L. Barclay, Alexander G. Briggs, W. E. Briggs
Aug 15, 1979
Citations
0
Influential Citations
4
Citations
Journal
Canadian Journal of Chemistry
Abstract
An esr study of the dediazoniation of 2,4,6-tri-tert-butylaniline with butyl nitrite in methylene chloride indicated the formation of the 2,4,6-tri-tert-butylphenyl radical which was spin trapped by the butyl nitrite. The persistent 2,4,6-tri-tert-butylphenoxy radical was also formed. Product studies from reactions catalyzed by pivalic acid indicate a novel rearrangement of an ortho-tert-butyl group under dediazoniation conditions forming such products as: 3-(3,5-di-tert-butylphenyl)-2-methylpropene (4), 1-(3,5-di-tert-butylphenyl)-2-methylpropene (5), 3-(3,5-di-tert-butylphenyl)-2-methyl-2-propanol (6), 3-(3,5-di-tert-butylphenyl)-2-butoxy-2-methylpropane (7), 3-(3,5-di-tert-butylphenyl)-2-methyl-2-trimethylacetoxypropane (8), 2,4,6-tri-tert-butylphenyl trimethylacetate (9), and 2,4,6-tri-tert-butyl-1,4-quinol (10). The major products (4–7) are accounted for by a free radical pathway by rearrangement of the 2,4,6-tri-tert-butyl-phenyl radical. The minor products (esters 8 and 9) probably form by competin...