| 摘要 |
1309928 Dioxatricyclodecanes KALI-CHEMIE AG 28 May 1970 [8 Dec 1969] 25864/70 Heading C2C The invention comprises compounds I (in which R 1 is alkoxy or aralkoxy and (a) R 2 and R 3 are both H and the 10, 11 double bond may be hydrogenated, or (b) R 2 is halogen or SCN and R 3 is acyl). The compounds I in which R 2 is halogen or SCN and R 3 is acyl are prepared by reacting a compound II (in which X is a group which can be eliminated, e.g. acyloxy, R<SP>1</SP> 1 is acyloxy, R<SP>1</SP> 2 is halogen or SCN and R 3 is H or acyl) with an alkanol or aralkanol in the presence of an acid catalyst. These compounds I may be converted into compounds I in which R 2 and R 3 are H, e.g. by hydrolysing the C-4 acyloxy group and catalytically reducing the C-3 halomethyl group. The same compounds can also be obtained by reacting 1-#-D-glucosido-4-isovaleroxymethyl - 6,7 - dihydroxy - 7 - methyl- 1,4a,5,6,7,7a - hexahydro - cyclopenta(c)pyran with an alkanol or aralkanol in the presence of a strong acid. The compounds I in which R 2 and R 3 are H and the 10, 11 double bond is hydrogenated are prepared from the corresponding 10-methylene compounds by conventional hydrogenation. They can also be prepared from compounds I in which R 2 is halogen and R 3 is acyl by catalytically hydrogenating the compound in an alcohol and in the presence of a strong base. Compounds II in which X is isovaleroxy are prepared by reacting didrovaltratum with a sodium halide or potassium thiocyanate. |
