JPH0381243A - 2-(2',2',2'-tripromoethyl)-4- chlorocyclobutane-1-on and its manufacture - Google Patents

Abstract

NEW MATERIAL: A compound of formula I (one of R₁ and R₂ is CH₃, and the other is H or CH₃, or R₁ and R₂ form 2-4C alkylene together).

EXAMPLE: 2-(2'2'2'-Tribromoethyl)-4-chlorocyclobutan-1-one.

USE: A starting material for preparating 2-(2'2'-dibromovinyl)-cyclopropane carboxylic acid in which three position of formula II (R is H, 1-4C alkyl or the like; R₄ is H, 1-4C alkyl, benzyl or the like; R₅ is H or 1-4C alkyl; R₆ is H, cyano, ethynyl or the like), is substituted, or an insecticidal active ester of the same.

PROCESS: A compound of formula IV is obtained by reacting a new 2-chloro-4,4,4- tribromobutyric acid chloride of formula III, with olefin of formula IV in the presence of an organic base such as triethyl amine or the like, preferably in a solvent, and the compound of IV is dislocated in the presence of an inorganic or organic protonic acid or the like, to obtain the compound of formula I.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel 2-(2: ward 2'-)! J Glo-7-ethyl)-4-riprocyclobutan-1-one, its production method, and novel intermediates that can be used for its production.

According to Hara Komei's Patent Application No. 38019 filed in 1972, the following formula ■: 2 (In the formula, one of B and R2 represents a methyl group, and the other represents a hydrogen atom or a methyl group, or R1 and R2 together represent an alkylene group having 2 to 4 carbon atoms; represented 2−<2z', 2″
-trihaloethyl)-4-halocyclobutan-1-one is produced.

The present FgJ is based on this original invention, 2-<2', 2:2'-
) Lihaloethyl)-4-halocyclobutan-1-one has been improved and developed.

Improvements and developments of the original invention according to the present invention are of the formula IaR1-C
OHtll [In the formula, one of R and R2 represents a methyl group, and the other represents a hydrogen atom or a methyl group, or R1
and R2 together represent an alkylene group having 5 to 4 carbon atoms] 2-(2:2:2'-)
An object of the present invention is to provide a method for producing (lipromoethyl)-4-chlorocyclobutan-1-one.

2-(2:2:2'-)lipromoethyl)- of formula (1)
4-Chlorocyclobutan-1-one is a useful intermediate and can be prepared by the inventive process in the form of 2- < 2 of formula I:
i, 2'-tribromoethyl)-4-bromocyclobutan-1-one by heating with a base, such as an alkali metal hydroxide and an alkali metal alcoholade, in a known manner (!Favorski reaction). −<
2: 2', -dibromovinyl)-cyclopropane-
1-carboxylic acid or its ester,
If this is further reacted with a suitable alcohol, such as m-72/xy-cyanobenzyl alcohol, an ester having insecticidal activity can be obtained. However, the formula 2-c2
',2',2'-tribromoethyl)-4-chlorocyclobutan-1-one is the corresponding 2-<2:2
: Obtained in a significantly better yield than 2'-tribromoethyl)-4-bromocyclobutan-1-one.

Therefore, 2-<2'z', -dibromovinyl)-cyclopropane-1-carboxylic acid and its insecticidal active ester are 2-C2',2',2'-)lipromoethyl) of formula (2).
Better yields are available via -4-prochlorocyclobutan-1-one. 2-<21 with insecticidal action
i-dibromovinyl)-cyclopropane-1-carboxylic acid ester is described, for example, in German Patent Application No. 2326.rho.
No. 77 and No. 2,439,177.

2- <2', 1.2'-)lipromoethyl) of formula Ia
-4-Chlorocyclobutan-1-one is, according to the invention, 2-chloro-4,4,4-)lipromobutyric acid chloride of the following formula: Br, 0-0H2-OH-0OCL 1(l) α In the presence of an organic base, it is reacted with an olefin represented by the following formula;
2 −<2z'
, 2'-)lipromoethyl)-2-chlorocyclobutan-1-one, which is then converted into 2- of the formula 臘 in the presence of a catalyst.
Section C 2: The substituted 2-chloro-4,4,4-)lipromobutyric acid chloride produced by rearrangement to 2'-tribromoethyl)-4-chlorocyclobutan-1-one is a new compound. Aru04,4.4-)! J-bromobutyranwo is first reacted with an inorganic acid chloride, 4,4.4-)
It can be produced by converting it into ripromobutyric acid chloride and chlorinating its position.

4.4.4-) IJ bromobutyric acid required as a starting material, obtained by reacting bromoform with acrylonitrile and then hydrolyzing the generated 4,4.4-)libromobutyric acid nitrile (J, Amar ,
Chew.

Soc, Vol. 67, pp. 601-602, 1945ai).

As inorganic acid chlorides, phosphorus trichloride, phosphorus oxychloride, phosgene, thionyl chloride and oxalyl chloride can be used. 4,4.4-) The reaction of lipromobutyric acid with the inorganic acid chloride is advantageously carried out in the presence of a catalytic amount of dimethylformamide. As a solvent, an excess of inorganic acid chloride can be used.

4.4.4-) Chlorination of the 2-position of lipromobutyric acid chloride is carried out by a conventional method. As chlorinating agent it is possible to use, for example, free chlorine or N-chlorosuccinimide. A preferred chlorinating agent is N-chlororosuccinimide. The chlorination is carried out immediately after the reaction of the inorganic acid chloride with the 4,4,4-tribromobutyric acid in an excess of the inorganic acid chloride as a solvent, without isolating the 4,4,4-tribromobutyric acid chloride. be able to. But 4,4
．． 4-) Isolation of lipromobutyric acid chloride followed by separate chlorination gives a -layer pure product.

Chlorination, 40-90°C1 especially 60-700CLr
) carried out at temperature. During the chlorination it is advantageous to irradiate the reaction mixture with UV radiation or to add some of the known free-radical initiators, such as dibenzoyl peroxide or azobisinbutyronitrile.

The reaction of the 2-chloro-4,4,4-tribromobutyric acid chloride with the olefin of formula I is advantageously carried out in the presence of a solvent. Such solvents include, for example, optionally halogenated aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene,
dichloro- and hydricchlorobenzene, n-pentane,
Suitable are n-hexane, n-octane, methylene chloride, chloroform, carbon tetrachloride, 1.1.2.2-tetrachloroethane and trichloroethylene. 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 1 carbon atoms or The 3-alkoxypropionitriles of #2 are particularly acetonitrile and 3-methoxypropionitrile.

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

As a solvent, it is also possible to use excess I/C of the olefin of the formula.

Suitable organic bases to be present when carrying out the reaction of the 2-chloro-4,4,4-)lipromobutyric acid chloride of the formula with the stratified olefins include, for example, tertiary amines, in particular those having a carbon atom number of the alkyl group, respectively. trialkyl amines, cyclic amines such as pyridine, quinoline, N-alkylpyrrolidine, N-alkylpiperidine, N,N-
Dialkylpiperazines and N-alkylmorpholines or dialkylanilines in which the alkyl group has 1 or 2 carbon atoms, respectively, such as 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.

Reaction of 2-chloro-4,4,4-)lipromobutyric acid chloride and an olefin of the formula π on the ceremony day] 1, carried out in the presence of a trialkylamine whose alkyl group has 11 to 4 carbon atoms, respectively. be exposed. 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-chloro-4,4,4-)lipromobutyric acid chloride of formula I.

The t-fin in formula (■) is also 2-chloro-4,4
, 4-) is used in at least an equimolar amount with respect to lipromobutyric acid chloride. However, it is generally advantageous to use an excess of the 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, the olefin of formula I is one in which one of R and R2 represents a methyl group and the other represents a hydrogen atom or a methyl group. Examples include those in which R and - taken together represent an alkylene group having 2 or 3 carbon atoms, ie, isobutylene, □propene, methylenecyclopropane, and methylenecyclobutan. Particularly preferred are isobutylene and methylenecyclopropane.

The reaction temperature can vary within a wide range. - generally 0 to 2000. Preferably it is between 20 and 16,000.

2-(2',2',2'-)lipromoethyl) of formula ■
-2-Chlorocyclobutan-1-one is also a new compound.

2-C2 of formula (1) produced in the above reaction: 2-(2,2',gutribromoethyl)-4-chloro of formula (2) As a catalyst for rearrangement to cyclobutan-1-one, an acid, a base or a 11!7th ammonium halide can be used.

2 of formula IV 2-<2:2:2'-)lipromoethyl)-2-cyclocyclobutan-1-one of formula I1m
The rearrangement according to the present invention to -(2',2;2'-tribromoethyl)-4-chlorocyclobutan-1-one was unexpected and resulted in monohalogenation at the σ-position. Not known about cyclobutanone0
This rearrangement proceeds in high and often quantitative yields.

Formula Ia of 2-<2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV according to the invention
The rearrangement to 2-(1,i,2'-tribromoethyl)-4-chlorocyclobutan-1-one is preferably carried out in the presence of a basic catalyst. As a basic catalyst, an organic base such as the following formula: are, independently of each other, a hydrogen atom or a carbon atom or an alkyl group of 1 to 8 carbon atoms. Suitable basic catalysts are, 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, and 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 1rjN-methyl- and N-ethyl-pyrrolidine, diamines such as N.

N, N', N'-tetramethylethylenediamine,
N, IJ, N'.

N'-tetramethyl-1,3-diaminobutane, N,N
'-Dialkylpiperazines such as N,N'-dimethylpiperazine, bicyclic amines such as 1,4-diazabicyclo(2,2゜2]octane and bicyclic amidines such as l,
5-diazabicyclo(5,4,0)undec-5-ene and 1,5-diazabicyclo(4,3,O)noney-5-
and polymeric basic compounds such as p-dimethylaminobutylpolystyrene.

Furthermore, as basic catalysts for the rearrangement of 2-<2:2', t-)lipromoethyl)-2-chlorocyclobutan-1-one of formula IV to cyclobutan-1-one of formula 1 according to the invention Also suitable are phosphines, especially trialkylphosphines such as tributylphosphine.

2-(2:2:2'-tribromoethyl)-2- of formula ■
Chlorocyclobutan-1-one E IL 2-(2'
As etching medium for the rearrangement to (tribromoethyl)-4-chlorocyclobutan-1-one, inorganic or organic protons can be used.

Suitable inorganic protons m are, for example, hydrohalic acids such as hydrogen chloride, hydrogen bromide, hydrogen chloride and hydrogen iodide, nitric acid, phosphoric acid and sulfuric acid. Particularly preferred inorganic protic acids are hydrohalic acids.

If wrinkles or bases are used in excess, they can 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-class, secondary and tertiary amines and heterocyclic nitrogen bases. Examples include: Aliphatic-class amines having up to 12 carbon atoms, such as methylamine, ethylamine, n-butylamine, n-octylamine, n-dodecylamine, hexamethylenediamine, cyclohexylamine, benzylamine: carbon atoms Aliphatic secondary amines of number 12 or less, 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 Amine examples: evatriethylamine, tri-n-butylamine,
N-methylpyrrolidine, N-methylmorpholine, 1.4
-diazabicyclo(2,2,2]octane, quinuclidine: optionally substituted primary, secondary and tertiary aromatic amines such as aniline, toluidine, naphthylamine, N-methylaniline, diphenylamine and N,N-
Diethylaniline; also pyridine, picoline, indoline and quinoline.

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

The following formula: (wherein M represents a fluorine, bromine, iodine or especially a chlorine atom.

Q4 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; q5, Hiki and Q? each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ) and N-alkyl-pyridiumolides with an alkyl group having 1 or 7 kt/"Li2, and especially the corresponding chlorides. Examples of these salts include: ammonium chloride, ammonium bromide. , methylamine hydrochloride, cyclohexylamine hydrochloride,
Aniline hydrochloride, dimethylamine hydrochloride, diimbutylamine #1j1! salt, triethylamine salt rR salt, triethylamine hydrobromide, 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, 7-enyltrimethylammonium-pro-mite t
h-chloride, hexadecylpyridinium-bromide and -chloride.

Other auxiliary catalysts which 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. sodium fluoride and lithium fluoride.

These auxiliary catalysts catalyze the reaction even in the absence of the ammonium salt, but in that case it is advantageous to add open-chain or macrocyclic polyethers (crown ethers) to speed up the reaction.

An example of such a crown ether is 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-cyclobentadecyl 5,14-diene.

The location of the 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 about 0.1 to 15 weight calculations of catalyst per compound of formula (1).

Suitable catalysts for the rearrangement in the molten state or in the molten state in inert organic solvents are in particular the organic bases mentioned above, especially trialkylamines having an alkyl group of 1 to 8 carbon atoms. 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 Among the ammonium halides are tetraalkylammonium chlorides, bromides and iodides in which each alkyl group has 1 to 18 carbon atoms.

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, Vq carbon chloride, trichloroethylene, 1,1,2,2-tetrachloroethane, nitromethane, chlorobenzene, dichlorobenzene and trichlorobenzene; lower aliphatic alcohols, e.g. 6 or less carbon atoms such as methanol, ethanol, propatool, isopropyl, butanol and pentanol; aliphatic diols such as ethylene glycol and diethylene glycol; ethylene glycol monoalkyl ethers and diethylene glycol monoalkyl, each having from 1 to 4 carbon atoms in the alkyl moiety. Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether: N4-shaped amides such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-E
- caprolactam: carboxylic acid amide such as tetramethylurea and dimorphol-7carbonyl: amide of phosphorous acid,
Amides of phosphoric acid, amides of phenylphosphonic acid, amides of aliphatic phosphonic acids having 1 to 3 carbon atoms in the ihm moiety, such as phosphoric triamide, phosphoric acid tris-(dimethylamide), phosphoric acid trimorpholide, phosphoric acid tripyrrolysate, phosphoric acid bis-( phosphoric acid (dimethylamide)-morpholide, phosphoric acid-dimethylamide diethyl-acid morpholide, tetramethyldiamide of phosphorous acid tris-(dimethylamide) and methanephosphonic acid; amides of sulfuric acid and amides of aliphatic or aromatic sulfonic acids such as tetramethylsulfuric acid. famid, dimethylamide of methanesulfonic acid or p-)luenesulfonamide; sulfur-containing solvents such as organic sulfones and sulfoxides such as dimethylsulfoxide and sulfolane; aliphatic and aromatic nitriles, 3-alkoxypropionitriles, aliphatic Ketones, alkyl and alkyl dialkyl 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-C30 aliphatic monocarboxylic acids in the acid part, especially N,N-dimethylformamide are used. , or dialkyl sulfoxides such as dimethyl sulfoxide.

Aprotic and strongly polar solvents, such as N,N-di1-converted amides of the aliphatic monocarboxylic acids, cyclic amides, carbonic acid amides, phosphorous acid amides, phosphoric acid amides, phenylphosphonic acid amides, or aliphatic Amides of phosphonic acids, amides of sulfuric acids, amides of aliphatic or aromatic sulfonic acids,
In 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 having 1 to 8 carbon atoms in each alkyl group, such as triethylamine, tri-n -butylammonium and tri-n-octylamine; hydrohalic acids, especially H(l and HEr), and tetraalkylammonium halides, especially tetraalkylammonium chlorides, bromides and iodides, each having from 1 to 8 carbon atoms in each alkyl group; Add.

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

The rearrangement reaction temperature in the presence of an inert organic solvent is generally about 0 to 150°C, preferably 80 to 1300°C.
It is.

By the method of the present invention, 2-(2:2
'-dibromovinyl)-cyclopropanecarboxylic acid derivatives of formula I, substituted at the 3-position, suitable as intermediates for the synthesis of cyclopropanecarboxylic acid derivatives
t's new 2-<2', 2', gutribromoethyl)-
4-Chlorocyclobutan-1-one is obtained simply and in good yields using readily available starting materials.

The method of the present invention involves reacting Nigon's 2-chloro-4,4,4-tribromobutyric acid chloride or the chloroketene produced by the elimination of hydrogen chloride with the olefin of the formula, to form a 2-chloro-4,4,4-tribromobutyric acid chloride substituted at the 3-position. -<2',2'-dibromovinyl)-cyclopropanecarbonyl (2-<z: 2'-tribromoethyl) of formula
-2-chlorocyclobutan-1-one is produced,
Next, this was converted to 2-(2:2'-')-bromovinyl)-cyclo, which was substituted at the 3-position, by a novel rearrangement reaction that had not been observed in conventional cyclobutanone monohalogenated at the 1-position. This is quite unexpected and quite surprising since it converts 2-(2:z',2'-tribromoethyl)-4-chlorocyclobutan-1-one of formula IS suitable for conversion into propanecarboxylic acid derivatives. An unforeseen process in which the 3-position Substituted 2-(2:2'
-dibromovinyl)-cyclopropanecarboxylic acid and its insecticidal active ester are represented by the following formula (1): [wherein R1 and R2 represent the meanings described in formula 1, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms] or the following formula ■; 4 3 (in the formula, R3 represents an oxygen atom, a sulfur atom or a vinylene group, and R4 is a hydrogen atom, a carbon atom or a 40-alkyl group,
Represents a benzyl group, phenoxy group or phenylmercapto group, R, tj represents a hydrogen atom or an alkyl group having 4 to 4 carbon atoms, R6 represents a hydrogen atom, a cyano group or an ethynyl group, or one of R1 and R2 represents a methyl group, the other represents a hydrogen atom or a methyl group, R3 represents a vinylene group, R4 represents a phenoxy group, and R
When 5 represents a hydrogen atom, VC also represents an alkyl group having 1fx to 5 carbon atoms. ) represents a group represented by ] It can be expressed as

The 2-<2;2'-dibromovinyl)-cyclopropanecarboxylic acid derivatives of the formula (2), in which R is a group (2), are suitable for controlling pests, especially insects, on various animals and plants. The nature, fields of application and application forms of these active compounds are described, for example, in the following document: Nature
246169-170 pages (1973): Natur
e 248710711 pages (1974) i Proc
eadings 7th Br1tish engineering n5e
cticicLe and? ungiCide
Conference.

pp. 721-728 (1973);
ngs 8thBritish ENG n5ecticl
de an+i Fungicide Confe
rance.

pp. 373-378 (1975) i J, Agr.
IFood Ohem.

U. 3-115 (1973) i U.S. Patent No. 3,961
,070 Specification: German Patent Publication No. 2,553,99
No. 1, No. 2,439,177, No. 2.326,077 and No. 2,614,648.

2-(2:2',2'-)lipromoethyl)4 of formula Ia
-Chlorocyclobutan-1-one formula ■2<2',
The conversion into the 2'-dibromovinyl)-cyclopropanecarboxylic acid derivative is carried out in a manner known per se by heating in the presence of a suitable base. Examples of suitable bases are alkali metal hydroxides and alkaline earth metal hydroxides such as aluminum 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, carbonate+tV-liu, sodium bicarbonate and potassium bicarbonate can also be used as bases. Other suitable bases are alcoholades derived from radicals R as defined above, in particular the corresponding sodium and potassium alcoholades. The use of such alcoholades has the advantage that the corresponding esters can be obtained directly. On the other hand, when alkali metal hydroxides and alkaline earth metal hydroxides are used, 2-<z' is formed with these bases.

The salt of 2-dibromovinyl)-cyclopropanecarboxylic acid is first formed. However, these salts can also be converted into esters 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.

Depending on the nature of the base used, 2-(2' of formula Ia).

1i-) 2-(2:2'-dibromovinyl) of the formula ■ of IJ dibromotyl)-4-chlorocyclobutan-1-one
-The conversion into the cyclopropanecarboxylic acid derivatives is advantageously carried out in an aqueous, aqueous-organic or 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 manner.
Performed in organic medium. The reaction in the presence of fully alkali hydroxides or alkaline earth metal hydroxides and alkali metal carbonates is also advantageously carried out in aqueous or aqueous-organic media. In this case, when the reaction mixture 2C is acidified, for example by adding concentrated hydrochloric acid, the free form of 2-(2:
2''-dibromovinyl)-cyclopropanecarboxylic acid is obtained.

2- of formula no. 1 in an aqueous-organic medium or an organic medium
For the conversion of 2',i,2'-)-lipromoethyl)-4-chloro-cyclobutan-1-one to the 2-<2:2'-dibromovinyl)-cyclopropanecarboxylic acid derivative of formula Solvents include 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,
These are cyclohexane, benzene, toluene and xylene.

Substituted 2-(2: 2'-1ribromoethyl)-4-chlorocyclobutan-1-one of formula 2 < 2: 2'
-dibromovinyl)-cyclopropanecarboxylic acid derivatives is generally carried out at the boiling point of the chosen reaction medium. Particular preference is given to reaction temperatures of 40 to 120°C.

The formula is 2- (2:2',2'-)lipromoethyl)4
″-Chlorocyclobutane-1-onka formula ■2 (2:
2-dibromovinyl)-cyclopropanecarboxylic acid derivative, the following formula X: (wherein R, R and R
2 represents the above meaning 0) corresponding 2-
A (2:2:2'-)lipromoethyl)-cyclopropanecarboxylic acid derivative is formed as an intermediate. This product can be isolated if the reaction temperature is kept below t-400 and/or if less than an equivalent amount of base is used. By doing so, it is converted to the corresponding 2-(2',2'-dibromovinyl)-cyclopropanecarboxylic acid derivative of formula (1) with elimination of HBr.

2-(ward 2', 2'-)lipromoethyl)- of formula X
The cyclopropanecarboxylic acid derivative has the formula 1fL of 2<
212',2'-tribromoethyl)-4-chlorocyclobutan-1-one, if necessary in the presence of a hydroxyl-containing reagent which can at the same time serve as a solvent, the usual sensitizers (e.g. ketones, e.g. 7 setone, cyclohexanone, benzophenone, acetophenone and higher alkylarylketones, thioxanthone, etc.).
It can also be synthesized photochemically by irradiating with ultraviolet light. Examples of hydroxyl-containing reagents are alkalines/ols such as methanol, ethanol, etc., and especially water.

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

Example 1 a) 4.4.4-) Production of lipromobutyric acid chloride 4.
4.4-) Repromobutyric @324.8g (1.0 mol)
600 g of thionyl chloride and l of dimethylformamide!
+11 first at 40°0 for 2 hours then 75° for 3 hours
Warm to C.

The excess thionyl chloride is then distilled off and the residue is purified under high vacuum. Boiling point 71-73°c10. 326.0 g of 4.4.4-tribromobutyric acid chloride at O5 mmHg (
95% of theory).

b) Production of 2-chloro-4,4,4-)libromobutyric acid chloride 4.4.4-Tribromobutyric acid chloride 343.2 g (
1.0 mol) was dissolved in 600 g of thionyl chloride, and at the same time, 266.0 g (2.0 mol) of N-chlorsuccinimide was added in portions at 600 ml after exposure with a mercury high-pressure lamp. After the addition of N-chlorsuccinimide is complete, the mixture obtained is stirred under light exposure for 5 hours at 600°C.

The thionyl chloride is distilled off and the residue is purified under high vacuum.

Boiling point 59-63010.05 mmHg No2-ri OI
l+-4,4,4 tribromobutyric acid chloride 309.7g
(81% of theory) O c ) Preparation of 2-(2', 2', 2')lipromoethyl)-2-chloro-3,3-dimethylcyclobutan-1-one In an autoclave, 360 m/ml of cyclohexane was added. middle 2
-Chloro-4,4,4-)ripromobutyric acid chloride90.
6 g (0.24 mol) and isobutylene 13
Press in 4 g (2.4 mol) f. Then 65 0 for 4
Triethylamine 24 hours in cyclohexane 120 m
．． 2 g (0.24 mol) of solution are pumped in. After the addition of the triethylamine solution is complete, the reaction mixture is
Hold at 65°C for an hour.

Triethylamine salt produced! ! The salts are filtered off and the solvent is distilled off. The residue is dissolved in a solvent mixture consisting of equal parts of torenine and hexane and filtered through silica gel. After evaporation of the solvent, the filtrate was dissolved into 2-(2
:2:2'-tribromoethyl)-2-chloro-3,3
-dimethylcyclobutan-1-one s 1.4 g (
311 &It's 54 Torr (l QQMHz,
CjDd3) (PI)In): 1.39 and 1.41 (ls each: 3H each).

2.86-3゜22 (m, 2H) 3.55-4.15 (m, 2H) a) 2-(2',2',2'-tribromoethyl)
-Preparation of 3,3-dimethyl-4-chlorocyclobutan-1-one After saturating 220 ffl of absolute ethanol with hydrogen chloride, 2'', 2'-)lipromoethyl)-
2-Chloro-3,3-dimethylcyclobutan-1-one 22.8 g (0,054 mol) t-Dissolve 0 The resulting solution is stirred at 800 °C for 5 hours. The reaction mixture is then concentrated in a rotary evaporator to about 1/3 of its original volume and mixed with water;
Extract with ether. The ether extract is washed first with saturated sodium chloride solution and then with sodium bicarbonate solution and dried over sodium sulfate. After distilling off the ether, the residue obtained is chromatographed on silica gel, using toluene as a solvent. After combining the pure fractions and evaporating, 2-B:2;z' with a melting point of 87-890
-tribromoethyl)-3,3-dimethyl-4-chlorocyclobutan-1-one 17, Ig (75% of theory)
f obtain 0 infrared absorption spectrum (acj4) (On);
1805 (Co), Proton nuclear magnetic resonance ()! −
NMR) spectrum (100MH2) (cDc13
) (ppm) + 1.14 and 1.67 (Ia, respectively; 3H, respectively) 3.08 3.68 (m,
3H) 4.77 (d, IH) ・) 2-(2: Production of 2'-dipromovinyl-3,3-dimethylcyclopropane-1-carboxylic acid 2- <212H2'-tribromoethyl) -3
,3-dimethy/l/-4-chlorocyclobutan-1-one 800 mg (2 mmol) are mixed in tank 00 with 5.6 mJ2 of 5% caustic soda. The diluted mixture is first heated to 0°
Stir for 18 hours at 800°C, then 1 hour at 800°C. continue,
The reaction mixture is first washed with diethyl ether and then acidified with concentrated hydrochloric acid and extracted with diethyl ether while cooling. The extract is washed with water, dried over magnesium sulphate and evaporated. The resulting 0.59 g (100% of theoretical amount) of 2-<2:i-dibromovinyl)-3,3-dimethylcyclopropane-1-carboxylic acid is 80% by weight of
is excluded from the cis-isomer and zoMf1% is excluded from the trans-isomer.

Infrared absorption spectrum (cHcj5) (Cm-1)
;1695 ((!O), proton nuclear magnetic resonance (H-
NMR) spectrum (100MHz, CD(-&3)
(PI)m), ■, 25 and 1.35 and 1,3
0 and 1.31 (IB, respectively; 0H3-groups of trans- and cis-compounds 2), 1.62-2.30 (1!l, 2H), 6.15 and 6.70 (Id, respectively, intensity ratio 1:4, total IH)
, Patent applicant Ciba Geigy Akchengesellschaft...°71 (and 2 others)

Claims (1)

[Claims] (1) The following formula I a; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I a) [In the formula, one of R_1 and R_2 is a methyl group, and the other is a hydrogen atom or a methyl group. represents a group or R_1
and R_2 together represent an alkylene group having 2 to 4 carbon atoms]
tribromoethyl)-4-chlorocyclobutan-1-one. (2) The following formula I a; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I a) [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 R_1
and R_2 together represent an alkylene group having 2 to 4 carbon atoms]
In order to produce (tribromoethyl)-4-chlorocyclobutan-1-one, 2-chloro-4,4,4-tribromobutyric acid chloride of the following formula II; is reacted with an olefin represented by the following formula III in the presence of an organic base; ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV); 2-(2',2',2'-tribromoethyl)- represented by [In the formula, R_1 and R_2 represent the above meanings]
2-(2',
Method for producing 2',2'-tribromoethyl)-4-chlorocyclobutan-1-one. (3) One of R_1 and R_2 represents a methyl group, and the other represents a hydrogen atom or a methyl group, or R_1
3. Process according to claim 2, characterized in that olefins of the formula III are used, in which R_2 and R_2 together represent an alkylene group having 2 or 3 carbon atoms. (4) The method according to claim 2, wherein isobutylene is used as the olefin of formula III. (5) The production method according to claim 2, wherein methylenecyclopropane is used as the olefin of formula III. (6) The reaction of 2-chloro-4,4,4-tribromobutyric acid chloride of formula II with the olefin of formula III is inhibited in the presence of pyridine or a trialkylamine having 1 to 4 carbon atoms in each alkyl group. 3. The method according to claim 2, which is carried out in the presence of an inert organic solvent. (7) Formula I
3. The process according to claim 2, wherein the reaction of 2-chloro 4,4,4-tribromobutyric acid chloride I with the olefin of formula III is carried out in the presence of triethylamine. (8) 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV is converted to 2-(2',2',2'-tribromoethyl)-2-(2',2',2'-tribromoethyl) of formula Ia. 3. The process according to claim 2, wherein an inorganic or organic protic acid is used as a catalyst for the rearrangement to ethyl)-4-chlorocyclobutan-1-one. (9) 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV is converted to 2-(2',2',2'-tribromoethyl)-2-(2',2',2'-tribromoethyl) of formula Ia. Claim 2 in which hydrohalic acid is used as a catalyst for the rearrangement to ethyl)-4-chlorocyclobutan-1-one.
Manufacturing method described in section. (10) 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV is converted to formula I a
2-(2',2',2'-tribromoethyl)-4-
3. The method according to claim 2, wherein an organic base is used as a catalyst for the rearrangement to chlorocyclobutan-1-one. (11) 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV is converted to 2-(2',2',2'-tribromoethyl) of Ia. ) -4-Chlorocyclobutan-1-one as a catalyst for rearrangement; ▲ Numerical formulas, chemical formulas, tables, etc. or 6 represents a cycloalkyl group, benzyl group, or phenyl group, and Q_2 and Q_3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Manufacturing method described in section. (12) 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV is converted to formula I a
2-(2',2',2'-tribromoethyl)-4-
3. The process according to claim 2, wherein a salt of a protic acid with ammonia or a nitrogen-containing organic base or a quaternary ammonium salt is used as a catalyst for the rearrangement to chlorocyclobutan-1-one. (13) 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV is converted to formula I a
2-(2',2',2'-tribromoethyl)-4-
As a catalyst for the rearrangement to chlorocyclobutan-1-one, a combination of a hydrohalic acid and an aliphatic, cycloaliphatic, araliphatic or aromatic primary, secondary or tertiary amine, or a heterocyclic nitrogen base is used as a catalyst for the rearrangement to chlorocyclobutan-1-one. The method according to claim 2, which uses salt. (14) 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV is converted to formula I a
2-(2',2',2'-tribromoethyl)-4-
As a catalyst for rearrangement to chlorocyclobutan-1-one, the following formula; ▲Mathematical formulas, chemical formulas, tables, etc. represents an alkyl group, cyclohexyl group, benzyl group, phenyl group, or naphthyl group having 1 to 18 atoms, and Q_5, Q_6 and Q_7 each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. 1 in the alkyl group, or in the alkyl group.
3. The process according to claim 2, wherein N-alkylpyridinium halides having 1 to 18 carbon atoms are used. (15) Formula I a of 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV
2-(2',2',2'-tribromoethyl)-4-
Rearrangement to chlorocyclobutan-1-one from 80 to 13
The manufacturing method according to claim 2, which is carried out at a temperature of 0°C. (16) Formula I a of 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV
2-(2',2',2'-tribromoethyl)-4-
The rearrangement to chlorocyclobutan-1-one is effected by the presence of a trialkylamine having 1 to 8 carbon atoms in each alkyl group or a tetraalkylammonium halide having 1 to 18 carbon atoms in each alkyl group. The manufacturing method according to claim 2, which is carried out in a molten state at a temperature of 80 to 130°C. (17) Formula I a of 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV
2-(2',2',2'-tribromoethyl)-4-
3. The process according to claim 2, wherein the rearrangement to chlorocyclobutan-1-one is carried out in the presence of an inert solvent. (18) Formula I a of 2-(2',2',2'-tribromoethyl)-2-chlorocyclobutan-1-one of formula IV
2-(2',2',2'-tribromoethyl)-4-
The rearrangement to chlorocyclobutan-1-one is carried out using C1 -C4 aliphatic alcohols, toluene, xylene, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionitrile, ethylene glycol, diethyl ether or diisopropyl as solvents. The method according to claim 2, which is carried out in a ketone.