DE2813337C2 - - Google Patents

Description

The present invention relates to 2- (2 ′, 2 ′, 2′-trihaloethyl) -4-halogenocyclo butan-1-one of the general formula I

in which one of the radicals R₁ and R₂ is methyl and the other Hydrogen or methyl or R₁ and R₂ together form an alkylene group with 2 to 4 carbon atoms and X and Y each Represent chlorine or bromine, but when X is bromine Y must also always be bromine.

The present invention further relates to a Process for the preparation of 2- (2 ′, 2 ′, 2 ′, - Trihalogenethyl) -4-halogenocyclobutan-1-one of the general formula I, and new intermediates that can be used in their manufacture.

It is known that, when heated in the presence of bases such as alkali metal hydroxides and alkali metal alcoholates, the α- halogenocycloalkanones are converted to carboxylic acids with the same carbon number or their esters with a narrowing ring in cycloalkane (Favorski reaction). This reaction forms the basis for a technically important process for the preparation of cyclopropanecarboxylic acid derivatives and their insecticidally active esters, the pyrethroids, from α- halo cyclobutanones. The use of this technically easy-to-carry out process for the preparation of pyrethroids, which differs from 2- (2 ', 2'-Dihalogenvinyl) -cyclopropanecarboxylic acid derived, however, was not possible because corresponding α- halocyclobutanones suitable for the preparation of such cyclopropanecarboxylic acid derivatives were not available.

It has already been proposed to produce α- halocyclobutanones by reacting a halogen chain with an olefin. Such methods are described, for example, in German Offenlegungsschrift 25 39 048, British Patent 11 94 604 and J.Amer.Chem.Soc. 87, 5257-5259 (1965) and in Tetrahedron Letters No. 1, 135-139 (1966). This synthetic principle has not previously been used to produce a -halogen butanones, which are suitable as intermediates for the preparation of 2- (2 ', 2'-dihalovinyl) cyclopropanecarboxylic acids and their insecticidally active esters. This is primarily due to the fact that the synthetic possibilities conceivable on the basis of the aforementioned method, namely

• a) Reaction of a halogenated olefin with a halogen ketene according to the equation: respectively. or
• b) Reaction of an unhalogenated olefin with a halogen ketene according to the equation: where in the above equations the symbols R₁, R₂, X and Y have the meaning given under the general formula I, not for the 2- (2 ′, 2 ′, 2′-trihaloethyl) -4-halogenocyclobutane-1- required as intermediates onen of the general formula I because the reaction according to a) does not take place because of the deactivation of the olefin associated with the halogen substitution and the reaction according to b) is a 2- (2 ', 2', 2'-trihaloethyl) -2 -Halogencyclobutan-1-one delivers that with alkali metal hydroxide or alkali metal alcoholate in a 2- (2 ', 2'-dihalovinyl) -cyclopropanecarboxylic acid or its ester can not be performed.

The present invention is therefore based on the object starting from easily accessible raw materials a simple Process to be carried out for the production of 2- (2 ′, 2 ′, 2′- trihalogenethyl) -4-halogenocyclobutan-1-ones of the general formula I ready deliver.

The present invention is also based on the object, the previously unknown 2- (2 ', 2', 2'-trihalogenethyl) -4-halocyclobutan-1-one of the general formula I, which when heated with strong bases, such as alkali metal hydroxides or Alkali metal alcoholates, ring narrowing and simultaneous elimination of 2 moles of hydrogen halide provide the corresponding 2- (2 ′, 2′-di halogenovinyl) -cyclopropanecarboxylic acid derivatives, and to make available, easily accessible intermediates available for the preparation of α- halocyclobutanones of the general formula I. .

It has now been found that 2- (2 ′, 2 ′, 2′-trihaloethyl) - 4-halogenocyclobutan-1-one of the general formula I in a simple manner can produce if you have a 2,4,4,4-tetrahalobutyric acid chloride of the general formula II

in which X and Y have the meaning given under general formula I. have, in the presence of an organic base with an olefin of the general formula III

in which R₁ and R₂ have the meaning given under the general formula I. have to a 2- (2 ′, 2 ′, 2′-trihaloethyl) -2-halogenocyclo butan-1-one of the general formula IV

in which R₁, R₂, X and Y are the bees specified under formula I. have interpretation, then implement it in the present an inorganic or organic sample acid, an organic base or of salts of protonic acids with ammonia, nitrogenous organic bases or quaternary ammonium salts as Catalyst at temperatures between 80 and 150 ° optionally  in the presence of an inert solvent.

The 2,4,4,4-tetrahalobutyric acid chlorides of the general formula II are new connections. They can be made in a manner known per se be made by using a tetrahalomethane of the general Formula V

in which X and Y have the meaning given under general formula I. have on a compound of general formula VI

CH₂ = CH - Z (VI)

in which Z is chlorocarbonyl, carboxyl, alkoxycarbonyl with 1 means up to 4 carbon atoms in the alkyl group or cyano, attaches and obtained compounds of general formula VII

in which X and Y have the meaning given under general formula I. have and Z means carboxyl, alkoxycarbonyl or cyano in Transfer compounds of general formula VII, in which Z is chlorine carbonyl means.

Another way to make 2,4,4,4-tetra Halogenbutasäurechloriden of the general formula II is that to obtain a compound of the general formula VIa  

in which Z has the meaning given under the general formula VI attached to 1,1-dichloroethylene and compounds obtained of the general formula VIIa

in which Z means carboxyl, alkoxycarbonyl or cyano in compounds transferred to the general formula VIIa, in which Z means chlorocarbonyl. When adding a tetrahalomethane of the general formula V. an acrylic acid derivative of the general formula VI, and in the addition of a dichloroacetic acid derivative of the general formula VIa on 1,1-dichloro ethylene can the tetrahalomethane of the general formula V or the Di chloroacetic acid derivative of the general formula VIa in a stoichiometric amount be used. However, an over is preferably used shot of tetrahalomethane of the general formula V or dichloroacetic acid acid derivative of the general formula VIa, for example about 0.5 to 2-fold molar excess, the tetrahalomethane of the general Formula V can also serve as a solvent.

The addition of a tetrahalomethane of the general formula V to a Compound of the general formula VI and the addition of a compound of the general formula VIa on 1,1-dichloroethylene is in the presence of Catalysts carried out. Metals are suitable as catalysts the main group VIII and the subgroups VIa, VIIa and Ib des  periodic systems, e.g. B. iron, cobalt, nickel, ruthenium, Rhodium, palladium, chrome, molybdenum, manganese and copper. These Metals can be in elemental form or in the form of compounds be used. Suitable compounds of these metals are for example oxides, halides, sulfates, sulfites, sulfides Nitrates, acetates, citrates, carbonates, cyanides and rhodanides, as well as complexes with ligands such as phosphines, phosphites, benzoin, Benzoyl and acetylacetonates, nitriles, isonitriles and coals monoxide.

Examples of compounds of the abovementioned metals which are suitable as catalysts are:
Copper (II) oxide, iron (III) oxide; Cu (I) Cu (II), Fe (II) and Fe (III) bromides and especially chlorides and the chlorides of ruthenium, rhodium, palladium, cobalt and nickel; Cu (II) sulfate, Fe (II) and Fe (III) sulfate; Cu (II) nitrate and iron (III) nitrate; Manganese (III) acetate, copper (II) acetate; Copper (II) stearate; Iron (III) citrate; Cu (I) cyanide; Ruthenium (II) dichloro-tris-triphenylphosphine, rhodium-tris (triphenylphosphine) chloride; Chron and nickel acetylacetonate, copper (II) acetylacetonate, iron (III) acetylacetonate, cobalt (II) and cobalt (III) acetylacetonate, manganese (II) acetylacetonate, copper (II) - benzoylacetonate; Iron carbonyl-cyclopentadienyl complex; Molybdenum carbonylcyclopentadienyl complex, chromium tricarbonyl aryl complexes, ruthenium (II) acetate complex, chromium and molybdenum hexacarbonyl, nickel tetracarbonyl, iron pentacarbonyl, cobalt and manganese carbonyl.

Mixtures of the metals mentioned with Metallver bindings and / or other additives are used, such as Copper powder in combination with one of the aforementioned copper links; Mixtures of copper powder with lithium halides, such as lithium chloride, or with isocyanides, such as tert-butyliso cyanide; Mixtures of iron powder with iron (III) chloride, opp if necessary with the addition of carbon monoxide; Mixtures of  Iron (III) chloride and benzoin; Mixtures of iron (II) - or Iron (III) chloride and trialkyl phosphites; Mixtures of iron pentacarbonyl and iodine.

Iron (II) and iron (III) salts and complexes are preferred as well as iron powder, but above all copper powder, copper (I) - and copper (II) salts and complexes, such as Cu (I) chloride, Cu (II) - chloride, Cu (I) bromide, Cu (II) bromide, Cu (II) acetylacetonate, Cu (II) benzoylacetonate, Cu (II) sulfate, Cu (II) nitrate and Cu (I) - cyanide.

Copper powder, copper (I) - and Copper (II) chloride or bromide and mixtures thereof.

The catalysts mentioned are generally in amounts from about 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based to the compound of the general formula III or 1,1-dichloroethylene, used.

The addition reactions are in an organic solution medium made. Suitable organic solvents are those in which the catalysts are sufficiently soluble or which can form complexes with the catalysts which but are inert to the starting compounds. Examples such solvents are especially alkyl nitriles those with 2-5 C atoms, such as acetonitrile, Pro pionitrile and butyronitrile; 3-alkoxypropionitrile with 1 or 2 carbon atoms in the alkoxy part, such as 3-methoxypropionitrile and 3-ethoxypropionitrile; aromatic nitriles, especially benzo nitrile; aliphatic ketones with preferably a total of 3-8 C atoms, such as acetone, diethyl ketone, methyl isopropyl ketone, di isopropyl ketone, methyl tert-butyl ketone; Alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids with a total of 2-6 C atoms, such as methyl and ethyl formate, acetic acid methyl, ethyl, n-butyl and isobutyl esters and 1-acetoxy 2-methoxyethane; cyclic ethers, such as tetrahydrofuran, tetra hydropyran and dioxane; Dialkyl ether with 1-4 C atoms in each  Alkyl parts such as diethyl ether, di-n-propyl ether and di-isopro pyl ether; N, N-Dialkylamides of aliphatic monocarboxylic acids with 1-3 carbon atoms in the acid part, such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and N, N-dimethyl methoxy acetamide; Ethylene glycol and diethylene glycol dialkyl ether with 1-4 carbon atoms in the alkyl parts, such as ethylene glycolide dimethyl, diethyl and di-n-butyl ether; Diethylene glycol diethyl and di-n-butyl sutures; Hexamethylphosphoric acid triamid (hexametapol).

Preferred solvents are alkyl nitriles with 2-5 C atoms and 3-alkoxypropionitriles with 1 or 2 C atoms in the alkoxy part, especially acetonitrile and 3-methoxypropio nitrile.

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

As a compound of the general formula VI or VIa is preferably used wise acrylic acid chloride or dichloroacetyl chloride. This will get the desired 2,4,4,4-tetrahalobutyl chlorides direct way in pure form and in high yields. Further preferred compounds of the general formula VI or VIa are acrylic acid or dichloroacetic acid. The free 2,4,4,4- Tetrahalobutanoic acids can then easily on themselves known manner by reaction with inorganic acid chlorides, such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, Phosgene, and thionyl chloride in the corresponding acid chlorides be transferred.

When using compounds of the general formula VI or VIa in which Z represents alkoxycarbonyl or cyano, obtained esters or nitriles of a 2,4,4,4-tetrahalobutyric acid of the general formula VII (Z = alkoxycarbonyl or cyano) are first in the presence strong acids, such as concentrated hydrochloric acid, to the corresponding  hydrolysed free 2,4,4,4-tetrahalobutyric acid then in the appropriate manner in the corresponding acid chloride is transferred.

The implementation of the 2,4,4,4-tetrahalobutyric acid chlorides of the general Formula II with olefins of the general formula III is advantageous in In the presence of an inert, organic solvent. As such z. B. optionally halogenated aromatic or aliphatic hydrocarbons, e.g. B. benzene, toluene, Xylenes, chlorobenzene, dichloro- and trichlorobenzenes, n-pentane, n-hexane, n-octane, methylene chloride, chloroform, carbon tetrachloride, 1,1,2,2-tetrachloroethane and trichlorethylene. Other suitable solvents are cycloaliphatic carbons hydrogen, e.g. B. cyclopentane or cyclohexane, cycloaliphatic Ketones, e.g. B. cyclopentanone and cyclohexanone, and aliphatic Ketones, aliphatic and cyclic ethers, alkyl nitriles and 3-alkoxypropionitriles with 1 or 2 carbon atoms in the Alkoxy group, especially acetonitrile and 3-methoxypropionitrile.

Particularly suitable solvents are aliphatic, cyclo aliphatic and aromatic hydrocarbons, especially Alkanes with 5 to 8 carbon atoms, benzene and toluene and especially n-hexane and cyclohexane.

However, excess olefin of the general can also be used as solvent Formula III serve.

Suitable organic bases, in the presence of which the reaction a 2,4,4,4-tetrahalobutyric acid chloride of the general formula II with an olefin of the general formula III is carried out, for example tertiary amines, especially trialkylamines each with 1 to 4 carbon atoms, in particular 2 to 4 carbon atoms, in the alkyl groups, cyclic amines, e.g. B. pyridine, quinoline, N-alkyl pyrrolidines, N-alkyl piperidines, N, N-dialkyl piperazines and N-alkylmorpholines or dialkylanilines, each with 1 or 2 Carbon atoms in the alkyl groups, e.g. B. N-methyl-pyrrolidine, N-ethyl piperidine, N, N'-dimethyl-piperazine, N-ethyl morpholine and N, N-dimethylaniline, and bicyclic amidines, e.g. B. 1.5-  Diazabicyclo [5.4.0] undec-5-ene and 1,5-diazabicyclo [4.3.0] non-5-enes, and bicyclic diamines e.g. B. 1,4-diazabicyclo [2.2.2] octane.

The implementation of 2,4,4,4-tetrahalobutyric acid chloride of general formula II with olefins of general formula III is preferably in Presence of trialkylamines each with 1 to 4 carbon atoms carried out in the alkyl groups. Particularly suitable bases are triethylamine and pyridine.

The organic base is in at least equimolar amount or in a slight excess with respect to the 2,4,4,4-tetra halobutyric acid chloride of the general formula II used.

The olefins of the general formula III are also at least equimolar amount with respect to the 2,4,4,4-tetrahalogen butter Acid chloride of the general formula II used. However, it is common consider advantageous to use an excess of olefin, the olefin, as already mentioned, also as a solvent can serve. When using volatile olefins the recation can be carried out under pressure. Particularly suitable olefins of the general formula III are those in which one of the radicals R₁ and R₂ methyl and the other water substance or methyl or R₁ and R₂ together form an alkylene group with 2 to 3 carbon atoms, namely isobutylene, Propene, methylene cyclopropane and methylene cyclobutane. Especially isobutylene and methylene cyclopropane are preferred.

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

The 2- (2 ′, 2 ′, 2′-trihaloethyl) -2-halogenocyclobutan-1-one of the general formula IV are new compounds and also a subject of the invention. As a cat gates, for the rearrangement of the initially received 2- (2 ', 2', 2'-trihaloethyl) -2-halocyclobutan-1-one of the general Formula IV in 2- (2 ′, 2 ′, 2′-trihaloethyl) -4-cyclobutan-1-one  of the general formula I can acids, bases or quaternary ammonium halides can be used.

The rearrangement according to the invention of 2- (2 ', 2', 2'-trihalogen ethyl) -2-halogenocyclobutan-1-ones of the general formula IV in 2- (2 ', 2', 2'-trihalogenethyl) -4-halogenocyclobutane -1-one of the general formula I is unexpected and is not known for cyclobutanones monohalogenated in the α position. It is particularly surprising that no HX elimination occurs on the trihalogenethyl group in the presence of a basic catalyst. The rearrangement proceeds in excellent, often quantitative yield.

The rearrangement of 2- (2 ', 2', 2'-trihalogen ethyl) -2-halogenocyclobutan-1-ones of the general formula IV in 2- (2 ′, 2 ′, 2′- Trihalogenethyl) -4-halocyclobutan-1-one of the general formula I is preferably in the presence of basic catalysts leads. Organic bases come in as basic catalysts Consider e.g. B. primary, secondary and especially tertiary Amines of the general formula

in which Q₁ alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, benzyl or phenyl and Q₂ and Q₃ independently of one another hydrogen or alkyl with 1 to 8 Mean carbon atoms. Suitable basic catalysts are, for example, triethylamine, tri-n-butylamine, tri-iso- pentylamine, tri-n-octylamine, N, N-dimethylcyclohexylamine, N, N- Dimethylbenzylamine, N, N-Dimethyl-2-ethylhexylamine, N, N-Diethyl aniline, and also cyclic amines, e.g. B. pyridine, quinoline, Lutidine, N-alkylmorpholines such as N-methylmorpholines, N-alkyl piperidines such as N-methyl and N-ethyl piperidine, N-alkyl pyrrolidines such as N-methyl and N-ethyl pyrrolidine, diamines, e.g. B. N, N, N ', N'-  Tetramethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-diamino butane, N, N'-dialkylpiperazines, such as N-N'-dimethylpiperazine, bicyclic amines, e.g. B. 1,4-diazabicyclo [2.2.2] octane and bi cyclic amidines, e.g. B. 1,5-diazabicyclo [5.4.0] unde-5-ene and 1,5-diazabicyclo [4.3.0] non-5-enes, and finally polymers basic compounds, e.g. B. p-Dimethylaminomethylpolystyrene.

Furthermore, as basic catalysts for the Invention moderate rearrangement of a 2- (2 ′, 2 ′, 2′-trihaloethyl) -2-halogen cyclobutan-1-one of the general formula IV in a 2- (2 ', 2', 2'-trihalogen ethyl) -4-halogenocyclobutan-1-one of the general formula I phosphines, ins special trialkylphosphines, for example tributylphosphine, suitable.

As acidic catalysts for the rearrangement of 2- (2 ′, 2 ′, 2′- Trihalogenethyl) -2-halogenocyclobutan-1-one of the general formula IV in 2- (2 ', 2', 2'-trihaloethyl) -4-halogeno-cyclobutan-1-one of the general Formula I inorganic or organic protonic acids be used. Suitable inorganic protonic acids are for example hydrohalic acid (hydrogen chloride, Hydrogen bromide, hydrogen fluoride and hydrogen iodide), saltpetre acid, phosphoric acid and sulfuric acid. Preferred inorganic Protonic acid are hydrohalic acids.

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

Furthermore, salts of protonic acids, especially halogen water Substance acids, with ammonia or a nitrogen containing organic base and quaternary ammonium halides used will. Organic bases containing nitrogen are aliphatic, cycloaliphatic, araliphatic and aromatic primary, secondary and tertiary amines as well heterocyclic nitrogen bases. Examples include: primary aliphatic amines with up to 12 carbon atoms, e.g. B. methyl amine, ethylamine, n-butylamine, n-octylamine, n-dodecylamine,  Hexamethylene diamine, cyclohexylamine, benzylamine; secondary ali phatic amines with up to 12 carbon atoms, e.g. B. dimethylamine, Di ethylamine, di-n-propylamine, dicyclohexylamine, pyrrolidine, Piperidine, piperazine, morpholine; tertiary aliphatic amines especially trialkylamines each with 1-4 C atoms in the alkyl parts, e.g. B. triethylamine, tri-n-butylamine, N-methylpyrrolidine, N-methyl morpholine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine; given if substituted primary, secondary and tertiary aromatic Amines, e.g. B. aniline, toluidine, naphthylamine, N-methylaniline, Di phenylamine and N, N-diethylaniline; further pyridine, picoline, Indoline and quinoline.

Salts of the general formula are preferred

wherein
M fluorine, bromine or iodine, especially chlorine,
Q₄ is hydrogen, alkyl with 1-18 carbon atoms, cyclohexyl, benzyl, phenyl or naphthyl and
Q₅, Q₆ and Q₇ independently of one another are hydrogen or alkyl having 1-18 C atoms
mean, and N-alkyl-pyridinium halides with 1-18 carbon atoms in the alkyl, especially the corresponding chlorides.

Examples of such salts are: ammonium chloride, ammonium bromide, Methylamine hydrochloride, cyclohecxylamine hydrochloride, aniline hydrochloride, dimethylamine hydrochloride, di-isobutylaminohydro chloride, triethylamine hydrochloride, triethylamine hydrobromide, Tri-n-octylamine hydrochloride, benzyldimethylamine hydrochloride, Tetramethyl, tetraethyl, tetra-n-propyl, tetra-n-butylammonium chloride, bromide and iodide, trimethylhexadecylammonium chloride, Benzyldimethylhexadecyclammonium chloride, benzyldimethyl tetra decyclammonium chloride, benzyl trimethyl, triethyl and tri n-butylammonium chloride, n-butyl-tri-n-propylammonium bromide, Octadecyltrimethylammonium bromide, phenyltrimethylammonium bromide or chloride, hexadecyl pyridinium bromide and chloride.

As additional co-catalysts, 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 use fluoride.

These co-catalysts catalyze the reaction even in the absence ammonium salts above, but then additives are more open-chain or macrocyclic polyether (crown ether) for rapid ab run an advantage. Examples of such crown ethers are: 15-Crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 5,6,14,15- Dibenzo-7,13-diaza-1,4-dioxa-cyclopentadeca-5,14-diene.

The amount of catalyst used can be broader within Limits vary. In some cases it is sufficient if the kata lysator is present in traces. In general, however, the Kata analyzer preferably in an amount of about 0.1 to 15 weight percent, based on the compound of general formula VI, used.

The rearrangement can take place both in the melt and in one inert organic solvents are made. The reaction temperatures for the rearrangement in the melt are between 80 and 150 ° C, especially between 80 and 130 ° C.  

Suitable as catalysts for the rearrangement in the melt especially the aforementioned organic bases, in particular Trialkylamines each with 1-8 C atoms in the alkyl parts; further Salts of hydrohalic acids with ammonia or organi rule nitrogenous bases, e.g. B. Trialkylamine hydrochloride and bromides, each with 1-8 C atoms in the alkyl parts, and whole especially tetraalkylammonium halides, especially chlorides, bromides and iodides, each with 1-18 carbon atoms in the alkyl parts.

Suitable inert organic solvents are e.g. B.

• - optionally nitrated or halogenated aliphatic, cyclo aliphatic or aromatic hydrocarbons, e.g. B. n-hexane, n-petane, cyclohexane, benzene, toluene, xylenes, nitrobenzene, Chloroform, carbon tetrachloride, trichlorethylene, 1,1,2,2- Tetrachloroethane, nitromethane, chlorobenzene, dichlorobenzenes and trichlorobenzenes;
• - lower aliphatic alcohols, e.g. B. those with up to 6 C atoms, e.g. B. methanol, ethanol, propanol, isopropanol, Butanols and pentanols;
• - aliphatic diols, e.g. B. ethylene glycol and diethylene glycol;
• - Ethylene glycol monoalkyl ether and diethylene glycol monoalkyl ether with 1-4 carbon atoms in the alkyl parts, e.g. B. ethylene glycol monomethyl and monoethyl ether, diethylene glycol mono methyl and monoethyl ether;
• - Cyclic amides, e.g. B. N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl- ε- caprolactam;
• - Amides of carbonic acid, e.g. B. tetramethyl urea and dimorpho linocarbonyl;
• - Amides of phosphorous acid, phosphoric acid, phenyl phosphonic acid or of aliphatic phosphonic acids with 1-3 C atoms in the acid part, such as phosphoric acid triamide, phosphoric acid tris (dimethylamide), phosphoric acid trimorpholide, phosphoric acid tripyrrolinide, phosphoric acid bis (dimethylamide) morpholide,  Phosphoric acid-dimethylamide-diethylamide-morpholide, phosphorous acid-tris (dimethylamide), tetramethyldiamide the methanephosphon acid;
• - Amides of sulfuric acid, aliphatic or aromatic Sulfonic acids, e.g. B. tetramethyl sulfamide, dimethyl amide of methane sulfonic acid or p-toluenesulfonic acid amide;
• - Sulfur-containing solvents, e.g. B. organic sulfones and Sulfoxides, e.g. B. dimethyl sulfoxide and sulfolane;
• - aliphatic and aromatic nitriles, 3-alkoxypropionitriles, aliphatic ketones, alkyl and alkoxyalkyl esters of aliphatic Monocarboxylic acids, cyclic ethers, dialkyl ethers, N, N-disubstituted amides of aliphatic monocarboxylic acids and ethylene glycol and diethylene glycol dialkyl ether under of process stage 1) mentioned art.

For the rearrangement in the presence of a protonic acid as a catalyst polar solvents are advantageously used, in particular lower alcohols, e.g. B. methanol, ethanol and butanols, N, N-Dialkylamides of aliphatic monocarboxylic acids with 1-3 C atoms in the acid part, especially N, N-dimethylformamide, or Dialkyl sulfoxides such as dimethyl sulfoxide.

In the rearrangement in the presence of an inert organic solvent, a catalyst is added, preferably an organic base with a pK _a value of over 9, in particular trialkylamines each having 1-8 C atoms in the alkyl parts, for. B. triethylamine, tri-n-butylamine and tri-n-octylamine; also hydrohalic acids, especially HCl and HBr, and tetraalkylammonium halides, especially chlorides, bromides and iodides, each with 1-18 carbon atoms in the alkyl parts.

Aliphatic alcohols are particularly preferred solvents with 1-4 C atoms, toluene, xylenes, chlorobenzene, dioxane, Acetonitrile, 3-methoxypropionitrile, ethylene glycol diethyl ether and di-isopropyl ketone.

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

With the process according to the invention, new 3- (2 ′, 2 ′, 2) suitable as intermediates for the production of 2- (2 ′, 2′-halovinyl) cyclopropanecarboxylic acid derivatives which are substituted in the 3-position are obtained '-Trihalogen ethyl) -4-halogeno-cyclobutan-1-one of the general formula I starting from readily available starting materials in a simple manner and available in good yield. The process according to the invention is particularly suitable for the preparation of 2- (2 ', 2', 2'-trichloroethyl) -4-halogenocyclobutan-1-ones of the general formula I substituted in the 3-position. The course of the process according to the invention is extremely surprising and completely unpredictable, since in the reaction of a 2,4,4,4-tetrahalobutyric acid chloride of the general formula II or a halogen ketene formed therefrom by splitting off hydrogen chloride in situ with an olefin of the general formula III, one is initially used for the further conversion into a 3-position substituted 2- (2 ', 2'-dihalogenvinyl) -cyclopropanecarboxylic acid derivative unsuitable 2- (2', 2'-trihalogenethyl) -2-halocyclobutan-1-one of the general formula IV, which is then formed by a novel , in the α- position monohalogenated cyclobutanones not previously observed rearrangement into a suitable for further transformation into a 3-substituted 2- (2 ′, 2′-dihalogen vinyl) cyclopropanecarboxylic acid derivative 2- (2 ', 2', 2'- trihaloethyl) -4-halogenocyclobutan-1-one of the general formula I is carried out.

The starting from new 2- (2 ′, 2 ′, 2′-trihalogen) -4-chlorocyclo butan-1-ones of the general formula I that can be prepared in the 3-position substi did 2- (2 ′, 2′-dihalovinyl) -cyclopropanecarboxylic acids and their insecticidally active esters can be obtained from the following general formula VIII can be described:

in which X, R₁ and R₂ have the meaning given under the general formula I. have and R is hydrogen, alkyl having 1 to 4 carbon atoms or a group of the general formula IX

represents in which R₃ is oxygen, sulfur or the vinylene Group, R₄ is hydrogen, alkyl having 1 to 4 carbon atoms, Benzyl, phenoxy or phenylmercapto, R₅ hydrogen or one Alkyl group with 1 to 4 carbon atoms and R₆ hydrogen, cyano or ethynyl or if one of the radicals R₁ and R₂ is methyl and the other is hydrogen or methyl, R₃ is the vinylene group, R₄ Phenoxy and R₅ are hydrogen, also alkyl with 1 to 5 carbons atoms means.  

The 2- (2 ', 2'-dihalovinyl) cyclopropanecarboxylic acid derivatives of the general formula VIII in which R represents a group of the general formula IX are suitable for combating various animal species or plant pests, especially insects. The own properties, areas of application and forms of use of these active ingredients are described in the literature (cf. e.g. Nature, 246, 169-170 [1973]; Nature, 248, 710-711 [1974]; Proceedings 7th British Insecticide and Fungicide Conference, 721-728 [1973]; Proceedings 8th British Insecticide and Fungicide Conferende, 373-78 [1975]; J. Arg. Food Chem. 23, 115 [1973]; U.S. Patent Specification 39 61 070; German Offenlegungsschriften 25 53 991, 24 39 177, 23 26 077 and 26 14 648).

The conversion of 2- (2 ′, 2 ′, 2′-trihaloethyl) -4-halogen cyclobutan-1-ones of the general formula I in 2- (2 ′, 2′-dihalovinyl) - Cyclopropanecarboxylic acid derivatives of the general formula VIII are carried out on known manner by heating in the presence of suitable ones Bases. Suitable bases are, for example, alkali metal and Alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide, Calcium hydroxide and barium hydroxide. Also alkali metal and earth alkali metal carbonates and bicarbonates, such as calcium carbonate, Barium carbonate, potassium carbonate, sodium carbonate, sodium hydrogen Carbonate and potassium hydrogen carbonate can be used as bases will. Also suitable as bases of the radical R according to the above Definition derived alcoholates, especially the corresponding ones Sodium and potassium alcoholates. The use of such Alcoholates has the advantage that the corresponding one is immediately Ester is obtained while using alkali metal and alkaline earth metal hydroxides first the salts of these bases with the 2- (2 ', 2'-dihalovinyl) cyclopropanecarbon formed acid can be obtained. However, these can also be on a simple and well-known way, for example by over guidance in the corresponding acid chloride and reaction with a alcohol derived from the radical R, are converted into esters.  

The transfer of a 2- (2 ′, 2 ′, 2′-trihaloethyl) -4-halogen cyclobutan-1-one of the general formula I into a 2- (2 ′, 2′-dihalovinyl) - Cyclopropanecarboxylic acid derivative of the general formula VIII is, depending on the type the base used expediently in aqueous, aqueous-organic or organic medium. If the base is an alkali metal or alkaline earth metal carbonate is used, so the reaction in aqueous or aqueous-organic medium carried out. The reaction in the presence of alkali metal or alkaline earth metal hydroxides and alkali metal bicarbonates becomes advantageous in aqueous or aqueous-organic medium performed. After acidifying the reaction mixture, e.g. B. by adding concentrated hydrochloric acid, the free 2- (2 ', 2'-dihalovinyl) cyclopropanecarboxylic acids of the general formula VIII (R = H) received.

Suitable solvents for the reaction of 2- (2 ', 2', 2'-tri halomethyl-4-halocyclobutan-1-ones of the general formula I in 2- (2 ', 2'-Dihalogenvinyl) -cyclopropanecarboxylic acid derivatives of the general Formula VIII are in aqueous-organic or organic medium lower alcohols, for example those with 1 to 6 carbon atoms, benzyl alcohol, aliphatic or cyclic ethers, such as Diethyl ether, di-n-propyl ether, di-isopropyl ether, tetrahydro furan and dioxane, as well as aliphatic, cycloaliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, cyclo hexane, benzene, toluene and xylenes.

The reaction of 2- (2 ', 2', 2'-trihaloethyl) -4-halogenocyclo butan-1-ones of the general formula I to 2- (2 ', 2'-dihalovinyl) -cyclo Propane carboxylic acid derivatives of the general formula VIII are generally at the boiling point of the chosen reaction medium. Reaction temperatures between 40 and are particularly suitable 120 ° C.

When converting 2- (2 ′, 2 ′, 2′-trihaloethyl) -4-halogen cyclobutan-1-ones of the general formula I in 2- (2 ', 2'-dihalovinyl) -cyclo Propanecarboxylic acid derivatives of the general formula VIII occur as intermediates  the corresponding 2- (2 ', 2', 2'-trihaloethyl) cyclopropane carboxylic acid derivatives of the general formula X

in which R, R₁, R₂ and X have the meaning given, as intermediates. These products can be taken if you keep the reaction temperature below 40 ° C and / or Base deficit used. These intermediates go above 40 ° C with addition of further base with elimination of HX into the corresponding 2- (2 ′, 2′-dihalovinyl) cyclopropanecarbon acid derivatives of the general formula VIII.

The 2- (2 ', 2', 2'-trihaloethyl) cyclopropanecarboxylic acid derivatives of the general formula X can also be countered by irradiation with UV light if necessary with the addition of conventional sensitizers (e.g. ketones, such as acetone, cyclohexanone, benzophenone, acetophenone and higher Alkylaryl ketones, thioxanthone, etc.), in the presence of hydroxyl group-containing reagents, which also act as solvents can serve photochemically from 2- (2 ′, 2 ′, 2′-trihaloethyl) -4- Halogencyclobutan-1-ones of the general formula I can be prepared. Hydroxyl Reagents containing groups are e.g. B. alkanols, such as methanol, Ethanol etc. and especially water.

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

example 1 Source material a) Preparation of 2,4,4,4-tetrachlorobutyric acid chloride

452.5 g (5 mol) of acrylic acid chloride (technical purity degrees), 1.5 liters of carbon tetrachloride, 1.5 liters of acetonitrile and 30 g of copper (I) chloride are heated at 115 ° C for 24 hours held. The reaction mixture is filtered clear and on Evaporated water jet vacuum. The residue is distilled. 922 g (76% of theory) of 2,4,4,4, tetrachlor are obtained butyric acid chloride; Bp 78-80 ° C / 14.7 mbar.

IR spectrum (CHCl₃) in cm ^-1 : 1780 (C = O).
Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl₃) in ppm: 3.16-3.94 (m, 2H CH₂); 4.84-4.96 (m, 1H, CH).

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

90.5 g (1 mol) acrylic acid chloride, 0.5 liters carbon tetrachloride fabric, 0.2 liters of butyronitrile and 3 g of copper powder are during Heated to 115 ° C for 20 hours. The reaction mixture is filtered and evaporated and the residue is distilled. You get 167.8 g (69% of theory) 2,4,4,4-tetrachlorobutyric acid chloride; Bp 80-81 ° C / 16 mbar. The spectroscopic data are identical with those of the 2,4,4,4- Carbon tetrachloride.

If the process is otherwise the same, the copper powder by copper (I) chloride and the butyronitrile by 3- Methoxypropionitrile replaced, so you get the 2,4,4,4-tetra chlorobutyric acid chloride in a yield of 71%. Th.  226 g (1 mole) 2,4,4,4-tetrachlorobutyric acid (made according to Israeli patent 18771 = CA, 63, 13089e [1965]), 600 g thionyl chloride and 1 ml N, N-dimethylforma become at 50 ° C for 2 hours and for 2 hours heated to 75 ° C. After evaporating the excess The residue is distilled in thionyl chloride. You get 227.6 g (93% of theory) 2,4,4,4-tetrachlorobutyric acid chloride; Sd .; 90-91 ° C / 20 mbar.

145.9 g (1.5 mol) 1,1-dichlorethylene, 147.4 g (1 mol) Dichloroacetyl chloride, 200 ml acetonitrile and 3 g copper (I) chloride are heated to 130 ° C over 8 hours. The The reaction mixture is evaporated and the residue becomes fractionally distilled. 2,4,4,4-Tetrachlor is obtained butyric acid chloride as a colorless liquid; Bp 78-80 ° C / 14.7 mbar. The spectroscopic data of the substance obtained are identical to those in accordance with paragraph 1 prepared 2,4,4,4-tetrachlorobutyric acid chloride.

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

In an autoclave, 122 g (0.5 mol) of 2,4,4,4, - Tetrachlorobutyric acid chloride in 600 ml cyclohexane 280 g Isobutylene pressed on. At 65 ° C in the course of 4 Hours a solution of 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane pumped in. Then the reaction gene mix kept at 65 ° C for 3 hours. The failed hydrochloride of triethyl  amines are filtered off and the filtrate is evaporated. The the resulting crystals are filtered off. You get 79.4 g of 2-chloro-2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethylcyclo butan-1-one with a mp. 75-76 ° C (60% of theory).

IR spectrum (CHCl₃) in cm ^-1 : 1805 (C = O).
1 H-NMR spectrum (100 MHz, CDCl₃) in ppm: 1.42 and 1.45 (each 1s, 6H, each 1 Ch₃); 2.91-3.28 (m, 2H, CH₂); 3.37-3.76 (m, 2H, Ch₂).
13 C NMR spectrum (CDCl₃) in ppm: 196 (s, CO); 95.3 (s, CH₃); 80.8 (s, C-2); 57.0 (t, CH₂); 56.4 (t, CH₂); 37.9 (s, C-3); 25.1 (q, CH₃); 28.8 (q, CH₃).
Elemental analysis for C₈H₁₀Cl₄O (molecular weight 263.98):
calculated C 36.40%; H 3.82%; O 6.02%; Cl 53.72%;
found C 36.4%; H 3.9%; O 6.2%; Cl 53.5%.

c) Preparation of 2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethyl-4- chlorcyclobutan-1-one

132 g (0.5 mol) of the 2-chloro-2- (2 ′, 2 ′, 2′-trichloroethyl) obtained - 3,3-dimethylcyclobutan-1-ones are dissolved in 700 ml of toluene, treated with 1 ml of triethylamine and heated under reflux. To 13 hours reaction time is again 1 ml triethylamine added give and continue cooking for 7 hours. After cooling, it will Reaction mixture first with dilute hydrochloric acid and then with Washed water, dried and evaporated. The froze Uniform residue by thin layer chromatography (124 g; 94% of theory) is crystallized from n-hexane. 105.8 g of 80.2% of theory are obtained. Th.) 2- (2 ′, 2 ′, 2′- Trichloroethyl) -3,3-dimethyl-4-chlorocyclobutan-1-one; Mp 56-57 ° C.

IR spectrum (CHCl₃) in cm ^-1 : 1800 (C = O).
1 H-NMR spectrum (100 MHz, CDCl₃) in ppm: 4.77 (d, J = 2 Hz, 1H, H at C-4); 3.47 (m, 1H, H at C-2); 2.73-3.26 (m, 2H, CH₂); 2.63 (s, 3H, CH₃); 1.14 (s, 3H, CH₃).
13 C NMR spectrum (CDCl₃) in ppm: 197.0 (s, CO); 97.8 (s, CCl₃); 69.4 (d, C-4); 60.6 (d, C-2); 49.5 (t, CH₂-CCl₃); 36.8 (s, C-3); 27.4 (q, CH₃); 18.6 (q, CH₃),

Elemental analysis for C₈H₁₀Cl₄O (molecular weight 263.98):
calculated C 36.40%; H 3.82%; O 6.02%; Cl 53.72%;
found C 36.6% H 3.8%; O 6.2%; Cl 53.6%.

The above connection can also be made as follows: 2.64 g (0.01 mol) of 2-chloro-2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3- dimethylcyclobutanone are mixed with 220 mg (0.008 mol) of tetra-n- Butylammonium chloride stirred at 124 ° C for 6.5 hours. The cooled melt is boiled with hot n-hexane and clear filtered. When the filtrate cools, they separate 2.19 g (83% of theory) 2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethyl-4- chlorocyclobutanone, mp. 53-56 ° C.

Further processing d) Preparation of 2- (2 ', 2'-dichlorovinyl) -3,3-dimethylcyclo propane-1-carboxylic acid

13.2 g (0.05 mol) of 2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethyl-4- chlorcyclobutan-1-one are ver in 150 ml 10% sodium hydroxide solution sets and intensely stirred. After 5 minutes there is a clear one Solution formed that at 100 ° C (bath temperature) for 1 hour is heated. The reaction solution is with diethyl ether washed, cooled with concentrated hydrochloric acid acidifies and extracted with diethyl ether. The ether phase will washed with water, dried over magnesium sulfate and a steamed. The solid residue (10.35 g; 99% of theory) settles in accordance with NMR spectrum of 80% by weight cis and 20% by weight trans-2- (2 ′, 2′- Dichlorovinyl) -3,3-dimetylcyclopropane-1-carboxylic acid together. Crystallization from n-hexane yields pure 7.8 g of cis acid; Mp 85-87 ° C.

IR spectrum (CHCl₃) in cm ^-1 : 1710 (CO), 1625 (C = O).
NMR spectrum (100 MHz, CDCl₃ / D₂O) in ppm: 1.30 (s, 6H, 2 times CH₃); 1.85 (d, J = 8.5 Hz, 1H, H C-1); 2.02-2.19 (m, 1H, H C-2); 6.17 (d, J = 8 Hz, 1H, CH = CCl₂).

Example 2 invention

In a 6.3 liter autoclave, 421 g of propylene, 244 g (1 mole) 2,4,4,4-tetrachlorobutyric acid chloride and 1.25 liters Cyclohexane submitted. At 50 ° C within 4 hours a solution of 101 g (1 mole) of triethylamine in 1 liter of cyclo pumped hexane, and then the reaction mixture Maintained at 50 ° C for 3 hours. The reaction mixture is filtered and the filtrate obtained is diluted with hydrochloric acid and then washed with water, dried over magnesium sulfate and evaporated. The residue is crystallized from n-hexane. 77.2 g (32.5% of theory) of 2-chloro-2- (2 ', 2', 2'-trichloroethyl) -3-methyl are obtained cyclobutan-1-one; Mp 80-81 ° C.

IR spectrum (CHCl3) in cm ^-1 : 1785 (CO).
1 H-NMR spectrum (100 MHz, CDCl₃) in ppm: 3.28-3.73 (m, 3H); 2.65-2.95 (m, 2H); 1.43 (d, J = 6.5 Hz, 3H, CH₃).
13 C-NMR spectrum (CDCl₃) in ppm: 196.5 (s, CO); 95.1 (s, CCl₃); 77.8 (s, C-2); 55.3 (t, C H₂-CCl₃); 50.9 (t, C-4); 38.1 (d, C-3); 15.8 (q, C H₃).

50 g (0.2 mol) of the 2-chloro-2- (2 ′, 2 ′, 2′-trichloroethyl) obtained - 3-methylcyclobutan-1-ones in 500 ml of toluene are mixed with 1 ml of tri Ethylamine added and ge for 18 hours at 120 ° C bath temperature stirs. The reaction mixture is filtered clear after cooling and 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) 2- (2 ′, 2 ′, 2′-trichloroethyl) -3-methyl-4-chlorocyclobutan-1-one; Bp 130-131 ° C / 16 mbar.

IR spectrum (CHCl₃) in cm ^-1 : 1805 (CO).
NMR spectrum (100 MHz, CDCl₃) in ppm: 1.20 (d, J = 7 Hz, O, 6 H, CH₃); 1.46 (d, J = 7 Hz, 0.45 H, CH₃); 1.66 (d, J = 6.5 Hz, 1.95 H, CH₃); 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 the NMR spectrum and gas chromatogram Compound of 3 stereosiomers in a weight ratio of 13: 4: 3.

Further processing

10.5 of the 2- (2 ', 2', 2'-trichloroethyl) -3-methyl-4-chloro-cyclobutan-2-one obtained are stirred with 100 ml of 10% sodium hydroxide solution for 50 minutes. The resulting solution is then heated to 100 ° C. for 1 hour. The reaction mixture is then washed with diethyl ether and carefully acidified with concentrated hydrochloric acid. Then it is extracted with diethyl ether. The ether extract is washed with water, dried over magnesium sulfate and evaporated. 6.4 g (67% of theory) of 2- (2 ′, 2′-dichlorovinyl) -3-methylcyclopropane-1-carboxylic acid are obtained; Mp 75-78 ° C (recrystallized from n-hexane).
IR spectrum (KBr) in cm ^-1 : 1685 (C = O), 1625 (C = C).
Nuclear Magnetic Resonance Spectrum (100 MHz, CDCl₂ / D₂O) in ppm: 1.25 (d, J = 5.5 Hz, 3H, CH₃); 1.54-2.18 (m, 3H); 3.96 (d, J = 8 Hz, 1H, C H = CCl₂).

Example 3 invention

A solution of 25.3 g (0.25 mol) of triethylamine in 50 ml of n-hexane becomes a under with stirring within 7 hours Refluxed solution of 25 g (0.37 mol) methylene cyclo butane and 61.1 g (0.25 mol) 2,4,4,4-tetrachlorobutyric acid chloride added dropwise in 200 ml of n-hexane. After another 2 Has stirred under reflux for hours, the still hot Re action mixture by filtration of the ammonium salt formed exempted. The filtrate is concentrated to approximately 1/3 of the volume. When cooled, 69.1 g (50% of theory) of 1-chloro-1- separated in crystalline form (2 ′, 2 ′, 2′-trichloroethyl) -spiro [3.3] heptan-2-one of the formula

from; Mp 93-94 ° C.

IR spectrum (CCl₄) in cm ^-1 : 1790 (C = O).
NMR spectrum (100 MHz, CDCl₃) in ppm: 1.70-2.80 (m, 6H); 3.15-3.60 (m, 4H).

A solution of 27.6 g (0.1 mol) of the 1-chloro-1- obtained (2 ′, 2 ′, 2′-trichloroethyl) spiro [3.3] heptan-2-ones in 100 ml of toluene together with 0.93 g (5 mmol) of tributylamine for 9 hours increased under reflux. Then the reaction mixture evaporated and the residue is distilled in vacuo. 26.2 g (95% of theory) of 1-chloro-3- (2 ′, 2 ′, 2′-trichloroethyl) spiro [3.3] heptane are obtained 2-one of the formula

in the form of a slightly yellowish oil; Bp 85-90 ° C / 0.006 mbar; n = 1.5242.

IR spectrum (film) in cm ^-1 : 1795 (C = O).
NMR spectrum (100 MHz, CDCl₃) in ppm: 1.80-3.85 (m, 9 H); 4.68, 4.93 (each ad, together 1 H).

Further processing

11.0 g (40 mmol) of the 1-chloro-3- (2 ', 2', 2'-trichlor obtained ethyl) spiro [3.3] heptan-2-ones are mixed with 95 ml (approx. 240 mmol) 10% sodium hydroxide solution for 6 hours at 95 ° C stirs. After cooling, add several portions of diethyl washed more, acidified with sulfuric acid and with diethyl ether extracted. The ether extracts are made after drying evaporated over sodium sulfate. By filtration of the residue from ten times the amount by weight of silica gel (eluent n-hexane / diethyl ether in a volume ratio of 1: 1) becomes one small amount of strongly polar impurities removed. To the concentration of the filtrate gives 6.3 g (71% of theory) of 2- (2 ′, 2′-dichlorovinyl) - spiro [2.3] hexane-1-carboxylic acid of the formula  

as a 2: 1 cis / trans mixture; Mp 121-28 ° C.

IR spectrum (CCl₄) in cm ^-1 : 1705 (C = O).
NMR spectrum (100 MHz, CDCl₃) in ppm: 1.60-2.60 (m, 8 H); 5.34, 5.97 (each d, together 1 H); 11.80-11.50 (broad s, 1H).

Example 4 invention

In an autoclave, 122 g (0.5 mol) of 2,4,4,4-tetra chlorobutyric acid chloride in 600 ml cyclohexane 280 g isobutylene pressed on. At 65 ° C in the course of 4 hours, 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane. Then the reaction mixture is kept at 65 ° C. for 3 hours, and then heated to 125 ° C for 18 hours. Here 2.0 g of triethylamine in 50 ml of cyclohexane are added every 3 hours pumped in. The reaction mixture is poured onto ice with Acidified hydrochloric acid and extracted with cyclohexane. The one evaporated extract is in toluene / cyclohexane (1: 1 volume Ge mixed) filtered over 1 kg of silica gel to remove highly polar contaminants to remove cleaning. The filtrate is evaporated and the residue is crystallized from n-hexane. Man he holds 31.8 g (26.3% of theory) 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethyl-4-chlorine cyclobutan-1-one; Mp 56-57 ° C.  

Example 5 Further processing

• a) 26.1 g (99 mmol) 2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethyl- 4-chlorocyclobutanone become 260 ml with stirring at 11 ° C given a 10% sodium hydroxide solution. Within 2.4 hours the temperature rises to 28 ° C and then falls within from 2 more hours to 20 ° C. The reaction mixture is diluted with 200 ml of water, washed with diethyl ether, with concentrated hydrochloric acid strongly acidified and with diethyl ether stripped. The extract is washed over with water Magnesium sulfate dried and evaporated. 24.3 g are obtained 100% of Th.) Of a pale yellow residue (mp. 80-81 ° C), which consists exclusively of cis- and trans-2- (2 ′, 2 ′, 2′-tri chloroethyl) -3,3-dimethylcyclopropanoic acid. By fractional crystallization or by column chromatography can mix the pure cis and trans compounds be separated. NMR spectrum (100 MHz, CDCl₃ / D₂O) in ppm: 2.75-3.33 (m, 2 H); 1.50-1.97 (m, 2H); 1.32 (s, 2 x CH₃ cis); 1.27 and 1.38 (2 · s, 2 · CH₃ trans).
• b) 8.0 g (30.3 mmol) of 2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethyl- 4-chlorocyclobutanone are dissolved in 400 ml acetone and 100 ml water through pyrex glass with a Philipps HPK 125 W lamp as long irradiated until chromatographically no more starting material can be determined. The reaction mixture is evaporated, and the residue is applied to acid as indicated under a) is working. 6.95 g (93% of theory) of a cis / trans Mixture of 2- (2 ', 2', 2'-trichloroethyl) -3,3-dimethylcyclo propenecarboxylic acid, the spectroscopic data of which those of the mixture obtained according to a) are identical.
• c) 24.55 g (0.1 mol) of 2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethyl- Cyclopropanecarboxylic acid are in 350 ml of 10% sodium hydroxide solution suspended and at 100 ° C bath temperature for 4.5 hours touched. The reaction solution is washed with diethyl ether,  acidified with hydrochloric acid and extracted with chloroform. The extract is washed with water, over magnesium dried sulfate and evaporated. You get after the Crystallization from n-hexane 17.55 g (84% of theory) colorless 2- (2 ', 2'-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid.

Example 6 invention

145 g (0.5 mol) of 2-bromo-4,4-trichlorobutyric acid chloride, 280 g (5 mol) of isobutylene and 600 ml of cyclohexane are in submitted to an autoclave. At 65 ° C for over 4 hours Pumped 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane. Then it is replenished at this temperature for 3 hours stirs. The reaction mixture is filtered. The filtrate is evaporated and the residue is made of n-hexane crystallized. 74.5 g (48% of theory) of 2-bromo-2- are obtained. (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethylcyclobutanone as light beige powder; Mp 46-49 ° C.

IR spectrum (CHCl₃) in cm ^-1 : 1885 (CO).
1 H-NMR spectrum (100 MHz, pyridine-d₅) in ppm: 3.79 (AB, 2H, CH₂); 3.10 (AB, 2H, CH₂); 1.37 and 1.42 (each 1s, total 6H, each CH₃).
13 C NMR spectrum (CDCl₃) in ppm: 196.8 (CO); 95.6 (CCl₃); 74.8 (C-2); 56.5 and 56.3 (each CH₂); 38.0 (C-3); 27.4 and 24.7 (each CH₃).

20 g (0.065 mol) of 2-bromo-2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3- dimethylcyclobutanone and 5 g tetrabutylammonium bromide are ver 30 minutes at 80 ° C and 10 minutes at 100 ° C. stirs. The solidified melt is chromato over silica gel graphed (elution with toluene / cyclohexane 1: 1). To this This gives 10.1 g (50% of theory), 2- (2 ', 2', 2'-trichloroethyl-3,3-dimethyl-4- bromocyclobutanone, which crystallizes on standing; Mp 56 ° C.

1 H-NMR spectrum (100 MHz, CDCl₃) in ppm: 4.99 (d, J = 2 Hz; 1 H, H at C-4); 3.58 (X part of the ABX, additionally split with J = 2 Hz, 1 H, H at c-2); 3.05 (AB part of ABX, 2H, CH₂); 1.22 and 2.67 (1 s each, 3 H each, CH₃ each).
13 C NMR spectrum (CDCl₃) in ppm: 196.7 (s, CO); 97.7 (s, CCL₃); 60.7 (d, C-2); 59.8 (d, C-4); 50.0 (t, C H₂-CCl₃); 36.4 (s, C-3); 27.6 (q, CH₃); 21.0 (q, CH₃).

Further processing

3.1 g (10.6 mmol) of 2- (2 ′, 2 ′, 2′-trichloroethyl) -3,3-dimethyl- 4-bromocyclobutanone are mixed with a solution of 3.2 g NaOH added to 70 ml of water and stirred for 2 hours. Subsequently is further stirred at 100 ° C for 3 hours. The reaction mixture is washed with diethyl ether and with dilute hydrochloric acid acidified. This aqueous phase is with diethyl ether extracted. The extract is washed over with water Magnesium sulfate dried and evaporated. The residue is crystallized from n-hexane. 1.55 g (73% of theory) of cis-2- are obtained (2 ', 2'-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid; Mp 86 ° C.

IR spectrum (CHCl₃) in cm ^-1 : 1710 (CO), 1625 (C = C).
NMR spectrum (100 MHz, CDCl₃ / D₂O) in ppm: 1.30 (s, 6 H, 2 · CH₃); 1.85 (d, J = 8.5 Hz, 1H, H C-1); 2.02-2.19 (m, 1H, H C-2); 6.17 (d, J = 8 Hz, 1 H, C H = CCl₂).

Example 7 Source material

90.5 g (1 mol) acrylic acid chloride, 364.8 g (1.1 mol) tetra Bromomethane, 200 ml acetonitrile and 5.0 g copper (I) chloride are heated to 115 ° C. for 6 hours. After cooling the reaction mixture is distilled directly. You get 136.6 g (33% of theory) 2,4,4,4-tetrabromobutyric acid chloride, Bp 153-140 ° C 16 mbar.

invention

350 g of cyclohexane are mixed with isobutylene at room temperature (20-25 ° C) saturated. 42.2 g (0.1 mol) of 2,4,4,4- Dissolved tetrabromobutyric acid chloride. Then you drip in Room temperature within 2 hours with stirring and a mild stream of isobutylene 10.1 g (0.1 mol) triethyl amine in 50 ml of cyclohexane. The reaction mixture obtained is stirred for 3 hours and then with water transferred. The organic layer is separated off with water washed, dried over magnesium sulfate and evaporated. The residue is filtered through silica gel (elution medium cyclohexane / toluene 1: 1 volume mixture). The filtrate is evaporated. The residue is crystallized from n-hexane.

0.6 g (24% of theory) of 2-bromo-2- (2 ', 2', 2'-tribromoethyl) -3,3-dimethyl are obtained cyclobutanone; Mp 61-63 ° C.

IR spectrum (CHCl₃) in cm ^-1 : 1780 (CO).
1 H-NMR spectrum (100 MHz, CDCl₃) in ppm: 3.97 (AB, 2 H, CH₂); 3.13 (AB, 2H, CH₂); 1.51 and 1.61 (1 s each, 3 H each, CH₃ each).
13 C NMR spectrum (CDCl₃) in ppm: 196.7 (CO); 76.8 (C-2); 60.0 and 56.6 (each CH₂); 38.1 (C-3); 31.7 (CBr₃); 27.7 and 25.0 (each CH₃).

9.6 g (21.8 mmol) 2-bromo-2- (2 ′, 2 ′, 2′-tribromoethyl) -3,3- dimethylcyclobutanone with 2.0 g of tetrabutylammonium bromide stirred at 90 ° C for 30 minutes. The cold one The melt is chromatographed on silica gel (elution with Touol / Cyclohexane 1: 1). 4.9% (51% of theory) of 2- (2 ′, 2 ′, 2′-tribromo) are obtained ethyl) -3,3-dimethyl-4-bromocyclobutanone as slowly crystallizing sier oil that recrystallized from diethyl ether / n-hexane becomes; Mp 91-93 ° C.

IR spectrum (CHCl₃) in cm ^-1 : 1795 (CO).
1 H-NMR spectrum (100 MHz, CDCl₃) in ppm: 4.96 (d, J = 2 Hz, 1 H, H at C-4); 3.12-3.67 (ABX, where the X part is additionally split with J = 2 Hz, 3 H, CH₂-CH); 1.18 and 1.67 (1 s each, 3 H each, CH₃ each).
13 C NMR spectrum (CDCl₃): 196.4 (s, CO); 63.2 (d, C-2); 59.9 (d, C-4); 54.6 (t, CH₂); 38.4 (s, CBr₃); 36.4 (s, C-3); 27.8 and 21.3 (each q, each CH₃).

Further processing

700 mg (1.56 mmol) 2- (2 ′, 2 ′, 2′-tribromoethyl) -3,3-dimethyl- 4-bromocyclobutanone are mixed with a solution of 190 mg NaOH in 5 ml of water, to which 0.5 ml of dioxane has been added, for 2 hours stirred at room temperature. Then 1 hour at 80 ° C stirred. As usual, the clear solution is based on acid worked up. 410 mg (88% of theory) of cis-2- (2 ′, 2′- Dibromo vinyl) -3,3-dimethylcyclopropane carboxylic acid.

IR spectrum (CHCl₃) in cm ^-1 : 1695 (CO).
NMR spectrum (100 MHz, CDCl₃ / D₂O) in ppm: 6.70 6d, J = 8 Hz, 1 H, C H -CBr₂); 1.82-2.14 (m, 2H); 1.30 and 1.33 (1 s each, total 6 H, each CH₃).

Example 8 invention

To a solution of 14 g (0.17 mol) of methylcyclopentane and 26.4 g (0.1 mole) 2,4,4,4-tetrachlorobutyric acid chloride in 220 ml of cyclohexane are stirred for 2 hours at 65 ° C 10.1 g (0.1 mol) of triethylamine in 100 ml of cyclohexane dripped. Then 3 hours at this temperature continued stirring. The reaction mixture is diluted with Hydrochloric acid, then washed with water, over magnesium sulfate dries and evaporated. The residue is made from n-hexane crystallized. 16.6 g (57.2% of theory) of 1-chloro-1- (2 ′, 2 ′, 2′- trichloroethyl) spiro [3,4] octan-2-ones of the formula

70-73 ° C.
IR spectrum (CHCl₃) in cm ^-1 : 1775 (CO).
NMR spectrum (100 MHz, CDCl₃) in ppm: 1.60-2.30 (m, 8 H); 3.08 (AB, 2H, CH₂); 3.60 (AB, 2H, CH₂).

12.0 g (0.041 mol) of 1-chloro-1- (2 ′, 2 ′, 2′-trichloroethyl) spiro [3,4] octan-2-one with 3.6 g of tetrabutylammonium chloride stirred at 125 ° C bath temperature. After 1.5 hours it will Chromatograph the reaction mixture over silica gel (elution with toluene / cyclohexane 1: 1). In this way, 9.7 g is obtained (81% of theory) of 1-chloro-3- (2 ′, 2 ′, 2′-trichloroethyl) spiro [3,4] octan-2-ones of the formula

in the form of a colorless oil.
IR spectrum (CHCl₃) in cm ^-1 : 1800 (CO).
NMR spectrum (100 MHz, CDCl₃) in ppm: 4.87 (d, J = 2 Hz, 1 H, C H Cl); 3.70 (X part of the ABX, additionally split with J = 2 Hz. 1 H, CH); 2.73-3.29 (AB part of ABX, 2H, CH₂); 1.45-2.23) m, 8H).

Further processing

4.83 g (16.6 mmol) of 1-chloro-3- (2 ′, 2 ′, 2′-trichloroethyl) spiro [3.4] octan-2-one become a solution of 2.0 g NaOH in 40 ml of water and 3 ml of dioxane added and 2 hours Room temperature and then stirred at 100 ° C for 3 hours. The reaction solution is washed with diethyl ether and acidified with dilute hydrochloric acid. The sour one Solution is extracted with diethyl ether. The extracts are washed with water, dried over magnesium sulfate and evaporated. The residue is crystallized from n-hexane. 3.3 g (84.6% of theory) of 2- (2 ′, 2′-dichlorovinyl) spiro [2.4] are obtained. heptane-1-carboxylic acid of the formula

as a white powder; Mp 90-105 ° C.

IR spectrum (CHCl₃) in cm ^-1 : 1705 (CO), 1620 (C = C).
NMR spectrum (100 MHz, CDCl₃ / D₂O) in ppm: 6.15 (d, J = 9 Hz, 0.8 H, CH = CCl₃cis); 5.51 (d, J = 9 Hz, 0.2 H, CH = CCl₂ trans); 2.00-2.40 (m, 2H); 1.60-1.95 (m, 8H).

Example 9 invention

In a 2.5 liter autoclave, 33.6 g (0.62 mol) Methylene cyclopropane and 152 g (0.62 mol) 2,4,4,4-tetra chlorobutyric acid chloride in 620 ml of n-pentane. At 60 ° C become 62.8 g (0.62 mol) tri within 6 hours Pumped ethylamine in 120 ml of n-pentane, and then the reaction mixture is kept at 60 ° C. for 6 hours.  

The reaction mixture is filtered, evaporated, and the The residue is distilled in vacuo. The faction with Boiling range 45-80 ° C / 0.12 mbar is then at 250 g Chromatograph silica gel with hexane / 0-50% by weight toluene. The pure fractions are evaporated and the residue is distilled. 21.1 g (13% of theory) of 1-chloro-1- (2 ', 2', 2'-tri are obtained chloroethyl) spiro [3,2] hexan-2-one of the formula

with bp 70-71 ° C / 0.1 mbar.

IR spectrum (CHCl₃) in cm ^-1 : 1776 (CO).
1 H-NMR spectrum (100 MHz, CDCl₃) in ppm: 0.81-1.8 (m, 4 H); 2.6-3.8 (m, 4H).

A solution of 11.0 g (42 mmol) of 1-chloro-1- (2 ′, 2 ′, 2′-tri chloroethyl) spiro [3,2] hexan-2-one and 1.17 g (6.3 mmol) tri butylamine in 15 ml of toluene is kept under for 5 hours Heated to reflux. After cooling, the reaction mixture diluted with n-pentane. It is washed with 2 N sulfur acid and then with saturated saline, dries over sodium sulfate and evaporates. The residue is distilled in vacuo. 9.1 g (83% of theory) of 1-chloro-3- (2 ′, 2 ′, 2′-trichloroethyl) spiro [3,2] hexan-2-one of the formula

with bp 60 ° C / 0.013 mbar.
IR spectrum (CCl₄) in cm ^-1 : 1780 (CO).
NMR spectrum (100 MHz, CDCl₃) in ppm: 0.8-1.7 (m, 4 H); 2.6-4.2 (m, 3H); 4.75, 5.15 (each d; together 1 H).

Further processing

7.1 g (27 mmol) of 1-chloro-3- (2 ′, 2 ′, 2′-trichloroethyl) spiro [3.2] hexan-2-one together with 54 ml (approx. 135 mmol) 10% NaOH heated under reflux for 2 hours. After the Ab cool is washed with several servings of diethyl ether, acidified with sulfuric acid and extracted with diethyl ether. The ether extracts are dried over sodium evaporated sulfate. Filtration on silica gel (elution medium diethyl ether) a small amount becomes strongly polar Impurities removed. After concentrating the filtrate 5.01 g (85% of theory) of 2- (2 ′, 2′-dichlorovinyl) spiro [2.2] pentane-1- are obtained carboxylic acid of the formula

as approx. 3: 1 cis / trans mixture; Mp 77-78 ° C.

IR spectrum (CCl₄) in cm ^-1 : 1675 (CO).
NMR spectrum (100 MHz, CDCl₃) in ppm: 0.8-2.85 (m, 6 H); 5.56 and 6.11 (each d, together 1 H); 10.8 (broad s, 1H).

Claims (14)

1. 2- (2 ', 2', 2'-trihaloethyl) -4-halocyclobutan-1-one of the general formula I in which one of the radicals R₁ and R₂ is methyl and the other is hydrogen or methyl or R₁ and R₂ together are alkylene with 2 to 4 carbon atoms and X and Y are each chlorine or bromine, but if X is bromine, Y is also always Bromine must be. 2. 2- (2 ', 2', 2'-trihaloethyl) -2-halocyclobutan-1-one of the general formula IV in which one of the radicals R₁ and R₂ is methyl and the other hydrogen or methyl or R₁ and R₂ together are alkylene having 2 to 4 carbon atoms and X and Y are each chlorine or bromine, but if X is bromine, Y is also always present Bromine must be. 3. A process for the preparation of 2- (2 ', 2', 2'-trihaloethyl) -4-ha logencyclobutan-2-ones according to claim 1, characterized in that a 2,4,4,4, -Tetrahalogenbuttersäurechlorid the general formula II in which X and Y have the meaning given in claim 1, in the presence of an organic base with an olefin of the general formula III in which R₁ and R₂ have the meaning given in claim 1 and the resulting 2- (2 ', 2', 2'-trihaloethyl) -2-halogen cyclobutan-1-one of the general formula IV, claim 2 then in the presence of a inorganic or organic protonic acid, an organic base or salts of protonic acids with ammonia, nitrogen-containing organic bases or quaternary ammonium salts as a catalyst at temperatures between 80 to 150 ° C, optionally in the presence of an inert solvent. 4. The method according to claim 3, characterized in that as 2,4,4,4-tetrahalobutyric acid chloride of the general formula II that 2,4,4,4-tetrachlorobutyric acid chloride is used. 5. The method according to claim 3, characterized in that one Use olefin of the general formula III, in which R₁ and R₂ together represent an alkylene group having 2 to 4 carbon atoms. 6. The method according to claim 3, characterized in that as Olefin of the general formula III uses isobutylene. 7. The method according to claim 3, characterized in that as Olefin of the general formula III uses methylene cyclopropane. 8. The method according to claim 3, characterized in that the Implementation of a 2,4,4,4-tetrahalobutyric acid chloride of the general my formula II with an olefin of the general formula III in  Presence of pyridine or a trialkylamine with 1 to 4 each Carbon atoms in the alkyl groups and in the presence of an inert organic solvent. 9. The method according to claim 3, characterized in that the Implementation of a 2,4,4,4-tetrahalobutyric acid chloride of the general my formula II with an olefin of the general formula III in In the presence of triethylamine. 10. The method according to claim 3, characterized in that an amine of the general formula as a catalyst for the rearrangement in which Q₁ is alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, benzyl or phenyl and Q₂ and Q₃ independently of one another are hydrogen or alkyl with 1 to 8 carbon atoms. 11. The method according to claim 3, characterized in that as Catalyst for the rearrangement of a hydrohalic acid puts. 12. The method according to claim 3, characterized in that as Catalyst for the rearrangement of a salt of a hydrogen halide acid with an aliphatic, cycloaliphatic, araliphatic or aromatic primary, secondary or tertiary amine or a heterocyclic nitrogen base. 13. The method according to claim 3, characterized in that a salt of the general formula as a catalyst for the rearrangement om which M is fluorine, chlorine, bromine or iodine, Q₄ hydrogen, alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl, phenyl or naphthyl and Q₅, Q₆ and Q₇ independently of one another are hydrogen or alkyl having 1 to 18 carbon atoms or an N-alkylpyridinium halide with 1 to 18 carbon atoms in the alkyl group. 14. The method according to claim 3, characterized in that the Rearrangement in an aliphatic alcohol with 1 to 4 carbon atoms, toluene, xylene, chlorobenzene, dioxane, acetonitrile, 3-methoxy propionitrile, ethylene glycol, diethyl ether or diisopropyl ketone as Performs solvent.