SU493473A1 - The method of obtaining 5-vinylamino-6-substituted uracils - Google Patents

Description

Shat in a vacuum over P205. After recrystallization from alcohol, 2.70 g (58%) of 5 (2-chloroethyl) vinylamino-6-methyluracil are obtained; colorless crystals with m.p. 214-216 ° C (with decomposition). Rf 0.31 in a thin layer of A12Oz III Art. Act. in the system butanol, sat. water; UV spectrum (methanol); h, ax 315 nm (Ig 3.66), Amaks 345 nm (Ig 8 2.85).

Found,%: C - 46.87; H 5.19; C1 - 15.21; N - 18.25; CgHnClNsOa.

Calculated,%: C 47.06; H - 5.27; C1 - 15.44; N - 18.30.

Example 2. 5- (2-Hydroxyethyl) vinylamino 6-methyluracil.

A mixture of 4 g (0.016 M) 5- (2-chloroethyl-2-oxyethyl) amino-6-methyluracil, 1.75 g (0.032 M) of dry potassium fluoride in 75 ml of absolute dimethyl sulfoxide is stirred for 3 hours iri 95-100 ° C . The hot solution is filtered from inorganic salts, the precipitate is washed with 20 ml of dimethyl sulfoxide and the filtrate is stirred under vacuum at a temperature not higher than 80 ° C. The residues are suspended in 100 ml of methylene chloride, the insoluble part is filtered off, which is recrystallized twice from absolute ethanol. Obtain 2.4 g (71%) of 5- (2oxyethyl) -vinylamino-6-methyluracil, colorless crystals with so pl. 221 - 223 ° С (with decomposition); Rj 0.21 in a thin layer of A1203 III. Act. in the system butanol saturated with water.

Found,%; C - 50.89; H - 6.21; N 19,99; CgHisNsOs.

Calculated,%: C - 51.17; H - 6.24; N - 19 92.

Example 3. 2,4-Difluoro-5- (2-chloroethyl) vinyl amino-6-methyl pyrimidine.

A mixture of 13.5 g (0.05 M) 2,4-difluoro-5-di (2 chloroethyl) amino-6-methyl-nerimidine, 12.7 g (0.1 L) of dry silver fluoride in 50 ml of absolute acetopitride is boiled with intepsivnym stirring for 6 hours. After cooling, the silver salts are filtered off, washed with acetope, the combined dark filtrate is passed through a layer of AloOa.

(2x15 cm), stir up acetop and evaporated in vacuo. The residue is treated with ether (4X50 ml), the insoluble part is reprecipitated from a small amount of warm acetone with an excess of ether. 5.6 g are obtained

(48%) 2,4-difluoro-5- (2-.chloroethyl) vinylamino-6-methyl-nitrimidine; yellow crystals with t. nl. 60-62 ° C (with decomposition).

Found,%: C 46.56; H - 4.09; N - 18.06; C1, 14.96; F - 16.14; CgHioClFoNj.

Calculated,%: C - 46.26; H - 4.31; N 17.98; Cl- 15.18; F- 16.26.

Example 4. 2,4-Dimethoxy-5- (2-chloroethyl) vinylamino-6-methylirimidin.

2.34 g (0.01 M) of 2,4-difluoro-5 (2-chloroethyl) vinylamino-6-methyl-irimidimide is dissolved in 15 ml of absolute methanol, 1.08 g (0.02 M) of sodium methoxide and the mixture is stirred at reflux for 1 hour, cooled, the solution is filtered, the filtrate is evaporated in vacuo and the residue is extracted with dry acetone. After re-precipitating from a minimal amount of acetone with excess petroleum ether, 1.54 g (60%) of 2,4-dimethoxy-5- (2-chloroethyl) vinylamino-6-methylpyrimidine, light yellow crystals with m.p. 69-79 ° C (with decomposition).

Paydepo,%: C - 50.99; H - 6.37: C1 - 14.01; N - 16.24; SpN1bS1Kz02.

Calculated,%: C - 51.26; H - 6.26; C1 - 13.76; N - 16.31.

The hydrolysis of this compound with hydrochloric acid gives 5- (2-chloroethyl) vinylamino-6-methyluracil (see above).

Under these conditions, compounds shown in the table are synthesized. e-VinylaminouracilK Y

Cts

AND

X / Tf-CHoCHoCl

L j

Note

 thin layer AljOs III degree of activity in the system:

"-Butanol saturated with water.

Everywhere; The first line is found, the second is calculated.

Subject invention

1. The method of obtaining 5-vinylamino-6-substituted. X uracils of general formula I

-R,

,,,

J and

,

wherein RI and R2 are hydroxy, alkoxy or halo, Cs is hydrogen or lower alkyl, R4 is hydrogen, alkyl, 3-halo or p-hydroxyethyl, characterized in that the compound of general formula II

R i

; j P lf-CH CHiCl

Claims (3)

1 N -R where is RI. R2, Rs and R. have the indicated values, are treated with metal fluoride of the first group in the medium of an organic solution with the subsequent release of the non-basic product by a lime intake. 2. A method according to claim 1, characterized in that the process is carried out with an excess of metal fluoride of the first group. 3. The method according to paragraphs. 1 and 2, that is, with the fact that the process is carried out in the temperature range 20-200 C.