EP0934275A1 - Thiopyridines substituees - Google Patents

Thiopyridines substituees

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Publication number
EP0934275A1
EP0934275A1 EP97944808A EP97944808A EP0934275A1 EP 0934275 A1 EP0934275 A1 EP 0934275A1 EP 97944808 A EP97944808 A EP 97944808A EP 97944808 A EP97944808 A EP 97944808A EP 0934275 A1 EP0934275 A1 EP 0934275A1
Authority
EP
European Patent Office
Prior art keywords
substituted
thiopyridines
nitro
chloro
alkyl
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.)
Withdrawn
Application number
EP97944808A
Other languages
German (de)
English (en)
Inventor
Gerhard Hamprecht
Joachim Gebhardt
Heinz Isak
Michael Rack
Joachim Rheinheimer
Peter Schäfer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0934275A1 publication Critical patent/EP0934275A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached

Definitions

  • the invention relates to new thiopyridines of the general formula I.
  • R 1 chlorine, -CC 3 fluoroalkyl, nitro or methylsulfonyl
  • R 2 is an unsubstituted or substituted by halogen, C 1 -C 4 alkoxy, C ⁇ -C 4 alkoxycarbonyl, di- (C ⁇ -C4-alkylamino) carbonyl, cyano or nitro-substituted Ci-Cio-alkyl, C 2 - C ⁇ 0 alkenyl or C 2 ⁇ c ⁇ o -A -lkinylrest, a C 3 -C 8 cycloalkyl group, a Phe in nylteil unsubstituted or substituted by halogen, C ⁇ -C 3 -alkyl, C 3 alkoxy, tri luormethyl, cyano or nitro substituted -CC 4 alkylenephenyl, phenyl or naphthyl radical mean.
  • halogen C 1 -C 4 alkoxy, C ⁇ -C 4 alkoxycarbonyl, di- (C ⁇ -C4-alkylamino) carbony
  • the invention further relates to processes for their preparation and their use as intermediates for the production of crop protection agents having a herbicidal action, as are known from WO-A-95/02580. Furthermore, the invention relates to the pyridine thioethers of the formula Ia suitable as intermediates for the preparation of the thiopyridines I.
  • thiopyridines mentioned in the abovementioned documents are used as herbicides or fungicides or intermediates for herbicides, the function responsible for the herbicidal action in the end molecule being built up in each case via the thio substituent, which thus remains in the end molecule.
  • the object of the present invention was to find new thiopyridine derivatives which are suitable as coupling components for the preparation of substituted phenylpyridines, as described in WO-A-95/02580.
  • the thio substituent acts as a leaving group here.
  • Another object was to find a process which makes the desired thiopyridines accessible in good yields. Accordingly, the thiopyridines of the general formula I defined at the outset were found
  • R 1 chlorine, -CC 3 fluoroalkyl, nitro or methylsulfonyl
  • R 2 is an unsubstituted or substituted by halogen, C 1 -C 4 alkoxy, C ⁇ -C 4 alkoxycarbonyl, di- (C ⁇ -C4-alkylamino) carbonyl, cyano or nitro-substituted Ci-Cio-alkyl, C 2 - C ⁇ o-alkenyl or C -C 10 alkynyl radical, a C 3 -C 8 cycloalkyl radical, one unsubstituted in the phenyl part or substituted by halogen, Cx-Cs-alkyl, C ⁇ -C 3 alkoxy, trifluoromethyl, cyano or nitro -CC alkylene phenyl, phenyl or naphthyl radical mean.
  • halogen C 1 -C 4 alkoxy, C ⁇ -C 4 alkoxycarbonyl, di- (C ⁇ -C4-alkylamino) carbonyl, cyano or nitro-substi
  • substituent R 2 in the formula I represent collective terms for individual lists of the individual group members. All carbon chains, that is to say all alkyl, alkenyl, alkynyl or alkoxy parts, can be straight-chain or branched. Halogenated substituents preferably carry 1-6 identical or different halogen atoms. Specifically, for example:
  • Fluorine, chlorine, bromine and iodine preferably fluorine and chlorine
  • Fluorine, chlorine, bromine and iodine preferably fluorine and chlorine
  • Ethynyl and C 3 -C 6 ⁇ alkynyl such as prop-1-in-l-yl, * prop-2-in-3-yl, n-but-1-in-l-yl, n-but-l-in -4-yl, n-but-2-in-1-yl, n-pent-1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4 -yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n-pent-2-in-5-yl , 3-methyl-but-1-in-l-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, n-hex-1-in -l-yl, n-hex-1-in-3-yl, n-hex-1-in-4-yl,
  • C 1 -C 3 -alkyl as mentioned above, where in each case 1-5 hydrogen atoms are replaced by fluorine, for example fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2, 2.2 Trifluoroethyl, pentafluoroethyl, 3, 3, trifluoropropyl, preferred are difluoromethyl, trifluoromethyl, 2, 2, 2 trifluoroethyl, pentafluoroethyl, 3, 3, 3 trifluoropropyl, particularly preferred is trifluoromethyl;
  • C ⁇ -C ⁇ o-alkyl as mentioned above, where in each case 1-6 hydrogen atoms are replaced by fluorine, chlorine and / or bromine, for example, chloromethyl, dichloroethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodi luormethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 3-chloropropyl, preferably trifluoromethyl; C 2 -C ⁇ o-haloalkenyl c 2 ⁇ -C ⁇
  • Substance atoms are replaced by fluorine, chlorine and / or bromine;
  • Ci-Cio-alkyl as mentioned above, where one hydrogen atom is replaced by the cyano group, e.g. Cyano-methyl, 1-cyanoeth-l-yl, 2-cyanoeth-l-yl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3-cyanoprop-l-yl, l-cyanoprop-2- yl, 2-cyano-prop-2-yl, 1-cyanobut-l-yl, 2-cyanobut-l-yl, 3-cyanobut-l-yl, 4-cyanobut-l-yl, l-cyanobut-2- yl, 2-cyanobut-2-yl, 1-cyano-but-3-yl, 2-cyanobut-3-yl, l-cyano-2-methyl-prop-3-yl,
  • R 1 is chlorine, nitro or C ⁇ -C 3 fluoroalkyl
  • R 2 is an unsubstituted or substituted by halogen, -CC 4 -alkoxy Ci-C ⁇ - alkyl, C 2 -C 8 alkenyl or C 3 -C 8 ralkynyl radical, an unsubstituted C 3 -Ca cycloalkyl radical or is a benzyl or phenyl radical which is unsubstituted in the phenyl moiety or substituted by halogen, C ⁇ -C-alkyl, C ⁇ -C 3 alkoxy, nitro, cyano or trifluoromethyl.
  • R 1 is chlorine, trifluoromethyl or difluoromethyl
  • R 2 is an unsubstituted or substituted by chlorine or methoxy - C 1 -C 8 alkyl radical, a benzyl or phenyl radical which is unsubstituted in the phenyl part or substituted by chlorine, methyl, methoxy or trifluoromethyl.
  • pyridine thioethers Ia from Tables 1-4, the pyridine sulfoxides Ib from Tables 5-1 and the pyridine sulfones Ic from Tables 9-12 are mentioned.
  • the pyridine thioethers Ia2.001 - Ia2.085 and Ia2.087 - Ia2.1l6 of the formula Ia2 are preferred, which differ from the compounds Ial.001 - Ial.085 and Ial.087 - Ial.116 in that in 5 Position on the pyridine ring is a trifluoromethyl group instead of chlorine.
  • the pyridine thioethers Ia3.001 - Ia3.116 of the formula Ia3 are preferred, which differ from the compounds Ial.001 - Ial.116 in that there is a methylsulfonyl group in the 5-position on the pyridine ring.
  • pyridine thioethers Ia4.001 - Ia4.116 of the formula Ia4 which differ from the compounds Ial.001 - Ial.116 in that there is a difluoroethyl group in the 5-position on the pyridine ring.
  • thiopyridines Ib3.001-Ib3.116 of the formula Ib3 which differ from the compounds Ia3.001-Ia3.116 in that the corresponding sulfoxides are present.
  • thiopyridines Ib4.001-Ib4.116 of the formula Ib4 which differ from the compounds Ia4.001-Ia4.116 in that the corresponding sulfones are present.
  • thiopyridines of the formula I can be prepared in surprisingly good yields.
  • the thiopyridines I are particularly preferably obtained when substituted 3-chloro-2-halogenopyridines of the formula II
  • R 1 has the abovementioned meaning and shark represents fluorine, chlorine or bromine, in a first step with a thio compound of the formula III
  • R 2 has the abovementioned meaning and m and n are 0, or the alkali metal or alkaline earth metal salt thereof, if appropriate in the presence of a base, is first converted to a pyridine thioether of the formula Ia and then converted stepwise to the sulfoxide Ib
  • peracetic acid or chlorine and bromine can be used analogously according to the above scheme.
  • the compounds I can be prepared starting from 2,3-dichloro-5-trifluoromethylpyridine and a benzenesulfinic acid salt as nucleophile, as described in the following scheme:
  • hydrocarbons such as pentane, hexane, cyclohexane, heptane, toluene, xylene, chlorinated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, 1, 1, 2, 2-tetrachloroethane, chlorobenzene are used as solvents for these reactions , 1,2-, 1,3- or 1, -dichlorobenzene, ethers such as diethyl ether, methyl tert.
  • glycol ethers such as dimethyl glycol ether, diethyl glycol ether, diethylene glycol dimethyl ether, esters such as ethyl acetate, propyl acetate, methyl isobutyrate, isobutyl acetate, carboxylic acid amides such as DMF, N-methylpyrrolidone such as nitro methane, nitroethane, nitropropane and nitrobenzene, ureas such as tetraethylurea, tetrabutylurea, dirnethylethyleneurea, dimethylpropyleneurea, sulfoxides such as dimethylsulfoxide, sulfones such as diethylsulfone, diethylsulfone, tetramethylene sulfone, nitriles such as acet
  • the molar ratios in which the starting compounds are reacted with one another are generally 0.9-1.4, preferably 0.95-1.1, for the ratio of thiol or sulfinic acid to 3-chloro-2-halopyridine II.
  • the concentration of the starting materials in the solvent is 0.1-5 mol / 1, preferably 0.2-2 mol / 1.
  • the thiols or sulfinic acids are expediently used in the form of their alkali or alkaline earth metal salts, that is to say their lithium, sodium, potassium, magnesium or calcium salts.
  • the reaction can also be carried out in the presence of an organic base, e.g. B. tri-ethylamine, tri-n-propylamine, N-ethyldiisopropylamine, pyridine, ⁇ -, ß-, ⁇ -picoline, 2,4-, 2,6-lutidine, N-methylpyrrolidine, triethylene dia in, diethylaniline , N, N-dimethylcyclohexylamine, quinoline or acridine.
  • an organic base e.g. B. tri-ethylamine, tri-n-propylamine, N-ethyldiisopropylamine, pyridine, ⁇ -, ß-, ⁇ -picoline, 2,4-, 2,6-
  • the hydrogen halide split off in the reaction can also be bound by adding an alkali metal or alkaline earth metal hydride, hydrogen carbonate or carbonate of the above-mentioned metals.
  • the thiols or sulfinic acids are converted into their corresponding salts with one of the abovementioned bases in an inert solvent and the reaction with the 3-chloro-2-halopyridine is then carried out.
  • the water formed during salt formation can be left in the reaction medium or removed azeotropically with a solvent. Salt formation can also be carried out in an aqueous phase from the outset and the water can then be removed.
  • salt formation can also be carried out with an alkali metal or alkaline earth metal hydride or alcoholate, preferably sodium methylate or ethylate, and excess alcohol can be removed before the reaction with the pyridine.
  • the reaction can also be carried out in an aqueous two-phase system, preferably in the presence of phase transfer catalysts such as quaternary ammonium or phosphonium salts.
  • phase transfer catalysts such as quaternary ammonium or phosphonium salts.
  • the reaction conditions described in EP-A-556 737 are suitable for the two-phase reaction.
  • the 3-chloro-2-halopyridine II is added over a period of 0.25-2 hours to a mixture of the thiol III or the sulfinic acid III or the respective salt in one of the abovementioned solvents at 10 to 80 ° C. and the mixture is stirred
  • the reaction after 0.5 to 16 hours, preferably 2 to 8 hours at 10 to 80 ° C in the case of thiol or at 80 to 180 ° C in the case of sulfinic acid.
  • the thiol III or the sulfinic acid III can also be added together or added via a separate feed in parallel with the addition of the base to the 3-chloro-2-halopyridine II and the reaction can then be completed as above.
  • the starting materials II and III can be added in any order to a mixture of the phase transfer catalyst in the two phases with stirring and then the reaction can be completed in the temperature range mentioned with the addition of base.
  • the reaction can be carried out under pressure or under pressure, continuously or batchwise.
  • the oxidation of the pyridine thioethers of the formula Ia to the thiopyridines I can preferably be carried out with hydrogen superoxide, the pyridine sulfoxides Ib being obtained with approximately equivalent amounts of the oxidant and the pyridine sulfones Ic being obtained with about double molar amounts.
  • the reaction can also be catalyzed by adding stronger acids such as trifluoroacetic acid or perchloric acid.
  • metal compounds are also suitable as catalysts, e.g. B. transition metal oxides such as vanadium pentoxide, sodium tungstate, potassium dichromate, iron oxide tungstate, sodium tungstate molybdic acid, osmic acid, titanium trichloride, selenium dioxide, phenylene selenic acid, oxovanadinyl-2, 4-pentanedionate.
  • the catalysts are generally used in an amount of 0.5 to 10%, but because of the easy filterability and recovery of the inorganic catalysts, stoichiometric amounts can also be used.
  • Another preferred oxidizing agent is peracetic acid or hydrogen superoxide / acetic anhydride, optionally also the peracetic acid present in equilibrium in a hydrogen superoxide / acetic acid mixture.
  • a preferred oxidizing agent is also pertrifluoroacetic acid or the mixture of hydrogen superoxide / trifluoroacetic acid or the mixture of hydrogen peroxide / trifluoroacetic anhydride.
  • Oxidation with hydrogen peroxide in glacial acetic acid is generally very selective, but often slow.
  • the reaction time can generally be shortened by adding trifluoroacetic acid (cf. synthesis example 5, variants a and b).
  • trifluoroacetic acid cf. synthesis example 5, variants a and b.
  • the oxidation with hydrogen superoxide in pure trifluoroacetic acid often leads, as also described in Chimia 29 (1975) 466, to the formation of the corresponding N-oxides.
  • Rapid and selective oxidation of the pyridine thioethers Ia to the corresponding sulfoxides Ib and sulfones Ic is achieved, for example, with solutions of hydrogen superoxide in mixtures of acetic acid and trifluoroacetic acid in a volume ratio of 10: 1 to 1: 1, in particular 6: 1 to 4: 1. These mixtures are therefore particularly preferred as solvents.
  • Petroleum ether the abovementioned solvents and the catalysts listed above can also be used as solvents.
  • perbenzoic acid In addition to peracetic acid and pertrifluoroacetic acid, perbenzoic acid, monoperphthalic acid or 3-chloroperbenzoic acid can also be used expediently in chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane.
  • Chlorine and bromine are also very suitable for the oxidation of the thiols to sulfoxides or sulfones.
  • Favorable solvents are water, acetonitrile, dioxane, two-phase systems such as aqueous potassium hydrogen carbonate solution / dichloromethane and, in the case of pyridine alkyl thioether, also acetic acid.
  • halogen As a source of active halogen can also tert. -Butyl hypochlorite, hypochlorous and hypobromous acid, their salts, and also N-halogen compounds such as N-bromine and N-chlorosuccinimide or sulfuryl chloride.
  • N-halogen compounds such as N-bromine and N-chlorosuccinimide or sulfuryl chloride.
  • N-halogen compounds such as N-bromine and N-chlorosuccinimide or sulfuryl chloride.
  • N-halogen compounds such as N-bromine and N-chlorosuccinimide or sulfuryl chloride.
  • N-halogen compounds such as N-bromine and N-chlorosuccinimide or sulfuryl chloride.
  • N-halogen compounds such as N-bromine and N-chlorosuccinimide or sulfuryl chloride.
  • N-halogen compounds such as N-bromine and N-chlorosuccinimide
  • Photosensitized oxygen transfer is also suitable for the oxidation, chlorophyll, protoporphyrin, Rose Bengal or methylene blue being recommended as photosensitizers.
  • Inert solvents are hydrocarbons such as pentane, hexane, heptane, cyclohexane, chlorinated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, 1, 1, 2, 2-tetrachloroethane, alcohols such as methanol, ethanol, n-propanol or isopropanol, ketones such as acetone, methyl ethyl ketone, polar aprotic solvents such as acetonitrile, propionitrile or aromatic hydrocarbons such as benzene, toluene, chlorobenzene or xylene.
  • ozone in the abovementioned solvents, in addition to ether, 1,4-dioxane or THF
  • catalysts are also recommended for oxygen oxidation.
  • B oxides and sulfides of nickel, copper, aluminum, tungsten, chromium, vanadium, ruthenium, titanium, manganese, molybdenum, magnesium and iron.
  • pyridine sulfoxides Ib or their pyridine sulfones Ic are obtained.
  • the molar ratios in which the starting compounds are reacted with one another are generally 0.9-1.8, preferably 1.05-1.3 for the ratio of pyridine thioether Ia to oxidizing agent in the case of oxidation to pyridine sulfoxide and in general 1.9-3.5, preferably 2.05-2.9 in the case of oxidation to pyridine sulfone.
  • the concentration of the starting materials in the solvent is generally 0.1-5 mol / 1, preferably 0.2-2 mol / 1.
  • the pyridine thioether or the pyridine sulfoxide is advantageously placed. with one of the abovementioned catalysts in one of the abovementioned solvents and then add the oxidizing agent with stirring for 0.25-20 hours.
  • the addition and reaction temperature depends on the optimal efficiency of the respective oxidizing agent and the avoidance of side reactions. If photosensitized oxygen is used, the procedure is generally from -20 to 80 ° C., but metal-catalyzed in general from 50 to 140 ° C. and at Use of ozone in general at -78 to 60 ° C.
  • a staggered addition of the liquid or dissolved oxidizing agent is also preferred.
  • the procedure is generally carried out at 0 - 90 ° C with ter. -Butyl hypochlorite in general at -78 to 30 ° C, with N-halogen compounds in general at 0 - 30 ° C and with nitric acid in general at 20 to 140 ° C.
  • a reaction temperature of 0 - 40 ° C is recommended.
  • the oxidations can be operated without pressure or under pressure, continuously or batchwise.
  • thiopyridines I according to the invention are valuable precursors for the production of crop protection agents, in particular herbicides from the class of the phenylpyridines, as are described in WO-A 95/02580.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention concerne des thiopyridines substituées de formule générale (I), dans laquelle n vaut 1 ou 2; R<1> représente chlore, fluoroalkyle C1-C3, nitro ou méthylsulfonyle; R<2> représente un reste alkyle C1-C10, alcényle C2-C10 ou alcynyle C2-C10 non substitué ou substitué par halogène, alcoxy C1-C4, alkoxycarbonyle C1-C4, di-(C1-C4-alkylamino)carbonyle, cyano ou nitro, un reste cycloalkyle C3-C8 ou bien un reste C1-C4 alkylenphényle, phényle ou naphtyle non substitué dans la partie phényle ou substituée par halogène, alkyle C1-C3, alcoxy C1-C3, trifluorométhyle, cyano ou nitro.
EP97944808A 1996-09-12 1997-08-29 Thiopyridines substituees Withdrawn EP0934275A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19636997 1996-09-12
DE19636997 1996-09-12
PCT/EP1997/004707 WO1998011072A1 (fr) 1996-09-12 1997-08-29 Thiopyridines substituees

Publications (1)

Publication Number Publication Date
EP0934275A1 true EP0934275A1 (fr) 1999-08-11

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EP97944808A Withdrawn EP0934275A1 (fr) 1996-09-12 1997-08-29 Thiopyridines substituees

Country Status (7)

Country Link
US (2) US6262273B1 (fr)
EP (1) EP0934275A1 (fr)
JP (1) JP2001500141A (fr)
KR (1) KR20000036038A (fr)
CN (1) CN1232454A (fr)
CA (1) CA2265483A1 (fr)
WO (1) WO1998011072A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0984935A1 (fr) 1997-05-30 2000-03-15 Basf Aktiengesellschaft Procede de fabrication de thiopyridines substituees
JP4147924B2 (ja) * 2002-12-03 2008-09-10 日産自動車株式会社 燃料電池システム
US7783380B2 (en) 2003-12-31 2010-08-24 Kimberly-Clark Worldwide, Inc. System and method for measuring, monitoring and controlling washroom dispensers and products
EP3159339B1 (fr) 2014-06-09 2020-11-25 Sumitomo Chemical Company, Limited Procédé de production d'un composé pyridinique

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5629504A (en) * 1979-08-16 1981-03-24 Ishihara Sangyo Kaisha Ltd Antibacterial for agriculture and horticulture
JPS60185764A (ja) * 1984-03-05 1985-09-21 Wako Pure Chem Ind Ltd ピリジン誘導体の新規な製造法
JPS60188370A (ja) * 1984-03-08 1985-09-25 Wako Pure Chem Ind Ltd ビピリジン誘導体の製造法
DE3852621D1 (de) 1987-12-07 1995-02-09 Ciba Geigy Ag 3-Aminobenzoylphenylharnstoffe.
US4983211A (en) 1990-03-30 1991-01-08 Dowelanco Substituted cyclohexanediones and their herbicidal use
MY110439A (en) 1991-02-07 1998-05-30 Ishihara Sangyo Kaisha N-phenylcarbamate compound, process for preparing the same and biocidal composition for control of harmful organisms
WO1992015576A1 (fr) 1991-03-07 1992-09-17 E.I. Du Pont De Nemours And Company Sulfonamide de pyridine herbicide
DE59309922D1 (de) 1992-02-20 2000-02-17 Clariant Gmbh Verfahren zur Herstellung von substituierten 2,3-Difluorpyridinen
DE4323916A1 (de) 1993-07-16 1995-01-19 Basf Ag Substituierte 2-Phenylpyridine
DE19636995A1 (de) 1996-09-12 1998-03-19 Basf Ag Verfahren zur Herstellung substituierter Phenylpyridine
EP0984935A1 (fr) * 1997-05-30 2000-03-15 Basf Aktiengesellschaft Procede de fabrication de thiopyridines substituees
US6420314B1 (en) 1997-05-30 2002-07-16 Basf Aktiengesellschaft Substituted 2-phenyl pyridines, their manufacture and use as herbicides

Non-Patent Citations (1)

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Title
See references of WO9811072A1 *

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CA2265483A1 (fr) 1998-03-19
CN1232454A (zh) 1999-10-20
US6407245B2 (en) 2002-06-18
US20010012897A1 (en) 2001-08-09
WO1998011072A1 (fr) 1998-03-19
JP2001500141A (ja) 2001-01-09
US6262273B1 (en) 2001-07-17
KR20000036038A (ko) 2000-06-26

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