ORIENTATION AND REACTIVITY IN FREE RADICAL AROMATIC SUBSTITUTION.

Abstract

It was shown that data from product analysis give valid rate factors for free radical aromatic substitution, not only removing current doubts but putting these rate factors on firmer footing than ever before. A method of analysis of biaryl mixtures was worked out that gives rate factors about ten times as accurate as previous methods have given; and a method was devised for collecting reference samples of biaryls that elimates the need for lengthy synthesis. Rate factors were measured by this method for eight peroxidesubstrate systems, and it was found that these results are consistent with the operation of polar effects. It was found that, in certain cases, the esters reported from peroxide decomposition are not the simple substituted phenyl benzoates previously assumed. Data were obtained about the effect of oxygen and peroxide concentration on yield of benzoic acid that strongly suggest the operation of a cage effect in free radical substitution.

Document Details

Document Type
Technical Report
Publication Date
Apr 17, 1964
Accession Number
AD0601695

Entities

People

  • Robert T. Morrison

Organizations

  • New York University

Tags

DTIC Thesaurus Topics

  • Benzoates
  • Benzoic Acids
  • Chemical Compounds
  • Decomposition
  • Elements
  • Esters
  • Free Radicals
  • Group 16 Elements
  • Nonmetals
  • Orientation (Direction)
  • Oxygen
  • Peroxides
  • Reactivities

Readers

  • Mathematics or Statistics
  • Organic Chemistry
  • Theoretical Analysis.