反丁烯二酸蔗糖甲酯的合成

Synthesis of sucrose methyl fumarate

反丁烯二酸蔗糖甲酯(SMF)的合成反应分为3步:顺酐先甲酯化和异构化为反丁烯二酸单甲酯(MMF);再与亚硫酰氯反应生成反丁烯二酸单甲酯酰氯(MMFC);MMFC在N,N-二甲基甲酰胺中与蔗糖反应可得SMF。用单因素试验法确定酯化度5 5的SMF合成工艺为:摩尔比为1∶1 2的顺酐和甲醇,在70℃下回流2h,加入异构化催化剂并保温3h,可得白色固体反丁烯二酸单甲酯。反丁烯二酸单甲酯和其摩尔数1 2倍的亚硫酰氯在90℃下回流约2h,得无色MMFC液体。摩尔比为6∶1的MMFC与蔗糖在40℃反应约1h,将反应液滴加入pH为8的碱液中,上层析出的浅白色固体即为反丁烯二酸蔗糖甲酯。

Sucrose methyl fumarate(SMF) was prepared in 3 steps.Firstly,maleic anhydride was esterified by methanol and followed by isomerization to form mono-methyl fumarate (MMF).MMF reacted with thionyl chloride to form mono-methyl fumarate chloride (MMFC).MMFC reacted with sucrose in N,N-dimethyl formamide and SMF was obtained.The technological process and conditions for preparation of SMF with esterification degree of 5.5 are: mole ratio of maleic anhydride to methanol 1∶1.2;reaction at 70 ℃ for 2 h under reflus condition;further reaction for 3 h after the additon of isomerization catalyst;then MMF was formed as a white solid material; mole ratio of MMF to thionyl chloride 1∶1.2; reaction at 90 ℃ for 2 h under feflux condition;MMFC was formed as a colorless liquid; mole ratio of MMFC to sucrose 6∶1; reaction at 40 ℃ for 1 h under reflux condition; add the reaction mixture gradually to an alkali solution at pH 8;then the SMF product separates and floats at the upper layer as a white solid material.