CN111217670A - 一种催化还原羰基化合物为亚甲基的方法 - Google Patents

一种催化还原羰基化合物为亚甲基的方法 Download PDF

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CN111217670A
CN111217670A CN201811411995.5A CN201811411995A CN111217670A CN 111217670 A CN111217670 A CN 111217670A CN 201811411995 A CN201811411995 A CN 201811411995A CN 111217670 A CN111217670 A CN 111217670A
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王文涛
王晓东
张万生
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Abstract

本发明公开了一种温和条件下催化还原羰基化合物为亚甲基的方法，包括以下步骤：将羰基化合物、氯化钯和水加入反应器中，其中羰基化合物和氯化钯催化剂的摩尔比例为100‑10000:1，通入1‑5MPa氢气，在室温至100℃下搅拌反应1‑6h，即可催化加氢还原羰基化合物为相应亚甲基，该方法操作简单、条件温和、催化剂用量极低、水作溶剂、绿色环保、具有工业化应用前景。

Description

一种催化还原羰基化合物为亚甲基的方法
技术领域
本发明涉及一种温和条件催化还原羰基化合物为亚甲基的方法，属于精细有机化工技术领域。
背景技术
还原反应在有机化工领域中是一类重要的反应，能够实现羰基制备亚甲基、烯烃制备饱和烃、硝基合成胺等官能团的转化。很多还原反应是通过直接加氢来实现，利用供氢剂如四氢铝锂、硼氢化钠或氢气催化底物氢化还原实现。上述有一类还原反应比较特殊，羰基还原为亚甲基，不但有加氢而且还有脱氧行为。最开始的研究中需要使用高活性试剂、高温高压才能实现，且收率不高，是一类比较难的还原反应。随着克莱门森反应和黄鸣龙反应的不断发展，为羰基还原为亚甲基提供了更多选择途径，在有机化工合成中有着重要的意义。但这两种方法采用化学计量还原剂(Zn-Hg+HCl、肼+KOH)，成本高、污染重、反应条件苛刻。
近年来，有报道以含有Cu-Cr、Fe或Ni催化剂来催化羰基化合物加氢脱氧还原亚甲基，然而这些催化剂活性较低，需要较高反应温度(200-400℃)。钯作为一种重要的催化加氢催化剂，其碳基还原成亚甲基的性能有所报道，如最近Adolfsson小组利用Pd/C催化剂，Maleczka课题组使用Pd(OAc)2，聚甲基氢硅烷为氢源，室温条件下分别实现催化还原羰基化合物为亚甲基反应。然而，这种方法使用硅烷作为氢源，价格昂贵，反应过程中生成大量硅醇副产物，分离较为困难(Org.Lett.2011,13,584-587；Angew.Chem.Int.Ed.2015,54,5122-5126)。杭州师范大学的Xu课题组使用PdCl2作为催化剂，聚甲基氢硅烷为氢源，同样实现了芳香醇和酮还原为亚甲基的反应，然而，催化剂用量高达10mol％(Adv.Synth.Catal.2013,355,341-347)，大量的副产物聚甲基硅醇生成，产物分离困难。
发明内容
为解决上述现有技术存在的问题，本发明提供了一种温和条件下钯催化还原羰基化合物为亚甲基的方法，该方法操作简单、反应条件温和、催化剂用量极低、水作溶剂、绿色环保、具有工业化应用前景。
为了实现目的，本发明采用以下技术方案：将羰基化合物、PdCl2和溶剂加入到反应器中，其中羰基化合物与催化剂PdCl2的摩尔比为100-10000:1，通入1-5MPa氢气，在室温至100℃条件下，搅拌反应1-6h，即可催化加氢还原羰基化合物为亚甲基。反应方程式如下：
Figure BDA0001878744630000021
羰基化合物通式中，R1为氢、C1-C5烷基或芳基，R2为氢、C1-C5烷基、或芳基，且R1和R2不同时为氢。
所述的芳基为苯基、含取代的苯基、萘基、含取代的萘基、吡啶基；苯基或萘基的取代基为甲基、乙基、丙基、羟基、氟、氯、溴、甲氧基、乙氧基中的一种或二种以上。
所述溶剂为水、甲醇、乙醇、四氢呋喃中的一种或二种以上，优选为水。
所述的催化剂为RhCl3、RuCl3、PdCl2、CoCl2、FeCl3中的一种，优选为PdCl2；催化剂用量为1mol％-0.01mol％，优选为0.5mol％-0.1mol％。
反应温度为室温-100℃，优选为80℃；反应时间为1-6h，优选为2h。
所述的还原剂为氢气，压力为1-5MPa，优选为2MPa。
本发明与现有技术相比，具有以下优点和效果：
1、该方法条件温和，氢气为氢源，无污染无残留，分离方便；
2、该方法以水为溶剂，绿色环保，反应产物易分离；
3、催化剂用量低(0.01mol％-1mol％)，目标产物收率高。
附图说明
图1化合物2a的气相色谱图；
图2化合物2a的质谱图。
具体实施方式
下面结合具体的实施例对本发明所述的制备方法做进一步说明，但是本发明的保护范围并不限于此。所使用的原料、试剂、溶剂等，如无特殊说明，均为市售常规药品。
实施例一：催化羰基化合物加氢脱氧制备亚甲基化合物条件优化
在反应器中加入0.1mol％-0.01mol％金属催化剂，碳基化合物底物1a(2mmol)，溶剂(6.0mL)，氮气置换后，充入1-5MPa氢气，室温-100℃搅拌反应1-6h，停止反应，产物2a经GC-MS分析测定，条件优化结果见表1。
表2反应条件优化
Figure BDA0001878744630000022
Figure BDA0001878744630000023
Figure BDA0001878744630000031
。
实施例二：温和条件钯催化还原羰基化合物为亚甲基底物扩展
在反应器中加入0.1mol％-0.01mol％PdCl2催化剂，碳基化合物底物1(2mmol)，水(6.0mL)，氮气置换后，充入2MPa氢气，80℃搅拌反应1-6h，停止反应，产物2结构经GC-MS分析测定，收率为产物分离收率，结果见表2。
表2反应底物拓展
Figure BDA0001878744630000032
Figure BDA0001878744630000033
Figure BDA0001878744630000041
Figure BDA0001878744630000051
Figure BDA0001878744630000061
。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上，还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (7)

1.一种催化还原羰基化合物为亚甲基的方法，其特征在于：以羰基化合物为原料，氢气为氢源，氯化钯为催化剂，其用量为原料的1mol％-0.01mol％，室温至100℃条件下，在溶剂中搅拌反应1-6h，即可加氢脱氧获得相应亚甲基化合物。
2.根据权利要求1所述的方法，其特征在于：
其反应方程式如下：
Figure FDA0001878744620000011
羰基化合物通式中，R1为氢、C1-C5烷基或芳基，R2为氢、C1-C5烷基、或芳基，且R1和R2不同时为氢。
3.根据权利要求2所述的方法，其特征在于：所述的芳基为苯基、含取代的苯基、萘基、含取代的萘基、吡啶基；苯基或萘基的取代基为甲基、乙基、丙基、羟基、氟、氯、溴、甲氧基、乙氧基中的一种或二种以上。
4.根据权利要求1或2所述的方法，其特征在于：所述溶剂为水、甲醇、乙醇、四氢呋喃中的一种或二种以上，优选为水。
5.根据权利要求1所述的方法，其特征在于：所述催化剂为RhCl3、RuCl3、PdCl2、CoCl2、FeCl3中的一种或二种以上，优选为PdCl2；催化剂用量为1mol％-0.01mol％，优选为0.5mol％-0.1mol％。
6.根据权利要求1所述的方法，其特征在于：所述反应温度为室温至100℃，优选为80℃；反应时间为1-6h，优选为2h。
7.根据权利要求1所述的方法，其特征在于：所述还原剂为氢气，压力为1-5MPa，优选为2MPa。
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