CN1202883A - 2－三氟甲氧基苯磺酰胺的生产方法 - Google Patents
2－三氟甲氧基苯磺酰胺的生产方法 Download PDFInfo
- Publication number
- CN1202883A CN1202883A CN96198418A CN96198418A CN1202883A CN 1202883 A CN1202883 A CN 1202883A CN 96198418 A CN96198418 A CN 96198418A CN 96198418 A CN96198418 A CN 96198418A CN 1202883 A CN1202883 A CN 1202883A
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- China
- Prior art keywords
- alcohol
- halogen
- crust
- compound
- trifluoromethoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229940124530 sulfonamide Drugs 0.000 title description 2
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical compound FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000005695 dehalogenation reaction Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- -1 alkoxyl alcohol Chemical compound 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 4
- KMVZDSQHLDGKGV-UHFFFAOYSA-N 2-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=CC=C1S(Cl)(=O)=O KMVZDSQHLDGKGV-UHFFFAOYSA-N 0.000 claims description 3
- BGGVOJPKCYCKGB-UHFFFAOYSA-N 4,5-dichloro-2-(trifluoromethoxy)benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC(Cl)=C(Cl)C=C1OC(F)(F)F BGGVOJPKCYCKGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- HIFGQHGWMTZMOH-UHFFFAOYSA-N 2-(trifluoromethoxy)benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1OC(F)(F)F HIFGQHGWMTZMOH-UHFFFAOYSA-N 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- ZFCOUBUSGHLCDT-UHFFFAOYSA-N 2-(trifluoromethoxy)aniline Chemical compound NC1=CC=CC=C1OC(F)(F)F ZFCOUBUSGHLCDT-UHFFFAOYSA-N 0.000 description 2
- JLTBWYIUMFEOTN-UHFFFAOYSA-N 2-(trifluoromethoxy)benzenesulfonyl chloride Chemical compound FC(F)(F)OC1=CC=CC=C1S(Cl)(=O)=O JLTBWYIUMFEOTN-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- QTDPJLBVWSUXGZ-UHFFFAOYSA-N 2-bromo-5-(trifluoromethoxy)benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC(OC(F)(F)F)=CC=C1Br QTDPJLBVWSUXGZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical class CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KAADJMTUBAFAKX-UHFFFAOYSA-N 2-chloro-5-(trifluoromethoxy)benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC(OC(F)(F)F)=CC=C1Cl KAADJMTUBAFAKX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 1
- GFTPCJDKZGDZRX-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC(Br)=CC=C1OC(F)(F)F GFTPCJDKZGDZRX-UHFFFAOYSA-N 0.000 description 1
- MVGMXURJMZKGJS-UHFFFAOYSA-N 5-chloro-2-(trifluoromethoxy)benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC(Cl)=CC=C1OC(F)(F)F MVGMXURJMZKGJS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LNJDRQXMGBUEFZ-UHFFFAOYSA-N C1(=CC=CC=C1)OC.[Cl] Chemical compound C1(=CC=CC=C1)OC.[Cl] LNJDRQXMGBUEFZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/22—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms
- C07C311/29—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/78—Halides of sulfonic acids
- C07C309/86—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/87—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
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Abstract
通式(Ⅰ)的2－三氟甲氧基苯磺酰胺是生产除草活性化合物的中间体。本发明涉及以很高的产率和高纯度生产该化合物的方法,该方法包括将其中X1表示卤素,X2表示氢或卤素的通式(Ⅱ)的卤化三氟甲氧基苯磺酰胺在催化剂和稀释剂存在下与氢反应,适当的,在酸受体存在下和在0℃—200℃温度范围内反应(脱卤),当“X2=卤素”时,用常规的方法分离得到的式(Ⅰ)化合物,而当“X2=H”时,用质子极性有机液体处理而转化成纯的结晶产物,并通过抽滤除去液体组分而分离出产物。
Description
本发明涉及生产2-三氟甲氧基苯磺酰胺的新方法，该化合物是生产除草活性化合物的原料。
已知将2-三氟甲氧基苯磺酰氯与氨反应可得到2-三氟甲氧基苯磺酰胺(参见Zh.Org.Khim.，8(1972)，1023-1-26(俄文)a.k.a.J.Org.Chem.USSR，8(1972)，1032-1035(英文)，引用于Chem.Abstracts，77：61964；还可参见US 4732711。
虽然反应顺利进行而且以高产率和高质量生成2-三氟甲氧基苯磺酰胺，但要求用2-三氟甲氧基苯胺通过米尔文(Meerwein)反应预先制备作为原料的2-三氟甲氧基苯磺酰氯，而此反应在技术上相对来说是比较复杂的。而且作为其前体的2-三氟甲氧基苯胺，能够得到的数量也是有限的。
现在，发现可以下述方法以很高的产率和高纯度得到式(I)的2-三氟甲氧基苯磺酰胺：
该方法是将下述通式(II)的卤化三氟甲氧基苯磺酰胺其中
X1表示卤素，和
X2表示氢或卤素，在催化剂和稀释剂存在下与氢反应，适当的，在酸受体存在下和在0℃-200℃温度范围内反应(脱卤)，当“X2＝卤素”时，得到的式(I)化合物可用常规的方法分离，而当“X2＝H”时，用质子极性有机液体处理而转化成纯的结晶产物，并通过抽滤除去液体组分而分离出产物。
通式(II)可表示为式(IIA)和(IIB)：
其中
在式(IIA)中
X1和X2如上文定义，和
在式(IIB)中
X1如上文定义和X2只表示氢。
意想不到的是，在氢化脱卤过程中三氟甲氧基基团不会发生变化。更意想不到的特点是，当“X2＝H”时，不需要的异构反应产物3-三氟甲氧基苯磺酰胺可用质子极性有机液体进行简单处理而溶解，从而很容易被除去；而所需要的式(I)产物因为实际上不溶解而留了下来，从而可以通过抽滤很容易地被分离。
本发明的方法极大地丰富了所属领域的技术内容。
式(II)给出了在本发明的方法中用作生产2-三氟甲氧基苯磺酰胺的原料的卤代三氟甲氧基苯磺酰胺的一般定义。
在式(II)中，
X1优选表示氯或溴，和
X2优选表示氢或氯。
当“X2＝H”时，使用的原料是式(IIA)和(IIB)化合物的混合物，优选式(IIA)化合物的量在60％以上。当“X2＝卤素”时，使用的原料是式(IIA)化合物。
式(II，其中X2＝H)的原料是已知的，和/或可按照本身已知的方法制备(参见EP-A23422，EP-A64322)。式(II，其中X2＝卤素)的原料是新的，并且也是本发明的技术主题(参见制备实施例)。
本发明的方法在稀释剂存在下进行。
优选的适当稀释剂是水和有机溶剂，特别是醇类如甲醇，乙醇，正或异丙醇，正、异、仲或叔丁醇；醚类如甲基叔丁基醚，甲基叔戊基醚，乙二醇二甲基醚或四氢呋喃；醚醇类如乙二醇单甲基醚或乙二醇单乙基醚；以及还有烃类溶剂如己烷，环己烷，甲基环己烷，甲苯或二甲苯，或者是上述溶剂的混合物。
在完成本发明的方法时，醇类，特别是甲醇或乙醇，是特别优选使用的稀释剂。
本发明的方法是在催化剂存在下进行的。优选的适当催化剂是在催化氢化反应中常用的金属催化剂，负载于适当载体物质上是合适的。优选的催化剂包括(阮内)钴、(阮内)镍、钯和铂(后面的数个可选择地负载于载体物质如活性炭、黏土、硅藻土或氧化铝之上)。
在本发明的方法中，负载于活性炭上的钯是特别优选使用的催化剂。
适当的，本发明的方法在酸受体存在下进行。一般来说，适当的酸受体是常规使用的有机或无机碱。优选的此类物质包括碱金属或碱土金属的乙酸盐、氨化物、碳酸盐、碳酸氢盐、氢化物、氢氧化物，或者是烷醇盐，例如乙酸钠、乙酸钾或乙酸钙，氨化锂、氨化钠、氨化钾或氨化钙，碳酸钠、碳酸钾或碳酸钙，碳酸氢钠、碳酸氢钾或碳酸氢钙，氢化锂、氢化钠、氢化钾或氢化钙，氢氧化锂、氢氧化钠、氢氧化钾或氢氧化钙，甲醇钠，乙醇钠，正或异丙醇钠，正、异、仲或叔丁醇钠，甲醇钾，乙醇钾，正或异丙醇钾，正、异、仲或叔丁醇钾；以及还包括碱性有机氮化合物，例如三甲胺，三乙胺，三丙胺，三丁胺，三辛胺，三(十二烷基)胺，乙基-二异丙基胺，N，N-二甲基-环己基胺，二环己基胺，乙基-二环己基胺，N，N-二甲基苯胺，N，N-二甲基苯甲胺，吡啶，2-甲基-、3-甲基-、4-甲基-、2，4-二甲基-、2，6-二甲基-、3，4-二甲基-或3，5-二甲基-吡啶，5-乙基-2-甲基吡啶，4-二甲氨基吡啶，N-甲基哌啶，1，4-二氮杂双环[2，2，2]辛烷(DABCO)，1，5-二氮杂双环[4，3，0]壬-5-烯(DBN)，和1，8-二氮杂双环[5，4，0]十一碳-7-烯(DBU)。
在进行本发明的方法时，反应温度可在一基本范围内变化。一般来说，本发明的方法可在0℃和200℃之间进行，优选在20℃和150℃之间，特别优选在40℃和120℃之间进行。
本发明的方法通常在大气压下，或是在提高的压力下进行，优选在1巴和100巴之间，特别优选在1巴和50巴之间进行。
在本发明的优选实施方案中，将式(IIA，其中X2＝卤素)的原料化合物或式(IIA，其中X2＝H)和(IIB)原料化合物的混合物加入适当的稀释剂中，向其中加入催化剂，以及如果需要加入酸受体，将混合物以常规的方式氢化，优选在提高的压力和提高的温度下氢化。
氢化结束后，遗留的氢用氮置换，混合物用水稀释，适当的，进行过滤。浓缩滤液，对残余物[当X2＝H时，其基本组成是2-三氟甲氧基苯磺酰胺和3-三氟甲氧基苯磺酰胺的混合物]进行处理，即用差不多二倍重量的质子极性有机液体一起搅拌。
适当的质子极性有机液体具体的是选择取代的羟烷基化合物。这类物质优选包括醇类如甲醇，乙醇，以及在各种情况下是直链的或支链的丙醇、丁醇、戊醇和己醇，还包括烷氧基醇如甲氧基乙醇和乙氧基乙醇。
为此目的，特别优选使用的是正和异丙醇，以及正、异、仲和叔丁醇。
然后，通过抽滤分离由本发明的方法得到的式(I)的三氟甲氧基-苯磺酰胺结晶。
用本发明的方法生产的式(I)化合物2-三氟甲氧基苯磺酰胺可用作制备具有除草活性的化合物的中间体(参见US4732711)。
制备实施例实施例1
71.6g 2-三氟甲氧基-5-氯苯磺酰胺(计量达75％)和5-三氟甲氧基-2-氯苯磺酰胺(计量达25％)的混合物，两种化合物的总含量71％，将其溶于500ml乙醇，用5g钯-碳(5％)处理，在100℃左右氢化20小时，初始压力为大约35巴。通入氮气，过滤出催化剂，浓缩滤液，残余物与260ml正丁醇一起搅拌，抽滤分离如此得到的结晶产物。
由此给出37.8g(理论产率的85％)2-三氟甲氧基-苯磺酰胺，熔点186℃。实施例2
13.1g 2-三氟甲氧基-5-溴苯磺酰胺(计量达86％)和5-三氟甲氧基-2-溴苯磺酰胺(计量达14％)的混合物，两种化合物的总含量76.1％，将其溶于40ml甲醇，用2.3g氢氧化钾的150ml甲醇溶液处理，然后用1g钯-碳(5％)处理，在50℃左右氢化20小时，初始压力为大约35巴。通入氮气，过滤出催化剂，浓缩滤液，将残余物溶于水，混合物与乙酸乙酯一起震荡，分离出有机相，用硫酸钠干燥和过滤。浓缩滤液，残余物与40ml正丁醇一起搅拌，抽滤分离如此得到的结晶产物。
由此给出6.7g(理论产率的89％)2-三氟甲氧基-苯磺酰胺，熔点186℃。实施例3
将5.6g(0.1mol)氢氧化钾的100ml甲醇溶液和0.5g钯-碳(5％)加入15.5g(0.05mol)2-三氟甲氧基-4，5-二氯苯磺酰胺的60ml甲醇溶液中。在高压釜中，于75℃，初始压力35巴的情况下，将混合物氢化20小时。为进行后处理，过滤出催化剂，滤液用水处理，中和混合物，将甲醇蒸出，过滤和干燥后得到产物。
由此给出9.65g(＝理论产率的80％)2-三氟甲氧基-苯磺酰胺，熔点185℃。式(IIA，其中X1＝X2＝Cl)原料化合物的制备a)步骤1
3，4-二氯-三氟甲氧基苯
在0℃下将200g(1.22mol)3，4-二氯苯酚和800ml氟化氢引入VA不锈钢高压釜，加入800ml四氯甲烷。注入15巴氮气，将混合物加热至116-120℃，同时剧烈搅拌，按28巴释放所形成的氯化氢的压力。7小时后，不再有氯化氢生成，此时将过量的氟化氢生成的三氯氟甲烷和过量的四氯甲烷蒸出。产物混合物在60-86℃/17毫巴蒸馏，得到213g蒸出物，其中含19.2％3，4-二氯-三氟甲氧基苯和80.1％3，4-二氯-二氟一氯甲氧基苯。
将该混合物与100ml氟化氢和1ml五氯化锑于125℃加热3小时。在25巴释放生成的氯化氢的压力。蒸馏产物，得到3，4-二氯-三氟甲氧基苯155g(＝理论产率的53％)，17毫巴时的沸点为62℃；GC测定其含量为99.8％。b)步骤2
2-三氟甲氧基-4，5-二氯苯磺酰氯
0℃下，用1小时时间将50g(0.216mol)3，4-二氯-三氟甲氧基苯滴加到85ml(1.28mol)的氯磺酸中。0℃下1小时后，滴加17g亚硫酰氯，混合物在40℃继续加热，间歇式地放出气体。
再连续搅拌反应混合物20小时，然后真空蒸出未反应的亚硫酰氯，把残余物冷却至20℃并转移至150克冰中。将产物溶于二氯甲烷，用水洗涤二次。蒸馏溶液，在0.4毫巴取沸点范围96-102℃，得到57g蒸馏产物，根据GC分析其含量为99％，相当于理论产率的80％。
此化合物是新的，并且是本发明的技术主题。c)步骤3
2-三氟甲氧基-4，5-二氯苯磺酰胺
于20℃，将57g(0.173mol)2-三氟甲氧基-4，5-二氯苯磺酰氯计量加入200ml浓氨水溶液中。在连续搅拌混合物1小时后，抽滤出固体，接着用水洗涤和干燥，得到44g(＝83％理论产率)；熔点181-185℃。
此混合物是新的，并且是本发明的技术主题。
Claims (9)
1.生产下述式(I)的2-三氟甲氧基苯磺酰胺的方法：其特征在于将下述通式(II)的卤化三氟甲氧基苯磺酰胺
其中
X1表示卤素，和
X2表示氢或卤素，在催化剂和稀释剂存在下与氢进行反应，适当的，在酸受体存在下和在0℃-200℃温度范围内反应(脱卤)，当“X2＝卤素”时，用常规的方法分离得到的式(I)化合物，而当“X2＝H”时，用质子极性有机液体处理而转化成纯的结晶产物，并通过抽滤除去液体组分而分离出产物。
2.按照权利要求1的方法，其特征在于所述反应在20℃至150℃的温度范围内进行。
3.按照权利要求1的方法，其特征在于所述反应在40℃至120℃的温度范围内进行。
4.按照权利要求1的方法，其特征在于所述反应在1巴至100巴之间的压力范围内进行，特别是在1巴至50巴之间的压力范围内进行。
5.按照权利要求1的方法，其特征在于用钯-碳作为催化剂。
6.按照权利要求1的方法，其特征在于用醇，特别是甲醇或乙醇作为稀释剂。
7.按照权利要求1的方法，其特征在于用选择取代的羟烷基化合物，优选使用醇或烷氧基醇作为质子极性液体。
8.按照权利要求7的方法，其特征在于所用的醇是正-或异-丙醇或正-、异-、仲-或叔-丁醇
9.化合物2-三氟甲氧基-4，5-二氯苯磺酰氯和2-三氟甲氧基-4，5-二氯苯磺酰胺。
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| DE19543323.8 | 1995-11-21 | ||
| DE19543323A DE19543323A1 (de) | 1995-11-21 | 1995-11-21 | Verfahren zur Herstellung von 2-Trifluormethoxy-benzolsulfonamid |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB00133106XA Expired - Lifetime CN1142906C (zh) | 1995-11-21 | 1996-11-08 | 用于生产2-三氟甲氧基苯磺酰胺的中间体 |
| CN96198418A Expired - Lifetime CN1068872C (zh) | 1995-11-21 | 1996-11-08 | 2－三氟甲氧基苯磺酰胺的生产方法 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB00133106XA Expired - Lifetime CN1142906C (zh) | 1995-11-21 | 1996-11-08 | 用于生产2-三氟甲氧基苯磺酰胺的中间体 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5925788A (zh) |
| EP (1) | EP0863869B1 (zh) |
| JP (1) | JP4010565B2 (zh) |
| KR (1) | KR100420494B1 (zh) |
| CN (2) | CN1142906C (zh) |
| AU (1) | AU7568396A (zh) |
| CA (1) | CA2237842C (zh) |
| DE (2) | DE19543323A1 (zh) |
| HK (1) | HK1016156A1 (zh) |
| HU (1) | HU224039B1 (zh) |
| MX (1) | MX9803996A (zh) |
| WO (1) | WO1997019056A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788347A (zh) * | 2015-03-23 | 2015-07-22 | 大连奇凯医药科技有限公司 | 2-(三氟甲氧基)苯磺酰胺的制备方法 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3904823B2 (ja) | 2000-02-22 | 2007-04-11 | セントラル硝子株式会社 | １，１，１−トリフルオロアセトンの製造方法 |
| WO2006080574A1 (ja) * | 2005-01-28 | 2006-08-03 | Taisho Pharmaceutical Co., Ltd. | １，３－ジヒドロ－２ｈ－インドール－２－オン化合物、及び芳香族複素環が縮合したピロリジン－２－オン化合物 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809194A (en) * | 1957-10-08 | Thiadiazine type natriuretic agents | ||
| US3021368A (en) * | 1959-04-22 | 1962-02-13 | Smith Kline French Lab | Substituted trifluoromethylthio- and trifluoromethoxyphenyl sulfonylureas |
| US3829487A (en) * | 1971-04-19 | 1974-08-13 | Merck & Co Inc | N-substituted-3,5-(trifluoromethyl or bromo)benzenesulfonamides |
| US4452628A (en) * | 1979-07-26 | 1984-06-05 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
| US4725305A (en) * | 1983-03-04 | 1988-02-16 | Bayer Aktiengesellschaft | N'-(substituted-1,3,5-triazin-2-yl)-N"-substituted-N",N"'-bis-(substituted-benzenesulphonyl)-guanidines as herbicides |
| US4874894A (en) * | 1987-04-29 | 1989-10-17 | Hilton Davis Co. | Process for the production of benzenesulfonamides |
| US5670691A (en) * | 1994-10-18 | 1997-09-23 | Rohm And Haas Company | Method for making a substituted benzene compound |
-
1995
- 1995-11-21 DE DE19543323A patent/DE19543323A1/de not_active Withdrawn
-
1996
- 1996-11-08 CA CA002237842A patent/CA2237842C/en not_active Expired - Lifetime
- 1996-11-08 WO PCT/EP1996/004895 patent/WO1997019056A1/de active IP Right Grant
- 1996-11-08 US US09/068,778 patent/US5925788A/en not_active Expired - Lifetime
- 1996-11-08 AU AU75683/96A patent/AU7568396A/en not_active Abandoned
- 1996-11-08 KR KR10-1998-0703094A patent/KR100420494B1/ko not_active IP Right Cessation
- 1996-11-08 DE DE59605764T patent/DE59605764D1/de not_active Expired - Lifetime
- 1996-11-08 HU HU9903699A patent/HU224039B1/hu active IP Right Grant
- 1996-11-08 CN CNB00133106XA patent/CN1142906C/zh not_active Expired - Lifetime
- 1996-11-08 CN CN96198418A patent/CN1068872C/zh not_active Expired - Lifetime
- 1996-11-08 JP JP51933497A patent/JP4010565B2/ja not_active Expired - Lifetime
- 1996-11-08 EP EP96938155A patent/EP0863869B1/de not_active Expired - Lifetime
-
1998
- 1998-05-20 MX MX9803996A patent/MX9803996A/es unknown
-
1999
- 1999-03-19 HK HK99101131A patent/HK1016156A1/xx not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788347A (zh) * | 2015-03-23 | 2015-07-22 | 大连奇凯医药科技有限公司 | 2-(三氟甲氧基)苯磺酰胺的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000500756A (ja) | 2000-01-25 |
| HUP9903699A3 (en) | 2001-05-28 |
| HU224039B1 (hu) | 2005-05-30 |
| AU7568396A (en) | 1997-06-11 |
| CN1308057A (zh) | 2001-08-15 |
| CA2237842A1 (en) | 1997-05-29 |
| HK1016156A1 (en) | 1999-10-29 |
| EP0863869A1 (de) | 1998-09-16 |
| CN1142906C (zh) | 2004-03-24 |
| CA2237842C (en) | 2007-01-16 |
| DE59605764D1 (de) | 2000-09-21 |
| US5925788A (en) | 1999-07-20 |
| CN1068872C (zh) | 2001-07-25 |
| WO1997019056A1 (de) | 1997-05-29 |
| DE19543323A1 (de) | 1997-05-22 |
| KR100420494B1 (ko) | 2004-08-18 |
| MX9803996A (es) | 1998-09-30 |
| KR19990067148A (ko) | 1999-08-16 |
| HUP9903699A2 (hu) | 2000-02-28 |
| JP4010565B2 (ja) | 2007-11-21 |
| EP0863869B1 (de) | 2000-08-16 |
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