SU917695A3 - Process for producing 2-(2',2',2'-trihaloethyl)-4-halocyclobutan-1-ones - Google Patents

Description

as intermediate products for the preparation of 2- (Z, 2-dihalogenvinyl) -cyclopropanoic acids and their esters having insecticidal activity. This can be explained first. the fact that the interaction of halogenoleptic with ketene does not occur due to the deactivation of the olefin associated with the presence of halogen substituents. The purpose of the invention is to develop a process for the preparation of new 2- (2,2,2 -trihaloethyl) - -halo-cyclobutan-1-ones of general formula 1, which when heated with such strong bases as alkali metal hydroxides or alkali metal alcohols during narrowing rings and simultaneous cleavage of 2 mol of hydrogen halide give the corresponding derivatives of 2- (2, 2 -dihalogenovinyl) cyclopropanecarboxylic acid. This goal is achieved by the fact that in the process for the preparation of 2- (2,2,2 -trihaloethyl) -A-halogenocyclobutane -1-ones of the general formula I, the acid chloride 2, k, k, k-tetrahalogenoic acid of the general formula XcC-CH - CH-COOC Y where X and Y have the above values, in the presence of pyridine or N-methylpiperidine, or trialkylamine from carbon in the alkyl groups in the CS CS aliphatic or cycloaliphatic hydrocarbon at a temperature of from 20 ° C to the boiling point of the reaction mixture with total olefins formulas where Rj. have the above values, and the resulting 2- (2, 2, 2 -trihaloethyl) -2-halogenocyclobutan-1-one of the general formula CXs-CHg-C 0 0 I 1 IV RI-C-CH, - where R and Rj , X and Y have the above meanings, undergo 80-125 rearrangements in the presence of trialkylamine with carbon atoms in alkyl G euppah or trialkylphosphine with 1-4 carbon atoms in alkyl groups, or pyridine, or lutidine, or morpholine, or N-methylpiperidine , or dimethylaniline, or dimethyl sulfoxide, or hydrogen halide, or tetraalkylammonium halide with 1-4 carbon atoms in alkyl grams ruppah As a rule, 2,4-4,4-tetrachlorobutyric acid chloride is used as the total 11 compound, isobutylene or methylene cyclopropane as the olefin of general formula III, and the rearrangement of the compound of general formula IV is carried out in toluene or in a melt. Acid chlorides; 2,4,4,4-tetrahalo-butyric acid, corresponding to formula I I, are new compounds. They are obtained in a known manner by reacting tetrahalomethane with the general formula XCY where X and Y have the above values, with a compound of the general formula where Z is a chlorocarbonyl residue, a carboxyl group, an alkoxycarbonyl residue containing 1, 4 carbon atoms in an alkyl group, or a nitrile group , and the resulting compound of the general formula XcS-sno-cn-I / where X and Y have the above meanings, and Z denotes a carboxyl group, an alkoxycarbonyl residue or a nitrile group, are converted into a compound rmules VII, in which Z means / chlorocarbonyl group. Another method for the preparation of 2,4,4,4-tetrahalo-butyric acid chlorides of general formula II is that a compound of formula CH-Z 59 where Z is as defined for this symbol in general formula Vl, is attached to 1.1 -dichloroethylene and the resulting compound of the formula C1 cijC-cH -CH-z, where Z is a carboxyl group, an alkoxycarbonyl residue or a nitrile group, is converted into a compound of formula VIJ, in which Z is a chloro carboxyl group. addition of tetrahalogenmethane formula V. derivative acryl howl acid of formula VI, as well as accession dichloroacetic acid derivative of formula Via to 1,1gdihloretilenu reagents may be used in a stoichiometric amount. However, an excess amount of tetrahalo methane of formula V or a dichloroacetic acid derivative of formula Via is preferably used, for example, about 0.5 to 2-fold molar excess, and tetrahalomethane of formula V can also serve as a solvent. The addition of tetrahalomethane of formula V to the compound of formula VI, as well as the addition of the compound of formula Via to 1,1-dichloroethylene, is carried out in the presence of a catalyst. The metal of the main VM I group and the side groups Via, Vila and Ib of the Periodic Table of Elements for example iron, cobalt; nickel, ruthenium, rhodium, palladium, chromium, molybdenum, manganese and copper. These metals can be applied in elemental form or in the form of compounds. Suitable compounds of these metals are, for example, oxides, halides, sulfates, sulfites, sulfides, nitrates, acetates, citrates, carbonates, cyanides and rhodanides, as well as complex compounds with ligands such as phosphines, phosphites, benzoin, benzoyl acetonates, acetylacetonates , nitriles, isonitriles and carbon monoxide. As an example, compounds of these metals, which can be used as a catalyst, may include copper oxide, ferric oxide, bromides and, above all, monovalent and divalent copper 56 and ferrous and ferric chloride, as well as ruthenium chlorides, rhodium, palladium, cobalt and nickel, bivalent copper sulfate, bivalent and ferric sulfates, bivalent copper nitrate and ferric nitrate, manganese acetate, bivalent acetate copper, bivalently; divalent manganese, divalent copper benzoylacetonate, carboniclcyclopentadienyl iron complex, carbonylcyclopentadienyl molybdenum complex, tricar onilarilny complex chromium acetate ksempleks divalent ruthenium geksakarbonilhrom, geksakarbonilmolibden, nickel tetracarbonyl, iron pentacarbonyl, and ct bonilkobalt karbonilmarganets. Mixtures of these metals with metal compounds and / or other additives can also be used, for example, copper powder in combination with one of the above-mentioned copper compounds, a mixture of powdered copper with lithium halides such as lithium chloride, or isocyanides such as tert-butyl isocyanide, a mixture of powdered iron with ferric chloride, in some cases, with the addition of carbon monoxide, a mixture of ferrous chloride and benzoin, a mixture of divalent or trivalent iron and trialkylphosphites, mixtures of pentacarbonyl iron and iodine. It is most preferable to use salts And complexes of divalent and trivalent iron, as well as powdered iron. Typically, powdered copper, salts of monovalent and divalent copper are used, for example, cuprous chloride, cuprous chloride, cuprous bromide, cupric bromide, cupric acetylacetonate, cupric bivalent copper sulfate, cupric sulphate 9

copper no, bivalent copper nitrate

and cyanide monovalent copper.

It is particularly preferable to use powdered copper, monovalent and divalent copper chlorides and bromides, as well as Their mixtures.

These catalysts are in most cases used in an amount of about 0.01-10 mol, preferably 0.1-5 mol, based on the compound of formula III or on 1,1-dichloroethylene.

The addition reaction is carried out in an environment of organic solvents in which the catalysts are sufficiently soluble or which can form complex compounds with the catalyst but which are inert with respect to the starting compounds m. As an example of such solvents, alkyl nitriles can be mentioned, in particular alkyl nitriles containing 2-5 atoms, carbon, in particular acetonitrile, propionitrile and butyronitrile, such 3-alkoxypropionitriles; containing 1 or 2 carbon atoms in an alkoxy fragment, such as 3-methoxypropionitrile and 3-ethoxypropionitrile, aromatic nitriles and, above all, benzonitrile; aliphatic ketones containing predominantly a total of 3 to 8 carbon atoms, such as acetone, diethyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tert-butyl. ketone, such alkyl- and alkoxyalkyl esters of aliphatic monocarboxylic acids, containing a total of 2-6 carbon atoms, like methyl ester of formic acid and ethyl ester of formic acid, ethyl ester of acetic acid, n-butyl ester of acetic acid and isobutyl ester of acetic acid, and 1-acetoxy-2-methoxyethane, cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane; such dialkyl esters containing 1-4 carbon atoms in the alkyl fragments, such as diethyl ether, di-n-propyl ether and diisopropyl ether, N, N-dialkylamides of aliphatic monocarboxylic acids containing 1-3 carbon atoms in the acid moiety, for example, M, M-dimethylformamide, N, N-dimethyl acetamide, N, N-diethylacetamide and N, N-dimethyl methyl methoxyethanol, ethylene glycol dialkyl ethers and diethylene glycol dialkyl ether 6958

ryl containing 1 carbon atom in each alkyl moiety, for example ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol di-n-butyl ether, diethylene glycol diethyl ether and distilen glycol di-n-butyl ether, phosphoric acid hexamethyltriamide. Most preferably, alkyl nitriles containing 2-5 carbon atoms and 3 alkoxypropionitriles containing 1 or 2 carbon atoms in the alkoxy moiety, especially acetonitrile and 3-methoxypropionitrile, are used as solvents.

In most cases, the temperature at which the reaction is carried out is not critical and may vary within wide limits. The reaction temperature lies in the range between approximately 60 and preferably 80-170 C.

Preferably, acrylic acid chloride or dichloroacetic acid chloride is used as the compound corresponding to formulas VI and, respectively, Via. Due to this, get the desired

2,4 chloranhydride - tetrahalo-butyric acid by direct route in pure form and in high yield. Other preferred compounds corresponding to formulas VI or Via are acrylic or dichloroacetic acid. The free compounds obtained using these compounds. 2, A, t-tetrahalomasna acids immediately after this can be easily transferred by known methods to the corresponding acid chlorides, for example, by reacting with such inorganic acid chlorides as phosphorus trichloride, phosphorus chloride, phosphorus chlorine, phosgene and thionyl chloride.

Compounds of formulas VI and Via obtained in which Z is an alkoxycarbonyl residue or a nitrile group, esters or nitriles of 2, 4,4-tetrahalo-butyric acid corresponding to formula VII (Z-alkoxycarbonyl residue or

 nitrile group), is first hydrolyzed in the presence of such strong acid as concentrated hydrochloric acid, resulting in the formation of .99 the corresponding free 2, C, C-tetrahalo-butyric acid, which is then converted into the corresponding acid chloride by the above method . The reaction of the acid chloride 2,, 4, -tetrahalogenoic acid of the formula M, with the fit formula olefin is advantageously carried out in the presence of an inert organic solvent. 8 for example, halogenated, aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, chloro benzene, dichlorobenzene and trichlorobenzene, normal pentane, normal hexane, normal octane, methylene chloride, chloroform, carbon tetrachloride; 1,1,2,2-tetrachloroethane and trichlorethylene. Cycloaliphatic hydrocarbons such as cyclopent n or cyclohexane, cycloaliphatic cytones, cyclopentanone and cyclohexanone, as well as aliphatic ketones, aliphatic and cyclic ethers, alkyl nitriles and 3-alkoxy-cyan nitriles can also be used as solvents. fragment, especially acetonitrip and 3-methoxypropionitrile. It is preferable to use aliphatic, cyclooliphatic and aromatic hydrocarbons and, above all, alkanes containing 5-8 carbon atoms, benzene and toluene, in particular, normal hexane and cyclohexane as solvents. However, as a solvent, it is also possible to use an excess of initial ochefin. As organic bases, in the presence of which the acid chloride 2, k, k, 4-tetrahalogenoic acid of general formula II is reacted with an olefin of general formula III, for example, tertiary amines, namely trialkylamines containing 1-carbon atoms, are used. in particular, 2 carbon atoms in each radical, cyclic amines such as pyridine, quinoline, M-alkyl pyrrolidines, N-alkyl piperidii, N, N-dialkyl piperazines and N-alkylation of morpholines or dialkylanylins containing 1 or 2 carbon atoms in each 5-kilyl radical, or 2-radicals containing dialkylanylins containing 1 or 2 carbon atoms in each 5-kilyl radicals for example N-me ylpyrrolidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-ethylmorpholine and M, M-dimethylaniline, as well as bicyclic amidines such as 1,5-diazabicyclo 5, 4, odecanan-5 and 1, 5-diazabicylo C, 3,0 nonen-5 and such bicyclic diamines as 1, -diazabicyclo 2,2.2 octane. The reaction of the acid chloride 2, k, k, 4-tetrahalogenoic acid of general formula II with an olefin of general formula III is preferably carried out in the presence of a trialkylamine containing an I -carbon in each alkyl radical. The most preferred bases are triethylamine and pyridine. The organic base is used at least in an equivalent amount or in a slight excess with respect to the acid chloride 2, k, k, k-tetrahalo-butyric acid of general formula II. Olefins of general formula III are also used in at least an equimolar amount with respect to acid chloride 2, t ,, -tetrahalogenoic acid of general formula 1. However, in most cases it is preferable to use an excess of olefin, and, as mentioned above, olefin can also serve as a solvent; In the case of using a volatile olefin, the reaction can be carried out under pressure. -. As olefins of general formula 111, in particular, the following can be used: olefins in which one of the residues K. and R represents a methyl radical, and the other hydrogen atom or methyl radical, or R2 together form an alkylene group containing 2- 3 carbon atoms, and it can be used isobutylene, drink it, methylene cyclopropane and methylene cyclobutane. Most preferably isobutylene and methylene cyclopropane are used. I. , - The temperature at which the reaction is carried out can vary over a wide range. 3 most cases. the reaction temperature is in the range between O and pre. respectfully between 20 and 1 ° C. 2- (2CH2CH2LTrigalogenethyl) -2-. -halocyclobutan-1-ones of general formula IV. are new compounds. As a catalyst in the conversion of 2- (2, 2, 2 -trihaloethyl) -2-halogenocyclobutan-1-itE of the general formula IV to 2- (2 2 2 -trihaloethyl) -4-; iklobutan-1-ones of the general formula I acids, bases and quaternary ammonium halides can be used. The rearrangement of 2- (2 -trihaloethyl) -2-halogencyclobutan-1-ones of the general formula IV in accordance with the present invention into 2- (2, 2 2 -trigalogen-ethyl) -halogen-cyclobutan-1-ones of the general formula I is not known for monohalogenated in alpha position of cyclobutanone. It was found that, when carrying out the rearrangement in the presence of a catalyst possessing the basic properties, the CN does not split off from the trihaloethyl group. Regrouping proceeds with a high, often quantitative, yield. The rearrangement of 2- (2, 2, 2 -trihaloethyl) -2-halogenocyclobutan-1-ones of the general formula IV in 2- (2, 2, 2 / -trigalogen-ethyl) - halogenocyclobutan-1-ones of the general formula I is carried out mainly in the presence of a catalyst with basic properties. As a catalyst with basic properties, such organic bases as primary, secondary and, in particular, tertiary amines are used, corresponding to the formula / QI to QZ, in which Q. is an alkyl radical containing 1-8 atoms carbon, - cycloalkyl residue, containing in its composition of carbon atoms, benzyl residue or phenyl residue, and 0, and Q independently of one another denote hydrogen atoms or alkyl radicals containing 1-8. carbon atoms. Basic catalysts are used, for example, triztilamine, tri-n-butylamine, triisopentylamine, tri-n-octylamine, N, N-dimethylcyclohex silminemine, N, N-dimethylbenzylamine, N, N-dimethyl-2-ethylhexylamine, H, M-diethylaniline as well as such cyclic amines as pyridine, quinoline, lutidine, N-alkylmorpholine, such as N-methylmorpholine, such N-alkilpipe512 ridiny like N-methylpiperidine and N-ethylpiperidine, such N-alkylpyrrolidin like N-methylpyrrolidine and N-ethylpyrrolidine, such diamines like N, N, N, N-tetramethylethylenediamine, M, M, M, M-tetramethyl-1, D Diaminobutane, such N, N dialkylpipe azines, such as N, N dimethyl piperaaine, such bicyclic amines as 1, -diazabicyclo {2, 2.2 octane, such bicyclic amines as 1-, 5 Diazabicyclo 5,, 0 undecanan-5 and 1.5 diazabicyclo tA, 3, OJnonen -5 and, finally, such polymeric basic compounds as p-dimethylaminomethyl polystyrene. In addition, as catalysts with basic properties, in the implementation of the proposed method of rearrangement of 2- (2 2 2 -trihaloethyl) -2-V -halogencyclobutan-1-ones of the general formula IV in 2- (2,2S2 -trigalogenethyl) - -halogenocyclobutan-1-one of the general formula .1 phosphines, in particular trialkylphosphines, for example tributylphosphine, can be used. Inorganic or organic protic acids can be used as acid catalysts in the rearrangement. Suitable inorganic proton acids are, for example, hydrohalic acids such as hydrochloric, hydrobromic, hydrofluoric and iodohydrogen, nitric acid, phosphoric acid and sulfuric acid. The most preferred inorganic proton acids are hydrohalic acids. If the acid or base is used in excess, they can also act as a solvent. In addition, salts of protic acids, especially hydrohalic acids, with ammonia or nitrogen-containing organic bases, as well as quaternary ammonium halides can be used; quaternary phosphonium halides and sulfonyl halides. Aliphatic, cycloaliphatic, aryl aliphatic and aromatic primary, secondary and tertiary amines, as well as heterocyclic nitrogen-containing bases, can be used as an organic base containing nitrogen. As an example of such compounds

1391

primary aliphatic amines containing up to 12 carbon atoms, such as methylamine, ethylamine, n-butylamine, n-octylamine, n-dodecylamine, hexamethylenediamine, cyclohexylamine, benzylamine, such secondary aliphatic amines containing up to 12 atoms, can be mentioned carbon dioxide, such as dimethylamine, diethy 1amine, di-n-propylamine, dicyclohexylamine, pyrrolidine, piperidine, piperazn, morpholine, tertiary aliphatic amines, especially trialkylamines, containing 1 - carbon atoms in each alkyl radical, for example triethylamine, three -n-butylamine, N-methylpyrrolidine, N-methylmorpholine, 1, L-diazabicyclo-2.2.2 octane, hiuclidine, containing in some cases primary, secondary and tertiary aromatic amines, for example aniline, toluidine, naphthylamine, N -methylaniline, diphenylamine and M, M-diethylaniline, further, pyridine, picoline, indoline and quinoline,

As quaternary phosphonium 1 halides, for example, hexadecyl.ributylphosphonium bromide, methyltriphenylphosphonium bromide and ethyltriphenylphosphonium bromide can be used, and, for example, trimethylsulfonium iodide can be used as a syphony of halide. ,

Formula salts are preferred.

 U5

Q7

where M is a fluorine, bromine or iodine atom, especially a chlorine atom,

0, c is a hydrogen atom, an alkyl radical containing 1-18 carbon atoms, a cyclohexyl residue, a benzyl residue, a phenyl residue, or a naphthyl residue, k,

0.5 it Qy - independently of each 6t each other, hydrogen atoms or alkyl radicals containing 1–18 carbon atoms, as well as N-alkyl pyridinium halides containing 1–18 carbon atoms in the alkyl radical, in particular, the corresponding chlorides.

As an example of salts of this type, ammonium chloride, ammonium bromide, methylamine hydrochloride, and cyclo5 hydrochloride can be mentioned. one

hexylamine, aniline hydrochloride, dimethylchloride; tetraethylammonium bromide, tetra-n-propylammonium bromide, tetragne-butylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetra-n-propyl iodide mony iodide, tetra-n-butylammonium chloride trimetilgeksadetsilammony chloride benzildimetilgeksadetsilammony chloride benzildimetiltetradetsilammony chloride, benzyltrimethylammonium chloride, benzyl-tri-n-buTilammoky bromide, n-butiltri-n-propylammonium bromide, octadecyl bromide,

phenyltrimethylammonium, phenyltrimethylammonium chloride, hexadecylpyridinium bromide and hexadecylpyridinium chloride.

As additional co-catalysts may be employed are alkali halides metallov.kak potassium iodide, sodium iodide, lithium iodide, potassium bromide, sodium bromide, lithium bromide, potassium chloride, sodium .hloristy, Risto hlbg lithium, potassium fluoride, sodium fluoride and lithium fluoride .

These cocatalysts catalyze the reaction also in the absence of

ammonium salts, but in this case it is favorable to add polyethers with an open one. chain or macrocyclic (crown ethers) for a fast reaction.

Examples of such crown ethers are 15-crown-5,18-crown-6, dibenzo-18-crown-6-dicyclohexyl-18-crown-6, 5,6,1,15-Dibenzo-7 13-diaza- 1,4-dioxacyclopentadione-5, 1A-diene.

The amount of catalizer used can vary widely. In some cases, the presence of traces of catalyst is sufficient. However, in most

The catalyst is preferably used in an amount of about 0.1-15% by weight. in the calculation of the connection of the General formula VI.

15 . 9 The rearrangement can be carried out both in the melt and in the medium of an inert organic solvent. The reaction temperature during the rearrangement in the melt is in most cases in the range, mainly B-TZ C.

When rearranging in the melt, the abovementioned organic bases, preferably trialkylamines containing 1-8 carbon atoms in each alkyl radical, can be used as a catalyst, then salts of hydrohalic acids with ammonia or organic nitrogen-containing bases, for example hydrochlorides and Hydrobromides of trialkylamines containing 1-8 carbon atoms in each carbonaceous radical, and especially halides and, above all, chlorides, bromides and tetraalkylammonium iodides containing 1-18 carbon atoms in each alkyl radical.

It is preferable to use inert organic solvents, for example, such in some cases nitrated or halogenated aliphatic, cycloaliphatic or; aromatic hydrocarbons such as normal hexane, normal pentane, cyclohexane, benzene, toluene, xylenes, nitrobenzene, chloroform, carbon tetrachloride, trichlorethylene, 1,1,2,2-tetrachloroethane, nitromethane, chlorobenzene, dichlorobenzene and trichlorobenzene, such lower lower aliphatic aliphatic, such as lower aliphatic, chlorobenzene, dichlorobenzene and trichlorobenzene. containing, for example, up to 6 carbon atoms, such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and pentanol, such aliphatic diodes as ethylene glycol and diethylene glycol, such monoalkyl ethers of ethylene glycol and monoa lkilovye diethylene glycol ethers containing 1 carbon atom in each alkyl moiety ohm as monometilny ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol diethyl ether i.monoetilovy cyclic amides such as the N-methyl-2-pyrrolidone, N-acetyl-2- pyrrolidone and M-methyl-1-capro-. lactam, carbonic acid amides such as tetramethylurea and dimorpholinocarbonyl, such amides of phosphorous acid, phosphoric acid, phenyl695 6

phosphoric acid or phosphonic acids with aliphatic 1-W carbon atoms in the acid moiety as a phosphoric acid triamide, tris (dime5 tilamid) phosphoric acid, phosphoric acid trimorfolid, tripirrolinid phosphoric acid bis (dimethylamide) morpholide phosphoric acid-dimethylamide, phosphoric dietilamidmorfolid

o acid, tris (dimethylamide) phosphorous acid, tetramethyldiamide methanephosphonic acid; sulfuric acid aliphatic or aliphatic sulphate aliphatic monocarboxylic esters,.

5 cyclic polymer esters, dialkyl esters, M, N-disubstituted amides of aliphatic monocarboxylic acids and dialkyl esters of ethylene glycol and diethylene glycol.

) When rearranging in the presence of an acid catalyst, polar organic solvents can be successfully used, in particular, lower alcohols such as methyl, ethyl and butyl, M, H-dialkylMIDs of aliphatic monocarbonic acids containing 1–3 carbon atoms in the acid fragment, especially N, N-dimethylformamide, or

 dialkyl sulfoxides such as dimethyl sulfoxide. .

in an aprotic, highly polar solvent, for example, M, N-disubstituted amides of aliphatic monocarboxylic acids, cyclic amides, amides of carbonic acid, amides of phosphorous acid, phosphoric acid, phenylphosphonic acids or aliphatic phosphonic acids, amides of sulfuric acid or aliphatic acids and sulfuric acids or aliphatic acids and sulfuric acids or aliphatic acids. (acids, as well as dialkyl sulfoxides, e.g. dimethyl sulfoxide, the reaction proceeds without adding a base or to 1slot, in these cases the solvent acts as a catalyst.

However, in most cases, when conducting a rearrangement in the presence of an inert organic solvent, a catalyst is added, a predominantly organic base with a pKa value above 9, in particular, such trialkylamines containing 1-8 carbon atoms in each alkyl fragment, such as triethylamine, tri-n -butylamine and tri-n-octylamine | further, hydrohalic acids, especially hydrochloric and hydrobromic and also tetraalkylammonium halides, especially tetraalkylammonium chloride, bromide and iodide, containing 1-18 carbon atoms in each alkyl fragment. Preferably, aliphatic alcohols containing l-j carbon atoms, toluene, xylenes, chlorobenzene, dioxane, acetonitrule, 3 methoxypropionitrile, ethylene glycol diethyl ether and diisopropyl ketone are used as solvents. The reaction temperature in the case of the rearrangement in an inert organic solvent medium is in most cases in the range between 0 and 150 ° C, preferably between about 80 and .. The structure of all the compounds obtained is confirmed by spectral methods of research. Example 1, A. Preparation of chlorine anhydride 2,, ft, -tetrachloric acid. , 5 (5 mol) of acrylic acid chloride (purity corresponds to the technical product), 1.5 liters of carbon tetrachloride, 1.5 liters of acetic acid nitrile, and 30. Monovalent copper chloride is kept for 2k h. The reaction mixture is filtered and the resulting clear filtrate is evaporated in a water jet vacuum. The resulting residue is distilled. As a result, 922 g (7b of the theoretically calculated value) of acid chloride 2,, A, -tetrachloromear acid, are obtained. T. Kip. product 7880 with / 11 mm Hg. The acid chloride 2, k, k, t-tetrachloroic acid can also be obtained as follows. 90.5 g (1 mol) of acrylic acid chloride, 0.5 l of carbon tetrachloride, 0.2 l of butyronitrile and 3 g of powdered copper are heated for 20 hours at 115 ° C. The reaction mixture is filtered and the filtrate is evaporated. The resulting residue is subjected to distillation. As a result, 167.8 g (B9 of the theoretically calculated value) of acid chloride 2,4, -tetrachlorohydric acid, b.p. which is 80-81 0/2 mm Hg. If, all other things being equal, the powdered copper is replaced by monovalent copper chloride, and the butyronitrile is replaced by 3 methoxypropionitrile ,. Then, at a yield of 711 from the theoretically calculated value, the acid chloride 2, D, 4, and tetrachloroformate is obtained. sour, you. 126 g (1 mol) of 2,4, +, 4-tetrachloroacid acid, 600 g of thionyl chloride and 1 ml of N, N-dimethylformamide are heated for 2 hours at. The residue obtained after distilling off the excess amount of thionyl chloride is distilled . As a result, 227.6 g (93 of the theoretically calculated value) of acid chloride 2.4, - tetrachloric acid, t, kip. which is 90-91 ° C / 15 mm Hg. 145.9 g (1.5 mol) of 1,2-Aichlorethylene, 147.4 g (1 mol) of dichloroacetic acid chloride, 200 ml of acetic acid nitrile and 3 g of copper monovalent chloride are heated for 8 hours at .130 ° C. Then the reaction mixture is evaporated and the resulting residue is subjected to fractional distillation. As a result, the acid chloride of 2, 4,4,4-tetrachlorobutyric acid is obtained in the form of a colorless liquid. T. bale product delivers C / 11 mm Hg. B. Preparation of 2-chloro-2- (2, -trichloroethyl) -3,3-dimethylcyclobutan-1-one. 280 g of isobutylene is added to 122 g (0.5 mol) of 2,4,4,4-tetrachlorobutyric acid chloride in 600 ml of cyclohexane in an autoclave. For 4 hours, a solution of 51 g (about 5 mol) of triethylamine in 500 ml of cyclohexane is pumped into the autoclave. The reaction mixture is then kept at 65 ° C for an additional 3 hours. The triethylamine hydrochloride chloride which is precipitated is filtered off and the resulting filtrate is evaporated. The crystalline formed. the product is filtered off. 79.4 g of 2-chloro-2- (2, 2, 2-trichloroethyl) -2,3-dimethylcyclobutan-1-one with m.p. 75-7bS (60% of the theoretically calculated value) spectrum (SCHEZ), see 1805; Found,%: C36 ,; H 3.9; About cr 53.5. . CgHioCl.O (mol. -Bes. 263.98). Calculated: C ST, 40; H 3.82, O 6.02, CE 53.72. With the same principle of operation using the different bases, the following outputs of 2- (2 2, 2-trichloroethyl) -3.3 dimethyl-2 chlorocyclobutan-1-one are taken out. Base Yield,% of theory Trimethylamine 8 Tributylamine N-Methyl-piperid Pyridine C. Preparation of 2- (2, 2, 2-trichloro ethyl) 3.3 Dimethyl-4-chloro-cyclobutane -1-one. :. . 132 g (0.5 mol) of the resulting 2-chloro (2, 2, 2-trn-chloroethyl) -3,3-dimethylcyclobutan-1-one is dissolved in 700 ml of toluene. Cooked. the solution is mixed with 1 ml of triethylamine and the reaction mixture is heated at its boiling temperature with a reflux condenser. After reaction for 13 hours, 1 ml of three ethylamine is again added to the reaction mixture and the reaction mass is heated at boiling point for 7 hours. After cooling, the reaction mixture is washed first with diluted hydrochloric acid and then with water, dried and evaporated.

Solvent

Ethanol

Dimethyl sulfoxide

Dimethylformamide

Toluene

Methoxypropionitrile

Toluene

Toluene

Toluene

Toluop

Output, from theory

77

68

82

73

71

82

86,

81

89

92 The solidified residue, according to chromatography in a thin layer, which is a homogeneous substance (12 g, 91 of the theoretically calculated value), is crystallized from normal hexane. The result 10.8 g of 2- (2, 2,2-trichloride |; yl) -3,3-dimethyl-chlorocylobutan-1-one, so pl. which is 5b-57 C: Found,%: C 36.6, H 3,8) O 6,2; Ct 53.6. CVI, (mol. Weight 2bЗ, 98). Calculated: C, 3.6, O; H 3.82, O 6.02; From 53.72. The above compound is also prepared as follows. 2. g (0.01 mol) 2-chloro-2- (2, 2, 2 ttrichloroethyl) -3.3 dimethylcyclobutan-1-it at 12 C is stirred for 6.5 h with 220 mg (0.008 mol) chloride tetra-n-butylammonium. The cooled melt is heated with hot normal m hexane, the reaction mixture is filtered, resulting in a clear filtrate. While cooling the filtrate, 2.19 g (83% of the theoretically calculated value) of 2- (2, 2, 2-trichloroethyl) -3.3 was isolated in the sediment. Dimethyl-4-chlorocyclobutan-1-one, mp. which is 53-5b C. With the same principle of operation using different catalysts and solvents, the following yields of 2t- (2, 2, 2 -trichloroethyl) -3, 3-Dimethyl-chlorocycrrbutan-1-one are obtained.

219

Example 2. In a 6.3 liter autoclave, put g of propylene, g (1 mol) of acid chloride 2 ,,, tetrachloroacid and 1.25 l of cyclohexane. At 50 t for A h, a solution of 101 g (1 mol) of triethylamine in 1 l of cyclohexane is pumped into the autoclave and immediately after that the reaction mixture is kept for 3 h at 50 C. Then the reaction mixture is filtered and the resulting filtrate is washed with dilute hydrochloric acid and then with water, dried over magnesium sulphate and evaporated. The residue obtained is crystallized from normal hexane. The result is 77.2 g

2-chloro-2- (2,2,2-trichloroethyl) -3-methylcyclobutan-1-one, mp, which is 80-81 C.

50 g (0.2 mol) of the obtained 2-chloro-2- (2.2 2-trichloroethyl) -3-methylcyclobutan-1-one in 500 ml of toluene is mixed with 1 ml of triethylamine and stirred for 18 hours at a temperature in the bath 120, C. After cooling, the reaction mixture is filtered and a clear filtrate is obtained, which is washed first with a dilute hydrochloric acid solution and then with water. The washed solution is heated at boiling point with activated carbon for a short time, then the filtrate is evaporated. After distillation of the residue, 38.7 g (77 of the theoretically calculated value) of 2- (, 2-trichloroethyl) -1 methyl-chlorocylobutan-1-one is obtained, b.p. which is 130131 ° C / 12 mm Hg.

According to the NMR spectrum and gas chromatography, the compound consists of three stereoisomers in a weight ratio of 13: 3. Example 3: A solution of 25.3 g (0.25 mol) of triethylamine in 50 ml of normal hexane is added over 7 hours while stirring. 25 g (0.37 mol) of methylenecyclobutane and 61.6 g (0.25 mol) of acid chloride 2, k ,, C-tetrachlorobutyric acid in 200 ml of normal hexane, which is kept in the boiling state a fridge. After further stirring for 2 hours at reflux, still

769522

hot reaction. the mixture is freed by filtration from the resulting ammonium salt. The filtrate is evaporated to approximately 1/3 volume. Upon cooling, precipitates precipitate in crystalline form of 1-chloro-1- (2, 2.2-trichloroethyl) -spiro 3.3 heptane-2-one of formula

ten

ABOUT

 ,

C1

m.p. which is 93-9 C. A solution of 27.6 g (0.1 mol) of the obtained 1-chloro-1 - (2, 2, 2-trichloroethyl) -spiro (3.3 heptan-2-one in 100 ml toluene together with 0.93 g (5 mmol) of tributylamine is heated for 9 hours at the boiling point of the reaction mixture with a reflux condenser. After that, the reaction mixture is evaporated and the resulting residue is distilled in vacuo to give 1-chloro-3- (2V , 2, 2-trichloroethyl) -spiro 3, s1 heptane-2on of the formula

C1-grSsO

SNGSS

five

in the form of a slightly oily yellow oily product with a boiling point. 85-90 0 / 0.6 mmHg, 1.52it2.

Example k. Q autoclave to 122 g

0 (0.5 mol) of acid chloride 2, k, k, k-tetrachlorobutyric acid in 600 ml of cyclohexane is fed under the pressure of 280 g of isobutylene. At 65 ° C for a period of h is served by a pump

51 g (0.5 mol) of triethylamine in 500 ml of cyclohexane. Then the reaction mixture was kept for 3 hours at 65 ° C and immediately after that it was heated at 125 ° C for 18 hours. At the same time, for all 3 hours, with the help of a pump, 2.0 g of triethylamine in 50 ml of cyclohexane are fed into the autoclave. The reaction mixture is then poured onto ice, acidified with hydrochloric acid, followed by extraction with cyclohexane. One stripped off extract in a mixture of toluene and cyclohexane (1: 1 volume ratio) is filtered through 1 kg of silica gel in order to remove strongly polar impurities. After that, the filtrate is evaporated and the resulting residue is crystallized from normal reKcaHBj. As a result, 31.8 g of 2- (2, 2, 2-trichloroethyl) 3 3 Dimethyl-4-chloro-cyclobutan-1-one is obtained from ... m.p. which is Zb-Zus. EXAMPLE 5: A. 26.1 g (99 mmol) of 2- (2, 2 2.-trichloroethyl) -3 3 dimethyl-chlorocylobutanone are added with stirring and at a temperature of 11 ° C to 2 BO 10 ml a solution of sodium hydroxide. Within 2 hours, the temperature is raised to 28 ° C and then lowered to 20 ° C over the next 2 hours. The reaction mixture is diluted with 200 ml of water, washed with diethyl ether, acidified with concentrated hydrochloric acid to a strong reaction, and then extracted with diethyl ether. The extract is washed with water, dried over magnesium sulphate and evaporated. As a result, 2.3 g (100% of the theoretically calculated value) of a pale yellow colored residue (Mp 80-81 s) are obtained, the only of which are cis and trans-2- (2 2.2 - trichloroethyl) 3J3 Dimethylcyclopropanecarboxylic acid. Using fractional crystallization or column chromatography, the mixture can be separated into pure cis and trans compounds. ti J, B. 8.0 g (30.3 mmol) of 2- (2, 2, 2-trichloroethyl) -3.3 Dimethyl-chlorocylobutanone in 400 ml of acetone and IOO ml of water are irradiated through a glass of Pyrex with a Phillips lamp with a capacity of 125 watts until chromatography is no longer able to detect the presence of starting material. The reaction mixture is then evaporated and the resulting residue is converted to an acid by analogy with that indicated in paragraph A. The result is 6.95 g (93% of the theoretically calculated value) cis / trans mixture of 2- (2-trichloroethyl) -3, 3-Dimethylcyclopropanecarboxylic acid. Example 6. g (0.5 mol), 2-bromo-4j chloride, trichloromethyl acid, 280 g (5 mol) of isobutylene, and 600 ml of cyclohexane are introduced into an autoclave. When for 9 5,2k h in the aktoklav served using a pump solution 51, (0.5 mol) of triztilamin in 600 ml of cyclohexane. After that, the reaction mixture is further stirred for 3 hours at the same temperature. Then the reaction mixture is filtered. The filtrate is evaporated and the resulting residue is crystallized from normal hexane. As a result, 7.5 g (k%% of the theoretical value) of 2-bromo-2- (2, 2, 2-rh-chloroethyl) -3,3-dimethylcyclobutane are obtained in the form of a light yellow colored powdery substance. M.p. the product is it6-i | 9 C. 20 g (0.065 mol) of 2-bromo-2- (2-trichloroethyl) -313 dimethylcyclobutanone and 5 g of tetrabutylammonium bromide are stirred for 30 minutes at 80 Siv for a further 10 minutes. The solidified melt is subjected to chromatography over silica gel (zoning is carried out with a mixture of toluene and cyclohexane, taken in a 1: 1 ratio). In this way, 2- (2, 2, 2-trichloroethyl) -3,3-dimethyl-4-bromocyclobutanoyl is obtained, which crystallizes on a hundred scientific research institutes. M.p. product is. Example 7. 90.5 g {1 mol) of acrylic acid chloride 364.8 g (1.1 mol) of tetrabromomethane, 200 ml of acetonitrile and 5.0 g of cuprous chloride are heated for 6 hours at. After cooling, the reaction mixture is directly distilled yut. As a result, 136.6 g (33% of the theoretically calculated value) of the acid chloride 2,4,4,4 tons of trabromic acid with a boiling point of 39% are obtained. 135-1 0 with at 12 mm Hg. 350 ml of cyclohexane is saturated with isobutylene at room temperature. In the prepared solution, 2 g (0.1 mol) of acid chloride 2 ,,, 4-tetrabromobutyric acid is dissolved. Then, at room temperature, with stirring and the introduction of a weak current of isobutylene, 10.1 g (0.1 mol) of triethylamine in .50 ml of cyclohexane is added dropwise to the resulting solution. The resulting reaction mixture is stirred for 3 hours and, immediately thereafter, it is mixed with water. The organic layer is separated, washed with water, dried over magnesium sulfate and then evaporated. The residue is filtered through silica gel (eluting agent is a mixture of cyclohexane and toluene, taken in a 1: 1 volume ratio). The filtrate is evaporated and the resulting residue is crystallized from normal hexane. 3, 2-bromo-2-2, 2,2-tribromoethyl-Z.ZDimethylcyclobutanone is obtained, m.p. which is B1-63 ° C. 9.6 g (21.8 mmol) of 2-bromo-2- (, 2, 2-tribromoethyl) -3.3 Dimethylcyclobutanone is stirred in 2.0 g of tetrabutylammonium bromide for 30 minutes at 90 ° C. The cooled melt is chromatographed over silica gel (elution is carried out with a mixture of toluene and cyclohexane, taken in a 1: 1 ratio). The result is 2,2-tribromoethyl), 3 Dimethyl-A-bromocyclobutanone in the form of a slowly crystallizing oily substance. The product obtained is recrystallized from a mixture of diethyl ether and normal hexane, after which it has a melting range of 91-93 ° C. Example 8. To a solution of 14 g (o, 17 mol) of methylene cyclopentane and 26 j4 g (0.1 mol) of acid chloride 2,4, t of 4-tetrachloroacid in 220 ml of cyclohexane over 2 hours with stirring and 65 ° С added 10.1 g (0.1 mol) of triethylamine in 100 ml of cyclohexane is dropped in drops. Not: After this, the reaction mixture is stirred for the next 3 hours at the same temperature. Then the reaction mixture is washed with dilute hydrochloric acid and then with water, the organic solution is dried over magnesium sulfate and evaporated. The residue obtained is crystallized from normal hexane. The result is 16.6 g of 1-chloro-1- (2 2, 2-trichloroethyl) -spiro |, C octan-2-one of the formula C1 Ti mp. the product is 7012, 0 g (0 mol) 1-chloro-1- (2 2,2-trichloroethyl) -spiro-octan-2-one is mixed with 3.6 g of tetrabutylammonium chloride at a bath temperature. After 1.5 h, the reaction was chromatographed over silica gel (elution was carried out with a mixture of toluene and cyclohexane, taken in a 1: 1 ratio). The specified method. Ohm, 9.7 g (811 of the theoretically calculated value) of 1-chloro-3- (2, 2, 2-trichloroethyl) -spiro f.tio Fetan-2-one of formula C1-V-t O are obtained in the form of a colorless oily substance. Example 9-A autoclave with a capacity of 2.5 liters is placed 33.6 g (0.62 mol) of methylenecyclopropane and 152 g (0.62 mol) of 2,4,4 chloride, chlorophylic acid and 620 ml of normal pentane. At 60 ° C for 6 hours, a solution of b2.8 g (o, 62 mol) of triethylamine in 120 ml of normal pentane is fed into the autoclave by means of a pump, and the reaction mixture is then kept for 6 hours at 60 ° C. Then the reaction mixture is filtered, the filtrate is evaporated and the resulting residue is subjected to distillation in vacuo. Immediately after this fraction with so Kip. in the area of C / 0.09 mm Hg, chromatography is carried out on 250 g of silica gel with a mixture of hexane and toluene containing 50 wt. last one. The pure fraction is evaporated and the residue obtained is subjected to distillation. The result is 1-chloro-1- (2,2,2 -trichloroethyl) -spiro [3.2 hexane-2-one of the formula CHjCCla with t. Kip. 70-71C / 0.08 mmHg A solution containing 11.0 g (42 mmol) of 1-chloro-1- (2.2H2-trichloroethyl) -spiro II, 2 hexan-2-one and 1.17 g (6.3 mol) of tributylamine in 15 ml of toluene, It is heated for 5 hours at reflux temperature. After cooling, the reaction mixture was diluted with normal pentane. The solution is washed with 2 n.

Claims (5)

Formula 'of the invention ²⁸ arguments Cij-Cj at a temperature of 20 C to the boiling point of the reaction mixture and the obtained 2- (2 *, 2 *, 2-trihaloethyl) -2-halogenocyclobutan-1-one of the general formula IV H OXvCVC-C = 0 Ri-lp-CH ₂ " I Rl where R _o R _t , X and Y have the above meanings, are rearranged at 80-125 C in the presence of a trialkylamine with 1-4th carbon atoms i in the alkyl groups or trialkylphosphine with 1-4th carbon atoms in the alkyl groups, or pyridine, or lutidine, or morpholine, or N-methylpiperidine, or dimethylaniline, ₍ or dimethyl sulfoxide, or hydrogen halide, or tetraalkylammonium halide with 1-4 carbon atoms in the alkyl groups. 2. The method according to π. 1, 2j and the fact that in the general formula are 2,4,4,4-tetrachlorobutyric acid acid chloride. ·· 3 · Pop. ^ characterized in that isobutylene is used as the olefin of the general formula I I I., 4. The method of pop. 1, with the fact that methyl encyclopropane is used as the olefin of general formula 111. 5 · 'Method pop. ^ characterized in that the process of rearrangement of the compounds of General formula IV is carried out in toluene or in a melt.