SU598900A1 - Method of obtaining derivatives of 8-azaxanthine - Google Patents

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(54) METHOD OF OBTAINING 8-AZAXANTINE DERIVATIVES - N-nitrosate with nitrous acid, refining nitrosogram with the help of sodium hydrosulfite, diazotization of the amine derivative, with simultaneous washing into a triazole cycle during processing of the application, and after the application of the same type of application, and after the application of the same volume of the application, also a man who also had a quest to use the same time to use the same time as the application, and also a man who had an imposes, and also a man who also had the same time to get the same amount of the application, and also the repo alti- ny? by subsequent saponification of the compounds obtained with hydrochloric acid. The reaction proceeds according to the scheme: OO R-N HNOg. ., shtzLnn n "2 11, Sh55, S -n JL"% onz5 | 1 "NOT TI" C / H / CHjS N N 2ZH, KO "E where R And (And, IV, VI, VIII,., XII) R CH3 (III, V, Vil, IX, XI, Xltl) The distinguishing features of the method are the use of 2-megyl-mercapto-5-amino-6-oxopyrimidine or its 3-methyl derivative as the starting compound as the methylating compound at the methylation stage, methyl iodide is used, the process is carried out in dimethyl form amide, and the 7-methyl derivative obtained at this stage is washed with hydrochloric acid. In this process, the process is reduced to five, eliminating the use of expensive palladium catalysts. The total yield of the desired products is 8-149. Example 1. Getting 7-methyl-8-azaksantina. 4.1 g of 2-methylthio-4-pmino-6-oxopyrimidine (II) are suspended in 185 ml of water and 8.2 ml of glacial acetic acid. 4.1 g of sodium nitrite dissolved in 20 ml of water are added. The mixture is stirred for 6 hours at room temperature, the blue precipitate is filtered off, washed with water and dried. 4.6 g of 2-methylthio-4-amino-5-nitroso-6-oxopyrimidine are obtained (yield 93.5%) (IV). In 100 ml of water heated to 40 ° C, 7.0 g of yitrosopyrimidine (IV) and sodium hydrosulfite are charged in portions. Moving 1 hour at 60 ° C, cool and filter. The resulting light yellow precipitate is washed with a node and acetone and dried. 3.6 g of 2-methylthio-4,5-diamino-6-oxopyrimidine are obtained (yield 55.5%), m.p. 195-197 ° C (VI). 3.6 g of diaminopyrimidine (VI) are suspended in 80 ml of water, 2.2 g of sodium nitrite are added, and 5.0 ml of glacial acetic acid is added dropwise with stirring. The mixture was stirred at 40 ° C for 1 hour, the solution was boiled with coal and cooled. An orange precipitate formed, after crystallization from water, 2.8 g of azapurine was obtained (yield: 73.2%) (VIII). T.PL. 254-256 ° С, X max 264 them, egE3.97 (water), PMR: 5 ppm 5СНз 2.78 in CFjCOOH for HMDS. Found,%: N 38.43, S 17.87. CjHsNsOS Calculated,%: N 38.30; S 17.50. 1 g of azapurine (VIII) is heated in a closed vessel with 10 ml of dimethylformamide and 0.5 ml of methyl iodide for 1 hour to 100 ° C, cooled and the solution is evaporated in vacuum on a water bath to dryness. The residue is crystallized from 40 ml of 50% alcohol with coal and produce 0.52 g (yield 41.5%) of product X. M.p. 260-262 ° C, times., Hmaks 260 them, t6E4,07 (water), PMR: 6 ppm CHNZ 2.71, N CHN 4.58 in UNHRA for GMDS. Found,%: N 33.69; S 16.42. CeHTNsGS Calculated,%: N 35.23; S 16.25. 0.2 g of the product (X) is boiled for 12 hours with 17 ml of 20% hydrochloric acid, the solution is evaporated in a water bath to dryness, adding water to completely remove the hydrogen chloride. The residue is crystallized from 30 ml of water with coal. A white crystalline powder of 7-methyl-8-azaxanthin (XII), 0.15 g (yield 88.3%) is obtained. M.p. 350 ° С, Hmaks 230, 274 nm, 3.82, 3.61 (water). PMR: b ppm NCHs 4.38 in UNHRI on GMDs. The total yield of the final product is 13.8%. Example 2. Getting 1,7-dimesh1-8 azaxanthin. 2.9 g of 1-mepl-2-methylthio-4-amino-6