丙醛与硫化氨环化缩合反应产物研究

Study on the Cyclocondensation Products of Propional with Ammonium Sulfide

摘要:

采用乙醇作溶剂，以0.10mol丙醛与0.18mol硫化铵水溶液为原料，在0℃下反应5h，制得2,4,6-三乙基-5,6-二氢-4H-1,3,5-二噻嗪香料化合物；并采用FTIR、傅立叶离子回旋变换质谱、1HNMR和13CNMR对其进行了结构表征。通过GC-MS对反应后所得粗品进行分析，确定了其组成成分主要为2,4,6-三乙基-5,6-二氢-4H-1,3,5-二噻嗪、六氢-1,3,5-三嗪、N-亚丙基-1-胺基-1-丙烯、3,5-二乙基-1,2,4-三硫杂环戊烷、2,4,6-三乙基-四氢-1,3,5-噻二嗪、N,N’-二亚丙基丙二胺、3,5-二乙基-4,5-二氢-1,2,4-二噻唑。文中探讨了该反应生成2,4,6-三乙基-5,6-二氢-1,3,5-二噻嗪及其副产物的机理，也探讨了2,4,6-三乙基-5,6-二氢--4H-1,3,5-二噻嗪、2,4,6-三乙基-六氢-1,3,5-三嗪和2,4,6-三乙基-四氢-1,3,5-噻二嗪等在GC-MS分析过程中发生分解的情况；最后对2,4,6-三乙基-5,6-二氢-4H-1,3,5-二噻嗪作为潜在的食品香料化合物的安全性问题做了相关的评价。

Abstract:

2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazine was synthesized by the reaction of 0.10mol propional with 0.18mol aqueous solution of ammonium sulfide in ethanol. Its structure was characterized by FTIR, FTMS,1HNMR and 13CNMR. The crude product obtained was analyzed by GC-MS. The analytical result showed that its constituents mainly included 2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazine, 2,4,6-triethyl-hexahydro-1,3,5-trizine, N-propylidene-1-amino-1-propene, 3,5-diethyl-1,2,4-trithiolane, 2,4,6-triethyl-tetrahydro-1,3,5-thiadizine, N,N’-dipropylidene-1,1-propylenediamine and 3,5-diethyl-4,5-dihydro-1,2,4-dithiazole. The formation mechanisms for main product and by-products were speculated. Meanwhile, thermal decomposition process of products, including 2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazine, 2,4,6-triethyl-tetrahydro-1,3,5-thiadizine and 2,4,6-triethyl-hexahydro-1,3,5-trizine, were discussed when they were analyzed by GC-MS. Finally, the safety issues of 2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazines as potential food flavor were evaluated.