CN1117726A - 羰基化方法 - Google Patents

羰基化方法 Download PDF

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CN1117726A
CN1117726A CN94191123A CN94191123A CN1117726A CN 1117726 A CN1117726 A CN 1117726A CN 94191123 A CN94191123 A CN 94191123A CN 94191123 A CN94191123 A CN 94191123A CN 1117726 A CN1117726 A CN 1117726A
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E·德雷特
M·哈塞拉尔
D·H·L·佩洛
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Abstract

本发明提供了一种不饱和烯属化合物羰基化方法，该方法是在实质性非酸性催化体系的存在下使不饱和烯属化合物和一氧化碳及一共反应物一起反应，该催化剂体系以钯化合物为配位中心及具有下式(I)结构的二齿配位体：R1R2M1RM2R3R4(I)，其中基团意义见说明书。另外，本发明提供了具有以下组成的催化剂体系：a)钯化合物；b)具有下式(II)结构的二齿配位体：R1R2PRPR3R4(II)，其中取代基意义见说明书；c)碱性化合物。

Description

羰基化方法
本发明涉及不饱和烯属化合物的羰基化方法，该方法是在含钯的催化剂体系存在下使不饱和烯属化合物与一氧化碳和一种共反应物一同发生反应。
在欧洲专利EP—A—0，495，547中公开了这一类型的不同羰基化反应。该专利方法是，一种非必须取代的不饱和烯属化合物与一氧化碳及各种共反应物在催化剂体系中反应，该催化剂体系包含：钯阳离子源；二齿配位体源；阴离子源。这里的配位体从具有通式Q1Q2PXPQ3Q4的二膦化合物中选出，这里Q1、Q2、Q3、Q4各自代表一非必须取代的脂肪族基团，或Q1加Q2和/或Q3加Q4代表非必须取代的二价脂肪族基团，X代表桥中含1到10个原子的二价桥连基团。阴离子源优选质子酸。尤其优选非配位阴离子或弱配位阴离子，即那些不能或仅微弱地与钯阳离子配位的阴离子。
与此同时欧洲专利EP—A—0,495,547公布的方法一般能高选择性和高产率地生产所需产物。从一些实验例中感受到反应速率能够进一步提高。从而通过进一步的努力获得了更高的反应速率，并且不妨碍选择性及催化剂稳定性等其它因素。
令人惊奇的发现是，使用实质上非酸性的催化剂体系及选择一特定类型的二齿配位体，大量羰基化反应的反应速率都有显著的提高。
本发明可以定义成一种涉及不饱和烯属化合物羰基化的方法，该方法是在实质性非酸性催化体系存在下使不饱和烯属化合物与一氧化碳及一共反应物反应，该催化体系以钯化合物为配位中心及下式结构的二齿配位体为配位体：
R1R2M1RM2R3R4    (I)这里M1和M2各自代表磷、砷或锑原子，R代表二价有机桥连基团，R1、R2、R3和R4各自代表取代的或非取代的脂肪基团，但须R1加R2和/或R3加R4代表至少含5个环内原子的二价环形基团，从而两个自由价键分别连在M1或M2上。
按照本发明方法的羰基化反应的进行受着含与二齿配位体配位的钯阳离子活性催化体系的影响。
钯阳离子可以来源于钯盐，例如硝酸钯、硫酸钯、磺酸钯、如对甲苯磺酸钯、甲磺酸钯或三氟甲烷磺酸钯。优选羧酸的钯盐，例如乙酸钯、三氟乙酸钯或丙酸钯。如果需要，还可使用金属元素或络和上如一氧化碳的零价钯络和物。但这要求有质子酸的存在并且应意识到为了避免酸性催化体系的生效应仔细选择质子酸的用量。
在式(I)表示的二齿配位体中，M1和M2都优选代表磷原子。R优选代表桥中含1到10个原子的二价有机桥连基团。R更优选代表桥中含1至4个原子的亚烷基基团。一般桥连基团仅由碳和氢原子构成，但它也可以包括链骨架上含有杂原子的碳链，如含氧原子的碳链。式(I)配位体中的R特别优选代表亚乙基。
由R1加R2和/或R3加R4形成的环形基团至少包含5个环内原子，尤其是6到9个原子。通常它们仅由碳原子组成环内原子，但也不排除环内含有1或2个杂原子，如环内氧或氮原子。二价的环形基团十分合适，它使得环含有7个或优选8个碳原子。两自由价键可以连在相邻的环内碳原子上，或分隔得更远一些的两个碳原子上。合适的环形基团有：1，2—亚环辛基、1，3—亚环辛基、1，4—亚环辛基、1，5—亚环辛基、1，4—亚环己基、1，3—亚环庚基和1，4—亚环庚基基团。二齿配位体的混和物也可使用，这里R1加R2代表不同的环形基团，R3加R4代表非成环基团或与R1加R2代表的环形基团相同或不同的环形基团。合适的二齿配位体选自：1，2—双(9—膦杂二环壬烷基)乙烷和1，2—双(9—膦杂二环壬烷基)丙烷的〔4.2.1〕和/或〔3.3.1〕的同分异构体；1，3—双〔9—膦杂二环〔3.3.1〕壬烷基)丙烷及1，3—双〔9—膦杂二环壬烷基)丙烷、1—二烷基膦基—2—P—(9—膦杂二环壬烷基)乙烷。如果R1加R2或R3加R4不代表二价环形基团，它们则适于代表一非必须取代的烷基，优选C1-6的烷基，或单价的环烷基，优选环C5—C10烷基。合适的烷基基团有甲基、乙基或丁基等基团。合适的烷基基团有环己烷基或环辛烷基等基团。
每一克原子数的钯所需的式(I)代表的配位体摩尔数范围优选从0.5到10，更优选从1到3。
本发明方法优选在碱性化合物存在下施行。据认为碱性化合物的存在不仅保证了催化剂体系在反应过程中始终处于非酸性环境，也有利于催化剂活性的发挥。相应地，至少有部分碱性化合物可能参与了催化剂体系。特别合适的碱性化合物是含氮碱，优选氮原子仅连在除氢原子之外的原子上的含氮化合物。合适的含氮碱的碱性化合物例子是三烷基胺，优选三—C1-6烷基－胺，特别是三乙基胺、三丙基胺、三正丁基胺和三叔丁基胺。合适的环形胺例子有吡啶和烷基吡啶，如(C1-4烷基)吡啶，例如2—甲基吡啶、3，4—二甲基吡啶和1，10—菲咯啉。碱性化合物的用量不重要，可以在大范围内变动。一般每克原子数的钯选用的碱性化合物摩尔数范围从1到100，优选从1到20。为了方便，催化剂体系用量相对较小。优选的使用量是每摩尔不饱和烯属化合物使用10-7到10-1克原子数钯，更优选相同标准的10-6到10-2克原子数的钯。
以下催化剂组合物为新型的且包括：
a)钯化合物；
b)具有下式结构的二齿配位体：
R1R2PRPR3R4    (II)这里R是桥中含1到10个原子的二价有机桥连基团，R1、R2、R3、R4各自代表取代的或非取代的脂肪族基团，但须R1加R2和/或R3加R4代表至少含6个环内原子的二价环形基团，从而两个自由价键连在磷原子上；
c)碱性化合物。
本发明也相应地涉及到这些新型催化剂组合物。本发明尤其涉及包含以下组份的催化剂组合物：钯化合物；具有式(II)结构的二齿配位体，这里R1R2P和R3R4P每一个都代表9—膦杂二环壬烷基的〔4.2.1〕和/或〔3.3.1〕同分异构体，R代表亚乙基；吡啶或三烷基胺。
具有式(II)结构的二齿配位体可以通过已知技术来制备，例如英国专利No.1,127,965的说明书中所述的技术。
不饱和烯属化合物可以具有一个或多个双键。优选每分子上具有2到20个碳原子的链烯。不饱和键可以位于链中间或优选链末端。尤其优选每分子上具有2至8个碳原子的链烯，例如乙烯、丙烯、1—丁烯、1—己烯、1—辛烯。
在不饱和烯属化合物中，一个或多个氢原子可以被其它原子如卤原子或原子基团如羟基基团、氰基基团、例如甲氧基或乙氧基、或如二甲基氨基及二乙基氨基的氨基基团，所取代。
另一类优选的不饱和烯属化合物由羧酸的不饱和酯及不饱和羧酸酯组成。例如，起始物料可以是如乙酸或丙酸的羧酸的乙烯酯，或者是不饱和酸的烷基酯，例如丙烯酸或甲基丙烯酸的甲酯或乙酯。
本发明方法的合适的共反应物包括含有一亲核部分及一流动氢原子的化合物。例如有链烷醇和链烷二醇，例如甲醇、乙醇、正丁醇、乙二醇、异丙醇、丁二醇及1—己醇和如乙基胺及二乙基胺的胺类。优选每分子具有1到6个碳原子的链烷醇及每分子具有2到6个碳原子的链烷二醇。尤其优选1—正丁醇、甲醇和1，4—丁二醇。使用这些化合物作共反应物能够产生有价值的羰基化产物，例如丙酸甲酯、丙酸丁酯及1，4—双酰氧基丁烷。
这些化合物具有商业价值，它们可以用做溶剂并且在香味组合物中可以用做香料。本发明方法中使用的不饱和烯属化合物或共反应物可以过量，相应地在反应过程中可以起溶剂本作用。也可以另一种液体稀释剂的存在下实施本反应，尤其是当反应物按化学计量投料时。适合的稀释剂是那些极性的、非质子化合物，例如酮类、醚类。优选的稀释剂有四氢呋喃和二乙二醇二甲醚(二甘醇二甲醚)。
如果需要，反应可以在助催化剂的存在下实施，例如一种干燥剂，合适的干燥剂包括缩醛，例如丙酮的乙醛缩二甲醇，缩酮等。优选的干燥剂是原甲酸三甲酯。
羰基化反应一般在温和的温度下完成，一般从30到200℃，优选从50到150℃。反应压力可以是大气压力或高于大气压力。尤其优选5到70巴。也不排除更高的压力，但通常这种压力并无优势。
本发明将用以下实施例来说明。实施例I—XI
实验的过程是：每次实验向250ml带磁力搅拌的“Hasteulloy C”(商标)牌高压釜中加入0.25mmol乙酸钯(II)、0.6mmol二膦配位体、50ml链烷醇类共反应物，如果实用，还可加入一种或多种添加剂。高压釜充满摩尔比为1.5∶1的一氧化碳和乙烯混合气体，并使总压力上升至50巴。然后密闭高压釜并将混合物加热至所需的反应温度。继续进行反应以完成乙烯的转化过程，随后反应混合物被冷却至室温并卸压。所用配位体、共反应物、添加剂(如果使用了)、反应温度及平均每小时酯形成速率列于表1。
表1中使用的缩略词具有以下意义：
BPBNP＝1，3—双(9—膦杂二环壬烷基)丙烷
MBPBNE＝1—甲基—1，2—双(9—膦杂二环壬烷基)乙烷1，2—双(9—膦杂二环壬烷基)丙烷
BPBNE＝1，2—双(9—膦杂二环壬烷基)乙烷
DMP＝3，4—二甲基吡啶(卢剔啶)
Phen＝1，10—菲咯啉
BBA＝2，6—二(仲丁氧基)苯甲酸
TEA＝三乙基胺
TMF＝原甲酸三甲酯
实施例V中获得的产物是丙酸甲酯；其它实施例中获得的是丙酸正丁酯。酯的选择率超过99％。从实施例I、II和III的结果可以看到碱性化合物的存在可以加快反应速率，添加干燥剂可以进一步加快反应速率。同样，比较实施例IV、VI、VII和VIII的结果也可以看到添加干燥剂或碱性化合物加快了反应速率。通过比较实施例IX和X的结果可以进一步说明干燥剂的效应。实施例B(不依照本发明方法，仅供比较)
在与实施例IV实质上相同的条件下实施本实验，但反应温度为130℃，而不是125℃，并且1，2—双(二环己烷基膦基)乙烷为配位体。反应速率为30mol/gat pd·h。实施例C(不依照本发明方法，仅供比较)
在与实施例II实质上相同的条件下实施本实验，但用1，3—双(二仲丁基膦基)丙烷做配位体。反应速率为50mol/gat pd.h。
                         表1
实施例  配位体  添加剂  链烷醇  反应温度  反应速率(mmol)   (mL)    (℃)   (mol/gat Pd.h)
  I     BPBNP     -     正丁醇50   125     35II      ”             DMP 10     ”           137     85III     ”               ”                   ”           137    330TMF 5 mLIV    BPBNE     -         ”            125    520y       ”              -      甲醇50    125    490VI      ”       TMF 1 ml   正丁醇50  125    600VII     ”       Phen 1        ”             125    630VIII    ”    Phen 2.5       ”              125    1150TMF 1 mLA*      ”       BBA 10         ”         120    360IX      ”       TEA 10         ”         133    275X       ”               ”                     ”       133    725TMF 5 mLXI      ”    DMP 10           ”      135    1160.     TMF 5 mL
*不依照本发明方法，仅供比较实施例XII
实施一实验，这里向高压釜(带磁力搅拌，250ml，“Hastelloy C”牌)加入0.25mmol乙酸钯(II)、0.6mmol二膦配位体(如前定义的BPBNP)、10mmol三乙基胺、5ml原甲酸三甲酯、50ml甲醇和20ml 1—正辛烯。高压釜充满一氧化碳并使压力上升至30巴。加热混和物至130℃。继续进行反应以完成辛烯的转化过程，随后反应混和物被冷却至室温并卸压。反应速率为100mol/gat pd.h。形成的壬酸甲酯的线性度为73％。实施例XIII
在与实施例XII实质上相同的条件下实施本实验，但用BPB-NE代替BPBNP做配位体(BPBNP和BPBNE如前所定义)。反应速率是170mol/gat pd.h。形成的壬酸甲酯的线性度为69％。实施例XIV
在与实施例I实质上相同的条件下实施本实验，但正丁醇的使用量为40ml而不是50ml，反应温度为130℃，用MBPBNE代替BPBNP做配位体(BPBNP和MBPBNE如前所定义)。反应速率为200mol/gat pd.h。丙酸正丁酯的选择率大于99％。

Claims (12)

1.一种不饱和烯属化合物的羰基化方法，该方法是在一实质性非酸性催化体系的存在下使不饱和烯属化合物与一氧化碳和一共反应物一同发生反应，该催化体系是以钯化合物为配位中心，一具有下式结构的二齿配位体为配位体；
R1R2M1RM2R3R4    (I)其中M1和M2各自代表磷、砷或锑原子，R代表二价有机桥连基团，R1、R2、R3、R4各自代表取代或非取代的脂肪族基团，但须R1加R2和/或R3加R4代表至少含5个环内原子的二价环形基团，从而两个自由价键分别连在M1或M2上。
2.根据权利要求1所要求的方法，其中M1和M2都代表磷原子。
3.根据权利要求1或2所要求的方法，其中R代表桥中含1到10个原子的二价有机桥连基团。
4.根据权利要求1至3中任一项所要求的方法，其中R代表亚乙基。
5.根据权利要求1至4中任一项所要求的方法，其中由R1加R2和/或R3加R4代表的二价环形基团上具有6至9个环内原子的亚环烷基基团。
6.根据权利要求5所要求的方法，其中R连在两个磷原子上，每个磷原子都是9—膦杂二环壬烷基基团的〔4.2.1〕和/或〔3.3.1〕同分异构体中的成员。
7.根据权利要求1至6中任一项所要求的方法，其中反应在一碱性化合物存在下完成。
8.根据权利要求7所要求的方法，这里用吡啶、取代吡啶或三烷基胺做碱性化合物。
9.根据权利要求1至8中任一项所要求的方法，其中反应在一液体稀释剂存在下完成。
10.根据权利要求9所要求的方法，其中用醚做稀释剂，尤其是用四氢呋喃或二乙二醇二甲醚。
11.催化剂组合物，其包括：
a)钯化合物；
b)具有下式结构的二齿配位体：
R1R2PRPR3R4    (II)其中R是桥中含1至10个原子的二价有机桥连基团，R1、R2、R3、R4各自代表取代或非取代的脂肪族基团，但须R1加R2和/或R3加R4代表至少含6个环内原子的二价环形基团，从而两个自由价键连在磷原子上。
c)碱性化合物。
12.根据权利要求11所要求的催化剂组合物，其中R1R2P和R3R4P每一个都代表着9—膦杂二环壬烷基基团的〔4.2.1〕和/或〔3.3.1〕同分异构体，其中用的碱性化合物为吡啶、取代吡啶或三烷基胺。
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