CN109438151B - 一种醛和酮还原为醇的方法 - Google Patents

一种醛和酮还原为醇的方法 Download PDF

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CN109438151B
CN109438151B CN201811139808.2A CN201811139808A CN109438151B CN 109438151 B CN109438151 B CN 109438151B CN 201811139808 A CN201811139808 A CN 201811139808A CN 109438151 B CN109438151 B CN 109438151B
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孙国峰
聂万丽
田冲
鲍尔佐夫·马克西姆
徐鑫
王鹏
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Leshan Normal University
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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    • C07—ORGANIC CHEMISTRY
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
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Abstract

本发明公开了一种醛和酮还原成醇的方法，以三(五氟苯基)硼烷为催化剂，以硅氢烷为还原剂，通过在反应体系中加入水，在常温条件下即可将醛或酮还原为相应的醇。与现有技术比，本发明反应在常温常压的条件下可快速完成，反应条件温和，反应效率高，经1H NMR检测，产率为95％～100％；本发明反应所用的溶剂可以为水，成本低、污染小；本发明的催化剂及还原剂中不含有重金属，不存在重金属污染等问题。

Description

一种醛和酮还原为醇的方法
技术领域
本发明属于有机合成技术领域，具体涉及一种在有水条件下醛酮还原为醇类化合物的方法。
背景技术
醛酮羰基还原为醇的研究一直以来都是有机化学研究的重要方向之一。其还原方法主要有催化氢化、金属还原、酶还原等。
催化氢化：该方法催化剂大多是基于Ni、Pd、Pt等贵金属或有毒的过渡金属催化体系，它们作为催化剂参与羰基的还原反应时，通常需要加热、高压等条件，反应条件苛刻，对设备要求较高。
金属还原：该方法使用金属氢化物还原醛酮，如文献《硼氢化钠体系作还原剂对羰基的还原》报道用NaBH4-Cu2SO4体系时可以将醛酮还原，但是硼氢化钠还原方法大多沿用经典的合成方法，存在反应时间长、反应条件苛刻、产率低、毒性溶剂的使用等缺点。
酶还原：酶催化还原醛酮具有反应专一性和立体选择性强、反应条件温和、耗能低、副反应和副产物少等优点，如文献《酶在羰基的还原中的应用》介绍了Baker酵母不对称还原羰基化合物的反应，其不但可以还原醛酮，还可以还原硫醚、亚砜、杂环羰基化合物等。但是酶还原反应也存在较大的局限性，如酶催化反应的发生及催化效率影响因素有很多，反应不具有普遍性，且酶有易失活、成本高、产物分离困难等缺点。
最近的研究发现受限路易斯酸碱对催化体系(FLPs)可以催化氢硅烷将醛酮还原为硅醚，硅醚再水解可以得到醇类化合物。该方法不能将醛酮直接转化为醇，必须经过进一步的水解硅醚才能获得醇类化合物。
发明内容
本发明所要解决的技术问题在于提供一种在温和条件下可以高效将醛酮还原为醇的方法。
解决上述技术问题所采用的技术方案是：将醛或酮、三(五氟苯基)硼烷均匀分散于去离子水中，或将醛或酮、三(五氟苯基)硼烷均匀分散于去离子水与三氯甲烷的混合溶剂中，然后在搅拌下加入氢硅烷，常温搅拌0.5～5小时，使醛或酮还原为相应的醇。
上述制备方法中，将醛或酮、三(五氟苯基)硼烷均匀分散于去离子水与三氯甲烷的混合溶剂中时，所述醛或酮与去离子水的摩尔比为1:1～100。
上述的醛或酮与三(五氟苯基)硼烷、氢硅烷的摩尔比为1:0.01～0.2:0.5～5。
上述的氢硅烷是指至少含有一个硅氢键的硅烷类化合物，具体如氢化硅、二苯基硅烷、三苯基硅烷、苯基甲基硅烷、三乙基硅烷、二乙基甲基硅烷、二甲基硅烷等。
上述的醛为脂肪族醛或芳香族醛，具体如苯甲醛、C1～C4烷基取代的苯甲醛、C1～C4烷氧基取代的苯甲醛、卤代苯甲醛、硝基取代的苯甲醛、C1～C4烷基取代的苯乙醛、C1～C4烷氧基取代的苯乙醛、卤代苯乙醛、C1～C8的脂肪醛等。
上述的酮为脂肪族酮、环酮、芳香族酮中任意一种，具体如C3～C8的脂肪酮、C4～C8的环酮、苯乙酮、C1～C4烷基取代苯乙酮、C1～C4烷氧基取代的苯乙酮、硝基取代的苯乙酮、茚酮、1-对溴苯基-2-溴-乙酮等。
本发明以三(五氟苯基)硼烷为催化剂，以硅氢烷为还原剂，通过在反应体系中加入水，在常温条件下即可将醛或酮还原为相应的醇。与现有技术比，本发明的有益效果如下：
1、本发明反应在常温常压的条件下可快速完成，反应条件温和，反应效率高，经1HNMR检测，产率为95％～100％。
2、本发明反应所用的溶剂可以为水，成本低、污染小。
3、本发明的催化剂及还原剂中不含有重金属，不存在重金属污染等问题。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
向反应瓶中依次加入10mL去离子水、102mg(0.2mmol)三五氟苯基硼烷、212mg(2.0mmol)苯甲醛，剧烈搅拌使三五氟苯基硼烷、苯甲醛均匀分散于水中，然后在搅拌下加入216mg(2.0mmol)苯硅烷，常温搅拌2小时，苯甲醛被还原为苯甲醇。经1H NMR检测，苯甲醇的产率为100％。
本实施例的苯硅烷也可用等摩尔的氢化硅、二苯基硅烷、三苯基硅烷、苯基甲基硅烷、三乙基硅烷、二乙基甲基硅烷、二甲基硅烷替换，苯甲醇的产率可达到95％～100％。
实施例2
在实施例1中，所用的苯甲醛用等摩尔的苯乙酮替换，其他步骤与实施例1相同，苯乙酮被还原为1-苯基乙醇。经1H NMR检测，1-苯基乙醇产率为100％。
实施例3
在实施例1中，所用的苯甲醛用等摩尔的正丁醛替换，其他步骤与实施例1相同，正丁醛被还原为正丁醇。经1H NMR检测，正丁醇的产率为96％。
实施例4
在实施例1中，所用的苯甲醛用等摩尔的对甲氧基苯甲醛替换，其他步骤与实施例1相同，对甲氧基苯甲醛为对甲氧基苯甲醇。经1H NMR检测，对甲氧基苯甲醇的产率为96％。
实施例5
在实施例1中，所用的苯甲醛用等摩尔的对氯苯甲醛替换，其他步骤与实施例1相同，对氯苯甲醛被还原为对氯苯甲醇。经1H NMR检测，对氯苯甲醇的产率为95％。
实施例6
在实施例1中，所用的苯甲醛用等摩尔的对甲氧基苯乙酮替换，所用的苯硅烷用等摩尔的三乙基硅烷替换，其他步骤与实施例1相同，对甲氧基苯乙酮被还原为1-对甲氧基苯基乙醇。经1H NMR检测，1-对甲氧基苯基乙醇的产率为99％。
实施例7
在实施例1中，所用的苯甲醛用等摩尔的环己酮替换，所用的苯硅烷用等摩尔的三乙基硅烷替换，其他步骤与实施例1相同，环己酮被还原为环己醇。经1H NMR检测，环己醇的产率为100％。
实施例8
在实施例1中，所用的苯甲醛用等摩尔的对硝基苯乙酮替换，其他步骤与实施例1相同，对硝基苯乙酮被还原为1-对硝基苯基乙醇。经1H NMR检测，1-对硝基苯基乙醇的产率为99％。
实施例9
在实施例1中，所用的苯甲醛用等摩尔的间硝基苯甲醛替换，其他步骤与实施例1相同，间硝基苯甲醛被还原为间硝基苯甲醇。经1H NMR检测，间硝基苯甲醇的产率为96％。
实施例10
在实施例1中，所用的苯甲醛用等摩尔的邻甲氧基苯甲醛替换，其他步骤与实施例1相同，邻甲氧基苯甲醛被还原为邻甲氧基苯甲醇。经1H NMR检测，邻甲氧基苯甲醇的产率为97％。
实施例11
在实施例1中，所用的苯甲醛用等摩尔的1-对溴苯基-2-溴-乙酮替换，其他步骤与实施例1相同，1-对溴苯基-2-溴-乙酮被还原为1-对溴苯基-2-溴-乙醇。经1HNMR检测，1-对溴苯基-2-溴-乙醇的产率为98％。
实施例12
在实施例1中，所用的苯甲醛用等摩尔的茚酮替换，其他步骤与实施例1相同，茚酮被还原为2-茚醇。经1H NMR检测，2-茚醇的产率为100％。

Claims (5)

1.一种醛和酮还原成醇的方法，其特征在于：将醛或酮、三(五氟苯基)硼烷均匀分散于去离子水中，然后在搅拌下加入氢硅烷，常温搅拌0.5～5小时，使醛或酮还原为相应的醇；
上述的醛或酮与三(五氟苯基)硼烷、氢硅烷的摩尔比为1:0.1:1；
上述的氢硅烷为苯硅烷、氢化硅、二苯基硅烷、三苯基硅烷、苯基甲基硅烷、三乙基硅烷、二乙基甲基硅烷、二甲基硅烷中任意一种。
2.根据权利要求1所述的醛和酮还原成醇的方法，其特征在于：所述的醛为脂肪族醛或芳香族醛。
3.根据权利要求2所述的醛和酮还原成醇的方法，其特征在于：所述的醛为苯甲醛、C1～C4烷基取代的苯甲醛、C1～C4烷氧基取代的苯甲醛、卤代苯甲醛、硝基取代的苯甲醛、C1～C4烷基取代的苯乙醛、C1～C4烷氧基取代的苯乙醛、卤代苯乙醛、 C1～C8的脂肪醛中的任意一种。
4.根据权利要求1所述的醛和酮还原成醇的方法，其特征在于：所述的酮为脂肪族酮、环酮、芳香族酮中任意一种。
5.根据权利要求4所述的醛和酮还原成醇的方法，其特征在于：所述的酮为碳原子数为C3～C8的脂肪酮、C4～C8的环酮、苯乙酮、C1～C4烷基取代苯乙酮、C1～C4烷氧基取代的苯乙酮、硝基取代的苯乙酮、茚酮、1-对溴苯基-2-溴-乙酮中任意一种。
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