Thione studies. Reactions of stable alicyclic thiones with methylenetriphenylphosphorane.

✍ Scribed by A. Paul Krapcho; Michael P. Silvon; Steven D. Flanders

• Book ID: 104243139
• Publisher: Elsevier Science
• Year: 1974
• Tongue: French
• Weight: 190 KB
• Volume: 15
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)92018-0

✦ Synopsis

One of the most extensively utilized reactions involving phosphorus ylides is the Wittig reaction with carbouyl compounds to produce olefins and a phosphine oxide. Numerous mechanistic aud synthetic investigations have appeared ou the Wittig reaction and the gross mechanistic features are reasouably well understood (1). Despite the extensive volume of literature couceruiug reactions of phosphorus ylidea with carbouyl coupouuds, no research appears to have beeu reported ou reactious of aliphatic or alicyclic thioues with ylides of this type. The aromatic thioue, thiobenzophenoue, has been reported to yield l,l-dipheuylethyleue (76%) aud tripheuylphosphiue aulfide (82%) ou treatment with uethylenetriphenylphosphorane (2 (2). As part of a continuing program of study of reactions of stable aliphatic thiones (31, we wiah to report several novel reactions of thiones with methylenetriphenylphosphorane Q).

Ad-tanethione (2) on treatment with 1 (all reactions were performed in ether and the ylide was generated by treatment of the phosphonium salt with a n-butyllithium solution in hexane; equimolar amounts of the ylide and the substrate were wed in all reactions except where noted) leads to episulfide 2 and triphenylphosphine (both isolated in 80% yields). In contrasting behavior, treatment of adamantanone (2, S * 0) with 1 leads to uethylenead-tane in an 80% yield (4).