Alkyl radical triggered: In situ SO2-capture cascades
An unprecedented in situ SO2-capture cascade triggered by alkyl radicals has been documented herein. Mechanistic investigations suggest that, triggered by alkyl radicals, SO2 was released in situ and subsequently fixed into polycyclic small molecules. A wide range of alkylsulfonyl substituted polycyclic compounds were easily prepared with high yields and good functional group tolerability.
Su, Xiaolong,Huang, Honggui,Hong, Wei,Cui, Jianchao,Yu, Menglin,Li, Yi
supporting information
p. 13324 - 13327
(2017/12/26)
Preparation of di-t-alkyl peroxides and t-alkyl hydroperoxides from n-alkyl ethers
A process for production of a t-alkyl peroxide compound includes the steps of: a) reacting an n-alkyl t-alkyl ether with a reactant mixture comprising an acid catalyst and a compound of the formula RO2H??(I) ?where R is H or t-alkyl, provided that if R is t-alkyl the t-alkyl peroxide compound product is a di-t-alkyl peroxide, and b) isolating a reaction product comprising said t-alkyl peroxide compound from the mixture resulting from step a). The process can be used to prepare t-butyl hydroperoxide or di-t-butyl peroxide from methyl t-butyl ether. Sulfuric acid may be used as the acid catalyst.
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(2008/06/13)
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Reaction of alkyl hydroperoxides (1(ary), 2(ary) or 3(ary)) upon tertiary alkyl trichloroacetimidates under acidic catalysis yielded unsymmetrical dialkyl peroxides with yields in the range 30-70%.
Bourgeois,Montaudon,Maillard
p. 2477 - 2484
(2007/10/02)
Substituent Effects in the Decomposition of t-Alkyl t-Butyl Peroxides
The decomposition rates and products of various t-alkyl t-butyl peroxides were examined in cumene at several temperatures.The decomposition of these peroxides took place homolytically, depending on the structure of the t-alkoxyl moieties (RC(CH3)2-O), and was retarded in the order: R = (CH3)3CCH2 > (CH3)2CH > CH3CH2CH2 > PhCH2 > CH3CH2 > ClCH2 > CH3.The rate constants for the electron-donating alkyl substituents at 150 deg C are correlated very well to a Taft equation (log kd = -10.93Σ?*-6.61 (correlation coefficient of 0.9501)), which is fairly different from the equation log kd = -0.131Σ?*-3.422 for electron-withdrawing polar substituents.From this correlation and a product analysis, the nature of the polar character at the transition state of the decomposition is discussed.
Matsuyama, Kazuo,Higuchi, Yoshiki
p. 259 - 265
(2007/10/02)
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