TWI657088B - 製造稠合雜環化合物之方法 - Google Patents
製造稠合雜環化合物之方法 Download PDFInfo
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- TWI657088B TWI657088B TW104118726A TW104118726A TWI657088B TW I657088 B TWI657088 B TW I657088B TW 104118726 A TW104118726 A TW 104118726A TW 104118726 A TW104118726 A TW 104118726A TW I657088 B TWI657088 B TW I657088B
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- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 150000002391 heterocyclic compounds Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 84
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 52
- -1 sulfonic acid compound Chemical class 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 33
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 230000026030 halogenation Effects 0.000 claims description 6
- 238000005658 halogenation reaction Methods 0.000 claims description 6
- 229910052744 lithium Chemical group 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 29
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 239000012044 organic layer Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 13
- 239000008096 xylene Substances 0.000 description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 238000010561 standard procedure Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ASDYMBLSNIBFMI-UHFFFAOYSA-N 2-amino-4-(trifluoromethylsulfonyl)phenol Chemical compound NC1=CC(S(=O)(=O)C(F)(F)F)=CC=C1O ASDYMBLSNIBFMI-UHFFFAOYSA-N 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- OZFYEDXYDBRDRC-UHFFFAOYSA-N 3-ethylsulfonylpyridine-2-carboxylic acid Chemical compound CCS(=O)(=O)C1=CC=CN=C1C(O)=O OZFYEDXYDBRDRC-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- HBNBMOGARBJBHS-UHFFFAOYSA-N dimethylarsane Chemical compound C[AsH]C HBNBMOGARBJBHS-UHFFFAOYSA-N 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229940071870 hydroiodic acid Drugs 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000006039 1-hexenyl 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
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 150000008282 halocarbons Chemical group 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
- 230000000749 insecticidal effect Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000004169 (C1-C6) alkyl 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
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 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
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- AIOUQYUFHADEHR-UHFFFAOYSA-N 3-methylpyridine-2-carboxamide Chemical compound CC1=CC=CN=C1C(N)=O AIOUQYUFHADEHR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000005997 bromomethyl group Chemical group 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
- 239000006227 byproduct Substances 0.000 description 1
- CCYWVXXWKRBHBI-UHFFFAOYSA-N carbonyl dichloride;pyridine Chemical compound ClC(Cl)=O.C1=CC=NC=C1 CCYWVXXWKRBHBI-UHFFFAOYSA-N 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 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
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- LEDOZLHKGFARFY-UHFFFAOYSA-N n-chloro-1-phenylpropan-2-amine Chemical compound ClNC(C)CC1=CC=CC=C1 LEDOZLHKGFARFY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TZGCJHAOBCFPNS-UHFFFAOYSA-M potassium;pyridine-4-carboxylate Chemical compound [K+].[O-]C(=O)C1=CC=NC=C1 TZGCJHAOBCFPNS-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 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
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/27—Sprue channels ; Runner channels or runner nozzles
- B29C45/28—Closure devices therefor
- B29C45/2806—Closure devices therefor consisting of needle valve systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/27—Sprue channels ; Runner channels or runner nozzles
- B29C45/28—Closure devices therefor
- B29C45/2806—Closure devices therefor consisting of needle valve systems
- B29C45/281—Drive means therefor
-
- 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
- C07D213/62—Oxygen or sulfur atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
Abstract
一種式(4)所示之化合物係藉由下述步驟A至C予以製造,步驟A:使式(2)所示之化合物
[式中,R1表示乙基等,R表示鹵素原子等,n表示0、1、2或3及M表示鉀等],與亞硫醯氯反應以獲得式(1)所示之化合物
;步驟B:使式(1)所示之化合物與式(5)所示之化合物
[式中,A1表示氮原子或=CH-,R5表示三氟甲基等,以及m表示1或2]反應以製得式(3)所示之化合物或其酸鹽
;以及步驟C:使式(3)所示之化合物或其酸鹽在酸存在下於100℃至180℃反應以獲得式(4)所示之化合物
Description
本發明係有關一種製造稠合雜環化合物之方法。
WO2013/018928述及包含2-(3-乙基硫烷基吡啶-2-基)-5-三氟甲基苯并唑之稠合雜環化合物具有優異之殺蟲防治效果,且製造方法2述及一種合成方法,其中,使胺基酚化合物與吡啶羰醯氯化合物反應,藉此合成醯胺化合物,然後對醯胺化合物施加環閉合反應。
藥物化學期刊,29,860-862(1986)亦述及使異煙鹼酸鉀與草醯氯反應以製造異煙醯氯。
本發明係提供一種製造式(4)所示之化合物之方法,
式中,R1表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或
視需要經鹵化之具有3至6個碳原子之脂環族烴基,R各自獨立表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或鹵素原子,R5表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,A1表示氮原子或=CH-,m表示1或2,以及n表示0、1、2或3。
原則上本發明如下所述。
[1]一種製造式(4)所示之化合物之方法,包括下列步驟A至C:步驟A:使式(2)所示之化合物
[式中,R1表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,R各自獨立表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或鹵素原子,n表示0、1、2或3,以及M表示鈉、鉀或鋰],與亞硫醯氯反應以獲得式(1)所示之化合物
[式中R1、R及n具有與上述相同之定義](以下稱為步驟A);步驟B:使式(1)所示之化合物與式(5)所示之化合物
[式中,A1表示氮原子或=CH-,R5表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,以及m表示1或2]反應,以製得式(3)所示之化合物
[式中R1、R、R5、A1、m及n具有與上述相同之定義](以下稱為步驟B);以及步驟C:使式(3)所示之化合物或其酸鹽在酸存在下於100℃至180℃反應以獲得式(4)所示之化合物
[式中R1、R、R5、A1、m及n具有與上述相同之定義](以下稱為步驟C)。
[2]依據[1]之製造方法,其中,步驟C中之酸為磺酸化合物。
[3]依據[1]之製造方法,其中,步驟C中之酸為對甲苯磺酸。
[4]依據[1]之製造方法,其中,步驟C中之酸為甲烷磺酸。
[5]一種製造式(3)所示之化合物或其酸鹽之方法,包括下
列步驟A以及步驟B:步驟A:使式(2)所示之化合物
[式中,R1表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,R各自獨立表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或鹵素原子,n表示0、1、2或3及M表示鈉、鉀或鋰],與亞硫醯氯反應以獲得式(1)所示之化合物
[式中R1、R及n具有與上述相同之定義];以及步驟B:使式(1)所示之化合物與式(5)所示之化合物
[式中,A1表示氮原子或=CH-,R5表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基及m表示1或2]反應,以製得式(3)所示之化合物
[式中R1、R、R5、A1、m及n具有與上述相同之定義]。
[6]依據[1]至[5]任一者之製造方法,其中,步驟B中所使用之溶劑含有醚溶劑。
[7]一種製造式(1)所示之化合物之方法,包括步驟A:使式(2)所示之化合物
[式中,R1表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,R各自獨立表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或鹵素原子,n表示0、1、2或3及M表示鈉、鉀或鋰],與亞硫醯氯反應以獲得式(1)所示之化合物
[式中R1、R、及n具有與上述相同之定義]。
式(1)所示之化合物、式(3)所示之化合物及式(4)所示之化合物可藉由,例如,下述製造方法來製造。
本發明中,鹵素原子表示氟原子、氯原子、溴原子及碘原子。
本發明中,具有1至6個碳原子之鏈烴基表
示具有1至6個碳原子之烷基,如甲基、乙基、丙基、異丙基、及己基;具有1至6個碳原子之烯基,如乙烯基、1-丙烯基、2-丙烯基及1-己烯基;以及具有1至6個碳原子之炔基,如乙炔基、炔丙基(propargyl group)、1-戊炔基及1-己炔基。
本發明中,視需要經鹵化之具有1至6個碳原子之鏈烴基包含視需要而具有鹵素原子之C1-C6烷基,如甲基、乙基、異丙基、丁基、第三丁基、己基、氟甲基、氯甲基、溴甲基、碘甲基、二氟甲基、二氯甲基、三氟甲基、三氯甲基、2-氟乙基、2-氯乙基、2,2-二氟乙基、2,2,2-三氟乙基、五氟乙基及七氟丙基;視需要而具有鹵素原子之C2-C6烯基,如乙烯基、2-丙烯基、1-甲基乙烯基、2-甲基-1-丙烯基、3-丁烯基、1-己烯基、1,1-二氟烯丙基及五氟烯丙基;以及視需要而具有鹵素原子之C2-C6炔基,如乙炔基、炔丙基、3-丁炔基、1-己炔基及4,4,4-三氟-2-丁炔基。
本發明中,具有3至6個碳原子之脂環族烴基表示具有3至6個碳原子之環烷基,如環丙基、環丁基及環己基;以及具有3至6個碳原子之環烯基,如1-環己烯基及3-環己烯基。
本發明中,磺酸化合物的實例包含對甲苯磺酸、苯磺酸、甲烷磺酸及樟腦磺酸。
本發明中,醯胺溶劑的實例包含N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮。
本發明中,醚溶劑的實例包含四氫呋喃、乙二醇二甲醚、第三丁基甲基醚及1,4-二烷。
(步驟A)
式(1)所示之化合物(以下稱為化合物(1))可藉由使式(2)所示之化合物(以下稱為化合物(2))與亞硫醯氯反應製造之。
反應通常係在溶劑中進行。使用於反應之溶劑的實例包含芳香族烴溶劑如甲苯、二甲苯、乙苯及氯苯;含鹵素之脂肪族烴溶劑如氯仿及二氯甲烷;醚溶劑如四氫呋喃、乙二醇二甲醚、第三丁基甲基醚及1,4-二烷;酯溶劑如乙酸乙酯及乙酸丁酯;腈溶劑如乙腈及丙腈;芳香族雜環溶劑如吡啶;含硫之化合物溶劑如二甲亞碸及環丁碸;醯胺溶劑如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮;及上述溶劑之混合溶劑。溶劑較佳為芳香族烴溶劑,含鹵素之脂肪族烴溶劑、酯溶劑、醯胺溶劑及上述溶劑之混合物,更佳為芳香族烴溶劑、醯胺溶劑及上述溶劑之混合物,最佳為N,N-二甲基甲醯胺。
以1質量份化合物(2)計,所使用之溶劑用量通常為0至100質量份,較佳為1至20質量份。
反應中,以1莫耳化合物(2)計,亞硫醯氯通常以1至15莫耳,較佳為以1至5莫耳之比例使用之。
反應之反應溫度通常為0至150℃之範圍,較佳為0至80℃。
反應之反應時間通常為0.1至24小時之範
圍,較佳為0.1至12小時。
反應完成後,可在藉由蒸餾移除過多的亞硫醯氯後,將所得之化合物以其原狀態使用於步驟B,或者可藉由蒸餾予以純化之。化合物(1)可藉由利用過濾移除副產出的氯化鋰、氯化鈉或氯化鉀,再濃縮濾液而單離之。
化合物(2)可藉由使下式之2-吡啶羧酸
與無機鹼如鹼金屬氫氧化物(氫氧化鈉、氫氧化鉀及氫氧化鋰)、鹼金屬碳酸鹽(碳酸鈉、碳酸鉀及碳酸鋰)及鹼金屬碳酸氫鹽(碳酸氫鈉、碳酸氫鉀及碳酸氫鋰)在溶劑如醇溶劑(甲醇、乙醇、2-丙醇等)中反應製造之。
(步驟B)
式(3)所示之化合物(以下稱為化合物(3))可藉由使化合物(1)與式(5)所示之化合物(以下稱為化合物(5))反應製造之。
反應通常係在溶劑中進行之。使用於反應之溶劑的實例包含芳香族烴溶劑如甲苯、二甲苯、乙苯及氯苯;含鹵素之脂肪族烴溶劑如氯仿及二氯甲烷;醚溶劑如四氫呋喃、乙二醇二甲醚、第三丁基甲基醚及1,4-二烷;酯溶劑如乙酸乙酯及乙酸丁酯;腈溶劑如乙腈及丙腈;芳香族雜環溶劑如吡啶;含硫之化合物溶劑如二甲亞碸及環丁碸;醯胺溶劑如N,N-二甲基甲醯胺,N,N-二甲基乙醯胺及N-甲基吡咯啶酮;及上述溶劑之混合溶劑。溶劑較佳
為含有醚溶劑之溶劑,更佳為含有四氫呋喃之溶劑。
以1質量份化合物(1)計,欲使用之溶劑用量通常為0至100質量份,較佳為1至20質量份。
反應中,視需要可添加鹼。使用於反應之鹼的實例包含鹼金屬碳酸鹽如碳酸鈉及碳酸鉀;鹼金屬碳酸氫鹽如碳酸氫鈉及碳酸氫鉀;以及三級胺如三乙胺、N,N-二異丙基乙胺、1,4-二氮雜雙環[2.2.2]辛烷、1,8-二氮雜雙環[5.4.0]十一碳烯、吡啶及4-二甲基胺基吡啶。
反應中,以1莫耳化合物(5)計,化合物(1)通常以1至3莫耳之比例使用之,以及鹼通常以1至10莫耳之比例使用之。較佳係化合物(1)通常以1至1.5莫耳之比例使用之,以及鹼通常以1至3莫耳之比例使用之。
反應之反應溫度通常為-20至100℃之範圍,較佳為0至80℃。反應之反應時間通常為0.1至24小時之範圍,較佳為0.1至12小時。
反應完成後,形成化合物(3)之鹽酸鹽,且可藉由經由過濾移除沉澱之結晶而單離化合物(3)之鹽酸鹽,然後此化合物可以其原樣使用於步驟C。當沒有單離而使用於步驟C時,此化合物可在以具有100℃或更高之沸點之溶劑取代後使用於步驟C。
化合物(3)可藉由施加後處理操作如添加水至反應混合物,視需要以鹼(如碳酸氫鈉水溶液)中和混合物,以及以有機溶劑萃取混合物,接著乾燥及濃縮有機層而單離之。亦可能藉由層析術、再結晶等進一步純化單離
之化合物(3)。化合物(3)可以水合物之形式取出,且可以其原樣使用於步驟C。
化合物(3)可藉由與無機酸如硫酸、鹽酸、氫溴酸、氫碘酸及磺酸化合物如對甲苯磺酸、苯磺酸、甲烷磺酸及樟腦磺酸混合而以鹽之形式取出,且可以其原樣使用於步驟C。
(步驟C)
式(4)所示之化合物(以下稱為化合物(4))可藉由使化合物(3)或其酸鹽在酸存在下於100℃至180℃反應製造之。
使用於反應之酸的實例包含無機酸如硫酸、鹽酸、氫溴酸及氫碘酸;磺酸化合物如對甲苯磺酸、苯磺酸、甲烷磺酸及樟腦磺酸;或安伯來特(Amberlite,註冊商標)酸性離子交換樹脂。酸較佳為磺酸化合物,更佳為對甲苯磺酸及甲烷磺酸。
反應通常係在溶劑中進行之。使用於反應之溶劑的實例包含芳香族烴溶劑如甲苯、二甲苯、乙苯、氯苯、枯烯(cumen)、均三甲苯(mesitylene)及二氯苯;醚溶劑如1,4-二烷;酯溶劑如乙酸丁酯;腈溶劑如丙腈;芳香族雜環溶劑如吡啶;含硫之化合物溶劑如二甲亞碸及環丁碸;醯胺溶劑如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮;及上述溶劑之混合溶劑。溶劑較佳為芳香族烴溶劑,更佳為二甲苯及氯苯。
以1質量份化合物(3)計,欲使用之溶劑用量通常為1至100質量份,較佳為1至20質量份。
反應中,以1莫耳化合物(3)計,酸通常以0.1至5莫耳,較佳為0.5至3莫耳之比例使用之。
反應之反應溫度通常為100至180℃之範圍,較佳為100至160℃。反應之反應時間通常為0.1至48小時之範圍,較佳為0.1至24小時。
反應中,較佳移除含於原料中之水及反應期間所產生之水。移除方法的實例包含藉由使用迪安-斯塔克(Dean-Stark)裝置等之共沸脫水移除水之方法,以及藉由使用脫水劑如分子篩、無水硫酸鈉及無水硫酸鎂移除水之方法,移除方法較佳為其中藉由共沸脫水移除水之方法。
反應中,為了移除分解產物,可添加吸附劑如活性碳、矽膠及矽藻土(Celite,註冊商標)。
反應完成後,可在藉由添加反應混合物至水或鹼性水溶液如鹼金屬碳酸鹽水溶液(例如,Na2CO3、K2CO3)及鹼金屬碳酸氫鹽水溶液(例如,NaHCO3、KHCO3),且以有機溶劑萃取混合物,並濃縮有機層;藉由過濾收集固體(其係藉由添加反應混合物至水所產生者);或者藉由過濾收集反應混合物中所產生之固體而單離化合物(4)。亦可能藉由層析術、再結晶等進一步純化單離之化合物(4)。化合物(4)可藉由與無機酸如鹽酸、氫溴酸和氫碘酸,以及磺酸化合物如對甲苯磺酸、苯磺酸、甲烷磺酸和樟腦磺酸混合而以鹽之形式取出。
本發明將藉由實施例進一步說明之,但本
發明不侷限於這些實施例。
實施例1
在氮氣氛圍下,混合0.50g之(3-乙基磺醯基)-2-吡啶羧酸鉀、2.50g之二甲苯及0.01g之N,N-二甲基甲醯胺並加熱至60℃,然後歷時5小時滴加0.35g亞硫醯氯,接著於60℃攪拌4小時。對此反應溶液添加異丁胺,並使用高效液相層析儀,藉由內參考標準法(內參考標準物質;聯苯)進行定量測量以獲得(3-乙基磺醯基)-2-吡啶醯氯,產率為95.1%。
實施例2
在氮氣氛圍下,混合25.00g之二甲苯、0.07g之N,N-二甲基甲醯胺及4.80g之亞硫醯氯並加熱至60℃,然後歷時5小時添加5.00g之(3-乙基磺醯基)-2-吡啶羧酸鉀,接著於60℃攪拌4小時。對此反應溶液添加異丁胺,並使用高效液相層析儀,藉由內參考標準法(內參考標準物質;聯苯)進行定量測量以獲得(3-乙基磺醯基)-2-吡啶醯氯,產率為96.9%。
實施例3
藉由下述方法製備2-胺基-4-(三氟甲基亞磺醯基)酚。
在氫氣氛圍下於35℃將5.0g之2-硝基-4-(三氟甲基亞磺醯基)酚、0.50g之鈀-碳(Pd 5%)及65ml之乙醇之混合物攪拌6小時。將反應混合物經由矽藻土(Celite,註冊商標)過濾冷卻至室溫並添加水,接著以乙酸乙酯萃取之。以水沖洗有機層,在無水硫酸鈉上乾燥,然後在減壓下予以濃縮。以氯仿沖洗所得固體以獲得3.87g之2-胺基-4-(三氟甲基亞磺醯基)酚。
在氮氣氛圍下,混合1.80g之2-胺基-4-(三氟甲基亞磺醯基)酚與9.00g之四氫呋喃並冷卻至0℃,然後歷時一小時滴加1.95g之(3-乙基磺醯基)-2-吡啶醯氯與3.90g之二甲苯之混合物,接著於0℃攪拌4小時。對此反應溶液添加碳酸氫鈉飽和水溶液,再以乙酸乙酯萃取此混合物,然後在減壓下濃縮有機層以獲得3-乙基磺醯基-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺,產率為95.6%。
1H-NMR(DMSO-d6)δ:11.47(1H,brs),10.42(1H,s),8.97(1H,dd),8.74(1H,s),8.43(1H,d),7.88(1H,dd),7.58(1H,dd),7.25(1H,d),3.68(2H,q),1.18(3H,t).
實施例4
在氮氣氛圍下,使1.00g之3-乙基磺醯基-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺、0.66g之對甲苯磺酸單水合物及5.00g之二甲苯之混合物於155ºC在迴流下脫水20小時。將冷卻至室溫之反應混合物添加至碳酸氫鈉飽和水溶液。分離後,添加5.00g之庚烷至有機層再進行冷卻結晶以獲得2-(3-乙基磺醯基吡啶-2-基)-5-(三氟甲基亞磺醯基)苯并唑,產率為88.2%。
1H-NMR(CDCl3)δ:9.04(1H,dd),8.61(1H,dd),8.35(1H,d),7.96-7.86(2H,m),7.77(1H,dd),4.01(2H,q),1.44(3H,t).
實施例5
在氮氣氛圍下,使0.30g之3-乙基磺醯基-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺、0.20g之對甲苯磺酸單水合物及1.50g之均三甲苯之混合物於180ºC在迴流下脫水7小時。將冷卻至室溫之反應混合物添加至碳酸氫鈉飽和水溶液。分離後,使用高效液相層析儀,藉由內參考標準法(內參考標準物質;聯苯)分析所得之有機層以獲得2-(3-乙基磺醯基吡啶-2-基)-5-(三氟甲基亞磺醯基)苯并唑,產率為81.8%。
實施例6
在氮氣氛圍下,混合1.80g之2-胺基-4-(三氟甲基磺醯基)酚與9.00g之四氫呋喃。冷卻至0℃後,歷時一小時滴加1.91g之(3-乙基磺醯基)-2-吡啶醯氯與3.82g之二甲苯之混合物,接著於0℃攪拌4小時。對此反應混合物添加碳酸氫鈉飽和水溶液,再以乙酸乙酯萃取此混合物,然後在減壓下濃縮有機層以獲得3-乙基磺醯基-N-[2-羥基-5-(三氟甲基磺醯基)苯基]甲基吡啶醯胺,產率為96.7%。
1H-NMR(DMSO-d6)δ:12.66(1H,brs),10.42(1H,s),8.97(1H,dd),8.85(1H,d),8.43(1H,dd),7.88(1H,dd),7.82(1H,dd),7.32(1H,d),3.68(2H,q),1.19(3H,t).
實施例7
在氮氣氛圍下,混合10.00g之2-胺基-4-(三氟甲基磺醯基)酚與50.00g之四氫呋喃並冷卻至0℃,然後歷時一小時滴加12.35g之(3-乙基磺醯基)-2-吡啶醯氯與27.00g之四氫呋喃之混合物,接著於0℃攪拌4小時。對此反應混合物添加碳酸氫鈉飽和水溶液,然後在減壓下濃縮此混合物。以乙酸乙酯萃取殘留物,在減壓下濃縮有機層以獲得
3-乙基磺醯基-N-[2-羥基-5-(三氟甲基磺醯基)苯基]甲基吡啶醯胺,產率為93.4%。
實施例8
在氮氣氛圍下,使1.00g之3-乙基磺醯基-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺、0.62g之對甲苯磺酸單水合物及5.00g之二甲苯之混合物於155℃在迴流下脫水15小時。將冷卻至室溫之反應混合物添加至碳酸氫鈉飽和水溶液。分離後,添加5.00g庚烷至有機層再進行冷卻結晶以獲得2-(3-乙基磺醯基吡啶-2-基)-5-(三氟甲基磺醯基)苯并唑,產率為86.5%。
1H-NMR(CDCl3)δ:9.05(1H,dd),8.61(1H,dd),8.59(1H,d),8.17(1H,dd),7.96(1H,d),7.80(1H,dd),3.98(2H,q),1.45(3H,t).
實施例9
在氮氣氛圍下,混合2.70g之2-胺基-4-(三氟甲基亞磺醯基)酚與8.10g之四氫呋喃再冷卻至0℃,然後歷時4小時滴加3.64g(3-乙基磺醯基)-2-吡啶醯氯與3.64g四氫呋喃之混合物,接著於0℃攪拌12小時。在減壓下濃縮此混合
物以獲得2.61g之3-乙基磺醯基-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺鹽酸鹽,產率為96.7%。
1H-NMR(DMSO-d6)δ:12.56(1H,brs),10.40(1H,s),8.97(1H,dd),8.86(1H,d),8.44(1H,dd),7.88(1H,dd),7.81(1H,dd),7.42(1H,d),3.68(2H,q),1.20(3H,t).
實施例10
在氮氣氛圍下,使3.00g之3-乙基磺醯基-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺鹽酸鹽、1.24g之對甲苯磺酸單水合物及15.00g之二甲苯之混合物於155℃在迴流下脫水20小時。將冷卻至室溫之反應混合物添加至碳酸氫鈉飽和水溶液。分離後,使用高效液相層析儀,藉由內參考標準法(內參考標準物質;聯苯)進行所得之有機層的定量測量以獲得2-(3-乙基磺醯基吡啶-2-基)-5-(三氟甲基亞磺醯基)苯并唑,產率為85.0%。
實施例11
在氮氣氛圍下,混合3.00g之2-胺基-4-(三氟甲基亞磺
醯基)酚與12.00g之四氫呋喃再冷卻至0℃,然後歷時4小時滴加4.11g之(3-乙基磺醯基)-2-吡啶醯氯與7.00g二甲苯之混合物,接著於0℃攪拌12小時。在減壓下濃縮此反應混合物,再將5.06g對甲苯磺酸單水合物、與16.90g二甲苯之混合物添加至所得之殘留物,接著於155℃在迴流下脫水24小時。將冷卻至室溫之反應混合物添加至碳酸氫鈉飽和水溶液。分離後,使用高效液相層析儀,藉由內參考標準法(內參考標準物質;聯苯)進行所得之有機層的定量測量以獲得2-(3-乙基磺醯基吡啶-2-基)-5-(三氟甲基亞磺醯基)苯并唑,產率為79.4%。
實施例12
在氮氣氛圍下,混合4.33g之2-胺基-4-(三氟甲基亞磺醯基)酚與34.72g之四氫呋喃再冷卻至0℃,然後歷時一小時滴加5.30g之(3-乙基磺醯基)-6-氯-2-吡啶醯氯與10.60g之四氫呋喃之混合物,接著於0℃攪拌4小時。對此反應混合物添加碳酸氫鈉飽和水溶液再以乙酸乙酯萃取此混合物,然後在減壓下濃縮有機層以獲得3-乙基磺醯基-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺,產率為99.2%。
1H-NMR(DMSO-d6)δ:11.55(1H,brs),10.45(1H,s),8.65(1H,s),8.38(1H,d),7.96(1H,d),7.57(1H,d),7.26(1H,d),3.84(2H,
q),1.32(3H,t).
實施例13
在氮氣氛圍下,使1.00g之3-乙基磺醯基-6-氯-N-[2-羥基-5-(三氟甲基亞磺醯基)苯基]甲基吡啶醯胺、0.74g之對甲苯磺酸單水合物及5.21g之氯苯之混合物於140℃在迴流下脫水8小時。將冷卻至室溫之反應混合物添加至碳酸氫鈉飽和水溶液。分離後,濃縮有機層以獲得0.95g之2-(6-氯-3-乙基磺醯基吡啶-2-基)-5-(三氟甲基亞磺醯基)苯并唑。
1H-NMR(CDCl3)δ:8.53(1H,d),8.36(1H,d),7.94(1H,dd),7.89(1H,dd),7.76(1H,d),4.01(2H,q),1.44(3H,t).
實施例14
在氮氣氛圍下,混合4.58g之2-胺基-4-(三氟甲基磺醯基)酚與36.82g之四氫呋喃再冷卻至0℃,然後歷時一小時滴加5.30g之(3-乙基磺醯基)-6-氯-2-吡啶醯氯與10.60g之四氫呋喃之混合物,接著於0℃攪拌4小時。對此反應混合物添加碳酸氫鈉飽和水溶液再以乙酸乙酯萃取此混合物,然後在減壓下濃縮有機層以獲得3-乙基磺醯基-6-氯
-N-[2-羥基-5-(三氟甲基磺醯基)苯基]甲基吡啶醯胺,產率為98.4%。
1H-NMR(DMSO-d6)δ:10.77(1H,brs),9.97(1H,s),9.09(1H,s),8.49(1H,d),7.85(1H,d),7.77(1H,d),7.18(1H,d),3.80(2H,q),1.22(3H,t).
實施例15
在氮氣氛圍下,使1.01g之3-乙基磺醯基-6-氯-N-[2-羥基-5-(三氟甲基磺醯基)苯基]甲基吡啶醯胺、0.72g之對甲苯磺酸單水合物及5.32g之氯苯之混合物於140℃在迴流下脫水8小時。將冷卻至室溫之反應混合物添加至碳酸氫鈉飽和水溶液。分離後,濃縮有機層以獲得0.95g 2-(6-氯-3-乙基磺醯基吡啶-2-基)-5-(三氟甲基磺醯基)苯并唑。
1H-NMR(CDCl3)δ:8.59(1H,d),8.54(1H,d),8.18(1H,dd),7.98(1H,d),7.79(1H,d),3.98(2H,q),1.45(3H,t).
比較例1
在氮氣氛圍下,混合3.00g之(3-乙基磺醯基)-2-吡啶羧酸、9.00g之甲苯及0.11g之N,N-二甲基甲醯胺再加熱至60℃,然後歷時5小時滴加2.03g之亞硫醯氯,接著於60℃
攪拌4小時。對此反應溶液添加正丁醇,並使用高效液相層析儀進行分析以獲得(3-乙基磺醯基)-2-吡啶醯氯,產率為65.3%。
本發明提供一種製造式(4)所示之化合物之方法,其具有優異之殺蟲防治效果。
Claims (7)
- 一種製造式(4)所示之化合物之方法,包括下列之步驟A至C:步驟A:使式(2)所示之化合物[式中,R1表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,R各自獨立表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或鹵素原子,n表示0、1、2或3,以及M表示鈉、鉀或鋰],與亞硫醯氯反應以獲得式(1)所示之化合物[式中R1、R及n具有與上述相同之定義];步驟B:使式(1)所示之化合物與式(5)所示之化合物[式中,A1表示氮原子或=CH-,R5表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,以及m表示1或2]反應,以製得式(3)所示之化合物[式中R1、R、R5、A1、m及n具有與上述相同之定義];以及步驟C:使式(3)所示之化合物或其酸鹽在酸存在下於100℃至180℃反應以獲得式(4)所示之化合物[式中R1、R、R5、A1、m及n具有與上述相同之定義]。
- 如申請專利範圍第1項所述之方法,其中,步驟C中之酸為磺酸化合物。
- 如申請專利範圍第1項所述之方法,其中,步驟C中之酸為對甲苯磺酸。
- 如申請專利範圍第1項所述之方法,其中,步驟C中之酸為甲烷磺酸。
- 一種製造式(3)所示之化合物或其酸鹽之方法,包括下列步驟A以及步驟B步驟A:使式(2)所示之化合物[式中,R1表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,R各自獨立表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或鹵素原子,n表示0、1、2或3及M表示鈉、鉀或鋰],與亞硫醯氯反應以獲得式(1)所示之化合物[式中R1、R及n具有與上述相同之定義];以及步驟B:使式(1)所示之化合物與式(5)所示之化合物[式中,A1表示氮原子或=CH-,R5表示視需要經鹵化之具有1至6個碳原子之鏈烴基、或視需要經鹵化之具有3至6個碳原子之脂環族烴基,以及m表示1或2]反應,以製得式(3)所示之化合物[式中R1、R、R5、A1、m及n具有與上述相同之定義]。
- 如申請專利範圍第1至5項中任一項所述之方法,其中,步驟B中所使用之溶劑含有醚溶劑。
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US10745398B2 (en) | 2015-09-28 | 2020-08-18 | Bayer Cropscience Aktiengesellschaft | 2-(het)aryl-substituted fused heterocycle derivatives as pesticides |
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