王浆酸的合成

Synthesis of Royal Jelly Acid

设计并完成了一条从1,6-己二醇出发,经单溴代、三氧化铬吡啶盐酸盐(PCC)氧化成醛、保护醛基、格氏试剂与环氧乙烷增加两碳成醇、去保护、与丙二酸发生Kaoevenaglel反应合成王浆酸(反-10-羟基-2-癸烯酸)的新路线。改进了PCC氧化醇的操作,优化了主要反应条件,第一步反应己二醇、甲苯和氢溴酸最佳用量比分别为:1 mmol∶2.5 mL∶1.1 mmol,第四步反应化合物3与环氧乙烷最佳用量摩尔比为:1∶1.1。该路线具有原料易得,各步反应条件温和、分离简单、产率高的特点。主要中间体及王浆酸结构被IR、MS、1HNMR、13C NMR所确证。

Herein a new approach to synthesize royal jelly acid （trans-10-hydroxy-2-decenoic acid） was introduced, including mono-bromination of 1,6-hexandiol,oxidiation of the primary alcohol to aldehyde by pyridinium chlorochromate （PCC） and elongation of the alkylchain by the coupling reaction between ethylene oxide and Grignard reagent after the aldehydegroup was protected, and finally Kaoevenaglel reaction between unprotected aldehyde group and malonic acid to yield the product. The PCC-oxidation of alcohol procedure was improved and the best conditions for the main reactions were found, namely, in the first step the ratio of 1,6-hexandiol, toluene and hydrobromic acid should be 1 mmol ： 2.5 mL： 1.1 mmol and in the fourth step the ratio of compound 3 and ethylene oxide should be 1 mol ： 1.1 mol. All the starting materials are easily available and the reactions were carried out under mild conditions with easily separated and high yield products. The structures of main intermediates and the product were confirmed by IR, MS,^1H NMR and ^13C NMR.