【摘要】 在DDQ/PPh3作用下,以2-异丙基苯甲酸或水杨酸为原料,在温和条件下以较高的收率合成、分离得到两个化合物(2)和(3)。化合物(2)和(3)与苯胺在氯仿中加热回流可分别转化为酰胺类化合物(4)和(5)。所有化合物通过元素分析、质谱、核磁共振进行了表征,并解析了化合物(2)和(3)的X-衍射单晶结构。化合物1,2-二(2-异丙基苯甲酸)-2,3-二氰-5,6-二氯苯(2)晶体属单斜晶系,空间群P21/c,其晶胞参数为:a=1.287 5(3)nm,b=1.518 6(2)nm,c=1.572 6(3)nm,β=122.23(3)°,V=2.601 0(1)nm3,Dc=1.331 g·cm-3,Z=4,F(000)=1 080,R1=0.057 2,wR2=0.126 0;化合物1,2-二(2-羟基苯甲酸)-2,3-二氰-5,6-二氯苯(3)晶体属三斜晶系,空间群P1,其晶胞参数为:a=0.877 76(16)nm,b=1.131 11(15)nm,c=1.186 39(17)nm,α=69.290(2)°,β=89.409(3)°,γ=67.878(2)°,V=1.010 4(3)nm3,Dc=1.542 g·cm-3,Z=2,F(000)=476,R1=0.038 3,wR2=0.093 1。强π-π堆积作用和分子间氢键将化合物(2)和(3)组装成稳定的三维结构。更多还原

【Abstract】 Treatment of 2-substituted benzoic acids(2-isopropylbenzoic acid and salicylic acid) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) mediated by PPh3 at room temperature produced two 1,4-disubstituted 2,3-dicyano-5,6-dichlorobenzenes(2 and 3) in good yields.Heating a chloroform solution of 2 and 3 to the reflux temperature in the presence of phenylamine generated amide derivatives 4 and 5,respectively.All the target compounds were fully characterized by elemental analysis,MS and1H NMR spectrometry,and the structures of compounds 2 and 3 were further confirmed by single-crystal determination.1,4-Bis(2-isopropylbenzoate)-2,3-dicyano-5,6-dichlorobenzene(2) crystallizes in monoclinic space group P21 /c with cell parameters:a=1.287 5(3) nm,b=1.518 6(2) nm,c=1.572 6(3) nm,β=122.23(3)°,V=2.601 0(1) nm3,Dc =1.331 g·cm-3,Z=4,F(000)=1 080,R1 =0.057 2,wR2 =0.126 0.1,4-Bis(2-hydroxybenzoate)-2,3-dicyano-5,6-dichlorobenzene(3) crystallizes in triclinic space group P1 with cell parameters:a=0.877 76(16) nm,b=1.131 11(15) nm,c=1.186 39(17) nm,α=69.290(2)°,β=89.409(3)°,γ=67.878(2)°,V=1.010 4(3) nm3,Dc =1.542 g·cm-3,Z=2,F(000)=476,R1 =0.038 3,wR2 =0.093 1.Strong π-π stacking interactions and intermolecular hydrogen bonds of the structures(2 and 3) stabilized the two intermediates.CCDC:921957,2;935976,3.更多还原