Photodissociation of tert-butyl hypochlorite and decomposition of the tert-butoxy radical fragment

1993 ◽  
Vol 97 (23) ◽  
pp. 6220-6225 ◽  
Author(s):  
M. A. Thelen ◽  
P. Felder ◽  
J. G. Frey ◽  
J. Robert Huber
Keyword(s):  
Tert Butyl ◽  
Butoxy Radical ◽  
Radical Fragment

ChemInform Abstract: Photodissociation of tert-Butyl Hypochlorite and Decomposition of the tert-Butoxy Radical Fragment.

ChemInform ◽  
2010 ◽  
Vol 24 (41) ◽  
pp. no-no
Author(s):  
M.-A. THELEN ◽  
P. FELDER ◽  
J. G. FREY ◽  
J. R. HUBER
Keyword(s):  
Tert Butyl ◽  
Butoxy Radical ◽  
Radical Fragment

Photolysis of Di-tert-butyl Peroxide at High Pressure

1972 ◽  
Vol 50 (10) ◽  
pp. 1531-1534 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Gaseous Phase ◽  
Chemical Reactivity ◽  
Hydrocarbon Concentration ◽  
Tert Butyl ◽  
Butyl Peroxide ◽  
Butoxy Radical ◽  
Peroxide Molecule

Di-tert-butyl peroxide has been photolyzed at 2537 Å in the gaseous phase in the presence of up to 47 amagats (2.10 mol/l) of propane and of cyclopropane. It was confirmed that no acetone is formed in the limit of infinite hydrocarbon concentration and therefore that the primary chemical act leading to the eventual formation of acetone is the formation of two tert-butoxy radicals from the excited peroxide molecule; in addition, some crude information was obtained concerning relative rates of photochemical vs. deactivation processes. It was also found that at these densities the tert-butoxy radical formed in the photolysis of di-tert-butyl peroxide did not appear to differ in chemical reactivity from the tert-butoxy radical formed in the thermal decomposition of di-tert-butyl peroxide.

Hydrogen atom abstraction from substituted toluenes by tert-butoxy radical

1968 ◽  
Vol 46 (16) ◽  
pp. 2752-2754 ◽  
Author(s):  
R. D. Gilliom ◽  
J. R. Howles
Keyword(s):  
Hydrogen Atom ◽  
Polar Effect ◽  
Hydrogen Atom Abstraction ◽  
Methyl Group ◽  
Tert Butyl ◽  
Hammett Correlation ◽  
Substituted Toluenes ◽  
Butoxy Radical

The relative rates of abstraction of benzylic hydrogen from substituted toluenes by tert-butoxy radicals generated from tert-butyl hypochlorite have been reexamined. Abstraction from para-methylanisole was shown to occur at the ether methyl as well as at the benzylic methyl group. For this reason the compound was excluded from an analysis of the polar effect. A slightly better Hammett correlation was obtained using sigma rather than sigma-plus values.

Reactions of Alkoxy Radicals. I. The Reactions of Di-tert.-butyl Peroxide with n-Butyric Acid and Ethyl n-Butyrate

1960 ◽  
Vol 13 (2) ◽  
pp. 244 ◽  
Author(s):  
ALJ Beckwith
Keyword(s):  
Butyric Acid ◽  
Electron Acceptor ◽  
Dicarboxylic Acids ◽  
Cupric Chloride ◽  
Hydrogen Atoms ◽  
Alkoxy Radicals ◽  
Tert Butyl ◽  
Butyl Peroxide ◽  
Butoxy Radical

The relative yields of meso- and racernic-2,3-diethylsucoinic and 2-ethyl-3-methyl-glutaric acids from the reaction of di-tert.-butyl peroxide with n-butyric acid indicate that abstraction of hydrogen atoms from the acid by tert.-butoxy radicals occurs preferentially at the α-position. A similar directive effect has been noted in the reaction of ethyl n-butyrate with di-tert.-butyl peroxide. These results suggest that the tert.-butoxy radical has negligible electron-acceptor properties and that polar effects do not influence the course of its reactions. Catalytic amounts of cupric chloride profoundly modify the reaction of di-tert.-butyl peroxide with n-butyric acid. New analytical methods for the separation and determination of hydroxy- and dicarboxylic acids are described.

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