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CN109942402A - 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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CN109942402A
CN109942402A CN201811562680.0A CN201811562680A CN109942402A CN 109942402 A CN109942402 A CN 109942402A CN 201811562680 A CN201811562680 A CN 201811562680A CN 109942402 A CN109942402 A CN 109942402A
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diisobutylene
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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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：
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：
。
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。
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能够形成络合物，
c) 添加配体L1：
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：
。
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任一项的方法，
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至3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°C至160°C的温度。
5.根据权利要求1至4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20 bar至60 bar的CO压力下进行。
CN201811562680.0A 2017-12-21 2018-12-20 二异丁烯的经Pd催化的羟基羰基化方法：溶剂的影响 Active CN109942402B (zh)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3641074A (en) * 1969-02-25 1972-02-08 Union Oil Co Carbonylation of olefins
US3968133A (en) * 1974-11-25 1976-07-06 Texaco Inc. Carboxylation process for preparing linear fatty acids or esters
US4619790A (en) * 1977-03-04 1986-10-28 Basf Aktiengesellschaft Manufacture of higher alkylcarboxylic acids
CN1073064C (zh) * 1994-12-19 2001-10-17 伊斯曼化学公司 烯烃的羰基化
WO2014005854A1 (de) * 2012-07-02 2014-01-09 Oxea Gmbh Verfahren zur herstellung von isononylderivaten
CN106187735A (zh) * 2016-07-07 2016-12-07 河北华旭化工有限公司 二异丁烯羰基合成特戊酸和2,2,4,4‑四甲基戊酸的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE887644C (de) * 1943-07-21 1953-08-24 Chemische Verwertungsgesellsch Verfahren zur Herstellung von Carbonsaeuren
US2470859A (en) * 1948-02-25 1949-05-24 Du Pont Nonanoic acid
SG49630A1 (en) * 1992-04-08 1998-06-15 Shell Int Research Carbonylation process using palladium phosphine catalyst
ZA965990B (en) 1995-07-17 1997-02-24 Shell Int Research Process for the continuous carbonylation of olefins.
CN106632509B (zh) * 2015-07-23 2020-07-07 赢创运营有限公司 膦配体和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂
ES2785564T3 (es) * 2017-12-21 2020-10-07 Evonik Degussa Gmbh Procedimiento para la conversión directa de diisobuteno en un ácido carboxílico

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3641074A (en) * 1969-02-25 1972-02-08 Union Oil Co Carbonylation of olefins
US3968133A (en) * 1974-11-25 1976-07-06 Texaco Inc. Carboxylation process for preparing linear fatty acids or esters
US4619790A (en) * 1977-03-04 1986-10-28 Basf Aktiengesellschaft Manufacture of higher alkylcarboxylic acids
CN1073064C (zh) * 1994-12-19 2001-10-17 伊斯曼化学公司 烯烃的羰基化
WO2014005854A1 (de) * 2012-07-02 2014-01-09 Oxea Gmbh Verfahren zur herstellung von isononylderivaten
CN106187735A (zh) * 2016-07-07 2016-12-07 河北华旭化工有限公司 二异丁烯羰基合成特戊酸和2,2,4,4‑四甲基戊酸的方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ANNE BRENNFUHRER等: "Palladium-Catalyzed Carbonylation Reactions of Alkenes", 《CHEMCATCHEM》 *
JAMES D. NOBB等: "Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst", 《ORGANOMETALLICS》 *
KAIWU DONG等: "Efficient Palladium-Catalyzed Alkoxycarbonylation of Bulk Industrial Olefins Using Ferrocenyl Phosphine Ligands", 《 ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 *
WENLONG REN等: "Pd-Catalyzed Regiodivergent Hydroesterification of Aryl Olefins with Phenyl Formate", 《ORGANIC LETTERS》 *

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US10494324B2 (en) 2019-12-03
CA3028181A1 (en) 2019-06-21
CN109942402B (zh) 2022-06-03
MX2018015528A (es) 2019-06-24
ES2777632T3 (es) 2020-08-05
TWI789467B (zh) 2023-01-11
ZA201808496B (en) 2019-09-25
US20190194111A1 (en) 2019-06-27
JP2019112399A (ja) 2019-07-11
PL3502082T3 (pl) 2020-07-27
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