三个磷酰化香豆素的合成及单晶结构

以二烷基亚磷酸酯和香豆素为原料,通过Atherton-Todd反应合成了3个新型含有磷酰基的香豆素类化合物,7-磷酰二乙基香豆素(2a)、4-甲基-7-乙酰氧基-6-磷酰二乙基香豆素(2b1)和7-羟基-4-甲基-6-磷酰二异丙基香豆素(2b2).单晶结构显示:化合物2a、2b1均为三斜晶系,P-1空间群,分子间有弱的π-π堆积,分子间主要靠范德华力紧密结合在一起.化合物2b2为单斜晶系,空间群为P2(1)/n,P=O的O原子和羟基氢原子之间存在分子间氢键,每一个分子分别与另外两个分子相连形成链状结构,由堆积图可以看到分子间有弱的π-π堆积,分子间主要靠范德华力紧密结合在一起.

Synthesis of Three Phosphoryl Coumarins and Their Crystal Structure

Three kinds of Phosphoryl Coumarins were synthesized by Atherton-Todd reaction with diethylphosphite(DEPPH) or diisopropylphophite(DIPPH) and Coumarins as materials.The molecular structures of the compound 2a-2b2 were determined by single-crystal X-ray diffraction analysis.The 2b2 molecule crystallizes in the monoclinic system,space group P2(1)/n.2a and 2b1 molecules crystallize in the triclinic system,space group P-1.Furthermore,there is intermolecular Hydrogen-bond in compound 2b2 between O atoms on P=O and H atoms on-OH groups exist.This O…H-O hydrogen bond serves to link the molecule into a 2-D sheet.The weak molecular interactions of van der Walls forces and π-π stacking play a very important role on catenulate molecular structure.