2540-60-5Relevant articles and documents
Convenient synthesis of unsymmetrical N,N′-disubstituted thioureas in water
Li, Zhengyi,Chen, Yuan,Yin, Yue,Wang, Zhiming,Sun, Xiaoqiang
, p. 670 - 673 (2016/11/18)
A simple and convenient two-step method has been developed and used to synthesise 25 (4 of which are novel) unsymmetrical N,N′-disubstituted thioureas in water. Alkylamines or variously substituted arylamines reacted smoothly with phenyl chlorothionoformate at room temperature to form thiocarbamates, which were then reacted with another alkyl- or arylamine in water at reflux to afford the unsymmetrical N,N′-disubstituted thioureas in good to excellent yields. Mild conditions, simple work-up, high yields as well as using water as solvent are the major advantages of the method.
Aminolyses of 4-nitrophenyl phenyl carbonate and thionocarbonate: Effect of modification of electrophilic center from C=O to C=S on reactivity and mechanism
Um, Ik-Hwan,Kim, Eun Young,Park, Hye-Ran,Jeon, Sang-Eun
, p. 2302 - 2306 (2007/10/03)
A kinetic study is reported for nucleophilic substitution reactions of 4-nitrophenyl phenyl carbonate (5) and 4-nitrophenyl phenyl thionocarbonate (6) with a series of primary amines. The thiono compound 6 is less reactive than its oxygen analogue 5 toward strongly basic amines but is more reactive toward weakly basic CF3CH2NH2. The Bronsted-type plots obtained from the aminolyses of 5 and 6 are curved downwardly. The reactions are proposed to proceed through a stepwise mechanism with a change in the RDS on the basis of the curved Bronsted-type plots. The microscopic rate constants (k1 and k2/k-1 ratio) associated with the current aminolyses are consistent with the proposed reaction mechanism. The replacement of the C=O bond in 5 by a polarizable C=S group results in a decrease in the k1 value but an increase in the k2/k-1 ratio. Besides, such a modification of the electrophilic center causes a decrease in pKac, defined as the pKa at the curvature center of curved Bronsted-type plots, but does not alter the reaction mechanism. The larger k 2/k-1 ratio for the reactions of 6 compared to those of 5 is proposed to be responsible for the decreased pKac value.
