一锅合成异硫氰酸酯

以N,N-二乙基乙胺(Et₃N)为碱,甲苯为溶剂,伯胺和CS₂为原料,叔丁基碳酸二乙基磷酸酐(3)为脱硫试剂,在n(伯胺):n(CS₂):n(Et₃N):n(3)=1:1.1:3.3:1.1,二硫代甲酸盐合成段反应温度为室温,脱硫反应段为-5 ℃至室温的实验条件下,两步一锅合成了系列烷基、芳基和双功能基异硫氰酸酯化合物,收率77%96%。 本方法底物适用范围广,操作简单,对胺的各种保护基团耐受,不引起消旋化副反应。 脱硫剂3作为一种新的脱硫试剂,商业易得,安全有效。

One-Pot Synthesis of Isothiocyanates

Alkyl, aryl and bifunctional isothiocyanates were synthesized in moderate to excellent yields(77%96%) in a two-step and one-pot reaction. The reaction were started with parent primary amines, carbon disulfide in toluene in presence of N,N-diethyl-ethanamine(Et₃N) at room temperature, followed by reaction of the thus formed dithiocarbamates with t-butylcarbonic diethylphoric anhydride(3) from -5 ℃ to room temperature. The best molar ratio of substrates was n(primary amines):n(CS₂):n(Et₃N):n(3)=1:1.1:3.3:1.1. The procedure was quite simple and the substrate scope is broad. This method is compatible with a variety of protecting groups and the chiral center in investigated compounds. Compound 3 was used as an new commericial available safe and efficient desulfurization reagent.