SU545258A3 - The method of obtaining 1-substituted pyrazolone-5 or their salts - Google Patents

Description

Especially 3-aminopyrazolones- (5) may also be in the following imino forms

one

..in t

V

BUT

HC-R,

Id

The proposed method for the preparation of 1-substituted pyrazolones (5) of formula I, based on a reaction known in organic chemistry, is that hydrazine of formula I

Кз-СН-Ж-Жг

II g

where Ra and Kz have the above meanings, are reacted with an acetic acid derivative of the formula III

III

where RI is as defined above, X is a hydroxy, alkoxy, aralkoxy, amino or alkylamino group; Y means a hydrogen atom,

G Y means nitrile or group

Y means a hydrogen atom, or alkyl with 1-4 carbon atoms, or phenyl or trifluoromethyl, or

/ Nh,

Y and Y mean group C

///

where Y means alkoxy, aryloxy-, aralkoxy, alkyl mercapto, or aralkyl mercapto or amino group at a temperature of from 10 to 200 ° C,

and isolate the desired product in free form or as a salt.

The process is carried out predominantly in the presence of an inert solvent and a basic or acidic catalyst as hydroxide or alkali or alkaline earth metal carbonate, or as a hydrogen halide, sulfuric or sulfonic acid.

The optical antipodes of the compounds are obtained by the interaction of the compounds and preferably by the exchange decomposition reaction of the compound according to the invention with a derivative of an optically active acid, for example campransulfone, bromocamphenesulfone or quinn, or an optically active base, for example brucin, morphine or strychnine, into a mixture of diastereometric reaction products, physicochemical methods, for example fractionation, are separated and obtained in pure form and decomposed again into their components or by reaction BMENA decomposition optically pure hydrazine of the formula II with acetic acid derivative of formula III.

As examples of the starting compounds of the formula II can be called:

a-methyl-3-chlorobenzylhydrazine,

cx-methyl-3-bromobenzylhydrazine, a-methyl-4-chlorobenzylhydrazine, a-methyl-4-chlorobenzylhydrazine, a-methyl-4-bromobenzylhydrazine, a-methyl-3,4-dichlorobenzylhydrazine,

a-methyl-3,4-dibromobenzylhydrazine,

a-methyl-3-bromo-4-chlorobenzylhydrazine, a-methyl-4-bromo-3-chlorobenzylhydrazine, a-methyl-4-methylbenzylhydrazine, a-methyl-3-methylbenzylhydrazine,

a-methyl-3-ethylbenzylhydrazine,

a-methyl-4-trifluoromethylbenzylhydrazine, a-methyl-3-chloro-4-methylbenzylhydrazine, a-methyl-4-chloro-3-methylbenzylhydrazine, a-methyl-4-methyl-3 - trifluoromethylbenzylhydrazine,

a-methyl-3-chloro-4-trifluoromethylbenzylhydrazine,

a-methyl-4-chloro-3-trifluoromethylbenzylhydrazine,

a-methyl-4-sulfonamidobenzylhydrazine,

a-methyl-4-chloro-3-sulfonamidobenzylhydrazine,

a-methyl-4-methoxybenzylg11Drazine, a-naphthyl- (2) -ethylhydrazia,

a-methyl-3,4-tetramethylbenzylhydrazine,

a-methyl-3,4-methylenedioxybenzylhydrazine, a-ethyl-4-chlorobenzylhydrazine, cc-ethyl-3-chlorobenzylhydrazine, a-ethyl-3,4-dichlorobenzylhydrazine,

a-ethyl-4-bromo-3-chlorobenzylhydrazine, a-ethyl-3-chloro-4-methylbenzylhydrazine. Examples of starting compounds of the formula III can be acid esters: cyano acetic acid methyl ester,

cyano acetic ethyl ether,

cyano acetic propyl ether, cyano acetic isopropyl ether, cyano acetic n-butyl ether, cyano acetic isobutyl ether,

cyano acetic tert-butyl ester, cyano acetic hexyl ester, cyano acetic benzyl ester, cyano acetic amide, cyano acetic methylamide,

cyano acetic diethylamide, cyano acetic butylamide, a-cyanopropionic methyl ester, a-cyanopropionic ethyl ester, a-cyanopropionic propyl ester,

isopropyl ester a-cyanopropionic, but; ol-butyl ester a-cyanopropionic, isobutyl ester a-cyanopionic, gret.-butyl ester a-cyanopropionic, hexyl ester a-cyanopropionic,

benzyl ester a-cyanopropionic,

amide a-cyanopropionic,

Methyl MFA ss-cyanopropionic,

diethyl amide a-cyanopropionic,

butylamide a-cyanopropionic,

ethyl ester is a-cyanobutton,

treg.-butyl ester a-cyanomer,

diethyl amide a-cyanobutton,

ethyl etsr p-amino-p-ethoxyacrylate,

p-amino-p-methoxyacrylic ethyl ester,

p-amino-p-butoxy acrylic butyl ester,

p-amino-p-phenoxyacrylic ester ethyl ester, p-amino-p-benzyloxyacrylic benzyl ester,

amide p-amino-p-ethoxyacrylic, diethylamide p-amio-p-ethoxyacrylic, ethyl ester p-amino-p-methylmercapto, ethyl ester p-amino-p-benzylmercaptoacrylate,

amide p-amino-p-methylmercaptoacrylic, ethyl ester of p, p-diaminoacrylic, amide p, p-diaminoacrylic, ethyl ester of p-amino-p-methoxymethacrylic, ethyl ester of p-amino-p-ethoxymethacrylic,

p-amino-p-butoxymethacrylic butyl ester, p-amino-p-phenoxymethacrylic ethyl ester, p-amino-p-becyloxymethyl acrylic ethyl ester, p-amino-p-methylmercaptomethacrylic ethyl ester, p-amino-p-benzylmercaptomethacrylate ethyl ester,

amide p-amino-p-ethoxymethacrylic, diethylamide p-amino-p-ethoxymethacrylic, amide p-amino-p-methylmercaptomethacrylic,

ethyl ester of p, p-diaminomethacrylic, amide of p, p-diaminomethacrylic, ethyl ester of p-amino-p-ethoxy-a-ethyl acrylic, ethyl ester of p-amino-p-methylmercapto-ethyl ethyl acryl,

amide p-amino-p-ethoxy-a-ethyl acrylic, ethyl ester p-amino-p-ethoxy-a-phenyl acrylic, ethyl ester p-amino-p-ethoxy-a-benzylacrylate,

ethyl ester , benzoyl acetic ethyl ester, pp-.acetylpropionic ethyl ester.

a-acetylpropionic n-butyl ester, a-acetylpropionic n-butyl ester, a-propionylpropionic ester ethyl ester, a-propionylpropioic isopropyl ester,

ethyl a-acetyl ether, ethyl a-propionyl ether, isopropyl a-propionyl oil, ethyl a-benzoylacetoacetate, ethyl ester, co, (o-trifluoroacetoacetic.

As solvents can be called all inert and, if they can be mixed with water, diluted with water, organic solvents. To them belong preferably hydrocarbons - benzene, toluene, xylene, halohydrocarbons - methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, alcohols - methanol, ethanol, propanol, butoNOL, benzyl alcohol, glycol monomethyl ether, ethers - tetrahydrofsphan, dehydrate, and aitrate, in a simple manner; dimethylacetamide, N-methylpyrrolidone, triamide hexamethylphosphoric acid, sulfoxides - dimethyl sulfoxide, sulfones - sulfolane and bases - pyridine, picoline, collidine, lutidine and quinoline. Inorganic and organic bases may be referred to as basic condensing agents. These preferably include alkali metal hydroxides, sodium hydroxide, potassium carbonate and alcohols — sodium alcoholate and potassium alcoholate. Inorganic and organic acids can be called acid catalysts. They preferably include hydrohalic acids, sulfuric acid and sulfonic acids - toluenesulfonic and trifluoromethylsulfonic. The process is preferably carried out at a temperature of 20-100 ° C.

They work at normal pressure, but it is also possible to work in closed vessels with increased pressure. The predominantly precipitated in crystalline form, the compounds according to the invention can be easily purified by recrystallization from an appropriate solvent.

The amounts indicated above can, of course, vary slightly. In addition to the compounds of formula I given in the examples, the following can be mentioned:

3-amino-4-methyl-1- (a-methyl-3 - chlorobenzyl) pyrazolone- (5),

3 - amino-4-methyl-1- (a-methyl-3,4-di.chlorobenzyl) -pyrazolone- (5),

3-amino - 4-methyl-1- (a-methyl - 3-chloro-4-methylbenzyl) -pyrazolone- (5),

3-amino-4-methyl-1- (a-methyl-4-trifluoromethylbenzyl) -pyrazolone- (5).

3-amino - 4-methyl-1- (a-methyl-3-x, tor-4-bromobenzyl) -pyrazolone- (5),

3-amino-4-methyl-1- (a-naphthyl - (2) -ethyl) pyrazolone- (5), 3-amino-4-methyl-1- (a-methyl-3-fluorobenzyl) -pyrazolone- ( 5), 3-amino-4-methyl-1 - (a-methyl-4-fluorobenzyl) -pyrazolone- (5), 3-amino-4-methyl-1- (a-methyl-3,4 - difluorobenzyl) -pyrazolone- (5), 3-amino-4-methyl-1- (a-methyl-3-chloro-4-fluorobenzyl) -pyrazolone- (5), 3-amino-4-methyl-1- (a- methyl 3,4-di- (fluoromethyl) -benzylpyrazolone- (5), 3-amino-4-methyl-1- (a-methyl-3,4 - tetramethylenebenzyl) -pyrazolone- (5), 3-amino- 4-methyl-1- (a-methyl-2,3-tetramethylenebenzyl) -iirazolone- (5), 3-amino-4-methyl- (4-pyridyl) -ethyl pyrazolone- (5), 3-amino-4 -methyl-1- a- (3-pyridyl) - ethyl irazolo - (5), 3,4-dimethyl-1 - (a-methyl-4-chlorobenzyl) -pyrazolone- (5), 3,4-dimethyl - 1- (a-methyl-3-chloro-4 - methylbenzyl) -pyrazolone- (5), 3,4-dimethyl - 1- (a-methyl-4-bromo-3 - chlorobenzyl) -pyrazolone- (5), 3,4-dimethyl-1- (a-methyl - 4 - trifluoromethylbenzyl) -pyrazolone- (5), 3,4-dimethyl-1-a- (naphthyl- (2) -ethyl-pyrazolone- (5), 1- (a-methyl-3,4-dichlorobenzyl) -pyrazolone- (5), 3-amino - 1- (a-methyl-3-chlorobenzyl) -pyrazolone- (5), 3-amino-1 - (a-methyl-3-bromobenzyl) -iirazolone- (5), 3- amino-1- (a-methyl-3-fluorobenzyl) -pyrazolone- (5), 3-amino-1 - (a-methyl-4-fluorobenzyl) -pyrazolone- (5), 3-amino-1- (a -methyl - 4-chlorobenzyl) -pyrazolone- (5), 3-amino - 1- (a-met L-4-iodobenzyl) -pyrazolone- (5), 3-amino-1- (a-methyl-4-trifluoromethylbenzyl) -pyrazolone- (5), 3-amino-1- (a-methyl-4-trifluoromethoxybenzyl) -pyrazolone- (5), 3-amino-1- (a-methyl-3-trifluoromethyl-4-methylbenzyl) -pyrazolone- (5), 3-amino-1- (a-methyl-3-chloro-4 - bromobenzyl) pyrazolone- (5), 3-amino-1-o-methyl-4-chloro-3-sulfonamidobenzyl) -pyrazolone- (5), 3-amino-1-a-naphthyl- (2) -ethyl-pyrazolone - (5), 3-amino-1 - (a-ethyl-4-nitrobenzyl) -pyrazolone- (5), 3 - amino-1- (a-ethyl-4-cyanobenzyl) -pyrazolone- (5), G -amino-1- (a-n-propyl-2-chloro-4-fluorobenzyl) -pyrazolone- (5), 3-amino-1- (a-methyl-3,4-difluorobenzyl) -pyrazolone- (5) 3rd no-1-a-methyl-3,4-di- (trifluoromethyl) -benzyl-pyrazolone- (5), 3-amino-1-a- (4-iridin) -ethyl-pyrazolone- (5), 3- amino - (3-pyridyl) -ethyl - pyrazolone- (5), 3-amino-1- (a-methyl-3,4-tetramethylenebenzyl) -pyrazolone- (5), 3-amino-1- (a-methyl -2,3 - tetramethylenebeizyl) -pyrazolone- (5), 3-methyl-1- (a-methyl-4-butylbenzyl) -pyrazole- (5), 3-methyl-1- (a-methyl-3-trifluoromethyl -4 chlorobenzyl) -iirazolone- (5), 3-methyl-1- (a-methyl-4-sulfonamidobenzyl) -pyrazolone- (5), 3-methyl-1- (a-methyl-4-dimethylaminobenzyl) -irazolone- (5), 3-methyl-1- (a-methyl-3,4-tetramethylenebenzyl) -irazolone- (5), 3-methyl-1- (a - methyl-3-chloroben yl) -pyrazolone- (5), 3-methyl-1- (a-methyl-2-chlorobenzyl) -pyrazolone- (5), 3-methyl-1- (a-methyl-3,5-dichlorobenzyl) -pyrazolone - (5), 3-methyl-1- (a-methyl-3-fluorobenzyl) - irazolo- (5), 3-methyl - 1- (a-methyl-4-chloro-3-bromobenzyl) pyrazolone- (5 ), 3-methyl-1- (a-methyl-4-fluoro-3-chlorobenzyl) pyrazolone-5, 3-methyl-1- (a-methyl-3-methylbenzyl) -pyrazolone- (5), 3-methyl -1 - (a-methyl-4-ethylbenzyl) -pyrazolone- (5), 3-methyl-1- (a-methyl-4-chloro-3-methyl) -pyrazolone- (5), 3-methyl-1 - (a-methyl-4-fluoro-3-methyl) -iirazolone- (5), 3-methyl-1- (a-methyl-3-methyl-5 - chlorobenzyl) pyrazolone- (5), 3-methyl - 1- (a-methyl-3,5-dimstilbenzyl) pyrazolone- (5), 3-methyl - 1- (a-methyl-3-chloro-4-trifluoromethylbenzyl) -pyrazolone- (5), 3-methyl-1- (a-methyl-3-methyl-4-trifluoromethylbenzyl) -pyrazolo- (5), 3- methyl 1- (a-methyl-3-methoxybenzyl) -pyrazolone- (5), 3-methyl-1- (a-methyl-4-etkeibenzyl) -pyrazolone- (5), 3-methyl-1- (a -methyl-3-ethylbenzyl) -pyrazolone- (5), 3-methyl-1- (a-methyl-3,4-difluorobenzyl) -pyrazolone- (5), 3-methyl- (3-pyridyl) -ethyl - pyrazolone- (5), 3-methyl-1- (a-methyl-3,4-tetramethylbenzyl) pyrazolone- (5), 3-methyl-1- (a-methyl-2,3 - tetramethylbenzyl) pyrazolone- (5 ), 3-ethyl-1- (a-methyl-3-methyl-4-chlorobenzyl) pyrazolone- (5), 3-ethyl-1- (a-methyl-3-chloro-4-methylbenzyl) pyrazolone- (5 ),

3-ethyl - 1- (o-methyl-3,4-dichlorobenzene) -pyrazolone- (5),

Z-ethyl-1- (a - methyl-4 - trifluoromethoxybenzyl) -pyrazolone- (5),

3-ethyl-1- (s-methyl-4-methyl-3 — trifluoromethylbenzyl) -pnrazolone- (5),

3-ethyl-1- (a-methyl-4-bromo-3-chlorobenzyl) pyrazolone- (5),

3-isopropyl-1- (a-methyl-3,4-dichlorobenzyl) pyrazolone- (5),

3-trifluoromethyl - 1- (a-methyl-4-chlorobenzyl) pyrazolo- (5),

3-trifluoromethyl-1- (a - methyl-3-chlorobenzyl) and irazoloi- (5),

3-trifluoromethyl-1- (a-methyl-4-bromobenzyl) pyrazolone- (5),

3-trifluoromethyl-1- (sb-methyl-4-fluorobenzyl) irazolone- (5),

3-trifluoromethyl - 1- (a-methyl-3-chloro - 4-methyl) -irazolone- (5),

3-trifluoromethyl - 1- a-naphthyl- (2) -ethyl-irazolone- (5),

3-trifluoromethyl-1 - (a-methyl-3-bromo-4-chlorobenzyl) -irazolo- (5),

3-phenyl-1- (a-methyl-3,4-dichlorobenzyl) - pyrazolo- (5),

3-phenyl-1- (a-methyl-3-chloro-4-methylbeisyl) -irazolone- (5),

3-phenyl-1- (a.-methyl-3-methyl-4-chlorobenzyl) -irazolone- (5),

3-phenyl-1- (cc-n.-proiylbenzyl) -iirazolone (5),

Z-feiil-1 - (an. - yropylbenzyl) - iirasoloi- (5),

3-phenyl-1- (cc-ethyl-3,4-dichlorobenzyl) - irazolone- (5),

3-feiil-4-methyl - 1- (a - methylbenzyl) -iirazolone- (5),

3-phenyl - 4-methyl-1- (a-methyl-4 - trifluoromethylbenzyl) -irazolone- (5),

3-phenyl - 4-methyl-1- (a-methyl-3,4-dichlorobenzyl) -pyrazolone- (5),

3-phenyl-4-ethyl - 1- (was-methyl-3-chloro-4-methylbenzyl) -pyrazolone- (5),

3-phenyl - 4-ethyl-1- (a-ethyl-3,4-dimethylbenzyl) -pyrazolone- (5).

Example 1. Preparation of 3-methyl-1- (a-methyl4-methylbeisyl) -pyrazolone- (5).

26 g (0.2 mol) of acetic acid ethyl ester are dissolved in 20 ml of absolute ethanol. To this solution, iodine nitrogen, is slowly added 30.0 g (0.2 mol) of a-methyl-4-methylbenzylhydrazine in absolute ethanol. After extinction of the exothermic reaction, the mixture is heated under reflux for 2 hours.

Upon cooling, the crude product crystallizes out and is purified by recrystallization from methanol; T. Il. 144-146 ° C; yield 28 g (65% of theory).

Example 2. By analogy with Example 1, the synthesis provides the following compound.

3-Methyl-1- (a-methyl-4-bromobenzyl) -iirazolone- (5) is obtained from ethyl acetate and a-methyl-4-bromobenzyl hydrazine. The product is recrystallized from dimethylformamide; T. Yl, 150-152 ° C; yield 86% of theory.

Example 3. 3-Methyl-1- (a-methyl-3,4-dichloroabisyl) -pyrazolone- (5) is obtained from acetic acid ethyl ester and a-methyl-3,4-dichlorobenzyl hydrazine. The resulting product is recrystallized from ethanol; T. Il. 143-145 ° C; yield 77.7% of theory.

Example 4. 3-Methyl-1- (a-methyl-3-chloro-4-methylbenzyl) -pyrazolo- (5) is prepared from acetic acetic acid ethyl ester and cc-methyl-3-chloro-4-methylbenzylhydrazine. The product obtained is recrystallized from metaiol; T. Il. 140-142 ° C; yield 80% of theory.

Example 5. 3-Methyl-1- (cc-methyl-4-fluorobenzyl) -pyrazolone- (5) is obtained from acetic acid ethyl ester and a-methyl-4 fluorobluzyl hydrazia. The resultant product and recrystallized from ethiol; m.p. 140-142 ° C; yield 75% of theory.

Example 6. 3-Metpl-4-methyl-1- (a-methyl4-methylbenzyl) -pyrazolone- (5) is obtained from

a-methyl acetic acid ethyl ester and a-methyl-4-methylbenzylhydrazine. The resulting product is recrystallized from metaiol; T. Il. 131 - 133 ° C; yield 59% of theory.

Pr and measures 7. 3-Methyl-4-methyl-1- (a-methyl 3, 4-dichlorobenzyl) -iirazolone- (5) is obtained from ethyl ester of c-methylacetoacetic acid and a-methyl-3,4-dichlorbeisyl hydrazine. The resulting product is recrystallized from

ethane-ethanol; m.p. 160-162 ° C; yield 60% of theory.

EXAMPLE 8. 3-Methyl-4-methyl-1- (a-methyl-3-chloro-4-methylbenzyl) -pyrazolone- (5) is obtained from a-methyl-acetic acid ethyl ester and cc-methyl-3- chloro-4-methylbenzylhydrazine. The resulting product is recrystallized from methanol; m.p. 145-147 ° C; output

65% of theory;

PRI me R 9. 3-Metl-4-methyl-1- (a-methyl-4-fluorobenzyl) -iirazoloy- (5) is obtained from a-methyl acetate acetic acid and a-methyl-4-fluorobenzyl hydrazine. The resulting product is recrystallized from ethiol; m.p. 102-104 ° C; yield 43% of theory.

Example 10. 3-Methyl-4-allyl-1- (a-methyl 3, 4-dichlorobenzyl) -iirazoloy (5) and obtained from a-allyl acetylacetic acid ethyl ester and os-methyl-3,4-dichlorobenzyl hydrazine. The resulting product is recrystallized from

ethanol; T. Il. 124-125 ° C; yield 75% of theory.

Example 11. 3-1-Methyl-4-allyl-1- (a-methyl 4-methyl-benzyl) -iirazolone- (5) and obtained from a-allyl acetylacetic acid ethyl ester and a-methyl-4-methyl-benzyl hydrazine. The resulting product is recrystallized from ethanol, so pl. 138-139 ° C; yield 49% of theory. Example 12. 3-Methyl-4-ethyl-1- (a-methyl 3, 4-dichlorobenzyl) -pyrazolone- (5) is obtained from

II

α-ethyl acetic acid ethyl ester and α-methyl-3,4-dichlorobenzyl hydrazine. The resulting product is recrystallized from ethanol. T. pl. 153-155 ° C. Output 60% of theory.

Example 13. 3-Methyl-4-phenyl-1- (a-methyl3, 4-dichlorbeisyl) -pyrazolone- (5) is obtained from cc-feiyl acetic acid ester ethyl ester. The resulting product is recrystallized from a mixture of ethanol-dimethylformamide.

Example 14. 3-Methyl-4- (4-methoxybenzyl) 1- (a-methyl-4-methylbenzyl) -iirazolone- (5) is obtained from a-methyl-4-methylbenzylhydrazine and a- (4-methoxybenzyl)-ethyl acetic acid ester. The resulting product is recrystallized from ethanol with a small amount of dimethylformamide; m.p. 146-147 ° C; yield 60% of theory.

Example 15. 3-Methyl-4- (4-methoxybenzyl) 1- (a-methyl-3,4-dichlorobenzyl) -pyrazolop- (5) is obtained from a-methyl-3,4-dichlorobenzyl hydrazine and a- (4- methoxybenzyl) ethyl acetic acid ester. The resulting product is recrystallized from ethiol; T. Il. 172-174 ° C; yield 64% of theory.

Example 16. 3-Methyl-4-benzyl-1- (a-methyl 3, 4-dichlorobenzyl) -pyrazolo- (5) is prepared from acet-acetic acid a-benzylethyl ester and and.-Methyl-3,4-dichlorobenzyl hydrazine. The resulting product is recrystallized from a mixture of dimethylformamide - ethanol; m.p. 175-177 ° C; yield 73% of theory.

Example 17. 3-Methyl-1 - (s, -aphyl- (2) ethyl) -pyrazolone- (5) and obtained from ethyl ester of acetoacetic acid and c-naphthyl- (2) ethyl hydrazine. The resulting product is recrystallized from ethanol; m.p. 145-147 ° C; yield 35% of theory.

Example 18. 3-Methyl-1-a-pyridyl- (4) ethyl-iirazolone- (5) is prepared from acetoacetate and a-pyridyl- (4) ethyl hydrazine. The resulting product is recrystallized from ethanol; m.p. 146-148 ° C; yield 42% of theory.

Example 19. 3-Trifluoromethyl-1- (a-methyl-4-fluorobisyl) -pyrazole- (5) is obtained from trifluoroacetoacetic acid ethyl ester and cc-methyl-4-fluorobizyl hydrazine. For purification, precipitated from ether with petroleum ether; m.p. 168-170 ° C, yield 32% of theory.

Example 20. 3-Trifluoromethyl-1- (cc-methyl3, 4-dichlorobenzyl) -pyrazolone- (5) is prepared from trifluoro and ethoacetic acid ethyl ester and cc-methyl-3,4-dichloro-isylhydrazine. The resulting product is recrystallized from ether - etaiol; m., -. 203-205 ° C; yield 23% of theory.

Example 21. 3-Phenyl-1- (a-ethylbenzyl) irazolo- (5) is prepared from benzoplucose ester and a-ethylbeisylhydrazine. The resulting product is recrystallized from dimethylformamide; m.p. 170-172 ° C; yield 78% of theory.

12

Example 22. 3-Phenyl-1- (a-methyl-3,4-dichlorobenzyl) -pyrazolone- (5) is obtained from benzoyl acetic ester and a-methyl-3,4-dichlorobenzyl hydrazine. The resulting product is not recrystallized from dimethylformamide; m.p. 155-157 ° C; yield 86% of theory.

Example 23. 3-Methyl-1- (a-methyl-3,4-tetramethylenebenzyl) -pyrazolone- (5) is obtained from ethyl acetate acetic acid and amethyl-3, 4-tetramethylybenzylhydrazine in ethanol. The resulting product is recrystallized from methanol; so nl 122-124 ° C; yield 78% of theory.

Example 24. 3-Methyl-4-methyl-1 - (a-methyl4-methylbenzyl) -pyrazolo- (5) is obtained from a-methyl acetic ester and a-methyl-4-methylbenzyl hydrazia. The resulting product is recrystallized from methanol; m.p. 131 -132 ° C; yield 59% of theory.

Example 25. 3-Methyl-4-methyl-1 - (o-methyl-Zchlor-4-methylbenzyl) -pyrazolone- (5) is obtained from a-methyl acetoacetate and a-methyl-3-chloro-4-methylbenzylhydrazine. The resulting product is recrystallized from methanol;

m.p. 145-147 ° C; yield 65% of theory.

Example 26. 3-Methyl. 1-4- (4-methoxybenzyl) (a-methyl-4-methylbenznl) -nirazolone- (5) is obtained from a-methyl-4-methylbeizylhydrazine and a- (4-methoxybenzyl) - acetoacetic the ether.

The product obtained is recrystallized from a mixture of ethanol and a small amount of dimethylformamide; m.p. 146-147 ° C; yield 60% of theory.

Example 27. 3-Amio-1- (a-methyl-3,4-dichlorobenzyl) -pyrazolone- (5) was prepared as follows.

To a solution of 31.8 g (0.2 mol) of ethyl ester of cc-aminoethoxyacrylic acid and 1.5 g of ha-toluenesulfonic acid in 150 ml of ethanol, and at room temperature, under zash, and nitrogen gas, are added dropwise 41 g ( 0.2 mol) a-methyl-3,4-dichlorobenzylhydrazine dissolved in absolute ethanol. After stirring for 2 hours and one hundred percent

overnight, the reaction solution maximally sugi:, ayut in a rotary evaporator. The remaining residue is dissolved in 2n. caustic soda solution. The reacted starting materials or by-products are extracted with ether. The aqueous phase of the vinegar of the acid is then set to the value of RP 5. Separate yush; in this case the oil is absorbed in methylene chloride and the organic phase is dried over Na2S04. After being picked

the solvent crystallizes the reaction product. It is recrystallized from metaiol. Melting point 127-129 ° C; yield 21 g (38.5% of theory).

Example 28. Analogously to Example 27, the following compounds are prepared.

Claims (2)

3-Amino-1- (a-methyl-3-chloro-4-methylbenzyl) -pyrazolone- (5) is prepared from p-amino-3 ethoxyacrylic acid ethyl ester and a-methyl-3-chloro-4-methylbenzylhydrazine . The product obtained is recrystallized twice from ethanol; m.p. 86-88 ° C; yield 33% of theory. Example 29. 3-Amino-1- (a-methyl-4-fluorobenzyl) -pyrazolone- (5) is prepared from p-amino-p-ethoxyacrylic acid ethyl ester and a-methyl-4-fluorobenzyl hydrazine. The resulting product is recrystallized from a small amount of ethanol; T. Il. 128-130 ° C; yield 29% of theory. Claims 1. A method for producing 1-substituted pyrazolones-5 of formula I where R is a hydrogen atom, an amino group, alkyl with 1-4 carbon atoms, alkenyl, phenyl or trifluoromethyl; RI means a hydrogen atom, alkyl or alkenyl with 1-4 carbon atoms, or unsubstituted or substituted aryl or aralkyl; R2 is alkyl with 1-4 carbon atoms; Hz is unsubstituted or substituted phenyl, aaphthyl or iridyl, or their salts, characterized in that the hydrazine of the formula II H3-CH-III-RR, where R2 and Ra have the above meanings, is reacted with an acetic acid derivative of the formula III TC -COX where RI is as defined above, X is hydroxy, alkoxy, aralkoxy, amino or alkylamino; Y means a hydrogen atom; Y means a nitrile or a group —C where Y means a hydrogen atom, alkyl with carbon atoms or phenyl, or trifluoromethyl or. .,. , - .. u, .... . f, j. d .., W where Y means an alkoxy, aryloxy, aralkoxy, alkyl mercito or aralkyl mercapto or amino group, and a temperature of 10 to 200 ° C, followed by isolation of the desired product in free form or as a salt. 2. The method according to p. 1, about tl and ch and y and; and with the fact that the process is carried out in the presence of an inert solvent and a basic or acidic catalyst, for example, hydroxides or carbonates of alkaline metals H1, earth-metal metals, or hydrohalic, sulfuric or sulfonic acids. Potential information taken into account during the examination: 1. A. Weissberger et. al. I. Amer. Chem. Soc., 64, 2183, 1942.