REACTIONS OF THIANTHRENE CATION-RADICAL WITH ACYCLIC AND CYCLIC ALCOHOLS

Authors
Citation
Hj. Shine et W. Yueh, REACTIONS OF THIANTHRENE CATION-RADICAL WITH ACYCLIC AND CYCLIC ALCOHOLS, Journal of organic chemistry, 59(13), 1994, pp. 3553-3559
Citations number
72
Categorie Soggetti
Chemistry Inorganic & Nuclear
ISSN journal
00223263
Volume
59
Issue
13
Year of publication
1994
Pages
3553 - 3559
Database
ISI
SICI code
0022-3263(1994)59:13<3553:ROTCWA>2.0.ZU;2-F
Abstract
Thianthrene cation radical perchlorate (Th(ClO4-)-Cl-+) reacted readi ly with cycloalkanols (C-5, C-7, C-8, and C-12), alkan-2-ols (C-3, C-5 , C-6, and C-8), 3-hexanol, neopentyl alcohol, a number of benzyl alco hols, dl- and (S)-1-phenylethanol, cyclopentyl- and cyclohexylmethanol s, the exo- and endo-borneols, and norborneols. Reactions were carried out with an excess of the alcohol in acetonitrile solution containing 2,6-di-tert-butyl-4-methylpyridine. Products were alkenes, ethers, an d N-substituted acetamides, depending on the structure of the alcohol. Thianthrene(Th) and its 5-oxide (ThO) were formed in equal amounts. T he sum of amounts of products from the alcohol was equal to the amount of ThO. All reactions are interpretable on the basis of the ultimate formation and further reactions of a 5-alkoxythianthreniumyl ion (ROTh (+)). The predominant formation of nortricyclene from the norborneols is striking and is discussed. Swern-Moffatt-type oxidations of the alc ohols were not observed.