威士忌内酯的合成研究  

Synthesis of whisky lactone

作　　者：郭春生[1] 祖萌萌[1] 祁林[1] 王政[1] 张峻松[1] 

机构地区：[1]郑州轻工业学院食品与生物工程学院,河南郑州450002

出　　处：《日用化学工业》2012年第3期205-208,共4页China Surfactant Detergent & Cosmetics

摘　　要：以过氧化苯甲酰和硼酸为催化剂,以戊醛和巴豆酸为起始原料经自由基加成反应合成了3-甲基-4-氧代辛酸,以硼氢化钠为还原剂和稀硫酸为脱水剂进行分子内脱水合成了顺反异构的威士忌内酯。以V(石油醚)∶V(乙酸乙酯)=5∶1的混合溶剂为洗脱剂,用柱层析法实现了威士忌内酯顺反异构体的分离。通过IR,1HNMR及MS确认了2种目标产物的结构。考察了溶剂、溶剂用量、反应时间、硼氢化钠用量和稀硫酸用量对目标产物收率的影响。最终的优化实验条件为:无水乙醇为溶剂,m(无水乙醇)∶m(3-甲基-4-氧代辛酸)=3∶1,室温下反应2 h,m(硼氢化钠)∶m(3-甲基-4-氧代辛酸)=1∶4,m(12%硫酸)∶m(3-甲基-4-氧代辛酸)=10∶1,全合成的总收率为61.9%。With benzoyl peroxide and boric acid as catalyst,3 -methyl -4 -oxooctanoic acid was synthesized by free radical addition reaction of valeraldehyde and crotonic acid as starting materials. Then it was reduced by sodium borohydride, and whisky lactone with cis and trans isomeric structure was obtained by intramoleeular dehydration under the action of dilute sulfuric acid. The cis - trans isomers were separated by column chromatography,with eluent composed of V（ petroleum ether）： V（ethyl acetate） = 5： 1. Structure of the two targeted products were confirmed by IR, 1HNMR and MS. Effect of factors on the yield such as kind of solvent, solvent amount, reaction time, dosage of sodium borohydride and dilute sulfuric acid were investigated. Optimum conditions for the reaction were found as follows：ethanol as solvent, m （ethanol）： m （3 -methyl -4 - oxooctanoic acid） = 3： 1, reaction time 2 h at room temperature, m （ sodium borohydride） ： m （ 3 - methyl - 4 - oxooctanoic acid） = 1 ： 4 ; m （ 12% sulfuric acid ） ： m （ 3 - methyl - 4 - oxooctanoie acid） = 10： 1. Overall yield of the complete synthesis process achieves 61.9%.

关 键 词：香料 威士忌内酯 合成 

分 类 号：TQ655[化学工程—精细化工]