JP5512551B2 - 置換ビフェニルアニリド類を調製する方法 - Google Patents
置換ビフェニルアニリド類を調製する方法 Download PDFInfo
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- JP5512551B2 JP5512551B2 JP2010547089A JP2010547089A JP5512551B2 JP 5512551 B2 JP5512551 B2 JP 5512551B2 JP 2010547089 A JP2010547089 A JP 2010547089A JP 2010547089 A JP2010547089 A JP 2010547089A JP 5512551 B2 JP5512551 B2 JP 5512551B2
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- Prior art keywords
- palladium
- compound
- carboxamide
- iii
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- JVRMUFJCFLXSMJ-UHFFFAOYSA-N n,2-diphenylbenzamide Chemical class C=1C=CC=C(C=2C=CC=CC=2)C=1C(=O)NC1=CC=CC=C1 JVRMUFJCFLXSMJ-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 19
- VIGVRXYWWFPORY-UHFFFAOYSA-N diphenylborinic acid Chemical compound C=1C=CC=CC=1B(O)C1=CC=CC=C1 VIGVRXYWWFPORY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 25
- -1 C 1 -C 6 -alkyl Chemical group 0.000 claims description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Chemical group 0.000 claims description 6
- 229910052801 chlorine Chemical group 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.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 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 6
- UYANAUSDHIFLFQ-UHFFFAOYSA-N borinic acid Chemical compound OB UYANAUSDHIFLFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- GTIPIQTXJYDTPL-UHFFFAOYSA-N bis(3,4-dichlorophenyl)borinic acid Chemical compound C=1C=C(Cl)C(Cl)=CC=1B(O)C1=CC=C(Cl)C(Cl)=C1 GTIPIQTXJYDTPL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- NZKCGJMEQDDBFJ-UHFFFAOYSA-N n-(2-bromo-4-fluorophenyl)-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=C(F)C=C1Br NZKCGJMEQDDBFJ-UHFFFAOYSA-N 0.000 claims description 4
- ZRXCBFVJKKISRA-UHFFFAOYSA-N n-(2-chloro-4-fluorophenyl)-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=C(F)C=C1Cl ZRXCBFVJKKISRA-UHFFFAOYSA-N 0.000 claims description 4
- FOUDIDNRZBCJFZ-UHFFFAOYSA-N 2-chloro-n-(2-chlorophenyl)pyridine-3-carboxamide Chemical compound ClC1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl FOUDIDNRZBCJFZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 3
- KMUQQVOKLYBAAD-UHFFFAOYSA-N (4-chlorophenyl)borinic acid Chemical compound OBC1=CC=C(Cl)C=C1 KMUQQVOKLYBAAD-UHFFFAOYSA-N 0.000 claims description 2
- 125000006727 (C1-C6) alkenyl group Chemical group 0.000 claims description 2
- 125000006728 (C1-C6) alkynyl group Chemical group 0.000 claims description 2
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 2
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- WLEYYNFKPBVDBE-UHFFFAOYSA-N n-(2-chlorophenyl)-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1Cl WLEYYNFKPBVDBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims 2
- 125000004399 C1-C4 alkenyl group Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 235000005152 nicotinamide Nutrition 0.000 claims 1
- 239000011570 nicotinamide Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 8
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 150000004074 biphenyls Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LDLMOOXUCMHBMZ-UHFFFAOYSA-N bixafen Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=C(F)C=C1C1=CC=C(Cl)C(Cl)=C1 LDLMOOXUCMHBMZ-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000008422 chlorobenzenes Chemical class 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- KFKVECZQALNWSR-UHFFFAOYSA-N 1-methyl-3-(trifluoromethyl)pyrazole-4-carbonyl chloride Chemical compound CN1C=C(C(Cl)=O)C(C(F)(F)F)=N1 KFKVECZQALNWSR-UHFFFAOYSA-N 0.000 description 1
- UTBJLKDVQNCKAS-UHFFFAOYSA-N 1-methyl-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound CN1C=C(C(N)=O)C(C(F)(F)F)=N1 UTBJLKDVQNCKAS-UHFFFAOYSA-N 0.000 description 1
- ZVXKYWHJBYIYNI-UHFFFAOYSA-N 1h-pyrazole-4-carboxamide Chemical compound NC(=O)C=1C=NNC=1 ZVXKYWHJBYIYNI-UHFFFAOYSA-N 0.000 description 1
- YLMFXCIATJJKQL-UHFFFAOYSA-N 2-bromo-4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1Br YLMFXCIATJJKQL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 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 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical class CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000404 calcium aluminium silicate Substances 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- 229940078583 calcium aluminosilicate Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- LCSNDSFWVKMJCT-UHFFFAOYSA-N dicyclohexyl-(2-phenylphenyl)phosphane Chemical group C1CCCCC1P(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1CCCCC1 LCSNDSFWVKMJCT-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- RMXGWLUCCKWPGK-UHFFFAOYSA-M magnesium;1,2-dichlorobenzene-5-ide;bromide Chemical compound [Mg+2].[Br-].ClC1=CC=[C-]C=C1Cl RMXGWLUCCKWPGK-UHFFFAOYSA-M 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical class [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- YOGZONLHPZCEGN-UHFFFAOYSA-N n-(2-bromo-4-fluorophenyl)-1-methyl-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound FC(F)(F)C1=NN(C)C=C1C(=O)NC1=CC=C(F)C=C1Br YOGZONLHPZCEGN-UHFFFAOYSA-N 0.000 description 1
- FYGRJQYUYKZMAZ-UHFFFAOYSA-N n-(2-bromo-6-fluorophenyl)-1-methyl-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound FC(F)(F)C1=NN(C)C=C1C(=O)NC1=C(F)C=CC=C1Br FYGRJQYUYKZMAZ-UHFFFAOYSA-N 0.000 description 1
- RDDDPHQCUDKACQ-UHFFFAOYSA-N n-(2-bromophenyl)-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1Br RDDDPHQCUDKACQ-UHFFFAOYSA-N 0.000 description 1
- ZJWNASNEHKLDGR-UHFFFAOYSA-N n-(2-chloro-4-fluorophenyl)-1-methyl-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound FC(F)(F)C1=NN(C)C=C1C(=O)NC1=CC=C(F)C=C1Cl ZJWNASNEHKLDGR-UHFFFAOYSA-N 0.000 description 1
- USOAQJTXQNSTMO-UHFFFAOYSA-N n-(2-chloro-6-fluorophenyl)-1-methyl-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound FC(F)(F)C1=NN(C)C=C1C(=O)NC1=C(F)C=CC=C1Cl USOAQJTXQNSTMO-UHFFFAOYSA-N 0.000 description 1
- BPRDJKZDKAIOHV-UHFFFAOYSA-N n-(2-chloro-6-fluorophenyl)-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=C(F)C=CC=C1Cl BPRDJKZDKAIOHV-UHFFFAOYSA-N 0.000 description 1
- LQBOMKDGIBJJTD-UHFFFAOYSA-N n-(2-chlorophenyl)-1-methyl-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound FC(F)(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1Cl LQBOMKDGIBJJTD-UHFFFAOYSA-N 0.000 description 1
- YJJQCALWJNPBRF-UHFFFAOYSA-N n-[2-(3,4-dichlorophenyl)-4-fluorophenyl]-1-methyl-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound FC(F)(F)C1=NN(C)C=C1C(=O)NC1=CC=C(F)C=C1C1=CC=C(Cl)C(Cl)=C1 YJJQCALWJNPBRF-UHFFFAOYSA-N 0.000 description 1
- IJRZHXOEFVOEPE-UHFFFAOYSA-N n-[2-(3,4-dichlorophenyl)phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide Chemical compound FC(F)C1=NN(C)C=C1C(=O)NC1=CC=CC=C1C1=CC=C(Cl)C(Cl)=C1 IJRZHXOEFVOEPE-UHFFFAOYSA-N 0.000 description 1
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical compound [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Information Transfer Between Computers (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
Description
から選択されるヘテロシクリル残基であり;
Xは、水素、フッ素又は塩素であり;
R1は、C1−C6−ハロアルキルであり;
R2は、シアノ、ニトロ、ハロゲン、C1−C6−アルキル、C1−C6−アルケニル、C1−C6−アルキニル、C1−C6−アルコキシ、C1−C6−ハロアルキル、(C1−C6−アルキル)カルボニル又はフェニルであり;
nは、1、2又は3であり、ここで、nが2又は3である場合、R2ラジカルは、異なっていてもよい〕
で表される置換ビフェニルアニリドを調製する方法に関し、ここで、該方法は、式(II)
で表される化合物を、溶媒中で、塩基の存在下、及び、パラジウム触媒[ここで、該パラジウム触媒は、以下のものから成る群から選択される:(a)パラジウムの酸化状態がゼロであるパラジウム−トリアリールホスフィン錯体若しくはパラジウム−トリアルキルホスフィン錯体、(b)錯体リガンドとしてのトリアリールホスフィン若しくはトリアルキルホスフィンの存在下におけるパラジウムの塩、又は、(c)トリアリールホスフィン若しくはトリアルキルホスフィンの存在下における、場合により担体に担持されていてもよい金属パラジウム]の存在下で、式(III)
から選択されるヘテロシクリル残基であり;
R1は、トリフルオロメチル又はジフルオロメチル、さらに好ましくは、ジフルオロメチルであり;
R2は、シアノ、ニトロ、フッ素、塩素、臭素、メチル、エチル、プロピル、ブチル、アリル、プロパルギル、メトキシ、エトキシ、トリフルオロメチル又はフェニル、さらに好ましくは、フッ素、塩素、メチル又はメトキシ、最も好ましくは、フッ素又は塩素であり;
nは、1又は2、好ましくは、2である。
N−(2−クロロ−4−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモ−4−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−クロロ−4−フルオロフェニル)−3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモ−4−フルオロフェニル)−3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−クロロ−6−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモ−6−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−クロロ−6−フルオロフェニル)−3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモ−6−フルオロフェニル)−3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−クロロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−クロロフェニル)−3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモフェニル)−3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、2−クロロ−N−(2−クロロフェニル)ピリジン−3−カルボキサミド、2−クロロ−N−(2−ブロモフェニル)ピリジン−3−カルボキサミド。N−(2−クロロ−4−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモ−4−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、2−クロロ−N−(2−クロロフェニル)ピリジン−3−カルボキサミド及び2−クロロ−N−(2−ブロモフェニル)ピリジン−3−カルボキサミドが特に好ましい。
2−クロロ−N−(4’−クロロビフェニル−2−イル)ピリジン−3−カルボキサミド、N−(3’,4’−ジクロロビフェニル−2−イル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(3’,4’−ジクロロ−5−フルオロビフェニル−2−イル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(3’,4’−ジクロロ−5−フルオロビフェニル−2−イル)−3−(トリフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド。
乾燥フラスコに、DCM中のトリブロモボラン(13mL、13mmol、1M)を添加した。この溶液を−62℃に冷却し、得られた***液に、ブロモ(3,4−ジクロロフェニル)マグネシウム(50mL、25mmol、THF中0.5M)を滴下して加えた。その反応混合物を室温まで昇温させ、一晩撹拌した。減圧下に溶媒を除去した。その残渣をDCMに溶解させ、1N HClをゆっくりと添加することによって加水分解した。有機層を分離し、ブラインで洗浄し、減圧下に溶媒を除去した。得られた油状物を、溶離剤として25%酢酸エチルを使用するシリカゲルクロマトグラフィーで精製した。これによって、標題化合物が固体として得られた(3.34g、10.4mmol、収率80%)。
0.5L容二重ジャケット反応器の中に、THF/トルエン混合物(2/3 w/w)中の、ジ(3,4−ジクロロフェニル)ボリン酸(0.2mol)の溶液178gと水13gを入れる。水酸化ナトリウムの10%水溶液(32g)を添加してpHを7.4に調節する。N−(2−ブロモ−4−フルオロフェニル)−1−メチル−3−(ジフルオロメチル)−1H−ピラゾール−4−カルボキサミド(56g、0.2mol)を添加し、次いで、その反応混合物を脱酸素し、75−80℃に加熱する。この温度で、水とトルエンの1/1混合物に溶解させた0.06g(0.2mmol)のトリ−tert−ブチルホスホニウムテトラフルオロボレートと0.06g(0.2mmol)のパラジウムアセチルアセトナートの混合物を入れる。10%(w/w)水酸化ナトリウム溶液(消費量 98g)を添加することによって、pHを8.0−8.5に調節し、そして、その範囲内に維持する。反応が終了した後、その反応混合物を20℃に冷却し、水相を分離除去する(195g)。有機層(190g)は、22%(w/w)(HPLC)のN−(3’,4’−ジクロロ−5−フルオロビフェニル−2−イル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミドを含んでいる(収率50%)。
Claims (15)
- 式(I)
Hetは、
から選択されるヘテロシクリル残基であり;
Xは、水素、フッ素又は塩素であり;
R1は、C1−C6−ハロアルキルであり;
R2は、シアノ、ニトロ、ハロゲン、C1−C6−アルキル、C1−C6−アルケニル、C1−C6−アルキニル、C1−C6−アルコキシ、C1−C6−ハロアルキル、(C1−C6−アルキル)カルボニル又はフェニルであり;
R3は、C1−C4−アルキル、C1−C4−アルケニル又はC1−C4−アルキニルであり;
nは、1、2又は3であり、ここで、nが2又は3である場合、R2ラジカルは、異なっていてもよい〕
で表される置換ビフェニルアニリドを調製する方法であって、式(II)
で表される化合物を、溶媒中で、塩基の存在下、及び、パラジウム触媒[ここで、該パラジウム触媒は、以下のものから成る群から選択される:
(a)テトラキス(トリフェニルホスフィン)パラジウム及びテトラキス(トリ−tert−ブチルホスフィン)パラジウムから選択され、パラジウムの酸化状態がゼロである、パラジウム−トリアリールホスフィン錯体若しくはパラジウム−トリアルキルホスフィン錯体;
(b)錯体リガンドとしてのトリアリールホスフィン若しくはトリアルキルホスフィンの存在下における、塩化パラジウム、酢酸パラジウム、パラジウムビスアセチルアセトナート(Pd(acac) 2 )及びビスアセトニトリルパラジウムクロリドから選択される、パラジウムの塩;又は、
(c)トリフェニルホスフィン(ここで、該トリフェニルホスフィンのフェニル基は、合計で1〜3のスルホネート基で置換されている)の存在下における、活性炭担持金属パラジウム]
の存在下で、式(III)
で表されるジフェニルボリン酸と反応させることを含む(ここで、使用するトリアリールホスフィン類又はトリアルキルホスフィン類は、置換されていてもよい)、前記方法。 - 使用する化合物(II)が、N−(2−クロロ−4−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、N−(2−ブロモ−4−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミド、2−クロロ−N−(2−クロロフェニル)ピリジン−3−カルボキサミド及び2−クロロ−N−(2−ブロモフェニル)ピリジン−3−カルボキサミドからなる群から選択される、請求項1に記載の調製方法。
- 出発化合物(III)が、3位及び4位において置換されているジフェニルボリン酸である、請求項1又は2に記載の調製方法。
- 3位及び4位にフッ素又は塩素を有しているジフェニルボリン酸(III)を使用する、請求項1又は2に記載の調製方法。
- 出発化合物(III)が、ジ(3,4−ジクロロフェニル)ボリン酸である、請求項1又は2に記載の調製方法。
- 請求項1に記載のパラジウム触媒(b)を使用する、請求項1〜5に記載の調製方法。
- パラジウム触媒(b)を使用し、そのパラジウム触媒(b)に関して、該パラジウム塩1当量当たり6〜60当量のトリフェニルホスフィンを使用する、請求項6に記載の調製方法。
- 化合物(II)の量に基づいて、0.001〜1.0mol%のパラジウム触媒を使用する、請求項1に記載の調製方法。
- 反応を50〜120℃の温度で実施する、請求項1に記載の調製方法。
- 反応を水と有機溶媒の混合物の中で実施する、請求項1に記載の調製方法。
- 使用する有機溶媒がエーテルである、請求項10に記載の調製方法。
- 反応を1〜6barの圧力で実施する、請求項1に記載の調製方法。
- 化合物(II)が、N−(2−クロロ−4−フルオロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミドであり、且つ、化合物(III)が、ジ(3,4−ジクロロフェニル)ボリン酸である、請求項1に記載の調製方法。
- 化合物(II)が、N−(2−クロロフェニル)−3−(ジフルオロメチル)−1−メチル−1H−ピラゾール−4−カルボキサミドであり、且つ、化合物(III)が、ジ(3,4−ジクロロフェニル)ボリン酸である、請求項1に記載の調製方法。
- 化合物(II)が、2−クロロ−N−(2−ブロモフェニル)ピリジン−3−カルボキサミドであり、且つ、化合物(III)が、(4−クロロフェニル)ボリン酸である、請求項1に記載の調製方法。
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CN104395326B (zh) * | 2012-08-20 | 2017-04-05 | 玛耐科股份有限公司 | 二取代硼酸衍生物的制造方法和新型二取代硼酸衍生物 |
CA2931931C (en) | 2013-11-29 | 2022-11-01 | Basf Se | Polyurethane system with long pot life and rapid hardening |
DE102019005561A1 (de) * | 2018-08-30 | 2020-03-05 | Merck Patent Gmbh | Löslicher katalysator in form von tabletten |
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BRPI0908261A2 (pt) | 2015-07-21 |
DK2257530T3 (da) | 2012-02-06 |
TW201002670A (en) | 2010-01-16 |
MX2010008663A (es) | 2010-09-24 |
JP2011515335A (ja) | 2011-05-19 |
CN101952253B (zh) | 2013-05-01 |
EP2257530B1 (en) | 2011-10-12 |
TWI427064B (zh) | 2014-02-21 |
EP2093216A1 (en) | 2009-08-26 |
WO2009106234A1 (en) | 2009-09-03 |
ATE528293T1 (de) | 2011-10-15 |
CN101952253A (zh) | 2011-01-19 |
KR101652360B1 (ko) | 2016-08-30 |
IL207020A0 (en) | 2010-12-30 |
EP2257530A1 (en) | 2010-12-08 |
KR20100136455A (ko) | 2010-12-28 |
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