反式-1-苯磺酰基-2-甲基-4-羟基-2-丁烯的合成  

Synthesis of trans-1-Phenylsulfonyl-2-Methyl-4-Hydroxy-2-Butene

作　　者：陈田[1] 杨运泉[1] 杨彦松[1] 陈健[1] 刘文英[1] 

机构地区：[1]湘潭大学化工学院,湖南湘潭411105

出　　处：《石油化工》2007年第4期374-377,共4页Petrochemical Technology

基　　金：湖南省科技厅科技攻关项目(04FJ4116)

摘　　要：以异戊二烯为原料,经与苯磺酰氯加成、水解乙酰化、皂化3步反应,合成了辅酶Q10的重要中间体——反式-1-苯磺酰基-2-甲基-4-羟基-2-丁烯(简称终产物);分别考察了3步反应的反应条件;用傅里叶变换红外光谱和核磁共振表征了其结构。实验结果表明,加成反应的适宜条件为:氯化亚铜为催化剂,三乙胺盐酸盐为相转移助催化剂,乙腈为溶剂,90～100℃下密闭带压(约0.6M Pa)反应2h,n(异戊二烯)∶n(苯磺酰氯)=1.2,中间产物反式-1-苯磺酰基-2-甲基-4-氯-2-丁烯的收率为75%;水解乙酰化、皂化反应的适宜条件为:120～125℃下常压回流反应4h,0～5℃下碱性水解反应3h,以体积比为1∶1的乙酸乙酯-乙醚混合溶剂进行结晶精制。3步反应终产物的总收率为60%;终产物经液相色谱法分析,纯度达到99%。A key intermediate for preparation of coenzyme Q10-trans- 1 -phenylsulfonyl- 2- methyl - 4 - hydroxy - 2 - butene was synthesized by addition reaction of isoprene and phenylsulfonyl chloride, and subsequent acetolysis and saponification. The structure of end product was identified by means of FTIR and ^1H NMR. Under optimal conditions of addition reaction： CuCl as catalyst, triethylamine hydrochloride as co -catalyst, acetonitrile as solvent, about 0.6 MPa, 90 - 100℃, 2 h and n（isoprene） ： n （phenylsulfonyl chloride ） 1.2, yield of intermediate product-tram- 1 - phenylsulfonyl-2 - methyl -4 -chloro -2 -butene is 75%. In the following acetolysis and saponification the above intermediate was refluxed at 120 - 125 ℃ for 4 h under atmospheric pressure and hydrolyzed under basic condition at 0 -5 ℃ for 3 h to obtain the end product. The crude product was purified by crystallization with ether -ethyl acetate mixture （volume ratio 1 ： 1 ）. The overall yield of trans - 1 - phenylsulfonyl -2 - methyl - 4 - hydroxy -2 - butene is 60% and its purity can reach 99%, analyzed by means of HPLC. The reaction conditions are moderate. Operation is simple and convenient.

关 键 词：辅酶Q10 异戊二烯 苯磺酰氯 反式-1-苯磺酰基-2-甲基-4-羟基-2-丁烯 催化 加成反应 水解乙酰化 皂化 

分 类 号：TQ032.4[化学工程]