JPH01216973A - Production of substituted pyridine based compound - Google Patents
Production of substituted pyridine based compoundInfo
- Publication number
- JPH01216973A JPH01216973A JP4126988A JP4126988A JPH01216973A JP H01216973 A JPH01216973 A JP H01216973A JP 4126988 A JP4126988 A JP 4126988A JP 4126988 A JP4126988 A JP 4126988A JP H01216973 A JPH01216973 A JP H01216973A
- Authority
- JP
- Japan
- Prior art keywords
- substituted pyridine
- formula
- based compound
- acid
- pyridine based
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 150000003222 pyridines Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 bromosulfonyl-substituted pyridine Chemical class 0.000 claims abstract description 37
- 239000005077 polysulfide Substances 0.000 claims abstract description 10
- 229920001021 polysulfide Polymers 0.000 claims abstract description 10
- 150000008117 polysulfides Polymers 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 240000008042 Zea mays Species 0.000 abstract description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 abstract description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 235000005822 corn Nutrition 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000004009 herbicide Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-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
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 238000005576 amination reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 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
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KELIOKHMUGLVGR-UHFFFAOYSA-N n,n-diethyl-2-sulfanylidene-1h-pyridine-3-carboxamide Chemical compound CCN(CC)C(=O)C1=CC=CN=C1S KELIOKHMUGLVGR-UHFFFAOYSA-N 0.000 description 2
- HYVMZYDJQLKOGW-UHFFFAOYSA-N n,n-dimethyl-2-sulfanylidene-1h-pyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1S HYVMZYDJQLKOGW-UHFFFAOYSA-N 0.000 description 2
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 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
- 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
- MPQHBWNDIOJYNP-UHFFFAOYSA-N 2,6-dimethylpyridine-3-carboxamide Chemical compound CC1=CC=C(C(N)=O)C(C)=N1 MPQHBWNDIOJYNP-UHFFFAOYSA-N 0.000 description 1
- GYXAUHYQIVWTPI-UHFFFAOYSA-N 3-(dimethylcarbamoyl)pyridine-2-sulfonyl bromide Chemical compound CN(C)C(=O)C1=CC=CN=C1S(Br)(=O)=O GYXAUHYQIVWTPI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000031709 bromination 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- WYFKZPLSYVJLRB-UHFFFAOYSA-N n,n-dimethyl-2-sulfamoylpyridine-3-carboxamide Chemical compound CN(C)C(=O)C1=CC=CN=C1S(N)(=O)=O WYFKZPLSYVJLRB-UHFFFAOYSA-N 0.000 description 1
- YEHJZXOSWCPETN-UHFFFAOYSA-N n,n-dimethyl-2-sulfanylidene-1h-pyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC=NC(S)=C1 YEHJZXOSWCPETN-UHFFFAOYSA-N 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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置換ピリ
ジン系化合物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a method for producing substituted pyridine compounds useful as raw materials for agricultural chemicals, medicines, and the like.
「先行技術及び本発明に至った経緯」
本発明は、１ケ又は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並びにブロモスルホニル基を
存する置換ピリジン系化合物の工業的有利な製造方法に
関する。"Prior Art and Background of the Present Invention" The present invention provides an industrially advantageous method for producing substituted pyridine compounds containing an aminocarbonyl group and a bromosulfonyl group which may be substituted with one or two alkyl groups. Regarding.
前記置換ピリジン系化合物は特開昭５９−３９８７８及
び同５９−９８０６６の各公報において広く一般式で示
されていることにより、概念的には知られている。しか
しながら前記化合物は各公報中には何ら具体的に開示さ
れていない。また、成る置換ピリジン系化合物は米国特
許第３．７５９．９３２号及び同第４．４３５，２０６
号各明細書に記載されているが、該明細書にはピリジン
環に前述のアミノカルボニル基を有する前記置換ピリジ
ン系化合物は記載されていない。The above-mentioned substituted pyridine compounds are conceptually known as they are broadly represented by general formulas in JP-A-59-39878 and JP-A-59-98066. However, the above compound is not specifically disclosed in each publication. In addition, the substituted pyridine compounds are disclosed in U.S. Patent Nos. 3.759.932 and 4.435,206.
However, the substituted pyridine compounds having the above-mentioned aminocarbonyl group in the pyridine ring are not described in these specifications.
本発明者等は、特開昭６２−１７８５８８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〕−
３−ジアルキルアミノカルボニル−２−ピリジンスルホ
ンアミドの原料として前記置換ピリジン系化合物が有用
であることに着目し、その工業的かつ経済的に有利な製
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]- for corn fields described in JP-A-62-178588.
Focusing on the usefulness of the above-mentioned substituted pyridine compounds as raw materials for 3-dialkylaminocarbonyl-2-pyridinesulfonamide, in order to find an industrially and economically advantageous production method, we have carried out production using various methods. Although attempts were made to produce the product satisfactorily, it was found that the desired effect could be obtained by the production method of the present invention.
「発明の開示」
本発明は、
一般式（Ｉ）
（式中Ｒ１及びＲ１は水素原子又はアルキル基であり、
Ｈａｌはハロゲン原子である）で表わされるハロゲノ置
換ピリジン系化合物とＭ、Ｓ、 （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、これを酸処理して、一般式（Ｉ
Ｉ）
（式中Ｒ３及び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系化合物及びその塩を生成させ
、次いでこのものを酸化及び臭素化して一般式（Ｉ［Ｉ
）
（式中Ｒ１及びＲ２は前述の通りである）で表わされる
ブロモスルホニル置換ピリジン系化合物を製造する方法
である。"Disclosure of the Invention" The present invention is based on the general formula (I) (wherein R1 and R1 are hydrogen atoms or alkyl groups,
A halogeno-substituted pyridine compound represented by (Hal is a halogen atom) is reacted with a polysulfide represented by M, S, (wherein M is an alkali metal element and X is 2 to 8). After acid treatment, the general formula (I
I) A mercapto-substituted pyridine compound and its salt represented by the formula (in which R3 and R2 are as described above) is produced, and then this is oxidized and brominated to form the general formula (I[I
) (wherein R1 and R2 are as described above) is a method for producing a bromosulfonyl-substituted pyridine compound.
前記一般式（Ｉ）〜（Ｉ［［）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る。The alkyl groups for R1 and R2 in the general formulas (I) to (I[[) include those having 1 to 6 carbon atoms, such as a methyl group,
Examples include ethyl group, propyl group, butyl group.
また、前記一般式（ｎ）のメルカプト置換ピリジン系化
合物の塩としては具体的にはメルカプト置換ピリジン系
化合物とリチウム、ナトリウム、カリウムなどのアルカ
リ金属元素との塩が挙げられる。Further, specific examples of the salt of the mercapto-substituted pyridine compound of the general formula (n) include salts of the mercapto-substituted pyridine compound and an alkali metal element such as lithium, sodium, or potassium.
本発明では、ハロゲノ置換ピリジン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及び酸処理
によりメルカプト置換ピリジン系化合物を製造し、次い
でこのものを酸化及び臭素化反応に供することにより目
的のブロモスルホニル置換ピリジン系化合物を製造する
ことができる。In the present invention, a mercapto-substituted pyridine compound is produced by a polysulfidation reaction in which a halogeno-substituted pyridine compound and a polysulfide are reacted and an acid treatment, and then this compound is subjected to an oxidation and bromination reaction to produce the desired bromosulfonyl-substituted pyridine. based compounds can be produced.
（ポリネルフィト化反応）
このハロゲノ置換ピリジン系化合物にフいては例えばハ
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又は６位に存在し
たものが望ましく、なかでもクロロ又はブロモ置換ピリ
ジン系化合物が望ましい、またポリスルフィドについて
は、アルカリ金属の水酸化物及びその水硫化物の混合物
或はアルカリ金属の硫化物に対し、その１〜７倍モル望
ましくは１〜２倍モルの硫黄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、これらをハロゲノ
置換ピリジン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、その水硫化物又は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、アルカリ金属の水酸化物
、その水硫化物又は硫化物の使用量はハロゲノ置換ピリ
ジン系化合物に対し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ユリト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系化合
物に対し通常１０〜１０００重量％、望ましくは１０〜
１００重量％である。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θ℃〜還流温度、望ま
しくは１００〜１５０℃、圧力は常圧〜数気圧、反応時
間は一般に０．５〜５時間である。(Polynelphitization reaction) This halogeno-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 compounds are preferably those in which a halogen atom is present at the 2.4 or 6-position of the pyridine ring, and chloro- or bromo-substituted pyridine compounds are particularly desirable.As for polysulfides, alkali metal hydroxides and A mixture of hydrosulfides or alkali metal sulfides may be reacted with sulfur in an amount of 1 to 7 times, preferably 1 to 2 times, by a conventional method. The alkali metal hydroxide, hydrosulfide or sulfide of the alkali metal may be lithium. , sodium, potassium, etc. Among them, sodium is preferred, and the amount of the alkali metal hydroxide, hydrosulfide or sulfide used is 0.75 to 5 times the mole of the halogeno-substituted pyridine compound, preferably 1
~1.5 times the mole. 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, and uritors such as acetonitrile can be used. The amount of this solvent used is usually 10 to 1000% by weight, preferably 10 to 1000% by weight, based on the halogeno-substituted pyridine compound.
It is 100% by weight. Other reaction conditions for this reaction cannot be absolutely specified, but the reaction temperature is usually θ℃ to reflux temperature, preferably 100 to 150℃, the pressure is normal pressure to several atmospheres, and the reaction time is generally 0.5 to 5 hours. be.
（酸処理）
この反応ではメルカプト置換ピリジン系化合物は通常ポ
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
系化合物を単離することができる。(Acid treatment) In this reaction, the mercapto-substituted pyridine 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 compound is liberated and hydrogen sulfide gas is generated. , 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 compounds can be isolated.
（酸化及び臭素化反応）
このメルカプト置換ピリジン系化合物及びその塩につい
てはポリスルフィ゛ド化反応及び酸処理の生成物に精製
、分離操作を加え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 and Bromination Reactions) Regarding the mercapto-substituted pyridine compounds and their salts, the products obtained by purifying and separating the products of the polysulfidization reaction and acid treatment may be used. may be used directly.
また、この酸化及び臭素化方法としては、一般にこのメ
ルカプト置換ピリジン系化合物及びその塩に対して臭素
を水、塩酸水溶液、酢酸或いは酢酸水溶液の存在下に反
応させる方法、次亜臭素酸塩を水或いは塩酸水溶液の存
在下に反応させる方法などが挙げられるが、前者の方法
がより望ましい。これらにおいて非プロトン性有機溶媒
を使用すると反応の後処理が筒便になって好ましい。そ
の溶媒としては例えばベンゼン、ヘキサン、トルエン、
キシレン、塩化メチレン、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、酢酸エチルなどが挙げられ、その使用量はハロゲノ
置換ピリジン系化合物に対し、普通、５０〜２０００重
量％である。The oxidation and bromination methods generally include a method in which the mercapto-substituted pyridine compound and its salt are reacted with bromine in the presence of water, aqueous hydrochloric acid, acetic acid, or an aqueous acetic acid solution, and a method in which hypobromite is reacted with water. Alternatively, there may be a method in which the reaction is carried out in the presence of an aqueous hydrochloric acid solution, but the former method is more desirable. In these cases, it is preferable to use an aprotic organic solvent because it makes post-treatment of the reaction more convenient. Examples of the solvent include benzene, hexane, toluene,
xylene, methylene chloride, chloroform, carbon tetrachloride,
Examples include ethylene dichloride, trichloroethylene, diethyl ether, and ethyl acetate, and the amount used is usually 50 to 2000% by weight based on the halogeno-substituted pyridine compound.
これらの方法において、臭素、次亜臭素酸などの使用量
はメルカプト置換ピリジン系化合物及びその塩に対し反
応理論量乃至それを若干上潮る量であり、また水、塩酸
水溶液、酢酸、酢酸水溶液などのそれは同様に５０〜２
０００重景％である置部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。これらの方法において、他の反応条件は
一概に規定できないが、反応温度は普通−２０〜＋５０
°Ｃ１望ましくは一１０〜＋１０°Ｃ１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ブロモスルホニル置換ピリジン系化
合物を分離することができる。In these methods, the amount of bromine, hypobromous acid, etc. used is the reaction stoichiometric amount or an amount slightly higher than the stoichiometric amount for the mercapto-substituted pyridine compound and its salt, and water, aqueous hydrochloric acid, acetic acid, acetic acid aqueous solution, etc. etc. it is similarly 50~2
When using an aqueous hydrochloric acid solution or aqueous acetic acid solution having a concentration of 0.000% by weight, the concentration thereof may be 1 to 30% by weight. In these methods, other reaction conditions cannot be absolutely specified, but the reaction temperature is usually -20 to +50
°C1 desirably -10 to +10 °C1 reaction time is 0.
1 to 5 hours. By subjecting this reaction product to conventional purification and separation operations, the desired bromosulfonyl-substituted pyridine compound can be separated.
本発明によって製造でき、前記−数式（Ｕ）及び（ＩＩ
Ｉ）で表わされる化合物の代表例を下記する。can be produced according to the present invention, and the formulas (U) and (II
Representative examples of the compound represented by I) are shown below.
化合物Ｎα１２−メルカプト−Ｎ、Ｎ−ジメチルニコチ
ンアミド ｍ、ｐ、 ２１４〜２１５°Ｃ〃 Ｎα２
２−メルカプト−Ｎ、Ｎ−ジメチルニコチンアミドのナ
トリウム塩
ｍ、ｐ、 ２６７〜２７１°Ｃ
〃 漱３２−ブロモスルホニル−Ｎ、Ｎ−ジメチルニコ
チンアミド
ｍ、ｐ、 １０８〜１１１℃
〃 Ｎα４２−メルカプト ニコチンアミドｓ＋、ｐ、
２４７〜２４９°Ｃ
〃 Ｎα５２−メルカプト ニコチンアミドのナトリウ
ム塩
〃 Ｎα６ Ｎ、Ｎ−ジエチル−２−メルカプトニコ
チンアミド ｍ、ｐ、 ２０７〜２１０°Ｃ化合物Ｎ
α７ Ｎ、Ｎ−ジエチル−２−メルカプトニコチンア
ミドのナトリウム塩
〃 Ｎα８２−７’ロモスルホニルーＮ、Ｎ−ジエチル
ニコチンアミド
〃 Ｎα９２−メルカプト−Ｎ−メチルニコチンアミド
ｍ、ｐ、 ２２５〜２２９°Ｃ〃 Ｎα１０
４−（Ｎ、Ｎ−ジメチルアミノカルボニル）−２−メル
カプトピリジン
前記−数式（Ｉ［［）で表わされる化合物は前述の通り
トウモロコシ畑用除草剤として有用なピリジンスルホン
アミド系化合物に容易に誘導することができる。例えば
前記−数式（Ｉｔ）で表わされるブロモスルホニル置換
ピリジン系化合物は−１０〜＋１００“Ｃでアンモニア
ガス又はアンモニア水と反応させてアミノスルホニル置
換ピリジン系化合物に誘導し、更にこのものに２−イソ
シアネート又は２−クロロカルボニルアミノ−４，６−
シメトキシピリミジンを一１０〜＋１００°Ｃで反応さ
せることによって、前記ピリジンスルホンアミド系化合
物に容易に誘導することができる。このピリジンスルホ
ンアミド系化合物は１アール当り０、１〜１００ｇ使用
すれば、各種有害雑草を良好に防除することができ、特
にトウモロコシに対しては安全性が高いのでトウモロコ
シ畑用除草剤として有用である。Compound Nα12-mercapto-N,N-dimethylnicotinamide m, p, 214-215°C〃 Nα2
Sodium salt of 2-mercapto-N,N-dimethylnicotinamide m, p, 267-271°C 〃 32-bromosulfonyl-N,N-dimethylnicotinamide m, p, 108-111°C〃 Nα42-mercapto Nicotine Amide s+, p,
247-249°C 〃 Nα52-Mercapto Sodium salt of nicotinamide〃 Nα6 N, N-diethyl-2-mercaptonicotinamide m, p, 207-210°C Compound N
α7 Sodium salt of N,N-diethyl-2-mercaptonicotinamide〃 Nα82-7'lomosulfonyl-N,N-diethylnicotinamide〃 Nα92-Mercapto-N-methylnicotinamide m, p, 225-229°C〃 Nα10
4-(N,N-dimethylaminocarbonyl)-2-mercaptopyridine The compound represented by the above-mentioned formula (I be able to. For example, the bromosulfonyl-substituted pyridine compound represented by formula (It) above is reacted with ammonia gas or aqueous ammonia at -10 to +100"C to form an aminosulfonyl-substituted pyridine compound, and this is further treated with 2-isocyanate. or 2-chlorocarbonylamino-4,6-
By reacting cymethoxypyrimidine at -10 to +100°C, the pyridine sulfonamide compound can be easily derived. This pyridine sulfonamide compound can effectively control various noxious weeds when used at 0.1 to 100 g per are, and is particularly safe for corn, so it is useful as a herbicide for corn fields. be.
次に本発明の実施例並びにアミノスルホニル置換ピリジ
ン系化合物の製造例を記載する。Next, Examples of the present invention and production examples of aminosulfonyl-substituted pyridine compounds will be described.
例−１
（ポリスルフィド化反応）
純度７０％の水硫化ナトリウム２４ｇ（０，３モル）、
硫黄９．６ｇ（０，３モル）、水酸化ナトリウム１２ｇ
（０，３モル）及び水１５ｍ！！を加熱下に還流し、硫
黄が完全に溶解して、均一な溶液になった時点で、２−
クロロ−Ｎ、Ｎ−ジメチルニコチンアミド５５．４ｇ（
０，３モル）を加え、２時間加熱下に還流（Ｉ２５℃）
してＮ、Ｎ−ジメチルニコチンアミド−２−ポリスルフ
ィドのナトリウム塩を生成させた。Example-1 (Polysulfidation reaction) 24 g (0.3 mol) of sodium bisulfide with a purity of 70%,
9.6 g (0.3 mol) of sulfur, 12 g of sodium hydroxide
(0,3 mol) and 15 m of water! ! 2-
Chloro-N,N-dimethylnicotinamide 55.4g (
0.3 mol) was added and heated under reflux (I25°C) for 2 hours.
The sodium salt of N,N-dimethylnicotinamide-2-polysulfide was produced.
（酸処理）
この生成物を室温まで放冷した後、水１５０ｍβを加え
、製塩酸約３０ｍ１を滴下してｐＨ２とした（この時硫
化水素が発生、硫黄が沈殿した）０滴下終了後、６０〜
７０°Ｃで３０分間撹拌した後保温下で硫黄を濾別し温
水１５０１Ｉ１１で残渣を洗浄し、２−メルカプト−Ｎ
、Ｎ−ジメチルニコチンアミドを含む濾液と洗浄液とを
得た。(Acid treatment) After cooling this product to room temperature, 150 mβ of water was added, and approximately 30 ml of hydrochloric acid was added dropwise to adjust the pH to 2 (hydrogen sulfide was generated and sulfur was precipitated at this time). ~
After stirring at 70°C for 30 minutes, sulfur was filtered off while keeping warm, the residue was washed with warm water 1501I11, and 2-mercapto-N
A filtrate and a washing liquid containing N-dimethylnicotinamide were obtained.
（酸化及び臭素化反応）
この濾液及び洗浄液を、食塩と氷とを混合したものによ
り冷却し、撹拌下５°Ｃ以下で臭素１４７ｇ（０，９２
モル）を滴下した後、冷水１００ｍＮを投入し、−５°
Ｃで１時間撹拌した０反応生成物を冷却した塩化メチレ
ン７００ｍＮで抽出し、２−ブロモスルホニル−Ｎ、Ｎ
−ジメチルニコチンアミドを含む抽出液を得た。(Oxidation and Bromination Reaction) The filtrate and washing liquid were cooled with a mixture of common salt and ice, and 147 g of bromine (0.92 g.
After dropping 100 mN of cold water, -5°
The reaction product was stirred for 1 hour at C and extracted with 700 mN of cold methylene chloride to give 2-bromosulfonyl-N,
- An extract containing dimethylnicotinamide was obtained.
（アミノ化反応）
上記の抽出液を撹拌下に冷却し、この中へ１０°Ｃ以下
で２８％のアンモニア水８７ｇ（Ｉ，４３モル）を滴下
し、更に室温で０．５時間撹拌し冷水１００ｍＡを加え
１０°Ｃ以下で濃塩酸を加えてρ１（３とした０反応物
を濾過、乾燥することにより２−アミツスルホニルーＮ
、Ｎ−ジメチルニコチンアミド５２．Ｏｇ（収率７５．
７％）を得た。(Amination reaction) The above extract was cooled with stirring, and 87 g (I, 43 mol) of 28% aqueous ammonia was added dropwise at 10°C or below, and the mixture was further stirred at room temperature for 0.5 hours, followed by cold water. Add 100 mA and add concentrated hydrochloric acid at below 10°C to make ρ1 (3). By filtering and drying the reaction product, 2-amitsusulfonyl-N
, N-dimethylnicotinamide 52. Og (yield 75.
7%).
例−２
前記例−１の酸化及び臭素化反応を下記の通り変更した
。２−メルカ７゛トーＮ、Ｎ−ジメチルニコチンアミド
５４．６ｇ（０，３モル）を水３００１Ｉｌｌに懸濁さ
せ、撹拌下に冷却して一６°Ｃ〜０°Ｃで臭素１４４ｇ
（０，９モル）を滴下した。滴下後前起倒１の場合と同
様に精製して２−ブロモスルホニル−Ｎ、Ｎ−ジメチル
ニコチンアミドを含む塩化メチレン溶液を得た。この塩
化メチレン溶液を氷水３００ ｍｌ及び１％のチオ硫酸
ナトリウム冷却水溶液２００ｎ／！、で洗浄し、内温３
０°Ｃ以下で塩化メチレンを留去し、真空乾燥後７６ｇ
の生成物を得た。この生成物を、加温したエチレンジク
ロライドに溶解し、ｎ−ヘキサンで再結晶して ｍ、ｐ
。Example 2 The oxidation and bromination reactions in Example 1 were changed as follows. 54.6 g (0.3 mol) of 2-merka7'-N,N-dimethylnicotinamide were suspended in 3001 Ill of water and cooled with stirring to give 144 g of bromine at -6°C to 0°C.
(0.9 mol) was added dropwise. After dropping, the mixture was purified in the same manner as in 1 to obtain a methylene chloride solution containing 2-bromosulfonyl-N,N-dimethylnicotinamide. This methylene chloride solution was mixed with 300 ml of ice water and 200 n/! of a cooled 1% sodium thiosulfate aqueous solution. , wash at internal temperature 3
Methylene chloride was distilled off at below 0°C, and after vacuum drying, 76g
of product was obtained. This product was dissolved in heated ethylene dichloride and recrystallized from n-hexane to give m, p
.
１０８〜１１１°Ｃの２−ブロモスルホニル−Ｎ、 Ｎ
−ジメチルニコチンアミド６４ｇ（収率７２．８％）を
得た。2-bromosulfonyl-N, N at 108-111 °C
-Dimethylnicotinamide 64g (yield 72.8%) was obtained.
例−３
（ポリスルフィド化反応）
２−クロロ−Ｎ、Ｎ−ジメチルニコチンアミド５５゜４
ｇ、純度７０％の水硫化ナトリウム２４ｇ、硫黄９，６
ｇ、水酸化ナトリウム１２ｇ及び水１５ｍ１を撹拌下に
約２時間加熱還流させ、Ｎ、Ｎ−ジメチルニコチンアミ
ド−２−ポリスルフィドのナトリウム塩を生成させた。Example-3 (Polysulfidation reaction) 2-chloro-N,N-dimethylnicotinamide 55°4
g, 70% purity sodium bisulfide 24 g, sulfur 9,6
12 g of sodium hydroxide and 15 ml of water were heated under reflux for about 2 hours with stirring to produce the sodium salt of N,N-dimethylnicotinamide-2-polysulfide.
（酸処理）
この生成物に水１５０ｍｊｌ！及び５０％の硫酸水溶液
３０ｍ１を加え、６０〜７０°Ｃで３０分間撹拌させ、
析出した硫黄を保温下に濾別した。温水１００ｍｆで硫
黄を洗浄し、濾液と洗浄液とを合わせて、２−メルカプ
ト−Ｎ、Ｎ−ジメチルニコチンアミドを含む溶液を得た
。(Acid treatment) Add 150 mjl of water to this product! and 30 ml of 50% sulfuric acid aqueous solution, stirred at 60-70°C for 30 minutes,
The precipitated sulfur was filtered off while keeping it warm. Sulfur was washed with 100 mf of warm water, and the filtrate and washing liquid were combined to obtain a solution containing 2-mercapto-N,N-dimethylnicotinamide.
（酸化及び臭素化反応）
この溶液を０°Ｃ以下に冷却し、塩化メチレン３５０１
Ｉｌｉを加え、臭素１４４ｇを約２０分間かけて滴下し
塩化メチレン層を分取して２−ブロモスルホニル−Ｎ、
Ｎ−ジメチルニコチンアミドの塩化メチレン溶液を得た
。(Oxidation and bromination reaction) This solution was cooled to below 0°C, and methylene chloride 3501
Ili was added, 144 g of bromine was added dropwise over about 20 minutes, the methylene chloride layer was separated, and 2-bromosulfonyl-N,
A methylene chloride solution of N-dimethylnicotinamide was obtained.
（アミノ化反応）
上記の塩化メチレン溶液を１０°Ｃ以下に冷却しながら
、この中へ２８％のアンモニア水５０ｇを滴下し、室温
で３０分間撹拌し、更に水１００ｍｆ及び５０％の硫酸
水溶液１０ｎｌを加えた後、析出した結晶を濾取し、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５６． Ｏｇ（収率８１．５％）を得た。(Amination reaction) While cooling the above methylene chloride solution to below 10°C, 50 g of 28% ammonia water was added dropwise thereto, stirred at room temperature for 30 minutes, and further added with 100 mf of water and 10 nl of 50% aqueous sulfuric acid solution. was added, the precipitated crystals were collected by filtration and dried to give 2-aminosulfonyl-N,N-dimethylnicotinamide 56. Og (yield 81.5%) was obtained.
「発明の効果」
本発明方法によれば、安価なハロゲノ置換ピリジン系化
合物を出発原料として筒便な方法によりブロモスルホニ
ル置換ピリジン系化合物を製造することができ、経済的
に有利でかつ工業的実施に適した方法である。また本発
明方法で製造されるブロモスルホニル置換ピリジン系化
合物は、トウモロコシ畑用除草剤の原料として有用であ
る。"Effects of the Invention" According to the method of the present invention, a bromosulfonyl-substituted pyridine compound can be produced by a convenient method using an inexpensive halogeno-substituted pyridine compound as a starting material, and is economically advantageous and industrially practical. This method is suitable for Further, the bromosulfonyl-substituted pyridine compound produced by the method of the present invention is useful as a raw material for a herbicide for corn fields.
Claims (1)
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、これを酸処理して、一般
式（II） ▲数式、化学式、表等があります▼ （式中Ｒ＿１及び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系化合物及びその塩を生成
させ、次いでこのものを酸化及び臭素化して一般式（I
II） ▲数式、化学式、表等があります▼ （式中Ｒ＿１及びＲ＿２は前述の通りである）で表わさ
れるプロモスルホニル置換ピリジン系化合物を製造する
ことを特徴とする置換ピリジン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 system The compound is reacted with polysulfide represented by M_2S_x (in the formula, M is an alkali metal element, and x is 2 to 8), and this is treated with an acid to form the general formula (II) ▲Mathematical formula, chemical formula, table, etc. A mercapto-substituted pyridine compound represented by the formula (wherein R_1 and R_2 are as described above) and its salt are produced, and then this is oxidized and brominated to form the general formula (I
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method for producing a substituted pyridine compound, which is characterized by producing a promosulfonyl-substituted pyridine compound represented by the following (in the formula, R_1 and R_2 are as described above).
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4126988A JPH01216973A (en) | 1988-02-24 | 1988-02-24 | Production of substituted pyridine based compound |
| CA000571150A CA1301761C (en) | 1987-07-10 | 1988-07-05 | Mercapto-substituted pyridine compounds and process for preparing the same |
| AT92117140T ATE115567T1 (en) | 1987-07-10 | 1988-07-07 | PROCESS FOR THE PREPARATION OF HALOGENSULFONYL-SUBSTITUTED PYRIDINES. |
| 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. |
| EP88306238A EP0298752B1 (en) | 1987-07-10 | 1988-07-07 | Mercapto-substituted pyridine compounds and process for preparing the same |
| AT88306238T ATE101135T1 (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. |
| DE3852506T DE3852506T2 (en) | 1987-07-10 | 1988-07-07 | Process for the preparation of halosulfonyl substituted pyridines. |
| EP92117140A EP0532058B1 (en) | 1987-07-10 | 1988-07-07 | Process for preparing halogenosulfonyl-substituted pyridine compounds |
| 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 |
|---|---|---|---|
| JP4126988A JPH01216973A (en) | 1988-02-24 | 1988-02-24 | Production of substituted pyridine based compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01216973A true JPH01216973A (en) | 1989-08-30 |
Family
ID=12603722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4126988A Pending JPH01216973A (en) | 1987-07-10 | 1988-02-24 | Production of substituted pyridine based compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01216973A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014504289A (en) * | 2010-12-14 | 2014-02-20 | ロレアル | Method for removing pigments of keratin components using thiopyridinone compounds |
-
1988
- 1988-02-24 JP JP4126988A patent/JPH01216973A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014504289A (en) * | 2010-12-14 | 2014-02-20 | ロレアル | Method for removing pigments of keratin components using thiopyridinone compounds |
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