SU526285A3 - The method of obtaining derivatives of 3-and / or 2-butenoic acid - Google Patents

Description

352 mules 1 are based on the fact that the connection is common. in which R and R, have the indicated meanings, are subjected to an exchange decomposition reaction with zinc or amalgamated zinc at 50 to 150 ° C in the presence of acid, followed by separation of the resulting mixture of 2- and 3-butenoic acids and / or by separation into 2- and 3-butenoic acids of general formula 1 and / or simultaneously into cis- and trans-isomers of these acids, and / or translation into esters, amides or salts of acids of general formula 1 using known methods it is desirable to conduct the process in an inert solvent and the presence of hydrochloric acid. It is also desirable to separate the 2 and 3-butenoic acids of general formula 1 and their cis and trans isomers by fractional crystallization and to obtain compounds of general formula 1, where R is an aminophenyl group, a compound of general formula 1, where R is an acylaminophenyl group, subjected to hydrolysis in an alkaline medium. Toluene or xylene can be used as an inert solvent. In this case, the acids of general formula 1 are obtained in good yields and the corresponding butyric acids are not formed, as might be expected. Under the influence of mineral acids, 4- (4-biphenylyl) -4-hydroxycrotic acids have been found to be converted by isomerization into 4- (4-biphenylyl) -4-oxo-butyric acids and that 4- (4-biphenylyl) -4-oxo-butyric acid , for example, according to the Clemmensens method. those. With the help of amalgamated zinc in the presence of hydrochloric acid, it is possible to reduce to the corresponding 4- (4-biphenylyl) -based acids. The proposed method produces mainly trans-3-butenoic acids and small amounts of cis-3-butenoic and trans -2-butenoic acids. The mixtures thus obtained can be separated, for example, by chromatography on a column or by fractional crystallization from suitable solvents. trans-buteno acids are also compounds in which the aryl and carboxyl-bearing radicals are in the trans position relative to the olefinic double bond. The compound of general formula I, in which B has the meaning of alkoxy group, is obtained by the usual esterification conditions by the reaction of the decomposition of a compound of general formula I, in which B means a hydroxy group, for example, alcohol in the presence of an acid catalyst, such as hydrochloric or sulfuric acid, or by treating chlorotic acid esters. When carbon dioxide is cleaved spontaneously, esters of the general formula 1 are obtained. When preparing mixtures of cis- and trans-3 and 2-butenoic acids, they can be divided into components. The fractional crystallisation from passing solvents was best justified. With an alkaline hydroligase, a compound of the general formula 1, in which R is an acylaminophenyl group, can be easily converted to a compound of the general formula 1, in which R is an aminophenyl group, for example, by heating with caustic lye. The resulting compounds of general formula I, in which B is a hydroxy group, can be converted, if desired, into their physiologically tolerable salts, for example alkali or alkaline earth metal salts, or salts with organic bases. As the latter, for example, cyclohexylamine, isobutylamine, morpholine, ethanolamine, diethanolamine or dimethylaminoethanol can be used. Compounds of general formula 1, in which R represents a piperidino or aminophenyl radical and / or an R, amino radical, can also be converted, if desired, into their physiologically tolerable salts with non-limiting or organic acids. Suitable acids include, in particular, hydrochloric, hydrobromic, sulfuric, acetic, fumaric or citric acids. The starting materials of general formula III are obtained, for example, from 4-arip-4-oxocrotonic acids of general formula. Cn-Sn-s-s by reduction with borane nitri in a water-alkaline medium; the latter can be obtained by condensation of aryl methyl ketones with glyoxylic acid hydrate in the presence of acid. Example 1. trans-4- (4-Cyclohexyl-phenyl) -3-butenoic acid. 401 g of zinc dust are suspended in 955 ml of water and, after adding 101 g of chlorine mercury, they are transferred for 10 minutes, 23.8 ml of concentrated hydrochloric acid is added and stirred vigorously for 10 minutes with a turbine. The aqueous layer is poured, to the amalgamated zinc, 955 ml of toluene and 310 ml of water and 833 ml of concentrated hydrochloric acid are successively added and, while stirring, the mixture is heated to 75 ° C. At this temperature, 177 g (0.673 mol) of 4- {4-cyclohexyl-phenyl) -4-hydroxyrotic acid (m.p. 115-117 ° C) are introduced in small portions, after adding 3/4 of the starting material under known conditions When a strong hydrogen evolution begins, the contents of the flask begin to boil strongly. The mixture is then heated under reflux for 150 minutes, cooled and added to 5 l of ice water. Extract three times with shaking, each time with 750 ml of ether, wash the ether extracts with water, dry them over sodium sulfate and evaporate in vacuo. The crystallizing residue is non-recrystallized from petroleum ether, ethyl acetate with the use of activated carbon and from hot ethanol. The product yield of 150.2 g (91% of theoretical); m.p. 132-134 ° C.

From the acid dissolved from acetone, the addition of an equivalent amount of cyclohexylamine is used to isolate the corresponding

salt. By treating the methanolic acid solution with a calculated amount of sodium methylate, the sodium salt is obtained. The sodium salt monohydrate is melted at a temperature above ZOO-C.

Example 2. trans-4- (3-Chloro-4-isopropyl-phenyl) -3-butenoic acid.

Preparation analogously to example 1 of 4- (3-chloro-4-isopropyl-phenyl) -4-hydroxyrotic acid with so pl. 77-78 ° C. T. pl. cyclohexylammonium salt 116-117 ° C. The product yield 53% of theoretical.

Example 3. trans-4- (3-Chloro-4-isobutyl) -3-butenoic acid.

Preparation as in Example 1 from the cyclohexylammonium salt of 4- (3-chloro-4-isobutythyl-phenyl) -4-hydroxy acid with m. Pl. 172-173 S. T. pl. cyclohexyl ammonium salt 137-138 ° C (from acetone). The product yield 83% of theoretical.

Example 4. trans-4- (3-Chloro-4-methyl-phenyl) -3-butenoba acid.

Preparation analogously to example 1 of 4- (3-chloro-4-methyl-phenyl) 4-hydroxyrotic acid with mp. 10-100 ° C. T. pl. free acid 112-113 ° C (from petroleum ether). M.p. cyclohexyl ammonium salt of 168-169 ° C. The output of the product is 57% of the theoretical.

Example 5. trans-4- (3-Bromo-4-isopropyl-phenyl) -3-butenoic acid.

Preparation analogously to example 1 of the cyclohexylammonium salt of 4- (Z-bromo-4-isopropyl-phenyl) -4-hydroxyrotic acid with m. Pl. 170-171 ° C. M.p. cyclohexylammonium salt 108-110 ° C (from ethyl acetate). The product yield is 25% of the theoretical.

Example 6. trans-4- (3-Chloro-4-cyclohexyl-phenyl) -3-butenoic acid.

Preparation analogously to example 1 of 4- (30-chloro-4-cyclohexyl-phenyl) -4-hydroxyrotic acid with m. Pl. 102-1ОЗ ° С. M.p. cyclohexylammonium salt 119-120 ° C. M.p. 93-940 ° C free acid (from cyclohexane). The product yield 83% of theoretical.

five

Example 7. trans-4- (3-chloro-4-piperidino-phenyl) -3-butenoic acid.

Preparation analogously to example 1 of the cyclohexylammonium salt of 4- (3-chloro-4-piperidino-phenyl) -4-exicrotonic acid with

0 t. Pl. 173 ° C. free acid 120123 ° C. M.p. cyclohexylammonium salt 123-124 ° C. The yield of the product is 94% of the theoretical.

Example 8. trans-4- (3-Brom-4 cyclohexyl-feshl) -3-butene acid.

Preparation analogously to example 1 of the cyclohexylammonium salt of 4- (Z-bromo-4-cyclohexyl-phenyl) -4-hydroxyrotic acid

0 s. 184-1850С (decomposition). M.p. free acid 113-114 ° C (petroleum ether). M.p. cyclohexylammonium salt 118-119 ° C (from ethyl acetate). The output of the project is 65% of the theoretical.

Example 9. trans-4- 4- (1-Cyclohexen-1-yl) -phenyl-3-bugenic acid. Preparation analogously to example 1 of the cyclohexylammonium salt of (1-shshloheken-1-yl) -phenyl-4-hydroxyrotic acid with m. Pl. 188-189 ° C. M.p. cyclohexylammonium salt 176-177 ° C. The product yield of 12% of theoretical.

Example 1O. trans-4- (3-Bromo - 4

5-isobutyl-phenyl) -3-butenoic acid.

Preparation analogously to example 1 of 4- (3-bromo-4-isobutyl-phenyl) -4-hydroxyrotic acid c. mp, 90-92 ° C. T. pl. cyclohexylammonium salt 126,5-127,5-С,

0 Output 9% of theoretical.

Example 11. trans-4- (3-Chloro-4-cycloheptyl-phenyl) -3-butenoic acid.

Preparation analogously to example 1 of the cyclohexylammonium salt of 4- (3-chloro-4-shsloheptil-phenyl) -4-hydroxy acid with m. Pl. 179-180 ° C. T. pl. free acid 65-67 ° C. The product yield is 32% of theoretical.

Example 12. Tpaiic52 ethyl cyclohexyl-phenyl) -3-buteic acid, 46 g, 3 g (0.189 mol) of 4-cyclohexyl-phenyl) -3-butepic acid in 300 ml of absolute tetrahydrofuran, gyder (1 willow. Temperature from -30 to - 20 ° C, 19.7 g (0.189 mol) of anhydrous triethylamine, then 20.4 g (0.189 mol) of ethyl ester of chloroic acid are added dropwise. Then the mixture is stirred for 2 at -20 ° C and placed in 1 kg of ice water and extracted with ether. The ether extracts are washed with water, then with saturated sodium bicarbonate solution and about water, cyaiaT over sodium sulfate and evaporated. The residue 3 is recrystallized twice from gasoline to isopropanol using activated carbon. Yield of product 17.4 g (34% of theoretical), mp 68-70 ° C Accordingly, one obtains: ethyl egrir trans-4- (3-chloro-4-cyclohexyl-phenyl) -3-butenoic acid; butyl ester trans-4- (3-bromo-4-cyclohexyl-phenyl) -3-butenoic acid ; trans-4- (3-cyano-4-cyclohexyl-fe1P {l) isopropyl ester - 3-butenoic acid. Example 13: AmideTrans-4- (4-Peak, Logex-phenyl) -3-Butenoic Acid. 36.0 g (0.132 mol) of ethyl tp ether, L1C-4- (4 cyclohexyl-fe-g 1x) -3-butenoic acid is dissolved in 600 ml of methanol, which is heated in an autoclave at an ammonia pressure of 20 atm. for 6 CPS up to 100 ° C. After cooling the o-; top} with the solvent, water is added and added with dilute hydrochloric acid. Then, they are extracted with ethyl acetate. Extracts of ethyl luminescent ether, saturated with sodium chloride, then with water, dried over sodium sulfate, and evaporated. The residue crystallizes upon trituration with ether. After chromatographic purification of amide trans-4 (4-cyclohexyl-phenyl: 3-butene acid on silica gel using acetic ester and ka; substance of eluepta and distilled acetone and ethyl ester of acetic acid, it melts at 132 133 ° C. Product yield 30% of theoretical. Accordingly, the following is obtained: amide trans-4 (3-chloro-4 cyclohexyl-phenyl-3-buteic acid; amide trans-4- (3-chloro-4 cyclohexyl-phenyl. -3-pentenoic acid; amide trans-4- (3-bromo-4-isobutyl-phenyl) -buthenic acid. Example 14. trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid. To 20 g a of algamated zinc, 15 ml of water, 35 ml of concentrated hydrochloric acid, 50 ml of toluene and 10 g of sodium salt of 4- (2-fluoro-4-biphenylyl) -4-hydroxyrotic acid (acid, mp, 109-111 ° C ) and after placing for 6 hours, it is heated under reflux, 10 ml of concentrated hydrochloric acid is added again after 3 hours, then suction is carried out from unreacted zinc and the filtrate is extracted three times with 10 ml of ether each time. The solvent is evaporated and, after recrystallization from cyclohexane / ethyl acetate, 8 g (92% of theory) of colorless trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid with m.p. 142-144 ° C. From the acid dissolved in acetic ester by the addition of cyclohexylamine, its cyclohexylamine salt is precipitated, which, after recrystallization from absolute ethanol, melts at 181-182 ° C. The sodium salt obtained with the calculated amount of sodium bicarbonate is melted at 31 ° C-312 ° C. Example 15. trans-4- (2-Chloro-4-biphenylyl) -3-butene acid. Preparation is analogous to example 14 of 4- (2-chloro-4-bife1 Shlyl) -4-hydroxyrotic acid (mp. 105-1O7 ° C). M.p. acids 127-128 ° C (from cyclohexane). The product yield 74% of theoretical. Patric salt; m.p. starting with 285-C (decomposition). Example 16. Trens-4- (2 -Brom-4 biphenylyl) -3-butenoic acid. Preparation as in Example 14 from the salt of morpholine (mp. 147-148 ° C) 4- (2-bromo-4-biphenylyl) -4-hydroxycrotic acid. In acetone, the cyclohexylamine salt of trans-4- (2-bromo-4-biphenylyl) -3-butenoic acid was isolated with m.p. 167-169OS. The product yield is 75% of theoretical. Example 17. A. trans-4- (2 -Acetamido-4-biphenylyl) -3-butenoic acid. Preparation is analogous to Example 14 from cyclohexylamino salt (mp: 130 ° C., decomposition) of 4- (2-acetamido-4-biphenylyl) -4-hydroxycrotic acid. trans-4- (2-acetamido-4-bipheilyl) -3-butenoic acid melts at 152-154 ° C. The yield of the product is 4O% of the theoretical. B. trans-442-amino-4-biphenylyl) -3-butep. L acid. 44 g of trans-4- (2-acetamido-4-biphenylyl) -3-buteic acid are heated for 9 hours in 30 ml of 1% 20% aqueous solution of potassium hydroxide in a boiling water bath. The initial mixture is then diluted with 700 ml of water and weakly acidified with formic acid. The residue that was separated out was filtered off with suction and recrystallized from 6O% methanol. Get 26 g (69% of theoretical) trans-4- (2-amino-4-biphenylyl) -3-butenoic acid.) Yuty with t, pl. 147-149 ° C Its cyclohexylamine salt after recrystallization from ethyl acetate / isopropanol has nol. 172-174 ° C. Example 18. Trux-4- {4-Chloro-4-b: (fccl) 3-butanoic acid. Preparation analogously to example 14 of cycloxylamine salt (so pl. 197-198-C. Decomposition) 4- (4-chloro-4-biphenylyl) -3-buteic acid in 63% yield and so on. 187-188 ° C (from cyclohexane / ethyl acetate); its cyclohexyl .-: min salt has so pl. 198-200 ° C (from ethanol} EXAMPLE 19 trans-4- (2-Far-4-bifennlil) -3-butenoic acid. A mixture of 3 g of ethyl 4- (2-fluoro) is heated 4-biphenylyl) -4-hydroxybutyric acid with 12 g of pyridine hydrochloride over 2 hours to 165 ° C. After cooling, hydrochloric acid is added to the reaction mixture, the precipitated is taken up in ether, the ether solution is washed with water and dried over sulfate sodium. From this ethereal solution, cyclohexylamine salt is precipitated by adding cyclohexylamine with a melting point of 178 ° C. Yield 2.8 g (79% of theoretical) Example 20. Am id trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid. A solution of 20.6 g of trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid chloride (mp. 106 -1O8 ° C) in 1OO ml of benzene, transferring further ammonia gas, are added dropwise in ZOO ml of benzene saturated with ammonia gas. After the addition is completed, stir for 15 min, then the reaction mixture is introduced into 500 ml of water, added 2OO ml of ethyl acetate are separated, the organic phase is separated, washed twice with water, dried over sodium sulfate and the solvent is distilled off. The solid residue is recrystallized from ethyl acetate. Obtain 12 g (62.7% of theoretical) amide of trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid with so pl. 1310С. Example 21. Amide of trans-4- (2-fluoro-4-biphenylyl) 3-butenoic acid. While stirring and cooling, a solution of 2.7 g of chloride of trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid in 25 ml of acetone is added dropwise to 50 ml of 30% aqueous ammonia. After the addition is complete, continue stirring in for Yu min and diluted in an amount of 1OO ml. The precipitate is filtered off with suction and recrystallized from cyclohexane / ethyl acetate; 1.5 g (60% of the theoretical) amide of trans 4- (2-fluoro-4-biphenylyl) -3-bug1 Ovic acid with m.p., l30-13lC is obtained. Example 22. Methyl amide HC-4- (2-fluoro-4-biphenyll) -3-bute1 Ovo; g of 3 parts 7 g of methylamine is dissolved in ZOO ml of benzene and, non-reggae; giva, drop by drop 20.6 g of trans-4 - (2-fluoro-4-bifeshil) -3-butenoic acid in 1OO ml of benzene. Obrabstich, -; from and .-% reamer l-l way. Yield 10.5 g (D 1.8% 01 Teopevi-scKoro) methylamcd; - (2-fluoro-4-bpfe and; h | l; -3-butenol acid with so-called 135 ° C (coxaceous Yfira). Pr i; meper 23. Methylamnd trans --- (2-fluoro-4-bnphenylyl) -3-butenose acid. To 5O ml of 35% -iioro aqueous mettlackmda, stirring, add a drop of 2.7 g of trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid chloride in 25 ml of acetone. Once the addition is complete, stir for 10 minutes and the precipitate is filtered off. After recrystallization from cyclohexane / ethyl acetate, 1.5 are obtained g (55.8% of theoretical) methyl amide trans-4 -12-fluoro 4-b fenilpl) -3-butenoic acid, m.p. 135-J3R ° C. Example 24. Etilamps trans-- - (2-fluoro-4-biphenylyl) -3-butenoic acid. This compound is crawled as in Example 23 from trans-4- (2-fluoro-4-β-biphenylyl) -3-butenoic acid chloride and an aqueous solution of ethylamine. Output 7 0.5 / o from theoretical ethylamide TRANS-4- (2-fluoro-4biphenylyl) -3-bu tonic acid with so pl. 10-14-10 ° C (from cyclohexane). Example 25. Trans-4- (2-fluoro-4-biphenyl-1sh) -3-butenoic acid isopropylamide. This compound was prepared analogously to example 23 from trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid chloride and an isopropylamine solution. The yield of trans-4- (2-fluoro-4-bifesh-shil) -3-butenoic acid isopropylamide is 51% of the theoretical (mp. 124-125 ° C, from cyclohexa-;). Example 26. Propylamide trans-- - (2-fluoro-4-biphenylyl) -3-butenoic acid. This compound is analogous to example 23 of tr and non-4- (2-fluoro-4biphenylyl) -3-butenoic acid chloride and an aqueous solution of propylamine. The yield of propyl amide trans-4- {2-fluoro-4-biphenylyl) -3-butene acid is 68% of the theoretical. Mp.107-109 ° C (from cyclohexane / ethyl acetate). Example 27. Amide of trans-4- (2-chloro-4-biphenylyl) -3-butenoic acid. This compound is obtained analogously with measure 21 of trans-4- (2-chloro-4-biphenylyl) -3-butenoic acid chloride. and 30% aqueous ammonia. M.p. 135-137 ° C (from 60% methanol). Yield 77% of theoretical. Example 28. Methylamide TRANS-4- (2-chloro-4-biphenylyl) -3-butenoic acid. This compound is prepared analogously to Example 23 from trans-4- (2-chloro-4-bi-phenylyl) -3-butenoic acid chloride and aqueous methylamine. M.p. 146-147 ° C (.KZ 70% methanol). Output 82% of theoretical. Example 29. Trans-4- (2-fluoro-4-biphenylyl) -3-butenoic acid 4-oxyfesch-amide. To a solution of 4.4 g of 4-aminophenol in 40 ml of acetone, while stirring, a solution of 5.4 g of trans-4- (2-fluoro-4-biphenipyl) -3-butenoic acid chloride in 25 ml of acetone is added dropwise. After the addition is complete, stirring is continued for 2.5 hours at room temperature and some water is added. The precipitate formed is filtered off with suction and re-precipitated from ethanol / water. The specified amide is obtained with m.p. 172-173 ° C and a yield of 6 g (87% of theoretical). Example 30. Amide of trans-4- (4-fluoro-4-biphenylyl) -3-butenoic acid. To a solution of 11 g of trans-4- (4-fluoro-4-biphenylyl) -3-butenoic acid chloride in 150 ml of benzene, stirring and cooling, add ammonia gas for 30 min, then stir for 15 min and add BOOO ml of ethyl acetate. This solution is washed with water, filtered over coal and freed of solvent. The residue is recrystallized from ethyl acetate. Get specified amide with so pl. 223 ° C; The output of 4.6 g (45% of theoretical). Example 31. Amide of trans-4- (4-chloro-4-biphenylyl) -3-butenoic acid. A solution of 9 g of trans-4- (4-chloro-4-biphenylyl) -3-butenoic acid chloride (mp. 96-97 C) in 50 ml of ether is added in 25O ml of ammonia-saturated ethereal solution while stirring. After stirring, the ammonia gas was injected for 30 minutes and the initial mixture was allowed to stand for 12 hours at room temperature. The resulting precipitate is sucked off, mixed with water and recrystallized from ethanol. Get „specified amide with so pl. 224 With and an exit of 3 g (33,4% of theoretical). Example 32 trans-4- (2-Chloro-4biphenylyl) -3-butenoic acid. This compound is prepared analogously to example 14 of 4- (2-chloro-4-biphenylyl) -4-hydroxyrotic acid with mp. 119-121 ° C. Yield 44% of theoretical. M.p. free acid 131-132 C (from benzene). M.p. salts of cyclohexylamine 154-1550С (from ethyl acetate with 5% methanol added). Example 33 trans-4- (2, 4-difluoro-4-biphenylyl) -3-butenoic acids a. Preparation analogously to example 14 of the cyc; Log-hexylamine salt of 4- (2, 4-biphenylyl) -4-hydroxyrotic acid with m.p. 181-, 183 ° С. Output 82% of theoretical. T. pl. free acid 171-172 0 (from ethyl acetate). M.p. cyclohexylamine salt 166-167 ° C. Example 34. trans-4- (2-Chloro-4-fluoro-4-biphenylyl) -3-butenoic acid. This compound was prepared analogously to example 14 from the salt of cyclohexylamine 4- (2-chloro-4-fluoro-4-biphenylyl) -4-hydroxycratic acid with m.p. 181-182 ° C. Output 78% of theoretical. M.p. free acid 138-139 ° C. M.p. salts of cyclohexylamine 170-171 ° C. Example 35 trans-4- (2-Cyan-4-biphenylyl) -3-butenoic acid. This compound was prepared analogously to example 14 from the salt of cyclohexylamine 4 (2-cyano-4-biphenylyl) -4-hydroxybutyric acid with mp. 167-168 ° C. Output 86% of theoretical. Melt free acid 176177 ° С (from ethyl acetate / tetrachloromethane 1: 1). M.p. salts cyclohexylamine 1b8-169 ° C (from ethyl acetate with 10% methanol). Example 36. trans-F- (3-Fluoro-4-biphenylyl) -3-butenoic acid. This compound is prepared analogously to example 14 of 4- (3-fluoro-4-biphenylyl) -4-hydroxyrotic acid with mp. 138-140-C. Yield 21% of theoretical. M.p. salts of cyclohexylamine 176-177 ° C. Example 37. trans-4- (3-Chloro-4-biphenylyl) -3-butenoic acid. This compound is prepared analogously to example 14 of 4- (3-chloro-4-bi (benlyl) -4-hydroxyrotic acid with a melting point of 122-123 ° C. Yield 38% of theoretical. Mp. Salt of cyclohexylamine 165- 166 ° C (from ethyl acetate with ethanol). Tpl. Free acid 149-151 ° C. Example 38. trans- 4- (2,2-Difluoro-4 biphenylyl) -3-butenoic acid. The compound is prepared analogously, when measure 14, from a salt of cyclohexylamine 4- (2,2-difluoro-4-biphenylyl) -4-hydroxycrotic acid with mp 159-161 ° C. Yield 13% of theory. Mp of cyclohexylamine salt 166-167, SC (from acetone with application activated carbon.) T.pl. free kispota 72-74 ° C (from ethyl acetate / petroleum ether). Example 39. trans-4- (2-Fluoro-4-biphenylyl; -3-butenoic acid. This A compound is prepared analogously to Example 14 of 4- (2-fluoro-4-biphenylyl) -4-hydroxy-crotonic acid with a melting point of 1.40-142 C. You run 44% of the theoretical. So the free acid is 127-129 With The melting point of the cyclohexnlamine salt is 175-176 ° C (from methanol / ethyl acetate - 2: 8). Example 40. Amide of trans-4- (3-chloro-4-biphenylyl) -3-butenoic acid. 30.9 g (0.09 mol) of trans-4- (3-chloro-4-biphenylyl) -3-butenoic acid ethyl ester is dissolved in 80 O ml of methanol, saturated with ammonia, and heated in an autoclave under an ammonia pressure of 20 atm. within 6 hours to 100 ° C. After cooling, the solvent is distilled off, water is added and acidified with dilute hydrochloric acid. Then it is extracted with ethyl acetate until exhaustion. The ethyl acetate extracts are washed first with a saturated solution of Macb, and then with water, dried over sodium sulfate and again evaporated. The residue crystallizes upon trituration with ethyl acetate. After recrystallization of amide, trans-4- (3-chloro-4-biphenylyl) -3-butenoic acid from ethanol and methanol, each time with the use of activated carbon, it has a melting point of mp. 1861880С. Yield 2.0 g (8% of theoretical). Example 41. trans-4- (4-Fluoro-4-biphenylyl) -3-butenoic acid. This compound was prepared analogously to example 14 of 4- (4-fluoro-4-biphenylyl) -4-hydroxyrotic acid (mp. 180-181 ° C). Mp. acids 198-199 ° C (from benzene and ethanol). Mp of cyclohexylamine 175176 ° C (from isopropanol). From the mother liquor, cis-4- (4-fluoro-4-biphenylyl) -3-butenoic acid is obtained with a yield of 4.1% of the theoretical. M.p. salts of cyclohexylamine 162-164 ° C (from isopropanol). of the invention of Formulas 1. A method for the preparation of derivatives of C- and / or 2-butenoic acid of a common forg-xsula S where K is a branched or unbranched alkyl radical with 1-7 carbon atoms, S-, 6- or 7-membered cycloalkyl or cycloalkenyl, piperidino - or a phenyl radical, unsubstituted or substituted by one or two halogen atoms, or an amino group, unsubstituted or substituted, with an aliphatic acyl radical with 1-4 carbon atoms; j is a hydrogen atom, a halogen, or if 1 has the indicated meanings, with the exception of an unsubstituted or substituted phenyl radical, the amino group, and if it means an unsubstituted feshne means a water atom, of the genus; B is a hydroxy group, an alkoxy radical with 1-4 carbon atoms or a radical of the general formula in which R, and jR. , identical or 4 different, denote hydrogen atoms or, if R denotes an unsubstituted or substituted fekyl radical of the indicated value, as well as alkyl radics;: with 1-3 carbon atoms and if it means bo4 denotes a nat, then RJ can also be an oxyphenyl radical ; A is a divalent radical —C — CH — CH — or —CH — CH — CH — CH and, if B is an oxy group, their salts with inorganic or organic bases or. if R or 1 contains basic groups, their salts with inorganic or organic acids, characterized in that the compounds of the general formula C — CCH and S-SOON in which L Y have the indicated meanings, undergo a reaction of exchange decomposition with zinc or amalgamated zinc with SO -ISO-C B in the presence of acid, followed by separation of the resulting mixture of 2- and 3-butenoic acids n / or separation into 2-- and 3-butekovy acids, total 15. „52 formulas I and / or simultaneously cis- and trans- isomers of these acids, and / or translation into esters, amides, or salts of acids about formula 1 known techniques. 2. A method according to claim 1, characterized in that hydrochloric acid is taken as the acid. 3. The method according to claim 1, that is, that the process is conducted in an inert solvent. 4. The method according to claim 1, wherein the separation into 2- and 3-butenoic acids of general formula I and their cisi trans-isomers is carried out by fractional crystallization. 5. The method according to claim 1, 1, tol and h and y with the fact that, in order to obtain compounds of general formula X, where R is an aminophenyl group, a compound of general formula I, where R is an acylaminophenyl group, is subjected to hydrolysis in an alkaline environment. Priority signs: 08. O2. 72 obtaining compounds of general formula I, where. -phenyl radical, unsubstituted or substituted by one or two halogen atoms or an amino group, unsubstituted or substituted by aliphatic acyl radicals with 1-4 carbon atoms, R., B, Ro, Ri and A have the indicated meanings; 15. 05. 72 obtaining compounds of general formula I, where R. is a branched or unbranched alkyl radical with 1-7 carbon atoms, 5-, 6- or 7-membered cycloalkyl, cycloalkenyl or piperidino radical.