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CN109384643B - 一种制备山梨醇的方法 - Google Patents

一种制备山梨醇的方法 Download PDF

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CN109384643B
CN109384643B CN201710683921.6A CN201710683921A CN109384643B CN 109384643 B CN109384643 B CN 109384643B CN 201710683921 A CN201710683921 A CN 201710683921A CN 109384643 B CN109384643 B CN 109384643B
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sorbitol
transition metal
isopropanol
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CN109384643A (zh
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李峰
王荣周
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种制备山梨醇的方法，利用过渡金属催化,使用异丙醇作氢源来合成山梨醇，该反应不仅使用廉价、环保的异丙醇作氢源和溶剂，而且具有产率高、环保等优点，因此该反应具有重要的发展意义。

Description

一种制备山梨醇的方法
技术领域
本发明属有机合成化学技术领域，具体涉及一种制备山梨醇的方法。
背景技术
山梨醇是一种重要的化合物，广泛存在于自然界植物之果实中，可以用作食品调湿剂、保香剂、抗氧化剂，化妆品原料，香烟、牙膏保湿剂，胶粘剂的原料及利尿和利胆药等。例如，在聚醚生产中，山梨醇作为引发剂；在医药工业中，山梨醇主要用于生产维生索C。(a)Takeda,T.；Takeda,S.；Kakigi A.Auris Nasus Larynx.2009,36,146-151；(b)Ayorinde,F.O.；Gelain,S.V.；Johnson,J.H.Rapid.Commu.Mass.Spec,2000,14,2116-2124；(c)Katarzyna,G.；Sylwester,G.J.Bio,Mater.Res.2006,79,128-138；(a)Lee,C.H.；Takagi,H.；Okamoto,H.J.Poly.Sci.Part.a-Poly.Chem.2009,47,6025-6031.
制备山梨醇的传统方法主要有催化还原法、电解氧化法和发酵法。(a)黄阳卫,宁文生,李小年浙江化工，2001,32,51-52；(b)鲁战光,鲁玉华,杨晓燕青岛化工学院学报,2003,23,44-47；(c)朱建良，吴振兴化工时刊，2006,20,47-51.
近年来，国内外制备山梨醇采用的还原法主要是高压催化加氢，虽然这种方法有着诸多优点，但是反应过程中使用氢气，安全系数低。(a)Barbaro,P.；Liguori,F.；Moreno-Marrodan,C.Green Chem.2016,18,2935-2940；(b)Guo,X.；Wang,X.；Guan,J.；Chen,X.；Qin,Z.；Mu,X.；Xian,M.Chin.J.Catal.2014,35,733-740；(c)Perrard,A.；Gallezot,P.；Joly,J.P.；Durand,R.；Baljou,C.；Coq,B.；Trens,P.App.Catal.A:Gen.2007.331,100-104；(d)Mathew,K.M.；Ravi,S.；Padmanabhan,D.；Unny,V.K.P.；Sivaprasad,N.J.Lab.Compd.Radiopharm.2006,49,333-337.
因此，从有机合成的角度，发展一类新的有机金属催化剂，通过使用廉价、安全、无毒的异丙醇作氢源和溶剂，能够在更环境友好和温和的状态下来催化这类反应有重要的意义。
发明内容
本发明的目的在于提供一种合成山梨醇的方法。
本发明通过下述技术方案实现：制备山梨醇(式Ⅰ)的方法，
Figure BDA0001376185800000011
由葡萄糖一水合物(式Ⅱ)
Figure BDA0001376185800000012
经加氢反应生成所述目标产物。
反应是在过渡金属催化剂存在下发生，其反应通式为
Figure BDA0001376185800000021
本发明合成山梨醇的方法通过下述具体步骤实现：
在反应容器中，加入葡萄糖一水合物，过渡金属催化剂铱的络合物和溶剂异丙醇；反应混合物在油浴中加热，反应数小时后，冷却到室温，旋转蒸发除去溶剂，得到目标化合物。
进一步地，所述反应中，铱的络合物结构为：
Figure BDA0001376185800000022
进一步地，所述反应中，铱的络合物用量为葡萄糖一水合物的0.2mol％。
进一步地，所述反应中，反应时间不少于12小时。
进一步地，所述反应中，反应温度不低于120℃。
同现有技术相比，本发明用葡萄糖一水合物做原料，使用异丙醇作氢源和溶剂，在过渡金属催化剂的参与下，通过氢转移，生成山梨醇。反应展现出两个个显著的优点：1)使用廉价、安全、无毒的异丙醇；2)反应原子经济性高；所以，该反应符合绿色化学的要求，具有广阔的发展前景。
具体实施方式
展示一下实例来说明本发明的某些实施例，且不应解释为限制本发明的范围。对本发明公开的内容可以同时从材料，方法和反应条件上进行许多改进，变化和改变。所有这些改进，变化和改变均确定地落入本发明的精神和范围之内。
实施例1:山梨醇
Sorbitol
Figure BDA0001376185800000023
将葡萄糖一水合物(198mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol％)和异丙醇(5mL)依次加入到25mL克氏管中，N2保护，120℃反应12h。冷却到室温，旋转蒸发除掉溶剂，然后通过柱层析(展开剂：石油醚/乙酸乙酯)得到纯净的目标化合物，产率：92％
1H NMR(500MHz,CDCl3)δ4.54(d,J＝4.6Hz,1H),4.47-4.45(m,2H),4.38(d,J＝5.8Hz,1H),4.31(t,J＝5.6Hz,1H),4.10(d,J＝6.7Hz,1H),3.67-3.66(m,1H),3.59-3.52(m,2H),3.47-3.44(m,2H),3.39-3.33(m,3H).13C NMR(125MHz,CDCl3)δ73.8,72.3,71.5,68.9,63.5,62.6.。

Claims (5)

1.制备山梨醇Ⅰ的方法，其特征在于，
Figure FDA0003035923520000011
由葡萄糖一水合物Ⅱ在过渡金属催化剂存在下，
Figure FDA0003035923520000012
经加氢反应生成所述目标产物；
其中，过渡金属催化剂为铱的络合物，其结构为：
Figure FDA0003035923520000013
2.如权利要求1所述的方法，其特征在于，过渡金属催化剂用量为葡萄糖一水合物的0.2mol％。
3.如权利要求1所述的方法，其特征在于，反应时间不少于12小时。
4.如权利要求1所述的方法，其特征在于，反应温度不低于120℃。
5.如权利要求1所述的方法，其特征在于，所述反应在溶剂异丙醇存在下进行。
CN201710683921.6A 2017-08-11 2017-08-11 一种制备山梨醇的方法 Expired - Fee Related CN109384643B (zh)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104203892A (zh) * 2012-02-23 2014-12-10 关东化学株式会社 脱氢用催化剂、使用该催化剂的羰基化合物及氢的制造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104203892A (zh) * 2012-02-23 2014-12-10 关东化学株式会社 脱氢用催化剂、使用该催化剂的羰基化合物及氢的制造方法

Non-Patent Citations (3)

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Title
Catalytic hydrogenation of fine chemicals: sorbitol production;K.van Gorp 等;《Catalysis Today》;19991117;第52卷;第357页 Table 8 *
Cooperative Catalysis by Iridium Complexes with a Bipyridonate Ligand: Versatile Dehydrogenative Oxidation of Alcohols and Reversible Dehydrogenation–Hydrogenation between 2-Propanol and Acetone;Ryoko Kawahara 等;《Angew.Chem.Int.Ed.》;20121107;第51卷;第12794-12790页 *
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