取代苯甲醛的取代基在硝基苄基鏻参与的Wittig反应中对二苯乙烯分子构型的影响  

Effect of Substituents on the Configuration of Stilbene Derivatives in Wittig Reaction of Substituted Benzaldehyde with Nitro-benzyltriphenylphosphonium Salt

作　　者：曹晨忠[1,2,3] 刘立秋[1,2,3] 陈冠凡[1,2,3] 周再春[1,2,3] 蒋荣清[1,2,3] 卢冰涛[1,2,3] 

机构地区：[1]湖南科技大学化学化工学院,湘潭411201 [2]湖南科技大学理论化学与分子模拟省部共建教育部重点实验室,湘潭411201 [3]湖南科技大学分子构效关系湖南省普通高等学校重点实验室,湘潭411201

出　　处：《有机化学》2010年第3期395-400,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.20772028);湖南省自然科学基金(No.06JJ2002)资助项目

摘　　要：用硝基苄基鏻与取代苯甲醛经Wittig反应合成了一系列含硝基的二苯乙烯型化合物.研究表明,用硝基苄基鏻在二氯甲烷中进行这类Wittig反应时,随着苯甲醛的取代基不同,得到二苯乙烯主要产物的构型不同,取代基为NMe2,OMe,Me,Cl,H等时主要得到E式产物,取代基为CN和NO2等时主要得到Z式产物;进一步比较3种苄基鏻原料分别与6种不同取代苯甲醛反应后产物的Z/E比,发现用含硝基的苄基鏻作原料时,随苯甲醛上取代基的吸电子效应减小,产物的Z/E比也减小,而用苄基鏻或对甲基苄基鏻作原料时,没有观察到这种Z/E比减小的趋势.通过测定产物的晶体结构,确证了6个目标化合物的分子构型,另外通过核磁共振谱、气-质联用色谱、紫外光谱和红外光谱对各二苯乙烯化合物的结构进行了详细表征.A series of nitro-containing stilbene derivatives were synthesized by Wittig reaction of substituted benzaldehyde with nitro-benzyltriphenylphosphonium salt. It was observed that the configuration of the stilbene derivatives depended on the substituents of the substituted benzaldehyde, when the Wittig reac- tions were carried out in CH2Cl2. The main products are the E-stilbene for the substituents NMe2, OMe, Me, Cl and H, but the Z-stilbene for the substituents CN and NO2. Furthermore the comparison of the Z/E ratio in the reactions of three benzyltriphenylphosphonium salts with six substituted benzaldehydes was made. The results showed that the Z/E ratio of stilbene products diminished as the substituent electron withdrawing effect of group Y in the benzaldehyde decreased in the reaction ofp-NO2C6H4CH/P＋Ph3 with YC6H4CHO, while the above Z/E change trend was not observed in the reactions of PhCH2P＋Ph3, p-MeC6H4CH2P＋Ph3 with YC6H4CHO, respectively. The molecular configuration of the target compounds was identified through the determination of their crystal structures, and their structures were also deliberately characterized by 1H NMR, GC-MS, IR and UV-Vis techniques.

关 键 词：二苯乙烯 硝基苄基鳞 取代苯甲醛 晶体结构 分子构型 

分 类 号：O621.25[理学—有机化学]