GLYCOSIDES

摘要

1506200 Daunomycin and adriamycin derivatives SOC FARMACEUTICI ITALIA SpA 21 April 1976 [30 April 1975] 18098/75 Heading C2C Daunomycin and the 41-epi derivatives and the novel 31,41-epi, 31,41-epi-61-hydroxy and 4 - demethoxy - 41 - epi derivatives of daunomycin and adriamycin (inα-anomer form) are prepared by reacting daunomycinone or its 4- demethoxy derivative with the appropriate N 1 O- protected 1-halo-daunosamine in an organic solvent in the presence of a soluble silver salt catalyst and a molecular sieve as dehydrating agent, removing the protecting groups and, if necessary, brominating or iodinating the resulting daunomycin or derivative thereof and hydrolysing the resulting 14-bromo or -iodo derivative with an alkali metal formate to form the corresponding adriamycin. 2,3 - Dideoxy - 4,6 - di - O - p - nitrobenzoyl - 3- N - trifluoro - acetyl -α- L - ribo - hexopyranosyl chloride is prepared by reacting 4,6-O- benzylidene - 2 - deoxy -α- L - erythro - hexopyranosoid-3-ulose with methanolic hydroxylamine, reducing the resulting oxime with LiAlH 4 , treating the resulting amine with methanolic HCl and then trifluoroacetic anhydride, reacting the resulting methyl 2,3- dideoxy - 3 - N - trifluoroacetyl -α- L - ribohexapyranoside with p-nitrobenzoyl chloride, treating the resulting di-p-nitrobenzoate with HCl, reacting the resulting pyranose with p-nitrobenzoyl chloride and chlorinating the resulting tri-O-p-nitrobenzoyl derivative. 2,3,6 - Trideoxy - 3 - N - trifluoroacetyl - 4- O - p - nitro - benzoyl -α- L@- ribo - hexopyranosyl chloride is prepared by brominating methyl 2,3 - dideoxy - 3 - N - trifluoroacetyl -α- L- ribopyranoside with N-bromosuccinimide, reducing the resulting 6-bromo derivative with Pd-C, treating the resulting methyl 2,3,6- trideoxy - 3 - trifluoroacetamido -α- L - ribohexopyranoside with p-nitrobenzoyl chloride, treating the resulting 4-O-p-nitrobenzoyl derivawith HCl, reacting the resulting pyranose with p-nitrobenzoyl chloride and chlorinating the resulting di-p-nitrobenzoyl derivative with HCl.