CN101331144B - 用于催化加氢甲酰基化和相关反应的四磷配体 - Google Patents

用于催化加氢甲酰基化和相关反应的四磷配体 Download PDF

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CN101331144B
CN101331144B CN2006800472010A CN200680047201A CN101331144B CN 101331144 B CN101331144 B CN 101331144B CN 2006800472010 A CN2006800472010 A CN 2006800472010A CN 200680047201 A CN200680047201 A CN 200680047201A CN 101331144 B CN101331144 B CN 101331144B
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X·张
Y·闫
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Abstract

四磷配体与过渡金属盐结合形成催化剂，该催化剂用于加氢甲酰基化、异构化-加氢甲酰基化、氢羧基化、氢氰化异构化-甲酰化、氢氨甲基化和类似的相关反应。

Description

用于催化加氢甲酰基化和相关反应的四磷配体
相关申请的交叉参考
本申请要求2005年12月15日提交的第60/750,733号临时专利申请的优选权，该临时申请在此引入作为参考。
发明领域
本发明涉及新的磷配体和它们在加氢甲酰基化及相关反应中的应用。更特别地，本发明涉及具有多螯合模式的螯合四磷配体的过渡金属复合物。具有多螯合模式的四磷配体可以增强过渡金属如Rh和Ni的配位能力，且因此增强催化反应的选择性。根据本发明的过渡金属-四磷复合物作为催化剂在加氢甲酰基化、异构化-加氢甲酰基化、氢羧基化、氢氰化、级联的反应如异构化-甲酰化、和氢氨甲基化中是有用的。
发明背景
1938年被Roelen发现的加氢甲酰基化已经是工业中最大的均相催化方法。每年已经生产出超过150亿磅基于Fe、Zn、Mn、Co、Cu、Ag、Ni、Pt、Pd、Rh、Ru和Ir基催化剂的醛和醇。在这些方法中，实现对直链产物的高选择性对于工业应用来说是极其重要的。尽管在学术上和工业集团如BASF、Dow、Shell和Eastman等有广泛的研究，关于选择性仍然存在根本的和实用的问题。在催化反应中对于控制选择性的新概念是非常重要的。高效选择催化剂使得一些大体积化学品在较温和的条件下以环境合理的方式生产。
钴催化剂(例如，HCo(CO)4)占据了工业的加氢甲酰基化直到20世纪70年代早期引入铑催化剂(例如，HRh(CO)2(PPh3)3)。在2004年，估计大约所有加氢甲酰基化方法中的75％基于三芳基磷铑催化剂。对于加氢甲酰基化和相关反应而言，实现对直链醛的高区域选择性是关键的。得到的醛转化为用作增塑剂、洗涤剂、表面活性剂、溶剂、滑润剂和化学中间体的醇、羧酸或者其他衍生物。
下面的流程图1表示Rh催化的加氢甲酰基化催化剂的离解。
HRh(CO)(PPh3)2技术的成功工业化是基于在Union Carbide的Pruett和在Union oil的Booth的重大发现，该重大发现即利用铑与过量的膦配体可以导致形成具有活性的、选择性的加氢甲酰基化催化剂。过量膦的需要是由于如流程图1所示的在催化系统中Rh-PPh3的易离解。PPh3从HRh(CO)(PPh3)2中的损失导致更有活性但较低区域选择性的加氢甲酰基化催化剂B和C。在工业方法中，对Rh高达820倍过量的PPh3用于1-己烯加氢甲酰基化，以确保高直链：支链选择性比率，即高达17∶1。在丙烯工业加氢甲酰基化中，已经进行对Rh过量400倍的PPh3，实现了直链：支链选择性比率为8-9∶1。
Ph/PPh3催化的加氢甲酰基化是制作所有含氧的醇的关键。丙烯是加氢甲酰基化产生丁醛的最大单烯烃，它能够被氢化产生丁醇，或者通过羟醛缩合使其二聚，然后被氢化形成2-乙基-1-己醇，2-乙基-1-己醇即通过加氢甲酰基化产生的最大的单产物(超过一年50亿磅)。2-乙基-1-己醇通常与邻苯二甲酸酐反应，产生邻苯二甲酸二烷基酯，其被用作增塑剂来保持聚氯乙烯塑料柔软和具有挠性。
在加氢甲酰基化方法中，获得较便宜的原料作为起始材料是重要的。例如，内高级烯烃(SHOP烯烃)如3-辛烯在将烯烃转化为直链醛上是期望的。残油液II(正-丁烯/丁烷的混合物)和1-丁烯和2-丁烯的混合物的直接使用对于加氢甲酰基化是有用的。对于正-烯烃的加氢甲酰基化，得到高直链选择性是重要的。烯丙醇的加氢甲酰基化和随后的还原可以生成1，4丁烯醇。功能化的内烯烃可以用作聚合物双功能构建嵌段的可替代的途径。3-戊烯酸甲酯的加氢甲酰基化导致制得聚酰胺和聚酯的起始材料。在级联-异构化(tandem-isomerization)和加氢甲酰基化的方法中，结合了对于末端醛高选择性的高异构化速率对于共轭化合物的最小化不期望的加氢反应和最小异构化是期望的。
为了克服在加氢甲酰基化方法中利用大量过量膦的需要和实现高的区域选择性，开发了利用双膦配体的新一代过渡金属催化剂。例如，EastmanChemical的Bisbi；Prof.Leeuwen的Xantphos(University of Amsterdam)，Bernhard Breit，Acc.Chem Res.2003，36，264-275，Bemhard Breit，WolfgangSeihe，Synthesis 2001，1，1-36)；和Union Carbide的UC-44。这些配体说明如下。
Figure GYZ000004454115800031
通过利用这些配体，通常400倍过量的PPh3已经被减少至5倍过量的螯合膦。该新一代的螯合膦已经导致高直链：支链比率以及较高的催化活性。例如，已经观察到1-己烯的加氢甲酰基化中直链对支链的比率为70-120∶1。Casey和van Leeuwen提出，在Rh-催化的加氢甲酰基化中的部分区域选择性是由于形成大约120度的金属双膦咬角，即“咬角假设(Bite angle hypothesis)”，说明如下。
Figure GYZ000004454115800041
尽管大量手性双磷配体被用作加氢甲酰基化和相关反应的催化剂，对加氢甲酰基化高选择性和活性的磷配体仍然是强烈研究兴趣的领域。然而，由于从Rh-CO配位离解膦是实现高区域选择性即生产高直链对支链比率产物的问题。开发有多螯合配位模式的磷配体家族是有吸引力的。本发明的四磷配体，由于它们通过多螯合配位模式的配位能力，导致在金属配体催化加氢甲酰基化和相关反应中高区域选择性的转化以提供比以前得到的更高的直链对支链比率。还有，这些配体的对称性质使得这些配体容易制备。
发明概述
在本发明中，我们引入如下所示的具有多螯合配位模式的各种各样的四磷配体(A型)以增强配位能力：
Figure GYZ000004454115800051
其中M是金属，选自Fe、Zn、Mn、Co、Cu、Ag、Ni、Pt、Pd、Rh、Ru和Ir；X选自O、NH、NR和CH2；Y选自Ar、OAr和吡咯；R是有机基团且Ar是芳基团。A型配体是本发明的四磷配体。B型配体是双磷配体。如下所示，四磷配体(A型)具有至少四种螯合配位模式以增强配位能力，而双磷配体(B型)具有一种单一模式，即，P1-M-P2。
Figure GYZ000004454115800052
与通常的双磷配体(B型)相比，本发明的多螯合四磷配体(A型)增强了配体的配位能力而没有配体电性能的主要改变。
发明详述
本发明涉及将具有多螯合配位模式的四磷配体作为催化剂用于加氢甲酰基化和相关反应。利用本发明四磷配体制备的过渡金属催化剂具有高活性和区域选择性。本发明的四磷配体具有以下通式结构：
Figure GYZ000004454115800061
其中i、j、k、l、m和n独立地是H、R、Ar、取代的Ar、OR、OAr、COOEt、卤化物、SO2R、SO3H、SO2NHR、POR2、POAr2或者NR2，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基；X1-X4独立地是R、Ar、OR、OAr、吡咯或者取代的吡咯，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基；Y1、Y1′、Y2、Y2′、Y3、Y3′、Y4、Y4′独立地是R、Ar、OR、OAr、吡咯或者取代的吡咯，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基，或者其中R、Ar、OR、OAr、吡咯或者取代的吡咯与碳-碳键、CH2、NH、NR和O相连接。取代的基团将包括，例如，甲基、乙基、叔-丁基和苯基。
下面说明本发明的第一个实施方案：
其中X是O、CH2、NH、NR、NSO2R或者NSO2Ar，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基；a、b、c、d、i、j、k、l、m和n独立地是H、烷基、芳基、取代的烷基、取代的芳基、OR、OAr、SiR3、CF3、COOR、SO3R、SO3H、POR2、卤化物，或者a、b、c、d、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基。
本发明的第二个实施方案说明如下：
Figure GYZ000004454115800071
其中X是O、CH2、NH、NR、NSO2R或者NSO2Ar，其中R是烷基、取代的烷基、芳基或者取代的芳基；且Ar是芳基；a、b、c、d、e、f、i、j、k、l、m和n独立地是H、烷基、芳基、取代的烷基、取代的芳基、OR、OAr、SiR3、COOR、SO3R、SO3H、POR2、卤化物，或者a、b、c、d、e、f、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基。
本发明的第三个实施方案说明如下：
其中X是O、CH2、NH、NR、NSO2R或者NSO2Ar，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基；a、b、c、d、e、i、j、k、l、m和n独立地是H、烷基、芳基、取代的烷基、取代的芳基、OR、OAr、SiR3、CF3、COOR、SO3R、SO3H、POR2、卤化物、NR2，或者a、b、c、d、e、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基。
本发明的第四实施方案说明如下：
Figure GYZ000004454115800081
其中X是O、CH2、NH、NR、NSO2R或者NSO2Ar，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基；Y是碳-碳键、O、CH2、NH或者NR，其中R是烷基、取代的烷基、芳基或者取代的芳基；a到n独立地是H、烷基、芳基、取代的烷基、取代的芳基、OR、OAr、SiR3、CF3、COOR、SO3R、SO3H、POR2、卤化物、NR2，或者a到n中的两个可以是环状的稠合环或者伸展的芳环，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基。
本发明的第五实施方案说明如下：
Figure GYZ000004454115800091
其中X是O、CH2、NH、NR、NSO2R或者NSO2Ar其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基；a、b、c、d、e、i、j、k、l、m和n独立地是H、烷基、芳基、取代的烷基、取代的芳基、OR、OAr、SiR3、CF3、COOR、SO3R、SO3H、POR2、卤化物、NR2，或者a、b、c、d、e、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基。
本发明的第六实施方案说明如下：
Figure GYZ000004454115800092
其中X是O、CH2、NH、NR、NSO2R或者NSO2Ar，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基；a到n独立地是H、烷基、芳基、取代的烷基、取代的芳基，OR、OAr、SiR3、CF3、COOR、SO3R、SO3H、POR2、卤化物、NR2，或者a到n中的两个可以是环状的稠合环或者伸展的芳环，其中R是烷基、取代的烷基、芳基或者取代的芳基且Ar是芳基。当d和e不是氢时，这些配体的对映异构体可以为不对称的催化反应制备。
本发明的四磷配体的实例(L1-L91)说明如下：
Figure GYZ000004454115800101
Figure GYZ000004454115800111
Figure GYZ000004454115800121
Figure GYZ000004454115800151
X＝H、SiMe3、Br、I、COOEt、CF3、Ph、取代的芳基
Figure GYZ000004454115800152
R′＝H、烷基、芳基
Figure GYZ000004454115800161
Y＝Br、Me、iPr、tBu    R′＝H、烷基、芳基，Y＝Br、Me、iPr、tBu
Figure GYZ000004454115800171
Figure GYZ000004454115800181
在加氢甲酰基化或者相关的反应中，过渡金属-四磷配体复合物通过混合过渡金属盐和配体来制备。过渡金属盐是过渡金属的盐，该过渡金属选自Fe、Zn、Mn、Co、Cu、Ag、Ni、Pt、Pd、Rh、Ru和Ir。过渡金属盐的例子有FeX3、Fe(OTf)3、Fe(OAc)3、Mn(OAc)3、Mn(OTf)3、MnX3、Zn(OTf)2、Co(OAc)2、AgX、Ag(OTf)、Ag(OTf)2、AgOAc、PtCl2、H2PtCl4、Pd2(DBA)3、Pd(OAc)2、PdCl2(RCN)2、(Pd(烯丙基)Cl)2、Pd(PR3)4、(Rh(NBD)2)X、(Rh(NBD)Cl)2、(Rh(COD)Cl)2、(Rh(COD)2)X、Rh(acac)(CO)2、Rh(乙烯)2(acac)、(Rh(乙烯)2Cl)2、RhCl(PPh3)3、Rh(CO)2Cl2、RuH(CO)2(PPh3)2、Ru(Ar)X2，、Ru(Ar)X2(PPh3)3、Ru(COD)(COT)、Ru(COD)(COT)X、RuX2(cymen)、Ru(COD)n、RuCl2(COD)、(Ru(COD)2)X、RuX2(PN)、RuCl2(＝CHR)(PR′3)2、Ru(ArH)Cl2、Ru(COD)(甲基烯丙基)2、(Ir(NBD)2Cl)2、(Ir(NBD)2)X、(Ir(COD)2Cl)2、(Ir(COD)2)X、CuX(NCCH3)4、Cu(OTf)、Cu(OTf)2、Cu(Ar)X、CuX、Ni(acac)2、NiX2、(Ni(烯丙基)X)2、Ni(COD)2、MoO2(acac)2、Ti(OiPr)4、VO(acac)2和MeReO3，其中各个R和R′独立地选自烷基或者芳基；Ar是芳基基团；X是反阴离子，例如，BF4，、ClO4，、OTf，、SbF6、CF3SO3、B(C6H3(CF3)2)4、Cl、Br或I；OTf是OSO2CF3；DBA是PhCH＝CHCOCH＝CHPh，NDB是降冰片二烯，COD是环辛二烯(cyclooctodiene)，COT是环辛三烯(cyclooctotriene)。将混合物放入用氮气清洗并充入CO和H2的高压釜中。
四磷配体的合成
下述实施例中的所有反应和操作是在充满氮气的手套箱里或者使用标准Schlenk技术进行的。在氮气下，将THF和甲苯从二苯甲酮羰游基钠中干燥蒸馏出来。将二氯甲烷从CaH2中蒸馏出来。在氮气下，将甲醇从Mg中蒸馏出来。利用EM硅胶60(230-400目)进行柱层析。在Bruker WP-200、AM-300和AMX-360分光光度计上记录1H、13C和31PNMR。在ppm低磁场中从四甲基硅烷和溶剂共振报告的化学位移作为内标准。在KRATOS质谱仪MS9/50上记录用于LR-EI和HR-EI的MS谱。利用手性毛细管柱在Helwett-Packard 6890气相色谱仪上进行GC分析。用WatersTM 600色谱仪进行HPLC分析。
下述步骤用于合成具有结构L1的配体。在室温下，向氯二吡咯基膦(4.4mmol，0.87g)的THF(10ml)溶液中逐滴加入1mL三乙胺以及在THF(5ml)中的四醇(tetraol)(1mmol，0.218g)溶液。根据Lindsten，G.；Wennerstroem，O.；Isaksson，R.，J.Org，Chem.1987，52，547-54合成四醇，根据van der Slot，S.C.；Duran，J.；Luten，J.；Kamer，P.C.J；van Leeuwen，P.W.N.M.Organometallics 2002，21，3873-3883制备氯二吡咯基膦。在加入之后立即形成三乙胺·盐酸盐。反应混合物在室温下搅拌6小时。然后过滤出三乙胺·盐酸盐，在真空下除去溶剂。将粗产物通过快速色谱法基于用己烷/EtOAc/NEt3(6∶1∶0.01)洗脱的碱性氧化铝纯化，制得配体L1(0.31g，36％)，其为空气稳定的无色固体。1H NMR(300Hz，CDCl2)δ7.23(t，2H，J＝8.3Hz)，6.68(m，20H)，6.21(m，16H)；13C NMR(90Hz，CDCl2)δ152.86(d，J＝12.2Hzl31.0，121.4(d，J＝16.8Hz)，118.1，115.3(d，J＝13.7Hz)，112.7；31P NMR(146Hz，CDCl2)δ107.3.HRMS(ES+)：对于C44H39N8O4P4[MH+]的计算值：867.2045，实测值：867.2021.
一般的加氢甲酰基化方法
向2mL带有磁力搅拌的管形瓶中加入前面实施例中制备的四磷配体L1(3μmol，2.6mg)和Rh(acac)(CO)2(1μmol，0.1mL的10mM甲苯溶液)。将混合物搅拌5分钟。然后加入2-辛烯(10mmol，1.56mL)，接着加入癸烷(0.01mL)作为内标准。将反应混合物转移到高压釜中。高压釜用氮气清洗三次，随后加入CO(5巴)和H2(5巴)。然后将高压釜加热至100℃(油浴)。在12h之后，高压釜用冰水冷却，并在通风良好的通风橱中小心释放压力。立即通过GC分析反应混合物。
表1显示了利用多螯合四磷配体L1对苯乙烯，1-辛烯和1-己烯的加氢甲酰基化的显著区域选择性。通常，当与现有技术双磷配体如xantphos和UC-44相比时，苯乙烯是实现直链与支链产物的比率超过2∶1的困难基底。如表1所示，新的四磷配体(A型)如L1是比现有技术双磷配体(B型)更具选择性的加氢甲酰基化配体。反应条件包括0.1mol％Rh(CO)2(acac)和配体，在20atm的CO和H2下，反应温度80℃，1小时。这些结果表明，具有多螯合配位的四磷配体可以用于增加双膦配体的配位能力。据目前的报道，A型的区域选择性是最高的。
表1：烯烃的区域选择性加氢甲酰基化
Figure GYZ000004454115800211
下表2总结了利用四磷配体(A型)对双磷配体(B型)加氢甲酰基化2-己烯和2-辛烯来生成醛的结果。在随后的表2到11中，“n∶i”是直链醛与支链醛比率，“TOF”是转换频率(转换每催化剂每小时)。本发明的四磷配体产生比双磷配体更高的“n∶i”比率。
表2：2-己烯和2-辛烯的加氢甲酰基化结果
Figure GYZ000004454115800212
加氢甲酰基化的条件是S/C＝10000，[Rh]是0.69mM(对于2-己烯)和0.57mM(对于2-辛烯)，配体/Rh比率是3∶l，反应温度是l00℃，CO/H2是5/5atm，甲苯是溶剂，癸烷是内标准。
下表3表明，利用四磷配体(A型)对双磷配体(B型)加氢甲酰基化l-己烯和1-辛烯来通过加氢甲酰基化反应生成醛的结果。
表3：1-己烯和1-辛烯的加氢甲酰基化结果
Figure GYZ000004454115800221
反应条件：S/C＝10000，Rh的浓度是0.2mM，配体/Rh比率是3∶l，温度是80℃，CO/H2是10/10atm，甲苯是溶剂，癸烷是内标准。
加氢甲酰基化反应高度依赖反应条件。一般的反应条件是S/C＝10000，配体金属的比率大约是3，过渡金属的浓度大约是0.2到0.7mM，反应温度是100℃，反应时间是12h。为了优化反应条件，已经利用四磷配体(L1)进行以下实验。如表2和3中的“n∶1”比率所证明，相对于利用双磷配体，利用本发明四磷配体对产生的直链醛的量有了实质性和显著的改进。
配体对金属的比率
首先，用不同配体对金属比率来进行加氢甲酰基化。如表4所示，提高配体金属的比率稍微降低反应速率。另一方面，配体对金属的比率显著影响区域选择性。在较低的比率下，观察到低区域选择性。配体对金属比率的最小值2对实现高区域选择性是必要的，其允许四磷配体以多配位模式配位。进一步增加配体对金属的比率不会显著改进区域选择性。
表4.利用配体L1用不同配体金属比率的2-辛烯的加氢甲酰基化
反应条件：基底是2-辛烯，S/C＝10000，Rh的浓度是0.57mM，温度是100℃，CO/H2是10/10atm，反应时间是1h，甲苯是溶剂，癸烷是内标准。表4的结果表明，两个带有四磷配体的游离磷配体的存在对于实现高区域选择性是重要的(n∶i从2.92到17.7)。下表5说明用2-己烯作基底的相似结果。
表5.利用配体L1用不同配体金属比率的2-己烯的加氢甲酰基化
反应条件：基底是2-己烯，S/C＝10000，Rh的浓度是0.69mM，反应温度是100℃，CO/H2是10/10atm，反应时间是1h，甲苯是溶剂，癸烷是内标准。表5的结果表明，两个带有四磷配体的游离磷配体的存在对于实现高区域选择性是重要的(n∶i从12.7到42)。
温度
反应温度也在加氢甲酰基化中起重要作用。如下表6和7所示，在低温下，虽然观察到高的区域选择性，但反应速率低。为了促进烯烃异构化和加氢甲酰基化，优选高温(100℃)来实现高反应速率和可接受的区域选择性。
表6.利用Rh-配体L1在不同温度下的2-辛烯的加氢甲酰基化
Figure GYZ000004454115800241
反应条件：基底是2-辛烯，S/C＝10000，Rh的浓度是0.57mM，配体/Rh的比率是3∶1，CO/H2是1O/10atm，反应时间是1h，甲苯是溶剂，癸烷是内标准。
表7.利用Rh-配体L1在不同温度下的2-己烯的加氢甲酰基化
Figure GYZ000004454115800242
反应条件：基底是2-己烯，S/C＝10000，Rh的浓度是0.69mM，配体/Rh的比率是3∶1，CO/H2是10/10atm，反应时间是1h，甲苯是溶剂，癸烷是内标准。
压力
CO/H2总压力也影响反应。在高压下，反应速率和区域选择性都低。降低压力通常导致较高的反应速率和区域选择性。将CO/H2压力从10/10atm降低到5/5atm不会改变反应速率很多，但是区域选择性进一步改进。2-辛烯和2-己烯的加氢甲酰基化的结果如表8和9所示。
表8.利用配体L1在不同压力下的2-辛烯的加氢甲酰基化
反应条件：基底是2-辛烯，S/C＝10000，Rh的浓度是0.57mM，配体/Rh的比率是3∶1，反应温度是100℃，反应时间是1h，甲苯是溶剂，癸烷是内标准。
表9.利用配体L1在不同压力下的2-己烯的加氢甲酰基化
Figure GYZ000004454115800252
反应条件：基底是2-己烯，S/C＝10000，Rh的浓度是0.69mM，配体/Rh的比率是3∶1，反应温度是100℃，反应时间是1h，甲苯是溶剂，癸烷是内标准。
反应时间
反应时间也影响加氢甲酰基化的选择性。如下表10和11所示，反应时间越长，区域选择性越低。反应时间从12h进一步增加到18h仅稍微改进转换数(TON)，即每催化剂的转换数，代价是降低的区域选择性。
表10.利用Rh-配体L1在不同时间下2-辛烯的加氢甲酰基化
Figure GYZ000004454115800261
反应条件：基底是2-辛烯，S/C＝10000，Rh的浓度是0.57mM，配体/Rh的比率是3∶1，反应温度是100℃，CO/H2为5/5atm，甲苯是溶剂，癸烷是内标准。
表11.利用Rh-配体L1在不同时间下2-己烯的加氢甲酰基化
Figure GYZ000004454115800271
反应条件：基底是2-己烯，S/C＝1 0000，Rh的浓度是0.69mM，配体/Rh的比率是3∶1，反应温度是100℃，CO/H2为5/5atm，甲苯是溶剂，癸烷是内标准。
已经参照几个优选的实施方案描述了本发明，对本领域技术人员而言，在阅读之前的详述时，可以预期到所述实施方案的各种改变和改进是显而易见的。因此，预期的是，下述附加权利要求应解释为包括落在本发明真正精神和范围内的所有这样的改变和改进。

Claims (7)

1.一种磷配体，所述磷配体具有以下结构：
Figure FFW00000069275400011
其中X是O、CH2或NH；并且a、b、c、d、i、j、k、l、m和n独立地是H、烷基、芳基、OR、SiR3、CF3、COOR、SO3R、SO3H或POR2，或者a、b、c、d、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R为烷基或芳基。
2.一种磷配体，所述磷配体具有以下结构：
Figure FFW00000069275400012
其中X是O、CH2或NH；并且a、b、c、d、e、f、i、j、k、l、m和n独立地是H、烷基、芳基、OR、SiR3、COOR、SO3R、SO3H或POR2，或者a、b、c、d、e、f、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R为烷基或芳基。
3.一种磷配体，所述磷配体具有以下结构：
Figure FFW00000069275400021
其中X是O、CH2或NH；并且a、b、c、d、e、i、j、k、l、m和n独立地是H、烷基、芳基、OR、SiR3、CF3、COOR、SO3R、SO3H、POR2或NR2，或者a、b、c、d、e、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R为烷基或芳基。
4.一种磷配体，所述磷配体具有以下结构：
Figure FFW00000069275400031
其中X是O、CH2或NH；Y是碳-碳键、O、CH2、NH或NR，其中R为烷基或芳基；并且a到n独立地是H、烷基、芳基、OR、SiR3、CF3、COOR、SO3R、SO3H、POR2或NR2，或者a到n中的两个可以是环状的稠合环或者伸展的芳环，其中R为烷基或芳基。
5.一种磷配体，所述磷配体具有以下结构：
Figure FFW00000069275400032
其中X是O、CH2或NH；并且a、b、c、d、e、i、j、k、l、m和n独立地是H、烷基、芳基、OR、SiR3、CF3、COOR、SO3R、SO3H、POR2或NR2，或者a、b、c、d、e、i、j、k、l、m和n中的两个可以是环状的稠合环或者伸展的芳环，其中R为烷基或芳基。
6.一种磷配体，所述磷配体具有以下结构：
Figure FFW00000069275400041
其中X是O、CH2或NH；并且a到n独立地是H、烷基、芳基、OR、SiR3、CF3、COOR、SO3R、SO3H、POR2或NR2，或者a到n中的两个可以是环状的稠合环或者伸展的芳环，其中R为烷基或芳基。
7.一种磷配体，所述磷配体具有以下结构：
Figure FFW00000069275400042
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