1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑及其酰胺、二酰亚胺的合成及晶体结构

2,6-二氯-4-三氟甲基苯胺经重氮化后与2,3-二氰基丙酸酯反应合成了1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑(1), 1与乙酸酐、顺丁烯二酸酐、苯甲酰氯反应得到1的乙酰胺2a、顺丁烯酰亚胺2b和苯甲酰胺2c. 通过元素分析、红外光谱、核磁共振氢谱、核磁共振碳谱、质谱等手段对其结构进行了表征. 用X射线单晶衍射测定了化合物2a, 2b和2c的晶体结构. 2a属于单斜晶系, C2/c空间群, 晶胞参数a＝1.88282(6) nm, b＝0.86541(3) nm, c＝1.90766(6) nm, β＝95.5830(10)°, V＝3.09362 nm³, Z＝8, R＝0.064, wR＝0.170. 2b属于单斜晶系, P2₁/n空间群, 晶胞参数 a＝1.28261(10) nm, b＝0.89942(7) nm, c＝1.46896(12) nm, β＝104.217(1)°, V＝1.6427(2) nm³, Z＝4, R＝0.055, wR＝0.165. 2c属于三斜晶系, P-1空间群, 晶胞参数a＝0.84613(11) nm, b＝0.98923(13) nm, c＝1.14305(15) nm, β＝96.002(2)°, V＝0.9326 nm³, Z＝2, R＝0.0684, wR＝0.1795.

Synthesis and Crystal Structure of 1-(2,6-Dichloro-4-trifluoromethyl- phenyl)-3-cyano-5-amino-pyrazole and Its Amides Plus Imide

Reaction of 2,6-dichloro-4-trifluoromethylaniline with a suspension of nitrosyl sulphuric acid, followed by the reaction with a solution of ethyl 2,3-dicyanopropionate in acetic acid, gave 5-amino-3- cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (1), which was then reacted with acetic anhydride to give 2a, with maleic anhydride to yield 2b, and with benzoyl chloride to afford 2c. All compounds were characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and MS spectra. The crystal and molecular structures of 2a, 2b and 2c have been determined by single crystal X-ray diffraction analysis. Compound 2a belongs to monoclinic system with space group C2/c and a＝1.88282(6) nm, b＝0.86541(3) nm, c＝1.90766(6) nm, β＝95.5830(10)°, V＝3.09362 nm³, Z＝8, R＝0.0639, wR＝0.170. 2b belongs to monoclinic system with space group P2₁/n and a＝1.28261(10) nm, b＝0.89942(7) nm, c＝1.46896(12) nm, β＝104.217(1)°, V＝1.6427(2) nm³, Z＝4, R＝0.055, wR＝0.165. 2c belongs to triclinic sys-tem with space group P-1 and a＝0.84613(11) nm, b＝0.98923(13) nm, c＝1.14305(15) nm, β＝96.002(2)°, V＝0.9326 nm³, Z＝2, R＝0.0684, wR＝0.1795.