CA2023464A1 - Butyric acid derivatives - Google Patents

Butyric acid derivatives

Info

Publication number
CA2023464A1
CA2023464A1 CA002023464A CA2023464A CA2023464A1 CA 2023464 A1 CA2023464 A1 CA 2023464A1 CA 002023464 A CA002023464 A CA 002023464A CA 2023464 A CA2023464 A CA 2023464A CA 2023464 A1 CA2023464 A1 CA 2023464A1
Authority
CA
Canada
Prior art keywords
chloro
hydrogen
acid
difluorobutyric acid
difluorobutyric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002023464A
Other languages
French (fr)
Inventor
Peter Maienfisch
Eginhard Steiner
Manfred Boger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of CA2023464A1 publication Critical patent/CA2023464A1/en
Abandoned legal-status Critical Current

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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
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    • A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
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Abstract

PS/5-17701/1+2/+

Butyric acid derivatives Abstract Novel 4-chloro-4,4-difluorobutyric acid derivatives of formula I
(I),

Description

2023~6~

PS/5-17701/1+2/+

Butyric acid derivatives The present invention relates to novel derivatives of 4-chloro-4,4-difluorobutyric acids, to processes and intermediates for their preparation, to pesticidal compositions that contain those compounds, and to their use in pest control.

The 4-chloro-4,4-difluorobu~yric acid derivatives according to the invention correspond to formula I

C1F2C--fH--fH--~;--X--R3 (I) wherein Rl and R2 independently of one another are hydrogen, Cl-C4alkyl or Cl-C4haloalkyl, R3 is hydrogen or an organic radical and X is oxygen or -NR4-, in which R4 is hydrogen or C1-C6aLkyl.

In the literature, the class of polyhalogenated butyric acid chlorides as intermediates for pyrethroidal haloketones is known from Helv. Chim. Acta 63, p. 1947-1957 (1980).
The organic radical mentioned in the definition of R3 is any organic radical that can be bonded in the form of an alcohol or of an amine to the carbonyl group of 4-chloro-4,4-di-fluorobutyric acid. Preferably, the alcohol or amino function of that organic radical is bonded to a carbon atom. Accordingly, the radical R3 is preferably bonded via a carbon atom to the -CO-X group. For example, R3 is Cl-C20alkyl, C3-qcycloalkyl, C3-C20alkenyl, C3-C20alkynyl, benzyl or aryl, each of which is substituted or unsubstituted. Within the scope of the present invention, R3 is preferably Cl-C20aL"yl, C3-C7cycloalkyl, C3-C20alkenyl, C3-C20alkynyl, aryl, C3-C20haloalkenyl, C3-C20halo-alkynyl; C3-C7cycloalkyl substituted by halogen or by Cl-C4alkyl; aryl substituted by halogen, Cl-C4alkyl, C1-C4haloalkyl, Cl-C12alkoxy, Cl-C4haloalkoxy, Cl-C4alkylthio, nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, Cl-C4alkylphenoxy, 2023~64 C1-C4haloalkylphenoxy, tri-C1-C4alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C1-C4alkylamino, di-C1-C4alkylamino, anilino, N-C1-C4alkylanilino, N-formylanilino, N-C1-C6alkylcarbonylanilino, phenylthio or by halophenylthio; phenyl substituted by an unsubstituted or substituted, aromatic or non-aromatic, monocyclic or bicyclic heterocycle that is bonded via oxygen or sulfur, in which both the heterocycle and the phenyl ring may each be substituted by halogen, C1-C4alkyl, nitro, C1-C4haloalkyl, C1-C4haloalkoxy, C1-C4alkoxy, C1-C4alkylthio or by cyclopropyl; or C1-C20alkyl substituted by hydroxy, halogen, di-C1-C4alkylamino, Cl-C4alkoxy, Cl-C4haloalkoxy, C2-C6alkoxyalkoxy, Cl-C~haloalkylthio, Cl-C4-alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkylsulfonyloxy, C1-C4alkyl-carbonyl, C1-C4alkoxycarbonyl, C1-C6alkylcarbonyloxy, C3-C7cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or by pyridyl, in which the aryl and pyridyl groups may each be substituted by halogen, C1-C4alkyl, C1-C4-haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.

In the definition of forrnula I according to the invention, the individual generic terms should be understood as having the following meanings:

Halogen atoms that come into consideration as substituents are fluorine and chlorine and also bromine and iodine, with fluorine, chlorine and bromine being preferred. Halogen is here to be understood as being an independent substituent or part of a substituent, such as in haloalkyl, haloaLkylthio, haloalkoxy, halophenylthio or halophenoxy.

Alkyl, alkylthio, alkoxyaikoxy and alkoxy radicals that come into consideration as substituents may be straight-chained or branched. Exarnples of such alkyl radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl or pentyl, hexyl, octyl, decyl, dodecyl and their isomers. Suitable alkoxy radicals are inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers. Alkylthio is, for example, methylthio, ethylthio, isopropylthio, propylthio or the isomers of butylthio.

If the alkyl, alkoxy, alkenyl, alkynyl or aryl groups that come into consideration as substituents are substituted by halogen, they may be only partially halogenated or also per-halogenated. The definitions given above apply here for halogen, alkyl and alkoxy.
Examples of the alkyl elements of those groups are methyl substituted from one to three times by fluorine, chlorine and/or by bromine, for example CHF2 or CF3; ethyl .
substituted from one to five times by fluorine, chlorine and/or by bromine, for example CH2CF3, CF2CF3, CF2CC13, CF2CHC12, CF2CHF2~ CF2CFC12. CF2CHBr2~
CF2CHCIF, CF2CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine andlor by bromine, for example CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or one of its isomers substituted from one to nine times by fluorine, chlorine and/or by bromine, for example CF(CF3)CHFCF3 or CH2(cF2)2cF3- ' If the alkyl, cycloalkyl or aryl groups defined under R3 are substituted by other substituents, they may be mono- or poly-substituted by identical or different substituents selected from those listed. Preferably, the substituted groups contain one or two further substituents.

The cycloalkyl radicals that come into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkenyl and alkynyl groups contain one or more, preferably not more than three, unsaturated carbon-carbon bonds. The double or triple bonds are separated from the point of linkage to the bridge X by at least one saturated carbon atom. Typical examples are allyl, mothallyl, 2-butenyl, 3-butenyl, propargyl, 2-butynyl or 3-butynyl.

Aryl is an aromatic hydrocarbon radical. Preferably, aryl is understood as being phenyl or naphthyl.

Examples of alkoxyalkoxy radicals are methoxymethoxy, methoxyethoxy, ethoxyethoxy, ethoxymethoxy, propoxymethoxy, propoxyethoxy, methoxypropoxy, butoxymethoxy and propoxyethoxy.

Examples of alkoxycarbonyl radicals are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl and butoxycarbonyl. Alkylcarbonyl is, for example, acetyl, propionyl, butyryl or valeryl, as well as isomers thereof.
Alkylcarbonyloxy is, for example, acetoxy, propionyloxy or butyryloxy.

Examples of aromatic and non-aromatic, monocyclic or bicyclic heterocycles that are bonded via an oxygen or sulfur atom to phenyl nuclei defined under R3 are the following cyclic basic structures: pyridine, pyrazine, pyridazine, pyrimidine, pyrrolidine, thiazole, .

-' ~
, 2023~64 thiadiazole, oxazole, benzothiazole, triazine, oxadiazole, quinoline, quinoxaline,quinazoline, isoquinoline, phthalazine, naphthyridine, cinnoline, pteridine, triazole, piperidine or benzoxazole. These heterocycles are preferably bonded via an oxygen or sulfur bridge to the 4-position of the phenyl nucleus. The oxygen or sulfur bridge itself is carried by a carbon atom of the heterocycle. Both the phenyl nucleus and the heterocycle may carry further substituents, for example they may each caIry up to three radicals from the group halogen, alkyl, haloalkyl and alkoxy or one or two substituents from the group nitro, haloalkoxy, alkylthio and cycloaLkyl. In general, the total number of substituents at the phenyl ring and at the heterocycle together is not more than four. ~referably, those two groups together carry not more than 3 further substituents from the group chlorine, bromine, methyl, ethyl and trifluoromethyl, and are bonded to one another via an oxygen atom.

Of those compounds, special mention should b~ made of those wherein R3 is phenylsubstituted in the 4-position by an aromatic monocyclic or bicyclic heterocycle bonded via oxygen and selected from the group pyridine, pyrimidine and benzothiazole, in which both aromatic rings are unsubstituted or together carry not more than three further substituents from the group chlorine, bromine, methyl, ethyl and trifluoromethyl.

Especially, the phenyl radicals that are substituted by a heterocycle via oxygen or sulfur under the definition of R3 may have, for example, the following individual meanings:
-4-(3-methylthiadiazol-S-yloxy)-phenyl, -4-(4-bromothiazol-2-yloxy)-phenyl, -4-(S-trifluoromethylpyrid-2-yloxy)-phenyl, -4-(3 ,5 -dichloropyrid-2-yloxy)-phenyl, -4-(3-chloro-S-trifluoromethylpyrid-2-yloxy)-phenyl, -3-(5-trifluoromethylpyrid-2-yloxy)-phenyl, -2,6-dimethyl-4-(4-trifluoromethylphenoxy)-phenyl, -2,6-diisopropyl-4-(N-formylanilino)-phenyl, -2,6-diisopropyl-4-(N-methylanilino)-phenyl, -4-phenylthiophenyl, -4-(2-cyclopropyl-4-trifluoromethylpyrimidin-6-yloxy)-phenyl, -4-(2-tert.-butyl-4-trifluoromethylpyrimidin-6-yloxy)-phenyl, -4-(2-methylthio-4-methylpyrimidin-6-yloxy)-phenyl, -4-(2-methyl-4-trifluoromethylpyrimidin-6-yloxy)-phenyl, æo23464 -4-(6-trifluoromethoxybenzothiazol-2-yloxy)-phenyl, -4-(6-chlorobenzothiazol-2-yloxy)-phenyl, -4-(6-nitrobenzothiazol-2-yloxy)-phenyl, -4-(6-methoxybenzothiazol-2-yloxy)-phenyl, -4-(5-trifluoromethylbenzothiazol-2-yloxy)-phenyl, -3,5-dichloro-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl, -2,6-dimethyl-4-(3-chloro-S-trifluoromethylpyrid-2-yloxy)-phenyl, -4-chloro-3-(3,5-bis-trifluoromethylpyrid-2-yloxy)-phenyl, -4-chloro-3-(5-chloro-3-fluoropyrid-2-yloxy)-phenyl, -2,6-dimethyl-4-[3-chloro-5-(2,2-dichloro- 1,1 ,2-trifluoroethyl)-pyrid-2-yloxy]-phenyl, -4-[3-chloro-5-(2,2-dichloro-1,1,2-trifluoroethyl)-pyrid-2-yloxy]-phenyl, -4-(N-acetylpyrid-3-ylamino)-phenyl, -2,4-dichloro-3-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl, -4-ethoxycarbonyl-3-(3-chloro-S-trifluoromethylpyrid-2-yloxy)-phenyl, -3-methyl-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl, -3,5-dichloro-4-(S-trifluoromethylpyrid-2-yloxy)-phenyl, -4-(6-chloro-4-trifluoromethylpyrid-2-yloxy)-phenyl, -4-bromo-3-(3-chloro-S-~ifluoromethylpyrid-2-yloxy)-phenyl, -3-(S-trifluoromethylpyrid-2-yloxy)-phenyl, -2,6-dimethyl-4-(3 ,S-dichloropyrid-2-ylthio)-phenyl, -2,6-dimethyl-4-(2-chloropyridazin-6-yloxy)-phenyl, -2,6-dimethyl-4-(pyrimidin-2-yloxy)-phenyl, -2,6-dimethyl-4-(pyrazin-2-yloxy)-phenyl, -2,6-dimethyl-4-(6-chloroquinoxalin-2-yloxy)-phenyl, -2,6-dimethyl-4-(6-trifluoromethylquinoxalin-2-yloxy)-phenyl, -2,6-dimethyl-4-(quinolin-2-yloxy)-phenyl, -4-chloro-2-fluoro-5-(3-methyl- 1 ,2,4-thiadiazol-S-yloxy)-phenyl, -2,6-dimethyl-4-(4-bromothiazol-2-yloxy)-phenyl or -4-methyl-3-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl.

Of the compounds of formula I, special mention should be made of those sub-groups in which either a) Rl and R2 independently of one another are hydrogen or Cl-C4alkyl, or b) X is oxygen, -NH-, -NCH3- or-NC2Hs-, or c) R3 is hydrogen, Cl-C20alkyl, C3-C7cycloalkyl, C3-C20alkenyl, C3-C20aL~cynyl, 2Q23~64 phenyl, naphthyl, C3-C20haloalkenyl, C3-C20haloalkynyl; C3-C7cycloalkyl substituted by fluorine, chlorine, bromine or by Cl-C3alkyl; phenyl or naphthyl substituted by fluorine, chlorine, bromine or Cl-C3alkyl, Cl-C3haloalkyl, Cl-C3alkoxy, Cl-C3haloalkoxy, Cl-C3alkylthio, nitro, cyano, phenoxy, halophenoxy, Cl-C4alkylphenoxy, Cl-C4haloaL~cylphenoxy, tri-Cl-C4alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyIrolidin-2-onyl, N-piperidin-2-onyl, Cl-C4alkylamino, di-Cl-C4alkylamino, anilino, N-Cl-C4aL~cylanilino, N-formylanilino, N-Cl-C6alkylcarbonylanilino, phenylthio or by halophenylthio, or Cl-C20aLkyl substituted by hyd~oxy, fluorine, chlorine, bromine, di-Cl-C4alkylamino, Cl-C4alkoxy, Cl-C4haloalkoxy, C2-C6alkoxyalkoxy, Cl-C4-haloalkylthio, Cl-C4alkylthio, Cl-C4alkylsulfinyl, Cl-C4alkylsulfonyl, Cl-C4aL~yl-sulfonyloxy, Cl-C4alkylcarbonyl, Cl-C4alkoxycarbonyl, Cl-C6alkylcarbonyloxy, C3-C7cycloalkyl, phenyl, phenoxy, phenylthio, phenylsul~onyloxy or by pyridyl, in which the phenyl and pyridyl groups may each be substituted by fluorine, chlorine, bromine, Cl-C3alkyl, Cl-C3haloalkyl, Cl-C3alkoxy, Cl-C3haloalkoxy, Cl-C3alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenyl-dhio, or d) R3 is phenyl substituted in the 4-position by an aromatic monocyclic or bicyclic heterocycle bonded via oxygen and selected from the group pyridine, pyIimidine and benzothiazole, in which both aromatic rings are unsubstituted or together carry not more than three further substituents from the group chlorine, bromine, methyl, ethyl and trifluoromethyl.

Of the compounds of sub-group a), those are preferred wherein Rl and R2 are hydrogen.

Of dhe compounds of sub-group b), those are preferred wherein X is oxygen or -NH-.

Special mention should be made of the group of compounds of formula I wherein Rl and R2 independendy of one another are hydrogen or Cl-C4alkyl, X is oxygen or -NR4- and R4 is hydrogen, methyl or ethyl. Very especially preferred compounds of fo~nula I are those wherein Rl and R2 are hydrogen.

Of the compounds of formula I of sub-group c), special mention should be made on the one hand of those compounds wherein R3 is phenyl, benzyl, naphthyl or 3-pyridylmethyl or phenyl, benzyl, naphthyl or 3-pyridylmethyl each of which is substituted by fluorine, chlonne, bromine, Cl-C3alkyl, Cl-C3haloalkyl, Cl-C3alkoxy, Cl-C3haloalkoxy, 20~3464 Cl-C3alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio. Of those compounds, preference is given in turn to those wherein Rl and R2 independently of one another are hydrogen or Cl-C4alkyl, X is oxygen or -NR4- and R4 is hydrogen,methyl or ethyl.

On the other hand, special mention should be made also of those compounds of fo~nula I
of sub-group c) wherein R3 is Cl-C12alkyl or Cl-C12alkyl substituted by hydroxy,fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or by phenoxy, in which the phenyl or phenoxy radical may be substituted by fluorine, chlorine, brornine, phenoxy, halophenoxy or by phenylthio. Of that group of compounds, preference is given to those wherein Rl and R2 independently of one another are hydrogen or Cl-C4alkyl, X is oxygen or -NR4- and R4 is hydrogen or Cl-C4alkyl. More especially, in preferred forms Rl and R2 are both hydrogen.

A very interesting group of compounds of formula I of sub-group c) comprises compounds wherein R3 is C3-C12alkenyl, C3-C12alkynyl or C3-C12alkenyl or C3-C12alkynyl each of which is substituted by fluorine, chlorine or by bromine. Of that group, preference is given to those compounds wherein Rl and R2 independently of one another are hydrogen or Cl-C4alkyl, X is oxygen or -NR4- and R4 is hydrogen or Cl-C4aLkyl. The meaning of hydrogen for Rl and R2 is especially preferred.

The following may be mentioned as preferred individual compounds of forrnula I:

4-chloro-4,4-difluorobutyric acid methyl ester, 4chloro-4,4-difluorobutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid isopropyl ester, 4-chloro-4,4-difluorobutyric acid tert.-butyl ester, 4-chloro-4,4-difluorobutyric acid n-butyl ester, 4-chloro-4,4-difluorobutyric acid (2,2-dimethylpropyl) ester, 4-chloro-4,4-difluorobutyric acid benzyl ester, 4-chloro-4,4-difluorobutyric acid phenyl ester, 4-chloro-4,4-difluorobutyric acid [2-(4-phenoxyphenoxy)-ethyl] ester, 4-chloro~,4-difluorobutyric acid cyclohexyl ester, 4-chloro-4,4-difluorobutyric acid cyclohexylmethyl ester, 4-chloro-4,4-difluorobutyric acid cyclopropylmethyl ester, ~U~6~

4-chloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid N-methylamide, 4-chloro-4,4-difluorobutyric acid N,N-dimethylamide, 4-chloro-4,4-difluorobutyric acid N,N-dihexylamide, 4-chloro-4,4-difluorobutyric acid N-ethylamide, 4-chloro-4,4-difluorobutyric acid N-isopropylamide, 4-chloro-4,4-difluorobutyric acid N-butylamide, 4-chloro-4,4-difluorobutyric acid N-tert.-butylaunide, 4-chloro-4,4-difluorobutyric acid N-benzylamide, 4-chloro-4,4-difluorobutyric acid anilide, 4-chloro-4,4-difluorobutyric acid N-methyl-N-pyrid-3-ylmethylamide, 4-chloro-4,4-difluorobutyric acid N-pyrid-3-ylmethylamide, 4-chloro-4,4-difluorobutyric acid (4-chloroanilide), 4-chloro-4,4-difluorobutyric acid (4-phenoxyanilide), 4-chloro 4,4-difluorobutyric acid (2-chloroanilide), 4-chloro-4,4-difluorobutyric acid (4-methoxyanilide), 4-chloro-4,4-difluorobutyric acid (4-methylanilide), 4-chloro-4,4-difluorobutyric acid (3-methylmercaptoanilide), 4-chloro-4,4-difluorobutyric acid (4-fluoroanilide), 4-chloro-4,4-difluorobutyric acid (4-chloro-2-nitroanilide), 4-chloro-4,4-difluorobutyric acid (3-phenoxybenzyl) ester, 4-chloro-4,4-difluorobutyric acid [4-(4-fluorophenoxy)-phenyl] ester, 4-chloro-4,4-difluorobutyric acid [4-(4-fluorophenoxy)-phenoxyethyl] ester, 4-chloro-4,4-difluorobutyric acid (4-nitrophenyl) ester, 4-chloro-4,4-difluorobutyric acid [4-(3,5-difluorophenoxy)-phenyl] ester, 4-chloro-4,4-difluorobutyric acid [4-(5-trifluoromethylpyrid-2-yloxy)-phenyl] ester, 4-chloro-4,4-difluorobutyric acid and 4-chloro-4,4-difluorobutyric acid amide.

The compounds of formula I according to the invention can be prepared analogously to known processes. For example, the compound of formula I is obtained by either a) reacting a 4-chloro-4,4-difluorobutyric acid halide of formula II

Rl R2 2~23464 wherein Rl and R2 are as defined under formula I and Hal is halogen, preferably chlorine or bromine, with a compound of formula III
H-X-R3 (III), wherein X and R3 are as defined under formula I, in the presence of a base, or b) reacting 4-chloro-4,4-difluorobutyric acid of formula Ic ClF2C--fH--fH--~-OH (Ic), , Rl R2 wherein Rl and R2 are as defined under forrnula I, with a compound of formula III in the presence of water-removing agent.

The reaction of process a) (II+III ~ I) is preferably carried out in an inert solvent that is free of hydroxy groups in the presence of an organic base, for exarnple pyridine, 4-di-methylaminopyridine, lutidine, collidine, a triaLkylamine or N,N-diaL~ylaniline, or bicyclic, non-nucleophilic bases, such as 1,4-diazabicyclo[2.2.2]octane (I)ABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (1.5-5) (DBU). The reaction is generally carried out at temperatures of from -30 to +70C, preferably from -10 to +50C. The reaction is advantageously carried out in the presence of an inert solvent or solvent mixture. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halo-genated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; esters, such as ethyl acetate, propyl acetate or butyl acetate; ketones, such as acetone, diethyl ketone, methyl ethyl ketone; compounds such as dimethyl sulfoxide (DMSO), dimethylformamide (DMP), and mixtures of such solvents with one another. However, the reaction may also be carried out in an excess of one of the above-mentioned bases or, if the compound of formula III is an amine (X = NR4), a second equivalent or even a relatively large excess of the compound of formula III may be used instead of the base.

In process variant b) (Ic + III ~ I), the reaction is advantageously carried out in the 202346~

presence of water-removing agents customarily used in esterification reactions, for example in the presence of a carbodiimide [dicyclohexylcarbodiimide (DCC)] or of a l-alkyl-2-halopyridinium salt, such as 1-methyl-2-chloropyridinium iodide. The reaction is advantageously carried out in the presence of an inert solvent or solvent mixture at temperatures of from -30C to +70C, preferably from -10C to +50C. The reaction is preferably carried out in the presence of a base, for example in the presence of an organic amine, such as a trialkylamine (trimethylamine, triethylamine, tripropylamine or diiso-propylethylamine), a pyridine (pyridine itself, 4-dimethylaminopy idine or 4-pyrrolidinopyridine), a morpholine (N-methylmorpholine) or an N,N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile;
esters, such as ethyl acetate, propyl acetate or butyl acetate; and mixtures of such solvents with one another.

If the compound of formula IlI is an alcohol (X = O), process variant b) may also be carried out in the presence of an acid catalyst, for example H2SO4, HCl or a sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid. In that case, the reaction is advantageously carried out with an excess of the alcohol of formula III. In this process, water that is liberated can be removed continuously from the reacdon mixture. A custo-mary method is the removal of the water of reaction by distilling off an azeotropic mixture of the solvent with water. Suitable solvents are benzene, toluene, xylene, methylene chloride or chloroform.

In principle, the various derivatives of formula I are also obtainable from the readily available lower alkyl esters of 4-chloro-4,4-difluorobutyric acid by transesterification or amidation.

For example, the derivatives of formula I of the ester type (X = O) can be obtained by base- or acid-catalysed transesterification of the lower alkyl esters of forrnula Ia L

2~234~

ClF2C-~H-~H~ O-Cl-C4-Alkyl (Ia) R~ R2 with the alcohols of formula IIIa H-O-R3 (IIIa) wherein R3 is as defined under formula I, with the exception of C1-C4alkyl. Especially suitable acid catalysts are HCl, H2SO4 or a sulfonic acid. In the case of base-catalysed transesterification there is preferably used as the base the sodium or potassium alcoholate of the alcohol of formula IIIa, which are obtainable from IIIa, for example, by the addition of sodium or potassium hydride. The transesterification reaction is preferably carried out at temperatures of from -20C to +120C, especially from 0C to +100C. The alcohol component IIIa is advantageously used in excess. Suitable solvents are ethers, such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran, halogenated hydrocarbons or aliphatic or aromatic hydrocarbons.

Derivatives of formula I of the amide type (X = NR4) are obtained from the lower alkyl esters of formula Ia by reacting those esters with amines of formula IIIb ~R3 H-N~ (IIIb) wherein R3 and R4 are as defined under formula I. The amidation reactions are carried out at temperatures of from 0C to +120C. Advantageously, the reactants are reacted in an inert solvent or mixture of solvents. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halo-genated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; alcohols, such as methanol, ethanol, propanol, isopropanol; or water. The amine component IIIb is advantageously used in excess.

The compounds of formula III are known and some of them are commercially available, or they can be prepared analogously to known preparation processes.

202~464 The acid halides of formula II can be obtained in customary manner from the 4-chloro-4,4-difluorobutyric acids of formula Ic by reaction with halogenating agents.
Suitable halogenating agents are especially SOC12, oxalyl chloride, PC13, POC13 or PCls.
The reaction is generally carried out at temperatures of from -20C to +120C, preferably from 0C to +100C. The reaction can be carried out without solvents or in admixture with an inert solvent. Suitable solvents are, for example, aromatic hydrocarbons, such as benzene or toluene, or halogenated hydrocarbons, such as methylene chloride, chloroform or chlorobenzene. The reaction is frequently carried out with the addition of a catalytic amount of DMF.

The intermediates of formula II are novel. They have been developed specifically for the synthesis of the compounds of forrnula I. The present invention therefore relates also to those intermediates.

The 4-chloro-4,4-difluorobutyric acids of formula Ic can be obtained from compounds of formula Ia by acid or basic hydrolysis. The reaction is generally carried out at tempera-tures of from -20C to +120C, preferably from +10C to +100C. In the case of acid hydrolysis it is preferable to use HCl or H2SO4 and in the case of basic hydrolysis NaOH
or KOH. The reaction is advantageously carried out in water or in a solvent mixture of water and an organic solvent. Especially suitable organic solvents are alcohols, such as methanol or ethanol; ethers, such as dioxane or tetrahydrofuran; dimethyl sulfoxide; or dimethylformamide.

The compounds of formula Ia, which form a sub-group of compounds of formula I and at the same time may be used as intermediates for the preparation of the various ester and amide types of formula I, are obtainable in accordance with the following process:

The compounds of formula Ia can be obtained by catalytically dehalogenating in the a-position an a-halo-4-chloro-4,4-difluorobutyric acid ester of formula IV

Rl R2 Y --O--Cl--C4--Alkyl (IV) wherein Rl and R2 are as defined under formula I and Y is chlorine or bromine, with hydrogen.

The compounds of the more limited sub-formula Ib ClF2C--fH--CH2~ O-Cl--C4--Alkyl (Ib), Rl O
wherein Rl is as defined under formula I, can be obtained from the a,a-dihalo-4-chloro-4,4-difluorobutyric acid esters of formula V

ClF2C--f ~ ~--O--Cl--C4--Alkyl(V), wherein Rl is as defined under formula I and Y and Z independently of one another are chlorine or bromine, by catalytic a-dehalogenation with hydrogen.

By a suitable selection of the catalyst and the reaction conditions it is also possible to replace the a-halo atoms Y and Z stepwise with hydrogen. In this manner, the compounds of formula IV wherein R2 is hydrogen can be prepared from the compounds of formula V
by mono-a-dehalogenation.

The catalytic dehalogenating processes using hydrogen (IV ~ Ia, V ~ Ib and V ~ IV) are car ied out with hydrogen in the presence of a noble metal catalyst or Raney nickel, optionally in the presence of a hydrogen halide acceptor and of a solvent, at a temperature of from 0C to +150C and under normal pressure or under a pressure of up to 150 bar.
The solvent is preferably selected from the group of the hydrocarbons, halogenated hydrocarbons, ethers, ketones, alcohols, carboxylic acid esters, sulfones, N,N-dialkyl-carboxylic acid amides, N-alkyl lactams and lactones. Some examples are petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetra-chloroethane, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, acetone, methyl isobutyl ketone, methyl or ethyl acetate, tetramethylenesulfone, dimethylformamide, N-methylpyrrolidone, ~-valerolactone, butyrolactone, methanol, ethanol or isopropanol. Preferably, the solvent is polar. Especially preferred solvents are ethyl acetate, tetrahydrofuran or alcohols. The amount of solvent can vary within wide limits. Advantageously, the amount of solvent used is equal to or up to ten times the amount of compound of formula IV or V. Hydrogen halide acceptors are generally known. They may be tertiary nitrogen bases having preferably a total of from 3 to 20, especially from 3 to 12, carbon atoms, alkali metal or alkaline earth metal salts of organic acids or of carbonic acid, or alkali meta1 or aL~aline earth metal oxides or hydroxides.
Some examples are sodium carbonate, sodium or calcium hydrogen carbonate, sodiumacetate, NaOH, KOH, MgO and CaO; or aromatic, aliphatic or cyclic tertiary nitrogen bases, such as trimethyl-? triethyl-, tripropyl-, tributyl-, triethanol- or butyldimethyl-amine, pyridine, 2,6-dimethylpyridine, N-methylpyrroline and N-methylmorpholine. Preferred hydrogen halide acceptors are tertiary nitrogen bases and MgO. 2,6-dimethylpyridine is especially preferred. The hydrogen halide acceptor may be used in a slightly lesser amount or slight excess relative to the amount of compound of formula IV or V. Equimolar amounts are preferably used. Suitable noble metal catalysts are, for example, iridium, rhodium, platinum, ruthenium and palladium. The use of palladium is especially preferred.
The noble metal is preferably used as the catalyst on a carrier. Examples of carriers are BaSO4, SiO2, A12O3 and, especially, active carbon. In addition to the carrier, the catalyst used generally contains from 0.1 to 20 % by weight of the noble metal. Sulfided catalysts may also be used. The amount employed may be from 0.1 to 20 % by weight, relative to the amount of compounds of formula IV or V. It may be advantageous to add catalyst that is regenerated or not used up during the reaction. The reaction temperature is preferably from 0C to +80C, especially from 0C to +30C. The pressure is preferably up to 20 bar. F?referably, the reaction is carried out under normal pressure.

The compounds of formula V are known from EF?-A-2206 or they can be obtained analogously to the process described therein. The intermediates of formula IV can be prepared by adding 1,1-difluoroethylene of formula VII
F2C=CH2 (VII) to a chloroacetic acid ester of formula VI
Cl~-O-CI-C4-Alkyl (VI)j wherein R2 is as defined under formula I and Y is chlorine or bromine, in the presence of a Cu(I) catalyst. Where Y = chlorine, this process is described in Helv. Chim. Acta 63, p.
1947-1957 (1980).
The catalysts that may be used contain as essential element copper in oxidation stage 1.

Examples thereof are copper(I) chloride and copper(l) bromide (CuCI, CuBr) and cuprous cyanide (CuCN). CuCI and CuBr and mixtures thereof are preferred. The catalysts are generally used in amounts of approximately from 0.01 to 10 mol%, preferably from 0.1 to S mol%, relative to the compound of formula VII. The reaction is carried out in an organic so1vent. Suitable organic solvents are those in which the catalysts are sufficiently soluble or which are able to form complexes with the catalysts but are inert towards the stardng compounds of formulae VI and VII. Examp1es of such solvents are alkylnitriles, especially those having from 2 to 5 carbon atoms, such as acetonitrile, propionitrile and butyronitrile; 3-alkoxypropionitriles having 1 or 2 carbon atoms in the alkoxy moiety, such as 3-methoxypropionitrile and 3-ethoxypropionitrile; aromadc nitriles, especially benzonitrile; aliphatic ketones having preferably a total of from 3 to 8 carbon atoms, such as acetone~ die*yl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tert.-butyl ketone; alkyl~ and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total of from 2 to 6 carbon atoms, such as formic acid methyl and ethyl esters, acetic acid methyl, ethyl, n-butyl and isobutyl esters, as well as 1-acetoxy-2-methoxyethane; cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxane; dialkyl ethers having from 1 to 4 carbon atoms in each aLkyl moiety, such as diethyl ether, di-n-propyl ether and diisopropyl ether, N,N-dialkylamides of aliphatic monocarboxylic acids having from 1 to 3 carbon atoms in the acid moiety, such as NjN-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide; ethylene glycol and di-ethylene glycol diaLkyl ethers having from 1 to 4 carbon atoms in each alkyl moiety, such as ethylene glycol dimethyl, diethyl and di-n-butyl ether, diethylene glycol diethyl and di-n-butyl ether or hexamethylphosphoric acid triamide. ~referred solvents are aLlcylnitriles having from 2 to 6 carbon atoms and 3-alkoxypropionitriles having 1 or 2 carbon atoms in the alkoxy moiety, especially acetonitrile and 3-methoxypropionitrile.
The reaction temperature is generally not critical and can vary within wide lirnits. The reaction temperatures are preferably from approximately +60C to +200C, especially from approximately +80C to +170C. The reaction may be carried out under pressure or without pressure.

The compounds of the more limited formula Id ClF2C-CI H-fH-f-X-R (Id).
Rl R2 `

-` 202346~

wherein Rl, R2 and X are as defined under formula I and R is hydrogen or Cl-C6alkyl, can be obtained from the 4-chloro-4,4-difluorocrotonic acid derivatives of formula VIII

ClF2C--f=C--C--x--R (VIII), Rl R2 wherein Rl, R2 and X are as defined under formula I and R is hydrogen or Cl-C6alkyl, by catalytic hydrogenation with hydrogen.

The resulting products of the more limited sub-formulae Ia, Ib, Ic and Id can be converted into the other derivatives of formula I by customary derivatising reactions, such as hydro-lysis, transesterification or transamidation.

The catalytic hydrogenation of the crotonic acids of formula VIII is carried out under conditions that are customary for that type of reaction. For example, the reaction is carried out in the presence of a noble metal catalyst or of Raney nickel, preferably in an inert solvent, under a hydrogen atmosphere, under a pressure of from 1 to 150 bar.

Suitable noble metal catalysts are, for example, iridium, rhodium, platinum, rutheniurn and palladium. The use of palladium is especially preferred. The noble metal is preferably used as the catalyst on a ca~Tier. Examples of carriers are BaS04, SiO2, A12O3 and, especially, active carbon. In addition to the carrier, the catalyst used generally contains from 0.1 to 20 % by weight of the noble metal. Sulfided catalysts may also be used. The amount employed may be from 0.1 to 20 % by weight, relative to the amount of compounds of formula VIII. It may be advantageous to add catalyst that is regenerated or not used up during the reaction. The reaction temperature is preferably from 0C to +80C, especially from 0C to +30C. The pressure is preferably up to 20 bar. Inparticular, the reaction is preferably carried out under normal pressure. The solvent is preferably selected from the group of the hydrocarbons, halogenated hydrocarbons, ethers, ketones, carboxylic acid esters, sulfones, N,N-dialkylcarboxylic acid amides, N-alkyl lactams and lactones. Some examples are petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, methylene chloride, chloro-form, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, acetone, methyl isobutyl ketone, methyl or ethyl acetate, tetramethylenesulfone, dimethylformamide, N-methylpyrrolidone, :- 2023464 ~-valerolactone, butyrolactone and methanol. Preferably, the solvent is polar. Especially preferred solvents are ethyl acetate and tetrahydrofuran. The amount of solvent can vary within wide limits. Advantageously, the amount of solvent used is equal to or up to ten times the amount of compound of formula VIII.

The compounds of formula VIII, with the exception of 4-chloro-4,4-difluorocrotonic acid, are novel. They have been developed as intermediates specifically for the synthesis of the compounds of formula I. The present invention relates also to those compounds. The novel compounds of formula VIII can be obtained analogously to the preparation process described for the free acid azvestiya Akademii Nauk SSSR, Ser. Khim, No. 2 ~1965), 300-307) or can be prepared from those products by customary derivatising reactions, such as esterification, transesterification or amidation.

Compounds of formula VIII wherein Rl and R2 are hydrogen can also be obtained from compounds of formula IX

CIF2C--CH--CH2--C--X--R (IX) O-A O
wherein A is hydrogen or an acyl group, by ~-elimination in accordance with known methods, for example Houben Weyl 6/lb 939 (1984).

Compounds of formula IX can be prepared from compounds of formula X
ClF2C--ICI--CH2--ICl--X--R (X) O O
by reduction, for example catalytic reduction with hydrogen in accordance with the method described by Reuben G. Jones in J. Amer. Chem. Soc., 70 (1948) 144.

Some of the compounds of formula X are known, or they can be prepared by known methods, for example Claisen condensation (Huang Weiynan et al.; Huaxne Xuebao 1983, 41(8) 723; C.A. 100, (1984) 22308s).

Compounds of formula X are further obtained by reacting chlorodifluoroacetyl chloride ClF2C-CO-Cl with ketene H2C=C=O and hydrolysing the resulting 4-chloro-4,4-difluoroacetic acid chloride of formula XI

ClF2C--ICl ~H2 ~11--Cl (XI) O O

to form the free acid, which is converted into the esters or amides of formula X by reaction with the appropriate alcohols or amines. Advantageously, those esters and amides can also be obtained direcdy by reacting the acid chloride of formula XI with an alcohol or amine.

For example, for compounds of formula I wherein Rl and R2 are hydrogen, X is oxygen and R3 is aLIcyl, synthesis in accordance with scheme 1 below is to be regarded as advantageous:

--` 202~464 Schema 1:
1l CIF2C~--CH~--COOAlkyl reduction ~ e.g. with H2/RhlAl2o3 OH
ClF2C--CH--CH2~00AL~cyl \ acylation \e.g. with (H3C-CO)zO
- H20 \~ o--CO--CH3 e.g. with P20s ClF2C--CH--CH2--COOALtcyl ~ ~ ~,/ e.g. with quinoline/heat ClF2C--CH=CH~OOALl~yl reduction ~ e.g. with H2/~h/Al203 ClF2C--CH2--CH2--COOAlkyl It has now been found that the compounds of formula I according to the invention are valuable active ingredients in pest control while being well tolerated by warm-blooded animals, fish and plants. The compounds according to the inslention can be used especially against insects and arachnids which occur on useful plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry, in the protection of stored goods and material stocks, and also in the hygiene sector, especially on domestic animals and productive livestock. They are effective against all or individual development stages of normally sensitive and also resistant species. Their action may manifese itself immediately in the death of the pests or only at a later date, for example at shedding, or in reduced oviposition andlor a reduced hatching rate. The above-mentioned pests include:
of the order Lepidoptera, for example, i-` 2023464 Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia arnbiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, (~yptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea,;Earias spp., Ephesda spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hel1ula undalis, Hyphantria cunea, Keiferia Iycopersicel1a, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Opewphtera spp., Ostrinia nubilalis, Pamme spp., ~Pandemis spp., Panolis flammea, Pecdnophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Torlrix spp., Trichoplusia ni and Yponomeuta spp.;, of the order Coleoptera, for example, Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema dbia1is, Cosmopolites spp., Cu~ lio spp., I)ennestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Lepdnotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otihynchus spp., Phlyctinus~spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; of the order Orthoptera, for example, Blatta spp., B1atte11a spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; :
of the order Isoptera, for examp1e, Redculitennes spp.; of the order Psocoptera, for example, Liposcelis spp.; of the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; of the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.;
of the order Thysanoptera, for example, Franldiniella spp., Hercinothrips spp., Taeniothrips spp., Thrips pa1mi, Thrips tabaci and Scirtothrips aurantii;
of the order Heteroptera, for example, Cimex spp., Distandella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlberge11a singu1aris, Scotinophara spp. and Triatoma spp.;
of the order Homoptera, for example, ; .
~ . .

2023~6~

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., TAaleurodes vaporariorum, Trioza erytreae and Unaspis citri;
of the order Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., DipTion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp.
and Vespa spp.;
of the order Diptera, for example, Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
of the order Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis, of the order Acarina, for example, Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomrna spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; and of the order Thysanura, for example, Lepisma saccharina.

The good pesticidal activity of the compounds of formula I according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests.

The activity of the compounds of the invention and of the compositions containing them 202346~

can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides. Examples of suitable additives include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granu-lates, and also encapsulations in polymer substances. As with the compositions, the methods of application, such as spraying~ atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing c*cumstances.

The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I, or combinations of those compounds with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 -carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-py~rolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of granulated 202~4~4 materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of formula I to be formulated, or of thecombinations of those compounds with other insecticides or acaricides, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g.
from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurin salts and modified and unmodified phospholipids as surfactants.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a Cg-C22alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxidel Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said 202~6~

derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the aLIcylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g.
stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described, for example, in the following publications:

"1985 International McCutcheon's Emulsifiers & Detergents", Glen Rock, NJ, USA, 1985, H. Stache, "Tensid-Taschenbuch",2nd edition, C. Hanser Verlag, Munich, Vienna, 1981, M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

The pesticidal compositions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combinations of that compound with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 20 %, of a surfactant. Whereas commercial products will preferably be formulated as concen-202346~

tra~es, the end user will norrnally employ dilute formulations containing considerably lower active ingredient concentrations. Typical application concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. The rates of application per hectare are generally from 1 to 1000 g of active ingredient per hectare, preferably from 25 to 500 g/ha.

Preferred formulations have especially the following compositions (% = percent by weight):

Emulsifiable concentrates:
active ingredient: 1 to 20 %, preferably 5 to lO %
surface-active agent: 5 to 30 %, preferably 10 to 20 %
liquid carrier: 50 to 94 %, preferably 70 to 85 %

Dusts:
active ingredient: 0.1 to lO %, preferably 0.1 to l %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:
active ingredient: 5 to 75 %, preferably 10 to S0 %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agent: 0.5 to 20 %, preferably 1 to lS %
solid carrier: 5 to 95 %, preferably 15 to 90 %

Granulates:
active ingredient: 0.5 to 30 %, preferably 3 to lS %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The compositions may also contain further auxiliaries such as stabilisers, antifoams, preservatives, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

The following Examples serve to illustrate the invention. They do not limit the invention.

Preparation Examples Example Pl: 4-Chloro-4~4-difluoro-2-trifluoromethvlbutvric acid ethYI ester ClF2C-CH;~-fH-COOC2H5 a) 2,4-Dichloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester.

22.5 g of 2,2-dichloro-3,3,3-trifluoropropionic acid ethyl ester are placed with 0.5 g of Cu(I) chloride and 100 ml of acetonitrile in an autoclave. After the introduction of 16.0 g of l,l-difluoroethylene under pressure, the mixture is heated at +160C for 8 hours. After cooling, the reaction mixture is freed of solvent and the oil that remains is rectified in vacuo. 7.4 g of 2,4-dichloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 54-56C/ll mbar.
Analvsis: qH7C12FsO2 (289.03) calc.: C 29.09 % H 2.44 % Cl 24.53 % F 32.87 %
found: C29.2 % H2.4 % C124.4 % F32.9 %

b) 28.9 g of 2,4-dichloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester in 200 ml of ethanol are treated with hydrogen gas in the presence of 2 g of 5 % platinum/-carbon catalyst, under normal pressure and at room temperature, until 1 equivalent of hydrogen has been absorbed. After the catalyst has been filtered off, the solvent is distilled off under nornal pressure and the residue is rectified. 15 g of 4-chloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 41-43C/16 mbar.
AnalYsis: qHgClFsO2 (254.58) calc.: C 33.03 % H 3.17 % Cl 13.92 % F 37.31 %
found: C33.2 % H3.1 % C114.1 % F37.0 %

202~464 Example P2: 4-Chloro-4~4-difluorobutYric acid ethYI ester 22.1 g of 2,4-dichloro-4,4-difluorobutyric acid ethyl ester are dissolved in 200 ml of absolute ethanol. After the addition of 8.2 g of anhydrous sodium acetate and 2.0 g of S %
platinumlcarbon catalyst, hydrogen gas is introduced under normal pressure until the amount of hydrogen absorbed is 100 % of the theoretical amount. After the catalyst has been filtered off and the ethanol has been distilled off, the oil that remains is poured onto water and the organic phase is separated off, dried with sodium sulfate, ~lltered and rectified under normal pressure. 14.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 154-156C.
Analysis: C6HgClF2O2 (186.59) calc.: C 38.62 % H 4.86 % Cl 19.00 % F 20.36 %
found: C38.6 % H4.8 % C119.1 % Fl9.9 %

Example P3: 4-Chloro-4.4-difluorobutYric acid ethvl ester ClF2C-CH2-CH2-COOC2H5 22.1 g of 2,4-dichloro-4,4-difluorobutyric acid ethyl ester are dissolved in 100 ml of absolute tetrahydrofuran. After the addition of 10.7 g of 2,6-dimethylpyridine and 2.0 g of S % palladiumlcarbon catalyst, hydrogen gas is introduced under normal pressure until the amount of hydrogen absorbed is 100 % of the theoretical amount. After the catalyst has been filtered off and the tetrahydrofuran has been distilled off, the oil that remains is poured onto water and the organic phase is separated off, dried with sodium sulfate, filtered and rectified under normal pressure. 14.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 154-156C.
AnalYsis: C6HgClF2O2 (186.59) calc.: C 38.62 % H 4.86 % Cl 19.00 % F 20.36 %
found: C38.6 % H4.8 % Cll9.1 % Fl9.9 %

2~2346~

Example P4: 4-Chloro-4.4-difluorobutyric acid ethvl ester ClF2C-CH2-CH2-COOC2H5 25.5 g of 2,2,4-trichloro-4,4-difluorobutyric acid ethyl ester are dissolved in 200 ml of absolute ethanol. After the addition of 16.4 g of anhydrous sodium acetate and 2.0 g of 5 % platinumlcarbon catalyst, hydrogen gas is introduced under normal pressure until the amount of hydrogen absorbed is 2 equivalents. After the catalyst has been filtered off and the ethanol has been distilled off, the oil that remains is poured onto water and the organic phase is separated off, washed with sodium sulfate, filtered and rectified under normal pressure. 14.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 154-156C.
Analvsis: C6HgClF2O2 ~186.59) calc.: C 38.62 % H 4.86 % Cl 19.00 % F 20.36 %
found: C38.6 % H4.8 % Cll9.1 % F19.9 %

Example P5: 4-Chloro-4~4-difluorobutyric acid N-methylamide 2.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are dissolved at 0~C in 10 ml of a 33 % solution of methylamine in ethanol. The resulting reaction mixture is stirred at room temperature for 3 days and then concentrated by evaporation. The resulting residue is recrystallised from hexane. 1.5 g of 4-chloro-4,4-difluorobutyric acid N-methylamide having a melting point of 61-63C are obtained.

Example P6: 4-Chloro-4~4-difluorobutvric acid benz-/l ester ClF2C-CH2-CH2-COO-cH2 ~
a) 4-Chloro-4,4-difluorobutyric acid.
18.6 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are stirred with 100 ml of 2N
NaOH at room temperature until a homogeneous solution has formed. The solution is then poured onto 150 ml of 2N HCI. The sep~rated organic phase is taken up in diethyl ether, dried with sodium sulfate and, after the ether has been distilled off, rectified in vacuo. 12.6 g of 4-chloro-4,4-difluorobutyric acid are obtained in the form of a colourless oil having a boiling point of 88-90C/l l mbar.
Analvsis: C4HsClF2O2 (158.53) calc.: C 30.31 % H 3.18 % Cl 22.36 % F 23.97 %
found: C 30.3 % H3.2 % C122.4 % F24.2 %

b) 4-Chloro-4,4-difluorobutyric acid chloride.
15.8 g of 4-chloro-4,4-difluorobutyric acid are mixed with 50 ml of thionyl chloride and 0.2 ml of dimethylformamide and the mixture is heated to +70C within a period of 2 hours and then l~ept at +70C for a further 30 rninutes. The reaction mixture is rectdfied in vacuo and the liquid that distils over at a boiling point of 35-37C/21 mbar is collected. 10.5 g of 4-chloro-4,4-difluorobutyric acid chloride are obtained in the form of a clear, colourless liquid.
Analysis: C4H4C12F2O (176.98) calc.: C 27.15 % H 2.28 % Cl 40.06 % F 21.47 %
found: C27.3 % H2.3 % C140.1 % F21.4 %

c) A solution of 1.84 g of benzyl alcohol and 3.74 g of pyridine in 6 ml of methylene chloride is added at 0C within a period of 30 minutes to a soludon of 3.35 g of4-chloro-4,4-difluorobutyric acid chloride in 15 ml of benzene. The resuldng reaction mixture is stirred at 0C for 16 hours and then poured onto 50 ml of lN HCl solution and extracted with 150 ml of diethyl ether. The organic phase is washed with 50 ml of saturated NaHCO3 solution and 50 ml of saturated NaCl solution, dried with magnesium sulfate and concentrated by evaporadon. The resuldng crude product is distilled in a bulb tube at 190-210C/120 mbar. 3.65 g of 4-chloro-4,4-difluorobutyric acid benzyl ester are obtained.
MS: m/e: 248 (M+, CllHllClF22) Example P7: 4-Chloro-4~4-difluorobutvric acid N-isopropvlamide ClF2C-CH2-CH2-CO-NH-C3H7-i A solution of 3.35 g of isopropylamine in 5 ml of methylene chloride is added at 0C to a soludon of 3.35 g of 4-chloro-4,4-difluorobutyric acid chloride in 15 ml of toluene. The resulting reacdon mixture is sdrred at 0C for 16 hours and then poured onto 50 ml of saturated NaHCO3 solution and extracted with 150 ml of diethyl ether. The organic phase is washed with 50 ml of saturated NaCl solution, dried with magnesium sulfate and concentrated by evaporation. 3.18 g of 4-chloro-4,4-difluorobutyric acid N-isopropylamide are obtained, m.p.: 84-85C.
Example P8: 2~4-Dichloro-4,4-difluorobutyric acid methYl ester ClF2C-CH2-CHCI-COOCH3 A solution of 2.4 g of 2,2,4-trichloro-4,4-difluorobutyric acid methyl ester in 20 ml of absolute ethanol is hydrogenated at room temperature, with the addition of 0.2 g of 5 %
platinum/carbon catalyst, until one equivalent of hydrogen has been absorbed (about one hour). After the catalyst has been filtered off, the resulting crude product is distilled in a bulb tube at +70C/20 m~ar. l.S g of 2,4-dichloro-4,4-difluorobutyric acid methyl ester are obtained in the form of a colourless oil.

Example W: 4-Chloro-4.4-difluorobut~ic acid ClF2C-CH2-CH2-COOH

15.6 g of 4-chloro-4,4-difluorocrotonic acid are dissolved in 160 ml of tetrahydrofuran and, after the addition of 0.8 g of 5 % Pd/BaS04 catalyst, treated with hydrogen gas at room temperature and under normal pressure until the amount of hydrogen absorbed is 100 % of the theoretical amount. After the catalyst has been filtered off and the solvent has been distilled off, the oil that remains is rectified in vacuo. There are obtained 12 g of a colourless oil which has a boiling point of 88-90C/11 mbar and is identical to the 4-chloro-4,4-difluorobutyric acid prepared in accordance with Exarnple P6a.

Example P10: 4-Chloro-4.4-difluoro-3-h~vdroxvbutyric acid ethvl ester ClF2C-CH-CH2-COOC2Hs I

OH

20.0 g of 4-chloro-4,4-difluoroacetoacetic acid ethyl ester are dissolved in 200 ml of tetrahydrofu-ran and, after the addition of 2.0 g of a S % rhodium/Al2O3 catalyst, hydro-genated with hydrogen gas under normal pressure and at room temperature until the theoretica1 arnount of hydrogen has been absorbed. It may be necessary to add additional fresh catalyst during the hydrogenation. The cata1yst is then filtered off and the so1vent is evaporated off under a waterjet vacuum. Rectification of the crude product yie1ds 18.0 g of pure 4-ch1Oro-4,4-difluoro-3-hydroxybutylic acid ethyl ester in the forrn of an oi1 that boi1s at 93-95C and 17 mbar and solidifies to form long needles.
Analvsis: C6HgClF2O3 (202.6) calc.: C 35.6 % H 4.5 % Cl 17.5 % F 18.8 %
found: C 35.5 % H 4.5 % Cl 17.1 % F 18.7 %

Examp1e Pl l: 4-Chloro-4.4-difluoro-3-acetoxYbutvric acid ethvl ester ClF2C-CH-CH2-COOC2Hs b-CO-CH3 20.2 g of 4-chloro-4,4-difluoro-3-hydroxybutyric acid ethyl ester and 0.1 g of anhydrous sodium acetate are dissolved in 50 m1 of acedc acid anhydride at +100C and stirred at that temperature for one hour. After the reaction mixture has been poured onto 150 ml of water, the product is taken up in diethyl ether. The ethereal phase is dried with sodium sulfate and the ether is then evaporated off in vacuo. Recdficadon of the crude product yields 20.1 g of 4-chloro-4,4-difluoro-3-acetoxybutyric acid ethyl ester in the forrn of a colourless oil that boils at 95-97C and 17 mbar.
AnalYsis: CgHl lClF2O4 (244.6) calc.: C 39.3 % H 4.5 % Cl 14.5 % F 15.5 %
found: C 39.2 % H 4.6 % Cl 14.4 % F 15.5 %

Example P12: 4-Chloro-4.4-difluorocrotonic acid ethyl ester ClF2C-CH=CH-COOC2Hs 24.4 g of 4-chloro-4,4-difluoro-3-acetoxybutyric acid ethyl ester and 40 ml of quino1ine are mixed together and heated in a disdlling apparatus. At a bath temperature of approxi-mately 200C, a colourless pungent oil having a boi1ing point of 140-145C disd1s off.
The crude product is taken up in diethy1 ether and washed with lN hydrochloric acid and with water. After the ether phase has been dried with sodium sulfate and the ether has been disdlled off, 14.0 g of 4-chloro-4,4-difluorocrotonic acid ethyl ester are obtained in the form of a colourless oil that boils at 41-43C and 12 mbar.
Analvsis: C6H7CIF2O2 (184.6) calc.: C39.0% H 3.8 % Cl 19.2% F20.6%
found: C39.3 % H 3.8 % Cl 19.0% F20.4%

The same product is obtained if 4-chloro-4,4-difluoro-3-hydroxybutyric acid ethyl ester is treated with phosphorus pentoxide in accordance with the method given by McBee et al.
in J. Amer. Chem. Soc.76 (1954) 3722 for 4,4,4-trifluoro-3-hydroxybutyric acid ethyl ester.

Example P13: 4-Chloro-4~4-difluorobutYric acid ethYl ester ClF2C-CEI2-CH2-COOC2Hs 18.4 g of 4-chloro-4,4-difluorocrotonic acid ethyl ester are dissolved in 200 ml of ethyl acetate and, after the addition of 2.0 g of a 5 % palladiumlbarium sulfate catalyst, treated with hydrogen gas under normal pressure and at room temperature. The hydrogenation is complete after a short time. After the catalyst has been filtered off, the solvent is evaporated off in vacuo and the residue is rectified. The product that distils at 154-156C
is identical to the 4-chloro-4,4-difluorobutyric acid ethyl ester prepared in accordance with Examples P2, P3 and P4.

The compounds mentioned in the following Tables are also prepared analogously to the above-described procedures.

Table 1:
ClF2C--fH--TH--CO--O--R3 Rl R2 Comp.
No- Rl _2 R3 PhYs. data 1.01 H H CH3 MS:(M+, CsH7ClF2O2) 1.02 H H C2H5 m/e. 186 1.03 H H C3H7~n 1.04 H H C3H7-i MS:(M+, C7HllclF2o2) 1.05 H H C4Hg-t Ms:(M+-l5~c7Hl lCIF202) 1.06 H H C4Hg-n MS:(M++l, C8Hl4clF2o2) 1.07 H H C6C13-n m/e: 242 1.08 H H CloH21-n m/e: 298 1.09 H H C20H4l-n m.p.: 33-35C
1.10 H H CH2C(CH3)3 m/e. 228 1.11 H H CH2CH2OH m/e: 202 1.12 H H CH2CH2O-COCH3 1.13 H H CH2CH2O-COOCH3 1.14 H H CH2CH2OCONHC6Hs 1.15 H H CH2CH2OC2H5 1.16 H H CH2CH20CH2CH20CH3 MS:(~I+, CgHlscL~2o4) 1.17 H H CH2Cc13 1.18 H H CH2CBr3 nD23 = l.SûS0 1.19 H H CH2CH2SCH3 1.20 H H CH2CH2OCH2C6Hs 1.21 H H CH2CH2Cl 1.22 H H CH2-C6HS m/e: 248 Table 1 (continued) Comp.
No- Rl _2 R3 PhYs. data 1.23 H H CH(CH3)C6Hs 1.24 H H CH(CH3)C6H5 (R) 1.25 H H CH(CH3)C6Hs (S) 1.26 H H CH2-C6H4-NO2-(4) 1.27 H H CH2-C6H4-NO2-(2) 1.28 H H CH2-C6H4-Cl-(2) 1.29 H H CH2-C6Hs-F-(4) 1.30 H H CH2-C6H4-O-C6Hs-(3) nD23= 1.5270 1.31 H H -C6H5 MS:(M+, CloHgclF2o2) m/e: 234 1.32 H H -C6H4-O-C6Hs-(4) nD23= 1.530 1.33 H H -C6H4-No2-(4) m.p. 81-82C
1.34 H H -C6H4-F-(4) 1.35 H H ~ Cl nD23 = 1.5109 1.36 H H -CH2CH2O ~ O ~ MS:(M+, Cl8Hl7clF2o4) mle: 370 1.37 H H -CH2CH2O ~ O ~ F m.p. 62-63C

1.38 H H -CH2CH2O ~ o ~ nD20 = 1.5380 FCl 1.39 H H -CH2cH2O ~ O ~ nD20= 1.5047 1.40 H H C6Hll-cycl. MS:(M+-35,ClOH15F2O2) mJe: 205 1.41 H H CsHg-cycl.

~2~4~4 Table 1 (continued) Comp.
No- Rl R2 R3 Phvs. data 1.42HHC3Hs-cycl.
1.43HH-c 1.44HH-CH2~

1.45HH-CH2~ MS:(M+-35.c8HllF2O2) m/e: 177 1.46HCF3-C2H5 MS:(M+,C7HgClFsO~) m/e: 254 1.47HH-CH2CH2O~

1.48HH ~ O~ F nD23 = 1.5150 1.49HHH b.p.88-90/11 mbar 1.50 HH-C16H33n l.51HH-CH(CH2CH2CH2cH3)2 1.52HH-CH2-(CH2)4~H2Cl 1.53HH-CH2-C(CH3)2CH2 ~ C2H5 1.54HH-CH2C(CH3)2-O ~ Cl 1.55HH-CH2CH2CH2CH2-CoHs 1.56 H H --CH2CH2--0~=~ Cl 1.57HH-CH2-CH=CH2 1.58HH-CH2CH=C(CH3)CH2CH2cH=c(cH3)2 1.59HH-CH2CH=C(CH3)CH2CH2CH=C(CH3)-CH2CH2CH=C(CH3)2 1.60HH-CH2-CH-CH

Table 1 (eontinued) Comp.
No. R1 R2 R3 Phys. data 1.61 H H -CH2CH2-C_C-(CH2)4CH3 1.62 H H -CH2CH20-SO2CH3 1.63 H H --CH2CH20--S02~ CH3 1.64 H H -CH2CH20-COC6Hs 1.65 H H {~} CH3 1.66 H H ~

1.67 H H ~3 Cl 1.68 H H ~ CH3 1.69 H H -CH2 ~3 - F F
1.70 H H -CH2 ~ F
F F

1.71 H H -CH2 ~ ,~

` 2023464 Table 1 (continued) Comp.
- No- Rl R2 B3 PhYs. data 1.72 H H -CH2 ~

1.73 H H -CH2-C6H4-Br-(4~
Br 1.74 H H -C

1.75 H H --CH2 ~ OCH2CH2CH2CH3 1.76 H H -CH2 ~ C (CH3) 3 1.77 H H -CH2~ Cl 1.78 H H -CH2-C6H4-Cl-(3) 1.79 H H -CH2-C6H4-CI-(4) 1.80 H H -CH
Cl 1.81 H H -CH2~ Cl 1.82 H H -CH (CH3) ~ Cl ~023464 Table 1 (continued) Comp.
No- Rl R2 R3 Phvs. data Cl 1.83 H H -CH2 ~3 1.84 H H -CH2~

1.85 H H -CH2 ~ CH3 1.86 H H -CH2 ~ OCH2CH3 1.87 H H -CH2-C6H4-C2Hs-(4) 1.88 H H -CH2-C6H4-F-(3) 1.89 H H -CH2-C6H4-OH-(4) 1.90 H H -CH2-C6H4-I-(4) 1.91 H H -CH2 ~ C3H7-i 1.92 H H -CHrC6H4-OCH3-(4) 1.93 H H -CH2-C6H4-CH3-(4) 1.94 H H -CH2(C2Hs)-C6H5 1.95 H H -CH2-C6H4-CF3-(4) 1.96 H H -CH2-C6H4-CF3-(3) 1.97 H H -CH2 ~ OCH3 2û23464 Table 1 (continued) Comp.
No- Rl R2 R3 Phvs.data 1.98 H H -CH2 ~ CH3 1.99 H H -CH2 ~L

1.100 H H -C6H4-Br-(4) 1.101 H H ~ O(CH2)3CH3 1.102 H H ~ C (CH3)3 1.103 H H ~ Cl 1.104 H H -C6H4-CI-(2) 1.105 H H -C6H4-C1-(3) 1.106 H H -C6H4-C1-(4) C(CH3)3 1.107 H H ~
C(CH3)3 Cl 1.108 H H ~

1.109 H H ~ Cl Cl 20~3464 Table 1 (continued) Comp.
No. Bl R2 R3 Phvs. data 1.110 H H ~F
F

1.111 H H ~

1.112 H H~ OC2H5 Cl Cl 1.113 H H~Cl .
Cl Cl F F
1.114 H H ~ F
F F

1.115 H H ~

F F
1.116 H H ~
F F

2~234~

Table 1 (continued) Comp.
No. Bl B2 B3 Cl Phys. data 1.117 H H ~l Cl 1.118 H H ~ CH3 1.119 H H ~ Cl 1.120 CH3 H -H
1.121 CH3 H -C6Hs 1.122 C2Hs H -C6Hs 1.123 C2Hs-n H -C6Hs 1.124 CH3 H -CH2CH2O~ ~3 1.125 CH(CH3)2 H -CH2CH20 ~ O ~ F
1.126 CH3 H -CH2c6Hs 1.127 C3H7-n H -H
1.128 H CF3 -CH2CH20 ~ O

~ .
.

2023~64 Table 1 (continued) Comp.
No- Rl R2 R3 PhYs. data 1.129 H H

1.130 H H

Cl 1.131 H H

Br 1.132 H H ~

1.133 H H {~ ~S_N

1.134 H H ~ S3/

Table 1 (continued) Comp.
No. Rl ~2 R3 PhYs. data 1.135 H H ~o~3CF3 m.p. 70C

1.136 H H ~3O~CI
N

1.137 H H ~O~CF3 N

1.138 C3H7-n H C2Hs 1.139 H H ~
O ~.3 CF3 1.140 H H -CH2-CH2-O ~ o ~Y
S-N

2023~4 Table 2:
ClF2C--fH--fH--CO--I--R4 Rl R2 R3 Comp.
No. Rl _2 ~4 R3 Phys. data 2.01 H H H -CH3 m.p. 61-63C
2.02 H H CH3 -CH3 MS:(M+, C6H10CIF2N) m/e: 185 2.03 H H C6H13-n -C6H13-n 2.04 H CF3 H -CH3 2.05 H H H -C2H5 m.p. 50-51C
2.06 H H H -C3H7-n 2.07 H H H -C3H7-i m.p. 84-85C
2.08 H H H -C4Hg-n m.p. 30C
2.09 H H H -C4Hg-t m.p. 97-98C
2.10 H H H -C6H13-n 2.11 H H H -C1oH21-n m.p. 4Q-41C
2.12 H H H -C20H4l-n 2.13 H H H -CH2C(CH3)3 2.14 H H H -CH2CH2OH
2.15 H H H -CH2CH2O-COC6Hs 2.16 H H H -CH2CH2O-COOCH3 2.17 H H H -CH2CH2O-CONHC6Hs 2.18 H H H -CH2CH2OC2Hs 2.19 H H H -CH2CF3 m.p. 55-56C
2.20 H H H -CH2CC13 2.21 H H H -cH(cH3)c6Hs m.p. 60-61C
2.æ H H H -CH(CH3)C6H5 (R) 2.23 H H H -CH(CH3)C6Hs (S) 2.24 H H H -CH2-C6H5 m.p. 74-75C
2.25 H H H -cH2-c6H4-No2-(4) 2.26 H H H -CH2-C6H4-F-(4) 2 27 H H H -CH2-C6H4-CI-(2) 228 H H H -C6Hs m.p. 121-122C
2.29 H H H -C6H4-NO2-(4) 2023~6~

Table 2 (continued) Comp.
No. Rl _2 R4 R3 PhYs. data 2.30 H H H -C6H4-F-(4) m.p.96-97C
2.31 H H H ~ ~ NO2 m.p. llO-111C
Cl 2.32 H H H ~Cl m.p.122-123C

2.33 H H CH3 -CH2 ~ MS:(M+,CllH13C~F2N20) m/e: 262 2.34 H H CH3 -CH2 ~ Cl N

2.35 H H H -CH2 ~ m.p.47-49C
N

2.36 H H H -C6H4-CN-(4) m.p.122-123C
2.37 H H H -C6H4-CF3-(2) m.p.106-107C
2.38 H H H -C6H4-c6Hs-(4) m.p.186-187C
2.39 H H H -C6H4-CF3-(3) m.p.77-79C

2.40 H H H ~ C ~ m.p.143-144C

2.41 H H H ~ ~ m.p.120-121C
2.42 H H H -C6H4-Cl-(2) m.p.105-106C
2.43 H H H -C6H4-Cl-(4) m.p.150-151C
2.44 H H H -C6H4-Cl-(3) m.p.93-94C
2.45 H H H -C6H4-OCH3-(4) m.p.113-114C
2.46 H H H -C6H4-CH3-(4) m.p.120-121C

Table2(continued) Comp.
No. RlR2 R4 R3 PhYs.data 2.47 HH H -C6H4-SCH3-(3) m.p. 88-89C
2.48 HH H H m.p.92-93C
2.49 HH H -Cl6H33-n 2.50 HH H -Cl8H37-n m.p. 71-72C
2.51 HH H -Cl2H2s-n 2.52 HH H -CgHlg-n 2.53 HH H -C8Hl7-n 2.54 HH H -CH2(CH3)-CH2CH2CH3 2.55 HH H -CH2CH2cH2cH2OH
2.56 HH H -CH2CH2CH2CH2OCH3 2.57 HH H -CH2CH2cH2cH2O-so2 ~ CH3 2.58 HH H -CH2CH2CH2CH2O-SO2CH3 2.59 HH H -CH2CH2O-CO~ Cl 2.60 HH H -CH2CH2O-CH2CF3 2.61 HH H -cH2cH2N(cH3)2 2.62 HH H -CH2(CH3)-CH2CH2CH2-N(CH2CH3)2 2.63 HH H -CH2CH2 {~OCH3 2.64 HH H -CH2CH2 ~

2.65 HH H -CH2(CH3)-C(CH3)3 2.66 HH H -CH2CH(OCH2CH3)2 2.67 HH H -CH2-CO-C6Hs 2.68 HH H -CH2~

20~346~

Table 2 (continued) Comp.
No. R1 R2 R4 R3 Phys. data 2.69 H H H -CH2 {>
2.70 H H H -CH2(CH3)-~H20CH3 2.71 H H H -cH2cH2-cH(cH3)2 2.72 H H H -CH2(CH2)7-CH=CH-(cH2~7cH3 2.73 H H CH3 -Cl8H37-n 2.74 H H CH3 -C3H7-n 2.75 H H CH3 -CH2cH2-c6Hs 2.76 H H H -CH2-C6H4-OCH3-(4) m.p. 106-108C
2.77 H H H -CH2-C6H4-F-(2) 2.79 H H H -CH2-C6H3-F2-(2,6) 2.80 H H H -cH2-c6H3-F2-(2~4) 2.80 H H H -CH2-C6H3-F2-(3.4) 2.81 H H H -CH2-C6H4-Cl-(4) m.p. 102-103C
2.82 H H H -CH2-C6H3-C12-(3,4) 2.83 H H H -CH2-C6H4-CF3-(4) 2.84 H H H -cH2-c6H4-No2-(3) 2.85 H H H -CH(C6Hs)2 2.86 H H H -CH2~ ~

2.87 H H H -CH2 (CH3)~ ~3 2.88 H H H -CH2 ~3 2Q2~64 Table 2 (continued) Comp.
No. Rl R2 R4 R3 PhYs. data 2.89 H H H -C

2.90 H H H -CH
N

2.91 H H H -CH2 ~N
2.92 H H CH3 -CH2-c6Hs 2.93 H H C2Hs -CH2-c6Hs 2.94 H H C3H7-i -CH2-c6Hs 2.95 H H C4Hg-n -CH2-C6H5 2.96 H H H -C6H1l-CYcl 2.97 H H H -C3Hs-cyclo 2.98 H H H {~ CH3 2.99 H H H ~

2.100 H H H -CH2-C_CH
2.101 H H CH3 -CH2-C_CH
2.102 H H H -CH2-CH_CH2 2.103 H H H -C6H4-COCH3-(4) 2.104 H H H -C6H4-CONH2-(3) 2.105 H H H -C6H4-CN-(3) Table 2 (continued) Comp.
No- Rl R2 R4 R3 Phvs. data 2.106 H H H o ~
W
2.107 H H H -C6H4-Br-(4) 2.108 H H H ~ CH3 Br 2.109 H H H ~ Br 2.110 H H H ~ Br Cl 2.111 H H H ~ sr 2.112 H H H ~ Cl 2.113 H H H ~ Cl Table 2 (continued) Comp.
No. Rl R2 R4 R3 Phvs. data 2.114 H H H ~ Cl 2.115 H H H ~ Cl 2.116 H H H ~ Cl Cl CH3 2.117 H H H ~ F

2.ll8 H H H

2.119 H H H ~ OCH3 2.120 H H H ~ CH3 2.121 H H H ~ CH2CH3 " 20~3~6~

Table 2 (continued) (~omp.
No. Rl R2 R4 R3 PhYs. data 2.122 H H H ~ CH3 2.123 H H H ~ I

2.124HH H ~ Cl CI

2.125 H H H ~F

2.126 H H H ~ CH3 2.127 H H H -C6H4-OH-(4) 2.128 H H H ~ O - S02~ CH3 2.12g H H H ~ OCH2CF3 ~023464 Table 2 (continued) Comp.
No. Rl R2 ~4 R3 Ph~/s. data 2.130 H H CH3 C6Hs 2.131 H H CH3 C6H4-No2-(4) 2.132 H H C2Hs C6H4-CI-(4) 2.133 CH3 H H -C6H5 2.134 CH3 H H -C2Hs 2.135 CH3 H H -CH2-c6Hs 2.136 C2H5 H H -CH2-c6Hs 2.137 C4Hg-n H H -CH2-C6Hs 2.138 H H CH3 -CH2-C6Hs 2.139 CH3 H CH3 -C6Hs 2.140 H H H ~o~3CF3m.p. 145-147C

2.141 H H H ~ N~ m.p. 207-208C

2.142 H H H ~ Si(CH3)3 m.p. 94-95C

2.143 H H H ~OC10H21-n m.p. 91-93C

2.144 H H H ~3N~3 m.p.62-64C

2023~64 Table 2 (continued) Comp.
No- Bl R2 ~4 B3 Phys. data 2.145 H H H ~}CH~ m.p. 179-l8loc Cl 2.146 H H H ~O-CF2-CF2H m.p. 114-115C

2.147 H H H ~O-CF2-CF2H m.p. 114-115C

2.148 H H H ~Br m.p. 149-151C

2.149 H H H -C(CH3)2 ~CI m.p. 131-133C

2.150 H H H ~OCF3 m.p. 88-90C

2.151 H H H ~S~ m.p. 130-133C

202'~464 Table 2 (continued) Comp.
No- Rl R2 R4 R3 Phvs. data 2.152 H H H ~}~m.p. 127-128C

2.153 H H H ~O~N

2.154 H H H ~O~N

2.155 H H H ~ ~CF3 2.156 H H H ~ N~` m.p. lB8-189C

2.157 H H H ~o~/ ~

2.158 H H H ~ N ~N2 2.159 H H H ~ N ~0~OCH3 - ss -Table 2 (continued) Comp.
No- Rl B2 R4 R3 Phys. data 2.160 H H H ~C ~/ ~CF3 2.161 H H H ~o~3CF3 m.p. 149-150~C

H3C Cl 2.162 H H H HaC CFI m.p.205-207C

~ Cl CF3 2.163 H O ~_ m.p. 107-109C
N

~CI F
2.164 H H H \=~ ~_ m.p. 137-139C
N

2.165 H H H ~O~CF2CFCI2 m.p. 130-132C
CH3 Cl 2.166 H H H ~O~CF2CFCI2 m.p. 122-124C

Table 2 (continued) Comp.
No- Rl R2 R4 R3 PhYs. data 2.167 H H H

~C
2.168 H H H Y ~g3cF3 ~ cooC2H5 2.169 H H H o~3CF3 2.170 H H H ~3 CF3 Cl 2,171 H H H ~O~CF3 Cl 2.172 H H H ~3 ~CF3 ~Br 2.173 H H H YO___~CF3 2~3464 Table 2 (continued) Comp.
No. Rl --2 R4 R3 Ph~s. data 2.174 H 0 ~3 CF3 2.175 H H H ~ S ~3 Cl ` .
H3C Cl 2.176 EI H H ~ N~

2.177 H H H ~N~

H3C~ N - N
2.178 H H H ~O~CI

2.179 H H H ~ o ~/N 3 2.180 H H H ~O~

-` 2023464 Table 2 (continued) Comp No. Rl R2 R4 R3 Phys. data 2.181 H H H ~ ~N

2.182 H H H ~~ \~
H3C N =~ CF3 2.183 H H H ~

2.184 H H H ~CI N~CH3 m.p.131-133 C
S N

2.185 H H H ~o~,N~Br 2.186 H H H -CH2CH2Cl m.p.43-44C
2.187 H H H -CH2-C6H4-N(CH3)2-(4) m.p.124-125C
2.188 H H H -CH2-C6H4-C(CH3)3-(4) m.p.121-122C
2.189 H H H -CH2-C6H4-CH3-(4) m.p.104-105C
2.190 H H H -CH(C2H~) ~O~m.p.97-98C

2.191 H H H -cH(C2Hs) ~~ F m.p.135C

~0`234~4 - 5~ -Table 2 (continued) Comp.
No- Rl R2 R4 R3 PhYs. data 2.192 H H H ~j 2.193 H H H ~ m.p. 135-136C

~CH3 2.194 H H H O ~ CF m.p. 93-96C

2.195 H H H ~~Cl m.p. 163-165C

2.196 H H H -CH2-C(CH3)2 ~OCH3 Formulation Examples (throughout, percentages are by weight) Exam~leFl: Emulsifiable concentrates a) b) c) compound no. 1.01 or 1.02 25 % 40 % 50 %
calcium dodecylbenzenesulfonate 5 % 8 % 6 %
castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 %
tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12 % 4 %
cyclohexanone - 15 % 20 %
xylenemixture 65 % 25 % 20 %

-`` 2023~64 Emulsions of any desired concentration can be produced from such concentrates bydilution with water.

Example F2: Solutions a) b) c) d) compoundno~ 1~04 80% 10% 5 % 95 %
ethylene glycol monomethyl ether 20 %
polyethylene glycol (mol. wt. 400) - 70 %
N-methyl-2-pyrrolidone - 20 % - -epoxidised coconut oil - - 1 % 5 %
ligroin (boiling range 160-190C) - - 94 %

The solutions are suitable for application in the form of micro-drops~

Example F3: Granulates a) b) compound no. 2.02 5 % 10 %
kaolin 94 %
highly dispersed silicic acid 1 %
attapulgite - 90 %

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

ExamPle F4: Dusts a) b) compound no. 1.45 2 % 5 %
highly dispe~sed silicic acid 1 % 5 %
ulcum 97 %
Icaolin 90 %

Ready-for-use dusts are obtained by intimately rnixing the carriers with the active ingredient.

.
' , ', .

202346~

Example F5: Wettable Powders a) b) c) compoundno. 2.09 25 % 50 % 75 %
sodium lignosulfonate 5 % 5 %
sodium laurylsulfate 3 % - 5 %
sodium diisobutylnaphthalene-sulfonate - 6 % 10 %
octylphenolpolyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 10 % 10 %
kaolin 62 % 27 %

The active ingredient is mixed with the adjuvants and the rnixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsifiable concentrate compound no. 2.01 10 %
oetylphenol polyethylene glycol ether (4-S moles of ethylene oxide) 3 %
calcium dodeeylbenzenesulfonate 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 %
cyclohexanone 30 %
xylene mixture S0 %

Emulsions of any desired concentration can be obtained from this concentrate by dilution with water.

Example F7: Dusts a) b) compound no. 2.24 S % 8 %
talcum 95 %
kaolin - 92 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and 202346~

grinding the mixture in a suitable mill.

Example F8: Extruder ~ranulate compound no. 2.08 10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %

The active ingredient is mixed and ground with the adjuvants, and the mixture ismoistened with water. The mixture is extruded, granulated and then dried in a stream of air.

Example F9: Coated ~ranulate compound no. 2.33 3 %
polyethylene glycol (mol. wt. 200) 3 %
kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.

Example F10: Suspension concentrate compound no. 2.07 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 %
water 32 %

The ~Inely ground active ingredient is intirnately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biolo~ical ExamPles Example Bl: Action a~ainst Boophilus microPlus Adult female ticks which are replete with blood are affixed to a PVC plate and covered with a cotton wool swab. For treatment, 10 ml of an aqueous test solution containing 125 ppm of the test compound are poured over the test insects. The cotton wool swab is then removed and the ticks are incubated for 4 weeks until oviposition has taken place.
The action against Boophilus microplus manifests itself either as mortality or ste~ility of the females or as ovicidal action in the eggs.

In this test, compounds of Tables 1 and 2 exhibit good activity against Boophilus microplus. In particular, compounds 1.01, 1.04, 1.05, 1.06, 1.10, 1.18, 1.21, 1.22, 1.30, 1.31, 1.33, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.45, 1.46, 2.01, 2.02, 2.05, 2.07, 2.0g, 2.09, 2.24, 2.28, 2.30, 2.31, 2.32, 2.33 and 2.35 are more than 80 % effective.

Example B2: Ovicidal action a~ainst Heliothis virescens Egg deposits of Heliothis virescens on filter paper are immersed for a short time in an aqueous acetone solution of the test compound having a concentration of 400 ppm. After the test solution has dried, the eggs are incubated in petri dishes. After 6 days, the percentage of eggs which have hatched is evaluated in compaIison with untreated controls (% reduction in the hatching rate).

Compounds of Tables 1 and 2 exhibit good activity against Heliothis virescens in this test.
In particular, compounds 1.01, 1.02, 1.04, 1.06, 1.10, 1.22, 1.31, 1.36, 1.40, 1.45, 1.46, 2.01, 2.02, 2.05, 2.07, 2.08, 2.24 and 2.28 are more than 80 % effective.

Example B3: Action a ainst Aonidiella aurantii Potato tubers are populated with crawlers of Aonidiella aurantii (red citrus scale). After about 2 weeks, the potatoes are immersed in an aqueous emulsion or suspension containing the test compound in a concentration of 400 ppm. After the treated potato tubers have dried, they are incubated in a plastics container. Evaluation is made 10-12 weeks later by comparing the survival rate of the crawlers of the first subsequent generation of the treated scale population with that of untreated controls.

Compounds of Tables 1 and 2 exhibit good activity against Aonidiella aurantii in this test.

2a23464 In particular, compounds 1.18, 1.21, 1.22, 1.30,1.31, 1.32, 1.33,1.35, 1.37, 1.38, 1.39, 1.48, 1.49, 2.01, 2.05, 2.07, 2.08, 2.30, 2.37, 2.42, 2.43, 2.44, 2.45, 2.46 and 2.48 are more than 80 % effective.

Example B4: Action a~ainst Nilaparvata lu~ens Rice plants are sprayed with an aqueous emulsion containing 400 ppm of test compound.
After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Nilaparvata lugens in this test.
In particular, compounds 1.10, 1.22, 1.30, 1.31, 1.33, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.45, 1.48, 1.49, 2.05, 2.07, 2.08, 2.24, 2.28, 2.30,2.31,2.32,2.33, 2.35, 2.3~,2.39, 2.41, 2.42, 2.43, 2.45, 2.46 and 2.47 are more than 80 % effective.

Example B5: Action a ainst Tetranvchus urticae Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion containing 400 ppm of the test compound.
The plants are then incubated for 6 days at 25C and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Tetranychus urticae in this test. In particular, compounds 1.30, 1.33, 1.35, 1.36, 1.38, 1.39, 2.28, 2.39, 2.41, 2.43 and 2.44 are more than 80 % effective.

Example B6: Action a~ainst Anthonomus ~randis adults Young cotton plants are sprayed with an aqueous emulsion containing 400 ppm of the test compound. After the spray coating has dried, the cotton plants are populated with 10 adults of Anthonomus grandis and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead beetles and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Anthonomus grandis in this test. In particular, compounds 1.22, 1.36, 1.37, 1.49, 2.28,2.32, 2.38 and 2.39 are more than 80 % effective.

Example B7: Action against Aphis craccivora Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture containing 400 ppm of the test compound, and incubated at 20C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Aphis craccivora in this test.
In particular, compounds 2.05, 2.07, 2.08, 2.24, 2.28, 2.35 and 2.39 are more than 80 %
effective.

Example B8: SYstemic action a~ainst Mvzus persicae Pea seedlings are infested with Myzus persicae and then placed with their roots in a spray mixture containing 400 ppm of the test compound and incubated at 20C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Myzus persicae in this test. In particular, compounds 2.05, 2.24 and 2.28 are more than 80 % effective.

Example B9: SYstemic action a~ainst Nilaparvata lu~ens Pots containing rice plants are placed in an aqueous emulsion solution containing 400 ppm of the test compound. The rice plants are then populated with larvae in the 2nd and 3rd stage. Evaluation is made 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of cicadas on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Nilaparvata lugens in this test.
In particular, compounds 1.01, 1.02, 1.04, 1.05, 1.06, 1.10, 1.18, 1.21, 1.22, 1.30, 1.31, 1.33, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.45, 1.46, 1.4~, 1.49, 2.01, 2.05, 2.07, 2.08, 2.09, 2.24, 2.28, 2.30, 2.31, 2.32, 2.33, 2.35, 2.36, 2.37, 2.38, 2.39,2.40, 2.41, 2.42,2.43, 2.44, 2.45, 2.46, 2.47 and 2.48 are still more than 80 % effective at 12.5 ppm.

202346~

Example B10: Ovicidal action against Adoxophves reticulana Egg deposits of Adoxophyes reticulana on filter paper are immersed for a short time in an aqueous acetone solution of the test compound having a concentration of 400 ppm. After the test solution has dried, the eggs are incubated in petri dishes. After 6 days, the percentage of eggs which have hatched is evaluated in comparison with untreated controls (% reduction in the hatching rate).

Compounds of Tables 1 and 2 exhibit good activity against Adoxophyes reticulana in this test. In particular, compounds 1.02, 1.22, 1.31, 1.36, 2.05, 2.07, 2.08 and 2.35 are more than 80 % effective.

Example B 11: Ovicidal/larvicidal action a~ainst Heliothis virescens Egg deposits of Heliothis virescens on cotton are sprayed with an aqueous emulsion containing 400 ppm of the test compound. 8 days later, the percentage of eggs which have hatched and the survival rate of the caterpillars are evaluated in comparison with untreated controls (% reduction in the population).

Compounds of Tables 1 and 2 exhibit good activity against Heliothis virescens in this test.
In particular, compounds 1.01, 1.02, 1.04, 1.05, 1.06,1.07, 1.08, 1.09, 1.10, 1.18, 1.21, 1.22, 1.30, 1.31, 1.32, 1.33, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.45, 1.46, 1.48, 1.49, 2.01, 2.02, 2.05, 2.07, 2.08, 2.09, 2.24, 2.28, 2.30, 2.31, 2.32, 2.33, 2.35, 2.36, 2.37, 2.38, 2.39, 2.40, 2.41, 2.42, 2.43, 2.44, 2.45, 2.46, 2.47 and 2.48 are more than 80 % effective.

Example B12: Action a~ainst Dermanvssus ~allinae 2 to 3 ml of a solution containing 10 ppm of test compound, and approximately 200 mites at various stages of development, are placed in a glass container that is open at the top.
The container is then closed with a cotton wool plug, shaken for 10 minutes until the mites are completely wetted, and then inverted for a short time so that the remaining test solution can be absorbed by the cotton wool. After 3 days, the mortality of the mites is determined.

Compounds of Tables 1 and 2 exhibit good activity against Dermanyssus gallinae in this test. In particular, compounds 1.04, 1.06, 1.10, 1.22, 1.31, 1.36, 1.40, 1.45, 2.01 and 2.02 are more than 80 % effective.

`` 202346~
-Example B13: Action a~ainst Heliothis virescens caterpillars Young soybean plants are sprayed with an aqueous emulsion containing 400 ppm of the test compound. After the spray coating has dried, the soybean plants are populated with 10 Heliothis virescens catelpillars in the first stage and placed in a plastics container.
Evaluation is made 6 days later. The percentage reduction in the population or the percen-tage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Heliothis virescens in this test.
In particular, compounds 2.01, 2.07, 2.24 and 2.33 are more than 80 % effective.
Example B 14: Ovicidal action a~ainst Cvdia pomonella Egg deposits of Cydia pomonella on filter paper are immersed for a short time in an aqueous acetone solution of the test compound having a concentration of 400 ppm. After the test solution has dlied, the eggs are incubated in petri dishes. After 6 days, the percentage of eggs which have hatched is evaluated in comparison with untreated controls (% reduction in the hatching rate).

Compounds of Tables 1 and 2 exhibit good activity against Cydia pomonella in this test.

Example B15: Action a ainst Nephotettix cincticeps Rice plants are sprayed with an aqueous emulsion containing 400 ppm of the test compound. After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of survi-ving cicadas on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Nephotettix cincticeps in this test. In particular, compounds 1.33, 1.37, 1.38, 1.49 and 2.48 are more than 80 %
effective.

Exam~le B16: Action a ainst Ctenocephalides felis 20 to 25 flea eggs are placed in a horizontal 50 ml cell culture bottle into which 15 g of flea larvae nutrient medium containing 100 ppm of the test compound have been ~0'~4~4 - ~8 -introduced beforehand. The test bottles are incubated in an incubator at 26-27C and 60-70 % humidity. After 21 days, the bottles are checked for the presence of adult fleas, unhatched pupae and larvae.

Compounds of Tables 1 and 2 exhibit good activity against Ctenocephalides felis in this test.

Example B 17: Action a~ainst Diabrotica balteata eggs 20 to 50 egg deposits of D. balteata on cloth filters are placed in a petti dish and sprayed with an aqueous emulsion containing 400 ppm of the test compound. The petri dishes are incubated at 24C. After 7 days, the percentage of eggs which have hatched is evaluated in comparison with untreated con~ols (% reduction in the hatching rate).

Compounds of Tables 1 and 2 exhibit good activity against Diabrotica balteata in this test.
In particular, compounds 2.05, 2.08 and 2.24 are more than 80 % effective.

Example ~18: Action against Bemisia tabaci e~s Dwarf bean plants are placed in gauze cages and populated with adults of Bemisia tabaci (whitefly). When oviposition has taken place, all the adults are removed and 2 days later the plants and the nymphs located thereon are sprayed with an aqueous emulsion of the test compounds (concentra~ion 400 ppm). Evaluation is made 10 days after application of the test compound by deterrnining the % hatching rate in comparison with untreated controls.

Compounds of Tables 1 and 2 exhibit good activity against Bemisia tabaci in this test.

Claims (21)

1. 4-Chloro-4,4-difluorobutyric acid derivatives of formula I
(I) wherein R1 and R2 independently of one another are hydrogen, C1-C4alkyl or C1-C4haloalkyl, R3 is hydrogen or an organic radical and X is oxygen or -NR4-, in which R4 is hydrogen or C1-C6alkyl.
2. Compounds according to claim 1, wherein R3 is hydrogen or C1-C20alkyl, C3-C7cycloalkyl, C3-C20alkenyl, C3-C20alkynyl, benzyl or aryl, each of which is substituted or unsubstituted.
3. Compounds according to claim 1, wherein R3 is hydrogen, C1-C20alkyl, C3-C7cycloalkyl, C3-C20alkenyl, C3-C20alkynyl,aryl, C3-C20haloalkenyl, C3-C20halo-alkynyl; C3-C7cycloalkyl substituted by halogen or by C1-C4alkyl; aryl substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C12alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, C1-C4alkylphenoxy, C1-C4haloalkylphenoxy, tri-C1-C4alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C1-C4alkylamino, di-C1-C4alkylamino, anilino, N-C1-C4alkylanilino, N-formylanilino, N-C1-C6alkylcarbonylanilino, phenylthio or by halophenylthio; phenyl substituted by an unsubstituted or substituted, aromatic or non-aromatic, monocyclic or bicyclic heterocycle that is bonded via oxygen or sulfur, in which both the heterocycle and the phenyl ring may each be substituted by halogen, C1-C4alkyl, nitro, C1-C4haloalkyl, C1-C4haloalkoxy, C1-C4alkoxy, C1-C4alkylthio or by cyclopropyl; or C1-C20alkyl substituted by hydroxy, halogen, di-C1-C4alkylamino, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkoxyalkoxy, C1-C4haloalkylthio, C1-C4-alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkylsulfonyloxy, C1-C4alkyl-carbonyl, C1-C4alkoxycarbonyl, C1-C6alkylcarbonyloxy, C3-C7cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or by pyridyl, in which the aryl and pyridyl groups may each be substituted by halogen, C1-C4alkyl, C1-C4-haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.
4. Compounds according to claim 1, wherein R1 and R2 independently of one another are hydrogen or C1-C4alkyl, but preferably hydrogen.
5. Compounds according to claim 1, wherein X is oxygen, -NH-, -NCH3- or -NC2H5-, but preferably oxygen or -NH-.
6. Compounds according to claim 3, wherein R3 is phenyl substituted in the 4-position by an aromatic monocyclic or bicyclic heterocycle bonded via oxygen and selected from the group pyridine, pyrimidine and benzothiazole, in which both aromatic rings are unsubstituted or together carry not more than three further substituents from the group chlorine, bromine, methyl, ethyl and trifluoromethyl.
7. Compounds according to claim 3, wherein R1 and R2 independently of one another are hydrogen or C1-C4alkyl, X is oxygen or -NR4- and R4 is hydrogen, methyl or ethyl and R3 is hydrogen, C1-C20alkyl, C3-C7cycloalkyl, C3-C20alkenyl, C3-C20alkynyl, phenyl, naphthyl, C3-C20haloalkenyl, C3-C20haloalkynyl, C3-C7cycloalkyl substituted by fluorine, chlorine, bromine or by C1-C3alkyl, phenyl or naphthyl substituted by fluorine, chlorine, bromine or C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, nitro, cyano, phenoxy, halophenoxy, C1-C4alkylphenoxy, C1-C4haloalkylphenoxy, tri-C1-C4alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C1-C4alkylamino, di-C1-C4alkylamino, amilino, N-C1-C4alkylanilino, N-formylanilino, N-C1-C6alkylcarbonylanilino, phenylthio or by halophenylthio, or C1-C20alkyl substituted by hydroxy, fluorine, chlorine, bromine, di-C1-C4alkylamino, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkoxyalkoxy, C1-C4-haloalkylthio, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-sulfonyloxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C6alkylcarbonyloxy, C3-C7cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfonyloxy or by pyridyl, in which the phenyl and pyridyl groups may each be substituted by fluorine, chlorine, bromine, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, nitro,cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.
8. Compounds according to claim 1, wherein R1 and R2 independently of one another are hydrogen or C1-C4alkyl, X is oxygen or -NR4-, R4 is hydrogen, methyl or ethyl, R3 is phenyl, benzyl, naphthyl or 3-pyridylmethyl or phenyl, benzyl, naphthyl or 3-pyridylmethyl each of which is substituted by fluorine, chlorine, bromine, C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C3alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.
9. Compounds according to claim 1, wherein R1 and R2 independently of one another are hydrogen or C1-C4alkyl, X is oxygen or -NR4-, R4 is hydrogen or C1-C4alkyl, R3 is C1-C12alkyl or C1-C12alkyl substituted by hydroxy, fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or by phenoxy, in which the phenyl or phenoxy radical may be substituted by fluorine, chlorine, bromine, phenoxy, halophenoxy or by phenylthio.
10. Compounds according to claim 1, wherein R1 and R2 independently of one another are hydrogen or C1-C4alkyl, X is oxygen or -NR4-, R4 is hydrogen or C1-C4alkyl, R3 is C3-C12alkenyl or C3-C12alkynyl or C3-C12alkenyl or C3-C12alkynyl each of which is substituted by fluorine, chlorine or by bromine.
11. Compounds according to claim 3, wherein R1 and R2 are hydrogen and X is oxygen, -NH-, -NCH3- or-NC2H5-.
12. Compounds according to claim 1, selected from the group 4-chloro-4,4-difluorobutyric acid methyl ester, 4-chloro-4,4-difluorobutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid isopropyl ester, 4-chloro-4,4-difluorobutyric acid tert.-butyl ester, 4-chloro-4,4-difluorobutyric acid n-butyl ester, 4-chloro-4,4-difluorobutyric acid (2,2-dimethylpropyl) ester, 4-chloro-4,4-difluorobutyric acid benzyl ester, 4-chloro-4,4-difluorobutyric acid phenyl ester, 4-chloro-4,4-difluorobutyric acid [2-(4-phenoxyphenoxy)-ethyl] ester, 4-chloro-4,4-difluorobutyric acid cyclohexyl ester, 4-chloro-4,4-difluorobutyric acid cyclohexylmethyl ester, 4-chloro-4,4-difluorobutyric acid cyclopropylmethyl ester, 4-chloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid N-methylamide, 4-chloro-4,4-difluorobutyric acid N,N-dimethylamide, 4-chloro-4,4-difluorobutyric acid N,N-dihexylamide, 4-chloro-4,4-difluorobutyric acid N-ethylamide, 4-chloro-4,4-difluorobutyric acid N-isopropylamide, 4-chloro-4,4-difluorobutyric acid N-butylamide, 4-chloro-4,4-difluorobutyric acid N-tert.-butylamide, 4-chloro-4,4-difluorobutyric acid N-benzylamide, 4-chloro-4,4-difluorobutyric acid anilide, 4-chloro-4,4-difluorobutyric acid N-methyl-N-pyrid-3-ylmethylamide, 4-chloro-4,4-difluorobutyric acid N-pyrid-3-ylmethylamide, 4-chloro-4,4-difluorobutyric acid (4-chloroanilide), 4-chloro-4,4-difluorobutyric acid (4-phenoxyanilide), 4-chloro-4,4-difluorobutyric acid (2-chloroanilide), 4-chloro-4,4-difluorobutyric acid (4-methoxyanilide), 4-chloro-4,4-difluorobutyric acid (4-methylanilide), 4-chloro-4,4-difluorobutyric acid (3-methylmercaptoanilide), 4-chloro-4,4-difluorobutyric acid (4-fluoroanilide), 4-chloro-4,4-difluorobutyric acid (4-chloro-2-nitroanilide), 4-chloro-4,4-difluorobutyric acid (3-phenoxybenzyl) ester, 4-chloro-4,4-difluorobutyric acid [4-(4-fluorophenoxy)-phenyl] ester, 4-chloro-4,4-difluorobutyric acid [4-(4-fluorophenoxy)-phenoxyethyl] ester, 4-chloro-4,4-difluorobutyric acid (4-nitrophenyl) ester, 4-chloro-4,4-difluorobutyric acid [4-(3,5-difluorophenoxy)-phenyl] ester, 4-chloro-4,4-difluorobutyric acid [4-(5-trifluoromethylpyrid-2-yloxy)-phenyl] ester, 4-chloro-4,4-difluorobutyric acid and 4-chloro-4,4-difluorobutyric acid amide.
13. A process for the preparation of the compounds of formula I according to claim 1, which comprises either a) reacting a 4-chloro-4,4-difluorobutyric acid halide of formula II
(II), wherein R1 and R2 are as defined under formula I and Hal is halogen, preferably chlorine or bromine, with a compound of formula III

H-X-R3 (III), wherein X and R3 are as defined under formula I, in the presence of a base, or b) reacting 4-chloro-4,4-difluorobutyric acid of forrnula Ic (Ic), wherein R1 and R2 are as defined under formula I, with a compound of formula III in the presence of water-removing agent.
14. A pesticidal composition, which contains as active ingredient at least one compound of formula I according to claim 1.
15. A composition according to claim 14, which contains in addition at least one carrier.
16. The use of a compound of formula I according to claim 1 for controlling pests on animals and plants.
17. The use according to claim 16, wherein the pests are plant-destructive insects and arachnids.
18. A method of controlling insects and arachnids that are harmful to animals and plants, which comprises treating the pests or the locus thereof with an effective amount of a compound of formula I according to claim 1.
19. 4-Chloro-4,4-difluorobutyric acid halides of formula II

(II), wherein R1 and R2 independently of one another are hydrogen, C1-C4alkyl or C1-C4haloalkyl, and Hal is halogen, preferably chlorine or bromine.
20. 4-Chloro-4,4-difluorocrotonic acid derivatives of formula VIII

(VIII), wherein R is C1-C6alkyl, R1 and R2 independendy of one another are hydrogen, C1-C4alkyl or C1-C4haloalkyl, X is oxygen or-NR4-, in which R4 is hydrogen or C1-C6alkyl.
21. A process for the preparation of the compounds of formula I, which compriseshydrogenating a 4-chloro-4,4-difluorocrotonic acid derivative of formula VIII

(VIII), wherein R is hydrogen or C1-C6alkyl, R1 and R2 independently of one another are hydrogen, C1-C4alkyl or C1-C4haloalkyl, R3 is hydrogen or an organic radical and X is oxygen or -NR4-, in which R4 is hydrogen or C1-C6alkyl, with hydrogen in the presence of a catalyst and convçrting the resulting compounds of formula Id (Id), wherein R1, R2, X and R are as defined above, into the other compounds of formula I
according to claim 1 by hydrolysis, transesterification or transamidation.
CA002023464A 1989-08-18 1990-08-16 Butyric acid derivatives Abandoned CA2023464A1 (en)

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