对硝基甲苯在多硫化钠溶液中氧化还原机理的质谱研究  

A Mass Spectroscopic Investigation to Redox Mechanism of p-Nitrotoluene in Sodium Polysulfide Solution

作　　者：高坡[1] 乐征宇[1] 陈念陔[1] 唐恢同[2] 

机构地区：[1]黑龙江大学化学化工与材料学院,哈尔滨150080 [2]北京大学化学与分子工程学院,北京100871

出　　处：《高等学校化学学报》2005年第8期1480-1483,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20271018);黑龙江省自然科学基金(批准号:B0109);黑龙江大学杰出青年基金(批准号:J200206)资助.

摘　　要：采用高分辨质谱仪跟踪监测对硝基甲苯在多硫化钠存在下于乙醇-碱性水溶液中生成对氨基苯甲醛过程中反应中间体的变化及转变规律.结果显示,在80℃时反应进行到120min之内,有数种分子量较大的缩合中间体生成,表明对氨基苯甲醛可能是经类席夫碱的多聚体水解生成的.同时,对席夫碱多聚体的形成提出了与文献不同的机理.The reaction of p-nitrotoluene in the ethanol/sodium polysulfide solution resulting in p-aminobenzaldehyde has been applied to industry. However the reaction mechanism is not accepted commonly since the accordant conclusion among the proposed mechanisms was not reached due to lacking of the verification mutually. In this paper, we monitored the reaction intermediates and their transition regularity by high resolution mass spectra. The results show that the condensation compounds emerged duringthe reaction at 80℃ with the reaction starting up to 120 min, strongly supporting the condensation and oxidation mechanisms proposed by Shchukina and Chen, respectively, that is, p-aminobenzaldehyde is derived from the hydrolysis of poly Schiff base. Meanwhile, we propose the possibility of formation process of poly Schiff base, which is different from that reported in literatures.

关 键 词：中间体 质谱 机理 氧化还原 对硝基甲苯 

分 类 号：O643[理学—物理化学]