CN107488183B - 一种1,4-失水山梨醇的制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明公开了一种1,4‑失水山梨醇的制备方法。该方法以山梨醇为底物，以强极性分子为溶剂，在酸式盐催化剂的作用下，高选择性的得到1,4‑失水山梨醇。该方法选用特殊溶剂与酸式盐类的组合，使得山梨醇脱水过程中的1,4‑失水山梨醇的选择性较高。
Description
技术领域
本发明涉及化学化工领域，具体地说是一种1,4-失水山梨醇的制备方法。
背景技术
1,4-失水山梨醇是山梨醇脱一分子水的产物，其在工业中用途广泛，它的脂肪酸酯类衍生物是优良的环境友好表面活性剂以及无毒的食品添加剂，1,4-失水山梨醇同时是Span和Tween类表面活性剂的原料。
近年来，随着石油资源的枯竭，生物质基资源越来越受到重视，1,4-失水山梨醇因其下游产品的优异性能而备受关注。1,4-失水山梨醇通常由山梨醇在无机酸催化作用下脱水得到。但是目前的方法很难得到高纯度的1,4-失水山梨醇。原因主要有两个方面，一是山梨醇有多个羟基，这使得它具有多种脱一分子水产物，即多种一脱水失水山梨醇。二是1,4-失水山梨醇在无机酸的存在下可以进一步脱水生成异山梨醇。而且传统路线的酸催化剂对设备产生腐蚀，并且需要在反应后用碱液中和酸催化剂；反应中碳化现象严重，副反应多，产品收率低。由于酸催化剂的诸多缺点，发展新的1,4-失水山梨醇的制备方法成为了一个重要的课题。文献(Catal.Sci.Technol.,2013,3,1540--1546)中提到，可以利用SnCl4和AlCl3作为催化剂来催化山梨醇脱水得到1,4-失水山梨醇和3,6-失水山梨醇，但是其并没有具体的指出1,4-失水山梨醇的比例。专利201410294984发展了一种利用甲酸替代无机酸催化剂的方法，但是该方法需要额外的贵金属Pd的参与，增加了催化剂的成本。因此，发展高效的1,4-失水山梨醇制备方法依旧是一个重要的课题。
硫酸氢钠等酸式盐呈现弱酸性，较低的酸性使其不容易继续催化1,4-失水山梨醇继续脱水得到异山梨醇，但较低的酸性使其催化山梨醇脱水的活性也较低，因此选用特殊的溶剂与其配合，使其能够高效的催化山梨醇脱水制备1,4-失水山梨醇。
发明内容
一种1,4-失水山梨醇的制备方法，该方法利用了强极性分子为溶剂，强极性分子作为溶剂可以促进酸式盐的解离，在一定程度上增强酸式盐的酸性，使其能够催化山梨醇脱水，而其酸性即使经过溶剂的促进解离，其酸性依旧很弱，不容易继续催化1,4-失水山梨醇继续脱水得到异山梨醇，因而能够较高选择性的得到1,4-失水山梨醇。
本发明的技术方案为：
本方法以山梨醇为底物，以强极性分子为溶剂，在酸式催化剂的作用下得到1,4-失水山梨醇。
所述酸式催化剂为硫酸氢钠，磷酸一氢钠，磷酸二氢钠，硫氢酸钠，硫酸氢钾，磷酸一氢钾，磷酸二氢钾，硫氢酸钾，硫酸氢铵，磷酸一氢铵，磷酸二氢铵，硫氢酸铵，硫酸氢钙，磷酸一氢钙，磷酸二氢钙或硫氢酸钙中的一种或者两种以上。
所述强极性溶剂为水、甲醇、乙醇、异丙醇、丙酮，四氢呋喃，甲基异丁基甲酮中的一种或两种以上。
催化剂的加入量为山梨醇质量的0.1-10％，溶剂的质量为山梨醇质量0.1-20倍。
催化剂的加入量优选为山梨醇质量的5％，溶剂的质量优选为山梨醇质量的5倍
反应温度为60至220℃，反应时间为0.5-10h。
反应温度优选为120℃,反应时间优选为1h。
具体的操作步骤为：向反应釜中加入溶剂，加热到范围40-60℃，将底物山梨醇在剧烈搅拌的条件下，滴加到溶剂当中去，搅拌均匀以后，加入酸式盐催化剂，升温至60～220℃，反应0.5-10h得到产物1,4-失水山梨醇。
本发明的优点：
相比于无机酸催化的方法，该方法能够高效率的得到1,4-失水山梨醇，反应过程中对设备的腐蚀较轻，反应后无需碱中和的步骤，后处理简单。
附图说明
图1为实施例1所得产品的HPLC谱图。
具体实施方式
下面结合实施例对本发明提供的方法进行详述，但不以任何形式限制本发明。
实施例1
向反应釜中加入水30g，加热到40℃，将3g山梨醇在剧烈搅拌的条件下，滴加到水当中去，搅拌均匀以后，加入0.3g硫酸氢钠催化剂，升温至140℃，反应4h，通过液相色谱，利用外标法对产物进行检验，山梨醇的转化率达到90％，产物1,4-失水山梨醇选择性达到81％。
实施例2～5
重复实施例1的反应过程，不同的是反应条件与所使用的溶剂、催化剂不同。各实施例的具体反应条件和结果列于表1中。
表1、实施例2～5具体反应条件
实施例6
向反应釜中加入甲基异丁基甲酮50g，加热至60℃，剧烈搅拌，加入催化剂NaH2PO40.2g，搅拌均匀后，将3.5g山梨醇在剧烈搅拌的条件下，滴加到溶剂当中去。升温至160℃，反应6h，通过液相色谱，利用外标法对产物进行检验，山梨醇转化率为95％，产物1,4-失水山梨醇选择性达到85％。
实施例7～10
重复实施例7的反应过程，不同的是使用的底物不同。各实施例的具体底物列于表2中。
表2、实施例7～10具体反应条件
Claims (2)
1.一种1,4-失水山梨醇的制备方法，其特征在于：以山梨醇为底物，以强极性分子为溶剂，在酸式盐催化剂的作用下得到1,4-失水山梨醇；
具体为：向反应釜中加入溶剂，加热到40-60 ℃，将底物山梨醇在剧烈搅拌的条件下，滴加到溶剂当中去，搅拌均匀以后，加入酸式盐催化剂，升温至60~160℃，反应0.5-10 h得到产物1,4-失水山梨醇；
所述酸式盐催化剂为硫酸氢钾，硫酸氢铵，磷酸一氢铵，硫氢酸铵，硫酸氢钙，磷酸一氢钙中的一种；
所述强极性溶剂为甲醇、乙醇、异丙醇、四氢呋喃或甲基异丁基甲酮中的一种；
催化剂的加入量为山梨醇质量的5-10 %，溶剂的质量为山梨醇质量5-20倍。
2.按照权利要求1所述的制备方法，其特征在于：所述升温的反应温度为120℃, 反应时间为1 h。
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| CN101045062A (zh) * | 2007-02-04 | 2007-10-03 | 杨喜鸿 | 多烯磷脂酰胆碱的肠溶制剂及其制备方法和药物应用 |
| CN101948451A (zh) * | 2010-08-18 | 2011-01-19 | 南京威尔化工有限公司 | 高纯度1,4-失水山梨醇的制备方法 |
| CN101967132A (zh) * | 2010-09-02 | 2011-02-09 | 江西铜业股份有限公司 | 一种乳化剂生产工艺 |
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| CN101045062A (zh) * | 2007-02-04 | 2007-10-03 | 杨喜鸿 | 多烯磷脂酰胆碱的肠溶制剂及其制备方法和药物应用 |
| CN101948451A (zh) * | 2010-08-18 | 2011-01-19 | 南京威尔化工有限公司 | 高纯度1,4-失水山梨醇的制备方法 |
| CN101967132A (zh) * | 2010-09-02 | 2011-02-09 | 江西铜业股份有限公司 | 一种乳化剂生产工艺 |
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