CS199523B2 - Method of producing 2-/2',2',2',-trihalogenethyl/-4-halogencyclobutane-1-ones - Google Patents

Abstract

A novel process for the preparation of 2-(2',2',2'-trihalogeno-ethyl)-4-halogenocyclobutan-l-ones of the formula in which one of the radicals R1 and R2 is methyl and the other is hydrogen or methyl, or R1 and R2 together are an alkylene group having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, but if X is bromine Y must always be bromine, is disclosed. The process comprises reacting a 2,4,4,4-tetrahalogeno-butyric acid chloride in the presence of an organic base with an ethylene compound which is disubstituted in 1-position by the radicals R1 and R2, as defined above, to form a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one and then rearranging the latter,in the presence of a catalyst, into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutann-1-one of formula I. The 2-(2',2',-2'-trihalogenoethyl)-4-halogenocyclo-butan-1-ones of formula 1 are valuable intermediates for the preparation of 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid and its insecticidally active esters. The 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the above formula and the intermediates used for their preparation are novel compounds.

Description

The present invention relates to 2- ⁽² ', 2', 2'-trihaloethyl) -4-halogencyklobutan-l-ones of Formula I

wherein one of R 1 and R 2 is methyl and the other is hydrogen or methyl, or R 1 and R 2 together are C 2 -C 4 alkylene; and

X and Y are each chlorine or bromine, but when X is bromine, Y must also be bromine.

The present invention further relates to novel 2 (2 ‘; 2‘, 2 ‘, 2‘ -tropyl halothenethyl) -4-halo-cyclobutan-1-ones of formula (I) as well as to novel intermediates useful for their preparation.

It is already known that α-halocycloalkanones are converted by heating in the presence of bases such as alkali metal hydroxides and alkoxides.

9 5.23. alkali metals to reduce the ring to cycloalkanecarboxylic acids with the same number of carbon atoms or to their esters (Favor reaction). This reaction constitutes the basis for a technically important process for the preparation of cyclopropanecarboxylic acid derivatives and their insecticidally active esters, i.e. pyrethroids, from α-halocyclobutanones. However, the use of this technically feasible process for the preparation of pyrethroids which are derived from 2- (2 ', 2', 2'-dihalo-vinyl) cyclopropanecarboxylic acid has not been possible so far; and the corresponding-halogencyklobutanony suitable к produce such de _t Rivato cyclopropanecarboxylic acid were к disposici.Nyní been proposed to produce a-halogencyklobutanony halogenketenu reacting with the olefin. Such processes are described, for example, in German Offenlegungsschrift 2,539,048, British Patent 1194,604, and in J · Am. Chem. Soc. 87, 5257-5259 (1965) and Tetrahedron Letters No. 1, 135-139 (1966). This synthesis principle has not yet been used to produce α-halobutanones. These α-halobutanones are useful in the preparation of 2- (2 ', 2'-dihalo-vinyl) cyclopropanecarboxylic acids and their insecticidally active esters. This suggests, first of all, that the synthesis possibilities based on this method, i.

(a) reacting halogenated olefins with a haloketene according to the equation

Хр-СН & СН .С-Y ^ + CH-C * ^p * A d A ^c ^ ^{přlp (s} .C ~ Y ^S CH ₃ C + X-CFF CRM> 0

Гс-сн

Ď *

i. ·, r. * r

b) reaction of non-halogenated olefins with haloketene according to the equation:

f 1 1 xc-ch-c = oo ♦. ) с = сн _л 3 * n.

.

Y '—_> ^X cc · cH · ⁰ . .

where both R 1, R 2, X, and Y in the equations are as defined in formula I, do not lead to 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutan-1-one of formula I, which are needed as intermediates, since the reaction of (a) does not take place due to the olefin deactivator which is associated with halogen substitution, and reaction (b) affords

2- (2''2 ', 2'-trihalomethyl) -2-halo-cyclobutan-1-one, which cannot be converted to' - (2'-dihalo-vinyl) -cyclopropanecarboxylic acid or its by the action of an alkali metal hydroxide or an alkali metal alkoxide ester.

It was therefore an object of the present invention to provide a process for the preparation of 2- (2, 2, 2, 2, 4, 4-aminobenzyl) -4-halo-cycloburan-1-one of the formula I, starting from readily available starting materials and .

It was also an object of the present invention to provide hitherto unknown 2- (2 ', 2', 2'-2-halogenethyl) -4-halo-cyclobutan-1-ones which by heating with strong bases such as alkali metal hydroxides and alkali metal alkoxides concomitant ring constriction and concomitant cleavage of 2 moles of hydrogen halide affords the corresponding 242 ', 2'-palaloeenvinyl) cyclopropanecarbone derivatives. xylic acids as well as readily available intermediates useful for. production of α-halocyclobutanones of the formula I.

It has now been found that 2- (2 ', 2', 2'-trihalothenethyl) -4-halo-cycloburan-1-ones of formula (I) can be prepared in a simple manner by reacting 2,44,4-thearae-butylamine chloride. of the acid of formula II

X3C — CH2 — CH — COCl '

AND

Y

- x (II), wherein X and Y are as defined in formula I, in the presence of an organic base with an olefin of formula III

Ri from CH2 = C \

^R2 .

. . (III) in which:

R1 and R2 are as defined in formula I,.

to give 2- (2 ‘, 2‘, 2‘-triaalogenerayl) -2-thalogencyclobutan-1-one of formula IV

X £ -CH ~ C — C = O? ^'1 CH RC »I · (V .Rl wherein R2, X. Y are as defined under formula I, which is then rearranged in the presence of a catalyst to 2- (2', 2 ', 2'-trihaloethyl ) -4-halo-cyclobutan-1-one.

2,4,4,4-Tetrahalobutyric acid chlorides of formula II are novel compounds. They can be prepared in a manner known per se by treating the tetrahalomethanes of the formula V

X

I. '

X — C — Y,

X · (V) in which

X and Y are as defined in Formula I, and adds to a compound of Formula VI

CH2 = CH — Z • 5 (VI), in which

Z represents a chlorocarbonyl group, a carboxyl group, a (C 1 -C 4) alkoxycarbonyl group and an obtained compound of formula VII

X 3 C-CH 2 -CH-Z

I.

Y (VII) wherein

X and Y · are as defined above and

Z represents a carboxyl group, an alkoxycarbonyl group or a cyano group, is converted to a compound of formula VII in which Z represents a chlorocarbonyl group.

Another possibility for the preparation of 2,4,4,4-tetrahalobutyric acid chlorides of the formula II is that the compounds of the formula

Cl \

CH — Z /

Cl

Cl

I ·

C13C-CH2-CH-Z (Vila) in which

Z is carboxyl, alkoxycarbonyl or cyano are converted to compounds of formula VIIa in which Z is chlorocarbonyl.

In addition to the 1,1-dichloroethylene derivative of the dichloroacetic acid derivative of formula (VI) and the addition of the dichloroacetic acid derivative of formula (VI) to the acrylic acid derivative of formula (VI) or the dichloroacetic acid derivative of formula (VIa) in a seechiomeomeric amount. of an excess of the ether halogenate of formula (V) or a dichloroacetic acid derivative of formula (VIa), for example about 0.5 to 2 times the molar excess, and the tetrahalogenate of formula (V) may also serve as a solvent.

Addition of tetrahalomethane (V) to compound (VI) and addition of compound (VIa) to 1,1-dichloroethylene. is carried out in the presence of catalysts. Suitable catalysts are metals VIII. main groups and minor groups · Via, Vila and Ib of the periodic system of elements such as iron, cobalt, nickel, ruithenium, rhodium, palladium, chromium, molybdenum, manganese and copper. These metals are suitable in elemental form or in the form of compounds. Suitable compounds of these metals are, for example, oxides, halides, sulfates, sulfites, sulfides, nitrates, acetates, citrates, carbonates, cyanides and rhodanldes, as well as ligandaml complexes such as phosphines, phosphites, benzoin, benzoyl and acetylacetonates, nitriles, isonitriles and carbon monoxide.

Examples of compounds of the above metals which are useful as catalysts include:

cuprous oxide, iron (III) oxide, bromides and especially copper, copper, ferrous and ferric chlorides, as well as ruthenium, rhodium, palladium, cobalt and nickel chlorides;

copper sulphate, ferrous sulphate and ferric sulphate;

copper nitrate; and. ferric nitrate; manganese acetate, copper acetate;

copper stearate, ferric citrate;

cuprous cyanide, ruthenium ^; (n) dichloro-tris-triphenylphosphine, rhodium-tris (triphenylphosphine) chloride, chromium and nickel acetylacetonate, copper acetylacetonate, ferric acetylacetonate, cobalt and cobalt acetylacetonate, manganese acetylacetonate, copper benzoylacetonate;

iron carbonylcyclopenitadienyl complex;

molybdenum carbonylcyclopentadienyl complex;

tricarbonylaryl chromium complex, acetate complex of divalent ruthenium (Via), in which:

Z has the meaning given by formula VI and adds to the 1,1-dichloroethylene and the compounds of the formula VIIa obtained chromium and molybdenum hexacarbonyl, nickltetracarbonyl, iron-pentacarbonyl, cobalt carbonyl and manganese carbonyl.

Mixtures of said metals with metal compounds and / or other additives may also be used, such as copper powder in combination with any of the above copper compounds; mixtures of powdered copper with lithium halides such as lithium chloride or isocyanates such as tert-butyl isocyanate; mixtures of iron powder with ferric chloride, optionally with the addition of carbon monoxide; mixtures of ferric chloride and benzoin; mixtures of ferrous or ferric chloride and trialkylphosphites; mixtures of iron and iodine pentacarbonyl.

Preferred are ferrous and ferric salts and ferric and ferrous complexes, as well as powdered iron, in particular, powdered copper, copper and copper salts, and corresponding complexes such as cuprous chloride, cuprous chloride, cuprous bromide, cuprous bromide, cuprous acetylacetonate, cuprous benzoylacetonate, cuprous sulfate. , copper nitrate and copper cyanide.

Particularly preferred are copper powder, copper (I) chloride and copper (I) chloride, or copper (I) and copper (I) bromide, and mixtures thereof.

Said catalysts are generally used in an amount of from about 0.01 to 10 mole%, preferably 0.1 to 5 mole%, based on the compound of formula III or 1,1-dichloroethylene.

The addition reactions are carried out in an organic solvent. Suitable organic solvents are those in which the catalysts are sufficiently soluble or can form complexes with the catalysts but which are inert to the starting materials. Examples of such solvents are alkylnitriles, especially those having 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; aromatic nitriles, especially benzonitrile; preferably aliphatic ketones with a total of 3 to 8 carbon atoms, such as acetone, diethylketone, methylisopropylketone, diisopropylketone, methyl tert-butylketone, alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids having 2 to 6 carbon atoms such as methyl and ethyl formate acetic acid methyl, ethyl, n-butyl and isobutyl ester 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 the alkyl moieties, such as diethyl ether, di-n-propyl ether and diisopropyl ether; Ν, Ν-dialkylamides of aliphatic monocarboxylic acids having 1 to 3 carbon atoms in the acid moiety, such as Ν, Ν-dimethylformamide, N, N-dimethylacetamide, Ν, Ν-diethylacetamide and N, N-dimethylmethoxyacetamide; dialkyl ethers of ethylene glycol and diethylene glycol having in each case 1 to 4 carbon atoms in the alkyl moieties, such as ethylene glycol dimethyl, -diethyl and -di-n-butyl ether; diethylene glycol diethyl and di-n-butyl ether; hexamethyltriamld phosphoric acid (hexametapol) ·

Preferred solvents are Cnit-C alkyl alkyl nitriles and C nebo-C nebo alkoxypropionitriles having 1 or 2 carbon atoms, in particular acetonitrile and 3-methoxypropionitrile.

The reaction temperature is generally not a critical condition and can vary within wide limits. Preferably, the reaction temperatures are between about 60 and 200 ° C, especially between about 80 and 170 ° C.

Acrylic acid chloride or dichloroacetyl chloride is preferably used as the compound of formula VI or VIa. This gives the desired 2,4,4,4-tetrahalobutyric acid chlorides directly in pure form and in high yields. Further preferred compounds of formulas VI and VIa are acrylic acid and dichloroacetic acid, respectively. The free 2,4,4,4-tetrahalobutyric acids thus obtained can then be converted into the corresponding acid chlorides by reaction with inorganic acid chlorides, such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene and thionyl chloride, in a simple manner.

2,4,4,4-Tetrahalobutyric acid esters or nitriles of formula VII (Z = alkoxycarbonyl or cyano) obtained using compounds of formula VI or VIa in which Z represents an alkoxycarbonyl or cyano group are first concentrated in the presence of strong acids, as concentrated hydrochloric acid, hydrolyzed to the corresponding free 2,4,4,4-tetrahalobutyric acid, which is then converted to the corresponding acid chloride as described above.

The reaction of 2,4,4,4-tetrahalobutyric acid chlorides of formula II with olefins of formula III is preferably carried out in the presence of an inert, organic solvent. Suitable halogenated aromatic or aliphatic hydrocarbons, such as benzene, toluene, xylene, chlorobenzene, dichlorochlorobenzenes, n-pentane, n-hexane, n-octane, methylene chloride, chloroform, carbon tetrachloride, 1,1,2,2 are suitable, for example. -tetrachloroethane and trichlorethylene. Other suitable solvents are cycloaliphatic hydrocarbons, such as cyclopentane or cyclohexane, cycloaliphatic ketones, such as cyclopentanone and cyclohexanone, as well as aliphatic ketones, aliphatic and cyclic ethers, alkylnitriles and 3-alkoxyproplonitriles having 1 or 2 carbon atoms and alkoxyitrile, in particular acetonitrile and 3 .

Particularly suitable solvents are aliphatic and aromatic hydrocarbons, in particular C5-C8 alkanes, benzene and toluene, and in particular n-hexane and cyclohexane.

However, an excess olefin of formula III may also serve as a solvent.

Suitable organic bases in which the reaction of the chloride is carried out

4,4-tetrahalobutyric acids of the formula II with an olefin of the formula III, for example tertiamines, in particular trialkylamines having from 1 to 4 carbon atoms, in particular from 2 to 4 carbon atoms in alkyl groups, cyclic amines such as pyridine, quinoline, N -alkylpyrrolidines, N-alkylpiperidines, N, N-dialkylpiperazines and N-alkylmorpholines or dialkylanilines having in each case 1 or 2 carbon atoms in alkyl groups such as N-methylpyrrolidine, N-ethylpiperidine, N, N'-dimethylmethylpiperazine, N-ethylmorpholine and Ν, Ν-dimethylalanine, as well as bicyclic amides such as 1,5-diazabicyclo [5.4.0] undec-5-ene and 5-diazabicyclo [4.3.0] non-5-ene, and bicyclic diamines such as is 1,4-diazabicyclo [2.2.2] octane.

The reaction of 2,4,4,4-tetrahalobutyric acid chlorides of formula II with olefins of formula III is preferably carried out in the presence of trialkylamines having from 1 to 4 carbon atoms in the alkyl groups. Particularly suitable bases are triethylamine and pyridine. >

The organic base is used in at least an equimolar amount or in a slight excess based on 2,4,4,4-tetrahalobutyric acid chloride of formula II.

The olefins of formula III are also used in at least equimolar amounts based on 2,4,4,4-tetrahalobutyric acid chloride of formula II. In general, however, it is preferred to use an excess of olefin, which olefin can, as already mentioned, also serve as a solvent. When using readily volatile olefins, the reaction can be carried out under pressure.

Particularly suitable olefins of the formula III are those in which one of the radicals R1 and R2 is a methyl group and the other of the radicals is hydrogen or a methyl group or R1 and R2 together represent an alkylene group having 2 to 3 carbon atoms, i.e. isobutylene, propene, methylene cyclopropane and methylene cyclobutane. Particularly preferred are isobutylene and methylene cyclopropane.

The reaction temperatures can be varied within wide limits. They are generally between 0 and 200 ° C, preferably between 20 and 160 ° C.

2- (2 ', 2', ² -Trihalogenethyl) -2-halogencyklobutan-l-ones of formula IV are also novel. As catalysts for rearrangement of the initially obtained 2- (2 ', 2', 2'-trihalogenethyl) -2-halo-cyclobutan-1-ones of the formula IV to 2 - (- 2 ', 2', 2'-trihalogenethyl) -4-cyclobutane The 1-ones of formula I may be used acids, bases or quaternary ammonium halides.

Rearrangement of 2- (2 ', 2', 2'-trihalogenethyl] -2-halo-cyclobutan-1-ones of formula IV to 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutan-1-ones of formula I It is particularly surprising that the rearrangement in the presence of a basic catalyst does not eliminate the HX compound on the trihalogenethyl group, and the rearrangement takes place in excellent, often quantitative yields.

Rearrangement of the Invention 2- (2 ', 2', 2'-Trihalogenethyl) -2-halo-cyclobutan-1-one of Formula IV to 2- (2 ', 2', 2'-Trihalogenethyl) -4-halo-cyclobutan-1-one Preferably, organic bases such as primary, secondary and in particular tertiary amines of the formula I are suitable.

Qi /

N — O2 \

Q3 in which

Q 1 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group or a phenyl group, and

Q 2 and Q 5 are each independently hydrogen or C 1 -C 8 alkyl.

Suitable basic catalysts are, for example, triethylamine, tri-n-butylamine, triisopentylamine, tri-n-octylamine, N, N-dimethylcyclohexylamine, NN-dimethylbenzylamine, N, N-dimethyl-2-ethylhexylamine, N, N-diethylaniline, as well as cyclic amines such as pyridine, quinoline, lutidine,

N-alkylmorpholines such as N-methylmorpholines, N-alkylpiperidines such as N-methyl- and N-ethylpiperidine; N-alkylpyrrolidines such as

N-methyl- and N-ethylpyrrolidine, diamines, such as NNN-4-NMetramethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-diaminobutane, N, N'-dialkylpiperazines such as N, N'-dimethylpiperazine, bicyclic amines such as

1,4-diazabicyclo (2,2,2] octane and bicyclic amidines such as

1,5-diazabicyclo [5.4.0] undec-5-ene

1,5-diazabicyclo [4.3.0] non-5-ene and polymeric basic compounds such as p-dimethylaminomethylpolystytene.

Further, as the basic catalysts for the rearrangement of 2- (2 ', 2', 2'-trihalogenethyl) -2-halo-cyclobutan-1-one of formula IV to 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutane 1-one of the formula I according to the invention suitable phosphines, in particular trlalkylphosphines, for example tributylphosphine.

Acidic catalysts for the rearrangement of 2- (2 ', 2', 2'-trihalogenethyl) -2-halo-99523 gencyclobutan-1-ones of the formula 'IV to 2- (2', 2 ', 2'-trihalogenethyl) - 4-halo-cyclobutan-1-ones of formula I use inorganic or organic protonic acids Suitable inorganic protonic acids are, for example, hydrohalic acids such as hydrochloric acid, hydrobromic acid, hydrofluoric acid and hydroiodic acid, nitric acid, phosphoric acid and sulfuric acid. The protonic acid is hydrohalic acid.

If the acids or bases are used in excess, they can also serve as solvents.

In addition, salts of protonic acids, e.g. in particular · hydrohalic acids, ammonia or a nitrogen-containing organic base, as well as quaternary ammonium halides, quaternary phosphonium halides and sulfonium halides. Aliphatic, cycloaliphatic, araliphatic and aromatic primary, secondary and tertiary amines as well as heterocyclic nitrogenous bases are suitable as nitrogen-containing organic bases. Examples include: primary aliphatic amines of up to 12 carbon atoms, such as methylamine, ethylamine, n-butylamine, n-octylamine, η-dodecylamine, hexamethylenediamine, cyclohexylamine, benzylamine; secondary aliphatic amines of up to 12 carbon atoms, such as dimethylamine, diethylamine, di-n-propylamine, dicyclohexylamine, pyrrolidine, piperidine, piperazine, morpholine; tertiary aliphatic amines, especially trialkylamines having from 1 to 4 carbon atoms in the alkyl moieties, such as triethylamine, tri-n-butylamine, N-methylpyrrolidine, N-methylmorpholine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine ; optionally substituted primary, secondary and tertiary aromatic amines such as aniline, toluidine, naphthylamine, N-methylaniline, diphenylamine and Ν, Ν-diethylaniline; pyridine, picoline, indoline, and quinoline.

It comes as quaternary phosphonium halides. for example: hexadecyltributylphosphonium bromide, methyl- and ethyl-triphenylphosphonium bromide; suitable sulfonium halides are, for example, trimethylsulfonium iodide.

Preferred are salts of the formula

Qs

I.

M-Q 4 —N + —Q 6

I.

Q7 in which

M is fluorine, bromine or iodine, especially chlorine,

Qa represents hydrogen, a C 1 -C 18 alkyl group, a cyclohexyl group, a benzyl group, a phenyl group or a naphthyl group; and

Q 5, Q 6 and Q 7 are each independently hydrogen or C 1 -C 18 alkyl, as well as N-C 1 -C 18 alkylpyridinium halides, especially the corresponding chlorides.

Examples of such salts include:

ammonium chloride, ammonium bromide, methylamine hydrochloride, cyclohexylamine hydrochloride, aniline hydrochloride, dimethylamine hydrochloride, di-isobutylamine hydrochloride, triethylamine hydrochloride, triethylamine hydrobromide, tri-n-octylamine hydrochloride, benzyldimethylamine hydrochloride, tetra-netramethyl, tetra-netramethyl, n-tetramethylamine, tetramethylamine; · -Bromide and iodide, trimethylhexadecylammonium chloride, benzyldiinethylhexadecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyltrimethyl-,

-triethyl- and • -tri-n-butylammonium chloride, n-butyl-tri-n-propylammonium bromide, octadecyltrimethylammonium bromide, phenyltrlmethylammonium bromide, or -chloride, hexadecylpyridinium bromide and -chloride.

Alkali metal halides such as potassium iodide, sodium iodide, lithium iodide, potassium bromide, sodium bromide, lithium bromide, potassium chloride, sodium chloride, lithium chloride, potassium fluoride, sodium fluoride and lithium fluoride can be used as additional cocatalysts.

These cocatalysts also catalyze the reaction in the absence of the above-mentioned ammonium salts, but then the addition of open-chain polyethers or macrocyclic polyethers (Crown ethers) for rapid reaction is preferred.

15-crown-5

18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 5,6,14,15-dibenzo-7,13-diaza-1,4-dioxacyclopentadeca-5,14-diene.

The amount of catalyst used can vary within wide limits. In many cases, it is sufficient that the catalyst is present in traces. In general, however, the catalyst is preferably used in an amount of from about 0.1 to 15 weight percent based on the compound of formula VI.

The rearrangement can be carried out both in the melt and in an inert organic solvent.

Reaction temperatures for melt rearrangement

199 are generally between 60 and 150 ° C, in particular between about 80 and 130 ° C.

Suitable catalysts for the melt rearrangement are, in particular, the above-mentioned organic bases, in particular trialkylamines having from 1 to 8 carbon atoms in the alkyl moieties; and hydrogen halide salts with ammonia or with organic nitrogen bases such as trialkylamine hydrochlorides and bromides having from 1 to 8 carbon atoms. in alkyl moieties and very particularly tetraalkylammonium halides, in particular -chlorides, -bromides and iodides, in each case having 1 to 18 carbon atoms in the alkyl moieties.

Suitable inert organic solvents are, for example:

optionally nitrated or halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons such as n-hexane, n-pentane, cyclohexane, benzene, toluene, xylenes, nitrobenzene, chloroform, carbon tetrachloride, trichlorethylene, 1,1,2,2-tetrachloroethane, nitromethane , chlorobenzene, dichlorobenzenes and trichlorobenzenes;

lower aliphatic alcohols such as alcohols having up to 6. carbon atoms such as methanol, ethanol, propanol, isopropanol, butanols and pentanols;

aliphatic diols such as ethylene glycol and diethylene glycol;

ethylene glycol monoalkyl ethers. and (C 1 -C 4) diethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl and monoethyl ether, diethylene glycol monomethyl and monoethyl ether;

cyclic amides such as N-methyl-2-pyrrolitonone, N-acetyl-2-pyrrolidone and N-methyl-s-caprolactam;

carbonic acid amides such as tetramethylurea and dimorpholinocarbonyl;

amides of phosphoric acid, phosphoric acid, phenylphosphonic acid or aliphatic phosphonic acids having 1 to 3 carbon atoms in the acid moiety, such as phosphoric triamide, phosphoric acid tris (dimethylamide), phosphoric acid trimorpholide, phosphoric tripyrrolinide, bis (dimethylamide) phosphoric acid phosphorous acid trisphdimethylamine, tetramethyldiamide methanesulfonic acid;

Sulfuric acid amides, aliphatic or aromatic sulfonic acids, such as tetramethylsulfamide, methanesulfonic acid dimethylamide or p-toluenesulfonic acid amide;

sulfur-containing solvents such as organic sulfones and sulfoxides, for example dlmethylsulfoxide and sulfolane;

aliphatic and aromatic nitriles, 3-alkoxypropionitriles, aliphatic ketones, alkyl and alkoxyalkylesters of aliphatic monocarboxylic acids, cyclic ethers, dialkyl ethers, N, N-disubstituted amides of aliphatic monocarboxylic acids and ethylene glycol and diethylene glycol dialysis grade ).

523. of

For rearrangement in the presence of an acid catalyst. preferably polar solvents, in particular lower alcohols such as methanol, ethanol and butanols, Ν, Ν-α-alkyl amides of aliphatic monocarboxylic acids having 1 to 3 carbon atoms in the acid moiety, especially N, N-dimethylformamide, or dialkyl sulfoxides, such as dimethylsulfoxide .

In aprotic, strongly polar solvents such as the above-mentioned N, N-disubstituted amides of aliphatic monocarboxylic acids, cyclic amides, carbonic amides, phosphorous acid amides, phosphoric acid, phenylphosphonic acid or aliphatic phosphonic acids, sulfuric acid amides or aliphatic or aromatic sulfonic acids, as well as dialkyl sulfoxides such as dimethyl sulfoxide, the reaction also proceeds without addition of a base or acid. In these cases, the solvent acts as a catalyst.

Generally, however, the rearrangement in the presence of an inert organic solvent, adding a catalyst, preferably an organic base having a pKa value _higher than 9, in particular trialkylamines having 1 to 8 carbon atoms in the alkyl portion, such as triethylamine, tri-n-butylamine and tri-n -octylamine; furthermore hydrohalic acids, in particular hydrochloric acid and hydrobromic acid, as well as tetraalkylammonium halides, in particular -chlorides, -bromides and iodides, in each case having 1 to 18 carbon atoms in the alkyl moieties.

Particularly preferred solvents are C 1 -C 4 aliphatic alcohols, toluene, xylenes, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionitrile, ethylene glycol diethyl ether and di-isopropyl ketone.

The rearrangement reaction temperatures in the presence of an inert organic solvent are generally between about 0 and 150 ° C, preferably between about 80 and 130 ° C.

According to the process of the present invention, novel 3-substituted substituted intermediates are available as intermediates for the preparation of the 3-substituted substituted 2- (2 ', 2', 2 ') cyclopropanecarboxylic acid derivatives. The process according to the invention is particularly suitable for the production in the 3-position of substituted 2- (2 ', 2'-2-hydroxy-4-halo-cyclobutan-1-ones of the formula I), starting from readily available starting materials. ', _{2'-trichloroethoxycarbonyl:} yl) -4-halogencyklobutan-one of the formula 1. the course of the process according to the invention is extremely surprising and quite unforeseeable because the reaction of 2,4,4,4 chloride, acid -tetrahalogenmáselné' formula 11 optionally halo ketene, which is formed from this compound by cleavage of hydrogen chloride in situ, with an olefin of formula (111): · firstly · 2- (2 ', 2'-trihalogenethyl) -2-halo-cyclobutan-1-one of formula (1V), position 3 substituted d 2- (2'-2'-dihalo-vinyl) -cyclopropanecarboxylic acid erivate, which is then converted to 2- (2 ', 2', 2 ', 2'-trihalogenethyl) -4-halo-cyclobutane The compound of formula (I) which is suitable for the further conversion to the 3-position in the 3-position is substituted. 2- (2 ', 2'-dihalo-vinyl) -cyclopropanecarboxylic acid rivate.

Substituted 2- (2 ', 2'-dihalo-vinyl) -cyclopropanecarboxylic acids and their insecticidally active esters which are obtainable from the novel 2- (2', 2 ', 2'-trihalogen) -4-chlorocyclobutan-1- of formula I, can be characterized by the following formula VIII

Z (WH) in which

X, R 1 and R 2 are as defined in formula I and

R is hydrogen, (C 1 -C 4) alkyl or (IX)

in which

R3 is oxygen, sulfur or vinylene,

R 4 is hydrogen, C 1 -C 4 alkyl, benzyl, phenoxy or phenyl mercapto,

R 5 is hydrogen or C 1 -C 4 alkyl and

R6 is hydrogen, cyano or ethynyl or, when one of R @ 1 and R @ 2 is methyl and the other is hydrogen or methyl, R @ 3 is vinylene, R @ 4 is phenoxy and R @ 5 is hydrogen, then R @ 1 is hydrogen; 5 carbon atoms.

The 2- (2 ', 2'-dihalo-vinyl) -cyclopropanecarboxylic acid derivatives of formula VIII in which R is a group of formula IX are suitable for controlling various animal or plant pests, particularly insects. literature (cf. e.g. Nature, 246, 169-170 (1973); Nature, 248, 710-711 (1974); Proceedings 7th British Insecticide and Fungicide Conference, 721-729 (1973); Proceedings 8th British Insecticide and Fungicide Conference , 373-78 (1975), J. Agr. Food Chem., 23, 115 (1973): U.S. Pat. No. 3,961,070, DOS 2,553,911, 2,439,177, 2,326,077 and 2,614,648).

Conversion of 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutan-1-ones of formula I to 2- (2 ', 2'-dihalogeninyl) -cyclopropanecarboxylic acid derivatives of formula VIII is carried out in a manner known per se by heating in the presence of suitable bases. Suitable bases are, for example, alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide. Alkali and alkaline earth metal carbonates and bicarbonates such as calcium carbonate, barium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate and calcium bicarbonate can also be used as bases. Also suitable as bases are alkoxides containing the radical R as defined above, in particular the corresponding sodium and potassium alkoxides. The use of such alkoxides has the advantage that the corresponding esters are immediately obtained, while the use of alkali metal and alkaline earth metal hydroxides first yields the salts of 2 (2, 2'-dihalo-ynyl) cyclopropanecarboxylic acid formed with these bases. However, these salts can also be converted into esters in a simple and known manner, for example by conversion to the corresponding acid chloride and by reaction with an alcohol derived from the residue R.

Conversion of the 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutan-1-one of formula (I) to the 2- (2 ', 2'-dihalo-vinyl) i) cyclopropanecarboxylic acid derivative of formula (VIII) it is expediently carried out in an aqueous, aqueous-organic or organic environment. When an alkali metal or alkaline earth metal carbonate is used as the base, the reaction is carried out in an aqueous or aqueous organic medium. Also, the reaction in the presence of alkali metal hydroxides or alkaline earth metal hydroxides and alkali metal hydrogencarbonates is preferably carried out in an aqueous or aqueous-organic medium. Thereby, after acidification of the reaction mixture, for example by the addition of concentrated hydrochloric acid, the free 2- (2 ', 2'-dihalo-vinyl) -cyclopropanecarboxylic acids of the formula VIII (R = H) are obtained. _#

Suitable solvents for the reaction of 2- (2 2 ', 2'-trihalogenmethylJ-4-haloC ₁ yklobutan-one of the Formula I · to derivatives of 2- (2', 2'-dlhalogenvinyl) -cyclopropanecarboxylic acid of the formula · VIII, in an aqueous organic or organic lower alcohols such as 1 to 6 carbon atoms, benzyl alcohol, aliphatic or cyclic ethers such as diethyl ether, di-n-propyl ether, di-isopropyl ether, tetrahydrofuran and dioxane, as well as aliphatic, cycloallphatic or aromatic hydrocarbons such as N-pentane, n-hexane, cyclohexane, benzene, toluene and xylenes.

Reaction of 2- (2 ‘, 2‘, 2 tr-trihalogenethyl) -4-halo-cyclobutan-1-ones of formula I to 2- (2 ‘, 2‘-dihaloquininyl) cyclopropanecarboxylic acid derivatives. xylic acids · of formula · VIII are generally pro-

at the boiling point of the chosen reaction medium. Particularly suitable are reaction temperatures between 40 and 120 ° C.

Conversion of 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutan-1-one of formula (I) to 2- (2'-dihalo-vinyl) -cyclopropanecarboxylic acid derivatives of formula (VIII) yields intermediates of the corresponding 2- (2 ') ^{1,2 '} , 2'-trihalogenethylcyclopropanecarboxylic acid of formula X'

- сн ^ -сн —ch-coor

W in which

R1, R2, R2 and X have the above meanings as intermediates. These products can be formed if the reaction temperature is kept below 40 ° C and / or when an excess of base is used. These intermediates convert at temperatures above 40 ° C with the addition of another base to cleave compound HX to the corresponding 2- (2 ‘, 2‘-dihalo vinyl) cyclopropanecarboxylic acid derivatives of formula VIII.

The 2- (2 *, 2 ', 2'-trihalogenethyl) cyclopropanecarboxylic acid derivatives of formula (X) can also be produced by irradiation with ultraviolet light, optionally with the addition of conventional sensitizer (e.g. ketones such as acetone, cyclohexanone, ), in the presence of agents containing hydroxyl groups which may also serve as solvents, photochemically from 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutan-1-ones of formula I. Reagents containing hydroxyl groups, are, for example, alkanols such as methanol, ethanol, etc., and especially water.

The process according to the invention is illustrated by the following examples.

He did

a) Preparation of 2,4,4,4-tetrachlorobutyric acid chloride 452.5 g (5 mol) of butyric acid chloride

452.5 grams (5 moles) of chloride (1.5 liters of carbon tetrachloride, 1.5 liters of acetonitrile and 30 grams of cuprous chloride) are kept at 115 ° C for 24 hours. The reaction mixture was filtered and the clear filtrate was evaporated in a water pump vacuum. The residue was distilled. 922 g (76% of theory) of 2,4,4,4-tetrachlorobutyric acid chloride of boiling point 78 DEG-80 DEG C./15 mm Hg are obtained.

iC-spectrum (CHCl3) in cm * ¹ :

1780 (C-O).

NMR spectrum (100 MHz, CDCl 3) in ppm:

3.16 to 3.94 (m, 2H, CH 2);

4.84 to 4.96 (m, 1H, CH).

2,4,4,4-tetrachlorobutyric acid chloride can be produced as follows:

90.5 g (1 mol) of acrylic acid chloride, 0.5 L of carbon tetrachloride, 0.2 L of butyronitrile and 3 g of copper powder were heated at 115 ° C for 20 hours. The reaction mixture was filtered and the filtrate was evaporated. The residue was distilled. It is obtained

167.8 g (69% of theory) of 2,4,4,4-tetrachlorobutyric acid chloride; boiling point 80-81 ° C / 1.596 KPa. The spectroscopic data are identical to those of the 2,4,4,4-tetrachlorobutyric acid chloride produced according to paragraph 1.

If, in an otherwise identical procedure, powdered copper was replaced with copper (I) chloride and butyronitrile with 3-methoxypropionitrile, 2,4,4,4-tetrachlorobutyric acid chloride was obtained in a yield of 71% of theory.

226 g (1 mol) of 2,4,4,4-tetrachlorobutyric acid [which was prepared according to Israeli patent specification 18 771; CA, 53, 13 089e (1965)], 600 g of thionyl chloride and 1 ml of Ν, Ν-dimethylformamide were heated at 59 ° C for 2 hours and at 75 ° C for 2 hours. After evaporation of the excess thionyl chloride, the residue is distilled. 227.6 g (93% of theory) of 2,4,4,4-tetrachlorobutyric acid chloride are obtained. Boiling point 90-91 ° C.

145.9 g (1.5 mol) of 1,1-dichloroethylene,

147.4 g (1 mol) of dichloroacetyl chloride, 200 ml of acetonitrile with 3 g of copper chloride are heated at 130 DEG C. for 8 hours. The reaction mixture was evaporated and the residue was fractionally distilled. 2,4,4,4-tetrachlorobutyric acid chloride is obtained as a colorless liquid. Boiling point 78-80 ° C / 1.463 kPa. The spectroscopic data of the substance obtained are identical to those of the 2,4,4,4-tetrachlorobutyric acid chloride obtained according to paragraph 1.

b) Preparation of 2-chloro-2- (2 ‘, 2‘, 2‘-trichloroethyl-3,3-dimethylcyclobutan-1-one)

To the autoclave was added to 122 g (0.5 mol) 2,4,4,4-tetrachlorobutyric acid chloride in 600. milliliters of cyclohexane presses 280 g of isobutylene. At 65 ° C, a solution of 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane is introduced via pump over 4 hours. The reaction mixture is then kept at 65 ° C for 3 hours.

The precipitated triethylamine hydrochloride was filtered off and the filtrate was evaporated. The crystals formed are filtered off. 79.4 g of 2-chloro-2- (2 ', 2', ^2'- trichloroethyl) -3,3-dimethylcyclobutan-1-one of melting point 75-76 ° C (60% of theory) are obtained.

iC-spectrum (CHCl 3) in cm ^-1 :

1805 (C-O).

¹ H-NMR spectrum (100 MHz, CDCl 3) in ppm:

1.42 and 1.45 (1s each, 6H, 1 each each);

2.91 to 3.28 (m, 2H, CH 2);

3.37 to 3.76 (m, 2H, CH 2).

¹³ C-NMR (CDCl 3) in ppm: 196 (s, CO);

95.3 ’(s, СНз);

80.8 (s, C-2);

57.0 (t, CH 2);

56.4 (t, CH 2);

37.9 (s, C-3);

25.1 (q, 2H);

28.8 (q, CH 3).

Elemental analysis for C 6 H 10 Cl 2 (263.98):

calculated:

36.40% C, 3.82% H, 6.02 O / o O,

53.72% Cl;

της1ρ * 7ρϊύπ ·

36.4 ° C, 3.9% H, 6.2% o,

53.5 o / o ci.

(c) Production of 2- (2 ‘, 2‘, 2‘-trichloroethyl) -3,3-dimethyl-4-chlorocyclobutan-1-one

132 g (0.5 mol) of the obtained 2-chloro-2- (2 ', 2,2'-trichloroethyl) -3,3-dimethylcyclobutan-1-one are dissolved in 700 ml of toluene, 1 ml of triethylamine is added and the mixture is refluxed. After 13 hours of reaction time, 1 ml of triethylamine is added again and the mixture is further boiled for 7 hours. After cooling, the reaction mixture was washed first with dilute hydrochloric acid and then with water, dried and evaporated. The solidified residue, which is a uniform product by thin layer chromatography (124 g, 94% of theory), is recrystallized from n-hexane. 105.8 g of 2- (2 ‘, 2‘, 2‘-trichloroethyl) -3,3-dimethyl-4-chlorocyclobutan-1-one are obtained, m.p. 56-57 ° C.

IR spectrum (СНС1з) in cm ¹ :

1800 (C = O).

1 H-NMR spectrum (100 MHz, CDCl 3) in ppm: 4.77 (d, J = 2 Hz, 1H, H on C-4);

3.47 (m, 1H, H on C-2);

2.73 to 3.26 [m, 2H, CH 2]

2.73 to 3.26 (m, 2H, CH 2);

2.63 (s, 3H, 2H);

1.14 (s, 3H, 2H).

¹³ C-NMR (CDCl3) in ppm:

197.0 (s, CO);

97.8 (s, CC 13);

69.4 (d, C-4);

60.6 (d, C-2);

49.5 (t, CH 2 -Cl 3);

36.8 (s, C-3);

27.4 (q, CH 3);

18.6 (q, cm).

Elemental analysis for C 6 H 10 CuO (263.98):

calculated:

C, 36.40, H, 3.82, O, 6.02,

53.72% Cl;

% C, 36.6%;% H, 3.8%;

53.6% Cl.

The above compound can also be produced as follows:

2.64 g (0.01 mol) of 2-chloro-2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethylcyclobutanone was stirred with 220 mg (0.0008 mol) of tetra-n-butylammonium chloride at 124 ° C for 6.5 hours. The obtained melt is boiled with hot n-hexane and filtered to a clear filtrate. On cooling the filtrate, 2.19 g (83% of theory) of (2 ', 2 ', 2 ' -trichloroethyl) -3,3-dimethyl-4-chloro-cyclobutan-2-one, m.p.

d) Preparation of 2- (2 ‘, 2‘-dichlorvinyl) -3,3-dimethylcyclopropane-1-carboxylic acid

To 150 ml of 10% sodium hydroxide solution was added 13.2 g (0.05 mol) of 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethyl-4-chlorocyclobutan-1-one and the mixture mixes intensively. After 5 minutes a clear solution was formed and heated to 100 ° C (bath temperature) for 1 hour. The reaction solution was washed with diethyl ether, acidified with concentrated hydrochloric acid under cooling, and extracted with diethyl ether. The ether phase is washed with water, dried over magnesium sulphate and evaporated. The solid residue (10.35 g) consisted of 80% by weight cis and 20% by weight trans-2- (2 ', 2'-dichlorvinyl) -3,3-dimethylcyclopropane-1-carboxylic acid according to NMR spectrum. Crystallization from n-hexane affords pure cis-acid. Mp 85-87 ° C.

iC-spectrum (CHCl 3) in cm ^-1 :

1710 (CO), 1625 (C-C).

NMR spectrum (100 MHz, CDCl 3 / D 2 O) in ppm:

1.30 (s, 6H, 2.times.N2);

1.85 (d, J = 8.5 Hz, 1H, 1H-1);

2.02-2.19 (m, 1H, 1H-2);

6.17 (d, J = 8 Hz, 1H, CH = CC 12).

Example 2

A 6.3 liter autoclave was charged with 421 g propylene, 244 g (1 mol) chloride

2,4,4,4-tetrachlorobutyric acid and 1.25 liters of cyclohexane. At 50 ° C, a solution of 101 g (1 mol) of triethylamine in 1 liter of cyclohexane was introduced through the pump over 4 hours, and the reaction mixture was then maintained at 50 ° C for 3 hours. The reaction mixture is filtered and the filtrate is washed with dilute hydrochloric acid and then with water, dried over magnesium sulphate and evaporated. The residue crystallized from n-hexane. 77.2 g of 2-chloro-2- (2 ', 2', 2'-trichloroethyl) -3-methylcyclobutan-1-one are obtained, m.p. 80-81 ° C.

IR (CHCl3): [delta] ¹ : 1785 (CO).

1 H-NMR spectrum (100 MHz, CDCl 3) in ppm: 3.28-3.73 (m, 3H);

2.65-2.95 (m, 2H);

1.43 (d, J = 6.5 Hz, Zn, Zn).

¹³ C-NMR (CDCl3) in ppm:

196.5 (s, CO);

95.1 (s, S1z);

77.8 (s, C-2);

55.3 (t, CH 2 -Cl 3);

50.9 (t, C-4);

38.1 (d, C-3);

15.8 (q, 2H).

g (0.2 mol) of the obtained 2-chloro-2- (2 ', 2', 2'-trichloroethyl) -3-methylcyclobutan-1-one in 500 ml of toluene are mixed with 1 ml of triethylamine and the mixture is stirred for 18 hours. hours at a bath temperature of 120 ° C. After cooling, the reaction mixture is filtered and the clear filtrate is washed first with dilute hydrochloric acid and then with water, briefly boiled with activated carbon, filtered again and evaporated. Distillation of the residue gives 38.7 g (77% of theory) of 2- (2 ', 2', 2'-trichloroethyl) -3-methyl-4-chlorocyclobutan-1-one, b.p. 130-131 ° C / 1.596 kPa. IR (CHCl 3) in cm ^-1: 1805 (CO).

Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl 3) in ppm: 1.20 (d, J = 7 Hz, 0.6 H, 2H);

1.46 (d, J 7 Hz, 0.45 H, 2H);

1.66 (d, J = 6.5 Hz, 1.95 H, 2H); 2.1-3.5 (m, 4H);

4.55 (dd, J = 8 and 2 Hz, 0.65 H, CH); 5.00 (dd, J = 9 and 2.5 Hz, 0.15 H, CH);

5.15 (dd, J = 9 and 1.5 Hz, 0.2 H, CH).

According to NMR spectrum and gas chromatogram, this compound consists of 3 stereoisomers in a weight ratio of 13: 4: 3.

10.5 g of the obtained 2- (2 ‘, 2‘, 2‘-trichloroethyl) -3-methyl-4-chlorocyclobutan-1-one were stirred with 100 ml of 10% sodium hydroxide solution for 50 minutes. The solution was then heated to 100 ° C for 1 hour. The reaction mixture was then washed with diethyl ether and carefully acidified with concentrated hydrochloric acid. Extraction with diethyl ether is then carried out. The ether extract was washed with water, dried (MgSO4) and evaporated. 2- (2 ‘, 2‘-dichlorvinyl) -3-methylcyclopropane-1-carboxylic acid is obtained. Mp 75-78 ° C (after recrystallization from n-hexane).

IR (KBr) cm ^-1 :

1685 (C = O), 1625 (C = C).

NMR spectrum (100 MHz, CDCl 3 / D 2 O) in ppm:

1.25 (D, J = 5.5 Hz, Zn, Zn);

1.54-2.18 (m, 3H);

3.96 (d, J = 8Hz, 1H, CH = CC 12).

Example 3

A solution of 25.3 g (0.25 mol) of triethylamine in 50 ml of n-hexane was added dropwise with stirring to a solution of 25 g (0.37 mol) of methylene cyclobutane and 61.1 g (0.25 mol) of chloride 2 over 7 hours. 4,4,4-tetrachlorobutyric acid in 200 ml of n-hexane, which is kept under reflux. After stirring for a further 2 hours under reflux, the hot reaction mixture was freed from the resulting ammonium salt by filtration. The filtrate is concentrated to about 1/3 of the original volume. Upon cooling, 1-chloro-1- (2 ‘, 2 *, 2‘-trichloroethyl) spiro [3,3] heptan-2-one of the formula precipitates in crystalline form

C '1

mp 93-94 ° C.

IR spectrum (CCU) in cm ^-1 :

1790 (C-O).

NMR spectrum (100 MHz, CDCl3) in ppm:

1.70 to 2.80 (m, 6H);

3.15 to 3.60 (m, 4H).

A solution of 27.6 g (0.1 mol) of the obtained 1-chloro-1- (2 ', 2', 2'-trichloroethyl) spiro [3,3] heptan-2-one in 100 ml of toluene is added together with 0, 93 grams (5 mmol) of tributylamine was heated to reflux for 9 hours. Then the reaction mixture was evaporated and the residue was distilled in vacuo to give 1-chloro-3- (2 ‘, 2‘, 2‘-trichloroethyl) spiro [3,3] heptan-2-one of formula

in the form of a slightly yellowish oil. Boiling point 85-90 ° C / 0.7 Pa.

n _D ²⁰ = 1.5242.

IR (film) in cm ^-1 : 1795 (C = O).

Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl 3) in ppm: 1.80 to 3.85 (m, 9H);

4.68, 4.93 (one d each, 1H each).

11.0 g (40 mmol) of the obtained 1-chloro-3- (2 ', 2 *, 2'-trichloroethyl) spiro [3,3] heptan-2-one are mixed together with 95 ml (about 240 mmol). % sodium hydroxide solution for 6 hours at 95 ° C. After cooling, the mixture was washed with several portions of diethyl ether, acidified with sulfuric acid and extracted with diethyl ether. The ether extracts were evaporated after drying the sulfur dioxide with sodium sulfate. Filtration of the residue from a 10-fold amount of silica gel (eluting with a 1: 1 v / v mixture of n-hexane and diethyl ether) removes a small amount of strongly polar impurities. Concentration of the filtrate affords 2- (2‘, 2‘-dichlorvinyl) -spiro [2,3] hexane-1-carboxylic acid of formula

in the form of a 2: 1 cis / trans isomer mixture. Melting point 121-128 ° C.

IR spectrum (CCl4) in cm ^{@ -1} :

1705 (C.dbd.O).

NMR spectrum (100 MHz, CDCl3) in ppm:

1.60-2.60 (m, 8H);

5.34, 5.97 (1 d each, together IH);

II, 80-11.50 (broad s, 1H).

Example 4

280 g of isobutylene are pressed into the autoclave to 122 g (0.5 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 600 ml of cyclohexane. At 65 [deg.] C., 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane are introduced by pump over 4 hours. The reaction mixture was maintained at 65 ° C for 3 hours and then heated to 125 ° C for 18 hours. To this end, 2.0 g of triethylamine in 50 ml of cyclohexane were fed through the pump for 3 hours. The reaction mixture was poured onto ice, acidified with hydrochloric acid and extracted with cyclohexane. The residue is chromatographed on 1 kg of silica gel using toluene / cyclohexane (1: 1, v / v) as eluent to remove strongly polar impurities. The filtrate was evaporated and the residue was crystallized from n-hexane. 31.8 g of 2 (2 *, 2‘, 2‘-trlchloroethyl) -3,3-dimethyl-4-chlorocyclobutan-1-one, m.p. 56-57 ° C, are obtained.

Example 5

a) 26.1 g (99 mmol) of 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethyl-4-chlorocyclobutanone are added to 260 ml of a 10% solution while stirring at 11 ° C. sodium hydroxide. The temperature rises to 28 ° C over 2.4 hours and then drops to 20 ° C over the next 2 hours. The reaction mixture was diluted with 200 mL of water, washed with diethyl ether, strongly acidified with concentrated hydrochloric acid and extracted with diethyl ether. The ether extract was washed with water, dried (MgSO4) and evaporated. It is obtained

24.3 g (100% of theory) of a light yellow residue (m.p. 80-81 ° C), consisting exclusively of cis- and trans-2- (2 ', 2', 2'-trichloroethyl) -3,3 -dimethylcyclopropanecarboxylic acids. By fractional crystallization or column chromatography, the mixture can be separated into pure cis and trans compounds.

NMR spectrum (100 MHz, CDCl 3 / D 2 O) in ppm:

2.75-3.33 (m, 2H);

1.50 to 1.97 (m, 2H);

1.32 (s, 2 X, cis);

1.27 and 1.38 (2.times.s, 2.times. Trans).

b) 8.0 g (30.3 mmol) of 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethyl-4-chlorocyclobutanone are irradiated through pyrex glass in 400 ml of acetone and 100 ml of water. 125 W lamp (Philipps HPK) until the presence of the starting material can no longer be detected by chromatography. The reaction mixture is evaporated and the residue is treated to the acid as described under a). 6.95 g (93% of theory) of a cis / trans-mixture of 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethylcyclopropanecarboxylic acid were obtained, the spectroscopic data of which were identical to those of the mixture which was obtained under (a).

c) 24.55 g (0.1 mol) of 2- (2 ', ^2', 2'-trichloroethyl) -3,3-dimethylcyclopropane carboxylic acid are suspended in 350 ml of 10% sodium hydroxide solution and the suspension is stirred at a bath temperature 100 ° C for 4½ hours. The reaction solution was washed with diethyl ether, acidified with hydrochloric acid. The extract was washed with water, dried over magnesium sulphate and evaporated. After crystallization from n-hexane, 17.55 g (84% of theory) of colorless 2- (2 ', 2 ' -dichlorvinyl) -3,3-dimethylcyclopropanecarboxylic acid are obtained.

Example 6

145 g (0.5 mol) of 2-bromo-4,4,4-trichlorobutyric acid chloride, 280 g (5 mol) of isobutylene and 600 ml of cyclohexane are introduced into the autoclave. At 65 ° C, 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane are fed through the pump for 4 hours. The reaction mixture was then stirred at this temperature for 3 hours. The reaction mixture was filtered, the filtrate was evaporated and the residue was crystallized from n-hexane. 74.5 g (48% of theory) of 2-bromo-2- (2 ', 2', 2 ', 2'-trichloroethyl) -3,3-dimethylcyclobutanone are obtained in the form of a light beige powder. Mp 46-49 ° C.

IR spectrum (CHCl3) in cm ^-1 :

1885 (CO) 1 H-NMR spectrum (100 MHz, pyridine-ds) in ppm:

3.79 (AB, 2H, CH 2);

3.10 (2H, 2H, CH2);

1.37 and 1.42 (always 1s, total 6H, always SN).

¹³ C-NMR (CDCl3) in ppm

196.8 (CO);

95.6 (CCl3);

74.8 (C-2);

56.5 and 56.3 (always Сг);

38.0 (C-3);

27.4 and 24.7 (always СНз).

g (0.085 mol) of 2-bromo-2- ( ² ', 2', 2'-trichloroethyl) -3,3-dimethylcyclobutanone and 5 g of tetrabutylammonium bromide are stirred at 80 ° C for 30 minutes and at 100 ° C for 10 minutes. The solidified melt is chromatographed on silica gel using toluene / cyclohexane 1: 1 as the eluent. There was thus obtained 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethyl-4-bromocyclobutanone which crystallized on standing;

Mp 56 ° C.

1 H-NMR spectrum (100 MHz, CDCl 3) in ppm:

4.99 (d, J = 2 Hz, 1H, H on C-4);

3.58 (X part of ABX, in addition with J = 2 Hz cleaved, 1H, H at C-2);

3.05 (AB-portion of ABX, 2H, CH2);

1.22 and 2.67 (1s each, 3H each, always NS).

¹³ C-NMR (CDCl3) in ppm:

196.7 (s, CO);

97.7 (s, CC 13);

60.7 (d, C-2);

59.8 (d, C-4);

50.0 (t, CH 2 -CCl 3;

36.4 (s, C-3);

27.6 (q, s);

21.0 (q, 2H).

To 3.1 g (10.6 mmol) of 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethyl-4-bromocyclobutanone is added a solution of 3.2 g of sodium hydroxide in 70 ml of water and the mixture is stirred for 2 hours. The reaction mixture was washed with diethyl ether and acidified with dilute hydrochloric acid. This aqueous phase is extracted with diethyl ether. The extract was washed with water, dried over magnesium sulphate and evaporated. The residue was crystallized from n-hexane. It is obtained

2.55 g of cis-2- (2 ‘, 2‘-dichlorinyl) -3,3-dimethylcyclopropanecarboxylic acid, m.p. 86 ° C.

iC-spectrum (СНС1з) in cm ^-1 :

1710 (CO), 1625 (C-C).

NMR spectrum (100 MHz, CDCl 3 / D 2 O) in ppm:

1.30 (s, 6H, 2.times.N2);

1.85 (d, J = 8.5Hz, 1H, HC-1); 2.02 to 2.19 (m, 1H, HC-2);

6.17 (d, J = 8 Hz, 1H, CH = CC 12).

Example 7

90.5 g (1 mol) of acrylic acid chloride, 364.8 g (1.1 mol) of tetrabromomethane, 200 µl of acetonitrile and 5.0 g of cuprous chloride were heated at 115 ° C for 6 hours. After cooling, the reaction mixture was distilled directly.

136.6 g (33% of theory) of chloride 2.4 are obtained.

4.4- tetrabromobutyric acids. Boiling point 135-140 ° C / 1.596 kPa.

350 ml of cyclohexane are saturated with isobutylene at room temperature (20-25 ° C). 42.2 g (0.1 mol) of chloride 2 are then dissolved.

4.4.4- tetrabromobutyric acid in this solution. Thereafter, 10.1 g (0.1 mol) of triethylamine in 50 ml of cyclohexanone are added dropwise at room temperature over 2 hours while stirring and gently feeding a stream of isobutylene. Water was added to the obtained reaction mixture, which was stirred first for 3 hours. The organic layer was separated, washed with water, dried over magnesium sulfate and evaporated. The residue was filtered through silica gel (eluent: cyclohexane / toluene 1: 1, v / v). The filtrate was evaporated. The residue was crystallized from n-hexane.

2-Bromo-2- (2 ', 2', 2'-tribromethyl) -3,3-dimethylcyclobutanone was obtained; mp 61-63 ° C.

IC spectrum (CHCl3) in cm ^-1 :

1780 (CO).

@ 1 H-NMR spectrum (100 MHz, CDCl3) .delta. Ppm: 3.97 (MH +, 2H, CH2);

3.13 (2H, 2H, CH2);

1.51 and 1.61 (always 1s, always 3H, always СНз).

¹³ C-NMR (CDCl3) in ppm:

196.7 (CO);

76.8 (C-2);

60.0 and 56.6 (each CH2);

38.1 (C-3);

31.7 (cm);

27.7 and 25.0 (always СНз).

9.6 g (21.8 mmol) of 2-bromo-2- (2 ‘, 2 *, 2‘-tribromethyl) -3,3-dimethylcyclobutanone was stirred with 2.0 g of tetrabutylammonium bromide at 90 ° C for 30 minutes. The cooled melt is chromatographed on silica gel (eluent: toluene / cyclohexane 1: 1). 2- (2 ‘, 2‘, 2‘-Tribromethyl) -3,3-dimethyl-4-bromocyclobutanone was obtained as a slowly crystallizing oil which was recrystallized from diethyl ether / n-hexane. Mp 91-93 ° C.

IR spectrum (СНС1з) in cm ^-1 :

1795 (CO).

1 H-NMR spectrum (100 MHz, CDCl 3) in ppm: 4.96 (d, J = 2 Hz, 1H, H on C 1-4);

3.12 to 3.67 (ABX, wherein part X is additionally cleaved with J 2Hz, Z 2, CH 2 -CH); 1.18 and 1.67 (1s each, 3H each, CHs each).

¹³ C-NMR (CDCl3):

196.4 (s, CO);

63.2 (d, C-2);

59.9 (d, C-4);

54.6 (t, CH 2);

38.4 (s, 1H);

36.4 (s, C-3);

27.8 and 21.3 (always q, always СНз).

Π. 700 mg (1.56 mmol) of 2- (2 ', 2', 2'-trifluoromethyl) -3,3-dimethyl-4-bromocyclobutanone together with a solution of 190 mg of sodium hydroxide in 5 ml of water to which 0.5 ml of dioxane was added, stirred for 2 hours at room temperature. The reaction mixture was then stirred at 80 ° C for 1 hour. The clear solution is treated to the acid in the usual manner. There were obtained 410 mg (88%) of cis-2- (2 ', 2'-dibromviny 1) -3,3-dimethylcyklopropankarbo- _A · - »carboxylic acid.

IR spectrum (CHCl 3) in cm ^-1 :

1695 (CO). <£

NMR spectrum (100 MHz, CDCl3 / D6) in ppm:

6.70 (6d, J = 8 Hz, 1H, C H-S);

1.82 to 2.14 (m, 2H);

1.30 and 1.33 (always 1s, total 6H, always SN).

Example 8

To a solution of 14 g (0.17 mol) of methylene cyclopentane and 26.4 g (0.1 mol) of 2,4,4,4, -tetrachloroformic acid chloride in 220 ml of cyclohexane are added dropwise with stirring at 65 ° C over 2 hours. 10.1 g (0.1 mol) of triethylamine in 100 ml of cyclohexane. The reaction mixture was then stirred at this temperature for 3 hours. The reaction mixture was washed with dilute hydrochloric acid, then with water, dried over magnesium sulfate and evaporated. The residue crystallized from n-hexane. 16.6 g of 1-chloro-1- (2‘, 2‘, 2‘-trichloroethyl) spiro [3,4] octan-2-one of the formula are obtained.

mp 70-73 ° C.

IR spectrum (CHCl3) cm ^-1 :

1775 (CO).

NMR spectrum (100 MHz, CDCl 3) in ppm:

1.60-2.30 (m, 8H);

3.08 (2H, 2H, CH2);

3.60 (MW, 2H, CH 2).

12.0 g (0.041 mol) of 1-chloro-1- (2R, 2R, 2'-trichloroethyl) spiro [3,4] octan-2-one are stirred

3.6 g of tetrabutylammonium chloride at a bath temperature of 125 ° C. After 1.5 hours, the reaction mixture is chromatographed on silica gel using toluene / cyclohexane (1: 1) as eluent. 9.7 g (81% of theory) of 1-chloro-3- (2 ', 2', 2 ', 2'-trichloroethyl) spiro [3,4] octan-2-one of the formula are obtained in the form of a colorless oil.

IC spectrum (CHCh) in cm ^-1 :

18000

Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl 3) in ppm: 4.87 (d, J = 2 Hz, 1H, CHCl);

3.70 ´ (part X ABX, in addition with split 7 Ί J = 2Hz, IH, CH);

*, V 2.73 to 3.29 (part AB ABX, 2H, CH2); Cyl 1.45-2.23 (m, 8H).

4.83 g (16.6 mmol) of 1-chloro-3- (2 ', 2', 2'-trick / chloroethylspiro [3,4] octan-2-one) is added to the m solution of 2.0 g sodium hydroxide in 40 ml of water and 3 ml of dioxane, and the mixture is stirred at room temperature for 2 hours and then at 100 DEG C. for 3 hours, and the reaction solution is washed with diethyl ether and acidified with dilute hydrochloric acid. The extracts were washed with water, dried over magnesium sulphate and evaporated, and the residue was recrystallized from n-hexane to give 3.3 g of 2- (2 ', 2'-dichlorvinyl) spiro [2,4] heptane-1- carboxylic acids of formula

in the form of a white powder. Melting point 90-105 ° C.

iC spectrum (CDCl3) in cm ^-1 : 1705 (COJ, 1620 (CDCl3)).

NMR spectrum (100 MHz, CDCl3 / D2O) in ppm:

6.15 (d, J = 9 Hz, 0.8 H, CH = CCl 3 cis);

5.51 (d, J = 9 Hz, 0.2 H, CH = CCl 2 trans);

2.00 to 2.40 (m, 2H);

1.60-1.95 (m, 8H).

Example 9

A 2.5 liter autoclave was charged with 33.6 g (0.62 mol) of methylene cyclopropane and 152 g (0.62 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 620 ml of n-pentane. At 60 [deg.] C., 62.8 g (0.62 mol) of triethylamine in 120 ml of n-pentane are fed through the pump over a period of 6 hours, and the reaction mixture is then maintained at 60 [deg.] C. for 6 hours.

The reaction mixture was filtered, evaporated and the residue distilled in vacuo. The fraction with a boiling range of 45-80 ° C / 12 Pa is then chromatographed on 250 g of silica gel using hexane containing 0-50% by weight of toluene as eluent. The pure fractions were evaporated, and the residue was distilled. There was obtained 1-chloro-1- (2 ', 2', 2'-trichloroethyl) spiro [3,2] hexan-2-one of formula

CH ₂ CCt _b boiling point 70-71 ° C / 1.0.7 Pa. .

IR spectrum (СНС1з) in cm ^-1 :

1776 (CO).

¹ H-NMR spectrum (100 MHz, CDCl 3) in ppm: 0.8-1.8 (m, 4H);

2.6-3.8 (m, 4H).

A solution of 11.0 g (42 mmol) of 1-chloro-1- (2 ', 2', 2'-trichloroethyl) spiro [3,2] hexan-2-one and 1.17 g (6.3 mmol) of trlbutylamine in 15 ml of toluene was refluxed for 5 hours. After cooling, the reaction mixture was diluted with n-pentane. It is then washed with a 2N sulfuric acid solution and then with a saturated sodium chloride solution, dried over sodium sulphate and evaporated. The residue was distilled under vacuum. There was thus obtained 1-chloro-3- (2 ‘, 2‘, 2 tr-trichloroethyl) sptro [3,2] hexan-2-one of formula

boiling point 60 ° C / 1.3 Pa.

IR spectrum (CCU) ν cm ^-1 : 1780 (CO).

Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl 3) in ppm: δ 0.8-1.7 (m, 4H);

2.6 to 4.2 (m, 3H);

4.75, 5.15 (one d each, 1 H together).

φ 7,1 g (27 mmol) of ε-ω-γ-γ-γ-γ-γ-γ-γ-γ-ethyl) spiro [3,2] hexan-2-one is heated with 54 ml (about 135 mmol) of 10% sodium hydroxide solution 2 hours to reflux. After cooling, the reaction solution was washed with several portions of diethyl ether, acidified with sulfuric acid and extracted with diethyl ether. The ether extracts were evaporated after drying over sodium sulfate. Filtration on silica gel (eluent: diethyl ether) removes a small amount of strongly polar impurities. Concentration of the filtrate affords 2- (2 ‘, 2‘-dichlorvinyl) spiro [2.2] pantane-1-carboxylic acid of formula

COOH as a cis / trans mixture of about 3: 1. Melting point 77-78 ° C.

IR spectrum (CCU) ν cm ^-1 : 1675 (CO).

Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl 3) in ppm: 0.8 to 2.85 (m, 6H);

5.56 and 6.11 (one d each, IH each);

10.8 (broad s, 1H).

The following examples describe the preparation of some insecticidal active ingredients.

Example 10

Preparation of 2- (2 ‘, 2'-Dichloro-vinyl) -3,3-dimethyl-cyclopropane-1-carboxylic acid m-phenoxybenzyl ester

a) 4.18 g (0.02 mol) of 2- (2 ', 2'-dlchlorinyl) -3,3-dimethylcyclopropane-1-carboxylic acid was heated at 70 ° C with 20 ml of thionyl chloride for 3 hours. Excess thlonyl chloride is evaporated, the residue is taken up in 100 ml of benzene and evaporated again. This residue [2- (2 ', 2'-dichlorvinyl) -3,3-dimethylcyclopropanecarboxylic acid chloride] is mixed with a solution of 4.0 g (0.02 mol) of m-phenoxybenzyl alcohol in 40 ml of absolute benzene and the mixture is heated to 40 ° C. Then, 2.2 g (0.022 mol) of triethylamine in 10 ml of absolute benzene was added dropwise over 1 hour, and the reaction mixture was further stirred at this temperature for 1 hour. The reaction mixture was washed with dilute hydrochloric acid, dried over magnesium sulfate and evaporated. The residue is chromatographed. Silica gel eluting with diethyl ether / n-hexane (1: 4 by volume). 2- (2 ', 2'-Dichloro-vinyl) -3,3-dimethyl-cyclopropane-1-carboxylic acid m-phenoxybenzyl ester having a refractive index n _D ²⁰ = 1.5628 was obtained.

b) 5.28 g (0.02 mol) of 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethyl-4-chlorocyclobutan-1-one, which is dissolved in 25 ml of absolute dimethoxyethane is added dropwise to a solution consisting of 4.0 g (0.02 mol) of m-phenoxybenzyl alcohol, 0.5 g (0.021 mol) of sodium hydride and 40 ml of absolute dimethoxyethane. After stirring for 1 hour at 45 ° C, 2.25 g (0.02 mol) of tartaric butoxide target was added to the reaction mixture and the mixture was refluxed for 3 hours. After pouring the reaction mixture into water, the mixture was acidified with dilute chloic acid. and the extraction of benze199523 nem. The extract was evaporated and the residue was chromatographed on silica gel using diethyl ether / n-hexane (1: 4, v / v) as eluent. 2- (2 ‘, 2‘-Dichloro-vinyl) -3,3-dimethyl-cyclopropane-1-carboxylic acid m-phenoxybenzyl ester is obtained in the form of a viscous oil having the same properties as the substance obtained under (a).

Example 11 cis-2- (2 ‘, 2‘-Dichloro-vinyl) -3,3-dimethyl-cyclopropanecarboxylic acid S-cyano-m-phenoxybenzyl ester

a) 10 g (0.047 mol) cis-2- (2 2, 2‘-dichlorvinyl) -3,3-dimethylcyclopropanecarboxylic acid in 100 ml benzene were stirred with 12.1 ml (0.141 mol) oxalyl chloride at room temperature for 24 hours. After evaporation of the reaction solution, the brown residue is distilled under reduced pressure. 9.1 g of a clear liquid having a boiling point of 50 ° C / 5.4 Pa are obtained. 3.0 g of this clear liquid was dissolved in 30 ml of toluene and 2 ml of pyridine was added. 2.9 g of .alpha.-cyano-m-phenoxybenzyl alcohol in 20 ml of toluene are added dropwise at room temperature, and the reaction mixture is then stirred at room temperature for 16 hours. Water was added to the reaction mixture first to wash, then washed with saturated sodium bicarbonate solution and then brine, dried over magnesium sulfate and evaporated. The residue was chromatographed on silica gel using diethyl ether / n-hexane (1: 2) as eluent. Pure α-cyano-m-phenoxybenzyl ester cis-2- (2 ‘, 2‘-dlchlorinyl) -3,3-dimethylcyclopropanecarboxylic acid is obtained as a mixture of dlastereol isomers.

NMR spectrum (60 MHz, CDCl 3) in ppm:

1.20 to 1.43 (m, 6H, 1H);

1.67 to 2.35 (m, 2H, 2 X CH);

6.25 (d, I = 9 Hz, 1H, CH-CC12), 6 JO and

6.45 (1 s each, 0.5 H each, CH-CN); 6.98 to 7.65 (m, 9H).

Example 12

To a solution of 22.75 g (0.1 mol) of crude 2- (2 ', 2'-dichlorinyl) -3,3-dimethylcyclopropanecarboxylic acid chloride [prepared according to example 1a)] and 21.5 g (0.1 mol) 3-Phenoxy-d-hydroxyethylbenzene in 250 ml of absolute toluene is added dropwise at room temperature to 7.8 g (0.1 mol) of absolute pyridine. The reaction mixture was stirred at room temperature (20-25 ° C) for 15 hours, washed with dilute hydrochloric acid, then water, dried (sodium sulfate) and evaporated. The residue is chromatographed on silica gel using a mixture of n-hexane and diethyl ether as eluent (1: 1 by volume). Give α-methyl-m-phenoxybenzyl 2- (2 * 2 * -dlchlorvinyl) -3,3-dimethylcyclopropanecarboxylate ester as a colorless oil with a refractive index n _D ²⁰ = 1.563.

Claims (18)

OBJECT OF THE INVENTION Process for the preparation of 2- (2 ', 2', 2'-trihaloethyl) -4-halo-cyclobutan-1-one of the general formula I wherein one of the radicals R 1 and R 2 is a methyl group and the other one is a hydrogen or a methyl group or R 1 and R 2 together represent an alkylene group having 2 to 4 carbon atoms and X and Y are each chlorine or bromine, but when. X is bromine, Y must also be bromine, characterized in that 2,4,4,4-tetrahalobutyric acid chloride of formula II СзС — CH2 — CH — COC1 in which X and Y are as defined in formula I, in the presence of an organic base, act with an olefin of formula III Ri OF CH2 = C \ R2 I (III), in which R 1 and R 2 are as defined in formula I to give 2- (2 *, 2 ‘, 2‘-trihalogenethyl) -2-halo-cyclobutan-1-one of formula IV Y Х _г С-СН.— С — С-0. I ¹ ρ, -c-fy (iv) (II), in which R 1, R 2, X and Y are as defined in formula I, and this compound is then rearranged to 2- (2 ', 2', 2'-trihalogenethyl) -4-halo-cyclobutan-1-one in the presence of a catalyst. Formula I. 2. A method according to claim 1, characterized in that as "2,4,4,4-tetrahalogenmáselné chloride acid chloride of Formula II uses _2.4> and 4-tсtrachtormáselné acid. Process according to claim 1, characterized in that an olefin of the formula III is used as starting material, in which one of the radicals R 1 and R 2 is a methyl group and the second is hydrogen or a methyl group or R 1 and R 2 together represent an alkylene group. C 2 -C 3; 4. A process according to claim 1, wherein the olefins of formula III are isobutylene. 5. The process of claim 1, wherein the olefin of formula III is methylene cyclopropane. 6. Process according to claim 1, characterized in that the reaction of 2,4,4,4-tetrahalobutyric acid chloride of formula II with an olefin of formula III is carried out in the presence of pyridine or trialkylamine having from 1 to 4 carbon atoms in the alkyl radicals; in the presence of an inert organic solvent. 7. The process of claim 1 wherein the reaction of 2,4,4,4-tetrahalobutyric acid chloride of formula II with an olefin of formula III is carried out in the presence of triethylamine. 8. A process according to claim 1, wherein the catalyst for the rearrangement of 2- (2 &apos;, -2 &apos; 2 &apos;, 6 &apos;) -2-halo-cyclobutarl-1-one of formula IV is 2- (2 &apos; The 2 ', 2', 2'-trihaloethyl) -4-halo-cyclobutan-1-one formula (I) uses inorganic or organic protonic acids. 9. The process of claim 1, wherein the catalyst for the rearrangement of 2- (2 ', 2', 2'-trihalogenethyl) -2-halo-cyclobutamyl of formula IV is 2- (2 ', 2', 2). The 4-halo-cyclobutan-1-one of formula (I) uses hydrohalic acids. , Process according to claim 1, characterized in that 2- (2 ', 2', 2'-trihalogenethyl) -2-halo-cyclobutan-1-one of the formula IV is switched to 2- (2 ', The 2 ', 2'-trihalo (methyl) -4-thalogencyclobutan-1-one of formula I uses an organic base. 11. A process according to claim 1, wherein the catalyst for the rearrangement of 2- (2,2 ^' , 2 &apos;, 2 &apos; -trihaloglyl) -2-halomethyl butan-1-one of formula IV is 2- (2 &apos;). (2 ', 2'-trihalogenethyl) -4-^ ^ е с с с 1 1 1 1 1-ст formulas I uses an amine of the general formula Qt OF N — Q2 \ Q5 in which Q 1 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group or a phenyl group - and Q2 and - - - Q3 - are independently hydrogen or - (C1-C8) -alkyl. 12. The process of claim 1 wherein the catalyst for the rearrangement of 2- (2 &apos;, 2 &apos;, 2 &apos;, 2 &apos; The 2 ', 2', 2'-1'-aminomethyl) -4-halo-cyclobutyl-III of formula (I) uses protonate salts with ammonia, nitrogenous organic bases or quaternary ammonium salts. 13. A process according to claim 1, wherein the catalyst for the rearrangement of 2- (2 ', 2', 2'-trihalogenethyl) -2-halo-cyclobutan-1-one of formula IV is 2- (2). The compound of formula (I) uses salts of hydrohalic acids with an aliphatic, cycloaliphatic, araliphatic or aromatic primary, secondary or tertiary amine or a heterocyclic nitrogen base. 14. A process according to claim 1, wherein the catalyst for the rearrangement of 2- (2 &apos;, 2 ^, 2 &apos;, 2 &apos; -trihalkyltenyl) -2-halomethylcyclobutan-1-one of the formula The (2 ', 2', 2'-trihalkylmethyl) -4-thiophenylcyclobutan-1-formula of formula I uses salts of the formula Qs I ' M-Q 4 —N + - Qe AND 017 in which M is fluorine, bromine or iodine, especially chlorine, Qd represents hydrogen, a C1-C18 alkyl group, a cyclohexyl group, a benzyl group, a phenyl group, or a naphthyl group; and Q 8, Q 6 and Q 7 are each independently hydrogen or C 1 -C 18 alkyl, or N-C 1 -C 18 alkylpyridmium halide; 15. A method according to claim 1, wherein the rearrangement of the 2t (2 &apos;, 2 &apos;, 2 &apos; -trihaloethyl) t-thiophene cyclobutanethane is of formula IV to 2- (2 &apos;, 2 &apos;, 2 &apos; The halocyclobutan-1-one of formula I is carried out at temperatures between 80 ° C and 130 ° C. 16. The process of claim 1 wherein the rearrangement of 2t (2 ', 2', 2'-trihaloethyl) -2-thiophenylcyclobutan-1-one of the formula IV to 2- (2 ', 2', 2'-trihalosulfonyl) - The 4-halo-cyclobutamyl-formula I is carried out in the melt at a temperature of between 80 and 130 ° C in the presence of a trialkylamine of from 1 to 8 carbon atoms in the alkyl radicals or of the tetraalkylammonium of 185252 halogen of 1 to 18 carbon atoms in the alkyl radicals. 17. The method of claim 1, wherein 2- (2 ', 2', 2'-trihalogenethyl) -2-halo-cyclobutan-1-one rearrangement of formula IV is converted to 2- (2 ', 2', 2 '). -trihalogenethyl) -4-halo-cyclobutan-1-one of formula I is carried out in the presence of an inert solvent. 18. The method of claim 1, wherein 2- (2 ', 2', 2'-trihaiethyl) -2-halo-cyclobutan-1-one rearrangement of formula IV is converted to 2- (2 ', 2', The 2'-trihalogenethyl) -4-halo-cyclobutan-1-one of formula I is carried out in a C 1 -C 4 aliphatic alcohol, toluene, xylene, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionyltril, ethylene glycol, diethyl ether or diisopropyl ketone as solvent.