Carbene Chemistry. I. Stereochemical Integrity at C Alpha in Ketone Tosylhydrazones. II. Hydrogen Migration in 2-Carbena-6,6-Dimethylnorbornane.

Abstract

The tosylhydrazones of exo-3-deuteriocamphor and 2-deuterio-2,4-dimethyl-3-pentanone were treated with N-bromosuccinimide (NBS) and pyruvic acid to regenerate the parent ketones. The ketones from the pyruvic acid cleavage show a significant loss of deuterium. The ketones from the NBS cleavage show no loss of deuterium, indicating that stereochemical integrity at C sub alpha is maintained during the NBS cleavage. The tosylhydrazones and corresponding lithium salts of exo and endo-3-deuterio-6,6-dimethylnorbornan-2-one are found to maintain their stereochemical integrity at C sub alpha. Thermal and photolytic decomposition of the lithium salts reveals a 3,2 hydride migration preference of 19:1 in favor of the exo hydrogen. Torsional interactions in the hydride migration transition state of a classical singlet carbene are suggested as an explanation for the observed stereo-selectivity.

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Document Details

Document Type
Technical Report
Publication Date
Feb 01, 1978
Accession Number
ADA133705

Entities

People

  • John Robert Balyeat

Organizations

  • Air Force Institute of Technology

Tags

Communities of Interest

  • Energy and Power Technologies

DTIC Thesaurus Topics

  • Alcohols
  • Alkanes
  • Alkenes
  • Chemical Synthesis
  • Chemistry
  • Cyclic Hydrocarbons
  • Ketones
  • Mass Spectroscopy
  • Methanols
  • Molecules
  • Organic Chemistry
  • Organic Compounds
  • Plastic Explosives
  • Spectra
  • Spectroscopy
  • Tensile Strength

Fields of Study

  • Chemistry

Readers

  • Organic Chemistry