(R)-甘油醛缩丙酮羟基磺酸盐的制备及其Wittig反应性  

Synthesis of(R)-glyceraldehyde Acetonide Hydroxysulfonate and Its Wittig Reaction

作　　者：谢可[1] 张瑞宁[1] 易莉莉[1] 苟蓉[1] 黄念红 陈明军[1] 钟柳[1] 刘治国[1] 

机构地区：[1]西华大学理学院,四川成都610039

出　　处：《广州化工》2017年第10期39-42,共4页GuangZhou Chemical Industry

基　　金：成都明方高新技术材料有限公司资助西华大学横向课题(NO:16233063)

摘　　要：(R)-甘油醛缩丙酮是重要的生物活性物质的重要中间体或前体,针对其易自聚和氧化反应的缺点,研究解决其储存问题具有实际意义。以D-甘露醇为原料和2,2-二甲氧基丙烷(DMP)作缩合剂,在氯化亚锡催化下得到1,2:5,6-二氧-异亚丙基-D-甘露醇,然后用NaIO_4氧化断链合成(R)-甘油醛缩丙酮粗品,不经分离直接与焦亚硫酸钠反应合成了[(4R)-2,2-二甲基-1,3-二氧环戊烷-4-基]羟基甲磺酸钠(缩写为羟基磺酸钠),并研究了羟基磺酸钠与Wittig试剂Ph_3P=C(CH_3)COOEt的反应性,当羟基磺酸钠与Ph_3P=(CH_3)COOEt摩尔比为1∶1.2,于DCM中Wittig反应产物收率为41.1%,采用FTIR、~1H NMR和^(13)C NMR表征了目标化合物的结构。（R）-glyceraldehyde acetonide is the key intermediate or precursor of the bioactive compounds. It is verypractical significance to solve the storage problem of （R）-glyceraldehyde acetonide because of its self-condensation andoxidation. Therefore, 1,2：5,6 - di- O- isopropylidene- D- mannitol was synthesized using D- mannitol as raw material,2,2-dimethoxy-propane condensation agent and stannous chloride catalyzer. The synthetic product was oxidized by NalO4to yield the .crude of R） -glyeeraldehyde aeetonide. Sodium （（4R） -2,2-dimethyl = 1,3 -dioxolan-4-yl） （hydroxyl）methanesulfonate （abbreviated as sodium hydroxysulfonate） was synthesized from the crude with sodium pyrosulfite. Thereactivity of sodium hydroxysulfonate instead of （R）-glyceraldehyde acetonide with the Wittig reagent Ph3 P = C （CH3 ）COOEt was studied. The yield of the Wittig product was 41.1% under the optimum reaction conditions as follows：n（ sodium hydroxysulformte） ： n（ Ph3P = C （CH3 ）COOEt）= 1 ： 1.2 with the solvent of DCM at 0 ℃ for overnight. Thestructure was confirmed by FTIR, 1H NMR and 13C NMR.

关 键 词：(R)-甘油醛缩丙酮 [(4R)-2 2-二甲基-1 3-二氧环戊烷-4-基]羟基甲磺酸钠 WITTIG反应 

分 类 号：O623[理学—有机化学]