10574-37-5Relevant articles and documents
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Dubois,J.E. et al.
, p. 1349 - 1350 (1971)
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Kramer
, p. 3453 (1968)
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Thermal reaction of (CH3)2C=C(CH3)2 in the presence of di-tert-butyl peroxide; reactions of the radicals ·CH3, (CH3)3C·C(CH3)2 and (CH3)2C=C(CH3)·CH2
Koertvelyesi,Seres
, p. 253 - 273 (2007/10/03)
A study of the thermal reaction of (CH3)2C=C(CH3)2 (23DMB2) in the presence of di-t-butyl peroxide (PODBT) at 389-451 K yielded kinetic data on some reactions of the radicals ·CH3, (CH3)3C·C(CH3)2 (1122TMP·) and (CH3)2C=C(CH3) ·CH2 (112TMA·). The ratio of the cross-combination ratios of the radicals o(112TMA·, 122TMP·)/φ(·CH3, 1122TMP·) and the rate constant for H-abstraction from 23DMB2 by ·CH3 relative to that of the recombination reaction, ·CH3 + (CH3)2C=C(CH3)2 → CH4 + (CH3)2C=C(CH3) ·CH2 (4) 2·CH3 → C2H6 (7) have been determined. The values are φ(1122TMP·, 112TMA·)/φ(·CH3, 1122TMP·) = 0.9 ± 0.3 log(k4/k71/2) = (3.74 ± 0.21) - (36.3 ± 2.2)/Θ where Θ = RT ln 10 and the units are dm3/2 mol-1/2 s-1/2 for k4/k71/2, and kJ mol-1 for the energy of activation.
Steric and electronic effects on the conformations and singlet oxygen ene regiochemistries of substituted tetramethylethylenes. The origin of the geminal effect
Clennan, Edward L.,Chen, Xiangning,Koola, Jaya J.
, p. 5193 - 5199 (2007/10/02)
The reactions of singlet oxygen with 22 allylically substituted tetramethylethylenes have been studied. Steric and electronic effects on the regiochemistries of the ene reactions have been discovered. Large groups and electron-rich groups increase geminal hydrogen abstraction. Molecular mechanics calculations have been conducted and reveal that the site of hydrogen abstraction is correctly predicted by the rotational barriers of the methyl groups.
