純硫酸中シクロヘキサンカルボン酸のニトロシル硫酸による三酸化硫黄触媒ニトロソ化反応の速度論的研究

概要

論文の詳細を見る
The rates of nitrosation of cyclohexanecarboxylic acid (CCA) with nitrosyl hydrogensulfate (NHS) in 7.29-14.28% oleum forming ε-caprolactam have been followed by the volumetric determination of evolved carbon dioxide. The reaction dose never occur without sulfur trioxide. The rate of the reaction is expressed by Rate={k_<2cs>-k_<3cns>C_<NHS>}C_<CCA>C_<SO_3>-{k_<2cc>-k_<3ccn>C_<NHS>}C^2_<CCA> A probable mechanism which involves pentamethyleneketene (PMK) formed by the elimination of sulfuric acid and proton from the protonated hexahydrobenzoyl hydrogensulfate (2) and proton, and the cyclohexanecarboxylic anhydride (CCAN) formed by the elimination of proton, sulfur trioxide and water from on adduct of 2 and CCA, was discussed.
公益社団法人日本薬学会の論文
1981-05-25