Reaction of halogenated hydrocarbon solvents with tertiary amines: Spectrophotometric and conductimetric study
作者:Alberto Hernandez Gainza
DOI:10.1002/kin.20022
日期:2004.9
Halogenated hydrocarbon solvents, SolvCl, (dichloromethane, chloroform, and 1,2-dichloroethane) react with various types of tertiary amines, A, such as tri-n-buthylamine, tropane derivatives (tropine and atropine) and quinine generating a quaternary ammonium salt, N-halogenalkylammonium chloride (SolvA+Cl−). Some tertiary amines, as well as secondary and primary amines, cannot react with these solvents
卤代烃溶剂 SolvCl(二氯甲烷、氯仿和 1,2-二氯乙烷)与各种类型的叔胺 A,如三正丁胺、托烷衍生物(托品和阿托品)和奎宁反应生成季铵盐, N-卤代烷基氯化铵 (SolvA+Cl−)。一些叔胺以及仲胺和伯胺不能与这些溶剂反应。该反应已通过电导率和可见分光光度法检测和研究——后者在添加少量染料后,如溴甲酚绿 (BCGH2)、溴酚蓝 (BPBH2) 或四溴酚酞乙酯 (TBPEH)。两种研究方法都允许确定动力学参数,并且它们非常一致。单质子 TBPEH 是机理最简单的染料,可用于研究行为不确定的胺如奎宁的动力学,而 BPBH2 是定量测定的最佳染料。该反应的动力学对于胺 A 和溶剂 SolvCl 都是一级的;还确定了活化能、Ea 和频率因子。速率常数随着胺碱度的增加和溶剂中卤素原子数的减少而增加。该反应缓慢但不可忽略,必须被视为这些普遍使用的溶剂的副反应。© 2004 Wiley Periodicals