CN108689845A - 戊烯酸酯的加氢甲酰化方法 - Google Patents

戊烯酸酯的加氢甲酰化方法 Download PDF

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CN108689845A
CN108689845A CN201810315758.2A CN201810315758A CN108689845A CN 108689845 A CN108689845 A CN 108689845A CN 201810315758 A CN201810315758 A CN 201810315758A CN 108689845 A CN108689845 A CN 108689845A
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S.贝伦斯
G.M.托雷斯
A.伯纳
R.弗兰克
D.泽伦特
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Abstract

本发明涉及戊烯酸酯的加氢甲酰化方法。包括下列方法步骤的方法：a)预先装载戊烯酸酯，b)加入根据结构1或2的配体和包含选自Rh、Ru、Co、Ir的金属原子的化合物，c)供给H2和CO，d)加热所述反应混合物以将所述戊烯酸酯转化成5‑甲酰基戊酸酯。

Description

戊烯酸酯的加氢甲酰化方法
技术领域
本发明涉及戊烯酸酯的加氢甲酰化方法。
背景技术
5-甲酰基戊酸酯（5-FMP）以及与支化醛的混合物的合成已多次成为研究对象一段时间。
US5264616介绍了使用具有双齿亚磷酸酯配体的铑络合物。反应条件是100℃和5bar合成气。其中具有最佳性能的亚磷酸酯配体在5 h后以95.5%的转化率和76.7%的选择性提供了所需的5-FMP。
WO95/18089描述了二亚磷酸酯改性的Rh-羰基络合物。在90℃和10 bar合成气压力下，最佳配体在27 h内以80.4%的选择性提供了54.2%转化率的5-FMP。
US6664427B1描述了使用双齿亚磷酰胺的实验。在此尤其使用了基于水杨酰苯胺的具有BINOL骨架的亚磷酰胺。该加氢甲酰化在100℃和10 bar合成气下进行，并以84.8%的选择性和80.3%的转化率提供了产物5-FMP。
US6017843同样描述了加氢甲酰化反应。在此所用的配体在100℃和6 bar合成气下以78%的n-选择性和82%的转化率提供了5-FMP。
WO2014/111446A1描述了使用甲苯/H2O (1:1)作为溶剂体系的双相催化。为了增加该催化剂的水溶性，使用TPPTS作为配体进行操作。因此可以在100℃和10 bar合成气下实现92%选择性的5-FMP。然而，转化率仅为15%。
发明内容
本发明的基本技术目的是提供从戊烯酸酯起始制备5-甲酰基戊酸酯（5-FMP）的方法。在此，收率和n-区域选择性均应高于85%。
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) 预先装载戊烯酸酯，
b) 加入根据结构1或2的配体
和包含选自Rh、Ru、Co、Ir的金属原子的化合物，
c) 供给H2和CO，
d) 加热所述反应混合物以将所述戊烯酸酯转化成 5-甲酰基戊酸酯。
在该方法的一个变体中，所述转化在80℃至130℃的温度和1至20 bar的压力下实现。
在该方法的一个优选变体中，所述转化在90℃至120℃的温度和1至15 bar的压力下实现。
在该方法的一个变体中，方法步骤b)中的金属是Rh。
在该方法的一个变体中，所述配体具有结构1：
。
在该方法的使用配体1的一个变体中，所述转化在单相中实现。
在本申请中所述的配体与金属原子，例如Rh一起形成络合物。这一络合物然后充当用于本申请中所述反应的催化剂。
“在单相中”的转化因此是均相催化。
在该方法的一个变体中，所述配体具有结构2：
。
在该方法的使用配体2的一个变体中，所述转化在双相中实现。
在本申请中所述的配体与金属原子，例如Rh一起形成络合物。这一络合物然后充当用于本申请中所述反应的催化剂。
“在双相中”的转化因此是双相催化。
具体实施方式
下面应参阅实施例更详细地阐述本发明。
一般程序说明
所用溶剂通过来自Innovative Technology Inc.公司的Pure Solv干燥装置进行干燥。
NMR波谱使用Bruker AC 250、ARX 300和AVANCE 500仪器在20℃下进行记录，其中所用溶剂的信号（CD2Cl2, H: 5.32 ppm）充当内标。信号赋值使用纯物质的1H实验和1H波谱进行。n-区域选择性借助醛官能质子的信号来测定。其在9-10 ppm的范围内，其中n-醛的醛基团的质子可作为三重峰识别。i-醛的相应质子的信分成双重峰且出现在较低的化学位移处。
气相色谱借助Hewlett Packard Agilent GC HP6890和7890A仪器来记录，两者均装有FI检测器。还进行校准以量化所包含的底物和反应产物甲基戊酸和甲酰基戊酸酯（5-FMP）的物质量，并最终用于计算转化率和收率。
所述加氢甲酰化在来自HEL公司的HP Chem-Scan II型的8罐高压釜中进行，其装有恒压-和恒温器、气流测量工具和磁力搅拌器并各具有20 mL的反应器（罐）体积。
4-戊烯酸甲酯（M4P）用作实验底物。
均相催化（单相）实验的进行
对于均相催化进行的实验，将所需配体在惰性条件下称入合适的Schlenk管中。该配体最终溶解于纯甲苯中并与事前准备的前体Rh(CO)2acac在甲苯中的溶液混合。高压釜的反应罐随后用氩气吹扫并装填所准备的溶液，并加入相应底物。将反应罐密封并用氩气吹扫5次（每次加压直至6 bar）。然后加热至50℃并用合成气将氩气压出反应罐。这通过用合成气3次加压（直至10 bar）和随后减压进行。最后，使反应溶液达到室温，并用合成气加压直至达到所示压力。现在将反应混合物在恒定温度和恒定压力下搅拌24小时。然后缓慢冷却至室温。取样进行分析。
配体
配体1和2用于根据本发明的方法中。配体3、4和5是对比配体。
均相催化（单相）的结果
均相催化进行的各个反应的数据和结果示于下表中。所述反应分别在100℃和5 bar压力下进行。溶解的Rh络合物的浓度是100 ppm，基于摩尔分数。
4-戊烯酸甲酯
配体 Rh:L:M4P 收率[%] n-区域选择性[%]
1* 1:4:2000 90.7 91.7
4 1:4:2000 68.8 87.2
5 1:4:2000 78.3 46.0
* 本发明的方法
L: 配体
M4P: 4-戊烯酸甲酯。
双相催化的进行
对于双相催化，首先将所需配体在氩气下称入合适的Schlenk管中。该配体随后通过添加去离子水溶解，并与前体溶液混合。该混合物充分混合并随后装载纯甲苯。然后如上述那样准备并装填高压釜。当反应混合物处于反应温度和-压力时，在恒定温度和恒定压力下搅拌24小时。冷却至室温后，取样进行分析。
双相催化的结果
所进行的反应的数据和结果示于下表中。所述反应分别在110℃和10 bar压力下进行。溶解的Rh络合物的浓度是100 ppm，基于摩尔分数。
4-戊烯酸甲酯
配体 Rh:L:M4P 收率[%] n-区域选择性[%]
2* 1:4:2000 90.5 95.5
3 1:4:2000 83.6 98.2
* 本发明的方法
L: 配体
M4P: 4-戊烯酸甲酯。
如由实验所示，通过本发明的方法实现这一目的。

Claims (8)

1.包括下列方法步骤的方法：
a) 预先装载戊烯酸酯，
b) 加入根据结构1或2的配体
和包含选自Rh、Ru、Co、Ir的金属原子的化合物，
c) 供给H2和CO，
d) 加热所述反应混合物以将所述戊烯酸酯转化成 5-甲酰基戊酸酯。
2.根据权利要求1的方法，
其中所述转化在80℃至130℃的温度和1至20 bar的压力下实现。
3.根据权利要求1的方法，
其中所述转化在90℃至120℃的温度和1至15 bar的压力下实现。
4.根据权利要求1至3任一项的方法，
其中在方法步骤b)中的金属是Rh。
5.根据权利要求1至4任一项的方法，
其中所述配体具有结构1：
。
6.根据权利要求5的方法，
其中所述转化在单相中实现。
7.根据权利要求1至4任一项的方法，
其中所述配体具有结构2：
。
8.根据权利要求7的方法，
其中所述转化在双相体系中实现。
CN201810315758.2A 2017-04-11 2018-04-10 戊烯酸酯的加氢甲酰化方法 Pending CN108689845A (zh)

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