WO2015190316A1 - ピリジン化合物の製造方法 - Google Patents
ピリジン化合物の製造方法 Download PDFInfo
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- WO2015190316A1 WO2015190316A1 PCT/JP2015/065512 JP2015065512W WO2015190316A1 WO 2015190316 A1 WO2015190316 A1 WO 2015190316A1 JP 2015065512 W JP2015065512 W JP 2015065512W WO 2015190316 A1 WO2015190316 A1 WO 2015190316A1
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- carbon atoms
- atom
- substituted
- fluorine atom
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- -1 pyridine compound Chemical class 0.000 title claims abstract description 157
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 83
- 150000001875 compounds Chemical class 0.000 claims abstract description 77
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 52
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 25
- 125000005843 halogen group Chemical group 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 51
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 5
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 5
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 3
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 claims description 3
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 claims description 3
- 239000002917 insecticide Substances 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 239000002904 solvent Substances 0.000 description 23
- 150000002430 hydrocarbons Chemical group 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 10
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- UWIVVFQECQYHOB-UHFFFAOYSA-M sodium;ethanesulfinate Chemical compound [Na+].CCS([O-])=O UWIVVFQECQYHOB-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- BAUKFIYTDAAFRE-UHFFFAOYSA-N 2-(3-chloropyridin-2-yl)-5-(trifluoromethylsulfinyl)-1,3-benzoxazole Chemical compound ClC=1C(=NC=CC=1)C=1OC2=C(N=1)C=C(C=C2)S(=O)C(F)(F)F BAUKFIYTDAAFRE-UHFFFAOYSA-N 0.000 description 2
- RVVWYYTXAOMQOY-UHFFFAOYSA-N 2-[3-ethylsulfonyl-5-(1,1,2,2,2-pentafluoroethyl)pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine Chemical compound CCS(=O)(=O)C1=CC(C(F)(F)C(F)(F)F)=CN=C1C1=NC2=CC(C(F)(F)F)=CN=C2N1C RVVWYYTXAOMQOY-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 2
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- FRYHCSODNHYDPU-UHFFFAOYSA-N ethanesulfonyl chloride Chemical compound CCS(Cl)(=O)=O FRYHCSODNHYDPU-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 2
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- LYPGDCWPTHTUDO-UHFFFAOYSA-M sodium;methanesulfinate Chemical compound [Na+].CS([O-])=O LYPGDCWPTHTUDO-UHFFFAOYSA-M 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- 125000006789 (C3-C7) alkenyloxycarbonyl group Chemical group 0.000 description 1
- VRLCFIBHVFTRES-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical group F[C](F)C(F)=C(F)F VRLCFIBHVFTRES-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 125000006420 1-fluorocyclopropyl group Chemical group [H]C1([H])C([H])([H])C1(F)* 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- IXGWJIHUZMMRDL-UHFFFAOYSA-N 2-(3-chloropyridin-2-yl)-5-(trifluoromethylsulfanyl)-1,3-benzoxazole Chemical compound ClC=1C(=NC=CC=1)C=1OC2=C(N=1)C=C(C=C2)SC(F)(F)F IXGWJIHUZMMRDL-UHFFFAOYSA-N 0.000 description 1
- RFEAQVDNQBXMBE-UHFFFAOYSA-N 2-(3-ethylsulfonylpyridin-2-yl)-5-(trifluoromethylsulfinyl)-1,3-benzoxazole Chemical compound CCS(=O)(=O)C1=CC=CN=C1C1=NC2=CC(S(=O)C(F)(F)F)=CC=C2O1 RFEAQVDNQBXMBE-UHFFFAOYSA-N 0.000 description 1
- PLZYVSZYUXDPJC-UHFFFAOYSA-N 2-[3-ethylsulfanyl-5-(1,1,2,2,2-pentafluoroethyl)pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine Chemical compound CCSC1=CC(C(F)(F)C(F)(F)F)=CN=C1C1=NC2=CC(C(F)(F)F)=CN=C2N1C PLZYVSZYUXDPJC-UHFFFAOYSA-N 0.000 description 1
- CVQLGCQIFRWVQM-UHFFFAOYSA-N 2-amino-4-(trifluoromethylsulfinyl)phenol Chemical compound NC1=CC(S(=O)C(F)(F)F)=CC=C1O CVQLGCQIFRWVQM-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- 125000006304 2-iodophenyl group Chemical group [H]C1=C([H])C(I)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- ZAFLZRNJFHWOQQ-UHFFFAOYSA-N 3-chloropyridine-2-carbonyl chloride Chemical compound ClC(=O)C1=NC=CC=C1Cl ZAFLZRNJFHWOQQ-UHFFFAOYSA-N 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000006305 3-iodophenyl group Chemical group [H]C1=C([H])C(I)=C([H])C(*)=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
- 125000004863 4-trifluoromethoxyphenyl group Chemical group [H]C1=C([H])C(OC(F)(F)F)=C([H])C([H])=C1* 0.000 description 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAPHFSRFSAZXQU-UHFFFAOYSA-M C(CCCC)S(=O)[O-].[Li+] Chemical compound C(CCCC)S(=O)[O-].[Li+] GAPHFSRFSAZXQU-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 125000005090 alkenylcarbonyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000004471 alkyl aminosulfonyl group Chemical group 0.000 description 1
- 125000005087 alkynylcarbonyl group Chemical group 0.000 description 1
- 125000005225 alkynyloxycarbonyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 125000006251 butylcarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([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
- 125000004472 dialkylaminosulfonyl group Chemical group 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 125000006263 dimethyl aminosulfonyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- SBBFZWWBMFILKH-UHFFFAOYSA-N ethanesulfonyl bromide Chemical compound CCS(Br)(=O)=O SBBFZWWBMFILKH-UHFFFAOYSA-N 0.000 description 1
- 125000006627 ethoxycarbonylamino group Chemical group 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 125000005290 ethynyloxy group Chemical group C(#C)O* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WCZSOHSGMBVYFW-UHFFFAOYSA-M heptyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCC)C1=CC=CC=C1 WCZSOHSGMBVYFW-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- JYTDYEZVDNSODN-UHFFFAOYSA-M lithium propane-1-sulfinate Chemical compound C(CC)S(=O)[O-].[Li+] JYTDYEZVDNSODN-UHFFFAOYSA-M 0.000 description 1
- CCHLGFJPIQGRGT-UHFFFAOYSA-M lithium;butane-1-sulfinate Chemical compound [Li+].CCCCS([O-])=O CCHLGFJPIQGRGT-UHFFFAOYSA-M 0.000 description 1
- ZUXCWQAXJCMKGZ-UHFFFAOYSA-M lithium;ethanesulfinate Chemical compound [Li+].CCS([O-])=O ZUXCWQAXJCMKGZ-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- GAZDQFVUWXUHPW-UHFFFAOYSA-M lithium;methanesulfinate Chemical compound [Li+].CS([O-])=O GAZDQFVUWXUHPW-UHFFFAOYSA-M 0.000 description 1
- ITYJDNHFRZSTJY-UHFFFAOYSA-N methanesulfonyl bromide Chemical compound CS(Br)(=O)=O ITYJDNHFRZSTJY-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- 125000006261 methyl amino sulfonyl group Chemical group [H]N(C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000004458 methylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])[H] 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 1
- 125000004675 pentylcarbonyl group Chemical group C(CCCC)C(=O)* 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HLVVVMPXONYIGM-UHFFFAOYSA-N propane-1-sulfonyl bromide Chemical compound CCCS(Br)(=O)=O HLVVVMPXONYIGM-UHFFFAOYSA-N 0.000 description 1
- KPBSJEBFALFJTO-UHFFFAOYSA-N propane-1-sulfonyl chloride Chemical compound CCCS(Cl)(=O)=O KPBSJEBFALFJTO-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000004673 propylcarbonyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FVJRSQFHCAAJRH-UHFFFAOYSA-M sodium pentane-1-sulfinate Chemical compound C(CCCC)S(=O)[O-].[Na+] FVJRSQFHCAAJRH-UHFFFAOYSA-M 0.000 description 1
- VOHJOJMSAGPWBW-UHFFFAOYSA-M sodium;2-methylpropane-2-sulfinate Chemical compound [Na+].CC(C)(C)S([O-])=O VOHJOJMSAGPWBW-UHFFFAOYSA-M 0.000 description 1
- DJSGLRVJPLXKRB-UHFFFAOYSA-M sodium;propane-1-sulfinate Chemical compound [Na+].CCCS([O-])=O DJSGLRVJPLXKRB-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 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
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- OCOTWWSGPAHHQW-UHFFFAOYSA-N trifluoro(trifluoromethylsulfinyl)methane Chemical compound FC(F)(F)S(=O)C(F)(F)F OCOTWWSGPAHHQW-UHFFFAOYSA-N 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
Definitions
- the present invention relates to a method for producing a pyridine compound.
- WO2013 / 018928 includes 2- (3-ethylsulfonyl-5-pentafluoroethylpyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine and the like.
- a 10 represents —NR 27 —, an oxygen atom or a sulfur atom.
- a 20 represents a nitrogen atom or ⁇ CR 28 —.
- a 30 represents a nitrogen atom or ⁇ CR 29 —.
- R 21 represents an optionally substituted chain hydrocarbon group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent.
- R 22 , R 23 and R 24 are each independently a C 1-6 chain hydrocarbon group which may have a substituent, a phenyl group which may have a substituent, or a substituent.
- a 5- or 6-membered heterocyclic group which may have, -OR 30 , -S (O) m R 30 , -S (O) 2 NR 30 R 40 , -NR 30 R 40 , -NR 30 CO 2 R 40 , —NR 30 C (O) R 40 , —CO 2 R 30 , —C (O) R 30 , —C (O) NR 30 R 40 , —SF 5 , a cyano group, a nitro group, a halogen atom or Represents a hydrogen atom.
- R 25 and R 26 each independently have a C 1-6 chain hydrocarbon group which may have a substituent, a phenyl group which may have a substituent, or a substituent.
- -OR 30 , -S (O) m R 30 , -S (O) 2 NR 30 R 40 , -NR 30 R 40 , -NR 30 CO 2 R 40 , —NR 30 C (O) R 40 , —CO 2 R 30 , —C (O) R 30 , —C (O) NR 30 R 40 , —SF 5 , a cyano group, a nitro group, a halogen atom or a hydrogen atom To express.
- R 25 and R 26 are not both hydrogen atoms.
- m represents an integer of 0-2.
- n represents an integer of 0-2.
- R 30 and R 40 each independently represents a chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a hydrogen atom.
- R 27 is an optionally substituted chain hydrocarbon group having 1 to 6 carbon atoms, —CO 2 R 30 , —C (O) R 30 , and optionally substituted carbon atoms. 3 to 6 alicyclic hydrocarbon groups or hydrogen atoms are represented.
- R 28 and R 29 each independently represent a chain hydrocarbon group having 1 to 6 carbon atoms which may have a halogen atom, —OR 30 , —S (O) m R 30 , —NR 30 R 40 , -CO 2 R 30 , -C (O) R 30 , a cyano group, a nitro group, a halogen atom or a hydrogen atom.
- a halogen atom —OR 30 , —S (O) m R 30 , —NR 30 R 40 , -CO 2 R 30 , -C (O) R 30 , a cyano group, a nitro group, a halogen atom or a hydrogen atom.
- WO2013 / 018928 discloses a process for producing 2- (3-ethylsulfonyl-5-pentafluoroethylpyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 2- (3-ethylsulfanyl-5-pentafluoroethylpyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine as m-chloroperbenzoic acid A method of oxidizing with is described.
- the present invention provides a new method for producing the above pyridine compound, and includes the following inventions.
- Formula (2) [Where: L 1 represents a halogen atom.
- R 2 , R 3 , R 4 , R 5 and R 6 may each independently have a C 1-6 chain hydrocarbon group or substituent which may be substituted with a fluorine atom.
- R 10 and R 13 each independently represents a chain hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a fluorine atom or a phenyl group which may have a substituent.
- R 11 and R 12 each independently represents a chain hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, a phenyl group which may have a substituent, or a hydrogen atom.
- a 1 represents —NR 7 —, an oxygen atom or a sulfur atom.
- a 2 represents a nitrogen atom or ⁇ CR 8 —.
- R 7 and R 8 each independently represents a chain hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom.
- the substituent is substituted with a fluorine atom.
- R 2 and R 4 are hydrogen atoms
- R 3 is a hydrogen atom or a trifluoromethyl group
- R 5 is a trifluoromethyl group, a tetrafluoroethyl group, a trifluoromethylthio group, a trifluoromethylsulfinyl group.
- R 6 is a hydrogen atom
- a 2 is a nitrogen atom or ⁇ CH—.
- the halogen atom represented by L 1 is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- a preferred halogen atom for L 1 is a fluorine atom or a chlorine atom.
- the hydrocarbon group include an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, an alkenyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom, and a fluorine atom.
- a good example is an alkynyl group having 2 to 6 carbon atoms.
- alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom
- examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a neopentyl group.
- alkenyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom
- alkenyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom
- examples of the alkenyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom include a vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 2-methyl-1-propenyl group, 1 -Butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1-hexenyl group, 1,1-difluoroallyl group and pentafluoroallyl group.
- alkynyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom
- alkynyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom
- examples of the alkynyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom include ethynyl group, propargyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 1-hexynyl group and 4,4 , 4-trifluoro-2-butynyl group.
- the phenyl group represented by R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 and R 13 has one or more substituents selected from the following group Z. May be.
- Group Z a chain hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, or a substituent substituted with a fluorine atom
- examples of the chain hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a fluorine atom are substituted with a fluorine atom represented by R 2 , R 3 , R 4 , R 5 and R 6
- a fluorine atom represented by R 2 , R 3 , R 4 , R 5 and R 6 The same as the examples of the chain hydrocarbon group having 1 to 6 carbon atoms which may be used.
- alkoxy group having 1 to 6 carbon atoms which may be substituted with a fluorine atom examples include a methoxy group, a trifluoromethoxy group, an ethoxy group, a 2,2,2-trifluoroethoxy group, a propoxy group, an isopropoxy group, Examples include butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group.
- alkylthio group having 1 to 6 carbon atoms which may be substituted with a fluorine atom
- examples of the alkylthio group having 1 to 6 carbon atoms which may be substituted with a fluorine atom include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, Examples include a hexylthio group, a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, and a pentafluoroethylthio group.
- alkylsulfinyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom examples include, for example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a pentylsulfinyl group, a hexylsulfinyl group, Examples thereof include a trifluoromethylsulfinyl group, a 2,2,2-trifluoroethylsulfinyl group, and a pentafluoroethylsulfinyl group.
- alkylsulfonyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom
- examples of the alkylsulfonyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, a hexylsulfonyl group, Examples thereof include a trifluoromethylsulfonyl group, a 2,2,2-trifluoroethylsulfonyl group, and a pentafluoroethylsulfonyl group.
- alkylcarbonyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom include an acetyl group, a propionyl group, a butyryl group, a pentanoyl group, a hexanoyl group and a trifluoroacetyl group.
- alkoxycarbonyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a tert-butoxycarbonyl group and 2 2,2-trifluoroethoxycarbonyl group.
- phenyl group optionally having one or more substituents selected from group Z include a phenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, and 2,3-difluoro.
- Examples of the chain hydrocarbon group having 1 to 6 carbon atoms represented by R 7 and R 8 include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkynyl group having 2 to 6 carbon atoms. Can be mentioned.
- alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group and hexyl group.
- alkenyl group having 2 to 6 carbon atoms include a vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, Examples thereof include 3-butenyl group, 1-pentenyl group and 1-hexenyl group.
- alkynyl group having 2 to 6 carbon atoms examples include ethynyl group, propargyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group and 1-hexynyl group.
- Examples of the alicyclic hydrocarbon group having 3 to 6 carbon atoms which may be substituted with a fluorine atom represented by R 1 include a cyclopropyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, 1 -Fluorocyclopropyl group, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
- R 10 represented by R 2 , R 3 , R 4 , R 5 and R 6 , for example, a methoxy group, a trifluoromethoxy group, an ethoxy group, a 2,2,2-trifluoromethoxy group, a propoxy group, 1 to 6 carbon alkoxy groups such as butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy; vinyloxy, 1-propenyloxy, 2-propenyloxy, 1 -2-6 carbon atoms such as methyl vinyloxy group, 2-methyl-1-propenyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 1-pentenyloxy group and 1-hexenyloxy group Alkenyloxy group; ethynyloxy group, propargyloxy group, 2-butynyloxy group, 3-butynyloxy group 1-pentynyloxy alkynyloxy group
- M in —S (O) m R 10 represented by R 2 , R 3 , R 4 , R 5 and R 6 is an integer of 0 to 2, preferably 1 or 2.
- R 10 in -S (O) m R 10 is preferably an alkyl group having 1 to 6 carbon atoms which may be substituted by a fluorine atom, a trifluoromethyl group.
- Examples of —S (O) m R 10 include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, neopentylthio group, hexylthio group, tri C1-C6 alkylthio groups such as fluoromethylthio group, 2,2,2-trifluoroethylthio group and pentafluoroethylthio group; methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl Group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group, neopenty
- —S (O) 2 NR 11 R 12 includes, for example, an aminosulfonyl group; carbon such as a methylaminosulfonyl group, an ethylaminosulfonyl group, a propylaminosulfonyl group, a butylaminosulfonyl group, a pentylaminosulfonyl group, and a hexylaminosulfonyl group.
- alkylaminosulfonyl group having 1 to 6 carbon atoms such as dimethylaminosulfonyl group, diethylaminosulfonyl group, dipropylaminosulfonyl group, dibutylaminosulfonyl group, dipentylaminosulfonyl group, dihexylaminosulfonyl group, and methylethylaminosulfonyl group; ⁇ 12 dialkylaminosulfonyl groups.
- Examples of —NR 10 R 13 include amino groups having 1 to 12 carbon atoms such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, dimethylamino group and diethylamino group. Can be mentioned.
- Examples of —NR 11 CO 2 R 13 include a methoxycarbonylamino group and an ethoxycarbonylamino group.
- Examples of —NR 11 C (O) R 12 include a methylcarbonylamino group.
- —CO 2 R 10 includes, for example, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group and a pentyloxycarbonyl group; a vinyloxycarbonyl group 1-propenyloxycarbonyl group, 2-propenyloxycarbonyl group, 1-methylvinyloxycarbonyl group, 2-methyl-1-propenyloxycarbonyl group, 1-butenyloxycarbonyl group, 2-butenyloxycarbonyl group, C3-C7 alkenyloxycarbonyl groups such as 3-butenyloxycarbonyl group, 1-pentenyloxycarbonyl group and 1-hexenyloxycarbonyl group; ethynyloxycarbonyl group, propargyloxycarbonyl group 2-butynyl-oxy group, 3-butynyl
- R 11 includes, for example, an alkylcarbonyl group having 2 to 7 carbon atoms such as a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group and a pentylcarbonyl group; a vinylcarbonyl group, and 1-propenylcarbonyl.
- Examples of —C (O) NR 11 R 12 include aminocarbonyl groups having 1 to 6 carbon atoms such as aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group and methylethylaminocarbonyl group.
- R 2 , R 3 and R 4 are each independently preferably a hydrogen atom or a chain hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a fluorine atom. It is more preferably an alkyl group having 1 to 6 carbon atoms which may be present, more preferably a trifluoromethyl group, a tetrafluoroethyl group or a hydrogen atom, and particularly preferably a hydrogen atom.
- a 1 is preferably —NR 7 — or an oxygen atom.
- Examples of the compound represented by formula (2) include compounds represented by formulas (2-1) to (2-39) described in Table 1.
- R 1 is preferably a chain hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group or an ethyl group.
- M + is preferably a sodium ion.
- Examples of the compound represented by the formula (3) include sodium methanesulfinate, sodium ethanesulfinate, sodium propanesulfinate, sodium tert-butanesulfinate, sodium pentansulphinate and the like.
- Sulfinic acid sodium salt lithium methanesulfinate, lithium ethanesulfinate, lithium propanesulfinate, lithium butanesulfinate, lithium pentansulphinate and the like.
- Compound (3) is preferably a sodium sulfinate salt, more preferably sodium methanesulfinate and sodium ethanesulfinate.
- a commercially available compound may be used, or the compound of the formula (4) (Wherein R 1 has the same meaning as described above, and X represents a halogen atom.) May be produced by reacting a compound represented by formula (hereinafter referred to as compound (4)) with a base and a reducing agent.
- the halogen atom represented by X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.
- Examples of the compound (4) include methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, methanesulfonyl bromide, ethanesulfonyl bromide, and propanesulfonyl bromide.
- Examples of the base include alkali metal hydrogen carbonates such as sodium hydrogen carbonate, lithium hydrogen carbonate, and potassium hydrogen carbonate; alkali metal carbonates such as sodium carbonate and potassium carbonate; and alkali metal phosphates such as dipotassium hydrogen phosphate. It is done.
- Examples of the reducing agent include alkali metal sulfites such as sodium sulfite, potassium sulfite, and lithium sulfite.
- the amount of the base to be used is generally 2-4 mol, preferably 2-3 mol, per 1 mol of compound (4).
- the amount of the reducing agent to be used is generally 1 to 3 mol, preferably 1 to 2 mol, per 1 mol of compound (4).
- Reaction of a compound (2) and a compound (3) is normally implemented by mixing a compound (2) and a compound (3).
- compound (3) may be added to compound (2), compound (2) may be added to compound (3), and compound (3) may be added at once or divided. May be added.
- the amount of compound (3) to be used is generally 1 to 10 mol, preferably 1 to 2 mol, per 1 mol of compound (2).
- the reaction between compound (2) and compound (3) is preferably carried out in the presence of a solvent.
- the solvent examples include water; aromatic hydrocarbon solvents such as benzene, chlorobenzene and toluene; halogen-containing hydrocarbon solvents such as chloroform and dichloromethane; alcohol solvents such as methanol, ethanol and normal butanol; 1,2-dimethoxyethane and diethylene glycol.
- Ether solvents such as dimethyl ether, polyethylene glycol, tetrahydrofuran and dioxane; nitrile solvents such as acetonitrile and propyl nitrile; sulfoxide solvents such as dimethyl sulfoxide; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone Solvent; and a mixed solvent thereof, and a sulfoxide solvent or an amide solvent is preferable.
- the amount of the solvent to be used is generally 1 to 100 parts by mass with respect to 1 part by mass of compound (2).
- the reaction of compound (2) and compound (3) may be carried out in the presence of a phase transfer catalyst.
- the phase transfer catalyst include quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, and benzyltributylammonium bromide; and quaternary phosphonium such as heptyltriphenylphosphonium bromide and tetraphenylphosphonium bromide. Salts, and quaternary ammonium salts are preferable, and tetrabutylammonium chloride is more preferable.
- the amount of the phase transfer catalyst to be used is generally 0.01 to 10 mol, preferably 0.1 to 0.5 mol, per 1 mol of compound (2).
- the reaction temperature of the compound (2) and the compound (3) is usually 60 to 150 ° C., preferably 80 to 120 ° C.
- the reaction time between compound (2) and compound (3) is usually 0.1 to 100 hours, preferably 3 to 24 hours.
- the compound represented by formula (1) (hereinafter referred to as compound (1)) can be taken out.
- the taken out compound (1) can be purified using a usual purification means such as washing, if necessary.
- Examples of the compound (1) include compounds represented by formulas (1-1) to (1-23) described in Table 2.
- Compound (2) has the formula (7) according to the description of WO2013 / 018928.
- a 1 , A 2 , R 2 , R 3 , R 4 , R 5 , R 6 and L 1 have the same meaning as described above.
- Examples of the compound (7) include compounds represented by formulas (7-1) to (7-10) shown in Table 3.
- the intramolecular condensation reaction of compound (7) is usually carried out by mixing compound (7) and an acid.
- the acid include sulfonic acids such as p-toluenesulfonic acid; carboxylic acids such as acetic acid; polyphosphoric acid and the like.
- the amount of the acid to be used is generally 0.1-5 mol per 1 mol of compound (7).
- the intramolecular condensation reaction temperature is usually 0 to 200 ° C., and the intramolecular condensation reaction time is usually 0.1 to 24 hours.
- the intramolecular condensation reaction is usually performed in a solvent.
- the solvent examples include ether solvents such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane; aliphatic hydrocarbon solvents such as hexane, heptane, and octane: aromatic hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene; ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; aprotic polar solvents such as N, N-dimethylformamide and N, N-dimethylformamide and mixed solvents thereof Is mentioned.
- the solvent is preferably an aromatic hydrocarbon solvent, more preferably xylene.
- the amount of the solvent to be used is generally 1-100 parts by mass with respect to 1 part by mass of compound (7).
- the compound (2) can be taken out by concentrating the obtained reaction mixture, for example.
- the removed compound (2) can be purified by washing, recrystallization, chromatography or the like.
- Compound (7) has the formula (5) (Wherein, A 1, A 2, A 3, R 5 and R 6 have the same meaning as above.)
- Examples of the compound (5) include compounds represented by formulas (5-1) to (5-8) described in Table 4.
- Examples of the compound (6) include compounds represented by formulas (6-1) to (6-4) described in Table 5.
- the amount of compound (6) to be used is generally 1 to 3 mol per 1 mol of compound (5).
- Reaction of a compound (5) and a compound (6) is normally implemented by mixing a compound (5) and a compound (6).
- the compound (6) is preferably added to the compound (5).
- the reaction temperature is usually ⁇ 20 to 100 ° C.
- the reaction time is usually 0.1 to 24 hours.
- Reaction of a compound (5) and a compound (6) is normally implemented in a solvent.
- the solvent include the same solvents as those used in the intramolecular condensation reaction of compound (7). Ether solvents are preferable, and tetrahydrofuran is more preferable.
- the amount of the solvent to be used is generally 1-100 parts by mass with respect to 1 part by mass of compound (5).
- the reaction of compound (5) and compound (6) may be carried out in the presence of a base.
- the base include alkali metal carbonates such as sodium carbonate and potassium carbonate; tertiary amines such as triethylamine and diisopropylethylamine; and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
- the amount of the base to be used is generally 1 to 10 mol per 1 mol of compound (5).
- the compound (7) can be taken out by concentrating the obtained reaction mixture, for example.
- the extracted compound (7) can be purified by chromatography, recrystallization and the like.
- Example 1 In a test tube at room temperature under a nitrogen atmosphere, 90.3 mg of 2- (3-chloropyridin-2-yl) -5- (trifluoromethylsulfinyl) benzoxazole obtained in Production Example 3 was obtained in Production Example 1. Further, 45.6 mg of sodium ethanesulfinate, 22.7 mg of tetrabutylammonium chloride, and 4.0 ml of N, N-dimethylacetamide were added. The mixture was stirred at 105 ° C. for about 23 hours under a nitrogen atmosphere, then cooled to room temperature, water and ethyl acetate were added, and the mixture was separated to obtain an organic layer and an aqueous layer.
- Example 2 Under a nitrogen atmosphere at room temperature, 50.2 mg of 2- (3-chloropyridin-2-yl) -5- (trifluoromethylthio) benzoxazole obtained in Production Example 3 in a test tube, 26.2 mg of sodium ethanesulfinate, Tetrabutylammonium chloride (12.6 mg) and N, N-dimethylacetamide (2.2 ml) were added. The mixture was stirred at 105 ° C. for 13 hours under a nitrogen atmosphere, and then 13.2 mg of sodium ethanesulfinate obtained in Production Example 1 was added thereto, and further stirred at 105 ° C. for 4 hours to give 2- (3 A mixture containing -ethylsulfonylpyridin-2-yl) -5- (trifluoromethylthio) benzoxazole was obtained.
- Example 3 In a test tube at room temperature under a nitrogen atmosphere, add 2- (3-chloro-5-trifluoromethyl-pyridin-2-yl) -3-methyl-6-pentafluoroethyl-3H-imidazo [4,5-b] 431 mg of pyridine, 83 mg of tetrabutylammonium chloride, 174 mg of sodium ethanesulfinate, and 2.5 mL of N, N-dimethylacetamide were added. The mixture was stirred at 100 ° C. for 4 hours under a nitrogen atmosphere, then cooled to room temperature, and water and ethyl acetate were added to separate the layers, whereby an organic layer and an aqueous layer were obtained.
- a compound represented by the formula (1) useful as an insecticide can be produced.
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Abstract
Description
[式中、
A10は-NR27-、酸素原子又は硫黄原子を表す。
A20は、窒素原子又は=CR28-を表す。
A30は、窒素原子又は=CR29-を表す。
R21は置換基を有していてもよい炭素数1~6の鎖式炭化水素基又は置換基を有していてもよい炭素数3~6の脂環式炭化水素基を表す。
R22、R23及びR24は、それぞれ独立して、置換基を有していてもよい炭素数1~6の鎖式炭化水素基、置換基を有していてもよいフェニル基、置換基を有していてもよい5もしくは6員複素環基、-OR30、-S(O)mR30、-S(O)2NR30R40、-NR30R40、-NR30CO2R40、-NR30C(O)R40、-CO2R30、-C(O)R30、-C(O)NR30R40、-SF5、シアノ基、ニトロ基、ハロゲン原子又は水素原子を表す。
R25及びR26は、それぞれ独立して、置換基を有していてもよい炭素数1~6の鎖式炭化水素基、置換基を有していてもよいフェニル基、置換基を有していてもよい5もしくは6員複素環基、-OR30、-S(O)mR30、-S(O)2NR30R40、-NR30R40、-NR30CO2R40、-NR30C(O)R40、-CO2R30、-C(O)R30、-C(O)NR30R40、-SF5、シアノ基、ニトロ基、ハロゲン原子又は水素原子を表す。但し、R25及びR26がともに水素原子であることはない。
mは0~2の整数を表す。nは0~2の整数を表す。
R30及びR40は、それぞれ独立して、置換基を有していてもよい炭素数1~6の鎖式炭化水素基、置換基を有していてもよいフェニル基又は水素原子を表す。
R27は、置換基を有していてもよい炭素数1~6の鎖式炭化水素基、-CO2R30、-C(O)R30、置換基を有していてもよい炭素数3~6の脂環式炭化水素基又は水素原子を表す。
R28及びR29は、それぞれ独立して、ハロゲン原子を有していてもよい炭素数1~6の鎖式炭化水素基、-OR30、-S(O)mR30、-NR30R40、-CO2R30、-C(O)R30、シアノ基、ニトロ基、ハロゲン原子又は水素原子を表す。]
で表されるピリジン化合物が殺虫剤として有用であることが記載されている。
WO2013/018928には、2-(3-エチルスルホニル-5-ペンタフルオロエチルピリジン-2-イル)―3-メチル-6-トリフルオロメチル-3H-イミダゾ[4,5-b]ピリジンの製造方法として、2-(3-エチルスルファニル-5-ペンタフルオロエチルピリジン-2-イル)―3-メチル-6-トリフルオロメチル-3H-イミダゾ[4,5-b]ピリジンをm-クロロ過安息香酸で酸化する方法が記載されている。
[1]式(2)
[式中、
L1はハロゲン原子を表す。
R2、R3、R4、R5及びR6は、それぞれ独立して、フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基、置換基を有していてもよいフェニル基、-OR10、-S(O)mR10、-S(O)2NR11R12、-NR10R13、-NR11CO2R13、-NR11C(O)R12、-CO2R10、-C(O)R11、-C(O)NR11R12、-SF5、シアノ基、ニトロ基又は水素原子を表す。
m及びnは、それぞれ独立して、0~2の整数を表す。
但し、R5及びR6が共に水素原子であることはない。
R10及びR13は、それぞれ独立して、フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基又は置換基を有していてもよいフェニル基を表す。
R11及びR12は、それぞれ独立して、フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基、置換基を有していてもよいフェニル基又は水素原子を表す。
A1は-NR7-、酸素原子又は硫黄原子を表す。
A2は、窒素原子又は=CR8-を表す。
R7及びR8は、それぞれ独立して、炭素数1~6の鎖式炭化水素基又は水素原子を表す。
R2、R3、R4、R5、R6、R10、R11、R12及びR13の置換基を有していてもよいフェニル基において、置換基は、フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基、フッ素原子で置換されていてもよい炭素数1~6のアルコキシ基、フッ素原子で置換されていてもよい炭素数1~6のアルキルチオ基、フッ素原子で置換されていてもよい炭素数1~6のアルキルスルフィニル基、フッ素原子で置換されていてもよい炭素数1~6のアルキルスルホニル基、フッ素原子で置換されていてもよい炭素数2~6のアルキルカルボニル基、フッ素原子で置換されていてもよい炭素数2~6のアルコキシカルボニル基、ハロゲン原子、シアノ基及びニトロ基からなる群より選ばれる一種以上である。]
で表される化合物と式(3)
(式中、
R1はフッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基又はフッ素原子で置換されていてもよい炭素数3~6の脂環式炭化水素基を表す。
M+は、ナトリウムイオン、カリウムイオン又はリチウムイオンを表す。)
で表される化合物とを反応させる式(1)
(式中、R1、R2、R3、R4、R5、R6、A1、A2及びA3は上記と同じ意味を表す。)
で表されるピリジン化合物の製造方法。
[3]A1が酸素原子であり、A2が=CH-である[2]に記載の方法。
[4]A1が-NR7-であり、R7がメチル基であり、A2が窒素原子である[2]に記載の方法。
[5]R1が炭素数1~6の鎖式炭化水素基である[3]に記載の方法。
[6]R1が炭素数1~6の鎖式炭化水素基である[4]に記載の方法。
[7]L1がフッ素原子又は塩素原子である[1]~[6]のいずれかに記載の方法。
L1で表されるハロゲン原子は、フッ素原子、塩素原子、臭素原子又はヨウ素原子である。L1の好ましいハロゲン原子はフッ素原子又は塩素原子である。
R1、R2、R3、R4、R5、R6、R10、R11、R12及びR13で表されるフッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基としては、フッ素原子で置換されていてもよい炭素数1~6のアルキル基、フッ素原子で置換されていてもよい炭素数2~6のアルケニル基及びフッ素原子で置換されていてもよい炭素数2~6のアルキニル基が挙げられる。
フッ素原子で置換されていてもよい炭素数2~6のアルケニル基としては、例えばビニル基、1-プロペニル基、2-プロペニル基、1-メチルビニル基、2-メチル-1-プロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、1-ペンテニル基、1-ヘキセニル基、1,1-ジフルオロアリル基及びペンタフルオロアリル基が挙げられる。
フッ素原子で置換されていてもよい炭素数2~6のアルキニル基としては、例えばエチニル基、プロパルギル基、2-ブチニル基、3-ブチニル基、1-ペンチニル基、1-ヘキシニル基及び4,4,4-トリフルオロ-2-ブチニル基が挙げられる。
群Z:フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基、フッ素原子で置換されていてもよい炭素数1~6のアルコキシ基、フッ素原子で置換されていてもよい炭素数1~6のアルキルチオ基、フッ素原子で置換されていてもよい炭素数1~6のアルキルスルフィニル基、フッ素原子で置換されていてもよい炭素数1~6のアルキルスルホニル基、フッ素原子で置換されていてもよい炭素数2~6のアルキルカルボニル基、フッ素原子で置換されていてもよい炭素数2~6のアルコキシカルボニル基、ハロゲン原子(フッ素原子、塩素原子、臭素原子及びヨウ素原子)、シアノ基及びニトロ基。
群Zにおいて、フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基の例は、R2、R3、R4、R5及びR6で表されるフッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基の例と同じである。
フッ素原子で置換されていてもよい炭素数1~6のアルコキシ基としては、例えばメトキシ基、トリフルオロメトキシ基、エトキシ基、2,2,2-トリフルオロエトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基、ペンチルオキシ基及びヘキシルオキシ基が挙げられる。
フッ素原子で置換されていてもよい炭素数1~6のアルキルチオ基としては、例えばメチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ブチルチオ基、sec-ブチルチオ基、tert-ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、トリフルオロメチルチオ基、2,2,2-トリフルオロエチルチオ基及びペンタフルオロエチルチオ基が挙げられる。
フッ素原子で置換されていてもよい炭素数1~6のアルキルスルフィニル基としては、例えばメチルスルフィニル基、エチルスルフィニル基、プロピルスルフィニル基、イソプロピルスルフィニル基、ブチルスルフィニル基、ペンチルスルフィニル基、ヘキシルスルフィニル基、トリフルオロメチルスルフィニル基、2,2,2-トリフルオロエチルスルフィニル基及びペンタフルオロエチルスルフィニル基が挙げられる。
フッ素原子で置換されていてもよい炭素数1~6のアルキルスルホニル基としては、例えばメチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、イソプロピルスルホニル基、ブチルスルホニル基、ペンチルスルホニル基、ヘキシルスルホニル基、トリフルオロメチルスルホニル基、2,2,2-トリフルオロエチルスルホニル基及びペンタフルオロエチルスルホニル基が挙げられる。
フッ素原子で置換されていてもよい炭素数2~6のアルキルカルボニル基としては、例えばアセチル基、プロピオニル基、ブチリル基、ペンタノイル基、ヘキサノイル基及びトリフルオロアセチル基が挙げられる。
フッ素原子で置換されていてもよい炭素数2~6のアルコキシカルボニル基としては、例えばメトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、ペンチルオキシカルボニル基、tert-ブトキシカルボニル基及び2,2,2-トリフルオロエトキシカルボニル基が挙げられる。
R7及びR8で表される炭素数1~6の鎖式炭化水素基としては、炭素数1~6のアルキル基、炭素数2~6のアルケニル基及び炭素数2~6のアルキニル基が挙げられる。
炭素数2~6のアルケニル基としては、例えばビニル基、1-プロペニル基、2-プロペニル基、1-メチルビニル基、2-メチル-1-プロペニル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、1-ペンテニル基及び1-ヘキセニル基が挙げられる。
炭素数2~6のアルキニル基としては、例えばエチニル基、プロパルギル基、2-ブチニル基、3-ブチニル基、1-ペンチニル基及び1-ヘキシニル基が挙げられる。
R1で表されるフッ素原子で置換されていてもよい炭素数3~6の脂環式炭化水素基としては、例えばシクロプロピル基、1-メチルシクロプロピル基、2-メチルシクロプロピル基、1-フルオロシクロプロピル基、2,2-ジフルオロシクロプロピル基、2,2-ジクロロシクロプロピル基、2,2-ジブロモシクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基が挙げられる。
R2、R3、R4、R5及びR6で表される-OR10としては、例えばメトキシ基、トリフルオロメトキシ基、エトキシ基、2,2,2-トリフルオロメトキシ基、プロポキシ基、ブトキシ基、イソブトキシ基、sec-ブトキシ基、tert-ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基等の炭素数1~6のアルコキシ基;ビニルオキシ基、1-プロペニルオキシ基、2-プロペニルオキシ基、1-メチルビニルオキシ基、2-メチル-1-プロペニルオキシ基、1-ブテニルオキシ基、2-ブテニルオキシ基、3-ブテニルオキシ基、1-ペンテニルオキシ基及び1-ヘキセニルオキシ基等の炭素数2~6のアルケニルオキシ基;エチニルオキシ基、プロパルギルオキシ基、2-ブチニルオキシ基、3-ブチニルオキシ基、1-ペンチニルオキシ基及び1-ヘキシニルオキシ基等の炭素数2~6のアルキニルオキシ基が挙げられる。
-S(O)mR10としては、例えばメチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ブチルチオ基、sec-ブチルチオ基、tert-ブチルチオ基、ペンチルチオ基、ネオペンチルチオ基、ヘキシルチオ基、トリフルオロメチルチオ基、2,2,2-トリフルオロエチルチオ基及びペンタフルオロエチルチオ基等の炭素数1~6のアルキルチオ基;メチルスルフィニル基、エチルスルフィニル基、プロピルスルフィニル基、イソプロピルスルフィニル基、ブチルスルフィニル基、sec-ブチルスルフィニル基、tert-ブチルスルフィニル基、ペンチルスルフィニル基、ネオペンチルスルフィニル基、ヘキシルスルフィニル基、トリフルオロメチルスルフィニル基、2,2,2-トリフルオロエチルスルフィニル基及びペンタフルオロエチルスルフィニル基等の炭素数1~6のアルキルスルフィニル基;メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、イソプロピルスルホニル基、ブチルスルホニル基、sec-ブチルスルホニル基、tert-ブチルスルホニル基、ペンチルスルホニル基、ネオペンチルスルホニル基、ヘキシルスルホニル基、トリフルオロメチルスルホニル基、2,2,2-トリフルオロエチルスルホニル基及びペンタフルオロエチルスルホニル基等の炭素数1~6のアルキルスルホニル基が挙げられる。
-S(O)2NR11R12としては、例えばアミノスルホニル基;メチルアミノスルホニル基、エチルアミノスルホニル基、プロピルアミノスルホニル基、ブチルアミノスルホニル基、ペンチルアミノスルホニル基及びヘキシルアミノスルホニル基等の炭素数1~6のアルキルアミノスルホニル基;ジメチルアミノスルホニル基、ジエチルアミノスルホニル基、ジプロピルアミノスルホニル基、ジブチルアミノスルホニル基、ジペンチルアミノスルホニル基、ジヘキシルアミノスルホニル基及びメチルエチルアミノスルホニル基等の炭素数2~12のジアルキルアミノスルホニル基が挙げられる。
-NR11CO2R13としては、例えばメトキシカルボニルアミノ基、エトキシカルボニルアミノ基が挙げられる。
-NR11C(O)R12としては、例えばメチルカルボニルアミノ基が挙げられる。
-CO2R10としては、例えばメトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、ブトキシカルボニル基及びペンチルオキシカルボニル基等の炭素数2~7のアルコキシカルボニル基;ビニルオキシカルボニル基、1-プロペニルオキシカルボニル基、2-プロペニルオキシカルボニル基、1-メチルビニルオキシカルボニル基、2-メチル-1-プロペニルオキシカルボニル基、1-ブテニルオキシカルボニル基、2-ブテニルオキシカルボニル基、3-ブテニルオキシカルボニル基、1-ペンテニルオキシカルボニル基及び1-ヘキセニルオキシカルボニル基等の炭素数3~7のアルケニルオキシカルボニル基;エチニルオキシカルボニル基、プロパルギルオキシカルボニル基、2-ブチニルオキシカルボニル基、3-ブチニルオキシカルボニル基、1-ペンチニルオキシカルボニル基及び1-ヘキシニルオキシカルボニル基等の炭素数3~7のアルキニルオキシカルボニル基が挙げられる。
-C(O)R11としては、例えばメチルカルボニル基、エチルカルボニル基、プロピルカルボニル基、ブチルカルボニル基及びペンチルカルボニル基等の炭素数2~7のアルキルカルボニル基;ビニルカルボニル基、1-プロペニルカルボニル基、2-プロペニルカルボニル基、1-メチルビニルカルボニル基、2-メチル-1-プロペニルカルボニル基、1-ブテニルカルボニル基、2-ブテニルカルボニル基、3-ブテニルカルボニル基、1-ペンテニルカルボニル基及び1-ヘキセニルカルボニル基等の炭素数3~7のアルケニルカルボニル基;エチニルカルボニル基、プロパルギルカルボニル基、2-ブチニルカルボニル基、3-ブチニルカルボニル基、1-ペンチニルカルボニル基及び1-ヘキシニルカルボニル基等の炭素数3~7のアルキニルカルボニル基が挙げられる。
-C(O)NR11R12としては、例えばアミノカルボニル基、メチルアミノカルボニル基、ジメチルアミノカルボニル基及びメチルエチルアミノカルボニル基等の炭素数1~6のアミノカルボニル基が挙げられる。
R2、R3及びR4は、それぞれ独立して、水素原子又はフッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基であることが好ましく、水素原子、ハロゲン原子を有していてもよい炭素数1~6のアルキル基であることがより好ましく、トリフルオロメチル基、テトラフルオロエチル基又は水素原子であることがさらに好ましく、水素原子であることが特に好ましい。
A2は、=CR8-であることが好ましく、R8が水素原子又は炭素数1~6のアルキル基である=CR8-であることがより好ましく、=CH-であることがさらに好ましい。
式(2)で表される化合物(以下、化合物(2)という。)としては、表1に記載の式(2-1)~(2-39)で表される化合物が挙げられる。
M+は、ナトリウムイオンが好ましい。
式(3)で表される化合物(以下、化合物(3)という。)としては、例えばメタンスルフィン酸ナトリウム、エタンスルフィン酸ナトリウム、プロパンスルフィン酸ナトリウム、tert-ブタンスルフィン酸ナトリウム、ペンタンスルフィン酸ナトリウム等のスルフィン酸ナトリウム塩:メタンスルフィン酸リチウム、エタンスルフィン酸リチウム、プロパンスルフィン酸リチウム、ブタンスルフィン酸リチウム、ペンタンスルフィン酸リチウム等のスルフィン酸リチウム塩が挙げられる。
化合物(3)は、スルフィン酸ナトリウム塩が好ましく、メタンスルフィン酸ナトリウム及びエタンスルフィン酸ナトリウムがより好ましい。
化合物(3)は、市販のものを使用してもよいし、式(4)
(式中、R1は上記と同じ意味を有し、Xはハロゲン原子を表す。)
で表される化合物(以下、化合物(4)という。)と塩基と還元剤とを反応させることにより製造してもよい。
Xで表されるハロゲン原子は、フッ素原子、塩素原子、臭素原子又はヨウ素原子であり、好ましくは塩素原子である。
塩基としては、例えば炭酸水素ナトリウム、炭酸水素リチウム、炭酸水素カリウム等のアルカリ金属炭酸水素塩;炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩;リン酸水素二カリウム等のアルカリ金属リン酸塩が挙げられる。
還元剤としては、例えば亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸リチウム等のアルカリ金属亜硫酸塩が挙げられる。
塩基の使用量は、化合物(4)1モルに対して、通常2~4モルであり、好ましくは2~3モルである。
還元剤の使用量は、化合物(4)1モルに対して、通常1~3モルであり、好ましくは1~2モルである。
化合物(3)の使用量は、化合物(2)1モルに対して、通常1~10モルであり、好ましくは1~2モルである。
化合物(2)と化合物(3)との反応は、溶媒の存在中で実施することが好ましい。
溶媒としては、例えば水;ベンゼン、クロロベンゼン、トルエン等の芳香族炭化水素溶媒;クロロホルム、ジクロロメタン等の含ハロゲン炭化水素溶媒;メタノール、エタノール、ノルマルブタノール等のアルコール溶媒;1,2-ジメトキシエタン、ジエチレングリコールジメチルエーテル、ポリエチレングリコール、テトラヒドロフラン、ジオキサン等のエーテル溶媒;アセトニトリル、プロピルニトリル等のニトリル溶媒;ジメチルスルホキシド等のスルホキシド溶媒;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド溶媒;及びこれらの混合溶媒が挙げられ、スルホキシド溶媒もしくはアミド溶媒が好ましい。
溶媒の使用量は、化合物(2)1質量部に対して、通常1~100質量部である。
相間移動触媒としては、例えばテトラブチルアンモニウムクロリド、テトラブチルアンモニウムブロミド、テトラブチルアンモニウムヨージド、ベンジルトリブチルアンモニウムブロミド等の4級アンモニウム塩;及びヘプチルトリフェニルホスホニウムブロミド、テトラフェニルホスホニウムブロミド等の4級ホスホニウム塩が挙げられ、4級アンモニウム塩が好ましく、テトラブチルアンモニウムクロリドがより好ましい。
相間移動触媒の使用量は、化合物(2)1モルに対して、通常0.01~10モルであり、好ましくは0.1~0.5モルである。
化合物(2)と化合物(3)との反応時間は、通常0.1~100時間であり、好ましくは3~24時間である。
得られた反応混合物を、例えば濃縮することにより、式(1)で表される化合物(以下、化合物(1)という。)を取り出すことができる。取り出された化合物(1)は、必要に応じて、洗浄等の通常の精製手段を用いて精製することができる。
化合物(1)としては、表2に記載の式(1-1)~(1-23)で表される化合物が挙げられる。
(式中、A1、A2、R2、R3、R4、R5、R6及びL1は上記と同じ意味を有する。)
で表される化合物(以下、化合物(7)という場合がある。)の分子内縮合反応により得ることができる。
化合物(7)としては、表3に記載の式(7-1)~(7-10)で表される化合物が挙げられる。
酸としては、パラトルエンスルホン酸等のスルホン酸;酢酸等のカルボン酸;ポリリン酸等が挙げられる。
酸の使用量は、化合物(7)1モルに対して、通常0.1~5モルである。
分子内縮合反応温度は、通常0~200℃であり、分子内縮合反応時間は、通常0.1~24時間である。
分子内縮合反応は、通常、溶媒中で行われる。溶媒としては、テトラヒドロフラン、エチレングリコールジメチルエーテル、tert-ブチルメチルエーテル、1,4-ジオキサン等のエーテル溶媒;ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素溶媒:トルエン、キシレン等の芳香族炭化水素溶媒;クロロベンゼン等のハロゲン化炭化水素溶媒;酢酸エチル、酢酸ブチル等のエステル溶媒;アセトニトリル等のニトリル溶媒;N,N-ジメチルホルムアミド、N,N-ジメチルホルムアミド等の非プロトン性極性溶媒及びこれらの混合溶媒が挙げられる。溶媒は、好ましくは芳香族炭化水素溶媒であり、より好ましくはキシレンである。
溶媒の使用量は、化合物(7)1質量部に対して、通常1~100質量部である。
(式中、A1、A2、A3、R5及びR6は上記と同じ意味を有する。)
で表される化合物(以下、化合物(5)という。)と、式(6)
(式中、R2、R3、R4及びL1は、上記と同じ意味を有する。)
で表される化合物(以下、化合物(6)という。)とを反応させることにより得ることができる。
化合物(5)としては、表4に記載の式(5-1)~(5-8)で表される化合物が挙げられる。
化合物(6)の使用量は、化合物(5)1モルに対して、通常1~3モルである。
反応温度は、通常-20~100℃であり、反応時間は通常0.1~24時間である。
化合物(5)と化合物(6)との反応は、通常、溶媒中で実施される。溶媒としては、化合物(7)の分子内縮合反応で用いられる溶媒と同じものが挙げられ、エーテル溶媒が好ましく、テトラヒドロフランがより好ましい。
溶媒の使用量は、化合物(5)1質量部に対して、通常1~100質量部である。
化合物(5)と化合物(6)との反応は、塩基の存在下で実施されてもよい。塩基としては、例えば炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩;トリエチルアミン、ジイソプロピルエチルアミン等の第3級アミン及びピリジン、4-ジメチルアミノピリジン等の含窒素芳香族化合物が挙げられる。
塩基の使用量は、化合物(5)1モルに対して、通常1~10モルである。
得られた反応混合物を、例えば濃縮することにより、化合物(7)を取り出すことができる。取り出された化合物(7)は、クロマトグラフィー、再結晶等により精製することができる。
室温、窒素雰囲気下、四つ口フラスコに、亜硫酸ナトリウム53.9g、炭酸水素ナトリウム65.34g及び水325mlを加えた。80℃で1.3時間撹拌した混合物に塩化エタンスルホニル50.0gを加え、さらに4.2時間撹拌した。反応混合物を濃縮して得られた残渣にエタノールを加え、さらに濃縮した。得られた残渣にトルエンを加え、濃縮して得た固体を乾燥した後、エタノール100mlを加えて加熱還流した。得られた混合物をろ過、エタノール洗浄を行った。ろ液と洗浄液とを合わせ、濃縮することでエタンスルフィン酸ナトリウム38.96gを得た。
室温、窒素雰囲気下、4つ口フラスコに、2-アミノ-4-[(トリフルオロメチル)スルフィニル]フェノール2.79g、脱水テトラヒドロフラン38.0mlを加えた。混合物を氷冷し、そこに3-クロロピリジン-2-カルボニルクロリド1.62gを含むテトラヒドロフラン溶液10.0mlを滴下し、室温で80分撹拌した。得られた反応混合物に、水、飽和重曹水及び飽和塩化アンモニウム水を加えて、pH8にした。得られた混合物を酢酸エチルで抽出した。有機層を飽和重曹水、水、飽和食塩水で順次洗浄した。得られた有機層を乾燥した後、濃縮して得た固体を乾燥し、3-クロロ-N-{2-ヒドロキシ-5-[(トリフルオロメチル)スルフィニル]フェニル}ピリジン-2-カルボキシアミドを含む混合物を3.66g得た。シリカゲルカラム(酢酸エチル:ヘキサン=1:1)で精製して得た固体0.40gを酢酸エチルに溶解し、塩酸で洗浄した。得られた酢酸エチル溶液を濃縮、乾燥して、3-クロロ-N-{2-ヒドロキシ-5-[(トリフルオロメチル)スルフィニル]フェニル}ピリジン-2-カルボキシアミド0.34mgを得た。
室温、窒素雰囲気下、二口フラスコに、製造例2で得た3-クロロ-N-{2-ヒドロキシ-5-[(トリフルオロメチル)スルフィニル]フェニル}ピリジン-2-カルボキシアミド0.28g、キシレン4.0ml及びp-トルエンスルホン酸一水和物0.30gを加えた。混合物を140℃で3時間撹拌した後、室温まで冷却し、飽和重曹水及び酢酸エチルを加えて抽出した。有機層を飽和重曹水、水及び飽和食塩水で洗浄した後、濃縮して、2-(3-クロロピリジン-2-イル)-5-(トリフルオロメチルスルホキシド)ベンズオキサゾールを含む混合物0.24gを得た。シリカゲルカラム(酢酸エチル:ヘキサン=56:44溶液)で精製して、2-(3-クロロピリジン-2-イル)-5-(トリフルオロメチルスルフィニル)ベンズオキサゾール0.091gを得た。
室温、窒素雰囲気下、試験管に、製造例3で得られた2-(3-クロロピリジン-2-イル)-5-(トリフルオロメチルスルフィニル)ベンズオキサゾール90.3mg、製造例1で得られたエタンスルフィン酸ナトリウム45.6mg、テトラブチルアンモニウムクロリド22.7mg、N,N-ジメチルアセトアミド4.0mlを加えた。混合物を窒素雰囲気下、105℃で、約23時間撹拌した後、室温まで冷却し、水及び酢酸エチルを加えて分液し、有機層と水層とを得た。水層を酢酸エチルで抽出して得た酢酸エチル層を先の有機層と合わせ、飽和食塩水で洗浄、乾燥した後、減圧下に濃縮して、2-(3-エチルスルホニルピリジン-2-イル)-5-(トリフルオロメチルスルフィニル)ベンズオキサゾール90mgを得た。
室温、窒素雰囲気下、試験管に製造例3で得られた2-(3-クロロピリジン-2-イル)-5-(トリフルオロメチルチオ)ベンズオキサゾール50.2mg、エタンスルフィン酸ナトリウム26.2mg、テトラブチルアンモニウムクロリド12.6mg、N,N-ジメチルアセトアミド2.2mlを加えた。混合物を窒素雰囲気下、105℃で、13時間撹拌した後、ここに製造例1で得られたエタンスルフィン酸ナトリウム13.2mgを加え、さらに、105℃で4時間撹拌して、2-(3-エチルスルホニルピリジン-2-イル)-5-(トリフルオロメチルチオ)ベンズオキサゾールを含む混合物を得た。
室温、窒素雰囲気下、試験管に、2-(3-クロロ-5-トリフルオロメチル-ピリジン-2-イル)-3-メチル-6-ペンタフルオロエチル-3H-イミダゾ[4,5-b]ピリジン431mg、テトラブチルアンモニウムクロリド83mg、エタンスルフィン酸ナトリウム174mg、N,N-ジメチルアセトアミド2.5mLを加えた。混合物を窒素雰囲気下、100℃で4時間撹拌した後、室温まで冷却し、水、酢酸エチルを加えて分液し、有機層と水層とを得た。水層を酢酸エチルで抽出して得た酢酸エチル層を先の有機層と合わせ、飽和食塩水で洗浄、乾燥した後、減圧下に濃縮して得た残渣をシリカゲルクロマトグラフィーに付し、2-(3-エタンスルホニル-5-トリフルオロメチル-ピリジン-2-イル)-3-メチル-6-ペンタフルオロエチル-3H-イミダゾ[4,5-b]ピリジン453mgを得た。
Claims (7)
- 式(2)
[式中、
L1はハロゲン原子を表す。
R2、R3、R4、R5及びR6は、それぞれ独立して、フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基、置換基を有していてもよいフェニル基、-OR10、-S(O)mR10、-S(O)2NR11R12、-NR10R13、-NR11CO2R13、-NR11C(O)R12、-CO2R10、-C(O)R11、-C(O)NR11R12、-SF5、シアノ基、ニトロ基又は水素原子を表す。
m及びnは、それぞれ独立して、0~2の整数を表す。
但し、R5及びR6が共に水素原子であることはない。
R10及びR13は、それぞれ独立して、炭素数1~6の鎖式炭化水素基又は置換基を有していてもよいフェニル基を表す。
R11及びR12は、それぞれ独立して、炭素数1~6の鎖式炭化水素基、置換基を有していてもよいフェニル基又は水素原子を表す。
A1は-NR7-、酸素原子又は硫黄原子を表す。
A2は、窒素原子又は=CR8-を表す。
R7及びR8は、それぞれ独立して、炭素数1~6の鎖式炭化水素基又は水素原子を表す。
R2、R3、R4、R5、R6、R10、R11、R12及びR13の置換基を有していてもよいフェニル基において、置換基は、フッ素原子で置換されていてもよい炭素数1~6の鎖式炭化水素基、フッ素原子で置換されていてもよい炭素数1~6のアルコキシ基、フッ素原子で置換されていてもよい炭素数1~6のアルキルチオ基、フッ素原子で置換されていてもよい炭素数1~6のアルキルスルフィニル基、フッ素原子で置換されていてもよい炭素数1~6のアルキルスルホニル基、フッ素原子で置換されていてもよい炭素数2~6のアルキルカルボニル基、フッ素原子で置換されていてもよい炭素数2~6のアルコキシカルボニル基、ハロゲン原子、シアノ基及びニトロ基からなる群より選ばれる一種以上である。]
で表される化合物と式(3)
(式中、
R1は置換基を有していてもよい炭素数1~6の鎖式炭化水素基又は置換基を有していてもよい炭素数3~6の脂環式炭化水素基を表す。
M+は、ナトリウムイオン、カリウムイオン又はリチウムイオンを表す。)
で表される化合物とを反応させる式(1)
(式中、R1、R2、R3、R4、R5、R6、A1、A2及びA3は上記と同じ意味を表す。)
で表されるピリジン化合物の製造方法。 - R2及びR4が水素原子であり、R3が水素原子又はトリフルオロメチル基であり、R5がトリフルオロメチル基、テトラフルオロエチル基、トリフルオロメチルチオ基、トリフルオロメチルスルフィニル基又はトリフルオロメチルスルホニル基であり、R6が水素原子であり、A2が窒素原子又は=CH-である請求項1に記載の方法。
- A1が酸素原子であり、A2が=CH-である請求項2に記載の方法。
- A1が-NR7-であり、R7がメチル基であり、A2が窒素原子である請求項2に記載の方法。
- R1が炭素数1~6の鎖式炭化水素基である請求項3に記載の方法。
- R1が炭素数1~6の鎖式炭化水素基である請求項4に記載の方法。
- L1がフッ素原子又は塩素原子である請求項1~6のいずれかに記載の方法。
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Also Published As
Publication number | Publication date |
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KR102343802B1 (ko) | 2021-12-28 |
EP3159339A1 (en) | 2017-04-26 |
US9708341B2 (en) | 2017-07-18 |
CN106536516A (zh) | 2017-03-22 |
EP3159339B1 (en) | 2020-11-25 |
JPWO2015190316A1 (ja) | 2017-04-20 |
EP3159339A4 (en) | 2017-12-06 |
KR20170013895A (ko) | 2017-02-07 |
US20170152270A1 (en) | 2017-06-01 |
CN106536516B (zh) | 2019-09-03 |
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