EP0931068A1 - Process for the production of substituted phenylpyridines - Google Patents

Process for the production of substituted phenylpyridines

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Publication number
EP0931068A1
EP0931068A1 EP97942894A EP97942894A EP0931068A1 EP 0931068 A1 EP0931068 A1 EP 0931068A1 EP 97942894 A EP97942894 A EP 97942894A EP 97942894 A EP97942894 A EP 97942894A EP 0931068 A1 EP0931068 A1 EP 0931068A1
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EP
European Patent Office
Prior art keywords
halogen
formula
methyl
haloalkyl
alkyl
Prior art date
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EP97942894A
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German (de)
French (fr)
Inventor
Gerhard Hamprecht
Joachim Gebhardt
Heinz Isak
Michael Rack
Joachim Rheinheimer
Peter Schäfer
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms

Definitions

  • the invention relates to a new process for the preparation of substituted phenylpyridines of the formula I.
  • R 1 is hydrogen, fluorine, chlorine or haloalkyl
  • R 2 is fluorine, chlorine or haloalkyl
  • R 3 is hydrogen, halogen or an organic radical which is inert under the reaction conditions
  • R 4 is alkyl, haloalkyl, halogen, alkylsulfonyl, haloalkylsulfonyl or haloalkoxy
  • R 5 is hydrogen , Halogen, haloalkyl, haloalkoxy, alkylsulfonyl or haloalkylsulfonyl.
  • the compounds I are precursors for crop protection agents having a herbicidal action, but can also be used as herbicides themselves (WO-A 95/02580).
  • sulfoxides and sulfones are also known as further leaving groups on the heterocycle.
  • 2-sulfonylpyridines can be coupled with arylmagnesium compounds, although no additional halogen substitution is mentioned in the Grignard part.
  • Heterocycles 2_i (1986), p. 3337 teaches that additional halogen substitution in the pyridyl sulfone reduces the yield of the coupling product, while donor substitution of the Grignard compound increases the yield.
  • the invention was therefore based on the object of providing a generally applicable preparation process for substituted phenylpyridines of the formula I from easily accessible starting materials in high yield and purity.
  • alkyl alkenyl, alkynyl, each optionally substituted by halogen or methoxy; also cycloalkyl or phenylalkyl; and optionally substituted phenyl or naphthyl,
  • the process according to the invention is based on pyridine derivatives of the formula II, which are obtainable, for example, from 2-halopyridines by reaction with corresponding thiolates and subsequent oxidation. They are reacted with Grignard or zinc compounds of the formula III, optionally catalyzed by transition metals, to give phenylpyridines of the formula I.
  • R 1 is fluorine in formula III
  • the compounds III are accessible, for example, by grignarding the correspondingly substituted o-fluorobromobenzene with magnesium at temperatures from -10 to 60 ° C.
  • the molar ratios in which the starting compounds II and III are reacted with one another can be, for example, in the range from 0.9 to 1.5, preferably 1.0 to 1.2 for the ratio of phenyl derivative III to pyridine compound II.
  • the concentration the starting material in the solvent is not critical, for example it is 0.1 to 5 mol / 1, preferably 0.5 to 2 mol / 1.
  • hydrocarbons such as pentane, hexane, heptane, cyclohexane, toluene or chlorobenzene, preferably solvents with electron donor character, in particular solvents with one or more ether oxygen atoms such as diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether , Dimethoxyethane, diethoxyheptane, ethylene glycol dimethyl ether, furan, 5, 6-dihydro-4H-pyran, tetrahydrofuran, tetrahydropyran, 1,3-, 1,4-dioxane, 4-methyl-l, 3-dioxane, anisole, Dimethyl formal, diethyl formal, dimethyl acetate, diethyl acetal, diisopropyl acetal, furthermore triethylamine, phosphoric acid tris dimethyl amide, 1, 2-
  • the reaction can be carried out by adding a catalyst, e.g. B. a transition metal can be accelerated.
  • a transition metal catalysts are iron, cobalt, nickel, rhodium, palladium or platinum compounds, especially nickel (0), nickel (II) and palladium (0) - and palladium (II) compounds.
  • Salts such as nickel chloride, palladium chloride, palladium acetate or even complexes can be used.
  • Phosphine ligands such as, for. B. aryl alkyl phosphines such as u. a.
  • Triphenylphosphine tritolylphosphine
  • trixylylphosphine trixylylphosphine
  • trihetarylphosphines such as trifurylphosphine or other phosphine
  • the complex used can be used directly in the reaction. So you can z. B. with bis (triphenylphosphine) nickel (I ⁇ ) bromide, bis (triphenylphosphine) nickel (II) chloride,
  • Nickel or palladium salt and, in addition, a suitable ligand, which then only form the catalytically active complex in situ.
  • This procedure offers z. B. in the above salts and phosphine ligands such.
  • Nickel or palladium complexes such as.
  • Bis (dibenzylidene acetone) palladium or 1, 5-cyclooctadienpal - ladium dichloride by the addition of ligands such as. B. trifuryl phosphine or tritolyl phosphine can be activated further.
  • the reaction can be carried out under pressure or under pressure, continuously or batchwise.
  • the process according to the invention provides the coupling product in high yields, even in the case of multiple halogen substitution in both substrates, which is always described as disruptive in the literature.
  • a preferred embodiment of the process according to the invention is the reaction of a pyridine derivative of the formula II, where Y is alkyl or aryl, with a Grignard compound of the formula purple.
  • the pyridine compound II if appropriate with a catalyst, is initially taken in a solvent and then the Grignard component purple.
  • the Grignard compound can also be initially introduced in one of the abovementioned solvents - advantageously from the Grignard synthesis - and then the pyridine derivative II, if appropriate together with the catalyst, can be introduced.
  • the pyridine derivative II is added at the end of the addition, for example under HPLC control, until it has just been used again. is needed.
  • the addition is advantageously carried out at a temperature of -20 to 50 ° C, in particular at 10 to 30 ° C.
  • the reaction time depends, inter alia, on the choice of solvent and the substituents and is usually completed in 0.1 to 16 hours, in particular after 0.5 to 6 hours at 10 to 140 ° C., in particular 20 to 80 ° C.
  • a particularly preferred embodiment of the process according to the invention consists in coupling, for example, the 2-alkyl- or 2-arylsulfonyl-3-chloro-5-trifluoromethylpyridine of the formula II 'or the corresponding 2-arylsulfoxides of the formula II' with 2-chlorine -4-fluoro-anisole-5-magnesium bromide purple 'to 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-chloro-5-trifluoromethylpyridine.
  • the alkyl or arylsulfonyl or sulfinylpyridines of the formula II can be reacted with an arylzinc halogen compound of the formula IIIb.
  • the compounds Illb are prepared from the arylgrignard compounds purple described above and reacted with zinc bromide or zinc chloride in a manner known per se.
  • This reaction can advantageously be carried out as a "one-pot synthesis” and can be connected directly to the formation of the Grignard compound, the temperature being between -40 and 50 ° C, in particular between 15 and 30 ° C.
  • This mixture can then be used directly for the transition metal-catalyzed couplings, so that the entire sequence can run in one reaction vessel.
  • Aliphatic radicals are, for example, alkyl, cycloalkyl, alkenyl or alkynyl radicals.
  • Alkyl generally represents C 1 -C 0 -alkyl, preferably C 1 -C 6 -alkyl, in particular C 1 -C 4 -alkyl. This also applies to alkyl combinations such as alkoxy or haloalkyl radicals.
  • the radicals can carry further substituents which are inert under the reaction conditions.
  • Cycloalkyl stands for C 3 to C 6 cycloalkyl.
  • Alkenyl stands for C 2 -C 6 ⁇ alkenyl and alkynyl for C 2 -C 6 alkynyl. This also applies to combinations of residues, such as alkenyloxy or alkynyloxy.
  • the radicals can carry further substituents which are inert under the reaction conditions.
  • Aryl generally represents phenyl or naphthyl or substituted phenyl or substituted naphthyl, e.g. B. substituted with 1 to 3 halogen atoms, Ci to C alkyl, such as methyl, halomethyl, such as Trif luormethyl and / or C ⁇ to C 4 alkoxy groups.
  • Phenylalkyl stands for benzyl, 1- or 2-phenylethyl
  • Hydrogen, halogen, an aliphatic or cycloaliphatic radical or an aryl radical, the organic radicals mentioned optionally being via CH 2 -, C (0> -, C (0) 0-, 0-, S-, C (0) NR 6 - or NR 6 bridges can be bound to the phenyl ring, where R 6 represents hydrogen, alkyl, alkenyl, alkynyl or aryl and two alkyl radicals can be linked via a bond or an oxygen atom to form a 5- or 6-membered ring.
  • R 3 The following are particularly preferred for R 3 :
  • Hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio; Cycloalkyl; CH CR 6 R 7 ; Alkylsulfonyloxy; Haloalkylsulfonyloxy; Arylsulfonyloxy; Dialkylaminosulfonyloxy; Alkoxysulfonyl; Dialkylaminosulfonyl; Aryloxysulfonyl or aryl-alkylamine sulfonyl; Alkoxycarbonyl; Dialkylaminocarbonyl; CR 8 (U-alkyl) (V-alkyl); UP- (V) -WR 9 XR 10 ; Aryl, aryloxy or arylthio; Alkylarylamino-, alkenylarylamino- or alky
  • R 7 formyl, alkoxycarbonyl or P (V) WR 9 XR 10 , R 8 is hydrogen or alkyl,
  • R 10 alkyl, alkenyl, alkynyl or aryl
  • R 11 is alkyl, alkenyl, alkynyl, formyl, alkanoyl, alkylsulfonyl or arylsulfonyl
  • U, V independently of one another are oxygen and / or sulfur W
  • X independently of one another are oxygen, sulfur and / or alkylamino.
  • Fluorine, chlorine, bromine and iodine preferably fluorine and chlorine
  • - alkyl e.g. B. -C-C 6 alkyl, such as
  • Alkenyl e.g. B. C 2 -C 6 alkenyl, such as ethenyl, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2 -yl, n-buten-3-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1 -yl and 2-methyl-prop-2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1 -Methyl-but-l-en-l-yl, 2-methyl-but-1-en-l-yl, 3-methyl-but-l-en-l-yl, 1-methyl-but-2 -en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-
  • alkynyl e.g. B. C 2 -C 6 alkynyl, such as
  • Haloalkyl e.g. B. Cx-Ce haloalkyl, such as
  • Alkyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, e.g. B., chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl,
  • Ci-Ce alkoxy such as
  • Haloalkoxy e.g. B. -C-C 6 haloalkoxy, as mentioned above, partially or completely by
  • Fluorine, chlorine, bromine and or iodine is substituted, ie z.
  • Alkylthio e.g. B. -C-C 6 alkylthio, such as methylthio, ethylthio, n-propylthio, 1-methyl-ethylthio, n-butylthio, 1-methyl-propylthio, 2-methyl-propylthio or 1, 1-dimethyl-ethylthio,
  • Alkylsulfinyl e.g. B. Ci-C ⁇ -alkylsulfinyl, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methyl-ethylsulfinyl, n-butylsulfinyl, 1-methyl-propylsulfinyl, 2-methyl-propylsulfinyl or 1, 1-dimethyl-ethylsulfinyl,
  • Alkylsulfonyl e.g. B. Ci-C ö alkylsulfonyl, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methyl-ethylsulfonyl, n-butylsulfonyl, 1-methyl-propylsulfonyl, 2-methyl-propylsulfonyl or 1, 1-dimethyl-ethyl-sulfonyl
  • Alkenyloxy e.g. B. C 2 -C 6 alkenyloxy, such as eth-1-en-l-yloxy, prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, n-butene-1 -yloxy, n-buten-2-yloxy, n-buten-3-yloxy, 1-methyl-prop-l-en-l-yloxy, 2-methyl-prop-1-en-l-yloxy, l-methyl -prop-2-en-l-yloxy, 2-methyl-prop-2-en-l-yloxy; Alkynyloxy, e.g. B. C -C6 ⁇ alkynyloxy such as
  • Cycloalkyl e.g. B. C 3 -C 6 cycloalkyl, such as
  • Alkylamino e.g. B. -C-C 6 alkylamino, such as
  • Di-alkylamino e.g. B. di- (-C 6 alkyl) amino, such as N, N-dimethylamino, N, N-diethylamino, N, -dipropylamino, N, N-di- (1-methyl-ethyl) amino, N , N-Dibutylamino, N, -Di- (1-methylpropyl) amino, N, N-Di- (2-methylpropyl) mino, N, N-Di- (1, 1-dimethyl-ethyl) amino, N-ethyl -N-methylamino, N-methyl-N-propylamino, N-methyl-N- (1-methylethyl) mino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) amino, N -Methyl-N- (2-methylpropyl) mino, N- (1, 1-dimethylethyl-N-
  • this solution was added to a mixture of 5.8 g (0.02 mol) of 3-chloro-2-n-propylsulfonyl-5-trifluoromethyl-pyridine and 0.65 g (1 mmol) of bis within 10 min (Triphenylphosphine) nickel (II) chloride added to 25 ml THF. The mixture was then stirred at 25 ° C for 14 h. 50 g of ice and 150 ml of saturated ammonium chloride were added to the reaction mixture.

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

Abstract

Process for the production of substituted phenylpyridines having formula (I), characterized by the fact that substituted pyridine having formula (II) is made to react with an aryl compound having formula (III).

Description

Verfahren zur Herstellung substituierter PhenylpyridineProcess for the preparation of substituted phenylpyridines
Beschreibungdescription
Die Erfindung betrifft ein neues Verfahren zur Herstellung von substituierten Phenylpyridinen der Formel IThe invention relates to a new process for the preparation of substituted phenylpyridines of the formula I.
worin wherein
R1 Wasserstoff, Fluor, Chlor oder Halogenalkyl, R2 Fluor, Chlor oder Halogenalkyl, R3 Wasserstoff, Halogen oder ein unter den Reaktionsbedingungen inerter organischer Rest R4 Alkyl, Halogenalkyl, Halogen, Alkylsulfonyl, Halogenalkylsul - fonyl oder Halogenalkoxy, R5 Wasserstoff, Halogen, Halogenalkyl, Halogenalkoxy, Alkylsul- fonyl oder Halogenalkylsulfonyl bedeuten.R 1 is hydrogen, fluorine, chlorine or haloalkyl, R 2 is fluorine, chlorine or haloalkyl, R 3 is hydrogen, halogen or an organic radical which is inert under the reaction conditions R 4 is alkyl, haloalkyl, halogen, alkylsulfonyl, haloalkylsulfonyl or haloalkoxy, R 5 is hydrogen , Halogen, haloalkyl, haloalkoxy, alkylsulfonyl or haloalkylsulfonyl.
Die Verbindungen I sind Vorprodukte für Pflanzenschutzmittel mit herbizider Wirkung, können aber auch selbst als Herbizide verwendet werden (WO-A 95/02580) .The compounds I are precursors for crop protection agents having a herbicidal action, but can also be used as herbicides themselves (WO-A 95/02580).
Für die Darstellung von Phenyl-substituierten Heterocyclen sind verschiedene Synthesewege bekannt. Beispielsweise kann man 2-Brompyridin mit aktiviertem Zink in das entsprechende 2-Pyri- dyl-zinkbromid umwandeln und dieses dann mit überschüssigem Jod- benzol unter Palladiumkatalyse in mäßiger Ausbeute zu dem 2-Phe- nylpyridin kuppeln [THL 21 (1992) 5373; J. Org. Che . ü£ (1991) 1445] .Various synthetic routes are known for the preparation of phenyl-substituted heterocycles. For example, you can convert 2-bromopyridine with activated zinc into the corresponding 2-pyridyl-zinc bromide and then couple it with excess iodobenzene with palladium catalysis in moderate yield to the 2-phenylpyridine [THL 21 (1992) 5373; J. Org. Che. ü £ (1991) 1445].
Die Reaktion benötigt zum einen häufig schlecht zugängliche Bro - heterocyclen, beispielsweise ist 2-Brom-3-chlor-5-trifluormethyl - pyridin nach JP-A 81/115776 in nur 10 % Ausbeute zugänglich. Zum anderen werden auf seiten der Aromatenkomponente teure Jodbausteine benötigt. Der hohe Preis des Palladiumkatalysators schließlich verlangt aufwendige Wiedergewinnungsoperationen. Eine andere Methode besteht in der Kupplung einer Phenylboron- säure mit einer aromatischen oder heterocyclischen Bromverbindung (Synthesis 1995, 1421; WO 95/2580) . Nachteilig sind hier die verlustreiche Darstellung aromatischer Boronsäuren (Houben Weyl , Methoden der Org. Chemie, IV. Auflage, Band 13/3a, S. 636), die aus metallorganischen Vorstufen hergestellt werden, sowie die Verwendung teurer Palladiumkatalysatoren.On the one hand, the reaction requires bro-heterocycles which are often difficult to access, for example 2-bromo-3-chloro-5-trifluoromethyl-pyridine according to JP-A 81/115776 is accessible in only 10% yield. On the other hand, expensive iodine components are required on the aromatic component side. Finally, the high price of the palladium catalyst requires complex recovery operations. Another method consists in coupling a phenylboronic acid with an aromatic or heterocyclic bromine compound (Synthesis 1995, 1421; WO 95/2580). Disadvantages here are the lossy representation of aromatic boronic acids (Houben Weyl, Methods of Org. Chemistry, 4th Edition, Volume 13 / 3a, p. 636), which are prepared from organometallic precursors, and the use of expensive palladium catalysts.
Neben Halogenen sind als weitere Abgangsgruppen am Heterocyclus auch Sulfoxide und Sulfone bekannt. Nach JP-A 61/280,474 kann man 2-Sulfonylpyridine mit Arylmagnesiumverbindungen kuppeln, wobei eine zusätzliche Halogensubstitution im Grignardteil jedoch nicht erwähnt ist. In Heterocycles 2_i (1986), S. 3337 wird gelehrt, daß zusätzliche Halogensubstitution im Pyridylsulfon die Ausbeute an Kupplungsprodukt verringert, während eine Donorsubstitution der Grignardverbindung die Ausbeute erhöht.In addition to halogens, sulfoxides and sulfones are also known as further leaving groups on the heterocycle. According to JP-A 61 / 280,474, 2-sulfonylpyridines can be coupled with arylmagnesium compounds, although no additional halogen substitution is mentioned in the Grignard part. Heterocycles 2_i (1986), p. 3337 teaches that additional halogen substitution in the pyridyl sulfone reduces the yield of the coupling product, while donor substitution of the Grignard compound increases the yield.
Pyridylsulfoxide als Abgangsgruppen geben bei unkatalysierter Kupplung mit Grignardverbindungen üblicherweise nur Bipyridyle [Bull. Chem. Soc . Jpn. 62 (1989) 2338; THL 25_ (1984) 2549]. Nur im Falle des Chinolin-2-sulfoxids konnte das Kupplungsprodukt in 20 % Ausbeute überhaupt isoliert werden.Pyridyl sulfoxides as leaving groups usually give only bipyridyls in the case of uncatalyzed coupling with Grignard compounds [Bull. Chem. Soc. Jpn. 62 (1989) 2338; THL 25_ (1984) 2549]. Only in the case of quinoline-2-sulfoxide could the coupling product be isolated in 20% yield.
Der Erfindung lag daher die Aufgabe zugrunde, ein allgemein an- wendbares Herstellverfahren für substituierte Phenylpyridine der Formel I aus leicht zugänglichen Ausgangsmaterialien in hoher Ausbeute und Reinheit bereitzustellen.The invention was therefore based on the object of providing a generally applicable preparation process for substituted phenylpyridines of the formula I from easily accessible starting materials in high yield and purity.
Demgemäß wurde ein Verfahren zur Herstellung substituierter Phenylpyridine der Formel I gefunden, das dadurch gekennzeichnet ist, daß man substituierte Pyridine der Formel II mit einer Aryl - Verbindung der Formel III gegebenenfalls in Gegenwart eines Übergangsmetallkatalysators umsetzt.Accordingly, a process has been found for the preparation of substituted phenylpyridines of the formula I which is characterized in that substituted pyridines of the formula II are reacted with an aryl compound of the formula III, if appropriate in the presence of a transition metal catalyst.
II IIIII III
Die Substituenten der Formeln II und III haben die bei Formel I genannten Bedeutungen, zusätzlich bedeuten: n 1 oder 2 undThe substituents of the formulas II and III have the meanings given for formula I, additionally mean: n 1 or 2 and
Y Alkyl, Alkenyl, Alkinyl, jeweils gegebenenfalls substituiert durch Halogen oder Methoxy; ferner Cycloalkyl oder Phenylal - kyl; sowie gegebenenfalls substituiertes Phenyl oder Naph- thyl,Y alkyl, alkenyl, alkynyl, each optionally substituted by halogen or methoxy; also cycloalkyl or phenylalkyl; and optionally substituted phenyl or naphthyl,
M Magnesium oder Zink undM magnesium or zinc and
Z Halogen.Z halogen.
Das erfindungsgemäße Verfahren geht von Pyridinderivaten der Formel II aus, die beispielsweise aus 2-Halogen-pyridinen durch Umsetzung mit entsprechenden Thiolaten und anschließender Oxidation zugänglich sind. Sie werden mit Grignard- oder Zinkverbindungen der Formel III, gegebenenfalls übergangsmetallkatalysiert, zu Phenylpyridinen der Formel I umgesetzt.The process according to the invention is based on pyridine derivatives of the formula II, which are obtainable, for example, from 2-halopyridines by reaction with corresponding thiolates and subsequent oxidation. They are reacted with Grignard or zinc compounds of the formula III, optionally catalyzed by transition metals, to give phenylpyridines of the formula I.
Sofern in Formel III R1 für Fluor steht, sind die Verbindungen III beispielsweise über die Grignardierung des entsprechend substituierten o-Fluorbrombenzols mit Magnesium bei Temperaturen von -10 bis 60°C zugänglich.If R 1 is fluorine in formula III, the compounds III are accessible, for example, by grignarding the correspondingly substituted o-fluorobromobenzene with magnesium at temperatures from -10 to 60 ° C.
Die molaren Verhältnisse, in denen die Ausgangsverbindungen II und III miteinander umgesetzt werden, können beispielsweise in dem Bereich von 0,9 bis 1,5 liegen, vorzugsweise 1,0 bis 1,2 für das Verhältnis von Phenylderivat III zu Pyridinverbindung II. Die Konzentration der Edukte im Lösungsmittel ist nicht kritisch, sie beträgt beispielsweise 0,1 bis 5 mol/1, bevorzugt 0,5 bis 2 mol/ 1.The molar ratios in which the starting compounds II and III are reacted with one another can be, for example, in the range from 0.9 to 1.5, preferably 1.0 to 1.2 for the ratio of phenyl derivative III to pyridine compound II. The concentration the starting material in the solvent is not critical, for example it is 0.1 to 5 mol / 1, preferably 0.5 to 2 mol / 1.
Als Lösungsmittel kann man für diese Umsetzungen Kohlenwasserstoffe, wie Pentan, Hexan, Heptan, Cyclohexan, Toluol oder Chlorbenzol, bevorzugt Lösungsmittel mit Elektronendonorcharakter, insbesondere Lösungsmittel mit einem oder mehreren Ethersauer- stoffato en wie Diethylether, Diisopropylether, Dibutylether, Methyl-tert.-butylether, Dimethoxyethan, Diethoxyheptan, Ethylen- glykoldimethylether, Furan, 5, 6-Dihydro-4H-pyran, Tetrahydrofu- ran, Tetrahydropyran, 1,3-, 1,4-Dioxan, 4-Methyl-l, 3-dioxan, Anisol, Dimethylformal, Diethylformal, Dimethylacetat, Diethyl- acetal, Diisopropylacetal, ferner Triethylamin, Phosphorsäure- tris-dimethylamid, 1, 2-Bis (dimethylamino) ethan, N-Ethylmorpholin, Tribenzylphosphinoxyd, Dimethylsulfid, Di ethylsulfoxid, Dirne- thylsulfon, Tetramethylylensulfon, N-Methylpyrrolidon oder Dirne - thylacetamid verwenden. Vorteilhaft ist oftmals die Verwendung von Mischungen z. B. von Ethern mit Aminen oder A iden. Vorteilhaft kann man die polare Komponente z. B. 1 bis 3 Mol Tetrahydro- furan, Triethylamin, N-Ethylmorpholin auch als Zusatz zu der weniger polaren Komponente wie Benzol, Toluol, Xylol oder Naphthalin zumischen.As a solvent for these reactions, hydrocarbons such as pentane, hexane, heptane, cyclohexane, toluene or chlorobenzene, preferably solvents with electron donor character, in particular solvents with one or more ether oxygen atoms such as diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether , Dimethoxyethane, diethoxyheptane, ethylene glycol dimethyl ether, furan, 5, 6-dihydro-4H-pyran, tetrahydrofuran, tetrahydropyran, 1,3-, 1,4-dioxane, 4-methyl-l, 3-dioxane, anisole, Dimethyl formal, diethyl formal, dimethyl acetate, diethyl acetal, diisopropyl acetal, furthermore triethylamine, phosphoric acid tris dimethyl amide, 1, 2-bis (dimethylamino) ethane, N-ethyl morpholine, tribenzylphosphine oxide, dimethyl sulfide, diethyl sulfoxide, dimethyl tetramethylsulfonyl, nylon tetramethyl sulfonyl Use methylpyrrolidone or wench - thylacetamide. It is often advantageous to use mixtures such. B. of ethers with amines or A iden. You can advantageously the polar component z. B. 1 to 3 moles of tetrahydro Furan, triethylamine, N-ethylmorpholine also as an additive to the less polar component such as benzene, toluene, xylene or naphthalene.
Die Umsetzung kann durch Zugabe eines Katalysators, z. B. eines Übergangsmetalls beschleunigt werden. Als Übergangsmetallkatalysatoren sind Eisen-, Kobalt-, Nickel-, Rhodium-, Palladium- oder Platinverbindungen, besonders Nickel (0), Nickel (II) und Palladium (0)- sowie Palladium (II) -Verbindungen geeignet. So können Salze wie Nickelchlorid, Palladiumchlorid, Palladiumacetat oder auch Komplexe verwendet werden. Voraussetzung ist lediglich, daß die Liganden am Palladium unter den Reaktionsbedindungen vom Substrat verdrängt werden können. Besonders geeignet sind Phosphin- liganden wie z. B. Aryl-Alkylphosphine wie u. a. Methyldiphenyl- phosphin, Isopropyldiphenylphosphin, Triarylphosphine wie u. a. Triphenylphosphin, Tritolylphosphin, Trixylylphosphin, Triheta- rylphosphine wie Trifurylphosphin oder di ere Phosphine. Gut geeignet sind auch olefinische Liganden wie u. a. Dibenzylidenace- ton oder seine Salze, Cycloocta-1, 5-dien oder Amine wie Trialky- lamine (z. B. Triethylamin, Tetra ethylethylendiamin, N-Methyl- morpholin) oder Pyridin.The reaction can be carried out by adding a catalyst, e.g. B. a transition metal can be accelerated. Suitable transition metal catalysts are iron, cobalt, nickel, rhodium, palladium or platinum compounds, especially nickel (0), nickel (II) and palladium (0) - and palladium (II) compounds. Salts such as nickel chloride, palladium chloride, palladium acetate or even complexes can be used. The only requirement is that the ligands on the palladium can be displaced from the substrate under the reaction conditions. Phosphine ligands such as, for. B. aryl alkyl phosphines such as u. a. Methyldiphenylphosphine, isopropyldiphenylphosphine, triarylphosphines such as u. a. Triphenylphosphine, tritolylphosphine, trixylylphosphine, trihetarylphosphines such as trifurylphosphine or other phosphines. Olefinic ligands such as u. a. Dibenzylideneacetone or its salts, cycloocta-1,5-diene or amines such as trialkylamines (eg triethylamine, tetraethylethylenediamine, N-methylmorpholine) or pyridine.
Man kann den verwendeten Komplex direkt bei der Reaktion einsetzen. So kann man z. B. mit Bis (triphenylphosphin) nik- kel (IΙ)bromid, Bis ( triphenylphosphin) nickel (II) Chlorid,The complex used can be used directly in the reaction. So you can z. B. with bis (triphenylphosphine) nickel (IΙ) bromide, bis (triphenylphosphine) nickel (II) chloride,
[1, 3-Bis (diphenylphosphin)propan] nickel (II) Chlorid, [1,2-Bis (di- phenylphosphin)ethan] nickel (II) Chlorid, Tetrakistriphenylphosp- hinpalladium (0) , Bistriphenylphosphinpalladiumdichlorid, Bistri- phenylphosphinpalladiumdiacetat, einem Dibenzylidenaceton-Palla- dium(0) -Komplex, Tetrakismethyldiphenylphosphinpalladiu (0) oder Bisd, 2-diphenylphosphinoethan)palladiumdichlorid verfahren. Man kann auch, ein Nickel- oder Palladiumsalz und zusätzlich einen geeigneten Liganden verwenden, die dann erst in situ den kataly- tisch aktiven Komplex bilden. Diese Vorgehensweise bietet sich z. B. bei den oben genannten Salzen und Phosphinliganden wie z. B. Trifurylphosphin oder Tritolylphosphin an. Auch können Nickeloder Palladiumkomplexe wie z. B. Tris (dibenzylidenaceton) dipalla- dium. Bis (dibenzylidenaceton) palladium oder 1, 5-Cyclooctadienpal - ladiumdichlorid durch die Zugabe von Liganden wie z. B. Trifuryl- phosphin oder Tritolylphosphin weiter aktiviert werden.[1,3-bis (diphenylphosphine) propane] nickel (II) chloride, [1,2-bis (diphenylphosphine) ethane] nickel (II) chloride, tetrakistriphenylphosphine palladium (0), bistriphenylphosphine palladium dichloride, bistriphenylphosphine palladium diacetate, a Process dibenzylidene acetone-palladium (0) complex, tetrakismethyldiphenylphosphine palladium (0) or bisd, 2-diphenylphosphinoethane) palladium dichloride. It is also possible to use a nickel or palladium salt and, in addition, a suitable ligand, which then only form the catalytically active complex in situ. This procedure offers z. B. in the above salts and phosphine ligands such. B. trifurylphosphine or tritolylphosphine. Nickel or palladium complexes such as. B. Tris (dibenzylidene acetone) dipalladium. Bis (dibenzylidene acetone) palladium or 1, 5-cyclooctadienpal - ladium dichloride by the addition of ligands such as. B. trifuryl phosphine or tritolyl phosphine can be activated further.
Üblicherweise werden 0,001 bis 12 mol-%, insbesondere 0,001 bis 5 mol-% des Katalysators, bezogen auf die Ausgangsstoffe, verwendet. Höhere Mengen sind möglich, aber in der Regel nicht erfor- derlich. Die Reaktion kann drucklos oder unter Druck, kontinuierlich oder diskontinuierlich durchgeführt werden.Usually 0.001 to 12 mol%, in particular 0.001 to 5 mol%, of the catalyst, based on the starting materials, are used. Larger quantities are possible, but are generally not necessary. The reaction can be carried out under pressure or under pressure, continuously or batchwise.
Nach der Umsetzung arbeitet man in an sich üblicher Weise auf, z. B. extrahiert man das Umsetzungsgemisch mit Wasser zur Entfernung der Salze, trocknet und reinigt die organische Phase, z. B. durch Chromatographie oder Destillation. Man kann jedoch auch direkt die organische Phase einengen und den Rückstand in einem Lösungsmittel digerieren.After implementation, you work on in a conventional manner, for. B. extracting the reaction mixture with water to remove the salts, drying and cleaning the organic phase, e.g. B. by chromatography or distillation. However, the organic phase can also be concentrated directly and the residue digested in a solvent.
Das erfindungsgemäße Verfahren liefert, auch bei mehrfacher - in der Literatur stets als störend bezeichneter Halogensubstitution in beiden Substraten - das Kupplungsprodukt in hohen Ausbeuten. Im Falle substituierter Pyridylsulfoxide der Formel II (n = 1) werden im erfindungsgemäßen Verfahren keine Bipyridylkupplungs- produkte, wie es nach der Literatur [Bull. Chem. Soc. Jpn. £2 (1989) 2338] zu erwarten wäre, sondern Phenylpyridine I als Hauptprodukte isoliert.The process according to the invention provides the coupling product in high yields, even in the case of multiple halogen substitution in both substrates, which is always described as disruptive in the literature. In the case of substituted pyridyl sulfoxides of the formula II (n = 1), no bipyridyl coupling products are used in the process according to the invention, as has been found in the literature [Bull. Chem. Soc. Jpn. £ 2 (1989) 2338] would be expected, but phenylpyridine I was isolated as the main product.
Wesentlich für das Gelingen des erfindungsgemäßen Verfahrens ist die Wahl eines Sulfinyl- oder Sulfonylrestes an der Pyridinkompo- nente. Diese Abgangsgruppe ermöglicht eine besonders glatte Umsetzung mit außergewöhlich hoher Selektivität, wenn R1 bis R5 weitere reaktive Substituenten darstellen.The choice of a sulfinyl or sulfonyl radical on the pyridine component is essential for the success of the process according to the invention. This leaving group enables a particularly smooth reaction with an exceptionally high selectivity if R 1 to R 5 represent further reactive substituents.
Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist die Umsetzung eines Pyridinderivates der Formel II, wobei Y für Alkyl oder Aryl steht, mit einer Grignardverbindung der Formel lila.A preferred embodiment of the process according to the invention is the reaction of a pyridine derivative of the formula II, where Y is alkyl or aryl, with a Grignard compound of the formula purple.
II lilaII purple
Zweckmäßig legt man die Pyridinverbindung II, gegebenenfalls mit Katalysator, in einem Lösungsmittel vor und gibt dann die Gri- gnardko ponente lila hinzu. Man kann jedoch auch die Grignardverbindung in einem der vorgenannten Lösungsmittel vorlegen - zweckmäßig aus der Grignardsynthese - und dann das Pyridinderivat II, gegebenenfalls zusammen mit Katalysator, zuführen. In einer besonderen Ausgestaltung des erfindungsgemäßen Verfahrens gibt man gegen Schluß der Zugabe, beispielsweise unter HPLC-Kontrolle, das Pyridinderivat II solange hinzu, bis es gerade wieder ver- braucht wird. Man arbeitet demgemäß wie unter den Bedingungen einer Titration und erleichtert sich so die Reinigung der Endprodukte von den Ausgangsmaterialien. Die Zugabe erfolgt zweckmäßig bei einer Temperatur von -20 bis 50°C, insbesondere bei 10 bis 30°C. Die Reaktionsdauer hängt u. a. von der Wahl des Lösungsmittels und den Substituenten ab und ist üblicherweise während 0,1 bis 16 Stunden, insbesondere nach 0,5 bis 6 Stunden bei 10 bis 140°C, insbesondere 20 bis 80°C abgeschlossen.Advantageously, the pyridine compound II, if appropriate with a catalyst, is initially taken in a solvent and then the Grignard component purple. However, the Grignard compound can also be initially introduced in one of the abovementioned solvents - advantageously from the Grignard synthesis - and then the pyridine derivative II, if appropriate together with the catalyst, can be introduced. In a special embodiment of the process according to the invention, the pyridine derivative II is added at the end of the addition, for example under HPLC control, until it has just been used again. is needed. One works accordingly as under the conditions of a titration and thus facilitates the cleaning of the end products from the starting materials. The addition is advantageously carried out at a temperature of -20 to 50 ° C, in particular at 10 to 30 ° C. The reaction time depends, inter alia, on the choice of solvent and the substituents and is usually completed in 0.1 to 16 hours, in particular after 0.5 to 6 hours at 10 to 140 ° C., in particular 20 to 80 ° C.
Eine besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht in der Kupplung beispielsweise des 2-Alkyl- oder 2-Arylsulfonyl-3-chlor-5-trif luormethylpyridins der Formel II' oder der entsprechenden 2-Aryl-Sulfoxide der Formel II' mit 2-Chlor-4-fluor-anisol-5-magnesiumbromid lila' zu 2-(4-Chlor- 2-fluor-5-methoxyphenyl) -3-chlor-5-trifluormethylpyridin.A particularly preferred embodiment of the process according to the invention consists in coupling, for example, the 2-alkyl- or 2-arylsulfonyl-3-chloro-5-trifluoromethylpyridine of the formula II 'or the corresponding 2-arylsulfoxides of the formula II' with 2-chlorine -4-fluoro-anisole-5-magnesium bromide purple 'to 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-chloro-5-trifluoromethylpyridine.
τ 1 ' lila' I' τ 1 'purple' I '
Die Reaktion wird zweckmäßig in Gegenwart eines Lösungsmittels bei Temperaturen zwischen -20 bis 140°C, vorzugsweise 20 bis 80°C, durchgeführt, wobei man in einer vorteilhaften Form des erfindungsgemäßen Verfahrens bei Verwendung der Pyridinderivate der Formeln Ha, Ilb oder Ilc Y = Aryl, n = 2 Y = Alkyl, n = 1 Y = Aryl, n = 1The reaction is advantageously carried out in the presence of a solvent at temperatures between -20 to 140 ° C, preferably 20 to 80 ° C, in an advantageous form of the process according to the invention using the pyridine derivatives of the formulas Ha, Ilb or Ilc Y = aryl , n = 2 Y = alkyl, n = 1 Y = aryl, n = 1
bereits ohne Einsatz von Katalysatoren sehr hohe Ausbeuten an Endprodukten I erhält.receives very high yields of end products I even without the use of catalysts.
In einer weiteren Ausgestaltung des erfindungsgemäßen Verfahrens kann man die Alkyl-, bzw. Arylsulfonyl- bzw. -sulfinylpyridine der Formel II mit einer Arylzinkhalogenverbindung der Formel Illb umsetzen. In a further embodiment of the process according to the invention, the alkyl or arylsulfonyl or sulfinylpyridines of the formula II can be reacted with an arylzinc halogen compound of the formula IIIb.
II IllbII Illb
Die Umsetzungen werden auf die vorbeschriebene Weise durchgeführt, wobei man in einer vorteilhaften Form des erfindungs- ge äßen Verfahrens bei Einsatz der Pyridinderivate der Formeln Ila, Ilb oder Ilc bereits ohne Verwendung von Katalysatoren bereits sehr hohe Ausbeuten an Endprodukten I erhält.The reactions are carried out in the manner described above, and in an advantageous form of the process according to the invention, when using the pyridine derivatives of the formulas Ila, Ilb or Ilc, very high yields of end products I are obtained even without the use of catalysts.
Zur Herstellung der Verbindungen Illb geht man von den oben beschriebenen Arylgrignardverbindungen lila aus und setzt diese mit Zinkbromid oder Zinkchlorid in an sich bekannter Art und Weise um. Diese Reaktion läßt sich vorteilhaft als "EintopfSynthese" durchführen und direkt an die Bildung der Grignard-Verbindung anschließen, wobei die Temperatur zwischen -40 und 50° C, insbesondere zwischen 15 und 30° C liegen kann. Diese Mischung kann dann direkt für die gegebenenfalls übergangsmetallkatalysierten Kupplungen eingesetzt werden, so daß die gesamte Sequenz in einem Reaktionsgefäß ablaufen kann.The compounds Illb are prepared from the arylgrignard compounds purple described above and reacted with zinc bromide or zinc chloride in a manner known per se. This reaction can advantageously be carried out as a "one-pot synthesis" and can be connected directly to the formation of the Grignard compound, the temperature being between -40 and 50 ° C, in particular between 15 and 30 ° C. This mixture can then be used directly for the transition metal-catalyzed couplings, so that the entire sequence can run in one reaction vessel.
Aus Kostengründen wird man bevorzugt die leicht zugänglichen unsubstituierten Derivate einsetzen. Die Substituenten von Y sind für das Gelingen des erfindungsgemäßen Verfahrens nicht entschei- dend.For cost reasons, preference will be given to using the easily accessible unsubstituted derivatives. The substituents of Y are not decisive for the success of the process according to the invention.
In den eingangs gegebenen Definitionen der Verbindungen werden allgemeine Ausdrücke verwendet, die für folgende Reste stehen:In the definitions of the compounds given at the beginning, general terms are used which stand for the following radicals:
Aliphatische Reste sind beispielsweise Alkyl-, Cycloalkyl-, Alke- nyl- oder Alkinylreste.Aliphatic radicals are, for example, alkyl, cycloalkyl, alkenyl or alkynyl radicals.
Alkyl steht generell für Cι-Cι0-Alkyl, bevorzugt für Cι-C6-Alkyl, insbesondere für Cι-C4-Alkyl. Das gilt auch für Alkylkombinatio- nen, wie Alkoxy- oder Halogenalkylreste. Die Reste können weitere, unter den Reaktionsbedingungen inerte Substituenten tragen.Alkyl generally represents C 1 -C 0 -alkyl, preferably C 1 -C 6 -alkyl, in particular C 1 -C 4 -alkyl. This also applies to alkyl combinations such as alkoxy or haloalkyl radicals. The radicals can carry further substituents which are inert under the reaction conditions.
Cycloalkyl steht für C3- bis C6-Cycloalkyl . Alkenyl steht für C2-C6~Alkenyl und Alkinyl für C2-C6-Alkinyl . Das gilt auch für Restekombinationen, wie Alkenyloxy oder Alkinyloxy. Die Reste können weitere, unter den Reaktionsbedingungen inerte Substituenten tragen.Cycloalkyl stands for C 3 to C 6 cycloalkyl. Alkenyl stands for C 2 -C 6 ~ alkenyl and alkynyl for C 2 -C 6 alkynyl. This also applies to combinations of residues, such as alkenyloxy or alkynyloxy. The radicals can carry further substituents which are inert under the reaction conditions.
Aryl steht generell für Phenyl oder Naphthyl oder substituiertes Phenyl oder substituiertes Naphthyl, z. B. substituiert mit 1 bis 3 Halogenatomen, Ci- bis C -Alkyl, wie Methyl, Halogenmethyl, wie Trif luormethyl und/oder Cι~ bis C4-Alkoxygruppen.Aryl generally represents phenyl or naphthyl or substituted phenyl or substituted naphthyl, e.g. B. substituted with 1 to 3 halogen atoms, Ci to C alkyl, such as methyl, halomethyl, such as Trif luormethyl and / or C ~ to C 4 alkoxy groups.
Phenylalkyl steht für Benzyl, 1- oder 2-Phenylethyl,Phenylalkyl stands for benzyl, 1- or 2-phenylethyl,
Im Hinblick auf die bestimmungsgemäße Verwendung der Phenylpyridine der Formel I sind Verbindungen bevorzugt, in denen R3 die folgende Bedeutung hat:With regard to the intended use of the phenylpyridines of the formula I, preference is given to compounds in which R 3 has the following meaning:
Wasserstoff, Halogen, ein aliphatischer oder cycloaliphatischer Rest oder ein Arylrest, wobei die genannten organischen Reste gegebenenfalls über CH2-, C(0>-, C(0)0-, 0-, S-, C(0)NR6- oder NR6-Brücken an den Phenylring gebunden sein können, wobei R6 für Wasserstoff, Alkyl, Alkenyl, Alkinyl oder Aryl steht und zwei AI - kylreste über eine Bindung oder ein Sauerstoffatom zu einem 5- oder 6-gliedrigen Ring verknüpft sein können.Hydrogen, halogen, an aliphatic or cycloaliphatic radical or an aryl radical, the organic radicals mentioned optionally being via CH 2 -, C (0> -, C (0) 0-, 0-, S-, C (0) NR 6 - or NR 6 bridges can be bound to the phenyl ring, where R 6 represents hydrogen, alkyl, alkenyl, alkynyl or aryl and two alkyl radicals can be linked via a bond or an oxygen atom to form a 5- or 6-membered ring.
Für R3 sind besonders bevorzugt:The following are particularly preferred for R 3 :
Wasserstoff, Halogen, Alkyl, Alkenyl, Alkinyl, Alkoxy, Alkenyloxy, Alkinyloxy, Alkylthio, Alkenylthio oder Alkinyl thio; Cycloalkyl; CH=CR6R7 ; Alkylsulfonyloxy; Halogenalkylsulfony- loxy; Arylsulfonyloxy; Dialkylaminosulfonyloxy; Alkoxysul - fonyl; Dialkylaminosulfonyl; Aryloxysulfonyl oder Aryl-alkyl- amin sulfonyl; Alkoxycarbonyl; Dialkylaminocarbonyl; CR8 (U- Alkyl) (V-Alkyl) ; U-P- (V) -WR9XR10; Aryl, Aryloxy oder Arylthio; Alkylarylamino-, Alkenylarylamino- oder Alkinylarylamino-car- bonyloxy; Dialkyla ino-, Alkyl-alkenylamino, Alkyl-alkinyla - mino-, Dialkenyla ino- oder Dialkinylamino-carbonyloxy, wobei im Falle von Dialkylamino-carbonyloxy die beiden Alkylreste über eine Bindung oder ein Sauerstoffatom zu einem 5- oder 6-gliedrigen Ring verknüpft sein können; Alkyl-, Alkenyl-, Alkinyl-carbonyloxy oder Alkoxy-; Alkenyloxy- oder Alkinyl - oxy-carbonyl-alkoxy, NR10R1:L oder NRÜOR10, wobeiHydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio; Cycloalkyl; CH = CR 6 R 7 ; Alkylsulfonyloxy; Haloalkylsulfonyloxy; Arylsulfonyloxy; Dialkylaminosulfonyloxy; Alkoxysulfonyl; Dialkylaminosulfonyl; Aryloxysulfonyl or aryl-alkylamine sulfonyl; Alkoxycarbonyl; Dialkylaminocarbonyl; CR 8 (U-alkyl) (V-alkyl); UP- (V) -WR 9 XR 10 ; Aryl, aryloxy or arylthio; Alkylarylamino-, alkenylarylamino- or alkynylarylamino-carbonyloxy; Dialkyla ino-, alkyl-alkenylamino, alkyl-alkinyla-mino-, dialkenyla-ino- or dialkinylamino-carbonyloxy, where in the case of dialkylamino-carbonyloxy the two alkyl radicals are linked via a bond or an oxygen atom to form a 5- or 6-membered ring can; Alkyl, alkenyl, alkynylcarbonyloxy or alkoxy; Alkenyloxy or alkynyl oxycarbonyl alkoxy, NR 10 R 1: L or NRÜOR 10 , where
R6 Halogen oder Alkyl,R 6 halogen or alkyl,
R7 Formyl, Alkoxycarbonyl oder P(V)WR9XR10, R8 Wasserstoff oder Alkyl,R 7 formyl, alkoxycarbonyl or P (V) WR 9 XR 10 , R 8 is hydrogen or alkyl,
R9 AlkylR 9 alkyl
R10 Alkyl, Alkenyl, Alkinyl oder Aryl, R11 Alkyl, Alkenyl, Alkinyl, Formyl , Alkanoyl, Alkylsul- fonyl oder Arylsulfonyl, U, V unabhängig voneinander Sauerstoff und/oder Schwefel W, X unabhängig voneinander Sauerstoff, Schwefel und/oder Alkylamino bedeuten.R 10 alkyl, alkenyl, alkynyl or aryl, R 11 is alkyl, alkenyl, alkynyl, formyl, alkanoyl, alkylsulfonyl or arylsulfonyl, U, V independently of one another are oxygen and / or sulfur W, X independently of one another are oxygen, sulfur and / or alkylamino.
Die vorstehend für die Substituenten R1 bis R11 in der Formel I genannten Bedeutungen stellen Sammelbegriffe für eine individuelle Aufzählung der einzelnen Gruppenmitglieder dar. Sämtliche Kohlenstof ketten, also alle Alkyl-, Alkenyl-, Alkinyl-, Halogenalkyl- und Halogenalkoxyteile, können geradkettig oder verzweigt sein.The meanings given above for the substituents R 1 to R 11 in the formula I are collective terms for an individual listing of the individual group members. All carbon chains, that is to say all alkyl, alkenyl, alkynyl, haloalkyl and haloalkoxy parts, can be straight-chain or be branched.
Für die Substituenten der Phenylpyridine der Formel I kommen ins - besondere folgende in Betracht:The following are particularly suitable for the substituents of the phenylpyridines of the formula I:
Halogenhalogen
Fluor, Chlor, Brom und Jod, vorzugsweise Fluor und Chlor;Fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine;
- Alkyl, z. B. Cι-C6-Alkyl, wie- alkyl, e.g. B. -C-C 6 alkyl, such as
Methyl, Ethyl, n-Propyl, 1-Methylethyl , n-Butyl, 1-Methyl- propyl , 2-Methylpropyl und 1, 1-Dimethylethyl;Methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl;
Alkenyl, z. B. C2-C6-Alkenyl , wie Ethenyl, Prop-1-en-l-yl, Prop-2-en-l-yl , 1-Methylethenyl, n- Buten-1-yl, n-Buten-2-yl, n-Buten-3-yl, 1-Methyl-prop- 1-en-l-yl, 2-Methyl-prop-l-en-l-yl, l-Methyl-prop-2-en-l-yl und 2-Methyl-prop-2-en-l-yl, n-Penten-1-yl, n-Penten-2-yl, n-Penten-3-yl, n-Penten-4-yl, 1-Methyl-but-l-en-l-yl, 2-Me- thyl-but-1-en-l-yl, 3-Methyl-but-l-en-l-yl, 1-Methyl-but- 2-en-l-yl, 2-Methyl-but-2-en-l-yl, 3-Methyl-but-2-en-l-yl, l-Methyl-but-3-en-l-yl, 2-Methyl-but-3-en-l-yl, 3-Methyl- but-3-en-l-yl, 1, l-Dimethyl-prop-2-en-l-yl, 1 , 2-Dimethyl- prop-1-en-l-yl, 1, 2-Dimethyl-prop-2-en-l-yl, 1-Ethylprop- l-en-2-yl, l-Ethyl-prop-2-en-l-yl, n-Hex-1-en-l-yl, n-Hex-Alkenyl, e.g. B. C 2 -C 6 alkenyl, such as ethenyl, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2 -yl, n-buten-3-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1 -yl and 2-methyl-prop-2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1 -Methyl-but-l-en-l-yl, 2-methyl-but-1-en-l-yl, 3-methyl-but-l-en-l-yl, 1-methyl-but-2 -en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-yl, 2 -Methyl-but-3-en-l-yl, 3-methyl-but-3-en-l-yl, 1, l-dimethyl-prop-2-en-l-yl, 1, 2-dimethyl-prop -1-en-1-yl, 1, 2-dimethyl-prop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethyl-prop-2-en-1-yl , n-hex-1-en-l-yl, n-hex
2-en-l-yl, n-Hex-3-en-l-yl, n-Hex-4-en-l-yl, n-Hex-5-en-l-yl , 1-Methyl-pent-l-en-l-yl, 2-Methylpent-l-en-l-yl, 3-Methyl- pent-1-en-l-yl, 4-Methyl-pent-l-en-l-yl, 1-Methyl-pent- 2-en-l-yl, 2-Methyl-pent-2-en-l-yl, 3-Methyl-pent-2-en-l-yl, 4-Methyl-pent-2-en-l-yl, l-Methyl-pent-3-en-l-yl, 2-Methyl- pent-3-en-l-yl, 3-Methyl-pent-3-en-l-yl, 4-Methyl-pent- 3-en-l-yl, l-Methyl-pent-4-en-l-yl, 2-Methyl-pent-4-en-l-yl, 3-Methyl-pent-4-en-l-yl, 4-Methyl-pent-4-en-l-yl, 1,1-Dime- thyl-but-2-en-l-yl, 1, l-Dimethyl-but-3-en-l-yl , 1, 2-Dimethyl- but-1-en-l-yl, 1, 2-Dimethyl-but-2-en-l-yl, 1, 2-Dimethyl-but- 3-en-l-yl, 1, 3-Dimethyl-but-l-en-l-yl , 1, 3-Dimethyl-but- 2-en-l-yl, 1, 3-Dimethyl-but-3-en-l-yl, 2, 2-Dimethyl-but- 3-en-l-yl, 2, 3-Dimethyl-but-l-en-l-yl , 2, 3-Dimethyl-but- 2-en-l-yl, 2, 3-Dimethyl-but-3-en-l-yl , 3, 3-Dimethyl-but- 1-en-l-yl, 3 , 3-Dimethyl-but-2-en-l-y'l, 1-Ethyl-but-l-en-l-yl , l-Ethyl-but-2-en-l-yl, l-Ethyl-but-3-en-l-yl, 2-Ethyl-but- 1-en-l-yl, 2-Ethylbut-2-en-l-yl , 2-Ethyl-but-3-en-l-yl , 1,1, 2-Trimethylprop-2-en-l-yl, l-Ethyl-l-methyl-prop-2- en-l-yl, l-Ethyl-2-methyl-prop-l-en-l-yl und l-Ethyl-2-me- thylprop-2-en-l-yl, vorzugsweise Ethenyl und Prop-2-en-l-yl;2-en-l-yl, n-hex-3-en-l-yl, n-hex-4-en-l-yl, n-hex-5-en-l-yl, 1-methyl-pent l-en-l-yl, 2-methylpent-l-en-l-yl, 3-methyl-pent-1-en-l-yl, 4-methyl-pent-l-en-l-yl, 1- Methyl-pent-2-en-l-yl, 2-methyl-pent-2-en-l-yl, 3-methyl-pent-2-en-l-yl, 4-methyl-pent-2-en- l-yl, l-methyl-pent-3-en-l-yl, 2-methyl-pent-3-en-l-yl, 3-methyl-pent-3-en-l-yl, 4-methyl pent-3-en-l-yl, l-methyl-pent-4-en-l-yl, 2-methyl-pent-4-en-l-yl, 3-methyl-pent-4-en-l- yl, 4-methyl-pent-4-en-l-yl, 1,1-dimethyl-but-2-en-l-yl, 1, l-dimethyl-but-3-en-l-yl, 1, 2-dimethyl-but-1-en-l-yl, 1, 2-dimethyl-but-2-en-l-yl, 1, 2-dimethyl-but-3-en-l-yl, 1, 3-dimethyl-but-l-en-l-yl, 1, 3-dimethyl-but-2-en-l-yl, 1, 3-dimethyl-but-3-en-l-yl, 2, 2- Dimethyl-but- 3-en-l-yl, 2,3-dimethyl-but-l-en-l-yl, 2,3-dimethyl-but-2-en-l-yl, 2,3-dimethyl-but-3- en-l-yl, 3, 3-dimethyl-but-1-en-l-yl, 3, 3-dimethyl-but-2-en-ly 'l, 1-ethyl-but-l-en-l- yl, l-ethyl-but-2-en-l-yl, l-ethyl-but-3-en-l-yl, 2-ethyl-but-1-en-l-yl, 2-ethylbut-2- en-l-yl, 2-ethyl-but-3-en-l-yl, 1,1, 2-trimethylprop-2-en-l-yl, l-ethyl-l-methyl-prop-2-en- l-yl, l-ethyl-2-methyl-prop-l-en-l-yl and l-ethyl-2-methylprop-2-en-l-yl, preferably ethenyl and prop-2-en-l -yl;
- Alkinyl, z. B. C2-C6-Alkinyl , wie- alkynyl, e.g. B. C 2 -C 6 alkynyl, such as
Ethinyl, 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-l-yl, n-Pent-1-in-l-yl, n-Pent-1- in-3-yl, n-Pent-l-in-4-yl, n-Pent-l-in-5-yl, n-Pent-2- in-l-yl, n-Pent-2-in-4-yl , n-Pent-2-in-5-yl, 3-Methyl-but-l- 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-l-in-3-yl, n-Hex-l-in-4-yl , n-Hex-1- in-5-yl, n-Hex-l-in-6-yl, n-Hex-2-in-l-yl , n-Hex-2-in-4-yl, n-Hex-2-in-5-yl, n-Hex-2-in-6-yl, n-Hex-3-in-l-yl, n-Hex- 3-in-2-yl, 3-Methyl-pent-l-in-l-yl , 3-Methyl-pent-l-in-3-yl , 3-Methyl-pent-l-in-4-yl, 3-Methylpent-l-in-5-yl , 4-Methyl- pent-1-in-l-yl, 4-Methyl-pent-2-in-4-yl und 4-Methyl-pent- 2-in-5-yl, vorzugsweise Prop-2-in-l-yl, l-Methyl-prop-2- in-l-ylEthynyl, 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-l-yl, n-pent-1-in-l-yl, n-pent-1-in-3-yl, n-pent-l-in-4-yl, n-pent-l- in-5-yl, n-pent-2-in-l-yl, n-pent-2-in-4-yl, n-pent-2-in-5-yl, 3-methyl-but-l- 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 l-in-3-yl, n-hex-l-in-4-yl, n-hex-1- in-5-yl, n-hex-l-in-6-yl, n-hex-2- in-l-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in- l-yl, n-hex-3-in-2-yl, 3-methyl-pent-l-in-l-yl, 3-methyl-pent-l-in-3-yl, 3-methyl-pent- l-in-4-yl, 3-methylpent-l-in-5-yl, 4-methylpent-1-in-l-yl, 4-methylpent-2-in-4-yl and 4- Methyl-pent-2-in-5-yl, preferably prop-2-in-l-yl, l-methyl-prop-2-in-l-yl
- Halogenalkyl, z. B. Cx-Ce-Halogenalkyl, wie- Haloalkyl, e.g. B. Cx-Ce haloalkyl, such as
Alkyl wie vorstehend genannt, das partiell oder vollständig durch Fluor, Chlor und/ oder Brom substituiert ist, also z. B. , Chlormethyl, Dichlormethyl, Trichlormethyl, Fluormethyl, Difluromethyl, Trifluormethyl, Chlorfluormethyl, Dichlorflu- ormethyl, Chlordifluormethyl, 1-Fluorethyl, 2-Fluorethyl,Alkyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, e.g. B., chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl,
2, 2-Difluorethyl, 2, 2, 2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2 , 2-difluorethyl , 2 , 2-Dichlor-2-fluorethyl , 2,2, 2-Trichlorethyl, Pentafluorethyl, 2-Fluorpropyl, 3-Fluor- propyl, 2, 2-Difluorpropyl, 2 , 3-Difluorpropyl, 2-Chlorpropyl, 3-Chloropropyl, 2, 3-Dichlorpropyl, 2-Brompropyl, 3-Brompro- pyl, 3, 3, 3-Trifluorpropyl, 3, 3, 3-Trichlorpropyl , 2, 2, 3, 3, 3-Pentafluorpropyl, Heptafluorpropyl, 1- (Fluormethyl) -2-fluorethyl, 1- (Chlormethyl) -2-chlorethyl, 1- (Brommethyl) -2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl oder 4-Brombu- tyl;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, 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2, 3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (Bromomethyl) -2-bromomethyl, 4-fluorobutyl, 4-chlorobutyl or 4-bromobutyl;
Alkoxy, z. B. Ci-Ce-Alkoxy, wieAlkoxy, e.g. B. Ci-Ce alkoxy, such as
Methoxy, Ethoxy, n-Propoxy, 1-Methylethoxy, n-Butoxy, 1-Me- thylpropoxy, 2-Methylpropoxy oder 1, 1-Dimethylethoxy, n-Pen- toxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 1,1-Di- methylpropoxy, 1, 2-Dimethylpropoxy, 2 , 2-Dimethylpropoxy, 1-Ethylpropoxy, n-Hexoxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1, 1-Dimethylbutoxy, 1,2-Di- methylbutoxy, 1, 3-Dimethylbutoxy, 2, 2-Dimethylbutoxy, 2,3-Di- methylbutoxy, 3 , 3-Dimethylbutoxy, 1-Ethylbutoxy, 2-Ethylbu- toxy, 1, 1, 2-Trimethylpropoxy, 1, 2, 2-Trimethylpropoxy, 1-Ethyl-l-methylpropoxy oder l-Ethyl-2-methylpropoxy,Methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy, n-penoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1,2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy, 2,3-dimethylbutoxy, 3, 3-dimethylbutoxy, 1- Ethyl butoxy, 2-ethyl butoxy, 1, 1, 2-trimethyl propoxy, 1, 2, 2-trimethyl propoxy, 1-ethyl-1-methyl propoxy or 1-ethyl-2-methyl propoxy,
Halogenalkoxy, z. B. Cι-C6-Halogenalkoxy, wie wie vorstehend genannt, das partiell oder vollständig durchHaloalkoxy, e.g. B. -C-C 6 haloalkoxy, as mentioned above, partially or completely by
Fluor, Chlor, Brom und oder Jod substituiert ist, also z. B. Difluromethoxy, Trifluormethoxy, Chlordifluormethoxy, Bromdi - fluromethoxy, 2-Fluorethoxy, 2-Chlorethoxy, 2-Bromethoxy, 2-Jodethoxy, 2 , 2-Difluroethoxy, 2, 2, 2-Trifluorethoxy, 2-Chlor-2-fluorethoxy, 2-Chlor-2, 2-difluorethoxy, 2,2-Di- chlor-2-fluorethoxy, 2, 2, 2-Trichlorethoxy, Pentafluorethoxy, 2-Fluorpropoxy, 3-Fluorpropoxy, 2-Chlorpropoxy, 3-Chlorpro - poxy, 2-Brompropoxy, 3-Brompropoxy, 2 , 2-Difluropropoxy, 2 , 3-Difluropropoxy, 2 , 3-Dichlorpropoxy, 3 , 3, 3-Trifluorpro- poxy, 3, 3 , 3-Trichlorpropoxy, 2, 2, 3 , 3 , 3-Pentafluorpropoxy, Heptafluorpropoxy, 1- (Fluormethyl) -2-fluorethoxy, 1- (Chlor - methyl ) -2-chlorethoxy oder 1- (Brommethyl) -2-bromethoxy,Fluorine, chlorine, bromine and or iodine is substituted, ie z. B. difluromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2,2-di-chloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2, 2-difluropropoxy, 2, 3-difluropropoxy, 2, 3-dichloropropoxy, 3, 3, 3-trifluoropropoxy, 3, 3, 3-trichloropropoxy, 2, 2, 3, 3, 3-pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy or 1- (bromomethyl) -2-bromoethoxy,
2, 2, 3, 3, 4 , 4 , 4-Heptafluorbutoxy, Nonafluorbutoxy, 2-Chlor- fluorbutoxy, 3-Chlorbutoxy, 4-Chlorbutoxy,2, 2, 3, 3, 4, 4, 4-heptafluorobutoxy, nonafluorobutoxy, 2-chlorofluorobutoxy, 3-chlorobutoxy, 4-chlorobutoxy,
Alkylthio, z. B. Cι-C6-Alkylthio, wie Methylthio, Ethylthio, n-Propylthio, 1-Methyl-ethylthio, n-Butylthio, 1-Methyl-propylthio, 2-Methyl-propylthio oder 1, 1-Dimethyl-ethylthio,Alkylthio, e.g. B. -C-C 6 alkylthio, such as methylthio, ethylthio, n-propylthio, 1-methyl-ethylthio, n-butylthio, 1-methyl-propylthio, 2-methyl-propylthio or 1, 1-dimethyl-ethylthio,
Alkylsulfinyl, z. B. Ci-Cβ-Alkylsulfinyl , wie Methylsulfinyl, Ethylsulfinyl, n-Propylsulfinyl, 1-Methyl- ethylsulfinyl, n-Butylsulfinyl, 1-Methyl-propylsulfinyl , 2-Methyl-propylsulfinyl oder 1, 1-Dimethyl-ethylsulfinyl,Alkylsulfinyl, e.g. B. Ci-Cβ-alkylsulfinyl, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methyl-ethylsulfinyl, n-butylsulfinyl, 1-methyl-propylsulfinyl, 2-methyl-propylsulfinyl or 1, 1-dimethyl-ethylsulfinyl,
Alkylsulfonyl, z. B. Ci-Cö-Alkylsulfonyl, wie Methylsulfonyl, Ethylsulfonyl, n-Propylsulfonyl, 1-Methyl- ethylsulfonyl, n-Butylsulfonyl, 1-Methyl-propylsul onyl, 2-Methyl-propylsulfonyl oder 1, 1-Dimethyl-ethyl-sulfonylAlkylsulfonyl, e.g. B. Ci-C ö alkylsulfonyl, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methyl-ethylsulfonyl, n-butylsulfonyl, 1-methyl-propylsulfonyl, 2-methyl-propylsulfonyl or 1, 1-dimethyl-ethyl-sulfonyl
Alkenyloxy, z. B. C2-C6-Alkenyloxy, wie Eth-1-en-l-yloxy, Prop-1-en-l-yloxy, Prop-2-en-l-yloxy, 1-Methylethenyloxy, n-Buten-1-yloxy, n-Buten-2-yloxy, n- Buten-3-yloxy, 1-Methyl-prop-l-en-l-yloxy, 2-Methyl-prop- 1-en-l-yloxy, l-Methyl-prop-2-en-l-yloxy, 2-Methyl- prop-2-en-l-yloxy; Alkinyloxy, z . B . C -C6~Alkinyloxy, wieAlkenyloxy, e.g. B. C 2 -C 6 alkenyloxy, such as eth-1-en-l-yloxy, prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, n-butene-1 -yloxy, n-buten-2-yloxy, n-buten-3-yloxy, 1-methyl-prop-l-en-l-yloxy, 2-methyl-prop-1-en-l-yloxy, l-methyl -prop-2-en-l-yloxy, 2-methyl-prop-2-en-l-yloxy; Alkynyloxy, e.g. B. C -C6 ~ alkynyloxy such as
Prop-1-in-l-yloxy, Prop-2-in-l-yloxy, n-But- 1-in-l-yloxy, n-Prop-1-in-l-yloxy, prop-2-in-l-yloxy, n-but-1-in-l-yloxy, n-
But-l-in-3-yloxy, n-But-l-in-4-yloxy, n-But-2-in-4-yloxy;But-l-in-3-yloxy, n-but-l-in-4-yloxy, n-but-2-in-4-yloxy;
- Cycloalkyl, z. B. C3-C6-Cycloalkyl, wieCycloalkyl, e.g. B. C 3 -C 6 cycloalkyl, such as
Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl;Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
Alkylamino, z. B. Cι-C6-Alkylamino, wieAlkylamino, e.g. B. -C-C 6 alkylamino, such as
Methyla ino, Ethylamino, n-Propylamino, 1-Methylethylamino, n-Butylamino, 1-Methylpropylamino, 2-Methylpropylamino und 1, 1-Dimethylethylamino, vorzugsweise Methylamino und Ethylamino;Methyl ino, ethylamino, n-propylamino, 1-methylethylamino, n-butylamino, 1-methylpropylamino, 2-methylpropylamino and 1, 1-dimethylethylamino, preferably methylamino and ethylamino;
Di-alkylamino, z. B. Di- (Cι-C6-alkyl ) amino, wie N, N-Dimethyl- amino, N,N-Diethylamino, N, -Dipropylamino, N, N-Di- (1-methyl- ethyl) amino, N,N-Dibutylamino, N, -Di- (1-methylpropyl) amino, N, N-Di- (2-methylpropyl ) mino, N,N-Di- (1 , 1-dimethyl-ethyl) amino, N-Ethyl-N-methylamino, N-Methyl-N-propylamino, N-Me- thyl-N- (1-methylethyl) mino, N-Butyl-N-methylamino, N-Methyl- N- (1-methylpropyl) amino, N-Methyl-N- (2-methylpropyl) mino, N- (1, 1-Dimethylethyl-N-methylamino, N-Ethyl-N-propyl-amino, N-Ethyl-N- (1-methylethyl) amino, N-Butyl-N-ethylamino, N- Ethyl-N- (1-methyl-propyl) amino, N-Ethyl-N- (2-methyl-propyl) amino, N-Ethyl-N- (1, 1-dimethylethyl) amino, N- (1-Methylethyl) - N-propylamino, N-Butyl-N-propylamino, N- (1-Methylpropyl) -N- propylamino, N- (2-Methylpropyl) -N-propylamino, N-(1,1-Dime- thylethyl) -N-propylamino, N-Butyl-N- (1-methylethyl) amino, N- (1-Methylethyl) -N- (1-methylpropyl) amino, N- (1-Methylethyl) - N- (2-methyl-propyl) amino, N- (1, 1-Dimethylethyl) -N- (1-methyl- ethyl) amino, N-Butyl-N- (1-methylpropyl) amino, N-Butyl-N-Di-alkylamino, e.g. B. di- (-C 6 alkyl) amino, such as N, N-dimethylamino, N, N-diethylamino, N, -dipropylamino, N, N-di- (1-methyl-ethyl) amino, N , N-Dibutylamino, N, -Di- (1-methylpropyl) amino, N, N-Di- (2-methylpropyl) mino, N, N-Di- (1, 1-dimethyl-ethyl) amino, N-ethyl -N-methylamino, N-methyl-N-propylamino, N-methyl-N- (1-methylethyl) mino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) amino, N -Methyl-N- (2-methylpropyl) mino, N- (1, 1-dimethylethyl-N-methylamino, N-ethyl-N-propyl-amino, N-ethyl-N- (1-methylethyl) amino, N- Butyl-N-ethylamino, N-ethyl-N- (1-methyl-propyl) amino, N-ethyl-N- (2-methyl-propyl) amino, N-ethyl-N- (1, 1-dimethylethyl) amino , N- (1-methylethyl) - N-propylamino, N-butyl-N-propylamino, N- (1-methylpropyl) -N-propylamino, N- (2-methylpropyl) -N-propylamino, N- (1, 1-dimethylethyl) -N-propylamino, N-butyl-N- (1-methylethyl) amino, N- (1-methylethyl) -N- (1-methylpropyl) amino, N- (1-methylethyl) - N - (2-methyl-propyl) amino, N- (1, 1-dimethylethyl) -N- (1-methyl-e thyl) amino, N-butyl-N- (1-methylpropyl) amino, N-butyl-N-
(2-methyl-propyl) amino, N-Butyl-N- (1, 1-dimethylethyl) amino, N- (1-Methylpropyl) -N- (2-methylpropyl) amino, N- (1 , 1-Dimetyhle- thyl) -N- (1-methylpropyl) amino und N- (1, 1-Dimethylethyl) -N- (2-methylpropyl) amino, vorzugsweise Dimethylamino und Diethy- lamino; Cyclopropylamino, Cyclobutylamino, Cyclopentylamino, Cyclohexylamino, Cycloheptylamino, Cyclooctylamino, 1,2-, 1,3-, 1,4-Oxazino.(2-methyl-propyl) amino, N-butyl-N- (1,1-dimethylethyl) amino, N- (1-methylpropyl) -N- (2-methylpropyl) amino, N- (1,1-dimetylene- thyl) -N- (1-methylpropyl) amino and N- (1, 1-dimethylethyl) -N- (2-methylpropyl) amino, preferably dimethylamino and diethylamino; Cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, 1,2-, 1,3-, 1,4-oxazino.
Die folgenden Beispiele sollen die Erfindung weiter verdeutli- chen.The following examples are intended to further illustrate the invention.
1) Herstellung von 2- (4-Chlor-2-fluor-5-methoxyphenyl) -3-chlor- 5-trifluor ethylpyridin1) Preparation of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-chloro-5-trifluoroethylpyridine
Ein Fünftel der Lösung von 5,3 g (22 mmol) l-Brom-4-chlor-One fifth of the solution of 5.3 g (22 mmol) l-bromo-4-chloro
2-fluor-5-methoxybenzol in 11 ml Tetrahydrofuran (THF) wurde zu 0,6 g (24,2 mmol) Magnesiumspänen gegeben. Nach Anspringen der Reaktion wurde die Temperatur bei 29 bis 31°C gehalten. Die Rest- lösung wurde innerhalb 1 h zugetropft und weiter 40 min bei 30°C nachgerührt. Die Lösung wurde von überschüssigem Magnesium abgetrennt, das mit THF gewaschen wurde. Bei 0°C wurde diese Lösung 5 innerhalb 10 min zu einer Mischung von 5,8 g (0,02 mol) 3-Chlor- 2-n-propylsulfonyl-5-trifluormethyl-pyridin und 0,65 g (1 mmol) Bis (triphenylphosphin) -nickel- (II) -chlorid in 25 ml THF gegeben. Anschließend wurde 14 h bei 25°C nachgerührt. Zu der Reaktionsmischung wurden 50 g Eis und 150 ml gesättigte Ammoniu chlorid-2-fluoro-5-methoxybenzene in 11 ml of tetrahydrofuran (THF) was added to 0.6 g (24.2 mmol) of magnesium shavings. After starting the In the reaction, the temperature was kept at 29 to 31 ° C. The residual solution was added dropwise over the course of 1 h and the mixture was stirred at 30 ° C. for a further 40 min. The solution was separated from excess magnesium, which was washed with THF. At 0 ° C., this solution was added to a mixture of 5.8 g (0.02 mol) of 3-chloro-2-n-propylsulfonyl-5-trifluoromethyl-pyridine and 0.65 g (1 mmol) of bis within 10 min (Triphenylphosphine) nickel (II) chloride added to 25 ml THF. The mixture was then stirred at 25 ° C for 14 h. 50 g of ice and 150 ml of saturated ammonium chloride were added to the reaction mixture.
10 Lösung gegeben, die Lösung extrahiert und die organische Phase mit gesättigter Ammoniumchlorid-Lösung gewaschen. Nach dem Trocknen, Einengen und Chromatographieren mit Methylenchlorid über Kieselgel erhielt man 8,2 g einer farblosen, kristallinen Masse, die nach der GC- und NMR-Untersuchung 3,73 g (54,9 %) der Titel -10 solution added, the solution extracted and the organic phase washed with saturated ammonium chloride solution. After drying, concentrating and chromatographing with methylene chloride over silica gel, 8.2 g of a colorless, crystalline mass were obtained which, according to GC and NMR analysis, gave 3.73 g (54.9%) of the title.
15 Verbindung enthielt.15 compound contained.
!H-NMR (CDC13), δ = 8,06 (s, 1H) , 8,6 (s, 1H, Pyridin) , 6,97 (d, 1H) , 7,25 (d, 1H, Phenyl)! H NMR (CDC1 3 ), δ = 8.06 (s, 1H), 8.6 (s, 1H, pyridine), 6.97 (d, 1H), 7.25 (d, 1H, phenyl)
20 2) Herstellung von 2- (4-Chlor-2-fluor-5-methoxyphenyl) -3-chlor- 5-trif luormethylpyridin aus Ha20 2) Preparation of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-chloro-5-trifluoromethylpyridine from Ha
Eine nach Beispiel 1 bereitete frische Lösung von 5,3 g (22 mmol) 4-Chlor-2-fluor-5-methoxyphenyl-magnesiumbromid in 11 ml THFA fresh solution prepared according to Example 1 of 5.3 g (22 mmol) of 4-chloro-2-fluoro-5-methoxyphenyl-magnesium bromide in 11 ml of THF
25 wurden innerhalb 5 min unter Rühren bei 0°C zu einer Mischung von 6,4g (0,02 mol) 3-Chlor-2-phenylsulfonyl-5-trifluormethylpyridin und 0,065 g (0,1 mmol) Bis (triphenylphosphin) nickel- (II) -chlorid in 25 ml THF gegeben. Anschließend wurde 1 h bei 25°C nachgerührt, nochmals 0,065 g (0,1 mmol) Katalysator zugegeben und 14 h bei25 were added within 5 min with stirring at 0 ° C. to a mixture of 6.4 g (0.02 mol) of 3-chloro-2-phenylsulfonyl-5-trifluoromethylpyridine and 0.065 g (0.1 mmol) of bis (triphenylphosphine) nickel (II) chloride added to 25 ml of THF. The mixture was then stirred at 25 ° C for 1 h, another 0.065 g (0.1 mmol) of catalyst was added and at 14 h
30 25°C nachgerührt. Nach Aufarbeitung wie in Beispiel 1 erhielt man 7,9 g einer kristallinen Masse, die nach der GC- und NMR-Analyse 4,4 g (64., 7 %) der Titelverbindung enthielt.30 25 ° C stirred. After working up as in Example 1, 7.9 g of a crystalline mass were obtained which, according to GC and NMR analysis, contained 4.4 g (64. 7%) of the title compound.
3) Herstellung von 2- (4-Chlor-2-fluor-5-methoxyphenyl) -3-chlor- 35 5-trifluormethylpyridin aus Ilb3) Preparation of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-chloro-35 5-trifluoromethylpyridine from Ilb
2,64 g (0,01 mol) einer nach Beispiel 1 bereiteten frischen Gri- gnardlösung von 4-Chlor-2-fluor-5-methoxy-phenylmagnesiumbromid in 30 ml THF wurden innerhalb 5min bei -15°C zu einer Mischung von 0 2,55 g (0,01 mol) 3-Chlor-2-n-propylsulfinyl-5-trifluormethylpyridin in 10 ml THF gegeben, wobei sich die Mischung auf -5°C erwärmte. Nach Erwärmen auf 25°C wurde unter HPLC-Kontrolle 2,5 h nachgerührt. Dann versetzte man das Reaktionsgemisch mit 50 g Eis und 100 ml gesättigter Ammoniumchloridlösung und extrahierte mit 5 Ether. Der Extrakt wurde mit gesättigter Ammoniumchloridlösung gewaschen, getrocknet und über neutralem Aluminiumoxid filtriert und mit Methylenchlorid vollständig eluiert. Nach dem Einengen erhielt man 2,2 g eines zähen Öls, das nach dem NMR-Spektrum und der GC-Analyse 1,9 g (56 % d. Th.) der Titelverbindung enthielt.2.64 g (0.01 mol) of a fresh Grignard solution of 4-chloro-2-fluoro-5-methoxy-phenylmagnesium bromide prepared according to Example 1 in 30 ml of THF became a mixture of 0 within 5 min at -15 ° C 2.55 g (0.01 mol) of 3-chloro-2-n-propylsulfinyl-5-trifluoromethylpyridine were added to 10 ml of THF, the mixture warming to -5 ° C. After warming to 25 ° C., stirring was continued for 2.5 hours under HPLC control. Then the reaction mixture was mixed with 50 g of ice and 100 ml of saturated ammonium chloride solution and extracted with 5 ether. The extract was washed with saturated ammonium chloride solution, dried and filtered over neutral aluminum oxide and completely eluted with methylene chloride. After constriction 2.2 g of a viscous oil were obtained which, according to the NMR spectrum and the GC analysis, contained 1.9 g (56% of theory) of the title compound.
4) Herstellung von 2- (4-Chlor-2-fluor-5-methoxyphenyl) -3-chlor- 5-trif luormethylpyridin aus Ha4) Preparation of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-chloro-5-trifluoromethylpyridine from Ha
5 ml einer Lösung von 13,8 g (57,5 mmol) l-Brom-4-chlor-5 ml of a solution of 13.8 g (57.5 mmol) of l-bromo-4-chloro
2-f luor-5-methoxybenzol in 25 ml THF wurden bei 20°C zu 1,46 g2-fluorous-5-methoxybenzene in 25 ml THF became 1.46 g at 20 ° C
(60,4 mmol) Magnesium unter Stickstoff gegeben. Nach Beginn der Reaktion wurde bei 28 bis 30°C die restliche obige Lösung innerhalb 20 min zugeführt. Es wurde mit THF nachgespült und 2 h bei 30 bis 25°C, anfangs unter Kühlung, gerührt. Die so erhaltene Grignardlösung wurde innerhalb 15 min bei 20 bis 25°C unter Stickstoff zu einer Mischung von 15,1 g (47 mmol) 3-Chlor-2-phenyl- sulfonyl-5-trifluormethylpyridin in 45 ml THF gegeben. Der Reaktionsverlauf wurde unter HPLC-Kontrolle verfolgt und die Reaktionsmischung nach 2,5 h Rühren bei 23 bis 24°C im Vakuum eingeengt. Der Rückstand wurde in Methylenchlorid aufgenommen und mit In' Salzsäure, In Natronlauge und mit Wasser extrahiert. Die organi - sehe Phase wurde im Vakuum eingeengt und bei 130 bis 135°C /(60.4 mmol) of magnesium added under nitrogen. After the start of the reaction, the remaining above solution was fed in at 20 to 30 ° C. within 20 minutes. It was rinsed with THF and stirred for 2 h at 30 to 25 ° C, initially with cooling. The Grignard solution thus obtained was added to a mixture of 15.1 g (47 mmol) of 3-chloro-2-phenylsulfonyl-5-trifluoromethylpyridine in 45 ml of THF at 20 to 25 ° C. under nitrogen over the course of 15 minutes. The course of the reaction was monitored under HPLC control and, after stirring for 2.5 h at 23 to 24 ° C., the reaction mixture was concentrated in vacuo. The residue was taken up in methylene chloride and extracted with In 'hydrochloric acid in sodium hydroxide solution and with water. The organic phase was concentrated in vacuo and at 130 to 135 ° C /
0,5 mbar destilliert. Man erhielt 14,9 g Produkt vom Fp. 100 bis 102°C, das nach GC-Analyse 13,7 g der reinen Titelverbindung enthielt.0.5 mbar distilled. 14.9 g of product of mp 100 ° to 102 ° C. were obtained which, according to GC analysis, contained 13.7 g of the pure title compound.
Ausbeute: 84,1 % bezogen auf Pyridin, 70,1 % bezogen auf AnisolYield: 84.1% based on pyridine, 70.1% based on anisole
5) Herstellung von 2- (4-Chlor-2-f luor-5-methoxyphenyl) -3-chlor- 5-trif luormethylpyridin aus Ilc5) Preparation of 2- (4-chloro-2-fluorine-5-methoxyphenyl) -3-chloro-5-trifluoromethylpyridine from Ilc
Eine Lösung von 13,9 g (43,9 mmol) 3-Chlor-2-phenylsulf inyl-5- trif luormethylpyridin in 25 ml THF wurde innerhalb 15 min bei 20 bis 25°C zu 30 ml einer nach Beispiel 1 bereiteten Grignardlösung aus 1,3 g (52,9 mmol) Magnesium und 12,1 g (50,4 mmol) l-Brom-4- chlor-2-f luor-5-methoxybenzol gegeben. Nach 2 h Rühren bei 24°C wurde die Reaktionslösung auf Eiswasser gegossen, mit 4n Salzsäure angesäuert und mit Methylenchlorid extrahiert. Die organische Phase wurde mit In Natronlauge und Wasser gewaschen, getrocknet und über Kieselgel filtriert. Man erhielt 16,3 g eines Gemisches vom Fp. 87 bis 90°C, das nach GC-Analyse 12,1 g der Ti - telverbindung enthielt.A solution of 13.9 g (43.9 mmol) of 3-chloro-2-phenylsulfinyl-5-trifluoromethylpyridine in 25 ml of THF was converted into 30 ml of a Grignard solution prepared according to Example 1 at 20 to 25 ° C. within 15 minutes 1.3 g (52.9 mmol) of magnesium and 12.1 g (50.4 mmol) of l-bromo-4-chloro-2-fluorous-5-methoxybenzene were added. After stirring at 24 ° C. for 2 h, the reaction solution was poured onto ice water, acidified with 4N hydrochloric acid and extracted with methylene chloride. The organic phase was washed with in sodium hydroxide solution and water, dried and filtered through silica gel. 16.3 g of a mixture of mp 87 to 90 ° C. were obtained which, according to GC analysis, contained 12.1 g of the title compound.
Ausbeute: 81 % bezogen auf Pyridin, 70,4 % bezogen auf Anisol Yield: 81% based on pyridine, 70.4% based on anisole

Claims

Patentansprüche claims
1 . Verf ahren zur Herstellung substituierter Phenylpyridine der Formel I1 . Process for the preparation of substituted phenylpyridines of the formula I.
worinwherein
R1 Wasserstoff, Fluor, Chlor oder Halogenalkyl, R2 Fluor, Chlor oder Halogenalkyl, R3 Wasserstoff, Halogen oder ein unter den Reaktionsbedingungen inerter organischer Rest R4 Alkyl, Halogenalkyl, Halogen, Alkylsulfonyl, Halogenal- kylsulfonyl oder Halogenalkoxy, R5 Wasserstoff, Halogen, Halogenalkyl, Halogenalkoxy, Alkyl sulfonyl oder Halogenalkylsulfonyl ,R 1 is hydrogen, fluorine, chlorine or haloalkyl, R 2 is fluorine, chlorine or haloalkyl, R 3 is hydrogen, halogen or an organic radical which is inert under the reaction conditions R 4 is alkyl, haloalkyl, halogen, alkylsulfonyl, haloalkylsulfonyl or haloalkoxy, R 5 is hydrogen , Halogen, haloalkyl, haloalkoxy, alkyl sulfonyl or haloalkylsulfonyl,
dadurch gekennzeichnet, daß man substituierte Pyridine der Formel IIcharacterized in that substituted pyridines of the formula II
in der in the
R4 und R→ die vorgenannte Bedeutung haben, n 1 oder 2 bedeutet und Y für Alkyl, Alkenyl, Alkinyl, jeweils gegebenenfalls substituiert durch Halogen oder Methoxy; ferner Cycloalkyl oder Phenylalkyl; sowie gegebenenfalls substituiertes Phenyl oder Naphthyl, steht, mit einer Arylverbindung der Formel IIIR 4 and R → have the abovementioned meaning, n denotes 1 or 2 and Y represents alkyl, alkenyl, alkynyl, in each case optionally substituted by halogen or methoxy; also cycloalkyl or phenylalkyl; and optionally substituted phenyl or naphthyl, with an aryl compound of formula III
in der in the
R1, R2 und R3 die vorgenannte Bedeutung haben und M für Magnesium oder Zink steht und Z Halogen bedeutet,R 1 , R 2 and R 3 have the abovementioned meaning and M represents magnesium or zinc and Z represents halogen,
umsetzt.implements.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Umsetzung in Gegenwart eines Übergangsmetallkata]ysators er- folgt.2. The method according to claim 1, characterized in that the reaction takes place in the presence of a transition metal catalyst.
3. Verfahren nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß Y in Formel II für für Alkyl, gegebenenfalls substituiert durch Halogen oder Methoxy; sowie gegebenenfalls substituier- tes Phenyl, steht.3. Process according to claims 1 or 2, characterized in that Y in formula II for alkyl, optionally substituted by halogen or methoxy; and optionally substituted phenyl.
4. Verfahren nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß man eine Grignard-Verbindung der Formel lila,4. The method according to claims 1 or 2, characterized in that a Grignard compound of the formula purple,
worin wherein
R1 Wasserstoff, Fluor, Chlor oder Halogenalkyl, R2 Fluor, Chlor oder Halogenalkyl,R 1 is hydrogen, fluorine, chlorine or haloalkyl, R 2 is fluorine, chlorine or haloalkyl,
R3 Wasserstoff, Halogen oder ein unter den Reaktionsbedingungen inerter organischer Rest bedeutet, umsetzt. R 3 represents hydrogen, halogen or an organic radical which is inert under the reaction conditions.
5. Verfahren nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß man eine Zink-Verbindung der Formel Illb,5. The method according to claims 1 or 2, characterized in that a zinc compound of the formula Illb,
worin wherein
R1 Wasserstoff, Fluor, Chlor oder Halogenalkyl, R2 Fluor, Chlor oder Halogenalkyl, R3 Wasserstoff, Halogen oder ein unter den Reaktionsbedingungen inerter organischer Rest bedeutet,R 1 is hydrogen, fluorine, chlorine or haloalkyl, R 2 is fluorine, chlorine or haloalkyl, R 3 is hydrogen, halogen or an organic radical which is inert under the reaction conditions,
umsetzt.implements.
6. Verfahren nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß man eine Grignard-Verbindung der Formel lila gemäß Anspruch 4 mit einem Pyridinderivat der Formeln Ila, Ilb oder Ilc6. The method according to claims 1 or 2, characterized in that a Grignard compound of the formula purple according to claim 4 with a pyridine derivative of the formulas Ila, Ilb or Ilc
Aryl, n = 2Aryl, n = 2
Alkyl, n = 1 Aryl, n = 1Alkyl, n = 1 Aryl, n = 1
umsetzt ,implements
7. Verfahren nach Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß man eine Zink-Verbindung der Formel Illb gemäß Anspruch 5 mit einem Pyridinderivat der Formeln Ila, Ilb oder Ilc gemäß Anspruch 6 umsetzt.7. Process according to Claims 1 or 2, characterized in that a zinc compound of the formula Illb according to Claim 5 is reacted with a pyridine derivative of the formulas Ila, Ilb or Ilc according to Claim 6.
8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Katalysatoren Nickel (0)-, Nickel (II)- und/oder Palla- dium(0)- sowie Palladium (II) -Verbindungen verwendet.8. The method according to claim 1, characterized in that the catalysts used are nickel (0) -, nickel (II) - and / or palladium (0) - and palladium (II) compounds.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Katalysatoren Palladium (0) - und/oder Palladiu (II ) -Verbindungen verwendet. 9. The method according to claim 1, characterized in that palladium (0) - and / or Palladiu (II) compounds are used as catalysts.
EP97942894A 1996-09-12 1997-08-29 Process for the production of substituted phenylpyridines Withdrawn EP0931068A1 (en)

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DE19636995A1 (en) 1996-09-12 1998-03-19 Basf Ag Process for the preparation of substituted phenylpyridines
JP2001500141A (en) 1996-09-12 2001-01-09 ビーエーエスエフ アクチェンゲゼルシャフト Substituted thiopyridine
JP2002507197A (en) 1997-05-30 2002-03-05 ビーエーエスエフ アクチェンゲゼルシャフト Substituted thiopyridine
WO1998054137A1 (en) * 1997-05-30 1998-12-03 Basf Aktiengesellschaft Substituted 2-phenyl pyridines, their manufacture and use as herbicides
IT1313664B1 (en) * 1999-10-12 2002-09-09 Norpharma S P A PROCESS FOR THE PREPARATION OF AN ARY-PYRIDIN COMPOUND.
US7075102B2 (en) * 2000-06-30 2006-07-11 E.I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
JP4208512B2 (en) * 2002-07-23 2009-01-14 株式会社クラレ Process for producing 5- (2'-pyridyl) -2-pyridone derivative
ES2364844T3 (en) * 2002-07-23 2011-09-15 Kuraray Co., Ltd. PROCEDURE TO PRODUCE A 2-SUBSTITUTED PIRIDINE DERIVATIVE.
WO2004039779A1 (en) * 2002-10-02 2004-05-13 Euticals Prime European Therapeuticals Spa Process for the preparation of pyridyl-aryl-sulphonic compounds
CN103755631B (en) * 2014-01-07 2016-03-02 常州工程职业技术学院 The direct aromatize technique of pyridine derivate
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