CN113461737A - 用于催化烯属不饱和化合物的烷氧基羰基化的具有基于苄基的二膦配体的铂配合物 - Google Patents

用于催化烯属不饱和化合物的烷氧基羰基化的具有基于苄基的二膦配体的铂配合物 Download PDF

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CN113461737A
CN113461737A CN202110280868.1A CN202110280868A CN113461737A CN 113461737 A CN113461737 A CN 113461737A CN 202110280868 A CN202110280868 A CN 202110280868A CN 113461737 A CN113461737 A CN 113461737A
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杨寄
R·杰克斯代尔
M·贝勒
R·弗兰克
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Abstract

本发明公开了用于催化烯属不饱和化合物的烷氧基羰基化的具有基于苄基的二膦配体的铂配合物。

Description

用于催化烯属不饱和化合物的烷氧基羰基化的具有基于苄基 的二膦配体的铂配合物
技术领域
本发明涉及用于催化烯属不饱和化合物的烷氧基羰基化的具有基于苄基的二膦配体的铂配合物。
背景技术
烯属不饱和化合物的烷氧基羰基化是一种重要性不断增加的方法。烷氧基羰基化应被理解为是指在金属配合物或金属和配体的存在下，烯属不饱和化合物(例如烯烃)与一氧化碳和醇的反应，从而得到相应的酯：
Figure BDA0002978325760000011
方案1：烯属不饱和化合物的烷氧基羰基化的通用反应方程式
WO 2011/083305 A1描述了烷氧基羰基化的方法。其中描述的配合物，除了配体外，还具有钯作为中心原子。
钯的缺点是其价格高。
发明内容
本发明要解决的技术问题是提供新配合物，其具有与钯相比价格更低的金属作为中心原子。另外，所述配合物还应在烷氧基羰基化中实现良好转化率。
这个目的通过根据权利要求1的配合物实现。
包含Pt和式(I)化合物的配合物
Figure BDA0002978325760000021
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C6-C20)-杂芳基；
所述R1、R2、R3、R4基团中的至少一个是具有至少6个环原子的-(C6-C20)-杂芳基基团；
和
如果R1、R2、R3、R4是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C6-C20)-杂芳基，则它们可各自彼此独立地被一个或多个选自-(C1-C12)-烷基、-O-(C1-C12)-烷基、-OH、-NH2、卤素的取代基取代。
表述“(C1-C12)-烷基”包括具有1至12个碳原子的直链和支化的烷基基团。这些优选是(C1-C8)-烷基基团，更优选(C1-C6)-烷基，最优选(C1-C4)-烷基。
表述“(C3-C12)-环烷基”包括具有3至12个碳原子的单环、二环、或三环的烃基基团。优选地，这些基团是(C5-C12)-环烷基。
表述“(C3-C12)-杂环烷基”包括具有3至12个碳原子的非芳族的、饱和的或部分不饱和的脂环族基团，其中环碳原子中的一个或多个被杂原子替代。所述(C3-C12)-杂环烷基基团优选具有3至8个，更优选5或6个环原子。在所述杂环烷基基团中，与所述环烷基基团不同，环碳原子中的一个或多个被杂原子或含杂原子的基团替代。所述杂原子或所述含杂原子的基团优选选自O、S、N。
表述“(C6-C20)-芳基”包括具有6至20个碳原子的单环或多环的芳族烃基。这些优选是(C6-C14)-芳基，更优选(C6-C10)-芳基。
表述“(C6-C20)-杂芳基”包括具有6至20个碳原子的单环或多环的芳族烃基，其中所述碳原子中的一个或多个被杂原子替代。优选的杂原子是N、O和S。所述(C6-C20)-杂芳基基团具有6至20个，优选6至14个和更优选6至10个环原子。因此，例如，在本发明范围内，吡啶基是C6-杂芳基基团；呋喃基是C5-杂芳基基团。
合适的具有至少6个环原子的(C6-C20)-杂芳基基团尤其是吡啶基、哒嗪基、嘧啶基、吡嗪基、苯并呋喃基、吲哚基、异吲哚基。
表述“卤素”尤其包括氟、氯、溴和碘。特别优选氟和氯。
在一个实施方案中，所述R1、R2、R3、R4基团中的至少两个是具有至少6个环原子的-(C6-C20)-杂芳基基团。
在一个实施方案中，所述R1和R3基团各自是具有至少6个环原子的-(C6-C20)-杂芳基基团。
在一个实施方案中，所述R1和R3基团各自是2-吡啶基。
在一个实施方案中，R2和R4是-(C1-C12)-烷基。
在一个实施方案中，R2和R4是叔丁基。
在一个实施方案中，所述化合物(I)具有结构(1)：
Figure BDA0002978325760000031
本发明进一步涉及根据本发明的配合物用于催化烷氧基羰基化反应的用途。
包括以下方法步骤的方法：
a)将烯属不饱和化合物初始加料；
b)添加上述配合物，或者
式(I)化合物和包含Pt的物质；
Figure BDA0002978325760000041
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C6-C20)-杂芳基；
所述R1、R2、R3、R4基团中的至少一个是具有至少6个环原子的-(C6-C20)-杂芳基基团；
和
如果R1、R2、R3、R4是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C6-C20)-杂芳基，则它们可各自彼此独立地被一个或多个选自-(C1-C12)-烷基、-O-(C1-C12)-烷基、-OH、-NH2、卤素的取代基取代；
c)添加醇；
d)输入CO；
e)将得自a)至d)的反应混合物加热，在此所述烯属不饱和化合物转化成酯。
在该方法中，方法步骤a)、b)、c)和d)可以任何希望的顺序实施。然而，通常，在共反应物已经在步骤a)至c)中被初始加料之后实施CO的添加。步骤d)和e)可同时实施或者相继实施。此外，也可以在两个或更多个步骤中输入CO，使得例如，首先输入所述CO的一部分，然后将混合物加热，和随后输入CO的另一部分。
在根据本发明的方法中用作反应物的烯属不饱和化合物含有一个或多个碳-碳双键。为了简化，这些化合物在下文中也被称为烯烃。所述双键可以在末端或内部。
所述烯属不饱和化合物，除了所述一个或多个双键外，还可含有另外的官能团。在此，所述烯属不饱和化合物优选包含总共2至30个碳原子，优选2至22个碳原子，更优选2至12个碳原子。
在所述方法的一个变化方案中，所述烯属不饱和化合物除了碳-碳双键外不包含任何另外的官能团。
在所述方法的一个变化方案中，所述烯属不饱和化合物选自乙烯、丙烯、1-丁烯、顺式-和/或反式-2-丁烯、异丁烯、1,3-丁二烯、1-戊烯、顺式-和/或反式-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯(Di-n-Buten)或它们的混合物。
在所述方法的一个变化方案中，所述烯属不饱和化合物选自丙烯、1-丁烯、顺式-2-丁烯、反式-2-丁烯或它们的混合物。
在所述方法的一个变化方案中，所述烯属不饱和化合物选自：1-戊烯、顺式-2-戊烯、反式-2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、3-甲基-1-丁烯或它们的混合物。
合适的烯属不饱和化合物的混合物是被称为提余液(Raffinate)I至III的那些。提余液I包含40％至50％的异丁烯、20％至30％的1-丁烯、10％至20％的顺式-和反式-2-丁烯、最高至1％的1,3-丁二烯和10％至20％的正丁烷和异丁烷。提余液II是在石脑油裂解中产生的C4级分的一部分，并且在从提余液I中分离出异丁烯后主要由异构的正丁烯、异丁烷和正丁烷组成。提余液III是在石脑油裂解中产生的C4级分的一部分，并且主要由异构的正丁烯和正丁烷组成。
在一个变化方案中，使用包含异丁烯、1-丁烯、顺式-和反式-2-丁烯的混合物。优选地，所述混合物包含1-丁烯、顺式-和反式-2-丁烯。
在所述方法的一个变化方案中，在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、叔丁醇、3-戊醇、环己醇、苯酚。
在所述方法的一个变化方案中，在方法步骤c)中的醇是甲醇。
在所述方法的一个变化方案中，所述包含Pt的物质选自二氯化铂(PtCl2)、乙酰丙酮铂(II)[Pt(acac)2]、乙酸铂(II)[Pt(OAc)2]、二氯(1,5-环辛二烯)铂(II)[Pt(cod)2Cl2]、双(二苄叉基丙酮)铂[Pt(dba)2]、双(乙腈)二氯铂(II)[Pt(CH3CN)2Cl2]、(肉桂基)二氯化铂[Pt(肉桂基)Cl2]。
在所述方法的一个变化方案中，所述包含Pt的物质选自二氯化铂(PtCl2)、乙酰丙酮铂(II)[Pt(acac)2]、乙酸铂(II)[Pt(OAc)2]。
优选在0.1至10MPa(1至100巴)，优选1至8MPa(10至80巴)，更优选2至6MPa(20至60巴)的CO分压下在步骤d)中输入CO。
在根据本发明的方法的步骤e)中将反应混合物优选加热到在60℃至160℃范围内，优选在80至140℃范围内，更优选在100至140℃范围内的温度，从而将所述烯属不饱和化合物转化成酯。
具体实施方式
下文将通过实施例详细说明本发明。
将1-辛烯转化成甲基酯
Figure BDA0002978325760000071
反应条件：1-辛烯(1.0mmol)，PtCl2(0.01mmol，1.0mol％)，配体：单齿膦配体(0.04mmol，4.0mol％)，双齿膦配体(0.02mmol，2.0mol％)，PTSA·H2O(对甲苯磺酸的一水合物)(5.0mol％)，MeOH(2.0ml)，压力(CO)：40巴，温度：120℃，反应时间：20小时。
采用以下配体进行该反应：
单齿膦配体：
Figure BDA0002978325760000072
双齿膦配体：
Figure BDA0002978325760000073
在配体下方说明了各自的产率和正/异构选择性。通过气相色谱法采用均三甲苯作为内标测定选择性和产率。
在使用的16种配体中，11种没有提供任何转化(0％)。只有采用一种配体(L12＝(1))，才能实现超过60％的转化率。如由该系列实验表明的，采用本发明的由Pt和(1)构成的配合物实现了最大的转化率。
Pt的价格低于Pd的价格。因此通过根据本发明的配合物实现了所述目的。

Claims (13)

1.包含Pt和式(I)化合物的配合物
Figure FDA0002978325750000011
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C6-C20)-杂芳基；
所述R1、R2、R3、R4基团中的至少一个是具有至少6个环原子的-(C6-C20)-杂芳基基团；
并且
如果R1、R2、R3、R4是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C6-C20)-杂芳基，则它们可各自彼此独立地被一个或多个选自-(C1-C12)-烷基、-O-(C1-C12)-烷基、-OH、-NH2、卤素的取代基取代。
2.根据权利要求1的配合物，其中所述R1、R2、R3、R4基团中的至少两个是具有至少6个环原子的-(C6-C20)-杂芳基基团。
3.根据权利要求1至2中任一项的配合物，其中所述R1和R3基团各自是具有至少6个环原子的-(C6-C20)-杂芳基基团。
4.根据权利要求1至3中任一项的配合物，其中所述R1和R3基团各自是2-吡啶基。
5.根据权利要求1至4中任一项的配合物，其中R2和R4是-(C1-C12)-烷基。
6.根据权利要求1至5中任一项的配合物，其中R2和R4是叔丁基。
7.根据权利要求1至6中任一项的配合物，其中所述化合物(I)具有结构(1)：
Figure FDA0002978325750000021
8.包括以下方法步骤的方法：
a)将烯属不饱和化合物初始加料；
b)添加根据权利要求1至7中任一项的配合物，或者
式(I)化合物和包含Pt的物质，
Figure FDA0002978325750000031
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基、-(C6-C20)-杂芳基；
所述R1、R2、R3、R4基团中的至少一个是具有至少6个环原子的-(C6-C20)-杂芳基基团；
并且
如果R1、R2、R3、R4是-(C1-C12)-烷基、-(C3-C12)-环烷基、-(C3-C12)-杂环烷基、-(C6-C20)-芳基或-(C6-C20)-杂芳基，则它们可各自彼此独立地被一个或多个选自-(C1-C12)-烷基、-O-(C1-C12)-烷基、-OH、-NH2、卤素的取代基取代；
c)添加醇；
d)输入CO；
e)将得自a)至d)的反应混合物加热，在此所述烯属不饱和化合物转化成酯。
9.根据权利要求8的方法，其中所述烯属不饱和化合物选自乙烯、丙烯、1-丁烯、顺式-和/或反式-2-丁烯、异丁烯、1,3-丁二烯、1-戊烯、顺式-和/或反式-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯或它们的混合物。
10.根据权利要求8和9中任一项的方法，其中在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、叔丁醇、3-戊醇、环己醇、苯酚。
11.根据权利要求8至10中任一项的方法，其中在方法步骤c)中的醇是甲醇。
12.根据权利要求8至11中任一项的方法，其中所述包含Pt的物质选自二氯化铂(PtCl2)、乙酰丙酮铂(II)[Pt(acac)2]、乙酸铂(II)[Pt(OAc)2]、二氯(1,5-环辛二烯)铂(II)[Pt(cod)2Cl2]、双(二苄叉基丙酮)铂[Pt(dba)2]、双(乙腈)二氯铂(II)[Pt(CH3CN)2Cl2]、(肉桂基)二氯化铂[Pt(肉桂基)Cl2]。
13.根据权利要求8至12中任一项的方法，其中所述包含Pt的物质选自二氯化铂(PtCl2)、乙酰丙酮铂(II)[Pt(acac)2]、乙酸铂(II)[Pt(OAc)2]。
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