SK31398A3 - Method for producing 2,6-pyridinedicarboxylic acids esters - Google Patents
Method for producing 2,6-pyridinedicarboxylic acids esters Download PDFInfo
- Publication number
- SK31398A3 SK31398A3 SK313-98A SK31398A SK31398A3 SK 31398 A3 SK31398 A3 SK 31398A3 SK 31398 A SK31398 A SK 31398A SK 31398 A3 SK31398 A3 SK 31398A3
- Authority
- SK
- Slovakia
- Prior art keywords
- alkyl
- bis
- aryl
- hydrogen
- process according
- Prior art date
Links
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 5
- -1 1,1'-ferrocenediyl Chemical group 0.000 claims abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 5
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical group [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 150000005748 halopyridines Chemical class 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 3
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- JUDXOKKZTISQDJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 JUDXOKKZTISQDJ-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 abstract 1
- 108010081348 HRT1 protein Hairy Proteins 0.000 abstract 1
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- VUWZPRWSIVNGKG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH2] VUWZPRWSIVNGKG-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000035484 reaction time Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- KTOBUCHVPBPHMK-UHFFFAOYSA-N diethyl pyridine-2,6-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC(C(=O)OCC)=N1 KTOBUCHVPBPHMK-UHFFFAOYSA-N 0.000 description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- GPAKJVMKNDXBHH-UHFFFAOYSA-N 2,3,6-trichloropyridine Chemical compound ClC1=CC=C(Cl)C(Cl)=N1 GPAKJVMKNDXBHH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- SJGUKBIVRJZPJZ-UHFFFAOYSA-N dibutyl pyridine-2,6-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC(C(=O)OCCCC)=N1 SJGUKBIVRJZPJZ-UHFFFAOYSA-N 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- QAAJZUVZYRFDEX-UHFFFAOYSA-N dicyclohexyl pyridine-2,6-dicarboxylate Chemical compound C=1C=CC(C(=O)OC2CCCCC2)=NC=1C(=O)OC1CCCCC1 QAAJZUVZYRFDEX-UHFFFAOYSA-N 0.000 description 1
- LPYPDJPITFHISV-UHFFFAOYSA-N diethyl 3-chloropyridine-2,6-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(Cl)C(C(=O)OCC)=N1 LPYPDJPITFHISV-UHFFFAOYSA-N 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 1
- SNQQJEJPJMXYTR-UHFFFAOYSA-N dimethyl pyridine-2,6-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=N1 SNQQJEJPJMXYTR-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical class OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 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
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Description
Spôsob výroby esterov 2,6-pyridíndikarboxylových kyselín
Oblasť techniky
Predložený vynákez sa týka spôsobu výroby esterov 2,6-pyridíndikarboxylových kyselín reakciou halogénovaných pyridínov s oxidom uhoľnatým a alkoholom v prítomnosti zásady a katalyzátora.
Doterajší stav techniky
Estery 2,6-pyridíndikarboxylových kyselín sú dôležité medziprodukty, napríklad na výrobu zlúčenín s protizápalovým účinkom (JP-A 93/143 799).
Estery 2,6-pyridíndikarboxylových kyselín pripraviteľné podľa vynálezu majú všeobecný vzorec I
(O kde R1 je Ci-C6-alkylová skupina, C3-C6-cykloalkylová skupina, arylová skupina alebo arylalkylová skupina a R2 a R3 je nezávisle na sebe atóm vodíka alebo chlóru a R4 je atóm vodíka, CrC6-alkylová skupina, Ci-C6-alkoxylová skupina alebo atóm fluóru.
Známe spôsoby výroby esterov 2,6-pyridíndikarboxylových kyselín sa zakladajú na priamej chemickej oxidácii 2,6-dimetylpyridínu (I. lovel, M. Shymanska, Synth. Commun. 1992, 22, 2691; G. Wang, D. E. Bergstrom, Synlett 1992, 422; BE-A 872 394, SU-A 568 642). I keď sa pri nich dosahujú čiastočne vysoké výťažky, ich nedostatkom je použitie drahých a/alebo toxických chemikálií.
Spôsob výroby esterov 2,6-pyridíndikarboxylových kyselín karbonyláciou 2,6-dichlórpyridínu za použitia katalyzátora na báze niklu je známy (WO 93/18005). Nedostatkom tohto spôsobu je to, že sa reakcia uskutočňuje pri vysokom tlaku, estery pyridíndikarboylových kyselín sa získajú len v malých výťažkoch a tvorí sa vysoký podiel monokarbonylovaných vedľajších produktov.
Úlohou predloženého vynálezu bolo teda poskytnúť ekonomický spôsob, ktorý by z východiskových halogénpyridínov umožnil vyrobiť estery 2,6-pyridíndikarboxylových kyselín všeobecného vzorca I vo vysokých výťažkoch.
Podstata vynálezu
Táto úloha sa podľa vynálezu rieši spôsobom podľa patentového nároku I. Pri ňom sa na halogénpyridíny všeobecného vzorca II
(II) kde R2, R3 a R4 majú hore uvedený význam a X znamená atóm chlóru alebo brómu, pôsobí oxidom uhoľnatým a alkoholom všeobecného vzorca III
R1—OH (IV) kde R1 má hore uvedený význam, v prítomnosti zásady a komplexu paládia s bisdifenylfosfínom všeobecného vzorca IV
(II)
P—Q—P
kde Q znamená C3-C6-alkandiylovú skupinu alebo 1,ľ-ferocéndiylovú skupinu s cyklopentadienylovými skupinami prípadne substituovanými Ci-C4-alkylovými alebo arylovými skupinami a R5 až R8 nezávisle na sebe znamenajú atóm vodíka, Cí-C^alkyl, CrC4-alkoxy, monofluórmetyl, difluórmetyl, trifluórmetyl, fluór, aryl, aryloxy, kyano alebo dialkylamino.
R1 je alkylová skupina s 1 až 6 atómami uhlíka s rovným reťazcom alebo je rozvetvená, cykloalkylové skupina s 3 až 6 atómami uhlíka, arylová skupina alebo arylalkylová skupina. Menovite sa jedná o metyl, etyl, propyl, izopropyl, butyl, izobutyl, terc.-butyl, pentyl a jeho izoméy ako i hexyl a jeho izoméry, cyklopropyl, cyklobutyl, cyklopentyl ako i cyklohexyl. Pod pojmom arylové skupiny sa tu rozumejú najmä mono- alebo polycyklické systémy, ako napríklad fenyl, naftyl, bifenylyl alebo antracenyl. Tie môžu niesť jeden alebo viacej rovnakých alebo rozdielnych substituentov, napríklad nízke alkylové skupiny ako metyl, halogenované alkylové skupiny ako trifluórmetyl, nízke alkoxyskupiny ako metoxy, alebo nízke alkyltioskupiny (alkánsulfanylové) alebo alkánsulfonylové skupiny, ako metyltio alebo etansulfonyl. Pod pojmom substituovaný fenyl sa tu a v nasledujúcom rozumejú najmä skupiny ako fluórfenyl, metoxyfenyl, tolyl alebo trifluórmetylfenyl, pričom sú substituenty výhodne v para polohe.
Obdobne sa pod pojmom arylalkyl rozumejú skupiny vytvorené z nízkych alkylových skupín, najmä z CpCe-alkylovej skupiny, výmenou atómu vodíka za hore definovanú arylovú skupinu, teda napríklad benzyl alebo fenyletyl.
Obzvlášť výhodne R1 znamená metyl, etyl, butyl a cyklohexyl. R2 a R3 znamenajú nezávisle na sebe atóm vodíka alebo chlóru. Obzvlášť výhodne znamenajú R2 a R3 atóm vodíka. R4 je atóm vodíka, alkylová skupina s 1 až 6 atómami uhlíka s rovným alebo s rozvetveným reťazcom, alkoxylová skupina s 1 až 6 atómami uhlíka s rovným alebo alebo rozvetveným reťazcom alebo atóm fluóru. Menovite sa jedná o metyl, etyl, propyl, izopropyl, butyl, izobutyl, terc.-butyl, pentyl a jeho izoméry ako i hexyl a jeho izoméry, metoxy, etoxy, propoxy, izopropoxy, butoxy, izobutoxy, terc.-butoxy, pentoxy a jeho izoméry ako i hexoxy a jeho izoméry. Obzvlášť výhodne R4 znamená atóm vodíka. X znamená atóm chlóru alebo brómu, obzvlášť výhodne znamená X atóm chlóru.
Halogénpyridíny všeobecného vzorca II sú komerčne dostupné.
Výhodne sa spôsobom podľa vynálezu vyrábajú metylestery, etylestery, butylestery alebo cyklohexylestery (R1 = metyl, etyl, butyl, cyklohexyl), pričom sa ako alkohol (III) použije metanol, etanol, butanol alebo cyklohexanol.
Reakcia sa uskutočňuje v prítomnosti zásady. Vhodné sú napríklad acetáty, karbonáty, hydrogénkarbonáty, fosfáty alebo hydrogénfosfáty alkalických kovov a kovov alkalických zemín. Menovite sa jedná o octan sodný, octan draselný, octan horečnatý, octan vápenatý, uhličitan sodný, uhličitan draselný, uhličitan horečnatý, uhličitan vápenatý, hydrogénuhličitan sodný, hydrogénuhličitan draselný, hydrogénuhličitan horečnatý, hydrogénuhličitan vápenatý, fosforečnan horečnatý, fosforečnan vápenatý, dihydrogénfosforečnan sodný, dihydrogénfosforečnan draselný, hydrogénfosforečnan sodný, hydrogénfosforečnan draselný, hydrogénfosforečnan horečnatý, hydrogénfosforečnan vápenatý. Obzvlášť vhodný je octan sodný.
Katalytický účinný komplex paládium-bis-difenylfosfín sa s výhodou tvorí in situ, pričom sa vnesie do reakcie soľ Pd(ll) (napr. chlorid alebo acetát) alebo vhodný komplex Pd(ll) (napr. chlorid bis(trifenylfosfín)paladnatý) s difosfínom. Ako soľ Pd(ll) alebo komplex Pd(ll) sa výhodne používajú octan paladnatý alebo chlorid bis(trifenylfosfín)paladnatý. Paládium sa výhodne používa v množstve 0.05 až 0.4 mol. % Pd(ll), vzťažené na halogénzlúčeninu (II). Difosfín sa výhodne používa v nadbytku (vzťažené na Pd), výhodne v množstve 0.2 až 5 mol. %, tiež vzťažené na halogénzlúčeninu (II).
Ako bis-difenylfosfíny (III) sa výhodne používajú také, v ktorých Q znamená alkándiylovú skupinu s 3 až 6 atómami uhlíka s rovným alebo rozvetveným reťazcom. Menovite sa jedná o propan-1,3-diyl, propan-1,2-diyl, butan-1,4-diyl, butan-1,3-diyl, butan-1,2-diyl, pentadiyl a jeho izoméry a hexandiyl a jeho izoméry. Výhodne sa používajú také, kde Q znamená alkándiylovú skupinu s 3—6 atómami uhlíka s rovným reťazcom. Menovite sa jedná o propan-1,3-diyl, butan-1,4-diyl, pentan-1,5-diyl ako i hexan-1,6-diyl. Obzvlášť výhodný je 1,4-bis(difenylfosfíno)butan.
Rovnako výhodne sa používajú bis-difenylfosfíny (III), v ktorých Q znamená
1,1'-ferocéndiylovú skupinu s cyklopentadienylovými skupinami prípadne substituovanými Ci-C4-alkylovými alebo arylovými skupinami. Ako Ci-C4-alkylové substituenty sa výhodne používajú metyl, etyl, propyl, izopropyl, butyl, izobutyl, terc.butyl, obzvlášť výhodné sú metyl a etyl. Ako arylové substituenty sa tu výhodne používajú fenyl alebo prípadne substituovaný fenyl. Ako obzvlášť výhodný sa používa 1,1 ’-bis(difenylfosfíno)ferocén.
R5 až R8 sú nezávisle na sebe atóm vodíka, C^C^alkyl, C1-C4-alkoxy, monofluórmetyl, difluórmetyl, trifluórmetyl, fluór, aryl, aryloxy, kyano alebo dialkylamino.
Ako Ci-C4-alkylové substituenty sa výhodne používajú metyl, etyl, propyl, izopropyl, butyl, izobutyl, alebo terc.-butyl, obzvlášť výhodné sú metyl a etyl. Ako CrC4-alkoxylové substituenty sa výhodne používajú metoxy, etoxy, propoxy, izopropoxy, butoxy, izobutoxy alebo terc.-butoxy, obzvlášť výhodné sú metoxy a etoxy. Ako arylové substituenty sa tu výhodne používajú fenyl alebo prípadne substituovaný fenyl. Ako aryloxylové substituenty sa tu výhodne používajú fenoxy a prípadne substituovaný fenoxy. Pod pojmom substituovaný fenoxy sa rozumejú najmä skupiny ako fluórfenoxy, metoxyfenoxy, tolyloxy alebo trifluórmetylfenoxy, pričom sa substituenty výhodne nachádzajú v para polohe.
Ako dialkylamínové substituenty sa výhodne používajú amíny s Ci-C2-alkylovými zvyškami. Menovite sa jedná o dimetylamino, dietylamino.
Alkohol (III) môže slúžiť aj ako rozpúšťadlo. Prípadne je možné použiť dodatočné rozpúšťadlo. Ako dodatočné rozpúšťadlo je možné použiť ako nepoláme rozpúšťadlá, ako je napríklad toluén alebo xylén, tak aj polárne organické rozpúšťadlá, ako je napríklad acetonitril, tetrahydrofurán alebo N,N-dimetylacetamid.
Reakcia sa výhodne uskutočňuje pri reakčnej teplote 100 až 250 °C, výhodne pri 140 až 195 °C a tlaku oxidu uhoľnatého výhodne 0.1 až 20 MPa, výhodne 0.5—5 MPa. Po zvyčajnej reakčnej dobe 1 až 20 hod. sa získa zlúčenina všeobecného vzorca I vo vysokých výťažkoch.
Nasledujúce príklady objasňujú uskutočnenie spôsobu podľa vynálezu.
Príklady uskutočnenia vynálezu
Príklad 1
Dimetylester kyseliny 2,6-pyridíndikarboxylovej
Do autoklávu sa vnieslo 1.48 g (10 mmol) 2,6-dichlórpyridínu, 166 mg
1,ľ-bis(difenylfosfíno)ferocénu (3 mol. % vzťažené na 2,6-dichlórpyridín), 4.6 mg octanu paladnatého (0.2 mol. % vzťažené na 2,6-dichlórpyridín), 1.72 g (21 mmol) octanu sodného a 25 ml metanolu. Autoklávom sa nechal viackrát prechádzať oxid uhoľnatý, aby sa vymenil vzduch za oxid uhoľnatý. Potom sa autokláv natlakoval oxidom uhoľnatým na 1.5 MPa. Reakčná zmes sa zohriala na 135 °C (teplota kúpeľa) a 1 hod. miešala. Po ochladení na teplotu miestnosti sa surový produkt zahustil vo vákuu (3.0 kPa) a podrobil chromatografii na kremičitanovom géli 60 (premávací prostriedok hexan/etylacetát 1:1).
T.t.: 120.8—122.5 °C
Výťažok: 1.52 g (78 %) biely prášok
MS; m/z: 195 (M+); 165; 137; 105 1H-NMR (CDCI3): δ= 8.31 (d, 2H);
8.02 (t, 1H);
4.02 (s, 6H).
Príklad 2
Dietylester kyseliny 2,6-pyridíndikarboxylovej
Postupovalo sa ako v príklade 1, ale namiesto metanolu sa použil rovnaký objem etanolu a miesto 21 mmol sa použilo 57 mmol octanu sodného. Po 1 hod.
reakčnej dobe pri teplote kúpeľa 135 °C sa získalo 1.96 g (88 %) bieleho prášku.
41.5—42.8 °C
T. t.:
MS; m/z:
1H-NMR (CDCI3): δ=
224; 223 (M+); 208; 179; 151; 123; 105
8.28 (d, 2H); 8.00 (t, 1H); 4.50 (q, 4H); 1.45 (t, 6H).
Príklad 3
Dietylester kyseliny 2,6-pyridíndikarboxylovej
Postupovalo sa ako v príklade 1, ale namiesto 25 ml metanolu sa použilo 25 ml tetrahydrofuránu a 30 ml etanolu. Po 3 hod.reakčnej dobe pri teplote kúpeľa 150 °C sa získalo 0.56 g (25.1 %) bieleho prášku.
Príklad 4
Dietylester kyseliny 2,6-pyridíndikarboxylovej
Postupovalo sa ako v príklade 1, ale namiesto metanolu sa použil rovnaký objem etanolu a namiesto 4.6 mg octanu paladnatého sa použilo 14.0 mg chloridu bis(trifenylfosfín)paladnatého. Po 2 hod. reakčnej dobe pri teplote kúpeľa 175 °C sa získalo 1.54 g (69 %) bieleho prášku.
Príklad 5
Dietylester kyseliny 2,6-pyridíndikarboxylovej
Postupovalo sa ako v príklade 2, ale namiesto 166 mg 1,ľ-bis(difenylfosfíno)ferocénu sa použilo 128 mg 1,4-bis(difenylfosfíno)butanu. Po 3 hod.
reakčnej dobe pri teplote kúpeľa 150 °C sa získalo 1.64 g (73.5 %) bieleho prášku.
Príklad 6
Dibutylester kyseliny 2,6-pyridíndikarboxylovej
Postupovalo sa ako v príklade 1, ale namiesto metanolu sa použil rovnaký objem butanolu. Po 1 hod. reakčnej dobe pri teplote kúpeľa 135 °C sa získalo 2.45 g (85 %) bieleho prášku.
T. t.: | 65.5—65.9 °C |
MS; m/z: Ή-NMR (CDCb): δ= | 280 (M+); 236; 224; 206; 179; 150; 123; 105; 78 8.28 (d, 2H); 7.98 (t, 1H); 5.32 (sept., 2H); 4.42 (t, 4H); 1.82 (kvint., 4H); 1.50 (sext., 4H); 0.99 (t, 6H). |
Príklad 7 |
Dicyklohexylester kyseliny 2,6-pyridíndikarboxylovej
Postupovalo sa ako v príklade 1, ale namiesto metanolu sa použil rovnaký objem cyklohexanolu. Po 1 hod. reakčnej dobe pri teplote kúpeľa 135 °C sa získalo 1.7 g (51 %) bieleho prášku.
T. t.: | 111.6—112.3 °C |
MS; m/z: 1H-NMR (CDCI3): Ô= | 331 (M+); 287; 250; 219; 205; 168; 150; 123 8.22 (d, 2H); 7.97 (t, 1H); 5.10 (sept., 2H); 2.1—1.3 (m, 22H). |
Príklad 8
Dietylester kyseliny 3-chlór-2,6-pyridíndikarboxylovej
Postupovalo sa ako v príklade 2, ale namiesto 1.48 g (10 mmol) 2,6dichlórpyridínu sa použilo 1.82 g (10 mmol) 2,3,6-trichlórpyridínu. Po 1 hod. reakčnej dobe pri teplote kúpeľa 135 °C sa získalo 1,98 g (76 %) bezfarebného oleja.
MS; m/z: 257 (M+); 213; 185; 139; 113 1H-NMR (CDCI3): δ= 8.15 (d, 1 H);
7.93 (d, 1H);
4.50 (q, 2H);
4.48 (d, 2H);
1.44 (t, 3H);
1.43 (t, 3H).
Claims (7)
- PATENTOVÉ NÁROKY1. Spôsob výroby esterov 2,6-pyridíndikarboxylových kyselín všeobecného vzorca IR3 (I) kde R1 je Ci-C6-alkylová skupina, C3-C6-cykloalkylová skupina, arylová skupina alebo arylalkylová skupina a R2 a R3 je nezávisle na sebe atóm vodíka alebo chlóru a R4 je atóm vodíka, Ci-C6-alkylová skupina, Ci-C6-alkoxyskupina alebo atóm fluóru, vyznačujúci sa tým, že sa na halogénpyridín všeobecného vzorca II kde R2, R3 a R4 majú hore uvedený význam a X znamená atóm chlóru alebo brómu, pôsobí oxidom uhoľnatým a alkoholom všeobecného'vzorca IIIR1—OH (III) kde R1 má hore uvedený význam, v prítomnosti zásady a komplexu paládia s bis-difenylfosfínom všeobecného vzorca IV kde Q znamená C3-C6-alkándiylovú skupinu alebo 1,ľ-ferocéndiylovú skupinu s cyklopentadienylovými skupinami prípadne substituovanými CrCA-alkylovými alebo arylovými skupinami a R5 * * až R8 nezávisle na sebe znamenajú atóm vodíka, CrC^alkyl, Ci-C4-alkoxy, monofluórmetyl, difluórmetyl, trifluórmetyl, fluór, aryl, aryloxy, kyano alebo dialkylamino.
- 2. Spôsob podľa nároku 1, vyznačujúci sa tým, že R1 je metylová skupina, etylová skupina, butylová skupina alebo cyklohexylová skupina.
- 3. Spôsob podľa nároku 1 alebo 2, vyznačujúci sa tým, že zásadou je acetát, karbonát, hydrogénkarbonát, fosfát alebo hydrogénfosfát alkalického kovu alebo kovu alkalických zemín.
- 4. Spôsob podľa jedného z nárokov 1 až 3, vyznačujúci sa tým, že paládium je vo forme chloridu bis(trifenylfosfín)paladnatého alebo octanu paladnatého.
- 5. Spôsob podľa jedného z nárokov 1 až 4, vyznačujúci sa tým, že bis-difenylfosfín je 1,ľ-bis(difenylfosfino)ferocén alebo 1,4-bis(difenylfosfino)butan.
- 6. Spôsob podľa jedného z nárokov 1 až 5, vyznačujúci sa tým, že tlak oxidu uhoľnatého je 0.1 až 20 MPa.
- 7. Spôsob podľa jedného z nárokov 1 až 6, vyznačujúci sa tým, že reakčná teplota je 100 až 250 °C.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CH59597 | 1997-03-12 |
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SK31398A3 true SK31398A3 (en) | 1998-10-07 |
SK283433B6 SK283433B6 (sk) | 2003-07-01 |
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SK313-98A SK283433B6 (sk) | 1997-03-12 | 1998-03-09 | Spôsob výroby esterov 2,6-pyridíndikarboxylových kyselín |
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US (1) | US6103906A (sk) |
EP (1) | EP0864565B1 (sk) |
JP (1) | JPH10251232A (sk) |
KR (1) | KR100600465B1 (sk) |
CN (1) | CN1158262C (sk) |
AT (1) | ATE218550T1 (sk) |
CA (1) | CA2231800C (sk) |
CZ (1) | CZ291059B6 (sk) |
DE (1) | DE59804277D1 (sk) |
DK (1) | DK0864565T3 (sk) |
ES (1) | ES2174345T3 (sk) |
HU (1) | HU225239B1 (sk) |
NO (1) | NO308531B1 (sk) |
PL (1) | PL191438B1 (sk) |
PT (1) | PT864565E (sk) |
SI (1) | SI0864565T1 (sk) |
SK (1) | SK283433B6 (sk) |
TW (1) | TW400326B (sk) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2001007415A1 (de) * | 1999-07-28 | 2001-02-01 | Lonza Ag | Verfahren zur herstellung von pyridazin-3,6-dicarbonsäureestern |
WO2001007416A1 (de) * | 1999-07-28 | 2001-02-01 | Lonza Ag | Verfahren zur herstellung von pyridazincarbonsäurederivaten |
WO2002034919A1 (en) * | 2000-10-27 | 2002-05-02 | Roche Diagnostics Gmbh | Variants of soluble pyrroloquinoline quinone-dependent glucose dehydrogenase |
US7547536B1 (en) | 2002-05-31 | 2009-06-16 | Jeol Usa, Inc. | Method for detecting bacterial spores |
CA2547600A1 (en) * | 2003-12-12 | 2005-06-30 | Syngenta Participations Ag | Novel herbicides |
JP4523834B2 (ja) * | 2004-11-26 | 2010-08-11 | ニチコン株式会社 | 電解コンデンサの駆動用電解液 |
CN103664767A (zh) * | 2013-12-06 | 2014-03-26 | 常熟市联创化学有限公司 | 一种2,6-吡啶二甲酸的制备方法 |
CN115838448B (zh) * | 2021-09-18 | 2024-01-09 | 中国科学技术大学 | 负载型催化剂及其制备方法和应用 |
CN113912533B (zh) * | 2021-11-23 | 2023-06-20 | 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 |
Family Cites Families (8)
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DE1620174B1 (de) * | 1965-11-19 | 1972-04-27 | Ruetgerswerke Ag | Verfahren zur oxidativen Herstellung von Pyridin-2,6-dicarbonsäure |
SU568462A1 (ru) * | 1974-12-03 | 1977-08-15 | Государственный Проектный Институт Строительного Машиностроения | Устройство дл нанесени лакокрасочного материала |
IT1089429B (it) * | 1977-12-01 | 1985-06-18 | Stoppani Luigi Spa | Procedimento in due stadi per preparare acido 2-6-piridin-bicarbossilico |
JPH0819009B2 (ja) * | 1987-03-12 | 1996-02-28 | 日本農薬株式会社 | カルボン酸アミド類の製造法 |
IL91083A (en) * | 1988-07-25 | 1993-04-04 | Ciba Geigy | Cyclohexanedione derivatives, their preparation and their use as herbicides |
TW371658B (en) * | 1992-03-06 | 1999-10-11 | Reilly Ind Inc | Process for producing 2-halo-nicotinic acid derivatives and precursor thereto |
JPH07126176A (ja) * | 1993-06-15 | 1995-05-16 | Hiroshi Sakurai | 活性酸素抑制剤 |
CA2209392C (en) * | 1996-07-23 | 2007-02-20 | Yves Bessard | Process for preparing pyridinecarboxylic esters |
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1998
- 1998-02-25 CZ CZ1998545A patent/CZ291059B6/cs not_active IP Right Cessation
- 1998-03-09 SK SK313-98A patent/SK283433B6/sk not_active IP Right Cessation
- 1998-03-09 JP JP10057271A patent/JPH10251232A/ja active Pending
- 1998-03-10 ES ES98104312T patent/ES2174345T3/es not_active Expired - Lifetime
- 1998-03-10 PT PT98104312T patent/PT864565E/pt unknown
- 1998-03-10 DK DK98104312T patent/DK0864565T3/da active
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- 1998-03-10 EP EP98104312A patent/EP0864565B1/de not_active Expired - Lifetime
- 1998-03-10 DE DE59804277T patent/DE59804277D1/de not_active Expired - Fee Related
- 1998-03-10 SI SI9830102T patent/SI0864565T1/xx unknown
- 1998-03-10 TW TW087103452A patent/TW400326B/zh not_active IP Right Cessation
- 1998-03-11 NO NO981062A patent/NO308531B1/no not_active IP Right Cessation
- 1998-03-11 CA CA002231800A patent/CA2231800C/en not_active Expired - Fee Related
- 1998-03-12 CN CNB981055915A patent/CN1158262C/zh not_active Expired - Fee Related
- 1998-03-12 US US09/038,977 patent/US6103906A/en not_active Expired - Fee Related
- 1998-03-12 HU HU9800540A patent/HU225239B1/hu not_active IP Right Cessation
- 1998-03-12 PL PL325304A patent/PL191438B1/pl not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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DE59804277D1 (de) | 2002-07-11 |
HU225239B1 (en) | 2006-08-28 |
CA2231800A1 (en) | 1998-09-12 |
JPH10251232A (ja) | 1998-09-22 |
HUP9800540A3 (en) | 1999-03-01 |
CA2231800C (en) | 2007-05-22 |
PL191438B1 (pl) | 2006-05-31 |
KR19980080185A (ko) | 1998-11-25 |
HUP9800540A2 (hu) | 1998-12-28 |
PL325304A1 (en) | 1998-09-14 |
SI0864565T1 (en) | 2002-08-31 |
CZ54598A3 (cs) | 1998-09-16 |
US6103906A (en) | 2000-08-15 |
ES2174345T3 (es) | 2002-11-01 |
NO308531B1 (no) | 2000-09-25 |
NO981062D0 (no) | 1998-03-11 |
DK0864565T3 (da) | 2002-09-16 |
ATE218550T1 (de) | 2002-06-15 |
TW400326B (en) | 2000-08-01 |
SK283433B6 (sk) | 2003-07-01 |
CN1193015A (zh) | 1998-09-16 |
PT864565E (pt) | 2002-10-31 |
CZ291059B6 (cs) | 2002-12-11 |
CN1158262C (zh) | 2004-07-21 |
HU9800540D0 (en) | 1998-05-28 |
KR100600465B1 (ko) | 2007-03-02 |
NO981062L (no) | 1998-09-14 |
EP0864565A1 (de) | 1998-09-16 |
EP0864565B1 (de) | 2002-06-05 |
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