CN1193015A - 制备2,6－吡啶二羧酸酯的方法 - Google Patents

制备2,6－吡啶二羧酸酯的方法 Download PDF

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CN1193015A
CN1193015A CN98105591A CN98105591A CN1193015A CN 1193015 A CN1193015 A CN 1193015A CN 98105591 A CN98105591 A CN 98105591A CN 98105591 A CN98105591 A CN 98105591A CN 1193015 A CN1193015 A CN 1193015A
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J－P·罗迪特
Y·贝萨特
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Abstract

本发明记述了一种制备通式Ⅰ的2,6－吡啶二羧酸酯的方法。通式Ⅰ为其中,R1是C1－C6烷基、C3－C6环烷基、芳基或芳烷基,R2和R3各自为氢或氯,R4为氢、C1－C6烷基、C1－C6烷氧基或氟。该2,6－吡啶二羧酸酯通过在碱以及钯与双二苯膦形成的配合物的存在下,由相应的卤代吡啶与一氧化碳和通式Ⅲ的醇反应而得到,醇的通式Ⅲ为R1－OH Ⅲ其中,R1具有上述意义。2,6－吡啶二羧酸酯是用于制备具有抗炎作用的化合物的中间体。

Description

制备2，6-吡啶二羧酸酯的方法
本发明涉及通过在碱和催化剂的存在下进行卤代吡啶和一氧化碳及醇的反应来制备2，6-吡啶二羧酸酯的方法。
2，6-吡啶二羧酸酯是重要的中间体，如用于制备具有抗炎作用的化合物(JP-A93/143 799)。
根据本发明可以制备的2，6-吡啶二羧酸酯具有通式其中，R1是C1-C6烷基、C3-C6环烷基、芳基或芳烷基，R2和R3各自为氢或氯，R4为氢、C1-C6烷基、C1-C6烷氧基或氟。
已知的2，6-吡啶二羧酸酯的制备方法是基于2，6-二甲基吡啶的直接化学氧化反应(I.Iovel，M.Shymanska，Synth.Commun.1992，22，2691；G.Wang，D.E.Bergstrom，Synlett 1992，422；BE-A 872 394，SU-A 568 642)。虽然在一些例子中得到了高产率，但是这些方法有其缺点，因为它们使用了昂贵的试剂和/或有毒的试剂。已知的一种制备2，6-吡啶二羧酸酯的方法是使用镍催化剂对2，6-二氯吡啶进行羰基化作用(WO 93/18005)。
该方法的一个缺点是反应在高压下进行，只能得到中等产率的吡啶羧酸酯，且形成较高比例的单羰基化的副产物。
因此，本发明的目的是得到一种经济的方法，通过该方法从卤代吡啶可以制备高产率的通式I的2，6-吡啶二羧酸酯。
根据本发明，发明目的通过下述的制备2，6-吡啶二羧酸酯的方法来实现，所述2，6-吡啶二羧酸酯的通式为其中，R1是C1-C6烷基、C3-C6环烷基、芳基或芳烷基，R2和R3各自为氢或氯，R4为氢、C1-C6烷基、C1-C6烷氧基或氟。在该方法中，在碱和钯配合物的存在下，使用通式IV的双二苯膦(bis-diphenylphosphine)，将通式II的卤代吡啶与一氧化碳和通式III的醇反应，其中，卤代吡啶的通式II为其中，R2、R3和R4具有上述意义，X是氯或溴；醇的通式III为
R1-OH                  III其中，R1具有上述意义；双二苯膦的通式IV为
Figure A9810559100052
其中，Q为C3-C6烷二基(alkanediyl group)或含有环戊二烯基的1，1′-二茂铁二基，环戊二烯基可任选地被C1-C4烷基或芳基所取代，R5至R8各自是氢、C1-C4烷基、C1-C4烷氧基、一氟代甲基、二氟代甲基、三氟代甲基、氟、芳基、芳氧基、氰基或二烷基氨基。
R1是含1至6个碳原子的直链或支链的烷基、含3至6个碳原子的环烷基、芳基或芳烷基。
特别可提及的有甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基及其异构体、己基及其异构体、环丙基、环丁基、环戊基，以及环己基。此处的芳基特别应被理解成单环或多环体系，例如苯基、萘基、联苯基或蒽基。它们可以有一个或多个相同或不同的取代基，例如低级烷基(如甲基)、卤代烷基(如三氟代甲基)、低级烷氧基(如甲氧基)，或者低级烷硫基(alkylthio(alkanesulphanyl))或链烷磺酰基(如甲硫基或乙磺酰基)。此处和下文的取代的苯基特别应被理解成是指如氟代苯基、甲氧苯基、甲苯基或三氟甲基苯基等，取代基较好的是在对位。
因此，芳烷基应被理解成由低级烷基(特别是C1-C6烷基)，通过用以上定义的芳基中的一个来取代一个氢原子而形成的基团，即例如苄基或苯乙基。
R1特别好的是指甲基、乙基、丁基或环己基。
R2和R3各自指氢或氯。
R2和R3特别好的是氢。R4是氢、含1至6个碳原子的直链或支链的烷基或含1至6个碳原子的直链或支链的烷氧基，或者是氟。特别可提及甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基及其异构体、己基及其异构体、甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、叔丁氧基、戊氧基及其异构体、己氧基及其异构体。特别好的R4是指氢。X指氯或溴；特别好的X是氯。
通式II的卤代吡啶是可以从市场上购得的。
较好地，甲酯、乙酯、丁酯或环己酯(R1＝甲基、乙基、丁基、环己基)通过本发明方法使用甲醇、乙醇、丁醇或环己醇作为醇(III)来制备。
该反应在碱的存在下进行。十分合适的碱是，例如碱金属和碱土金属的乙酸盐、碳酸盐、碳酸氢盐、磷酸盐或磷酸氢盐。特别提及乙酸钠、乙酸钾、乙酸镁、乙酸钙、碳酸钠、碳酸钾、碳酸镁、碳酸钙、碳酸氢钠、碳酸氢钾、碳酸氢镁、碳酸氢钙、磷酸镁、磷酸钙、磷酸二氢钠、磷酸二氢钾、磷酸氢二钠、磷酸氢二钾、磷酸氢镁、磷酸氢钙。特别合适的是乙酸钠。
催化活性的钯双二苯膦配合物最好是现场形成，通过Pd(II)盐(如氯化物或乙酸盐)或者合适的Pd(II)配合物(如氯化双(三苯膦)钯(II))与二膦的反应。所用的Pd(II)盐或Pd(II)配合物较好的是乙酸钯(II)或氯化双(三苯膦)钯(II)。钯的用量较好的是0.05-0.4％(摩尔)的Pd(II)，以卤代化合物(II)计。二膦的用量较好的是过量(以Pd计)，较好的用量是0.2-5％(摩尔)，同样以卤代化合物(II)计。
较好的是使用那些其中Q是含3至6个碳原子的直链或支链的烷二基的双二苯膦(III)。特别可提及1，3-丙二基、1，2-丙二基、1，4-丁二基、1，3-丁二基、1，2-丁二基、戊二基及其异构体、己二基及其异构体。所用的较好的那些双二苯膦(III)中的Q是含3-6个碳原子的直链烷二基。特别可提及的有1，3-丙二基、  1，4-丁二基、1，5-戊二基和1，6-己二基。特别好的是1，4-双(二苯膦基)丁烷。
同样所用的较好的那些双二苯膦(III)中的Q是含有环戊二烯基的1，1′-二茂铁二基，环戊二烯基可任选地被C1-C4烷基或芳基所取代。所用的C1-C4烷基取代基较好的为甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基；特别好的是甲基和乙基。此处所用的芳基取代基较好的是苯基或者可任选取代的苯基。特别好的是使用1，1′-双(二苯膦基)二茂铁。
R5至R8各自是氢、C1-C4烷基、C1-C4烷氧基、一氟代甲基、二氟代甲基、三氟代甲基、氟、芳基、芳氧基、氰基或二烷基氨基。
所用的C1-C4烷基取代基较好的是甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基；特别好的是甲基和乙基。所用的C1-C4烷氧基取代基较好的是甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基或叔丁氧基；特别好的是甲氧基和乙氧基。此处所用的芳基取代基较好的是苯基或被任选取代的苯基。所用的芳氧基取代基较好的是苯氧基和被任选取代的苯氧基。取代的苯氧基应被理解成特别指如下基团，如氟代苯氧基、甲氧苯氧基、甲苯氧基或三氟甲基苯氧基，取代基较好的是在对位。所用的二烷基氨基取代基较好的是含C1-C2烷基基团的胺。特别提及二甲氨基和二乙氨基。
醇(III)还可以作为溶剂。如果需要，可以使用附加溶剂。附加溶剂可以是非极性的有机溶剂，例如甲苯或二甲苯，也可以是极性的有机溶剂，例如乙腈、四氢呋喃或N，N-二甲基乙酰胺。
反应较好的是在100至250℃的反应温度下进行，最好在140至195℃的反应温度下进行，一氧化碳的压力较好的在1×105至2×107帕斯卡(1至200巴(bar))，较好的是5×105至5×106帕斯卡(5-50巴)。经过一段反应时间之后(通常为1至20个小时)，得到高产率的通式I的化合物。
以下实施例描述了本发明方法的过程。
实施例1  2，6-吡啶二羧酸二甲酯
在压热器中最初加入1.48克(10毫摩尔)2，6-二氯吡啶、166毫克1，1′-双(二苯膦基)二茂铁(2，6-二氯吡啶的3％(摩尔))、4.6毫克乙酸钯(II)(2，6-二氯吡啶的0.2％(摩尔))、1.72克(21毫摩尔)乙酸钠和25毫升甲醇。将一氧化碳数次通过压热器，为的是用一氧化碳来代替空气。然后，将1.5×106帕斯卡(15巴)的一氧化碳注入压热器中。将反应混合物加热至135℃(浴温)并搅拌1个小时。冷却至室温后，粗产物在真空(3×103帕斯卡(30毫巴))下浓缩，在硅胶60上用色谱法分析(洗脱液为1∶1的己烷/乙酸乙酯)。
熔点： 120.8-122.5℃
产率： 1.52克(78％)的白色粉末
质谱(MS)；m/e：195(M+)，165，137，1051H-NMR(CDCl3)：δ＝8.31(d，2H)；
                          8.02(t，1H)；
                          4.02(s，6H)。
实施例2  2，6-吡啶二羧酸二乙酯
制备过程如实施例1所述，但是用相同体积的乙醇代替甲醇，用57毫摩尔乙酸钠代替21毫摩尔的乙酸钠。在浴温为135℃下反应1个小时以后，得到1.96克(88％)的白色粉末。
熔点：41.5-42.8℃
质谱(MS)；m/e：224，223(M+)；208；179；151；123；105
1H-NMR(CDCl3)：δ＝8.28(d，2H)；
                                8.00(t，1H)；
                                4.50(q，4H)；
                                1.45(t，6H)。
实施例3  2，6-吡啶二羧酸二乙酯
制备过程如实施例1中所述，但是使用25毫升的四氢呋喃和30毫升的乙醇来代替25毫升的甲醇。在浴温为150℃下反应3小时，得到0.56克(25.1％)的白色粉末。
实施例4  2，6-吡啶二羧酸二乙酯
制备过程如实施例1中所述，但是使用相同体积的乙醇代替甲醇，使用14.0毫克氯化双(三苯膦)钯(II)代替4.6毫克乙酸钯(II)。在浴温为175℃下反应2小时后，得到1.54克(69％)的白色粉末。
实施例5  2，6-吡啶二羧酸二乙酯
制备过程如实施例2中所述，但是使用128毫克1，4-双(二苯膦基)丁烷来代替166毫克的1，1′-双(二苯膦基)二茂铁。在浴温为150℃下反应3小时后，得到1.64克(73.5％)的白色粉末。
实施例6  2，6-吡啶二羧酸二丁酯
制备过程如实施例1中所述，但是用相同体积的丁醇代替甲醇。在浴温为135℃下反应1小时以后，得到2.45克(85％)的白色粉末。
熔点：65.5-65.9℃
质谱(MS)；m/e：280(M+)；236；224；206；179；150；123；105；78
1H-NMR(CDCl3)：δ＝8.28(d，2H)；
                               7.98(t，1H)；
                               5.32(sept，2H)；
                               4.42(t，4H)；
                               1.82(quint，4H)；
                               1.50(sext，4H)；
                               0.99(t，6H)。
实施例7 2，6-吡啶二羧酸二环己酯
制备过程如实施例1中所述，但是用相同体积的环己醇代替甲醇。在浴温为135℃下反应1小时以后，得到1.7克(51％)的白色粉末。
熔点：111.6-112.3℃
质谱(MS)；m/e：331(M+)；287；250；219；205；168；150；123
1H-NMR(CDCl3)：δ＝8.22(d，2H)；
                                7.97(t，1H)；
                                5.10(sept，2H)；
                                2.1-2.3(m，22H)。
实施例8  3-氯-2，6-吡啶二羧酸二乙酯
制备过程如实施例2中所述，但是使用1.82克(10毫摩尔)的2，3，6-三氯吡啶代替1.48克(10毫摩尔)的2，6-二氯吡啶。在浴温为135℃下反应1小时以后，得到1.98克(76％)的无色油状物。
质谱(MS)；m/e：257(M+)；213；185；139；113。
1H-NMR(CDCl3)：δ＝8.15(d，1H)；
                               7.93(d，1H)；
                               4.50(q，2H)；
                               4.48(d，2H)；
                               1.44(t，3H)；
1.43(t，3H)。

Claims (7)

1.制备2，6-吡啶二羧酸酯的方法，所述2，6-吡啶二羧酸酯的通式为其中，R1是C1-C6烷基、C3-C6环烷基、芳基或芳烷基，R2和R3各自为氢或氯，R4为氢、C1-C6烷基、C1-C6烷氧基或氟，其特征在于在碱和钯配合物的存在下，使用通式IV的双二苯膦，将通式II的卤代吡啶与一氧化碳和通式III的醇反应，其中，卤代吡啶的通式II为
Figure A9810559100022
其中，R2、R3和R4具有上述意义，X是氯或溴；醇的通式III为
R1-OH                  III其中，R1具有上述意义；双二苯膦的通式IV为其中，Q为C3-C6烷二基或含有环戊二烯基的1，1′-二茂铁二基，环戊二烯基可任选地被C1-C4烷基或芳基所取代，R5至R8各自是氢、C1-C4烷基、C1-C4烷氧基、一氟代甲基、二氟代甲基、三氟代甲基、氟、芳基、芳氧基、氰基或二烷基氨基。
2.如权利要求1所述的方法，其特征在于R1是甲基、乙基、丁基或环己基。
3.如权利要求1或2所述的方法，其特征在于碱是碱金属或碱土金属的乙酸盐、碳酸盐、碳酸氢盐、磷酸盐或磷酸氢盐。
4.如权利要求1至4中至少一项所述的方法，其特征在于钯以氯化双(三苯膦)钯(II)或乙酸钯(II)的形式使用。
5.如权利要求1至5中任一项所述的方法，其特征在于双二苯膦是1，1′-双(二苯膦基)二茂铁或1，4-双(二苯膦基)丁烷。
6.如权利要求1至6中任一项所述的方法，其特征在于一氧化碳的压力为1×105至2×107帕斯卡(1至200巴)。
7.如权利要求1至7中任一项所述的方法，其特征在于反应温度为100至250℃。
CNB981055915A 1997-03-12 1998-03-12 制备2,6-吡啶二羧酸酯的方法 Expired - Fee Related CN1158262C (zh)

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CN115838448A (zh) * 2021-09-18 2023-03-24 中国科学技术大学 负载型催化剂及其制备方法和应用

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CN113912533A (zh) * 2021-11-23 2022-01-11 西安凯立新材料股份有限公司 一种制备3,6-二氯吡啶甲酸的方法

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