純硫酸中シクロヘキサンカルボン酸フェニルエステルのニトロシル硫酸によるニトロソ化反応の速度論

概要

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The rates of the nitrosation of phenyl cyclohexanecarboxylate (abbreviated as PCC) with nitrosyl hydrogensulfate (NHS) in 0-7% oleum to form ε-caprolactam have been investigated by measuring the volume of evolved carbon dioxide. The rate equation of the reaction is written as follows : Rate=(κ_<1e>+κ_<2es>C_<so3>+κ_<2en>C_<NHS>)C_<PCC> A probable mechanism which involves the rate-determining steps of formation of pentamethylene ketene (PMK) by deprotonation from cyclohexanecarbonyl cation formed by elimination of phenolate anion and sulfur trioxide from an adduct of PCC and SO_3 (κ_1,main path, 90.4%), and by the elimination of SO_3,phenol and proton from the adduct (κ_<2es>, 5.3%) followed by a rapid attack of NHS on the double bond of PMK, and a rate-determining formation of cyclohexanone oxime hydrogensulfate from the adduct of NHS and PCC (κ_<2en>, 4.3%) was discussed and postulated.
公益社団法人日本薬学会の論文
1981-11-25