 fenchiorazole-ethyl
I-c-9 fenchlorazole-ethyl I-c-15 isoxadifen-ethyl
I-c-9 isoxadifen-ethyl I-c-15 mefen r-di eth l
I-c-9 mefenpyr-diethyl I-c-15 fenclorim
I-c-9 fenclorim I-c-15 cumyluron
I-c-9 cumyluron I-c-15 S4-1
I-c-9 S4-1 I-c-15 S4-5
I-c-9 S4-5 I-c-16 clo uintocet mexyl
I-c-10 cloquintocet-mexyl 1-c-16 fenchlorazole-ethyl
I-c-10 fenchlorazole-ethyl I-c-16 isoxadifen-ethyl
I-c-10 isoxadifen-ethyl I-c-16 mefen r-diethyl
I-c-10 mefenpyr-diethyl I-c-16 fenclorim
I-c-10 fenclorim I-c-16 cumyluron
I-c-10 cum luron I-c-16 S4-1
I-c-10 S4-1 I-c-16 S4-5
1-c-10 S4-5 I-c-17 cloquintocet-mexyl
I-c-11 clo uintocet-mex l I-c-17 fenchlorazole-ethyl
I-c-11 fenchlorazole-ethyl I-c-17 isoxadifen-ethyl
I-c-11 isoxadifen-ethyl I-c- 17 mefen yr-diethyl
I-c-11 mefenpyr-diethyl I-c- 17 fenclorim
I-c-11 fenclorim I-c-17 cumyluron
I-c-I 1 cumyluron I-c-17 S4-1
I-c-11 S4-1 I-c-17 S4-5
I-c-11 S4-5 I-c-18 cloquintocet-mexyl
I-c-12 clo uintocet-mex l I-c-18 fenchlorazole-ethyl
I c 12 fenchlorazole-ethyl I-c-18 isoxadifen ethyl
I-c-12 isoxadifen-ethyl I-c-18 mefenpyr-diethyl

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-39-
Active compound of Safener Active compound of Safener
the formula the formula
I-c-18 fenclorim I-c-24 cumyluron
I-c-1 8 cumyluron 1-c-24 S4-1
I-c-18 S4-1 I-c-24 S4-5
I-c-18 S4-5 I-c-25 clo uintocet mex l
I-c-19 clo uintocet-mex 1 I c 25 fenchlorazole-ethyl
I-c- 19 fenchlorazole-ethyl I-c-25 isoxadifen-ethyl
I-c-19 isoxadifen-ethyl I-c-25 mefen r-dieth l
I-c-19 mefen r-diethyl I-c-25 fenclorim
I-c-19 fenclorim I-c-25 cumyluron
I-c-1 9 cumyluron I-c-25 S4-1
I-c-19 S4-1 I-c-25 S4-5
I-c-19 S4-5 I-c-26 clo uintocet-mexyl
I-c-20 clog uintocet-mexyl I-c-26 fenchlorazole-ethyl
I-c-20 fenchlorazole-ethyl I-c-26 isoxadifen-ethyl
I-c-20 isoxadifen-ethyl I-c-26 mefen r-dieth l
I-c-20 mefen yr-diethyl I-c-26 fenclorim
I-c-20 fenclorim I-c-26 cumyluron
I-c-20 cumyluron I-c-26 S4-1
I-c-20 S4-1 I-c-26 S4-5
I-c-20 S4-5 I-c-27 cloquintocet-mexyl
I-c-21 cloquintocet-mexyl 1-c-27 fenchlorazole-ethyl
I-c-21 fenchlorazole-ethyl I-c-27 isoxadifen-ethyl
I-c-21 isoxadifen-ethyl I-c-27 mefenpyr-diethyl
I-c-21 mefenpyr-diethyl I-c-27 fenclorim
I-c-21 fenclorim I-c-27 cum luron
I-c-21 cumyluron I-c-27 S4-1
I-c-21 S4-1 I-c-27 S4-5
I-c-21 S4-5 I-c-28 cloquintocet-mexyl
I-c-22 clog uintocet-mex l I-c-28 fenchlorazole-ethyl
I-c-22 fenchlorazole-ethyl I-c-28 isoxadifen-ethyl
I-c-22 isoxadifen-ethyl I-c-28 mefenpyr-diethyl
I-c-22 mefen r-dieth l I-c-28 fenclorim
I-c-22 fenclorim I-c-28 cum luron
I-c-22 cumyluron I-c-28 S4-1
1-c-22 S4-1 I-c-28 S4-5
I-c-22 S4-5 I-c-29 clo uintocet-mex l
I-c-23 clo uintocet-mexyl I-c-29 fenchlorazole-ethyl
I-c-23 fenchlorazole-ethyl I-c-29 isoxadifen-ethyl
I-c-23 isoxadifen-ethyl I-c-29 mefen r-diethyl
I-c-23 mefen r-dieth 1 I-c-29 fenclorim
I-c-23 fenclorim I-c-29 c umyl uron
I-c-23 cumyluron I-c-29 S4-1
I-c-23 S4-1 I-c-29 S4-5
I-c-23 S4-5 I-c-30 clo uintocet-mexyl
I-c-24 cloquintocet-mexyl I-c-30 fenchlorazole-ethyl
I-c-24 fenchlorazole-ethyl I-c-30 isoxadifen-ethyl
I-c-24 isoxadifen-ethyl I-c-30 mefen r-dieth l
I-c-24 mefenpyr-diethyl I-c-30 fenclorim
I-c-24 fenclorim I-c-30 cumyluron

CA 02739870 2011-04-07
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-40-
Active compound of Safener Active compound of Safener
the formula the formula
1-c-30 S4-1 I-c-36 S4-5
I-c-30 S4-5 I-c-37 cloquintocet-mexyl
I-c-3I clo uintocet-mexyl I-c-37 fenchlorazole-ethyl
I-c-31 fenchlorazole-ethyl I-c-37 isoxadifen-eth 1
I-c-31 isoxadifen-ethyl I-c-37 mefen yr-diethyl
I-c-31 mefen yr-diethyl I-c-37 fenclorim
I-c 31 fenclorim. I-c-37 cum luron
1-c-31 cum luron I-c-37 S4-1
I-c-31 S4-1 I-c-37 S4-5
I-c-31 S4-5 1-c-38 clo uintocet-mexyl
I-c-32 clo uintocet-mex 1 I-c-38 fenchlorazole-ethyl
I-c-32 fenchlorazole-eth 1 I-c-38 isoxadifen-ethyl
1-c-32 isoxadifen-ethyl I-c-38 mefen yr-diethyl
I-c-32 mefen r-dieth l I-c-38 fenclorim
I-c-32 fenclorim I-c-38 cumyluron
I-c-32 cumyluron I-c-38 S4-1
I-c -32 S4-1 I-c-3 8 S4-5
1-c-32 S4-5 1-c-39 clo uintocet-mex l
I-c-33 clo uintocet-mex 1 I-c-39 fenchlorazole-ethyl
I-c-33 fenchlorazole-ethyl I-c-39 isoxadifen-ethyl
I-c-33 isoxadifen-ethyl 1-c-39 mefenpyr-diethyl
I-c-33 mefen yr-dieth 1 I-c-39 fenclorim
I-c-33 fenclorim -I-C-39 cum luron
I c 33 cumyluron I-c-39 S4-1
I c 33 S4-1 -I-C-39 S4-5
I-c-33 S4-5 I-c-40 cloquintocet-mexyl
I-c-34 cloquintocet-mexyl I-c-40 fenchlorazole-ethyl
I-c-34 fenchlorazole-ethyl I-c-40 isoxadifen-ethyl
I-c-34 isoxadifen-ethyl 1-c-40 mete thyl
I-c 34 mefen yr diethyl 1-c40 fenclorim
1-c-34 fenclorim I-c-40 cumyluron
I-c-34 cumyluron I-c-40 S4-1
I-c 34 S4-1 I-c-40 S4-5
I-c-34 S4-5 I-c-41 cloquintocet-mexyl
I-c-35 clo uintocet-mexyl 1-c-41 fenchlorazole-ethyl
1-c-35 fenchlorazole-ethyl I-c-41 isoxadifen-ethyl
I-c-35 isoxadifen-ethyl I-c-41 mefen 'r-diethyl
I-c-35 mefen yr-diethyl I-c-41 fenclorim
1-c-35 fenclorim I-c-41 cum luron
I-c-35 cum luron I-c-41 S4-1
1-c-35 S4-1 I-c-41 S4-5
1-c 35 S4-5 I-c-42 clo uintocet-mexyl
I-c-36 clo uintocet-mex l 1-c-42 fenchlorazole-ethyl
I-c-36 fenchlorazole-ethyl 1-c-42 isoxadifen-ethyl
I-c-36 isoxadifen-ethyl I-c-42 mefen yr-diethyl
I-c-36 mefenpyr-diethyl 1-c-42 fenclorim
I-c-36 fenclorim I-c-42 cum luron
I-c-36 cumyluron I-c-42 S4-1
I-c c 36 S4-1 1-c-42 S4-5

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-41 -
Active compound of Safener Active compound of Safener
the formula the formula
I-c-43 clo uintocet-mexyl I-c-49 fenchlorazole-ethyl
I-c-43 fenchlorazole-ethyl 1-c-49 isoxadifen-ethyl
I-c-43 isoxadifen-ethyl I-c-49 mefenpyr-diethyl
I-c-43 mefen r-dieth l I-c-49 fenclorim
I-c-43 fenclorim I-c-49 cumyluron
I-c-43 cumyluron I-c-49 S4-1
I-c-43 S4-1 I-c-49 S4-5
I-c-43 S4-5 1-c-50 clo uintocet-mex 1
I-c-44 clog uintocet-mexyl 1-c-50 fenchlorazole-ethyl
I-c-44 fenchlorazole-ethyl I-c-50 isoxadifen-ethyl
I-c-44 isoxadifen-ethyl I-c-50 mefen r-dieth l
I-c-44 mefen yr-diethyl I-c-50 fenclorim
I-c-44 fenclorim I-c-50 cumyluron
1-c-44 cum luron I-c-SO S4-1
I-c-44 S4-1 I-c-50 S4-5
1-c-44 S4-5 I-c-51 cloquintocet-mexyl
1-c-45 clo uintocet-mexyl I-c-51 fenchlorazole-ethyl
I-c-45 fenchlorazole-ethyl I-c-S 1 isoxadifen-ethyl
I-c-45 isoxadifen-ethyl I-c-51 mefenpyr-diethyl
I-c-45 mefenpyr-diethyl I-c-51 fenclorim
I-c-45 fenclorim I-c-51 cumyluron
I-c-4S cum luron I-c-51 S4-1
I-c-45 S4-1 I-c-S 1 S4-5
I-c-45 S4-5 I-c-S2 clo uintocet-mexyl
I-c-46 clo uintocet-mexyl I-c-52 fenchlorazole-ethyl
I-c-46 fenchlorazole-ethyl 1-c-52 isoxadifen-ethyl
I-c-46 isoxadifen-ethyl I-c-S2 mefenpyr-diethyl
I-c-46 mefenpyr-diethyl I-c-S2 fenclorim
I-c-46 fenclorim I-c-52 cumyluron
I-c-46 cumyluron I-c-52 S4-1
I-c-46 S4-1 I-c-52 S4-5
I-c-46 S4-5 I-c-53 clo uintocet-mex l
I c 47 clo uintocet mex l 1-c-53 fenchlorazole eth 1
I-c-47 fenchlorazole-ethyl I-c-53 isoxadifen-ethyl
1-c-47 isoxadifen-ethyl I-c-53 mefenpyr-diethyl
I-c-47 mefenpyr-diethyl I-c-53 fenclorim
I-c-47 fenclorim I-c-53 cumyl uron
I-c-47 cumyluron I-c-53 S4-1
I-c-47 S4-1 I-c-53 S4-5
I-c-47 S4-5 I-c-54 clog uintocet-mex l
I-c-48 cloquintocet-mexyl I-c-S4 fenchlorazole-ethyl
I-c-48 fenchlorazole-ethyl 1-c-54 isoxadifen-ethyl
I-c-48 isoxadifen-ethyl I-c-S4 mefen r-dieth l
I-c-48 mefenpyr-diethyl I-c-54 fenclorim
I-c-48 fenclorim I-c-54 cumyluron
1-c-48 cumyluron I-c-54 S4-1
I-c-48 S4-1 I-c-54 S4-5
I-c-48 S4-5 I-c-55 clo uintocet-mexyl
I-c-49 cloquintocet-mexyl I-c-55 fenchlorazole-ethyl

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-42-
Active compound of Safener Active compound of Safener
the formula the formula
I-c-55 isoxadifen-ethyl 1-c-61 mefen r-diethyl
I-c-55 mefen p yr-diethyl I-c-61 fenclorim
I-c-55 fenclorim I-c-61 cum luron
I-c-55 cum luron I-c-61 54-1
I-c-55 S4-1 I-c-61 S4-5
I-c-55 S4-5 I-c-62 cloquintocet-mexyl
l-c-56 clo uintocet-mex 1 I-c-62 fenchlorazole-ethyl
I-c-56 fenchlorazole-ethyl I-c-62 isoxadifen-eth 1
I-c-56 isoxadifen-ethyl 1-c-62 mefenpyr-diethyl
I-c-56 mefenpyr-diethyl I-c-62 fenclorim
I-c-56 fenclorim I-c-62 cumyluron
1-c-56 cumyluron I-c-62 S4-1
1-c-56 S4-1 I-c-62 S4-5
I-c-56 S4-5 I-c-63 clo uintocet-mex l
I-c-57 clo uintocet-mex l I-c-63 fenchlorazole-eth 1
I-c-57 fenchlorazole-ethyl I-c-63 isoxadifen-ethyl
I-c-57 isoxadifen-ethyl I-c-63 mefenpyr-diethyl
I-c-57 mefen r-dieth 1 1-c-63 fenclorim
I-c-57 fenclorim I-c-63 cum luron
I-c-57 cumyluron I-c-63 S4-1
I-c-57 S4-I 1-c-63 S4-5
I-c-57 S4-5 I-c-64 clog uintocet-mex l
I-c-58 clo uintocet-mexyl I-c-64 fenchlorazole-ethyl
I-c-58 fenchlorazole-ethyl I-c-64 isoxadifen-ethyl
1-c-58 isoxadifen-ethyl I-c-64 mefen r-dieth 1
I-c-58 mefen yr-diethyl I-c-64 fenclorim
I-c-58 fenclorim I-c-64 cumyluron
1-c-58 cum luron I-c-64 S4-1
I-c-58 S4-1 I-c-64 S4-5
I-c-58 S4-5 1-c-65 clo uintocet-mexyl
I-c-59 clo uintocet-mexvl 1-c-65 fenchlorazole-ethyl
I-c-59 fenchlorazole eth 1 I-c-65 isoxadifen-ethyl
I-c-59 isoxadifen-ethyl I-c-65 mefen r-diethyl
I-c-59 mefen yr-diethyl I-c-65 fenclorim
1-c-59 fenclorim I-c-65 cumyluron
1-c-59 cumvluron I-c-65 S4-1
1-c-59 S4-1 1-c-65 S4-5
I-c-59 S4-5 I-c-66 cloquintocet-mexyl
I-c-60 clo uintocet-mex l I-c-66 fenchlorazole-ethyl
I-c-60 fenchlorazole-ethyl I-c-66 isoxadifen-ethyl
I-c-60 isoxadifen-eth 1 I -c-66 mefen yr-dieth 1
1-c-60 mefen yr-dieth l I-c-66 fenclorim
I-c-60 fenclorim I-c-66 cum luron
I-c-60 cumyluron I-c-66 S4-1
I-c-60 S4-1 I-c-66 S4-5
I-c-60 S4-5 I-c-67 clo uintocet-mex 1
I-c-61 clo uintocet-mex 1 I-c-67 fenchlorazole-ethyl
I-c-61 fenchlorazole-ethyl I-c-67 isoxadifen-ethyl
I-c-61 isoxadifen-ethyl I-c-67 mefeTyr-diethyl

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Active compound of Safener Active compound of Safener
the formula the formula
I-c-67 fenclorim I-c-73 cum luron
1-c-67 cumyluron I-c-73 S4-1
I-c-67 S4-1 I-c-73 S4-5
I-c-67 S4-5 I-c-74 clo uintocet mex l
I-c-68 clo uintocet-mexyl I-c-74 fenchlorazole-ethyl
I-c-68 fenchlorazole-ethyl I-c-74 isoxadifen-ethyl
I-c-68 isoxadifen-ethyl I-c-74 mefenpyr-diethyl
I-c-68 mefen r-diethyl I-c-74 fenclorim
I-c-68 fenclorim I-c-74 cumyluron
I-c-68 cumyluron I-c-74 S4-1
I-c-68 S4-1 I-c-74 S4-5
I-c-68 S4-5 I-c-75 cloquintocet-mexyl
I-c-69 cloquintocet-mexyl I-c-75 fenchlorazole-ethyl
I-c-69 fenchlorazole-ethyl I-c-75 isoxadifen-ethyl
I-c-69 isoxadifen-ethyl I-c-75 mefen r-dieth l
I-c-69 mefenpyr-diethyl I-c-75 fenclorim
I-c-69 fenclorim I-c-75 cumvluron
I-c-69 cum luron I-c-75 S4-1
I-c-69 S4-1 I-c-75 S4-5
I-c-69 S4-5 I-c-76 cloquintocet-mexyl
I-c-70 cloquintocet-mexyl I-c-76 fenchlorazole-ethyl
I-c-70 fenchlorazole-ethyl 1-c-76 isoxadifen-ethyl
I-c-70 isoxadifen-ethyl I-c-76 mefenpyr-diethyl
I-c-70 mefenpyr-diethyl I-c-76 fenclorim
I-c-70 fenclorim I-c-76 cumyluron
I-c-70 cumyluron I-c-76 S4-1
I-c-70 S4-1 I-c-76 S4-5
I-c-70 S4-5 I-c-77 cloquintocet-mexyl
I-c-71 clo uintocet-mex l 1-c-77 fenchlorazole-ethyl
I-c-71 fenchlorazole-ethyl I-c-77 isoxadifen-ethyl
I-c-71 isoxadifen-ethyl I-c-77 mcfenpyr-di ethyl
I-c-71 mefen r-dieth l I-c-77 fenclorim
I-c-71 fenclorim I-c-77 cumyluron
I-c-71 cumyluron I-c-77 S4-1
I-c-71 S4-1 I-c-77 S4-5
I-c-71 S4-5 I-c-78 clo uintocet-mex l
I-c-72 clo uintocet-mexyl I-c-78 fenchlorazole-ethyl
I-c-72 fenchlorazole-ethyl I-c-78 isoxadifen-ethyl
I-c-72 isoxadifen-ethyl I-c-78 mefen r-dieth l
I-c-72 mefen yr-diethyl I-c-78 fenclorim
I-c-72 fenclorim I-c-78 cumyluron
I-c-72 cumyluron I-c-78 S4-1
I-c-72 S4-1 I-c-78 S4-5
I-c-72 S4-5 I-c-79 clo uintocet mexyl
I-c-73 cio uintocet-mexyl I-c-79 fenchlorazole-ethyl
I-c-73 fenchlorazole-ethyl I-c-79 isoxadifen-ethyl
I-c-73 isoxadifen-ethyl I-c-79 mefenpy -diethyl
I-c-73 mefen yr-diethyl I-c-79 fenclorim
I-c-73 fenclorim I-c-79 cumyluron

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Active compound of Safener Active compound of Safener
the formula the formula
I-c-79 S4-1 I-c-85 S4-5
I-c-79 S4-5 I-c-86 clo uintocet-mexyl
I-c-80 cloquintocet-mexyl I-c-86 fenchlorazole-ethyl
I-c-80 fenchlorazole-ethyl I-c-86 isoxadifen-ethyl
I-c-80 isoxadifen-ethyl I-c-86 mefenyrdiethyl
I-c-80 mefen yr-dieth 1 I-c-86 fenclorim
I-c-80 fenclorim I-c-86 cum luron
I-c-80 cumyluron I-c-86 S4-1
I-c-80 S4-1 I-c-86 S4-5
I-c-80 S4-5 I-c-87 clo uintocet-mex 1
I-c-81 clo uintocet-mex 1 I-c-87 fenchlorazole-ethyl
I-c-81 fenchlorazole-ethyl I-c-87 isoxadifen-eth 1
I-c-81 isoxadifen-ethyl I-c-87 mefen yr-diethyl
I-c-81 mefen r-dieth 1 I-c-87 fenclorim
I-c-81 fenclorim I-c-87 cum luron
I-c-81 cumyluron I-c-87 S4-1
I-c-81 S4-1 I-c-87 S4-5
I-c-81 S4-5 I-c-88 clo uintocet mexyl
I-c-82 clo uintocet-mexyl I-c-88 fenchlorazole-ethyl
I-c-82 fenchlorazole-ethyl I-c-88 isoxadifen-eth 1
1-c-82 isoxadifen-ethyl I-c-88 mefen r-diethyl
I-c-82 mefen r-diethyl I-c-88 fenclorim
I-c-82 fenclorim 1-c-88 cumyluron
I-c-82 cumyluron I-c-88 S4-1
I-c-82 S4-1 I-c-88 S4-5
I-c-82 S4-5 I-c-89 clo uintocet-mexyl
I-c-83 cloquintocet-mexyl I-c-89 fenchlorazole-ethyl
I -c-83 fenchlorazole-ethyl I-c-89 isoxadifen-ethyl
I-c-83 isoxadifen-eth 1 I-c-89 mefen r-diethyl
I-c-83 mefen r-diethyl I-c-89 fenclorim
I-c-83 fenclorim I-c-89 cumyluron
1-c-83 cum luron I-c-89 S4-1
I-c-83 S4-1 I-c-89 54-5
I-c-83 S4-5 I-d-1 clo uintocet mex l
I-c-84 cloquintocet-mexyl I-d-1 fenchlorazole-ethvl
I-c-84 fenchlorazole-ethyl 1-d-1 isoxadifen-eth l
I-c-84 isoxadifen-ethyl I-d-1 mefen yr-diethyl
I-c-84 mefenpyr-diethyl I-d-1 fenclorim
I-c-84 fenclorim I-d-I cumyluron
I-c-84 cumyluron I-d-l S4-1
I-c-84 54-1 I-d-1 S4-5
I-c-84 S4-5 I-d-2 cloquintocet-mex 1
1-c-85 clo uintocet-mex l I-d-2 fenchlorazole-ethyl
I-c-85 fenchlorazole-ethyl I-d-2 isoxadifen-eth
I-c-85 isoxadifen-ethyl I-d-2 mefenpyr-diethyl
I-c-85 mefen yr-diethyl I-d-2 fenclorim
I-c-85 fenclorim I-d-2 cum luron
I-c-85 cumyluron I-d-2 S4-1
I-c-85 S4-1 1-d-2 S4-5

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Active compound of Safener Active compound of Safener
the formula the formula
I-d-3 clo uintocet-mexyl I-d-9 fenchlorazole-ethyl
1-d-3 fenchlorazole-ethyl I-d-9 isoxadifen-eth l
I-d-3 isoxadifen-ethyl I-d-9 mefenpyr-diethyl
I-d-3 mefen -dieth l I-d-9 fenclorim
I-d-3 fenclorim I-d-9 cumyluron
1-d-3 cumyluron 1-d-9 S4-1
1-d-3 S4-1 I-d-9 S4-5
I-d-3 S4-5 I-d-10 clo uintocet-mex l
I-d-4 clo uintocet-mexyl I-d-10 fenchlorazole-ethyl
I-d-4 fenchlorazole-ethyl 1-d-10 isoxadifen-ethyl
1-d-4 isoxadifen-ethvl I-d-10 mefen r-diethyl
I-d-4 mefen r-diethyl 1-d-10 fenclorim
I-d-4 fenclorim I d-l0 cumyluron
1-d-4 cum luron I-d-10 54-1
1-d-4 S4-1 I-d-10 S4-5
I-d-4 54-5 I-d-11 clo uintocet-mexyl
I-d-5 cloquintocet-mexyl I-d-I I fenchlorazole-ethyl
I-d-5 fenchlorazole-eth l I-d-1l isoxadifen-ethyl
I-d-5 isoxadifen-ethyl I-d- II mefen yr-diethyl
I-d-5 mefen yr-diethyl I-d-11 fenclorim
I-d-5 fenclorim I-d-11 cumyluron
I-d-5 cumyluron I-d- l l S4-1
I-d-5 S4-1 1-d-11 S4-5
1-d-5 S4-5 I-d-12 clo uintocetanexyl
1-d-6 clo uintocet-mex 1 I-d-12 fenchlorazole-eth 1
I-d-6 fenchlorazole-ethyl I-d-12 isoxadifen-eth 1
I-d-6 isoxadifen-ethyl I-d-12 mefen yr-diethyl
I-d-6 mefen yr-diethyl I-d- 12 fenclorim
I-d-6 fenclorim 1-d-12 cumyluron
I-d-6 cumyluron I-d-12 S4-1
I-d-6 54-1 I-d-12 S4-5
I-d-6 S4-5 I-d-13 clo uintocet mex I
I-d-7 clo uintocet-mex l I-d-13 fenchlorazole-eth l
I-d-7 fenchlorazole-ethyl 1-d-13 isoxadifen-ethyl
I-d-7 isoxadifen-eth 1 1-d-13 ) mefen yr-diethyl
1-d-7 mefen r-dieth 1 I-d-13 fenclorim
1-d-7 fenclorim I-d-13 cum luron
I-d-7 cumyluron I-d-13 S4-1
1-d-7 S4-1 I-d-13 S4-5
I-d-7 S4-5 1-d-14 clo uintocet mex 1
1-d-8 clo uintocet-mex 1 I-d-14 fenchlorazole-ethyl
I-d-8 fenchlorazole-ethyl 1-d-14 isoxadifen-ethyl
I-d-8 isoxadifen-ethyl I-d-14 mefen yr-dieth 1
I-d-8 mefen r-diethvl 1-d-14 fenclorim
I-d-8 fenclorim I-d-14 cum luron
I-d-8 cumyluron I-d-14 S4-1
I-d-8 S4-1 I-d-14 S4-5
I-d-8 S4-5 I-d-15 clo uintocet-mexyl
I-d-9 clo uintocet-mex 1 I-d- 15 fenchlorazole-ethyl

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Active compound of Safener Active compound of Safener
the formula the formula
I-d-15 isoxadifen-ethyl 1-f-6 mefenpyr-diethyl
I-d-15 mefenpyr-diethyl I-f-6 fenclorim
I-d- 15 fenclorim I-f-6 cumyluron
I-d-15 cumyluron 1-f-6 S4-1
I-d- 15 S4-1 14-6 S4-5
I-d- 15 S4-5 1-f-7 cloquintocet-mexyl
1-f-I clo uintocet-mex l 1-f-7 fenchlorazole-ethyl
I-f-1 fenchlorazole-ethyl I-f-7 isoxadifen-ethyl
1-f-1 isoxadifen-ethyl I-f-7 mefenpyr-diethyl
I-f-I mefenpyr-diethyl I-f-7 fenclorim
1-f- I fenclorim I-f-7 cumyluron
I-f-I cumyluron I-f-7 S4-1
I-f-I S4-1 I-f-7 S4-5
I-f-I S4-5 I-f-8 cloquintocet-mexyl
I-f-2 clo uintocet-mexyl 1-f-8 fenchlorazole-ethyl
I-f-2 fenchlorazole-ethyl I-f-8 isoxadifen-ethyl
I-f-2 isoxadifen-ethyl I-f-8 mefenpyr-diethyl
I-f-2 mefen r-dieth l I-f-8 fenclorim
I-f-2 fenclorim I-f-8 cumyluron
I-f-2 cumyluron I-f-8 S4-1
I-f-2 S4-1 1-f-8 S4-5
I-f-2 S4-5 I-f-9 clo uintocet-mex l
I-f-3 cloquintocet-mexyl I-f-9 fenchlorazole-ethyl
I-f-3 fenchlorazole-ethyl I-f-9 isoxadifen-ethyl
I-f-3 isoxadifen-ethyl I-f-9 mefenpyr-diethyl
I-f-3 mefenpyr-diethyl I-f-9 fenclorim
I-f-3 fenclorim 1-f-9 cumyluron
I-f-3 cumyluron I-f-9 S4-1
I-f-3 S4-1 I-f-9 S4-5
I-f-3 S4-5 I-f 10 clo uintocet-mexyl
I-f-4 cloquintocet-mexyl I-f- 10 fenchlorazole-ethyl
I-f-4 fenchlorazole-ethyl 1-f- 10 isoxadifen-ethyl
I-f-4 isoxadifen-ethyl 1-f-10 mefen r-dieth l
I-f-4 mefen yr-diethyl 1-f- 10 fenclorim
I-f-4 fenclorim 14- 10 cumyluron
I-f-4 cumyluron I-f-10 S4-1
I-f-4 S4-1 I-f- 10 S4-5
I-f-4 S4-5 14- 11 cloquintocet-mexyl
I-f-S clo uintocet-mex l 14- 11 fenchlorazole-ethyl
I-f-S fenchlorazole-ethyl 14- 11 isoxadifen-ethyl
I-f-S isoxadifen-ethyl I-f-I1 mefen yr-diethyl
I-f-S mefen yr-diethyl I-f-I1 fenclorim
1-f-S fenclorim I-f-I1 cumyluron
I-f-S cumyluron I-f-I1 S4-1
I-f-S S4-1 1-f- I I S4-5
I-f-S S4-5 1-f- 12 clo uintocet-mex l
I-f-6 clo uintocet-mex l I-f- 12 fenchlorazole-ethyl
I-f-6 fenchlorazole-ethyl 1-f- 12 isoxadifen-ethyl
1-f-6 isoxadifen-ethyl 1-f- 12 mefenpyr-diethyl

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Active compound of Safener fActive compound of Safener
the formula the formula
I-f-12 fenclorim 1-f- 18 cumyluron
I-f-12 cumyluron I-f-18 S4-1
I-f-12 S4-1 I-f-18 S4-5
I-f-12 S4-5 I-f-19 clo uintocet-mex l
I-f-13 cloquintocet-mexyl I-f-19 fenchlorazole-ethyl
I-f-13 fenchlorazole-ethyl 1-f-19 isoxadifen-ethyl
I-f-13 isoxadifen-ethyl I-f-19 mefen r-dieth l
I-f-13 mefen r-dieth l I-f-19 fenclorim
1-f-13 fenclorim 1-f-19 cumyluron
I-f-13 cumvluron I-f-19 S4-1
I-f-13 S4-1 I-f-19 S4-5
I-f-13 S4-5 I-f-20 cloquintocet-mexyl
I-f-14 cloquintocet-mexyl I-f-20 fenchlorazole-ethyl
1-f-14 fenchlorazole-ethyl I-f-20 isoxadifen-ethyl
I-f-14 isoxadifen-ethyl 1-f-20 mefen r-diethyl
I-f-14 mefenpyr-diethyl 1-f-20 fenclorim
I-f-14 fenclorim I-f-20 cumyluron
I-f-14 cumvluron 1-f-20 S4-1
I-f-14 S4-1 1-f-20 S4-5
I-f-14 S4-5 I-f-21 clo uintocet-mexyl
1-f- 15 cloquintocet-mexyl I-f-21 fenchlorazole-ethyl
1-f- 15 fenchlorazole-ethyl I-f-21 isoxadifen-ethyl
I-f-15 isoxadifen-ethyl I-f-21 mefen r-dithyl
I-f-15 mefen yr-dieth l I-f-21 fenclorim
1-f- 15 fenclorim I-f-21 cum luron
1-f-15 cumyluron I-f-21 S4-1
1-f- 15 S4-1 I-f-21 S4-5
1-f-15 S4-5 I-f-22 clo uintocet-mexyl
I-f-16 clog uintocet-mex l I-f-22 fenchiorazole-ethyl
I-f-16 fenchlorazole-ethyl I-f-22 isoxadifen-ethyl
1-f-16 isoxadifen-ethyl I-f-22 mefenpyr-diethyl
I-f-16 mefen r-dieth 1 I-f-22 fenclorim
I-f-16 fenclorim 1-f-22 cum luron
I-f-16 cumyluron I-f-22 S4-1
I-f-16 S4-1 1-f-22 S4-5
I-f-16 S4-5 1-f-23 clo uintocet-mex l
I-f-17 clo uintocet-mexyl -f-f-23) fenchlorazole-ethyl
I-f- 17 fenchlorazole-ethyl I-f-23 isoxadifen-ethyl
1-f- 17 isoxadifen-ethyl I-f-23 mefen r-dieth l
I-f-17 mefen r dieth 1 I-f-23 fenclorim
I-f-17 fenclorim I-f-23 cumyluron
I-f-17 cumyluron I-f-23 S4-1
I-f-17 S4-1 I-f-23 S4-5
14- 17 S4-5 1-f-24 cio uintocet-mexyl
I-f-18 clo uintocet-mexyl I-f-24 fenchlorazole-ethyl
1-f- 18 fenchlorazole-ethyl I-f-24 isoxadifen-ethyl
1-f- 18 isoxadifen-ethyl I-f-24 mefen r-dieth l
I-f-18 mefen yr-diethyl 1-f-24 fenclorim
I-f-18 fenclorim I-f-24 cumyluron

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Active compound of Safener Active compound of Safener
the formula the formula
I-f-24 S4-1 I-f-25 fenclorim
I-f-24 S4-5 1-f-25 cumyluron
I-f-25 clo uintocet-mexyl I-f-25 S4-1
1-f-25 fenchlorazole-ethyl I-f-25 S4-5
1-f-25 i soxadi fen-ethyl
I-f-25 mefenpyr-diethyl
It has now surprisingly been found that the above-defined active compound
combinations of
compounds of the general formula (1) and safeners (antidotes) from group (b')
set out above combine
very good compatibility with useful plants with a particularly high herbicidal
activity and can be used
in various crops, in particular in cereals (especially wheat), but also in
soya beans, potatoes, maize
and rice, for the selective control of weeds.
In this context, it is considered surprising that, from a multiplicity of
known safeners or antidotes
capable of antagonizing the damaging effect of a herbicidal crop plant, it is
specifically the
compounds of group (b') set out above which are suitable for compensating -
almost completely - the
damaging effect of compounds of the formula (1) on the crop plants, without at
the same time
having any substantial adverse effect on the herbicidal activity against the
weeds.
Emphasis may be given here to the particularly advantageous effect of the
preferred and most
preferred combination partners from group (b'), particularly with regard to
the sparing of cereal
plants, such as, for example, wheat, barley and rye, but also maize and rice,
as crop plants.
The formula (I) provides a general definition of the compounds according to
the invention.
Preferred substituents or ranges of the radicals given in the formulae
mentioned above and below
are illustrated below:
X preferably represents C,-C4-alkyl, C3-C6-cycloalkyl or Ct-C4-alkoxy,
Y preferably represents hydrogen, C,-C4-alkyl or C,-C4-alkoxy,
Z preferably represents hydrogen, C,-C4-alkyl or C3-C6-cycloalkyl,
A, B and the carbon atom to which they are attached preferably represent C3-C8-
cycloalkyl or
C5-C8-cycloalkenyl, in which optionally one or two ring members are replaced
by oxygen
and/or sulphur and which are optionally mono- to tetrasubstituted by Cl-CB-
alkyl, C1-C8-
alkenyl, C,-C4-alkylene, C,-C8-halogenalkyl, C,-C6-alkoxy-C,-C4-alkyl, C,-C6-
alkoxy, Cj-
C6-halogenalkoxy, hydroxyl, hydroxy-C,-C4-alkyl or benzyloxy, or a further
fused-on C3-

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C8-cycloalkyl ring in which optionally one or two ring members are replaced by
oxygen or
sulphur, or which is optionally mono- or disubstituted by CI-C8-alkyl, or
A, B and the carbon atom to which they are attached preferably represent a
carbonyl group,
represent a Cl-C4-alkylene group or represent a =N-OR9 group,
G preferably represents hydrogen (a) or represents one of the groups
O L R4
1 R2 SO- R3 P s
R (b), M ' (c), ? (d), R (e),
R6
E (fl or N R~ (9),
L
in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur, and
M represents oxygen or sulphur,
R' preferably represents in each case optionally halogen-substituted C,-C20-
alkyl, C2-
C20-alkenyl, C,-Cs-alkoxy-C,-C8-alkyl, C,-C8-alkylthio-C,-C8-alkyl, poly-C1-C8-
alkoxy-C,-C8-alkyl or optionally halogen-, C,-C6-alkyl- or C,-C6-alkoxy-
substituted C3-C8-cycloalkyl in which optionally one or more (preferably not
more
than two) not directly adjacent ring members are replaced by oxygen and/or
sulphur,
preferably represents optionally halogen-, cyano-, nitro-, C,-C6-alkyl-, C,-C6-
alk-
oxy-, C,-C6-halogenalkyl-, Cl-C6-halogenalkoxy-, C,-C6-alkylthio- or C,-C6-
alkyl-
sulphonyl-substituted phenyl,
preferably represents optionally halogen-, nitro-, cyano-, C,-C6-alkyl-, C,-C6-
alk-
oxy-, C,-C6-halogenalkyl- or C,-C6-halogenalkoxy-substituted phenyl-C,-C6-
alkyl,
preferably represents optionally halogen- or C,-C6-alkyl-substituted 5- or 6-
membered hetaryl (for example pyrazolyl, thiazolyl, pyridyl, pyrimidyl,
furanyl or
thienyl),

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preferably represents optionally halogen- or C,-C6-alkyl-substituted phenoxy-
C,-
C6-alkyl or
preferably represents optionally halogen-, amino- or C,-C6-alkyl-substituted 5-
or
6-membered hetaryloxy-Ct-C6-alkyl (for example pyridyloxy-C,-C6-alkyl,
pyrimidyloxy-C,-C6-alkyl or thiazolyloxy-C1-C6-alkyl),
R2 preferably represents in each case optionally halogen-substituted C,-C20-
alkyl, C2-
Czo-alkenyl, C,-Cs-alkoxy-C2-C8-alkyl, poly-C,-C8-alkoxy-C2-C8-alkyl,
preferably represents optionally halogen-, C,-C6-alkyl- or C,-C6-alkoxy-
substituted
C3-C8-cycloalkyl or
preferably represents in each case optionally halogen-, cyano-, nitro-, C,-C6-
alkyl-,
C,-C6-alkoxy-, C,-C6-halogenalkyl- or C,-C6-halogenalkoxy-substituted phenyl
or
benzyl,
R3 preferably represents optionally halogen-substituted C,-Cg-alkyl or
represents in
each case optionally halogen-, C,-C6-alkyl-, C,-C6-alkoxy-, C,-C4-halogenalkyl-
,
C,-C4-halogenalkoxy-, cyano- or nitro-substituted phenyl or benzyl,
R4 and R5 independently of one another preferably represent in each case
optionally
halogen-substituted C,-C8-alkyl, C,-C8-alkoxy, C,-C8-alkylamino, Di-(C,-C8--
alkyl)amino, C,-C8-alkylthio, C2-C8-alkenylthio, C3-C7-Cycloalkylthio or
represent
in each case optionally halogen-, nitro-, cyano-, C1-C4-alkoxy-, C1-C4-
halogenalkoxy-, C,-C4-alkylthio-, C1-C4-halogenalkylthio-, C,-C4-alkyl- or C,-
C4-
halogenalkyl-substituted phenyl, phenoxy or phenylthio,
R6 and R7 independently of one another preferably represent hydrogen,
represent in each
case optionally halogen-substituted C,-C8-alkyl, C3-C8-cycloalkyl, C,-C8-
alkoxy,
C3-C8-alkenyl, Cj-C8-alkoxy-C,-C8-alkyl, represent optionally halogen-, C,-C8-
halogenalkyl-, C,-C8-alkyl- or Cl-C8-alkoxy-substituted phenyl, optionally
halogen-, C,-C8-alkyl-, C,-C8-halogenalkyl- or C,-C8-alkoxy-substituted benzyl
or
together represent an optionally C,-C4-alkyl-substituted C3-C6-alkylene
radical in
which optionally one carbon atom is replaced by oxygen or sulphur,
R9 preferably represents hydrogen, represents C,-C6-alkyl, C3-C6-cycloalkyl,
CH2C3-
C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkinyl, each of which is optionally mono-
to

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pentasubstituted by halogen, or represents phenyl-C,-C2-alkyl or hetaryl-C,-C2-
alkyl, each of which is optionally mono- to trisubstituted by alkyl, halogen,
alkoxy,
halogenalkyl or halogenalkoxy.
In the radical definitions mentioned as being preferred, halogen represents
fluorine, chlorine,
bromine and iodine, in particular fluorine, chlorine and bromine. The terms
alkyl, alkylidene and
alkenyl refer both to straight-chain and to branched hydrocarbon radicals.
X particularly preferably represents methyl, ethyl, cyclopropyl, methoxy or
ethoxy,
Y particularly preferably represents hydrogen, methyl or ethyl,
Z particularly preferably represents hydrogen, methyl, ethyl or cyclopropyl,
A, B and the carbon atom to which they are attached particularly preferably
represent C3-C8-
cycloalkyl or C5-C8-cycloalkenyl in which optionally one or two ring members
are
replaced by oxygen and/or sulphur and which is optionally mono- to
tetrasubstituted by C,-
C4-alkyl, C,-C4-alkenyl, a=CHI group, trifluoromethyl, Cl-C4-alkoxy, C,-C4-
alkoxy-C,-C2-
alkyl or by one of the groups
-0\ -0>-CH 3 -0XCH3
or
-0 -0 -0 CH3 or
or
A, B and the carbon atom to which they are attached particularly preferably
represent a carbonyl
group, represent a C,-C4-alkylene group or represent a =N-OR9 group,
G particularly preferably represents hydrogen (a) or represents one of the
groups
O L R4
2 3
R' (b), M' R (c) SO-2 R (d) I R5 (e),
L
R6
E (f) or
N
L
in which

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E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R' particularly preferably represents C,-C8-alkyl, C2-C8-alkenyl, CI-C4-alkoxy-
C,-C2-
alkyl, C,-C4-alkylthio-C1-C2-alkyl, each of which is optionally mono- to
trisubstituted by fluorine or chlorine, or represents C3-C6-cycloalkyl which
is
optionally mono- or disubstituted by fluorine, chlorine, C,-C2-alkyl or C,-C2-
alkoxy and in which optionally one or two not directly adjacent ring members
are
replaced by oxygen,
particularly preferably represents phenyl which is optionally mono- or
disubstituted by fluorine, chlorine, bromine, cyano, nitro, C,-C4-alkyl, C,-C4-
alkoxy, C,-C7-haloalkyl or C,-C2-haloalkoxy,
R2 particularly preferably represents C,-C8-alkyl, C2-C8-alkenyl or C,-C4-
alkoxy-C2-
C4-alkyl, each of which is optionally mono- to trisubstituted by fluorine,
particularly preferably represents C3-C6-cycloalkyl which is optionally
monosubstituted by C,-C,-alkyl or C,-C2-alkoxy or
particularly preferably represents phenyl or benzyl, each of which is
optionally
mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, C,-C4-
alkyl,
C,-C3-alkoxy, trifluoromethyl or trifluoromethoxy,
R3 particularly preferably represents C,-C6-alkyl which is optionally mono- to
trisubstituted by fluorine or represents phenyl which is optionally
monosubstituted
by fluorine, chlorine, bromine, C,-C4-alkyl, C,-C4-alkoxy, trifluoromethyl,
trifluoromethoxy, cyano or nitro,
R4 particularly preferably represents C,-C6-alkyl, C,-C6-alkoxy, C,-C6-
alkylamino, di-
(C,-C6-alkyl)amino, C,-C6-alkylthio, C3-C4-alkenylthio, C3-C6-cycloalkylthio,
each
of which is optionally mono- to trisubstituted by fluorine or chlorine, or
represents
phenyl, phenoxy or phenylthio, each of which is optionally monosubstituted by
fluorine, chlorine, bromine, nitro, cyano, C,-C3-alkoxy, C,-C3-haloalkoxy, C,-
C3-
alkylthio, C,-C3-haloalkylthio, C,-C3-alkyl or trifluoromethyl,

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R5 particularly preferably represents Cl-C6-alkylthio or C,-C6-alkoxy which is
optionally monosubstituted by chlorine,
R6 particularly preferably represents hydrogen, C,-C6-alkyl, C3-C6-cycloalkyl,
C1-C6-
alkoxy, C3-C6-alkenyl, C,-C6-alkoxy-CI-C4-alkyl, represents phenyl which is
optionally monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, C,-
C4-
alkyl or C,-C4-alkoxy, represents benzyl which is optionally monosubstituted
by
fluorine, chlorine, bromine, C,-C4-alkyl, trifluoromethyl or C,-C4-alkoxy,
R7 particularly preferably represents C,-C6-alkyl, C3-C6-alkenyl or C,-C6-
alkoxy-C,-
C4-alkyl,
R6 and R' together particularly preferably represent an optionally methyl- or
ethyl-
substituted C4-C5-alkylene radical in which optionally one methylene group is
replaced by oxygen or sulphur,
R9 particularly preferably represents hydrogen, represents C,-C4-alkyl, C3-C6-
cycloalkyl, CH2-C3-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkinyl, each of which
is
optionally mono- to trisubstituted by fluorine or chlorine, represents benzyl
or
pyridinylmethyl, each of which is optionally mono- or disubstituted by C,-C2-
alkyl, C,-Cz-alkoxy, fluorine, chlorine, bromine, trifluoromethyl or
trifluoromethoxy.
In the radical definitions mentioned as being particularly preferred, halogen
represents fluorine,
chlorine and bromine, in particular fluorine and chlorine. The terms alkyl,
alkylidene and alkenyl
are referred both to straight-chain and to branched hydrocarbon radicals.
X very particularly preferably represents methyl, ethyl, cyclopropyl, methoxy
or ethoxy
(with emphasis ethyl),
Y very particularly preferably represents hydrogen, methyl or ethyl (with
emphasis methyl),
Z very particularly preferably represents hydrogen, methyl, ethyl or
cyclopropyl (with
emphasis ethyl),
A, B and the carbon atom to which they are attached very particularly
preferably represent C3-
C7-cycloalkyl or C5-C7-cycloalkenyl in which optionally one or two ring
members are
replaced by oxygen and/or sulphur and which is optionally mono-, di-, tri- or
tetrasubstituted by methyl, in each case monosubstituted by ethyl, a =CH2
group, methoxy

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or ethoxy,
A, B and the carbon atom to which they are attached very particularly
preferably represent a
carbonyl group, represent a =CH2 group, represent a =CH2-CH3 group, represent
a =CH2-
C2H5 group or represent a =N-OR9 group,
G very particularly preferably represents hydrogen (a) or represents one of
the groups
O L
~RZ ~S02 Ri O d
R 1 (b), M (c), or E
(fl
in which
E represents a metal ion equivalent (Na' or Kt),
L represents oxygen or sulphur and
M represents oxygen or sulphur,
R1 very particularly preferably represents C,-C6-alkyl, C-2-C6-alkenyl, C,-C,-
alkoxy-
C,-alkyl, C,-C2-alkylthio-C,-alkyl or C3-C6-cyclopropyl which is optionally
monosubstituted by fluorine, chlorine, methyl or methoxy or represents C,-C4-
alkyl which is monosubstituted by chlorine,
very particularly preferably represents phenyl which is optionally
monosubstituted
by fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy, trifluoromethyl
or
trifluoromethoxy,
R2 very particularly preferably represents CI-C8-alkyl, Cz-C6-alkenyl or C,-C4-
alkoxy-
C7-C3-alkyl, each of which is optionally mono- to trisubstituted by fluorine,
represents phenyl or benzyl,
R3 very particularly preferably represents C,-C6-alkyl or represents phenyl
which is
optionally monosubstituted by chlorine or C,-C4-alkyl,
R9 very particularly preferably represents hydrogen, represents in each case
optionally
fluorine-substituted methyl, ethyl, propyl, n-butyl, isobutyl, s-butyl or tert-
butyl,
represents allyl, chloroallyl, propinyl, butinyl, chlorobenzyl,
chloropyridylmethyl,
CH(CH3)-C=CH, cyclopropyl, cyclobutyl, cyclopentyl, CH2-cyclopropyl, CH2-

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cyclobutyl or CH,-cyclopentyl.
X especially preferably represents methyl, ethyl or methoxy,
Y especially preferably represents methyl or ethyl,
Z especially preferably represents hydrogen, methyl or ethyl,
A, B and the carbon atom to which they are attached especially preferably
represent C5-C,-
cycloalkyl or C7-cycloalkenyl in which optionally two ring members are
replaced by
oxygen and/or sulphur and which is optionally mono-, di- or tetrasubstituted
by methyl, in
each case monosubstituted by ethyl, a =CH2 group, methoxy, ethoxy or
benzyloxy,
A, B and the carbon atom to which they are attached especially preferably
represent a carbonyl
group, represent a =CH2 group or represent a =N-OR9 group,
G especially preferably represents hydrogen (a) or represents one of the
groups
0 L
~ z R SOZ -- R3
R (b), M (c), (d) or E
in which
E represents a metal ion equivalent,
L represents oxygen and
M represents oxygen,
R' especially preferably represents C,-C6-alkyl or C,-Cz-alkoxy-C,-alkyl or C,-
C4-
alkyl which is monosubstituted by chlorine,
especially preferably represents phenyl which is optionally monosubstituted by
chlorine, methyl or methoxy,
R' especially preferably represents C,-Cg-alkyl,
R3 especially preferably represents methyl, phenyl or p-methylphenyl,
R9 especially preferably represents hydrogen, methyl, isopropyl, isobutyl,
tert-butyl,
CH2CF3, propinyl (CH2-C CH), CH(CH3)-C=-CH, cyclopropyl, cyclopentyl, CH2-

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cyclopropyl, CH2-cyclopentyl.
The general or preferred radical definitions or illustrations listed above can
be combined with one
another as desired, i.e. including combinations between the respective ranges
and preferred ranges.
They apply both to the end products and, correspondingly, to the precursors
and intermediates.
Preference according to the invention is given to the compounds of the formula
(I) which contain a
combination of the meanings listed above as being preferred (preferable).
Particular preference according to the invention is given to the compounds of
the formula (I) which
contain a combination of the meanings listed above as being particularly
preferred.
Very particular preference according to the invention is given to the
compounds of the formula (1)
which contain a combination of the meanings listed above as being very
particularly preferred.
Emphasis according to the invention is given to the compounds of the formula
(1) which contain a
combination of the meanings listed above as emphasized.
Special preference according to the invention is given to the compounds of the
formula (I) which
contain a combination of the meanings listed above as being especially
preferred.
Saturated or unsaturated hydrocarbon radicals, such as alkyl, alkanediyl or
alkenyl, can in each
case be straight-chain or branched as far as this is possible, including in
combination with
heteroatoms, such as, for example, in alkoxy.
Optionally substituted radicals may be mono- or polysubstituted unless
indicated otherwise, and in
the case of multiple substitutions the substituents can be identical or
different.
With particular emphasis, G represents hydrogen.
In addition to the compounds mentioned in the Preparation Examples, the
following compounds of
the formula (I-1-a) may be specifically mentioned:
OH X
A Y
B
O Z
Table 1: X = CH3, Y = CH;, Z = CH3

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A B
-O-(CH2)2-0-
-O-(CH2)4-0-
-O-CHCH3-CH2-O-
-O-CHCH3-CHCH3-O-
-O-(CH2)3-0-
-O-CHCH3-(CH2)2-0-
-O-CHCH3-CHz-CHCH3-O-
-O-CH7-CH(CH3)-CHz-O-
-O-CH2-CH(OCH3)-CH2-O-
-O-CH2-C(CH3)2-CH2-O-
-O-CH7-C- CH7-O-
11
CH7
-O-CH7-CH=CH-CH2-O-
-S-(CH2)2-5-
-S-(CH2)3-5-
-O-CH7-O-CH2-
-O-C(CH3)2-0- CH2-
Table 2: A and B as mentioned in Table I and
X = CzHs; Y =CH3; Z = CH3
Table 3: A and B as mentioned in Table I and
X=C2H5i Y=CH3; Z=C7H5
Table 4: A and B as mentioned in Table I and
X = C2H5; Y =CzHs; Z = C2H5
Table 5: A and B as mentioned in Table I and
X=[~--; Y=CH3; Z=CH3
Table 6: A and B as mentioned in Table I and
X= >-; Y=CH3; Z=CzHs
Table 7: A and B as mentioned in Table 1 and
X = OCH3i Y = CH3; Z = CH3
Table 8: A and B as mentioned in Table I and
X = OC2H5; Y = CH3; Z = CH3
Table 9: A and B as mentioned in Table I and

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X = OCH3; Y = CH3; Z = C7H5
Table 10: A and B as mentioned in Table 1 and
X = OGH5; Y = CH3; Z = GH5
Table 11: A and B as mentioned in Table I and
X=GH5i Y=CH3; Z=H
Table 12: A and B as mentioned in Table I and
X= > Y=CH3; Z=
Table 13: A and B as mentioned in Table 1 and
X=GH5i Y=GH5; Z=CH3
In the literature it has already been described how the action of various
active compounds can be
boosted by addition of ammonium salts. The salts in question, however, are
detersive salts (for
example WO 95/017817) or salts which have relatively long alkyl substituents
and/or aryl
substituents and which have a permeabilizing action or which increase the
active compound's
solubility (for example EP-A0453086, EP-A0664081, FR-A2600494, US 4 844 734,
US 5 462 912, US 5 538 937, US-A 03/0224939, US-A 05/0009880, US-A
05/0096386).
Moreover, the prior art describes the action only for particular active
compounds and/or particular
applications of the corresponding compositions. In other cases, in turn, the
salts in question are
those of suiphonic acids, where the acids themselves have a paralytic action
on insects
(US 2 842 476). A boost to action by ammonium sulphate, for example, is
described by way of
example for the herbicides glyphosate, phosphinothricin and for phenyl-
substituted cyclic
ketoenols (US 6 645 914, EP-A2 0 036 106, WO 07/068427). A corresponding boost
of action in
the case of insecticides has already been described in WO 07/068428.
The use of ammonium sulphate as a formulating assistant has also been
described for certain active
compounds and applications (WO 92/16108), but its purpose therein is to
stabilize the formulation,
not to boost the action.
It has now been found, surprisingly, that the action of insecticides and/or
acaricides and/or
herbicides from the class of the phenyl-substituted bicyclooctane-l,3-dione
derivatives of the
formula (I) can be boosted significantly through the addition of ammonium
salts or phosphonium
salts to the application solution or through the incorporation of these salts
into a formulation
comprising phenyl-substituted bicyclooctane-l,3-dione derivatives of the
formula (I). The present
invention therefore provides for the use of ammonium salts or phosphonium
salts for boosting the

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action of crop protection compositions which comprise as their active compound
herbicidal and/or
insecticidal and/or acaricidal phenyl-substituted bicyclooctane-1,3-dione
derivatives of the formula
(I). The invention likewise provides compositions which comprise herbicidal
and/or acaricidal
and/or insecticidal phenyl-substituted bicyclooctane-l,3-dione derivatives of
the formula (1) and
action-boosting ammonium salts or phosphonium salts, including not only
formulated active
compounds but also ready-to-use compositions (spray liquors). The invention
further provides,
finally, for the use of these compositions for controlling insect pests and/or
spider mites and/or
unwanted vegetation.
The active compounds can be used in the compositions according to the
invention in a broad
concentration range. The concentration of the active compounds in the
formulation is typically
0.1 % - 50% by weight.
Formula (ITT") provides a definition of the ammonium salts and phosphonium
salts which,
according to the invention, boost the activity of crop protection compositions
comprising fatty acid
biosynthesis inhibitors
R 26
29 1 + 27 30 n-
R -D-R
R
128 (III')
n
in which
D represents nitrogen or phosphorus,
D preferably represents nitrogen,
R26, R27, R28 and R29 independently of one another represent hydrogen or in
each case optionally
substituted Ci-C8-alkyl or mono- or polyunsaturated, optionally substituted C,-
C8-alkylene, the
substituents being selectable from halogen, nitro and cyano,
R26, R27, R28 and R29 independently of one another preferably represent
hydrogen or in each case
optionally substituted C,-C4-alkyl, the substituents being selectable from
halogen, nitro and cyano,
R26, R27, R28 and R29 independently of one another particularly preferably
represent hydrogen,
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-
butyl,

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R26, R27, R28 and R29 very particularly preferably represent hydrogen,
n represents 1, 2, 3 or 4,
n preferably represents I or 2,
R30 represents an organic or inorganic anion,
R30 preferably represents hydrogencarbonate, tetraborate, fluoride, bromide,
iodide, chloride,
monohydrogenphosphate, dihydrogenphosphate, hydrogensulphate, tartrate,
sulphate, nitrate,
thiosulphate, thiocyanate, formate, lactate, acetate, propionate, butyrate,
pentanoate or oxalate,
R30 particularly preferably represents lactate, sulphate, nitrate,
thiosulphate, thiocyanate,
oxalate or formate.
R3O very particularly preferably represents sulphate.
The ammonium salts and phosphonium salts of the formula (III') can be used in
a broad
concentration range to boost the activity of crop protection compositions
comprising phenyl-
substituted bicyclooctane-1,3-dione derivatives of the formula (I). In general
the ammonium salts
or phosphonium salts are used in the ready-to-use crop protection composition
in a concentration
of 0.5 to 80 mmol/l, preferably 0.75 to 37.5 mmol/l, more preferably 1.5 to 25
mmol/l. In the case
of a formulated product the ammonium salt and/or phosphonium salt
concentration in the
formulation is chosen such that it is within these stated general, preferred
or particularly preferred
ranges after the formulation has been diluted to the desired active compound
concentration. The
concentration of the salt in the formulation is typically 1%-50% by weight.
In one preferred embodiment of the invention the activity is boosted by adding
to the crop
protection compositions not only an ammonium salt and/or phosphonium salt but
also,
additionally, a penetrant. It is considered entirely surprising that even in
these cases an even
greater boost to activity is observed. The present invention therefore
likewise provides for the use
of a combination of penetrant and ammonium salts and/or phosphonium salts to
boost the activity
of crop protection compositions which comprise insecticidal and/or acaricidal
and/or herbicidal
phenyl-substituted bicyclooctane-l,3-dione derivatives of the formula (1) as
active compound. The
invention likewise provides compositions which comprise herbicidal and/or
acaricidal and/or
insecticidal phenyl-substituted bicyclooctane-l,3-dione derivatives of the
formula (I), penetrants
and ammonium salts and/or phosphonium salts, including specifically not only
formulated active
compounds but also ready-to-use compositions (spray liquors). The invention
additionally

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provides, finally, for the use of these compositions for controlling harmful
insects and/or spider
mites and/or unwanted vegetation.
In the present context, suitable penetrants are all those substances which are
usually employed to
improve penetration of agrochemically active compounds into plants. In this
context, penetrants
are defined in that they penetrate from the aqueous spray liquor and/or the
spray coating into the
cuticles of the plant, thus increasing the mobility of active compounds in the
cuticles. The method
described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152)
can be used for
determining this property.
Examples of suitable penetrants include alkanol alkoxylates. Penetrants of the
invention are
alkanol alkoxylates of the formula (IV')
R-O-(-AO)v-R' (IV')
in which
R represents straight-chain or branched alkyl having 4 to 20 carbon atoms,
R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
tert-butyl,
n-pentyl or n-hexyl,
AO represents an ethylene oxide radical, a propylene oxide radical, a butylene
oxide
radical or represents mixtures of ethylene oxide and propylene oxide radicals
or
butylene oxide radicals, and
v represents a number from 2 to 30.
One preferred group of penetrants are alkanol alkoxylates of the formula
R-O-(-EO-)n R' (IV'-a)
in which
R is as defined above,
R' is as defined above,
EO represents -CH1-CH2-O-, and
n represents a number from 2 to 20.

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A further preferred group of penetrants are alkanol alkoxylates of the formula
R-O-(-EO-)p-(-PO-)q R' (IV'-b)
in which
R is as defined above,
R' is as defined above,
EO represents -CH2-CH2-O-,
PO represents CH2 1 H-O-
CH3
p represents a number from I to 10, and
q represents a number from I to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula
R-O-(-PO-)r (EO-)s-R' (IV'-c)
in which
R is as defined above,
R' is as defined above,
EO represents -CH,-CH,-O-,
PO represents CH2 1 H-O-
CH3
r is a number from 1 to 10, and
s is a number from 1 to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula
R-O-(-EO-)p (-BO-)a-R' (IV'-d)

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in which
R and R are as defined above,
EO represents -CH,-CHz-O-,
BO represents -CHZCH - i H-O
CH3
p is a number from 1 to 10 and
q is a number from 1 to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula
R-O-(-BO-)r (-EO-)s-R' (IV' -e)
in which
R and R are as defined above,
BO represents -CH-CH-CH-0-
2 CHi CH3
EO represents -CH2-CH2-O-,
r represents a number from 1 to 10 and
s represents a number from 1 to 10.
A further preferred group of penetrants are alkanol alkoxylates of the formula
CH3-(CH,),-CH-,-O-(-CH2-CH,,-O-)u R' (IV--f)
in which
R' is as defined above,
t represents a number from 8 to 13,
u represents a number from 6 to 17.

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In the formulae indicated above,
R preferably represents butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-
hexyl, isohexyl,
n-octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, n-dodecyl,
isododecyl, lauryl,
myristyl, isotridecyl, trimethylnonyl, palmityl, stearyl or eicosyl.
As an example of an alkanot alkoxylate of the formula (IV'-c) mention may be
made of 2-
ethylhexyl alkoxylate of the formula
CH3 CH2 CH2 CH2 CH CH2 O (PO)8 (EO)6-H
(IV'-c-1)
C2H5
in which
EO represents -CH7-CH7-O-,
PO represents CH2 1 H-O- , and
CH3
the numbers 8 and 6 represent average values.
As an example of an alkanol alkoxylate of the formula (IV'-d) mention may be
made of the
formula
CH3-(CH,),o-O-(-EO-)6-(-BO-)2-CH3 (IV`-d-1)
in which
EO represents -CH7-CH2-O-,
BO represents -CH2 CH2 i -CH-0- . and
CH3
the numbers 10, 6 and 2 represent average values.
Particularly preferred alkanol alkoxylates of the formula (TV'-f) are
compounds of this formula in
which

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t represents a number from 9 to 12 and
u represents a number from 7 to 9.
Mention may be made with very particular preference of alkanol alkoxylate of
the formula
(IV'-f-l)
CH3-(CH,),-CH,-O-(-CH,-CHz-O-),,-H (IV'-f-1)
in which
t represents the average value 10.5 and
u represents the average value 8.4.
A general definition of the alkanol alkoxylates is given by the formulae
above. These substances
are mixtures of compounds of the stated type with different chain lengths. The
indices therefore
have average values which may also deviate from whole numbers.
The alkanol alkoxylates of the formulae stated are known and in some cases are
available
commercially or can be prepared by known methods (cf. WO 98/35 553, WO 00/35
278 and
EP-A 0 681 865).
Suitable penetrants also include, for example, substances which promote the
availability of the
compounds of the formula (1) in the spray coating. These include, for example,
mineral or
vegetable oils. Suitable oils are all mineral or vegetable oils - modified or
otherwise - which can
typically be used in agrochemical compositions. Mention may be made by way of
example of
sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maize seed oil,
cotton seed oil and soya
bean oil, or the esters of said oils. Preference is given to rapeseed oil,
sunflower oil and their
methyl or ethyl esters.
The concentration of penetrant in the compositions of the invention can be
varied within a wide
range. In the case of a formulated crop protection composition it is in
general 1% to 95%,
preferably 1% to 55%, more preferably 15%-40% by weight. In the ready-to-use
compositions
(spray liquors) the concentrations are generally between 0.1 and 10 g/l,
preferably between 0.5 and
5 g/l.
Crop protection compositions of the invention may also comprise further
components, examples
being surfactants and/or dispersing assistants or emulsifiers.

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Suitable nonionic surfactants and/or dispersing assistants include all
substances of this type that
can typically be used in agrochemical compositions. Preferably mention may be
made of
polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol
ethers of linear
alcohols, reaction products of fatty acids with ethylene oxide and/or
propylene oxide, and also
polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and
polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic
esters, and
additionally alkyl ethoxylates and alkylaryl ethoxylates, which optionally may
be phosphated and
optionally may be neutralized with bases, mention being made, by way of
example, of sorbitol
ethoxylates, and, as well, polyoxyalkylenamine derivatives.
Suitable anionic surfactants include all substances of this type that can
typically be used in
agrochemical compositions. Preference is given to alkali metal salts and
alkaline earth metal salts
of alkylsulphonic acids or alkylarylsulphonic acids.
A further preferred group of anionic surfactants and/or dispersing assistants
are the following salts
that are of low solubility in plant oil: salts of polystyrenesulphonic acids,
salts of
polyvinylsulphonic acids, salts of naphthalenesulphonic acid-formaldehyde
condensation products,
salts of condensation products of naphthalenesulphonic acid, phenolsulphonic
acid and
formaldehyde, and salts of lignosulphonic acid.
Suitable additives which may be included in the formulations of the invention
are emulsifiers,
foam inhibitors, preservatives, antioxidants, colorants and inert filling
materials.
Preferred emulsifiers are ethoxylated nonylphenols, reaction products of
alkylphenols with
ethylene oxide and/or propylene oxide, ethoxylated arylalkylphenols, and also
ethoxylated and
propoxylated arylalkylphenols, and also sulphated or phosphated arylalkyl
ethoxylates and/or
arylalkyl ethoxypropoxylates, mention being made by way of example of sorbitan
derivatives, such
as polyethylene oxide-sorbitan fatty acid esters, and sorbitan fatty acid
esters.
The active compounds of the invention, in combination with good plant
tolerance and favourable
toxicity to warm-blooded animals and being tolerated well by the environment,
are suitable for
protecting plants and plant organs, for increasing the harvest yields, for
improving the quality of
the harvested material and for controlling animal pests, in particular
insects, arachnids, helminths,
nematodes and molluscs, which are encountered in agriculture, in horticulture,
in animal
husbandry, in forests, in gardens and leisure facilities, in the protection of
stored products and of
materials, and in the hygiene sector. They may be preferably employed as crop
protection agents.
They are active against normally sensitive and resistant species and against
all or some stages of

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development. The abovementioned pests include:
From the order of the Anoplura (Phthiraptera), for example, Damalinia spp.,
Haematopinus spp.,
Linognathus spp., Pediculus spp., Trichodectes spp..
From the class of the Arachnida, for example, Acarus spp., Aceria sheldoni,
Aculops spp., Aculus
spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp.,
Brevipalpus
spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus
spp., Epitrimerus
pyri, Eutetranychus spp., Eriophyes spp., Halotydeus destructor,
Hemitarsonemus spp., Hyalomma
spp., Nodes spp., Latrodectus mactans, Metatetranychus spp., Nuphersa spp.,
Oligonychus spp.,
Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,
Polyphagotarsonemus latus, Psorop-
tes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio
maurus, Stenotarsonemus
spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
From the class of the Bivalva, for example, Dreissena spp..
From the order of the Chilopoda, for example, Geophilus spp., Scutigera spp..
From the order of the Coleoptera, for example, Acalymma vittatum,
Acanthoscelides obtectus,
Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis,
Anobium punctatum,
Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia spp.,
Atomaria spp.,
Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma
trifurcata, Ceutor-
rhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp.,
Cosmopolites spp.,
Costelytra zealandica, Ctenicera spp., Curculio spp., Cryptorhynchus lapathi,
Cylindrocopturus
spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Diloboderus spp.,
Epilachna spp., Epitrix
spp., Faustinus spp., Gibbium psylloides, Hellula undalis, Heteronychus
arator, Heteronyx spp.,
Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp.,
Lachnostema
consanguinea, Lema spp., Leptinotarsa decemlineata, Leucoptera spp.,
Lissorhoptrus oryzophilus,
Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp., Melanotus spp.,
Meligethes aeneus,
Melolontha spp., Migdolus spp., Monochamus spp., Naupactus xanthographus,
Niptus hololeucus,
Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae,
Otiorrhynchus spp.,
Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllotreta spp.,
Popillia japonica,
Premnotrypes spp., Psylliodes spp., Ptinus spp., Rhizobius ventralis,
Rhizopertha dominica,
Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp.,
Tanymecus spp., Tenebrio
molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp.,
Zabrus spp..
From the order of the Collembola, for example, Onychiurus armatus.

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From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Diptera, for example, Aedes spp., Agromyza spp.,
Anastrepha spp.,
Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus,
Calliphora erythrocephala,
Ceratitis capitata, Chironomus spp., Chrysomyia spp., Cochliomyia spp.,
Contarinia spp.,
Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dasyneura
spp., Delia spp.,
Dermatobia hominis, Drosophila spp., Echinocnemus spp., Fannia spp.,
Gastrophilus spp.,
Hydrellia spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza
spp., Lucilia spp.,
Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia spp., Phorbia
spp., Prodiplosis
spp., Psila rosae, Rhagoletis spp., Stomoxys spp., Tabanus spp., Tannia spp.,
Tetanops spp., Tipula
spp..
From the class of the Gastropoda, for example, Arion spp., Biomphalaria spp.,
Bulinus spp.,
Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp.,
Succinea spp..
From the class of the helminths, for example, Ancylostoma duodenale,
Ancylostoma ceylanicum,
Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp.,
Brugia malayi,
Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia
spp., Dicrocoelium
spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis,
Echinococcus
granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola
spp., Haemonchus spp.,
Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus
spp.,
Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp.,
Paragonimus
spp., Schistosomen spp, Strongyloides fuelleborni, Strongyloides stercoralis,
Stronyloides spp.,
Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa,
Trichinella britovi,
Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp.,
Trichuris trichuria,
Wuchereria bancrofti.
It is furthermore possible to control protozoans, such as Eimeria.
From the order of the Heteroptera, for example, Anasa tristis, Antestiopsis
spp., Blissus spp.,
Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp.,
Creontiades
dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus
spp., Euschistus
spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp.,
Leptoglossus
phyllopus, Lygus spp., Macropes excavatus, Miridae, Monalonion atratum, Nezara
spp., Oebalus
spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta
persea, Rhodnius
spp., Sahibergella singularis, Scaptocoris castanea, Scotinophora spp.,
Stephanitis nashi, Tibraca
spp., Triatoma spp.

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From the order of the Homoptera, for example, Acyrthosipon spp., Acrogonia
spp., Aeneolamia
spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus
spp., Amrasca spp.,
Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia
apicalis, Aspidiella
spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp.,
Brachycaudus helichrysii,
Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala
fulgida,
Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii,
Chionaspis
tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus,
Cicadulina mbila,
Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes
spp., Diaphorina
spp., Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca
spp., Eriosoma
spp., Erythroneura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae,
Hieroglyphus spp.,
Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp.,
Idioscopus spp., Lao-
delphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi,
Macrosiphum spp.,
Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium
dirhodum, Monellia
costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix
spp., Nilaparvata
lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza
spp., Parlatoria
spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus
passerinii, Phorodon
humuli, Phylloxera spp., Pirmaspis aspidistrae, Planococcus spp.,
Protopulvinaria pyriformis,
Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp.,
Pyrilla spp.,
Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp.,
Saissetia spp.,
Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata
spp., Sogatella
furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis,
Tinocallis caryaefoliae,
Tomaspis spp., Toxoptera spp., Trialeurodes spp., Trioza spp., Typhlocyba
spp., Unaspis spp.,
Viteus vitifolii, Zygina spp..
From the order of the Hymenoptera, for example, Athalia spp., Diprion spp.,
Hoplocampa spp.,
Lasius spp., Monomorium pharaonis, Vespa spp..
From the order of the Isopoda, for example, Armadillidium vulgare, Oniscus
asellus, Porcellio
scaber.
From the order of the Isoptera, for example, Acromyrmex spp., Atta spp.,
Comitermes cumulans,
Microtermes obesi, Odontotermes spp., Reticulitermes spp..
From the order of the Lepidoptera, for example, Acronicta major, Adoxophyes
spp., Aedia
leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp.,
Anticarsia spp.,
Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella,
Bupalus piniarius,
Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana,
Carpocapsa pomonella,

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Carposina niponensis, Cheimatobia brumata, Chilo spp., Choristoneura spp.,
Clysia ambiguella,
Cnaphalocerus spp., Cnephasia spp., Conopomorpha spp., Conotrachelus spp.,
Copitarsia spp.,
Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias
spp., Ecdytolopha
aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia kuehniella,
Epinotia spp.,
Epiphyas postvittana, Etiella spp., Eulia spp., Eupoecilia ambiguella,
Euproctis spp., Euxoa spp.,
Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp.,
Hedylepta spp., Helicoverpa
spp., Heliothis spp., Hofmannophila pseudospretella, Homoeosoma spp., Homona
spp.,
Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia
molesta, Leucinodes
orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia
spp., Loxagrotis
albicosta, Lymantria spp., Lyonetia spp., Malacosoma neustria, Maruca
testulalis, Mamestra
brassicae, Mocis spp., Mythimna separata, Nymphula spp., Oiketicus spp., Oria
spp., Orthaga spp.,
Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp., Pectinophora
spp., Perileucoptera
spp., Phthorimaea spp., Phyllocnistis citrella, Phyllonorycter spp., Pieris
spp., Platynota stultana,
Plusia spp., Plutella xylostella, Prays spp., Prodenia spp., Protoparce spp.,
Pseudaletia spp.,
Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp.,
Scirpophaga spp.,
Scotia segetum, Sesamia spp., Sparganothis spp., Spodoptera spp., Stathmopoda
spp., Stomopteryx
subsecivella, Synanthedon spp., Tecia solanivora, Thermesia gemmatalis, Tinea
pllionella,
Tineola bisselliella, Tortrix spp., Trichoplusia spp., Tuta absoluta,
Viraehola spp..
From the order of the Orthoptera, for example, Acheta domesticus, Blatta
orientalis, Blattella
germanica, Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, Locusta
spp., Melanoplus
spp., Periplaneta americana, Schistocerca gregaria.
From the order of the Siphonaptera, for example, Ceratophyllus spp.,
Xenopsylla cheopis.
From the order of the Symphyla, for example, Scutigerella spp..
From the order of the Thysanoptera, for example, Anaphothrips obscurus,
Baliothrips biformis,
Drepanothris reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips
spp., Hercinothrips
femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips
cardamoni, Thrips spp..
From the order of the Thysanura, for example, Lepisma saccharina.
The plant-parasitic nematodes include, for example, Aphelenchoides spp.,
Bursaphelenchus spp.,
Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp.,
Meloidogyne spp.,
Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus
semipenetrans, Xiphinema
spp..

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If appropriate, the compounds according to the invention can, at certain
concentrations or
application rates, also be used as herbicides, safeners, growth regulators or
agents to improve plant
properties, or as microbicides, for example as fungicides, antimycotics,
bactericides, viricides
(including agents against viroids) or as agents against MLO (Mycoplasma-like
organisms) and
RLO (Rickettsia-like organisms). If appropriate, they can also be employed as
intermediates or
precursors for the synthesis of other active compounds.
The active compounds can be converted to the customary formulations, such as
solutions, emulsions,
wettable powders, water- and oil-based suspensions, powders, dusts, pastes,
soluble powders, soluble
granules, granules for broadcasting, suspension-emulsion concentrates, natural
materials impregnated
with active compound, synthetic materials impregnated with active compound,
fertilizers and
microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the
active compounds
with extenders, that is liquid solvents and/or solid carriers, optionally with
the use of surfactants, that
is emulsifiers and/or dispersants and/or foam-formers. The formulations are
prepared either in
suitable plants or else before or during the application.
Suitable for use as auxiliaries are substances which are suitable for
imparting to the composition
itself and/or to preparations derived therefrom (for example spray liquors,
seed dressings)
particular properties such as certain technical properties and/or also
particular biological
properties. Typical suitable auxiliaries are: extenders, solvents and
carriers.
Suitable extenders are, for example, water, polar and nonpolar organic
chemical liquids, for
example from the classes of the aromatic and non-aromatic hydrocarbons (such
as paraffins,
alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols
(which, if
appropriate, may also be substituted, etherified and/or esterified), the
ketones (such as acetone,
cyclohexanone), esters (including fats and oils) and (poly)ethers, the
unsubstituted and substituted
amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the
sulphones and
sulphoxides (such as dimethyl sulphoxide).
If the extender used is water, it is also possible to employ, for example,
organic solvents as auxiliary
solvents. Essentially, suitable liquid solvents are: aromatics such as xylene,
toluene or
alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic
hydrocarbons such as
chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons
such as cyclohexane
or paraffins, for example petroleum fractions, mineral and vegetable oils,
alcohols such as butanol or
glycol and also their ethers and esters, ketones such as acetone, methyl ethyl
ketone, methyl isobutyl

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ketone or cyclohexanone, strongly polar solvents such as dimethyl sulphoxide,
and also water.
According to the invention, a carrier is a natural or synthetic organic or
inorganic substance which
may be solid or liquid and with which the active compounds are mixed or bonded
for better
applicability, in particular for application to plants or parts of plants. The
solid or liquid carrier is
generally inert and should be suitable for use in agriculture.
Suitable solid carriers are:
for example, ammonium salts and ground natural minerals such as kaolins,
clays, talc, chalk, quartz,
attapulgite, montmorillonite or diatomaceous earth, and ground synthetic
minerals, such as finely
divided silica, alumina and silicates; suitable solid carriers for granules
are: for example, crushed and
fractionated natural rocks such as calcite, marble, pumice, sepiolite and
dolomite, and also synthetic
granules of inorganic and organic meals, and granules of organic material such
as paper, sawdust,
coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or
foam-formers are: for
example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid
esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers,
alkylsulphonates, alkyl
sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants
are nonionic and/or
ionic substances, for example from the classes of the alcohol-POE and/or -POP
ethers, acid and/or
POP-POE esters, alkylaryl and/or POP-POE ethers, fat- and/or POP-POE adducts,
POE- and/or
POP-polyol derivatives, POE- and/or POP-sorbitan or -sugar adducts, alkyl or
aryl sulphates, alkyl-
or arylsulphonates and alkyl or aryl phosphates or the corresponding PO-ether
adducts.
Furthermore, suitable oligo- or polymers, for example those derived from
vinylic monomers, from
acrylic acid, from EO and/or PO alone or in combination with, for example,
(poly)alcohols or
(poly)amines. It is also possible to employ lignin and its sulphonic acid
derivatives, unmodified
and modified celluloses, aromatic and/or aliphatic sulphonic acids and their
adducts with
formaldehyde.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers
in the form of
powders, granules or latices, such as gum arabic, polyvinyl alcohol and
polyvinyl acetate, as well as
natural phospholipids such as cephalins and lecithins, and synthetic
phospholipids, can be used in the
formulations.
It is possible to use colorants such as inorganic pigments, for example iron
oxide, titanium oxide and
Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo
dyestuffs and metal
phthalocyanine dyestuffs, and trace nutrients such as salts of iron,
manganese, boron, copper, cobalt,
molybdenum and zinc.

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Other possible additives are perfumes, mineral or vegetable, optionally
modified oils, waxes and
nutrients (including trace nutrients), such as salts of iron, manganese,
boron, copper, cobalt,
molybdenum and zinc.
Stabilizers, such as low-temperature stabilizers, preservatives, antioxidants,
light stabilizers or
other agents which improve chemical and/or physical stability may also be
present.
The formulations generally comprise between 0.01 and 98% by weight of active
compound,
preferably between 0.5 and 90%.
The active compound according to the invention can be used in its commercially
available
formulations and in the use forms, prepared from these formulations, as a
mixture with other active
compounds, such as insecticides, attractants, sterilizing agents,
bactericides, acaricides, nematicides,
fungicides, growth-regulating substances. herbicides, safeners, fertilizers or
semiochemicals.
A mixture with other known active compounds, such as herbicides, fertilizers,
growth regulators,
safeners, semiochemicals, or else with agents for improving the plant
properties, is also possible.
When used as insecticides, the active compounds according to the invention can
furthermore be
present in their commercially available formulations and in the use forms,
prepared from these
formulations, as a mixture with synergists. Synergists are compounds which
increase the action of
the active compounds, without it being necessary for the synergist added to be
active itself.
When used as insecticides, the active compounds according to the invention can
furthermore be
present in their commercially available formulations and in the use forms,
prepared from these
formulations, as a mixture with inhibitors which reduce degradation of the
active compound after
use in the environment of the plant, on the surface of parts of plants or in
plant tissues.
The active compound content of the use forms prepared from the commercially
available
formulations can vary within wide limits. The active compound concentration of
the use forms can
be from 0.00000001 to 95% by weight of active compound, preferably between
0.00001 and 1%
by weight.
The compounds are employed in a customary manner appropriate for the use
forms.
All plants and plant parts can be treated in accordance with the invention.
Plants are to be
understood as meaning in the present context all plants and plant populations
such as desired and
undesired wild plants or crop plants (including naturally occurring crop
plants). Crop plants can be
plants which can be obtained by conventional plant breeding and optimization
methods or by

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biotechnological and genetic engineering methods or by combinations of these
methods, including
the transgenic plants and including the plant cultivars protectable or not
protectable by plant
breeders' rights. Plant parts are to be understood as meaning all parts and
organs of plants above
and below the ground, such as shoot, leaf, flower and root, examples which may
be mentioned
being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds,
roots, tubers and rhizomes.
The plant parts also include harvested material, and vegetative and generative
propagation
material, for example cuttings, tubers, rhizomes, offshoots and seeds.
Treatment according to the invention of the plants and plant parts with the
active compounds is
carried out directly or by allowing the compounds to act on their
surroundings, habitat or storage
space by the customary treatment methods, for example by immersion, spraying,
evaporation,
fogging, scattering, painting on, injection and, in the case of propagation
material, in particular in
the case of seeds, also by applying one or more coats.
As already mentioned above, it is possible to treat all plants and their parts
according to the
invention. In a preferred embodiment, wild plant species and plant cultivars,
or those obtained by
conventional biological breeding methods, such as crossing or protoplast
fusion, and parts thereof,
are treated. In a further preferred embodiment, transgenic plants and plant
cultivars obtained by
genetic engineering methods, if appropriate in combination with conventional
methods
(Genetically Modified Organisms), and parts thereof are treated. The terms
"parts", "parts of
plants" and "plant parts" have been explained above.
Particularly preferably, plants of the plant cultivars which are in each case
commercially available
or in use are treated according to the invention. Plant cultivars are to be
understood as meaning
plants having novel properties ("traits") which have been obtained by
conventional breeding, by
mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or
genotypes.
Depending on the plant species or plant cultivars, their location and growth
conditions (soils,
climate, vegetation period, diet), the treatment according to the invention
may also result in
superadditive ("synergistic") effects. Thus, for example, reduced application
rates and/or a
widening of the activity spectrum and/or an increase in the activity of the
substances and
compositions which can be used according to the invention, better plant
growth, increased
tolerance to high or low temperatures, increased tolerance to drought or to
water or soil salt
content, increased flowering performance, easier harvesting, accelerated
maturation, higher harvest
yields, higher quality and/or a higher nutritional value of the harvested
products, better storage
stability and/or processability of the harvested products are possible, which
exceed the effects
which were actually to be expected.

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The transgenic plants or plant cultivars (obtained by genetic engineering)
which are preferably to
be treated according to the invention include all plants which, by virtue of
the genetic
modification, received genetic material which imparted particularly
advantageous, useful traits to
these plants. Examples of such traits are better plant growth, increased
tolerance to high or low
temperatures, increased tolerance to drought or to water or soil salt content,
increased flowering
performance, easier harvesting, accelerated maturation, higher harvest yields,
higher quality and/or
a higher nutritional value of the harvested products, better storage stability
and/or processability of
the harvested products. Further and particularly emphasized examples of such
traits are a better
defence of the plants against animal and microbial pests, such as against
insects, mites,
phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance
of the plants to certain
herbicidally active compounds. Examples of transgenic plants which may be
mentioned are the
important crop plants, such as cereals (wheat, rice), maize, soya beans,
potatoes, sugar beet,
tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape
and also fruit plants
(with the fruits apples, pears, citrus fruits and grapes), and particular
emphasis is given to maize,
soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are
emphasized are in particular
increased defence of the plants against insects, arachnids, nematodes and
slugs and snails by virtue
of toxins formed in the plants, in particular those formed in the plants by
the genetic material from
Bacillus thuringiensis (for example by the genes CrylA(a), CrylA(b), CryIA(c),
CryIIA, CryIIIA,
Cryll[B2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof)
(referred to
hereinbelow as "Bt plants"). Traits that are also particularly emphasized are
the increased defence
of the plants against fungi, bacteria and viruses by systemic acquired
resistance (SAR), systemin,
phytoalexins, elicitors and resistance genes and correspondingly expressed
proteins and toxins.
Traits that are furthermore particularly emphasized are the increased
tolerance of the plants to
certain herbicidally active compounds, for example imidazolinones,
sulphonylureas, glyphosate or
phosphinotricin (for example the "PAT" gene). The genes which impart the
desired traits in
question can also be present in combination with one another in the transgenic
plants. Examples of
"Bt plants" which may be mentioned are maize varieties, cotton varieties, soya
bean varieties and
potato varieties which are sold under the trade names YIELD GARD (for example
maize, cotton,
soya beans), KnockOut (for example maize), StarLink (for example maize),
Bollgard
(cotton), Nucotn (cotton) and NewLeaf (potato). Examples of herbicide-
tolerant plants which
may be mentioned are maize varieties, cotton varieties and soya bean varieties
which are sold
under the trade names Roundup Ready (tolerance to glyphosate, for example
maize, cotton, soya
bean), Liberty Link (tolerance to phosphinotricin, for example oilseed rape),
IMI (tolerance to
imidazolinones) and STS (tolerance to sulphonylureas, for example maize).
Herbicide-resistant
plants (plants bred in a conventional manner for herbicide tolerance) which
may be mentioned

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include the varieties sold under the name Clearfield (for example maize). Of
course, these
statements also apply to plant cultivars having these genetic traits or
genetic traits still to be
developed, which plant cultivars will be developed and/or marketed in the
future.
The plants listed can be treated according to the invention in a particularly
advantageous manner
with the compounds of the general formula (I) or the active compound mixtures
according to the
invention. The preferred ranges stated above for the active compounds or
mixtures also apply to
the treatment of these plants. Particular emphasis is given to the treatment
of plants with the
compounds or mixtures specifically mentioned in the present text.
The compounds of the formula (I) according to the invention (active compounds)
have excellent
herbicidal activity against a broad spectrum of economically important
monocotylidonous and
dicotylidonous annual harmful plants. The active compounds also act
efficiently on perennial
harmful plants which produce shoots from rhizomes, root stocks or other
perennial organs and
which are difficult to control.
The amount of active compound used may vary within a relatively wide range. It
depends
essentially on the nature of the desired effect. In general, the application
rates are between I g and
10 kg of active compound per hectare of soil area, preferably between 5 g and
5 kg per ha.
The advantageous effect of the compatibility with crop plants of the active
compound
combinations according to the invention is particularly pronounced at certain
concentration ratios.
However, the weight ratios of the active compounds in the active compound
combinations can be
varied within relatively wide ranges. In general, from 0.001 to 1000 parts by
weight, preferably
from 0.01 to 100 parts by weight, particularly preferably from 0.05 to 20
parts by weight, of one of
the crop plant compatibility-improving compounds (antidotes/safeners)
mentioned above under (b')
are present per part by weight of active compound of the formula (1).
The active compound combinations according to the invention are generally
applied in the form of
finished formulations. However, the active compounds present in the active
compound
combinations can, as individual formulations, also be mixed during use, i.e.
be applied in the form
of tank mixtures.
For certain applications, in particular in the post-emergence method, it may
furthermore be
advantageous to include in the formulations, as further additives, mineral or
vegetable oils which
are tolerated by plants (for example the commercial preparation "Rako Binol"),
or ammonium
salts, such as, for example, ammonium sulphate or ammonium thiocyanate.

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The novel active compound combinations can be used as such, in the form of
their formulations or
the use forms prepared therefrom by further dilution, such as ready-to-use
solutions, suspensions,
emulsions, powders, pastes and granules. The application is in the customary
manner, for example
by watering, spraying, atomizing, dusting or broadcasting.
The application rates of the active compound combinations according to the
invention can be
varied within a certain range; they depend, inter alia, on the weather and on
soil factors. In general,
the application rates are from 0.001 to 5 kg per ha, preferably from 0.005 to
2 kg per ha,
particularly preferably from 0.01 to 0.5 kg per ha.
Depending on their properties, the safeners to be used according to the
invention can be used for
pretreating the seed of the crop plant (seed dressing) or can be introduced
into the seed ferrules
prior to the seed or be used separately prior to the herbicide or together
with the herbicide, before
or after emergence of the plants.
Examples of plants which may be mentioned are important crop plants, such as
cereals (wheat,
barley, rice), maize, soya beans, potatoes, cotton, oilseed rape, beet, sugar
cane and also fruit
plants (with the fruits apples, pears, citrus fruits and grapevines), greater
emphasis being given to
cereals, maize, soya beans, potatoes, cotton and oilseed rape.
All plants and plant parts can be treated with the active compounds according
to the invention.
Here, plants are to be understood as meaning all plants and plant populations
such as wanted and
unwanted wild plants or crop plants (including naturally occurring crop
plants). Crop plants can be
plants which can be obtained by conventional plant breeding and optimization
methods or by
biotechnological and recombinant methods or by combinations of these methods,
including the
transgenic plants and inclusive of the plant cultivars protectable or not
protectable by plant
breeders rights. Plant parts are to be understood as meaning all parts and
organs of plants above
and below the ground, such as shoot, leaf, flower and root, examples which may
be mentioned
being leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seed
and also roots, tubers and
rhizomes. The plant parts also include harvested material, and also vegetative
and generative
propagation material, for example cuttings, tubers, rhizomes, offshoots and
seeds.
Treatment according to the invention of the plants and plant parts with the
active compounds is
carried out directly or by allowing the compounds to act on their
surroundings, habitat or storage
space by the customary treatment methods, for example by immersion, spraying,
evaporation,
fogging, broadcasting, painting on or injection and, in the case of
propagation material, in
particular in the case of seed, also by applying one or more coats.

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The present invention therefore also relates to a method of controlling
unwanted plants or for
regulating the growth of plants, preferably in crops of plants, where one or
more compound(s)
according to the invention is/are applied to the plants (for example harmful
plants such as
monocotyledonous or dicotyledonous weeds or unwanted crop plants), to the seed
(for example
grains, seeds or vegetative propagules such as tubers or shoot parts with
buds) or to the area on
which the plants grow (for example the area under cultivation). In this
context, the compounds
according to the invention can be applied for example pre-planting (if
appropriate also by
incorporation into the soil), pre-emergence or post-emergence. Examples of
individual
representatives of the monocotyledonous and dicotyledonous weed flora which
can be controlled
by the compounds according to the invention shall be mentioned, without the
mention being
intended as a limitation to certain species.
Monocotyledonous harmful plants of the genera: Aegilops, Agropyron, Agrostis,
Alopecurus,
Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus,
Dactyloctenium,
Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca,
Fimbristylis,
Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum,
Paspalum,
Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda,
Anthemis,
Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia,
Centaurea, Chenopodium,
Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis,
Galinsoga,
Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria,
Mentha,
Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum,
Portulaca, Ranunculus,
Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis,
Solanum, Sonchus,
Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,
Xanthium.
The plants listed can be treated according to the invention in a particularly
advantageous manner
with the compounds of the general formula (1) or the active compound mixtures
according to the
invention. The preferred ranges stated above for the active compounds or
mixtures also apply to
the treatment of these plants. Particular emphasis is given to the treatment
of plants with the
compounds or mixtures specifically mentioned in the present text.
If the compounds according to the invention are applied to the soil surface
before germination,
either the emergence of the weed seedlings is prevented completely or the
weeds grow until they
have reached the cotyledon stage, but then stop their growth and, finally, die
completely after three
to four weeks have elapsed.

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When the active compounds are applied post-emergence to the green plant parts,
growth stops after
the treatment, and the harmful plants remain in the growth stage of the time
of application or die
fully after a certain period of time, so that competition by weeds, which is
harmful to the crop
plants, is thus eliminated at an early point in time and in a sustained
manner.
Although the compounds according to the invention display an outstanding
herbicidal activity
against monocotyledonous and dicotyledonous weeds, crop plants of economically
important
crops, for example dicotyledonous crops of the genera Arachis, Beta, Brassica,
Cucumis,
Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum,
Lycopersicon,
Miscanthus, Nicotiana. Phaseolus, Pisum, Solarium, Vicia, or monocotyledonous
crops of the
genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum,
Secale,
Sorghum, Triticale, Triticum, Zea, are damaged only to an insignificant
extent, or not at all,
depending on the structure of the respective compound according to the
invention and its
application rate. This is why the present compounds are highly suitable for
the selective control of
unwanted vegetation in plant crops such as agriculturally useful plants or
ornamentals.
Moreover, the compounds according to the invention (depending on their
respective structure and
the application rate applied) have outstanding growth-regulatory properties in
crop plants. They
engage in the plant metabolism in a regulatory fashion and can therefore be
employed for the
influencing, in a targeted manner, of plant constituents and for facilitating
harvesting, such as, for
example, by triggering desiccation and stunted growth. Moreover, they are also
suitable for
generally controlling and inhibiting unwanted vegetative growth without
destroying the plants in
the process. Inhibiting the vegetative growth plays an important role in many
monocotyledonous
and dicotyledonous crops since for example lodging can be reduced, or
prevented completely,
hereby.
As already mentioned above, it is possible to treat all plants and their parts
according to the
invention. In a preferred embodiment, wild plant species and plant cultivars,
or those obtained by
conventional biological breeding methods, such as crossing or protoplast
fusion, and parts thereof,
are treated. In a further preferred embodiment, transgenic plants and plant
cultivars obtained by
genetic engineering methods, if appropriate in combination with conventional
methods
(Genetically Modified Organisms), and parts thereof are treated. The terms
"parts", "parts of
plants" and "plant parts" have been explained above.
Particularly preferably, plants of the plant cultivars which are in each case
commercially available
or in use are treated according to the invention. Plant cultivars are to be
understood as meaning
plants having novel properties ("traits") which have been obtained by
conventional breeding, by

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mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or
genotypes.
Depending on the plant species or plant cultivars, their location and growth
conditions (soils,
climate, vegetation period, diet), the treatment according to the invention
may also result in
superadditive ("synergistic") effects. Thus, for example, reduced application
rates and/or a
widening of the activity spectrum and/or an increase in the activity of the
substances and
compositions which can be used according to the invention, better plant
growth, increased
tolerance to high or low temperatures, increased tolerance to drought or to
water or soil salt
content, increased flowering performance, easier harvesting, accelerated
maturation, higher harvest
yields, higher quality and/or a higher nutritional value of the harvested
products, better storage
stability and/or processability of the harvested products are possible, which
exceed the effects
which were actually to be expected.
Owing to their herbicidal and plant-growth-regulatory properties, the active
compounds can also
be employed for controlling harmful plants in crops of known genetically
modified plants or
genetically modified plants which are still to be developed. As a rule, the
transgenic plants are
distinguished by especially advantageous properties, for example by
resistances to certain
pesticides, mainly certain herbicides, resistances to plant diseases or
causative organisms of plant
diseases, such as certain insects or microorganisms such as fungi, bacteria or
viruses. Other special
properties relate for example to the harvested material with regard to
quantity, quality, storability,
composition and specific constituents. Thus, transgenic plants with an
increased starch content or a
modified starch quality or those with a different fatty acid composition of
the harvested material
are known. Further particular properties may be tolerance or resistance to
abiotec stresses, for
example heat, cold, drought, salt and ultraviolet radiation.
It is preferred to use the compounds of the formula (1) according to the
invention in economically
important transgenic crops of useful plants and ornamentals, for example of
cereals such as wheat,
barley, rye, oats, sorghum and millet, rice, cassava and maize or else crops
of sugar beet, cotton,
soya bean, oilseed rape, potato, tomato, peas and other vegetables.
It is preferred to employ the compounds of the formula (1) as herbicides in
crops of useful plants
which are resistant, or have been made resistant by recombinant means, to the
phytotoxic effects of
the herbicides.
Conventional ways of generating novel plants which, in comparison with
existing plants, have
modified properties are, for example, traditional breeding methods and the
generation of mutants.
Alternatively, novel plants with modified properties can be generated with the
aid of recombinant

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methods (see, for example, EP-A-0221044, EP-A-0131624). For example, the
following have been
described in several cases:
- recombinant modifications of crop plants for the purposes of modifying the
starch
synthesized in the plants (for example WO 92/11376, WO 92/14827, WO 91/19806),
- transgenic crop plants which are resistant to certain herbicides of the
glufosinate type (cf.,
for example, EP-A-0242236, EP-A-242246) or of the glyphosate type (WO
92/00377) or
of the sulphonylurea type (EP-A-0257993, US-A-5013659),
- transgenic crop plants, for example cotton, which is capable of producing
Bacillus
thuringiensis toxins (Bt toxins), which make the plants resistant to certain
pests
(EP-A-0142924, EP-A-0193259),
- transgenic crop plants with a modified fatty acid composition (WO 91/13972),
- genetically modified crop plants with novel constituents or secondary
metabolites, for
example novel phytoalexins, which bring about an increased disease resistance
(EPA
309862, EPA0464461),
- genetically modified plants with reduced photorespiration which feature
higher yields and
higher stress tolerance (EPA 0305398),
- transgenic crop plants which produce pharmaceutically or diagnostically
important
proteins ("molecular pharming"),
- transgenic crop plants which are distinguished by higher yields or better
quality,
- transgenic crop plants which are distinguished by a combination, for example
of the
abovementioned novel properties ("gene stacking").
A large number of molecular-biological techniques by means of which novel
transgenic plants with
modified properties can be generated are known in principle; see, for example,
I. Potrykus and
G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995).
Springer Verlag
Berlin, Heidelberg. or Christou, "Trends in Plant Science" 1 (1996) 423-431.
To carry out such recombinant manipulations, it is possible to introduce
nucleic acid molecules
into plasmids, which permit a mutagenesis or sequence modification by
recombination of DNA
sequences. For example, base substitutions can be carried out, part-sequences
can be removed, or

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natural or synthetic sequences may be added with the aid of standard methods.
To link the DNA
fragments with one another, it is possible to add adapters or linkers to the
fragments; see, for
example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd
ed., Cold Spring
Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene and
Klone", VCH
Weinheim 2nd ed., 1996
The generation of plant cells with a reduced activity for a gene product can
be achieved for
example by the expression of at least one corresponding antisense RNA, a sense
RNA for
achieving a cosuppression effect or by the expression of at least one
correspondingly constructed
ribozyme, which specifically cleaves transcripts of the abovementioned gene
product.
To this end, it is possible firstly to use DNA molecules which comprise all of
the coding sequence
of a gene product, including any flanking sequences which may be present, or
else DNA molecules
which only comprise parts of the coding sequence, it being necessary for these
parts to be long
enough to bring about an antisense effect in the cells. It is also possible to
use DNA sequences
which have a high degree of homology with the coding sequences of a gene
product, but which are
not entirely identical.
When expressing nucleic acid molecules in plants, the protein synthesized may
be localized in any
compartment of the plant cell. In order to achieve localization in a
particular compartment,
however, it is possible for example to link the coding region to DNA sequences
which ensure the
localization in a specific compartment. Such sequences are known to the
skilled worker (see, for
example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc.
Natl. Acad. Sci. USA
85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic
acid molecules can
also be expressed in the organelles of the plant cells.
The transgenic plant cells can be regenerated by known techniques to give
intact plants. In
principle, the transgenic plants may be plants of any plant species, that is
to say both
monocotyledonous and dicotyledonous plants.
Thus, transgenic plants can be obtained which feature modified properties as
the result of
overexpression, suppression or inhibition of homologous (= natural) genes or
gene sequences or
expression of heterologous (= foreign) genes or gene sequences.
It is preferred to employ the compounds (1) according to the invention in
transgenic crops which
are resistant to growth regulators such as, for example, dicamba, or to
herbicides which inhibit
essential plant enzymes, for example acetolactate synthases (ALS), EPSP
synthases, glutamine
synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides
from the group

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of the sulphonylureas, glyphosate, glufosinate or benzoylisoxazoles and
analogous active
compounds.
When the active compounds according to the invention are used in transgenic
crops, effects are
frequently observed - in addition to the effects on harmful plants which can
be observed-in other
crops - which are specific for the application in the transgenic crop in
question, for example a
modified or specifically widened spectrum of weeds which can be controlled,
modified application
rates which may be employed for application, preferably good combinability
with the herbicides to
which the transgenic crop is resistant, and an effect on growth and yield of
the transgenic crop
plants.
The invention therefore also relates to the use of the compounds of the
formula (I) according to the
invention as herbicides for controlling harmful plants in transgenic crop
plants.
The compounds according to the invention can be used in the form of wettable
powders,
emulsifiable concentrates, sprayable solutions, dusting products or granules
in the customary
formulations. The invention therefore also provides herbicidal and plant
growth-regulating
compositions which comprise the compounds according to the invention.
The compounds according to the invention can be formulated in various ways
according to which
biological and/or physicochemical parameters are required. Possible
formulations include, for
example: wettable powders (WP), water-soluble powders (SP), water-soluble
concentrates,
emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-
in-oil emulsions,
sprayable solutions, suspension concentrates (SC), oil- or water-based
dispersions, oil-miscible
solutions, capsule suspensions (CS), dusting products (DP), seed-dressing
products, granules for
scattering and soil application, granules (GR) in the form of microgranules,
spray granules, coated
granules and adsorption granules, water-dispersible granules (WG), water-
soluble granules (SG),
ULV formulations, microcapsules and waxes.
These individual formulation types are known in principle and are described,
for example, in:
Winnacker-Kuchler, "Chemische Technologie" [Chemical technology], Volume 7, C.
Hauser
Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, "Pesticide Formulations",
Marcel Dekker,
N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd.
London.
The necessary formulation assistants, such as inert materials, surfactants,
solvents and further
additives, are likewise known and are described, for example, in: Watkins,
"Handbook of
Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell
N.J., H.v. Olphen,
"Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C.
Marsden, "Solvents

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Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and
Emulsifiers Annual",
MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface
Active Agents",
Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflachenaktive
Athylenoxidaddukte"
[Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart
1976; Winnacker-
Kuchler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th Ed.
1986.
Based on these formulations, it is also possible to prepare combinations with
other pesticidally
active compounds, such as, for example, insecticides, acaracides, herbicides,
fungicides, and also
with safeners, fertilizers and/or growth regulators, for example in the form
of a finished
formulation or as a tank mix.
Wettable powders are preparations which can be dispersed uniformly in water
and, as well as the
active compound, apart from a diluent or inert substance, also comprise
surfactants of the ionic
and/or nonionic type (wetting agents, dispersants), for example
polyoxyethylated alkylphenols,
polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol
polyglycol ether
sulphates, alkanesulphonates, alkylbenzenesulphonates, sodium lignosul
phonate, sodium
2,2'-dinaphthylmethane-6,6'-disulphonate, sodium dibutylnaphthalenesulphonate
or else sodium
oleylmethyltauride. To prepare the wettable powders, the active herbicidal
compounds are ground
finely, for example in customary apparatus such as hammer mills, blower mills
and air jet mills
and simultaneously or subsequently mixed with the formulation assistants.
Emulsifiable concentrates are prepared by dissolving the active compound in an
organic solvent,
for example butanol, cyclohexanone, dimethylformamide, xylene or else
relatively high-boiling
aromatics or hydrocarbons or mixtures of the organic solvents with addition of
one or more
surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers
used may, for example,
be: calcium alkylarylsuiphonates such as calcium dodecylbenzenesulphonate, or
nonionic
emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers,
fatty alcohol
polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl
polyethers,
sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene
sorbitan esters, for
example polyoxyethylene sorbitan fatty acid esters.
Dusting products are obtained by grinding the active compound with finely
divided solid
substances, for example talc, natural clays such as kaolin, bentonite and
pyrophyllite, or
diatomaceous earth.
Suspension concentrates may be water- or oil-based. They may be prepared, for
example, by wet
grinding by means of commercial bead mills and optional addition of
surfactants as have, for

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example, already been listed above for the other formulation types.
Emulsions, for example oil-in-water emulsions (EW), can be prepared, for
example, by means of
stirrers, colloid mills and/or static mixers using aqueous organic solvents
and optionally
surfactants, as have, for example, already been listed above for the other
formulation types.
Granules can be produced either by spraying the active compound onto
adsorptive granulated inert
material or by applying active compound concentrates by means of adhesives,
for example
polyvinyl alcohol, sodium polyacrylate or else mineral oils, onto the surface
of carriers such as
sand, kaolinites or of granulated inert material. It is also possible to
granulate suitable active
compounds in the manner customary for the production of fertilizer granules -
if desired in a
mixture with fertilizers.
Water-dispersible granules are prepared generally by the customary processes
such as spray-
drying, fluidized bed granulation, pan granulation, mixing with high-speed
mixers and extrusion
without solid inert material.
For the preparation of pan, fluidized bed, extruder and spray granules, see,
for example, processes
in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E.
Browning,
"Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's
Chemical Engineer's
Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
For further details regarding the formulation of crop protection compositions,
see, for example,
G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New
York, 1961, pages
81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell
Scientific
Publications, Oxford, 1968, pages 101-103.
The agrochemical formulations contain generally from 0.1 to 99% by weight, in
particular from
0.1 to 95% by weight, of compounds according to the invention.
In wettable powders, the active compound concentration is, for example, from
about 10 to 90% by
weight; the remainder to 100% by weight consists of customary formulation
constituents. In the
case of emulsifiable concentrates, the active compound concentration may be
from about I to 90%
by weight, preferably from 5 to 80% by weight. Dust-type formulations contain
from 1 to 30% by
weight of active compound, preferably usually from 5 to 20% by weight of
active compound;
sprayable solutions contain from about 0.05 to 80% by weight, preferably from
2 to 50% by weight
of active compound. In water-dispersible granules, the active compound content
depends partly on
whether the active compound is present in solid or liquid form and which
granulation assistants,

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fillers, etc. are used. In the granules dispersible in water, the content of
active compound is, for
example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
In addition, the active compound formulations mentioned optionally comprise
the respective
customary adhesives, wetting agents, dispersants, emulsifiers, penetrants,
preservatives, antifreeze
agents and solvents, fillers, carriers and dyes, defoamers, evaporation
inhibitors and agents which
influence the pH and the viscosity.
The term "active compounds" or "compounds" in each case also includes the
active compound
combinations mentioned herein.
According to the invention, the preparation of the compounds of the general
structure (1) can be
carried out by processes A to H.
Using, for example, according to process (A) methyl 2,2-dimethyl-8-[(2,6-
diethyl-4-
methyl)phenylacetyl] - 1,3 -di oxa- [4.4. 0] -bicycl ononane-7-carboxyl ate,
the course of the process
according to the invention can be represented by the reaction scheme below:
COZCH3
O CA S OH C2H5
H 1. base H3C~0 \ / \ CH3
3 2.H "3C O
H3C O C2H5 0 C2H5
Using, for example, according to process (B) 5'-(2,6-diethyl-4-methylphenyl)-
6'-hydroxy-2,2-
dimethyl-1',3',3a',6a'-tetrahydro-4'H-spiro[1,3-dioxolan-4,2'-pentalen]-4'-one
and pivaloyl
chloride as starting materials, the course of the process according to the
invention can be
represented by the reaction scheme below:
CH3
H3C
CH3 CH3
HsC O OH C2H5 H3C+COC1 O O CZHS
-
y HC _
3 0
CZHS base
0 C2H5
Using, for example, according to process (B) 5'-(2,6-diethyl-4-methylphenyl)-
6'-hydroxy-2,2-
dimethyl-I',3',3a',6a'-tetrahydro-4'H-spiro[l,3-dioxolan-4,2'-pentalen]-4'-one
and acetic
anhydride as starting materials, the course of the process according to the
invention can be
represented by the reaction scheme below:

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CH3
OH C H H3C-CO 0--(
z5 O O CH
H3_yO \ - H3C-CO H3C O z
H 3 e 0 \/ c"3 H c~ cw3
base 3 O
O C2H5 0 C2H5
Using, for example, according to process (C) 5'-(2,6-diethyl-4-methylphenyl)-
6'-hydroxy-2,2-
dimethyl-1',3',3a',6a'-tetrahydro-4'H-spiro[I,3-dioxolan-4,2'-pentalen]-4'-one
and ethyl
chloroformate as starting materials, the course of the process according to
the invention can be
represented by the reaction scheme below:
0CzHS
O
OH CH0
0 zH5
H3C~ CIOC2H5 H3C O C
H3C" 10 C"3 H C" \ \ \ / C"3
X*O s O
O C2H5 base
O C2H5
Using, for example, according to process (D) 5'-(2,6-diethyl-4-methylphenyl)-
6'-hydroxy-2,2-
dimethyl-1',3',3a',6a'-tetrahydro-4'H-spiro[1,3-dioxolan-4,2'-pentalen]-4'-one
and methyl
chloromonothioformate as starting materials, the course of the process
according to the invention
can be represented by the reaction scheme below:
OCH3
OH C2H5 S S~ O C
HC z"5
3 CI OCH3 H3C 0 \
H3C_ 10O _ \ / C"3 H C~ C"3
\ / _
base s O
O C2H5 O C2H5
Using, for example, according to process (E) 5'-(2,6-diethyl-4-methylphenyl)-
6'-hydroxy-2,2-
dimethyl-1',3',3a',6a'-tetrahydro-4'H-spiro[ l,3-dioxolan-4,2'-pentalen]-4'-
one and
methanesulphonyl chloride as starting materials, the course of the reaction
can be represented by
the reaction scheme below:
OH CA CH3SO2\0 CA
" ~0 + CI- base %Y*O SO2-CH3 H32 5
H C 0 C"3 H3C CH3
O CA 0 C2H5
Using, for example, according to process (F) 5'-(2,6-diethyl-4-methylphenyl)-
6'-hydroxy-2,2-
dimethyl-1',3',3a',6a'-tetrahydro-4'H-spiro[I,3-dioxolan-4,2'-pentalen]-4'-one
and 2,2,2-

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trifluoroethyl methanethiophosphonyl chloride as starting materials, the
course of the reaction can
be represented by the reaction scheme below:
H3C S
OH C S OCH CF CF3CH2O-P~
2H5 + CI-P, z s 0 CH"3C O CH3 H3C H3C O \ CH3 H Ck CH3
base 3 O X*O
O 2H5 0 C2H5
Using, for example, according to process (G) 5'-(2,6-diethyl-4-methylphenyl)-
6'-hydroxy-2,2-
dimethyl-I',3',3a',6a'-tetrahydro-4'H-spiro[1,3-dioxolan-4,2'-pentalen]-4'-one
and NaOH as
components, the course of the process according to the invention can be
represented by the
reaction scheme below:
OH C2H5 Na+ O C "sC 0 - NaOH H3 2H5
O NaOH
H3c/ o \ \ / cH3 H 3% c"3
3 0
O C2H5
Using, for example, according to process (H), variant a, 5'-(2,6-diethyl-4-
methylphenyl)-6'-
hydroxy-2,2-dimethyl-1',3',3a',6a'-tetrahydro-4'H-spiro[1,3-dioxolan-4,2'-
pentalen]-4'-one and
ethyl isocyanate as starting materials, the course of the reaction can be
represented by the reaction
scheme below:
H
,N-C2HS
OH C2H5 0~
H3C O - C2H5 N=C=O 0 C"
~ H3C
H3c' 1c \ \ / c"3 HC ~~ c"3
base O
O C2H5
0 C2H5
Using, for example, according to process (H), variant 13, 5'-(2,6-diethyl-4-
methylphenyl)-6'-
hydroxy-2,2-dimethyl-1',3',3a',6a'-tetrahydro-4'H-spiro[1,3-dioxolan-4,2'-
pentalen]-4'-one and
dimethylcarbamoyl chloride as starting materials, the course of the reaction
may be represented by
the scheme below:

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H3C
O N-CH3
OH CA S\
H3C O CIN CH3 H 3Q O C2H5
H3C" 1 CH3 CH3 _ HC
" \ O \ CH3
\ /
O C2H5 HCI 3 O
O CA
The compounds, required as starting material in process (A) according to the
invention, of the
formula (II)
:R8
(ll)
O X Y
in which
A, B, X, Y, Z and R8 have the meaning given above
are novel.
They can be prepared by methods known in principle.
The 5-aryl-4-ketocarboxylic esters of the formula (II) are obtained, for
example, when 5-aryl-4-
ketocarboxylic acids of the formula (XIII)
C02H
A Z
B
I (XIII)
X Y
in which
X, Y, Z, A and B have the meaning given above
are esterified (cf., for example, Organikum, 15th Edition, Berlin, 1977, page
499) or alkylated (see
Preparation Example).
The arylketocarboxylic acids of the formula (XIII)

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CO2H
A Z
(XIII)
O X Y
in which
A, B, X, Y and Z have the meaning given above
are novel; however, they can be prepared by methods known in principle (WO
07/080066,
WO 96/01 798, WO 97/14667, WO 98/39281, WO 0 1/74770).
The arylketocarboxylic acids of the formula (XIII) are obtained, for example,
when 2-phenyl-3-
oxoadipic esters of the formula (XIV)
8
C0R
2
A CO2R$ Z
B (XIV)
0 X Y
in which
A, B, X, Y and Z have the meaning given above and
R8 and R" represent alkyl (in particular Cl-C8-alkyl) and,
when the compound of the formula (XVI) is used, R$ represents hydrogen
are decarboxylated, if appropriate in the presence of a diluent and if
appropriate in the presence of
a base or acid (cf., for example, Organikum, 15th Edition, Berlin, 1977, pages
519-521).
The compound of the formula (XIV)

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$
COR
2
A CO2R$ Z
B
(XIV)
O I ~ Y
in which
A, B, X, Y, Z, R8, Rs' have the meaning given above and,
when the compound of the formula (XVI) is used, R8 represents hydrogen
are novel.
The compounds of the formula (XIV) are obtained, for example,
when dicarboxylic semiester chlorides of the formula (XV)
A CO2R8
B CHaI Xv
( )
11
0
in which
A, B and R8 have the meaning given above and
Hal represents chlorine or bromine
or carboxylic anhydrides of the formula (XVI)
0
A
B ?C40 (XVI)
O
in which

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A and B have the meaning given above
are acylated with a phenylacetic ester of the formula (XVII)
X
OR$
Y (XVII)
Z
in which
X, Y, Z and R8 have the meaning given above
in the presence of a diluent and in the presence of a base (cf., for example,
M.S. Chambers,
E. J. Thomas, D.J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228, cf.
also the Preparation
Examples).
A further proven method for preparing the compounds, required as starting
materials for process
(A), of the formula (II) in which A, B, X, Y, Z and R8 have the meaning given
above is also, for
example, the coupling of benzyl zinc compounds of the general formula (XVIII)
X
Y -0- C H 2 -Zn-Hal
Z (XVIII)
in which X, Y and Z have the meaning given above and Hal represents a halogen
atom, preferably
chlorine or bromine,
if appropriate in the presence of a catalyst, with a dicarboxylic semiester
chloride of the general
formula (XV) or a carboxylic anhydride of the general formula (XVI).
Both the preparation and the reaction of organic zinc compounds with carbonyl
chlorides and
carboxylic anhydrides are known in principle and can be carried out in close
analogy to the
processes described in the literature. More details are described, for
example, in Chem. Commun.
2008, 5824, WO 2007/113294, Tetrahedron Letters 30, 5069-5072 (1989) or Chem.
Rev. 1993, 93,
2117-2188.
The acid halides of the formula (III), carboxylic anhydrides of the formula
(IV), chloroformic

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esters or chloroformic thioesters of the formula (V), chloromonothioformic
esters or
chlorodithioformic esters of the formula (VI), sulphonyl chlorides of the
formula (VII),
phosphorus compounds of the formula (VIII) and metal hydroxides, metal
alkoxides or amines of
the formulae (IX) and (X) and isocyanates of the formula (XI) and carbamoyl
chlorides of the
formula (XII) furthermore required as starting materials for carrying out the
processes (B), (C),
(D), (E), (F), (G) and (H) according to the invention are generally known
compounds of organic of
inorganic chemistry.
Some of the compounds of the formulae (XV), (XVI) and (XVII) are known
compounds of organic
chemistry or known from the patent applications cited at the outset and/or can
be prepared in a
simple manner by methods known in principle or can be prepared by the methods
described in the
patent applications cited at the outset.
To prepare benzyl zinc compounds of the formula (XVIII), benzyl compounds of
the formula
(XIX)
X
Y C -Hal
- HZ
Z (XIX)
where X, Y and Z have the meaning given above and Hal represents a halogen
atom, preferably
chlorine or bromine, are used as starting material. Some benzyl compounds of
the formula (XIX)
are known, or they can be prepared by known processes (see, for example, Chem.
Ber. 118, 1968
(1985), Monatshefte Chemie 135, 251 (2004), Acta Chem. Scand. 1963, 17 and
Preparation
Examples).
The process (A) is characterized in that compounds of the formula (II), in
which A, B, X, Y, Z and
R8 have the meaning given above are subjected to an intramolecular
condensation in the presence
of a base.
Suitable for use as diluents in the process (A) according to the invention are
all organic solvents
which are inert towards the reaction participants. Preference is given to
using hydrocarbons, such
as toluene and xylene, furthermore ethers, such as bibutyl ether,
tetrahydrofuran, dioxane, glycol
dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as
dimethyl sulphoxide,
sulpholane, dimethylformamide and N-methylpyrrolidone. It is furthermore
possible to use
alcohols, such as methanol, ethanol, propanol, isopropanol, butanol,
isobutanol, tert-butanol.

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Suitable bases (deprotonating agents) for carrying out the process (A)
according to the invention
are all customary protonic ceptors. Preference is given to using alkali metal
and alkaline earth
metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium
hydroxide,
magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and
calcium carbonate,
which may also be used in the presence of phase-transfer catalysts, such as,
for example,
triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464
(= methyltrialkyl(C8-CIO)ammonium chloride) or TDA 1 (=
tris(methoxyethoxyethyl)amine). It is
furthermore possible to use alkali metals, such as sodium or potassium.
Further, it is possible to
employ alkali metal and alkaline earth metal amides and hydrides, such as
sodium amide, sodium
hydride and calcium hydride, and additionally also alkali metal alkoxides,
such as sodium
methoxide, sodium ethoxide and potassium tert-butoxide.
When carrying out the process (A) according to the invention, the reaction
temperatures may be
varied within a relatively wide range. In general, the process is carried out
at temperatures between
0 C and 250 C, preferably between 50 C and 150 C.
The process (A) according to the invention is generally carried out under
reduced pressure.
When carrying out the process (A) according to the invention, the reaction
components of the
formula (II) and the deprotonating bases are generally employed in about
doubly equimolar
amounts. However, it is also possible to use a relatively large excess (up to
3 mol) of one
component or the other.
The process (B-a) is characterized in that compounds of the formula (1-a) are
in each case reacted
with carbonyl halides of the formula (III), if appropriate in the presence of
a diluent and if
appropriate in the presence of an acid binder.
Suitable for use as diluents in the process (B-(x) according to the invention
are all solvents which
are inert towards the acid halides. Preference is given to using hydrocarbons,
such as benzine,
benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons,
such as methylene
chloride, chloroform, carbon tetrachloride, chlorobenzene and o-
dichlorbenzene, moreover
ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such
as diethyl ether,
tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl
acetate, and also strongly
polar solvents, such as dimethyl sulphoxide and sulpholan. If the acid halide
is sufficiently stable
to hydrolysis, the reaction can also be carried out in the presence of water.
Suitable acid binders for the reaction according to process (B-a) according to
the invention are all

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customary acid acceptors. Preference is given to using tertiary amines, such
as triethylamine,
pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU),
diazabicyclononene
(DBN), Hiinig-Base and N,N-dimethylaniline, furthermore alkaline earth metal
oxides, such as
magnesium oxide and calcium oxide, moreover alkali metal carbonates and
alkaline earth metal
carbonates, such as sodium carbonate, potassium carbonate and calcium
carbonate, and also alkali
metal hydroxides, such as sodium hydroxide and potassium hydroxide.
The reaction temperatures in the process (B-a) according to the invention can
be varied within a
relatively wide range. In general, the process is carried out at temperatures
between -20 C and
+150 C, preferably between 0 C and 100 C.
When carrying out the process (B-a) according to the invention, the starting
materials of the
formula (I-a) and the carbonyl halide of the formula (III) are generally each
employed in
approximately equivalent amounts. However, it is also possible to use a
relatively large excess (up
to 5 mol) of the carbonyl halide. Work-up is carried out by customary methods.
The process (B-B) is characterized in that compounds of the formula (I-a) are
reacted with
carboxylic anhydrides of the formula (1V), if appropriate in the presence of a
diluent and if
appropriate in the presence of an acid binder.
Suitable diluents for use in the process (B-B) according to the invention are,
preferably, the
diluents which are also preferred when using acid halides. Besides this a
carboxylic anhydride
used in excess may simultaneously act as diluent.
Suitable acid binders, which are added, if appropriate, for process (B-B) are,
preferably, the acid
binders which are also preferred when using acid halides.
The reaction temperatures in the process (B-B) according to the invention may
be varied within a
relatively wide range. In general, the process is carried out at temperatures
between -20 C and
+150 C, preferably between 0 C and 100 C.
When carrying out the process (B-B) according to the invention, the starting
materials of the
formula (I-a) and the carboxylic anhydride of the formula (IV) are generally
each employed in
approximately equivalent amounts. However, it is also possible to use a
relatively large excess (up
to 5 mol) of carboxylic anhydride. Work-up is carried out by customary
methods.
In general, diluent and excess carboxylic anhydride and the carboxylic acid
formed are removed by
distillation or by washing with an organic solvent or with water.

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The process (C) is characterized in that compounds of the formula (I-a) are in
each case reacted
with chloroformic esters or chloroformic thio esters of the formula (V), if
appropriate in the
presence of a diluent and if appropriate in the presence of an acid binder.
Suitable acid binders for the reaction according to the process (C) according
to the invention are
all customary acid acceptors. Preference is given to use tertiary amines, such
as triethylamine,
pyrridine, DABCO, DBU, DBA, Hunig-Base and N,N-dimethylaniline, furthermore
alkaline earth
metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal
carbonates and
alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate
and calcium
carbonate, and also alkali metal hydroxides, such as sodium hydroxide and
potassium hydroxide.
Suitable diluents for use in the process (C) according to the invention are
all solvents which are
inert towards the chloroformic esters or chloroformic thio esters. Preference
is given to using
hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin,
furthermore halogenated
hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride,
chlorobenzene and
o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl
ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally
carboxylic esters, such as
ethyl acetate, and also strongly polar solvents, such as dimethyl sulphoxide
and sulpholan.
When carrying out the process (C) according to the invention, the reaction
temperatures can be
varied within a relatively wide range. If the process is carried out in the
presence of a diluent and
an acid binder, the reaction temperatures are generally between -20 C and +100
C, preferably
between 0 C and 50 C.
The process (C) according to the invention is generally carried out under
atmospheric pressure.
When carrying out the process (C) according to the invention, the starting
materials of the formula
(I-a) and the appropriate chloroformic ester or chloroformic thio ester of the
formula (V) are
generally each employed in approximately equivalent amounts. However, it is
also possible to use
a relatively large excess (up to 2 mol) of one component or the other. Work-up
is carried out by
customary methods. In general, precipitated salts are removed and the reaction
mixture that
remains is concentrated by removing the diluent under reduced pressure.
The process (D) according to the invention is characterized in that compounds
of the formula (I-a)
are in each case reacted with compounds of the formula (VI) in the presence of
a diluent and, if
appropriate, in the presence of an acid binder.
In preparation process (D), about one mol of chloromonothioformic ester or
chlorodithioformic

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ester of the formula (VI) is employed per mole of the starting material of the
formula (1-a) at from
0 to 120 C, preferably from 20 to 60 C.
Suitable diluents which are added, if appropriate, are all inert polar organic
solvents, such as
ethers, amides, sulphones, sulphoxides, and also halogenated alkanes.
Preference is given to using dimethyl sulphoxide, tetrahydrofuran,
dimethylformamide or
methylene chloride.
If, in a preferred embodiment, the enolate salt of the compounds (1-a) is
prepared by addition of
strong deprotonating agents, such as, for example, sodium hydride or potassium
tert-butoxide, the
further addition of acid binders may be dispensed with.
If acid binders are used, these are customary inorganic or organic bases;
sodium hydroxide, sodium
carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by
way of example.
The reaction can be carried out at atmospheric pressure or under elevated
pressure and is
preferably carried out at atmospheric pressure. Work-up is carried out by
customary methods.
The process (E) according to the invention is characterized in that compounds
of the formula (I-a)
are in each case reacted with sulphonyl chlorides of the formula (VII), if
appropriate in the
presence of a diluent and if appropriate in the presence of an acid binder.
In preparation process (E), about one mol of sulphonyl chloride of the formula
(VII) is reacted per
mole of the starting material of the formula (I-a) at from -20 to 150 C,
preferably from 20 to 70 C.
Suitable diluents which are added, if appropriate, are all inert polar organic
solvents, such as
ethers, amides, nitrides, sulphones, sulphoxides or halogenated hydrocarbons,
such as methylene
chloride.
Preference is given to using dimethyl sulphoxide, tetrahydrofuran,
dimethylformamide, methylene
chloride.
If, in a preferred embodiment, the enolate salt of the compounds (I-a) is
prepared by addition of
strong deprotonating agents (such as, for example, sodium hydride or potassium
tert-butoxide), the
further addition of acid binders may be dispensed with.
If acid binders are used, these are customary inorganic or organic bases, for
example sodium
hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

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The reaction can be carried out at atmospheric pressure or under elevated
pressure and is
preferably carried out at atmospheric pressure. Work-up is carried out by
customary methods.
The process (F) according to the invention is characterized in that compounds
of the formula (I-a)
are in each case reacted with phosphorus compounds of the formula (VIII), if
appropriate in the
presence of a diluent and if appropriate in the presence of an acid binder.
In preparation process (F), to obtain compounds of the formula (I-e), from 1
to 2, preferably from 1
to 1.3, mol of the phosphorus compound of the formula (VIII) are reacted per
mole of the
compounds of the formula (I-a), at temperatures between -40 C and 150 C,
preferably between -10
and 110 C.
Suitable diluents which are added, if appropriate, are all inert polar organic
solvents, such as
ethers, amides, nitriles, alcohols, sulphides, sulphones, sulphoxides, etc..
Preference is given to using acetonitrile, dimethyl sulphoxide,
tetrahydrofuran,
dimethylformamide, methylene chloride.
Suitable acid binders which are added, if appropriate, are customary inorganic
or organic bases,
such as hydroxides, carbonates or amines. Sodium hydroxide, sodium carbonate,
potassium
carbonate, pyridine and triethylamine may be mentioned by way of example.
The reaction can be carried out at atmospheric pressure or under elevated
pressure and is
preferably carried out at atmospheric pressure. Work-up is carried out by
customary methods of
organic chemistry. The arising end products are preferably purified by
crystallization,
chromatographic purification or "incipient distillation" i.e. removal of the
volatile components
under reduced pressure.
The process (G) is characterized in that compounds of the formula (I-a) are
reacted with metal
hydroxides or metal alkoxides of the formula (IX) or amines of the formula
(X), if appropriate in
the presence of a diluent.
Suitable diluents for use in the process (G) according to the invention are,
preferably, ethers, such
as tetrahydrofuran, dioxane, diethyl ether, or else alcohols, such as
methanol, ethanol, isopropanol,
and also water.
The process (G) according to the invention is generally carried out under
atmospheric pressure.
The reaction temperatures are generally between -20 C and 100 C, preferably
between 0 C and

CA 02739870 2011-04-07
BCS 08-3052-Foreign countries
-99-
50 C.
The process (H) according to the invention is characterized in that compounds
of the formula (I-a)
are in each case reacted with (H-a) compounds of the formula (XI), if
appropriate in the presence
of a diluent and if appropriate in the presence of a catalyst, or (H-13) with
compounds of the
formula (XII), if appropriate in the presence of a diluent and if appropriate
in the presence of an
acid binder.
In preparation process (H-(x), about I mol of isocyanate of the formula (XI)
is reacted per mole of
starting material of the formula (1-a), at from 0 to 100 C, preferably from 20
to 50 C.
Suitable diluents which are added, if appropriate, are all inert organic
solvents, such as ethers,
amides, nitrides, sulphones, sulphoxides.
If appropriate, catalysts may be added to accelerate the reaction. Suitable
for use as catalysts are,
very advantageously, organotin compounds, such as, for example dibutyl tin
dilaurate. The
reaction is preferably carried out at atmospheric pressure.
In preparation process (H-B), about I mol of carbamoyl chloride of the formula
(XII) is reacted per
mole of starting material of the formula (I-a), at from -20 to 150 C,
preferably at from 0 to 70 C.
Suitable diluents which are added, if appropriate, are all inert polar organic
solvents, such as
ethers, amides, sulphones, sulphoxides or halogenated hydrocarbons.
Preference is given to using dimethyl sulphoxide, tetrahydrofuran,
dimethylformamide or
methylene chloride.
If, in a preferred embodiment, the enolate salt of the compound of the formula
(1-a) is prepared by
addition of strong deprotonating agents (such as, for example, sodium hydride
or potassium tert-
butoxide), the further addition of acid binders may be dispensed with.
If acid binders are used, then customary inorganic or organic bases are
suitable, for example
sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or
pyridine. The reaction
can be carried at an atmospheric pressure or under elevated pressure and is
preferably carried out
at atmospheric pressure. Work-up is carried out by customary methods. The
preparation and the
use of the active compounds according to the invention is illustrated by the
examples below.
Preparation Examples

CA 02739870 2011-04-07
BCS 08-3052-Foreign countries
- 100-
Examples I-a-1 and I-a-2
O CZHS O CZHS
O O CH
H3C CH3 H3C~Q ' 3
O
H3C OH CZHS H3C OH CZHS
Example I-a-1 Example I-a-2
anti syn
In 50 ml of anhydrous N,N-dimethylformamide, 4.62 g (11.5 mmol) of methyl 8-
[(2,6-diethyl-4-
methylphenyl)acetyl]-2,2-dimethyl-l,3-dioxaspiro[4.4]nonane-7-carboxylate
(according to
Example (11-5)) and 2.57 g of potassium tert-butoxide are heated at 50 C for 2
h. After cooling, the
mixture is poured into ice-water, acidified to pH 3 using conc. hydrochloric
acid and extracted
three times with ethyl acetate. The organic phase is dried (magnesium
sulphate), and the solvent is
then distilled off and the residue is chromatographed on silica gel (ethyl
acetate/hexane = 50:50).
Fraction A:
anti-isomer (I-a-1); yield 1.70 g (40%); colourless crystals of m.p. 104-105 C
Fraction B:
syn-isomer (I-a-2); yield 1.40 g (34%); colourless crystals of m.p. 88-89 C

CA 02739870 2011-04-07
BCS 08-3052-Foreign countries
- 101 -
Example I-a-3
O C2H5
HO
CH3
0
OH
C2H5
(I-a-3)
In 40 ml of toluene, 0.79 g (2.64 mmol) of 2-(2,6-diethyl-4-methylphenyl)-3-
hydroxy-3a,4,6,6a-
tetrahydropentalene-l,5-dione (according to Example (1-a-4)), 0.58 g (6.6
mmol) of 2-
methylidenepropane-l,3-diol and 20 mg of p-toluene sulphonic acid are heated
on a water
separator for 3 h, and the mixture is then concentrated using a rotary
evaporator and taken up in
ethyl acetate. The mixture is extracted with bicarbonate solution and water,
dried (magnesium
sulphate), the solvent is distilled off and the residue is chromatographed on
silica gel (ethyl
acetate/hexane v:v=35:65), which then affords the compound of the formula (I-a-
3) in the form of
colourless crystals.
Yield: 0.52 g (53%)
'H-NMR (400 MHz, CDCl3): 6 = 1.07 and 1.09 (in each case t, in each case 3H),
3.12 and 3.38 (in
each case mc, in each case I H), 4.10-4.37 (m, 4 H), 4.39 (mc, 2 H) ppm
Example I-a-4
O C2H5
O CH3
OH C H
2 5 (1-a-4)
2 ml of a 2.5% strength solution of osmium tetroxide in t-butanol are added to
2.50 g (8.43 mmol)
of 2-(2,6-diethyl-4-methylphenyl)-3-hydroxy-5-methylidene-4,5,6,6a-
tetrahydropentalen-](3aH)-
one (according to Example I-a-5) and 9.02 g (42.16 mmol) of sodium meta-
periodate in 50 ml of a
water/tert-butanol mixture (v/v=50:50), and the mixture is stirred at room
temperature for
10 minutes. 50 ml of ethyl acetate are then added, and the mixture is stirred
at room temperature
for a further 2 h. The reaction mixture is then added to ice, taken up in
ethyl acetate and extracted
with water. After drying (magnesium sulphate) and distillative removal of the
solvent, the residue
is chromatographed on silica gel using ethyl acetate/hexane (v/v=30:70). This
gives 1.86 g (74.1%)
of the compound of the formula (1-a-4) as a viscose oil.

CA 02739870 2011-04-07
BCS 08-3052-Foreign countries
- 102 -
`H-NMR (400 MHz, CDCl3): 6 = 2.31 (s, 3H), 2.52 and 2.74 (in each case mc,
broad, in each case
2H), 3.41 and 3.68 (in each case mc, broad, in each case 1 H) ppm
Example I-a-S
O C2H5
H
H - CH 3 (1-a-5)
OH C2H5
In 80 ml of N,N-dimethylformamide, 7.85 g (23.9 mmol) of methyl 2-[(2,6-
diethyl-4-methyl-
phenyl)acetyl]-4-methylidenecyclopentanecarboxylate (according to Example (II-
1)) and 5.36 g
(47.8 mmol) of potassium tert-butoxide are heated at 50 C for 2 h. After
cooling, the mixture is
added to ice-water, acidified to pH 2 using conc. hydrochloric acid and
extracted with ethyl
acetate. The organic phase is washed twice with water, dried (magnesium
sulphate) and
concentrated using a rotary evaporator. Chromatographic purification on silica
gel (mobile phase
ethyl acetate/hexane v:v = 40:60) gives 4.30 g (61%) of the compound of the
formula (I-a-5) in the
form of colourless crystals of melting point 127-128 T.
'H-NMR (400 MHz, CDC13): 6 = 0.94 and 1.08 (in each case t, in each case 3H),
2.28 (s, 3H), 2.51
(mc, 4H), 4.89 (s, 2 H) ppm
Example I-a-18
0 C2H5
N CH3
H3C-O
CZH5
(I-a-18)
0,164 g (1.62 mmol) of triethylamine is added to 0.161 g (0.54 mmol) of 2-(2,6-
diethyl-4-
methylphenyl)-3-hydroxy 3a,4,6,6a-tetrahydropentalen-1,5-dione (Example I-a-4)
and 0.090 g
(1.08 mmol) of N-methylhydroxylamine hydrochloride in 10 ml of acetonitrile,
and the mixture is
stirred at room temperature for 6 h. The mixture is then added to ice and
taken up in ethyl acetate,
and the organic phase is separated off and washed with water. Drying
(magnesium sulphate),
distillative removal of the solvent and chromatography on silica gel using
ethyl acetate/hexane
(v/v=25:75) finally affords 0.154 g (87%) of the desired compound of the
formula (I-a-18) as a
viscose yellowish oil.

CA 02739870 2011-04-07
BCS 08-3052-Foreign countries
-103-
'H-NMR (400 MHz, CDC13): 6 = 2.62 (mc, 1H), 3.20 and 3.48 (in each case mc, in
each case I H),
3.82 (s, 3 H) ppm

08-3052 Foreign countries CA 02739870 2011-04-07
104-
=
C
0
C
E
C
C
L
U
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vO
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00
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x N z M
O \ O O TS O " M N rUn
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C
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C '
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U' U U U U
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C U U ~ = U
p O ~ U O
w .T. X = Z 2
N U U~ U U U U
~ U U IU U U U
3 0 ~C U$ U~ U~ U U~ U
oo O O ~
E~ n W Z cc

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-105-
o
o
` o C
C)Y -.Y
3 o
s L U
cn ,J rn
M ccCC N N
G ^ (1 ^ r -r N
uo V
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O cr U c' ^ U O C Z
U pc "C O 'O U N rn O -C
ccc M =~ cC :~ O l U U cc
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M cC N M C N CC CC - CC d.) CC N
O O
U O Z U v = U
U =' II T U Z U
U Z U U
U ^
O v cis II U
U U
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N U~ U U~ U U' U' U~ U~
Z Z T Z 2
~+ U U U U U U U U
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M ~n ~O t o0 6~
W CC CC$ CC cC CC c~ cC

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
106-
y
E k
E
U
N
z
C
o Z d -' O N
r l- c, a
v - N - o o ~o 0
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C U
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D O O U U. z U i O
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d O UO O
I I I Z Z 2 Z = T Z I
N N 1
UN NU UI UI UN UN N 1
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1 1 N N N N 1 1 N N N
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O N M to ~O N 00 C' O
N N N N N N N N N N M
W Z ci cc m cC cG z cl m

B(.-S 08-3052 Foreign countries CA 02739870 2011-04-07
107-
a) CD
k x
o C C
U
0
z
C
C M O N d N
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N O N N N N
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N U U U U U U U U U U U U
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M M M M M M M M
W z cc ctl cC ctl c cc cc

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 108-
Q
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C.
M N
N
Y M
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C~z
C d
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w U
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o o ~? 't o C
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O O O M Z 00 O O 7t
N N N N cG M N N N N
p 0
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i z i z z z' z z, ~
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T T U U U U U U U U U
~C U U O O O O 0 0 0 0 0
M 'U' V-1 '0 N 00 C O N M
IT IT IT IT 17 17 IT

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-109-
E
O N
E o
C
U M
U = ~o
N
o N U
NNE
V] r n
by N U
F+1 N
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<v of iv - U i ~i N cv
U U O U U U U T Z U
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O O O O U ~j O
U U O O
d O O
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N U U U U U U U U U T
z I T =' = z = z z
~+ U U U U U U U U U U U
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x 0 tl N
UN
U U U U U U U U U
~t v'~ ~C N GO G1 O N M mot'
W Z c3 c~ cii ca cC c~ cd z cd cC

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
110-
E
E
G j N N U
CL = C
cp p CN M M
M U M "
A z U N
U s
~ O U z
rN N N
M+y" M U
73
z
O N U - C U - N
,yam^ U U N
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M O O c) a) \O a)
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n N N U -
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a3 cc C z CT N ac
l~ 0 C U 'C N a) 'C
p O
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z I z U Y
U U U II ~~
U U U C C U u C
c o ~~ z
U
d o
N z z z ( ( (' I (3 z
Z Z 4 Z Z 2 2
~+ U U U U ~U U U U U
Z ~ 'Z Z T z Z ^" 2
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n O N oc G~ O N M
1 'C N N N N
~. cd cd cd 1f cC c~ cd cC cd

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 111 -
bb
U U
Q U
otm~
v, ~ 3
bb
I
N
7
0
~r o
o
x
o U
Z o
N U U
U U
0
r, r`

CA 02739870 2011-04-07
BCS 08-3052 Foreign countries
-112-
Example 1-b-1
O CzH5
O
H3C0 CH3 (I b 1)
H3C
Ozz~ O C2H5
CH3
At room temperature, 0.100 g (0.27 mmol) of the compound I-a-I according to
the invention (anti-
isomer), 23.3 mg (0.297 mmol) of acetyl chloride and 82 mg (0.297 mmol) of
triethylamine are
stirred in 5 ml of dichloromethane for 2 h. The reaction mixture is poured
onto ice, taken up in
dichloromethane, washed with water, dried (magnesium sulphate) and
concentrated using a rotary
evaporator. Chromatography on silica gel (mobile phase ethyl acetate/hexane
v:v= 30:70) gives the
compound of the formula (I-b-1) according to the invention as a colourless
oil. Yield 76.6 mg
(68%).
'H-NMR (400 MHz, CDC13): 6 1.39 (s, 6 H), 2.10 (s, 3 H), 2.21 (s, 3 H), 3.85
(dd, 2 H) ppm

08-3052 Foreign countries CA 02739870 2011-04-07
-113-
C
O
C
C
fl.
o E
cs
~ S
N -
bA -G _
V N M
ON v d Z
a a-
CIO
_L M N N T _
p O C r v - O
op M N
/ : O h M N
o M ~ `t II ~
cf)
~ Q m C U U ~, U U' U
0
C~j
1 rl r, ~ , ~ , lV
~ Z Z Z Z Z Z
~ ~ ~ U U U U
O Q Q
U U U U U U
O O O p U U
O O
~. Q
N
c U U ~ U U U~ U
O
a M
E U U U U U U
cq
3 X = I T
= z z
U U Cj' U N N
U
~ N M d' Vl ~D l~

RCS 08-3052 Foreign countries CA 02739870 2011-04-07
114-
o
C r
O
L V]
0 Q.
E O CA
r
C i
G cG U
_^ _ 00 U N
x
o 7, cl
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p N Ln
N -O 00 U N
Ln E Z . .E M
a N 0 O N G1 N Z
,~ O ~O vi O N - O
~Q c~ II M II _ 00
V [~ c0 a0 M w cC ~
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2 Z T I Z I
o
0 0 0
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U Z U
O U I U U
N Z Z ;Z Z ~ S T .i
U U U U U~ U U U
U U U U U U U U
U U U U U U U U
O N M v~
c0 G1

RCS 08-3052 Foreign countries CA 02739870 2011-04-07
115-
X' k X
~ ~ c c
- v V) N
U U U
F N M
N `t T O T v
~" M T O N M M CO M ~
N V' vi ^ dJ ~.,~
O U ~~ O N M
E U
Ef -=
N ^ N
~_ M O O
0 E r E
~_ M pA ^ N ...i U M
G U M O N U ^ N N
a fl z D = M N
~. _ tr)
.~ M E M M M ~~i M
L T M N O O T O E
c c c'
T T T T i T
T U U U U T
~ U U U ~ ~ ~ ~ U
q o
o z
:
T z o o '0 0 0 0
p Z Z' ~' Z' 2 T' Z'
U U U U U U U
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N T T T T T T T T
U U U U U U U U
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U U U U U U
~ ~. ~ T T T ~. T z'
~O N 00 O' O N M
N N N N

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-116-
E
vUi ~ U
v M c
.~ O U cV
U N t
U ~ .1.
o
Z ^ N N
N y N ti
-~i
v E U
C.U c ,- o c ~n " N o
z
z - - p = z
-- U 7 U U
0 0 0 0 0 0
u u u u
0 o q o o o f
N ~ z T T z, _ _
U U U U U U' U
~ z' z z z' z' T z'
U U U U U U U
r (`I fl r rl rl N r \N CI
V U U U
v~ ~D N 00 O~ O
N N N N N N M

W, -S 08-3052 Foreign countries CA 02739870 2011-04-07
-117-
E
8
O
au
6 U
N
N O ^ C N
'-ri 0 'J O =
N ~-. ~p . r N U
S U ^ ci v .~ cC
_ C N
~i t1. O N N r. z
F~ N O C cc z N
oc
N N
O M U O M N CJ N
7z 110 cz;
U N
Q O O\ N C M CO _ NN N
U U M N N N N N M cc
T
z
U
r c U z
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O O O C C O
I 2 z z z T Z'
U U U U U U U
O O O O O C
N M
_ 2 Z 2
U U U U U U U
U U U U U U U
z = z
7C = `r '`' z
U U' U' U U' U U
N M C l
M M M M M M M

BSS 08-3052 Foreign countries CA 02739870 2011-04-07
-118-
E
0
E
N
= O
IW ~ ~ M U M U ~
= O = N M 'G
"f Z U _ = ^ ~j ~ U M
~..~ ~p ~p OQ U E Q
W N V~ .~ 0
L v~ O v) pp c~ v~ M
Z =B V 'O V GO -n U
00 ~. ~ k ~ ~ X M X Z
x - T
s. T 0 Z a co
c _ E z 0 c E E
cc oc
"'O N 7D M ..; 00 u 'D O to 00
N cz N M CC M c'I N M
c"I 7z; 00
M O T C =
U N G N r^ O c~ M M
a U U U U U U
O
O O O U U
'- ,- ~\ rL
1 21 CI U
U U U U U =
O O O U
I'' Z
U UO
N z z z z
U U U U U U
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GO Q O N M
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BCS 08-3052 Foreign countries CA 02739870 2011-04-07
119-
5... L Lam.. L ice. L
Y J J C C C
VJ ^
C
si
= r 00 "O M n
N .~ 7a 00
oc 0, ca
M ~ M c1 ~ C5
M U N 7:3 00 ._
C ^ ^ ^ T M = N x
U Z RS N
73 N 000
~ .~' ~ ~ M U fr1 ~ ~ fh ~
GO N 00 U U CC
r^~ ~. CO o m T= :C 00 ,~ vl
Mrl L-' - M -- N N U I O GO
F+I U M N N M
O = O U = a)
U t0 V M ~ U N ~ ~ U ~ ~ ~ M
00 M CO
Qr 00 = i : -C 00 C' O \p
Q DD U C T V M ' N
O CO U~ U O N
I
U
I O
U U U' U
Z Z 2 Z Z
U U U U U U
O O O O O
U U U U U U
U U U U U U
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N ~ Z T ,.iZ ZU U U U U U
U U U U U U
JC T
U jU U U U U
00 ol

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-120-
1.)
r x
U U U C
N N
w: U ~ N -~ vi ~ U =--
M O U cf U U M "G
N rUn U U , .. vUi e U
M N o N U M
I -~ U U U M U
r
cd M U U
cz ca
cl) fn
cf~
C U U ~_ cz M
V q U U U G cf) O Ui CD cn
cz ca m
M N RS N U
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U U U
U U U U
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O O
zO O O
U U
U U
O O
U U IU U U
= T z z z
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U U U U U
O N M
YC O n0 .D .~ .O
wz

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-121-
E
U r
O
o U - o
N N C N
M N N O T M
~ N M U ~ N ~ 't7 ~ N ^ N
cC M
N s~ N cz c O N
U
Z N O Z N X U C N
C
CIZ
V M OMO U M ,~ ~' U =~ U oc
71- rr)
q) N A ~D ^ GO O O ^ v'~ O T O "
V O ~t O M o N
z
z z X z z
U T
U U U U U
Cq
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U U
III III
U U
O i0 U U O O
O O
z z
T z z z s z
U U U U U U U
4~ 41
U U U U U U U
Z
Z Z T Z I 2 U
U U U U U U 0
v';, o N co c\ O

ICS 08-3052 Foreign countries CA 02739870 2011-04-07
-122-
E
E
c~G 00 U '0 C O C CC N
U vi U N
U ~ M M M ~ ~ U 'G M
N :~ ~ ^ \O ^ vUi ^ ~ ~ M N
cz V1
G' M O _ O U X -' U 00 N M
O N v rU M Q) U U - vU
-O p vi - O" U "G M .~
Z O M 0 N O QJ
U U '' '' 0 C cd a is
O Q Z p p O I T r _ v Z d X I)
C 'C U .o a O M U M
U
cf)
m Z E
C. A O O MO z O M U O x O V O N
V vi CO N ' 0) M N '23 ~:.~
Z Z Z
U U U U U U
cv ~
i
C a Q U U
of ~' i~ i= C C
U
II U U U U U.
O O
' U U
U O O
d O
N ~ z ^= z z
U U U U U U
U U U U U U
U U U U -
O 0 O O U~ U~

ECS 08-3052 Foreign countries CA 02739870 2011-04-07
-123-
E
Y
E
c~ n h o
c N
U
4N 'C3
++ N X c X .J-. N M U
tl M N 10 W
cY X X `~ .. U vi N
E
- OD - _ r
.~.1 O c . E T7
E U U N - v cC3
of C. X vN O oC X
r. cj U M V O -B
N ...M M O X X U
CO CC C OC C r.'
~.. ~, [~ O X OcG
V v
N N 1
T T
U U U
O O O II II
U U U U U
U U U
I I
O O O
N Z T Z T z 2
U U U U U U
U U U U U U
'N XI ~I N 'N PI
U U U ~U U U
oC C O N M

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
124-
E
E
U U
Irl
r+y m
DW~II M _~ ~
E N ri
`", V M 2 N M
M 00
A O T O 00 c c c Tr
~v t
~ U U U U U U
q O O
O U U O O O
U U
Z II I II
U
o ~ o .o 0
o o
U U U U U U
U U U U U U
U U U U U
c
wz

08-3052 Foreign countries CA 02739870 2011-04-07
-125-
Example Ic-1
O C2H5
O
H3C_41O \ / CH3 (I-c-1)
H3C
Ozz~ O 2H5
O
H3C
At room temperature, 82 mg (0.81 mmol) of triethylamine are added to 0.100 g
(0.27 mmol) of the
compound (I-a-1) according to the invention and 28 mg (0.30 mmol) of methyl
chloroformate in
5 ml of dichloromethane, and the mixture is stirred for another 1 h. The
reaction mixture is poured
into ice-water, taken up in dichloromethane, washed with water, dried
(magnesium sulphate), and
the solvent is distilled off.
Chromatographic purification on silica gel (ethyl acetate/hexane v/v=20:80)
gives 104 mg (90%)
of the desired compound of the formula (1-c-1) in the form of colourless
crystals of melting point
111-112 C.

08-3052 Foreign countries CA 02739870 2011-04-07
-126-
Example I-c-17
O C2H5
O =C: / CHs (I-c-17)
OZ.~O C2H5
OC2H5
0.98 ml of 2.5% strength solution of osmium tetroxide in n-butanol is added to
1.50 g (4.05 mmol)
of 2-(2,6-diethyl-4-methylphenyl)-5-methylidene-3-oxo-3,3a,4,5,6,6a-
hexahydropentalen-l-yl ethyl
carbonate (Example I-c-5) and 4.33 g (20.24 mmol) of sodium meta-periodate in
150 ml of a
water/tert-butanol mixture (v/v=50:50), and the mixture is stirred at room
temperature for
minutes. 50 ml of ethyl acetate are then added, and the mixture is stirred at
room temperature
for another 2 h.
The reaction mixture is poured onto ice, taken up in ethyl acetate and
extracted with water. After
10 drying (magnesium sulphate) and distillative removal of the solvent, the
residue is
chromatographed on silica gel using ethyl acetate/hexane (v/v=30:70). This
gives 1.00 g (66%) of
the desired compound of the formula (I-c-17) as a viscose oil.
`H-NMR (400 MHz, CDCI3): b =1.26 (t, 3 H), 3.51 and 4.31 (in each case mc, in
each case 1 H),
4.20 (mc, 2 H) ppm

08-3052 Foreign countries CA 02739870 2011-04-07
G
127-
' =~
a.
n
I)
c
0
E
I
E
Y : C
~ - Ce (/1 V1
y
U a, ~ N
o oo ^ -
a ~- E Z =
ca oo - -
It C X 0
^ U U ~ N
~ M U
C. p U 00 p ^ M ONp
L5 E Ti N
N a M
^, '~ N M M N
N ~A ~~ M II
~"=~ V rq N rq M op
0 0
r N
Y2~w C4 U U U U
w
O
T O C O C
In
o Q m
0
c
U U U
0 0 O
z
o ^ ^ ^ U
P I 2 Z II
U U U
U
C C O
I 1
v
I N =, Z ^r =
o U U U U
Q., ~ U U U U
o i
U
a~D yC y _ 2 Z
3 U U U U
0
W z U U U U
F-i

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 128-
cn
0
ap
I
U
i-+
~, 3 cn
s U C
E E E
C - Y
^ C 1
VI U VJ r-~-i
V p U U U N
I+
O 00
N - N
N u ~ ~
N o - .Z N
~-N J Vn m dam'.
C `^ E 'a
G U M N M
O N -
..r c~ ^ i O N
a \O o0 ^ - N CO CO U
~ U~ U U U~ U U U
O O O O O O O
O O O
Ca p U~
U O Z O U U
U U
U ~ U ~ U T, U-U
T C U U I U
U o z U
U I
O o 0 0
41
U U U U U U U
U U U U U U U
U~ U~ UUU U~ U
o - N
o U U U U U U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-129-
U
U
O _
r L
o
E c s
o ~ o I;
N
C Z M - U
n
N N
~ M U N U ~ U ~ M i--~ Z
U E^ E' Z N
E
E U V'1 r"' p U
C''.r ^ _ o Z O M M U
L G V'~ N M M N N
N N d I C
¾ A II C o II 1 Z N `O N r
cc -t o0 rq .~ U N ^ N
C: U U U U U U U
O O O O O O O
O
Pa U
U O v~l v~ U O
U z Z 0 U z
U U U U
2 O vD U
U ~U
U O
N Z Z = Z r Z ~"
U U U U U U~ U
U U U U U U U
n n n n vi vi n
~ z z z z z z
U' U U U' U U U
M ~ V') ~O 00 G1
W Z U U U U U U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 130 -
U
y O R3
c~J
L U
U
E
E
M Z U Z Z
N N ^ O M
t!1 - .Y^. .-. M M ^ w
00 -LS T M
M N N E M .-.
N O vi M C M cz QJ E
~y O~ .. U f` N W z N c v'~
U
cz _ ^ N N ti ^ ccc
N U
E N ' .E N N
C0 " M N O
O M M M
cc U ^ N N G M M 00 U N
Lr' N 00 U C.O M Lt N M M V'1
A O O 00 N O O N O O
V N U ~' OA M V' N
~C U U U U U U U
O O O O O O O
O
O O O ^ O
U U U I U U
' Z r U Z
i U x x" U U
U -- U U U O O
Y U U U U z
U U U U =
O O U O O
O
N U U U U U U U
U U U U U U U
Z .~.. T ~ Z Z m
T yN N ri ~i ~i
U U U U U U U
O N M mot' v'~ ~D
N N N N N N N
y U U U U U U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 131 -
L L L L
y C ~
C C ~
M M U U
00
N
~., ~ ~ oo cNC ~t vi ^ N ,^N
^ ~ ~ ~ r M .-^-. ~ N M^ M U ^
x R N N N O N O U
O C2. ^ ^ O T N C
C
N M V'1 N N j N i--~ ^
o - O O T
`' U N M N
O. V O ' N M O r: v ~j M r:
A O O N Z O O C N
N N N N '' C M N N
v, T
T T
C~ U U U U U U U
O O O O O O O
O O
O T T
= z = o 0 0 0
^
U U O U U U U
T T T
U U U
U U U
~ O O O
N T T -41
T T T
U U U U U U U
U U U U U U U
x z ~ z z z z z
U U U' U U U' U~
N oo G O N M
N N N M M M M
W ~ U U U U U U U

13CS 08-3052 Foreign countries CA 02739870 2011-04-07
-132-
E
M ,- V
C' U M Z N N N U
M - '-`U Z O U
pp N ^ M U C1 ~` G1
Z '^ E 00 U -
M I N ~ Z .E M
O ~O M 00 Z ~/'? N
i-: ^ N M C' T O N ,0~, 0
V U T GO T ., ,~ U N O0 N
o r E ^ N C
G Q N U M O p N ~ ,- N N N
z -r
fs; U U U U C.) U U U
O O 0 O 0 0 C O
r r1.
O O O O L
~ 17 ~ i~ U O U
U U U U O O T U
O C O O z U C U
z I
U U' U U U' U U U'
U U U U U U U U
[I rl N N ~1 rl N CI
U U U U U U ~U U
M M M M M M M ~
W~ U U U U U U U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-133-
E
E
c
Z N M E
cn N _ N ~ c~ ~
C =' U N N w G~ N -~= E
~-. C .~ M M M U ~.
~, U .J.. `"i M O ca QJ U , U N
a N N O N 2 Z
-e ~? U U '~t' O U N N
N N fr1 - ^ N _ U ,_-. N U N O
Z i-. I U GO r - 00 cUC C N ~t
x N d ~. - O N N C ~..~ N cal
N M J- .-. vi M ^ v1 ~' M
U U , M M U ^_ N M N ^ U
co
V) W) CD '"""' ^-~ N M U U N N U
Q o0 N N ~O N = N = N cUC c
"a ~' U U' U' U U
o O o 0 0 0
U U O
U ~~ % II I
O O = U U U
J O
z O
z
I I
N I = z T
U' U U U U U
U U U U U U
U' U' U' U U U
N M V O
YC ~ U U U U U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 134-
E
0
E E
r. ^
U M N M N
t7 U ^ U
~" N ti Z = rte- E
v M M N r- N
_ N 1 U U
E .~ M
G+ N C N ~_ 00 _ ~t N
U pp M M 73 U M ^ M "C'i U
E E
N c~ CD 00 V-1
N I l~ d' N N ~1 N E
V M - O N ~' M O N r
z = M = z
U U~ U U~ U~ U U
O O O O O O O
O O O p
p Z ~~
U U U U
O O O z
_' U r' = U U U
U Z UZ U U~ I Z
U
U c
N U U U U U U U
U U U U U U U
U U U U U U U
t~ c0 G~ O N M
z U U U U V U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-135-
C X >C
E
a~ C
c c c
M U -O ~ ~ M U ~ N ~
CZ C75
N U ~j cd U GD
U U -
oc U Z M ^ 00 N ~; N
C p U Z y i O M
V GD -~ p `~ cc3
cq Z,
~' O =~ 00 U 00 , 00 V'J
A N M "~' M ~"' O~ N 00 '
U ^ N ^ U M U M U N N
U U U U U U
O O O O O O
p ~~ Z Z
0 0 0
.~ O o
z I n u U~
U U U O
U U U
0 0 o z
N U U U U U U
U U U U U U
U U U U U U
l
L? L?
y U U U U U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 136 -
E
E O r
N O [~ G~ N N U O
O 'C3 = N ' N v Vl
O Z C ^ C N cd CO
N - C I d N U
_ U U _ O of M , N ^ N L' M
Z N N N O T C c~
~y N _ N U CD
O O
.~ \O M T. _ vi M M ' N M
Z
O .-~ ti 00 'O
vT 2 Z
x Z N 0 N z vi ~"~ N M
L^. M M oc O M OO - ~j V) N N , -- U
Q N O M M N N _
M N N N N U N U
z z U z z z
U' U U U U U
O 0 O O O O
jo 0
U u
O U U
2 U O
U U U U U U
U U U U U U
U U U U U U
O 0 O O 0
O N N M
y U U U U U U

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-137-
E
~-r ~ ~ F M O' M T ~ ~ y
M O M N M N V7 `--~ N I `n
7t, ~--~ M CC C cn T C
U G U U
M 'Z TS M U ~ E U N ~ M U
r
N N U
O U N cC .--. 00 O U 0
00
L. M C- N U M ^ frl
o yr 2 M Z M _
V7 = M .-r ._
r r
02n N a~ y v O M O O C
A N N c N O N o [~ T
U U O U M N
O O o 0 0 0
O
U o o o
0 0 o
U
I'D Z U U U U
N z z ~ s z z I~
U U U~ Cj' U U~
U U U U U U
U U U U U U
o O o O O O
N co
W '' U U U U U U ~

,BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-138-
E
I
E
0
0 N
O .- C M r
M U ^ ~_ N T U U
qj q)
Z C N oc M C
..~ N N U M M ^ oc N u
Q Q
U ~O ^ M V)
U T.. M
V U U N O O N O
Ct, U U U U U U U
O j0 O O O O O
it O O O ~' it U U U
T II
U U U
yl I II II T
U U U
U U U U
O N N O
= Z ='
U U U
O O O N U U U U U U U
y' U U U U U U U
~ T Z ~ T Z
fl N N hl (`I ~I rl
U U U U U U U
N M ~t ~n 'O N
U U U U U U U
wz

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
- 139
y y y
L - L
i-+
~ C C O
n >, T T
[~ U M CG U ~
M U O
U N
O
p ^ y N y a~ _
Y U cd n
E
M N Uq N
FBI T.. '27 ^ oc
L G O - N N y
O C ^_ vyi ^ O O
00 G, F4 frl Ce - N
UO M M U M 'C7 ^ TS ^
v C _
6w a) 00 a)
V M ~ .~ c~ U O U N O N cc
C4 U U U~ U U U U
O O O O O O O
O O
i
O O O
~~ ~~
=' Z
U U U U O U U
u U
O O O O N ,=' Z Z T Z
U U U
U U U
~ _ ~ = Z = Z T
U U U U UI U U~
yC = ~" ~ Z Z Z .i
U U U UI U UI U
co C, O N M ~t
N
YC O U U U U U U U
z

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-140-
x
p
cz
E C
N
T
O T
7 N N
r U
z T 0c
N
C C _
a
ci.
A o
~; L) U U U U
O O O O O
O O O O U
zZ ~U U U U
X
0 0 0 o
U
U
U U U U U
U U U U U
r oc
C
OF OF cl? 0? 0?
i'C O U U U U U

08-3052 Foreign countries CA 02739870 2011-04-07
-141-
Example I-d-1
0 C2H5
0~
CH3 (1-d-1)
O
\S/0 C2H5
0
At room temperature, 57 mg (0.29 mmol) of p-toluenesulphonyl chloride and 0.1
ml of
triethylamine are added to 100 mg (0.27 mmol) of the compound (1-a-1) in 5 ml
of dichlormethane.
After I h of stirring, the mixture is diluted with water and the organic phase
is separated off and
washed twice with 1 N hydrochloric acid. Drying with magnesium sulphate and
distillative
removal of the solvent affords 120 mg (87%) of the desired substance as a
colourless oil.
`H-NMR (400 MHz, CDC13): 6 = 0.98 and 1.03 (in each case t, in each case 3H),
2.30 and 2.39 (in
each case s, in each case 1H), 3.15 and 3.90 (in each case mc, in each case
1H), 3.98-4.35 (m, 4H),
5.65 (s, 2H) ppm.

08-3052 Foreign countries CA 02739870 2011-04-07
- 142-
c
O
C
C
L
Q) Q) y
L J L
x x x
c E E c
v C C C
- '.. r C C
F1 CC c3 V7 V1 Vl
-6 tz
Q) F M ^
C 7
U
y M cC
y N N U
U 7 oc U N
E
-73
L v 0 f1 M
n p C
G O ^ ~ cCi M
^L G f^ z o
-O O a> M
C _ , T N
(,~ U M
O'c ca
V
G ~O ,^, N U U O
a) N A . ~ ri E cz
O- / O
U)- 0
0
-~ U
Q U
C~ U U U U
73
~_
`~ T~ Z~ T Z ZI
U U U U U
G
O O O O
L
U U U U U
U U U U U
Q O O O O O
O N U U U U U
O
U U U U U
=--
N M R
f!1 N
z 04

-BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-143-
E
E
U
L) O v,
cc
o O O Nd r- 110 -t
N N
Z ZZ
U U U
0 0 0
I' ~ z' z f z
x I O C U U U
U U U ^
Z I T U U U U U U
U U U Y Y
z ~z0 0 o z z z ~
U U0
0
N U U U U U U U U U
Z Z 2 Z T T Z x
U U U U U U U U U
:E .~ Z Z w
U U U U U U U U U
O , N M rh V7
IN

CA 02739870 2011-04-07
BCS 08-3052 Foreign countries
= -144-
Example I-f-1
0 C2H5
C :CH3
0 C2H5
Na
0.040 g (0.242 mmol) of sodium methoxide are added to 0.094 g (0.242 mmol) of
the compound
(1-a-17) in 3 ml of absolute methanol, and the mixture is stirred at room
temperature for another
30 min.
Distillative removal of the solvent gives 0.096 g (96%) of the compound of the
formula (1-f-1)
according to the invention in the form of colourless crystals of melting point
> 300 C.
' H-NMR (400 MHz, d6-DMSO): 6 = 0.92 and 0.95 (in each case t, in each case 3
H), 2.22 (s, 3 H),
6.68 (mc, 2 H) ppm

08-',.052 Foreign countries CA 02739870 2011-04-07
-145-
C
0
a~ o c
Y Y
r - V Y V
0 0 0
0 4 C
r
U U y
C U U
0 Z 0
00
N aJ v) a~
3 N C
U Z Z U
cUC >- C` N U cU6 cC
U U
00 N C
U N U N ~--~ N N M
O \ O ^O Q N U "O "C M "O
+
C1
w w z z z z z z
Q CO _ -~ 0 0 0 U
0 U U U U U Z
o
U U O
O O
T T
o N U U U U U v
-a
~ T T Z T.. .~.. Z
9. U U U U U U
o
U
~ Z U U U U
3 >C U U O O O O
0
N N M d ~ ~ ~
wz

BCS 08-3052 Foreign countries CA 02739870 2011-04-07
-146-
E
E
O
00
-O N v N - r C
U V1 N =,= U
c N Ln 00 E
O N '-S U M M U oc
~~Ii C N -O 'C ,~ M M
/C U C
73
z Ce I N a .O N ' \p U .~r^. M N U - U
N N N M E , Ce
^p tai ^ .~ ^ vUi I
i CO
~ ~ Z U cn ~ 1, Z Z ~ Z U ~ v _
al CIA
C2,, A O 00 C O N M 00 U N U
cr,
O 'C C' 'C C C' U
!~ ~O N v
ZS n O M U N O O O O O
C C C C C C C Ce
w z z z z z z z z
o 0 o 0 0
UI U o O U U U o
U ~U T U
U ~. U Z Z
O O U U O
U U' U U~ Z~
o U
I O O O
~ T Z Z Z Z Z
N U U U U U U~ U~ U
U U U U U U U U
7 Z T Z i =
~C U U U U U U~ U U
O N M v~
00

RCS 08-3052 Fomign countries CA 02739870 2011-04-07
- 147-
4-. O
O o
V U c
G
CU
Gf~
N r. r
U N l) N
U N U C U
N t ^ y N cCS -
M r` U c U
cl~
00 r ~,~ U cn
p N N .-~ M V U AO
N 0 C ccz ry ~t N N
N"' N E U N C N C vi
Z O r;. l r; U _C x \O
N .= -- r, M U C- N N
r'i
O^ _ N E N r: C d L
Q
M CC ~..~ ' Q> N U
G A N ~- . N r d O N c~ C- C O v
_ O Vl Q1 '~ G~ CC
~o = oc
O CC C- "C V
C C C C
w z z z z z z z z
0 0
U U
O U U U N
_ ~ II II II
I U=U I' I ZI
U U U U U U
U U U
T Q
U O '
O I O
N U U U ~UI U U U U
~ U U U ~U U U U U
~C U~ U U~ U U' U C U
D [~ oc J O N M
N N N N
w Z 4= 4= '7'. 4 4 +
I 1 I I 1

P:CS 08-3052 Foreign countries CA 02739870 2011-04-07
-148-
E
N
N Z
c.A~ N
+ +
z z
o z0
N U U
>0 u
T
ry o u
N N
wz~

CA 02739870 2011-04-07
08-3052 Foreign countries
- 149-
Preparation of starting materials
2-[(2,6-diethyl-4-methylphenyl)acetyll-4-methylidenecyclohexanecarboxylic acid
-
Example (XIII-1)
0 CzHs CO ,H C2H5 CO,H 0 C2H5
H H3C02C 2 0 Ci "JIJ CiH3
O * CH'
H
0 HS H Meo2C CzHs H CzHs
H H
(XVI-1) (XVI I-1) (XIV-1) (XI I I-1)
At -30 C, 14.48 g (65.7 mmol) of methyl 2-ethyl-4,6-dimethylphenyl acetate
(XVII-1) are slowly
added dropwise to a solution of lithium diisopropylamide in 250 ml of THF,
prepared from 16.3 g
(164 mmol) of diisopropylamine and the equimolar amount of a solution of n-
butyllithium in
hexane, and the mixture is stirred at room temperature for 45 min. At -20 C,
10.00 g (65.7 mmol)
of 4-methylenecyclopentane-1,2-dicarboxylic anhydride (XVI-1), dissolved in 20
ml of THF, are
then added, and the mixture is stirred at room temperature for around 12 h.
For work-up, 100 ml of
sat. ammonium chloride solution are added, a layer of ethyl acetate is added
on top and the mixture
is washed with water, dried (magnesium sulphate) and concentrated using a
rotary evaporator. This
gives 223 g of the compound (XIV-1) as a reddish oil which can be reacted
without further
purification.
'H-NMR (400 MHz, CDCI3): 6 =1.1.1 and 1.12, in each case t, in each case 3H),
2.25-2.50 (m,
4 H), 235 (s, 3 H), 2.69 (mc, 2H), 2.72-2.90 (m, 4H), 3.66 (s, 3H), 4.85 (s,
2H) ppm
10 g of potassium hydroxide in 100 ml of water are added to 22.3 g of
intermediate (XIV-1), and
the mixture is heated at reflux for 24 h. The mixture is then allowed to cool
to room temperature,
acidified to pH 2 with 2N hydrochloric acid and stirred at room temperature
for I h, and the
precipitated solid is filtered off with suction. This gives 10.3 g (45%) of 2-
[(2,6-diethyl-4-methyl-
phenyl)acetyl]-4-methylidenecyclohexanecarboxylic acid (XIII-1) as a yellowish
solid which can
be used without further purification for the next reaction step.
`H-NMR (400 MHz, CDC13): 6 = 1.12 (t, 6H), 2.45 (q, 4H), 3.90 (s, 2H), 4.91
(mc, 2H), 6.89 (s,
2H) ppm
The following intermediates of the general formula (XIII) were prepared
analogously:

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C02 H O Z
i Y
(XIII)
B X
A
Ex. X V Z A B M.p. [ C] or'H-NMR (400 MHz, CDC13, 6 in
No. Ppm)
XIII-2 OCH3 CH3 C,H5 CHI= 3.28-3.40 (m, 2H), 3.78 (mc, 2H), 3.72 and 3.80
(s, in total 3H), 4.88 (mc, 2H)
XIII-3 CH3 CH3 CH3 CH,= 2.15 (s, 6H), 2.25 (s, 3H), 3.83 (mc, 2H), 4.90
(mc, 2H)
XIII-4 C7H5 CH3 CH3 CHI= 1.20 (t, 3H), 2.12 (s, 3H), 2.22 (s, 6H), 3.70 (s,
2H), 4.90 (mc, 2H)
XIII-5 OCH3 CH3 C2HS CH,= 1.17 (mc, 3H), 3.28-3.40 (m, 2H), 3.72 and 3.79
(in each case s, he 3H), 4.89 (mc, 2H)
XIII-6 C2H5 CH3 H CH3= 96-100
The following intermediates of the general formula (XIV) were prepared
analogously:
CO2H O Z
Y (XIV)
B O O X
A
R$
Ex. X Y Z A B R8 M.p. [ C] or'H-NMR (400 MHz, CDCI3, S in
No. PPM)
XIV-2 CH3 CH3 CH3 CHz= CH5 118-119
XIV-3 CH5 CH3 CH3 CH,= CH3 167-168
2.20 and 2.31 (in each case s, in each case 3H),
XIV-4 OCH3 CH3 CH3 CH,)= CH3 3.13 and 3.58 (in each case s, in each case 3H),
4.85 (mc, 2H)
XIV-5 OCH3 CH3 1 C2H5 CH,= CH3 1.08-1.18 (m, 3H), 2.69-3.00 (m, 4H), 4.88
(mc, 2H), 13.20 (s, br, 1H)
CH
XIV-6 CzHs CH3 H CH2= 3 106-107

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Methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-
methylidenecyclopentanecarboxylate
Example (11-1)
COMe CH
CO2H O C2H5 2 O 2 CH
CH3 3
H
H C2H5 C2H5
H
(XI I I-1) (I I-1)
5.45g (17.33 mmol) of 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-
methylidenecyclohexane-
carboxylic acid (XIII-1), together with 2.38 g of potassium carbonate and 2.62
g (20.8 mmol) of
dimethylsulphate, are boiled at reflux in 50 ml of acetone for 5 h, and after
cooling, the reaction
mixture is taken up in ethyl acetate, extracted with water and dried
(magnesium sulphate), and the
solvent is distilled off. Chromatography on silica gel using ethyl
acetate/hexane (v/v=30:70) gives
3.93 g (69%) of methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-
methylidenecyclohexane-
carboxylate of the formula (II-1).
`H-NMR (400 MHz, CDC13): 6 = 3.58 (s, 3 H), 3.89 (s, 2H), 4.88 (s, 2H), 6.89
(s, 2H) ppm
Ethyl2-[(2-ethyl-4,6-dimethylphenyl)acetyl]-4-oxocyclopentanecarboxylic
Example (11-2)
COP COZEt O C 2 H 5
2 CH3
C' I O H3C
5.62 g (25.7 mmol) of 2-ethyl-4,6-dimethylbenzyl chloride in 30 ml of THE are
slowly added
dropwise to a suspension of 3.85 g (28.3 mmol) of dry zinc chloride, 1.56 g
(64.2 mmol) of
magnesium turnings and 1.36 g (42.4 mmol) of lithium chloride such that the
internal temperature
does not exceed 35 C. After the addition has ended, the mixture is stirred at
room temperature for
another 2 h. At room temperature, the solution formed is slowly added dropwise
to a mixture of
5.62 g (25.7 mmol) of ethyl 2-(chlorocarbonyl)-4-oxocyclopentanecarboxylate
and 85 mg of
bis(triphenylphosphine)palladium(II) chloride in 40 ml of THF, and the mixture
is then stirred at
room temperature for another 3 h.

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The mixture is added to water, extracted twice with in each case 50 ml of
methyl tert-butyl ether
and dried (magnesium sulphate), and the solvent is distilled off.
Chromatography on silica gel
using ethyl acetate/hexane (v/v=30:70) gives 4.89 g (57%) of the desired
intermediate in the form
of colourless crystals of M.p. 75 C.
`H-NMR (400 MHz, CDC13): 6 =,1.14 and 1.27 (in each case t, in each case 3H),
3.42-3.58 (m,
2H), 3.90 (s, 2H), 4.19 (q, 2H) ppm
Ethyl2-[(2,4,6-trimethylphenyl)acetyl]-4-oxocyclopentanecarboxylate
Example (11-3)
CO Et COZEt OH3C
2 CH3
O o
C' l 3
O HC
Over a period of 2 h, 4.08 g (17.4 mmol) of 2,4,6-trimethylbenzylchloride in
40 ml of THE are
added dropwise to 1.70 g (26.1 mmol) of zinc dust, activated with hydrochloric
acid and dried
under reduced pressure, and 0.50 g of trimethylsilyl chloride in 30 ml of THF,
and the mixture is
stirred at room temperature for another 2 h.
Under reduced pressure, 1.56 g (17.4 mmol) of copper(I) cyanide and 1.65 g
(38.8 mmol) of
lithium chloride are heated at 150 C for 8 h and, after cooling, vented with
argon and taken up in
ml of THE At -25 C, the solution of 2,4,6-trimethylbenzylzinc chloride
prepared above is
added dropwise over a period of 20 min, and the mixture is stirred at this
temperature for a further
20 min.
The mixture is cooled to -40 C, and a solution of 3.77 g (17.3 mmol) of ethyl
2-(chlorocarbonyl)-4-
20 oxocyclopentanecarboxylate in 20 ml of THE is added over a period of 30
min, and the mixture is
allowed to warm to room temperature and stirred for another 3 h.
For work-up, 100 ml of water are added, the mixture is extracted with ethyl
acetate and the extract
is dried (magnesium sulphate) and concentrated using a rotary evaporator.
Chromatography on
silica gel (ethyl acetate / hexane v/v=30:70) gives 1.98 g (27%) of the
desired product.
25 'H-NMR (400 MHz, CDCl-): 6 = 2.18 (s, 6H), 2.23 (s, 3H), 3.48 (mc, 2H),
3.82 and 3.88 (in each
case d, in each case 1H), 4.18 (q, 2H) ppm

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- 153 -
Methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-hydroxy-4-(hydroxymethyl)cyclo-
pentanecarboxylate Example (11-4)
H3CO2C O C2H5
(II-4) CH3
HO OH C2H5
2.39 g (7.27 mmol) of methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-
methylidenecyclohexane-
carboxylate according to Example (11-2) are added to 1.37 ml of osmium
tetroxide solution (2.5%
strength solution in n-butanol) and 1.02 g (8.7 mmol) of N-methylmorpholine N-
oxide in 25 ml of
acetone/water (v/v=5:1), and the mixture is stirred at room temperature for 14
h. 0.745 g
(3.64 mmol) of sodium dithionite is then added, the mixture is stirred at room
temperature for
min and the solvent is then removed under reduced pressure. The residue is
taken up in ethyl
10 acetate, and the mixture is extracted with water, dried (magnesium
sulphate) and then concentrated
using a rotary evaporator. This gives 2.45 g (92%) of a yellowish viscose oil
which can be reacted
further without further purification.
`H-NMR (400 MHz, CDC13): 6 = 1.70-2.25 (m, 4 H), 3.34 (mc, 1 H), 3.89 (dd, 2
H) ppm
Methyl 8- [(2,6-diethyl-4-methylphenyl)acetyl]-2,2-dimethyl-1,3-dioxaspiro
[4.4] nona ne-7-
carboxylate (Example 11-5)
0 ..CO2CH3
H3C_~_ 0 C2H5
H3C
C2H5 C H 3 (II-5)
1.16 g (3.19 mmol) of methyl 2-[(2.6-diethyl-4-methylphenyl)acetyl]-4-hydroxy-
4-
(hydroxymethyl)cyclopentanecarboxylate, 10 ml of 2,2-dimethoxypropane and 30
mg of p-toluene
sulphonic acid are heated at reflux for 1 h. After cooling, the mixture is
added to ice-water and
extracted with ethyl acetate, the extract is washed successively with 1 N
sodium bicarbonate
solution and water and dried (magnesium sulphate) and the solvent is distilled
off under reduced
pressure. Chromatography on silica gel (mobile phase ethyl acetate/hexane
v/v=35:65) gives 0.92 g
(71%) of a colourless oil. According to 'H-NMR, an endo/exo isomer mixture of
the compound of
the formula (11-5) is present.

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154-
'H-NN/FR (400 MHz, CDC13): 6 = 1.33-137 (Singlets split, in total 6 H), 2.26
(s, 3 H), 3.22 (mc, 1
H), 3.80-3.90 (m, 4 H), 6.89 (s, 2 H) ppm
Ethyl 8-[(2-ethyl-4,6-dimethylphenyl)acetyl]-1,4-dioxaspiro[4.4]nonane-7-
carboxylate
(Example 11-16)
CO2Et O C2H5 CH3 CO2Et O C2H5
CH3
O
0 H3C ~/o H3C
(11-16)
1.20 g (3.63 mmol) of ethyl 2-[(2-ethyl-4,6-dimethylphenyl)acetyl]-4-
oxocyclopentanecarboxylate
according to Example (11-2), 338 mg (5.4 mmol) of ethanediol, 578 mg (5.4
mmol) of trimethyl
orthoformate and 20 mg of p-toluene sulphonic acid in 30 ml of toluene are
stirred at room
temperature for 24 h. The solvent is then distilled off and the residue is
chromatographed on silica
gel (mobile phase ethyl acetate/hexane v/v=15:85). This gives 819 mg (60%) of
the desired
compound in the form of colourless crystals of m.p. 72-73 C.

CA 02739870 2011-04-07
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-155-
E
c
y C C C
C Lam, - U U LYcS,
O Y Y Y Y
HI
C'
M Z C C y
_ OOC ~ ^ C C C 1
CJ
1-4 u R3 6' 6"' y
u
)
E r M N U C.)^ C -C
U U U N R Cc
M R'. CC ~..~ y
oc M ~ r-+
~. M N M M
00
A UN = E ~c ~ = Mz U
03
U Ri cG N y
I-- E
N ~,j M M fn 00 N 00 n cc M
X _ T U N
T M O C
~y M Vp O M CF' M M 01 M U
N E U 'r
cc ^ ^ ' '- E R;
0 00 N i-. M O N N N U C' N y, N
x r1 ^ -~- ~p V N Z
>' M M N N N M M U U N ^ U N ^
U1 N
O TT TT
v z z z z
c Q U U U U U
cz m
y
C
a O
U I
U O O
3 ?
.-. I I I I I I~ I I I I U
U U U U U
U O O
O
I N = ~ ~ y X Z Z T
U U U U U U U U
U U ~ y4 ~ z.T.z Z T Z y
U U U U U U U
0
o - N r,
y W

CA 02739870 2011-04-07
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-156-
E
y C
cl,
i L i... L i. = L) Y L L L ,L
C
~~ i1 n. rli I c O M
Z 'C o Z o C
N O C
N to vdJi V' M '~' 00 h ON
U M G C M O U d v
O N M U
x N M
C N U (~'1 M O ''~ N d' U
M 00
^ N N v N r - N j G N p v
U 00 Q) C'. l" i1 E i--~ to = C' N M
U ^ OHO r 00 O CC C OOC ONO N E C
~j z U d' ~t U M z U 7t m
M M M ..C M .-~ N M O t-- M N
~` U^ M U ^ z U -. c V> CO O .
U rM CC z CO E
N '.- N M M U N N ~p M M d' c~ ~L
r N z
M O N 00 M N M U oc
^ M U ^ U N O N M V
z M M M u U M i z M CC - U M U
Z N 00 ~n r` oc -C v~ O O O ~t ~O ~j ~n .= 00 O Ln
w.1 M O N M N N N M O E rt N O M C 00
M Cn N M N d' N N M Ch ^- M ct' O ~..i M U M
U U U U U~ U~ U U U~ U U U
O y i
O
p O ~ O V O
UZ O U U a-~~_, O U p U
U II ^ ~~
I I y~ z ". 101 y' Z U U= U
U O O O '~ 3 0 ~ U ~ ~
U
U M U
d O U '~ U O
N 4 = y' _ Z 2 X r Z
U U U U U' U' U' U~ U U U U~
U U U U U U U U U U U U
U U~ U~ U~ U U~ U U U U p
~t n D N oc G O N M tt kn

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E
F
E
N
N
E U
C^.r M cC
A M "~
rM N
M
T W _
M U
cz Cc-.
U +i U
M U V"~ U
W U ~t N
fx z
U
U
'Jy .Z
z
U
Z N

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158 -
2,6-Diethyl-4-methylbenzyl chloride Example (XIX-1)
C2H5 C2H5 C2 H5 C2H5
Br OHC CH3 - HOCH2 O CICH2 CH3
C2H5 C2H5 C2H5 C2H5
tXIX-1)
With ice-cooling, 48.0 g (3 equivalent) of N,N-dimethylformamide, dissolved in
50 ml of THF, are
slowly added dropwise to a solution of 2,6-diethyl-4-methylphenylmagnesium
bromide, prepared
from 6.00 g of magnesium turnings and 50 g of 1-bromo-2,6-diethyl-4-
methylbenzene in 220 ml of
THF, and the mixture is stirred at room temperature for another 3 h. The
mixture is poured onto a
sat. ammonium chloride solution and extracted with ethyl acetate, and the
extract is dried
(magnesium sulphate) giving, after distillative removal of the solvent, 38.70
g (99%) of 2,6-
diethyl-4-methylbenzaldehyde as a colourless oil, 'H-NMR (400 MHz, CDC13): 6 =
1.22 (t, 6H),
2.32 (s, 3H), 2.93 (q, 4H), 6.91 (s, 2H), 10.52 (s, 1H)
The following compounds were prepared analogously:
2-ethyl-4,6-dimethylbenzaldehyde:
'H-NMR (400 MHz, CDC13): 1.22 (t, 3H), 2.32 (s, 3H), 2.57 (s, 3H), 2.95 (q,
2H), 6.92 (mc, 2H),
10.55 (s, 1 H) ppm
2-methoxy-4,6-dimethylbenzaldehyde
2-methoxy-6-ethyl-4-methylbenzaldehyde
2-cyclopropyl-6-ethyl-4-methylbenzaldehyde
2,6-cyclopropyl-4-methylbenzaldehyde
A solution of 35.5 g (201.4 mmol) of 2,6-diethyl-4-methylbenzaldehyde,
dissolved in 80 ml of
diethyl ether is added dropwise to a suspension of 2.10 g (55.4 mmol) of
lithium aluminium
hydride in 200 ml of diethyl ether. The mixture is then heated at reflux for
another I h. After
cooling, the mixture is hydrolyzed with water and 10% strength sulphuric acid,
the phases are
separated and the aqueous phase is extracted two more times with diethyl
ether. Drying
(magnesium sulphate), distillative removal of the solvent and chromatography
of the resulting
crude product on silica gel (ethyl acetate/hexane = 30:70) gives 33.10 g (92%)
of 2,6-diethyl-4-
methylbenzyl alcohol in the form of colourless crystals of m.p. 71-72 C. 'H-
NMR (400 MHz,
CDC13): 6 = 1.22 (t, 6H), 2.30 (s, 3H), 2.74 (q, 4H), 4.71 (s, 2H), 6.90 (s,
2H).

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Direct preparation of 2,6-diethyl-4-methylbenzyl alcohol from 1-bromo-2,6-
diethyl-4-
methylbenzene
C2H5 C2H5
Br \ CH3 HOCH2 O-CH3
C2H5 C2H5
Over a period of 30 min, gaseous formaldehyde (generated from 5.56 g of
paraformaldehyde) is
introduced with stirring into a solution of 2,6-diethyl-4-
methylphenylmagnesium bromide,
prepared from 12.40 g (54.6 mmol) of 1-bromo-2,6-diethyl-4-methylbenzene and
1.47 g
(60.65 mmol) of magnesium turnings in 50 ml of THF, and the mixture is then
stirred at room
temperature for another 2 h. Distillative removal of the solvent and
chromatography on silica gel
(see above) gives 6.88 g (71%) of 2,6-diethyl-4-methylbenzyl alcohol.
The following compounds are prepared analogously:
2-ethyl-4,6-dimethylbenzyl alcohol: m.p. 40-41 C
2-methoxy-4,6-dimethylbenzyl alcohol: m.p. 63-65 C
2-cyclopropyl-6-ethyl-4-methylbenzyl alcohol
2,6-cyclopropyl-4-methylbenzyl alcohol
11.20 g (94.16 mmol) of thionyl chloride are slowly added dropwise to 15.26 g
(85.6 mmol) of 2,6-
diethyl-4-methylbenzyl alcohol in 200 ml of dichloromethane, and the mixture
is then heated at
reflux for 2 h. After cooling, the mixture is stirred with 50 ml of water for
10 min, and the organic
phase is separated off, dried (magnesium sulphate), concentrated using a
rotary evaporator and
chromatographed in silica gel (ethyl acetate/hexane = 15:85). This gives 16.18
g (96%) 2,6-
diethyl-4-methylbenzyl chloride as a colourless oil. `H-NMR (400 MHz, CDC13):
6 = 1.26 (t, 6H),
2.30 (s, 3H), 2.76 (q, 4H), 4.70 (s, 2H), 6.88 (s, 2H).
2,6-Diethyl-4-methylbenzyl bromide Example (XIX-2)
C2H5
BrCH2 CH3
C2H5

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160-
14.7 g (82.5 mmol) of 2,6-diethyl-4-methylbenzyl alcohol in 150 ml of
hydrobromic acid are
stirred at 100 C for 4 h. After cooling, the mixture is extracted with
dichloromethane and the
extract is washed with water, dried (magnesium sulphate) and concentrated
using a rotary
evaporator. Distillation (l 10 C bath temperature, 0.3 mbar) gives 17.82 g
(89%) of 2,6-diethyl-4-
methylbenzyl bromide as a colourless oil. 'H-NMR (400 MHz, CDC13): 6 = 1.28
(t, 6H), 2.30 (s,
3H), 2.73 (q, 4H), 4.61 (s, 2H), 6.90 (s, 2H).
The following precursors and intermediates of the formula (XIX) were obtained
in an analogous
manner:
Z
Y CH2-Hal
X (XIX)
Ex. No. Hal X y Z M.p. C or'H-NMR (400 MHz,
CDC13, 6 in ppm)
1.26 (t, 3H), 2.28 (s, 3H), 2.41 (s, 3H),
XIX 3 Cl C2H5 CH3 CH3 2.72 (q, 2H), 4.69 (s, 2H)
2.28 (s, 3H), 2.39 (s, 3H), 2.73 (q, 2H),
XIX-4 Br C7H5 CH3 CH3 4.60 (s, 2H), 6.85 and 6.88 (in each case
s, in each case 1H)
2.21 and 2.38 (in each case s, in each
XIX-5 Cl OCH3 CH3 CH3 case 3H), 3.75 (s, 3H), 4.72 (s, 2H), 6.59
and 6.62 (in each case s, in each case
I H)
XIX-6 Cl cyclopropyl CH3 C2H5
XIX-7 Br cyclopropyl CH3 C2H5

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Example No. 1
1. Herbicidal pre-emerge7tee action
Seeds of monocotylidonous and dicotylidonous weed and crop plants are placed
in
sandy loam in wood fibre pots and covered with soil. The test compounds,
formulated in the form of wettable powders (WP), are then, as an aqueous
suspension
with a water application rate of 600 1/ha (converted), with 0.2% of wetting
agent added,
applied to the surface of the covering soil in different amounts.
After the treatment, the pots are placed in a greenhouse and kept under good
growth
conditions for the test plants. The visual assessment of the emergence damage
on the test
plants is carried out after a trial period of three weeks by comparison with
the untreated
controls (herbicidal effect in percent: 100% effect = the plants have died, 0%
effect = like
control plants).
In addition to the compounds mentioned above, the following compounds, applied
by the
pre-emergence method at 320 g/ha a.i., show an effect of > 80% against
Alopecurus
myosuroides, Echinocloa crus-galli, Lolium multiflorum and Setaria viridis: I-
a-3, I-a-6, I-
a-7, I-a-8, I-a-9, I-a-10, I-a-11, I-a-12, I-a-13, I-a-14, I-b-4, I-b-5, I-b-
6, I-b-7, I-b-8, I-c-3, I-
c-4, 1-c-5, I-c-7, I-c-9, I-c-10, I-c-11, I-c-12, I-c-14
2. Herbicidal post-emergence action
Seeds of monocotyledonous and dicotylidonous weed and crop plants are placed
in
sandy loam in wood fibre pots, covered with soil and cultivated in a
greenhouse
under good growth conditions. Two to three weeks after sowing, the test plants
are
treated at the one-leaf stage. The test compounds, formulated as wettable
powders
(WP), are then with a water application rate of 600 l/ha (converted), with
0.2% of wetting
agent added, sprayed onto the green parts of the plants in different amounts.
After the test
plants have been kept in the greenhouse under optimum growth conditions for
about three
weeks, the effect of the preparations is assessed visually in comparison to
untreated
controls (herbicidal effect in percent: 100% effect = the plants have died, 0%
effect = like
control plants).
In addition to the compounds mentioned above, the following compounds, applied
by the
pre-emergence method at 80 g/ha, show an effect of > 80% against Alopecurus

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myosuroides, Echinocloa crus-galli, Lolium multiflorum and Setaria viridis: I-
a-2, I-a-3, I-
a-6, I-a-7, I-a-8, I-a-10, I-a-1l, I-a-12, I-a-13, I-a-14, I-b-2, I-b-6, I-b-
7, I-c-3, I-c-7, I-c-8, I-
c-9, I-c-10, I-c-11, I-c-12, I-c-14, I-c-15, I-f-1
Use of safeners:
If it is to be additionally tested as to whether safeners can improve the
plant compatibility
of test substances in the case of crop plants, the following options are used
for applying the
safeners:
Seeds of the crop plants are, before sowing, dressed with safener substance
(the
amount of safener stated in percent, based on the weight of the seed)
- Before the application of the test substances, the crop plants are sprayed
with the
safener at a certain application rate per hectare (usually one day before the
application of the test substances)
The safener is applied together with the test substance as a tank mix (the
amount of
safener stated in g/ha or as a ratio, based on the herbicide).
Container trials with cereals in the greenhouse
Mefenpyr 1 day prior to herbicide application
28 days after application
Application rate Summer wheat
g of a.i./ha observed (%)
I-a-2 50 60
25 50
12.5 40
I-a-2 50 + 50 5
+ mefenpyr 25 + 50 5
12.5+50 0

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days after application
Application rate Summer wheat
g of a.i./ha observed (%)
I-a-1 0 50 60
25 50
12.5 30
I-a-10 50 + 50 5
+mefenpyr 25 + 50 3
12.5+50 2
10 days after application
Application rate Summer wheat
g of a.i./ha observed (%)
1-c-7 50 60
25 50
12.5 40
I-c-7 50 + 50 5
+ mefenpyr 25 + 50 5
12.5+50 3

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days after application
Application rate Summer wheat
g of a.i./ha observed (%)
I-a-11 50 70
25 50
12.5 30
I-a-11 50 + 50 10
+mefenpyr 25 +50 10
12.5+50 8
10 days after application
Application rate Summer wheat
g of a.i./ha observed (%)
I-a-14 50 60
25 60
12.5 50
I-a-14 50 + 50 10
+ mefenpyr 25 + 50 10
12.5+50 5

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days after application
Application rate Summer wheat
g of a.i./ha observed (%)
I-a-13 50 60
25 50
12.5 40
I-a-13 50 + 50 5
+ mefenpyr 25 + 50 2
12.5+50 2
28 days after application
Application rate Summer wheat
g of a.i./ha observed (%)
I-c-9 100 50
50 40
25 30
I-c-9 100 + 50 10
+ mefenpyr 50 + 50 5
25 +50 0

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Application rate Summer wheat
g of a.i./ha observed (%)
days after application
5 I-a-8 100 60
50 50
25 40
12.5 20
10 I-a-8 100 + 50 5
+mefenpyr 50 + 50 5
25 + 50 2
12.5+50 0
Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
10 days after application 10 days after application
I-a-8 100 20 30
50 20 30
10 20
25 I-a-8 100 + 50 10 5
+mefenpyr 50 + 50 8 5
25 + 50 5 3

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Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
I-c-14 100 20 70
50 10 60
25 50
12.5 40
I-c-14 100 + 50 5 5
+mefenpyr 50 + 50 0 5
25 + 50 5
12.5+50 0
Application rate Summer wheat
g of a.i./ha observed (%)
28 days after application
I-c-7 100 30
50 30
30
25 12.5 10
I-c-7 100 + 50 2
+mefenpyr 50 + 50 2
25+50 0
12.5+50 0

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Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
I-a-11 100 10 70
50 8 60
25 50
12.5 10
I-a-11 100 + 50 0 2
+mefenpyr 50 + 50 0 0
25+50 0
12.5+50 0
Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
I-c-3 100 95 99
50 30 60
15 20
25 12.5 10
I-c-3 100 + 50 20 15
+mefenpyr 50 + 50 15 10
25+50 10 5
12.5+50 5

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Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
I-a-3 100 70 85
50 60 70
25 20 60
12.5 10
I-a-3 100 + 50 20 20
+mefenpyr 50 + 50 10 10
25+50 10 8
12.5+50 5
Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
I-a-14 100 20 70
50 10 30
8 30
25 12.5 5 10
I-a-14 100 + 50 8 8
+mefenpyr 50 + 50 5 5
25+50 0 5
12.5+50 0 0

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Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
I-c-10 100 95
50 50 95
25 50
12.5 15
I-c-10 100 + 50 30
+mefenpyr 50 + 50 20 40
25 + 50 20
12.5+50 10
Application rate Summer barley Summer wheat
g of a. i./ha observed (%) observed (%)
28 days after application 28 days after application
I-a-25 100 85 85
50 60 70
30
25 12.5 10
I-a-25 100 + 50 20 10
+mefenpyr 50 + 50 10 8
25 + 50 5
12.5 + 50 0

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Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
I-b-13 100 50 85
50 20 80
25 40
12.5 20
I-b-13 100 + 50 10 10
+mefenpyr 50 + 50 5 10
25 + 50 5
12.5+50 0
Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
1-f-19 100 50 99
50 20 97
10 90
25 12.5 10 20
I-f-19 100 + 50 10 20
+mefenpyr 50 + 50 5 10
25+50 0 10
12.5+50 0 10

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Application rate Summer barley Summer wheat
g of a.i./ha observed (%) observed (%)
28 days after application 28 days after application
1-a-58 100 15 60
50 10 20
25 5 15
12.5 10
I-a-58 100 + 50 5 5
+mefenpyr 50 + 50 0 0
25+50 0 0
12.5+50 0

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Pre-emergence method
80 g/ha
Example ALOMY AVEFA ECHCG LOLMU SETVI
I-a-1 90 80 50 100 60
I-a-2 90 50 90 100 50
1-a-3 100 80 100 100 100
1-a-5 60 60 80 90 70
I-a-6 100 60 60 100 60
I-a-7 100 80 70 90 70
I-a-8 100 60 90 100 90
I-a-9 90 70 100 100 90
I-a-10 70 50 80 100 60
1-a-11 90 50 100 100 70
I-a-12 100 80 100 100 90
I-a-13 90 80 100 100 90
I-a-14 100 80 100 100 90
1-a-15 80 40 70 100 70
I-a-19 90 20 0 too 20
I-a-25 100 70 90 100 90
I-a-26 100 70 100 100 100
I-a-27 90 80 100 100 90
I-a-28 100 80 100 100 90
I-a-29 90 70 80 20
I-a-30 80 0 70 70
I-a-31 80 40 100 100 90
I-a-32 90 60 40 100 20
I-a-35 80 80 70 100 70
I-a-36 60 70 80 90 80
I-a-38 100 40 40 100 90
I-a-39 80 70 0 100 30
I-a-40 50 40 80 100 50
I-a-41 60 60 50 100
I-a-45 80 60 100 80 100
I-a-48 80 60 40 80 70
I-a-49 100 90 100 100 90
I-a-50 100 60 80 100 70
I-a-55 60 60 100 50 90
I-a-57 1 80 60 100 100 90
I-a-58 70 70 100 100 100
I-a-61 70 60 80 100 60
I-a-62 100 40 100 100 90
I-a-68 11 40 40 50 80 0

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I-a-69 50 70 20 70 80
I-a-70 80 60 80 80 60
I-b-1 90 40 40 100 70
I-b-2 90 50 30 100 40
I-b-3 90 60 0 100 50
I-b-4 90 50 70 100 60
I-b-S 90 10 100 60
I-b-6 100 80 30 100 60
I-b-7 100 80 60 100 70
I-b-8 100 80 90 100 90
I-b-12 100 70 loo 1 00 90
1-b-13 100 80 100 100 100
I-b-14 100 70 100 100 100
I-b-15 80 50 100 80
1-b-16 100 80 100 100 100
I-b-17 90 80 100 100 90
1-b-18 100 70 80 100 70
I-b-19 100 100 100 90
I-b-20 100 90 80 100 90
I-b-21 80 80 80 100 20
I-b-22 100 70 100 100 80
I-b-23 90 70 100 100 50
I-b-24 70 70 100 100 40
I-b-25 90 70 100 100 60
I-b-27 70 100 100 70
I-b-28 90 50 100 100 70
I-b-29 70 100 100 80
I-b-30 100 70 100 100 90
I-b-37 90 40 70 70 70
1-b-38 80 70 80 60 80
I-b-39 60 50 10 80 0
1-b-40 90 50 50 100 30
I-b-41 50 40 0 100 50
I-b-42 70 60 100 90
I-b-43 90 40 20 90 60
I-b-45 90 40 20 60 30
I-b-46 90 60 0 100 0
I-b-48 80 20 0 70 0
I-b-49 90 70 50 70 0
I-b-51 80 30 30 70 0
I-b-62 50 40 70 70 80
I-b-63 70 100 100 70
1-b-64 60 50 0 100 90
I-b-65 60 70 90 100 70

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I-b-66 80 80 100 100 80
1-b-67 90 90 100 100 90
1-b-69 100 80 100 100 80
1-b-70 100 80 100 100 90
I-b-72 80 60 100 100 100
1-b-73 80 80 90 100 100
I-b-74 60 60 100 100 70
I-b-75 60 60 100 100 70
I-b-76 100 60 100 100 70
I-b-77 60 40 90 60
1-b-78 100 60 100 100 60
1-b-79 70 70 100 100 80
I c 2 90 50 40 100 60
1 c-3 100 80 40 100 70
I c 4 90 80 60 90 50
I-c-5 80 80 90 80 80
I-c-6 50 10 90 80 60
I-c-7 100 70 100 90 70
I-c-8 60 40 60 100 50
1-c-9 100 70 100 100 70
1-c-10 100 80 100 100 90
1-c-11 90 70 100 90 90
I-c-12 100 80 100 100 100
I-c-13 90 50 60 80 60
I-c-14 90 70 90 100 70
I-c-18 90 0 100 100 10
1-c-19 100 70 50 90 90
I-c-21 90 70 100 100 100
1-c-22 100 70 100 100 100
Ic 23 100 70 100 100 100
I-c-24 90 70 100 70
I-c-25 100 90 100 100 80
I-c-26 100 80 100 100 100
1-c-27 100 80 100 100 90
I-c-28 90 60 100 50
I-c-30 100 90 80 100 60
I-c-31 90 80 60 0 60
I-c-32 80 70 100 100 70
I-c-33 90 90 90 100 60
I-c-34 90 60 100 100 80
I-c-35 80 70 100 70
I-c-39 100 70 80 60 70
I-c-39 20 20 100 80 20
I-c-40 90 60 0 80 40

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I-c-41 90 40 60 100 40
I-c-43 80 40 80 80 0
I-c-44 50 50 0 100 0
I-c-45 60 80 80 80 80
I-c-46 80 50 80 70 80
I-c-50 30 0 0 100 0
I-c-51 l00 60 30 90 90
I-c-52 60 70 50 100 70
I-c-53 100 50 0 90 60
I-c-54 90 40 0 90 0
I-c-56 90 20 20 90 0
I-c-61 70 60 90 50 90
I-c-62 60 50 80 80 90
1-c-63 80 70 50 100 50
I-c-64 60 70 50 100 70
I-c-65 100 60 80 100 90
I-c-66 100 70 100 100 60
I-c-71 70 70 100 100 90
I-c-72 60 50 100 100 80
1-c-73 70 40 50 100 60
I-c-74 70 60 100 100 100
I-c-75 70 60 100 100 60
I-c-76 80 20 100 90 90
I-c-77 80 80 80 90 100
I-c-78 100 90 100 100 80
1-c-79 90 80 100 100 80
I-c-80 100 60 100 100 60
1-f-2 90 50 90 100 60
I-f-4 0 50 90 100 50
I-f-S 90 70 70 90 90
I-f-6 60 90 70 90 70
I-f-7 100 70 80 100 90
I-f-8 30 40 0 100 70
I-f-9 30 50 60 100 50
I-f-11 40 50 0 100 20
I-f-12 1 100 70 100 70 90
1-f-13 100 0 100 100 90
If 14 100 70 100 100 100
I-f-15 100 60 100 100 90
I-f-16 80 80 60 90 90
1-f-17 80 60 90 100 90
I-f-19 100 60 100 100 100
1-f-20 100 70 100 100 100
1-f-21 90 70 100 100 90

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I-f-22 80 70 J J 80 100
Post-emergence method
80 glha
Example i ALOMY AVEFA ECHCG LOLMU SETVI
I-a-1 100 90 100 100
I-a-2 100 70 100 100 90
1-a-3 90 90 100 100 100
1-a-4 60 30 100 20 100
I-a-S 60 50 100 90 100
1-a-6 90 70 100 100 90
I-a-7 90 60 100 100 90
I-a-8 too 100 100 100 100
I-a-9 60 60 100 90 90
I-a-10 90 80 100 100 90
I-a-I1 90 90 100 100 100
I-a- 1 2 100 100 100 100 100
1-a-13 90 90 100 100 90
I-a-14 90 90 100 100 100
I-a-15 90 90 100 100 90
1-a-16 30 30 90 80 80
I-a- 17 30 40 90 90 80
I-a-18 90 60 100 100 90
I-a-19 80 0 90 100 50
I-a-20 90 80 100 100 90
1-a-25 100 100 100 100 100
I-a-26 100 100 100 100 100
I-a-27 100 100 100 100 90
I-a-28 100 100 100 100 100
I-a-29 100 60 100 100 80
1-a-30 90 0 100 90 50
I-a-31 1 00 80 100 100 100
1-a-32 80 0 100 100 20
I-a-33 100 0 100 100 90
I-a-35 100 80 100 100 90
I-a-36 50 0 90 90 90
I-a-37 60 90 100 100 60
1-a-38 100 90 80 100 90
1-a-39 100 20 90 100 90
I-a-40 80 60 90 90 80
I-a-41 100 40 90 100 100

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I-a-43 20 0 90 40 40
I-a-44 20 0 100 E 20 80
I-a-45 0 0 80 0 80
I-a-46 0 0 100 0 40
I a 47 20 80 100 100 100
I-a-48 80 90 100 100 100
I-a-49 100 100 100 100 100
I-a-50 100 100 1.00 100 100
I-a-55 20 0 100 40 100
I-a-56 0 0 100 0 100
1-a-57 100 100 100 100 100
I-a-58 100 100 100 100
I-a-60 100 90 100 100 100
I-a-61 90 90 100 100 90
I-a-62 100 80 100 100 90
I-a-68 90 0 100 100 E40
1-a-69 90 30 100 100 80
1-a-70 90 0 100 100 60
I-b-1 100 60 100 100 40
1-b-2 100 60 90 100 80
1-b-31 100 40 100 100 20
1-b-4 100 90 100 100 60
1-b-5 90 20 80 100 0
I-b-6 90 100 100 100 90
I-b-7 90 100 100 100 90
I-b-8 90 70 80 100 60
I-b-9 90 0 90 40 40
I-b-10 90 20 90 70 70
I-b-12 90 100 100 100 100
1-b-13 100 100 100 100 100
I-b-14 100 100 100 100 100
I-b-15 100 90 100 100 100
I-b-16 100 90 100 100 100
I-b-17 90 90 100 100 90
I-b-18 100 100 100 100 100
1 -b-19 20 30 100 40 80
I-b-20 0 30 100 60 0
I-b-21 90 90 100 100 90
I-b-22 100 100 100 100 100
Ib-23 100 100 100 100 100
I-b-24 100 100 100 100 100
I-b-25 100 100 100 100 100
I-b-27 100 100 100 100 100
1-b-28 100 100 100 100 100

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I-b-29 100 90 100 100 100
1-b-30 20 100 100 100 90
I-b-37 0 0 90 70 90
I-b-38 40 0 90 70 90
I-b-39 60 20 100 100 90
I-b-40 40 20 90 100 80
I-b-41 40 0 100 100 80
I-b-42 100 80 100 100 100
1-b-43 100 80 90 100 100
I-b-44 80 80 80 100 60
I-b-45 80 0 90 90 40
1-b-46 90 40 90 100 80
I-b-47 90 80 100 90 0
I-b-48 90 40 90 90 80
I-b-49 90 80 100 100 60
1-b-50 100 0 90 100 80
I-b-51 90 0 100 60 40
I-b-52 0 0 100 0 90
I-b-53 20 0 100 0 90
I-b-54 20 0 100 0 100
I-b-55 ' 0 0 90 0 90
I-b-56 20 0 100 0 100
I-b-57 0 0 100 0 100
I-b-58 0 0 80 60 20
I-b-59 20 0 80 80 0
I-b-60 0 0 100 0 80
I-b-62 30 0 100 90 90
I-b-63 100 100 100 100 100
I-b-64 100 100 100 100 loo
I-b-65 90 90 100 100 100
I-b-66 100 90 100 100 80
I-b-67 100 70 100 100 90
I-b-69 90 10 100 100 60
I-b-70 70 0 100 100 40
1-b-71 0 0 100 0 100
I-b-72 0 0 100 0 90
I-b-73 0 0 100 70 100
I-b-74 80 80 100 100 80
I-b-75 100 90 100 100 100
I-b-76 90 90 100 100 100
I-b-77 100 60 100 100 90
I-b-78 100 70 100 100 70
I-b-79 90 100 100 100 100
1-c-1 100 60 60 100 40

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I-c-2 I 90 40 40 100 40
I-c-3 90 80 90 100 80
I-c-4 90 90 100 100 0
I-c-5 20 30 100 90 90
I-c-7 90 70 100 100 80
I-c-S 90 60 100 100 90
I-c-9 90 80 100 100 90
1-c-10 90 100 100 100 90
1-c-l1 80 80 100 90 90
I-c-12 90 90 100 100 100
I-c-13 70 80 100 100 90
1-c-14 90 70 100 100 100
I-c-1S 90 60 90 90 90
I-c-16 0 30 90 80 30
I-c-17 30 0 100 40 90
I-c-18 60 0 80 90 0
1-c-19 100 100 100 too 100
I-c-20 90 90 100 100 100
I-c-21 90 100 1 00 100 100
1-c-22 100 100 100 100 100
I-c-23 100 100 100 100 100
I-c-24 100 80 100 100 100
I-c-25 100 100 100 100 100
I-c-26 100 100 100 100 100
I-c-27 100 100 100 100 100
I-c-28 100 100 100 100 100
1-c-30 80 40 100 100 70
1-0-31 70 90 100 100 90
I-c-32 80 90 90 90 80
I-c-33 80 90 100 90 80
I-c-34 100 100 100 100 90
I-c-35 100 100 100 100 100
1-c-38 70 0 80 90 30
-f-C-39 90 0 100 100 70
1-c-39 20 0 100 100 20
[-c-40 100 0 100 100 100
1-c-41 100 80 100 100 20
I-c-42 0 0 100 0 100
I-c-43 100 0 l00 100 0
I-c-44 40 80 100 100 90
1-c-45 40 0 90 100 90
I-c-46 11 40 0 80 90 90
I-c-47 100 90 100 100 60
I-c-48 20 20 90 100 80

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PI-c-49 100 80 90 100 60 0 80 100 100 40 100 100 80 90 100 100
I-c-53 100 80 90 100 90
I-c-54 90 0 90 80 40
I-c-55 80 20 100 100 30
I-c-56 90 20 80 80 40
I-c-57 90 0 100 0 90
I-c-58 0 0 100 0 100
I-c-59 0 0 100 60 20
I-c-60 20 0 100 80 0
I-c-61 40 0 90 70 90
1-c-62 0 50 100 90 100
1-c-63 100 100 100 100 100
I-c-64 80 80 too 100 100
I-c-65 100 100 too 100 100
1-c-66 100 100 100 100 too
1-c-71 80 90 100 100
I-c-72 100 70 100 100 100
1-c-73 100 0 100 100 100
I-c-74 60 70 100 100 100
1-c-75 60 50 100 100 100
I-c-76 10 0 100 90 100
1-c-77 0 0 100 90 90
1-c-78 100 0 90 100 80
I-c-79 100 70 100 100 90
1-c-80 90 70 100 100 90
I-f-1 80 40 90 90 80
14--2 80 90 100 100 90
1-f-3 90 0 90 90 80
I f 4 100 90 100 100 100
1-f-5 100 100 100 100 100
1-f-6 100 80 100 100 100
1-f-7 100 100 100 100 100
1-f-8 100 90 100 100 100
I-f-9 80 90 80 100 100
1-f-10 100 80 90 100 90
1-f-11 60 40 90 100 80
I-f-12 100 100 100 100 100
1-f-13 100 100 100 100 100
I-f-14 100 100 100 100 100
I-f-15 80 90 100 100 100
1-f-16 100 100 100 100 100

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1-f-17 100 100 100 100 100
I-f-19 100 100 100 100 100
1-f-20 100 100 100 100 100
1-f-21 80 80 100 100 100
1-f-22 30 40 too 80 100
I - f - 2 3 0 0 90 60 80
ALOMY: Alopecurus myosuroide
AVEFA: Avena fatua
ECHCG: Echinochloa crus-galli
LOLMU: Lolium multiflorum
SETVI: Setaria viridis

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Example No. 3
Method crop compatibility small plot trial outdoors:
Customary sowing using a single seed seeder
Plot size: 11.25 m2 / two repetitions
Treatment was carried out using a plot sprayer. The safener was applied
together with the test
substance as a tank mix using 300 1 of water/ha (amounts of herbicide and
safener are stated in g of
ai/ha). Post-emergence application was carried out at the five-leaf stage of
maize. Crop
compatibility was assessed visually 14 and 27 days after the treatment (in
percent compared to an
untreated control), 100% damage = the plants have died, 0% damage = like
control plants).
Outside trial with maize (Magixx Duo is cycloxidim-tolerant
Post-emergence method
Cultivar Magixx Duo Oldham Magixx Duo Oldham
days after application / % damage
g ai/ha 14 days 14 days 27 days 27 days
Ex.l-a-8 60 0% 94% 0% 93%
SL 450
Ex. 1-a-8 + 60 + 60 0% 23% 0% 13%
cyprosulphamid
eWP50

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Example No. 4
Myzus test (MYZUPE spray treatment)
Solvents: 78.0 parts by weight of acetone
1.5 parts by weight of dimethylformamide
Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, one part by weight of
active compound is
mixed with the stated amounts of solvents and emulsifier, and the concentrate
is diluted with
emulsifier-containing water to the desired concentration.
Discs of Chinese cabbage leaves (Brassicapekinensis) which are infested by all
stages of the green
peach aphid (Myzus persicae) are sprayed with an active compound preparation
of the desired
concentration.
After six days, the effect in percent is determined. 100% means that all
aphids have been killed;
0% means that none of the aphids have been killed.
In this test, for example, the following compounds of the Preparation Examples
show an effect of
> 80% at an application rate of 500 g/ha:
Ex.: I-a-10, I-c-10, I-c-14

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Example No. 5
Heliothis virescens test - Treatment of transgenic plants
Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, one part by weight of
active compound is
mixed with the stated amount of solvent and the stated amount of emulsifier,
and the concentrate is
diluted with water to the desired concentration.
Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trademark of
Monsanto Comp.
USA) are treated by being dipped into the preparation of active compound of
the desired
concentration and are populated with the tobacco budworm Heliothis virescens
while the leaves
are still moist.
After the desired period of time, the kill of the insects is determined.

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Example No. 6
Critical concentration test / Soil insects - Treatment of transgenic plants
Test insect: Diabrotica balteata - Larvae in the soil
Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, one part by weight of
active compound is
mixed with the stated amount of solvent, the stated amount of emulsifier is
added and the
concentrate is diluted with water to the desired concentration.
The preparation of active compound is poured onto the soil. Here, the
concentration of active
compound in the preparation is virtually immaterial; only the amount by weight
of active
compound per volume unit of soil, which is stated in ppm (mg/1) matters. The
soil is filled into
0.25 1 pots, and these are allowed to stand at 20 C.
Immediately after the preparation, five pregerminated maize corns of the
cultivar YIELD GUARD
(trademark of Monsanto Comp., USA) are placed into each pot. After two days,
the appropriate
test insects are placed into the treated soil. After a further seven days, the
efficacy of the active
compound is determined by counting the maize plants that have emerged (1 plant
= 20% activity).

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Example No. 7
Increase of penetration into the plant by ammonium or phosphonium salts and
synergistic increase
of penetration into the plant by ammonium / phosphonium salts in combination
with penetrants.
In this test, the penetration of active compounds through enzymatically
isolated cuticles of apple
tree leaves was measured.
Use was made of leaves which, fully developed, were cut from apple trees of
the cultivar Golden
Delicious. The cuticles were isolated by
- initially filling leaf discs punched out and stained with dye on the
underside by vacuum
infiltration with a pectinase solution (0.2 to 2% strength) buffered to a pH
between 3 and 4,
- then sodium azide was added and
- allowing the leaf discs treated in this manner to stand until the original
leaf structure has
dissolved and the non-cellular cuticles have detached.
Only the cuticles, free from hairs and stoma, of the upper sides of the leaves
were then used. They
were washed repeatedly alternating with water and a buffer solution of pH 7.
The clean cuticles
obtained were then mounted on Teflon plates and smoothed and dried with a
gentle stream of air.
In the next step, the cuticle membranes obtained in this manner were placed
into stainless steel
diffusion cells (= transport chambers) for membrane transport studies. To this
end, the cuticles
were placed with a pincet into the centre of the edges, coated with silicone
fat, of the diffusion
cells and closed with a ring, which had also been treated with fat. The
arrangement was chosen
such that the morphological outside of the cuticles was facing outwards, i.e.
exposed to air,
whereas the original inside was facing the interior of the diffusion cells.
The diffusion cells were filled with a 30% strength ethylene glycol/water
solution. To determine
the penetration, in each case 10 l of the spray liquor of the composition
below were applied to the
outside of the cuticles. The spray liquor was prepared using local tap water
of medium hardness.
After the spray liquors had been applied, the water was allowed to evaporate
and the chambers
were inverted and placed into thermostatic taps in which temperature and
atmospheric humidity
over the cuticles could be adjusted using a gentle stream of air onto the
cuticles with the spray
coating (20 C, 60% rh). At regular intervals, an autosampler took aliquots and
the active
compound content was determined by HPLC.

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The test results are shown in the table below. The stated numbers are average
values of eight to ten
measurements.
Penetration after 24h /%
Active compound a.i. + a.i. +
a.i. +
a.i. Edenor Me SU 500 Edenor ME SU 500 EW +
AS
EW AS
Example 1-a-1 2.5 4 11.5 13
Example I-a-14 0 3 5 16
Example I-a-42 0 2 23 39
a.i. (0.2 g/1)
AS = ammonium sulphate (0.7 g/1)
Edenor Me SU 500 EW (2 g/l)

Representative Drawing