CYCLIC POLYOLEFINS. XXV. CYCLOOCTANEDIOLS. MOLECULAR REARRANGEMENT OF CYCLOOCTENE OXIDE ON SOLVOLYSIS
Abstract
Hydroxylation of cis-cycloacctene with performic acid, and hydrolysis of solvolysis with HCOOH of cis-cycloacctene oxide, yielded more 1, 4-cycloacctanediol than the expected product, trans-1, 2-cycloacctanediol. The structure of 1, 4-cycloacctanediol was established by conversion to cycloacctane through the diacetate and cycloacctadiene, and by Oppenauer oxidation to 1, 4-cycloacctanedione, which by an intramolecular aldol condensation formed the known ketone, bicyclo (3.3.0) - 1 (5)-octen-2-one. The molecular rearrangement resulting in formation of the 1, 4-glycol was interpreted as a chemical transannular effect which permits participation in the solvolysis of the epoxide by a C-H bond which is sterically adjacent because of its location across the compact 8-membered ring. The 8-membered cyclic acyloin suberion and cis-1, 2- cycloacctanediol were prepared and characterized.(Contractor's abstract) (Prepared for publication in J.Am.Chem.Soc.)
Document Details
- Document Type
- Technical Report
- Publication Date
- Nov 10, 1952
- Accession Number
- AD0002228
Entities
People
- Arthur C. Cope
- Claude F. Spencer
- Stuart W. Fenton
Organizations
- Massachusetts Institute of Technology