CN111315755B - 用于烯烃加氢甲酰化的高异构选择性催化剂 - Google Patents
用于烯烃加氢甲酰化的高异构选择性催化剂 Download PDFInfo
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- CN111315755B CN111315755B CN201880072696.5A CN201880072696A CN111315755B CN 111315755 B CN111315755 B CN 111315755B CN 201880072696 A CN201880072696 A CN 201880072696A CN 111315755 B CN111315755 B CN 111315755B
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- NMFCUXDFBMUBKH-UHFFFAOYSA-L octanoate;rhodium(2+) Chemical compound [Rh+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NMFCUXDFBMUBKH-UHFFFAOYSA-L 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- DPQSFPWSRVODTR-UHFFFAOYSA-L rhodium(2+) diacetate dihydrate Chemical compound O.O.C(C)(=O)[O-].[Rh+2].C(C)(=O)[O-] DPQSFPWSRVODTR-UHFFFAOYSA-L 0.000 description 1
- ITDJKCJYYAQMRO-UHFFFAOYSA-L rhodium(2+);diacetate Chemical compound [Rh+2].CC([O-])=O.CC([O-])=O ITDJKCJYYAQMRO-UHFFFAOYSA-L 0.000 description 1
- BTZFRWBQBSCKGO-UHFFFAOYSA-L rhodium(2+);dibenzoate Chemical compound [Rh+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 BTZFRWBQBSCKGO-UHFFFAOYSA-L 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical compound OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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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
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Abstract
本文描述了与用在加氢甲酰化反应中的催化剂组合物一起使用的配体。该配体与多种八氟甲苯或烃类溶剂一起使用,并实现了异构选择性随温度升高而增加、TON随温度升高而增加,和/或与使用普通溶剂的加氢甲酰化反应相比,显示出令人惊讶地高的异构选择性。
Description
联合研究协议缔约方
本文所公开或要求保护的发明是根据伊士曼化工公司(Eastman ChemicalCompany)和圣安德鲁斯大学的大学法院(University Court of the University ofSt.Andrews)(一个在苏格兰注册的慈善机构)之间的联合研究协议而作出的。
背景技术
加氢甲酰化反应,也称为羰基合成反应(oxo reaction),广泛用于通过一摩尔烯烃与一摩尔氢气和一摩尔一氧化碳反应来制备醛的工业方法中。该反应的一个特别重要的用途是由丙烯制备正构(n-)和(iso-)丁醛。这两种产物均为合成许多化学中间体的关键结构单元,该化学中间体如醇、羧酸、酯、增塑剂、二醇、必需氨基酸、调味剂、香料、聚合物、杀虫剂、液压液和润滑剂。
目前,高正构选择性更容易实现,而实现高异构选择性仍有挑战性。多年来已经尝试了不同的办法来解决这个问题,包括使用多种配体(Phillips,Devon,Puckette,Stavinoha,Vanderbilt,(伊士曼柯达公司,Eastman Kodak Company),美国专利No.4,760,194)以及在含水条件下进行反应(Riisager,Eriksen,Fehrmann,J.Mol.Catal.A:Chem.2003,193,259)。结果通常不令人满意,要么是异构选择性表现平平,和/或因为反应需要在不希望的温度下进行。所记录的最高异构选择性为63%——在19℃进行的反应中(Norman,Reek,Besset,(伊士曼化工公司),美国专利No.8,710,275)。然而,在某些情况下,这是不希望的,因为在较低温度下进行的加氢甲酰化反应可导致较低的反应速率,因此在工业上通常优选在较高温度下进行反应。在这种情况下,当反应在80℃下进行时,异构选择性降低到38%。因此,仍然需要在高于19℃的温度下具有高异构选择性的催化剂。
发明内容
根据一实施例,本公开教导了在加氢甲酰化温度和压力条件下制备至少一种醛的方法。该方法包括:在至少一种溶剂和过渡金属基催化剂组合物存在下,使至少一种烯烃与氢气和一氧化碳接触,该过渡金属基催化剂组合物包括磷杂环戊烷亚磷酸酯配体,该烯烃在一些实施例中可以是丙烯,该过渡金属基催化剂组合物在一些实施例中可以是铑基的。该配体由以下通式表示:
其中:
R1和R2独立地选自取代及未取代的含有1至40个碳原子的芳基、烷基、芳氧基或环烷基;
R3和R4独立地选自取代及未取代的含有1至20个碳原子的芳基、烷基、烷氧基、三烷基甲硅烷基、三芳基甲硅烷基、芳基二烷基甲硅烷基、二芳基烷基甲硅烷基和环烷基,其中烷基甲硅烷基的硅原子在取代基的α位;
R5独立地选自H或烷基。
在一替代的实施例中,配体由以下通式表示:
在替代的实施例中,该方法可以用衍生自非手性双酚二醇组分的磷杂环戊烷亚磷酸酯配体完成。代表性的例子包括并选自以下配体(A)至(D),配体(A)至(D)由它们的通式表示:
不管使用何种配体,该方法使用或者氟化溶剂或者烃类溶剂,该氟化溶剂可以是八氟甲苯或全氟苯基辛基醚,该烃类溶剂可以是正壬烷、正癸烷、正十一烷或正十二烷。在一些实施例中,该方法的醛产物包含如下的异构选择性:约55%至约80%、约55%至约77%、约58至约73%、约60%至约70%或约55%或更大。
此外,在一些实施例中,该方法在如下的压力范围内进行:约2atm至约80atm、约5atm至约70atm、约8atm至约20atm、约8atm或约20atm。在一些实施例中,该方法还在如下的温度范围内进行:约40至约150摄氏度、约40至约120摄氏度、约40至约100摄氏度、约50至约90摄氏度、约50摄氏度、约75摄氏度或约90摄氏度。
本公开还提供了过渡金属基催化剂组合物,其包括由以下通式表示的磷杂环戊烷亚磷酸酯配体:
其中:
R1和R2独立地选自取代及未取代的含有1至40个碳原子的芳基、烷基、芳氧基或环烷基;
R3和R4独立地选自取代及未取代的含有1至20个碳原子的芳基、烷基、烷氧基、三烷基甲硅烷基、三芳基甲硅烷基、芳基二烷基甲硅烷基、二芳基烷基甲硅烷基和环烷基,其中烷基甲硅烷基的硅原子在取代基的α位;
R5独立地选自H或烷基。
在一替代的实施例中,过渡金属基催化剂组合物包括由以下通式表示的磷杂环戊烷亚磷酸酯配体:
在又一实施例中,过渡金属基催化剂组合物包括衍生自非手性双酚二醇组分的磷杂环戊烷亚磷酸酯配体,磷杂环戊烷亚磷酸酯配体选自以下配体(A)至(D),配体(A)至(D)由它们的通式表示:
附图标记
图1说明了本文所述的配体组合物。
图2说明了本文所述的多种配体的合成和化学结构
具体实施例
本公开提供了用于制备至少一种醛的加氢甲酰化方法,其包括:在至少一种溶剂和过渡金属基催化剂组合物存在下,使至少一种烯烃与氢气和一氧化碳接触,该过渡金属基催化剂组合物包含磷杂环戊烷亚磷酸酯配体。代表性的磷杂环戊烷亚磷酸酯可以是前手性或非手性组合物,并由以下通式表示:
其中:
R1和R2独立地选自取代及未取代的含有1至40个碳原子的芳基、烷基、芳氧基或环烷基;
R3和R4独立地选自取代及未取代的含有1至20个碳原子的芳基、烷基、烷氧基、三烷基甲硅烷基、三芳基甲硅烷基、芳基二烷基甲硅烷基、二芳基烷基甲硅烷基和环烷基,其中烷基甲硅烷基的硅原子在取代基的α位,
R5独立地选自H或烷基。
从R1和R2开始,在一些实施例中,R1和R2中的一个或两个独立地选自取代或未取代的芳基。在一些实施例中,R1、R2或两者上的芳基取代基是取代或未取代的萘基或苯基。在一些实施例中,R1、R2或两者上的芳基取代基是取代或未取代的苯基。在一些实施例中,R1和R2或两者上的芳基是取代的苯基,其中取代基是独立地选择的。在一些实施例中,R1和R2或两者上的芳基是取代的苯基,其中取代基独立地选自三氟甲基、三氯甲基、氰基、磺酸酯基、羧酸基、羧酸酯基、羧酸盐、磺酸盐、季铵基、卤素原子和硝基。在一些实施例中,R1和R2上的取代基相同。在一些实施例中,R1和R2上的取代基均为三氟甲基。在一些实施例中,相对于苯基所键合的磷原子,苯基上的取代基在间位。
在一些实施例中,R3和R4基团独立地选自具有一至四个碳的烷基及三烷基甲硅烷基。在一些实施例中,所有R3和R4基团均为甲基。在一些实施例中,所有R3和R4基团均为叔丁基或三甲基甲硅烷基。在一些实施例中,所有R3和R4基团均为叔丁基。在一些实施例中,R3基团均为叔丁基或三甲基甲硅烷基,并且R4基团均为甲基。在一些实施例中,R3基团均为叔丁基,R4基团均为甲基。
具体的表达方式(formulation)在本文全文中由数字(1)至(3)表示,并且包括以下配体:
除非另有说明,否则说明书和权利要求中使用的表示成分、特性(如分子量)、反应条件等的数量的所有数字应理解为在所有情况下都由术语“约”修饰。因此,除非相反地说明,否则在以下说明书和所附权利要求中阐述的数值参数是近似值,其可根据本发明寻求获得的期望特性而变化。至少,每个数值参数应该至少根据所记录的有效数字的数值并通过应用普通的舍入技术来解释。此外,本公开和权利要求中声称的范围旨在具体地包括整个范围,而不仅仅是端点。例如,声称的范围为0至10是旨在公开0到10之间的所有整数(诸如,例如1、2、3、4等)、0到10之间的所有分数(例如1.5、2.3、4.57、6.1113等),以及端点0和10。
尽管阐述了本发明的宽范围的数值范围和参数是近似值,但是在具体实例中阐述的数值旨在基于测量方法精确地记录。然而,任何数值固有地含有某些误差,这些误差必然地来自于它们各自的测试测量中发现的标准偏差。
应当理解,提及一个或多个方法步骤并不排除:在组合的所列举的步骤之前或之后存在额外的方法步骤,或者在明确指出的那些步骤之间插入方法步骤。此外,在本申请中公开或要求保护的方法步骤、成分或信息的其它方面的命名(使用字母、数字等)是用于识别分立的活动或成分的便利手段,除非另有说明,否则所叙述的注记(lettering)可以以任何顺序排列。
如本文所用,单数形式“一(个/种)”和“该/所述”包括复数指代物,除非上下文另有明确说明。例如,提及Cn醇等价物,旨在包括多种类型的Cn醇等价物。因此,即使在一个位置中采用如“至少一(个/种)”或“至少一些”的语言也并不旨在意味着“一(个/种)”和“该/所述”排除复数指代物,除非上下文另有明确说明。类似地,在一个位置采用如“至少一些”的语言并非旨在意味着,在其它地方不存在这样的语言时是意味着旨在“全部”,除非上下文另有明确说明。
如本文所用,术语“和/或”当用于两个或更多个项目的列表中时,是指可单独使用所列项目中的任一个,或可使用所列项目中的两个或更多个的任何组合。例如,如果组合物被描述为含有组分A、B和/或C,则该组合物可含有:单独的A;单独的B;单独的C;A和B的组合;A和C的组合;B和C的组合;或A、B和C的组合。
本文所述的方法要求烯烃与氢气和一氧化碳在过渡金属催化剂和配体的存在下接触。在一实施例中,烯烃是丙烯。还预期有另外的烯烃可以在该方法中起作用,诸如,例如丁烯、戊烯、己烯、庚烯和辛烯。
该方法的所得催化剂组合物含有过渡金属以及本文所述的配体。在一些实施例中,过渡金属催化剂含有铑。
铑的可接受形式包括铑(II)或铑(III)的羧酸盐、羰基铑类,以及铑有机膦配合物。铑(II)或铑(III)的羧酸盐的一些例子包括四乙酸二铑二水合物、乙酸铑(II)、异丁酸铑(II)、2-乙基己酸铑(II)、苯甲酸铑(II)和辛酸铑(II)。羰基铑类的一些例子包括[Rh(acac)(CO)2]、Rh4(CO)12和Rh6(CO)16。铑有机膦配合物的例子是可使用的三(三苯基膦)铑羰基氢化物。
反应混合物或溶液中过渡金属的绝对浓度可从约1mg/升变化到约5000mg/升;在一些实施例中,其高于约5000mg/升。在本发明的一些实施例中,反应溶液中过渡金属的浓度在约20至约300mg/升的范围里。配体摩尔数与过渡金属摩尔数的比可以在宽范围内变化,例如配体摩尔数:过渡金属摩尔数比为:约0.1:1至约500:1,或约0.5:1至约500:1。对于含铑催化剂体系,在一些实施例中,配体摩尔数:铑的摩尔数比在约0.1:1至约200:1的范围内,在一些实施例中,该比在约1:1至约100:1或约1:1至约10:1的范围内。
在一些实施例中,催化剂由过渡金属化合物(如[Rh(acac)(CO)2])和配体原位形成。本领域技术人员可以理解,当与配体、氢气和一氧化碳接触时,多种Rh类将形成相同的活性催化剂,因此对Rh预催化剂的选择没有限制。
在另外的实施例中,该方法在至少一种溶剂的存在下进行。合适的溶剂包括:氟化溶剂,如八氟甲苯或全氟苯基辛基醚;或烃类溶剂,诸如,例如正壬烷、正癸烷、正十一烷和正十二烷。还预期的是,其它溶剂可与这些溶剂组合使用。
本公开进一步提供了如本文一般性描述和以下实例中具体描述的用于合成方法的方法。
对于配制催化剂体系,制备本发明的催化剂体系和溶液不需要特殊或不寻常的技术,尽管在一些实施例中,如果铑和配体组分的所有操作在惰性气氛(例如氮气、氩气等)下进行,可以观察到更高的活性。此外,在一些实施例中,可能有利的是将配体和过渡金属一起溶解在溶剂中,以允许配体和过渡金属的络合,随后金属配体络合物结晶,如美国专利No.9,308,527中所述的,在此将其全文引入作为参考。
可以使用如本段中详述的用于有效加氢甲酰化条件的合适的反应条件。在一些实施例中,该方法在如下的温度范围内进行:约40至约150摄氏度、约40至约120摄氏度、约40至约100摄氏度、约50至约90摄氏度、约50摄氏度、约75摄氏度或约90摄氏度。在一些实施例中,总反应压力可以为约2atm至约80atm、约5atm至约70atm、约8atm至约20atm、约8atm或约20atm。
在一些实施例中,在反应器中氢气:一氧化碳的摩尔比可以在约10:1至约1:10的范围内显著变化,氢气和一氧化碳的绝对分压之和可以在约0.3至约36atm的范围内。在一些实施例中,对于每种气体,反应器中氢气和一氧化碳的分压保持在约1至约14atm的范围内。在一些实施例中,反应器中一氧化碳的分压保持在约1至约14atm的范围内,并且独立于氢气分压而变化。氢气与一氧化碳的摩尔比可以在氢气和一氧化碳的这些分压范围内有很大变化。在合成气[synthesis gas](合成气[syngas]——一氧化碳和氢气)中,氢气和一氧化碳的比以及其各自的分压可以通过向合成气流中加入氢气或一氧化碳而容易地改变。
反应混合物中存在的烯烃的量也不挑剔(critical)。在丙烯的加氢甲酰化的一些实施例中,反应器中蒸气空间的分压在约0.07至约35atm的范围里。在涉及丙烯的加氢甲酰化的一些实施例中,丙烯的分压大于约1.4atm,例如约1.4至约10atm。在丙烯加氢甲酰化的一些实施例中,反应器中丙烯的分压大于约0.14atm。
任何有效的加氢甲酰化反应器设计或构造可用于实施本发明所提供的方法。因此,可以使用如本文阐述的实例中所公开的气体喷射液体溢流反应器(a gas-sparged,liquid overflow reactor)或蒸气取出反应器(vapor take-off reactor)设计。在这种操作模式的一些实施例中,在压力下溶解在高沸点有机溶剂中的催化剂不与醛产物一起离开反应区,该醛产物由未反应的气体从塔顶(overhead)带出。然后在蒸气/液体分离器中冷却塔顶气体以冷凝醛产物,并且可以将气体再循环到反应器。将液体产物降至大气压下,通过常规技术分离和纯化。该方法也可以以间歇方式通过使丙烯、氢气和一氧化碳与本发明的催化剂在高压釜中接触来实施。
这样的反应器设计也是合适的:将催化剂和原料泵入反应器并允许它们与产物醛一起溢流,即液体溢流反应器设计。在一些实施例中,醛产物可通过常规方法(如通过蒸馏或萃取)与催化剂分离,然后将催化剂再循环回到反应器中。水溶性醛产物可以通过萃取技术与催化剂分离。滴流床反应器设计也适用于该方法。对于本领域技术人员来说显然的是,其它反应器方案可以用于本发明。
对于连续操作的反应器,可能希望的是,随着时间加入补充量的配体(化合物),以替代经氧化或其它过程而损失的那些材料。这可以通过将配体溶解到溶剂中并根据需要将其泵入反应器中来进行。可以使用的溶剂包括在该方法中发现的化合物,如烯烃、产物醛、衍生自醛的缩合产物,以及可以容易地由产物醛形成的其它酯和醇。溶剂例子包括丁醛、异丁醛、丙醛、2-乙基己醛、2-乙基己醇、正丁醇、异丁醇、异丁酸异丁酯、乙酸异丁酯、丁酸丁酯、乙酸丁酯、2,2,4-三甲基戊烷-1,3-二醇二异丁酸酯、2-乙基己酸正丁酯、八氟甲苯、全氟苯基辛基醚、正壬烷、正癸烷、正十一烷和正十二烷。还可使用酮,如环己酮、甲基异丁基酮、甲基乙基酮、二异丙基酮和2-辛酮,以及三聚醛酯-醇,如TexanolTM酯醇(2,2,4-三甲基-1,3-戊二醇单(2-甲基丙酸酯))。
在一些实施例中,用于本发明加氢甲酰化方法的试剂基本上不含可能降低催化剂活性或使催化剂完全失活的物质。在一些实施例中,反应中不包括这样的材料,如共轭二烯、乙炔、硫醇、无机酸、卤化有机化合物和游离氧。
本发明可以通过实施例的以下实例进一步说明,但是应当理解,除非另有明确说明,这些实例仅用于说明的目的,而非旨在限制本发明的范围。
实例
在表1(比较例)、表2、表3和表4中记录了用不同溶剂、在不同温度和压力下、使用(轴安定,R,R,R)-1配体的铑催化的丙烯加氢甲酰化的研究。用气相色谱法(gaschromatography,GC)将异构醛和正构醛产物均用1-甲基萘内标物进行校准。可以计算反应的两种产物的量,以得出异构/正构的比,并且可以使用转化数(turn over number,TON)来量化催化剂的生产率。TON是指催化剂负载和使用该方程形成的产物的量之间的关系;TON=(异构醛+正构醛)(mmol)/[Rh(acac)(CO)2](mmol)。然后可以比较反应之间催化剂的相对反应性。对于在90℃下进行的反应,在所用的设备中,在20巴的压力下一次充入气体(10%丙烯,45%CO,45%H2),对应于100%转化率的最大TON为~1450。在不同压力和温度下,本文所述的反应将具有不同的最大理论转化数。如表1所示,当在普通溶剂(如甲苯)中进行反应时,达到中等的异构选择性(<60%)。当施加较低的压力时,观察到了异构选择性上的增加。反应温度的升高也导致异构选择性的降低。
表1:在普通溶剂中使用(轴安定,R,R,R)-1的丙烯加氢甲酰化
Ex. | 溶剂 | 温度(℃) | 压力(atm) | 时间(hr) | TON | 异构体% |
1 | 甲苯 | 50 | 8 | 16 | 784 | 57.2 |
2 | 甲苯 | 50 | 20 | 16 | 1348 | 54.5 |
3 | 甲苯 | 75 | 8 | 1 | 512 | 56.4 |
4 | 甲苯 | 75 | 20 | 1 | 1131 | 53.3 |
5 | 甲苯 | 90 | 8 | 1 | 500 | 56.0 |
6 | 甲苯 | 90 | 20 | 1 | 782 | 48.9 |
7 | 正戊醛 | 50 | 8 | 16 | 122 | 54.1 |
8 | 氯苯 | 50 | 8 | 16 | 755 | 56.5 |
9 | Texanol | 50 | 8 | 16 | 692 | 48.3 |
L:Rh=1.25:1
在表1中,在常规溶剂中,如所预测的那样,当在较低的温度和较低的压力下进行反应时,使用(轴安定,R,R,R)-1配体/Rh的丙烯加氢甲酰化显示出较高的异构选择性。这些条件对工业不利,因为工业上倾向于在较高温度下进行反应,并获得更高的TON或更高的异构选择性。因此,需要替代的溶剂来适应工业相关条件。另外,所用的普通溶剂没有证明出高于57%的异构选择性。
相反,下面的表2、表3和表4将显示,在某些情况下,异构选择性随温度升高而增加,TON随温度升高而增加,和/或将显示这样的异构选择性,与表1中在普通溶剂中使用(轴安定,R,R,R)-1配体进行丙烯加氢甲酰化结果相比,该异构选择性出乎意料地高。
表2:使用八氟甲苯溶剂的丙烯加氢甲酰化,使用(轴安定,R,R,R)-1配体
Ex. | 溶剂 | 温度(℃) | 压力(atm) | 时间(hr) | TON | 异构体% |
10 | 八氟甲苯 | 50 | 8 | 16 | 788 | 76.7 |
11 | 八氟甲苯 | 75 | 8 | 1 | 490 | 73.4 |
12 | 八氟甲苯 | 75 | 20 | 1 | 1020 | 58.8 |
13 | 八氟甲苯 | 90 | 8 | 1 | 550 | 64.7 |
14 | 八氟甲苯 | 90 | 20 | 1 | 1447 | 55.1 |
L:Rh=1.25:1
表3:使用全氟苯基辛基醚溶剂的丙烯加氢甲酰化,使用(轴安定,R,R,R)-1配体
Ex. | 溶剂 | 温度(℃) | 压力(atm) | 时间(hr) | TON | 异构体% |
15 | 全氟苯基辛基醚 | 90 | 20 | 1 | 1257 | 66.7 |
16 | 全氟苯基辛基醚 | 75 | 20 | 1 | 674 | 70.3 |
17 | 全氟苯基辛基醚 | 50 | 8 | 16 | 608 | 73.6 |
L:Rh=1.25:1
表4:使用烃类溶剂进行丙烯加氢甲酰化,使用(轴安定,R,R,R)-1配体
Ex. | 溶剂 | 温度(℃) | 压力(atm) | 时间(hr) | TON | 异构体% |
18 | 正壬烷 | 50 | 8 | 16 | 624 | 70.4 |
19 | 正壬烷 | 90 | 20 | 1 | 1150 | 61.7 |
20 | 正癸烷 | 50 | 8 | 16 | 641 | 70.8 |
21 | 正癸烷 | 90 | 20 | 1 | 1335 | 54.2 |
22 | 正十一烷 | 50 | 8 | 16 | 640 | 70.8 |
23 | 正十一烷 | 75 | 8 | 1 | 442 | 66.4 |
24 | 正十一烷 | 75 | 20 | 1 | 680 | 68.3 |
25 | 正十一烷 | 82 | 20 | 1 | 887 | 66.7 |
26 | 正十一烷 | 90 | 8 | 1 | 508 | 61.2 |
27 | 正十一烷 | 90 | 20 | 1 | 1276 | 62.7 |
28 | 正十二烷 | 50 | 8 | 16 | 675 | 70.3 |
29 | 正十二烷 | 90 | 20 | 1 | 1497 | 60.1 |
L:Rh=1.25:1
(轴安定,R,R,R)-1配体1是对映体纯的,因此需要长时间合成和分离对映体,因为其被设计用于前手性烯烃的加氢甲酰化。对于非手性丙烯,非对映体纯的配体在经济上将具有吸引力。设计了具有降低的手性元素的配体1衍生物以降低合成成本。
配体2和3衍生自二醇,其并非使用具有轴向手性的单一对映异构体——如在配体1中描述为轴安定[atropos](tropos[轴不安定]为希腊文翻转[to turn];atropos[轴安定]—不翻转[not to turn]),而是使用构型不稳定的轴不安定二醇。由于对映体的拆分不是必需的,这种类型的二醇可以以显著更低的成本来得到,并且更容易获得。(轴不安定,反式)-2和(轴不安定,反式)-3不仅含有衍生自非手性二醇的亚磷酸酯单元,而且以磷杂环戊烷环(phospholane ring)为特征,该环是单一的反式非对映异构体,但有外消旋性(即(R,R)/(S,S)),进一步降低了成本并提高合成的可及性。测试了这些配体(配体2和3)的不同异构体,结果示于表5和表6中。
当在作为溶剂的八氟甲苯或全氟苯基醚或烃中使用时,不是对映体纯的配体(配体2和3)也给出高的异构选择性,在下表5和表6中,证明:或者异构选择性随温度升高而增加,或者TON随温度升高而增加。
表5:使用配体2和3的丙烯加氢甲酰化,使用1.25:1的L:Rh
L:Rh=1.25:1
表6:使用配体2和3的丙烯加氢甲酰化,使用2:1的L:Rh
如表7所示,当在作为溶剂的烃中使用时,非对映体纯(diasteromerically pure)但外消旋的混合物配体((轴安定,R,R,R)-1/(轴安定,S,S,S)-1)也给出高异构选择性。
表7:使用((轴安定,R,R,R)-1/(轴安定,S,S,S)-1)配体的丙烯加氢甲酰化
L:Rh=1.25:1
下面进一步描述利用本文所公开的配体的加氢甲酰化反应的实例,以及本文所述的多种配体的合成和化学结构。
所有操作是使用标准Schlenk技术在氮气或氩气的惰性气氛下进行的。从溶剂蒸馏器或SPS溶剂纯化系统中得到干燥的且脱气的溶剂。在用之前,将三乙胺和CDCl3干燥并脱气。直到使用之前,才对正戊醛、氯苯、甲苯、八氟甲苯、全氟苯基辛基醚、正壬烷、正癸烷、正十一烷、正十二烷、2,2,4-三甲基-1,3-戊二醇单异丁酸酯进行脱气。除非另有说明,所有化学品均以商购获得并按原样使用。从BOC获得预混合的CO/H2(1:1)和丙烯/CO/H2(10:45:45)。
在Bruker Advance 300、400或500MHz仪器上记录NMR光谱。质子化学位移参照内部残留溶剂质子。碳化学位移参照氘化溶剂的碳信号。信号的多重性以s(单峰)、d(双峰)、t(三重峰)、q(四重峰)、m(多重峰)、br.s(宽单峰)或以上的组合给出。其中合适的偶合常数(J)以Hz表示,并以精确到0.1Hz来记录。在室温下记录所有光谱,并在括号中给出用于光谱的溶剂。在惰性气氛下,在干燥的且脱气的溶剂中记录含磷化合物的NMR。
质谱分析法在Micromass GCT光谱仪、Micromass LCT光谱仪、Waters(沃特世)ZQ4000、Thermofisher(赛默飞世尔)LTQ Orbitrap(轨道离子阱)XL或Finnigan MAT900XLT仪器上进行。
气相色谱法在Agilent Technologies(安捷伦科技)7820A机器上进行。
快速柱色谱法使用Merck(默克)Geduran Si 60(40-63μm)硅胶或Sigma Aldrich(西格玛奥德里奇)活化的中性Brockmann I氧化铝,在惰性气氛下使用干燥的且脱气的溶剂进行。
使用POLYGRAM SIL G/UV254或POLYGRAM ALOX N/UV254塑料板进行薄层色谱(thin layer chromatographic,TLC)分析。TLC板使用UV显影仪显影,或使用高锰酸钾浸染然后温和加热来染色。预备TLC是在具有荧光指示剂254nm在氧化铝玻璃板上进行的。
加氢甲酰化的一般程序:
加氢甲酰化反应是在Parr 4590微型台式反应器(Micro Bench Top Reactors)中进行的,Parr 4590微型台式反应器有0.1L的体积容量、具有气体夹带头(设定为1200RPM)的顶置式搅拌器、温度控制器、压力计以及与气瓶连接的能力。
在每个实验中遵循以下一般程序。
通过将10.0mg[Rh(acac)(CO)2]溶解在5.0mL甲苯中制备[Rh(acac)(CO)2]储备溶液。
在Schlenk烧瓶中,在N2(或氩气)下,将合适的配体(6.40μmol或10.24μmol)与0.65mL铑催化剂溶液(含有5.12μmol来自上述储备溶液的[Rh(acac)(CO)2])和内标物(1-甲基萘)(0.1mL)一起溶解在19.35mL的合适的溶剂中,以产生如下摩尔比:Rh:配体为1:1.25,或Rh:配体为2。
将空的高压釜密封,并用5-10atm合成气(CO/H2,1:1)冲洗3次,每次释放至1atm。然后通过进样口来加入20mL来自Schlenk烧瓶的溶液。通过在表1-7中规定的反应温度和压力下搅拌,使用合成气来活化所得的催化剂溶液一小时。释放高压釜压力,并用丙烯/CO/H2(10:45:45)气体混合物来重新加压。将反应在反应温度下保持搅拌表中规定的时间长度。反应完成后,将反应器冷却至室温,并释放反应器压力。然后通过气相色谱法(GC)分析样品,其中两种异构体都用1-甲基萘作为内标物进行了校准。GC结果被用于测定TOF(或反应时间超过一小时时的TON)和异构选择性,即异丁醛占总的丁醛产物的百分比。
配体合成:
(轴安定,R,R,R)-1配体是按照文献程序(Noonan,Fuentes,Cobley,Clarke,Angew.Chem.Int.Ed.2012,51,2477)合成的,在此将该文献全文引入作为参考。
合成3,3'-二叔丁基-5,5'-二甲氧基-[1,1'-联苯]-2,2'-二醇5:
将可商购的2-(叔丁基)-4-甲氧基苯酚4(2.00g,11.10mmol)溶解在甲醇(60mL)中。向其中缓慢加入氢氧化钾(1.25g,22.19mmol)和铁氰化钾(3.65g,11.10mmol)的水(60mL)溶液,超过1小时。加入后,将该反应在室温下搅拌1小时。将反应混合物在乙酸乙酯(100mL)和水(40mL)之间分配。收集有机产物,水层用乙酸乙酯洗涤(2×50mL)。将乙酸乙酯/甲醇中的有机产物合并,用盐水洗涤,用硫酸镁干燥并真空浓缩。用己烷洗涤所得固体以提供化合物5,化合物5为白色固体(1.31g,3.65mmol,66%)。1H NMR(CDCl3,400MHz)δ6.99(d,J=3.1Hz,2H,2×Ar-H),6.66(d,J=3.1Hz,2H,2×Ar-H),5.07(s,2H,2×OH),3.80(s,6H,2×O-CH3),1.46(s,18H,2×C(CH3)3)。13C NMR(CDCl3,101MHz)δ153.20(s,2C,2×ArC-OCH3),145.90(s,2C,2×ArC-OH),138.94(s,2C,2×ArC-C(CH3)3),123.21(s,2C,2×ArC-ArC),115.28(s,2C,2×ArCH),111.75(s,2C,2×ArCH),55.75(s,2C,2×O-CH3),35.19(s,2C,2×C(CH3)3),29.51(s,6C,2×C(CH3)3)。HRMS(ES+)C22H30O4-[M+Na]+m/z:发现381.2028,需要381.2042。
(反式-外消旋)-6和(R,R)-6是按照文献程序(Noonan,Fuentes,Cobley,Clarke,Angew.Chem.Int.Ed.2012,51,2477)合成的。
合成硼烷保护的-(内消旋)-2,5-二苯基磷杂环戊烷10,(内消旋)-10:
化合物(内消旋)-10是按照以下文献程序(L.Hintermann,M.Schmitz,O.V.Maltsev,P.Naumov,Synthesis,2013,45,308-325)合成的,在此将该文献全文引入作为参考。
除非另有说明,否则该程序在Ar下进行。将化合物(内消旋)-9(0.66g,2.43mmol)悬浮于甲苯(10mL)中,加入苯基硅烷(0.52g,4.86mmol),并将混合物加热回流16小时。使反应冷却至室温,加入硼烷二甲基硫醚络合物(0.23mL,2.43mmol),并将反应在室温下保持搅拌24小时。将反应混合物通过硅胶短垫[short pad of silica gel](硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体。粗产物通过硅胶柱色谱纯化(硅胶60,40-63μm),使用0-5%乙醚的己烷溶液作为洗脱剂以提供化合物(内消旋)-10,(内消旋)-10为白色固体(0.31g,1.20mmol,49%)。1H NMR(CDCl3,500MHz)δ9.71(s,1H,POOH),7.26–7.08(m,10H,Ar-H),3.33–3.02(m,2H,2×P-CH-Ar),2.45–2.18(m,4H,2×CH-CH2)。13C NMR(101MHz,CDCl3)δ135.90(s,2C,ArC),128.36(s,2C,ArCH),128.35(s,2C,ArCH),128.14(s,2C,ArCH),128.09(s,2C,ArCH),126.57(s,ArCH),126.55(s,ArCH),43.18(d,J=86.0Hz,2C,CH-P),27.95(s,CH-CH2),27.80(s,CH-CH2)。31P{1H}NMR(CDCl3,126MHz)δ68.0。
合成硼烷保护的-((内消旋)-2,5-二苯基磷杂环戊-1-基)甲醇6,(内消旋)-6:
化合物(内消旋)-6是按照以下文献程序(L.Hintermann,M.Schmitz,O.V.Maltsev,P.Naumov,Synthesis,2013,45,308-325)合成的。
将化合物(内消旋)-10(0.31g,1.20mmol)和多聚甲醛(0.43,14.43mmol)悬浮于甲醇(15mL)中。缓慢加入氢氧化钾(0.24g,4.21mmol)的甲醇(15mL)溶液。将反应混合物在室温下保持搅拌16小时。将反应混合物在乙酸乙酯(100mL)和水(100mL)之间分配。收集有机产物,水层用乙酸乙酯(2×50mL)洗涤。将乙酸乙酯/甲醇中的有机产物合并,用盐水洗涤,用硫酸镁干燥并真空浓缩。粗产物通过硅胶柱色谱纯化(硅胶60,40-63μm),使用20%己烷的二氯甲烷溶液作为洗脱剂,以提供化合物(内消旋)-6,(内消旋)-6为白色固体(0.25g,0.89mmol,89%)。1H NMR(CDCl3,400MHz)δ7.52–7.26(m,10H,Ar-H),3.84(q,J=7.8,7.0Hz,2H,O-CH2-P),3.38(s,2H),2.87–2.66(m,2H,2×P-CH-Ar),2.51(m,2.7Hz,2H,2×Ar-CH-CH2),0.64(s,3H,BH3)。13C NMR(CDCl3,101MHz)δ136.11(s,ArC),136.06(s,ArC),129.02(m,4C,ArCH),127.39(m,6C,ArCH),56.21(d,J=28.3Hz,O-CH2-P),44.13(d,J=26.8Hz,2C,CH-P),31.37(s,2C,CH-CH2)。31P{1H}NMR(CDCl3,126MHz)δ49.2(d,J=61.9Hz)。
合成4,8-二叔丁基-6-(((内消旋)-2,5-二苯基磷杂环戊-1-基)甲氧基)-2,10-二甲氧基二苯并[d,f][1,3,2]二氧杂磷杂庚环2,(轴不安定,内消旋)-2
除非另有说明,否则该程序在Ar下进行。将二酚5(0.20g,0.56mmol)悬浮于甲苯(7mL)中,加入三乙胺(0.19mL,1.35mmol)。然后将溶液冷却至0℃,然后缓慢加入三溴化磷(0.06mL,0.68mmol)的甲苯(4mL)溶液。将反应在室温下保持搅拌16小时。通过套管过滤出难溶盐,并将滤液真空浓缩。将所得固体溶在甲苯(5mL)中,并加入到化合物(内消旋)-6(0.16g,0.56mmol)的甲苯(5mL)溶液中。缓慢加入1,4-二氮杂双环[2.2.2]辛烷(0.32g,2.82mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。将反应混合物通过硅胶短垫(硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体。粗产物通过硅胶柱色谱和接下来的预备TLC纯化,其中,硅胶柱色谱(硅胶60,40-63μm,用95:5的甲苯:三乙胺溶液预处理)是在N2下用0-10%乙醚的己烷溶液作为洗脱剂,预备TLC是氧化铝在玻璃板上(中性)且使用15%乙醚的己烷溶液作为洗脱剂;从而提供化合物(轴不安定,内消旋)-2,(轴不安定,内消旋)-2为白色固体(0.12g,0.19mmol,33%)。1H NMR(CDCl3,500MHz)δ7.27–7.20(m,8H,Ar-H),7.19–7.11(m,2H,Ar-H),6.87(d,J=3.1Hz,2H,Ar-H),6.61(d,J=3.1Hz,2H,Ar-H),3.86(s,6H,2×O-CH3),3.75(m,2H,2×O-CH2-P),3.62(d,J=5.7Hz,2H,2×Ar-CH-CH2),2.34(m,4H,2×Ar-CH-CH2),1.34(s,18H,6×CH3)。13C NMR(CDCl3,101MHz)δ155.17(s,2C,ArC-OCH3),142.22(m,2C,ArC-O-P),141.93(s,2C,ArC-CCH3),138.98(s,2C,ArC),133.12(m,2C,ArC-CH-P),128.48(s,4C,ArCH),127.39(s,2C,ArCH),127.35(s,2C,ArCH),125.96(s,2C,ArCH),114.41(s,2C,ArCH),112.49(s,2C,ArCH),58.84(d,J=19.8Hz,O-CH2-P),55.53(s,2C,OCH3),46.04(d,J=16.9Hz,2C,CH-P),35.23(s,2C,ArC-C(CH3)3),31.87(m,2C,CH-CH2),30.77(s,6C,ArC-C(CH3)3)。31P{1H}NMR(CDCl3,126MHz)δ133.1(s);6.1(s)。HRMS(ES+)C39H46O5P2-[M+H]+m/z:发现657.2886,需要657.2899。
合成4,8-二叔丁基-6-(((反式)-2,5-二苯基磷杂环戊-1-基)甲氧基)-2,10-二甲氧基二苯并[d,f][1,3,2]二氧杂磷杂庚环2,(轴不安定,反式)-2:
除非另有说明,否则该程序在Ar下进行。将双酚5(0.33g,0.91mmol)悬浮于甲苯(5mL)中,并加入三乙胺(0.38mL,2.74mmol)。然后,将该溶液冷却至0℃,之后缓慢加入三溴化磷(0.10mL,1.10mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。通过套管过滤出难溶盐,并将滤液真空浓缩。将所得固体溶在甲苯(5mL)中,并加入到化合物(反式-外消旋)-6(0.28g,0.99mmol)的甲苯(5mL)溶液中。缓慢加入1,4-二氮杂双环[2.2.2]辛烷(0.56g,4.95mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。将反应混合物通过硅胶短垫(硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体。粗产物通过硅胶柱色谱和接下来的预备TLC纯化,其中硅胶柱色谱(硅胶60,40-63μm,用95:5的甲苯:三乙胺溶液预处理)是在N2下用0-20%乙醚的己烷溶液作为洗脱剂,预备TLC是氧化铝在玻璃板上(中性)且使用20%乙醚的己烷溶液作为洗脱剂;从而提供化合物(轴不安定,反式)-2,(轴不安定,反式)-2为白色固体(0.10g,0.16mmol,17%)。1H NMR(CDCl3,500MHz)δ7.36–7.17(m,10H,Ar-H),6.98(dd,J=10.8,3.1Hz,2H,Ar-H),6.73(dd,J=10.8,3.1Hz,2H,Ar-H),3.92–3.80(m,8H,2×O-CH3,P-CH2-O),3.69–3.60(m,2H,2×P-CH-Ar),2.64–2.55(m,1H,Ar-CH-CH2),2.37–2.29(m,2H,Ar-CH-CH2),2.00–1.84(m,1H,Ar-CH-CH2),1.42(s,9H,3×CH3),1.38(s,9H,3×CH3)。13C NMR(CDCl3,126MHz)δ155.57(s,ArC-OCH3),155.47(s,ArC-OCH3),144.15(s,ArC-CCH3),144.01(s,ArC-CCH3),142.14(m,2C,ArC-O-P),138.04(m,2C,ArC-CH-P),133.49(m,ArC),133.34(m,ArC),128.48(m,4C,ArCH),127.94(s,ArCH),127.87(s,ArCH),127.42(s,ArCH),127.39(s,ArCH),125.88(m,2C,ArCH),114.55(s,ArCH),114.37(s,ArCH),112.74(s,ArCH),112.54(s,ArCH),62.31(d,J=29.0Hz,O-CH2-P),55.59(s,2C,OCH3),46.10(d,J=13.6Hz,CH-P),45.78(d,J=15.5Hz,CH-P),36.74(s,CH-CH2),35.32(s,2C,ArC-CCH3),32.80(s,CH-CH2),30.84(s,6C,ArC-CCH3)。31P{1H}NMR(CDCl3,126MHz)δ136.6(s);9.7(s)。HRMS(ES+)C39H46O5P2-[M+H]+m/z:发现657.2888,需要657.2899。
合成4,8-二叔丁基-6-(((2R,5R)-2,5-二苯基磷杂环戊-1-基)甲氧基)-2,10-二甲氧基二苯并[d,f][1,3,2]二氧杂磷杂庚环2,(轴不安定,R,R)-2:
除非另有说明,否则该程序在Ar下进行。将双酚5(0.75g,2.10mmol)悬浮于甲苯(10mL)中,加入三乙胺(0.97mL,6.93mmol)。然后将溶液冷却至0℃,然后缓慢加入三溴化磷(0.30mL,3.15mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。通过套管过滤出难溶盐,并将滤液真空浓缩。将所得固体溶在甲苯(5mL)中,并加入到化合物(R,R)-6(0.42g,1.47mmol)的甲苯(5mL)溶液中。缓慢加入1,4-二氮杂双环[2.2.2]辛烷(0.82g,7.35mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。将反应混合物通过硅胶短垫(硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体。粗产物通过硅胶柱色谱和接下来的预备TLC纯化,其中,硅胶柱色谱(硅胶60,40-63μm,用95:5的甲苯:三乙胺溶液预处理)是在N2下用0-20%乙醚的己烷溶液作为洗脱剂,预备TLC是氧化铝在玻璃板上(中性)且使用10%乙醚的己烷溶液作为洗脱剂;从而提供化合物(轴不安定,R,R)-2,(轴不安定,R,R)-2为白色固体(0.20g,0.31mmol,21%)。1H NMR(CDCl3,500MHz)δ7.37–7.17(m,10H,Ar-H),6.98(dd,J=8.8,3.1Hz,2H,Ar-H),6.74(dd,J=8.8,3.1Hz,2H,Ar-H),3.93–3.80(m,8H,2×O-CH3,P-CH2-O),3.71–3.59(m,2H,2×P-CH-Ar),2.66–2.54(m,1H,Ar-CH-CH2),2.38–2.29(m,2H,Ar-CH-CH2),2.01–1.87(m,1H,Ar-CH-CH2),1.42(s,9H,3×CH3),1.38(s,9H,3×CH3)。13C NMR(CDCl3,101MHz)δ155.54(s,ArC-OCH3),155.45(s,ArC-OCH3),144.15(s,ArC-CCH3),143.98(s,ArC-CCH3),142.13(m,2C,ArC-O-P),138.03(m,2C,ArC-CH-P),133.48(s,ArC),133.34(s,ArC),128.46(m,4C,ArCH),127.93(s,ArCH),127.85(s,ArCH),127.41(s,ArCH),127.37(s,ArCH),125.86(m,2C,ArCH),114.53(s,ArCH),114.35(s,ArCH),112.74(s,ArCH),112.53(s,ArCH),62.28(d,J=29.1Hz,O-CH2-P),55.60(s,2C,OCH3),46.09(d,J=13.6Hz,CH-P),45.76(d,J=15.5Hz,CH-P),36.72(s,CH-CH2),35.33(s,2C,ArC-C(CH3)3),32.79(s,CH-CH2),30.80(s,6C,ArC-C(CH3)3)。31P{1H}NMR(CDCl3,126MHz)δ136.6(s);9.7(s)。HRMS(ES+)C39H46O5P2-[M+H]+m/z:发现657.2884,需要657.2899。
合成3,3'-二叔丁基-5,5'-二甲基-[1,1'-联苯]-2,2'-二醇8:
将市售2-(叔丁基)-4-甲基苯酚7(1.63g,9.93mmol)溶于庚烷(10mL)。向其中加入氧化锰(1.15g,13.24mmol),并将混合物加热回流1.5小时。将反应混合物通过赛力特(celite)过滤,并将滤液真空浓缩。粗产物通过硅胶柱色谱(硅胶60,40-63μm)纯化,硅胶柱色谱使用10%乙醚的己烷溶液作为洗脱剂,以提供化合物8,化合物8为淡黄色固体(1.02g,3.13mmol,63%)。1H NMR(CDCl3,400MHz)δ7.20(d,J=2.1Hz,2H,2×Ar-H),6.95(d,J=2.1Hz,2H,2×Ar-H),5.23(s,2H,2×OH),2.36(s,6H,2×Ar-CH3),1.49(s,18H,2×Ar-C(CH3)3)。13C NMR(CDCl3,101MHz)δ149.87(s,2C,2×ArC-OH),136.91(s,2C,2×ArC-C(CH3)3),129.57(s,2C,2×ArC-CH3),128.78(s,2C,2×ArCH),128.48(s,2C,2×ArCH),122.57(s,2C,2×ArC-ArC),34.93(s,2C,2×C(CH3)3),29.66(s,6C,2×C(CH3)3),20.84(s,2C,2×Ar-CH3)。HRMS(ES+)C22H30O2-[M-H]-m/z:发现325.2171,需要325.2173。
合成4,8-二叔丁基-6-(((2R,5R)-2,5-二苯基磷杂环戊-1-基)甲氧基)-2,10-二甲基二苯并[d,f][1,3,2]二氧杂磷杂庚环3(轴不安定,R,R)-3:
除非另有说明,否则该程序在Ar下进行。将双酚8(0.40g,1.23mmol)悬浮于甲苯(10mL)中,加入三乙胺(0.64mL,4.62mmol)。然后将溶液冷却至0℃,然后缓慢加入三溴化磷(0.17mL,1.85mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。通过套管过滤出难溶盐,并将滤液真空浓缩。将所得固体溶在甲苯(5mL)中,并加入到化合物(R,R)-6(0.35g,1.23mmol)的甲苯(5mL)溶液中。缓慢加入1,4-二氮杂双环[2.2.2]辛烷(0.69g,6.15mmol)的甲苯(10mL)溶液。将反应在室温下保持搅拌16小时。将反应混合物通过硅胶短垫(硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体。粗产物通过预备TLC纯化,预备TLC是氧化铝在玻璃板上(中性)并用己烷作为洗脱剂,从而提供化合物(轴不安定,R,R)-3,(轴不安定,R,R)-3为白色固体(0.08g,0.12mmol,10%)。1H NMR(CDCl3,500MHz)δ7.36–7.15(m,12H,Ar-H),7.02–6.97(m,2H,Ar-H),3.89–3.83(m,2H,P-CH2-O),3.70–3.58(m,2H,2×P-CH-Ar),2.63–2.52(m,1H,P-CH-CH2),2.42(s,3H,Ar-CH3),2.39(s,3H,Ar-CH3),2.36–2.28(m,2H,P-CH-CH2),1.99–1.87(m,1H,P-CH-CH2),1.40(s,9H,C(CH3)3),1.38(s,9H,C(CH3)3)。13C NMR(CDCl3,101MHz)δ146.40(m,2C,ArC-O-P),144.25(s,ArC-CCH3),144.07(s,ArC-CCH3),140.31(s,ArC-CH-P),138.12(s,ArC-CH-P),133.28(s,ArC),133.14(s,ArC),132.73(s,2C,ArC-CH3),129.96(s,ArCH),129.87(s,ArCH),128.47(m,4C,ArCH),127.97(m,4C,ArCH),127.50(s,2C,ArCH),125.88(s,2C,ArCH),62.19(d,J=29.4Hz,O-CH2-P),46.18(d,J=13.7Hz,CH-P),45.63(d,J=15.4Hz,CH-P),36.73(s,CH-CH2),35.06(s,2C,ArC-C(CH3)3),32.83(s,CH-CH2),31.02(s,6C,ArC-C(CH3)3),21.22(s,2C,ArC-CH3)。31P{1H}NMR(CDCl3,126MHz)δ136.5(s);10.2(s)。HRMS(ES+)C39H46O3P2-[M+H]+m/z:发现625.2990,需要625.3000。
合成4,8-二叔丁基-6-(((反式)-2,5-二苯基磷杂环戊-1-基)甲氧基)-2,10-二甲基二苯并[d,f][1,3,2]二氧杂磷杂庚环3,(轴不安定,反式)-3:
除非另有说明,否则该程序在Ar下进行。将二酚8(0.24g,0.72mmol)悬浮于甲苯(7mL)中,加入三乙胺(0.24mL,1.73mmol)。然后将溶液冷却至0℃,然后缓慢加入三溴化磷(0.08mL,0.86mmol)的甲苯(4mL)溶液。将反应物在室温下保持搅拌16小时。通过套管过滤出难溶盐,并将滤液真空浓缩。将所得固体溶于甲苯(5mL)中,并加入到化合物(反式)-6(0.20g,0.72mmol)的甲苯(5mL)溶液中。缓慢加入1,4-二氮杂双环[2.2.2]辛烷(0.40g,3.60mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。将反应混合物通过硅胶短垫(硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体。粗产物通过硅胶柱色谱和接下来的预备TLC纯化,其中,硅胶柱色谱(硅胶60,40-63μm,用95:5的甲苯:三乙胺溶液预处理)是在N2下用己烷作为洗脱剂,预备TLC是氧化铝在玻璃板上(中性)且使用10%乙醚的己烷溶液作为洗脱剂;从而提供化合物(轴不安定,反式)-3,(轴不安定,反式)-3为白色固体(0.10g,0.15mmol,21%)。1H NMR(CDCl3,400MHz)δ7.40–7.33(m,4H,Ar-H),7.32–7.18(m,8H,Ar-H),7.05–7.02(m,2H,Ar-H),3.94–3.81(m,2H P-CH2-O),3.75–3.61(m,2H,2×P-CH-Ar),2.68–2.56(m,1H,P-CH-CH2),2.47–2.45(m,3H,Ar-CH3),2.44–2.41(m,3H,Ar-CH3),2.40–2.31(m,2H,P-CH-CH2),2.02–1.89(m,1H,P-CH-CH2),1.45(s,9H,C(CH3)3),1.42(s,9H,C(CH3)3)。13C NMR(CDCl3,101MHz)δ146.32(m,2C,ArC-O-P),144.26(s,ArC-CCH3),144.08(s,ArC-CCH3),140.31(m,ArC-CH-P),138.14(s,ArC-CH-P),133.29(s,ArC),133.15(s,ArC),132.75(m,2C,ArC-OCH3),129.98(s,2C,ArCH),129.89(s,2C,ArCH),128.48(m,4C,ArCH),127.99(m,4C,ArCH),127.51(s,ArCH),127.48(s,ArCH),125.89(s,ArCH),125.84(s,ArCH),62.22(d,J=29.4Hz,O-CH2-P),46.20(d,J=13.7Hz,CH-P),45.67(d,J=15.4Hz,CH-P),36.74(s,CH-CH2),35.08(s,2C,ArC-C(CH3)3),32.88(s,CH-CH2),31.05(s,6C,ArC-C(CH3)3),21.24(s,ArC-CH3),21.20(s,ArC-CH3)。31P{1H}NMR(CDCl3,126MHz)δ136.5(s);10.2(s)。HRMS(ES+)C39H46O3P2-[M+H]+m/z:发现625.2997,需要625.3000。合成4,8-二叔丁基-6-(((内消旋)-2,5-二苯基磷杂环戊-1-基)甲氧基)-2,10-二甲氧基二苯并[d,f][1,3,2]二氧杂磷杂庚环2,(轴不安定,内消旋)-2
除非另有说明,否则该程序在Ar下进行。将二酚5(0.20g,0.56mmol)悬浮于甲苯(7mL)中,加入三乙胺(0.19mL,1.35mmol)。然后将溶液冷却至0℃,然后缓慢加入三溴化磷(0.06mL,0.68mmol)的甲苯(4mL)溶液。将反应在室温下保持搅拌16小时。通过套管过滤出难溶盐,并将滤液真空浓缩。将所得固体溶于甲苯(5mL)中,并加入到化合物(内消旋)-6(0.16g,0.56mmol)的甲苯(5mL)溶液中。缓慢加入1,4-二氮杂双环[2.2.2]辛烷(0.32g,2.82mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。将反应混合物通过硅胶短垫(硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体。粗产物通过硅胶柱色谱和接下来的预备TLC纯化,其中,硅胶柱色谱(硅胶60,40-63μm,用95:5的甲苯:三乙胺溶液预处理)是在N2下用0-10%乙醚的己烷溶液作为洗脱剂,预备TLC是氧化铝在玻璃板上(中性)且使用15%乙醚的己烷溶液作为洗脱剂;从而提供化合物(轴不安定,内消旋)-2,(轴不安定,内消旋)-2为白色固体(0.12g,0.19mmol,33%)。1H NMR(CDCl3,500MHz)δ7.27–7.20(m,8H,Ar-H),7.19–7.11(m,2H,Ar-H),6.87(d,J=3.1Hz,2H,Ar-H),6.61(d,J=3.1Hz,2H,Ar-H),3.86(s,6H,2×O-CH3),3.75(m,2H,2×O-CH2-P),3.62(d,J=5.7Hz,2H,2×Ar-CH-CH2),2.34(m,4H,2×Ar-CH-CH2),1.34(s,18H,6×CH3)。13C NMR(CDCl3,101MHz)δ155.17(s,2C,ArC-OCH3),142.22(m,2C,ArC-O-P),141.93(s,2C,ArC-CCH3),138.98(s,2C,ArC),133.12(m,2C,ArC-CH-P),128.48(s,4C,ArCH),127.39(s,2C,ArCH),127.35(s,2C,ArCH),125.96(s,2C,ArCH),114.41(s,2C,ArCH),112.49(s,2C,ArCH),58.84(d,J=19.8Hz,O-CH2-P),55.53(s,2C,OCH3),46.04(d,J=16.9Hz,2C,CH-P),35.23(s,2C,ArC-C(CH3)3),31.87(m,2C,CH-CH2),30.77(s,6C,ArC-C(CH3)3)。31P{1H}NMR(CDCl3,126MHz)δ133.1(s);6.1(s)。HRMS(ES+)C39H46O5P2-[M+H]+m/z:发现657.2886,需要657.2899。
合成(轴安定,R,R,R)-1/(轴安定,S,S,S)-1混合物:
该方法改编自(Sax,S,S)-BOBPHOS的合成(P.Dingwall,J.A.Fuentes,L.Crawford,A.M.Z.Slawin,M.Bühl,M.L.Clarke,J.Am.Chem.Soc.,2017,139,15921)
除非另有说明,否则该程序在Ar下进行。将双酚11(为Rax/Sax混合物)(0.37g,1.06mmol)悬浮于甲苯(10mL)中,加入三乙胺(0.37mL,2.66mmol)。然后将溶液冷却至0℃,然后缓慢加入三溴化磷(0.12mL,1.27mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。通过套管过滤出难溶盐,并将滤液真空浓缩。将所得固体溶于甲苯(5mL)中,并加入到((反式)-2,5-二苯基磷杂环戊-1-基)甲醇6(为(R,R)/(S,S)混合物)(0.30g,1.06mmol)的甲苯(5mL)溶液中。缓慢加入1,4-二氮杂双环[2.2.2]辛烷(0.47g,4.23mmol)的甲苯(5mL)溶液。将反应在室温下保持搅拌16小时。将反应混合物通过硅胶短垫(硅胶60,40-63μm)过滤,用甲苯洗脱。将滤液真空浓缩以提供粗固体(为(Rax,R,R)/(Rax,S,S)/(Sax,R,R)/(Sax,S,S)异构体的等同混合物)。粗产物通过从庚烷中重结晶而纯化,以提供化合物(为(Rax,R,R)/(Sax,S,S)混合物),该化合物为白色固体(0.12g,0.16mmol,18%)。光谱数据与以前记录的(Sax,S,S)对映体的全部表征数据一致。(Noonan,Fuentes,Cobley,Clarke,Angew.Chem.Int.Ed.2012,51,2477)
Claims (5)
1.一种在加氢甲酰化温度和压力条件下制备至少一种醛的方法,所述方法包括:在至少一种溶剂和过渡金属基催化剂组合物的存在下,使至少一种烯烃与氢气和一氧化碳接触,所述过渡金属基催化剂组合物包括由以下通式表示的磷杂环戊烷亚磷酸酯配体或衍生自非手性双酚二醇组分的磷杂环戊烷亚磷酸酯配体,所述衍生自所述非手性双酚二醇组分的磷杂环戊烷亚磷酸酯配体选自以下配体(A)至(D),所述配体(A)至(D)由它们的通式表示:
其中所述至少一种溶剂是八氟甲苯或全氟苯基辛基醚或者其中所述至少一种溶剂选自正壬烷、正癸烷、正十一烷和正十二烷,
其中所述压力在2atm至80atm的范围内且所述温度在40至120摄氏度的范围内。
2.根据权利要求1所述的方法,其中,所述方法的产物具有55%至80%的异构选择性。
3.根据权利要求1所述的方法,其中,所述烯烃为丙烯。
4.根据权利要求1所述的方法,其中,所述过渡金属基催化剂为铑基催化剂。
5.一种用于权利要求1-4中任一项所述的方法的过渡金属基催化剂组合物,其包括衍生自非手性双酚二醇组分的磷杂环戊烷亚磷酸酯配体,其中,所述配体选自以下配体(A)至(D),所述配体(A)至(D)由它们的通式表示:
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- 2018-10-29 US US16/173,207 patent/US10351583B2/en active Active
- 2018-11-27 EP EP18830029.7A patent/EP3717494B1/en active Active
- 2018-11-27 WO PCT/US2018/062522 patent/WO2019108502A1/en unknown
- 2018-11-27 CN CN201880072696.5A patent/CN111315755B/zh active Active
Patent Citations (2)
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WO2012016147A2 (en) * | 2010-07-30 | 2012-02-02 | Dr. Reddy's Laboratories Ltd. | Ligands for selective asymmetric hydroformylation |
US20150258536A1 (en) * | 2014-03-17 | 2015-09-17 | Eastman Chemical Company | Phosphorous compounds useful as ligands and compositions and methods regarding them |
Non-Patent Citations (4)
Title |
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An Asymmetric Hydroformylation Catalyst that Delivers Branched Aldehydes from Alkyl Alkenes;Gary M. Noonan et al;《Angew. Chem. Int. Ed.》;20121231;第51卷;第2477-2480页 * |
Diastereoselective and Branched-Aldehyde-Selective Tandem Hydroformylation −Hemiaminal Formation: Synthesis of Functionalized Piperidines and Amino Alcohols;Rachael Pittaway et al;《Org. Lett.》;20171231;第19卷;第2845-2848页 * |
Rhodium/phospholane–phosphite catalysts give unusually high regioselectivity in the enantioselective hydroformylation of vinyl arenes;Gary M. Noonan et al;《Chem. Commun.》;20131216;第50卷;第1475-1477页 * |
Understanding a Hydroformylation Catalyst that Produces Branched Aldehydes from Alkyl Alkenes;Dingwall, Paul et al;《Journal of the American Chemical Society》;20171025;第139卷;第15921-15932页 * |
Also Published As
Publication number | Publication date |
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US20190161508A1 (en) | 2019-05-30 |
US10351583B2 (en) | 2019-07-16 |
WO2019108502A1 (en) | 2019-06-06 |
EP3717494B1 (en) | 2023-11-01 |
EP3717494A1 (en) | 2020-10-07 |
US10144751B1 (en) | 2018-12-04 |
CN111315755A (zh) | 2020-06-19 |
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