Oxido compds review

Thioenolethers. An ethanolic soln. of isopropyl mercaptan added at 35-40° during 1.5 hrs. to a soln. of 2,3-epoxycyclohexanone and 15%-NaOH in ethanol, allowed to stand 12 hrs. at room temp., then distilled -> 2-thioisopropyl-2-cyclohexen-1-one. Y 81%. - Strongly nucleophilic but weakly basic substrates give the best yields. The intermediate 2-subst. 3-hydroxycyclohexanones are generally dehydrated in situ or during work-up. F. e. s. M. A. Tobias, J. G. Strong, and R. P. Napier, J. Org. Chem. 55, 1709 (1970) reactions of oxido compds., review, cf. D. Swern, J. Am. Oil Chemists Soc. 47, 424 (1970). 

A soln. of cyclooctene oxide in benzene passed at 180 with the aid of Ng through a column packed with Li-orthophosphate pellets 3-hydroxycyclooctene. Y 70%. - Li-diethylamide causes mostly rearrangement to 2-hydroxybicyclo[3.3.0]-octane. M. N. Sheng, Synthesis 1972, 194 allyl alcohol from propylene oxide s. A. G. Polkovnikova, N. S. Usacheva, and A. E. Folomeeva, Khim. Prom. 49, 325 (1973) C. A. 79, 31412 2-ethylenealcohols preferably with Li-di-n-propylamide or Li-di-n-butylamide s. C. L. Kissel and B. Rickborn, J. Org. Chem. 37, 2060 (1972) by thermal rearrangement without added acids or bases s. R. J. Anderson et al., Am. Soc. 94, 5379 (1972) basic rearrangements of oxido compds., review s. V. N. Yandovskii and B. A. Ershov, Russ. Chem. Rev. 41, 403 (1972) (Eng. transl.). 

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