JPH01246262A - Production of substituted pyridine-n-oxide based compound - Google Patents
Production of substituted pyridine-n-oxide based compoundInfo
- Publication number
- JPH01246262A JPH01246262A JP7277188A JP7277188A JPH01246262A JP H01246262 A JPH01246262 A JP H01246262A JP 7277188 A JP7277188 A JP 7277188A JP 7277188 A JP7277188 A JP 7277188A JP H01246262 A JPH01246262 A JP H01246262A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- substituted pyridine
- reaction
- acid
- compound expressed
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- -1 mercapto-substituted pyridine-N-oxide compound Chemical class 0.000 claims description 44
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000005077 polysulfide Substances 0.000 claims description 6
- 229920001021 polysulfide Polymers 0.000 claims description 6
- 150000008117 polysulfides Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 238000010306 acid treatment Methods 0.000 abstract description 6
- 238000005660 chlorination reaction Methods 0.000 abstract description 6
- 238000005893 bromination reaction Methods 0.000 abstract description 5
- 238000005576 amination reaction Methods 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 4
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 230000031709 bromination Effects 0.000 abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 150000003222 pyridines Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 125000001246 bromo group Chemical group Br* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000194 fatty acid Chemical group 0.000 description 2
- 229930195729 fatty acid Chemical group 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OFNGHAYJUVTBAK-UHFFFAOYSA-N 2,3,3-trichlorooxepane Chemical compound ClC1OCCCCC1(Cl)Cl OFNGHAYJUVTBAK-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- QNZRJGJNLOMEGJ-UHFFFAOYSA-N 2-chloro-n,n-dimethylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1Cl QNZRJGJNLOMEGJ-UHFFFAOYSA-N 0.000 description 1
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DDCFNGVKPDJUPW-UHFFFAOYSA-N CN(C)C(=O)C1=CC=C[N+]([O-])=C1S Chemical compound CN(C)C(=O)C1=CC=C[N+]([O-])=C1S DDCFNGVKPDJUPW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000005587 bubbling Effects 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
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DKIXSCPMGCKCHS-UHFFFAOYSA-N n,n-dimethyl-1-oxido-2-sulfamoylpyridin-1-ium-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=C[N+]([O-])=C1S(N)(=O)=O DKIXSCPMGCKCHS-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、農薬、医薬などの原料として有用なアミノス
ルホニル置換ピリジン−Ｎ−オキシド系化合物（以下置
換ピリジン−Ｎ−オキシド系化合物という）の製造方法
に関する。Detailed Description of the Invention "Field of Industrial Application" The present invention relates to the use of aminosulfonyl-substituted pyridine-N-oxide compounds (hereinafter referred to as substituted pyridine-N-oxide compounds) useful as raw materials for agricultural chemicals, medicines, etc. Regarding the manufacturing method.
「先行技術及び本発明に至った経緯」
本発明は１ケまたは２ケのアルキル基で置換されていて
もよいアミノカルボニル基ならびにアミノスルホニル基
を存する置換ピリジン−Ｎ−オキシド系化合物の工業的
に有利な製造方法に関する。"Prior art and background leading to the present invention" The present invention is directed to the industrial use of substituted pyridine-N-oxide compounds containing an aminocarbonyl group and an aminosulfonyl group which may be substituted with one or two alkyl groups. Concerning an advantageous manufacturing method.
前記置換ピリジン−Ｎ−オキシド系化合物はヨーロッパ
特許出願第２３２，０６７号公開公報においてその製造
方法が開示されているが、その製法は反応工程が長（、
かつ収率も低いため工業的に実施する上ではかならずし
も満足のいくものでない。A method for producing the substituted pyridine-N-oxide compound is disclosed in European Patent Application No. 232,067, but the method involves long reaction steps (
Moreover, since the yield is low, it is not always satisfactory for industrial implementation.
本発明者等は、前記ヨーロッパ特許出願公開公報におい
て記載されたトウモロコシ畑用除草剤Ｎ−（（４，６−
シメトキシピリミジンー２−イル）アミノカルボニル−
２−ピリジンスルホンアミドまたは同ピリジン−Ｎ−オ
キシドスルホンアミドの原料として前記置換ピリジン−
Ｎ−オキシド系化合物が有用であることに着目し、その
工業的に有利な製造方法を見出すべく、種々の方法によ
り製造を試みたものの、満足すべき製造法を見出できな
かったが、本発明の製造方法によって所期の効果が得ら
れることを見出した。The present inventors have developed the herbicide N-((4,6-
cymethoxypyrimidin-2-yl)aminocarbonyl-
The above-mentioned substituted pyridine-
Focusing on the usefulness of N-oxide compounds, various attempts were made to produce them in an attempt to find industrially advantageous production methods, but no satisfactory production method could be found. It has been found that the desired effect can be obtained by the manufacturing method of the invention.
「発明の開示」
本発明は、−最大（１）
（式中Ｒ，およびＲ２は水素原子またはアルキル基であ
り、１ｌａｌ はハロゲン原子である）で表わされるハ
ロゲノ置換ピリジン−Ｎ−オキシド系化合物とＭｚＳＸ
（式中Ｍはアルカリ金属元素であり、Ｘは２〜８である
）で表わされるポリスルフィドとを反応させ、酸処理し
て、−最大（ｎ）↓
（式中Ｒ１およびＲ２は前述の通りである）で表わされ
るメルカプト置換ピリジン−Ｎ−オキシド系化合物を生
成させ、このものを酸化し塩素化または臭素化して一般
式（ＩＩＩ）
■
（式中Ｘは塩素原子または臭素原子であり、Ｒ１および
Ｒ２は前述の通りである）で表わされるクロロ（マタは
ブロモ）スルホニル置換ピリジン−Ｎ−オキシド系化合
物を生成させ、次いでこのものとアンモニアと反応させ
、−ａ式（■）↓
（式中Ｒ１およびＲ２は前述の通りである）で表わされ
るアミノスルホニル置換ピリジン−Ｎ−オキシド系化合
物を製造する方法である。"Disclosure of the Invention" The present invention relates to a halogeno-substituted pyridine-N-oxide compound represented by the formula (1) (wherein R and R2 are a hydrogen atom or an alkyl group, and 1lal is a halogen atom); MzSX
(In the formula, M is an alkali metal element and A mercapto-substituted pyridine-N-oxide compound represented by A chloro(bromo)sulfonyl-substituted pyridine-N-oxide compound represented by the formula -a (■)↓ (wherein R1 and R2 are as described above).
前記−最大（１）〜（ＩＶ）のＲ１及びＲ２のアルキル
基としては、炭素数１〜６のもの、例えばメチル基、エ
チル基、プロピル基、ブチル基などが挙げられ、また−
最大（［）のハロゲン原子としては弗素原子、塩素原子
、臭素原子、沃素原子が挙げられる。The above-mentioned alkyl groups for R1 and R2 (1) to (IV) include those having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, and -
Examples of the maximum ([) halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
前記−最大（１）のハロゲノ置換ピリジン−Ｎ−オキシ
ド系化合物は、ハロゲノ置換ピリジン系化合物と過酸化
物とを反応させるＮ−オキシド化反応により容易に製造
することができる。The halogeno-substituted pyridine-N-oxide compound of maximum (1) above can be easily produced by an N-oxidation reaction in which a halogeno-substituted pyridine compound and a peroxide are reacted.
（Ｎ−オキシド化反応）
このハロゲン置換ピリジン系化合物は例えばハロゲノピ
コリン酸に対し塩化チオニルを反応させ次いで塩化メチ
レンのような溶媒中でアミン類を反応させれば容易に得
られる。ハロゲノ置換ピリジン系化合物としてはハロゲ
ン原子がピリジン環の２．４または６位に存在したもの
が望ましく、またクロロ又はブロモ置換ピリジン系化合
物が望ましい。(N-Oxidation Reaction) This halogen-substituted pyridine compound can be easily obtained, for example, by reacting halogenopicolinic acid with thionyl chloride and then reacting it with an amine in a solvent such as methylene chloride. The halogeno-substituted pyridine compound preferably has a halogen atom at the 2.4 or 6-position of the pyridine ring, and chloro- or bromo-substituted pyridine compounds are preferable.
前記Ｎ−オキシド化反応では通常、ハロゲノ置換ピリジ
ン系化合物を溶媒、例えば水、アルコール類、エーテル
類、エステル類、ニトリル類、ハロゲン原子で置換され
ていてもよい脂肪族炭化水素類、同脂肪酸類、芳香族炭
化水素類など、好ましくは水、ハロゲン原子で置換され
ていてもよい脂肪酸に溶解させ、過酸化物と反応させる
。溶媒の使用量は、ハロゲノ置換ピリジン系化合物に対
してｇ通ＩＯ〜ｔｏ、ｏｏｏ重量％である。また過酸化
物としては、過安息香酸、メタクロロ過安息香酸、モノ
ペルオキシフタル酸、過蟻酸、過酢酸、トリフルオロ過
酢酸のような有機過酸類、過酢酸ターシャリ−ブチルエ
ステル、過安息香酸ターシャリ−ブチルエステルのよう
な有機過酸エステル類、ターシャリ−ブチルヒドロペル
オキシド、ターシャリ−アミルヒドロペルオキシドのよ
うなアルキルヒドロペルオキシド類、過酸化水素などが
挙げられ、好ましくは過蟻酸、過酢酸、トリフルオロ過
酢酸、過酸化水素であり、その使用量は、ハロゲン置換
ピリジン系化合物に対し、１〜１０倍モル、望ましくは
２〜５倍モルである。反応温度はｔｉｆｆｌＯ−１２０
℃、望ましくは３０〜１００℃、反応時間は一般に１〜
１０時間である。In the N-oxidation reaction, the halogeno-substituted pyridine compound is usually mixed with a solvent such as water, alcohols, ethers, esters, nitriles, aliphatic hydrocarbons optionally substituted with halogen atoms, and fatty acids. , aromatic hydrocarbons, etc., preferably water, or a fatty acid which may be substituted with a halogen atom, and reacted with a peroxide. The amount of the solvent used is 10 to 100% by weight based on the halogeno-substituted pyridine compound. Examples of peroxides include organic peracids such as perbenzoic acid, metachloroperbenzoic acid, monoperoxyphthalic acid, performic acid, peracetic acid, and trifluoroperacetic acid, peracetic acid tert-butyl ester, and perbenzoic acid tert-butyl ester. Examples include organic peracid esters such as butyl ester, alkyl hydroperoxides such as tert-butyl hydroperoxide and tert-amyl hydroperoxide, hydrogen peroxide, and preferably performic acid, peracetic acid, and trifluoroperacetic acid. , hydrogen peroxide, and the amount used is 1 to 10 times the mole, preferably 2 to 5 times the mole of the halogen-substituted pyridine compound. The reaction temperature is tifflO-120
℃, preferably 30-100℃, reaction time generally 1-100℃
It is 10 hours.
本発明では、ハロゲノ置換ピリジン−Ｎ−オキシド系化
合物とポリスルフィドとを反応させるポリスルフィド化
反応次いで酸処理反応により、メルカプト置換ピリジン
−Ｎ−オキシド系化合物を製造することができる。In the present invention, a mercapto-substituted pyridine-N-oxide compound can be produced by a polysulfidization reaction in which a halogeno-substituted pyridine-N-oxide compound and a polysulfide are reacted, followed by an acid treatment reaction.
（ポリスルフィド化反応）
前記ポリスルフィドについては、アルカリ金属の水酸化
物およびその水硫化物の混合物、あるいはアルカリ金属
の硫化物とその１〜７倍モル望ましくは、１〜２倍モル
の硫黄とを常法により予め反応させて得られたものを使
用してもよいが、これらをハロゲン置換ピリジン−Ｎ−
オキシド系化合物との共存下に反応させ反応系内で生成
したものを直接使用してもよい。アルカリ金属の水酸化
物、その水硫化物またはその硫化物のアルカリ金属とし
てはリチウム、ナトリウム、カリウムなどが挙げられ、
なかでもナトリウムが好ましく、前記水酸化物、水硫化
物または硫化物の使用量はハロゲノ置ｌ負ピリジンーＮ
−オキシド系化合物に対し、それぞれ０．７５〜５倍モ
ル、望ましくは１〜１．５倍モルである。この反応では
通常、溶媒として水を使用するが、有機溶媒についても
ポリスルフィド及び水と混和するものならば使用するこ
とができ、例えばメタノール、エタノール、プロパツー
ルなどの低級アルコール、エチレングリコール、プロピ
レングリコールなどのポリアルコール、テトラヒドロフ
ランのようなエーテル類、ジオキサン、ジメチルスルホ
キシドなどの非プロトン性極性溶媒、メチルエチルケト
ンのようなケトン類、アセトニトリルのようなニトリル
類などが使用できる。この溶媒の使用量は、ハロゲノ置
換ピリジン−Ｎ−オキシド系化合物に対し通常１０〜１
０００重量％、望ましくは１０〜１００重■％である。(Polysulfidation reaction) Regarding the polysulfide, a mixture of an alkali metal hydroxide and its hydrosulfide, or an alkali metal sulfide and 1 to 7 times the mole of sulfur, preferably 1 to 2 times the mole thereof, is used. Although those obtained by reacting in advance by the method may be used, these may be used as halogen-substituted pyridine-N-
A product produced in the reaction system by reaction in the presence of an oxide compound may be used directly. Examples of alkali metal hydroxides, hydrosulfides or sulfides of alkali metals include lithium, sodium, potassium, etc.
Among them, sodium is preferable, and the amount of the hydroxide, hydrosulfide, or sulfide used is such that the amount of the hydroxide, hydrogen sulfide, or sulfide used varies from halogen to negative pyridine to N.
- 0.75 to 5 times the mole, preferably 1 to 1.5 times the mole of the oxide compound. In this reaction, water is usually used as a solvent, but organic solvents that are miscible with polysulfide and water can also be used, such as lower alcohols such as methanol, ethanol, propatool, ethylene glycol, propylene glycol, etc. Polyalcohols, ethers such as tetrahydrofuran, aprotic polar solvents such as dioxane and dimethyl sulfoxide, ketones such as methyl ethyl ketone, nitriles such as acetonitrile, and the like can be used. The amount of this solvent to be used is usually 10 to 1
000% by weight, preferably 10 to 100% by weight.
この反応の他の反応条件は一概に規定できないが、反応
温度は普通Ｏ℃〜還流温度、望ましくは８０〜１５０℃
、圧力は常圧〜数気圧、反応時間は一般に０．５〜５時
間である。Other reaction conditions for this reaction cannot be absolutely specified, but the reaction temperature is usually 0°C to reflux temperature, preferably 80 to 150°C.
, the pressure is normal pressure to several atmospheres, and the reaction time is generally 0.5 to 5 hours.
（酸処理）
この反応ではメルカプト置換ピリジン−Ｎ−オキシド系
化合物は通常ポリスルフィドのアルカリ金属塩として生
成するので、反応生成物に常法の酸処理を施せばメルカ
プト置換ピリジン−Ｎ−オキシド系化合物が遊離し、硫
化水素ガスが発生、硫黄が生成する。その酸処理として
は例えば濃塩酸、希硫酸などの酸化作用のない鉱酸を反
応生成物にｐＨが３以下になるように加えることにより
おこなわれ、その後通常の精製、分離操作を施すことに
よってメルカプト置換ピリジン−Ｎ−オキシド系化合物
を単離することができる。(Acid treatment) In this reaction, the mercapto-substituted pyridine-N-oxide compound is usually produced as an alkali metal salt of polysulfide, so if the reaction product is subjected to a conventional acid treatment, the mercapto-substituted pyridine-N-oxide compound is produced. It is liberated, hydrogen sulfide gas is generated, and sulfur is produced. The acid treatment is carried out by adding a non-oxidizing mineral acid such as concentrated hydrochloric acid or dilute sulfuric acid to the reaction product so that the pH becomes 3 or less, and then performing normal purification and separation operations to remove mercapto. Substituted pyridine-N-oxide compounds can be isolated.
次にメルカプ１−置換ビリジン−Ｎ−オキシド系化合物
は、酸化し塩素化または臭素化してクロロ（またはブロ
モ）スルホニル置換ピリジン−Ｎ−オキシド系化合物を
製造することができる。The mercap-1-substituted pyridine-N-oxide compound can then be oxidized and chlorinated or brominated to produce a chloro(or bromo)sulfonyl-substituted pyridine-N-oxide compound.
（酸化反応、塩素化または臭素化反応）メルカプト置換
ピリジン−Ｎ−オキシド系化合物については前述の反応
生成物から単離したものを使用してもよいが、その生成
物を直接使用してもよい。(Oxidation reaction, chlorination or bromination reaction) Mercapto-substituted pyridine-N-oxide compounds may be isolated from the above-mentioned reaction products, but the products may also be used directly. .
また、この酸化反応、塩素化または臭素化する方法とし
ては、一般にこのメルカプトｉＷ換ピリジンーＮ−オキ
シド系化合物に対して塩素ガスまたは臭素と、水、塩酸
水溶液、酢酸或いは酢酸水溶液とを反応させる方法、次
亜塩素酸塩または次亜臭素酸塩と、水あるいは塩酸水溶
液とを反応させる方法などが挙げられるが、なかでも前
者の方法が望ましい。前記塩素化または臭素化反応では
ヘンゼン、ヘキサン、ｌ−ルエン、キシレン、塩化メヂ
レン、クロロホルム、四塩化炭素、二塩化エチレン、ト
リクロロエチレン、ジエチルエーテル、酢酸エチルなど
の非プロトン性有機溶媒を存在させてもよい。溶媒の使
用量は、メルカプト置換ピリジン−Ｎ−オキシド系化合
物に対し、通常５０＝２．０００重■％である。The oxidation reaction, chlorination or bromination is generally carried out by reacting the mercapto iW-converted pyridine-N-oxide compound with chlorine gas or bromine and water, an aqueous solution of hydrochloric acid, acetic acid or an aqueous acetic acid solution. , a method of reacting hypochlorite or hypobromite with water or an aqueous hydrochloric acid solution, among others, the former method is preferred. In the chlorination or bromination reaction, an aprotic organic solvent such as hexane, hexane, l-luene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, trichloroethylene, diethyl ether, or ethyl acetate may be present. good. The amount of the solvent used is usually 50=2.000% by weight based on the mercapto-substituted pyridine-N-oxide compound.
これらの方法において、塩素、臭素、次亜塩素酸、次亜
臭素酸などの使用量はメルカプト置換ピリジン−Ｎ−オ
キシド系化合物に対し反応理論量乃至それを若干土建る
量であり、また水、塩酸水溶液、酢酸、酢酸水溶液など
のそれは同様に５０〜２０００重量％である。また塩酸
水溶液又は酢酸水溶液を使用する場合、それらの濃度は
１〜３０重量％のものを用いればよい０反応温度は普通
−２０〜＋５０℃、望ましくは一１０〜＋１０℃、反応
時間は０．１〜５時間である。この反応生成物に通常の
精製、分離操作を施せば所望のクロロ（またはブロモ）
スルホニル置換ピリジン−Ｎ−オキシド系化合物を分離
することができる。In these methods, the amount of chlorine, bromine, hypochlorous acid, hypobromous acid, etc. to be used is the reaction stoichiometric amount to the mercapto-substituted pyridine-N-oxide compound, or an amount slightly higher than that amount, and water, Hydrochloric acid aqueous solution, acetic acid, acetic acid aqueous solution, etc. are similarly 50 to 2000% by weight. Further, when using an aqueous hydrochloric acid solution or an aqueous acetic acid solution, the concentration thereof may be 1 to 30% by weight.The reaction temperature is usually -20 to +50°C, preferably -10 to +10°C, and the reaction time is 0. 1 to 5 hours. If this reaction product is subjected to normal purification and separation operations, the desired chloro (or bromo) can be obtained.
Sulfonyl-substituted pyridine-N-oxide compounds can be separated.
さらに、クロロ（またはブロモ）スルホニル置換ピリジ
ン−Ｎ−オキシド系化合物をアミノ化してアミノスルホ
ニル置換ピリジン−Ｎ−オキシド系化合物を製造するこ
とができる。Furthermore, an aminosulfonyl-substituted pyridine-N-oxide compound can be produced by aminating a chloro(or bromo)sulfonyl-substituted pyridine-N-oxide compound.
（アミノ化反応）
クロロ（またはブロモ）スルホニル置換ピリジン−Ｎ−
オキシド系化合物についても前述の反応生成物から単離
したものを使用してもよいが、その生成物を直接使用し
てもよい。(Amination reaction) Chloro(or bromo)sulfonyl-substituted pyridine-N-
Regarding the oxide compound, one isolated from the above-mentioned reaction product may be used, but the product may also be used directly.
また、このアミノ化反応では、一般にクロロ（またはブ
ロモ）スルホニル置換ピリジン−Ｎ−オキシド系化合物
とアンモニアガスまたはアンモニア水とを反応させる。In this amination reaction, a chloro(or bromo)sulfonyl-substituted pyridine-N-oxide compound and ammonia gas or aqueous ammonia are generally reacted.
このアンモニアの使用■はクロロ（またはブロモ）スル
ボニル置換ピリジン−Ｎ−オキシド系化合物に対し、２
〜５倍モル、望ましくは２．５〜３．５倍モルである。This use of ammonia
~5 times the mole, preferably 2.5 to 3.5 times the mole.
反応温度は普通０〜５０℃であり、反応時間は０．１〜
２時間である。反応後通常の精製、分離操作を施すこと
によって反応生成物からアミノスルホニル置換ピリジン
−Ｎ−オキシド系化合物を４’−離することができる。The reaction temperature is usually 0-50℃, and the reaction time is 0.1-50℃.
It is 2 hours. After the reaction, the aminosulfonyl-substituted pyridine-N-oxide compound can be 4'-separated from the reaction product by performing conventional purification and separation operations.
さらに前記アミ７１スルホニル置換ピリジン−Ｎ−オキ
シド系化合物は３価のリン化合物または金属亜鉛との還
元反応により、あるいは触媒の存在下での接触水素還元
反応により、容易に脱Ｎ−オキシド化反応を行なうこと
ができる。Furthermore, the above-mentioned ami71sulfonyl-substituted pyridine-N-oxide compound can easily undergo a de-N-oxidation reaction by a reduction reaction with a trivalent phosphorus compound or metal zinc, or by a catalytic hydrogen reduction reaction in the presence of a catalyst. can be done.
「実施例」
本発明の製造方法をより詳しく述べるため、以下に実施
例を記載するが、これらは本発明方法を限定するもので
ない。"Examples" Examples are described below to describe the manufacturing method of the present invention in more detail, but these are not intended to limit the method of the present invention.
例
（１）Ｎ−オキシド化反応
２−クロロ−Ｎ、Ｎ−ジメチルニコチンアミド１００ｇ
をトリフルオロ酢酸１００ｍ１に溶解させ、８０〜９０
℃に加熱し、３０％過酸化水素水２４０８を約１時間に
亘って滴下し、トリフルオロ酢酸２００ｎ＋ｊ！を加え
、２時間反応させた。Example (1) N-oxidation reaction 100 g of 2-chloro-N,N-dimethylnicotinamide
was dissolved in 100 ml of trifluoroacetic acid, and 80 to 90
℃, 30% hydrogen peroxide solution 2408 was added dropwise over about 1 hour, and trifluoroacetic acid 200n+j! was added and reacted for 2 hours.
反応終了後、反応溶液中の水およびトリフルオロ酢酸を
減圧下で留去し、シリカゲルカラムクロマ１−グラフィ
ーにより精製を行ない、純度９８％の２−クロロ−Ｎ、
Ｎ−ジメチルニコチンアミド−に純度８５％のそれを５
０．０ｇを得た。After the reaction, water and trifluoroacetic acid in the reaction solution were distilled off under reduced pressure and purified by silica gel column chromatography to obtain 2-chloro-N with a purity of 98%.
N-dimethylnicotinamide with a purity of 85%
0.0g was obtained.
（２）ポリスルフィド化反応および酸処理硫化ナトリウ
ム・９水和物１３．３ｇ、硫黄１．６ｇ及び水１０ｍｆ
を混合し、加熱溶解させて予めポリスルフィドのナトリ
ウム塩を調製した。そこへ前記（１１で得られた純度９
８％の２−クロロ−Ｎ。(2) Polysulfidation reaction and acid treatment Sodium sulfide nonahydrate 13.3g, sulfur 1.6g and water 10mf
A sodium salt of polysulfide was prepared in advance by mixing and heating and dissolving. There, the above (purity 9 obtained in 11)
8% 2-chloro-N.
Ｎ−ジメチルニコチンアミド−１−オキシド１０ｇを加
え、９５℃で２時間反応させた。10 g of N-dimethylnicotinamide-1-oxide was added and reacted at 95°C for 2 hours.
反応終了後、反応物に水３０ｎｊ！および濃塩酸１０ｍ
１を加えて硫黄を析出させ、保温下に濾過を行ない、硫
黄を温水約５０＋ｎｊ！で洗浄し、濾液と洗浄液を合わ
せて２・−メルカプ）−Ｎ、Ｎ−ジメｆ−ルニコチンア
ミドー１−オキシドの水溶液１２０ｍ１を得た。このも
ののｍ、ｐは１１．５．５〜１１８℃であった。After the reaction is complete, add 30nj of water to the reactant! and concentrated hydrochloric acid 10m
1 to precipitate sulfur, filter while keeping warm, and remove sulfur from warm water at about 50+nj! The filtrate and the washing solution were combined to obtain 120 ml of an aqueous solution of 2.-mercap)-N,N-dimef-lnicotinamide 1-oxide. The m and p of this product were 11.5.5 to 118°C.
（３）酸化および塩素化反応
前記（２）で得られた２−メルカプト−Ｎ、Ｎ−ジメチ
ルニコチンアミド−１−オキシドの水溶液１２０１Ｉ１
１を０〜５℃に冷却し、塩素ガスを吸収しなくなるまで
導入しながら反応させた。(3) Oxidation and chlorination reaction Aqueous solution 1201I1 of 2-mercapto-N,N-dimethylnicotinamide-1-oxide obtained in (2) above
1 was cooled to 0 to 5° C. and reacted while introducing chlorine gas until no longer absorbed.
反応終了後、反応物中にエアーバブリングを行ない、過
剰の塩素を除去した後、塩化メチレン６０ｎ＋６および
水６０ｍ／を加えて抽出し、２−クロロスルホニル−Ｎ
、Ｎ−ジメチルニコチンアミド−１−オキシドの塩化メ
チレン溶液６５ｍｊｌ！を得た。このもののｍ、ｐは９
６，５〜１００℃であった。After the reaction was completed, air bubbling was performed in the reaction mixture to remove excess chlorine, followed by extraction with methylene chloride 60n+6 and water 60ml/2-chlorosulfonyl-N.
, 65 mjl of a methylene chloride solution of N-dimethylnicotinamide-1-oxide! I got it. m and p of this are 9
The temperature was 6.5-100°C.
（４）アミノ化反応
前記（３）で得られた２−クロロスルホニル−Ｎ、Ｎ−
ジメチルニコチンアミド−１−オキシドの塩化メチレン
溶液６５ｍＪに２８％アンモニア水１０ｇを滴下しなが
ら反応させた。(4) Amination reaction 2-chlorosulfonyl-N,N- obtained in the above (3)
A reaction was carried out while dropping 10 g of 28% aqueous ammonia to 65 mJ of a methylene chloride solution of dimethylnicotinamide-1-oxide.
反応終了後、反応物を濃塩酸で中和して、生成した結晶
を濾過、乾燥して、２−アミノスルホニル−Ｎ、Ｎ −
ジメチルニコチンアミド−１−オキシド（ｍ、ｐ ：
２１３〜２１５℃）８゜Ｏｇを得た。After the reaction is complete, the reaction product is neutralized with concentrated hydrochloric acid, and the resulting crystals are filtered and dried to give 2-aminosulfonyl-N,N-
Dimethylnicotinamide-1-oxide (m, p:
213-215°C) 8°Og was obtained.
（参考例）脱Ｎ−オキシド化反応
前記（４）で得られる２−アミノスルホニル−Ｎ、Ｎ−
ジメチルニコチンアミド−１−オキシド４ｇ、酢酸２０
ｍｆｆおよび水４ ｍｌを７０〜８０℃に加熱し溶解さ
せ、そこへ亜鉛２ｇを加えて３０分間攪拌しながら反応
させた。(Reference example) De-N-oxidation reaction 2-aminosulfonyl-N,N- obtained in (4) above
4g dimethylnicotinamide-1-oxide, 20g acetic acid
mff and 4 ml of water were heated to 70 to 80°C to dissolve them, 2 g of zinc was added thereto, and the mixture was reacted with stirring for 30 minutes.
反応終了後、反応物を２０％水酸化ナトリウム水溶液で
中和し、不純物を濾別した後、エバポｊ／−ターにより
溶媒を留去し、１５ｍｊ！の氷水を加えて無機塩を溶解
させた。析出した結晶を濾過、乾燥して２−アミノスル
ホニル−Ｎ、Ｎ−ジメチルニコチンアミド２．Ｏｇを得
た。After the reaction was completed, the reaction product was neutralized with a 20% aqueous sodium hydroxide solution, impurities were filtered off, and the solvent was distilled off using an evaporator. of ice water was added to dissolve the inorganic salt. The precipitated crystals were filtered and dried to obtain 2-aminosulfonyl-N,N-dimethylnicotinamide2. Obtained Og.
「発明の効果」
本発明は、従来の方法に比し、反応工程は短かく、比較
的収率も高く、工業的実施に適したアミノスルホニル置
換ピリジン−Ｎ−オキシド系化合物の製造方法であり、
その生成物は農薬、医薬などの原料として有用である。"Effects of the Invention" The present invention is a method for producing aminosulfonyl-substituted pyridine-N-oxide compounds, which has shorter reaction steps and relatively high yields than conventional methods, and is suitable for industrial implementation. ,
The products are useful as raw materials for agricultural chemicals, medicines, etc.
Claims (1)
であり、Ｈａｌはハロゲン原子である）で表わされるハ
ロゲノ置換ピリジン−Ｎ−オキシド系化合物とＭ＿２Ｓ
＿ｘ（式中Ｍはアルカリ金属元素であり、ｘは２〜８で
ある）で表わされるポリスルフィドとを反応させ、酸処
理して、一般式（II） ▲数式、化学式、表等があります▼ （式中Ｒ＿１およびＲ＿２は前述の通りである）で表わ
されるメルカプト置換ピリジン−Ｎ−オキシド系化合物
を生成させ、このものを酸化し塩素化または臭素化して
一般式（III） ▲数式、化学式、表等があります▼ （式中Ｘは塩素原子または臭素原子であり、Ｒ＿１およ
びＲ＿２は前述の通りである）で表わされるクロロ（ま
たはブロモ）スルホニル置換ピリジン−Ｎ−オキシド系
化合物を生成させ、次いでこのものとアンモニアと反応
させ、一般式（IV） ▲数式、化学式、表等があります▼ （式中Ｒ＿１およびＲ＿２は前述の通りである）で表わ
されるアミノスルホニル置換ピリジン−Ｎ−オキシド系
化合物を製造することを特徴とする置換ピリジン−Ｎ−
オキシド系化合物の製造方法。[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 are hydrogen atoms or alkyl groups, and Hal is a halogen atom.) Halogeno-substituted pyridine- N-oxide compounds and M_2S
It is reacted with polysulfide represented by _x (in the formula, M is an alkali metal element, and x is 2 to 8) and treated with acid to form the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( A mercapto-substituted pyridine-N-oxide compound represented by the formula (R_1 and R_2 are as described above) is produced, and this compound is oxidized and chlorinated or brominated to form the general formula (III) ▲ Numerical formula, chemical formula, table etc. ▼ (wherein X is a chlorine atom or a bromine atom, and R_1 and R_2 are as described above) is produced, and then this and ammonia to produce an aminosulfonyl-substituted pyridine-N-oxide compound represented by the general formula (IV) ▲Mathematical formula, chemical formula, table, etc.▼ (in the formula, R_1 and R_2 are as described above) A substituted pyridine-N- characterized in that
A method for producing an oxide compound.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7277188A JPH01246262A (en) | 1988-03-26 | 1988-03-26 | Production of substituted pyridine-n-oxide based compound |
| CA000571150A CA1301761C (en) | 1987-07-10 | 1988-07-05 | Mercapto-substituted pyridine compounds and process for preparing the same |
| ES92117140T ES2068663T3 (en) | 1987-07-10 | 1988-07-07 | PROCEDURE FOR THE PREPARATION OF PIRIDINE COMPOUNDS SUBSTITUTED WITH HALOGENOSULFONIL. |
| DE3887579T DE3887579T2 (en) | 1987-07-10 | 1988-07-07 | Mercapto-substituted pyridines and process for their preparation. |
| ES88306238T ES2061657T3 (en) | 1987-07-10 | 1988-07-07 | SUBSTITUTED PYRIDINE MERCAPT COMPOUND AND PROCEDURE FOR ITS PREPARATION. |
| AT92117140T ATE115567T1 (en) | 1987-07-10 | 1988-07-07 | PROCESS FOR THE PREPARATION OF HALOGENSULFONYL-SUBSTITUTED PYRIDINES. |
| AT88306238T ATE101135T1 (en) | 1987-07-10 | 1988-07-07 | MERCAPTO-SUBSTITUTED PYRIDINES AND PROCESS FOR THEIR PREPARATION. |
| EP92117140A EP0532058B1 (en) | 1987-07-10 | 1988-07-07 | Process for preparing halogenosulfonyl-substituted pyridine compounds |
| EP88306238A EP0298752B1 (en) | 1987-07-10 | 1988-07-07 | Mercapto-substituted pyridine compounds and process for preparing the same |
| DE3852506T DE3852506T2 (en) | 1987-07-10 | 1988-07-07 | Process for the preparation of halosulfonyl substituted pyridines. |
| US07/471,337 US5168113A (en) | 1987-07-10 | 1990-01-29 | Mercapto-substituted pyridine compounds |
| US07/558,545 US5128474A (en) | 1987-07-10 | 1990-07-27 | Mercapto-substituted pyridine compounds, aminocarbonyl-substituted pyridinesulfinic acid compounds and process for preparing the same |
| GR940404068T GR3015273T3 (en) | 1987-07-10 | 1995-03-03 | Process for preparing halogenosulfonyl-substituted pyridine compounds. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7277188A JPH01246262A (en) | 1988-03-26 | 1988-03-26 | Production of substituted pyridine-n-oxide based compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01246262A true JPH01246262A (en) | 1989-10-02 |
Family
ID=13498972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7277188A Pending JPH01246262A (en) | 1987-07-10 | 1988-03-26 | Production of substituted pyridine-n-oxide based compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01246262A (en) |
-
1988
- 1988-03-26 JP JP7277188A patent/JPH01246262A/en active Pending
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