Synthesis and radical decomposition of α-hydroxydiazenes. II. tert-Butylazodiphenylcarbinol

1976 ◽  
Vol 54 (9) ◽  
pp. 1349-1354 ◽  
Author(s):  
Dominic W. K. Yeung ◽  
John Warkentin
Keyword(s):  
Carbon Tetrachloride ◽  
Azo Compounds ◽  
Radical Mechanism ◽  
Chain Decomposition ◽  
Tert Butyl ◽  
Radical Decomposition ◽  
Nitrogen Radicals ◽  
Induced Decomposition ◽  
Hydroxyl Hydrogen

tert-Butylazodiphenylcarbinol (Ph2C(OH)N=NCMe3, 3) decomposes in oxygen-free benzene by the unimolecular radical mechanism characteristic of most azo compounds. In benzene or in carbon tetrachloride, with or without air present, decomposition of 3 is also induced by radicals through abstraction of hydroxyl hydrogen in concert with the formation of nitrogen. Radicals which induce decomposition of 3 include trichloromethyl, tert-butyl, phenylthiyl, tert-butylperoxy and possibly oxygen. The failure of inhibitors like thiophenol to stop chain decomposition of 3 is interpreted in terms of the thermochemistry of induced decomposition.

ChemInform Abstract: Induced Decomposition of Di(tert-butyl)trioxide

ChemInform ◽  
2010 ◽  
Vol 28 (42) ◽  
pp. no-no
Author(s):  
S. L. KHURSAN ◽  
A. F. KHALIZOV ◽  
V. V. SHERESHOVETS
Keyword(s):  
Tert Butyl ◽  
Induced Decomposition

Electron spin resonance study of tert-butyl halides and carbon tetrachloride, neopentane and carbon tetrachloride binary mixtures irradiated at 77 °K

1969 ◽  
Vol 47 (2) ◽  
pp. 273-278 ◽  
Author(s):  
F. C. Thyrion
Keyword(s):  
Electron Spin Resonance ◽  
Carbon Tetrachloride ◽  
Binary Mixtures ◽  
Electron Spin ◽  
High Efficiency ◽  
Broad Band ◽  
Electron Spin Resonance Study ◽  
Tert Butyl ◽  
Spin Resonance ◽  
High Concentrations

Tert-butyl halides and carbon tetrachloride, neopentane and carbon tetrachloride binary mixtures were irradiated at 77 °K and electron spin resonance spectra were recorded at increasing temperatures until the radicals disappeared.Even at high concentrations of tert-butyl halides, the radicals obtained from CCl4 predominate, indicating that CCl4 has a high efficiency for electron capture. Maximum radical yields and the appearance of a narrow line spectrum with rising temperature were observed in (CH3)3C—X – CCl4 mixtures (X = Cl, Br, I) in concentration ranges where only a single phase exists. This spectrum consists of 17 lines which appear to belong to one odd-numbered spectrum (7 lines due to (CH3)2Ċ—X radical) and two even-numbered spectra (4 and 10 lines, the last being due to (CH3)3Ċ radical). The disappearance of the CCl4 broad band and the appearance of these radicals with increasing temperature can be interpreted as due to charge transfer from carbon tetrachloride cation to tert-butyl halide, facilitated by greater freedom of movement in the solid solutions. In contrast, neopentane and carbon tetrachloride mixtures do not display these features.

Déplacements homolytiques intramoléculaires. 2. Décomposition du perpentène-4 oate de tert-butyle dans les éthers

1984 ◽  
Vol 62 (11) ◽  
pp. 2385-2390 ◽  
Author(s):  
A. Kharrat ◽  
C. Gardrat ◽  
B. Maillard
Keyword(s):  
Double Bond ◽  
Main Product ◽  
Similar Reaction ◽  
Tert Butyl ◽  
Lower Temperature ◽  
Induced Decomposition

The thermolysis of tert-butyl perpent-4-enoate 1 in THF led to several compounds; the main product, 5-(2-tetrahydrofuryl)-4-pentanolide (yield 42%) comes from an induced decomposition of the perester occurring with the addition of 2-tetrahydrofuryl radical to the double bond. A similar reaction was performed at a lower temperature, using butyl perdicarbonate as initiator, but did not define the mechanism (concerted or two-step). The thermolysis of 1 in ethers (THP, oxepane, 1,4-dioxane, dipropyl ether) appears to be a useful synthetic tool: several new γ-lactones have been obtained in this way.

scholarly journals THE REACTION OF tert-BUTOXY RADICALS WITH 2,6-Di-tert-BUTYL-4-METHYLPHENOL AND 2,6-Di-tert-BUTYLPHENOL

1963 ◽  
Vol 41 (11) ◽  
pp. 2807-2815 ◽  
Author(s):  
K. U. Ingold
Keyword(s):  
Carbon Tetrachloride ◽  
Isotope Effect ◽  
Satisfactory Agreement ◽  
Deuterium Isotope Effect ◽  
Tert Butyl

The products of the reaction of t-butoxy radicals with 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butylphenol in carbon tetrachloride have been analyzed quantitatively. There is a satisfactory agreement between the measured and calculated yields of t-butanol with both phenols. The deuterium isotope effect (kh/kd) for abstraction of the phenolic hydrogen from 2,6-di-t-butyl-4-methylphenol is about 6.4.

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