不对称环磷酸肟酯的合成和生物活性研究  

Synthesis and Bioactivities of Novel 1,3,2 Dioxaphosphorinane 2 one Containing Arylglyoxylonitrile Oxime

作　　者：马治华[1] 邵瑞链[1] 马红敏[1] 成俊然[1] 黄润秋[1] 

机构地区：[1]南开大学元素有机化学研究所,天津300071

出　　处：《高等学校化学学报》1999年第10期1574-1577,共4页Chemical Journal of Chinese Universities

基　　金：天津市自然科学基金;元素有机化学国家重点实验室基金

摘　　要：通过反式－２－氯－２－氧－４－苯基－５，５－二甲基－１，３，２－二氧磷杂环己烷（Ⅱ）和α－氰基－芳基甲醛肟（Ⅰａ—Ⅰｆ）在相转移催化条件下反应， 制得新型的１，３，２－二氧磷杂环磷酸肟酯（Ⅲａ＿ Ⅲｆ）， 产物中的非对映异构体经１Ｈ ＮＭＲ、３１ＰＮＭＲ和单晶Ｘ射线衍射确证． 但化合物Ⅱ与芳基甲醛肟反应， 得到芳基甲腈和环磷酸， 这可能是生成不稳定的环磷酸醛肟酯（Ⅳ）经Ｂｅｃｋｍ ａｎｎ 裂解所致．生物活性测试表明， 化合物ｃｉｓ－ⅢｄThe reaction of trans 2 chloro 2 oxo 4 phenyl 5,5 dimethyl 1,3,2 dioxaphosphorinane(Ⅱ) with arylglyoxylonitrile oximes in the presence of PTC resulted in diastereomers of novel cyclic phosphate of arylglyoxylonitrile oxime(Ⅲ). The configuration and ratio of cis/trans diastereomers of Ⅲ were confined by 1H NMR, 31 P NMR and X ray diffraction analysis. The reaction of arylaldoxime with trans Ⅱ yielded an unstable arylaldoxime cyclic phosphate which was decomposed through Beckmann fragmentation to give nitrile and cyclic phosphate acid. The bioassay indicated that compound cis Ⅲd showed a high antiviral activity against TMV.

关 键 词：肟衍生物 二氧磷杂 环磷酸肟酯 生物活性 

分 类 号：O626.4[理学—有机化学] TQ450.2[理学—化学]