PubMed:596853 JSONTXT

{"project":"SCAI-Test","denotations":[{"id":"T1","span":{"begin":29,"end":44},"obj":"CHED"},{"id":"T2","span":{"begin":152,"end":176},"obj":"CHED"},{"id":"T3","span":{"begin":185,"end":197},"obj":"CHED"},{"id":"T4","span":{"begin":260,"end":266},"obj":"CHED"},{"id":"T5","span":{"begin":273,"end":277},"obj":"CHED"},{"id":"T6","span":{"begin":316,"end":323},"obj":"CHED"},{"id":"T7","span":{"begin":384,"end":391},"obj":"CHED"},{"id":"T8","span":{"begin":455,"end":458},"obj":"CHED"},{"id":"T9","span":{"begin":461,"end":468},"obj":"CHED"},{"id":"T10","span":{"begin":492,"end":507},"obj":"CHED"},{"id":"T11","span":{"begin":566,"end":572},"obj":"CHED"},{"id":"T12","span":{"begin":597,"end":619},"obj":"CHED"},{"id":"T13","span":{"begin":657,"end":697},"obj":"CHED"},{"id":"T14","span":{"begin":710,"end":735},"obj":"CHED"},{"id":"T15","span":{"begin":800,"end":821},"obj":"CHED"},{"id":"T16","span":{"begin":868,"end":889},"obj":"CHED"},{"id":"T17","span":{"begin":977,"end":999},"obj":"CHED"},{"id":"T18","span":{"begin":1041,"end":1057},"obj":"CHED"},{"id":"T19","span":{"begin":1074,"end":1081},"obj":"CHED"},{"id":"T20","span":{"begin":1140,"end":1155},"obj":"CHED"},{"id":"T21","span":{"begin":1287,"end":1308},"obj":"CHED"},{"id":"T22","span":{"begin":1380,"end":1396},"obj":"CHED"},{"id":"T23","span":{"begin":1400,"end":1408},"obj":"CHED"},{"id":"T24","span":{"begin":1421,"end":1432},"obj":"CHED"},{"id":"T25","span":{"begin":1450,"end":1502},"obj":"CHED"},{"id":"T26","span":{"begin":1513,"end":1522},"obj":"CHED"},{"id":"T27","span":{"begin":1661,"end":1673},"obj":"CHED"}],"text":"[Synthesis and properties of carminomycinone derivatives].\nSintez i svoĭstva proizvodnykh karminomitsinona.\nThe possibility of chemical modification of carminomycinone-aglycone (II) of carminomicin, a side product in the antibiotic production was studied. The methyl group C-14 was functionilized by introducing the bromine atom and performing a number of exchange reactions with the bromine atom. It was found that under definite conditions (1. 1 equiv. Br2in dioxane, 20 degrees, 24 hours) carminomycinone (II) was subjected to selective bromination into the side acetyl group with formation of 14-bromcarminomycinone (III). On interaction with anhydrous potassium acetate 14-bromcarminomycinone (III) yield 14-acetoxycarminomycinone (IV). In its turn the latter compound (IV) easily hydrolized to 14-oxycarminomycinone (V) in treatment with aqueous alkali or acid. 14-oxycarminomycinone (V) was also prepared with a high yield (80 per cent) by direct alkaline hydrolysis of 14-bromcarminomycinone (III) in treatment with 0.1N solution of sodium carbonate in a mixture of dioxane and water. The structure of 14-substituted derivatives of carminomycinone was proved by analytical and spectral data and confirmed by their transformation. Thus, according to the data of mass-spectrometry 14-oxycarminomycinone (V) had a molecular weight of 400 c. u. In treatment with an excess of acetic anhydride in pyridine it formed a hexa-acetyl derivative, i.e. 4, 6, 7, 9, 11, 14-hexa-acetyl-14-oxycarminomycinone (VI). The aglycones (III-V) prepared by us may serve a starting material in chemical synthesis, as well as biosynthesis of semi-synthetic preparations of the carminomycin series."}