CN102245577B - 2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸及其在制备除草咪唑啉酮中的用途 - Google Patents
2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸及其在制备除草咪唑啉酮中的用途 Download PDFInfo
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- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical class O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000002363 herbicidal effect Effects 0.000 title abstract description 3
- BIMBYYNPGDQOLD-UHFFFAOYSA-N 5-(chloromethyl)-2-(1-cyanopropylcarbamoyl)pyridine-3-carboxylic acid Chemical class CCC(C#N)NC(=O)C1=NC=C(CCl)C=C1C(O)=O BIMBYYNPGDQOLD-UHFFFAOYSA-N 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 7
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 40
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- -1 1-cyanopropyl Chemical group 0.000 claims description 22
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000009333 weeding Methods 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- PVNIIMVLHYAWGP-UHFFFAOYSA-N nicotinic acid Natural products OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229960003512 nicotinic acid Drugs 0.000 claims description 12
- 235000001968 nicotinic acid Nutrition 0.000 claims description 12
- 239000011664 nicotinic acid Substances 0.000 claims description 12
- 229940117389 dichlorobenzene Drugs 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 150000002825 nitriles Chemical class 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 7
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 125000005219 aminonitrile group Chemical group 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical group 0.000 claims description 4
- 229940043232 butyl acetate Drugs 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000011133 lead Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 150000001768 cations Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- NUPJIGQFXCQJBK-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-5-(methoxymethyl)nicotinic acid Chemical compound OC(=O)C1=CC(COC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 NUPJIGQFXCQJBK-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000005566 Imazamox Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010561 standard procedure Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 0 C*c1c(*)c(CCl)c(*)nc1C(CNC(*)(*)C#N)=O Chemical compound C*c1c(*)c(CCl)c(*)nc1C(CNC(*)(*)C#N)=O 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JLJSCLYUDCQETH-UHFFFAOYSA-N 3-(chloromethyl)furo[3,4-b]pyridine-5,7-dione Chemical compound ClCC1=CN=C2C(=O)OC(=O)C2=C1 JLJSCLYUDCQETH-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FSNCEEGOMTYXKY-JTQLQIEISA-N Lycoperodine 1 Natural products N1C2=CC=CC=C2C2=C1CN[C@H](C(=O)O)C2 FSNCEEGOMTYXKY-JTQLQIEISA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229950001902 dimevamide Drugs 0.000 description 1
- MCQOWYALZVKMAR-UHFFFAOYSA-N furo[3,4-b]pyridine-5,7-dione Chemical compound C1=CC=C2C(=O)OC(=O)C2=N1 MCQOWYALZVKMAR-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- C07D213/81—Amides; Imides
Abstract
本发明涉及式(I)的2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸,其中Z为氢或卤素;Z1为氢、卤素、氰基或硝基;R1为C1-C4烷基;R2为C1-C4烷基、C3-C6环烷基或R1和R2连同它们连接的原子一起代表任选甲基取代的C3-C6环烷基;R3为氢或优选选自碱金属、碱土金属、镁、铜、铁、锌、钴、铅、银、镍、铵和有机铵的阳离子;式(I)的2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸为合成除草咪唑啉酮的有用中间体。
Description
本发明涉及2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸,这些化合物的制备及其在制备除草咪唑啉酮如咪草啶酸(imazamox)中的用途。
2-(2-咪唑啉-2-基)烟酸的衍生物,如下式的咪草啶酸(2-[(RS)-4-异丙基-4-甲基-5-氧代-2-咪唑啉-2-基]-5-甲氧基甲基烟酸),为有用的选择性除草剂,其用作ALS抑制剂并可用于出苗前和出苗后施用。
合成这些化合物的各种方法从文献中已知,例如参见EP-A 0322616、EP-A 0747360、EP-A 0933362或Q.Bi等人,Modern Agrochemicals6(2)(2007)10-14。
尽管工业规模上的合成通过这些方法进行但其仍有改进的空间,尤其是从经济学和生态学方面考虑,例如改进总收率或避免特定溶剂或试剂。
EP-A 0322616公开了通过使5-氯甲基-2,3-吡啶二甲酸酐与α-氨基-α-甲基戊酰胺反应合成2-[(1-氨基甲酰基-1,2-二甲基丙基)氨基甲酰基]-5-氯甲基烟酸并进一步通过与NaOCH3反应和随后的酸化使该化合物转化成咪草啶酸。
本发明的一个任务是提供用于合成除草咪唑啉酮的新的有用中间体及其制备方法。本发明的另一任务是提供一种制备除草咪唑啉酮如咪草啶酸的改进方法。
已经发现2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸是制备除草咪唑啉酮的有用中间体。
EP-A 0184027和EP-A 0144595描述了使吡啶-2,3-二甲酸酐与2-氨基-2,3-二甲基丁腈反应并进一步转化成除草咪唑啉酮,然而没有公开5-氯甲基取代的化合物实例。
因此,本发明的一个方面是提供一种式(I)的2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸:
其中
Z为氢或卤素;
Z1为氢、卤素、氰基或硝基;
R1为C1-C4烷基;
R2为C1-C4烷基、C3-C6环烷基或R1和R2连同它们连接的原子一起代表任选甲基取代的C3-C6环烷基;
R3为氢或优选选自碱金属、碱土金属、镁、铜、铁、锌、钴、铅、银、镍、铵和有机铵的阳离子。
本发明的另一方面是提供一种制备式(I)2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸的方法,其包括如下步骤:
(i)使式(II)的5-氯甲基吡啶-2,3-二甲酸酐
其中Z、Z1如式(I)所定义,与2-氨基烷基腈(III)反应
H2N-CR1R2-CN(III)
其中R1和R2如式(I)所定义。
本发明的另一方面是提供式(I)化合物在制备式(IV)除草咪唑啉酮中的用途,
其中Z、Z1、R1、R2、R3如式(I)所定义。
本发明的另一方面是提供制备式(IV)的除草咪唑啉酮化合物的方法,其包括如下步骤:
(i)水解式(I)的腈获得式(V)的酰胺,
其中Z、Z1、R1、R2、R3如式(I)所定义,和
(ii)使化合物(V)与CH3OM或MOH/CH3OM(其中M为碱金属,优选Na或K)反应,任选然后酸化形成除草咪唑啉酮(IV)。
在除草咪唑啉酮的合成中使用新的中间体(I)导致制备酰胺(V)中收率提高并因此提高了合成过程的总收率。甚至不加入EP-A 0144595中推荐的氮碱,酸酐开环的位置选择性也非常好。
在式(I)中的符号优选具有下列含义:
Z优选为氢;
Z1优选为氢;
R1优选C1-C4烷基;
R2优选C1-C4烷基;
R3优选氢、碱金属或NR4R5 3,其中R4为氢或R5,且R5为C1-C4烷基。
优选其中所有符号具有优选含义的式(I)化合物。
特别优选的式(I)化合物为化合物(Ia)及其盐:
以合成优选的化合物(Ia),其中R1和R2如式(III)所定义为例,化合物(I)可以通过使酸酐(II)与氨基腈(III)反应制备:
氨基腈(III)可商购或可以通过现有技术已知的方法制备。通常使用每当量化合物(II)0.8-1.2当量,优选0.95-1.1当量氨基腈(III)。
若乙酸不用作主溶剂,则加入0.5-10当量,优选1-3当量(基于化合物(II))是有利的。
其它提高开环反应(2对3位)选择性的有利添加剂列出在US 4,562,257中,并且包括吡啶、4-甲基吡啶、2-甲基吡啶和喹啉。然而,尽管可以使用这些添加剂,但是根据本发明没有必要使用这些添加剂,且在实施方案中,所列添加剂没有出现在反应混合物中。
反应通常在约40-120℃、优选约60-100℃的温度下进行。反应时间通常为约1-3h。
在优选的实施方案中,将化合物(II)溶于溶剂中并升至反应温度,并逐渐加入氨基腈(III)。反应完全并冷却后,可将腈化合物(I)通过标准方法分离。
然而,在优选的实施方案中,不将化合物(I)分离而将反应混合物直接用于随后腈的水解。
在本发明的优选实施方案中,用于制备化合物(I)的酸酐(II)通过包括如下步骤的方法获得:
(i)在选自卤代烃,优选二氯乙烷、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯和四氯甲烷的溶剂中,任选在自由基引发剂存在下,使式(VI)化合物与氯化剂反应,
其中符号具有式(I)中给出的含义,和
(ii)将步骤(i)中形成的化合物(II)从选自如下物质的溶剂中结晶:1,2-二氯乙烷、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、三氯甲烷、二氯甲烷、甲苯、二甲苯、乙酸烷基酯(例如乙酸乙酯、乙酸丁酯、乙酸甲酯)、甲基叔丁基醚、二异丙基醚、环戊基甲基醚及其混合物。
式(V)化合物及其制备例如从EP-A 0933362中已知。
合适的氯化剂包括氯、硫酰氯、N-氯琥珀酰亚胺和三氯异氰脲酸。优选的氯化剂为氯和硫酰氯(SO2Cl2)。
吡啶化合物(VI)与氯化剂的摩尔比通常为1∶0.5-1.5,优选1∶0.7-1.2,更优选1∶0.8-1.1。
适合用于引发反应的自由基引发剂为在选定反应温度下分解的那些,即通过自身分解的那些和在氧化还原体系存在下分解的那些。优选的引发剂实例为自由基引发剂,例如偶氮化合物和过氧化物。然而,其也可以使用氧化还原体系,尤其是基于氢过氧化物的那些,例如氢过氧化枯烯。也可以为光引发的氯化而不加入引发剂。
适合用于本发明方法的自由基引发剂包括2,2’-偶氮二异丁腈(AIBN)、2,2’-偶氮二(2-甲基丁腈)、2,2’-偶氮二(2,4-二甲基戊腈)、1,1’-偶氮二(环己烷甲腈)、有机和无机过氧化物如过氧化二月桂酰、过氧化氢、过氧化苯甲酰等,优选2,2’-偶氮二异丁腈、2,2’-偶氮二(2-甲基丁腈)和过氧化二月桂酰,特别优选2,2’-偶氮二异丁腈。
优选引发剂在整个反应过程中连续加入。
引发剂与氯化剂的摩尔比优选为0.001-0.1∶1,更优选0.002-0.05∶1。
用于步骤(i)的有机溶剂为卤代烃,优选氯代烃,更优选氯代脂族或芳族烃。最优选为选自如下物质的溶剂:氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、1,2-二氯乙烷和四氯甲烷,优选1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、1,2-二氯乙烷和氯苯。特别优选氯苯。在此所用的术语溶剂包括上述化合物的两种或更多种的混合物。另外该术语包括包含至多20重量%,优选至多10重量%,尤其至多5重量%非卤代烃的其它溶剂的溶剂。
有机溶剂的用量可以在宽范围内变化。优选使用每摩尔化合物(V)250-1500g,更优选500-1000g有机溶剂。
在优选的实施方案中(其中氯化剂为液体)步骤(i)通过将化合物(VI)溶于有机溶剂中,加热,并缓慢加入引发剂在氯化剂中的溶液进行。反应完全后将溶剂部分或全部蒸馏出,并将混合物缓慢冷却以沉淀产物。
在另一优选实施方案中,将化合物(VI)溶于溶剂中,并将气态氯装入反应容器中或通过溶液。反应完全后,将溶剂至少部分蒸馏出以除去过量氯和气态副产物如HCl。然后将反应混合物冷却并将化合物(II)沉淀。
在另一优选实施方案中,反应(步骤(i))作为连续操作进行。
若将氯用作氯化剂,则反应通常在约0-160℃,优选约60-140℃,特别优选约80-120℃的温度下进行。
若使用液态的氯化剂,尤其是硫酰氯,则反应通常在约0-140℃,优选约50-120℃,特别优选约70-90℃的温度下进行。
反应可在大气压下或在高达6巴,优选高达2巴的升高的压力下进行。若将氯用作氯化剂则优选升高的压力。
反应时间(对于步骤(i))随反应参数而不同但通常在5min至300h之间。在连续反应的情况下,反应容器中的停留时间优选为2-10min,尤其是约5min。
在反应的步骤(ii)中,化合物(II)从选自如下物质的溶剂中结晶:氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、1,2-二氯乙烷、三氯甲烷、甲苯、二甲苯、乙酸乙酯、乙酸丁酯、乙酸甲酯、甲基叔丁基醚、二异丙基醚、环己基甲基醚及其混合物。
在此所用的术语溶剂包括溶剂混合物。
优选氯苯和二氯苯,特别优选氯苯。
用于结晶的溶剂可以包含高达90重量%,优选10-80重量%,尤其是20-60重量%的反溶剂,即在其中式(I)化合物基本不溶的液体,例如脂族烃如正己烷、异己烷或环己烷。
结晶通常在约-40℃至30℃、优选约0-20℃的温度下进行。化合物(I)在其结晶的溶剂中的浓度通常为5-60重量%,优选10-50重量%。
结晶可以通过标准方法进行,例如通过冷却化合物(II)的饱和溶液、用纯化合物(I)接种、加入反溶剂或结合这些方法进行。
根据本发明,化合物(II)必须至少一次从上述溶剂的一种或这些溶剂的两种或更多种的混合物中结晶。
在本发明的优选实施方案中,步骤(i)的氯化在可用于步骤(ii)结晶的溶剂中进行。优选在步骤(i)完成后然后将化合物(II)从反应混合物中结晶。
任选有机溶剂可以部分(或完全)蒸馏出,且也可以例如加入其它溶剂以弥补蒸馏出的溶剂。
进一步优选将化合物(II)重结晶一次或两次,优选一次以提高产物的纯度。重结晶通常在和初始溶剂相同的溶剂中进行,但当然其也可以使用来自所列组中的不同溶剂或溶剂混合物。
优选将重结晶的母液再循环至第一结晶步骤以使收率损失最小。
在本发明的另一优选实施方案中,步骤(i)的氯化在与用于步骤(ii)结晶的溶剂不同的溶剂中进行。在该实施方案中,将步骤(i)的溶剂除去,并且将粗化合物(I)溶于步骤(ii)的溶剂中并结晶。当然可以用相同或不同的溶剂进行一个或多个重结晶步骤,并且可将母液如上所述再循环。
优选将相同的溶剂用于步骤(i)和(ii),尤其是氯苯或二氯苯。
(重)结晶后化合物(I)的纯度通过HPLC(被分析物用甲醇淬火后)测定,优选为至少95%,更优选至少98%。
(重)结晶后化合物(II)的分离可以通过标准方法进行,例如通过过滤、用合适溶剂洗涤并干燥。
因为其纯度,如上所述制备的化合物(II)对于合成本发明的中间体(I)特别有用。因此,在优选的实施方案中,制备化合物(I)的方法包括如下步骤:
(i-1)在选自卤代烃的溶剂中,任选在自由基引发剂的存在下,使式(VI)化合物与氯化剂反应,
其中符号具有式(I)中给出的含义,
(i-2)将步骤(i)中形成的化合物(II)从选自如下物质的溶剂中结晶获得酸酐(II):1,2-二氯乙烷、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、三氯甲烷、二氯甲烷、甲苯、二甲苯、、乙酸烷基酯(例如乙酸乙酯、乙酸丁酯、乙酸甲酯)、甲基叔丁基醚、二异丙基醚、环戊基甲基醚及其混合物,和
(i-3)使酸酐(II)与2-氨基烷基腈(III)反应,
H2N-CR1R2-CN(iii)
其中R1和R2如式(I)所定义。
式(I)化合物为合成除草咪唑啉酮(IV)的有用中间体。
以优选的化合物(Ia)和(Va)为例,在第一步中将腈官能团水解得到相应的酰胺(V):
在通常的程序中,将稍微过量(例如基于(I)1.1-1.5当量)的无机强酸,优选硫酸(优选浓度30-98%)和水(例如2-10当量)在通常为约30-120℃,优选50-90℃的温度下加入。混合物进一步搅拌直到转化完全。反应时间通常为1-8h,优选1-5h。
处理和分离可以通过标准方法实现,例如从水溶液中沉淀(例如作为它的铵盐)。在优选的实施方案中,将反应混合物直接用于随后的反应步骤。
在本发明的其它方法中,除草咪唑啉酮化合物(IV)通过包括如下步骤的方法制备:
(i)制备式(V)的酰胺基化合物,和
(ii)使化合物(V)与CH3OM或MOH/CH3OH(其中M为碱金属阳离子,优选Na或K)反应,然后酸化形成除草咪唑啉酮化合物(IV)。
在一个实施方案中,类似于EP 0322616实施例11,在步骤(ii)中使酰胺基化合物(V),优选以铵盐形式(R3为HNR3)与碱金属甲醇盐,优选NaOCH3在甲醇中反应。所得悬浮液保持回流直至转化完全。冷却后将混合物酸化获得或者作为铵盐(酸化至pH约4)或者作为游离酸(酸化至pH≤2)的化合物(IV)。
在另一优选实施方案中,在步骤(ii)中使来自步骤(i)的反应混合物与甲醇(通常基于(V)2-100当量)在含水碱(通常基于(V)3-100当量)的存在下反应,该碱优选选自MOH和MOCH3,其中M为碱金属阳离子,优选Na或K,特别是Na。
反应在20-120℃,优选40-90℃的温度下进行。反应可以在大气压或升高的压力下进行,优选压力在所需反应温度下形成。反应时间通常为1-8h,优选1-5h。
咪唑啉酮产物(IV)的分离可以通过标准方法实现。在优选实施方案中,加入水并蒸馏出有机溶剂。残余物可以吸收在水中并酸化,由此化合物(IV)沉淀。过滤后粗产物可以例如通过与水搅拌或重结晶进一步纯化。
在本发明的另一优选实施方案中提供了制备式(IV)除草咪唑啉酮的方法,包括如下步骤:
(i)在甲醇中,使化合物(I)与选自MOH和MOCH3,其中M为碱金属的碱和(含水)H2O2反应,任选然后酸化。
该反应可以类似于描述在EP-A 0144595中的程序进行。
本发明通过下列实施例说明但不因此对其限定。
实施例1
合成2-[(1-氰基-1,2-二甲基丙基)氨基甲酰基]-5-氯甲基烟酸(Ia):
将9.6g(48mmol)5-氯甲基吡啶-2,3-二甲酸酐(IIa)、40.0g(435mmol)甲苯和6.7g(112mmol)乙酸装入反应器中并加热至69℃。在25min内在72℃-76℃的温度下加入7.2g(51mmol)α-氨基-1,2-二甲基丁腈。混合物在75℃下搅拌另外90min。冷却后将混合物直接用于腈的水解。
实施例2
合成咪草啶酸(IVa)
(a)合成2-[(1-氨基甲酰基-1,2-二甲基丙基)氨基甲酰基]-5-氯甲基烟酸(Va)
在5min内在69-80℃下将6.0g(59mmol)硫酸(98%)加入14.9g(48mmol)腈(Ia)(来自实施例1)中。在70-78℃下加入4.1g(228mmol)水并在69℃下连续搅拌5h。出现的产物形成甲苯不溶性油。反应混合物不经处理用于随后的步骤。
(b)合成咪草啶酸(IVa)
在65℃下将94g(2.94mol)甲醇加入15.7g(48mmol)酰胺基化合物(Va)(来自步骤(a)的反应混合物)中,随后加入42g(525mmol)NaOH(在水中50%)。溶液变成悬浮液,然后连续搅拌另外90min。
加入80g水并在50℃和80-8毫巴下除去溶剂。将残余物溶于水并且用29g硫酸(98%)将碱性溶液酸化。从pH4起沉淀咪草啶酸。悬浮液在室温下过滤并用100ml水洗涤。
收率:16.5g(82%纯度,44mmol,92%)
通过搅拌粗产物与水纯度增加至>95%。
实施例3
合成5-氯甲基-2,3-吡啶二甲酸酐(IIa)
将106.8g(0.65mol)5-甲基-2,3-吡啶二甲酸酐溶于427g氯苯中并加热至85℃。在45min内加入0.64g(0.004mol)AIBN在99.0g(0.66mol)SO2Cl2中的溶液。混合物在85℃下搅拌另外90min。将氯苯部分蒸馏出并且经过10小时将溶液缓慢冷却至10℃。过滤出沉淀并用氯苯/己烷洗涤。
收率:85.0g(0.40mmol,60%),其中58.1g(0.27mmol)可以在沉淀后分离。
Claims (14)
1.一种式(I)的2-[(1-氰基丙基)氨基甲酰基]-5-氯甲基烟酸:
其中
Z为氢或卤素;
Z1为氢、卤素、氰基或硝基;
R1为C1-C4烷基;
R2为C1-C4烷基、C3-C6环烷基或R1和R2连同它们连接的原子一起代表任选甲基取代的C3-C6环烷基;
R3为氢或阳离子。
2.根据权利要求1的化合物,其中Z和Z1为H。
3.根据权利要求1或2的化合物,其中
R1为CH(CH3)2;
R2为CH3。
4.根据权利要求1或2的化合物,其中
Z和Z1为H;
R1为CH(CH3)2;
R2为CH3;
R3为H。
6.根据权利要求5的方法,其中酸酐(II)与氨基腈(III)的比例为1:0.8-1.2。
7.根据权利要求5或6的方法,其中或者乙酸为溶剂;或者将基于(II),0.5-10当量乙酸加入溶剂中。
8.根据权利要求5或6的方法,其中所述反应在40-120℃的温度下进行。
10.根据权利要求9的方法,其中所述乙酸烷基酯选自乙酸乙酯、乙酸丁酯和乙酸甲酯。
13.一种制备式(IV)的除草咪唑啉酮化合物的方法,
其中Z、Z1、R1、R2、R3如权利要求1中的式(I)所定义,
所述方法包括如下步骤:
(i)水解根据权利要求1的式(I)腈获得根据权利要求12的式(V)酰胺,和
(ii)使化合物(V)与CH3OM或MOH/CH3OM反应,任选然后酸化形成除草咪唑啉酮(IV),其中M为碱金属。
14.根据权利要求13的方法,其包括如下步骤:
(i-1)通过使根据权利要求5的式(II)酸酐与根据权利要求5的氨基腈(III)反应而制备根据权利要求1的式(I)化合物,其中所述反应在选自芳烃、氯代芳烃、氯代脂族烃、乙酸及其混合物的溶剂中进行,反应混合物基本不含吡啶、甲基吡啶和喹啉,和
(i-2)水解由此获得的式(I)化合物得到根据权利要求12的式(V)的酰胺化合物。
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US61/114,238 | 2008-11-13 | ||
PCT/EP2009/064495 WO2010054952A1 (en) | 2008-11-13 | 2009-11-03 | 2-[(1-cyanopropyl)carbamoyl]-5-chloromethyl nicotinic acids and the use thereof in manufacturing herbicidal imidazolinones |
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CN102245577B true CN102245577B (zh) | 2014-03-26 |
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EP (1) | EP2370410B1 (zh) |
JP (1) | JP5619761B2 (zh) |
CN (1) | CN102245577B (zh) |
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WO2010054954A1 (en) | 2008-11-13 | 2010-05-20 | Basf Se | Process for manufacturing 5-chloromethyl-2,3-pyridine dicarboxylic acid anhydrides |
WO2010055139A1 (en) | 2008-11-13 | 2010-05-20 | Basf Se | Process for manufacturing substituted 3-pyridylmethyl ammonium bromides |
JP5570524B2 (ja) | 2008-12-09 | 2014-08-13 | ビーエーエスエフ ソシエタス・ヨーロピア | 5−ホルミル−ピリジン−2,3−ジカルボン酸エステルの製造方法 |
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EP0322616A2 (en) * | 1987-12-31 | 1989-07-05 | American Cyanamid Company | Novel 5(and/or 6)substituted 2-(2-imidazolin-2-yl)nicotinic acids, esters and salts, useful as herbicidal agents and nivel intermediates for the preparation of said nicotinic acids, esters and salts |
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DE3330604A1 (de) | 1983-08-25 | 1985-03-28 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von brommethylthiophen-carbonsaeureestern |
US4782157A (en) | 1984-12-03 | 1988-11-01 | American Cyanamid Co. | Preparation of substituted and unsubstituted 2-carbamoyl nicotinic and 3-quinolinecarboxylic acids |
US5334576A (en) * | 1986-07-28 | 1994-08-02 | American Cyanamid Company | 5 (and/or 6) substituted 2-(2-imidazolin-2-yl)nicotinic acids, esters and salts, useful as herbicidal agents and novel intermediates for the preparation of said nicotinic acids, esters and salts |
US5026859A (en) * | 1989-12-27 | 1991-06-25 | American Cyanamid Company | Alkyl esters of 5-heterocyclic-pyridine-2,3-dicarboxylic acids |
US5215568A (en) | 1991-10-31 | 1993-06-01 | American Cyanamid Company | Oxime derivatives of formylpyridyl imidazolinones, the herbicidal use and methods for the preparation thereof |
US5288866A (en) * | 1991-12-20 | 1994-02-22 | American Cyanamid Company | 5,6-disubstituted-3-pyridylmethyl ammonium halide compounds useful for the preparation of 5- (substituted methyl)-2,3-pyridinedicarboxylic acids |
DE69615276T2 (de) | 1995-06-05 | 2002-07-25 | Basf Ag | Verbessertes Verfahren zur Herstellung von 5-(Alkoxymethyl)-pyridin-2,3-dicarboxylat Salz |
US5892050A (en) | 1998-01-28 | 1999-04-06 | American Cyanamid Company | Process for the preparation of pyridine dicarboxylate derivatives |
US5973154A (en) * | 1999-05-03 | 1999-10-26 | American Cyanamid Company | Process for the preparation of chiral imidazolinone herbicides |
US6339158B1 (en) * | 1999-05-03 | 2002-01-15 | American Cyanamid Co. | Process for the preparation of chiral nicotinic, quinolinic or benzoic acid imidazolinone herbicides |
US20100055042A1 (en) * | 2008-05-23 | 2010-03-04 | Vinith Yathindranath | Enhancing Clot Busting Medication in Stroke with Directed Drug Convection using Magnetic Nano-Particles |
EP2145682A1 (de) | 2008-07-18 | 2010-01-20 | Roche Diagnostics GmbH | Testelement zur Analyse einer Körperflüssigkeitsprobe auf einen darin enthaltenen Analyten, Analysesystem und Verfahren zur Steuerung der Bewegung einer in einem Kanal eines Testelements enthaltenen Flüssigkeit |
WO2010055042A1 (en) | 2008-11-13 | 2010-05-20 | Basf Se | 2-[(1-cyanopropyl)carbamoyl]-5-methoxymethyl nicotinic acids and the use thereof in manufacturing herbicidal imidazolinones |
WO2010055139A1 (en) | 2008-11-13 | 2010-05-20 | Basf Se | Process for manufacturing substituted 3-pyridylmethyl ammonium bromides |
WO2010054954A1 (en) | 2008-11-13 | 2010-05-20 | Basf Se | Process for manufacturing 5-chloromethyl-2,3-pyridine dicarboxylic acid anhydrides |
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2009
- 2009-11-03 EP EP09745045.6A patent/EP2370410B1/en not_active Not-in-force
- 2009-11-03 CN CN200980149746.6A patent/CN102245577B/zh not_active Expired - Fee Related
- 2009-11-03 US US13/128,782 patent/US8563734B2/en not_active Expired - Fee Related
- 2009-11-03 BR BRPI0921883-1A patent/BRPI0921883A2/pt not_active Application Discontinuation
- 2009-11-03 WO PCT/EP2009/064495 patent/WO2010054952A1/en active Application Filing
- 2009-11-03 JP JP2011535961A patent/JP5619761B2/ja not_active Expired - Fee Related
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EP0144595A1 (en) * | 1983-11-07 | 1985-06-19 | American Cyanamid Company | Preparation of 2-carbamoyl nicotinic and 3-quinoline carboxylic acids |
EP0322616A2 (en) * | 1987-12-31 | 1989-07-05 | American Cyanamid Company | Novel 5(and/or 6)substituted 2-(2-imidazolin-2-yl)nicotinic acids, esters and salts, useful as herbicidal agents and nivel intermediates for the preparation of said nicotinic acids, esters and salts |
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JP5619761B2 (ja) | 2014-11-05 |
EP2370410A1 (en) | 2011-10-05 |
BRPI0921883A2 (pt) | 2020-08-04 |
CN102245577A (zh) | 2011-11-16 |
IL212807A0 (en) | 2011-07-31 |
IL212807A (en) | 2016-02-29 |
WO2010054952A1 (en) | 2010-05-20 |
JP2012508709A (ja) | 2012-04-12 |
EP2370410B1 (en) | 2013-10-23 |
US20110218340A1 (en) | 2011-09-08 |
US8563734B2 (en) | 2013-10-22 |
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