光学活性香料化合物3-甲硫基己醇及其乙酸酯的制备
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国家自然科学基金资助项目(20676003);北京市属高等学校人才强教计划资助项目(PHR201008244)。


Preparation of Optically Active Flavors 3-Methylthio Hexanol and Its Acetate
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    摘要:

    本文研究了以(E)-2-己烯醛为起始原料,通过还原、Sharpless不对称环氧化、区域选择性还原、SN2亲核取代等反应制备光学活性的3-甲硫基己醇和3-甲硫基己基乙酸酯的方法。首先(E)-2-己烯醛通过NaBH4还原得到(E)-2-己烯醇,产率91%左右。(E)-2-己烯醇通过Sharpless不对称环氧化,得到光学活性2, 3-环氧己醇,化学产率86%左右,产物e.e.值94%左右。2, 3-环氧己醇用Red-Al进行区域选择性还原得到光学活性的1, 3-己二醇,产率82%左右。将1, 3-己二醇的伯羟基选择性转化为乙酸酯,3位羟基转化为甲磺酸酯,然后与自制的甲硫醇钠反应,经过SN2亲核取代反应后得到3-甲硫基己醇,三步反应总产率59%左右。3-甲硫基己醇用乙酸酐酯化得到3-甲硫基己基乙酸酯,产率87%左右。最终产物3-甲硫基己醇和3-甲硫基己基乙酸酯e.e.值均在94.0 %左右。

    Abstract:

    The syntheses of optically active 3-methylthio hexanol and 3-methylthio hexyl actetate were studied starting from (E)-2-hexenal through reduction, the Sharpless asymmetric epoxidation, regioselective reduction and SN2 nucleophilic substitution. (E)-2-hexenal was reduced by NaBH4 to give (E)-2-hexenol in about 91% yield. The optically active 2, 3-epoxy hexanol was obtained through the Sharpless asymmetric epoxidation of (E)-2-hexenol with about 94% e.e. in about 86% yield. 2, 3-Epoxy hexanol was regioselectively reduced with Red-Al to give optically active 1, 3-hexanediol in about 82% yield. After the primary hydroxy group of 1, 3-hexanediol was transformed to acetate and 3-hydroxy was transformed to mesylate, an SN2 nucleophilic substitution by the reaction with self-made sodium thiomethoxide was carried out to form 3-methylthio hexanol. The overall yield of these three steps was about 59%. 3-Methylthio hexanol was esterified with acetic anhydride to give 3-methylthio hexyl acetate in about 87% yield. The final products 3-methylthio hexanol and 3-methylthio hexyl actate were obtained with about 94% e.e..

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余洁菲,田红玉,孙宝国,欧阳天惠.光学活性香料化合物3-甲硫基己醇及其乙酸酯的制备[J].精细化工,2010,27(4):

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  • 收稿日期:2009-12-14
  • 最后修改日期:2010-01-06
  • 录用日期:2010-01-20
  • 在线发布日期: 2010-01-26
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