Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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s - 1 -
,, ,, ._ .
4~ ~ . . . . i
Fluo~butenyl estels
The present invention relates to novel fluorobutenyl esters, processes for theirpreparation and their use for controlling animal pests, in particular insects,
arachnids and nematodes encountered in agriculture, in forestry, in the
5 protection of stored products and materials, and in the hygiene sector.
It is akeady known that certain fluorobutenyl compounds are active as
nematicides (cf. for example WO 88/00183). However, the potency and the
spectrum of activity of these compounds is not always entirely s~ti~f~ctory, in
particular at low application rates and concentrations.
10 This invention, then provides novel compounds ofthe formula (I)
CF2=C--CH2--CH2--R2
l1 (I)
in which
R' represents hydrogen or halogen and
R2 represents one of the groups (a) or (b)
Y Y
--O--C--Z--R3 (a) or --S--C--S--R3 (b)
in which
Y represents oxygen or sulphur,
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Z represents oxygen, sulphur or NR4,
R3 represents hydrogen or respectively optionally substituted alkyl,
alkenyl, cycloalkyl, aryl, aralkyl, alkoxycarbonyl, aryloxycarbonyl,
arylsulphonyl or hetaryl and
R4 represents hydrogen or respectively optionally substituted alkyl,
alkylthio, alkenyl, cycloalkyl, aryl, aralkyl or hetaryl or
R3 and R4 form together with the nitrogen atom to which they are
attached an optionally substituted ring which optionally contains
oxygen, sulphur or nitrogen (which is optionally substituted by
alkyl, aryl or aralkyl),
or
represents the group (c)
S
Il 5
--S--C--V--R (c)
in which
V represents oxygen or NR6 and
R~ and R6 each represent independently of one another hydrogen,
an aliphatic group having one to twelve carbon atoms, an aromatic or
heterocyclic group, each of which is optionally substituted by at least one
substituent from the group consisting of alkyl, cyano, trimethylsilyl,
hydroxy, alkoxy, halogen, nitro, amino, alkylamino, dialkylamino, SH,
alkylthio, phenyl, or by a carboxylic acid radical, sulphonic acid radical,
phosphonic acid radical or phosphinic acid radical or an ester, thioester
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or an amide of the acids mentioned, the amide being optionally mono-
or disubstituted by alkyl, or
R5 and R6 replesent together with the nitrogen atom to which they are
attached an amino acid or an optionally additionally oxygen-, sulphur-
or nitrogen-containing heterocyclic group, each of which is optionally at
least monosubstituted by alkyl, cyano, trimethylsilyl, hydroxyl, alkoxy,
halogen, nitro, amino, alkylamino, dialkylamino, SH, alkylthio, phenyl
or a carboxylic acid radical, sulphonic acid radical, phosphonic acid
radical or phosphinic acid radical or an ester, thioester or an amide of
the acids mentioned, the amide being optionally mono- or disubstituted
by alkyl, or
R5 represents, in the case that R6 represents hydrogen, where one of the
radicals oR7, CoR7, NR7Rg, SO2R9 or P(=O)RI~R~l, where
R7 and Rg each represent independently of one another hydrogen,
alkyl or aryl,
R9 represents hydrogen, alkyl, halogenoalkyl or aryl and
R'~ and R" each represent independently of one another hydrogen,
alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, amino, alkylamino,
dialkylamino or arylamino,
20 and their salts.
The compounds ofthe formula (I) can be present as geometrical and/or optical
isomers or as mixtures of isomers of different compositions. The invention
relates to the pure isomers and also to the mixtures of isomers.
The compounds of the formula (I) having a carboxyl or a hydroxyl group can
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be present as salts in combination with different cations, for example alkali
metals or alkaline earth metals such as sodium, potassium, calcium, magnesium
or quaternary ammonium ions such as the isopropylammonium ion or the
pyridinium ion.
S Taking into account the different meanings of the radical R2, the structures
(Ia), (Ib) and (Ic) are obtained:
CF2=CR'-CH2-CH2-O--C-Z-R3 (Ia)
F2=CR'-CH2-CH2-S--C-S-R3 (Ib)
F2=CR'-CH2-CH2-S--C-V-Rs (Ic)
10 in which
R', R3, R5, V, Y and Z have the abovementioned meaning
Furthermore, it was found that the compounds of the formula (Ia) or (Ib) are
obtained when
A) fluorobutenols of the formula (II)
CF2 = C--CH2--CH2--OH
R' (II)
in which
Rl has the abovementioned meanings
are reacted
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a) with compounds of the formula (III)
I l 3 (III)
Cl--C--Z--R
in which
Y, Z and R3 have the abovementioned meanings,
in the presence of a diluent and optionally in the presence of a
base,
or
~) with an iso(thio)cyanate of the formula (IV)
YCN-R3 (I~
in which
Y and R3 have the abovementioned meanings,
in the presence of a diluent and optionally in the presence of a
catalyst,
or
B) fluorobutenethiols ofthe forrnula (IIa)
CF = C--CH CH SH
f 2 1 2 2 (IIa)
in which
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R' has the abovementioned meaning
are reacted with a compound of the formula (IIIa)
I l 3 (IIIa)
Cl--C--S--R
in which
5Y and R3 have the abovementioned meanings,
in the presence of a diluent and optionally in the presence of a base,
or
C) compounds of the formula (V)
CF2=f CH2 CH2--O C Cl (V)
R'
in which
Rl and Y have the abovementioned meanings
are reacted with a compound of the formula (VI)
H-Z-R3 (VI)
in which
Z and R3 have the abovementioned meanings,
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in the presence of a diluent and optionally in the presence of a base,
or
D) compounds ofthe formula (VII)
CF2=C--CH2--CH2--S--C--Cl (VII)
R1
in which
- Rl and Y have the abovementioned meanings
are reacted with the compound of the formula (VIII)
H-S-R3 (VIII)
in which
R3 has the abovementioned meaning
in the presence of a diluent and optionally in the presence of a base.
Using known methods, the compounds of the formula (Ic) can be prepared
from known compounds, some of which are commercially available, or from
compounds which are easy to prepare by known methods (cf. preparation
1 5 examples).
Finally, it has been found that the novel compounds of the formula (I) have
pronounced biological properties and are especially suitable for controlling
animal pests, in particular insects, arachnids and nematodes encountered in
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agriculture, in forestry, in the protection of stored products and materials, and
in the hygiene sector.
Formula (I) provides a general definition of the compounds according to the
invention.
S Preferred substituents or ranges ofthe radicals listed in the formulae mentioned
hereinabove and hereinbelow will now be illustrated.
Rl preferably represents hydrogen, fluorine or chlorine.
R2 pre~lably represents one of the groups
Y Y
--O--C--Z--R3 or --S--C--S--R3
in which
Y represents oxygen or sulphur,
Z represents oxygen, sulphur or NR4,
R3 represents hydrogen,
or Cl-C~0-alkyl which is optionally substituted by halogen, cyano,
carboxyl, phenyl, amino (which is optionally substituted by C2-C7-
alkanediyl or mono- or disubstituted by identical or different Cl-C8-
alkyl), Cl-C8-alkoxy, Cl-C8-alkylthio or aminocarbonyl (which is
optionally substituted by C2-C7-alkanediyl, mono- or disubstituted by
identical or different Cl-C8-alkyl, Cl-C8-halogenoalkyl, Cl-C8-alkoxy,
C3-C8-cycloalkyl, C3-C8-halogenocycloalkyl, Cl-C4-alkyl-C3-C8-cyclo-
alkyl, or by phenyl or benzyl, each of which is optionally substituted by
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g
halogen, cyano, nitro, Cl-Cg-alkyl, C~-C8-halogenoalkyl, Cl-C8-alkoxy,
Cl-C8-halogenoalkoxy, Cl-C8-alkylthio or C,-C8-halogenoalkylthio),
or optionally halogen-substitllte~ C3-C8-alkenyl,
or optionally halogen- or Cl-C6-alkyl-substituted C3-C8-cycloalkyl,
or phenyl, benzyl, phenyloxycarbonyl or phenylsulphonyl, each of which
is optionally substituted by halogen, cyano, nitro, Cl-C8-alkyl, Cl-C8-
halogenoalkyl, Cl-C8-alkoxy, Cl-C8-halogenoalkoxy, Cl-C8-alkylthio,
Cl-C8-halogenoalkylthio, C,-C8-alkoxycarbonyl or SCN,
or an optionally halogen- or Cl-C6-allyl-substituted 5- or 6-membered
heterocycle having one to three nitrogen atoms
or optionally halogen- or Cl-C6-alkoxy-substituted Cl-C8-alkoxy-
- carbonyl.
R4 preferably represents hydrogen,
or Cl-C10-alkyl which is optionally substituted by halogen, cyano, amino
- 15 (which is optionally substituted by C2-C7-alkanediyl or optionally mono-
or disubstituted by identical or different Cl-C8-alkyl), Cl-C8-alkoxy,
Cl-C8-alkylthio or aminocarbonyl (which is optionally substituted by
C2-C7-alkanediyl, mono- or disubstituted by identical or different Cl-C8-
alkyl, Cl-C8-halogenoalkyl, C3-C8-cycloalkyl, C3-C8-halogenocycloalkyl,
Cl-C4-alkyl-C3-C8-cycloalkyl, or by phenyl or benzyl, each of which is
optionally substituted by halogen, cyano, nitro, Cl-C8-alkyl, Cl-C8-
halogenoalkyl, Cl-C8-alkoxy, Cl-Cg-halogenoalkoxy, Cl-C8-alkylthio or
Cl-C8-halogenoalkylthio),
- or optionally halogen-substituted C,-C6-alkylthio,
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or optionally halogen-substituted C3-C8-alkenyl,
or optionally halogen- or Cl-C6-alkyl-substituted C3-C8-cycloalkyl,
or phenyl or benzyl, each of which is optionally substituted by halogen,
cyano, nitro, Cl-C8-alkyl, C,-C8-halogenoalkyl, Cl-C8-alkoxy, Cl-C8-
S halogenoalkoxy, Cl-C8-alkylthio, Cl-C8-halogenoalkylthio, C,-C8-
alkoxycarbonyl or SCN,
or an optionally halogen- or C,-C6-alkyl-substituted 5- or 6-membered
heterocycle having one to three nitrogen atoms
or
R3 and R4 form together with the nitrogen atom to which they are
attached a 4- to 8-membered, optionally Cl-C8-alkyl-substituted ring
which optionally contains oxygen, sulphur or nitrogen (which is
optionally substituted by C,-C8-alkyl, phenyl or benzyl).
Rl particularly preferably represents fluorine.
15 R2 particularly preferably represents the group
ll
--O--C--Z--R
in which
Y represents oxygen or sulphur,
Z represents oxygen, sulphur or NR4,
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R3 represents hydrogen,
or C,-C6-alkyl which is optionally substituted by fluorine, chlorine,
cyano, carboxyl, phenyl, amino (which is optionally substituted by
C2-C6-alkanediyl or mono- to ~ bstit~lted by identical or different
S Cl-C6-alkyl), Cl-C6-alkoxy, Cl-C6-alkylthio or aminocarbonyl (which is
optionally substituted by C2-C6-alkanediyl, mono- or disubstituted by
identical or different Cl-C6-alkyl, Cl-C6-halogenoalkyl, Cl-C6-alkoxy,
C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl, Cl-C3-alkyl-C3-C7-cyclo-
alkyl, or by phenyl or benzyl, each of which is optionally substituted by
halogen, cyano, nitro, C,-C6-alkyl, C,-C6-halogenoalkyl, Cl-C6-alkoxy,
Cl-C6-halogenoalkoxy, C,-C6-alkylthio or Cl-C6-halogenoalkylthio),
or optionally fluorine-, chlorine-, or Cl-C4-alkyl-substituted C4-Cg-
cycloalkyl,
- or phenyl, benzyl, phenoxycarbonyl or phenylsulphonyl, each of which
is optionally substit~lted by fluorine, chlorine, cyano, nitro, Cl-C6-alkyl,
Cl-C6-halogenoalkyl, Cl-C6-alkoxy, Cl-C6-halogenoalkoxy, Cl-C6-
alkylthio, Cl-C6-halogenoalkylthio, Cl-C6-alkoxycarbonyl or SCN
or optionally fluorine-, chlorine- or Cl-C4-alkoxy- substituted Cl-C6-
alkoxycarbonyl .
20 R4 particularly preferably represents hydrogen,
- or Cl-C6-alkyl, optionally fluorine- or chlorine-substituted Cl-C4-
alkylthio, or C4-Cg-cycloalkyl
or
R3 and R4 form together with the nitrogen atom to which they are attached to
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a 4- to 8-membered, optionally C,-C6-alkyl-substituted ring
which optionally contains oxygen, sulphur or nitrogen (which is
optionally substituted by C,-C6-alkyl, phenyl or benzyl).
R~ very particularly pref~lably represel-ts fluorine.
S R2 very particularly pref~lably represents the group
Il 3
--O--C--Z--R
- in which
Y represents oxygen,
Z represents oxygen, sulphur or NR4,
10 R3 represents hydrogen,
or C~-C6-alkyl which is optionally substituted by fluorine, chlorine,
cyano, carboxyl, phenyl, amino (which is optionally substituted by
C2-C6-alkanediyl or mono- or disubstit~lte~l by identical or different
C,-C6-alkyl), C,-C6-alkoxy, C,-C6-alkylthio or aminocarbonyl (which is
optionally substituted by C2-C6-alkanediyl, mono- or disubstituted by
identical or different C,-C4-alkyl, C,-C4-alkoxy or by phenyl or benzyl,
each of which is optionally substituted by halogen, cyano, nitro, C,-C6-
alkyl, C,-C6-halogenoalkyl, C~-C6-alkoxy, C~-C6-halogenoalkoxy, C~-C6-
alkylthio or C,-C6-halogenoalkylthio),
or optionally C,-C4-alkyl-substituted C4-C8-cycloalkyl,
- or phenyl, benzyl, phenoxy or phenylsulphonyl, each of which is
optionally substituted by fiuorine, chlorine, cyano, C,-C4-alkyl, C~-C4-
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halogenoalkyl, C 1- C4- alkoxy, C 1- C4- halogenoalkoxy, C ,- C4- alkylthio,
Cl-C4-halogenoalkylthio or C~-C4-alkoxycarbonyl
or optionally fluorine-, chlorine- or Cl-C4-alkoxy-substitllte~l Cl-C4-
alkoxycarbonyl.
5 R4 very particularly preferably represents hydrogen,
or Cl-C4-alkyl, optionally fluorine- or chlorine-substituted C~-C3-
alkylthio
or C4-C6-cycloalkyl
or
~0 R3 and R4 form together with the nitrogen atom to which they are attached
a 4- to 8-membered, optionally Cl-C4-alkyl-substituted ring
which optionally contains oxygen, sulphur or nitrogen (which is
optionally substituted by C,-C4-alkyl or benzyl).
The abovementioned general or preferred definitions of radicals or illustrations15 apply to the end products and, correspondingly, to the starting materials andintermediates. These radical definitions can be combined with each other as
desired, that is to say combinations between the respective ~rer~lled ranges arealso possible.
Preference is given according to the invention to compounds of the formulae
20 (Ia) and (Ib) which contain a combination ofthe meanings mentioned above as
being preferred (preferable).
Particular ~re~lellce according to the invention is given to the compounds of
the formulae (Ia) and (Ib) which contain a combination of the meanings
mentioned above as being particularly preferred.
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Very particular yler~lellce according to the invention is given to compounds of
the formulae (Ia) and (Ib) which contain a combination of the meanings
mentioned above as being very particularly yrer~lled.
A further ~rer~ d group of compounds are compounds of the formula (Ic), in
5 particular those in which Z reyresellts oxygen and R5 represents an aliphatic
group, preferably lower alkyl, in particular ethyl.
In the radical definitions given hereinabove and hereinbelow, hydrocarbon
radicals, such as alkyl or alkenyl, are - also in connection with heteroatoms
such as alkoxy or alkylthio - in each case straight-chain or branched as far as
10 this is possible.
The terms used in the definitions ofthe radicals R5, R6, R7, R8, R9, Rl~ and R'
are to be understood as follows:
The term "halogen" means fiuorine, chlorine, bromine, iodine.
The term "alkyl" represents straight-chain or branched C,-C7-alkyl.
15 The term "lower alkyl" represents straight-chain or branched Cl-C4-alkyl.
The term '~lip~l~tic~ r~resents saturated or lln~tllrated, straight-chain or
branched alkyl having one to ten carbon atoms (or as stated) or straight-chain
or branched alkenyl having two to ten carbon atoms (or as stated).
The term "alkoxy" represents lower alkyl which is attached via an oxygen atom.
20 The term "alkylthio" represents lower alkyl which is attached via a sulphur
atom.
The term "alkoxycarbonyl" represents a lower alkyl ester of a carboxyl group.
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The term "ca~boxylic acid l~dicql sulphonic acid ~dical, phosphonic acid
~dical or phosphir~ic acid ladical or an ester, thioester or amide of the acids
mentioned" means an aliphatic group in which at least one carbon atom has
been replaced by a carboxyl group or in which at least one hydrogen atom has
5 been replaced by a sulphonic acid group, phosphinic acid group or phosphonic
acid group, and lower alkyl esters, lower alkyl thioesters or amides (which are
optionally substitl1te~1 by one or two lower alkyl groups) ofthe acids mentioned.
The term "amino acid" means that NRsR6 is the optionally substituted amino
group of a natural or a not naturally occurring amino acid.
10 The terms "a~matic group" or "alyl" mean phenyl which is optionally
substituted as described above.
The term "hete~cyclic group" means any cyclic group containing at least one
non-carbon element in the ring. The heteroatom may be oxygen, nitrogen,
sulphur or another element. Examples of heterocycles are: tl~ 7ole, pyridine,
15 thiazole, isothiazole, oxazole, imidazole, pyrazole, triazole, benzothiazole,sulphur-containing heterocycles, morpholine, piperidine, piperazine or
pyrrolidine which are optionally substituted by at least one radical from the
group consisting of cyano, trimethylsilyl, hydroxyl, alkoxy, halogen, nitro,
amino, SH, alkylthio, carboxyl, alkoxycarbonyl, phenyl, a carboxylic acid
- 20 radical, a sulphonic acid radical, a phosphonic acid radical or a phosphinic acid
radical, or an ester, thioester or an amide of these acids.
I~ in the preparation of compounds of the formula (I) according to process
Aa), for example 3,4,4-trifluoro-but-3-enol and ethyl chloroformate are used
as starting materials, then the reaction may be illustrated by the following
25 reaction scheme:
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1~l
CF2 = CF--CH2--CH2--OH + Cl - C--OC2H5
CF2 = CF - CH2--CH2- O - C - Oc2Hs
If, in the preparation of compounds of the formula (I) according to process
A~), for example 3,4,4-trifluoro-but-3-enol and phenyl isocyanate are used as
starting materials, then the reaction may be illustrated by the following reaction
S scheme:
CF2=CF--CH2--CH2--OH + OCN~ _
CF2 = CF - CH2 CH2--O--C--N H ~
If, in the preparation of compounds ofthe formula (I) accordingto process B),
for example 3,4,4-trifluorobut-3-ene-thiol and methyl chlorothioformate are
used as starting materials, then the reaction may be illustrated by the following
10 reaction scheme:
CF2 = CF--CH2--CH2--SH + Cl - 8--s - CH3
CF2 = CF - CH2--CH2--S--C - S--CH3
If, in the preparation of compounds ofthe formula (I) accordingto process C),
for example 3,4,4-trifluorobut-3-enyl chloroformate and cyclohexylamine are
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used as starting materials, then the reaction may be illustrated by the following
reaction scheme:
Il r~
- CF2 = CF--CH2--CH2--O--C--Cl + H2N
CF2=CF-CH2--CH2 O--C--NH~
If, in the preparation of compounds ofthe formula (I) accordingto process D),
5 for example 3,4,4-trifluorobut-3-enyl chlorothioformate and 2,6-
dimethylmorpholine are used as starting materials, then the reaction may be
- illustrated by the following reaction scheme:
O CH3
Il /~
CF2=CF--CH2 CH2--S--C--Cl + HN O
CH3 CH3
Il ~
CF2 = CF - CH2--CH2--S--C--NyO
CH3
All of the above-described processes Aa, A~, B, C and D for preparing
10 compounds ofthe formula (I) are characterized in that the reactions are carried
out in the presence of a diluent.
Suitable diluents in these processes are all conventional solvents.
.
Particularly suitable are optionally halo~enated aliphatic or aromatic
hydrocarbons, ethers or nitriles such as, for example, cyclohexane, toluene,
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chlorobenzene, chloroform, dichloromethane, dichloroethane, dioxane,
tetrahydrofuran, diethyl ether or acetonitrile.
All ofthe above-described processes Ao, B, C and D for preparing compounds
of the formula (I) are characterized in that the reactions are optionally carried
out in the presence of a base.
Suitable bases for the processes Ao, B, C and D are all conventional proton
acceptors. Particularly suitable are alkali metal hydroxides, or alkaline earth
metal hydroxides, alkali metal carbonates, or alkaline earth metal carbonates,
or alkali metal hydrogen carbonates, or alkaline earth metal hydrogen
10 carbonates, or nitrogen bases. Examples include sodium hydroxide, calcium
hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine,
dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclooctane
(DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU).
The above-described process A~B for preparing compounds of the formula (I) is
15 characterized in that the reaction is optionally carried out in the presence of a
catalyst.
Suitable catalysts are for example diazabicyclooctane (DABCO), triethylamine
or pyridine or organic tin compounds, such as, for example, dibutyltin
dilaurate.
The reaction temperatures in the above-described processes Ao, A~, B, C and
D may in each case be varied over a relatively wide range. In the processes Ao,
B, C and D, the reaction is generally carried out at temperatures between -1 0~Cand 150~C, preferably between 0~C and 90~C. In the process A~, the reaction
is generally carried out at temperatures between 0~C and 120~C, preferably
between 20~C and 100~C.
The ratio of the starting materials of the formulae (II) and (III) in the process
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Aa and of the formulae (IIa) and (III) in the process B, respectively, is
generally 1:1 to 2:1.
The ratio of the starting materials of the formulae (II) and (IV) in the processA~B is generally between 2:1 and 1:2; prefe~ably, equivalent amounts are
5 employed.
The ratio of the starting materials of the formulae (V) and (VI) in the process
C and of the formulae (VII) and (VIII) in the process D, respectively, are
generally between 1:1 and 10:1.
The above-described processes Aa) A~, B, C and D are generally carried out at
10 atmospheric pressure. Work-up in the above-described processes Ao, A~, B, C
and D is carried out by diluting the reaction mixture for example with water,
extracting with an organic solvent and concentrating the organic phase.
The starting materials of the formula (III) employed in the process Aa and A~
are known and may be prepared by known methods (cf. for example WO 92/ 15
555)-
The starting materials of the formula (III) or (IIIa) also employed in the
process Aa and B are known and/or may be prepared by known methods. The
compounds of the formula (III) or (IIIa) are for example obtained by reacting
alcohols, thiols or amines ofthe formula (VI) in a known manner and phosgene
20 or thiophosgene (cf. for example Houben-Weyl, Methoden der Organischen
Chemie, Volume E 4, page 407 ff., Georg Thieme Verlag Stuttgart, New York,
1983).
The iso(thio)cyanates of the formula (IV) employed as starting materials in the
process A~ are generally known chemicals for synthesis in organic chemistry.
25 The starting materials of the formula (V) employed in process C are novel but
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may be prepared by known methods. The compounds ofthe formula (V) are for
example obtained by reacting compounds of the formula (II) in a conventional
manner (see above) with phosgene or thiophosgene.
The starting materials of the formula (VI) also employed in the process C are
5 generally known chemicals for synthesis in organic chemistry.
The starting materials ofthe formula (VII) employed in the process D are novel
but may be prepared by known methods. The compounds of the formula (VII)
are for example obtained by reacting compounds of the formula (IIa) in a
manner known per se (see above) with phosgene or thiophosgene.
10 The starting materials of the formula (VIII) also employed in the process D are
generally known chemicals for synthesis in organic chemistry.
The active compounds are suitable for controlling animal pests, in particular
insects, arachnids and nematodes, which are encountered in agriculture, in
forestry, in the protection of stored products and of materials, and in the
15 hygiene field. They are particularly suitable for use as crop protection agents.
They are active ~q~in~t normally sensitive and resistant species and ~in~t all
or some stages of development. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium
vulgare and Porcellio scaber.
20 From the order ofthe Diplopoda, for example, Blaniulus ~Itt~ t~ls.
From the order of the Chilopoda, for example, Geophilus carpophagus and
Scutigera spec..
From the order of the Symphyla, for example, Scutigerella immaculata.
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From the order of the Thysanura, for example, Lepisma saccharina.
From the order ofthe Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta
americana, Leucophaea maderae, Blattella germanica, Acheta domesticus,
5 Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
From the order ofthe Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp..
From the order of the Anoplura, for example, Pediculus humanus corporis,
10 Haematopinus spp. and Linognathus spp..
From the order of the Mallophaga, for example, Trichodectes spp. and
Damalinea spp..
From the order ofthe Thysanoptera, for example, Hercinothrips femoralis and
Thrips tabaci.
15 From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus
intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and
Triatoma spp..
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia
tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae,
20 Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus
arundinis, Phylloxera vastatrix, Penphigus spp., Macrosiphum avenae, Myzus
spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis
bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax
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striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,
Pseudococcus spp. and Psylla spp..
From the order of the Lepidoptera, for example, Pectinophora gossypiella,
Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella,
S Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis
chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella,
Agrotis spp., Euxoa spp., Feltia spp., Earias in~~ Heliothis spp.,
Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura,
Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo
10 spp., Pyrausta nubilalis, Ephestia kuehn1ella, Galleria mellonella, Tineola
bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia
- podana, Capua reticulana, Choristoneura filmiferana, Clysia ambiguella,
Homona magnanima and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum,
15 Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,
Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon
cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis,
Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp.,
Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus ~imili~,
20 Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus
spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium
psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp.,
Melolontha melolontha, Amphimallon sol.~titi~ and Costelytra zealandica.
From the order ofthe Hymenoptera, for example, Diprion spp., Hoplocampa
25 spp., Lasius spp., Monomorium pharaonis and Vespa spp.
From the order ofthe Diptera, for example, Aedes spp., Anopheles spp., Culex
spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora
erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus
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spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus
spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia
hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis,
5 Ceratophyllus spp..
From the order ofthe Arachnida, for example, Scorpio maurus and Latrodectus
mactans.
From the order of the Acarina, for example, Acarus siro, Argas spp.,
Ornithodoros spp., Dermanyssus ~llin~e, Eriophyes ribis, Phyllocoptruta
10 oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma
spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus
spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp..
The phytoparasitic nematodes include Pratylenchus spp., Radopholus simili~,
Ditylenchus dipsaci, Tylenchulus semipenekans, Heterodera spp., Globodera
15 spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp.
and Trichodorus spp..
The compounds of the formula (I) according to the invention show, in
particular, an outstanding insecticidal and nematicidal activity. When employed
~,~in~ leaf-and soil-dwelling insects, they show a potent action for example
20 ~in.~t mustard beetle lavae (Phaedon cochleariae) and caterpillars of the
diamond-back moth (Plutella maculipennis). When employed ~in~t
nematodes, they have a potent action ~inst for example, Meloidogyne
incognita.
The active compounds according to the invention not only show protective, but
25 also leaf-systemic and root-systemic properties.
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The active compounds of the formula (I) according to the invention
furthermore also have fungicidal action, for example ~in~t Pyricularia oryzea
in rlce.
The active compounds can be converted into the customary formulations, such
5 as solutions, emulsions, wettable powders, suspensions, powders, dusting agents,
pastes, soluble powders, granules, suspension-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
10 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 andlor dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for
example, also be used as auxiliary solvents. As liquid solvents, there are suitable
15 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
20 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.
Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins,
25 clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth,
and ground synthetic minerals, such as highly disperse silica, alumina and
silicates, suitable solid carriers for granules are: for example crushed and
fractionated natural rocks such as calcite, marble, pumice, sepiolite and
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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
S esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, allyl sulphates, arylsulphonates as well as albumen
hydrolysis products; suitable dispersing agents are: for example lignin-sulphitewaste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers
10 in the form of powders, granules or latices, such as gum arabic, polyvinyl
alcohol and polyvinyl ~cet~te, 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
15 oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin
dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrientssuch as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general comprise between 0.1 and 95 per cent by weight of
active compound, prer~lably between 0.5 and 90%.
20 The novel active compound can be present 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 or herbicides. The insecticides include, for example,
25 phosphates, carb~ tes, carboxylates, chlorinated hydrocarbons, phenylureas
and substances produced by microorganisms, inter alia.
Examples of particularly advantageous components are the following
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Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2',6'-dibromo-2-
methyl-4'-trifluoromethoxy-4'-trifluoro-methyl- 1,3-thiazole-5-carboxanilide;
2,6-dichloro-N-(4-trifluoromethylbenzyl)-ben7~mide; (E)-2-methoxyimino-N-
S methyl-2-(2-phenoxyphenyl)-~cet~mi(le; 8-hydroxyquinoline sulphate; methyl
(E)-2- {2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}3-methoxyacrylate;
methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]~cet~te; 2-phenylphenol
(OPP), aldimorph, ampropylfos, ~nil~7ine, azaconazole,
benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S,
10 bromuconazole, bupirimate, buthiobate,
calcium polysulphide, captafol, captan, carbendazim, carboxin,
quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,
cufraneb, cymoxanil, cyproconazole, cyprofuram,
dichlorophen, diclobutrazol, diclofluanid, diclomezine, dicloran, diethofencarb,- 15 difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap,
diphenylamine, dipyrithione, ditalimfos, clit~i~non, dodine, drazoxolon,
edifenphos, epoxyconazole, ethirimol, etridiazole,
fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin,
fenpropimorph, fentin ~cet~te, fentin hydroxide, ferbam, ferimzone, fluazinam,
20 fludioxonil, fuoromide, fluquinconazole, flusilazole, flusulphamide, flutolanil,
flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl,
furmecyclox,
~l~7~tine,
hexachlorobenzene, hexaconazole, hymexazol,
25 im~7~1il, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,
isoprothiolane,
kasugamycin, copper preparations such as: copper hydroxide, copper
naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper
and Bordeaux mixture,
30 mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,
metconazole, methasulphocarb, methfuroxam, metiram, metsulphovax,
myclobutanil,
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nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,
ofurace, oxadixyl, oxamocarb, oxycarboxin,
pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin,
piperalin, polycarb~m~te, polyoxin, probenazole, prochloraz, procymidone,
5 propamocarb, propiconazole, propineb, pyrazophos, pyrifenox~ pyrimethanil,
pyroquilon,
quintozene (PCNB),
sulphur and sulphur preparations,
tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen,
10 thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon,
triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,
triforine, triticonazole,
validamycin A, vinclozolin,
zmeb, ziram.
15 Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,
kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole,
streptomycin, tecloftalam, copper sulphate and other copper preparations.
Insecticides/Acal;~id-s/Nemat;cides:
abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,
- alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,
Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin,
bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin,
butocarboxim, butylpyridaben,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap,
CGA 157419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,
chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin,
clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin,
cyhexatin, cypermethrin, cyromazine,
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deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,
diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,
diflubenzuron, dimethoate, dimet~ylvinphos, dioxathion, disulfoton,
eclif~nphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,
5 ethoprophos, etrimphos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,
fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion,
fenvalerate, fipronil, flll~7.in~m, flucycloxuron, flucythrinate, flufenoxuron,
flufenprox, fluv~lin~te, fonophos, formothion, fost~i~7~te7 fubfenprox,
10 furathiocarb,
HCH, heptenophos, hexaflumuron, hexythiazox,
imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,
ivermectln,
lambda-cyhalothrin, lufenuron,
15 m~l~tllion, mecarbam, mevinphos, mesulphenfos, metaldehyde, methacrifos,
methamidophos, methidathion, methiocarb, methomyl, metolcarb,
milbemectin, monocrotophos, moxidectin,
naled, NC 184, NI 25, nitenpyram,
omethoate, oxamyl, oxydemethon M, oxydeprofos,
20 parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,
phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,
profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,
pymetrozin, pyrachlofos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben,
pyrimidifen, pyriproxyfen,
25 quinalphos,
RH 5992,
salithion, sebufos, silafluofen, sulphotep, sulprofos,
tebufenozid, tebufenpyrad, tebupirimifos, teflubenzuron, tefluthrin, temephos,
terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox,
30 thiomethon, thionazin, thuringiensin, tralomethrin, triarathene, triazophos,
triazuron, trichlorfon, triflumuron, trimethacarb,
vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
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It is also possible to admix other known active compounds, such as herbicides,
or fertilisers and growth-promoting substances.
The active compounds according to the invention can furthermore be present
in their commercially available formulations and in the use forms prepared from
5 these formulations, as a mixture with synergistic agents. Synergistic agents are
compounds which increase the action ofthe active compounds, without it being
necessary for the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the commercially
available formulations can vary within wide lirnits. The active compound
concentration of the use forms can be from 0.0000001 to 95% by weight of
active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner a~propliate for the use
forms.
.
When used ~in~t hygiene pests and pests of stored products, the active
15 compound has an excellent residual action on wood and clay as well as a good
stability to alkali on limed substrates.
The active compounds according to the irivention are not only active ~in~
plant, hygiene and stored-product pests, but also, in the veterinary medicine
~ctor, ~g~in~t animal parasites (ectoparasites), such as ixodid ticks, argasid
20 ticks, scab mites, trombiculid mites, flies (stinging and sucking), parasitic fly
larvae, lice, hair lice, bird lice and fleas. The~ parasites include:
From the order of the Anoplurida, for example, Haematopinus spp.,
Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp..
From the order of the Mallophagida and the sub-orders Amblycerina and
25 Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,
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Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,
Trichodectes spp., Felicola spp..
From the order of the Diptera and the sub-orders Nematocerina and
Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium
5 spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,
Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp.,
Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp.,
Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp.,
Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp.,
10 Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and
Melophagus spp..
From the order of the Siphonapterida, for example, Pulex spp.,
Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus spp..
- From the order of the Heteropterida, for example, Cimex spp., Triatoma spp.,
15 Rhodnius spp. and Panstrongylus spp..
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta
americana, Blattela germanica and Supella spp..
From the sub-class of the Acaria (Acarida) and the orders of the Meta- and
Mesostigrn~t~, for example, Argas spp., Ornithodorus spp., Otabius spp., Ixodes
20 spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis
spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,
Pneumonyssus spp., Sternostoma spp. and Varroa spp..
From the order ofthe Actinedida (Prosti~n~t~) and Acaridida (Astigmata), for
example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp.,
25 Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus
spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp.,
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Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., C~todites spp. and Laminosioptes spp..
For example, they show an outstanding activity ~in~t Boophilus microplus
and Lucilia cuprina.
5 The active compounds of the formula (I) according to the invention are also
suitable for controlling arthropods which attack agricultural livestock, such as,
for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes,
rabbits, chickens, turkeys, ducks, geese, honeybees, other domestic ~nim~lc,
such as, for example, dogs, cats, cage birds, aquarium fish, and so-called
10 experimental ~nim~l~, such as, for example, h~rn~ters, guinea-pigs, rats and
mice. By controlling these arthropods, it is intended to reduce deaths and
decreased performances (in meat, milk, wool, hides, eggs, honey and the like),
so that more economical and simpler animal keeping is made possible by using
the active compounds according to the invention.
15 In the veterinary sector, the active compounds according to the invention areused in a known manner by enteral ~tlmini.~ration, for example in the form of
tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-throu~hmethod, suppositories, by parenteral ~-lmini~ration, such as, for example, by
means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal
20 and the like), implants, by nasal ~lmini~tration~ by dermal ~(lmini~tration, for
example in the form of dipping or bathing, spraying, pouring-on and spotting-
on, washing, dusting, and with the aid of shaped articles which comprise active
compound, such as collars, ear tags, tail marks, limb bands, halters, marking
devices and the like.
25 When ~lmini~tered to livestock, poultry, domestic animals and the like, the
active compounds of the formula (I) can be used as formulations (for example
powders, emulsions, flowables) which comprise the active compounds in an
amount of 1 to 80%, either directly or after dilution by a factor of 100 to
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10 000, or they may be used in the form of a chemical bath.
Furthermore, it has been found that the compounds ofthe formula 1 according
to the invention have a potent insecticidal action ~&qin~t insects which destroyindustrial materials.
5 The following insects may be mentioned by way of example and as being
preferred, but without any limit~tion:
Beetles, such as
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium
rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis,
10 Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus
linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus
spec., Tryptodendron spec., Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
Dermapterans, such as
15 Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.
Termites, such as
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,
Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus,
Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
20 Bristletails, such as Lepisma saccharina.
Industrial materials are to be understood as meaning, in the present context,
non-live materials, such as, preferably, synthetic materials, glues, sizes, paper
and board, leather, wood and timber products, and paint.
The materials to be very particularly preferably protected against attack by
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insects are wood and timber products.
Wood and timber products which can be protected by the composition
according to the invention or mixtures comprising such a composition are to be
understood as meaning, for example, construction timber, wooden beams,
5 railway sleepers, bridge components, jetties, wooden vehicles, boxes, pallets,containers, telephone poles, wood lagging, windows and doors made of wood,
plywood, particle board, joiner's articles, or wood products which, quite
generally, are used in the construction of houses or in joinery.
The active compounds can be used as such, in the form of concentrates or
10 generally customary formulations, such as powders, granules, solutions,
suspensions, emulsions or pastes.
.
The formulations mentioned can be prepared in a manner known per se, for
example by mixing the active compounds with at least one solvent or diluent,
emulsifier, dispersant and/or binder or fixative, water repellent, if appropriate
desiccants and UV stabilizers and, if appropriate, colorants and pigments and
other processing auxiliaries.
The insecticidal compositions or concentrates used for the protection of wood
and wooden materials comprise the active compound according to the
invention at a concentration of 0.0001 to 95% by weight, in particular 0.001 to
60% by weight.
The amount of the compositions or concentrates employed depends on the
species and the occurrence of the insects and on the medium. The optimum
rate of application can be determined upon use in each case by a test series.
However, in general, it suffices to employ 0.0001 to 20% by weight, preferably
0.001 to 10% by weight, of the active compound, based on the material to be
protected.
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- The solvent and/or diluent used is an organochemical solvent or solvent
mixture and/or an oily or oil-type organochemical solvent or solvent mixture of
low volatility and/or a polar organochemical solvent or solvent mixture and/or
water and, if appropliate, an emulsifier and/or wetting agent.
- S Organochemical solvents which are pref._.ably employed are oily or oil-type
solvents having an evaporation number of above 35 and a flashpoint of above
30~C, preferably above 45~C. Substances which are used as such oily and oil-
type solvents which have low volatility and are insoluble in water are suitable
mineral oils or their aromatic fractions, or mineral-oil-containing solvent
mixtures, preferably white spirit, petroleum and/or alkylbenzene.
Substances which are advantageously used are mineral oils with a boiling range
of 170 to 220~C, white spirit with a boiling range of 170 to 220~C, spindle oil
with a boiling range of 250 to 350~C, petroleum or aromatics of boiling range
160 to 280~C, essence of terpentine and the like.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range
of 180 to 210~C or high-boiling mixtures of aromatic and aliphatic
hydrocarbons with a boiling range of 180 to 220~C and/or spindle oil and/or
monochloronaphthalene, preferably a-monochloronaphthalene, are used.
The organic oily or oil-type solvents of low volatility having an evaporation
number of above 35 and a flashpoint of above 30~C, pref~,ably above 45~C, can
be partially replaced by organochemical solvents of high or medium volatility,
with the proviso that the solvent mixture also has an evaporation number of
above 35 and a flashpoint of above 30~C, prer~,lably above 45~C, and that the
insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.
In a preferred embodiment, part of the organochemical solvent or solvent
mixture or an aliphatic polar org~nochemical solvent or solvent mixture is
replaced. Substances which are preferably used are aliphatic organochemical
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solvents havinghydroxyl and/or ester and/or ether groups, such as, for example,
glycol ether, esters and the like.
The organochemical binders used within the scope of the present invention are
the synthetic resins and/or binding drying oils which are known per se and can
S be diluted with water and/or are soluble or dispersible or emulsifiable in the
organochemical solvents employed, in particular binders composed of, or
comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate,
polyester resin, polycondensation or polyaddition resin, polyurethane resin,
alkyd resin or modified allyd resin, phenol resin, hydrocarbon resin, such as
10 indene/coumarone resin, silicone resin, drying vegetable and/or drying oils
and/or physically drying binders based on a natural and/or synthetic resin.
The synthetic resin used as the binder can be employed in the form of an
emulsion, dispersion or solution. Up to 10% of bitumen or bituminous
substances can also be used as binders. In addition, colorants, pigments, water
15 repellents, odour-m~kingsubstances and inhibitors or anticorrosives known per se and the like can also be employed.
The composition or the concentrate preferably comprises, in accordance with
the invention, at least one alkyd resin or modified alkyd resin and/or a drying
vegetable oil as the organochemical binder. Preferably used according to the
invention are alkyd resins with an oil content of over 45% by weight, preferably- 50 to 68% by weight.
All or some of the abovementioned binder can be replaced by a fixative
(mixture) or a plastici_er (mixture). These additives are intended to prevent
vol~tili7~tion ofthe active compounds and cryst~lli7~tion or precipitation. Theypreferably replace 0.01 to 30% of the binder (based on 100% of binder
employed).
The plastici_ers are from the chemical classes of the phthalic esters, such as
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dibutyl pht~ te, dioctyl phthalate or benzylbutyl ph~ te, the phosphoric
esters, such as tributyl phosphate, the adipic esters, such as di-(2-ethylhexyl)adipate, the stearates, such as butyl stearate or amyl stearate, the oleates, such
as butyl oleate, the glycerol ethers or relatively high-molecular-weight glycol
5 ethers, glycerol esters and p-toluenesulphonic esters.
Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example,
polyvinyl methyl ether, or ketones, such as benzophenone or
ethylenebenzophenone .
Particularly suitable as a solvent or diluent is also water, if a~prop~iate as a10 mixture with one or more of the abovementioned organochemical solvents or
diluents, emulsifiers and dispersants.
Particularly effective protection of wood is achieved by large-scale industrial
impregnation processes, for example vacuum, double-vacuum or pressure
processes.
15 If appropriate, the ready-to-use compositions can additionally comprise other insecticides and, if ap~uro~liate, additionally one or more fungicides.
Suitable additional components which may be admixed are, preferably, the
insecticides and fungicides mentioned in WO 94/29 268. The compounds
mentioned in that document are expressly incorporated into the present
20 application by reference.
Very particularly preferred components which may be admixed are insecticides,
such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin,
cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron,
hexaflumuron and triflumuron,
25 and fungicides, such as epoxyconazole, hexaconazole, azaconazole,
propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,
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dichlofluanid, tolyl~uanid, 3-iodo-2-propinylbutyl carb~ te, N-octyl-
isothiazolin- 3 - one and 4, 5- dichloro-N - octylisothiazolin- 3- one .
The preparation and the use of the active compounds according to the
invention can be seen from the examples which follow.
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Prepa~tion eY~nlples
Fl~an~ple I-1
CF2= CF-CH2-CH2-O-CO-OC2Hs (I-l)
5.4 g (50 mmol) of ethyl chloroformate and then, while cooling with ice, 5.4 g
(53 mmol) of triethylamirle are added dropwise to a solution of 6.3 g (50 mmol)
of 3,4,4-trifluorobut-3-enol in 50 ml of methylene chloride. The solution is
allowed to warm to 20~C, and stirring is continued overnight. After dilution
with water, the product is extracted with ethylene chloride and the extract is
concentrated under reduced pressure. The residue is distilled at 30 mm, the
ethyl (3,4,4-trifluorobut-3-enyl) carbonate ~ tilling over at 80~C.
Yleld 2.9 g (30% of theory).
Example I-2
F O F
~--' O--C--NH~ (I-2)
3.5 g (22.5 mmol) of 2,6-difluorophenyl isocyanate are added to a solution of
2.8 g (20 mmol) of 3,4,4-trifluorobut-3-enol in 20 ml of methylene chloride.
A~er stirring overni~ht at 40~C, the solution is washed with water and the
organic phase is separated off and dried over magnesium sulphate. Under
reduced pressure, the solvent is removed and the residue is triturated with
cyclohexane.
Yield 5.4 g (96% of theory).
mp. 56-60~C
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Example I-3
f
F ~--~ o--CH2 CON~ (I - 3)
With stirring~ 5.65 g (30 mmol) of 3,4,4-trifiuorobut-3-enyl chloroformate are
added dropwise at 10~C to a solution of 5.0 g(32 mmol) of hydroxy~cet~mido-
S N,N-hexamethylene and 3.1 g (30 mmol) of triethylamine in 50 ml of
dichloromethane. The solution is stirred overnight, diluted with
dichloromethane and washed with water. The organic phase is separated o~and
evaporated under reduced pressure, and the oily residue is chromatographed on
silica gel using the eluent system chloroform/ethyl acetate (4:1). 4.2 g (Yleld
45.6% of theory) of the desired carbonate are obtained as an oil of log p=2.47.
The following compounds of the formula (I) are obtained analogously and in
accordance with the general preparation instructions:
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Table 1
CF2 C--CH2 CH2--R2
R' (I)
- E~ No. R' R2 Physical
constant
I-4 F O n20= 1.4055
--O--C--NH-CH3
I-5 F o log p* (pH 2 ) =
--O--C--NH~CI 3.31
I-6 F ~ CF3 logp (pH 2) =
11 /~< 3.55
--O--C--NH~>
I-7 F o Cl logp (pH 2) =
Il /~< 3.82
--O--C--NH ~CI
I- 8 F F3C log p (pH 2)
Il ~\ 3.22
--o--C--NH~>
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E~ No. R' R2 Physical
constant
I-9 ~ 0\2Hs logp (pH 2) =
Il )~\ 2.44
--0--C--NH--S02~
I-10 F CH3 logp (pH 2) =
e >~ 2.46
--0--C--NH--S02~
I- 11 F Cl log p (pH 2)
8 ~, 2.37
--0--C--NH--S02~
I-12 FCH300C logp (pH 2) =
e ~ 2.31
--0--C--NH--S02~
I-13 F O Cl logp (pH 2) =
--0--C--NH ~ 3 .98
CF3
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E~ No. Rl R2 Physical
constant
I-14 F ~ CH3 logp (pH 7,5)
--O--C--N O = 2.56
\ <
CH3
I-15 F r~ logp (pH 2) =
1~l Y 4.20
--O--C--N
C2H5
I- 16 F 8 n20 = 1.3890
--O--C--OCH2CH(CH3)2
I-17 F 8 1~l logp (pH 2) =
--O--C--NH--C--O-(CH2)2 OCH3 1.47
I- 18 F 8 nD~ = 1.4570
--O--C--NH2
I- 19 F 8 o n20 = 1.4465
--O--C--NH--C--O-CH2--CCI3
I-20 O o o\cH(cH3)2 logp (pH 2) =
--O--C--NH--C--0~ 2.86
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E~ No. R' R2 Physical
constant
I-21 F R mp. 132~C
--O--C--O--CH2~CI
I-22 F R logp (pH 2) =
--O--C--NH--CH2~CI 3.12
I-23 F R R ~ logp (pH 2) =
--O--C--O--CH2--C N~ j 2.47
I-24 F R logp (pH 7,5)
--o--c--s--cH2~ = 4.10
I-25 F 1~l 1~l nD~= 1.4380
--O--C--NH--C--O--(CH2)2--C, H--CH2 C(CH3)3
I-26 F O logp pH 2 =
CF2=CF--CH2--CH2 0--1--N~ 2,40
I-27 F CF2=CF-CH2-CH2-O-CO-NH-CO- nD~= 1.4290
OC2H5
I-28 F ~CH3 nD~ = 1.4780
CF2=CF--CH2--CH2--O--CO--N~
S-CCI3
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Ex. No. R' R2 Physical
constant
I-29 F ~~ n20= 1.4261
CF2=CF--CH2--CH2--O -CO--O--CH2--C
CH30 CH3
I-30 F 8 fH3 ~CH3 nD = 1.4800
CF2=CF--CH2--CH2--O--C--N ~
I-31 F R ~CH(CH3)2 logp (pH 2) =
CF2=CF--CH2--CH2--O--C--N [~3 3 54
OCH3
I-32 F CF2=CF--CH2--CH2--o--co--NH--CH2COOH n20 = 1.4280
I-33 F R f mp.: 56~C
CF2=CF--CH2 CH2--O--C--NH--CH-COOH
I-34 F R mp.: 96~C
CF2=CF--CH2--CH2--O--C--NH--fH-COOH
CH2
- I-35 F 1~l mp.: 54~C
~ - CF2=CF--CH2--CH2--O--C--NH ~OCF3
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- E~ No. R' R2 Physical
constant
I-36 o CH3 Cl logp (pH 2) =
CF2=CF--CH2--cH2--o--c--l~c~ 3,92
I-37 F 1l mp.: 52~C
CF2=CF--CH2--CH2 0--C--NH--O
~ log p = Logarithm of the partition coefficient p of the substance between
- the solvents octanol and water, experimentally determined by
reversed phase HPCL.
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~n~ple I-38
Il
CF2=CF-CH2-CH2-S-C--NH-CH2-COOCH3
3 ml (0.05 mol) of CS2 are added dropwise at room temperature to 10.1 g (0.1
mol) oftriethylamine and 6 g (0.048 mol) of methyl glycinate hydrochloride in
S 50 ml of tetrahydrofuran (THF). After stirring for about 25 minutes at room
temperature, 9.45 g (0.05 mol) of 4-bromo- 1,1,2-trifluorobut- 1-ene are slowly
added and stirring at room temperature is continued overnight. The solvent is
removed under reduced pressure and the residue is taken up in ether. The
solution is washed 4 times with water and dried over magnesium sulphate, and
10 the ether is removed under reduced pressure. The residue is chromatographed
(silica gel, HPLC using 14% ethyl ~cet~te/hexane). 7.8 g of crude product are
obtained, 4.3 g of which are kept in the freezer until crystals have formed. Afcer
fast filtration and drying under reduced pre~re, 2.5 g of the above-illustrated
compound are obtained as a colourless solid of mp: 37-39~C.
- 15 Elemental analysis:
Element calculated found
- C 35.16 35.26
H 3.69 3.70
- N 5.13 5.10
S 23.46 23.40
Example I-39
ls
F2=CF-CH2-CH2-S-c--O-C2H5
While coolingwith ice, 6.24 g(0.033 mol) of 4-bromo-l~l~2-kifiuorobut-l-ene
are added to S g (0.03 mol) of potassium ethylxanthate in 35 ml of
25 dimethylformamide (DMF), and stirring is continued overnight at room
temperature. The mixture is poured onto 300 ml of water and extracted with
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ether. The ether phase is washed 4 times with water, dried over magnesium and
concentrated under reduced pressure. 5.52 g ofthe above-illustrated compound
are obtained as a clear yellow liquid.
Elemental analysis:
Element calculated found
C 36.51 36.63
- H 3.94 3.97
S 27.85 27.74
Fx~mple I-40
IS
CF2=CF-CH2-CH2-S-C--NH-CH2-COOC(CH3)3
The compound is prepared by the method of Example I-38 employing in~tea(l
of methyl glycinate hydrochloride an equivalent amount of tert-butyl glycinate
hydrochloride.
- The crude product obtained after workup is recryst~lli7ecl 2 times from 20%
15 ethyl acetate/hexane. 2.35 gofthe above-illustrated compound are obtained as
a colourless solid of mp: 70-72~C.
Elemental analysis:
Element calculated found
C 41.89 42.04
H 5.11 5.05
N 4.44 4.43
- S 20.33 20.27
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~n~ple I-41
lSI
CF2=CF-CH2-CH2-S-C--O-CH2-P(=O)(OC2H5)2
Step A
41.43 g (0.3 mol) of diethyl phosphite, 9 g (0.3 mol) of paraformaldehyde and
3.04 g (0.03 mol) of triethylamine are heated at 60 to 70~C. An exothermic
reaction sets in, the temperature rises to 120 to 125~C and the solution becomesclear. The solution is stirred for 10 minutes at 120~C, cooled, some methylene
chloride is added and the solution is concentrated under reduced pressure. The
residue is dried under reduced pressure. 49.6 g of the compound of the formula
10 HO-CH2-P(=O)(OC2H5)2 is obtained as a clear liquid.
Step B
While cooling with ice, 3.89 g (0.059 mol) of 85% strength KOH are added
slowlyto 10 g(0.059 mol) ofthe compound obtained in step Ain 20 ml of CS2.
The solution is stirred for 2 hours at room temperature, 150 ml of ether are
added and stirring is continued for a further 2 hours. The precipitate is filtered
of~ washed with ether and dried under reduced pressure. 13.69 g of the
- compound of the formula
lSI
K S-C-O-CH2-P(=O) (~C2H5)2 are obtained as a yellow solid.
Step C
At room temperature, 5 g (0.0177 mol) ofthe compound obtained in step B are
added a little at a time to 4 g (0.022 ml) of 4-bromo-1,1,2-trifluorobut-1-ene
in 30 ml of DMF. The reaction mixture is stirred overnight at room
- temperature, poured on 300 ml of water and extracted with ether. The ether
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phase is washed 4 times with water, dried over magnesium sulphate and
concentrated. 4.76 g of the above-illustrated final product are obtained as a
clear yellow liquid.
Elemental analysis:
Element calculated found
C 34.09 34.18
H 4.58 4.58
S 18.20 18.14
Example I-42
s
10CF2=cF-cH2-cH2-s-a--O-CH2-P(=O)(OH)2
While coolingwith ice, 10.3 ml (0.078 mol) oftrimethylsilyl bromide in 10 ml
of acetonitrile are added dropwise to 2.3 g (0.0065 mol) of the compound of
Example I-41 in 15 ml of acetonitrile. The solution is stirred overni~ht at roomtemperature, and the solvent is removed under reduced pressure. The residue is
15 stirred for 4 hours at room temperature with an excess of methanol. The
methanol is subsequently removed under reduced pressure and the product is
dried under reduced pressure. 1.96 g of the above-illustrated compound are
obtained as a colourless solid of mp: 73-75~C.
Elemental analysis:
Element calculated found
C 24.33 24.38
H 2.72 2.70
S 21.65 21.75
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~,Y~n~le I-43
S
CF2=cF-cH2-cH2-s-c--N(CH3)-CH2-COOC(CH3)3
This compound is prepared by the method of Example I-38 employing in~te~1
of methyl glycinate hydrochloride an equivalent amount of tert-butyl
S N-methylglycinate hydrochloride.
Colourless solid of mp: 35-37~C.
Elemental analysis:
Element calculated found
C 43.76 43.83
H 5.51 5.52
N 4.25 4.23
S 19.47 19.40
FYan~ple I-44
S
CF2=cF-cH2-cH2-s-c--N(CH(CH3)2)2
15 EYample I-45
S
CF2=CF-CH2-CH2-S-c--N(C2H5)2
EYample I-46
s
CF2=CF-CH2-CH2-S-C--NH-CH2-CH2-CN
The compounds of Examples I-44, I-45 and I-46 are prepared by the method
20 of Example I-38 starting from the corresponding precursors.
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Prep~n~tion of sta~ t~nals
F,Y~n~le V-1
F
F ~'~ OCOCI (V- 1)
F
.
While cooling with ice and stirring, 28 g (0.28 mol) of phosgene are passed
S through 30 g (0.24 mol) of 3,4,4-trifluorobut-3-enol, and the mixture is then
stirred at 20~C for a further S h. A~er blowing off excess phosgene with
nitrogen, the oily residue is distilled. 21.2 g of colourless chloride of boiling
point 72-74~C/ 100 mm are obtained. (Yleld 46.8 of theory).
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Fx~mple A
Critical concentration test
Test hematode: Meloido~ne incognita
Solvent: 4 parts by weight of acetone
S Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable ~r~alation 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 ~ ted with water to the desired
concentration.
.
10 The preparation of active compound is intimately mixed with soil heavily
cont~min~ted with test nematodes. The concentration ofthe active compound
in the preparation is of practically no importance, only the amount of active
compound per unit volume of soil, which is given in ppm (= mg/l), being
decisive. The treated soil is transferred into pots and these are seeded with
15 lettuce and kept at a greenhouse temperature of 25~C.
After three weeks, the lettuce roots are examined for inf~st~tion with nematodes(root knots) and the degreee of effectiveness of the active compound in % is
determined. The degree of effectiveness is 100% if inf~st~tion has been
prevented completely, and it is 0% if the level of infestation is as high as in the
20 control plants in untreated but equally contaminated soil.
In this test, a degree of effectiveness of 100% was shown for example by the
compounds of Preparation Examples I-4 and I-5 at an exemplary active
compound concentration of 20 ppm.
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Fx~n~ple R
Phaedon larvae test
Soivent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
5 To produce a suitable preparation of active compound, 1 part by weight of
active compound is mixed with the stated amount of solvent and the stated
amount of emulsifier, and the concenkate is diluted with water to the desired
concentration.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the
10 preparation of the active compound of the desired concentration and are
infested with mustard beetle larvae (Phaedon cochleariae), as long as the leavesare still moist.
After the specified period of time, the destruction in % is determined. 100%
means that all the beetle larvae have been killed; 0% means that none of the
15 beetle larvae have been killed.
In this test, a destruction of 100% was brought about, after 7 days, for exampleby the compound of Preparation Example I-6 at an exemplary active
compound concentration of 0.1%.
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Ex~mple C
Plutella test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
5 To produce a suitable preparation of active compound, 1 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.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the
10 preparation of active compound of the desired concentration and are infested
with caterpillars of the diamond-back moth (Plutella maculipennis) while the
leaves are still moist.
A~er the specified period of time, the destruction in % is determined. 100%
- means that all the caterpillars have been killed; 0% means that none of the
15 caterpillars have been killed.
In this test, a destruction of 100% was brought about, a~er 7 days, for example
by the compounds of Preparation Example I-2, I-4, I-5, I-6 and I-8 at an
exemplary active compound concentration of 0.1%.
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Fx~mple D
Spodoptera test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of allylaryl polyglycol ether
5 To produce a suitable preparation of active compound, 1 part by weight of
active compound is mixed with the stated amount of solvent and the stated
amount of emulsifier, and the concentrate is (lilllte~l with water to the desired
concentration.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the
10 preparation of active compound of the desired concentration and are infested
with caterpillars of the owlet moth (Spodoptera frugiperda), as long as the
leaves are still moist.
After the specified period of time, the destruction in % is determined. 100%
means that all the caterpillars have been killed; 0% means that none of the
15 caterpillars have been killed.
In this test, a destruction of 100% was brought about, after 7 days, for exampleby the compounds of Preparation Examples I-5 and I-7 at an exemplary active
compound concentration of 0.1%
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Example ~
Nephotettix test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
5 To produce a suitable preparation of active compound, 1 part by weight of
active compound is mixed with the stated amount of solvent and the stated
amount of emulsifier, and the concenkate is diluted with water to the desired
concentration.
Rice see~1lings (Oryzae sativa) are treated by being dipped into the prearation of
10 the active compound ofthe desired concnetration and are infested with larvae
ofthe green rice lea~opper (Nephotettix cincticeps) while the see~llings are still
moist.
After the desired period of time, the destruction in % is determined. 100%
means that all the leafhoppers have been killed; 0% means that none of the
15 leafhoppers have been killed.
In this test, a destruction of 100% was brought about, after 6 days, for exampleby the compounds of Preparation Examples, I-2, I-4, I-5, I-6, I-7 and I-8 at
an exemplary active compound concentration of 0.1%.
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Example F
Test with boophilus microplus resistant/Sp-resistant Parkhurst strain
Test ~nim~ adult females which have sucked.
Solvent: 35 parts by weight of ethylene glycol monmethyl ether
5 Emulsifier: 35 parts by weight of nonylphenol polyglycol ether
To produce a suitable formulation, 3 parts by wei~ht of active compound are
mixed with seven parts by weight of the solvent-emulsifier mixture indicated
above, and the concentrate thus obtained is diluted with water to the desired
concentration.
10 10 adult Boophilus microplus res. are immersed for 1 minute in the active
compound ~r~a~alion to be tested. After transfer to plastic beakers and storage
in a controlled environment chamber, the degree of destruction is determined.
100% means that all ticks have been killed; 0% means that no ticks have been
killed.
15 In this test, a destruction of 100% was brought about for example by the
compounds of the Preparation Examples I-5, I-6 and I-7 at an exemplary
active compound concentration of 1000 ppm.
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mple G
Test with blow~y larvae/ development-inhibitory action
Test animals: lucilia cuprina larvae
Solvent: 35 parts by weight of ethylene glycol monomethyl ether5 Emulsifier: 35 parts by weight of nonylphenol polyglycol ether
To produce a suitable formulation, 3 parts by weight of active compound are
mixed with seven parts by weight of the abovementioned solvent-emulsifier
mixture, and the resulting emulsion concentrated is diluted with water to the
desired concentration.
10 About 20 larvae are inkoduced into a test tube which contains about 1 cm3 of
horse meat and 0.5 ml of the active compound preparation to be tested. A~er
24 and 48 hours, the activity of the active compound preparation is examined.
The test tubes are transferred to beakers whose bottom is covered with sand.
After a further 2 days, the test tubes are removed and the pupae are counted.
15 The activity of the active compound preparation is judged by the number of
hatched flies after 1.5 times the development time of an untreated control.
100% means that no flies have hatched; 0% means that all flies have hatched
normally.
In this test, a destruction of 100% was brought about, for example, by the
20 compounds of Preparation Examples I- 1, I-4 and I-8 at an exemplary active
compound concentration of 1000 ppm.
CA 02204241 1997-0~-01
T e A 30 693-Forei~ Col]ntries
59
Example H
Nematode test (tomato and soya bean)
The test is carried out as described in US patent no. 5.389.680. This description
is expressly incorporated in the present application.
S In this test (Method 2) the compound of Preparation Example I-39 showed an
activity of 91 to 100% at a concentration of 1 mg per pot, an activity of 75 to
90% at a concentration of 0.2 mg per pot, and an activity of less than 50% at
a concentration of 0.04 mg per pot.
