CN109942398A - 用于二异丁烯的Pd-催化的羟基羰基化的方法：乙酸/二异丁烯比例 - Google Patents

用于二异丁烯的Pd-催化的羟基羰基化的方法：乙酸/二异丁烯比例 Download PDF

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CN109942398A
CN109942398A CN201811562138.5A CN201811562138A CN109942398A CN 109942398 A CN109942398 A CN 109942398A CN 201811562138 A CN201811562138 A CN 201811562138A CN 109942398 A CN109942398 A CN 109942398A
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diisobutylene
acetic acid
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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

本发明涉及用于二异丁烯的Pd‑催化的羟基羰基化的方法：乙酸/二异丁烯比。

Description

用于二异丁烯的Pd-催化的羟基羰基化的方法：乙酸/二异丁 烯比例
技术领域
本发明涉及用于二异丁烯的Pd-催化的羟基羰基化的方法：乙酸/二异丁烯比例。
背景技术
羧酸，包括丙酸、己二酸和脂肪酸，在制备聚合物、药物、溶剂和食品添加剂中使用。烃、醇或醛的氧化，烯烃通过臭氧解的氧化裂解，甘油三酯、腈、酯或酰胺的水解，格氏试剂或有机锂试剂的羧化和甲基酮在卤仿反应中的卤化和随后的水解通常属于产生羧酸的途径。
烯烃的加氢羧化是一种非常有前途和环境友好的获得羧酸的方法。通过甲醇的羰基化制备乙酸，其用碘化物进行。在Koch反应中，通过强碱催化水和一氧化碳在烯烃上的加成。该方法对于形成仲和叔碳阳离子的烯烃效果良好，例如，异丁烯生成新戊酸。同时进行CO和H2O 在烯烃/炔烃上的加成的加氢羧化提供了一种用于合成羧酸的直接且方便的方法。
发明内容
本发明的目的在于，提供一种在二异丁烯（DIBN）的Pd催化的羟基羰基化中提供好的转化率的方法。在此，该反应应在一个步骤中进行。
所述目的通过根据权利要求1的方法得以实现。
包括以下方法步骤的方法：
a) 加入二异丁烯，
b) 加入包含Pd的化合物，其中所述Pd能够形成配合物，
c) 加入配体L1：
d) 加入乙酸，
其中以每mol二异丁烯5mol-8mol乙酸的量加入乙酸，
e) 供入CO，
f) 加热反应混合物，以使二异丁烯转化为化合物P1：
(P1)。
在该方法的一个变体中，方法步骤b）中的所述化合物选自：PdCl2、PdBr2、Pd(acac)2、Pd(dba)2 (dba =二亚苄基丙酮)、PdCl2(CH3CN)2。
在该方法的一个变体中，方法步骤b）中的所述化合物是Pd(acac)2。
在该方法的一个变体中，以每mol二异丁烯6mol-7mol乙酸的量加入乙酸。
在该方法的一个变体中，在工艺步骤f）中将反应混合物加热至80℃-160℃的温度。
优选至100℃-140℃的温度。
在该方法的一个变体中，在工艺步骤e）中如此供入CO，使得该反应在10巴-40巴的CO压力下进行。
优选10巴-30巴。
在该方法的一个变体中，其包括另外的方法步骤g）：
g) 加入硫酸。
具体实施方式
下面借助于工作实施例更详细地解释本发明。
向4ml小瓶中加入[Pd(acac)2] (1.94 mg, 0.25 mol%)、L1 (4.92 mg, 0.375mol%)、H2SO4 (1.3 mg, 0.52 mol%)和在烘箱中干燥的搅拌棒。然后用隔膜（涂覆PTFE的苯乙烯-丁二烯橡胶）和酚醛树脂盖密封小瓶。将小瓶三次抽真空并再填充以氩气。用注射器将H2O (0.23 ml)、乙酸(0.87 ml)和二异丁烯 (DIBN) (2.5 mmol)加入到小瓶中。将小瓶置于合金板中，在氩气氛下将其转移至Parr Instruments的4560系列高压釜（300ml）中。在用CO三次吹扫高压釜后，在室温下将CO压力升高至15巴，并且随后用N2升高至25巴的压力。该反应在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（100μl）作为内标。通过GC分析测量转化率。
改变CH3COOH/DIBN比率，重复上述实验。保持所有其他参数。
结果汇总在下表中。
进料 CH<sub>3</sub>COOH/DIBN (mmol/mmol) 转化率 (%)
1 4/1 75
2* 5/1 80
3* 6/1 83
4* 7/1 83
5* 8/1 81
6 9/1 78
* 根据本发明的方法。
如实验结果所示，所述目的通过根据本发明的方法得以实现。

Claims (6)

1.包括下述方法步骤的方法：
a) 加入二异丁烯,
b) 加入包含Pd的化合物，其中所述Pd能够形成配合物，
c) 加入配体L1：
d) 加入乙酸,
其中以每mol二异丁烯5mol-8mol乙酸的量加入乙酸，
e) 供入CO，
f) 加热反应混合物，以使二异丁烯转化成化合物P1：
(P1)。
2.根据权利要求1所述的方法，
其中方法步骤b）中的所述化合物选自：
PdCl2、PdBr2、Pd(acac)2、Pd(dba)2 (dba =二亚苄基丙酮)、PdCl2(CH3CN)2。
3.根据权利要求1至2中任一项所述的方法，
其中以每mol二异丁烯6mol-7mol乙酸的量加入乙酸。
4.根据权利要求1至3中任一项所述的方法，
其中在方法步骤f）中将反应混合物加热至80℃-160℃的温度。
5.根据权利要求1至4中任一项所述的方法，
其中在方法步骤e）中如此供入CO，以使反应在10巴-40巴的CO压力下进行。
6.根据权利要求1至5中任一项所述的方法，
其中该方法包括另外的方法步骤g）：
g）加入硫酸。
CN201811562138.5A 2017-12-21 2018-12-20 用于二异丁烯的Pd-催化的羟基羰基化的方法：乙酸/二异丁烯比例 Active CN109942398B (zh)

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