微波辐射下4-胡椒基-2,6-二甲基-3,5-乙氧羰基-1,4-二氢吡啶的合成、芳构化及产物的晶体结构

用胡椒醛、乙酰乙酸乙酯和醋酸铵在微波辐射下干反应得4-胡椒基-2,6-二甲基-3,5-乙氧羰基-1,4-二氢吡啶 1(C20H23NO6),4-胡椒基-2,6-二甲基-3,5-乙氧羰基-1,4-二氢吡啶在NDC (烟酸三氧化铬) 存在下经微波辐射得到4-胡椒基-2,6-二甲基-3,5-乙氧羰基吡啶 2 (C20H21NO6)。产物的结构通过单晶X-射线衍射法确定, 1 属单斜晶系, 空间群P21/c, a = 14.864(3), b = 9.830(1), c = 14.517(3)? b = 115.25(1), V = 1918.6(6)?, Z = 4, Mr = 373.39, Dc = 1.293g/cm3, m(MoKa)=0.096mm-1, F(000)=792。最终的偏离因子为R = 0.0496, wR = 0.1368。2 属三斜晶系,空间群Pī, a = 8.915(1), b = 10.575(1), c = 11.904(1)?α = 102.19(1),b = 109.43(1),γ=108.94(1), V=934.79(16) 3, Z = 2, Mr = 371.38, Dc = 1.319g/cm3 , m(MoKa) = 0.098mm-1, F(000) = 392。最终的偏离因子为R=0.0412, wR=0.1011。1 的二氢吡啶环为信封式结构, 2的吡啶环为平面结构。

Synthesis, Aromatization and Crystal Structure of Diether 4-(3,4-methylene dioxylphenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate under Microwave Irradiation

Diether 4-(3,4-methylene dioxylphenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate 1 (C20H23NO6) has been synthesized by the reaction of 3,4-methylenedioxylbenzaldehyde, ethyl acetoacetate and ammonium acetate under microwave irradiation without solvent. Diether 4-(3,4-methylene dioxylphenyl)-2,6-dimethyl-3,5-dicarboxylate 2 was obtained by the reaction of 1 with NDC under microwave irradiation without solvent. Their structures were determined by single-crystal X-ray diffraction. The crystal of 1 is monoclinic, space group P21/c with a =14.864(3), b =9.830(1), c =14.517(3)? b =115.25(1), V =1918.6(6) 3, Z=4, Mr=373.39, Dc =1.293g/cm3 , m(MoKa)=0.096mm-1, F(000)=792. The structure was solved by direct methods and refined by full-matrix least squares method to the final R=0.0496 and wR=0.1368. The crystal of 2 is triclinic, space group P with a =8.915(1), b =10.575(1), c =11.904(1)? =102.19(1), b =109.43(1), ?108.94(1), V = 934.8(2) 3, Z = 2, Mr = 371.38, Dc =1.319g/cm3 , m(MoKa) = 0.098mm-1, F(000) = 392, R = 0.0412 and wR = 0.1011.