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

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

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,α=β=γ=90°,V=8.1691nm3,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=0.9546nm3,Z=2,R=0.049,wR=0.135.

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） nm, c=3.10857（13） nm, α=β=γ=90°, V=8.1691 nm^3, Z=24, R=0.1089, wR=0.2545, 2a to monoclinic system with space group C2/c and α=3.35144（18） nm, b=0.97948（5） nm, c=2.44717（12） nm, t= 102.460（1）°, V=7.8440（7） nm^3, Z=8, R=0.1831, wR=0.2600, and 2c to triclinic system with space group P-1 and a=0.84681（7） nm, b=0.89652（83） nm, c= 1.43497（12） nm, a=75.198（2）°, β=87.918（1）°, γ =65.395（1）°, V=0.9546 nm^3, Z=2, R=0.049, wR=0.135.