CN109381833B - 甲酸的Pd催化分解 - Google Patents

甲酸的Pd催化分解 Download PDF

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CN109381833B
CN109381833B CN201810890315.6A CN201810890315A CN109381833B CN 109381833 B CN109381833 B CN 109381833B CN 201810890315 A CN201810890315 A CN 201810890315A CN 109381833 B CN109381833 B CN 109381833B
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桑睿
刘劼
董开武
R.雅克施特尔
M.贝勒
R.弗兰克
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Abstract

本发明涉及Pd催化分解甲酸的方法。所述方法包括以下方法步骤：a）存在甲酸；b）加入含Pd的化合物，其中Pd能够形成络合物；c）加入通式（I）化合物：
Figure RE-DEST_PATH_IMAGE001
（I）其中R1、R2、R3、R4各自彼此独立地选自：‑H、‑(C1‑C12)‑烷基、‑O‑(C1‑C12)‑烷基、‑(C4‑C14)‑芳基、‑O‑(C4‑C14)‑芳基、环烷基、‑(C1‑C12)‑杂烷基、‑O‑(C1‑C12)‑杂烷基、‑(C3‑C14)‑杂芳基、‑O‑(C3‑C14)‑杂芳基、‑COO‑烷基、‑COO‑芳基、‑C‑O‑烷基、‑C‑O‑芳基、NH2、卤素和也能够形成更大的稠合环的基团；其中所述烷基、芳基、环烷基、杂烷基、杂芳基可以如下被取代了的：‑(C1‑C12)‑烷基、‑O‑(C1‑C12)‑烷基、卤素；并且基团R1、R2、R3、R4中的至少一个不代表苯基；d）加入MeOH；e）加热反应混合物，其中甲酸被分解。

Description

甲酸的Pd催化分解
本发明涉及Pd催化分解甲酸（HCOOH）的方法。
甲酸在化学反应中例如作为酸或溶剂被添加，但也可作为反应的副产物产生。由于其腐蚀性或发出强烈气味的性质，可以值得期望的是，将甲酸去除。
本发明的目的在于提供一种其中借助催化方法将甲酸有效分解的方法。
该目的通过根据权利要求1的方法实现。
方法，其包括以下方法步骤：
a）存在甲酸；
b）加入含Pd的化合物，其中Pd能够形成络合物；
c）加入通式（I）化合物：
Figure 110821DEST_PATH_IMAGE001
（I）
其中R1、R2、R3、R4各自彼此独立地选自：-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-(C4-C14)-芳基、-O-(C4-C14)-芳基、环烷基、-(C1-C12)-杂烷基、-O-(C1-C12)-杂烷基、-(C3-C14)-杂芳基、-O-(C3-C14)-杂芳基、-COO-烷基、-COO-芳基、-C-O-烷基、-C-O-芳基、NH2、卤素和也能够形成更大的稠合环的基团；
其中所述烷基、芳基、环烷基、杂烷基、杂芳基可以如下被取代了的：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素；
并且基团R1、R2、R3、R4中的至少一个不代表苯基；
d）加入MeOH；
e）加热反应混合物，其中甲酸被分解。
在该方法的一个变型方案中，方法步骤b）中的化合物选自：
Pd(acac)2、PdCl2、Pd(dba)3*CH3Cl（dba =二亚苄基丙酮）、Pd(OAc)2、Pd(TFA)2、Pd(CH3CN)Cl2。
在该方法的一个变型方案中，方法步骤b）中的化合物是Pd(OAc)2。
在该方法的一个变型方案中，该方法包括额外的方法步骤f）：
f）加入酸。
在该方法的一个变型方案中，方法步骤f）中的酸选自：H2SO4、CH3SO3H、CF3SO3H、PTSA。
在该方法的一个变型方案中，方法步骤f）中的酸是PTSA。
在该方法的一个变型方案中，R1、R2、R3、R4各自彼此独立地选自：-(C1-C12)-烷基、-O-(C1-C12)-烷基、-(C4-C14)-芳基、-O-(C4-C14)-芳基、环烷基、-(C1-C12)-杂烷基、-O-(C1-C12)-杂烷基、-(C3-C14)-杂芳基、-O-(C3-C14)-杂芳基、-COO-烷基、-COO-芳基、-C-O-烷基、-C-O-芳基、NH2、卤素和也能够形成更大的稠合环的基团；
其中所述烷基、芳基、环烷基、杂烷基、杂芳基可以如下被取代了的：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素；
并且基团R1、R2、R3、R4中的至少一个不代表苯基。
在该方法的一个变型方案中，R1、R2、R3、R4各自彼此独立地选自：-(C1-C12)-烷基、-(C4-C14)-芳基、环烷基、-(C1-C12)-杂烷基、-(C3-C14)-杂芳基、卤素和也能够形成更大的稠合环的基团；
其中所述烷基、芳基、环烷基、杂烷基、杂芳基可以如下被取代了的：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素；
并且基团R1、R2、R3、R4中的至少一个不代表苯基。
在该方法的一个变型方案中，R1、R2、R3、R4各自彼此独立地选自：-(C1-C12)-烷基、环烷基、-(C3-C14)-杂芳基和也能够形成更大的稠合环的基团；
其中所述烷基、环烷基、杂芳基可以如下被取代了的：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素，
并且基团R1、R2、R3、R4中的至少一个不代表苯基。
在该方法的一个变型方案中，R1、R4各自彼此独立地选自：-(C1-C12)-烷基、环烷基和也能够形成更大的稠合环的基团；
其中所述烷基、环烷基可以如下被取代了的：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素。
在该方法的一个变型方案中，R2、R3各自彼此独立地代表-(C3-C14)-杂芳基，
其中所述杂芳基可以如下被取代了的：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素。
在该方法的一个变型方案中，通式（I）化合物选自结构（1）至（3）：
Figure 27961DEST_PATH_IMAGE002
（1）
Figure 994649DEST_PATH_IMAGE003
（2）
Figure 389858DEST_PATH_IMAGE004
（3）。
在该方法的一个变型方案中，通式（I）化合物是结构（2）：
Figure 204231DEST_PATH_IMAGE003
（2）。
在该方法的一个变型方案中，通式（I）化合物是结构（3）：
Figure 26693DEST_PATH_IMAGE005
（3）。
下面借助实施例更详细地阐述本发明。
Pd催化分解甲酸的试验
Figure 231410DEST_PATH_IMAGE006
在氩气氛下，将[Pd(OAc)2]（4.48mg，0.02mmol，0.05mol％）、配体L（0.08mmol，0.2mol％）、PTSA·H2O（76mg，0.4mmol，1.0mol％）放入高压釜中。（按照下表，在各个试验中无需加入各个成分。）随后用注射器注入MeOH（6.5ml）和HCOOH（40mmol，1.50ml）。然后用氮气（5bar）吹扫高压釜三次。将反应混合物加热至100℃并保持该温度18小时。在该时间后，将高压釜冷却至室温。压力通过高压釜压力的电子记录探针测量。通过气体-GC-分析测定CO、H2和CO2的选择性。
结果总结在下表中：
表：
Figure 430310DEST_PATH_IMAGE007
+：已加入
-：没有加入
如上述试验所示，该目的通过根据本发明的方法实现。

Claims (9)

1.方法，其包括以下方法步骤：
a)存在甲酸；
b)加入含Pd的化合物，其中Pd能够形成络合物；
c)加入通式(I)化合物：
Figure FDA0002576739960000011
其中R1、R4各自彼此独立地选自：-(C1-C12)-烷基、环烷基；
其中所述烷基、环烷基可以被如下基团取代：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素；
其中R2、R3各自彼此独立地代表-(C3-C14)-杂芳基，
其中所述杂芳基可以被如下基团取代：
-(C1-C12)-烷基、-O-(C1-C12)-烷基、卤素；
d)加入MeOH；
e)加热反应混合物，其中甲酸被分解。
2.根据权利要求1所述的方法，其中方法步骤b)中的化合物选自：Pd(acac)2、PdCl2、Pd(dba)3*CH3Cl(dba＝二亚苄基丙酮)、Pd(OAc)2、Pd(TFA)2、Pd(CH3CN)Cl2。
3.根据权利要求1或2所述的方法，其中方法步骤b)中的化合物是Pd(OAc)2。
4.根据权利要求1或2所述的方法，其中所述方法包括额外的方法步骤f)：
f)加入酸。
5.根据权利要求4所述的方法，其中方法步骤f)中的酸选自：H2SO4、CH3SO3H、CF3SO3H、PTSA。
6.根据权利要求5所述的方法，其中方法步骤f)中的酸是PTSA。
7.根据权利要求1或2所述的方法，其中通式(I)化合物选自结构(1)至(3)：
Figure FDA0002576739960000012
Figure FDA0002576739960000021
8.根据权利要求1或2所述的方法，其中通式(I)化合物是结构(2)：
Figure FDA0002576739960000022
9.根据权利要求1或2所述的方法，其中通式(I)化合物是结构(3)：
Figure FDA0002576739960000023
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JP2019089690A (ja) 2019-06-13
CN109381833A (zh) 2019-02-26
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