3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪及其衍生物的合成和晶体结构

Synthesis and Structures of 3-Aryl-6-methyl-1,6-dihydro-1,2,4,5-tetrazines and Their Derivatives

以乙腈和芳基腈为原料,经过醚化、环化和还原三步方便且有效地合成了3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪,并在此基础上合成了一系列新的3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪衍生物,通过元素分析,1HNMR,IR和HRMS对这些化合物进行了表征.对化合物N-邻甲基苯-3-苯基-6-甲基-1,6-二氢-1,2,4,5-四嗪-1-甲酰胺(5a)的X射线晶体衍射研究表明:其属于单斜晶系,P21/c空间群,晶胞参数a=1.3941(6)nm,b=0.5675(2)nm,c=2.0614(8)nm;α=γ=90°,β=102.055(6)°;V=1.5949(11)nm3,此类化合物的四嗪环采用不对称船式结构,且具有同芳香性.

A convenient and effective method was developed from the starting materials acetonitrile and aryl nitrile via three steps to synthesize 3-aryl-6-methyl-1,6-dihydro-1,2,4,5-tetrazines. On the basis of which, some 3-aryl-6-methyl-1,6-dihydro-1,2,4,5-tetrazine derivatives were synthesized and characterized by elemental analysis, ^1H NMR, IR and HRMS techniques. The X-ray single crystal diffraction study of 6-methyl-3-phenyl-N-（2-tolyl）-1,6-dihydro-1,2,4,5-tetrazine- 1-carboxamide （Sa） indicates that 5a belongs to a monoclinic system, with α=1.3941（6） nm, b=0.5675（2） nm, c=2.0614（8） nm; α=γ=90°, β= 102.055（6）°; V= 1.5949（11） nm^3. The central tetrazine ring adopts an unsymmetrical boat structure. It could be considered that the molecule had a homoaromaticity.