Reduction of nitro- and nitroso-compounds by tervalent phosphorus reagents. Part III. Kinetic study of the triethyl phosphite reduction of 2-nitrosobiphenyl to carbazole
Reduction of nitro- and nitroso-compounds by tervalent phosphorus reagents. Part III. Kinetic study of the triethyl phosphite reduction of 2-nitrosobiphenyl to carbazole
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用三价磷试剂还原硝基和亚硝基化合物。
DOI：
10.1039/j29690000883
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发表时间：
1969
期刊：
影响因子：
--
通讯作者：
A. Cooper
中科院分区：
文献类型：
--
作者：
J. Cadogan;A. Cooper
亚磷酸三乙酯还原2-亚硝基联苯为咔唑的反应在两种反应物中均为一级反应，反应活化能为11.56kcal。摩尔-1，在25°时的活化熵ΔS*为-29 E.E.这些数据与MenShukin和Arbusov反应获得的数据的相似性表明，速度决定步骤涉及形成涉及这两种试剂的中间络合物，可能是(ETO)3P+-O-NAR，然后迅速分解得到产物。氮化物可能的中间体既没有被证明，也没有被反驳。
The triethyl phosphite reduction of 2-nitrosobiphenyl to carbazole in triethyl phosphate as solvent is of the first order in both reactants; the activation energy is 11·56 kcal. mole–1, and the entropy of activation ΔS*, at 25° is –29 e.u. The similarity of these data to those obtained for the Menshutkin and Arbusov reactions indicates that the rate-determining step involves the formation of an intermediate complex involving both reagents, possibly (EtO)3P+–O––NAr, which then decomposes rapidly to give products. The possible intermediacy of a nitrene is neither proved or disproved.