SU649315A1 - Method of obtaining pyrazole derivatives or their salts, or organic acid esters - Google Patents

Description

Where G, R, N have the above values / The salts of compounds I include from monovalent to trivalent metal ions, for example, sodium, calcium, calcium, magnesium, aluminum, jellium, manganese, zinc, nickel, cobalt or copper; salts with complex ions, for example, the formulas: Cu (, MncNgO3 f, Ni (H.jO), de (OH) Zn (OH) - LCu (OH) (1 salt with an ammonium ion, for example, the formula, (CHglj ,,,, CH (CHn,) 2, M NeFCH (0113) 2 f N fljCHj CH OH or N-HgCHgCHgOCgH-, salts with mineral acids, for example hydrochloric, sulfuric nitric or hydrobromic acid. The acid forming esters are lower, 1) Aliphatic , alicyclic or aromatic carboxylic acids of the formula RjCOOH; where Rj is normal or iso-alkyl, containing 7 g of methyl, ethyl, n.propyl, isoproxy, n.butyl, isobutyl, tert.butyl, hept. l, undecyl, tetradecyl or heptadecyl; alkyl C, preferably 1 or 2 carbon atoms and less than 1-4 halogen atoms, such as chloromethyl, bromomethyl, iodomethyl, 2,2,2-trichloroethyl, 2 2-dibromoethyl, 2,2, 2-tribromo ethyl, 2-iodoethyl, 2,2-diiodoethyl or 1,2,2-tetrafluoroethyl; normal or iso-alkenyl, especially Cd-Cg, for example, vinyl, isopropenyl, propylene, 1-methyl-2-propynyl , 2-methyl-2-propyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl 3-butenyl, 1-methyl-3-butenyl, 2-methyl, 3-butenyl, 2- heptenyl, 2-undecenyl, 2-tetradecenyl, 2-heptadecene 3-heptadecenyl, or 8.11-heptadec dienyl 5 or 7-membered cycloalkyl for example cyclopentyl, cyclohexyl or cycloheptyl; phenyl containing 1-3 substituents selected from nitro

 fll group, halogen and alkyl containing C, | - C, preferably one carbon atom, for example, 2-nitrophenyl, 4-nitrophenyl, 2-tapil, 3-tolyl, 4 tolyl, 2-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 4-bromophenyl, 2,4-dichlorophenyl , 2,4, b-trichlorophenyl or 2-chloro-4-nitrophenyl; phenyl alkyl, which may have 1-3 substituents selected from nitro groups and halogen atoms in the phenyl radical, and alkyl C - is better than 1 or 2 carbon atoms, for example benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, 4-nitrobenzyl , 4-nitrophenylstil, 2-chlorobenzyl, 4-chlorophenylethyl, 2-bromobenzyl, 4-bromophenylstil, 3- (2,4-dichlorophenyl), propyl or 4- (2,4, b-trichlorophenyl) -butyl; styril; or phenoxy alkyl and 1 or 2 substituents, selected from halogen atoms and methyl groups in the phenyl residue, containing alkyl 2) Carbamic acid derivatives of the formula where each value of E and H is normal alkyl or isotope, for example, methyl, ethyl, n, propyl , isopropyl, n-butyl or isobutyl, or b and Hg together o6pa3jfiOT pentamethylene group; 3) Sulfonic acid of the formula Sg — SO —OH where y is alkyl normal or iso-C, for example methyl, ethyl, n, propyl, isopropyl, n butyl or isobutyl; alkyl substituted with 1 to 3 halogen atoms, more preferably, for example, chloromethyl, bromglethyl, iodomethyl, trifluoromethyl, 1-chlorostil, 1 bromethyl, or 1,1-dichloroethyl; or phenyl, which may be substituted with C-C normal alkyl or isostatyl, better, for example, methyl, ethyl, n, propyl, isopropyl, n, butyl, isobutyl or dodecyl, or halogen, for example chlorine; 4 Diester thiophosphoric acid of the formula S, P, 0 where the same or different substituents Ry are alkyl, normal or iso-e.g. methyl, ethyl, n-propyl, isopropyl, n, butyl or isobutyl; 5) Monoester of carbonic or thioulaic acid of the formula. where RQ is lower alkyl, normal or iso-structure, for example methyl, ethyl, n, propyl, isopropyl, n-butyl, isobutyl or sec. butyl; phenyl, or phenylalkyl with 1-3 substituents selected from nitro groups and halogen atoms in the phenyl residue, for example, benzyl phenylethyl, 2-bromobenzyl, 2-4-dichlorobyl, or 2,4,6-trichlorobenzyl; a have oxygen or sulfur; 6j A dibasic acid of the formula O O but with {t o-s-} it, tn is 0, or 1, - Rg is alkylene, for example methylene, ethylene, trimethylene tetramethylene, octamethylene or decametylen, vinylene, o-, m -or p-phenylene or a bond between carbon atoms; 7), s-Oxo-4-isoxazolin-2-yl-carboxylic acid of the formula "L, where hydrogen or halogen. Preferred acids are for carrying out the esterification: carboxylic acid of the above formula, where R j is haloalkyl and 1-4 halogen, alkenyl, 5- or 6-membered cycloalkyl, phenyl, optionally containing 1-3 substituents selected from nitro / methyl groups and halogen; phenylalkyl C or Cj to alkylene and possibly containing 1-3 substituents selected from nitro groups to halogen atoms in the phenyl residue; or phenoxyalkyl containing 1 or 2 halogen atoms in alkyl and optionally 1 or 2 substituents selected from halogen atoms and nitro groups; the sulfonic acids of the above formula, where Rg is alkyl Cd, haloalkyl C or C and 1-3 halogen atoms or phenyl, possibly containing alkyl substituents or halogen atom; and dibasic acids of the above formula, where R, j is alkylene,, or 1. Compounds of formula 1, their salts and esters of organic acids can be obtained by the following method. Example 1. A. The compounds of Formula 1 can be prepared by heating the corresponding 5-halo derivatives, hemi-pyrazole with alkali metal hydrosulfites, such as sodium hydrosulfide, or alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide. and P are as defined above. In the above reaction, water or a mixture of water with organic solvents can be used as a solvent. As organic solvents, for example, ethers, such as tetrahydrofuran or dioxane, and alcohols, for example, methanol or ethanol, can be mentioned. The process can be carried out at room temperature or at the boiling point of the solvent. In particular, the reaction is preferably carried out at the boiling point of the solvent. The reaction time mainly depends on the reaction temperature and on the reagents used, but it is usually 1-10 hours. B. Esters of organic acids of compounds of formula 1 are easily obtained by reacting compounds of formula 1 with an acylating agent according to the following scheme X II / —Ac / -NH where R, X, Y, and P have values, the residue is organic as above. The process can preferably be carried out in the presence of a solvent. In particular, ethers or mixtures of them, for example, diethyl ether, tetrahydrofuran, a mixture of diethyl ether with dioxane, a mixture of tetrahydrofuran and dioxane are used; aromatic hydrocarbons, such as benzene, toluene, xylene; halogenated hydrocarbons, such as dichloromethane, chloroform, carbon tetrachloride, and especially aromatic carbon compounds and ethers; halogen acyls, such as acid chlorides and acid bromides, are used as acylating agents; carboxylic acids in the presence of carboxylic amides, for example 1,3-dichlorohexylcarbodiimide; or acid anhydrides. The use of spiopanhydrides is preferred, and the reaction is carried out in the presence of an acid acceptor. The process is usually carried out at a temperature from room temperature to the boiling point of the solvent. The reaction time 764 may vary depending mainly on the temperature of the procession and on the reagents used, but usually it is 1-24 hours. B. Co2 compounds of the formula i with metals, a complex ion and an ammonium ion in the presence of a cation, have a pH 3. .. The solvent used is, for example, water} alcohols, such as methanol or ethanol; ethers, for example tetrahydrofuran or dioxane; aromatic carbon, for example benzene; halogenated carbon hydrogens, for example, dichloromethane or chloroform, or mixtures of these organic solvents with a vault. Depending on the valence of the cation and the solvent, various salts are obtained with different ratios. Compounds of formula i and cation, Islf 1: 2, 1; 3, etc. D. Salts of the compound of formula 1 and mineral acid are obtained by mixing the compound of formula 1 with mineral acid in an environment of a suitable solvent. The solvent used is, for example, water; alcohols, for example methanol or ethanol; ethers, for example tetrahydrofuran or dioxane; aromatic hydrocarbons, such as benzene; halogenated hydrocarbons, for example dichloromethane. or chloroform; or mixtures of these organic solvents with water. Salts with a mineral acid have a pH of 3. PRI mme p 2. 1,3, -dimethyl-4- (2, dichlorobenzoyl) -5-mercaptopyrazole. and .. 1.0 g of 5-HLOR-1,3-dimethylpyrazo. 1.05 g of anhydrous aluminum chloride and 1.66 g of 2-chloride of 4-dichlorobenzoic acid are dissolved in 6 MP of tetrachloroethane, and the resulting solution is heated under reflux for 8 hours. After completion of the reaction, the mixture is poured into water and the organic layer is separated. 7 ml of a 5% aqueous solution of sodium hydroxide are added, and the mixture is stirred for an hour. Then the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off. The oily residue obtained is crystallized from ethanol. 1.82 g of 5-chloro-4- (2,4-dichlorobenzoyl) -1, 3-dimethylpyrazole are obtained in the form of colorless prisms, m.p. 101.5-102, ... yield 78.3%. Calculated.%: C 47.48; H 2.99; N 9.23; ce 35.04 12. "se, N" 0 .. Found,% :, with 47.49; H 2.96; N 9.31; All 34.91. B. A mixture of 0.3 g of 5-chloro-4- (2,4-dichlrrbeneyl) -1,3-dimethylpyrazole, 2.1 g of sodium hydrosulfide dihydrate and 6 ml of ethanol are refluxed in a water bath for 3 hours After completion of the reaction, ethanol was distilled off under vacuum from the reaction mixture, and 15 ml of water was added, followed by extraction with benzene. Concentrated hydrochloric acid to pH 1 was added to the aqueous layer, and the mixture was extracted with chloroform. The extract is washed with water and then dried over anhydrous sodium sulfate. The solvent is distilled off; The crystalline substance is recrystallized from hexane and 0.10 g of the expected product is obtained in the form of a yellow powder, m.p. 85-86C. Output . Calculated,%: C, 47.85; 8.3.35; N 9.30; S 10.65; Se23.54 H., oN20SCe2 Found,%: C 47.76; H 3.43; N 9.38; S 11.02; every 23.24. Example 3. 1, 3-dimethyl - 4- (2, 6-dichlorobenzoyl) -5-hydroxypyrazole. 0.56 g of potassium hydroxide is dissolved in 5 ml of water, and a solution of 1.56 g of 5-chloro-4- (2,6-dichlorobenzoyl) -1,3-dimethylpyrazole in 10 ml of ethanol is added to the resulting solution. The mixture was heated under reflux for 12 hours. After completion of the reaction, the reaction mixture is gradually cooled and extracted with benzene. The aqueous layer was separated and 2N was added. a solution of hydrochloric acid to rp 3-4, when this occurs precipitation of the crystalline substance. The resulting crystals are recovered by filtration and recrystallized from ethanol to obtain 0.68 g of the desired product as colorless needles, mp. 249.5-250.5 ° C. Yield 48.0%; Calculated,%; C 50.55; H 3.53; N E, 82; All 24.88. CegN 02 Found,%: C 50.38; H, 3.53; N, 9.90; All 24.57. According to the procedure described in Example 2, the following compound is obtained: 1, 3-dimethyl-4 (2,4-dimethylbenzoyl) -5-oxypyrazole, m.p. 95-96s, 1, 3-dimethyl-4- (2-methylbenzyl) -5-hydroxypyrazole, mp. 82-83C. Example 4. 1, 3-dimethyl-4- (2-chlorobenzoyl) -5-acetoxypyrazole. In a mixture of 20 mp benzene and 0.51 g of triethylamine, 1.25 g of 1,3-dimethyl-4- (2- chlorobenzoyl) -5-hydroxy-razole, and 0.4 g of acetyl chloride is added dropwise at room temperature and with stirring. The mixture is then stirred at room temperature for another 3 hours. After the reaction was completed, water was added to the reaction mixture to dissolve the salts, and the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting oily substance is recrystallized from hexane to give a crude crystalline substance, which is recrystallized.

from methanol, 1.20 g of the desired product is obtained in the form of colorless prisms; mp. 78-79 ° C. The yield is 82.2%.

Calculated,%: C 57.45; n4.48 N 9.57; ce 12.11

See Human Oz

Found,%: C 57.50; H 4.45; N 9.61; cr 12.23;

IR spectrum; (liquid paraffin)

l) С с О 1793 cM-t

Example 5. 1,3-dimethyl-4- (2,4 dichlorobenzoyl) -B-lauroyloxypyrazole,

0.285 1, 3-dimethyl-4- (27-4-dichloro-benzoyl) -5-hydroxypyrazole is dissolved in 10 ml of benzene, and then 0.2 ml of triethylamine is added. Under cooling with ice, a solution of Cy27 g of lauric acid chloride in 5 ml of benzene is added dropwise. The resulting mixture was stirred at room temperature for 19 hours. After completion of the reaction, ether is added to the reaction mixture, then the reaction mixture is washed successively with water, hydrochloric acid, a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride. The reaction mixture is then dried over anhydrous sodium sulphate and the solvent is distilled off. The resulting residue is recrystallized from hexane under ice-cooling, and 0.46 g of the expected product is obtained in the form of white crystals, m.p. B6 ° C. The yield is 98.0%.

Calculated: C 61,66; H 6.90; N 5.99; every 15,17

Found,%: C, 61.27; H, 6.94; N 5.84; every 15.11.

IR spectrum: (liquid paraffin)

 1790 cm

Example 6. 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-chloroacetoxypyrazole ..

In a mixture of 10 MP of benzene and 0.2 ml of triethylamine, 0.285 g of 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole is dissolved, and then a solution of 0.18 g of chloride is added dropwise to the solution. chloroacetyl in 5 ml of benzene with ice-cooling and stirring. The resulting mixture was stirred at room temperature for 2 hours. After completion of the reaction, ether is added to the reaction mixture, after which the mixture is washed successively (3 x 50 ml) of water and dried over anhydrous sodium sulfate. The solvent is then distilled off and the resulting residue is recrystallized from hexa, to give 0.297 g of the desired product as white crystals, m.p. 120-122s. Yield 82.0%. 3.07; Calculated,%: C 46.50; N N 7.25 ce 29.41 C 4H 1Sezes ,, Oz

Found,%: C 46.25; H 3.08; N 7.81; every 29,32.

IR spectrum (liquid paraffin) 1790 cm

The following compounds are prepared according to the procedures described in examples 4-6.

1, 3-dimethyl-4- (2-chlorobenzoyl) -5- (N, M-dimethylcarbamoyloxy) -pyrazole, so pl. 115-11bs.

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-stearoylxypyrazole, mp 57-61 s,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-crotonyloxypyrazole, mp 87-89 C,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -. -5-benzoyloxypyrazole, m.p. 138-139 C,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-acetoxypyrazole, so pl. 81-82 s,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-acetylthiopyrazole, P. P 1.5890,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-propionyloxypyrazole, mp, 48 ° C

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-isobutyryloxypyrazole, t, mp, 101102 ° C,

1, 3H-dimethyl-4- (2,4-dichlorobenzoyl) -5-linoleloxypyrazal, L ® 1.5196,

1, 3g-dimethyl-4- (2-chloro-4-nitrobenzoyl) -5-beisoyloxypyrazop, tg,

1, 3-dimethyl-4- (2-chloro-4-nitrobenzoyl) -5- (4-chlorobenzoyloxy) -pyrazole, so pl. 194 ° C

1, 3-dimethyl-4- (2-chloro-4-nitrobenzoic) -5- (2-chloro-4-nitrobenzoyloxy) -pyrazole, so pl. 182-184 ° C

1, 3-dimethyl-4- (2-chloro-4-nitrobenzoyl) -5-cinnamoyloxypyrazole, t, pl.164 C,

, H-dimethyl-4- (2-chloro-4-nitrobenzoyl) -5-pyrazolyl succinate, mp 203 ° C,

1, 3-dimethyl-4- (2-chloro-4-nitrobenzoyl) -5-acetoxypyrazole, m.p. 133 C,

1, 3-dimethyl-4- (2-chloro-4-nitrobenzoyl) -5-pivaloyloxypyrazole, T..PL. 157-158 ° C,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-phenylacetoxypyrazole, mp 74-76 ° C,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5- (4-chlorophenylacetoxy) -pyrazole, m.p. 130-131 C,

1, 3-dimethyl-4- (4-nitrobenzoyl) -5-acetoxypyrazole, so pl. 179-180 s

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-cyclohexylcarbonyloxy pyrazole, t, mp, 98-99 C,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) 5- (2,4-dichlorophenoxyacetoxy) -pyrazole, mp,

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5- (2,4-dichlorobenzoyloxy) -pyrazole, mp, 168-169 ° C,

, 3-dimethyl-4- (2,4-dichloroben-zoyl) -5-pyrazolyl sebacate, mp, 143144 C,

Claims (1)

1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5- (4-methylbenzoyloxy) -pyrazole, G, pl. 197-198 ° C. 65 Example 7. 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-pyrazolyl methanesulfonate. 0.29 is dissolved in a mixture of 0.1 g of triethylamine and 5 dry benzene. g 1,3 "imethyl-4 (2,4-dichlorobenzoyl) -5-oxyl 1 shrazol, and then 0, 1 g of chloric anhydride and methanesulfonic acid is added dropwise at a comatose temperature and at the same time, the resulting mixture is stirred at room temperature temperature for 12 wt. then to reaction. The mixture was diluted with 10 l of water and the organic layer was separated. The organic layer was dried with anhydrous sodium sulfate, and the solvent was distilled off. The residue obtained is recrystallized from hexangg, and Of3 g of the expected product is obtained in the form of 73-74 C. of white needles, mp, 83.3%. Calculated% C 42.99; H 3.33; N 7.71 S 8.83; SI 19.25; 42.64; And 3.37; 7.76 S 9.15; Si 19.23, IR spectrum: (liquid paraffin) up to 1355 cm; 1180 According to the procedure described: (nn and Example 7, the following compounds were prepared: 1, 3 di 1 -ethyl-4 {2, 4-dichlorobenzoyl-5-pyrazolyl-4-toluenesulfone s.t., mp, 124–24 ° C, 1, 3; cimethyl-4- (2,. Orbenzoyl-5-pyragon: and 1 methyl benzene sulfonate, mp 88-89 C, If 3-dimethyl - 4 {2-nitro-4-chloroben zoyl) -5-pyrazolyl -4-toluensulfonate T. PlL29-130s, 1, 3-dit.1ethyl-4 (2 nitro-4-chloroben zoyl) -5 - pyrazolylbenzenesulfonate, t, pl. 12-7--138 ° С, 1-ethyl -3-methyl-4- (2,4-dichlorobenzyl) 5-pyrazolyl-4 toluenesulfonate, m.p, 115-116 ° C, 1-ethyl-3-methyl-4- (2-nitro-4-chloro benzoyl) -5-pyrazolyl-4-toluenesulphate, t, pl.lOO-lOl C, 1, 3-dim.ethyl-4- (2-chlorobenzoyl) -5-pi azolyl methanesulfonate, m.p., 9798 ° C. EXAMPLE 1, 3 dimethyl 4, - (2,4-dichlorobenzoyl) -5- (5-M8THNL-3-oxo-4-isoxazoline -2-yl-carbonyl onc-pyrazole, 4 MP of dry benzene is dissolved in 01, g of 3-hydroxy-5-methyl-isoxaol, and then 0.5 liquid phosgene is added. After perekashivanie: at room temperature for 1 hour the mixture boils t t under reflux for an hour. Mix gradually. is cooled, the excess (yusgene and benzene is distilled off under vacuum. The residue is taken up in 5 ml of dry benzene and dropwise. and a solution of 0.3 g of 4- (2,4-dichlorobenzoyl) -1.3 is added with stirring -dimethyl-5-hydroxypyrazole and 0.1 g of triethylamine in 5 ml of dry benzene at room temperature and with stirring. The mixture is stirred at room temperature for another 12 hours, 10 ml of water are added to the reaction mixture and the organic layer is separated. the layer is washed successively with 1N hydrochloric acid solution, saturated aqueous bicarbonate sodium and water and dried over anhydrous sodium sulfate. The solvent is then distilled off, and the resulting residue is recrystallized from benzene / hexane system to obtain 0.25 g of the desired product as white needles, mp 180-182 ° C. , 0%, Calculated,%: from 49.78; H 3.19; N 10.24; Se 17.28. Found,%: C 49.75; H 3.31; N 10, 31 ;, Ce 17 , 05. IR spectrum: (liquid paraffin) -N) 1785 cm According to the procedure described in example 8, the following compound is obtained: 1, 3-dimethyl-4- (2, 4 dichlorobenzoyl) -5- (3 oxo-4 -chloro-5-methyl-4-isoxazolin-2-yl-carbonyloxy) -pyrazole, m.p. 204 206 ° C. Example 9. 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-methoxycarbonyloxypyrazole. In a mixture of 20 ml of dry benzene and 0.28 g of triethylamine, 0.72 g of 1,3-dimethyl-4- (2, 4-dichlorobenzoyl) -5-hydroxypyrazole is dissolved, and then 0.26 methyl ester is added dropwise. chlorogolic acid at room temperature and with stirring. After completion of the reaction, the reaction mixture was allowed to stand for 12 hours, and then 30 ml of water, Benzene, was added. the layer is cooled, and the aqueous layer is extracted with benzene. The benzene layer and the benzene extract are combined, and the mixture is washed with water and dried over anhydrous sodium sulfate. Then the solvent is distilled off and the resulting residue is recrystallized from a small amount of hexane, to obtain 0.17 g of the desired product as white crystals 86-88c, Yield 92%, Calculated,%: C 49.00; H 3.52; N 8.16; All 20.66 C 4H 2C62N204 Found: C 18.05; H 3.56; N 8.33; every 20,44. IR spectrum: (liquid paraffin) 1771 cm-. According to the procedure described in Example 9, the following compounds are obtained: 1, 3-dimethyl-4- (2-chlorobenzoyl) -5-methoxycarbonyloxypyrazole, t., PL76976C, 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -B-propoxycarbonyloxypyrazole, i.e., 60-62 s, 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) 5-benzyloxycarbonyloxypyrazole, pl. 87-9,. , 3-dimethyl-4 (2,4-dichlorobenzoyl) 5 pyrazolyl carbonate, t, pLo166168 ° C, 1, 3-dimethyl-4- (2,4-dichloro-isonel-5-phenoxycarbonnloxypyrazole, t.r.159-160 ° C , 1, 3-dimethyl-4- (2,4-dichlorobenoyl-5-phenylthiocarbonyloxypyrazole, m, 83-84 ° C, 1, 3-dimethyl-4- (2,4-dichloro-benzoyl-5-butylthiocarbonyloxypyrazole, 5618, 1, 3-dimethyl-4- (2,4-dichlorobenzoyl-5-ethylthiocarbonyloxypyrazole, P2,1,5751,, 3 dimethyl-4- (2,4-dichlorobenoyl-5-benzylthiocarboxyloxypyrazole, 1.5904, I will try it on. O, 0-diethyl-O-11, dimethyl-4 (2-chlorobenzoyl) 5 pyrazolyl thiophosphate, a mixture of 1.0 g of 4- (2-chlorobenzoyl) -1, dimethyl-5-oxypyrazole, 20 ml of benzene , 0.433 g triethylamine and 0.81 g of o-0-diethylthiophosphoric acid chloride are refluxed with stirring for 6.5 h. After the completion of the reaction, the mixture is gradually cooled and water is added to dissolve the salts.The organic layer is separated, washed with water , dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting oily residue was subjected to chromatography on a 10 silica gel column, and then recrystallized from hexane, to give 0.28 g of the desired product, mp. 71-74 C, Exit 17, Calculated: From 47.41; H 5.00 N 6.95; every 8.80; R 7.69 CifiH CBN O P S Found,%: C 47.83; H 4.94; N 6.76; All 9.08; P 7.35, Example 11. Calcium salt 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5 oxypyrazole. Suspended in 50 ml of water with 2,85 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5 -oxypyrazole and the suspension is dissolved in 5 ml of 2N sodium hydroxide solution. A solution of 1.11 g of calcium chloride in 10 ml of water is added and the mixture is stirred. The precipitate is filtered off and dried to obtain 2.4 g of the desired product as a white powder, t, pl. 260 ° С, Yield 79, С%, Calculated,%: С 44.73; H 3.44; C 2HgN20gCa., F Found: C 47.88; H 3.23; N, 8.83. According to the procedure described in example 10, the following compounds are obtained: magnesium salt 1, 3-dimethyl-4- (2, -dichlorobenzoyl) -5-oxypyrazole, t, mp, 270 ° C, aluminum salt 1, 3 dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole m.p. , 1,3-dimethyl-4 (2,4-dichlorobenzoyl) -5-hydroxypyrazole iron salt, m.p. 170C, 1, 3-3-dimethyl-4- (2,4-dichlorobenzoyl) -5-oxypyrazole copper salt, m.p. above, the sodium salt of 1, 3-dimethyl-4- (2,4-dichlorobeneoyl) -5-hydroxypyrazole, so pl. above 300 ° c. Example 12. Isopropylamino salt of 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole. 2.85 g of 1, 3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole is suspended in 50 ml of benzene and 0.7 g of isopropylamine is added to the suspension with stirring. The mixture is then stirred at room temperature for one hour. The solvent is distilled off and the residue is cooled. The solid is recovered by filtration, washed with petroleum ether and dried to give 3.2 g of the expected product as a white powder. footprint substance, so pl. 130-140s Yield 93.2%. Calculated: C 52.34; H 5.56; 12.21 C 5 Found: C 52.05; H 5.72 12.59. Example 13. 1,3-Dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole hydrochloride. , To 0.3 g of 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole was added 2 ml of concentrated hydrochloric acid and the resulting mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction mixture is gradually cooled, the target product is filtered off. The product is washed with a small amount of methanol and then hexanem, dried, and 0.20 g of the expected product is obtained in the form of a white powder, m.p. 115-125 ° C (with dec,). Output 57.1%; Calculated,%: C 44.82; H 3.45; N 8.71 Cr 33.07; S. hN, Found,%: C 45.16; H 3.57; N 8.85; All 32.93. According to the procedure described in example 12, the following compound is obtained: 1, 3-dimethyl-4- (3,4- {dimethoxybenzoyl) -5-oxypyrazole hydrochloride, m, 164-1b5 ° C, Example 14.1-allyl- 3-methyl-4- (2,4-dichlorobenzoyl) -5-oxypyrazole. A suspension of 1.4 g of 1-allyl-3-methyl-2-pyrazolinone-5 and 0.74 g of Kszci hydroxide in 20 ml of isopropanol is boiled under reflux with stirring for 1.5 hours. After cooling, 2.3 g of 2,4-dichlorobenzoyl chloride are added dropwise to the resulting mixture. After completion of the dropwise addition, the mixture was refluxed for 5.5 hours. After completion of the reaction, the solvent was distilled off and 3 ml of 2N hydrochloric acid solution was added to the residue to pfi 3.0. The mixture is then extracted with chloroform and the solvent is distilled off. The residue is dissolved in a small amount of benzene, and the solution is washed with water, dried over anhydrous sodium sulfate and the solvent is distilled off. The residue obtained is recrystallized from isopropyl ether containing a small amount of dichloromethane and 1.18 g of the whole product are obtained in the form of white crystals, m.p. 161-163 s. Yield 40.7%; Calculated,%: C, 47.86; H, 3.35; N 9.30; CE 23.54. eNgCgsOg Found: С С 47.33; H 3.41; N 9.06; ce 23.31, Example 15 1-allyl-3-methyl-4- (2,4-dichlorobepzoyl) 5-pyrazalyl-4-toluyl fonat. A solution of 180 mg of G-allyl-3-methyl-4- (2,4-di: chlorobenzoyl-5 hydroxypyrazole in 6 ml of benzene and 58.4 mg of triethylamine. Stir at room temperature for an hour and add 110 .mg of acid chloride. 4-toluenesulphonic acid. The resulting mixture is then refluxed for one hour. After the reaction is complete, water is added to the reaction mixture and the organic layer is separated. The organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off and the oily residue recrystallized from a mixture of benzene and hexane to give 173 g of the desired product in the form of colorless prisms, mp, 113114 C. Then the solvent is distilled off about the mother liquor and recrystallized from goxane, 26 ml of the desired product are obtained. - Yield 73.9%. Calculated: C 54, 20; H 3.90; N 6.09; S 6.89; Ce Cr NgSCe Found,%: C 54.45; H 3.98; N 6.09 S 6.80; se 15.19. According to the above The following compounds are prepared according to the procedures: 1-allyl-3-methyl-4- (2-chloro-4-nitrobenzoyl) -5-pyrazolyl-4-toluenesulfonate, m.p. B9 ° Cf 1-allyl-3-methyl- 4- (2,4-dichlorobenzoyl) -5- (4-chlorobenzoyloxy -) - pyrazole, m.p. 155- 57C. 516 1 tallyl-3-methyl-4- (2,4-dichlorobenzoyl) -5-isobutyr 1-shoxypyrazole, m.p. 62-63s. Claim 1, A method of producing pyrazole derivatives of the formula </ BR> where R is hydrogen or alkyl R alkyl SuC or alkenyl.; X is halogen, no rogroup, alkyl, mono-trihalogenated alkyl alkoxy, alkanesulfonyl, cyano, alkylthio aliphatic acyl or benzoyl; , 2,3 or 4, and if, 3 or 4, the substituents X can be the same or different, Y is oxygen or sulfur, provided that X is not a 2-chloro or 4-nitro substituent, if R and. H-methyl groups, Y-oxygen, or their salts or esters of organic acids, characterized in that the 5-halopyrazole derivative of the formula OL1 / g: -c - // where V., 2 and n have the values indicated above, and Hag - halogen, -contacted with hydroxide or alkali metal hydrosulfide in the medium of solvent, and the target product is isolated in free form or as a salt or ester of organic acids. Sources of information taken into account in the examination 1. Chemical heterocyclic compounds; No. 6, 1972, pp. 799-804.