Accession Number : AD0002228


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


Corporate Author : MASSACHUSETTS INST OF TECH CAMBRIDGE


Personal Author(s) : COPE, ARTHUR C ; FENTON, STUART W ; SPENCER, CLAUDE F


Full Text : https://apps.dtic.mil/dtic/tr/fulltext/u2/002228.pdf


Report Date : 10 Nov 1952


Pagination or Media Count : 31


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.)


Descriptors :   *POLYETHYLENE PLASTICS , EPOXY COMPOUNDS , KETONES , OLEFIN POLYMERS , SOLVOLYSIS


Subject Categories : Polymer Chemistry
      Plastics


Distribution Statement : APPROVED FOR PUBLIC RELEASE