Accession Number:

AD0002228

Title:

CYCLIC POLYOLEFINS. XXV. CYCLOOCTANEDIOLS. MOLECULAR REARRANGEMENT OF CYCLOOCTENE OXIDE ON SOLVOLYSIS

Descriptive Note:

Corporate Author:

MASSACHUSETTS INST OF TECH CAMBRIDGE

Report Date:

1952-11-10

Pagination or Media Count:

31.0

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.Contractors abstract Prepared for publication in J.Am.Chem.Soc.

Subject Categories:

  • Polymer Chemistry
  • Plastics

Distribution Statement:

APPROVED FOR PUBLIC RELEASE