CN1118455C - 吡啶二羧酸酯衍生物的制备方法 - Google Patents
吡啶二羧酸酯衍生物的制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 6
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical class OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 title description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 pyridine dicarboxylate compound Chemical class 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 claims abstract description 7
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- 239000003513 alkali Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- JDXYSCUOABNLIR-UHFFFAOYSA-N diethyl 2-oxobutanedioate Chemical compound CCOC(=O)CC(=O)C(=O)OCC JDXYSCUOABNLIR-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920004449 Halon® Polymers 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
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- 238000009833 condensation Methods 0.000 abstract description 3
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- KHPXUQMNIQBQEV-UHFFFAOYSA-L oxaloacetate(2-) Chemical compound [O-]C(=O)CC(=O)C([O-])=O KHPXUQMNIQBQEV-UHFFFAOYSA-L 0.000 abstract 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VZTIIQRYWOIVKA-UHFFFAOYSA-N n,n-diethylethanamine;oxalyl dichloride Chemical class ClC(=O)C(Cl)=O.CCN(CC)CC VZTIIQRYWOIVKA-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 229960004756 ethanol Drugs 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007975 iminium salts Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- DXLSXNUUWQHAFK-UHFFFAOYSA-N oxalyl dichloride;pyridine Chemical class C1=CC=NC=C1.ClC(=O)C(Cl)=O DXLSXNUUWQHAFK-UHFFFAOYSA-N 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Peptides Or Proteins (AREA)
Abstract
本发明提供了一种制备具有通式I的吡啶二羧酸酯化合物的单罐法，这是通过将烷基乙烯基醚依次与Vilsmeier反试剂、草乙酸酯和氨源缩合而实现的。
Description
吡啶-2，3-二羧酸及酯是许多生物活性产物，尤其是咪唑啉酮除草剂的基本原料，例如美国专利4,758,667。通过氧化合适的喹啉或烷基吡啶前体来制备吡啶-2，3-二羧酸酯衍生物的已知方法常受困于以下因素：使用昂贵的氧化剂，例如KMnO4、H2Cr2O、SeO2等；反应周期长，例如在使用臭氧、电解法等的反应中；不需要的副反应，例如脱羧反应、N-氧化物的形成等。所以，人们一直在寻找一种制备所需的吡啶-2，3-二羧酸酯衍生物的新方法。
已经发现，通过将合适的烷基乙烯基醚依次与Vilsmeier试剂、草乙酸酯和氨源缩合，可以方便地获得一种制备吡啶-2，3-二羧酸酯衍生物的快速单罐法。
本发明提供了一种制备具有通式I的吡啶-2，3-二羧酸酯衍生物的高效方法
其中，R1是H或可被C1-C4烷氧基或卤素取代的C1-C4烷基；R2和R3各自独立地是C1-C6烷基，优选甲基或乙基。该方法包括：
1)具有通式II的烷基乙烯基醚化合物与至少一摩尔当量的Vilsmeier试剂任选地在第一溶剂中形成第一中间体；
其中通式II化合物是顺式异构体、反式异构体或其混合物，R是C1-C4烷基，R1的定义与通式I中的相同；
2)所述的第一中间体与至少一摩尔当量的具有通式III的草乙酸酯，在至少2摩尔当量碱存在下形成第二中间体；其中R2和R3的定义与通式I中的相同；
3)第二中间体与氨源任选地在第二溶剂中形成具有通式I的吡啶二酯产物。
通式I化合物可用于制备咪唑啉酮除草剂。
在制备吡啶-2，3-二羧酸酯衍生物的的已知方法中，包括降解法，例如适当取代的喹啉或烷基吡啶前体的氧化。但是，氧化反应过程通常成本高而且危险。可喜的是，已发现，通过将合适的通式II烷基乙烯基醚与Vilsmeier试剂、通式III草乙酸酯和氨源依次缩合，可以在一个反应罐中高效制得吡啶-2，3-二羧酸酯衍生物。该反应如流程图I所示，其中X-表示Cl-或PO2Cl2 -。
流程图I
根据本发明的方法，顺式、反式或其混合物形式的通式II烷基乙烯基醚与至少一摩尔当量Vilsmeier反应剂或可性地在第一溶剂中形成第一中间体插烯亚胺盐(vinylogous imidate salt)，后者然后与至少一摩尔当量的通式III草乙酸酯在至少二摩尔当量碱(以有机胺碱为佳)存在下形成第二中间体(亚铵盐(iminium salt))，任选地(且是较好的)在第二溶剂中与氨源形成所需的通式I吡啶-2，3-二羧酸酯衍生物。
Vilsmeier试剂在说明书和权利要求书中指二甲基甲酰胺与活化剂(例如草酰氯、碳酰氯、磷酰氯、亚硫酰氯等)原地反应而生成的产物，可以表示为通式IV的亚铵盐或其插烯物，其中X-表示Cl-或PO2Cl2 -。
卤素在说明书和权利要求书中指Cl、Br、I或F。
适合用作本发明第一溶剂的溶剂是任何惰性有机溶剂，例如烃类，如己烷、戊烷、庚烷等；卤化烃，如二氯甲烷、氯仿、二氯乙烷等，以二氯乙烷或二氯甲烷为佳；芳香烃，如苯、甲苯、二甲苯等；卤化芳香烃，如氯苯、邻二氯苯或其混合物。最好，反应在第一溶剂中进行，而且，最好，第一溶剂是卤化烃，例如二氯乙烷或二氯甲烷。
适用于本发明方法的碱是有机胺碱，例如三乙胺、吡啶、二甲基吡啶、N，N-二甲基哌啶、N-甲基吡咯烷酮等，以三乙胺或吡啶为佳。
适用于本发明方法的氨源是任何原地产生NH3的常规方法，其中包括氨气、铵盐等，以铵盐为佳，例如乙酸铵、氨基磺酸铵等。
适合用作本发明中的第二溶剂的溶剂是极性溶剂，例如水；醇，如乙醇、甲醇、丙醇、丁醇之类的C1-C4烷醇等，以乙醇为佳；有机酸，例如乙酸、丙酸之类C1-C4羧酸等，以乙酸为佳，或以上所述物质的混合物。
反应产物的形成速度一般与反应温度成正比。总的说来，低温将减慢反应速度而高温将加速反应。但是，温度不宜过高，这可能降低产品的得率和纯度。较好的温度范围是从0℃至120℃。
为了帮助理解本发明，给出以下实施例，为的是说明某些更具体的细节。本发明并不受实施例的限定，而仅由权利要求限定。NMR表示核磁共振。
实施例1
吡啶-2，3-二羧酸二乙酯
二甲基甲酰胺(73g，1.00mole)的二氯乙烷溶液在冷却条件下与草酰氯(88ml，1.00mole)缓慢反应，在环境温度下搅拌16小时，与乙基乙烯基醚(72.1g，1.00mole)反应1小时，在环境温度下搅拌16小时。该反应混合物依次与草乙酸二乙酯(199.28g，1.06mole)和(冷却条件下)与三乙胺(224g，2.2mole)反应，搅拌0.5小时，与浓盐酸(200ml)和浓NH4OH(200ml)在100ml水中预混而成的溶液反应。该反应混合物再与水(250ml)、浓NH4OH(70ml)和乙酸(200ml)反应。所得的混合物在N2下，在88℃常压蒸馏去除1850g馏出液。然后用无水乙醇(1.0L)和NH4OCOCH3(180g)处理蒸馏罐，在回流温度加热16小时，并在100℃蒸馏去除887g馏出液。冷却蒸馏罐，将残留物分配在水和2∶1乙酸乙酯/己烷中。分离出有机相，依次用水和盐水洗涤，真空浓缩得到油状标题化合物，179.5g(纯度77％)，得率58.5％，用NMR分析鉴定。
实施例2-7
使用与实施例1基本相同的方法，使用适当取代的乙烯基醚底物，可得到表I所示的结果。
表I
实施例编号 R R1 酰氯 碱 Y- 得率
(第一溶剂) (摩尔当量) (第二溶剂) (％)
2 正丁基 H 草酰氯 三乙胺 -OCOCH3 52.8
(ClCH2CH2Cl) (2.2) (C2H5OH)
3 正丁基 H 草酰氯 吡啶 -OCOCH3 39.6
(ClCH2CH2Cl) (2.2) (C2H5OH)
4 C2H5 H POCl3 三乙胺 -OCOCH3 62.3
(CH2Cl2) (3.5) (C2H5OH)
5 C2H5 CH3 草酰氯 三乙胺 -SO3NH2 48
(CH2Cl2) (2.5) (CH3CO2H)
6 C2H5 C2H5 草酰氯 三乙胺 -OCOCH3 42
(CH2Cl2) (2.5) (CH3CO2H)
7 CH3 CH2OCH3 POCl3 三乙胺 OH 17.7
(CH2Cl2) (3.5) (H2O/CH3CO2C2H5)1草乙酸二乙酯
Claims (8)
1.制备通式I化合物的方法，其中，R1是H或可被C1-C4烷氧基或卤素取代的C1-C4烷基；R2和R3各自独立地是C1-C6烷基；该方法包括：
a)具有通式II的烷基乙烯基醚化合物与至少一摩尔当量的Vilsmeier试剂任选地在第一溶剂中形成第一中间体；其中通式II化合物是顺式异构体、反式异构体或其混合物，R是C1-C4烷基，R1的定义与通式I中的相同；
b)所述的第一中间体与至少一摩尔当量的具有通式III的草乙酸酯，在至少2摩尔当量碱存在下反应形成第二中间体；
其中R2和R3的定义与通式I中的相同；
c)第二中间体与氨源任选地在第二溶剂中形成具有通式I的吡啶二酯产物；
以上反应在0-120℃之间进行。
2.根据权利要求1所述的方法，其中存在第一溶剂并且是卤化烃。
3.根据权利要求1所述的方法，其中的碱是三乙胺。
4.根据权利要求1所述的方法，其中存在第二溶剂并且是C1-C4烷基醇或C1-C4羧酸或其混合物。
5.根据权利要求1所述的方法，其中的氨源是乙酸铵。
6.根据权利要求1所述的方法，其中的R1是H、甲基、乙基或甲氧基甲基。
7.根据权利要求6所述的方法，其中的R1是H。
8.根据权利要求1所述的方法，其中的R2和R3各自独立地是甲基或乙基。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/014,546 | 1998-01-28 | ||
| US09/014,546 US5892050A (en) | 1998-01-28 | 1998-01-28 | Process for the preparation of pyridine dicarboxylate derivatives |
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| Publication Number | Publication Date |
|---|---|
| CN1227222A CN1227222A (zh) | 1999-09-01 |
| CN1118455C true CN1118455C (zh) | 2003-08-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 98125974 Expired - Fee Related CN1118455C (zh) | 1998-01-28 | 1998-12-28 | 吡啶二羧酸酯衍生物的制备方法 |
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|---|---|
| US (1) | US5892050A (zh) |
| EP (1) | EP0933362B1 (zh) |
| JP (1) | JP4346141B2 (zh) |
| KR (1) | KR100566502B1 (zh) |
| CN (1) | CN1118455C (zh) |
| AR (1) | AR014500A1 (zh) |
| AT (1) | ATE215533T1 (zh) |
| AU (1) | AU756604B2 (zh) |
| BR (1) | BR9900179B1 (zh) |
| CA (1) | CA2260469C (zh) |
| CZ (1) | CZ295307B6 (zh) |
| DE (1) | DE69901130T2 (zh) |
| DK (1) | DK0933362T3 (zh) |
| ES (1) | ES2175899T3 (zh) |
| HU (1) | HUP9900194A1 (zh) |
| IL (1) | IL127853A (zh) |
| NZ (1) | NZ333916A (zh) |
| PL (1) | PL190302B1 (zh) |
| PT (1) | PT933362E (zh) |
| SG (1) | SG74697A1 (zh) |
| SK (1) | SK283297B6 (zh) |
| TW (1) | TW466234B (zh) |
| ZA (1) | ZA99615B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7032119B2 (en) * | 2000-09-27 | 2006-04-18 | Amphus, Inc. | Dynamic power and workload management for multi-server system |
| EP2365965B1 (en) | 2008-11-13 | 2019-01-09 | Basf Se | Process for manufacturing substituted 3-pyridylmethyl ammonium bromides |
| WO2010054952A1 (en) * | 2008-11-13 | 2010-05-20 | Basf Se | 2-[(1-cyanopropyl)carbamoyl]-5-chloromethyl nicotinic acids and the use thereof in manufacturing herbicidal imidazolinones |
| EP2358678B1 (en) | 2008-11-13 | 2015-01-14 | Basf Se | Process for manufacturing 5-chloromethyl-2,3-pyridine dicarboxylic acid anhydrides |
| TWI506019B (zh) | 2008-12-08 | 2015-11-01 | Basf Se | 製造經取代５－甲氧基甲基吡啶－２，３－二羧酸衍生物之方法 |
| DK2982673T3 (en) | 2008-12-09 | 2018-06-06 | Basf Se | PROCEDURE FOR PREPARING 5-CHLORMETHYLPYRIDINE-2,3-DICARBOXYLYAIC ANHYRIDE |
| CN103724257B (zh) * | 2012-10-11 | 2015-06-10 | 中国中化股份有限公司 | 一种制备2,3-二羧酸酯吡啶类化合物的方法 |
| CN104447527B (zh) * | 2013-09-23 | 2017-06-06 | 中国中化股份有限公司 | 一种制备吡啶‑2，3‑二羧酸酯化合物的方法 |
| CN107759516B (zh) * | 2016-08-16 | 2021-04-27 | 沈阳化工研究院有限公司 | 一种烷基醚取代吡啶-2，3-二羧酸衍生物的制备方法 |
| EP3782985A1 (en) | 2019-08-19 | 2021-02-24 | BASF Agrochemical Products B.V. | Process for manufacturing 5-methoxymethylpyridine-2,3-dicarboxylic acid derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4656283A (en) * | 1982-05-25 | 1987-04-07 | American Cyanamid Company | Alkyl esters of substituted 2-methyl-3-quinolinecarboxylic acid and quinoline-2,3-dicarboxylic acid |
| US5252538A (en) * | 1984-05-21 | 1993-10-12 | American Cyanamid Company | (2-imidazolin-2-yl) fused heteropyridine compounds, intermediates for the preparation of and use of said compounds as herbicidal agents |
| US4723011A (en) * | 1985-10-28 | 1988-02-02 | American Cyanamid Company | Preparation of substituted and disubstituted-pyridine-2,3-dicarboxylate esters |
| ATE82279T1 (de) * | 1986-02-10 | 1992-11-15 | Ciba Geigy Ag | Verfahren zur herstellung von 2-(imidazolin-2-yl)-pyridin- und -chinolin-3-carbonsaeuren. |
| JPS62207238A (ja) * | 1986-03-07 | 1987-09-11 | Mitsubishi Paper Mills Ltd | β−アルコキシアクロレイン誘導体の製造法 |
| EP0296109A3 (de) * | 1987-06-18 | 1989-12-20 | Ciba-Geigy Ag | 2-(Imidazolin-2-yl)nicotinsäurederivate |
| DE4025076A1 (de) * | 1990-08-08 | 1992-02-13 | Hoechst Ag | Verfahren zur herstellung von estern der 5-alkylpyridin-2,3-dicarbonsaeure |
| DE19501478A1 (de) * | 1995-01-19 | 1996-07-25 | Bayer Ag | Verfahren zur Herstellung von in 5-Stellung substituierten 2-Chlorpyridinen |
| US5925764A (en) * | 1998-06-15 | 1999-07-20 | Wu; Wen-Xue | Process and intermediated for the manufacture of pyridine-2, 3-dicarboxylate compounds |
-
1998
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Also Published As
| Publication number | Publication date |
|---|---|
| SK283297B6 (sk) | 2003-05-02 |
| ZA99615B (en) | 2000-07-27 |
| CZ295307B6 (cs) | 2005-07-13 |
| AR014500A1 (es) | 2001-02-28 |
| BR9900179B1 (pt) | 2010-02-09 |
| ES2175899T3 (es) | 2002-11-16 |
| NZ333916A (en) | 1999-07-29 |
| JP4346141B2 (ja) | 2009-10-21 |
| CN1227222A (zh) | 1999-09-01 |
| PL331068A1 (en) | 1999-08-02 |
| DE69901130D1 (de) | 2002-05-08 |
| CA2260469A1 (en) | 1999-07-28 |
| ATE215533T1 (de) | 2002-04-15 |
| TW466234B (en) | 2001-12-01 |
| KR19990068247A (ko) | 1999-08-25 |
| PL190302B1 (pl) | 2005-11-30 |
| AU756604B2 (en) | 2003-01-16 |
| PT933362E (pt) | 2002-09-30 |
| HU9900194D0 (en) | 1999-03-29 |
| HUP9900194A1 (hu) | 2000-03-28 |
| US5892050A (en) | 1999-04-06 |
| BR9900179A (pt) | 2000-05-09 |
| SK10699A3 (en) | 1999-08-06 |
| DE69901130T2 (de) | 2002-08-29 |
| CZ23499A3 (cs) | 1999-08-11 |
| DK0933362T3 (da) | 2002-07-01 |
| CA2260469C (en) | 2008-11-25 |
| IL127853A (en) | 2003-04-10 |
| SG74697A1 (en) | 2000-08-22 |
| EP0933362A1 (en) | 1999-08-04 |
| EP0933362B1 (en) | 2002-04-03 |
| IL127853A0 (en) | 1999-10-28 |
| AU1423599A (en) | 1999-08-19 |
| KR100566502B1 (ko) | 2006-03-31 |
| JPH11255749A (ja) | 1999-09-21 |
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