JP6310939B2 - 4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリネートの調製方法 - Google Patents
4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリネートの調製方法 Download PDFInfo
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- JP6310939B2 JP6310939B2 JP2015547527A JP2015547527A JP6310939B2 JP 6310939 B2 JP6310939 B2 JP 6310939B2 JP 2015547527 A JP2015547527 A JP 2015547527A JP 2015547527 A JP2015547527 A JP 2015547527A JP 6310939 B2 JP6310939 B2 JP 6310939B2
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- alkyl
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- 238000000034 method Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 3
- -1 4- Amino-5-fluoro-3-chloro-6- (substituted) picolinaldehyde Chemical class 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 20
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 10
- 239000003880 polar aprotic solvent Substances 0.000 claims description 10
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 9
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 8
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 8
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 8
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- TZUYFNORLRBWLP-UHFFFAOYSA-N ethanimidoyl chloride Chemical compound CC(Cl)=N TZUYFNORLRBWLP-UHFFFAOYSA-N 0.000 claims description 5
- 125000005270 trialkylamine group Chemical group 0.000 claims description 5
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 4
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- 238000010511 deprotection reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 29
- 239000000203 mixture Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 235000019439 ethyl acetate Nutrition 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 6
- STYNYSYPRAIQPI-UHFFFAOYSA-N 5,5-diethoxy-1,1,1-trifluoro-n-(4-methoxyphenyl)pent-3-yn-2-imine Chemical compound CCOC(OCC)C#CC(C(F)(F)F)=NC1=CC=C(OC)C=C1 STYNYSYPRAIQPI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- CIRVADWNFWYATJ-UHFFFAOYSA-N 2,2,2-trifluoro-n-(4-methoxyphenyl)ethanimidoyl chloride Chemical compound COC1=CC=C(N=C(Cl)C(F)(F)F)C=C1 CIRVADWNFWYATJ-UHFFFAOYSA-N 0.000 description 5
- JYXGYRJXENJFQX-UHFFFAOYSA-N 2-(4-chlorophenyl)-6-(diethoxymethyl)-3-fluoro-n-(4-methoxyphenyl)pyridin-4-amine Chemical compound FC=1C(C=2C=CC(Cl)=CC=2)=NC(C(OCC)OCC)=CC=1NC1=CC=C(OC)C=C1 JYXGYRJXENJFQX-UHFFFAOYSA-N 0.000 description 5
- LACYBKRKMZRLHF-UHFFFAOYSA-N 4-amino-3-chloro-6-(4-chlorophenyl)-5-fluoropyridine-2-carbaldehyde Chemical compound O=CC1=C(Cl)C(N)=C(F)C(C=2C=CC(Cl)=CC=2)=N1 LACYBKRKMZRLHF-UHFFFAOYSA-N 0.000 description 5
- LOQVCQHCRSPHEM-UHFFFAOYSA-N 4-amino-3-chloro-6-(4-chlorophenyl)-5-fluoropyridine-2-carboxylic acid Chemical compound OC(=O)C1=C(Cl)C(N)=C(F)C(C=2C=CC(Cl)=CC=2)=N1 LOQVCQHCRSPHEM-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical class N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- KNVAGLXJVUATKG-UHFFFAOYSA-N benzyl 4-amino-3-chloro-6-(4-chlorophenyl)-5-fluoropyridine-2-carboxylate Chemical compound ClC=1C(N)=C(F)C(C=2C=CC(Cl)=CC=2)=NC=1C(=O)OCC1=CC=CC=C1 KNVAGLXJVUATKG-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 229960002218 sodium chlorite Drugs 0.000 description 3
- YMVFJGSXZNNUDW-UHFFFAOYSA-N (4-chlorophenyl)methanamine Chemical compound NCC1=CC=C(Cl)C=C1 YMVFJGSXZNNUDW-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- RGUXEWWHSQGVRZ-UHFFFAOYSA-N 3,3-diethoxyprop-1-yne Chemical compound CCOC(C#C)OCC RGUXEWWHSQGVRZ-UHFFFAOYSA-N 0.000 description 2
- WWJYYMPLMIVRHS-UHFFFAOYSA-N 4-[5-chloro-2-(4-chlorophenyl)-6-(diethoxymethyl)-3-fluoropyridin-4-yl]iminocyclohexa-2,5-dien-1-one Chemical compound ClC=1C(C(OCC)OCC)=NC(C=2C=CC(Cl)=CC=2)=C(F)C=1N=C1C=CC(=O)C=C1 WWJYYMPLMIVRHS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- WGHKKEJHRMUKDK-UHFFFAOYSA-N cyclohexa-2,5-dien-1-one Chemical compound O=C1C=CCC=C1 WGHKKEJHRMUKDK-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229940081066 picolinic acid Drugs 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 description 1
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 1
- WRHDYOGDDZYNMT-UHFFFAOYSA-N 4-amino-3-chloro-5-fluoropyridine-2-carboxylic acid Chemical compound NC1=C(F)C=NC(C(O)=O)=C1Cl WRHDYOGDDZYNMT-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 229910019142 PO4 Chemical class 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005897 peptide coupling reaction Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
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- 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
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/12—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton being acyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—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
- C07D213/72—Nitrogen atoms
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- 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
- C07D213/72—Nitrogen atoms
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- 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
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Description
本出願は、その開示が参照により本明細書に明確に組み込まれている、2012年12月13日出願の米国仮特許出願第61/736,835号の利益を主張する。
(式中、
R1は、C1〜C4アルキル、シクロプロピル、C2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表し、
R2は、C1〜C12アルキル、または無置換もしくは置換C7〜C11アリールアルキルを表す)
を調製する方法であって、
以下のステップ:
a) 四塩化炭素溶媒中、トリアリールホスフィンおよびトリアルキルアミン塩基の存在下、トリフルオロ酢酸をp−メトキシアニリンと接触させて、式Aの塩化アセトイミドイル
を生成するステップ、
b) 極性非プロトン性溶媒中、ヨウ化銅(I)、アルカリ金属ヨウ化物、およびアルカリ金属リン酸塩の存在下、式Aの塩化アセトイミドイルを3,3−ジアルコキシプロパ−1−イン(式B)
(式中、R3はC1〜C4アルキルを表す)
と接触させて、式Cの(イミノ)ペンタ−2−インジアルキルアセタール
(式中、R3は、先に定義した通りである)
を生成するステップ、
c) 極性非プロトン性溶媒中、無機アルカリ金属塩基の存在下、およそ周囲温度から約100℃の温度で、式Cの(イミノ)ペンタ−2−インジアルキルアセタールを式Dのアミン
(式中、R1は、先に定義した通りである)
により環化させて、式Eの4−(4−メトキシフェニル)アミノ−5−フルオロ−6−(置換)ピリジン−2−ジアルキルアセタール
(式中、R1およびR3は、先に定義した通りである)
を生成するステップ、
d) 極性溶媒中、式Eの4−(4−メトキシフェニル)アミノ−5−フルオロ−6−(置換)ピリジン−2−ジアルキルアセタールを、1,3−ジクロロ−5,5−ジメチルイミダゾリジン−2,4−ジオン(式F)
により塩素化して、式Gの保護4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピリジン−2−ジアルキルアセタール
(式中、R1およびR3は先に定義した通りである)
を生成するステップ、
e) 極性溶媒中、式Gの保護4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピリジン−2−ジアルキルアセタールを無機酸により脱保護および加水分解して、式Hの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリンアルデヒド
(式中、R1は、先に定義した通りである)
を生成するステップ、
f) 水性アルコール溶媒中、無機酸および次亜塩素酸捕捉剤の存在下、式Hの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリンアルデヒドをアルカリ金属亜塩素酸塩により酸化して、式Jの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリン酸
(式中、R1は、先に定義した通りである)
を生成するステップ、および
g) 式Jの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリン酸を以下の式の化合物
R2X
(式中、
Xは、OH、Cl、BrまたはIを表し、
R2は、先に定義した通りである)
でエステル化することにより、式Iの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリネートを生成するステップ、
を含む
方法が本明細書において提供される。
(式中、R3は、C1〜C4アルキルを表す)
である。
(式中、
R1は、C1〜C4アルキル、シクロプロピル、C2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表し、
R3は、C1〜C4アルキルを表す)
である。
R1は、C1〜C4アルキル、シクロプロピル、C2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表し、
R3は、C1〜C4アルキルを表す)
である。
(式中、
R1は、C1〜C4アルキル、シクロプロピル、C2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表す)
である。
2,2,2−トリフルオロ−N−(4−メトキシフェニル)アセトイミドイルクロリド
[実施例2]
[実施例3]
[実施例4]
[実施例5]
[実施例6]
[実施例8]
Claims (5)
- 式Iの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリネート
(式中、
R1は、C1〜C4アルキル、シクロプロピル、C2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表し、
R2は、C1〜C12アルキル、または無置換もしくは置換C7〜C11アリールアルキルを表す)
を調製する方法であって、
以下のステップ:
a) 四塩化炭素溶媒中、トリアリールホスフィンおよびトリアルキルアミン塩基の存在下、トリフルオロ酢酸をp−メトキシアニリンに接触させて、式Aの塩化アセトイミドイル
を生成するステップ、
b) 極性非プロトン性溶媒中、ヨウ化銅(I)、アルカリ金属ヨウ化物、およびアルカリ金属リン酸塩の存在下、式Aの塩化アセトイミドイルを3,3−ジアルコキシプロパ−1−イン(式B)
(式中、R3は、C1〜C4アルキルを表す)
に接触させて、式Cの(イミノ)ペンタ−2−インジアルキルアセタール
(式中、R3は先に定義した通りである)
を生成するステップ、
c) 極性非プロトン性溶媒中、無機アルカリ金属塩基の存在下、およそ周囲温度から約100℃の温度で、式Cの(イミノ)ペンタ−2−インジアルキルアセタールを式Dのアミン
(式中、R1は先に定義した通りである)
により環化させて、式Eの4−(4−メトキシフェニル)アミノ−5−フルオロ−6−(置換)ピリジン−2−ジアルキルアセタール
(式中、R1およびR3は先に定義した通りである)
を生成するステップ、
d) 極性溶媒中、式Eの4−(4−メトキシフェニル)アミノ−5−フルオロ−6−(置換)ピリジン−2−ジアルキルアセタールを、1,3−ジクロロ−5,5−ジメチルイミダゾリジン−2,4−ジオン(式F)
により塩素化して、式Gの保護4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピリジン−2−ジアルキルアセタール
(式中、R1およびR3は先に定義した通りである)
を生成するステップ、
e) 極性溶媒中、式Gの保護4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピリジン−2−ジアルキルアセタールを無機酸により脱保護および加水分解して、式Hの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリンアルデヒド
(式中、R1は先に定義した通りである)
を生成するステップ、
f) 水性アルコール溶媒中、無機酸および次亜塩素酸捕捉剤の存在下、式Hの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリンアルデヒドをアルカリ金属亜塩素酸塩により酸化して、式Jの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリン酸
(式中、R1は先に定義した通りである)
を生成するステップ、および
g) 式Jの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリン酸を以下の式の化合物
R2X
(式中、
Xは、OH、Cl、BrまたはIを表し、
R2は先に定義した通りである)
でエステル化することにより、式Iの4−アミノ−5−フルオロ−3−クロロ−6−(置換)ピコリネートを生成するステップ、
を含む
方法。 - 式Cの化合物
(式中、
R3は、C1〜C4アルキルを表す)。 - 式Eの化合物
(式中、
R1は、C1〜C4アルキル、シクロプロピル、C2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表し、
R3は、C1〜C4アルキルを表す)。 - 式Gの化合物
(式中、
R1は、C1〜C4アルキル、シクロプロピル、C2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表し、
R3は、C1〜C4アルキルを表す)。 - 式Hの化合物
(式中、
R1は、C1〜C4アルキル、C 2〜C4アルケニル、または1〜4つのハロゲン、C1〜C4アルキル、C1〜C4ハロアルキル、C1〜C4アルコキシまたはC1〜C4ハロアルコキシから独立して選択される置換基により置換されたフェニルを表す)。
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SU680613A3 (ru) * | 1971-12-07 | 1979-08-15 | Циба-Гейги Аг (Фирма) | Средство борьбы с насекомыми и клещами |
ATE356807T1 (de) * | 2000-01-14 | 2007-04-15 | Dow Agrosciences Llc | 4-aminopicolinate und ihre verwendung als herbizide |
AR037228A1 (es) | 2001-07-30 | 2004-11-03 | Dow Agrosciences Llc | Compuestos del acido 6-(aril o heteroaril)-4-aminopicolinico, composicion herbicida que los comprende y metodo para controlar vegetacion no deseada |
TW200307669A (en) * | 2002-04-15 | 2003-12-16 | Nippon Soda Co | Novel oxime o-ether compound, production process thereof, and agricultural or horticultural bactericide |
UA82358C2 (uk) * | 2003-04-02 | 2008-04-10 | Дау Агросайенсиз Ллс | 6-алкіл або алкеніл-4-амінопіколінати гербіцидна композиція, спосіб боротьби з небажаною рослинністю |
WO2006062979A1 (en) * | 2004-12-06 | 2006-06-15 | E.I. Dupont De Nemours And Company | Herbicidal 6-cyclopropyl-substitute 4-aminopicolinic acid derivatives |
CN102731382B (zh) | 2006-01-13 | 2015-09-02 | 美国陶氏益农公司 | 6-(多取代芳基)-4-氨基吡啶甲酸酯及其作为除草剂的用途 |
WO2012041873A1 (en) * | 2010-09-29 | 2012-04-05 | Intervet International B.V. | N-heteroaryl compounds |
TWI529163B (zh) * | 2011-01-25 | 2016-04-11 | 陶氏農業科學公司 | 用於製備4-胺基-5-氟-3-鹵素-6-(經取代之)吡啶甲酸酯的方法 |
TWI596088B (zh) | 2011-01-25 | 2017-08-21 | 陶氏農業科學公司 | 4-胺基-6-(經取代的苯基)吡啶甲酸酯及6-胺基-2-(經取代的苯基)-4-嘧啶羧酸酯之芳烷酯以及其等作為除草劑之用途 |
CN104994733B (zh) * | 2012-12-13 | 2017-03-15 | 美国陶氏益农公司 | 制备4‑氨基‑5‑氟‑3‑氯‑6‑(取代的)吡啶甲酸酯的方法 |
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US9981911B2 (en) | 2018-05-29 |
CN104994733A (zh) | 2015-10-21 |
EP2931043B1 (en) | 2017-08-02 |
US20140296533A1 (en) | 2014-10-02 |
KR20150093799A (ko) | 2015-08-18 |
IL239225A0 (en) | 2015-07-30 |
ZA201504166B (en) | 2016-11-30 |
RU2015127993A (ru) | 2017-01-18 |
EP2931043A1 (en) | 2015-10-21 |
WO2014093588A1 (en) | 2014-06-19 |
JP2016504319A (ja) | 2016-02-12 |
US20140171653A1 (en) | 2014-06-19 |
AU2013359255B2 (en) | 2017-01-05 |
RU2653855C2 (ru) | 2018-05-15 |
EP2931043A4 (en) | 2016-06-08 |
CA2895180A1 (en) | 2014-06-19 |
PL2931043T3 (pl) | 2018-01-31 |
US9822077B2 (en) | 2017-11-21 |
US9212141B2 (en) | 2015-12-15 |
US20170349549A1 (en) | 2017-12-07 |
IL239225A (en) | 2017-12-31 |
MX2015007526A (es) | 2015-10-14 |
AR093977A1 (es) | 2015-07-01 |
CN104994733B (zh) | 2017-03-15 |
NZ708680A (en) | 2018-05-25 |
BR102013032003A2 (pt) | 2014-10-21 |
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