CN109942401B - 将烯烃直接转化为羧酸的方法 - Google Patents

将烯烃直接转化为羧酸的方法 Download PDF

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CN109942401B
CN109942401B CN201811562676.4A CN201811562676A CN109942401B CN 109942401 B CN109942401 B CN 109942401B CN 201811562676 A CN201811562676 A CN 201811562676A CN 109942401 B CN109942401 B CN 109942401B
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桑睿
P.库米尔齐克
董开武
R.雅克斯特尔
M.贝勒
R.弗兰克
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Abstract

本发明涉及将烯烃直接转化为羧酸的方法。本发明的目的是提供可用于将烯烃直接转化为羧酸的方法。所述方法包括下列方法步骤：a)添加烯烃；b)添加包含根据结构(1)的化合物的络合物以及Pd，或根据结构(1)的化合物和含Pd的物质；c)进料CO；d)将反应混合物加热以使得烯烃转化为羧酸，其中所述烯烃直接转化为羧酸。所述方法用于将烯烃直接转化为羧酸。

Description

将烯烃直接转化为羧酸的方法
技术领域
本发明涉及将烯烃直接转化为羧酸的方法。
背景技术
羧酸用于制备聚合物、药物、溶剂和食品添加剂。产生羧酸的路线通常包括烃、醇或醛的氧化、通过臭氧分解的烯烃的氧化裂解、甘油三酯、腈、酯或酰胺的水解、格氏或有机锂试剂的羧化，以及在卤仿反应中甲基酮的卤化和随后水解。
本发明的目的是提供可用于将烯烃直接转化为羧酸的方法。
在本申请的上下文中，“直接转化”旨在表示反应在一个步骤中进行，即没有中间产物的分离或后处理等。
这不排除在反应过程中暂时形成直接进一步转化的中间体。
发明内容
该目的通过根据权利要求1的方法实现。
包括下列方法步骤的方法：
a) 添加烯烃；
b) 添加包含根据结构(1)的化合物的络合物以及Pd，
或根据结构(1)的化合物和含Pd的物质
Figure 100002_DEST_PATH_IMAGE001
c) 进料CO；
d) 将反应混合物加热以使得烯烃转化为羧酸，
其中该烯烃直接转化为羧酸。
在该方法的一个变体中，方法步骤b)中的物质选自：
PdCl2、PdBr2、Pd(acac)2、Pd(dba)2 (dba = 二亚苄叉丙酮)、PdCl2(CH3CN)2。
在该方法的一个变体中，方法步骤b)中的物质是Pd(acac)2。
在该方法的一个变体中，该方法包括额外的方法步骤e)：
e) 添加乙酸。
在该方法的一个变体中，该方法包括额外的方法步骤f)：
f) 添加水。
在该方法的一个变体中，该方法包括额外的方法步骤g)：
g) 添加对甲苯磺酸（PTSA）。
在该方法的一个变体中，将反应混合物在方法步骤d)中加热到80°C至160°C的温度。
在该方法的一个优选变体中，将反应混合物在方法步骤d)中加热到100°C至140°C的温度。
在该方法的一个变体中，在方法步骤c)中进料CO以使得所述反应在20 bar至60bar的CO压力下进行。
在该方法的一个优选变体中，在方法步骤c)中进料CO以使得所述反应在30 bar至50 bar的CO压力下进行。
具体实施方式
下面参考实施例更详细地阐述本发明。
配体的改变
Figure 348873DEST_PATH_IMAGE002
向4ml小瓶中装入[Pd(acac)2]（3.05mg，0.25mol％）、配体(X)（1.0mol％）、对甲苯磺酸（28.5mg，3.75mol％）和经烘箱干燥的搅拌棒。然后用隔膜（经PTFE涂覆的苯乙烯-丁二烯橡胶）和酚树脂盖密封小瓶。将小瓶抽真空并用氩气再填充三次。用注射器将H2O（0.5ml）、乙酸（1.5ml）和二异丁烯（DIBN）（4.0mmol）加入到小瓶中。将小瓶置于合金板中，将其转移至氩气气氛下的来自Parr Instruments的4560系列的高压釜（300ml）中。 用CO吹扫高压釜三次后，将CO的压力增加到室温下40 bar。反应在120℃下进行20小时。在反应结束后，将高压釜冷却至室温并小心地减压。然后加入异辛烷（100μl）作为内标。通过GC分析测量转化率。
重复上述实验，其中改变配体(X)，其中X = 1至8。
结果汇编在下表1中：
表1：
配体 收率(%)
(1)* > 99
(2) 7
(3) 39
(4) 26
(5) 16
(6) 8
(7) 13
(8) 29
*本发明的方法。
改变烯烃
Figure DEST_PATH_IMAGE003
向4ml小瓶中装入[Pd(acac)2]（3.07mg，0.25mol％）、配体(1)（20.64mg，1.0mol％）、对甲苯磺酸（28.5 mg，3.75 mol％）和经烘箱干燥的搅拌棒。然后用隔膜（经PTFE涂覆的苯乙烯-丁二烯橡胶）和酚树脂盖密封小瓶。然后用针将小瓶连接到大气。将小瓶抽真空并用氩气再填充三次。用注射器将H2O（0.5ml）、乙酸（1.5ml）和烯烃（4.0mmol）加入到小瓶中。将小瓶置于合金板中，将其转移至氩气气氛下的来自Parr Instruments的4560系列的高压釜（300ml）中。用CO洗脱高压釜三次后，CO的压力增加到室温下40 bar。反应在120℃下进行20小时。在反应结束后，将高压釜冷却至室温并小心地减压。然后加入异辛烷（100μl）作为内标。通过GC分析测量转化率。
重复上述实验，其中改变烯烃。
结果汇编在下表2中：
表2：
Figure 100929DEST_PATH_IMAGE004
如实验结果所示，该目的通过根据本发明的方法实现。

Claims (7)

1.将烯烃直接转化为羧酸的方法，其包括下列方法步骤：
a) 添加烯烃；
b) 添加包含根据结构(1)的化合物的络合物以及Pd，
或根据结构(1)的化合物和含Pd的物质
Figure DEST_PATH_IMAGE001
c) 进料CO；
d) 将反应混合物加热以使得烯烃转化为羧酸，
其中所述烯烃直接转化为羧酸。
2.根据权利要求1的方法，
其中方法步骤b)中的物质选自：
PdCl2、PdBr2、Pd(acac)2、Pd(dba)2、PdCl2(CH3CN)2，其中dba表示二亚苄叉丙酮。
3.根据权利要求1或2任一项的方法，
其中该方法包括额外的方法步骤e)：
e) 添加乙酸。
4.根据权利要求1至2任一项的方法，
其中该方法包括额外的方法步骤f)：
f) 添加水。
5.根据权利要求1至2任一项的方法，
其中该方法包括额外的方法步骤g)：
g) 添加对甲苯磺酸。
6.根据权利要求1至2任一项的方法，
其中将反应混合物在方法步骤d)中加热到80°C至160°C的温度。
7.根据权利要求1至2任一项的方法，
其中在方法步骤c)中进料CO以使得所述反应在20 bar至60 bar的CO压力下进行。
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