手性α-溴代异长叶烯酮的合成研究  

Synthesis of α-Brominated Isolongifolenone with Chirality

作　　者：丁志彬[1] 孙楠[1] 张齐[1] 曹晓琴[1] 徐徐[1,2,3] 王石发[1,2,3] 

机构地区：[1]南京林业大学化学工程学院,江苏南京210037 [2]南京林业大学江苏省林业资源高效加工利用协同创新中心,江苏南京210037 [3]江苏省生物质绿色燃料与化学品重点实验室,江苏南京210037

出　　处：《林产化学与工业》2016年第5期30-36,共7页Chemistry and Industry of Forest Products

基　　金：国家自然科学基金资助项目(31170538;31470592)

摘　　要：研究了以(2R,4aS)-异长叶烯酮为原料合成α-溴代异长叶烯酮的溴代反应。采用乙酸乙酯为溶剂,异长叶烯酮与溴化铜进行溴代反应得到两种同分异构体,经制备液相色谱分离纯化后,用~1H NMR,FT-IR,GC-MS,比旋光度和X射线单晶衍射等分析手段,确定其结构分别为(2R,4aR,6R)-(+)-6-Br-异长叶烯酮液体([α]_D^(25)+81°)和(2R,4aR,6S)-(-)-6-Br-异长叶烯酮晶体([α]_D^(25)-58°);探讨了制备工艺条件对溴代产物的影响。结果表明:在以乙醇为溶剂、溴化铜为溴代试剂的反应体系中,异长叶烯酮能选择性溴代生成(2R,4aR,6S)-(-)-6-Br-异长叶烯酮,且最佳制备工艺条件为异长叶烯酮6.54 g(0.03 mol),溴化铜与异长叶烯酮的物质的量之比为3∶1,溶剂乙醇用量60 m L,反应温度为78℃,反应时间为3 h。在此条件下,异长烯酮转化率为95.72%,(2R,4aR,6S)-(-)-6-Br-异长叶烯酮的得率为88.39%。The bromo-reaction of（ 2R,4aS）-isolongifolenone to α-brominated isolongifolenone was investigated. Isolongifolenone was reacted with copper bromide in ethyl acetate,and the two isomerides,（ 2R,4aR,6R）-（ ＋）-6-Br-isolongifolenone（ [α]_D^（25）＋ 81°） and（ 2R,4aR,6S）-（-）-6-Br-isolongifolenone（ [α]_D^（25）- 58°）,were obtained by purification with preparative liquid chromatography. The structures of the two compounds were characterized by^1H NMR,FT-IR,GC-MS,specific rotation,and singal crystal X-ray diffraction. Furthermore,the effects of preparing conditions on the products were also explored. It was shown that（ 2R,4aR,6S）-（-）-6-Br-isolongifolenone could be obtained through a selective bromination of isolongifolenone by using ethanol as solvent and copper bromide as the reaction reagent. The optimum conditions of preparing（ 2R,4aR,6S）-（-）-6-Brisolongifolenone were the molar ratio of copper bromide/isolongifolenone 3 ∶ 1,ethanol dosage 60 m L,reaction time 3 h and reaction temperature 78 ℃. Under the foresaid conditions,the reaction selectivity and the yield of（ 2R,4aR,6S）-（-）- 6-brominated isolongifolenone were 93% and 88%,respectively.

关 键 词：(2R 4aS)-异长叶烯酮 α-溴代反应 (2R 4aR 6R)-(+)-6-Br-异长叶烯酮 (2R 4aR 6S)-(-)-6-Br-异长叶烯酮 

分 类 号：TQ35[化学工程]