CN109942405B - 二异丁烯的经Pd催化的羟基羰基化方法：配体/Pd比率 - Google Patents

二异丁烯的经Pd催化的羟基羰基化方法：配体/Pd比率 Download PDF

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CN109942405B
CN109942405B CN201811592718.9A CN201811592718A CN109942405B CN 109942405 B CN109942405 B CN 109942405B CN 201811592718 A CN201811592718 A CN 201811592718A CN 109942405 B CN109942405 B CN 109942405B
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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：配体/Pd比率。

Description

二异丁烯的经Pd催化的羟基羰基化方法：配体/Pd比率
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：配体/Pd比率。
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 100002_DEST_PATH_IMAGE001
其中配体L1的加入量为每摩尔Pd 1.0mol至2.0mol配体，
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 791403DEST_PATH_IMAGE002
(P1)。
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，配体L1的加入量为每摩尔Pd 1.25mol至1.75mol配体。
在该方法的一个变体中，在方法步骤f)中将反应混合物加热至80℃至160℃的温度，优选100℃至140℃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10 bar至40bar，优选10 bar至30 bar的CO压力下进行。
在该方法的一个变体中，该方法包括额外的方法步骤g)：
g) 添加硫酸。
具体实施方式
下面参考实施例更详细地阐述本发明。
Figure 589594DEST_PATH_IMAGE003
向4ml小瓶中装入[Pd(acac)2]（1.75mg，0.25mol％）、L1（4.44mg，0.375mol）、H2SO4（3.1mg，1.4mol％）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（0.29ml）、乙酸（0.85ml）和二异丁烯（DIBN）（2.3mmol）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。在用CO吹扫高压釜三次后，CO压力增加至室温下15 bar，随后用N2增加至25 bar的压力。反应在120℃下进行3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L1/Pd比率。保持所有其它参数。
结果汇编在下表中。
条目 L1/Pd (mmol/mmol) – L1 (x mol%) 转化率(%)
1* 1.5/1 – 0.375 92
2* 2/1 – 0.5 83
3 3/1 – 0.75 74
4 4/1 – 1.0 69
* 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 (6)

1.制备如下式化合物P1的方法，其包括下列方法步骤：
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 DEST_PATH_IMAGE001
其中配体L1的加入量为每摩尔Pd 1.0mol至2.0mol配体，
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
(P1)。
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、PdCl2(CH3CN)2，其中dba表示二亚苄叉丙酮。
3.根据权利要求1至2任一项的方法，
其中配体L1的加入量为每摩尔Pd 1.25mol至1.75mol配体。
4.根据权利要求1至2任一项的方法，
其中在方法步骤f)中将反应混合物加热至80℃至160℃的温度。
5.根据权利要求1至2任一项的方法，
其中在方法步骤e)中进料CO，以使得所述反应在10 bar至40 bar的CO压力下进行。
6.根据权利要求1至2任一项的方法，
其中所述方法包括额外的方法步骤g)：
g) 添加硫酸。
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