HRP940499A2 - Butric acid derivatives - Google Patents

Abstract

Novel 4-chloro-4,4-difluorobutyric acid derivatives of the formula I <IMAGE> in which R1 and R2 independently of one another are hydrogen, C1-C4-alkyl or C1-C4-haloalkyl, R3 is hydrogen or an organic radical and X is oxygen or -NR4-, where R4 represents hydrogen or C1-C6-alkyl, can be employed as pesticides. Insects and arachnids can preferably be controlled.

Description

The proposed invention relates to new derivatives of 4-chloro-4,4-difluorobutyric acid, to the process and intermediate products for their preparation, to means for destroying pests containing these compounds, as well as to their use in pest control.

Derivatives of 4-chloro-4,4-difluorobutyric acid according to the invention correspond to formula 1

[image]

in which R1 and R2 are independently hydrogen, C1-C4-alkyl or C1-C4-haloalkyl,

R3 is hydrogen or an organic residue and X is oxygen or -NR4-,

wherein R 4 is hydrogen or C 1 -C 6 -alkyl.

A number of polyhalogenated butyric acid chlorides are known from the literature as products for pyrethroid haloketones from Helv.Chim.Acta 63, p. 1947-1957 (1980).

In the definition for R3, the named organic residue means any organic residue, which can be attached in the form of an alcohol or an amine to the carbonyl group of 4-chloro-4,4-difluorobutyric acid. First of all, the alcohol or amino group of that organic residue is attached to a carbon atom. Thus, the residue R3 is primarily attached via the carbon atom to the -CO-X group. R 3 denotes, for example, always substituted or unsubstituted C 1 -C 20 -alkyl, C 3 -C 7 -cycloalkyl, C 3 -C 20 -alkenyl, C 3 -C 20 -alkynyl, benzyl or aryl. In the context of the proposed invention, R3 preferably denotes C1-C20 alkyl, C3-C7-cycloalkyl, C3-C20-alkenyl, C3-C20-alkynyl, aryl, C3-C20 haloalkenyl, C3-C20-haloalkynyl; C3-C7-cycloalkyl substituted with halogen or C1-C4-alkyl; halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C12-alkoxy, C1-C4-halogenalkoxy, C1-C4-alldlthio, nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, C1-C4-alkylphenoxy, C1-C4-haloalkylphenoxy, tri-C1-C4-alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C1-C4-alkylamino, di-C1-C4- alkylamino, anilino, N-C1-C4-alkylanilino, N-formylanilino, N-C1-C6-alkylcarbonylanilino, phenylthio or halophenylthio substituted aryl; phenyl substituted with an unsubstituted or substituted aromatic or non-aromatic, mono- or bicyclic heterocycle bound via oxygen or sulfur, wherein both the heterocyclic and phenyl rings are always substituted with halogen, C1-C4-alkyl; nitro, C1-C4-haloalkyl, C1 -C4-halogenalkoxy, C1-C4-alkoxy, C1-C4-alkylthio or cyclopril; or C1-C20-alkyl substituted with hydroxy, halogen, di-C1-C4-alkylamino, C1-C4- alkoxy, C1-C4 halo- alkoxy, C2-C6- alkoxyalkoxy, C1-C4-haloalkylthio, C1-C4-alkylthio, C1 -C4-alkylsulfinyl, C1-C4-alkylsulfonyloxy, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C6-alkylcarbonyloxy, C3-C7-cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl , wherein the aryl and pyridyl groups can always be substituted with halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C4-alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio.

In the definition of compounds of formula I in terms of the invention, individual generic terms have the following meaning:

Substituents that appear as halogen atoms are fluorine and chlorine, as well as bromine and iodine, with fluorine, chlorine and bromine being preferred. By halogen is meant either an independent substituent or a part of a substituent as in halocyclo, haloalkyl, haloalloythio, haloalkoxy, halophenylthio or halophenoxy.

Substituents that come into consideration as alkyl-, alkylthio, alkoxyalkoxy- and lkoxy radicals can be straight-chain or branched. Examples of such alkyls are methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl, tert-butyl or pentyl, hexyl, octyl, decyl, dodecyl and their isomers. Examples of alkoxy radicals include: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers. Alkylthio stands for example for methylthio, ethylthio, isopropylthio, propylthio or butylthio isomers.

If the substituents appearing as alkyl, alkoxy, alkenyl, alkynyl or aryl groups are substituted with halogen, they may be partially or completely perhalogenated. At the same time, the above definitions apply to halogen, alkyl and alkoxy. Examples of alkyl elements of these groups are mono- to tri-substituted methyl with fluorine, chlorine and/or bromine, such as CHF2 or CF3; from one to five times fluorine, chlorine and/or bromine substituted ethyl, for example CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2 CF2CHF2, CF2CHF2, CH2CHBr2, CH2CHClF, CH2CHBrF or CClFCHClF; propyl or isopropyl substituted one to seven times with fluorine, chlorine and/or bromine, for example CH2CHBrCH2Br, CF2CHFCF5, CH2CF2CF3 or CH(CF3)2; bulyl substituted one to nine times with fluorine, chlorine and/or bromine or one of its isomers, such as CF(CF3)CHFCF3 or CH2 (CF2)2CF3.

When the alkyl, cycloalkyl or aryl groups defined by R3 are substituted with other substituents, they can be single or multiple substituted either with the same or with different listed substituents. Exceptionally, substituted groups include one or two of the following substituents.

Substituents appearing as cycloalkyl residues denote, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkenyl and alkynyl groups have one or more, preferably no more than three unsaturated carbon-carbon bonds. Double or triple bonds are separated at the binding site by a bridge X with at least one saturated carbon atom. Typical representatives are allyl, methallyl, 2-butenyl, 3-butenyl, propargyl, 2-butmyl or 3-butynyl.

Aryl denotes an aromatic hydrocarbon residue. First of all, by aryl we mean phenyl or naphthyl.

Examples of alkoxyloxy radicals are methoxymethoxy, methoxyethoxy, ethoxyethoxy, ethoxymethoxy, propoxymethoxy, ethoxymethoxy, propoxyethoxy, methoxypropoxy, butoxymethoxy or propoxyethoxy.

Examples of alkoxycarbonyl radicals are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl. Alkylcarbonyl denotes, for example, acetyl, propionyl, butyne or valeryl, as well as their isomers. Alkylcarbonyloxy means, for example, acetoxy, propionyloxy or butyryloxy.

Examples of aromatic and non-aromatic, mono- or bicyclic heterocycles that are attached to phenyl nuclei defined by R3, attached via an oxygen or sulfur atom, are the following basic cyclic skeletons: pyridine, pyrazine, pyridazine, pyrimidine, pyridoline, thiazole, thiadiazole, oxazole, benzothiazole, triazine, oxadiazole, quinoline, cmoxaline, quinazoline, isoquinoline, phthalazine, naphthyridine, cinnoline, pteridine, triazole, piperidine or benzoxazole. These heterocycles are preferably attached via an oxygen or sulfur bridge at position 4 of the phenyl ring. The oxygen or sulfur bridge alone carries the carbon atom of the heterocyclic heterocycle. Both the phenyl nucleus and the heterocyclic one can carry additional substituents, for example up to three residues from the halogen, allyl, haloalkyl and alkyl groups, or always one or two substituents from the nitro, halogen alkoxy, alkylthio and cycloalkyl groups. The total number of substituents on the phenyl ring and heterocycle is usually no more than four. Generally, these groups carry a maximum of three further substituents from the chlorine, bromine, methyl, ethyl and trifluoromethyl groups, and they are connected through an oxygen atom.

Among these compounds, it is worth mentioning above all those in which R3 denotes aromatic mono- or bicyclic heterocycles from the group of pyridine, pyrimidine or benzothiazole substituted by phenyl at position 4 through oxygen, where both aromatic rings are unsubstituted or together bear a maximum of three further substituents from chlorine, bromine, methyl, ethyl and trifluoromethyl groups.

First of all, of individual meaning are the following by definition for R3. phenyl radicals substituted with a heterocycle via oxygen or sulfur:

-4-(3-methylthiadiazol-5-yloxy)-phenyl,

-4-(4-bromothiazol-2-yloxy)-phenyl,

-4-(5-trifluoromethylpyrid-2-yloxy)-phenyl,

-4-(3,5-dichloropyrid-2-yloxy)-phenyl,

-4-(3-chloro-5-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-(phenylthio)-phenyl,

-4-(2-cyclopropyl-4-trifluoromethyl-pyrimidin-6-yloxy)-phenyl,

-4-(2-tert.butyl-4-trifluoromethyl-pyrimidin-6-yloxy)-phenyl,

-4-(2-methylthio-4-methyl-pyrimidin-6-yloxy)-phenyl,

-4-(2-methyl-4-trifluoromethyl-pyrimidin-6-yloxy)-phenyl,

-4-(6-trifluoromethoxy-benzothiazol-2-yloxy)-phenyl,

-4-(6-chlorobenzothiazol-2-yloxy)-phenyl,

-4-(6-nitrobenzothiazol-2-yloxy)-phenyl,

-4-(6-methoxybenzothiazol-2-yloxy)-phenyl,

-4-(5-trifluoromethyl-benzothiazol-2-yloxy)-phenyl,

-3,5-dichloro-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl,

-2,6-dimethyl-4-(3-chloro-5-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-14,2trifluoroethyl)-pyrid-2-yloxy]-phenyl,

-4-[3-chloro-5-(2,2-dichloro-1,1,2-trifluoroethyl)-pyrido-2-floxy]-phenyl,

-4-(N-acetyl-pyrid-3-ylamino)-phenyl,

-2,4-dichloro-3-(3-chloro-5-trifluonetylpyrid-2-yloxy)-phenyl,

-4-ethoxycarbonyl-3-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl,

-3-methyl-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl,

-3,5-dichloro-4-(5-trifluoromethylpyrid-2-yloxy)-phenyl,

-4-(6-chloro-4-trifluoromethylpyrid-2-yloxy)-phenyl,

-4-bromo-3-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl,

-3-(5-trifluoromethylpyrid-2-yloxy)-phenyl,

-2,6-dimethyl-4-(3,5-dichloropyrid-2-ylthio)-phenyl,

-2,6-dimethyl-4-(2-chloropyridazine-6-floxy)-phenyl,

-2,6-dimethyl-4-(pyrimidin-2-yloxy)-phenyl,

-2,6-dimethyl-4-(pyrazin-2-yloxy)-phenyl,

-2,6-dimethyl-4-(6-chloro-quinoxalin-2-yloxy)-phenyl,

-2,6-dimethyl-4-(6-trifluoromethfl-ildnoxaline-2-floxy)-phenyl,

-2,6-dimethyl-4-(quinolin-2-yloxy)-phenyl,

-4-chloro-2-fluoro-5-(3-methyl-1,2,4-thiadiazol-5-yloxy)-phenyl,

-2,6-dimethyl-4-(4-bromo-thiazol-2-yloxy)phenyl but

-4-methyl-3-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl.

Among the compounds of formula I, above all there are such subgroups, in which

a) R1 and R2 independently of each other mean hydrogen or C1-C4-alkyl, or

b) X denotes oxygen, -NH-, -NCH3- or NC2H5-, or

c) R3 denotes hydrogen, C1-C20-alkyl, C3-C7-cycloalkyl, C3-C20-alkenyl, C3-C20-alkynyl, phenyl, naphthyl, C3-C20-haloalkenyl, C3-C20-haloalkynyl; C3-C7-cycloalkyl substituted by fluorine, chlorine, bromine or C1-C3-alkyl; fluoro, chloro, bromo or C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkyloxy, C1-C3-alkylthio, nitro, cyano, phenoxy, halophenoxy, C1-C4-alkylphenoxy, C1-C4-haloalkylphenoxy, tri-C1-C4-alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C1-C4-alkylamino, di-C1-C4- alkylamino, anilino, N-C1-C4-alkylanilmo, N-formylanilino, N-C1-C6-alkylcarbonylanilino, phenylthio or halophenylthio substituted phenyl or naphthyl or with hydroxy, fluoro, chloro, bromo, di-C1-C4-alkylamino, C1 -C4-Alkoxy, C1-C4-halogenalkoxy, C2-C6-Alkoxyalkoxy, C1-C4-halogenalkylthio, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkylsulfonyloxy, C1-C4 C1-C20-alkyl substituted by -alkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C6 alkylcarbonyloxy, C3-C7-cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfonyloxy or pyridyl, whereby phenyl and pyridyl groups can always be substituted with fluorine, chlorine , bromine, C1-C3-alkyl, C1-C 3-Haloalkyl, C1-C3-Alkoxy, C1-C3-Haloalkyloxy, C1-C3-Alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio, or

d) R3 denotes phenyl substituted in position 4 by an aromatic mono- or bicyclic heterocycle from the pyridine, pyrimidine or benzothiazole type, where both aromatic rings are unsubstituted or together have at most three further substituents from the chlorine, bromine, methyl ethyl and trifluoromethyl group.

Among the compounds of subgroup a), those in which R1 and R2 denote hydrogen are preferred.

The compounds of subgroup b) are preferably those in which X denotes oxygen or -NH-.

A particularly exceptional group of active substances of formula I is important in that R 1 and R 2 independently of each other denote hydrogen or C 1 -C 4 -alkyl., X is oxygen or NR 4 and R 4 is hydrogen, methyl or ethyl. When R1 and R2 are hydrogen, particularly important compounds of formula I are characterized.

From the subgroup of compounds c) of formula I, preferred are those in which R3 denotes phenyl, benzyl, naphthyl, 3-pyridylmethyl or always with fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3 -Alkoxy, C1-C3-halogenal coco si, C1-C3-alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio substituted phenyl, benzyl, naphthyl or 3-pyridylniethyl. Among these compounds, those where R1 and R2 independently of each other denote hydrogen or C1-C4-alkyl, X is oxygen or -NR4 and R4 is water, methyl or ethyl.

On the other hand, in subgroup c) of compounds of formula I, those in which R3 denotes C1-C12-alkyl, or with hydroxy, fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or phenoxy substituted C1-C12-alkyl, wherein the phenyl or phenoxy residue may be substituted with fluorine, chlorine, bromine, phenoxy, halophenoxy or phenylthio. Of this group of compounds, those in which R1 and R2 independently of one another denote hydrogen or C1-C4-alkyl, X is oxygen or -NR4 and R4 is hydrogen or C1-C4alkyl. The special designations R1 and R2 in preferred embodiments always denote hydrogen.

A very interesting group of compounds from subgroup c) of formula I is distinguished by the fact that R3 denotes C3-C12-alkenyl, C3-C12-alkynyl, or always C3-C12 alkenyl or C3-C12-alkynyl substituted by fluorine, chlorine or bromine. From this group of compounds, those in which R1 and R2 independently of each other denote hydrogen or C1-C4-alkyl, X is oxygen or -NR4 and R4 is hydrogen or C1-C4-alkyl. The R1 and R2 designations for hydrogen are particularly advantageous.

The following individual compounds of formula I are preferred:

4-chloro-4,4-difluorobutyric acid methyl ester,

4-chloro-4,4-difluorobutyric acid ethyl ester,

4-chloro-4,4-difluorobutyric acid isopropyl ester,

tert-butyl ester of 4-chloro-4,4-difluorobutyric acid,

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 phenylene,

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 cyclopropyl methyl ester 4,4 difluorobutyric acid, 4-chloro-4,4-difluoromethylbutyric acid ethyl ester,

N-methylamide of 4-chloro-4,4-difluorobutyric acid,

4-chloro-4,4-difluorobutyric acid N,N-dimethylamide,

N,N-dihexylamide of 4-chloro-4,4-difluorobutyric acid,

4chloro-4,4-difluorobutyric acid N-ethylamide,

N-isopropylamide of 4-chloro-4,4-difluorobutyric acid,

N-butylamide of 4-chloro-4,4-difluorobutyric acid,

N-tert-butylamide of 4-chloro-4,4-difluorobutyric acid,

N-benzylamide of 4-chloro-4,4difluorobutyric acid,

4-chloro-4,4-difluorobutyric acid anilide,

4-chloro-4,4-difluorobutyric acid N-methyl-N-pyrid-3ylmethylamide,

N-pyrid-3-ylmethylamide of 4-chloro-4,4-difluorobutyric acid,

(4-chloro-anilide) 4-chloro-4,4-difluorobutyric acid,

(4-phenoxy-anilide) 4-chloro-4,4-difluorobutyric acid,

(4-chloro-anilide) 4-chloro-4,4-difluorobutyric acid,

(4-methoxy-anilide) 4-chloro-4,4-diluorobutyric acid,

(4-methyl-anilide) 4-chloro-4,4-difluorobutyric acid,

(3-methylmercaplo-anilide) 4-chloro-4,4difluorobutyric acid,

(4-fluoro-anilide) 4-chloro-4,4-difluorobutyric acid,

(4-chloro-2-nitro-anilide) 4-chloro-4,4-difluorobutyric acid,

4-chloro-4,4-difluorobutyric acid (3-phenoxy-benzyl)-ester,

4-chloro-4,4-difluorobutyric acid [4-(4-fluoro-phenoxy)-phenyl]-ester,

4-chloro-4,4-difluorobutyric acid [4-(4-fluoro-phenoxy)-phenoxy-ethyl]-ester,

4-chloro-4,4-difluorobutyric acid (4-nitro-phenyl)-ester,

4-chloro-4,4-difluorobutyric acid [4-(3,5-difluoro-phenoxy)-phenyl]-ester,

4-chloro-4,4-difluorobutyric acid [4-(5-trifluorothiethyl-pyrid-2-yloxy)-phenyl]ester,

4-chloro-4,4-difluorobutyric acid

and 4-chloro-4,4-difluorobutyric acid amide.

Compounds of formula I in terms of the invention can be prepared by analogy with known procedures.

Compounds of formula I can be obtained, for example, by

a) 4-chloro-4,4-difluorobutyric acid halide of formula II

[image]

which has R1 and R2 of the meaning stated in formula I and Hal which denotes halogen, preferably chlorine or bromine, convert in the presence of a base, by reaction with the compound of formula III

[image]

which have X and R3 as defined in formula I, or

b) 4-chloro-4,4-difluorobutyric acid of formula Ic

[image]

which have R1 and R2 of the meaning stated in formula I, convert in the presence of a water-extracting agent, by reaction with the compound of formula III.

The conversion in process a) (II + III = I) takes place primarily in an inert solvent without hydroxyl groups in the presence of an organic base, for example pyridine, 4-dimethylaminopyridine, lutidine, collidre, trialkylamine, N,N-dialkylamine or a bicyclic non-nucleophilic base such as l, 4-diazabicyclo[2.2.2]-octane (DABCO), 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 performed at temperatures from -30 to +, mostly from -10 to +. We work deliberately in the presence of solvents or solvent mixtures that are inert to the reaction. Suitable for this purpose are, for example, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, petroleum ether, hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachlorocarbon, tetrachloroethylene; ether and ether compounds such as dialkylether (diethylether, diisopropylether, tert-butylmethylether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (ethyl acetate), propyl acetate or butyl acetate; ketones such as acetone, diethyl ketone, methyl ethyl ketone; compounds such as dimethylsulfoxide (DMSO), dimethylformamide (DMF), and mixtures of such solvents. The reaction can also be carried out in an excess of the above-mentioned bases, and when the compound of formula III is an amine (X = NR4), another equivalent or a larger excess of the compound of formula III can be used instead of the base.

In method b) (Ic +III = I), the reaction is validly performed in the presence of a common reagent for esterification that extracts water, for example in the presence of carbodiimide |dicyclohexylcarbodiimide (DCC)] or 1-alkyl-2-halogen pyridinium salt as 1-methyl- 2-Halogen pyridinium salt, eg 1-methyl-2-chloropyridinium iodide. We work intentionally in the presence of a solvent that is inert in the reaction, or a mixture of solvents, at temperatures from -30 to +, mostly -10 to +. We work mainly in the presence of a base, for example in the presence of an organic aromatic such as a trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyridine), morpholine (N-methylmorpholine) or N,N-diallidlaniline ( N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, petroleum ether, hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ether and ether compounds such as dialkylether (diethylether, diisopropylether, tert-butylmethylether), anisole, dioxane, tetrahydrofluorine; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; and mutual mixtures of such solvents.

If the compound of formula III is an alcohol (X = O), the variant of procedure b) can be carried out in the presence of an acid catalyst such as H2SO4, HCl or sulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid. In doing so, we successfully work with an excess of formula III alcohol. In this process, we can continuously remove the released water from the reaction mixture. The usual method for removing water from the reaction product is the distillation of the azeotrope with water. Solvents such as benzene, toluene, xylene, methylene chloride or chloroform are therefore suitable. Basically, various derivatives of formula I can be obtained by transesterification or amidation from the easily available lower alkyl ester of 4-chloro-4,4-difluorobutyric acid.

Derivatives of the ester type of formula I (X = O) can be obtained by base- or acid-catalyzed transesterification of lower alkyl esters of formula la

[image]

with lilac formula alcohols

[image]

where R 3 has, with the exception of C 1 -C 4 -alkyl, the meaning given in formula I. HCl, H 2 SQ 4 or sulfonic acid are particularly suitable as acid catalysts. In base-catalyzed transesterification, we primarily use as bases sodium or potassium alcoholates of alcohols of the formula Lila, which can be obtained from Lila, for example, by adding sodium or potassium hydride. The transesterification reaction is preferably carried out at temperatures from -20 to +, and especially from 0 to . We successfully use the alcoholic component of lilac in excess. Ethers, such as diethylether, diisopropylether, dioxane or tetrahydrofuran, halogenated hydrocarbons or aliphatic or aromatic hydrocarbons come into consideration as solvents.

Amide derivatives of formula I (X = NR4) can be obtained from lower alkyl esters of formula I by reaction with amide of formula IIIb

[image]

which have R3 and R4 of the meaning specified in formula I. The am and touching reaction is performed at temperatures between 0 and +. The reactants react successfully in an inert solvent or solvent mixture. Suitable for example are aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, petroleum ether, hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ether compounds such as dialkylether (diethylether, diisopropylether, tertbutylmethylether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; alcohols such as methanol, ethanol, propanol, isopropanol; or water. The amine component Illb is successfully used in excess.

Compounds of formula III are known and can be readily obtained on the market or can be prepared according to analogous preparation procedures.

Acid halides of formula II can be used in the usual way in a reaction with a halogenating agent from 4-chloro-4,4-difluorobutyric acid of formula Ic. Particularly suitable halogenating agents are SOCl2-, oxalyl chloride, PCl3 POCl3 or PCl5. It is generally done at temperatures between -20 and +, mostly between 0 and +. The reaction can proceed without a solvent or in a mixture with a solvent that is inert in the reaction. 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 often carried out with the addition of catalytic amounts of DMF.

Intermediates of formula II are new. They were developed especially for syntheses of active substances of formula I. Thus they form the subject of the proposed invention.

4-chloro-4,4-difluorobutyric acid of formula Ic can be obtained from compounds Ia by acid or basic hydrolysis. The reaction is generally carried out at temperatures between -20 and +, mainly between +10 and +. In acid hydrolysis, we primarily use HCl or H2SO4, and in basic hydrolysis, NaOH or KOH. Alcohols such as methanol or ethanol are particularly suitable as organic solvents; ethers such as dioxane or tetrahydrofuran; dimethylsulfoxide; or dimethylformamide.

Compounds of formula Ia, which represent a subgroup of compounds of formula I and at the same time serve as intermediates for the preparation of various ether and amide types of formula I, can be obtained according to the following procedures:

Compounds of formula Ia can be obtained by converting esters of α-halo-4-chloro-4,4-difluorobutyric acid of formula IV

[image]

which has R1 and R2 of the meaning specified in the formula I, and Y denotes chlorine or bromine, by catalytic dehalogenation with hydrogen in position α.

Compounds specified by subformula lb

[image]

which have R1 meaning stated in formula I, can be prepared by catalytic α-dehalogenation with hydrogen from α,α-dihalo-4chloro-4,4-difluorobutyric acid of formula V

[image]

where R1 has the meaning given in formula I, and X and Z independently of each other denote chlorine or bromine.

With a suitable choice of catalyst and reaction conditions, it is also possible to replace the α-halogen atoms Y and Z with hydrogen. Thus, we can prepare compounds of formula IV by mono-α-dehalogenation, where R2 denotes hydrogen from compounds of formula V.

Catalytic dehalogenation processes are carried out using hydrogen (IV —> I a, V —> lb and V —> IV) with hydrogen in the presence of noble metal catalysts or Ranay nickel in the given example in the presence of hydrogen halide scavengers and solvents at temperatures from 0 to and at normal pressure or pressure up to 150 bar. Solvents are primarily selected from the group of hydrocarbons, halohydrocarbons, ethers, ketones, alcohols, esters of carboxylic acids, sulfones, amides, N,N-dialkylcarboxylic acids, N-alkyllactams and lactones. Examples are petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran. , dioxane, acetone, methylisobutyl ketone, ethyl or methyl ester of acetic acid, tetramethylsulfone, dimethylformamide, N-methylpyrrolidone, γ-valerotactone, butyrolactone, methanol, ethanol or isopropanol. A polar solvent is preferred. Particularly suitable solvents are acetic acid ethyl ester, tetrahydrofuran or alcohol. The amount of solvent can be chosen within wide limits. With care, the same or tenfold amount of solvent can be used in relation to the amount of compound IV or V. Hydrogen halide scavengers are generally known. This applies to tertiary nitrogen bases primarily with a total of 3 to 20, especially 3 to 12 carbon atoms, for alkaline or alkaline earth salts of organic acids or carboxylic acids, or for oxides or hydroxides of alkaline or alkaline earth metals. Some examples are sodium carbonate, sodium or calcium bicarbonate, sodium acetate, NaOH, KOH, MgO and CaO; or aromatic, aliphatic or cyclic tertiary nitrogen bases, such as trimethyl-, triethyl-, tripropyl-, tributyl-, triethanol- or butyldimethylamine, pyridine, 2,6-dimethylpyridine, N-methylpyrroline and N-methylmorpholine. Tertiary nitrogen bases and MgO are preferred as scavengers of hydrogen halides. 2,6-dimethylpyridine is particularly suitable. Hydrocarbon scavengers can be added in a slight deficit or in excess of the amount of compounds of formula IV or V. It is best to use equimolar amounts. Examples of noble metals as catalysts are iridium, rhodium, platinum, ruthenium and palladium. Palladium has a particular advantage when used. Noble metals are preferred as supported catalysts. Examples of carriers are BaSO4, SiO2, Al2O3 and especially activated carbon. The catalyst used contains, in addition to the carrier, generally 0.1 to 20 wt. % precious metal. We can also use catalysts that contain sulfur. The added amount can be 0.1 to 20 /mass. % regarding the amount of compound of formula IV or V. We can carefully add regenerated or unused catalyst to the reaction. The reaction temperature is mainly between 0 and +, and especially 0 to +. Pressure up to 20 bar is advantageous. The reaction is mainly carried out at normal pressure.

Compounds of formula V are known from EP-A-2206, or they can be obtained by analogous procedures described there. Intermediates of formula IV can be prepared by converting chloroacetic acid esters of formula VI

[image]

where R 2 has the meaning given in formula I, and Y represents chlorine or bromine, in the presence of Cu-(I) catalyst 1,1-difluoroethylene of formula VII

[image]

This procedure is described for Y = chlorine in Helv. Chem. Acta 63, p. 1947-1957 (1980).

Added catalysts contain copper as an essential element in oxidation state 1. Examples of this are copper(I) chloride and bromide (CuCl, CuBr), copper cyanide (CuCN). Advantageous are CuCl and CuBr as well as their mixtures. Catalysts are generally used in amounts of about 0.01 to 10 mol % in relation to the compound of formula VII. We perform the conversion in an organic solvent. Suitable organic solvents are those in which the catalysts are well soluble or can form complexes with the catalysts that are inert in relation to the compounds of formulas VI and VII. Examples of such solvents are alkylnitriles, especially those with 2 to 5 carbon atoms, such as acetonitrile, propionitrile and butyronitrile; 3-Alkoxypropionitrile with 1 to 2 carbon atoms in the alkoxy part, such as 3-methoxypropionitrile 3-ethoxypropionitrile; aromatic nitriles, primarily benzonitrile; aliphatic ketones with a total of 3 to 8 carbon atoms, such as acetone, diethyl ketone, methyl-isopropyl ketone, -di-isopropyl ketone, methyl-tert-butyl ketone; alkyl and alkoxy ester of aliphatic monocarboxylic acids with a total of 2 to 6 carbon atoms, as methyl and ethyl ester of formic acid, methyl and ethyl, n-butyl and isobutyl ester of acetic acid, as l-acetoxy-2-methoxyethane; cyclic ether, as tetrahydrofuran , tetrahydropyran and dioxane; dialkyl ether with 1 to 4 carbon atoms in the alkyl part, such as diethyl ether, di-n-propyl ether and di-isopropyl ether; N,N-dialkylamides of aliphatic monocarboxylic acids with 1 to 3 carbon atoms in the acid part, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxy acetamide; ethylene glycol and diethylene glycol diethyl ether with 1 to 4 carbon atoms in the alkyl part, such as ethylene glycol dimethyl, diethyl and di-n-butyl ether, diethylene glycol diethyl and di-n-butyl ether or hexamethylphosphoric acid triamide. Solvents which are preferred are alkylnitrile with 2 to 6 carbon atoms and 3-a.lkoxypropionitrile with 1 to 2 carbon atoms in the alkoxy part, especially aetonitrile and 3-methoxypropionitrile. R with or without pressure. Compounds of the narrower formula Id

[image]

where R1, R2 and X have the meaning given in formula I and R denotes hydrogen or C1-C6-alkyl, can be prepared by catalytic hydrogenation with hydrogen from 4-chloro-4,4-difluorocrotonic acid of formula VIII

[image]

where R1, R2 and X have the meaning given in formula I, and R denotes hydrogen or C1-C6-alkyl.

Thus obtained products of narrower subformulas. Ia, lb, Ic and Id can be converted into derivatives described by formula I by conventional derivatization reactions, such as hydrolysis, transesterification or preamidation.

Catalytic hydrogenation of crotonic acid of formula VIII can be carried out under conditions customary for this type of reaction. Thus, the reaction is carried out in the presence of a noble metal or Raney nickel catalyst, preferably in an inert solvent, in a hydrogen atmosphere at a pressure of 1 to 150 bar.

Examples of noble metal catalysts are, for example, iridium, rhodium, platinum, ruthenium and palladium. The use of palladium is particularly suitable. Noble metals are generally applied as a catalyst on a support. Examples of carriers are BaSO4, SiO2, Al2O3 and especially activated carbon. The catalyst used contains, in addition to the carrier, generally 0.1 to 20 wt. % precious metal. We can also use it as sulphide catalysts. The amount used is from 0.1 to 20 wt. % regarding the amount of compound of formula VIII. Carefully add regenerated or unused catalyst to the reaction. The reaction temperature is generally 0 to +, preferably 0 to +. The pressure is most suitable up to 20 bar. It is best to perform the reaction at normal pressure. Solvents from the group of hydrocarbons, halohydrocarbons, ethers, ketones, carboxylic acid esters, sulfones, N,N-dialkylcarboxylic acid amides, N-alkyllactams and lactones are preferred. Individual examples are petroleum ether, pentane, hexane, cyclohexane, methylcyclobexane, benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane. , acetone, methylisobutyl ketone, ethyl or methyl ester of acetic acid, tetramethylene sulfone, dimethylformamide, N-methylpyrrolidone, γ-valerolactone, butyrolactone, methanol. Polar solvents are preferred. Particularly suitable solvents are ethyl acetate and tetrahydrofuran. The amount of solvent can be chosen within wide limits. It is useful to use an equal amount of up to a tenfold excess of the solvent relative to the amount of the compound of formula VIII.

The compounds of formula VIII are new, with the exception of 4-chloro-4,4-difluorocrotonic acid. These compounds were developed especially for the synthesis of compounds of formula I as intermediates. They thereby become part of the proposed invention. New compounds of formula VIII can be prepared analogously to the described procedure for the preparation of a simple acid (Izvestiya Akademii nauk SSSR, Ser. Khim. 2 (1965) 300-307) or they can be prepared from these products by usual derivatization reactions, such as esterification, transesterification or amidation.

Compounds of formula VIII in which R1 and R2 are hydrogen can be obtained from compounds of formula IX

[image]

where A represents hydrogen or an acyl group, by ß-elimination according to known methods, eg Houben Weyl 6/1 b 939 (1984).

Compounds of formula IX can be prepared from compounds of formula X

[image]

reduction, for example catalytic with hydrogen according to Reuben G. Jones in J.Amer.Chem.Soc. 70 (1984) 144, by the methods described there.

Compounds of formula X are partially known or can be prepared according to known methods such as Claisen condensation (1 luang Weiynan et al; Huaxne Huebau 1983, 41(8) 723; C.A. 100 (1984) 22308s).

Furthermore, the compounds of formula X can be obtained by reacting chlorodifluoroacetyl chloride ClF2C-CO-Cl with ketone H2C:=C=O, resulting in 4-chloro-4,4-difluoroacetic acid chloride of formula XI

[image]

hydrolyzed to a simple acid and converted in a reaction with an added alcohol or amine into an ester or amide of formula X. These esters and amides can also be successfully obtained directly by converting the acid chloride of formula XI with alcohol or amine.

For example, the synthesis of compounds of formula 1, where R1 and R2 are hydrogen, X is oxygen, and R3 is alkyl, is carried out according to the following scheme 1:

Scheme 1:

[image]

We have now found that the compounds of formula 1 of the invention, with suitable tolerability for warm-blooded creatures, fish and plants, are valuable substances in the destruction of pests. The use of the substance in terms of invention is particularly good for insects and spiders that appear on useful and ornamental plants in agriculture, especially in cotton plantations, vegetables and fruit trees, in forests and protection of stored materials, as well as in the hygiene sector, especially in domestic and useful animal. They are effective against all or normally sensitive or resistant species at individual developmental stages. At the same time, their effect can be shown immediately by the death of pests or only after a certain time, for example in changing the skin or in reduced egg laying and/or the proportion of changing the skin. The above-mentioned pests include:

from the order of Lepidoptera, e.g.

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 niponensis, Chilo spp. , Choristoneura spp., Clysia ambiguella, Cnaphalosrosis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia bonotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia amgibuella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp. ., Malacosoma spp., Maraestra brassicae, Manduca sextâ, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea opercullella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortri spp., Trichoplusia and Yponomeuta spp.;

from the order Coleoptera, e.g.

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetochema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Erem-nus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp. , Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp., and Trogoderma spp.,

from the order Orthoptera e.g.

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp., and Schistocerca spp.,

from the order of Isoptera, e.g.

Reticulitermes spp.,

from the Psocoptera order, e.g.

Liposcelis spp.,

from the order Anoplura e.g.

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.,

from the order of Mallophaga, e.g.

Damalinea spp., and Trichodectes spp.,

from the order Thysanoptera, e.g.

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thips tabaci and Scirtothrips auranti;

from the Heteroptera order, e.g.

cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Euiygaster spp., leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp., and Triatoma spp.,

from the Homoptera order, e.g.

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., Trialeurodes vaporariorum, Trioza erytreae in Unaspis citri;

from the order Hymenoptera, e.g.

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp., and Vespa spp.,

from the order Diptera, e.g.

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp. Dacus spp., Drosophilamelanogaster, 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, Phoriba spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp., and Tipula spp.,

from the Siphonaptera order, e.g.

Ceratophyllus spp., Xenopsylla cheopis,

from the order Acarina e.g.

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp. In

from the order Thysanura e.g.

Lepisma saccharina.

A good pesticidal effect of the compounds of formula I in terms of the invention corresponds to the requirement for a degree of destruction (mortality) of at least 50-60% of the mentioned pests.

The effect of the compounds in terms of the invention, that is, the means that contain them, can be significantly expanded and adapted to the given circumstances by the addition of other insecticides and/or acaricides. As additives, for example, the following classes of active substances come into consideration: organic phosphorus compounds, nitrophenols and derivatives, formamidines, carbamates, pyrethroids, chlorinated hydrocarbons and preparations of Bacillus thurmgiensis.

The compounds of formula I are used in their unchanged form or mainly with auxiliaries that are common in the formulation technique, and therefore it is possible to process them in a known manner into emulsion concentrates, solutions that can be directly dispersed or diluted, diluted emulsions, spray powders, soluble powders , agents for dusting, granulates, and also for making capsules, for example in black substances. The method of application, such as spraying, misting, dusting, sprinkling or pouring, is chosen as well as the means, depending on the desired goal and existing circumstances.

The formulation, i.e. means, preparations and compositions containing the active substance of formula 1, i.e. combinations of these substances with other insecticides or acaricides, and in the given example a solid or liquid additional base, is prepared in a known way, for example by thoroughly mixing and/or grinding the active substance with full lim a such as solvents, solid support bases, and in the given example surface-active compounds (surfactants).

As solvents, aromatic hydrocarbons, especially C8-C12 fractions, such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane, paraffins, alcohols and glycols as well as their ethers and esters can be considered. such as ethanol, ethylene glycol, methylene glycol monomethyl- or ethyl ether, ketones such as cyclohexane, highly polar solvents such as N-methyl-2-pyrrolidone. dimethylsulfoxide or dimethylformamide, as well as in the given example epoxidized vegetable oils, such as spoxidized coconut oil or soybean oil, or water.

As a rule, flours from natural rocks, such as calcite, talc, kaolin, tnontmorillonite and atapuigite, are used as solid carrier bases, for example in dusting agents and dispersible powders. To improve the physical properties, we can also add highly dispersed siliceous earth or highly dispersed polymers that have the ability to absorb. Porous types such as pumice, crushed brick, sepiolite or bcntinite can be considered as granular adsorptive carriers for granulates, as carrier materials that do not have the ability to absorb, for example calcite or sand. In addition, many granular materials of an inorganic or organic nature can be used, especially dolomite or crushed plant residues.

As surfactants, nonionic, cationic and/or anionic active surfactants with good emulsifying, dispersing and wetting properties come into consideration, depending on the type of active substance of the formula and to be formulated, or combinations of these substances with other insecticides or acaricides. Surfactants also include surfactant mixtures.

Suitable anionic surfactants can be so-called water-soluble soaps as well as water-soluble synthetic surface-active compounds.

Suitable soaps are alkaline, alkaline earth or, in the given example, substituted ammonium salts of higher fatty acids (C10-C22), for example Na or K salts of oleic or stearic acid, or natural mixtures of fatty acids that can be obtained, for example, from oil, coconuts or vegetable oil. Furthermore, methyl-taurine salts of fatty acids as well as modified and unmodified phospholipids should be mentioned as surfactants.

So-called synthetic surfactants are often used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Fat sulfonates or sulfates appear as a rule as alkaline, alkaline earth, or in the given example as substituted ammonium salts, and generally have an alkyl residue with 8 to 22 carbon atoms, whereby alkyl also includes the alkyl part of acyl residues, for example Na or Ca salt of ligninsulfonic acids, esters of dodecylsulphuric acid or mixtures of sulphates of fatty alcohols prepared from natural fatty acids. This also includes salts of esters of sulfuric acid and sulfonic acids of ethylene oxide adducts of fatty alcohols. Sulfonated benzimidazole derivatives mainly contain 2 sulfonic acid groups and one fatty acid residue with about 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the condensation product of naphthalenesulfonic acid and formaldehyde. Furthermore, suitable phosphates come into consideration, as phosphoric acid ester salts of p-nonylphenol -(4-14)-ethyl enoxide adduct.

Nonionic surfactants are mainly polyglycoether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycoether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in the alkyl residue. alkylphenols. Furthermore, suitable nonionic surfactants are water-soluble polyethylene oxide adducts, having 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, with polypropylene glycol, ethylenediaminepolypropylene glycol and alkylpolypropylene glycol, containing 1 to 10 carbon atoms in the alkyl chain. Said compounds usually contain 1 to 5 ethylene glycol units per propyl glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanol, castor oil polyglycol ethers, castor oil thioxylate, polypropylene-polyethylene-oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Furthermore, fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, also come into consideration.

Cationic surfactants are first of all quaternary ammonium salts that contain as substituents at least one alkyl residue with 8 to 22 carbon atoms and which have as further substituents lower, in the given example halogenated alkyl, benzyl or lower hydroxyalkyl residues. The salts appear primarily as halides, methylsulfates or ethylsulfates, eg stearyltrimethylammonium chloride or benzyl-di-(2-chloroethol)-ethylammonium bromide.

In the formulating technique, the usual surfactants, among others, are described, for example, in subsequent publications.

"1985 International Me Cutcheon's Emulsifiers & Detergents", Glen Rock NJ USA, 1985",

"H. Stäche, "Tensid Taschenbuch", 2. Aufl., C. Hanser Verlag Muenchcn, Wien 1981,

M. and J. Ash. "Encyclopedia of Surfactants", Vol. Chemical

Publishing Co., New York, 1980-1981.

Pesticide preparations usually contain 0.1 to 99%, especially 0.1 to 95% of the active substance of formula I or a combination of this substance with other insecticides or acaricides, 1 to 99.9% of solid or liquid additional base and 0 to 25%, especially 0.1 up to 20% surfactant. However, since concentrated means are more favorable as marketable goods, the final consumer uses, as a rule, diluted preparations that have a significantly lower concentration of the active substance. Typical usable concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. Application amounts per hectare are generally 1 to 500 g/ha of active substance per hectare.

The best formulations are composed as follows:

(% = mass percentage)

Emulsifiable concentrates

[image]

Powders

[image]

Suspension concentrates

[image]

Soaking powders

[image]

Granules

[image]

The agents may contain further additives, such as stabilizers, defoamers, preservatives, viscosity regulators, binders, encapsulating agents as well as fertilizers or other substances to achieve special effects.

The following examples serve to explain the invention. They do not limit the invention.

Examples of preparation

Example H1: 4-chloro-4,4-difluoro-2-trifluoromethyl-butyric acid ethyl ester

[image]

a) ethyl ester of 2,4-dichloro-4,4-difluoro-2-trifluoromethylbutyric acid

of 2,2-dichloro-3,3,3-trifluoropropionic acid ethyl ester with Cu(I) chloride and 100 ml of acetonitrile in an autoclave. To this, add 1,1-difluoroethylene under pressure and heat the mixture for 8 hours at +. After cooling, the reaction mixture is freed from the solvent and the remaining oil is rectified in a vacuum. We obtain 2,4-dichloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester in the form of a colorless oil, boiling point 54-55 °C/11 mbar.

Analysis: C7H7ClF5O2 (289.03)

[image]

b) ethyl ester of 2,4-dichloro-4,4-difluoro-2-trimethyl-butyric acid is treated in 200 ml of ethanol in the presence of 5% platinum on carbon at normal pressure and room temperature with hydrogen gas, until one equivalent of hydrogen is bound . After filtering the catalyst, the solvent is removed by distillation at normal pressure and the residue is rectified.

We obtain 4-chloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester in the form of a colorless oil, boiling point 41-43 °C/16 mbar.

Analysis: C7H8ClF5O2 (254.58)

[image]

Example H2: 4-chloro-4,4-difluorobutyric acid ethyl ester

ClF2C-CH2-CH2-COOC2H5

of 2,4-dichloro-4,4-difluorobutyric acid ethyl ester is dissolved in 200 ml abs. of ethanol. After adding anhydrous sodium acetate and a 5% platinum/carbon catalyst, hydrogen gas is introduced at normal pressure until 100% of the theoretical amount is bound. After filtering the catalyst and removing the ethanol by distillation, the remaining oil is poured into water, the organic phase is separated, dried with sodium sulfate, filtered and rectified at normal pressure. We obtain 4-chloro-4,4-difluorobutyric acid ester in the form of a colorless oil with a boiling point of 154-.

Analysis: C6H9ClF2O2 (186.59)

[image]

Example H3: Ethyl ester of 4-chloro-4,4-difluorobutyric acid

ClF2C-CH2-CH2-COOC2H5

of 2,4-dichloro-4,4-difluorobutyric acid ethyl ester is dissolved in 100 ml of abs. tetrahydrofuran. After the addition of 2,6-dimethylpyridine and 5% palladium/carbon catalyst, hydrogen gas is introduced at normal pressure until binding of 100% theor. amount. After filtering the catalyst and removing the tetrahydrofuran by distillation, the remaining oil is poured into water, the organic phase is separated, dried with sodium sulfate, filtered and rectified at normal pressure. We obtain ethyl ester of 4-chloro-4,4~ difluorobutyric acid in the form of a colorless oil with a boiling point of 154-.

Analysis: C6H9ClF2O2 (186.59)

[image]

Example H4: 4-chloro-4,4-diluorobutyric acid ethyl ester

ClF2C-CH2-CH2-COOC2H5

of 2,2,4-trichloro-4,4-difluorobutyric acid ethyl ester is dissolved in 200 ml abs. of ethanol. After the addition of anhydrous sodium acetate and 1 5% platinum/carbon catalyst, hydrogen gas is introduced at normal pressure until binding, which is 2 equivalents. After filtering the catalyst and removing the ethanol by distillation, pour the remaining oil into water, separate the organic phase, dry with sodium sulfate, filter and rectified at normal pressure. We obtain 4-chloro-4,4-difluorobutyric acid ethyl ester in the form of a colorless oil with a boiling point of 154-.

Analysis: C6H9ClF2O2 (186.59)

[image]

Example H5: N-methylamide of 4-chloro-4,4-difluorobutyric acid

ClF2-CH2-CH2-CO-NH-CH3

of 4-chloro-4,4-difluorobutyric acid ethyl ester is dissolved in 10 ml of a 33% solution of methylamine in ethanol. The resulting reaction mixture is stirred for 3 days at room temperature, after which it is evaporated. The resulting residue is recrystallized from hexane. We obtain N-methylamide 4 of chloro-4,4-difluorobutyric acid, melting point 61-.

Example H6: 4-chloro-4,4-difluorobutyric acid benzyl ester

[image]

a) 4-chloro-4,4-difluorobutyric acid

4-chloro-4,4-difluorobutyric acid ethyl ester is mixed with 100 ml of 2 N NaOH at room temperature until a homogeneous solution is formed. The solution is then poured into 150 ml of 2 N HCl. The secreted organic phase is taken up in diethyl ether, dried with sodium sulfate and, after removing the ether by distillation, rectified in a vacuum. We obtain 4-chloro-4,4-difluorobutyric acid in the form of a colorless oil with a boiling point of 88-90 °C/mbar.

Analysis: C4M5ClF2O2 (158.53)

[image]

b) 4-chloro-4,4-difluorobutyric acid chloride

4-ldor-4,4-difluorobutyric acid is mixed with 50 ml of thionyl chloride and 0.2 ml of dimethylformamide, heated for 2 hours at + and maintained at a temperature of + for another 30 minutes. The reaction mixture is rectified in a vacuum and the liquid that comes out at a boiling point of 35-37 °C/21 mbar is collected. We obtain 4-chloro-4,4-difluorobutyric acid chloride in the form of a clear, colorless liquid.

Analysis: C4H4Cl2F2O (176.98)

[image]

c) To a solution of 4-chloro-4,4-difluorobutyric acid chloride in 15 ml of benzene, a solution of benzyl alcohol and pyridine in 6 ml of methylene chloride is added over 30 minutes. The resulting reaction mixture was stirred for 16 hours at , then poured into 50 ml of 1 N HCl 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 evaporated. The obtained crude product is distilled in a ball tube at 190-210 °C/120 mbar. We get 4-chloro-4,4-difluorobutyric acid benzyl ester.

MS: m/e: 248 (M+ , CHClFO)

Example H7: N-isopropylamide of 4-chloro-4,4-difluorobutyric acid

ClF2C-CH2-CH2-CO-NH-C3H7-i

A solution of 4-chloro-4,4-difluoroacetic acid chloride in 15 ml of toluene is added to a solution of isopropylamine in 5 ml of methylene chloride. The resulting reaction mixture was stirred for 16 hours at , then poured into 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 evaporated. We obtain 4-chloro-4,4-difluorobutyric acid N-isopropylamide, m.p. 84-.

Example H8: 2,4-dichloro-4,4-difluorobutyric acid methyl ester

ClF2C-CH2-CHC1-COOCH3

A solution of 2,2,4-trichloro-4,4-difluorobutyric acid methyl ester is hydrogenated in 20 ml of abs. of ethanol with the addition of 5% platinum/carbon catalyst until the reaction of 1 equivalent of hydrogen at room temperature (about 1 hour). After filtering the catalyst, the obtained crude product is distilled in a ball tube at 4-70 °C/20 mbar. We obtain 2,4-dichloro-4,4-difluorobutyric acid methyl ester as a colorless oil.

Example H9: 4-chloro-4,4-difluorobutyric acid

ClF2C-CH2-CH2-COOH

Dissolve 4-chloro-4,4-difluorocrotonic acid in 160 ml of tetrahydrofuran and after adding 5% Pd/BaSCO4 catalyst, process at room temperature and normal pressure with hydrogen gas until reaction with hydrogen in 100% theoretical amount. After filtering the catalyst and removing the solvent by distillation, the remaining oil is rectified in a vacuum. We obtain a colorless oil with a boiling point of 88-90 °C/11 mbar, which is identical to the 4-chloro-4,4-difluorobutic acid prepared in example H6a.

Example H10: 4-chloro-4,4-difluoro-3-hydroxybutyric acid ethyl ester

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of 4-chloro-4,4-difluoroacetic acid ethyl ester is dissolved in 200 ml of tetrahydrofuran and after addition of 5% rhodium/Al2O3 catalyst, hydrogenated at normal pressure and room temperature with hydrogen until the theoretical amount of hydrogen is bound. It may be necessary to add more fresh catalyst during hydrogenation. Then the catalyst is filtered off and the solution is evaporated with the vacuum of a water pump. Rectification of the crude product yields pure ethyl ester of 4-chloro-4,4-difluoro-3-hydroxy-butyric acid in the form of an oil with a boiling point of 93- and 17 mbar, which turns into a solid state in the form of long needles.

Analysis: C6H9ClF2O3 (202.6)

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Example H11: 4-chloro-4,4-difluoro-3-acetoxy-butyric acid ethyl ester

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ethyl ester of 4-chloro-4,4-difluoro-3-hydroxy-butyric acid and anhydrous sodium acetate are dissolved in 50 ml of acetic anhydride at + and stirred for 1 hour at that temperature. After pouring the reaction mixture into 150 ml of water, the product is taken up in diethyl ether. The ether phase is dried with sodium sulfate and then the ether is evaporated in a vacuum. Rectification of the crude product yields 4-chloro-4,4-difluoro-3-acetoxy-butyric acid ethyl ester in the form of a colorless oil boiling at 95 and 17 mbar.

Analysis: C8H11ClF2O4 (244.6)

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Example H12: ethyl ester of 4-chloro-4,4-difluoro-crotonic acid

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4-chloro-4,4-difluoro-3-acetoxybutyric acid ethyl ester and 40 ml of quinoline are mixed and heated in a distillation apparatus. At a bath temperature of approx., a colorless oil with a sharp smell, boiling at 140-. The crude product is taken up in diethyl ether, washed with 1 N hydrochloric acid and water. After drying the ether phase with sodium sulfate and evaporating the ether, 4-chloro-4,4-difluorocrotonic acid ethyl ester is obtained in the form of a colorless oil boiling at 41 and 12 mbar.

Analysis: C6H7ClF2O2 (184.6)

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

Example H13: 4-chloro-4,4-difluorobutyric acid ethyl ester

ClF2C-CH2-CH2-COOC2H5

of ethyl ester of 4-chloro-4,4-difluoro-crotonic acid is dissolved in 200 ml of ethyl ester of acetic acid and after addition of 5% palladium/barium sulfate catalyst, treated with gaseous hydrogen at normal pressure and room temperature. Hydrogenation was soon completed. After filtering the catalyst, the solvent is evaporated in a vacuum and the residue is rectified. The product, which distills at 154-, is identical to the ethyl ester of 4-chloro-4,4-difluorobutyric acid, prepared according to examples H2, 113 and H4. Analogous to the described working procedures, we prepared the following compounds, listed in the tables.

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 1 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Table 2 (continued)

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Formulated examples (% = wt.%)

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Emulsions of any desired concentration can be prepared from such concentrations by diluting them with water.

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Solutions are suitable for use in the form of the smallest droplets.

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Dissolve the active substance in methylene chloride, sprinkle the carrier, and then evaporate the solvent in a vacuum.

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By thoroughly mixing the carrier with the active substance, we get ready-made dusting agents.

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Mix the active ingredient with additives and grind well with a suitable grinder. We obtain spray powders that can be diluted with water into suspensions of any desired concentration.

Example F6: Emulsion concentrates

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An emulsion of any desired concentration can be prepared from such a concentrate by diluting it with water.

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The ready-to-use dusting agent is obtained by mixing the active substance and the carrier and grinding it in a suitable mill.

Example F8: Extruded granulate

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Mix the active substance with additives, grind and moisten with water. The mixture is squeezed out, granulated and then dried with air flow.

Example F9: Coated granules

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Apply the well-mixed active substance evenly on the polyethylene glycol-moistened kaolin. In this way, we get coated granulates without powder.

Example F10: Suspension concentrate

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Thoroughly mix the finely ground active ingredient with the additives. Thus, we obtain a suspension concentrate from which, by diluting with water, suspensions of any desired concentration can be prepared.

Biological examples

Example B1: Effect against Boophilus microplus

Adult female ticks, fully engorged, are glued to a PVC board and covered with a ball of cotton wool. During treatment, we pour over the tested animals with 10 ml of the tested solution containing 125 ppm of the tested active substance. Then we remove the cotton ball and incubate the ticks for 4 weeks to lay eggs. The effect against Boophilus microplus is manifested in females either as mortality or as sterility, or in eggs as an ovicidal effect.

The compounds according to Tables 1 and 2 show a good effect against Boophilus microplus in this test. Especially 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, 2.07, 2.07, 2.05 2.09, 2.24, 2.28, 2.30, 2.31, 2.32, 2.33 and 2.35 have an effect greater than 80%.

Example B2: Ovicidal effect on Heliotbis vircseens

Eggs of Heliothis virescens hatched on filter paper are immersed for a short time in an acetone-water test solution containing 400 ppm of the tested active substance. After drying the test solution, the eggs are incubated in Petri dishes. After 6 days, we determine the percentage of hatched eggs compared to the untreated control plantations (% reduction in laying). 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 have more than 80% effectiveness.

Example B3: Effect against Aonidiella aurantii

Potato tubers are populated with migratory larvae ("crawler" Aodiniella aurantii, red lemon cochineal). After about 2 weeks, we immerse the potatoes in an aqueous emulsion or a suspension of a spray mixture that contains the tested active substance in a concentration of 400 ppm. After drying, the treated potato tubers are incubated in a container made of artificial materials. For evaluation, we compare 10 to 12 weeks later the degree of survival of the first successive generation of the treated cochineal population with those in untreated control plantations.

The compounds according to Tables 1 and 2 show a good effect against Aonidiella aurantii in this test. Especially compounds 1.18, 1.21, 1.2, 1.30, 1.31, 1.32, 1.33, 1.35, 1.37, and .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 have an effect greater than 80%.

Example B4: Effect against Nilaparvata lugens

We treat the rice plants with an aqueous emulsion spray mixture containing 400 ppm of the active substance. After drying the sprayed layer, we plant rice plants with cricket larvae in the 2nd and 3rd stages. After 21 days, an assessment is made. According to the comparison of the number of surviving crickets on treated and untreated plants, the percentage reduction of the population (% effect) is determined.

The compounds from Tables 1 and 2 show a good effect against Nilaparvata lugens in this test. Especially 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, 2.12, 2.35, 2.3 2.36, 2.39, 2.41, 2.42, 2.43, 2.45, 2.46 and 2.47 have an effect of over 80%.

Example B5: Effect against Tetranychus urticae

Young bean plants are planted with a mixed population of Tetranychus urticae and 1 day later we spray with an aqueous emulsion spray mixture containing 400 ppm of the active substance. The plants are then incubated for 6 days at and then evaluated. By comparing the number of dead eggs, larvae and adults on treated and untreated plants, we determine the percentage reduction of the population (% effect).

The compounds from Tables 1 and 2 show a good effect against Tetranychus urticae in this test. Especially compounds 1.30, 1.33, 1.35, 1.36, 1.38, 1.39, 2.28, 2.39, 2.41, 2.43 12.44 show more than 80% effect.

Example B6: Effect against Anthonomus grandis (adults)

Young cotton plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm of the active substance. After drying the sprayed layer, we plant cotton plants with 10 adult Anthonomus grandis and put them in a container made of artificial material. The assessment is done 3 days later.

The compounds from Tables 1 and 2 show a good effect against Anthonomus grandis in this test. Especially compounds 1.22, 1.36, 1.37, 1.49, 2.28, 2.32, 2.38 and 2.39 have an effect of more than 80%.

Example B7: Effect against Aphis craccivora

Bean seedlings are infected with Aphis craccivora and then sprayed with a spray mixture containing 400 ppm of the active substance, and incubated at . 3 and 6 days later the assessment is done. By comparing the number of dead aphids on treated plants and those on untreated plants, we calculate the percentage reduction of the population (% effect).

The compounds from Tables 1 and 2 show a good effect against Aphis accivora in this test. Especially compounds 2.05, 2.07, 2.08, 2.24, 2.28, 2.35 and 2.39 have an effect of more than 80%.

Example B8: Systemic effect against Myzus persicae

Bean seedlings are infected with Myzus pesicae, then placed with the roots in a spray mixture containing 400 ppm of the active substance, and incubated at . 3 to 6 days later the assessment is done. By comparing the number of dead aphids on treated and untreated plants, we determine the percentage reduction of the population (% effect).

The compounds from Tables 1 and 2 show good performance in this test against Mvzus persicae. Especially compounds 2.05, 2.24 and 2.28 have an effect of more than 80%.

Example B9: Systemic effect against Nilaparvata lugens

Place the pot with rice plants in an aqueous emulsion solution containing 400 ppm of the active substance. Then we plant rice plants with larvae in the 2nd and 3rd stages. 6 days later the assessment is done. By comparing the number of crickets on treated and untreated plants, we determine the percentage reduction of the population (% effect).

The compounds from Tables 1 and 2 have a good effect against Nilaparvata lugens in this test. Especially 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, 1.45, 1.42, 1.0, 1.4, 1.0, 1.4. 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, 2.47, 2.47 and 2.12 already have 5 ppm effect over 80%.

Example B10: Ovicidal effect against Adoxophyes reticulana

Eggs of Adoxopfyes reticulana hatched on filter paper are immersed for a short time in an acetone-water test solution containing 400 ppm of the active substance. After drying the test solution, the eggs are incubated in Petri dishes. 6 days later, we evaluate the percentage of egg laying by comparing it with untreated control embryos (% reduction in laying)

The compounds from Tables 1 and 2 show a good effect against Adoxophyes reticulana in the tora test. Especially compounds 1.02, 1.22, 1.31, 1.36, 2.05, 2.07, 2.08 and 2.35 have an effect of more than 80%.

Example B11: Ovo/larvicidal effect on Heliothis virescens

We spray Heliothis virescens eggs hatched on cotton with an aqueous emulsion spray mixture containing 400 ppm of the active substance. After 8 days, we evaluate the percentage of hatched eggs and the degree of survival of caterpillars compared to the untreated control plantation (% population reduction).

The compounds from Tables 1 and 2 show a good effect against Heliothis virescens in this test. Particular compounds 1.01, 1.02 1.04, 1.05, 1,06, 1,08,10, 1,10, 1.18, 1.21, 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 , 20.1, 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, 2.38, 2.38, 2.40, 2.41, 2.42, 2.43, 2.44, 2.45, 2.46, 2.47 and 2.48 have an effect greater than 80%.

Example B12: Effect against Dermanyssus gallinae

We add 2 to a solution containing 10 ppm of the active substance in a glass container, open from above, about 200 mites in different stages of development. Then close the container with a ball of cotton wool, shake it for ten minutes until the mites are completely soaked, and turn it briefly so that the cotton wool absorbs the remaining test solution. After 3 days, we determine the mortality of mites.

The compounds from Tables 1 and 2 show a good effect against Dermanvssus galinae in this test. Especially compounds 1.04, 1.06, 1.10, 1.2, 1.31, 1.36, 1.40, 1.45, 2.01 and 2.02 have an effect of more than 80%.

Example B13: Effect against Heliothis virescens caterpillars

Spray the young soybean plants with an aqueous emulsion spray mixture containing 400 ppm of the effective mixture. After drying the sprayed mixture, plant soybean plants with 10 caterpillars of the first stage of Heliothis virescens, and place them in a container made of artificial material. Estimated 6 days later. Using a comparison of the number of dead caterpillars and the damage caused by eaten treated plants with those of untreated ones, we determine the percentage reduction of the population, i.e. the percentage reduction of damage caused by eaten plants (% effect).

The compounds from Tables 1 and 2 show a good effect against Heliothis virescens in this test. Especially compounds 2.01, 2.07, 2.24 and 2.33 have an effect of more than 80%.

Example B14: Ovicidal effect on Cydia pomonella

Eggs of Cydia pomonella hatched on filter paper are briefly soaked in an acetone-water test solution containing 400 ppm of the tested active substance. After drying the test solution, the eggs are incubated in Petri dishes. 6 days later we evaluate the percentage of egg laying compared to untreated control embryos (% reduction in laying).

The compounds from Tables 1 and 2 have a good effect against Cydia pomonella in this test.

Example B15: Effect against Nephotettix cincticeps

Treat the rice plants with an aqueous emulsion spray mixture that contains 400 ppm of the active substance. After drying the sprayed layer, plant rice plants with 2nd and 3rd stage cricket larvae. We estimate 21 days later. By comparing the number of surviving crickets on treated plants and those on untreated ones, we determine the percentage reduction of the population (% effect).

The compounds from Tables 1 and 2 show good performance in this test against Nephoteuix cincticeps. Especially compounds 1.33, 1.37, 1.38, 1.39 and 2.48 have an effect of more than 80%.

Example B16: Effect against Ctenocephalides felis

We put 20 to 25 flea eggs in a horizontal standing jar with a cell culture in which we previously put a nutrient for flea larvae, which contains 400 ppm of the tested active substance. We incubated the test jars in an incubator at 26 to 60-70% air humidity. After 21 days, we check the presence of adult fleas, unhatched bugs and larvae.

The compounds from Tables 1 and 2 show a good effect against Ctenocephalides felis in this test.

Example B17: Effect against the eggs of Diabrotica balteata

Place 20 to 50 Diabrotica balteata eggs hatched on a fabric filter in a Petri dish and treat with an aqueous emulsion spray containing 400 ppm of the effective mixture. Petri dishes are incubated at . After 7 days, we evaluate the percentage of egg laying in comparison with untreated control plantations (% reduction in laying).

The compounds from Tables 1 and 2 show a good effect against Diabrotica balteata in this test. Especially compounds 2.05, 2.08 and 2.24 have an effect of more than 80%.

Example B18: Effect against eggs of Bemisia tabaci

Place the bush bean plants in gauze cages and we plant them with adult Bemisia tabaci (white fly). After the end of egg laying, remove all the adults and 2 days later, treat the plants with the nymphs on them, with an aqueous emulsion mixture for dispersing the tested solution (concentration 400 ppm). It is evaluated 10 days after the application of the effective substance with regard to the percentage of lying in comparison with the untreated control; plantations.

The compounds from Tables 1 and 2 show a good effect against Bemisia in this test. tap.

Claims (21)

1. Derivatives of 4-chloro-4,4-difluoroacetic acid of formula I [image] indicated by the fact that they are R1 and R2 are independently hydrogen, C1-C4-alkyl or C1-C4-haloalkyl, R3 is hydrogen or an organic residue and X is oxygen or -NR4-, where R4 is hydrogen or C1-C6-alkyl. 2. Compounds according to claim 1, characterized in that R3 denotes hydrogen or always substituted or unsubstituted C1-C20-alkyl, C3-C7-cycloalkyl, C3-C20-alkenyl, C3-C20-alkynyl, benzyl or aryl. 3. Compounds according to claim 1, characterized in that R3 denotes substituted or unsubstituted C1-C20-alkyl, C3-C7-cycloalkyl, C3-C20-alkenyl, C3-C20 alkynyl, benzyl or aryl. Above all, R3 denotes within the scope of the proposed invention C1-C20-alkyl, C3-C7-cycloalkyl, C3-C20-alkenyl, C3-C20-alkynyl, aryl, C3-C20-halogenalkenyl, C3-C20-halogenalkynyl; C3-C7-cycloalkyl substituted with halogen or C1-C4 alkyl; with halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C12-alkoxy, C1-C4-halogenalkoxy, C1-C4-alkylthio, nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, C1-C4-alkylphenoxy , C1-C4-haloalkylphenoxy, tri-C1-C4-alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C1-C4-alkylamino, di-C1-C4 -alkylamino, anilino, N-C1-C4-alkylanilino, N-formylanilino, N-C1-C6-alkylcarbonylanilino, phenylthio or halophenylthio substituted aryl; phenyl substituted by an unsubstituted or substituted aromatic or non-aromatic mono- or bicyclic heterocycle bound via oxygen or sulfur, whereby both the heterocyclic and the phenyl ring can always be substituted with halogen, C1-C4-alkyl, nitro, C1-C4-haloalkyl, C1 -C4-halogenalkoxy, C1-C4-alkoxy, C1-C4-alkylthio, or eclopril; or with hydroxy, halogen, di-C1-C4-alkylamino, C1-C4- alkoxy, C1-C4-halogenalkoxy, C2-C6-alkoxyalkoxy, C1-C4haloalkylthio, C1-C4-alkylthio, C1-C4-alkylsulfimyl, C1- C1-C20-alkyl substituted by C4-alkylsulfonyloxy, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyl, C1-C6-alkylcarbonyloxy, C3-C7-cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or pyridyl, wherein the aryl and pyridyl groups can always be substituted with halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C4-alkylthio, nitro, cyano, phenoxy, halophenoxy , enylthio or halophenylthio. 4. Compounds according to claim 1, characterized in that R1 and R2 independently of each other denote hydrogen or C1-C4-alkyl, preferably hydrogen. 5. Compounds according to claim 1, characterized in that X denotes oxygen, -NH-, -NCH3- or -NC2H5-, preferably oxygen or -NH-. 6. Compounds according to claim 3, indicated by the fact that R3 denotes phenyl substituted in position 4, with an aromatic mono- or bicyclic heterocycle from pyridine, pyrimidine or benzothiazole bound through oxygen, where both aromatic rings are unsubstituted or together have at most three further substituents from a series of chlorine, bromine, methyl, ethyl and trifluoromethyl. 7. Compounds according to claim 3, characterized in that R1 and R2 independently of each other denote hydrogen or C1-C4-alkyl, X oxygen or -NH4- and R4 hydrogen, methyl or ethyl, and R3 denotes hydrogen, C1-C20- alkyl, C3-C7-cycloalkyl, C3-C20-alkenyl, C3-C20-alkynyl, phenyl, naphthyl, C3-C20-haloalkenyl, C3-C20-haloalkynyl; C3-C7-cycloalkyl substituted with fluorine, chlorine, bromine or C1-C3-alkyl; with fluorine, chlorine, bromine, or C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-halogenalkoxy, C1-C3-alkylthio, nitro, cyano, phenoxy, halophenoxy, C1-C4-alkylphenoxy , C1-C4-haloalkylphenoxy, tri-C1-C4-alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C1-C4-alkylamino, di-C1-C4 -alkylamino, anilino, N-C1-C4-alkylanilino, N-formylanilino, N-C1-C6-alkylcarbonylanilino, phenylthio or halophenylthio substituted phenyl or naphthyl, or with hydroxy, fluoro, chloro, bromo, di-C1-C4-alkylamino . , C1-C20-alkyl substituted by C1-C4-alkoxycarbonyl, C1-C6-alkylcarbonyloxy, C3-C7-cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfonyloxy or pyridyl, whereby phenyl and pyridyl groups can always be substituted by fluorine, chlorine, bromine , C1-C3-alkyl, C1-C3-halo genalkyl, C1-C3-alkoxy, C1-C3-halogenalkoxy, C1-C3-alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio. 8. Compounds according to claim 1, characterized in that. R1 and R2 independently of each other denote hydrogen or C1-C4-alkyl, X oxygen or -NR4-, R4 hydrogen, methyl or ethyl, R3 phenyl, benzyl, naphthyl, 3-pyridylmethyl or always fluorine, chlorine, bromine, C1- phenyl, benzyl, naphthyl or 3-pyridylmethyl substituted by C3-alkyl, C1-C3-halogenalkyl, C1-C3- alkoxy, C3-C3-halogenalkoxy, C1-C3-alkylito, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio. 9. Compounds according to claim i, characterized in that R1 and R2 independently of each other denote hydrogen or C1-C4-alkyl, X oxygen or -NR4-, R4 hydrogen or C1-C4-alkyl, R3 C1-C12-alkyl or hydroxy , fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or phenoxy substituted C1-C12-alkyl, whereby the phenyl or phenoxy residue can always be substituted by fluorine, chlorine , bromine, phenoxy, halophenoxy or phenylthio. 10. Compounds according to claim 1, characterized in that R1 and R2 independently of each other denote hydrogen or C1-C4-alkyl, X oxygen or -NR4-, R4 hydrogen or C1-C4-alkyl, R3 C3-C12-alkenyl, C3- C12-alkynyl, or always C3-C12-alkynyl or C3-C12-alkynyl substituted by fluorine, chlorine or bromine. 11. Compounds according to claim 3, characterized in that R1 and R2 are hydrogen and X is oxygen, -NH-, -NCH3- or -NC2H5-. 12. Compounds according to claim 1, indicated by this, selected from the group consisting of: 4-chloro-4,4-difluorobutyric acid methyl ester, 4-chloro-4,4-diluorobutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid isopropyl ester, 4-chloro-4,4-difluorobutyric acid tert-butyl ester, n-butyl ester of 4-chloro-4,4-di(fluorobutyric acid, (2,2dimethylpropyl)-ester of 4-chloro-4,4-difluorobutyric acid, 4-chloro-4,4-difluorobutyric acid benzyl ester, phenylester of 4-chloro-4,4-difluorobutyric acid, 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, cyclopropyl methyl ester of 4-chloro-4,4-difluorobutyric acid, 4-chloro-4,4-difluoromethylbutyric acid ethyl ester, N-methylamide of 4-chloro-4,4-difluorobutyric acid, 4-chloro-4,4-difluorobutic acid N,N-dimethylamide, N,N-dihexylamide of 4-chloro-4,4-difluorobutyric acid, N-ethylamide of 4-chloro-4,4-difluorobutyric acid, N-isopropylamide of 4-chloro-4,4-difluorobutyric acid, 4chloro-4,4-difluorobutyric acid N-butylamide, N-tertbutylamide of 4-chloro-4,4-difluorobutyric acid, N-benzylamide of 4-chloro-4,4-difluorobutyric acid, 4-chloro-4,4-difluorobutyric acid anilide, 4-Chloro-4,4-difluorobutyric acid N-methyl-N-pyrid-3ylmethylanide, N-methyl-3-ylmethylamide of 4-chloro-4,4-difluorobutyric acid, (4-chloro-anilide) 4-chloro-4,4-difluorobutyric acid, (4-phenoxyanilide) 4-chloro-4,4-difluorobutyric acid, (4-chloro-anilide) 4-chloro-4,4-difluorobutyric acid, (4-methoxy-anilide) 4-chloro-4,4-difluoromasphaic acid, (4-methyl-anilide) 4-chloro4,4-difluorobutyric acid, (3-mercapto-anilide) 4-chloro-4,4difluorobutyric acid, (4-fluoroanilide) 4-chloro-4,4difluorobutyric acid, (4-chloro-2-nitro-anilide) 4-chloro-4,4difluorobutyric acid, (3-Phenoxy-benzyl)-ester of 4-chloro-4,4-difluorobutacic acid, 4-chloro-4,4-difluorobutyric acid [4-(4-fluoro-phenoxy)-phenyl]-ester, 4-chloro-4,4-difluorobutyric acid [4-(4-fluoro-phenoxy)-phenoxy-ethyl]-ester, 4-chloro-4,4-difluorobutyric acid (4-nitro-phenyl)-ester, 4-chloro-4,4-difluorobutyric acid [4(3,5-difluoro-phenoxy)-phenyl]-ester, 4-chloro-4,4-difluorobutyric acid [4-(5-trifluoro-methyl-pyrid-2-yloxy)-phenyl]ester, 4-chloro-4,4-difluorobutyric acid and 4-chloro-4,4-difluorobutyric acid amide. 13. Process: for the preparation of compounds of the formula i, according to claim 1, indicated that either a) 4-chloro-4,4-difluorobutyric acid halide of formula II [image] where R1 and have the meanings given in formula I, and Hal denotes halogen, preferably chlorine or bromine, convert in the presence of a base using the compound of formula III [image] where X and R:; meaning of formula I, or b) 4-chloro-4,4-difluorobutyric acid of formula Ic [image] in which R1 and R2 have the meanings given in formula 1, convert in the presence of a water extraction agent using a compound of formula III. 14. Means for destroying pests characterized by the fact that it contains as an active component at least one compound of formula I according to claim 1. 15. Means according to claim 14, characterized in that it contains at least one more carrier. 16. Use of the compound of formula 1, according to claim 1, indicated by this, for the destruction of pests on animals and plants. 17. Use according to claim 16, characterized by the fact that it is valid for phytopathogenic insects and mites. 18. A method for destroying animal parasitic and phytoparasitic insects and mites, according to claim 1, characterized in that we treat the pests or their living space with an effective amount of the compound of formula I. 19. Balogenides of 4-chloro-4,4-difluorobutyric acid of formula II [image] indicated that R1 and R2 independently of each other denote hydrogen, C1-C4-alkyl or C1-C4-haloalkyl, and Hal halogen, preferably chlorine or bromine. 20. Derivatives of 4-chloro-4,4-difluorocrotonic acid of formula VIII [image] indicated by the fact that they are R C1-C6-alkyl, R1 and R2 are independently hydrogen, C1-C4-alkyl or C1-C4-haloalkyl, X oxygen or -NR4, where R4 is hydrogen or C1-C6-alkyl. 21. Process for the preparation of compounds of formula I, characterized in that the derivative of 4-chloro-4,4,-difluorocrotonic acid of formula VIII [image] in which R is hydrogen or C1-C6-alkyl, R1 and R2 are independently hydrogen, C1-C4-alkyl C1-C4-haloalkyl, R3 is hydrogen or an organic residue and X is oxygen or -NR4-, where R4 denotes hydrogen or C1-C6-alkyl, we hydrogenate with hydrogen in the presence of a catalyst, and the resulting compounds of formula Id [image] where R1, R2, X and R have the above-mentioned meaning, convert by hydrolysis, transesterification reaction or amidation reaction into the remaining compounds of formula I, according to claim 1.