STUDY OF ANTIRADIATION DRUGS Ⅲ. SYNTHESIS OF SOME TERTIARY AMINO DERIVATIVES OF 1,2-DITHIOLANE

Some tertiary amino derivatives of 1,2-dithiolane (Ⅷ) were synthesized as follows: Allylbromide was reacted with conc. sulfuric acid and paraformaldehyde to give 4-bromomethyl-1,3-dioxane(Ⅹ),which was reacted with excess secondary amine to yield the corresponding tertiary amino derivatives of 1,3-dioxane (Ⅺ). (Ⅺ) was hydrolyzed by hydrochloric acid in methanol to give (Ⅻ). When (Ⅺ) or (Ⅻ) was treated With conc. hydroiodic acid in the presence of thiourea, the dithiol intermediate formed was then oxidized by iodine to yield the final product (Ⅷ).When (Ⅻ) was treated with hydrobromic acid instead of hydroiodic acid in the presence of thiourea, only the monothiol derivative of the corresponding amino alcohol (ⅩⅣ) was obtained, the exact position of the thiol or the hydroxy group in the molecule remained unknown. An attempt to prepare the primary aminoderivative of 1,2-dithiolane through the reaction of (ⅩⅧ) with thiourea or potassium thioacetate, followed by hydrolysis and oxidation of the intermediate failed. In these cases only the monosubstitution product (ⅩⅨ) or (ⅩⅩ) was obtained.Compd (ⅩⅪ) wasobtained by the treatment of (Ⅻ) with thionylchloride, it failed to react with sodium polysulfide to yield the corresponding amino dithiolane derivative. Compds Ⅷ_a and ⅩⅣ_e exhibited weak protective activity against ionization radiation in mice.