1-(2,6-二氯-4-三氟甲基苯基)-3-氰基-5-氨基吡唑及其磺酰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与苯磺酰氯、对甲基苯磺酰氯、甲基磺酰氯反应, 得到1的苯磺酰胺2a、对甲基苯磺酰胺2b和双甲基磺酰胺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1, 2a和2c的晶体结构. 1属于正交斜方晶系, Pbca空间群, 晶胞参数 a＝1.61739(7) nm, b＝1.62480(7) nm, c＝3.10857(13) nm, ＝＝＝90, V＝8.1691 nm³, Z＝24, R＝0.1089, wR＝0.2545. 2a属于单斜晶系, C2/c空间群, 晶胞参数 a＝3.35144(18) nm, b＝0.97948(5) nm, c＝2.44717(12) nm, β＝102.460(1), V＝7.8440(7) nm³, Z＝8, R＝0.1831, wR＝0.2600. 2c属于三斜晶系, P-1空间群, 晶胞参数 a＝0.84681(7) nm, b＝0.89652(83) nm, c＝1.43497(12) nm, α＝75.198(2), β＝87.918(1), γ＝65.395(1), V＝0.9546 nm³, Z＝2, R＝0.049, wR＝0.135.

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

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 benzenesulfonyl chloride to yield 2a, with 4-methylbenzenesulfonyl chloride to 2b, and with methansulfonyl chloride to 2c. All compounds were characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and MS spectra. The crystal and molecular structures of 1, 2a and 2c have been determined by single crystal X-ray diffraction analysis. Compound 1 belongs to orthorhombic system with space group Pbca and a＝1.61739(7) nm, b＝1.62480(7), c＝3.10857(13) nm, α＝β＝γ＝90, V＝8.1691 nm³, Z＝24, R＝0.1089, wR＝0.2545, 2a to monoclinic system with space group C2/c and a＝3.35144(18) nm, b＝0.97948(5) nm, c＝2.44717(12) nm, β＝102.460(1), V＝7.8440(7) nm³, Z＝8, R＝0.1831, wR＝0.2600, and 2c to triclinic sys-tem with space group P-1 and a＝0.84681(7) nm, b＝0.89652(83) nm, c＝1.43497(12) nm, α＝75.198(2), β＝87.918(1), γ＝65.395(1), V＝0.9546 nm³, Z＝2, R＝0.049, wR＝0.135.