Decomposition du percarbonate de 0,O-t-butyle et 0-isopropbnyle en solution: acetonylation des esters, acides et nitriles - Химия - Рефераты - Учебные материалы - Для тех кто учится!!!
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Decomposition du percarbonate de 0,O-t-butyle et 0-isopropbnyle en solution: acetonylation des esters, acides et nitriles
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Decomposition du percarbonate de 0,O-t-butyle et 0-isopropbnyle en solution: acetonylation des esters, acides et nitriles The Free-Radical Decomposition of 0,O-t-Butyl and 0-Isopropenyl Peroxycarbonate in Solution: the Acetonylation of Esters, Acides and Nitriles Summary The free-radical decomposition of 0.0- t- butyl and 0 -isopropenyl peroxycarbonate in substrates possessing

mobile H-atoms (S—H) consists mainly in an induced chain process leading to acetonylated derivatives of the solvent. Fairly good yields are obtained but the acetonylation of functional substrates often gives mixtures of isomers. In the case of methyl acetate, the acetonylation occurs on the C-atoms adjacent to the carboayl (acyloxy moiety) and to the 0-atom (alkoxy moiety). However, the relative amounts of the isomeric products depend on the concentration of the peroxycarbonate

solutions; at lowest concentration, methyl 4-oxopentanoate (acyloxy moiety) is obtained selectively. It is assumed that the free radicals issued from the solvent are able to abstract H-atoms of other molecules of solvent before adding to the double bond of the peroxycarbonate; the more the peroxycarbonate solution is diluted the more the transfers from the C-atom adjacent to the carbonyl to the radicals adjacent to the 0-atom are favoured.

In the case of methyl alkanoates, H-transfers from the a-C-atoms to j? -radicals of the acyloxy moiety may account for the orientation of the process. Owing to similar H-transfer processes, the acetonylation of functional esters, of acids and nitriles is selective in most cases. La decomposition du percarbonate de 0. 0-t-butyle et 0-isopropenyle (1) en solu­tion dans de nombreux composes (S-H) possedant des atomes d'hydrogene labiles permet de rtaliser

Категория: Химия | Добавил: Warior | Теги: O-t-butyle et 0-isopropbnyle en sol, Decomposition du percarbonate de 0, acides et nitriles реферат
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