一种β,γ-不饱和醛的合成及其光化学反应研究  

Synthesis and photochemical study on one of β,γ-unsaturated aldehyde

作　　者：杨一坤[1] 马满玲[1] 

机构地区：[1]哈尔滨医科大学第一临床医学院药学部,黑龙江哈尔滨150001

出　　处：《中国药物化学杂志》2013年第1期42-46,共5页Chinese Journal of Medicinal Chemistry

摘　　要：目的设计合成β,γ-不饱和醛,并研究其光化学反应机制,为天然产物及其中间体的光化学合成提供新的参考。方法以异丁醛为原料,经缩合、醛基保护、氧化、Wittig反应、脱水、脱保护基6步反应制得目标化合物。用高压汞灯照射目标化合物后所得产物与β,γ-不饱和甲基酮进行比较分析。结果目标化合物的结构经高分辨质谱、核磁共振谱确证。目标化合物经光照后发生NorrishⅠ型裂解反应,与β,γ-不饱和甲基酮相比,没有发生ODPM重排反应。结论甲基对β,γ-不饱和酮(醛)的光化学反应行为有一定的影响。Photochemistry plays an important role in the synthesis of natural products and their intermediates with the advantages of cleanliness and safety. In the photochemical reactions, ODPM rearrangement and Nor- fish type I reaction are widely applied, especially in the syntheses of prostaglandins, terpene and aldosterone compounds, β,γ-Unsaturated methyl ketones （ R = CH3 ） were reported to undergo ODPM rearrangements and Norrish type I reactions under irradiation. But no synthetic process was given in the paper. In order to analyze the effect of R group, the synthetic route and irradiation experiment of β,γ-unsaturated aldehyde （ R = H） were designed based on the related literatures. The target compound was synthesized from isobutyr- aldehyde via six steps including condensation, aldehyde protection, oxidation, Wittig reaction, hydroxy elimi- nation and deprotection. Under the irradiation ,β,γ-unsaturated aldehyde （ R = H） underwent only Norrish type I reaction. Which was different with β,γ-unsaturated methyl ketones （ R = CH3 ）. The results indicated that β,γ-unsaturated ketone and aldehyde showed a different photochemical reaction behavior.

关 键 词：合成 光化学 β γ-不饱和醛 

分 类 号：R914[医药卫生—药物化学]