30095-63-7Relevant articles and documents
Reactions of Oxygenated Radicals in the Gas Phase. Part 7. Reactions of Methylperoxyl Radicals and Alkenes
Osborne, David A.,Waddington, David J.
, p. 925 - 930 (1980)
The reactions of methylperoxyl radicals with alkenes have been studied between 373 and 403 K.The peroxyl radicals were generated by the oxidation of di-t-butyl peroxide.Arrhenius parameters for reaction (18) have been determined for 2-meth
Reactions of Oxygenated Radicals in the Gas Phase. Part 15. Reactions of t-Butylperoxyl Radicals with Alkenes
Morgan, Morag E.,Osborne, David A.,Waddington, David J.
, p. 1869 - 1873 (1984)
The photo-oxidation of mixtures of trans-2,2'-azoisobutane and some aliphatic alkenes has been studied between 313 and 393 K.Rate constants for the reaction between t-butylperoxyl radicals with ethene, 2-methylpropene, 2-methylbut-1-ene, 2-methylbut-2-ene, and 2,3-dimethylbut-2-ene have been determined at 393 K.Arrhenius parameters for the reaction (22) have been determined for 2-methylbut-2-ene and 2,3-dimethylbut-2-ene.They are log (A22/dm3mol-1s-1) of 8.16+/-0.38 and 8.58+/-0.61, and E22/kJ mol-1 of 56.6+/-2.4 and 48.7+/-4.1, respectively.The data obtained in this work are compared with that obtained for the series hydroperoxyl, and isopropylperoxyl radicals, and with rate data obtained for the addition reaction between alkenes and peracetyl radicals.
Regioselective Carbonylation of 2,2-Disubstituted Epoxides: An Alternative Route to Ketone-Based Aldol Products
Hubbell, Aran K.,Lapointe, Anne M.,Lamb, Jessica R.,Coates, Geoffrey W.
supporting information, p. 2474 - 2480 (2019/02/14)
We report the regioselective carbonylation of 2,2-disubstituted epoxides to β,β-disubstituted β-lactones. Mechanistic studies revealed epoxide ring-opening as the turnover limiting step, an insight that facilitated the development of improved reaction conditions using weakly donating, ethereal solvents. A wide range of epoxides can be carbonylated to β-lactones, which are subsequently ring-opened to produce ketone-based aldol adducts, providing an alternative to the Mukaiyama aldol reaction. Enantiopure epoxides were demonstrated to undergo the carbonylation/ring-opening process with retention of stereochemistry to form enantiopure β-hydroxy esters.
Dissociation of Positively Charged Aliphatic Epoxides. II. +. Epoxides and α,β Unsaturated Ethers
Bouchoux, Guy,Djazi, Feycal,Hoppilliard, Yannik,Jaudon, Pascale,Nouts, Nathalie
, p. 33 - 41 (2007/10/02)
The unimolecular dissociations of C5 epoxides ions mono- or disubstituted at C1 give exclusive loss of CH3 and exclusive formation of methoxyvinyl carbenium ion, both in the source and in the 2nd field-free region.In the case of the 1,2-disubstituted ion in the 2nd field-free region the loss of ethene is the only pathway, while a competition occurs for the trisubstituted ion leading to +. and +. ions, the structure of which are demonstrated.The first step of the different mechanisms is the cleavage of the heterocyclic C-C bond.
