CN1076191A - 2，3-吡啶二羧酸二烷酯及其衍生物的制备方法 - Google Patents

2，3-吡啶二羧酸二烷酯及其衍生物的制备方法 Download PDF

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CN1076191A
CN1076191A CN93101489A CN93101489A CN1076191A CN 1076191 A CN1076191 A CN 1076191A CN 93101489 A CN93101489 A CN 93101489A CN 93101489 A CN93101489 A CN 93101489A CN 1076191 A CN1076191 A CN 1076191A
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罗伯特·弗朗西斯·迪纳
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

本发明提供了一种制备商业上有用的吡啶二羧 酸酯化合物的方法，即通过使α，β—不饱和肟和氨基 马来酸酯或氨基富马酸酯或其混合物进行缩合而制 得。

Description

吡啶-2，3-二羧酸酯是在制备重要的除草剂2-（2-咪唑啉-2-基）烟酸、酯及其盐中有用的中间体。在美国专利第4，798，619和4，758，667号中揭示了所述的除草剂及其制备方法，咪唑啉基烟酸酯及其衍生物在低剂量施用时是极有效的除草剂并在主要的经济农作物存在下对毒草显示出选择性的控制，而且，它对哺乳动物的毒性格外低。
吡啶二羧酸酯衍生物的重要性，特别是它在制备除草剂2-（2-咪唑啉-2-基）烟酸中作为必不可少的中间体，引起该技术领域中对其制备有效方法的明显要求。
因此，本发明的一个目的是提供一种取代或未取代吡啶二羧酸酯的制备方法，该类产物是在酸及任选地有溶剂存在下使α，β-不饱和肟与氨基丁烯二酸酯进行一步缩合而制得的。
本发明的另一个目的是提供作为制备除草剂2-（2-咪唑啉-2-基）烟酸、酯及盐的关键的中间体的吡啶二羧酸酯化合物及所述化合物衍生物的简便来源。
本发明的这些目的及进一步的目的通过以下的描述将更为明了。
本发明提供了经济上重要的式Ⅰ吡啶二羧酸酯的制备方法：
Figure 931014891_IMG4
其中R1和R2各自为苯基或任选地用苯基取代的C1～C4烷基，Y和Z各自是氢或是任选地用1至3个卤素取代的C1～C4烷基或是C1～C4烷氧基，该方法包括使式Ⅱ的α，β-不饱和肟，
Figure 931014891_IMG5
其中Y和Z与式Ⅰ中的定义相同，与式Ⅲ的氨基丁烯二酸酯在酸存在下及任意地有溶剂存在下于升高的温度下进行反应，
Figure 931014891_IMG6
其中R3和R4各自为氢、C1～C6烷基、C3～C8环烷基、苯基，或者R3和R4和其它原子结合在一起形成任选地有氧介入的5或6元脂族环，R1和R2与式Ⅰ中的定义相同。
式Ⅲ化合物包括式Ⅳ（a）的氨基马来酸酯、式Ⅳ（b）的氨基富马酸酯或它们的混合物，其中R1、R2、R3和R4的定义与式Ⅲ中的相同。
Figure 931014891_IMG7
用诸如在J.March  Advanced  Organic  Chemistrg，3rd  Edition，805～806页中所报告的标准文献方法，从适当的醛或酮前体可容易地制得式Ⅱ的肟。例如，如流程Ⅰ所示，可使合适的α，β-不饱和羰基化合物前体与羟胺反应以得到所需的肟。
Figure 931014891_IMG8
如流程Ⅱ所示，通过使所需的胺与乙炔二羧酸二烷酯反应可以常规地制得式Ⅲ的氨基丁烯二酸酯化合物。
Figure 931014891_IMG9
可替换的是，用美国专利第4，766，218号所述的方法可制得包括式Ⅳ（a）氨基马来酸酯的氨基马来酸酯及式Ⅳ（b）氨基富马酸酯。
现已发现，可选择地在有机溶剂存在下，将式Ⅰα，β-不饱和肟与式Ⅲ氨基丁二酸酯混合，用酸处理该混合物，在室温至约回流温度下加热所得的反应混合物，可有效地制备5-取代、6-取代、5、6-取代或未取代的吡啶2，3-二羧酸酯化合物。较好的是将式Ⅰα，β-不饱和肟和式Ⅲ的氨基丁烯二酸酯以约1∶1至1∶1.5（摩尔当量）的比例进行混合。这样形成的式Ⅰ吡啶二羧酸酯产物可用诸如萃取、分馏、色谱等等的标准技术进行分离。为了便于叙述，在流程Ⅲ中用式Ⅲ的氨基丁烯二酸酯来表示该方法。
流程Ⅲ
Figure 931014891_IMG10
当然，应当明白式Ⅳ（a）的氨基马来酸酯、式Ⅳ（b）的氨基富马酸酯以及氨基丁烯二酸酯的混合物也可有效地用于本发明的方法中。
可用于本发明的方法的酸是通常用于缩合反应中的酸，如乙酸、丙酸、对-甲苯磺酸、甲磺酸、硫酸、磷酸、磷酰氯、三氯化磷、三溴化磷、氢氯酸、氢溴酸等等。较好的酸是诸如硫酸、盐酸、氢溴酸之类的无机强酸，最好是盐酸。
适用于本发明方法的溶剂是诸如二甲苯、甲苯、苯、卤代苯、二卤代苯之类的芳烃及卤代芳烃类，诸如二卤乙烷、二卤甲烷之类的卤代脂族溶剂，诸如乙酸乙酯、丙酸乙酯等的脂族酯类，以及诸如甲醇、乙醇、丙醇之类的醇类。总之，沸点约50-180℃的溶剂是合适的。
式Ⅰ吡啶二羧酸酯产物形成的速率依赖于温度，因而，通过在高于室温，较好在回流温度下加热反应混合物可以有效地减少反应时间。
为有利于进一步理解本发明，现提出下列实施例。这些实施例仅以阐述更具体详细为目的，本发明并不为其所限制。除非另作说明，所有的份数为重量份数，术语NMR指核磁共振。
实施例1
从2-乙基丙烯醛肟和2-氨基丁烯二酸二乙酯制备5-乙基-2，3-吡啶二羧酸二乙酯
Figure 931014891_IMG11
在室温下，用一次添加的浓H2SO4（5.2克，0.05摩尔）处理2-乙基丙烯醛肟（4.95克，0.05摩尔）和2-氨基丁烯二酸二乙酯（9.35克，0.05摩尔）在乙酸中的混合物，在室温下搅拌2.5小时，在回流温度下加热2.5小时，冷却并真空浓缩得到油状残留物，油状残留物在乙酸乙酯和水之间分配。真空浓缩有机相以得到油状的标题产物，用NMR谱作检定。
实施例2
从丙烯醛肟和2-氨基丁烯二酸二乙酯制备2，3-吡啶二羧酸二乙酯
Figure 931014891_IMG12
Figure 931014891_IMG13
在搅拌下，用一次添加的浓H2SO4（5.2克，0.05摩尔）来处理丙烯醛肟（6.8克，0.096摩尔）和2-氨基丁烯二酸二乙酯（9.35克，0.05摩尔）在25ml乙酸乙酯中的混合物，放出了大量热量。将反应混合物在回流温度下加热1小时，冷却并真空浓缩得到焦油状残留物。该残留物在二氯甲烷和水之间分配。将有机相真空浓缩，得到油状的标题化合物，2.4克，如NMP分析测得，粗得率为21%。
实施例3
从2-甲基丙烯醛肟和N，N-二丁基氨基丁烯二酸二乙酯制备5-甲基-2，3-吡啶二羧酸二乙酯。
Figure 931014891_IMG14
在冰浴温度下，在搅拌下，用Hcl气体对2-甲基丙烯醛肟（2，21克，0.026摩尔）和N，N-二丁基氨基丁烯二酸二乙酯（7.8克，0.026摩尔）在二氯乙烷中的混合物作缓慢处理达5分钟，搅拌1/2小时，让其温至室温，渐渐冷却至约22℃，再用HCl气体处理至反应混合物均匀，在85℃下加热2小时，冷至室温并用乙酸乙酯和水淬灭。将有机相进行真空浓缩以得到油状残留物的标题化合物6.3克，用NMR分析测得53%纯度，54%收率。
基本上用相同的过程并采用0.10摩尔2-甲基丙烯醛肟和0.15摩尔N，N-二丁基氨基丁烯二酸乙二酯，得到了标题产物，用NMR分析测得产物为75%得率，53%纯度。
实施例4
从2-甲基丙烯醛肟和N-环己基氨基丁烯二酸二乙酯制备5-甲基-2，3-吡啶二羧酸二乙酯
Figure 931014891_IMG15
在冰浴温度下，在搅拌下，用HCl气体处理2-甲基丙烯醛肟（2.13克，0.025摩尔）和N-环己基氨基丁烯二酸二乙酯（6.3克，0.026摩尔）在二氯乙烷中的混合物直至不再观察到放热，在70～75℃下加热约2小时，冷却并用乙酸乙酯和水淬灭。将有机相真空浓缩得到油状残留物的标题产物3.25克，NMR分析测得62%粗得率。
实施例5
从2-甲基丙烯醛肟和吗啉代丁烯二酸二乙酯制备5-甲基-2，3-吡啶二羧酸二乙酯
Figure 931014891_IMG16
在搅拌下，在约25℃（冰浴冷却），允许其放热至53℃下，用HCl气体处理2-甲基丙烯醛肟（5.2克，0.05摩尔）和吗啉代丁烯二酸二乙酯（13.0克，0.05摩尔）在二氯乙烷中的混合物达10分钟，加热回流约1小时，冷却并用水和二氯甲烷淬灭。真空浓缩有机相以得到油状残留物的标题产物，10.6克，NMR分析测得其为45%纯度，40%得率。

Claims (10)

1、一种下式Ⅰ化合物的制备方法，
其中R1和R2各自是苯基或是任选地用苯基取代的C1～C4烷基Y和Z各自是氢或是任选地用1至3个卤素取代的C1～C4烷基或是C1～C4烷氧基
其特征在于该方法包括使式Ⅱ的α，β-不饱和肟
其中Y和Z与式Ⅰ中的定义相同，与式Ⅲ的氨基丁烯二酸酯在酸及任选地有溶剂存在下于升高的温度下进行反应，
其中R3和R4各自是氢、C1～C6烷基、C3～C8环烷基、苯基或者R3和R4与其它原子结合在一起形成任选地有氧介入的5元或6元脂族环，
R1和R2的定义与式Ⅰ中的相同。
2、根据权利要求1所述的方法，其特征在于其中式Ⅱ的α，β-不饱和肟和式Ⅲ的氨基丁烯二酸以约1∶1至1∶1.5摩尔当量的比例存在。
3、根据权利要求1所述的方法，其特征在于其中酸选自由乙酸、对-甲苯磺酸、甲磺酸、硫酸、磷酸、磷酰氯、三氯化磷、三溴化磷、盐酸和氢溴酸所组成的组。
4、根据权利要求3所述的方法，其特征在于其中的酸是盐酸。
5、根据权利要求1所述的方法，其特征在于其中的反应在溶剂存在下进行。
6、根据权利要求5所述的方法，其特征在于其中的溶剂系选自由二甲苯、甲苯、苯、卤代苯、二卤代苯、二卤乙烷、二卤甲烷、乙酸乙酯、丙酸乙酯、甲醇、乙醇、丙醇和丁醇所组成的组。
7、根据权利要求6所述的方法，其特征在于在于其中的溶剂为二氯乙烷。
8、根据权利要求1所述的方法，其特征在于其中的温度约为50～180℃。
9、根据权利要求1所述的方法，其特征在于式Ⅰ化合物中Z为氢，Y为任选地用一个卤素取代的C1～C4烷基或是C1～C4烷氧基。
10、根据权利要求9所述的方法，其特征在于其中所制得的化合物是选自由5-乙基-2，3-吡啶二羧酸二烷酯、2，3-吡啶二羧酸二烷酯、5-甲基-2，3-吡啶二羧酸二烷酯、5-（甲氧基甲基）-2，3-吡啶二羧酸二烷酯及5-（氯甲基）-2，3-吡啶二羧酸二烷酯所组成的组。
CN93101489A 1992-03-10 1993-02-04 2,3－吡啶二羧酸二烷酯及其衍生物的制备方法 Expired - Fee Related CN1042332C (zh)

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HU210903B (en) 1995-09-28
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AU3408493A (en) 1993-09-16
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EP0560019B1 (en) 1996-04-24
DK0560019T3 (da) 1996-05-13
IL104956A0 (en) 1993-07-08
HUT64030A (en) 1993-11-29
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CA2091213A1 (en) 1993-09-11
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FI101961B1 (fi) 1998-09-30
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CZ13493A3 (en) 1994-01-19
TW276250B (zh) 1996-05-21
US5227491A (en) 1993-07-13
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EP0560019A1 (en) 1993-09-15
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ZA931676B (en) 1993-10-06
ATE137222T1 (de) 1996-05-15
AU659283B2 (en) 1995-05-11
SK8393A3 (en) 1993-10-06
SK279565B6 (sk) 1999-01-11
CN1042332C (zh) 1999-03-03
DE69302309D1 (de) 1996-05-30
CZ283077B6 (cs) 1997-12-17
MX9301127A (es) 1994-01-31
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