Abstract
Facile routes to trichloromethyl-containing aldoses and polyalcohols from low telomers of vinylenecarbonate with carbon tetrachloride are described. 3, 3, 3-Trichloro-3-deoxyglyceraldehyde derived from n=1 adduct was dimerized to five-membered 1, 3-dioxolane derivative preferentially, in contrast to the corresponding 3, 3-dichloro compound which gave the dimer in 1, 4-dioxane structure. Three-step procedure involving acetalization followed by removal of cyclic carbonate groups and subsequent deacetalization was mild and selective enough to permit the hydrolysis of n=2 telomers to 5, 5, 5-trichloro-5-dioxy-DL-lyxose and -xylose in excellent yields, while acid hydrolysis under more drastic conditions (at 100-110°) gave the rearranged 5, 5, 5-trichloro-3, 5-dideoxy-pentosulose in dimeric form exclusively. Reduction of telomers (n=1 and 2) and the derivatives with sodium borohydride gave polyalcohols of the type Cl3C-(CHOH)n-H (n=2, 3, and 4), among which some compounds showed considerable sedative activities.
