CA2204241A1 - Fluorobutenyl esters and their use for controlling animal pests - Google Patents

Abstract

Fluorobutenyl esters have the formula (I), in which R1 stands for hydrogen or a halogen, and R2 stands for one of the groups (a), (b) or (c), in which V, Y, Z, R3 and R5 have the meanings given in the description. Also disclosed are a process and intermediate products for preparing said esters, as well as their use for controlling animal pests.

Description

T e A 30 693-Forei~ Co~lntries / Ba/Kr/bo/SP
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, CA 02204241 1997-0~-01 - Le A 30 693-Forei~ colmtries 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 CA 02204241 1997-0~-01 Le A 30 693-Forei3~ co~mtries 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 CA 02204241 1997-0~-01 - ' T e A 30 693-Fore~ countries 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 Le A 30 693-Foreif~ collntries 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 T e A 30 693-Forei~ co~lntries 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, CA 02204241 1997-0~-01 Le A 30 693-Forei3~ collntries 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) 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 Le A 30 693-Forei~ collntries 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 CA 02204241 1997-0~-01 Le A 30 693-Forei~ countries 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, CA 02204241 1997-0~-01 T e A 30 693-Forei~ co~ tries 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, CA 02204241 1997-0~-01 Le A 30 693-ForeiPn collntries 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 CA 02204241 1997-0~-01 Le A 30 693-Forei~ co-lntries 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-CA 02204241 1997-0~-01 Le A 30 693-Foreigr countries 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.

CA 02204241 1997-0~-01 e A 30 693-Forei~ co--ntries 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.

CA 02204241 1997-0~-01 .
Le A 30 693-Forei~ countries 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:

CA 02204241 1997-0~-01 Le A 30 693-Foreigr countries 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 Le ~ 30 693-Forei~ collntries 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:

Il /~
CF2=CF--CH2 CH2--S--C--Cl + HN O

Il ~
CF2 = CF - CH2--CH2--S--C--NyO

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, CA 02204241 1997-0~-01 I e A 30 693-Fore~ collntries 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 CA 02204241 1997-0~-01 Le A 30 693-Forei~ collntries 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 CA 02204241 1997-0~-01 T e A 30 693-Forei~ collntries 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.

CA 02204241 1997-0~-01 Le A 30 693-Forei~ countries 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 CA 02204241 1997-0~-01 T e A 30 693-ForeiPn collntries 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 CA 02204241 1997-0~-01 Le A 30 693-Forei~ collntries 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.

CA 02204241 1997-0~-01 T e A 30 693-Forei~ collntries 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 CA 02204241 1997-0~-01 Le A 30 693-Forei~ countries 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 CA 02204241 1997-0~-01 T e A 30 693-Forei~ countries 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, CA 02204241 1997-0~-01 Le A 30 693-Foreigr countries 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, CA 02204241 1997-0',-01 ~ T e A 30 693-ForeiPn co~-ntries 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.

CA 02204241 1997-0~-01 - I e A 30 693-Forei~ countries 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., CA 02204241 1997-0~-01 Le A 30 693-Forei~ collntries 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., CA 02204241 1997-0~-01 T e A 30 693-Forei~ collntries 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 - CA 02204241 1997-0~-01 T e A 30 693-Foreigr countries 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 CA 02204241 1997-0~-01 Le A 30 693-Forei~ co-lntries 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.

CA 02204241 1997-0~-01 Le A 30 693-Forei~ collntries - 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 CA 02204241 1997-0~-01 r e A 30 693-Forei~ countries 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 CA 02204241 1997-0~-01 T e A 30 693-Forei~ co-]ntries 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, T e A 30 693-Fore~ countries 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.

CA 02204241 1997-0~-01 T e A 30 693-Forei~ countries 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

CA 02204241 1997-0~-01 T e A 30 693-Forei~ collntries 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:

T e A 30 693-Fore~ Co--ntries Table 1 R' (I) - E~ No. R' R2 Physical constant I-4 F O n20= 1.4055 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~>

T e A 30 693-Forei~ Collntries 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 Le A 30 693-Forei~ Countries E~ No. Rl R2 Physical constant I-14 F ~ CH3 logp (pH 7,5) --O--C--N O = 2.56 \ <

I-15 F r~ logp (pH 2) =

1~l Y 4.20 --O--C--N

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 I- 19 F 8 o n20 = 1.4465 I-20 O o o\cH(cH3)2 logp (pH 2) =
--O--C--NH--C--0~ 2.86 T e A 30 693-Fore~ Countries 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 I-28 F ~CH3 nD~ = 1.4780 CF2=CF--CH2--CH2--O--CO--N~

Le A 30 693-Forei~ Countries Ex. No. R' R2 Physical constant I-29 F ~~ n20= 1.4261 CF2=CF--CH2--CH2--O -CO--O--CH2--C

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 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

- I-35 F 1~l mp.: 54~C
~ - CF2=CF--CH2--CH2--O--C--NH ~OCF3 ~,e A 30 693-Forei~ Collntries - 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.

-CA 02204241 1997-0~-01 Le A 30 693-Forei~ Countries ~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 CA 02204241 1997-0~-01 -T e A 30 693-Forei~ Collntries 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 CA 02204241 1997-0~-01 T e A 30 693-Forei~ Collntries ~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 CA 02204241 1997-0~-01 T e A 30 693-Fore~ Collntries 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 CA 02204241 1997-0~-01 e A 30 693-ForeigJl Collntries ~,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.

T,e A 30 693-Fore~ Countries 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).

CA 02204241 1997-0~-01 T e A 30 693-Forei~ Collntries 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.

CA 02204241 1997-0~-01 - T e A 30 693-Fore~ Collntries 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%.

CA 02204241 1997-0~-01 - / T e A 30 693-Forei~ Co-lntries 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%.

CA 02204241 1997-0~-01 T e A 30 693-Forei~ Col-ntries 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%

CA 02204241 1997-0~-01 .
T e A 30 693-Fore~ Collntries 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%.

CA 02204241 1997-0~-01 -l e A 30 693-Forei~ Countries 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.

CA 02204241 1997-0~-01 T e A 30 693-Forei~ Collntries 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 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.

Claims (11)

claims

1. Compounds of the formula (I) (I) in which R1 represents hydrogen or halogen and R2 represents one of the groups (a) or (b) (a) or (b) in which Y represents oxygen or sulphur, 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) (c) in which V represents oxygen or NR6 and R5 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, hydroxyl, 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 or an amide of the acids mentioned, the amide being optionally mono- or disubstituted by alkyl, or R5 and R6 represent 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 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, one of the radicals OR7, COR7, NR7R8, SO2R9 or P(=O)R10R11, R7 and R8 each representing independently of one another hydrogen, alkyl or aryl, R9 representing hydrogen, alkyl, halogenoalkyl or aryl and R10 and R11 each representing independently of one another hydrogen, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, amino, alkylamino, dialkylamino or arylamino, and their salts.

2. Compounds of the formula (Ia) CF2= (Ia) in which R1, R3, Y and Z have the meaning given in Claim 1.

3. Compounds of the formula (Ib) F2= (Ib) in which R1, R3, and Y have the meaning given in Claim 1.

4. Compounds of the formula (Ic) (Ic) in which R1, R5, and V have the meaning given in Claim 1.

5. Process for preparing compounds of the formula (Ia) or (Ib) according to Claim 2, characterized in that A) fluorobutenols of the formula (II) (II) in which R1 has the meaning given in Claim 1 are reacted a) with compounds of the formula (III) (III) in which Y, Z and R3 have the meanings given in Claim 1, in the presence of a diluent and optionally in the presence of a base, or .beta.) with an iso(thio)cyanate ofthe formula (IV) YCN-R3 (IV) 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 of the formula (IIa) (IIa) in which R1 has the abovementioned meaning are reacted with a compound of the formula (IIIa) (IIIa) in which Y 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) (V) in which R1 and Y have the abovementioned meanings are reacted with a compound ofthe formula (VI) H-Z-R3 (VI) in which Z and R3 have the abovementioned meanings, in the presence of a diluent and optionally in the presence of a base, or D) compounds of the formula (VII) (VII) in which R1 and Y have the abovementioned meanings are reacted with a 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.

6. Compounds of the formula (V) (V) in which R1 and Y have the meanings given in Claim 1.

7. Compounds of the formula (VII) (VII) in which R1 and Y have the meanings given in Claim 1.

8. Pesticides, characterized in that they comprise at least one compound of the formula (I) according to Claim 1.

9. Use of compounds of the formula (I) according to Claim 1 for controlling animal pests.

10. Method for controlling animal pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on the pests and/or their habitat.

11. Process for preparing compositions for the control of animal pests, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and/or surface-active agents.