Jørgensen K A, Ghattas A B, Lawesson S O
IARC Sci Publ. 1982(41):159-68.
The reaction between N-nitrosamides and 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (LR) at low temperature (20-50 degrees C) gives the corresponding thioamides as the main products. In the reaction between N-nitroso-2-pyrrolidone and LR, dihydro-2-(3H)-thiophenone (III) is also isolated. Mechanistic considerations for the formation of III are presented. The nitrosation of thiono compounds gives the corresponding oxo analogues. N-Nitroso-2-pyrrolidone is obtained after nitrosation of 2-pyrrolidinethione. A kinetic investigation of this reaction has been performed using the theory of consecutive reactions with 2-pyrrolidone as an intermediate. The rate constants for these two reactions are found to be k1 = 0.055 s-1 for the formation of 2-pyrrolidone, using a first order plot of the change of 2-pyrrolidinethione; for the formation of N-nitroso-2-pyrrolidone, the rate constant obtained by computer simulation is k2 = 0.032 mol(-1)1 s-1.
N-亚硝基酰胺与2,4-双(4-甲氧基苯基)-1,3,2,4-二硫代二磷杂环丁烷-2,4-二硫化物(LR)在低温(20 - 50℃)下反应，生成相应的硫代酰胺作为主要产物。在N-亚硝基-2-吡咯烷酮与LR的反应中，还分离出了二氢-2-(3H)-噻吩酮(III)。文中给出了生成III的机理探讨。硫酮化合物的亚硝化反应生成相应的氧代类似物。2-吡咯烷硫酮亚硝化后得到N-亚硝基-2-吡咯烷酮。以2-吡咯烷酮为中间体，利用连续反应理论对该反应进行了动力学研究。对于生成2-吡咯烷酮的反应，用2-吡咯烷硫酮变化的一级图得到速率常数k1 = 0.055 s-1；对于生成N-亚硝基-2-吡咯烷酮的反应，通过计算机模拟得到的速率常数k2 = 0.032 mol(-1)1 s-1。
