JPH0225898B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is based on the following formula: (In the formula, one of R ₁ and R ₂ represents a methyl group, and the other represents a hydrogen atom or a methyl group, or
or R ₁ and R ₂ together represent an alkylene group having 2 to 4 carbon atoms, and X and Y each represent a chlorine or bromine atom, provided that when X represents a bromine atom, Y always also represents a bromine atom represent. ) An intermediate for the production of novel 2-(2',2',2'-trihaloethyl)-4-halo-cyclobutan-1-ones.

[Conventional technology]

When α-halocycloalkanones are heated in the presence of a base, such as an alkali metal hydroxide or alkali metal alcoholate, ring reduction occurs, converting them to cycloalkane carboxylic acids or their esters with the same number of carbon atoms (Huabolski reaction) is known. This reaction is the basis of an industrially important method for producing cyclopropanecarboxylic acid derivatives and their insecticidal esters, ie, pyrethroids, from α-halocyclobutanone.
This method, which can be easily implemented industrially, is
Application to the production of pyrethroids derived from 2′,-dihalobinyl)-cyclopropanecarboxylic acid was not possible since the corresponding α-halocyclobutanone suitable for the production of such cyclopropanecarboxylic acid derivatives was not available. It wasn't possible.

It has also already been proposed to produce α-halocyclobutanone by reacting a haloketene with an olefin. Such methods are described, for example, in German Patent Publication No. 2539048, British Patent No. 1194604,
Journal of the American Chemical Society, Vol. 87, pp. 5257-5259 (1965) and Tetrahedron Letters No. 1, pp. 135-139 (1966)
It is described in.

[Problem that the invention seeks to solve]

This synthetic method has not hitherto been utilized for the production of α-halobutanones, which are suitable as intermediates for the production of 2-(2',2'-dihalobinyl)-cyclopropanecarboxylic acid and its insecticidal esters. This is primarily due to the synthetic possibilities considered on the basis of the above method, namely a reaction of halogenated olefins and haloketenes according to the following reaction scheme: or or b Reaction of unhalogenated olefin and haloketene according to the following reaction formula: (In the formula, R ₁ , R ₂ , X and Y have the above meanings.) is 2-(2', 2',
This is attributable to the fact that it does not lead to 2'-trihaloethyl)-4-halo-cyclobutan-1-one. That is, the above reaction a does not occur due to the inactivation of the olefin by halogen substitution, and the reaction b does not occur due to the inactivation of olefin by halogen substitution, and the reaction b does not occur due to the inactivation of olefin by halogen substitution. 2-(2′,2′,
2'-trihaloethyl)-2-halo-cyclobutan-1-one.

Therefore, the object of the present invention is to solve the equation 2-(2', 2',
The object of the present invention is to provide a readily available intermediate that can be used in the production of 2'-trihaloethyl)-4-halo-cyclobutan-1-one.

[Means for solving problems]

The inventors have determined that the following formula: (In the formula, X and Y represent the above meanings.) 2,4,4,4-tetrahalobutyric acid chloride represented by the following formula: (In the formula, R ₁ and R ₂ have the above meanings.) By reacting with an olefin represented by the following formula: (In the formula, R ₁ , R ₂ , X and Y have the above meanings.) 2-(2', 2', 2'-trihaloethyl)
-2-halo-cyclobutan-1-one, which is then rearranged in the presence of a catalyst, gives the formula 2-
It has been found that (2',2',2'-trihaloethyl)-4-halo-cyclobutan-1-one can be easily produced.

2,4,4,4-tetrahalobutyric acid chloride of the formula is a new compound. They are: (In the formula, X and Y represent the above meanings.) Tetrahalomethane represented by the following formula: CH ₂ = CH-Z () (In the formula, Z is the number of carbon atoms in the chlorocarbonyl group, carboxyl group, or alkyl moiety) (1 to 4 alkoxycarbonyl groups or cyano groups) is added to a compound represented by the following formula to produce: (In the formula, X and Y represent the above-mentioned meanings, and Z represents a carboxyl group, an alkoxycarbonyl group, or a cyano group.) By changing the compound represented by the formula into a compound of the formula in which Z represents a chlorocarbonyl group, It can be manufactured by a method known per se.

Another method for synthesizing 2,4,4,4-tetrahalobutyric acid chloride of the formula is the following formula a: (In the formula, Z represents the meaning described in the formula.) The following formula a is produced by adding the compound represented by to 1,1-dichloroethylene: (In the formula, Z represents a carboxyl group, an alkoxycarbonyl group, or a cyano group.) This is a method of converting a compound represented by the formula into a compound of formula a, where Z represents a chlorocarbonyl group.

In the addition of tetrahalomethanes of formula to acrylic acid derivatives of formula a and in the addition of dichloroacetic acid derivatives of formula a to 1,1-dichloroethylene, stoichiometric amounts of tetrahalomethanes of formula or dichloroacetic acid derivatives of formula a are used. can do. Preferably, however, the tetrahalomethane of formula or the dichloroacetic acid derivative of formula a is used in excess, e.g.
Use in a 0.5 to 2-fold molar excess. In this case the tetrahalomethane of the formula can also serve as a solvent.

The addition of tetrahalomethanes of formula to compounds of formula a and the addition of compounds of formula a to 1,1-dichloroethylene are carried out in the presence of a catalyst. Catalysts include metals of groups a, a and b of the periodic table, such as Fe, Co, Ni, Ru, Rh, Pd, Cr,
Mo, Mn and Cu are suitable. These metals can be used in elemental form or in the form of compounds. Suitable compounds for these metals include, for example, oxides,
halides, sulfates, sulfites, sulfides, nitrates,
acetates, citrates, carbonates, cyanides and thiocyanates as well as phosphines, phosphites,
Complexes with ligands such as benzoin, benzoyl and acetylacetonate, nitriles, isonitriles and carbon monoxide.

Examples of the aforementioned metal compounds which are suitable as catalysts include: copper oxide (), iron oxide (); bromide and especially chloride-copper (), -copper (), -iron () and iron (), and chlorides of Ru, Rh, Pd, Co and Ni; copper sulfate (), iron sulfate (), iron sulfate ();
Copper nitrate () and iron nitrate (); manganese acetate (), copper acetate (); copper stearate (); iron citrate (); copper cyanide (); ruthenium () dichloro-tris-triphenylphosphine, Rhodium-tris(triphenylphosphine) chloride; chromium- and nickel-acetylacetonate, copper ()-acetylacetonate, iron ()-acetylacetonate, cobalt ()- and cobalt ()-acetylacetonate, manganese ()-acetylacetonate, copper ()-benzoylacetonate; iron carbonyl-
Cyclopentadienyl complex; molybdenum carbonyl-cyclopentadienyl complex, chromium tricarbonyl-aryl complex, ruthenium ()acetate complex, chromium- and molybdenum-hexacarbonyl, nickel tetracarbonyl, iron pentacarbonyl, cobalt- and manganese-carbonyl .

Mixtures of said metals with metal compounds and/or other additives, for example mixtures of copper powder and one of the copper compounds mentioned above; mixtures of copper powder with lithium halides, such as lithium chloride, or isocyanides, such as tert-butyl isocyanide; A mixture of iron powder and iron chloride () and possibly carbon monoxide;
It is also possible to use mixtures of iron chloride () and benzoin; mixtures of iron chloride () or iron chloride () and trialkyl phosphites; mixtures of iron pentacarbonyl and iodine.

Iron()- and iron()-salts and complexes and iron powders, but especially copper powders, copper()- and copper()-salts and complexes such as copper() chloride, copper() chloride, copper bromide (), copper bromide (), copper () acetylacetonate, copper () benzoylacetonate, copper sulfate (), copper nitrate () and copper cyanide ()
is preferred.

Particular preference is given to copper powder, chlorinated- or bromated-copper() and bromide-copper(), and mixtures thereof.

The catalyst is generally a compound of the formula or 1,1
- used in an amount of about 0.01 to 10 mol %, preferably 0.1 to 5 mol %, based on dichloroethylene.

The addition reaction is carried out in an organic solvent. Suitable organic solvents are those that dissolve well or are capable of forming complexes with the catalyst, but are inert towards the starting materials. Examples of such solvents are alkylnitriles, especially those having 2 to 5 carbon atoms;
For example, acetonitrile, propionitrile and butyronitrile; 3-alkoxypropionitrile having 1 or 2 carbon atoms in the alkoxy moiety, for example 3
- methoxypropionitrile and 3-ethoxypropionitrile; aromatic nitriles, especially benzonitrile; aliphatic ketones having a total number of preferably 3 to 8 carbon atoms, such as acetone, diethyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl Tributylketone; alkyl- and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total of 2 to 6 carbon atoms, such as methyl and ethyl formate, methyl acetate, ethyl acetate,
n-butyl and -isobutyl esters and 1-
Acetoxy-2-methoxyethane; cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane; dialkyl ethers each having 1 to 4 carbon atoms in the alkyl part, such as diethyl ether, di-n-propyl ether and di-isopropyl ether; carbon atoms in the acid part N,N-dialkylamides of aliphatic monocarboxylic acids of numbers 1 to 3, such as N,N-dimethylformamide,
N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide; ethylene glycol- and diethylene glycol-dialkyl ethers each having 1 to 4 carbon atoms in the alkyl moiety, such as ethylene glycol-dimethyl-, -diethyl- and -ji-
n-butyl ether; diethylene glycol
Diethyl- and -di-n-butyl-ether; hexamethylphosphoric acid triamide (hexametapole)
It is.

Preferred solvents are C2 -C5 alkylnitriles and 3-alkoxypropionitriles having 1 or 2 carbon atoms in the alkoxy moiety, especially acetonitrile and 3-methoxypropionitrile.

The reaction temperature is generally not limited and can be varied within a range. The preferred reaction temperature is about 60 to
200°C, especially about 80 to 170°C.

As compound of formula or a, preference is given to using acrylic acid chloride or dichloroacetyl chloride. This results in the desired 2,
4,4,4-Tetrahalobutyric acid chloride is obtained directly in pure form and in high yield. Other preferred compounds of formula or a are acrylic acid or dichloroacetic acid. The free form of 2,4,4,4-tetrahalobutyric acid obtained in this case can then be easily reacted with inorganic acid chlorides such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosgene and thionyl chloride by known methods. can be converted to the corresponding acid chloride.

A 2,4,4,4-tetrahalobutyric acid ester or nitrile of the formula (Z = alkoxycarbonyl group or cyano group) obtained by using a compound of the formula or a in which Z represents an alkoxycarbonyl group or a cyano group can then be prepared by e.g. Hydrolysis in the presence of a strong acid such as concentrated hydrochloric acid gives the corresponding free form of 2,4,4,4-tetrahalobutyric acid, which is further converted to the corresponding acid chloride by the method described above.

The reaction of the 2,4,4,4-tetrahalobutyric acid chloride of the formula with the olefin of the formula is advantageously carried out in the presence of an inert organic solvent. Such solvents include, for example, optionally halogenated aromatic or aliphatic hydrocarbons such as benzene,
Toluene, xylene, chlorobenzene, dichloro- and trichloro-benzene, n-pentane, n
-Hexane, n-octane, methylene chloride, chloroform, carbon tetrachloride, 1,1,2,2
-Tetrachloroethane and trichloroethylene are suitable. Other suitable solvents are cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, cycloaliphatic ketones such as cyclopentanone and cyclohexanone, and aliphatic ketones, aliphatic and cyclic ethers, alkyl nitriles, alkoxy moieties having 1 or 2 carbon atoms. 3-alkoxypropionitriles, especially acetonitrile and 3-methoxypropionitrile.

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

As a solvent it is also possible to use an excess of the olefin of the formula.

Suitable organic bases to be present when carrying out the reaction of 2,4,4,4-tetrahalobutyric acid chloride of the formula with olefins of the formula are, for example, tertiary amines, in particular tribases whose alkyl radicals each have from 1 to 4 carbon atoms. Alkylamines, cyclic amines such as pyridine, quinoline, N-alkylpyrrolidine, N-alkylpiperidine, N,N-dialkylpiperazine and N-alkylmorpholine or dialkylanilines in which the alkyl group has 1 or 2 carbon atoms, for example N- Methylpyrrolidine, N-ethylpiperidine, N,N'-dimethylpiperazine,
N-ethylmorpholine and N,N-dimethylaniline, and bicyclic amidines such as 1,5-diazabicyclo[5.4.0]undec-5-ene and 1,
5-diazabicyclo[4.3.0]non-5-ene,
and bicyclic diamines such as 1,4-diazabicyclo[2.2.2]octane.

The reaction of the 2,4,4,4-tetrahalobutyric acid chloride of the formula with the olefin of the formula is carried out, inter alia, in the presence of a trialkylamine whose alkyl group has in each case 1 to 4 carbon atoms. Particularly preferred bases are triethylamine and pyridine.

The organic base is used in at least an equimolar amount or in slight excess relative to the 2,4,4,4-tetrahalobutyric acid chloride of the formula.

The olefin of the formula is also 2, 4, 4,
It is used in at least an equimolar amount to 4-tetrahalobutyric acid chloride. However, it is generally advantageous to use an excess of olefin, in which case the olefin can also serve as a solvent, as mentioned above.
If readily volatile olefins are used, the reaction can also be carried out under pressure.

In particular, olefins of the formula R ₁ and R ₂ represent a methyl group and the other a hydrogen atom or a methyl group, or R ₁ and R ₂ taken together have 2 or 3 carbon atoms. Mention may be made of those representing alkylene groups, namely isobutylene, propene, methylenecyclopropane and methylenecyclobutane. Particularly preferred are isobutylene and methylenecyclopropane.

The reaction temperature can vary within a wide range. Generally the temperature is 0 to 200°C, preferably 20 to 160°C.

2-(2′,2′,2′-trihaloethyl)-2 of the formula
-Halo-cyclobutan-1-one is also a new compound. The formula 2-(2′,
2',2'-trihaloethyl)-2-halo-cyclobutan-1-one is then converted to 2-(2',2',2'-trihaloethyl)-4-halo-cyclobutan-1-
As catalyst for the on-transposition, acids, bases or quaternary ammonium halides can be used.

2-(2′,2′,2′-trihaloethyl)-2 of the formula
2- of the formula -halo-cyclobutan-1-one
The rearrangement according to the invention to (2',2',2'-trihaloethyl)-4-halo-cyclobutan-1-one was unexpected and for cyclobutanones monohalogenated in the α-position. was unknown. What is particularly surprising is that no HX elimination occurs at the trihaloethyl group even when the rearrangement is carried out in the presence of a basic catalyst. This rearrangement proceeds in high and often quantitative yields.

2-(2',2',2'-trihaloethyl)-4 of the formula 2-(2',2',2'-trihaloethyl)-2-halo-cyclobutan-1-one according to the invention −
The rearrangement to halo-cyclobutan-1-one is preferably carried out in the presence of a basic catalyst. As the basic catalyst, an organic base such as the following formula: (In the formula, Q ₁ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms,
Represents a benzyl group or phenyl group, Q ₂ and
Q ₃ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Primary, secondary and especially tertiary amines are mentioned. Suitable basic catalysts include, for example, triethylamine, tri-n-butylamine, tri-isopentylamine, tri-n-octylamine, N,
N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-2-
Ethylhexylamine, N,N-diethylaniline, as well as cyclic amines such as pyridine, quinoline, lutidine, N-alkylmorpholines such as N
- methylmorpholine, N-alkylpiperidines such as N-methyl- and N-ethyl-piperidine,
N-alkylpyrrolidines such as N-methyl- and N-ethyl-pyrrolidine, diamines such as N,
N,N',N'-tetramethylethylenediamine,
N,N,N',N'-tetramethyl-1,3-diaminobutane, N,N'-dialkylpiperazine e.g. N,N'-dimethylpiperazine, bicyclic amines e.g. 1,4-diazabicyclo [2.2.2 ] octane and bicyclic amidines such as 1,5-diazabicyclo[5.4.0] undec-5-ene and 1,5
-diazabicyclo[4.3.0]non-5-ene and polymeric basic compounds such as p-dimethylaminomethylpolystyrene.

Furthermore, 2-(2',2',2'-trihaloethyl)- of the formula 2-(2',2',2'-trihaloethyl)-2-halo-cyclobutan-1-one according to the invention
Also suitable as basic catalysts for the rearrangement to 4-halo-cyclobutan-1-one are phosphines, especially trialkylphosphines, such as tributylphosphine.

2-(2′,2′,2′-trihaloethyl)-2 of the formula
2- of the formula -halo-cyclobutan-1-one
Inorganic or organic protic acids can be used as acid catalysts for the rearrangement to (2',2',2'-trihaloethyl)-4-halo-cyclobutan-1-one. Suitable inorganic protic acids are, for example, hydrohalic acids such as hydrogen chloride, hydrogen bromide, hydrogen fluoride and hydrogen iodide, nitric acid, phosphoric acid and sulfuric acid. Particularly preferred inorganic protic acids are hydrohalic acids.

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

It is also possible to use salts of protic acids, especially hydrohalic acids, with ammonia or nitrogen-containing organic bases, as well as quaternary ammonium halides, quaternary phosphonium halides and sulfonium halides. Suitable nitrogen-containing organic bases are aliphatic, cycloaliphatic, aromatic-aliphatic and aromatic primary, secondary and tertiary amines as well as heterocyclic nitrogen bases. Examples include: aliphatic primary amines with up to 12 carbon atoms, such as methylamine, ethylamine, n-butylamine, n-octylamine, n-dodecylamine, hexamethylenediamine, cyclohexylamine, benzylamine; Aliphatic secondary amines of up to 12, such as dimethylamine, diethylamine, di-n-propylamine, dicyclohexylamine, pyrrolidine, piperidine, piperazine, morpholine; aliphatic tertiary amines, especially trialkyl having 1 to 4 carbon atoms in the alkyl group Amines such as triethylamine, tri-n-butylamine, N-methylpyrrolidine, N-methylmorpholine, 1,4-diazabicyclo[2.2.2]octane, quinuclidine; optionally substituted primary, secondary and tertiary aromatics group amines such as aniline,
Toluidine, naphthylamine, N-methylaniline, diphenylamine and N,N-diethylaniline; also pyridine, picoline, indoline and quinoline.

Examples of the quaternary phosphonium halide include hexadecyltributylphosphonium bromide and methyl- and ethyl-triphenylphosphonium bromide, and examples of the sulfonium halide include trimethylsulfonium iodide.

The following formula: (In the formula, M represents a fluorine, bromine, iodine or especially a chlorine atom, Q ₄ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, a benzyl group, a phenyl group or a naphthyl group, Q ₅ , Q ₆ and Q ₇ independently represent a hydrogen atom or a C 1 -C 18 alkyl group) and alkyl groups C 1 -C 18 N-alkyl-pyridinium halides, especially the corresponding chlorides is preferred. Examples of these salts include: ammonium chloride, ammonium bromide, methylamine hydrochloride, cyclohexylamine hydrochloride, aniline hydrochloride, dimethylamine hydrochloride, di-isobutylamine hydrochloride, triethylamine hydrochloride, triethylamine bromide. Hydrogen salt,
Tri-n-octylamine hydrochloride, benzyl-dimethylamine hydrochloride, tetramethyl-, tetraethyl-, tetra-n-propyl-, tetra-n-
Butyl-ammonium chloride, -bromide and iodide, trimethyl-hexadecyl ammonium chloride, benzyldimethylhexadecyl ammonium chloride, benzyldimethyltetradecylammonium chloride, benzyl-trimethyl-, -triethyl- and -tri-n-butyl, ammonium chloride , n-butyl-tri-n-propylammonium bromide, octadecyltrimethylammonium bromide, phenyltrimethylammonium bromide or -chloride, hexadecylpyridinium-bromide and -chloride.

Other cocatalysts that may be used are 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, fluoride, etc. sodium fluoride and lithium fluoride.

These cocatalysts catalyze the reaction even in the absence of the ammonium salt, in which case closed or macrocyclic polyethers (crown ethers)
It is advantageous to speed up the reaction by adding . Examples of such crown ethers are 15-crown-5,
18-crown-6, dibenzo-18-crown-
6, dicyclohexyl-18-crown-6 and 5,6,14,15-dibenzo-7,13-diaza-
1,4-dioxa-cyclopentadeca-5,14-
It's Jien.

The amount of catalyst used can vary within wide limits.
In some cases, the presence of trace amounts of catalyst is sufficient. However, it is generally preferred to use from about 0.1 to 15% by weight of catalyst based on the compound of formula.

The rearrangement may be carried out in the melt or in an inert organic solvent. The rearrangement reaction temperature in the molten state is generally about 60 to 150°C, especially about 80 to 130°C.

Suitable catalysts for the rearrangement in the melt are in particular the organic bases mentioned above, especially trialkylamines having an alkyl group of C1 to C8. Also suitable are the salts of hydrohalic acids with ammonia or organic nitrogen bases, such as the hydrochlorides and hydrobromides of trialkylamines in which each alkyl radical has 1 to 8 carbon atoms, and very preferred are the tetraalkyl Ammonium halides, especially tetraalkylammoniums in which each alkyl group has 1 to 18 carbon atoms.
These are chloride, bromide and iodide.

Examples of suitable inert organic solvents are optionally nitrated or halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons such as n-hexane, n-pentane, cyclohexane, benzene, toluene. , xylene, nitrobenzene, chloroform, carbon tetrachloride, trichloroethylene,
1,1,2,2-tetrachloroethane, nitromethane, chlorobenzene, dichlorobenzene and trichlorobenzene; lower aliphatic alcohols such as those having 6 or less carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol and pentanol; aliphatic diols For example ethylene glycol and diethylene glycol;
Ethylene glycol monoalkyl ethers and diethylene glycol monoalkyl ethers each having 1 to 4 carbon atoms in the alkyl moiety, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; cyclic amides, such as N-
Methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-ε-caprolactam;
Carboxylic acid amides such as tetramethylurea and dimorpholinocarbonyl; amides of phosphorous acid, amides of phosphoric acid, amides of phenylphosphonic acid or amides of aliphatic phosphonic acids having 1 to 3 carbon atoms in the acid moiety, such as phosphoric acid triamide, phosphoric acid triamide ( dimethylamide), phosphoric acid trimorpholide, phosphoric acid tripyrrolidide, phosphoric acid bis-(dimethylamide)-morpholide, phosphoric acid-dimethylamide-diethylamide-
Morpholide, tris-(dimethylamide) phosphite
and tetramethyldiamide of methanephosphonic acid;
Amides of sulfuric acid and amides of aliphatic or aromatic sulfonic acids such as tetramethylsulfamide, dimethylamide of methanesulfonic acid or p-toluenesulfonic acid amide; sulfur-containing solvents such as organic sulfones and sulfoxides such as dimethylsulfoxide and sulfolane; Aliphatic and aromatic nitriles, 3-alkoxypropionitriles, aliphatic ketones, alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids, cyclic ethers, dialkyl ethers, N,N- of aliphatic monocarboxylic acids
Disubstituted amides and ethylene glycol dialkyl ethers and diethylene glycol dialkyl ethers of the type mentioned in the first step.

For the rearrangement in the presence of acid catalysts, polar solvents, especially lower alcohols such as methanol, ethanol and butanol, N,N-dialkylamides of C1 -C3 aliphatic monocarboxylic acids in the acid part, especially N,N-dimethyl Preference is given to using formamide or dialkyl sulfoxides such as dimethyl sulfoxide.

Aprotic and strongly polar solvents, such as N,N-disubstituted amides of the aliphatic monocarboxylic acids, cyclic amides, amides of carbonic acid, amides of phosphorous acid, amides of phosphoric acid, amides of phenylphosphonic acid, or amides of aliphatic phosphonic acids. In amides, amides of sulfuric acids, amides of aliphatic or aromatic sulfonic acids, and dialkyl sulfoxides such as dimethyl sulfoxide, the reaction proceeds without the addition of base or acid. In this case, the solvent acts as a catalyst.

However, in general, when the rearrangement is carried out in the presence of an inert organic solvent, the catalyst is preferably an organic base having a pKa value greater than 9, in particular a trialkylamine in which each alkyl group has 1 to 8 carbon atoms, such as triethylamine, tri- n-butylamine and tri-n
-octylamine; hydrohalic acid, especially HCl and HBr, and tetraalkylammonium.
Halides, especially those containing 1 or more carbon atoms in each alkyl group
18 tetraalkylammonium chloride,
Add bromide and iodide.

Particularly preferred solvents are C1 -C4 aliphatic alcohols, toluene, xylene, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionitrile, ethylene glycol diethyl ether and di-isopropyl ketone.

The rearrangement reaction temperature in the presence of an inert organic solvent is generally about 0 to 150°C, preferably 80 to 150°C.
The temperature is 130℃.

By the method of the present invention, 2-
A novel 2-(2',2',2'-trihaloethyl)-4- substituted at the 3-position, suitable as a synthetic intermediate for (2',2'-dihalobinyl)-cyclopropanecarboxylic acid derivatives. Halo-cyclobutan-1-ones are obtained conveniently and in good yields using readily available starting materials.

The method of the present invention is based on the 2-
It is particularly suitable for the production of (2',2',2'-trichloroethyl)-4-halo-cyclobutan-1-one.
The method of the present invention involves reacting 2,4,4,4-tetrahalobutyric acid chloride of the formula or a haloketene produced by the elimination of hydrogen chloride with an olefin of the formula, and 2-(2' , 2'-dihalobinyl)-cyclopropanecarboxylic acid derivatives of the formula 2-(2',2',2'-
trihaloethyl)-2-halo-cyclobutane-1
-one is first generated, and then it is converted into 2-(2′,2′, 2-(2',2',2'-trihaloethyl)-4- of the formula suitable for conversion to '-dihalovinyl)-cyclopropanecarboxylic acid derivatives.
This is a very surprising and totally unforeseeable method since it changes to halo-cyclobutan-1-one.

As starting material a novel 2-(2',2',2'-trihaloethyl)-4-halo-cyclobutane-1-
2 substituted at the 3-position, which can be prepared using
-(2′,2′-dihalobinyl)-cyclopropanecarboxylic acid has the following formula: [In the formula, X, R ₁ and R ₂ represent the meanings described in the formula, and R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or the following formula: (In the formula, R ₃ represents an oxygen atom, a sulfur atom, or a vinylene group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a benzyl group, a phenoxy group, or a phenylmercapto group, and R ₅ represents hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₆ represents a hydrogen atom, a cyano group or an ethynyl group, or one of R ₁ and R ₂ represents a methyl group and the other represents a hydrogen atom or When R 3 represents a methyl group, R ₃ represents a vinylene group, R ₄ represents a phenoxy group, and R ₅ represents a hydrogen atom, it also represents an alkyl group having 1 to 5 carbon atoms.) represents a group. ] It can be expressed as

2-(2′,2′-dihalobinyl)-cyclopropanecarboxylic acid derivatives of the formula, where R is a group of the formula,
Suitable for controlling pests of various animals and plants, especially insects. the nature of these active compounds;
The fields of application and the applicable dosage forms are described, for example, in the following documents: Nature 246, pages 169-170 (1973);
Nature 248 pp. 710-711 (1974); Proceedings
7th British Insecticide and Fungicide
Conference, pp. 721-728 (1973); Proceedings
8th British Insecticide and Fungicide
Conference, pp. 373-378 (1975); J.Agr.Food
Chem. 23 115 pages (1973); US Pat.
No. 2326077 and 2614648.

2-(2′,2′,2′-trihaloethyl)-4 of the formula
2- of the formula -halo-cyclobutan-1-one
The conversion to the (2',2'-dihalobinyl)-cyclopropanecarboxylic acid derivative is carried out by a method known per se.
This is carried out by heating in the presence of a suitable base. Examples of suitable bases are alkali metal hydroxides and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide. Alkali metal carbonates and bicarbonates and alkaline earth metal carbonates and bicarbonates such as calcium carbonate, barium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate and potassium bicarbonate can also be used as bases. Other suitable bases are alcoholates derived from the radical R as defined above, in particular the corresponding sodium and potassium alcoholates. The use of such alcoholates has the advantage that the corresponding esters are obtained directly. On the other hand, when alkali metal hydroxides and alkaline earth metal hydroxides are used, these bases and the generated 2
A salt of -(2',2'-dihalobinyl)-cyclopropanecarboxylic acid is formed first. However, these salts can be prepared in simple ways known per se, for example by converting them into the corresponding acid chlorides and reacting with alcohols derived from the radical R.
It can also be converted into an ester.

Depending on the nature of the base used, 2-(2′,
The conversion of 2',2'-trihaloethyl)-4-halo-cyclobutan-1-one into a 2-(2',2'-dihalovinyl)-cyclopropanecarboxylic acid derivative can be carried out in an aqueous medium, an aqueous-organic It is advantageously carried out in a medium or an organic medium. If the base used is an alkali metal carbonate or an alkaline earth metal carbonate, the reaction is carried out in an aqueous or aqueous-organic medium. The reaction in the presence of alkali metal hydroxides or alkaline earth metal hydroxides and alkali metal carbonates is also advantageously carried out in aqueous or aqueous-organic media. In this case, acidification of the reaction mixture, for example by addition of concentrated hydrochloric acid, results in the free form of the formula (R=H)
2-(2',2'-dihalobinyl)-cyclopropanecarboxylic acid is obtained.

2 of formula in aqueous-organic medium or organic medium
-(2′,2′,2′-trihaloethyl)-4-halo-cyclobutan-1-one for conversion to 2-(2′,2′-dihalovinyl)-cyclopropanecarboxylic acid derivatives of the formula Suitable solvents are lower alcohols such as those having 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, and aliphatic, cycloaliphatic or aromatic hydrocarbons such as n-pentane, n-hexane, cyclohexane, benzene, toluene and xylene.

2-(2′,2′,2′-trihaloethyl)-4 of the formula
2- of the formula -halo-cyclobutan-1-one
The conversion to the (2',2'-dihalobinyl)-cyclopropanecarboxylic acid derivative is generally carried out at the boiling point of the chosen reaction medium. Reaction temperatures of 40 to 120°C are particularly preferred.

2-(2′,2′,2′-trihaloethyl)-4 of the formula
-Halo-cyclobutan-1-one of the formula 2-
When converted to a (2',2'-dihalobinyl)-cyclopropanecarboxylic acid derivative, the following formula X: The corresponding 2-(2 _' ,2 _' ,2'-trihaloethyl)-cyclopropanecarboxylic acid derivative represented by
Produced as an intermediate. This product can be isolated if the reaction temperature is kept below 40°C and/or if less than an equivalent amount of base is used. Above 40°C, these intermediates are converted to the corresponding 2-(2',2'-dihalobinyl)-cyclopropanecarboxylic acid derivatives of the formula by addition of further base with elimination of HX. .

The 2-(2′,2′,2′-trihaloethyl)-cyclopropanecarboxylic acid derivative of the formula
(2',2',2'-trihaloethyl)-4-halo-cyclobutan-1-one, if necessary with customary sensitizers (e.g. ketone For example, it can be photochemically synthesized by adding acetone, cyclohexanone, benzophenone, acetophenone, higher alkylaryl ketone, thioxanthone, etc.) and irradiating it with ultraviolet rays. Examples of hydroxyl-containing reagents are alkanols such as methanol, ethanol, etc., and especially water.

〔Example〕

Next, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 Production of 2,4,4,4-tetrachlorobutyric acid chloride Acrylic acid chloride (industrial use) 452.5 g (5
mole), carbon tetrachloride 1.5, acetonitrile 1.5
and 30 g of copper chloride () were held at 115° C. for 24 hours.
The reaction mixture was filtered and the clear liquid obtained was evaporated under water pump vacuum. Distill the residue to boiling point
922 g (76% of theory) of 2,4,4,4-tetrachlorobutyric acid chloride was obtained at 78-80 DEG C./11 mmHg.

Infrared absorption (IR) spectrum ( _CHC3 ) (cm
^-1 ): 1780 (C=O) Nuclear magnetic resonance (NMR) spectrum [100 megahertz (MHz), ( _CDC3 ] (pmm): 3.16-3.94 (m, 2H, _CH2 ) 4.84-4.96 (m, 1H) , CH) 2,4,4,4-tetrachlorobutyric acid chloride can also be prepared as follows: 90.5 g (1 mol) of acrylic acid chloride, 0.5 g of carbon tetrachloride, 0.2 g of butyronitrile and 3 g of copper powder.
was heated at 115°C for 20 hours. filter the reaction mixture;
The liquid was evaporated and the residue was distilled. As a result, 2,4,4,4-tetrachlorobutyric acid chloride
167.8 g (69% of theory) was obtained (boiling point 80-81
℃/12mmHg). The spectral data were identical to that of 2,4,4,4-tetrachlorobutyric acid chloride prepared in Section 1 above.

2,4,4,4-tetrachlorobutyric acid chloride was obtained in a yield of 71% by carrying out the same procedure except that the copper powder was replaced with copper chloride (2) and the butyronitrile was replaced with 3-methoxypropionitrile.

2,4,4,4-tetrachlorobutyric acid [Israel Patent No. 18771 = CA 63 13089e (1965)
Manufactured according to. ] 226 g (1 mol), 600 g of thionyl chloride and 1 part of N,N-dimethylformamide
ml was heated at 50°C for 2 hours and at 75°C for 2 hours. After removing excess thionyl chloride, the residue was distilled. This gave 227.6 g (93% of theory) of 2,4,4,4-tetrachlorobutyric acid chloride (boiling point 90-91 DEG C./15 mmHg).

1,1-dichloroethylene 145.9g (1.5mol),
Dichloroacetyl chloride 147.4g (1 mol),
200ml of acetonitrile and 3g of copper chloride (130ml)
Heated at ℃ for 8 hours. The reaction mixture was evaporated and the residue was fractionally distilled. As a result, 2, 4,
4,4-Tetrachlorobutyric acid chloride was obtained in the form of a colorless liquid (boiling point 78-80°C/11 mmHg). The spectral data of the material obtained was identical to that of 2,4,4,4-tetrachlorobutyric acid chloride prepared in Section 1 above.

Reference example 1 a 2-chloro-2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutane-1-
Preparation of 2,4,4,4-tetrachlorobutyric acid chloride in 600 ml of cyclohexane in an autoclave.
280 g of isobutylene was injected into 122 g (0.5 mol). A solution of 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane was pumped in at 65° C. for 4 hours. The reaction mixture was then held at 65°C for an additional 3 hours. The precipitated triethylamine hydrochloride was filtered off and the liquid was evaporated. The crystals thus obtained were filtered. This results in 2-chloro-2
-(2′,2′,2′-trichloroethyl)-3,3-dimethylcyclobutan-1-one 79.4 g (theoretical amount)
60%) (melting point 75-76°C).

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1805 (C=O) ¹ H NMR spectrum (100MHz, CDCl ₃ )
(ppm): 1.42 and 1.45 (1s, 6H and _1CH3 , respectively) 2.91-3.28 (m, 2H, _CH2 ) 3.37-3.76 (m, 2H, _CH2 ) ^13C NMR spectrum ( _CDCl3 ) (ppm): 196 (s, CO); 95.3 (s, CH ₃ ); 80.8 (s, C-
2); 57.0 (t, CH ₂ ); 56.4 (t, CH ₂ ); 37.9
(s, C-3); 25.1 (q, CH ₃ ); 28.8 (q,
CH ₃ ) Elemental analysis C ₈ H ₁₀ Cl ₄ O (molecular weight 263.98): C H O Cl Calculated value (%) 36.40 3.82 6.02 53.72 Measured value (%) 36.4 3.9 6.2 53.5 b 2-(2', 2', 2′-trichloroethyl)-3,
3-dimethyl-4-chlorocyclobutane-1-
Production of 2-chloro-2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutane-
132 g (0.5 mol) of 1-one were dissolved in 700 ml of toluene, 1 ml of triethylamine was added and the mixture was boiled under reflux. After reacting for 13 hours,
Another 1 ml of triethylamine was added and the mixture was boiled for a further 7 hours. After cooling the reaction mixture was washed first with dilute hydrochloric acid and then with water, dried and evaporated. Solidified residue (124g: 94% of theoretical amount)
was a single compound by thin layer chromatography, which was crystallized from n-hexane. This results in 2-(2',2',2'-trichloroethyl)-3
，
5-dimethyl-4-chloro-cyclobutane-1-
Obtained 105.8 g of on (melting point 56-57°C).

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1800 (C=O) ¹ H NMR spectrum (100MHz, CDCl ₃ )
(ppm): 4.77 (d, J=2Hz, 1H, H on C-4) 3.47 (m, 1H, H on C-2) 2.73-3.26 (m, 2H, CH ₂ ) 2.63 (s, 3H , CH ₃ ) 1.14 (s, 3H, CH ₃ ) ¹³ C NMR spectrum (CDCl ₃ ) (ppm): 197.0 (s, CO); 97.8 (s, CCl ₃ ); 69.4 (d, C
-4); 60.6 (d, C-2); 49.5 (t, CH ₂ -
CCl ₃ ); 36.8 (s, C-3); 27.4 (q, CH ₃ );
18.6 (q, CH ₃ ) Elemental analysis As C ₈ H ₁₀ Cl ₄ O (molecular weight 263.98): C H O Cl Calculated value (%) 36.40 3.82 6.02 53.72 Measured value (%) 36.6 3.8 6.2 53.6 The above compound is as follows. It can also be manufactured by

2-chloro-2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutanone 2.64g
(0.01 mol) and 220 mg (0.0008 mol) of tetra-n-butylammonium chloride at 124°C.
Stirred for 6.5 hours. The melt was cooled, boiled with hot n-hexane and filtered to give a clear liquid.
When the liquid was cooled, 2.19 g (83% of theory) of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chloro-cyclobutanone precipitated (melting point 53-56°C). .

c Production of 2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropane-1-carboxylic acid 2-(2',2',2'-trichloroethyl)-3,3
-Dimethyl-4-chloro-cyclobutan-1-one 13.2 g (0.05 mol) were added to 150 ml of 10% sodium hydroxide solution and the mixture was stirred vigorously.
A clear solution formed after 5 minutes and was heated at 100° C. (bath temperature) for 1 hour. The reaction solution was washed with diethyl ether and acidified with concentrated hydrochloric acid while cooling.
Extracted with diethyl ether. The ether phase was washed with water, dried over magnesium sulphate and evaporated.
Solid residue (10.35g) according to NMR spectrum
is cis-2-(2',2'-dichlorovinyl)-3,5
80% by weight of -dimethylcyclopropane-1-carboxylic acid and 20% by weight of trans-2-(2',2'-dichlorovinyl)-3',3-dimethylcyclopropane-1-carboxylic acid. Crystallization from n-hexane gave the pure cis-acid (mp 85-87°C).

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1710 (C=
O), 1625 (C=C) NMR spectrum (100MHz, CDCl ₃ /D ₂ O)
(ppm): 1.30 (s, 6H, 2×CH ₃ ) 1.85 (d, J=8.5Hz, 1H, HC−1) 2.02−2.19 (m, 1H, HC−2) 6.17 (d, J=8Hz, 1H,CH= _CCl2 ) Reference Example 2 421 g of propylene, 244 g (1 mol) of 2,4,4,4-tetrachlorobutyric acid chloride and 1.25 g of cyclohexane were first introduced into a 6.3 autoclave. A solution of 101 g (1 mol) of triethylamine in 1 mol of cyclohexane is pumped at 50° C. for 4 hours and the reaction mixture is
It was held at 50°C for 3 hours. The reaction mixture was filtered and the resulting solution was washed with dilute hydrochloric acid and then with water.
Dry with magnesium sulphate and evaporate. The residue was crystallized from n-hexane. This results in 2-chloro-2-(2',2',2'-trichloroethyl)-3
77.2 g of -methylcyclobutan-1-one were obtained (melting point 80-81 DEG C.).

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1785 (CO) ¹ H NMR spectrum (100MHz, CDCl ₃ )
(ppm): 3.28-3.73 (m, 3H) 2.65-2.95 (m, 2H) 1.43 (d, J = 6.5Hz, 3H, _CH3 ) ^13C NMR spectrum ( _CDCl3 ) (ppm): 196.5 (s, CO); 95.1 (s, CCl ₃ ); 77.8 (s, C
-2);55.3(t, _CH2 - _CCl3 );50.9(t,C-
4); 38.1 (d, C-3); 15.8 (q, CH ₃ ) 1 ml of triethylamine was added to the resulting 2-chloro-2-(2',2',2'-trichloroethyl)- in 500 ml of toluene. 3-Methylcyclobutan-1-one
50g (0.2 mol) of water, and the mixture was heated to a bath temperature of 120°C.
Stirred at ℃ for 18 hours. After cooling, the reaction mixture was filtered to obtain a clear liquid, which was first diluted with dilute hydrochloric acid.
It was then washed with water, briefly boiled with activated charcoal, filtered again and evaporated. Distill the residue 2
38.7 g (77% of theory) of -(2',2',2'-trichloroethyl)-3-methyl-4-chlorocyclobutan-1-one was obtained (boiling point 130-131°C/12 mm
Hg).

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1805 (CO) NMR spectrum (100MHz, CDCl ₃ ) (ppm): 1.20 (d, J = 7 Hz, 0.6H, CH ₃ ) 1.46 (d, J = 7 Hz, 0.45H, CH ₃ ) 1.66 (d, J = 6.5Hz, 1.95H, CH ₃ ) 2.1-3.5 (m, 4H) 4.55 (dd, J = 8 and 2Hz, 0.65H, 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, this compound consists of three stereoisomers (weight ratio 13: 4:3).

Obtained 2-(2′,2′,2′-trichloroethyl)
-3-Methyl-4-chlorocyclobutan-1-one 10.5 g and 100 ml of 10% sodium hydroxide solution
Stir for a minute. The resulting solution was then heated at 100°C for 1 hour. The reaction mixture was washed with diethyl ether and carefully acidified with concentrated hydrochloric acid. This was then extracted with diethyl ether. The ethereal extract phase was washed with water, dried over magnesium sulphate and evaporated. This gave 2-(2',2'-dichlorovinyl)-3-methylcyclopropane-1-carboxylic acid. Melting point 75-78°C (recrystallized from n-hexane).

IR spectrum (KBr) (cm ^-1 ): 1685 (C=O),
1625 (C=C) NMR spectrum (100MHz, CDCl ₃ /D ₂ O)
(ppm): 1.25 (d, J = 5.5Hz, 3H, CH ₃ ) 1.54-2.18 (m, 3H) 3.96 (d, J = 8Hz, 1H, CH-CCl ₂ ) Reference example 3 In 50 ml of n-hexane Triethylamine 25.3g
(0.25 mol) of methylenecyclobutane in 200 ml of n-hexane kept under reflux.
(0.37 mol) and 61.1 g (0.25 mol) of 2,4,4,4-tetrachlorobutyric acid chloride,
The mixture was added dropwise over 7 hours while stirring. After the reaction mixture was stirred under reflux for a further 2 hours, the ammonium salt formed was removed by filtration while still hot. The liquid was concentrated to about 1/3 volume. After cooling, the following equation: 1-chloro-1-(2',2',2'-trichloroethyl)-spiro[3,3]heptane-2 represented by
-one was precipitated in the form of crystals. Melting point 93-94℃.

IR spectrum ( _CCl4 ) (cm ^-1 ): 1790 (C=O) NMR spectrum (100MHz, _CDCl3 ) (ppm): 1.70-2.80 (m, 6H) 3.15-3.60 (m, 4H) in 100ml of toluene The generated 1-chloro-1-
(2′,2′,2′-trichloroethyl)-spiro[3,
3] A solution of 27.6 g (0.1 mol) of heptane-2-one was refluxed for 9 hours with 0.93 g (5 mmol) of tributylamine. The reaction mixture was then evaporated and the residue was distilled under reduced pressure. This gives the following formula: 1-chloro-3-(2',2',2'-trichloroethyl)spiro[3,3]heptane-2-
was obtained in the form of a pale yellow oil. boiling point 85−90
℃／0.005mmHg. ^n20D ₌ 1.5242.

IR spectrum (film) (cm ^-1 ): 1795 (C=
O) NMR spectrum (100MHz, CDCl ₃ ) (ppm): 1.80-3.85 (m, 9H) 4.68, 4.93 (d, 1H, respectively) Produced 1-chloro-3-(2', 2', 2'-trichloro 11.0 g (40 mmol) of ethyl)spiro[3,3]heptan-2-one were stirred with 95 ml (approximately 240 mmol) of 10% sodium hydroxide solution at 95 DEG C. for 6 hours. After cooling, the mixture was washed several times with diethyl ether, acidified with sulfuric acid and extracted with diethyl ether. The ether extract phase was dried over sodium sulfate and then evaporated. The residue was filtered through 10 times the weight of silica gel [eluent: n-hexane/diethyl ether = 1:1 (volume ratio)] to remove a small amount of highly polar impurities. After concentrating the liquid, the following formula: 2-(2′,2′-dichlorovinyl)-spiro[2.3]hexane-1-carboxylic acid represented by 2:1
was obtained in the form of a cis/trans mixture of melting point
121−28℃.

IR spectrum (CCl4) (cm ^-1 ₎ : 1705 (C=O) NMR spectrum (100MHz, _CDCl3 ) (ppm): 1.60-2.60 (m, 8H) 5.34, 5.97 (d, 1H, respectively) 11.80-11.50 (Broad s, 1H) Reference example 4 2,4,4,4-tetrachlorobutyric acid chloride in 600 ml of cyclohexane in an autoclave.
280 g of isobutylene was injected into 122 g (0.5 mol). 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane were pumped in at 65° C. over a period of 4 hours. The reaction mixture was then held at 65°C for 3 hours and then heated at 125°C for 18 hours. During this time, triethylamine in 50ml of cyclohexane
2.0 g was pumped every 3 hours. The reaction mixture was poured onto ice, acidified with hydrochloric acid, and extracted with cyclohexane. The extract phase was evaporated and passed through 1 kg of silica gel in toluene/cyclohexane (1:1 mixture by volume) to remove highly polar impurities. The liquid was evaporated and the residue was crystallized from n-hexane. This results in 2−(2′, 2′,
2'-trichloroethyl)-3,3-dimethyl-4
31.8 g of -chlorocyclobutan-1-one was obtained.
Melting point 56-57℃.

Reference example 5 a 2-(2',2',2'-trichloroethyl)-3,
3-dimethyl-4-chlorocyclobutanone 26.1
g (99 mmol) in 10% sodium hydroxide solution
The mixture was added to 260 ml at 11°C with stirring. The temperature is 2.4
The temperature rose to 28℃ in an hour, and then 20℃ after another 2 hours.
It fell down. The reaction mixture was diluted with 200 ml of water, washed with diethyl ether, made strongly acidic with concentrated hydrochloric acid,
Then it was extracted with diethyl ether. The extract was washed with water, dried over magnesium sulphate and evaporated. This allows cis- and trans-2-
(2',2',2'-trichloroethyl)-3,3-dimethylcyclopropanecarboxylic acid (melting point 80-81°C) 24.3 g (theoretical amount)
100%). This mixture could be separated into pure cis and trans compounds by fractional crystallization or column chromatography.

NMR spectrum (100MHz, CDCl ₃ /D ₂ O)
(ppm): 2.75-3.33 (m, 2H) 1.50-1.97 (m, 2H) 1.32 (s, 2 x CH ₃ cis) 1.27 and 1.38 (2 x s, 2 x CH ₃ trans) b 400 ml of acetone and 100 ml of water 2-(2′, 2′,
2'-trichloroethyl)-3,3-dimethyl-
8.0 g (30.3 mmol) of 4-chlorocyclobutanone were irradiated through a Pyrex glass with a Philips HPK 125 Watt lamp until no more starting material was detected by chromatography. The reaction mixture was evaporated and the residue was treated as the acid as described in a). This gave 6.95 g (93% of theory) of a cis/trans mixture of 2-(2',2',2'-trichloroethyl)-3,3-dimethyl-cyclopropanecarboxylic acid, whose spectral data were a )
It was the same as that of the mixture obtained in .

c 2-(2',2',2'-trichloroethyl)-3,
3-dimethylcyclopropanecarboxylic acid 24.55
g (0.1 mol) of 10% sodium hydroxide solution 350
ml, and this suspension was heated to 4.5 ml at a bath temperature of 100°C.
Stir for hours. The reaction solution was washed with diethyl ether, acidified with hydrochloric acid, and extracted with chloroform. The extract was washed with water, dried over magnesium sulphate and evaporated. Crystallization from n-hexane gave 17.55 g (84% of theory) of colorless 2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid.

Example 2 Production of 2-bromo-4,4,4-trichlorobutyric acid chloride 90.5 g (1 mol) of acrylic acid chloride, 218.1 g (1.1 mol) of bromotrichloromethane, 200 ml of acetonitrile, and 5.0 g of copper chloride () were heated at 120°C. It was held for 6 hours. The reaction mixture was then filtered and the liquid was distilled under water pump vacuum. In this method, 2-bromo-
4,4,4-trichlorobutyric acid chloride 89.5g
(31% of theory) was obtained.

Infrared absorption (IR) spectrum (CHCl ₂ ) (cm ^-1 ): 1775 (C=O) Nuclear magnetic resonance (NMR) spectrum [100 megahertz (MHz), CDCl ₃ ] (ppm): 3.93 (d×d, CH ₂ ) 4.29 (d x d, CH) Reference example 6 2-bromo-4,4,4-trichlorobutyric acid chloride 145 g (0.5 mol), isobutylene 280 g (5 mol)
mol) and 600 ml of cyclohexane were first introduced into the autoclave. 51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane at 65℃
Pumped over time. The mixture was then stirred for a further 3 hours at this temperature. The reaction mixture was filtered, the liquid was evaporated and the residue was crystallized from n-hexane. This results in 2-bromo-2-(2′,
74.5 g (48% of theory) of 2',2'-trichloroethyl)-3,3-dimethylcyclobutanone were obtained in the form of a light beige powder. Melting point 46-49℃.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1885 (CO) ¹ H NMR spectrum (100MHz, pyridine-
d ₅ ) (ppm): 3.79 (AB, 2H, CH ₂ ) 3.10 (AB, 2H, CH ₂ ) 1.37 and 1.42 (1 s each, 6 H total, each
_CH3 ) ^13C NMR spectrum ( _CDCl3 ) (ppm): 196.8 (CO); 95.6 ( _CCl3 ); 74.8 (C-2); 56.5
and 56.3 (respectively CH ₂ ); 38.0 (C-3); 27.4
and 24.7 (each _CH3 ) 2-bromo-2-(2',2',2'-trichloroethyl)-3,3-dimethylcyclobutanone 20 g
(0.065 mol) and 5 g of tetrabutylammonium bromide were stirred at 80°C for 30 minutes and at 100°C for 10 minutes. The solidified melt was subjected to silica gel chromatography (eluent: toluene/cyclohexane=1:1). In this way, 2−(2′, 2′, 2′−
Trichloroethyl)-3,3-dimethyl-4-bromocyclobutanone was obtained, which crystallized on standing. Melting point 56℃.

^1H NMR spectrum (100MHz, _CDCl3 )
(ppm): 4.99 (d, J = 2Hz, 1H, H on C-4) 3.58 (X section of ABX, further analyzed at J = 2Hz, 1H,
H on C-2) 3.05 (AB part of ABX, 2H, _CH2 ) 1.22 and 2.67 (1s, 3H, _CH3, respectively) ^13C NMR spectrum ( _CDCl3 ) (ppm): 196.7 (s, CO); 97.7 (s, CCl ₃ ); 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, CH ₃ );
21.0 (q, CH ₃ ) A solution of 3.2 g of NaOH in 70 ml of water is converted to 2-(2', 2',
2'-trichloroethyl)-3,3-dimethyl-4
- Bromocyclobutanone 3.1 g (10.6 mmol)
and the mixture was stirred for 2 hours. This was then stirred for an additional 3 hours at 100°C. The reaction mixture was washed with diethyl ether and acidified with dilute hydrochloric acid. This aqueous phase was extracted with diethyl ether.
The extract was washed with water, dried over magnesium sulphate and evaporated. The residue was crystallized from n-hexane. This gave 2.55 g of cis-2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid. Melting point 86℃ IR spectrum (CHCl ₃ ) (cm ^-1 ): 1710 (CO),
1625 (C=C) NMR spectrum (100MHz, CDCl ₃ /D ₂ O)
(ppm): 1.30 (s, 6H, 2×CH ₃ ) 1.85 (d, J=8.5Hz, 1H, HC−1) 2.02−2.19 (m, 1H, HC−2) 6.17 (d, J=8Hz, 1H, CH=CCl ₂ ) Example 3 Acrylic acid chloride 90.5g (1 mol), carbon tetrabromide 364.8g (1.1 mol), acetonitrile 200ml
and 5.0 g of copper chloride () were heated at 115° C. for 6 hours. After cooling, the reaction mixture was directly distilled. This gave 136.6 g (33% of theory) of 2,4,4,4-tetrabromobutyric acid chloride. boiling point 135−
140℃/12mmHg.

Reference Example 7 350 ml of cyclohexane was saturated with isobutylene at room temperature (20-25°C). 2, 4, 4, 4 to this
-Tetrabromobutyric acid chloride 42.2g (0.1 mol)
was dissolved. Next, 10.1 g (0.1 mol) of triethylamine in 50 ml of cyclohexane was added dropwise at room temperature over 2 hours while stirring and slowly passing in isobutylene. The resulting reaction mixture was stirred for 3 hours,
Then water was added. The organic phase was separated, washed with water, dried over magnesium sulphate and evaporated. The residue was passed through silica gel [eluent: cyclohexane/toluene = 1:1 (volume)]. The liquid was evaporated and the residue was crystallized from n-hexane. 2-Bromo-2-(2',2',2'-tribromoethyl)-3
，
3-dimethylcyclobutanone was obtained. Melting point 61−63
℃.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1780 (CO) ¹ H NMR spectrum (100MHz, CDCl ₃ )
(ppm): 3.97 (AB, 2H, CH ₂ ) 3.13 (AB, 2H, CH ₂ ) 1.51 and 1.61 (1s, 3H, CH ₃ respectively) ¹³ C NMR spectrum (CDCl ₃ ) (ppm): 196.7 (CO) ; 76.8 (C-2); 60.0 and 56.6 (each CH ₂ ); 38.1 (C-3); 31.7 (CBr ₂ ); 27.7 and 25.0 (each CH ₃ ) 2-bromo-2-(2', 2',2'-tribromoethyl)-3,3-dimethylcyclobutanone 9.6g
(21.8 mmol) and 20.g of tetrabutylammonium bromide were stirred at 90°C for 30 minutes. The cooled melt was chromatographed on silica gel (eluting with a 1:1 mixture of toluene/cyclohexane). This gives 2-(2',2',2'-tribromoethyl)-3,3-dimethyl-4-bromocyclobutanone in the form of a slowly crystallizing oil, which is separated from diethyl ether/n-hexane. It was recrystallized from Melting point 91-93℃.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1795 (CO) ¹ H NMR spectrum (100MHz, CDCl ₃ )
(ppm): 4.96 (d, J = 2Hz, 1H, H on C-4) 3.12-3.67 (ABX, further analyze part X at J = 2Hz,
3H, _CH2 -CH) 1.18 and 1.67 (1s, 3H, _CH3 ) ^13C NMR spectrum ( _CDCl3 ): 196.4 (s, CO); 63.2 (d, C-2); 59.9 (d,
C-4); 54.6 (t, CH ₂ ); 38.4 (s, CBr ₃ );
36.4 (s, C-3); 27.8 and 21.3 (q, respectively
CH ₃ ) NaOH190 in 5 ml water with 0.5 ml dioxane
mg solution was stirred with 700 mg (1.56 mmol) of 2-(2',2',2'-tribromoethyl)-3,3-dimethyl-4-bromocyclobutanone for 2 hours at room temperature. This mixture was then stirred at 80°C for 1 hour. This clear solution was processed to form an acid using conventional methods. cis-2-(2',2'-dibromovinyl)-3,
3-dimethylcyclopropanecarboxylic acid 410mg
(88% of theoretical amount) was obtained.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1695 (CO) NMR spectrum (100MHz, CDCl ₃ /D ₂ O)
(ppm): 6.70 (6d, J=8Hz, 1H, CH-CBr ₂ ) 1.82-2.14 (m, 2H) 1.30 and 1.33 (1s each, total 6H, each
CH ₃ ) Reference example 8 Triethylamine in 100ml of cyclohexane
10.1g (0.1mol) of cyclohexane at 65℃
It was added dropwise over 2 hours to a solution of 14 g (0.17 mol) of methylenecyclopentane and 26.4 g (0.1 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 220 ml with stirring. The mixture was then stirred for a further 3 hours at this temperature. The reaction mixture was washed with dilute hydrochloric acid and then with water, dried over magnesium sulphate and evaporated. The residue was crystallized from n-hexane.
This gives the following equation: 16.6 g of 1-chloro-1-(2',2',2'-trichloroethyl)spiro[3.4]octan-2-one represented by the following formula was obtained. Melting point 70-73℃.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1775 (CO) NMR spectrum (100MHz, CDCl ₃ ) (ppm): 1.60-2.30 (m, 8H) 3.08 (AB, 2H, CH ₂ ) 3.60 (AB, 2H , CH ₂ ) 1-chloro-1-(2',2',2'-trichloroethyl)spiro[3.4]octan-2-one 12.0g
(0.041 mol) was stirred with 3.6 g of tetrabutylammonium chloride at a bath temperature of 125°C. After 1.5 hours,
The reaction mixture was chromatographed on silica gel (eluted with a 1:1 mixture of toluene/cyclohexane). In this way: 9.7 g (81% of theory) of 1-chloro-3-(2',2',2'-trichloroethyl)spiro[3.4]octan-2-one (81% of theory) were obtained in the form of a colorless oil.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1800 (CO) NMR spectrum (100MHz, CDCl ₃ ) (ppm): 4.87 (d, J = 2 Hz, 1H, CHCl) 3.70 (X part of ABX, further J = Analysis at 2Hz, 1H,
CH) 2.73−3.29 (AB part of ABX, 2H, CH ₂ ) 1.45−2.23 (m, 8H) 1-chloro-3-(2′,2′,2′-trichloroethyl)spiro[3.4]octane-2 -On 4.83g
(16.6 mmol) in 40 ml of water and 3 ml of dioxane.
and the mixture was stirred at room temperature for 2 hours and then at 100° C. for 3 hours. The reaction solution was washed with diethyl ether and acidified with dilute hydrochloric acid. This acidic solution was extracted with diethyl ether. The extract was washed with water, dried over magnesium sulphate and evaporated. The residue was crystallized from n-hexane. This gives the following formula: 3.3 g of 2-(2',2'-dichlorovinyl)spiro[2.4]heptane-1-carboxylic acid represented by: were obtained in the form of a white powder. Melting point 90-105℃.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1705 (CO),
1620 (C=C) NMR spectrum (100MHz, CDCl ₃ /D ₂ O)
(ppm): 6.15 (d, J = 9Hz, 0.8H, CH = CCl _3cis ) 5.51 (d, J = 9Hz, 0.2H, CH = CCl _2trans ) 2.00-2.40 (m, 2H) 1.60-1.95 ( Reference Example 9 33.6 g (0.62 mol) of methylenecyclopropane and 152 g (0.62 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 620 ml of n-bentane were initially introduced into a 2.5 autoclave. 62.8g triethylamine (0.62g) in 120ml n-pentane
mol) was pumped at 60°C for 6 hours. The reaction mixture was then held at 60°C for 6 hours. The reaction mixture was filtered, the liquid was evaporated and the residue was distilled under reduced pressure. Next boiling point range 45-80℃/0.09mm
The Hg fraction was chromatographed on 250 g of silica gel using a hexane/toluene mixture (0-50% by weight of toluene). The pure fractions were evaporated and the residue was distilled. This gives the following formula: 1-chloro-1-(2',2',2'-trichloroethyl)spiro[3.2]hexan-2-one represented by was obtained. Boiling point 70-71℃/0.08mmHg.

IR spectrum (CHCl ₃ ) (cm ^-1 ): 1776 (CO) ¹ H NMR spectrum (100MHz, CDCl ₃ )
(ppm): 0.8-1.8 (m, 4H) 2.6-3.8 (m, 4H) 1-chloro-1-(2', 2',
A solution of 11.0 g (42 mmol) of 2'-trichloroethyl)spiro[3.2]hexan-2-one and 1.17 g (6.3 mmol) of tributylamine was refluxed for 5 hours. After cooling, the reaction mixture was diluted with n-pentane. The mixture was washed with 2N sulfuric acid and then with saturated sodium chloride solution, dried over sodium sulphate and evaporated. The residue was distilled under reduced pressure. This gives the following formula: 1-chloro-3-(2',2',2'-trichloroethyl)spiro[3.2]hexan-2-one represented by was obtained. Boiling point 60℃/0.01mmHg.

IR spectrum ( _CCl4 ) (cm ^-1 ): 1780 (CO) NMR spectrum (100MHz, _CDCl3 ) (ppm): 0.8-1.7 (m, 4H) 2.6-4.2 (m, 3H) 4.75 and 5.15 (each 1 d, both 1H) 1-chloro-3-(2',2',2'-trichloroethyl)-spiro[3.2]hexan-2-one 7.1 g
(27 mmol) was refluxed for 2 hours with 54 ml (approximately 135 mmol) of 10% NaOH. After cooling, the mixture was washed several times with diethyl ether, acidified with sulfuric acid,
Then it was extracted with diethyl ether. The ether extract was dried over sodium sulfate and evaporated. A small amount of highly polar impurities was removed by filtration over silica gel (eluent: diethyl ether). Concentrate the liquid and use the following formula: 2-(2',2'-dichlorovinyl)spiro[2.2]pentane-1-carboxylic acid represented by was obtained as a cis/trans mixture of approximately 3:1. melting point
77-78℃ IR spectrum ( _CCl4 ) (cm ^-1 ): 1675 (CO) NMR spectrum (100MHz, _CDCl3 ) (ppm): 0.8-2.85 (m, 6H) 5.56 and 6.11 (1 d each, Both 1H) 10.8 (Broads, 1H) The following reference examples describe the preparation of several insecticidal active compounds.

Reference Example 10 Production of m-phenoxybenzyl ester of 2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropane-1-carboxylic acida 2-(2',2'-dichlorovinyl) )-3,3-dimethylcyclopropane-1-carboxylic acid 4.18g
(0.02 mol) and 20 ml of thionyl chloride at 70℃
heated for an hour. The excess thionyl chloride was then distilled off, the residue was taken up in 100 ml of benzene and the mixture was evaporated again. This residue [2-(2′,2′-
m-phenoxybenzyl alcohol in 40 ml of anhydrous benzene.
4.0 g (0.02 mol) of solution was added and the mixture was heated to 40°C. To this mixture was added dropwise 2.2 g (0.022 mol) of triethylamine in 10 ml of anhydrous benzene over the course of 1 hour, and the reaction mixture was stirred for a further 1 hour at room temperature. The reaction mixture was washed with dilute hydrochloric acid, dried over magnesium sulfate, and Evaporated. The residue was chromatographed on silica gel using diethyl ether/n-hexane (1:4 mixture by volume) as eluent. This gave m-phenoxybenzyl ester of 2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropane-1-carboxylic acid. Refractive index n ²⁰ _D = 1.5628.

b 2- dissolved in 25 ml of anhydrous dimethoxyethane
(2',2',2'-trichloroethyl)-3,3-dimethyl-4-chlorocyclobutan-1-one
5.28g (0.02mol), m-phenoxybenzyl alcohol 4.0g (0.02mol), NaH0.5g
(0.021 mol) and 40 ml of anhydrous dimethoxyethane. The reaction mixture was then heated at 45°C for 1
Stir for an hour, then potassium tert-butyrate 2.25
g (0.02 mol) was added and the mixture was refluxed for 3 hours. This was poured into water, acidified with dilute hydrochloric acid, and extracted with benzene. The extract was evaporated and chromatographed on silica gel using diethyl ether/n-hexane (1:4 mixture by volume) as eluent. This results in 2-(2′,2′-dichlorovinyl)
The m-phenoxybenzyl ester of -3,3-dimethylcyclopropane-1-carboxylic acid was obtained in the form of a viscous oil, which exhibited the same properties as the material obtained according to a).

Reference example 11 cis-2-(2',2'-dichlorovinyl)-3,3
-β-cyano-m-phenoxybenzyl dimethylcyclopropanecarboxylic acid 1 cis-2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylic acid 10 g (0.047 mol) in 100 ml benzene was stirred with 12.1 ml (0.141 mol) of oxalyl chloride at room temperature for 24 hours. After evaporating the reaction solution, the brown residue was distilled under reduced pressure. This makes the boiling point 50
9.1 g of a clear liquid with a temperature of 0.04 mmHg was obtained. 3.0 g of this clear liquid was dissolved in 30 ml of toluene and 2 ml of pyridine was added. To this mixture was added dropwise 2.9 g of α-cyano-m-phenoxybenzyl alcohol in 20 ml of toluene at room temperature, and then the reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was washed first with water, then with saturated sodium bicarbonate solution and then with brine, dried over magnesium sulfate and evaporated. The residue was chromatographed on silica gel (eluting with diethyl ether/n-hexane=1:2). This gave pure α-cyano-m-phenoxybenzyl cis-2-(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate as a diastereomer mixture.

NMR spectrum (60MHz, _CDCl3 ) (ppm): 1.20-1.43 (m, 6H, _CH3 ) 1.67-2.35 (m, 2H, 2xCH) 6.25 (d, J=9Hz, 1H, CH- _CCl2 ) 6.40 and 6.45 (1s, 0.5H, CH-CN respectively) 6.98-7.65 (m, 9H) Reference example 12 Crude 2-(2',2'-dichlorovinyl)-3,3-dimethylcyclo in 250 ml of anhydrous toluene Propanecarboxylic acid chloride (prepared according to Example 1a)
To a solution of 22.75 g (0.1 mol) and 21.5 g (0.1 mol) of 3-phenoxy-α-hydroxyethylbenzene was added dropwise 7.8 g (0.1 mol) of anhydrous pyridine at room temperature. The reaction mixture was heated at room temperature (20−25 °C) for 15 min.
Stirred for an hour, washed with dilute hydrochloric acid, then water, dried over sodium sulfate and evaporated. The residue was chromatographed on silica gel using n-hexane/diethyl ether (1:1 mixture by volume) as eluent. This results in 2
α-Methyl-m-phenoxybenzyl -(2',2'-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate was obtained in the form of a colorless oil. refractive index
^n20D ₌ 1.563.

Claims (1)

[Claims] Primary formula: X ₃ C-CH ₂ -CHY-COCl () (wherein, (also always represents a bromine atom) 2,4,4,4-tetrahalobutyric acid chloride. The compound according to claim 1, which is represented by the following formula: _CCl3 - _CH2 -CHCl-COCl. 3. The compound according to claim 1, which is represented by the following formula: _CBr3 - _CH2 -CHBr-COCl. 4. The compound according to claim 1, which is represented by the following formula: _CCl3 - _CH2 -CHBr-COCl.