CN109942402B - 二异丁烯的经Pd催化的羟基羰基化方法：溶剂的影响 - Google Patents

二异丁烯的经Pd催化的羟基羰基化方法：溶剂的影响 Download PDF

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CN109942402B
CN109942402B CN201811562680.0A CN201811562680A CN109942402B CN 109942402 B CN109942402 B CN 109942402B CN 201811562680 A CN201811562680 A CN 201811562680A CN 109942402 B CN109942402 B CN 109942402B
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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

本发明涉及二异丁烯的经Pd催化的羟基羰基化方法：溶剂的影响。

Description

二异丁烯的经Pd催化的羟基羰基化方法：溶剂的影响
技术领域
本发明涉及二异丁烯的经Pd催化的羟基羰基化方法：溶剂的影响。
背景技术
包括丙酸、己二酸和脂肪酸的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。
烯烃的加氢羧化是用于获得羧酸的非常有前途和环境友好的方法。通过甲醇的羰基化制备乙酸，其用碘化物进行。在Koch反应中，通过强碱催化而使水和一氧化碳加成到烯烃上。该方法对于形成二级和三级碳阳离子的烯烃，例如异丁烯产生特戊酸而言是有效的。通过同时将CO和H2O加成到烯烃/炔烃上而发生的加氢羧化提供了合成羧酸的直接且方便的方法。
发明内容
本发明的目的是提供在二异丁烯（DIBN）的经Pd催化的羟基羰基化中提供良好转化的方法。该反应应在一个步骤中进行。
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) 添加二异丁烯；
b) 添加含Pd的化合物，其中Pd能够形成络合物，
c) 添加配体L1：
Figure 140682DEST_PATH_IMAGE001
d) 添加乙酸，
e) 进料CO，
f) 将反应混合物加热以使得二异丁烯转化为化合物P1：
Figure 588981DEST_PATH_IMAGE002
。
在该方法的一个变体中，方法步骤b)中的化合物选自：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)中的化合物是Pd(acac)2。
在该方法的一个变体中，所述方法包括额外的反应步骤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f)中加热到80°C至160°C的温度，优选100°C至140°C的温度。
在该方法的一个变体中，在方法步骤e)中进料CO以使得所述反应在20 bar至60bar，优选30 bar至50 bar的CO压力下进行。
具体实施方式
下面通过实施例更详细地阐述本发明。
Figure 775243DEST_PATH_IMAGE003
向4ml小瓶中装入[Pd(acac)2]（3.05mg，0.25mol％）、L1（20.64mg，1.0mol％）、PTSA*H2O（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，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（100 µl）作为内标。通过GC分析测量转化率。
重复上述实验，其中改变溶剂。保持所有其它参数。
结果汇编在下表中。
条目 溶剂 转化率(%)
1 3,5,5-三甲基己酸 88
2 甲酸 48
3* 乙酸 >99
* 本发明的方法。
如实验结果所示，该目的通过本发明的方法实现。

Claims (5)

1.包括下列方法步骤的方法：
a) 添加二异丁烯；
b) 添加含Pd的化合物，其中Pd能够形成配合物，
c) 添加配体L1：
Figure DEST_PATH_IMAGE001
d) 添加乙酸，
e) 进料CO，
f) 将反应混合物加热以使得二异丁烯转化为化合物P1：
Figure DEST_PATH_IMAGE002
。
2.根据权利要求1的方法，
其中方法步骤b)中的化合物选自：
PdCl2、PdBr2、Pd(acac)2、Pd(dba)2 (dba = 二亚苄叉丙酮)、PdCl2(CH3CN)2。
3.根据权利要求1或2的方法，
其中所述方法包括额外的反应步骤g)：
g) 添加对甲苯磺酸。
4.根据权利要求1或2的方法，
其中在方法步骤f)中将反应混合物加热至80°C至160°C的温度。
5.根据权利要求1或2的方法，
其中在方法步骤e)中进料CO，以使得所述反应在20巴至60巴的CO压力下进行。
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