Note: Descriptions are shown in the official language in which they were submitted.
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~ulnhonXlaminocarbonyltuiazolnnones having ha ~enoalkoxv swbstituents
The invention relates to navel sulphonylaminocarbonyltriazolinones having
halogenoalkoxy substituents, to a plurality of processes and to novel
intermediates for their preparation and to their use as herbicides and
fungicides.
Certain sulphonylaminocarbonyltriazolinones are known to have herbicidal
properties (cf. EP-A 34148, EP-A 422469, EP-A 425948, EP-A 431291, EP-A
507171). However, the activity of these compounds is not in all aspects
satisfactory.
This invention, then, provides sulphonylaminocarbonyltriazolinones having
halogenoalkoxy substituents of the general formula (I)
o o
R3
R'
S02_N ~~ N (I)
N =-C
O-R2
in which
R' represents hydrogen, hydroxyl, amino, alkylideneamino or a respectively
optionally substituted radical from the group consisting of alkyl, alkenyl,
alkynyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino,
cycloalkyl, cycloalkylalkyl, cycloalkylamino, aryl and arylalkyl,
Ra represents respectively halogen-substituted~alkyl or alkenyl, and
R3 represents a respectively optionally substituted radical from the group
consisting of alkyl, aralkyl, aryl and heteroaryl,
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h
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and salts of the compounds of the formula (I).
The novel sulphonylaminocarbonyltriazolinones having halogenoalkoxy
substituents of the general formula (I) are obtained when
(a) triazolinones of the general formula (II)
0
H~N~N~R~
(II)
N=
O-RZ
in which
R' and R2 are each as defined above
are reacted with sulphonyl isocyanates of the general formula (III)
R3-S02-N=C=O (III)
' in which
R3 is as defined above,
if appropriate in the presence of a reaction auxiliary and if appropriate in
the presence of a diluent,
or
(b) triazolinone derivatives of the general formula (I~
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o O
R'
- ~N~N~
Z
N (IV)
O-R2
in which
R1 and R2 are each as defined above, and
Z represents halogen, alkoxy, aralkoxy or aryloxy,
are reacted with sulphonamides of the general formula (V)
R3-S~z-NH2
in which
R3 is as defined above,
if appropriate in the presence of an acid acceptor and if appropriate in
the presence of a diluent,
or
(c) triazolinones of the general formula (II)
O
H~N~N~R'
N (II)
O-RZ
in which
rl
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R' and R2 are each as defined above
are reacted with sulphonamide derivatives of the general formula (VI)
R3-S02-NH-CO-Z (VI)
in which
S R3 is as defined above, and
Z represents halogen, alkoxy, aralkoxy or aryloxy,
if appropriate in the presence of an acid acceptor and if appropriate in
the presence of a diluent,
or
(d) triazolinones of the general formula (II)
O
H~N~N~R'
v (II)
N
O-RZ
in which
R' and R2 are each as defined above
are reacted with sulphonyl halides of the general formula (VII)
R3- SO2- X (VI I )
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in which
R3 is as defined above and
X represents halogen
and metal cyanates of the general formula (VIII)
MOCN (VIII)
in which
M represents an alkali metal equivalent or an alkaline earth metal
equivalent,
if appropriate in the presence of a reaction auxiliary and if appropriate in
the presence of a diluent,
and, if appropriate, the compounds of the formula (I) obtained by
process (a), (b), (c) or (d) are converted by customary methods into
salts.
The novel sulphonylaminocarbonyltriazolinones having halogenoalkoxy
substituents ofthe general formula (I) have a strong herbicidal and/or
fungicidal
activity.
The invention preferably provides compounds of the formula (I) in which
Ri represents hydrogen, hydroxyl, amino, C1-C6-alkylideneamino,
optionally fluorine-, chlorine-, bromine-, cyano-, CI-C4-alkoxy-, CI-C4-
alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted CI-C6-alkyl,
respectively, optionally fluorine-, chlorine- and/ or bromine-substituted
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C2-C6-alkenyl or C2-C6-alkynyl, respectively optionally fluorine- and/or
chlorine-substituted C1-C6-alkoxy or C2-C6-alkenyloxy, respectively
optionally fluorine- and/or chlorine-substituted CI-C6-alkylamino, di-
(C 1-C4-alkyl)-amino or C,-C4-alkanoylamino, respectively optionally
fluorine-, chlorine-, bromine- and/or CI-C4-alkyl-substituted C3 C6-
cycloalkyl or C3-C6-cycloalkyl-CI-C4-alkyl, or respectively optionally
fluorine-, chlorine-, bromine-, cyano-, nitro-, Cl-C4-alkyl-,
trifluoromethyl-, CI-C4-alkoxy- and/or C1-C4-alkoxy-carbonyl-
substituted phenyl or phenyl-C1-C4-alkyl,
R2 represents respectively fluorine-, chlorine- and/or bromine-substituted
C,-C6-alkyl or C2-C6-alkenyl, and
_ R5
R3 . represents the grouping \ /
R4
in which
R4 and RS are identical or different and each represent hydrogen,
fluorine, chlorine, bromine, iodine, nitro, C1-C6-alkyl (which is
optionally substituted by fluorine, chlorine, bromine, cyano,
carboxyl, C,-C4-alkoxycarbonyl, CI-C4-alkylamino-carbonyl, di-(C1-
C4-alkyl)-amino-carbonyl, hydroxyl, CI-C4-alkoxy, formyloxy,
C I-C4 alkyl-carbonyloxy, C,-C4-alkoxy-carbonyloxy, C 1-C4
alkylamino-carbonyloxy, C 1-C4-alkylthio, C 1-C4-alkylsulphinyl,
Ci-C4-alkylsulphonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-
cycloalkyl or phenyl), or C2-C6-alkenyl (which is optionally
substituted by fluorine, chlorine, bromine, cyano, CI-C4 alkoxy-
CA 02214752 1997-09-OS
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carbonyl, carboxyl or phenyl), or CZ-C6-allc5myl (which is optionally
substituted by fluorine, chlorine, bromine, cyano,_ C1-C4-alkoxy-
carbonyl, carboxyl or phenyl), or C1-C4-alkoxy (which is optionally
substituted by fluorine, chlorine, bromine, cyano, carboxyl, C,-C4-
alkoxy-carbonyl, CI-C4-alkoxy, C1-C4-alkylthio, CI-C4-
alkylsulphinyl or C,-C4-alkylsulphonyl), or C 1-C4-alkylthio (which is
optionally substituted by fluorine, chlorine, bromine, cyano,
carboxyl, C,-C4-alkoxy-carbonyl, C1-C4-alkylthio, CI-C4-
alkylsulphinyl or C1-C4-alkylsulphonyl), or C2-C6-alkenyloxy (which
is optionally substituted by fluorine, chlorine, bromine, cyano or
CI-C4-alkoxy-carbonyl), or C2-C6-alkenylthio (which is optionally
substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C3-
alkylthio or C,-C4-alkoxycarbonyl), C3-C6-alkynyloxy, C3-C6-
alkynylthio or the radical -S(O)p-R6, where
p represents the numbers 1 or 2, and
R6 represents C1-C4-alkyl (which is optionally substituted by fluorine,
chlorine, bromine, cyano or CI-C4-alkoxy-carbonyl), C3-C6-alkenyl,
C3-C6-alkynyl, C,-C4-alkoxy, Cl-C4-alkoxy-C,-C4-alkylamino,
CI-C4-alkylamino, di-(CI-C4-alkyl)-amino, phenyl or the radical
-NHOR', where
R' represents C t-C 1z-alkyl (which is optionally substituted by fluorine,
chlorine, cyano, C 1-C4-alkoxy, C 1-C4-alkylthio, C 1-CQ-
alkylsulphinyl, C1-C4-alkylsulphonyl, C,-C4-alkyl-carbonyl, C~-C4-
alkoxy-carbonyl, C,-C4-alkylamino-carbonyl or di-(C,-C4-alkyl)-
amino-carbonyl), or C3-C6-alkenyl (which is optionally substituted
by fluorine, chlorine or bromine), C3-C6-alk5myl, C3-C6-cycloalkyl,
C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-Ci-C2-alkyl (which is
optionally substituted by fluorine, chlorine, vitro, cyano, C i-C4-
alkyl, CI-C4-alkoxy or C1-C4-alkoxy-carbonyl), or benzhydryl or
CA 02214752 1997-09-OS
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phenyl (which is optionally substituted by fluorine, chlorine, nitro,
cyano, CI-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C,-C2-
fluoroalkoxy, CI-C4 alkylthio, trifluoromethylthio or C1-C4-alkoxy-
carbonyl),
R4 and/or RS further represent phenyl or phenoxy, or C,-C4-alkyl-
carbonylamino, CI-C4-alkoxy-carbonylamino, CI-C4-alkylamino-
carbonyl-amino, di-(C1-C4-alkyl)-amino-carbonylamino, or the
radical -CO-R8, where
R8 represents hydrogen, C,-C6-alkyl, C3-C6-cycloalkyl, C,-C6-alkoxy,
C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, C~-C4-
alkylthio, C,-C4 alkylamino, C1-C4-alkoxyamino, C,-C4-alkoxy-
CI-C4-allcylamino or di-(C1-C4-alkyl)-amino (each of which is
optionally substituted by fluorine and/ or chlorine),
R4 and/or RS further represent trimethylsilyl, thiazolinyl, CI-C4-alkyl-
sulphonyloxy, di-(C1-C4-alkyl)-aminosulphonylamino or the radical
-CH=N-R9, where
R9 represents optionally fluorine-, chlorine-, cyano-, carboxyl-, C,-C4-
alkoxy-, C1-C~-allcylthio-, C,-C4-alkylsulphinyl- or C,-C4
alkylsulphonyl-substituted C I-C6-alkyl, or optionally fluorine- or
chlorine-substituted benzyl, or optionally fluorine- or chlorine-
substituted C3-C6-alkenyl or C3-C6-alkynyl, or optionally fluorine-,
chlorine-, bromine-, C I-C4-alkyl-, C,-C4-alkoxy-, trifluoromethyl-,
trifluoromethoxy- or trifluoromethylthio-substituted phenyl, or
optionally fluorine- and/or chlorine-substituted CI-C6-alkoxy,
C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, or amino, C I-C4-
alkylamino, di-(C1-C4-alkyl)-amino, phenylamino, C,-C4-alkyl-
carbonyl-amino, C1-C4-alkoxy-carbonylamino, C1-C4-alkyl-
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sulphonylamino or optionally fluorine-, chlorine-, bromine- or
methyl-substituted phenylsulphonylamino,
furthermore
- Rio
- R~2
R3 represents the radical -CH ~
R' 1
in which
R'° represents hydrogen or C,-C4-alkyl,
R" and R'2 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, CI-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is
optionally substituted by fluorine and/ or chlorine), carboxyl, C I-C4-
alkoxy-carbonyl, dimethylaminocarbonyl, C1-C4 alkyl-sulphonyl or di-
(C I-C4-alkyl)-aminosulphonyl;
furthermore
R3 represents the radical R~3 ~ ~ ~ Rya
in which
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R'3 and R'4 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, C,-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine) or C1-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine);
furthermore
R, s
R3 represents the radical
N R16
in which
R'S and R'6 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, nitro, cyano, C,-C4-alkyl (which is optionally
substituted by fluorine and/or chlorine), Ci-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine), or C1-C4-alkylthio,
C,-C4-alkylsulphinyl or CI-C4-alkylsulphonyl (each of which are
optionally substituted by fluorine and/or chlorine), or aminosulphonyl,
mono-(CI-C4-alkyl)-aminosulphonyl, or di-(Cl-C4-alkyl)-amino-
sulphonyl or CI-C4-alkoxy-carbonyl or dimethylaminocarbonyl;
furthermore
R3 represents the radical R" ~ ~ ~ R'$
-N
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in which
R" and R'8 are identical or different and each represent hydrogen, fluorine,
chlorine, bromine, C,-C4-alkyl (which is optionally substituted by
fluorine and/or bromine), C1-C4-alkoxy (which is optionally substituted
by fluorine and/or chlorine), or C1-C4-alkylthio, C1-C4-alkylsulphinyl or
C1-C4-alkylsulphonyl (each of which are optionally substituted by
fluorine and/or chlorine), or di-(C1-C4-alkyl)-aminosulphonyl;
furthermore
R, s
R3 represents the radical ~ I R2o
A
in which
R'9 and R2° are identical or different and each represent hydrogen,
fluorine,
chlorine, bromine, cyano, nitro, CI-C4 alkyl (which is optionally
substituted by fluorine and/or chlorine), CI-C4-alkoxy (which is
optionally substituted by fluorine and/or chlorine), CI-C4-alkylthio,
C1-C4-alkylsulphinyl or CI-C4-alkylsulphonyl (which is optionally
substituted by fluorine and/or chlorine), di-(C1-C4 alkyl)-amino-
sulphonyl, CI-C4-alkoxy-carbonyl or dimethylamiglocarbonyl, and
A represents oxygen, sulphur or the grouping N-Z', where
Z' represents hydrogen, C 1-C4-alkyl (which is optionally substituted by
fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl
(which is optionally substituted by fluorine, chlorine, bromine or nitro),
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C,-C4-alkylcarbonyl, C1-C4-alkoxy-carbonyl or di-(CI-C4-alkyl)-
aminocarbonyl; .
furthermore
R2'
R3 represents the radical ~ ~ R22
Y'
in which
R21 and R~ are identical or different and each represent hydrogen, C1-C4-
alkyl,
halogen, CI-C4-alkoxycarbonyl, C,-C4-alkoxy or C,-C4-halogenoalkoxy,
Y' represents sulphur or the grouping N-R'~, where
R'~ represents hydrogen or CI-C4-alkyl;
furthermore
Rzs
R2s
R3 represents the radical N~
~N
R24
in which
R24 represents hydrogen, C,-C4-alkyl, benzyl, pyridyl, quinolyl or phenyl,
' ' . CA 02214752 1997-09-OS
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R~ represents hydrogen, halogen, cyano, vitro, C,-C4-alkyl (which is
optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which
is optionally substituted by fluorine and/or chlorine), dioxolanyl or
C I-C4-alkoxy-carbonyl, and
S R26 represents hydrogen, halogen or C1-C4-alkyl,
Additionally, the invention preferably provides the sodium, potassium,
magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(Cl-C4 alkyl)-
ammonium, tri-(C,-C4-alkyl)-ammonium, tetra-(C1-C4-alkyl)-ammonium, tri-
(C1-C4-alkyl)-sulphonium, CS- or C6-cycloalkyl-ammonium and di-(C1-C2-
alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which n, R1,
R2 and R3 have the preferred meanings given above.
The invention in particular provides compounds of the formula (I) in which
R' represents respectively optionally fluorine-, chlorine-, cyano-, methoxy-
or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
or represents respectively optionally fluorine-, chlorine- or bromine-
substituted propenyl, butenyl, propynyl or butynyl, or represents
respectively optionally fluorine- and/or chlorine-substituted methoxy,
ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, propenyloxy or
butenyloxy, or represents methylamino, ethylamino, n- or i-
propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino,
or represents respectively optionally fluorine-, chlorine-, bromine-,
methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or
cyclohexylmethyl, or represents respectively optionally fluorine-,
chlorine-, bromine-, cyano-, methyl-, trifluoromethyl-, or methoxy-
substituted benzyl or phenyl,
R2 represents fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-
CA 02214752 1997-09-OS
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propyl, n-, i-, s- or t-butyl, and
- R5
R3 represents the radical \ /
R4
in which
R4 represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl,
trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy,
trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, methylthio,
ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,
methylsulphonyl, ethylsulphonyl, dimethylaminosulphonyl,
diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl,
phenoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
and
RS' represents hydrogen, methyl, ethyl, fluorine, chlorine or bromine;
furthermore
R"
_ R' 2
R3 represents the radical -CH
\ /
Rio
in which
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R'° represents hydrogen,
R'I represents fluorine, chlorine, bromine, methyl, methoxy,
difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl,
ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and
R12 represents hydrogen;
furthermore
R3 represents the radical RO-C S
'J
O
in which
R represents methyl, ethyl, n- or i-propyl, or
RZS R2s
R3 represents the radical ~ ~N
N
R24
in which
R24 represents methyl, ethyl, n- or i-propyl, phenyl or pyridyl,
CA 02214752 1997-09-OS
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R25 represents hydrogen, fluorine, chlorine or bromine, and
R26 represents fluorine, chlorine, bromine, methoxycarbonyl or
ethoxycarbonyl.
The abovementioned general or preferred radical definitions apply both to the
end products of the formula (I) and, correspondingly, to the precursors or
intermediates required in each case for the preparation. These radical
definitions can be combined with one another as desired, thus including
combination between the preferred ranges indicated.
In the definitions of the radicals, hydrocarbon radicals such as alkyl,
alkenyl or
alkynyl are straight-chain or branched, even in combination with hetero atoms,
as in alkoxy, alkylthio or alkylamino, even if this is not explicitly stated .
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably
fluorine, chlorine or bromine, in particular fluorine or chlorine.
Using, for example, 2-trifluoromethoxy-phenylsulphonyl isocyanate and 4-
ethyl-5-difluoromethoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting
materials, the course of the reaction in the process (a) according to the
invention can be illustrated by the following equation:
O-CF3
O-CFa ~ ~ O O
+ w
H~N N~CzI-Is ~ SOz' C~,N~N~C2H5
SOZ N=C=O N NH
N
~O-CHFz O-CHF
z
Using, for example, 2-ethylthio-benzenesulphonamide and 2-chlorocarbonyl-4-
benzyl-5-(2,2-difluoro-ethoxy)-2,4-dihydro-3H-1,2,4-triazol-3-one as starting
materials, the course of the reaction in the process (b) according to the
invention can be illustrated by the following equation:
CA 02214752 1997-09-OS .
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O O / S-CzHs
/ S-CzHs ~ I O O
I + .N N~CI-Iz CsHs W
CI ~ -i SOz.N~N~N~CH2 CsHS
w
SOZ NHz N=~ - HCI
O-CH2CHFz N
O-CHaCHFz
Using, for example, N-methoxycarbonyl-2-methoxy-benzenesulphonamide and
5-(2-chloro-ethoxy)-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one as~ starting
materials, the course of the reaction of the process (c) according to the
invention can be illustrated by the following equation:
O-CH3
O CH3 + ~ \ I O O
H~N N~CH3 ~ SO ~ ~ ~CH3
I ~ _ -HOCH z~NH N N
SOz NH-COOCH3 N~ 3 N=--C
O-CH2CHzCi O-CH2CH2CI
Using, for example, 2-chloro-6-methyl-benzenesulphonyl chloride, 4-allyl-5-
(2,3,3-trifluoro-propoxy)-2,4-dihydro-3H-1,2,4-triazol-3-one and sodium
cyanate as starting materials, the course of the reaction of the process (d)
according to the invention can be illustrated by the following equation:
CH3 O / CH3
+H~N~N~CH2 CH=CHz ~ I O O
S02 CI ~ ~ + NaOCN SO ~ N ~ N ~ CHz CH=CHz
N ~ z NH
CI O-CHZCHFCHFz - NaCI CI N
O-CHzCHFCHFz
A general definition of the triazolinones to be used as starting materials in
the
processes (a), (c) and (d) according to the invention for preparing compounds
of the formula (I) is given by the formula (II).
In the formula (II), R' and R2 each preferably or in particular have that
meaning which has already been indicated above, in connection with the
description of the compounds of the formula (I) according to the invention, as
CA 02214752 1997-09-OS
- 18-
being preferable or particularly preferable for R1 and RZ.
The triazolinones of the general formula (II) have not been disclosed in the
literature; as novel substances, they also form part of the subject matter of
the
present application.
The novel triazolinones of the formula (II) are obtained when carbazates of
the
general formula (I~
O
NH~ O OX)
I I
NHz R
in which
R represents alkyl (preferably methyl or ethyl)
are reacted with diesters of alkyliminocarbonic acid of the general formula
(X~
R'
N
z ~ z ~X)
R~O O~R
in which
R' and R2 are as defined above,
if appropriate in the presence of a diluent such as methanol at temperatures
between 0°C and 100°C and the thus-formed compounds ofthe
general formula
(
CA 02214752 1997-09-OS .
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O
H.N~O.R _
I (XI)
N~NHR~ .
IO~R2
in which
R, R' and R2 are as defined above
are cyclocondensed - if appropriate after intermediate isolation - if
appropriate
in the presence of a diluent such as toluene at temperatures between
20°C and
150°C (cf. the preparation examples).
The triazolinones of the formula (II) in which RZ represents difluoromethyl
(R'
being as defined above) are preferably prepared by reacting urazoles of the
general formula (~I)
O
R,
H~N~N'
(XII)
~N
H O
in which
R' is as defined above
with chlorodifluoromethane in the presence of an acid acceptor such as sodium
hydroxide and in the presence of a diluent such as isopropanol aiZd/or water,
at
IS temperatures between 0°C and 100°C (cf. the preparation
examples).
A'general definition of the sulphonyl isocyanates also to be used as starting
CA 02214752 1997-09-OS .
- 20 -
materials in the process (a) according to the invention for preparing
compounds
of the formula (I) is given by the formula (III).
In the fprmula (III), R3 preferably or in particular has that meaning which
has
already been indicated above, in connection with the description of the
compounds of the formula (I) according to the invention, as being preferable
or
particularly preferable for R3.
The starting materials of the formula (III) are known and/or can be prepared
by methods knovv~l per se (cf. US-P 4127405, US-P 4169719, US-P 4371391,
EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139,
EP-A 35893; EP-A 44808; EP-A 44809, EP-A 48143, EP-A 51466, EP-A
64322, EP-A 70041, EP-A 173312).
A general definition of the triazolinone derivatives to be used as starting
materials in the process (b) according to the invention for preparing
compounds
of the general formula (I) is given by the formula (I~. In the formula (I~, R'
and R2 each preferably or in particular have that meaning which has already
been indicated above, in connection with the description of the compounds of
the formula (I), as being preferable or particularly preferable for R' and R2;
Z
preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy,
phenoxy, halogeno- or nitro-phenoxy, and in particular represents methoxy,
phenoxy or 4-nitro-phenoxy.
The starting materials of the formula (I~ have not been disclosed in the
literature; as novel substances, they are also part of the subject matter of
the
present application.
The novel compounds of the formula (I~ are obtained when triazolinones of
the general formula (II)
CA 02214752 1997-09-OS
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O
H~N~N~R' _
N _ (I I)
v~
O-Rz
in which
R' and R2 are each as defined above,
are reacted with carbonic acid derivatives of the general formula (XIII)
Z-CO-Z' (XIII)
in which
Z is as defined above and
Z' represents halogen, alkoxy, aralkoxy or aryloxy,
if appropriate in the presence of an acid acceptor, such as, for example,
potassium t-butoxide, and if appropriate in the presence of a diluent, such
as,
for example, tetrahydrofuran or dimethoxyethane, at temperatures between
0°C
and 100°C.
A general definition of the sulphonamides also to be used as starting
materials
in the process (b) according to the invention for preparing compounds of the
general formula (I) is given by the formula (~. In the formula (~, R3
preferably or in particular has that meaning which has already been indicated
above, in connection with the description of the compounds of the formula (I),
as being preferable or particularly preferable for R3.
The starting materials of the formula (~ are known andl or can be prepared by
CA 02214752 1997-09-OS
- 22 -
methods known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-
A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139,
EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A S 1466, EP-A
64322, EP-A 70041, EP-A 173312).
A general definition of the sulphonamide derivatives to be used as starting
materials in the process (c) according to the invention for preparing
compounds
of the formula (I) is given by the formula (VI). In the formula (VI), R3
preferably or in particular has that meaning which has already been indicated
above, in connection with the description of the compounds of the formula (I),
as being preferable or particularly preferable for R3; Z preferably represents
fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy or phenoxy, and in
particular represents methoxy or phenoxy.
The starting materials of the formula (VI) are known and/ or. can be prepared
by
methods known per se.
A general definition of the sulphonyl halides to be used as starting materials
in
the process (d) according to the invention for preparing compounds of the
formula (I) is given by the formula (VII). In the formula (VII), R3 preferably
or
in particular has that meaning which has already been indicated above, in
connection with the description of the compounds of the formula (I), as being
preferable or particularly preferable for R3; X preferably represents
fluorine,
chlorine or bromine, and in particular represents chlorine.
The starting materials of the formula (VII) are known and/or can be prepared
by methods known per se.
The processes (a), (b), (c) and (d) according to the invention for the
preparation of the novel compounds of the formula (I) are preferably carried
out using diluents. Suitable diluents in this context are virtually all inert
organic
solvents. These include, preferably, aliphatic and aromatic, optionally
CA 02214752 1997-09-OS
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halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane,
petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene
chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene
and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether, glycol
dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane;
ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and
methyl isobutyl ketone; esters such as methyl acetate and ethyl acetate;
nitrites,
for example acetonitrile and propionitrile; amides, for example
dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also
dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric
triamide.
As reaction auxiliaries and/ or as acid acceptors in the processes (a), (b),
(c) and
(d) according to the invention it is possible to employ all acid-binding
agents
which can customarily be used for such reactions. Preference is given to
alkali
metal hydroxides, for example sodium hydroxide and potassium hydroxide,
alkaline earth metal hydroxides, for example calcium hydroxide, alkali metal
carbonates and alkoxides, such as sodium carbonate and potassium carbonate,
sodium tent-butoxide and potassium tert-butoxide, and also basic nitrogen
compounds, such as trimethylamine, triethylamine, tripropylamine,
tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine,
ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline,
pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2
ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4,3,0]-non-S
ene (DBN), 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo
[2,2,2]-octane (DABCO).
The reaction temperatures in the processes (a), (b), (c) and (d) according to
the
invention can be varied within a relatively wide range. The reactions are in
general carried out at temperatures of between -20°C and +
100°C, preferably at
temperatures between 0°C and +80°C.
CA 02214752 1997-09-OS
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The processes (a), (b), (c) and (d) according to the invention are generally
carried out under atmospheric pressure. However, it is also possible to
operate
under elevated or reduced pressure.
For carrying out processes (a), (b), (c) and (d) according to the invention,
the
starting materials required in each case are in general employed in
approximately equimolar quantities. However, it is also possible to use one of
the components employed in each case in a relatively large excess. The
reactions are in general carried out in a suitable diluent in the presence of
an
acid acceptor, and the reaction mixture is stirred for a number of hours at
the
particular temperature required. Work-up in the case of the processes (a),
(b),
(c) and (d) according to the invention is in each case carried out by
customary
methods (cf. the Preparation Examples).
Salts of the compounds of the general formula (I) according to the invention
.,
can be prepared if desired. Such salts are obtained in a simple manner by
customary methods of forming salts, for example by dissolving or dispersing a
compound of the formula (I) in an appropriate solvent, for example methylene
chloride, acetone, tert-butyl methyl ether or toluene, and adding an
appropriate
base. The salts can then - if desired after prolonged stirring - be isolated
by
concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants,
desiccants, haulm killers and, especially, as weed-killers. By weeds, in the
broadest sense, there are to be understood all plants which grow in locations
where they are not wanted. Whether the substances according to the invention
act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in
connection with the following plants:
Dicotvledonous weeds of the nera~ Sinapis, Lepidium, Galium, Stellaria,
CA 02214752 1997-09-OS
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Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,
Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia,
Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium,
Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,
Trifolium, Ranunculus and Taraxacum.
j Dicotyledonous crops of the nge era:era: Gossypium, Glycine, Beta, Daucus,
Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vcia, Nicotiana, Lycopersicon,
Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum,
Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena,
Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria,
Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium,
Agrostis, Alopecurus and Apera.
Monocotyledonous crops of the ~en,_ era: Oryza, Zea, Triticum, Hordeum,
Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the. active compounds according to the invention is in no
way restricted to these genera, but also extends in the same manner to other
plants.
The compounds are suitable, depending on the concentration, for the total
control of weeds, for example on industrial terrain and rail tracks, and on
paths
and squares with or without tree plantings. Equally, the compounds can be
employed for controlling weeds in perennial crops, for example afforestations,
decorative tree plantings, orchards, vineyards, citrus groves, nut orchards,
banana plantations, coffee plantations, tea plantations, rubber plantations,
oil
palm plantations, cocoa plantations, soft fruit plantings and hopfields, in
lawns,
turf and pasture-land, and for the selective control of weeds in annual crops.
CA 02214752 1997-09-OS
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The compounds of the formula (I) according to the invention are preferably
suitable for the selective control of monocotyledonous and dicotyledonous
weeds in monocotyledonous and dicotyledonous crops, both pre-emergence and
post-emergence.
Additionally, the active compounds according to the invention have a potent
microbicidal action and can be practically employed for controlling
undesirable
microorganisms. The active compounds are suitable for use as crop protection
agents, in particular as fungicides.
Fungicides in plant protection are employed for controlling
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,
Ascomycetes, Basidiomycetes and Deuteromycetes.
Bactericides in plant protection are employed for controlling
Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and
Streptomycetaceae.
Some causative organisms of fungal and bacterial diseases which come under
the generic names listed above may be mentioned as examples, but not by way
of limitation:
Xanthomonas species, such as Xanthomonas campestris pv. oryzae;
Pseudomonas species, such as Pseudomonas syringae pv. lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or
Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Bremia species, such as Bremia lactucae; t
Peronospora species, such as Peronospora pisi or P. brassicae;
CA 02214752 1997-09-OS
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Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea
(conidia form: Drechslera, syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus
(conidia form: Drechslera, syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Sclerotinia species, such as Sclerotinia sclerotiorum;
Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such-as Pellicularia-sasakii; -
Pyricularia species, such as Pyricularia oryzae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as Alternaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.
The good toleration, by plants, of the active compounds, at the concentrations
required for controlling plant diseases, permits treatment of aerial parts of
plants, of vegetative propagation stock and seeds, and of the soil.
The compounds of the formula (I) are particularly suitable for the protective
treatment of pomaceous fruit, such as apples, against the causative organism
of
powdery mildew in apple (Podosphaera leucotricha) and to a certain extent also
for use in rice against Pyricularia oryzae.
CA 02214752 2005-05-13
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The active compounds can be converted into the
customary formulations, such as solutions, emulsions,
wettable powders, suspensions, powders, dusting agents,
pastes, soluble powders, granules, suspo-emulsion
concentrates, natural and synthetic materials impregnated
with active compound, and very fine capsules 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 surface-active agents, that is emulsifying
agents and/or dispersing agents and/or foam-forming agents.
For example, a herbicidal or fungicidal composition
comprising a herbicidally or fungicidally effective amount
of a compound of the invention in admixture with a solid
diluent or carrier, a liquefied normally gaseous diluent or
carrier, or a liquid diluent or carrier containing a surface
active agent.
In the case of the use of water as an extender,
organic solvents can, for example, also be used as auxiliary
solvents. Suitable liquid solvents are in the main:
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 as well as their ethers and esters, ketones, such as
acetone, methyl ethyl ketone, methyl isobutyl ketone or
cyclohexanone, strongly polar solvents, such as
dimethylformamide and dimethyl sulphoxide, as well as water.
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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, as well as synthetic granules of
inorganic and organic meals, and granules of organic
material such as sawdust, coconut shells, maize cobs and
tobacco stalks; suitable emulsifying and/or foam-forming
agents are: for example non-ionic and anionic emulsifiers,
such as polyoxyethylene fatty acid
CA 02214752 1997-09-OS
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esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol
ethers, allcylsulphonates, alkyl sulphates, arylsulphonates as well as protein
hydrolysates; suitable dispersing agents are: for example lignin-sulphite
waste
liquors and methylcellulose.
Adhesives 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. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron
oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin
dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as
salts
of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of
active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as
such or in the form of their formulations, can also be used as mixtures with
known herbicides, ready-to-use formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example
anilides, such as diflufenican and propanil; arylcarboxylic acids, such as
dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as
2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-
phenoxy-alkanoic esters, such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-
butyl, haloxyfop-methyl and quizalofop-ethyl; azinones, such as chloridazon
and norflurazon; carbamates, such as chlorpropham, desmedipham,
phenmedipham and propham; chloroacetanilides, such as alachlor, acetochlor,
butachlor, metazachlor, metolachlor, pretilachlor and propachlor;
CA 02214752 1997-09-OS
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dinitroanilines, such as oryzalin, pendimethalin and trifluralin; diphenyl
ethers,
_ such as aciffuorfen, bifenox, ffuoroglycofen, fomesafen, halosafen, lactofen
and
oxyfluorfen; areas, such as chlorotoluron, diuron, fluometuron, isproturon,
linuron and methabenzthiazuron; hydroxylamines, such as alloxydim,
clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as
imazethapyr, imazamethabenz, imazapyr and imazaquin; nitrites, such as
bromoxynil, dichlobenil and jioxynil; oxyacetamides, such as mefenacet;
sulphonyl-areas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-
ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron,
primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and
tribenuron-methyl; thiocarbamates, such as butylate, cycloate, diallate, EPTC,
esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such
as
atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine;
triazinones, such as hexazinone, metamitron and metribuzin; others, such as
1 S aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid,
defenzoquat, dithiopyr, ethofumesate, ffuorochloridone, glufosinate,
glyphosate,
isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides,
acaricides, nematicides, bird repellents, plant nutrients and agents which
improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or
in the use forms prepared therefrom by further dilution, such as ready-to-use
solutions, suspensions, emulsions, powders, pastes and granules. They are used
in the customary manner, for example by watering, spraying, atomizing or
scattering.
The active compounds according to the invention can be applied either before
or after emergence of the plants. They can also be incorporated into the soil
before sowing.
CA 02214752 1997-09-OS
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The amount of active compound used can vary within a substantial range. It
depends essentially on the nature of the desired effect. In general, the
amounts
used are between 1 g and 10 kg of active compound per hectare of soil surface,
preferably between 5 g and 2 kg per ha.
The preparation and use of the active compounds according to the invention
can be seen from the examples below.
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Preparation Exam~s_
Exam in a 1
COOCH3 O
O
CH3
SOZ, ~N~N
NH ~
N
O-CH2CF3
(Process (a))
A solution of 1.9 g (9.5 mmol) of 4-methyl-S-(2,2,2-trifluoro-ethoxy)-2,4-
dihydro-3H-1,2,4-triazol-3-one in 50 ml of acetonitrile is mixed with 2.4 g
(10
mmol) of 2-methoxycarbonyl-phenylsulphonyl isocyanate, and the mixture is
stirred at 20°C for 12 hours. The mixture is then concentrated under
reduced
pressure and the residue is crystallized from diethyl ether.
3.7 g (89% of theory) of 2-(2-methoxycarbonyl-
phenylsulphonylaminocarbonyl)-4-methyl-5-(2,2,2-trifluoro-ethoxy)-2,4-
dihydro-3H-1,2,4-triazol-3-one of melting point 153°C are obtained.
CA 02214752 1997-09-OS
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H3C ~OCH3
N
I
S02 O
O
SOZ_ ~N~N~CH3
NH ~
N
O-CHZCF3
(Process (b))
3.8 g(12 mmol)of4-methyl-2-phenoxycarbonyl-5-(2,2,2-trifluoroethoxy)-2,4-
dihydro-3H-1,2,4-triazol-3-one are dissolved in 20 ml of acetonitrile and
admixed with 3.4 g (12 mmol) of 2-(N-methoxy-N-methyl-aminosulphonyl)-
benzenesulphonamide and 1.9 g (12.5 mmol) of diazabicycloundecene (DBU).
After the mixture has been stirred at 20°C for 1 hour, it is poured
into a mixture
of methylene chloride/ 5% strength hydrochloric acid, and the organic phase is
separated off, dried with sodium sulphate and concentrated under reduced
pressure. The residue is crystallized using diethyl ether.
3.3 g (55% of theory) of 2-[2-(N-methoxy-N-methyl-aminosulphonyl)-
phenylsulphonyl-aminocarbonyl~-4-methyl-5-(2,2,2-trifluoroethoxy)-2,4-
dihydro-3H-1,2,4-triazol-3-one of melting point 183°C are obtained.
CA 02214752 1997-09-OS
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By the methods of Examples 1 and 2 and in accordance with the general
description of the preparation processes according to the invention, it is
also
possible to prepare, for example, the compounds of the formula (I) listed in
Table 1 below.
0 0
R3 ,1
S02. NH N N ~ R CI)
N=C
O-RZ
Table L. Examples of compounds of the formula (I)
Ex. R' R2 R3 Melting
No. point (°C)
OCF3
3 CH3 CH2CF3 I 168
w
CF3
4 CH3 CH2CF3 I 189
OCzHs
5 CH3 CH2CF3 ~ ~ 135
SCH3
6 CH3 CH2CF3 ~ ~ 159
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Ex R' R2 R3 Melting
No. point (°C)
CH3
7 CH3 CH2CF3 ~ ~ 178
w
OCH3 -
8 CH3 CH2CF3 ~ ~ 144
CH30
COOCZHS
9 CH3 CH~CF3 ~ ~ 119
COOC3H~ n
CH3 CH2CF3 ~ ~ 120
.,
CI
11 CH3 CH2CF3 ~ I 203
Br
12 CH3 CH2CF3 ~ ~ 193
OCHFZ
13 CH3 CH~CF3 ~ ( 144
w
OCH3
10 14 CH3 CH2CF3 ~ I 180
CA 02214752 1997-09-OS
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Ex Ri R2 R3 Melting
No. point (C)
SC2H5
. 15 CH3 CH2CF3 ~ ~ 162
CI
16 CH3 CH2CF3 ~ ~ 216
CH3
O-CHZ CH=CHz
17 CH3 CHZCF3 ~ ~ 102
_ COOCH3
18 , CH3 ~ CH2CC13 ~ ~ 129
OCHF2
19 CH3 CH2CC13 ~ I 122
CF3
20 CH3 CH2CC13 ~ ~ 153
OCF3
21 CH3 CH2CC13 ~ ~ 140
COOCZHS
22 CH3 CH2CC13 ~ ~ 146
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, - 37 -
Ex. R' R2 R3 Melting
No. point (C)
COOC3H~
~
23 CH3 CH2CC13 ~ 148
OCH3
~
24 CH3 CH2CC13 ~ 145
OCZHS
~
25 CH3 CH2CC13 ( 142
Br
26 CH3 CH2CC13 ~ ~ 155
w
SCH3
27 CH3 CH2CC13 ~ ~ 136
SCzHs
~
28 CH3 CH2CC13 ~ 158
C~
29 CH3 CH2CC13 ~ ~ 153
CH3
30 CH3 CH2CC13 ~ ~ 150
CA 02214752 1997-09-OS
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Ex. R1 R2 R3 Melting
No. point
(C)
OCH3
~
31 CH3 CH2CC13 ~ 160
CH30
CI
32 CH3 CH2CC1~ ~ ~ 196
CH3
H3C
CH3
~
33 CH3 CH2CC13 . ~ 182
CH3
COOCH3
~
34 CH3 CHZ CFA-CHF2 ~ 120
OCHFZ
. ~
35 CH3 CH2-CF2-CHF2 ~ 116
CF3
36 CH3 CH2-CF2-CHF2 ~ ~ 163
OCF3
~
37 CH3 CH2-CF2-CHF2 ~ 154
COOCZHS
~
38 CH3 CH2-CFz CHF2 ~ 126
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Ex R' R2 R3 Melting
No. point (C)
COOC3H~ n
~
39 CH3 CH2-CF2-CHF2 ~ 109
OCH3
~
40 CH3 CH2-CF2-CHF2 ~ 160
OCZHS
~
41 CH3 CH2-CF2-CHF2 ~ 153
Br
42 CH3 CH2-CF2-CHF2 ~ ~ 163
SCH3
~
43 CH3 CH2-CF2-CHF~ I 150
SC2H5
~
44 CH3 CH2-CF2-CHF2 ~ 159
CI
45 CH3 CH2-CF2-CHF~ ~ ~ 168
CH3
46 CH3 CH2-CF2-CHF2 ~ ~ 163
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Ex R' . R2 R3 Melting
No. - point (°C)
OCH3
47 CH3 CHI-CF2-CHF2 s ~ 117
W
CH30
CH3
48 CH3 CH2-CF2-CHF2 ~ ~ 142
cl
CI
49 CH3 CH2-CF2-CHF2 ~ ~ 154
CI
COOCH3
50 C2H5 CHa-CF3 ~ 96
OCHFZ
51 C2H5 CH2-CF3 ~ 117
CF3
52 C2H5 ~ CH2-CF3 ~ 108
OCF3
53 C2H5 CH2-CF3 ~ 133
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Ex. R' R2 R3 Melting
No. point (C)
COOCZHS
~
54 C~HS CH2-CF3 ~ 152
COOC3H~
~
55 C2H5 CHI CF3 ~ 117
OCH3
~
56 C~HS CH2-CF3 ~ 148
OC2H5
~
57 C~HS CH2 CF3 ~ 108
Br
58 C2H5 CH2-CF3 ~ ~ 119
SCZHS
~
59 C2H5 CHZ CF3 ~ 89
SCH3
~
60 CZHS CH2-CF3 ~ 140
CI
6I CZHS CH2-CF3 ~ ( 127
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Ex. R' R2 R3 Melting
No. point (°C) _
CH3
62 C2H5 CHI-CF3 ~ ~ 120
OCH3
63 C2H5 CH2-CF3 ~ I 143
CH30
CI
64 C~HS CHZ-CF3 i I 141
CH3
CH
65 C2H5 CH2-CF3 H3~ ~ I 3 152
CH3
COOCH3
66 CH2-CH=CH2 C1-i2-CF3 ~ ~ 125
OCHFZ
67 CH2-CH=CH2 CH2-CF3 ~ ~ 86
68 CH2-CH=CH2 CH2-CF3 ~ I CF3 108
. CA 02214752 1997-09-OS
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Ex. R' R2 R3 Melting
No. point (C)
OCH3
69 CH2-CH= CHZ CHZ-CF3 ~ I 93
COOC2H5
70 CH2-CH= CH2 CH2-CF3 ~ ~ 162
COOC3H,
71 CHZ-CH=CH2 CH2-CF3 ~ ~ 103
OCH3
72 CH2 CH= CH2 CHa CF3 ~ I 144
OCZHS
73 CH2-CH =CH2 CH2-CF3 ~ I 110
Br
74 CHa-CH =CHI CH2-CF3 ~ I 115
SC2H5
75 CH2-CH =CH2 CH2-CF3 ~ ~ 126
76 CHz CH =CH2 CHi CF3 ~ ~ 118
CA 02214752 1997-09-OS
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_ 4q. -
Ex. Rl R2 R3 Melting
No. , point (°C)
CH3
77 CH2-CH=CH2 CH2-CF3 ~ ~ 104
OCH3
78 CH2-CH=CH2 CH2-CF3 ~ I 128
CH30
CI
79 C~~~-CH=CH2 CHZ-CF3 i I 119
CH3
CH
80 CH2-CH=CHa CHZ-CF3 H3G ~ I 3 123
CH3
scH3 'H-NMR
81 CH2-CH=CH2 CH2-CF3 ~ ( (CDC13, ~:
2.52 (s,
SCH3), 6.13
(q, CH2_
CF3) ppm
S~2CH3
82 CH2-CH=CH2 CH2-CF3
CA 02214752 1997-09-OS
-45-
Ex. R' R2 R3 Melting
No. point (°C)
COOCH3 108
83 ~ CH2-CF3
OCF3 132
84 ~ CH2-CF3
C F3 124
85 ~ CH2-CF3
OCZHS 120
86 ~ CH2-CF3
oCHF2 1H-NMR
87 ~ CH2-CF3 ~ I (CDC13, b>:
4.74
(q, CH2CF3),
6.66 (t,
OCHF~,
ppm
Bf 1s4~
88 ~ CH2-CF3
lss
89 ~ CH2-CF3
CA 02214752 1997-09-OS
- 46 -
Ex. Ri R2 R3 Melting
No. point (°C)
OCH3 141
90 ~ CH2-CF3
I
SCH3 121
91 ~ CH2-CF3 ~ I
SCZHS i t9
92 ~ CH2-CF3 ~ I
COOCzHS 116
93 ~ CH2-CF3
COOC3H~ n 114
94 ~ CH2-CF3
CH3 143
95 ~ CHI CF3
CH3 174
96 ~ CH2-CF3
ci
CA 02214752 1997-09-OS
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- 47 -
Ex RI R2 R3 Melting
No. point (°C)
CH3
97 , ~ CH2-CF3 / SO -N~ 154
2 OCH3
(
O-CH2 CH=CH2
98 ~ CH2-CF3 ~ ~ 117
CI
99 ~ CH2-CF3 ~ ~ 175
CI
COOCH3
100 CH3 - CHF2 ~ ~ 178
OCF3
101 CH3 CHF2 ~ ~ 189
CHZCHZCF3
102 CH3 CHI-CF3 ~ I 142
103 CH3 CH2-CF3 ~ I COOCHZC=CH SS
104 CH3 . CH2-CF3 ~ oso2CH3 127
OCFZCHFZ
105 CH3 CH2-CF3 ~ I 128
w
CA 02214752 2005-05-13
28976-337
-48-
Ex. R' R2 R3 Melting point
No. (°C)
106 '~"~ CHz-CF3 ~ OCFZCHFz
( 118
COOCsH~-f
107 CH3 CH=-CF3 ~ I 121
OCsH~-~
108 CH3 CH:-CF3 ~ I 118
OC3H~ i
109 '~ CH2-CF3 ~ I 79
OC~H~-n
110 CH3 CHI-CF3 ~ I 94
OC3HT-n
Ill ~ CHZ-CF3 ~ ( 105
112 '-~ CHi-CF3 i I COOC3H, i
154
113 CH3 CH2-CF3 '~ CzH~ 167
I
CA 02214752 1997-09-OS
-49-
0
H~N~N~CH3
N
O-CHZCF2CHFz
Step 1: D ibutyltin bis-2, 2, 3, 3-tetrafluoropropoxide
723 g (2.45 mol) of dibutyltin dimethoxide with 777 g (5.89 mol) of 2,2,3,3-
tetrafluoro-propanol are heated to 120°C under nitrogen. Most of the
methanol
liberated in this process is distilled off over a column. The remaining
methanol and
excess 2,2,3,3-tetrafluoro-propanol are then substantially removed under water
pump
vacuum (about 15 mbar), the dibutyltin bis-2,2,3,3-tetrafluoropropoxide
remaining
as residue.
Step ~: Bis-(2,2,3,3-tetrafluoropropyl) methyliminocarbonate
At 40°C, 175 g (2.39 mol) of methyl isothiocyanate are added dropwise
to dibutyltin
bis-2,2,3,3-tetrafluoropropoxide obtained as described above, and the mixture
is then
heated under nitrogen to 120°C for 36 hours. The mixture is then
subjected to a crude
distillation, first under water pump vacuum and then under oil pump vacuum
(final
temperature in the bottom: 170°C at 1 mbar). Rectification under oil
pump vacuum
affords 555 g (77% of theory) of bis-(2,2,3,3-tetrafluoropropyl)
methyliminocarbonate.
Boiling point: 73°C (15 mbar), purity: 98.3%
CA 02214752 1997-09-OS
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-50-
Step 3: 4-Methyl-5-(2,2,3,3-tetrafluoro-propoxy)-2,4-dihydro-3H-1,2,4-triazol-
3-one
555 g (1.83 mol) of bis-(2,2,3,3-tetrafluoropropyl) methyliminocarbonate are
dissolved
in X00 ml of tetrahydrofuran and, with ice cooling (0°C to 5°C),
admixed with 18.7
g.(183 mmol} of pivalic acid (catalyst) and 278 g (1.83 mol) of phenyl
carbazate. The
mixture is stirred for 2 hours at 20°C and then warmed to 50°C,
resulting in a crystal
pulp that can be stirred only with difficulty. When this is heated to
80°C, the solution
becomes homogeneous again. First, at about 200 mbar, most of the
tetrahydrofuran and
then, at about 15 mbar, most of the 2,2,3,3-tetrafluoro-propanol and phenol
are distilled
off. The residue is then freed of the remaining volatile components at a head
temperature of 130°C and a pressure of about 0.5 mbar and then taken up
in 400 ml
of hot toluene. After cooling to 0°C, the crystalline product is
isolated by filtration
under suction.
280 g (67% of theory) of 4-methyl-5-(2,2,3,3-tetrafluoro-propoxy)-2,4-dihydro-
3H-
1,2,4-triazol-3-one of melting point 141°C are obtained.
CA 02214752 1997-09-OS
-51-
O
H~N~N~CH3
N
O-CH F2
11.85 g (0.10 mol) of 4-methylurazole are dissolved in a mixture of 100 ml of
isopropanol, 25 ml of water and 12 g of 45% strength aqueous sodium hydroxide
solution (0.30 mol ofNaOH). At 40°C, difluorochloromethane (Frigen 22)
is slowly
passed through with stirring. After 27.7 g (0.41 mol) have been passed
through, the
reaction is interrupted and the reaction mixture is cooled. The isopropanol
phase is
separated off and concentrated under reduced pressure. The residue is stirred
with
diethyl ether and insoluble components are filtered off. The ether phase is
concentrated under reduced pressure and the residue that remains is purified
by
preparative layer chromatography (eluent methylene chloride/methanol = 20/3).
0.9 g(5.5% oftheory) of5-difluoromethoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-
3-one of melting point 111°C is obtained.
By the methods of Examples (II-1) and (II-2), it is also possible to prepare,
for
example, the compounds of the formula (II) listed in Table 2 below.
O
H~N~N~R
(il)
N
O-RZ
CA 02214752 1997-09-OS
- 52 -
Table 2: Examples of compounds of the formula (II)
Ex. R' R2 Melting
No. point (C)
II-3 CH3 CH2CF3 128
II-4 CH3 CH~CC13 139
II-5 CH3 CH2-CF2-CHF2 101
II-6 C2H5 CH2-CF3 95
II-7 CH2-CH=CH2 CH2-CR3 62
II-8 ~ CH2-CF3 113
II-9 CH2-CF3
C H 2--
II-10 CHF2
CH~--
II-11 ~ CZHS CI-IF2
II-12 CHI-CH=CHI CHF2
II-13 ~ CHF2
II-14 CH3 CI-I(CF3)2
II-15 C2H5 CH(CF3)2
CA 02214752 1997-09-OS
T.e A 30 930-Foreign co~?ntries
- 53 -
Ex. R' R2 Melting
No. point (°C) _
II-16 CH2-CH=CHa CH(CF3)2
II-17 ~ CH(CF3)2
II-18 ~H ~ CH(CF3)2
2
II-19 CH3 CH2-CH2-F
II-20 C~HS CH2-CH2-F
II-21 CH2-CH=CHZ CHZ-CH2-F
II-22 ~ CH2-CH2-F
II-23 CH2-CH2-F
CH2--.-
II-24 NH2 CHZ-CH2-F
II-25 NH-CH3 CH2-CH2-F
II-26 N(CH3)2 CH2-CH2-F
II-27 NH2 CH2-CF3
CA 02214752 1997-09-OS
T a 1~ 30 930-Foreign countries
- 54 -
Ex. R' R2 Melting
No. - point (°C)
II-28 NH-CH3 CH2-CF3
II-29 N(CH3)2 CH2-CF3 =
II-30 NH2 CHF2
II-31 NH-CH3 CHF2
II-32 N(CH3)2 CHF2
II-33 CH3 CH2-CHF2
II-34 C~HS CH2-CHF2
II-35 CH2-CH=CH2 CH2-CHF2
II-36 ~ CH2-CHF2
II-37 CH2-CHF2
CHz-
CA 02214752 1997-09-OS
- 55 -
~ CH
H5C6'O/ 'N N 3 .
N=
O-CH2CF3
At 20°C, 51.7 g (0.33 mol) of phenyl chloroformate are added dropwise
with efficient
stirring to a mixture of 59. I g (0.30 mol) of 4-methyl-5-(2,2,2-trifluoro-
ethoxy)-2,4-
dihydro-3H-1,2,4-triazol-3-one, 100 ml of water, 400 ml of methylene chloride,
13.2 g (0.33 mol) of sodium hydroxide and 1.0 g of tetrabutylammonium bromide.
After the addition, stirring is continued for a further 16 hours and the
organic phase
is then separated o~ washed with water, dried and concentrated. The residue is
crystallized from diisopropyl ether.
87.6 g (92% of theory) of 4-methyl-2-phenoxycarbonyl-5-(2,2,2-trifluoro-
ethoxy)-
2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 105°C are obtained.
By the method of Example (IV 1) it is also possible to prepare, for example,
the
compounds of the formula (I~ listed in Table 3 below.
CA 02214752 1997-09-OS
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count
- 56 -
Table 3:3:
Examples
of compounds
of the
formula
(IV)
Ex R' R2 Z Melting
No. point (C)
IV-2 ~ CH2-CF3 O-C6H5 91
IV 3 C2H5 CH2-CF3 O-C6H5
IV 4 CH2-CH=CH2 CHI-CF3 O-C6H5
IV 5 CH3 CH2CC13 O-C6H5
IV 6 C2H5 CHaCCI3 O-C6H5
IV 7 CH2-CH=CH2 CH2CC13 O-C6H5
IV-8 ~ CH2CC13 O-C6H5
IV 9 CH2CC13 O-C6H3
C H 2-
IV CH2-CF3 O-C6H5
CH2
IV NH2 CHI-CF3 O-C6H5
11
IV NH-CH3 CH2-CF3 O-C6H5
12
IV N(CH3)2 CH2-CF3 O-C6H5
13
IV CH3 CH2-CF2-CHFZ O-C6H5
14
CA 02214752 1997-09-OS
Ex R' R2 Z Melting
No. point (C)
IV C2H5 CH2-CF2-CHF2 O-C6H5
15
IV CH2-CH=CHZ CH2-CF2-CHF2 O-C6H5
16
IV ~ CHz CF2-CHF2 O-C6H5
17
IV 18 CHZ-CFA-CHFZ O-C6H5
CHZ-Q
IU 19 N(CH3)2 CHZ CFA-CI~F2 O-C6H5
CA 02214752 1997-09-OS
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Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 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.
Seeds of the test plants are sown in normal soil. After 24 hours, the soil is
watered
with the preparation of the active compound. It is advantageous to keep
constant the
amount of water per unit area. The concentration of the active compound in the
preparation is of no importance, only the amount of active compound applied
per
unit area being decisive. After three weeks, the degree of damage to the
plants is rated
in % damage in comparison to the development of the untreated control. The
figures
denote:
0% - no action {like untreated control)
100% = total destruction
In this test, the compounds according to Preparation Examples 1, 2, 3, 4, 5,
6, 9, 1 l,
12, 15, 16, 17, 25, 50, 54, 66, 83, 84, 85, 86, 87, 88, 89, 91, 93, 94, 95,
96, 97, 98,
99, 100 and 101, for example, exhibit a strong action against weeds.
CA 02214752 1997-09-OS
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Table A: Pre-emergence test/ greenhouse
Compound Applica-Bro- Lo- Poa Ama- Galin- Matri-Sina- Sola-
of tion mus lium ranthussoga cariapis num
Preparationrate
Example (g/ha)
No.
83 125 95 95 95 90 95 90 90 95
84 125 90 90 90 90 95 90 90 95
85 125 90 95 90 90 95 95 90 95
86 125 95 80 90 90 95 95 95 95
1 125 95 95 95 90 90 90 80 95
3 125 95 90 80 80 70 95 80 90
4 125 95 95 95 95 95 90 95 95
125 95 - 80 95 95 95 95 95
6 125 95 50 95 95 70 60 90 95
50 125 95 90 90 90 80 90 90 90
54 125 95 90 90 90 95 90 70 90
87 125 90 90 90 90 70 SO 80 90
88 .125 90 90 90 80 95 95 80 90
89 125 90 80 80 90 95 95 80 90
91 125 90 70 80 80 80 70 80 90
CA 02214752 1997-09-OS
- 60 -
Table A: (cont.)
Compound Applica-Bro- Lo- Poa Ama- Galin-Matri-Sina-Sola-
of tion mus lium ranthussoga caria pis num
Preparationrate
Example (g/ha)
9 125 95 95 95 95 95 100 80 95
11 125 - 60 SO 90 100 100 80 70
12 125 80 80 80 95 100 80 80 80
15 125 95 - 60 95 70 95 90 90
16 125 80 90 95 95 60 80 90 90
93 125 95 95 95 95 95 95 95 95
94 125 90 90 90 80 95 90 80 90
95 125 80 90 - 90 95 90 90 90
-
96 125 95 95 90 90 90 90 90 80
97 250 95 95 90 95 95 95 90 95
2 250 95 95 95 95 95 80 80 95
17 125 95 70 80 90 90 90 80 90
98 125 90 70 80 90 90 80 80 90
25 125 - - 90 60 100 95 90 70
66 125 90 95 90 70 95 95 70 95
CA 02214752 1997-09-OS
-61-
Table A: (cont.)
Compound Applica-Bro- Lo- Poa Ama- Galin-Matri-Sina-Sola-
of tion mus lium ranthussoga caria pis num
Preparationrate ',
Example (gJha)
99 125 90 90 95 100 70 50 90 90
100 125 - 95 95 50 - 70 80 95
101 125 70 95 90 90 80 50 80 90
CA 02214752 1997-09-OS
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Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 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.
Test plants which have a height of 5 - 15 clri are sprayed with the
preparation of the
active compound in such a way as to apply the particular amounts of active
compounds desired per unit area. The concentration of the spray liquor is
chosen so
that the particular amounts of active compounds desired are employed in 2000 1
of
water/ha. After three weeks, the degree of damage to the plants is rated in %
damage
in comparison to the development of the untreated control.
The figures denote:
0% - no action (like untreated control)
100% = total destruction
In this test, the compounds of Preparation Examples l, 2, 4, 5, 9, 16, 17, 25,
50, 66,
83, 84, 85, 86, 87, 88, 89, 93, 94, 95, 96, 98, 99 and 100 show a strong
action against
weeds.
CA 02214752 1997-09-OS
-63-
Tahle B:B: Post-emergence test/greenhouse
Compound flpplic-Alope-AvenaLo- Ama- DaturaGalium Heli- Sola-Vero-
of ation Gurus lium ranthus anthusnum nica
Preparationrate
Example (g/ha)
No.
83 250 90 90 95 90 90 90 90 90 90
84 250 - 95 70 70 90 80 90 90 95
85 250 - - 95 70 90 90 90 80 95
86 500 - 80 90 100 90 90 100 95 100
1 250 90 90 100 80 80 70 90 90 95
4 250 90 70 90 80 90 70 90 90 90
250 80 SO - 95 90 70 95 90 100
87 125 70 80 50 80 95 70 80 90 90
50 60 80 50 80 95 50 85 - 90 70
88 250 80 - 70 95 95 90 100 90 90
89 125 50 - 80 95 95 90 95 95 95
9 60 100 95 80 95 90 90 80 95 90
16 125 - 50 70 95 80 50 100 95 70
93 125 95 90 80 95 95 90 100 95 70
94 125 80 90 80 70 90 70 80 90 -
95 60 70 70 - 90 - 95 70 70 80
17 125 50 - - 90 80 50 100 95 90
98 125 - - - 95 50 - 100 80 90
96 60 95 70 90 95 70 90 80 - 50
2 125 60 60 50 80 80 - 95 80 80
25 60 60 50 - 80 80 50 100 90 -
66 60 50 - - 80 80 50 100 90 -
99 60 60 50 50 90 95 95 60 90 70
100 . 125 - 90 80 90 90 90 - 95 90
CA 02214752 1997-09-OS
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Podosphaera test (apple)/protective
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkyl-aryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated quantities of solvent and emulsifier, and
the
concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation
of active
compound. After the spray coating has dried on, the plants are inoculated by
dusting
with conidiae ofthe causative ~r~a";~", ~fa""tP ",;mP~x. ~n",~"~...,~,~o..~
,~.......~_:_L_~
--- - --~-__~___ ,.a rj,.... ~~~aa.wvr ~a vuvyr11av1ci lGlit;V6L1GL1CL~.
The plants are then placed in a greenhouse at 23°C and a relative
atmospheric
humidity of about 70%.
Evaluation is carried out 10 days after the inoculation.
In this test, the compounds of Preparation Examples l, 3, 83 and 85, for
example,
have an efficacy of 87 to 100% at an active compound concentration of 25 ppm.
CA 02214752 1997-09-OS
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- 65
Table C:C:
Podosphaera test (apple)/protective
Active compound (compound of ~ Effcacy in % of the untreated
Preparation Example No.) control at an active compound
concentration of 25 ppm
1 89
3 g~
$3 100
99
CA 02214752 1997-09-OS
- 66 -
Exam lp a D
Sphaerotheca test (cucumber)/protective
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkyl-aryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of
active
compound is mixed with the stated quantities of solvent and emulsifier, and
the
concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation
of active
compound. After the spray coating has dried on, the plants are dusted with
conidiae
of the fungus Sphaerotheca fuliginea.
The plants are then placed in a greenhouse at 23 to 24°C and at a
relative
atmospheric humidity of about 75%.
Evaluation is carried out 10 days after the inoculation.
In this test, the compound of Preparation Example 50, for example, has an
efficacy
of 92% at an active compound concentration of 100 ppm.
CA 02214752 1997-09-OS
' Le A 30 930-Forei,~;n countries
- 67 -
:able D
Sphaerotheca test (cucumber)/protective
Active compound (compound of E~cacy in % of the untreated
Preparation Example No.) control at an active compound
concentration
of 100 ppm
50 9~
