R. Ratz, Arthur D. Bliss
Mar 1, 1966
Citations
0
Influential Citations
4
Citations
Journal
Journal of Heterocyclic Chemistry
Abstract
3, 9-Dichloro-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro[5. 5]undecane-3,9-disulfide (I), has been synthesized by treating a dimethylacetamide solution of 2, 4, 8, 10-tetraoxa-3,9-diphosphaspiro[5. 5]undecane-3, 9-disulfide (III) with carbon tetrachloride. A number of other known methods for converting dialkyl phosphorothioites to thiophosphorochloridates were also applied to III, but all failed to produce I. Chlorination of either I or III gave an acyclic product, 4, 4-bis(chloromethyl)-1, 1, 7, 7-tetrachloro-2, 6-dioxa-1, 7-di-phosphaheptane-1, 7-dioxide (IV), in nearly quantitative yield. The same compound was also obtained by the previously known method of chlorinating 3, 9-dichloro-2,4,8,10-tetraoxa-3, 9-diphosphaspiro[5.5]undecane (II). The treatment of pentaerythritol with phosphorus pentachloride gave IV in minor amount along with a 25% yield of 4,4-bis-(chloromethyl)-1-chloro-2, 6-dioxa-1-phosphacyclohexane-1-oxide (VII). The hydrolysis of I in heated aqueous sodium carbonate gave, after acidification, 3,9-dihydroxy-2,4,8,10-tetraoxa-3, 9-diphosphaspiro[5. 5]undecane-3, 9-disulfide (VIII). A number of derivatives were prepared by reaction of I with phenoxides and amines. The corresponding thio-phosphorofluoridate XI was prepared by treatment of I with potassium fluoride in dioxane.