化学学报 ›› 2007, Vol. 65 ›› Issue (17): 1897-1901. 上一篇    下一篇

研究论文

3-取代甲撑肼基二硫代甲酸甲酯类化合物热裂解的研究

陈玲珍, 边高峰,蒋可志, 邬继荣, 来国桥*   

  1. (杭州师范大学有机硅化学及材料技术教育部重点实验室和浙江省有机硅材料重点实验室 杭州 310012)
  • 投稿日期:2006-11-09 修回日期:2007-02-12 发布日期:2007-09-14
  • 通讯作者: 来国桥

Thermal Decomposition Study of Methyl Arylmethylidenehydra-zinedithiocarboxylate

CHEN Ling-Zhen; BIAN Gao-Feng; JIANG Ke-Zhi; WU Ji-Rong; LAI Guo-Qiao*   

  1. (Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education and Zhejiang Prov-ince, Hangzhou Normal University, Hangzhou 310012)
  • Received:2006-11-09 Revised:2007-02-12 Published:2007-09-14

首次采用气质联用仪研究了3-取代甲撑肼基二硫代甲酸甲酯类化合物的热裂解反应, 发现其在气化室可热裂解产生芳香腈、甲硫醇和异硫氰酸. 考察了3-苯基甲撑肼基二硫代甲酸甲酯在不同温度时的热裂解效率, 发现温度对其热裂解具有重要的影响, 该化合物在230 ℃时就能基本完全裂解. 同时还考察了含有不同取代基的化合物在210 ℃下的热裂解情况, 结果表明含推电子基的化合物比吸电子基化合物在气化室中裂解得完全, 热稳定性更差, 并根据实验结果推测了热裂解反应的可能机理.

关键词: 3-取代甲撑肼基二硫代甲酸甲酯, 气质联用, 热裂解反应, 芳香腈

The gas-phase pyrolytic reactions of 3-methyl arylmethylidenehydrazinedithiocarboxylate were studied by GC/MS firstly. The results showed that these compounds could be cleavaged to aromatic cyanate, methylthiol and HNCS in the inlet of the GC/MS instrument. The relationship of thermal decomposition with the base temperature of the inlet was studied, finding that the temperature was an important key to the gas-phase pyrolytic reaction. The series of these compounds were decomposed completely at the base temperature of 230 ℃. Meanwhile the pyrolytic cleavage of compounds with different substituents at 210 ℃ was also studied. The results showed that the compounds substituted with electron donating groups could be cleavaged much more completely than the ones substituted with electron withdrawing groups at the same temperature. A possible mechanism for the gas-phase pyrolytic reaction was proposed.

Key words: methyl arylmethylidenehydrazinethiocarboxylate, GC/MS, gas-phase pyrolytic reaction, aromatic cyanate