10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮的合成和晶体结构

Synthesis and crystal structure of 10-chloro-5-(diethoxymethyl)-1,3-dimethylchromeno[4,3-d]pyrazolo[3,4-b]pyridin-6(3H)-one

利用L-脯氨酸催化的5-氯水杨醛(1)与6-甲基-4-羟基吡喃酮(2)的缩合反应及硫酸铜催化下与1,3-二甲基-5-氨基吡唑(3)的串联反应,合成得到了10-氯-1,3-二甲基-5-(2-氧代丙基)色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(4)和10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(5).化合物5的结构通过单晶X射线衍射法确定:晶体属于三斜晶系,空间群P-1;相对分子质量Mr=803.68;晶胞参数a=1.03160(10)nm,b=1.42900(13)nm,c=1.44268(15)nm;V=1.9448(3)nm^3;Z=2;晶胞密度Dc=1.372g/cm^3;吸收系数μ=0.228mm-1;单胞中电子的数目F(000)=840.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为R=0.0681,w R=0.2051.在晶体结构中色烯环与吡啶环及吡唑环近似于共平面.

10-Chloro-1,3-dimethyl-5-（2-oxopropyl）chromeno[4,3-d]pyrazolo[3,4-b]pyridin-6（3H）-one（4） and 10-chloro-5-（diethoxymethyl）-1,3-dimethylchromeno[4,3-d]pyrazolo[3,4-b]pyridin-6（3H）-one（5） have been synthesized by the tandem reaction of 5-chloro-2-hydroxybenzaldehyde（1）, 4-hydroxy-6-methyl-2H-pyran-2-one（2） and 1,3-dimethyl-1H-pyrazol-5-amine（3） catalyzed by L-proline and Cu SO4, respectively. The structure of compound 5 was determined by single crystal X-ray diffraction analysis. The crystal is triclinic, space group P-1, with Mr=803.68, a=1.031 60（10） nm, b=1.429 00（13） nm, c=1.442 68（15） nm, V=1.944 8（3） nm^3, Z=2, Dc=1.372 g/cm^3, μ=0.228 mm-1, F（000）=840. The structure was solved by direct methods and refined by full-matrix least squares method to the final R=0.068 1, w R=0.205 1. X-ray analysis reveals that the chromene ring, pyridine ring and pyrazole ring in the crystal structure are in a coplanar.