JPH034071B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to novel substituted 5-haloalkylpyridines and methods for producing the same.

This novel 5-haloalkylpyridine is represented by the following formula.

In the formula, R is a _C2 - _C10 -alkyl group homogeneously or heterogeneously substituted with 1 to 21 halogen atoms, and X is a halogen.

Halogen atoms or halogens include fluorine,
Chlorine or bromine are preferred.

Of interest are compounds of the formula in which R is an ethyl group homogeneously or heterogeneously substituted by 1 to 5 fluorine or chlorine atoms and X is fluorine or chlorine. Specifically, R is −CH ₂ −
CF ₃ , CF ₂ −CF ₂ Cl, −CF ₂ −CFCl ₂ , −CCl ₂ −
CCl ₃ , −CF ₂ −CCl ₃ , −CF ₂ −CH ₃ , −CCl ₂ −CH ₃ ,
A compound which is a group selected from the group consisting of _-CF2 - _CF3 , _-CH2 - _CH2Cl , _-CH2 - _CHCl2 or _-CH2 - _CCl3 .

Particularly preferred are compounds of the formula in which X is chlorine.

The compounds of the formula can be used as raw materials for the preparation of various active substances, in particular substances effective for the protection of plants, such as insecticides, herbicides, fungicides, after one or more intermediate steps.

For example, starting from a compound of formula (In the formula, R ₁ and R ₂ are hydrogen, methyl group, or halogen, R ₃ and R ₄ are hydrogen or halogen, R ₅ is chlorine, and R has the same meaning as in the formula.) A useful insecticide can be obtained as shown in

Chloropyridines substituted with trichloromethyl or trifluoromethyl groups have hitherto been produced only through a complex number of steps. Chlorination of 3-methylpyridine generally produces several isomers in addition to the desired compound. Chlorination of 2,3-dichloro-5-methylpyridine yields 2,3-dichloro-5-trichloromethylpyridine, which can be converted into 2 by replacing the chlorine atom of the trichloromethyl group with a fluorine atom. , 3-dichloro-5-trifluoromethyl-pyridine (see for example European Patent Publication No. 004414). 2-halo-5-trifluoromethylpyridine and 2,3-dichloro-5-trifluoromethylpyridine are prepared in a similar manner according to DE 2812607.

Furthermore, halogen-substituted 5-trifluoromethyl-
and 5-difluoromethyl-pyridine and the process for its preparation are known from published UK Patent Application No. 2002368.

According to the invention, compounds of formula are prepared by reaction of aldehydes of formula with acrylonitrile. In this reaction, an addition reaction first forms an intermediate of the formula which is then cyclized - optionally in situ - to give a pyridine compound of the formula.

As can be seen from the above reaction scheme, when the operation is carried out in situ, ie without isolating the intermediate of the formula where X is chlorine, compounds of the formula where X is chlorine are obtained. If an intermediate of the formula is isolated, it can be reacted with a hydrogen halide HX to obtain a compound of the formula in which X represents not only chlorine but also fluorine or bromine. In addition, in the compound of the generated formula, the group R can be further halogenated, preferably chlorinated, if desired, or the halogen atom present in the R group can be replaced with another halogen atom, preferably chlorine with a fluorine atom, Substitution can be made to obtain other compounds of the corresponding formula.

In the above formulas and, R represents the same meaning as in the formulas.

R is −CH ₂ −CCl ₃ , −CH ₂ −CHCl ₂ or −
Aldehydes of the formula CH ₂ -CH ₂ Cl are preferred as raw materials. The pyridine of the formula obtained by the addition reaction of this preferred aldehyde with acrylonitrile and the cyclization of the addition product of the formula can be chlorinated in a particularly advantageous manner to produce 2,3-dichloro-5-(pentachloroethyl)-pyridine. In this compound, the chlorine atom in the pentachloroethyl side chain can be preferably replaced with a fluorine atom by a conventional fluorination method. The number of fluorine atoms introduced by substitution depends on the selected fluorination conditions.

Trichloroformylbutyronitrile 2,3,
A structurally similar sequential reaction to 5-trichloropyridine is described in European Patent Publication No. 12117. However, the cyclization of the present invention with the formation of an aromatic ring to give pyridines of formula was unexpected. Rather, the formation of a 2-pyridone derivative was expected. The reaction process according to the invention is therefore quite surprising.

The novel aldehydes of the formula can be prepared by the reaction of trichloroacetaldehyde with the corresponding ethylenically unsaturated compound, e.g. (wherein Y is hydrogen or halogen, preferably chlorine).

Addition reactions to form compounds of formula can be carried out in open or closed systems, preferably at temperatures of 70-160°C. The addition reaction is preferably carried out in a closed system under a pressure corresponding to the reaction temperature, for example 1-30 bar.

According to the invention, the catalyst used for the addition reaction is a metal of the main group and subgroups a, a, b and b of the periodic table, such as iron, cobalt, nickel, ruthenium, palladium, chromium, molybdenum, manganese, copper and zinc. These metals may be used in their elemental state or in the form of suitable compounds, such as oxides and halides, sulfates, sulfites, sulfides, nitrates, acetates, stearates, citrates, carbonates. , salts such as cyanide and rhodanide, and phosphine,
It is used in the form of complexes with ligands such as phosphites, benzoyl- and acetyl-acetonates, nitriles, isonitriles and carbon monoxide.

Examples include: copper() oxide or iron() oxide; copper()-, copper()
-, iron () - and iron () - bromide, - iodide and especially - chloride, zinc chloride and chlorides of ruthenium, rhodium, palladium, cobalt and nickel; copper () sulfate, iron () - and Iron () - sulfate; copper () nitrate and iron () nitrate; manganese () acetate, copper ()
Acetate, copper () stearate, iron () citrate and copper () cyanide; ruthenium () dichloro-tris-triphenylphosphine, rhodium dichloro-tris-triphenyl-
Phosphine; chromium- and nickel-acetylacetonate, copper ()acetylacetonate,
Iron () acetylacetonate, cobalt ()
- and cobalt ()-acetylacetonate,
Manganese () acetylacetonate and copper () benzoylacetonate; iron carbonyl-
Cyclopentadienyl complexes; molybdenumcarbonylcyclopentadienyl complexes, chromium tricarbonyl aryl complexes, ruthenium ()acetate complexes, chromium- and molybdenum hexacarbonyls, nickel tetracarbonyls, iron pentacarbonyls, and cobalt- and manganese-carbonyls.

It is also possible to use mixtures of the metals mentioned above with metal compounds and/or other additives. That is, for example, a combination of copper powder and the above-mentioned copper compound; a mixture of copper powder and a lithium halide such as lithium chloride or an isocyanide such as t-butyl isocyanide; a mixture of iron powder and iron () chloride; Mixture with optional addition of carbon monoxide; mixture of iron() chloride and benzoin; iron()-
Alternatively, mixtures of iron() chloride and trialkyl phosphite; and mixtures of iron pentacarbonyl and iodine can be used.

The following are particularly preferred; copper powder, bronze, copper() chloride, and iron()- and iron()-
Chloride and iron powder; Ruthenium () chloride,
Ruthenium() dichloro-tris-triphenylphosphine, copper powder, bronze, copper()- and copper()-salts and complexes, such as copper() chloride, copper() chloride, copper() bromide and copper ()bromide; copper()acetate, copper()acetylacetonate, copper()benzoylacetonate, copper()sulfate, copper()nitrate, copper()cyanide and copper()iodide.

More specifically, the following are preferred: copper powder, bronze, copper ()- and copper () chlorides and -bromides and copper () iodide, and mixtures thereof.

Catalysts are typically about 0.01 to
It is used in an amount of 10 mol%, preferably 0.1-5 mol%.

The addition reaction between the aldehyde of the formula and acrylonitrile is advantageously carried out in the presence of an inert organic solvent. A suitable solvent is one in which the catalyst is sufficiently soluble or capable of forming a complex with the catalyst and is inert to the reaction reagents. Examples of suitable solvents are nitrites of alkanecarboxylic acids, especially those having 2 to 5 carbon atoms, such as for example acetonitrile, propionitrile and butyronitrile;
3-Alkoxypropionitriles in which the alkoxy group has 1-2 carbon atoms, such as 3-methoxypropionitrile and 3-ethoxypropionitrile; aromatic nitriles, especially benzonitrile; total number of carbon atoms in 3-8 aliphatic ketones, such as acetone, diethyl ketone, methyl isopropyl ketone, diisopropyl ketone or methyl-t-butyl ketone; alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total number of 2 to 6 carbon atoms, such as methyl formate and - Ethyl esters, methyl acetate, -ethyl, -n-butyl and -isobutyl esters, and 1-acetoxy-2-methoxyethane; cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxane; each alkyl group has from 1 carbon atom to dialkyl ether of 4, such as diethyl ether,
Di-n-propyl ether and diisopropyl ether; N,N-dialkylamides of alkanecarboxylic acids in which the alkyl group has 1 to 3 carbon atoms;
For example, N,N-dimethylformamide, N,N-
Dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide; ethylene glycol and diethylene glycol dialkyl ethers in which each alkyl group has 1 to 4 carbon atoms, such as ethylene glycol dimethyl ether, -diethyl ether and -di-
n-butyl ether; diethylene glycol diethyl ether and -di-n-butyl ether;
Phosphoric acid-tris-N,N-dimethylamide (hexametapol).

It is also possible to use excess acetonitrile as solvent.

Preferred solvents for the addition reaction are alkanecarboxylic acid nitriles having 2 to 5 carbon atoms, and 3-alkoxypropionitriles in which the alkoxy group has 1 to 2 carbon atoms, especially acetonitrile, butyronitrile and 3-methoxypropionitrile, or the reaction Acrylonitrile is used as a reagent.

The addition product of formula is a new compound. This compound has been developed for the synthesis of compounds of the formula: The cyclization of compounds of the formula can be carried out in open or closed systems at temperatures of about 0 to 220°C, especially 100 to 200°C. This cyclization is preferably carried out in an open system,
In that case, the reaction is carried out in the presence of a hydrogen halide or with a substance that generates a hydrogen halide under the reaction conditions, such as phosgene, boron trichloride, aluminum chloride, a trialkyl group in which each alkyl group has 1 to 4 carbon atoms. ammonium chloride, phosphorus pentachloride,
It is advantageous to carry out in the presence of phosphorus oxychloride, phosphorus trichloride or the corresponding bromine or fluorine compounds. The cyclization reaction is preferably carried out in the presence of hydrogen chloride, hydrogen bromide or hydrogen fluoride.

Preferably, the cyclization reaction is carried out by simply heating the compound of the formula in the liquid or gas phase without the addition of a solvent. However, this reaction can also be carried out in the presence of an organic solvent. Suitable organic solvents are, for example, chlorinated aliphatic hydrocarbons (such as chloroform, methylene chloride and tetrachloroethane); N,N-dialkylamides of alkanecarboxylic acids having 1 to 3 carbon atoms (N,N-dimethylformamide, N,N-dimethylformamide, etc.);
N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide, etc.; cyclic amide (N-methyl-2-
pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-ε-caprolactam, etc.); amides of carboxylic acids (tetramethylurea and dimorpholinocarbonyl, etc.); phosphorous acid, phosphoric acid, phenylphosphonic acid, carbon atoms of alkyl groups number 1-3
Amides (phosphoric triamide, phosphoric acid tris-(N,N-dimethylamide), phosphoric acid trimorpholide, phosphoric acid tripyrrolinide, phosphoric acid tris-(N,N-dimethylamide), methane) of alkylphosphonic acids of phosphonic acid-bis-(N,N-dimethylamide), etc.); amides of sulfuric acid, aliphatic or aromatic sulfonic acids (tetramethylsulfamide, methanesulfonic acid dimethylamide or p
-toluenesulfonic acid amide, etc.); aliphatic ketone,
Cyclic ethers, dialkyl ethers, and ethylene glycol and diethylene glycol dialkyl ethers of the aforementioned types, phosphorus trichloride and phosphorus oxychloride.

Preferred solvents for the cyclization reaction are chloroform, methylene chloride, cyclic ethers and dialkyl ethers in which each alkyl group has 1 to 4 carbon atoms, especially dioxane and diethyl ether, and N of alkane carboxylic acids having 1 to 3 carbon atoms. , N-dialkylamides, especially N,N-dimethylformamide.

The process according to the invention can advantageously be carried out by first isolating the compound of the formula formed by the addition reaction and then cyclizing this compound in a second step. The individual steps are carried out as described above.

An advantageous embodiment of the process according to the invention is to prepare an aldehyde of the formula with acrylonitrile in a closed system in the solvent acetonitrile, butyronitrile or 3-methoxypropionitrile, such as copper powder, bronze, copper()- or copper(). 70 to 70 in the presence of 0.1 to 6 mol% of - chloride or - bromide or copper () iodide or in the presence of mixtures of these substances
It consists of reacting at a temperature of 160°C. After separation of the solvent, the compound of the formula thus obtained is then heated in the open system in the presence of hydrogen halide or in the presence of a substance that produces hydrogen halide under the reaction conditions at a temperature of 100 to 200 °C. cyclization to give a compound of formula.

However, when X is chlorine, it is possible to omit the isolation of the addition product of the formula and perform the addition reaction and cyclization reaction in one operation. In this case, the reaction to obtain the pyridine of the formula from the aldehyde of the formula and acrylonitrile is carried out at a temperature of 70 to 220°C, especially 130 to 200°C.
It is preferable to carry out the reaction at a temperature of . This method can be performed in an open or closed system. When the reaction is carried out in an open system, the reaction can be advantageously carried out in the presence of hydrogen chloride or a substance that produces hydrogen chloride under the reaction conditions.

Examples of such substances are phosgene, boron trichloride, aluminum chloride, trialkylammonium chlorides in which each alkyl group has 1 to 4 carbon atoms, phosphorus pentachloride, phosphorus oxychloride or phosphorus trichloride. The single-step preparation of the pyridine of the formula, however, is preferably carried out in a closed system under a pressure corresponding to the reaction temperature at hand. The pressure depends on the reaction temperature and ranges, for example, from 1 to 50 bar. Particular preference is given to synthesizing the compounds of the formula in a single step in a closed system under a pressure of 1 to 30 bar. The single-step synthesis described above can also advantageously be carried out in the presence of a catalyst and in the presence of an inert organic solvent. Suitable catalysts and solvents are of the type described above, and what has been said above regarding preferred catalysts and amounts of catalyst also applies exactly.

Preferred solvents when carried out in a single step are alkanecarboxylic acid nitriles having 2 to 5 carbon atoms;
and 3- with an alkoxy group having 1 to 2 carbon atoms.
It is an alkoxypropionitrile. Particularly suitable solvents are acetonitrile, butyronitrile and
- methoxypropionitrile, or excess acrylonitrile used as a reaction reagent.
After the reaction is complete, the chloropyridine of the formula can be isolated in a conventional manner, for example by distilling off the solvent and purifying the crude product by distillation or steam distillation.

A further advantageous embodiment of the process according to the invention is the direct reaction of an aldehyde of the formula with acrylonitrile to give a pyridine of the formula, the reaction being carried out in acetonitrile, butyronitrile or 3-methoxypropionitrile as solvent. , copper powder,
In the presence of bronze, copper()- or copper()-chloride or-bromide or copper()-iodide, or mixtures of these substances at 130-200°C, in a closed system corresponding to the reaction temperature at hand It is carried out under pressure.

The compound of the formula produced by the above method can be prepared by further halogenating the side chain group R on the pyridine ring, or substituting the halogen atom in this R group with another halogen atom, if desired. , can be converted into other compounds of different formulas within the scope of the invention. This halogenation reaction and halogen exchange reaction are carried out by methods known per se. For example, a hydrogen atom in the R group can be replaced with a halogen atom by halogenation reactions such as chlorination and bromination. The halogen exchange reaction of the R group is preferably carried out to introduce a fluorine atom, such as by substituting a halogen atom, such as a chlorine atom, with a fluorine atom using a suitable metal fluoride.

Reference example (Manufacture of raw material compound) Manufacture of 2,2,4,4,4-pentachlorobutyraldehyde a) Add 10 g of HCl gas to 200 ml of dimethylformamide while cooling, then add 10 g of chlorine at 60 to 65°C.
will be introduced. Next, 2,4,
210g of 4,4-tetrachlorobutyraldehyde
in 300 ml of dimethylformamide is added dropwise to the slightly yellow solution, and at the same time approximately an aliquot of chlorine is introduced until the reaction solution remains slightly yellow. The temperature is kept at 65° C. for 1 hour and the reaction mixture is then steam distilled. The distilled organic phase was separated and rectified under vacuum to yield a pale yellow oil b.
Collect p.15mm at 95-99°C.

b) Vinylidene chloride 145.3g, trichloroacetaldehyde 148.0g, copper () chloride 3.0
g and 300 ml of acetonitrile are heated at 125° C. for 12 hours in an enamel autoclave.
The solvent is then distilled off under a water jet vacuum and the residue is taken up in 500 ml of diethyl ether. After separating off the precipitated copper sludge, the diethyl ether is distilled off and the residue is rectified under a water jet vacuum to give the title compound bp 15 mm 95-99°C.

Preparation of 2,2,4,4-tetrachlorobutyraldehyde 125.0 g of vinyl chloride, 148.0 g of trichloroacetaldehyde, 3 g of copper() chloride and 300 ml of acetonitrile are heated to 140 DEG C. for 4 hours in an enamel autoclave. After cooling, the solvent is distilled off under a water jet vacuum at room temperature. The residue is treated with 500 ml of diethyl ether to remove the precipitated copper() chloride. The diethyl ether is distilled off and the residue is rectified under a water jet vacuum. The product thus obtained is a colorless liquid,
bp12mm78~80℃.

Production of 2,2,4-trichlorobutyraldehyde Ethylene 56.1g, trichloroacetaldehyde
148.0g, copper() chloride 3.0g and acetonitrile 300ml in an enamel autoclave at 140℃
Heat for 4 hours. After cooling, the solvent is distilled off under a water jet vacuum at room temperature. The residue is treated with 500 ml of diethyl ether to remove the precipitated copper() chloride. After distilling off the diethyl ether, the residue is rectified under a water jet vacuum. colorless liquid b.
Obtain p.15mm64-66℃.

Example 1 (Production of 2,3-dichloro-5-(2,2,2-trichloroethyl)-pyridine) 244.3 g of 2,2,4,4,4-pentachlorobutyraldehyde produced according to Example 1, acrylonitrile 110g, 400ml acetonitrile and CuCl5
4 g at 180℃ in a tantalum autoclave.
Heat for an hour. After cooling, acetonitrile and excess acrylonitrile are distilled off under vacuum. The black residual oil is extracted with diethyl ether. The ether is then dried over Na ₂ SO ₄ and evaporated under vacuum and the residue is steam distilled. 2,3-dichloro-5-
(2,2,2-Trichloroethyl)-pyridine precipitates in the distillate in the form of almost white flakes. The melting point of the product after once recrystallized from ethanol diluted with water is 98-99°C.

Example 2 2,3-dichloro-5-(2-chloroethyl)-
Production of pyridine) 2,2,4-trichlorobutyraldehyde
175.4 g are heated with 132.5 g of acronitrile, 400 ml of acetonitrile and 5 g of CuCl in a tantalum autoclave for 3 hours to 180° C. and kept at this temperature for 2 hours. After cooling, acetonitrile and excess acrylonitrile are distilled off under vacuum. Extract the black residual oil with diethyl ether and remove the ether.
Dry over Na ₂ SO ₄ and then evaporate under vacuum.
Steam distillation of the residue yields 2,3-dichloro-
5-(2-chloroethyl)-pyridine precipitates in the distillate in the form of a colorless oil. When distilled under high vacuum, the boiling point is bp0.1mm 97-100℃.

Example 3 (Production of 2,3-dichloro-5-(pentachloroethyl)-pyridine) a) 279.4 g of 2,3-dichloro-5-(2,2,2-trichloroethyl)-pyridine was dissolved in carbon tetrachloride. Dissolve to 3%. 120 g of HCl gas is introduced into this solution within about 1 hour while cooling. During this process, some of the hydrochloride of the pyridine compound precipitates. The reaction mixture is then heated to 50 °C and treated with chlorine gas while irradiated with light from a Hg high-pressure lamp (125 W). The reaction solution is then concentrated under vacuum and the remaining crystal sludge is recrystallized from methanol.
Colorless crystals of the title compound are obtained. Melting point 97.5-98℃ b) 2,3-dichloro-5-(2-chloroethyl)
- 210.5 g of pyridine (obtained according to Example 2) are chlorinated and worked up in the same manner as in a) above.
The melting point of the product is 97-98°C, corresponding to that obtained in a).

c) 2,3-dichloro-5-(2,2-dichloroethyl)-pyridine (obtained in Example 6 below)
244.9g was chlorinated by the method described in a),
Post-process. The product corresponds to that obtained in a) above.

Example 4 (2,3-dichloro-5-(1,1,2,2-
(Production of tetrafluoro-2-chloroethyl)-pyridine) 2,3-dichloro-5-(pentachloroethyl)
- Melt 348.2 g of pyridine with 1000 g of antimony trifluoride and 30 g of antimony pentachloride at 210 DEG C. for 2 hours. After cooling the melt to 90° C., 2 portions of water are added and the whole is steam distilled. The upper distillate layer, a colorless oil, is separated, dried over Na ₂ SO ₄ and then rectified under aqueous jet vacuum. Collect the product distilling at 97-100 °C in bp 11 mm.

Example 5 (Preparation of 2,3-dichloro-5-(1,1,2-trifluoro-2,2-dichloroethyl)-pyridine) The distillation residue according to Example 4 was further distilled and b.
p.11 mm Collect the product distilling at 120-122 °C.

Example 6 (Production of 2,3-dichloro-5-(2,2-dichloro-ethyl)-pyridine) 2,2,4-trichlorobutyladehyde of Example 2 was converted to 2,2,4,4-tetra Instead of using 210.0g of chlorobutyraldehyde, the other operations were the same,
2,3-Dichloro-5-(2,2-dichloroethyl)-pyridine is obtained in a white crystalline state with a melting point of 89-90°C.

Similarly, compounds of the following formulas are obtained by the same operations as above.

bp0.01mmCrystallizes when left standing at 72-73℃.

Claims (1)

[Claims] 1 formula (wherein R is a _C2 - _C10 -alkyl group homogeneously or heterogeneously substituted with 1 to 21 halogen atoms, and X is a halogen.) 2 _C2 in which R is homogeneously or heterogeneously substituted with 1 to 21 fluorine, chlorine or bromine atoms
A compound of the formula according to claim 1, which is a _-C10 -alkyl group and X is fluorine, chlorine or bromine. 3. A compound of the formula according to claim 2, wherein R is an ethyl group homogeneously or heterogeneously substituted with 1 to 5 fluorine or chlorine atoms, and X is fluorine or chlorine. 4 R is -CH ₂ -CF ₃ , -CF ₂ -CF ₂ Cl, -CF ₂ -
CFCl ₂ , −CCl ₂ −CCl ₃ , −CF ₂ −CCl ₃ , −CF ₂ −
CH ₃ , −CCl ₂ −CH ₃ , −CF ₂ −CF ₃ , −CH ₂ −
A compound of the formula according to claim ₃ which is a group selected from the group consisting of CH2Cl, _-CH2 - _CHCl2 or _{-CH2 -} CCl3. 5. A compound of the formula according to any one of claims 1 to 4, wherein X is chlorine. 6 formula is The compound according to claim 4, which is represented by: 7 The formula is The compound according to claim 4, which is represented by: 8 formula is The compound according to claim 4, which is represented by: 9 formula is The compound according to claim 4, which is represented by: 10 formula is The compound according to claim 4, which is represented by: 11 The formula is The compound according to claim 4, which is represented by: 12 formula is The compound according to claim 4, which is represented by: 13 formula By reacting the compound represented by with acrylonitrile through an addition reaction, the formula and the intermediate of formula ( ₎ is _a hydrogen halide H and X is a halogen), and the resulting formula
(In the formula, R and X represent the same meanings as described above.) If desired, the R group of the compound is halogenated, or
Alternatively, a method for producing a compound of the formula, which comprises replacing the halogen atom bonded to the R group with another halogen atom. 14 R is uniformly or heterogeneously substituted with 1 to 21 fluorine, chlorine or bromine atoms
Process for the preparation of compounds of the formula according to claim 13, which is a _C2 - _C10 -alkyl group and X is fluorine, chlorine or bromine. 15 R is an ethyl group homogeneously or heterogeneously substituted with 1 to 5 fluorine or chlorine atoms, and X is fluorine or chlorine, Production method. 16 R is -CH ₂ -CF ₃ , -CF ₂ -CF ₂ Cl, -CF ₂ -
CFCl ₂ , −CCl ₂ −CCl ₃ , −CF ₂ −CCl ₃ , −CF ₂ −
CH ₃ , −CCl ₂ −CH ₃ , −CF ₂ −CF ₃ , −CH ₂ −
A process for producing a compound of the formula according to claim 15, which is a group selected from the group consisting of CH2Cl, _{-CH2 - CHCl2} or _-CH2 - _CCl3 . 17 A method for producing a compound of the formula according to any one of claims 13 to 16, wherein X is chlorine. 18 formula is A method for producing the compound according to claim 16. 19 formula is A method for producing the compound according to claim 16. 20 formula is A method for producing the compound according to claim 16. 21 The formula is A method for producing the compound according to claim 16. 22 The formula is A method for producing the compound according to claim 16. 23 The formula is A method for producing the compound according to claim 16. 24 The formula is A method for producing the compound according to claim 16. 25, where X is chlorine, characterized in that the intermediate of formula is reacted directly in situ, without isolation, and the reaction is carried out without addition of hydrogen halide HX or with HCl as hydrogen halide. 14. A method according to claim 13 for preparing a compound of the formula. 26. The method according to claim 13 or 25, wherein the R group of the resulting compound of formula is chlorinated or fluorinated. 27. The method according to claim 13, wherein the addition reaction is carried out at a temperature of 70-160°C. 28 The addition reaction is carried out in a closed system at a temperature of 70-160℃,
14. The method according to claim 13, which is carried out under a pressure corresponding to the reaction temperature. 29 The cyclization of the compound of formula
14. The method according to claim 13, carried out at a temperature of -200<0>C. Claim 13, wherein the cyclization of the compound of formula 30 is carried out in an open system in the presence of hydrogen chloride or in the presence of a substance that generates hydrogen chloride under the reaction conditions at a temperature of 100 to 200°C. the method of. Claim 1 wherein the cyclization of the compound of formula 31 is carried out by heating in the liquid phase or gas phase in the absence of a solvent.
The method described in Section 3. 14. The method of claim 13, wherein the compound of formula 32 is first isolated and then cyclized in a second step. 33. The method according to claim 13 or 25, wherein the reaction is carried out in the presence of a catalyst. 34. Process according to claim 33, wherein the reaction is carried out at a temperature of 70 to 220C, in particular 130C to 220C. 35. The method according to claim 33, wherein the reaction is carried out in a closed system under a pressure corresponding to the reaction temperature at that time. 36 The catalyst used is copper powder, bronze, copper()-
or copper()-chloride or-bromide or copper()-iodide, or mixtures thereof. 37 0.01 to 10 mol of catalyst to aldehyde
34. The method according to claim 33, wherein the amount of mol. 38. The method according to claim 13 or 25, wherein the reaction is carried out in the presence of an inert organic solvent. 39 The addition reaction is carried out in acetonitrile, butyronitrile or 3-methoxypropionitrile as solvent with 0.1 to 6 mol of copper powder, bronze, copper()- or copper()-chloride or -bromide or copper()-iodide. 70 to 70 in a closed system in the presence of % or mixtures of these substances
The reaction is carried out at a temperature of 160°C, and the resulting compound of the formula is heated in an open system in the presence of hydrogen halide or a substance that generates hydrogen halide under the reaction conditions at 100-200°C.
39. The method of claim 38, wherein the cyclization is carried out at a temperature of . 40 Claim 38: The reaction is carried out in an alkanecarboxylic acid nitrile having 2 to 5 carbon atoms, 3-alkoxypropionitrile having an alkoxy group having 1 to 2 carbon atoms, or an excess of acrylonitrile as a solvent. The method described in section. 41 Copper powder, bronze, copper()- or copper()- in acetonitrile, butyronitrile or 3-methoxypropionitrile as a solvent for the reaction
Chloride or -bromide or copper ()iodide
The method according to claim 33, which is carried out in a closed system at 130-200° C. under a pressure corresponding to the temperature in the presence of 0.1-6 mol % or a mixture of these substances. .