Free Radical Reactions Initiated by Ionizing Radiation. II. Rate Constants for Hydrogen Atom Addition Reactions with Mono-olefins, Butadiene and Benzene

1962 ◽  
Vol 84 (20) ◽  
pp. 3795-3799 ◽  
Author(s):  
Kang. Yang
Keyword(s):  
Free Radical ◽  
Hydrogen Atom ◽  
Ionizing Radiation ◽  
Rate Constants ◽  
Radical Reactions ◽  
Addition Reactions ◽  
Free Radical Reactions

Polar effects in free-radical reactions. Rate constants in phenylation and new methods of selective alkylation of heteroaromatic bases

1986 ◽  
Vol 51 (23) ◽  
pp. 4411-4416 ◽  
Author(s):  
Francesco Minisci ◽  
Elena Vismara ◽  
Francesca Fontana ◽  
Giampiero Morini ◽  
Marco Serravalle ◽  
...  
Keyword(s):  
Free Radical ◽  
Rate Constants ◽  
Radical Reactions ◽  
Free Radical Reactions ◽  
New Methods ◽  
Selective Alkylation

Sterically hindered aromatic compounds. VIII. Comparative photochemistry of 2,4,6-tri-tert-butyl- and 2,5-tert-butylnitrosobenzenes

1978 ◽  
Vol 56 (20) ◽  
pp. 2665-2672 ◽  
Author(s):  
L. Ross C. Barclay ◽  
Derek Leigh Carson ◽  
Jean A. Gray ◽  
Michael Grossman ◽  
Prabhaker G. Khazanie ◽  
...  
Keyword(s):  
Nitric Oxide ◽  
Free Radical ◽  
Hydrogen Atom ◽  
Aromatic Compounds ◽  
Complex Mixture ◽  
Radical Reactions ◽  
Product Analysis ◽  
Free Radical Reactions ◽  
Tert Butyl ◽  
Conformational Effects

Ultraviolet irradiation of hydrocarbon solutions of 2,4,6-tri-tert-butylnitrosobenzene (1) formed [Formula: see text] The initial products were 2-methyl-1-nitroso-2-(3,5-di-tert-butyl)-phenylpropane (Ar—C(CH3)2CH2NO)2 (3) and a mixed dimer (4). Secondary and minor photoproducts isolated included 2-methyl-2-(3,5-di-tert-butyl)phenylpropanal oxime (5), 2-methyl-2-(3,5-di-tert-butyl)phenylpropanal (6) derived from 5, and 1,3,5-tri-tert-butylbenzene (7). The initial products are explained by formation of a tri-tert-butylphenyl radical (15), rearrangement of a hydrogen atom from an orthotert-butyl to the ring in 15, and rapid recombination of the neophyl radical with nitric oxide. Photolysis of 2,5-di-tert-butylnitrosobenzene (2) initially gave [Formula: see text] (10). Product analysis indicated a comparatively complex mixture including 1,4-di-tert-butylbenzene (11), 2,5-di-tert-butylphenol (12), and 2,5-di-tert-butylanilino-p-(2,5-di-tert-butyl)quinone (13). Evidence indicates that 12 and 13 form from free radical reactions involving 10 and the 2,5-di-tert-butylphenyl radical. The different photochemistry of 1 and 2 is discussed in terms of differential steric and conformational effects on the nitroso function which also is evident in their ultraviolet spectra.

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