CN114621300A - 用于催化烯属不饱和化合物的羟基羰基化的具有二茂铁二膦配体的铂配合物 - Google Patents
用于催化烯属不饱和化合物的羟基羰基化的具有二茂铁二膦配体的铂配合物 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 239000003446 ligand Substances 0.000 title abstract description 12
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title abstract description 8
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title abstract description 5
- 150000003057 platinum Chemical class 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 4
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- NSWGBUVHSQEDRN-UHFFFAOYSA-L acetonitrile;platinum(2+);dichloride Chemical compound [Cl-].[Cl-].[Pt+2].CC#N.CC#N NSWGBUVHSQEDRN-UHFFFAOYSA-L 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
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- QCSGLAMXZCLSJW-UHFFFAOYSA-L platinum(2+);diacetate Chemical compound [Pt+2].CC([O-])=O.CC([O-])=O QCSGLAMXZCLSJW-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
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- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 2
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- LXFQSRIDYRFTJW-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=CC(C)=C(S(O)(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-N 0.000 claims description 2
- WCBWZBSYSCYPTM-UHFFFAOYSA-N 2-hydroxypropane-2-sulfonic acid Chemical compound CC(C)(O)S(O)(=O)=O WCBWZBSYSCYPTM-UHFFFAOYSA-N 0.000 claims description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 2
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 claims description 2
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- MYDYJYREWLWDJL-UHFFFAOYSA-L C(C=CC1=CC=CC=C1)[Pt](Cl)Cl Chemical compound C(C=CC1=CC=CC=C1)[Pt](Cl)Cl MYDYJYREWLWDJL-UHFFFAOYSA-L 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- PLOJTLDPQLZWMO-UHFFFAOYSA-N [Pt].O=C(C=Cc1ccccc1)C=Cc1ccccc1 Chemical compound [Pt].O=C(C=Cc1ccccc1)C=Cc1ccccc1 PLOJTLDPQLZWMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 claims description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 2
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 claims description 2
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 238000007083 alkoxycarbonylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
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Abstract
本发明公开了用于催化烯属不饱和化合物的羟基羰基化的具有二茂铁二膦配体的铂配合物。
Description
技术领域
本发明涉及用于催化烯属不饱和化合物的羟基羰基化的具有二茂铁二膦配体的铂配合物。
背景技术
烯属不饱和化合物的羟基羰基化是一种越来越重要的方法。羟基羰基化应被理解为是指在金属或金属配合物和配体的存在下，烯属不饱和化合物(例如烯烃)与一氧化碳的直接反应，从而得到相应的酸：
方案1：烯属不饱和化合物的羟基羰基化的通用反应方程式
EP 3121186 A2中描述了基于二茂铁的化合物及其用于烷氧基羰基化的用途。此处使用的催化剂是包含这些配体的Pd配合物。
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的配合物，其具有与钯相比价格更低的金属作为中心原子。另外，采用所述配合物还应实现羟基羰基化的良好转化率。
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
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C6-C20)-杂芳基。
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“(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基团，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，特别优选6至10个环原子。因此，例如，在本发明的范围内，吡啶基是C6-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。
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)：
本发明进一步涉及根据本发明的配合物用于催化羟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)添加如上文所述配合物，或式(I)化合物和包含Pt的物质
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C6-C20)-杂芳基；
c)添加酸；
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羧酸。
在此，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)中初始加料之后实施CO的添加。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，并然后输入另一部分CO。
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。所述双键可以是末端的或内部的。
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、二正丁烯或它们的混合物。
在所述方法的一个变化方案中，在方法步骤c)中的酸选自：乙酸、高氯酸、硫酸、磷酸、甲基膦酸、甲磺酸、三氟甲磺酸、叔丁烷磺酸、对甲苯磺酸(PTSA)、2-羟基丙烷-2-磺酸、2,4,6-三甲基苯磺酸、十二烷基磺酸、樟脑磺酸。
在所述方法的一个变化方案中，在方法步骤c)中的酸是乙酸(AcOH)。
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]。
在步骤d)中，优选在0.1至10Mpa(1至100巴)之间，优选在1至8MPa(10至80巴)之间，更优选在2至6MPa(20至60巴)之间的CO分压下输入CO。
在根据本发明的方法的步骤e)中优选将所述反应混合物加热到在60℃至160℃，优选80至140℃，特别优选80至120℃范围内的温度，从而将所述烯属不饱和化合物转化成酸。
具体实施方式
下文将通过实施例更详细举例说明本发明。
将1-辛烯转化成酸
反应条件：1-辛烯(1.0mmol)，PtCl2(0.01mmol，1.0mol％)，配体：双齿膦配体(0.022mmol，2.2mol％)，硫酸[0.3M]0.5mL，AcOH(1.5mL)，压力(CO)：40巴，温度：120℃，反应时间：18小时。
在根据本发明的方法中采用配体(1)进行所述反应，并且采用配体(2)进行所述反应作为对比实验：
在此，采用配体(1)的根据本发明的方法提供了41％的产率。相反，在使用配体(2)的对比实验中，仅能实现13％的产率。
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
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C6-C20)-杂芳基。
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)：
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，或式(I)化合物和包含Pt的物质
其中
R1、R2、R3、R4各自彼此独立地选自-(C1-C12)-烷基、-(C6-C20)-杂芳基；
c)添加酸；
d)输入CO；
e)将得自a)至d)的反应混合物加热，其中所述烯属不饱和化合物转化成羧酸。
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或9中任一项的方法，其中在方法步骤c)中的酸选自：乙酸、高氯酸、硫酸、磷酸、甲基膦酸、甲磺酸、三氟甲磺酸、叔丁烷磺酸、对甲苯磺酸、2-羟基丙烷-2-磺酸、2,4,6-三甲基苯磺酸、十二烷基磺酸、樟脑磺酸。
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)中的酸是乙酸。
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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