Accession Number : AD0601695
Title : ORIENTATION AND REACTIVITY IN FREE RADICAL AROMATIC SUBSTITUTION.
Descriptive Note : Final technical rept., 1961-63,
Corporate Author : NEW YORK UNIV N Y
Personal Author(s) : Morrison,Robert T.
Report Date : 17 APR 1964
Pagination or Media Count : 8
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.
Descriptors : (*FREE RADICALS, SUBSTITUTION REACTIONS), (*AROMATIC COMPOUNDS, SUBSTITUTION REACTIONS), MOLECULAR STRUCTURE, REACTION KINETICS, CHROMATOGRAPHIC ANALYSIS, OXYGEN, PEROXIDES, SOLVENTS, BENZOIC ACIDS
Distribution Statement : APPROVED FOR PUBLIC RELEASE