CYCLIC POLYOLEFINS, XXVI. CONVERSION OF CYCLOOCTATETRAENYL PHENYL KETONE TO AN ACYCLIC TETRAENE

Abstract

Cyclooctatetraenyllithium was converted to bicyclooctatetraenyl by coupling in the presence of CoClsub2, and to cyclooctatetraenyl phenyl ketone (I)(mp = 38 deg to 39.5 deg C) by reaction with benzonitrile followed by hydrolysis of the intermediate imine. The ketone I formed a 1:1 complex with AgNOsub3 and a 2, 4-dinitrophenylhydrazone. Hydrogenation of I yielded benzycyclooctane and 1-cyclooctenyl phenyl ketone (II); reduction with LiAlHsub4 formed cyclooctatetraenylphenyl-carbionl, characterized by IR spectrum bands at 2.78 and 2.93 microns. On reaction with PhMgBr, I underwent ring opening and yielded the acyclic ketone 1, 9-diphenylnona-2, 4, 6, 8-tetraen-1-one (III)(mp = 125 deg to 126.2 deg C) which was sensitive to atmospheric O. III was identical with a sample prepared from 7-phenyl-hepta-2, 4, 6-trienal and acetophenone. Hydrogenation of III yeidled 1, 9-diphenylnonan-1-one. The reaction of PhMgBr and II yielded 2-phenylcyclooctyl phenyl ketone (mp = 136.4 deg to 137.8 deg C). (Prepared for publication in J. Am. Chem. Soc)

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Document Details

Document Type
Technical Report
Publication Date
Apr 24, 1953
Accession Number
AD0011809

Entities

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  • Arthur C. Cope
  • David J. Marshall

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  • Massachusetts Institute of Technology

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  • C4I

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  • Absorption
  • Alcohols
  • Alkanes
  • Calcium Compounds
  • Chemical Synthesis
  • Chemistry
  • Hydrochloric Acid
  • Hydrogen
  • Hydroxides
  • Infrared Spectra
  • Ketones
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  • Organic Chemistry
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