WO2007115685A1 - Verfahren zum herstellen von biphenylaminen über vinylaniline - Google Patents

Verfahren zum herstellen von biphenylaminen über vinylaniline Download PDF

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WO2007115685A1
WO2007115685A1 PCT/EP2007/002720 EP2007002720W WO2007115685A1 WO 2007115685 A1 WO2007115685 A1 WO 2007115685A1 EP 2007002720 W EP2007002720 W EP 2007002720W WO 2007115685 A1 WO2007115685 A1 WO 2007115685A1
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formula
alkyl
chlorine
meanings given
fluorine
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PCT/EP2007/002720
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French (fr)
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Alexander Straub
Thomas Himmler
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Bayer Cropscience Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/10—Cyclisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a novel process for preparing substituted biphenylamines, novel intermediates and their preparation, and to a process for preparing fungicidally active carboxamides.
  • biphenyl derivatives can be prepared from phenylboronic acids and phenyl halides by Suzuki or Stille coupling (cf., for example, WO 01/42223, WO 02/064562, WO 03/070705, Robertson and Hansen (eds.) PCBs, The University Press of Kentucky 2001, 57-60). Furthermore, it is known to obtain biphenyl derivatives by reacting aryl-zinc halides with aryl halides (Bull. Korean Chem. Soc. 2000, 21, 165-166).
  • a disadvantage of these methods are the high production costs.
  • the preparation of a boronic acid requires a Grignard reaction, and transition metal-catalyzed cross-coupling (eg Suzuki) requires relatively high levels of palladium catalysts or (Bull. Korean Chem. Soc. 2000, 21, 165-166) the use of nearly equivalent amounts of zinc which must be disposed of as waste. To activate the zinc, moreover, the carcinogenic dibromoethane is needed.
  • biphenyl derivatives are obtained by reacting alkynylanilides via a Diels-Alder reaction with dichlorothiophene dioxide (compare WO 2006/024388).
  • the disadvantage here is that the alkynylanilide must be prepared over two stages, that it is decomposable and tends to form 2 + 2 adducts as by-products during the Diels-Alder step, which reduces the yield.
  • the object of the present invention was therefore to provide a new, economical process by which biphenylamines can be obtained with high overall yield and high purity.
  • the present invention thus relates to a process for the preparation of biphenylamines of the general formula (I)
  • R 1 represents hydrogen, fluorine, chlorine, dC 4 alkyl, C r C 4 alkoxy, Ci-C 4 alkylthio or C 1 -C 4 -
  • X 1 is fluorine, chlorine or bromine
  • X 2 is fluorine, chlorine or bromine
  • Hal is chlorine, bromine or iodine
  • R 2 is hydrogen
  • R 3 is hydrogen or the group A-CO- or a protecting group, or
  • A is one of the following radicals A 1 to A 7:
  • R 5 is C r C 3 -alkyl
  • R 6 is hydrogen, halogen, C 3 alkyl or C r C 3 -haloalkyl having 1 to 7 fluorine,
  • R 7 is hydrogen, halogen or C 1 -C 3 -alkyl
  • R 8 is hydrogen, halogen, C 1 -C 3 -alkyl, amino, mono- or di (C 1 -C 3 -alkyl) -amino
  • R 9 is hydrogen, halogen, C 1 -C 3 -alkyl or C 1 -C 3 - Haloalkyl having 1 to 7 fluoro
  • R 10 is 3 alkyl or C 3 -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms is halogen, C, -C, R 11 is halogen, C r C 3 - alkyl or C r C 3 -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms,
  • R 12 is hydrogen, halogen, C r C 3 -alkyl or Ci-C is 3 -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms, R 1 has the meanings given above, reacted with ethene,
  • R 2 is hydrogen and R 3 is a protecting group, or
  • R 2 and R 3 together represent a protecting group
  • R 1 , X 1 and X 2 have the meanings given above, the protective group split off at the nitrogen.
  • the biphenylamines of the formula (I) can be prepared in good yields from inexpensive starting materials without a Grignard and Suzuki reaction by means of this reaction sequence.
  • the Diels-Alder reaction of the ethenyl aniline compounds with the thiophene derivatives surprisingly proceeds already at lower temperatures than with the alkynylanilides and thus allows a more selective course of the reaction with better yields and fewer side reactions of the reactants involved ,
  • process A according to the invention can be exemplified over all four stages by the following formula scheme.
  • the protecting group can also be removed before the oxidation step, ie steps (3) and (4) can also be carried out in reverse order [first step (4) followed by step (3)].
  • the preferred, particularly preferred and very particularly preferred meanings apply to all compounds in which the respective radicals occur.
  • Hal is preferably chlorine.
  • HaI is also preferred for bromine.
  • HaI is also preferred for iodine.
  • Hal is particularly preferably bromine.
  • R 1 is preferably hydrogen.
  • R 1 furthermore preferably represents fluorine, where fluorine is particularly preferably in the 3-, 4- or 5- position, very particularly preferably in the 3- or 5-position, in particular in the 5-position of the respective compound [cf. eg formula (I)].
  • R 1 furthermore preferably represents chlorine, chlorine being particularly preferably in the 3- or 5-position of the respective compound.
  • R 1 also preferably represents methyl or iso-propyl, with methyl or iso-propyl particularly preferably being in the 6-position of the respective compound.
  • R 1 furthermore preferably represents trifluoromethyl, trifluoromethyl being particularly preferably in the 4- or 5-position of the respective compound.
  • R 1 furthermore preferably represents methoxy or methylthio, with methoxy or methylthio particularly preferably being in the A, 5- or 6-position of the respective compound.
  • R 2 and R 3 are each preferably hydrogen.
  • R 2 is preferably hydrogen and
  • R 3 is the group A-CO- or a protective group selected from methoxycarbonyl, 9-fluorenylmethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, 2-
  • Trimethylsilylethoxycarbonyl 1,1-dimethylpropoxycarbonyl, 1-methyl-1-phenylethoxycarbonyl, 1-methyl-1 - (4-biphenylyl) ethoxycarbonyl, 1, 1-dimethyl-2-haloethoxycarbonyl (wherein "halo" is fluorine or chlorine), 1, 1-dimethyl-2-cyanoethoxycarbonyl, t-butoxycarbonyl, cyclobutyloxycarbonyl, 1-methylcyclobutyloxycarbonyl, 1-adamantyloxycarbonyl, vinyloxycarbonyl, allyloxycarbonyl, cinnamyloxycarbonyl, 8-quinolyloxycarbonyl, N-hydroxypiperidinyloxycarbonyl, benzyloxycarbonyl, p-nitrobenzyloxycarbonyl, 3,4-dimethoxy-6-nitrobenzyloxycarbonyl, 2,4-dichlorobenzyloxycarbonyl, 5-benzisoxazoly
  • R 2 and R 3 together with the nitrogen atom to which they are attached, are preferably 4,5-diphenyl-3-oxazolin-2-one, N-phthaloyl, N-dithiasuccinoyl, N, N'-isopropylidene, benzyli -, nitrobenzylidene or salicylidene. More preferably, R 2 is hydrogen and
  • R 3 is a protective group selected from methoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, 1,1-dimethylpropoxycarbonyl, 1-methyl-1-phenylethoxycarbonyl, 1-methyl-1 - (4-biphenylyl) -ethoxycarbonyl, 1,1-dimethyl -2-haloethoxycarbonyl (in which "halo" is fluorine or chlorine), 1,1-dimethyl-2-cyanoethoxycarbonyl, t-butoxycarbonyl, cyclobutyloxycarbonyl, 1-methylcyclobutyloxycarbonyl, 1-adamantyloxycarbonyl, vinyloxycarbonyl,
  • R 2 and R 3 together with the nitrogen atom to which they are attached are particularly preferred for N-phthaloyl, N, N'-isopropylidene, benzylidene or nitrobenzylidene.
  • R 2 is hydrogen and
  • R 3 is a protective group selected from methoxycarbonyl, trichloroethoxycarbonyl, 1,1-dimethylpropoxycarbonyl, t-butoxycarbonyl, formyl, acetyl, pivaloyl, chloroacetyl, trichloroacetyl, trifluoroacetyl, acetoacetyl, benzoyl, mesyl, tosyl, phenylsulfonyl.
  • A is preferably Al, A2, A3, A4 or A5.
  • A is particularly preferably Al or A2.
  • R 5 is preferably methyl.
  • R 6 is preferably iodine, methyl, difluoromethyl or trifluoromethyl.
  • R 6 particularly preferably represents methyl, difluoromethyl or trifluoromethyl.
  • R 7 is preferably hydrogen, fluorine, chlorine or methyl.
  • R 7 particularly preferably represents hydrogen or fluorine.
  • R 8 is preferably hydrogen, chlorine, methyl, amino or dimethylamino.
  • R 8 particularly preferably represents methyl
  • R 9 is preferably methyl, difluoromethyl or trifluoromethyl.
  • R 10 is preferably chlorine, bromine, iodine, methyl, difluoromethyl or trifluoromethyl.
  • R 10 particularly preferably represents iodine, difluoromethyl or trifluoromethyl.
  • R 11 is preferably bromine or methyl.
  • R 11 particularly preferably represents methyl.
  • R 12 is preferably methyl or trifluoromethyl.
  • R 12 particularly preferably represents methyl or trifluoromethyl.
  • X 1 is preferably fluorine.
  • X 1 is also preferably chlorine.
  • X 1 is also preferably bromine.
  • X 2 is preferably fluorine. X 2 is also preferably chlorine.
  • X 2 is also preferably bromine.
  • Preferred starting materials are aniline compounds of the formula (II-a)
  • R 4 is hydrogen, C r C 4 alkyl or Ci-C 4 alkoxy
  • R 4 is preferably hydrogen, methyl, ethyl, iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy or tert-butoxy.
  • R 4 particularly preferably represents methyl, tert-butyl, methoxy or tert-butoxy.
  • R 4 is very particularly preferably methyl.
  • aniline compounds of the formula (II) to be used as starting materials in carrying out the process A according to the invention in the first stage are known in some cases or can be obtained by known processes [cf. e.g. Synlett, 2003, (14), 2231; Recl. Trav. Chim. Pay-Bas. 1964, 83, 1142 ;. J. Het. Chem. 1969, 6, 243].
  • the ethenyl-aniline compounds of the formula (III) to be used as starting materials in carrying out the process A according to the invention in the second stage are partly new (in the case where R 1 is fluorine) and are also the subject of this application.
  • Ethenyl-aniline compounds of the formula (III) are obtained by the first step of the process A according to the invention.
  • the thiophene dioxides of the formula (IV) to be used as starting materials in carrying out process A according to the invention in the second stage are known (cf., for example, J. Org. Chem. 1961, 26, 346-351, J. Fluorine Chem , 143-151; J. Amer. Chem. Soc. 2000, 122, 2440-2445).
  • the first step of the process A according to the invention is carried out in the presence of a transition metal.
  • a palladium catalyst such as Pd (OAc) 2 , Pd (OH) 2 , PdCl 2 , Pd (acac) 2 (
  • a of the invention is carried out in the presence of an inorganic or organic base.
  • organic bases are diethylamine, dipropylamine, dibutylamine, dicyclohexylamine, piperidine, triethylamine, tripropylamine, tributylamine, DBU, DABCO.
  • inorganic bases are potassium acetate, sodium acetate, potash, soda, potassium tert-butoxide, sodium tert-butoxide, sodium tert-amylate. Preferred are triethylamine, tributylamine, sodium acetate and potassium acetate.
  • a of the invention can be carried out with or without the addition of ligands.
  • ligands which may be mentioned are triarylphosphines, diarylalkylphosphines, diarylphosphines, dialkylphosphines, dialkylarylphosphines, trialkylphosphines, diaryl (dialkylamino) phosphines and arylbis (dialkylamino) phosphines.
  • tri (o-tolyl) phosphine triphenylphosphine, diphenyl-menthylphosphine, diphenyl-neomenthylphosphine, BINAP and mixtures of these phosphines.
  • the molar ratio between metal and ligand can be varied widely, it is preferable to work at 1-6 equivalents.
  • the ligands are added either in the amount required for the desired molar ratio to the reaction mixture containing a ligand-free precursor of the catalyst such as a palladium salt such as PdCl 2 or Pd (OAc) 2 ; or one uses a complex already containing the ligand such as dichloro-bis (triphenylphosphine) palladium (II) or tetrakis (triphenylphosphine) palladium (0) and optionally additionally the same or a different ligand to set the desired molar ratio is.
  • a ligand-free precursor of the catalyst such as a palladium salt such as PdCl 2 or Pd (OAc) 2 ; or one uses a complex already containing the ligand such as dichloro-bis (triphenylphosphine) palladium (II) or tetrakis (triphenylphosphine) palladium (0) and optionally additionally the same or a different ligand to
  • the first step of process A according to the invention is carried out in the presence of water, it is also possible to use triarylphosphines which are substituted on the aromatic such that the water solubility of the palladium complexes formed is increased.
  • substituents may be, for example, sulfonic acid residues, carboxyl groups, phosphonic acid residues, phosphonium groups, peralkylammonium groups, hydroxy groups and polyether groups.
  • tetraalkonium salts such as tetrabutylammonium bromide, tetrabutyl ammonium acetate, AryUP-X (in which aryl is phenyl or o-tolyl and X is chlorine or bromine) can be used.
  • Suitable ligands are, for example, EDTA, substituted diazabutadienes or 1,3-bis (aryl) imidazole carbenes.
  • reaction is carried out in solvents or solvent mixtures.
  • solvents or solvent mixtures By way of example, mention may be made of N, N-dialkylalkanamides, e.g. N-methylpyrrolidone, dimethylformamide and dimethylacetamide, ketones such as acetone,
  • Dioxane e.g. Methanol, ethanol, n-propanol, isopropanol and isoamyl alcohol, water, ethylene carbonate or propylene carbonate.
  • alcohols such as e.g. Methanol, ethanol, n-propanol, isopropanol and isoamyl alcohol, water, ethylene carbonate or propylene carbonate.
  • first step of the process A according to the invention is generally carried out at temperatures in the range of 20 0 C to 15O 0 C, preferably in the range of 50 0 C to 130 0 C.
  • first stage of the method A according to the invention for 1 mole of anilide of the formula (II) is generally an excess of ethylene (3-120 bar) and between 0.001 and 10 mol% transition metal catalyst and 0.5 to 10 moles of a base.
  • Products of the first stage can also be obtained from 2-alkynyl-aniline compounds by reduction of the triple bond, for example with the aid of a Lindlar catalyst.
  • the second stage of the process A operates in the common AIl- at temperatures between 20 0 C and 150 0 C.
  • the temperature is selected as low as possible to minimize side reactions and decomposition of the starting materials to be avoided, but high enough for the reaction to still running fast enough.
  • the second stage of process A according to the invention is preferably carried out in the presence of a solvent.
  • Suitable solvents for carrying out the second step of process A according to the invention are: aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, nitriles, alcohols, ketones, ethers, amides or esters. Specific examples which may be mentioned are: toluene, xylene, methylcyclohexane, mesitylene, decalin, tetralin, chlorobenzene, dichlorobenzene, nitrobenzene, nitrotoluene, butyronitrile, valeronitrile, cyclohexanone, ethylene glycol monoethyl ether, anisole, dimemylformamide, ethyl acetate, isopropyl acetate, butyl acetate. Toluene, xylene, butyronitrile or valeronitrile are preferably used.
  • an ethenyl anilide of the formula (III) can be initially charged in a solvent and a thiophene dioxide of the formula (IV) can be added.
  • thiophene dioxide of the formula (TV) per mole of ethenyl anilide of the formula (III), 0.5 mol to 1.5 mol, preferably 0.9 mol to 1.25 mol, of thiophene dioxide of the formula (TV). In general, however, the thiophene dioxide of the formula (TV) is used in approximately equimolar amounts.
  • the purification of the product is carried out by conventional methods of organic chemistry, for example by crystallization.
  • the oxidation of the dihydro stage to the aromatic can be carried out by oxidants, with the aid of oxidation catalysts, or by combination of oxidants with suitable Oxidationskata- catalysts.
  • Catalysts which may be mentioned are noble metal catalysts such as Pd, Pt, iridium, Rhodium.
  • the noble metals may be present on support materials such as activated carbon, Al 2 O 3 or silica gel, or as nanoparticles. They can be used either individually or as mixtures.
  • the addition of other metals such as Fe, Co, Ni, Cu, Ag, V, Mn either in metallic form or as salts, such as halides, sulfates, nitrates or acetates, may be useful.
  • Metals such as Fe, Co 5 Ni, Cu, Ag, V, Mn either in metallic form or as salts, such as halides, sulfates, nitrates or acetates and molybdovanadophosphoric also come as catalysts for air or oxygen-driven aromatizations in question.
  • Molybdovanadophosphoric acids eg H 5 [PMO IO V 2 O 40 ] X 32.5 H 2 O
  • a carrier material such as activated carbon
  • hydrogen acceptors may also be useful.
  • all systems which are capable of accepting hydrogen such as e.g. Nitroaromatics such as nitrobenzene or nitrotoluene, alkenes such as cyclopentene or cyclohexene, diethyl malonate, maleic anhydride, tetralin or acetylenes such as methyl butynol.
  • Suitable oxidizing agents are, for example, potassium permanganate, barium manganate, manganese dioxide, selenium dioxide, sodium periodate, lead (IV) acetate, ammonium molybdate, hydrogen peroxide, persulfates such as oxones, activated carbon, sulfur, oxygen, quinones such as benzoquinone, chloranil, 2,3-dichloro-5 , 6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene, nitric acid, nitric acid esters, ceric ammonium nitrate, t-butyl nitrite, nitrogen oxides, K 3 Fe [(CN) 6 ] or electrochemical processes.
  • the oxidizing agents may optionally be recycled in situ.
  • Suitable solvents are all solvents which are inert under the conditions, e.g. aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, nitriles, alcohols, ketones, ethers, amides or esters. In detail, be mentioned.
  • oxidizing agent it works depending on the oxidizing agent at temperatures between -10 ° and 200 0 C. Of oxidizing agents must be used for a quantitative conversion at least equimolar amounts based on the oxidation equivalent. In some cases, up to 10 equivalents may be required. In the case of catalysts, 0.01 to 10 mol% are generally sufficient.
  • the removal of the protective group [-C (OO) R 4 ] on the nitrogen can be carried out either basic or acidic by known methods (cf., for example, TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, Ed. 3, New York, Wiley & Sons, 1999).
  • Steps 2, 3 and 4 of process A according to the invention are generally carried out under atmospheric pressure, unless stated otherwise. However, it is also possible to work under elevated or reduced pressure.
  • the biphenylamines of the formula (I) are valuable intermediates for the preparation of fungicidal active compounds.
  • R 1 is hydrogen, fluorine, chlorine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio or QC 4 -haloalkyl,
  • X 1 is fluorine, chlorine or bromine, - -
  • X 2 is fluorine, chlorine or bromine
  • A is one of the following radicals A1 to A7:
  • R 5 is C r C 3 alkyl
  • R 6 is hydrogen, halogen, Ci-C 3 alkyl or C r C 3 -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms,
  • R 7 is hydrogen, halogen or C 1 -C 3 -alkyl
  • R 8 is hydrogen, halogen, C 3 alkyl, amino, mono- or di (Ci-C 3 alkyl) amino
  • R 9 is hydrogen, halogen, Ci-C3 alkyl or Ci-C3 haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms
  • R 10 is halogen, C r C 3 alkyl or C r C 3 haloalkyl having 1 to 7 fluorine, chlorine and / or
  • R 11 is halogen, C r C 3 alkyl or Ci-C 3 haloalkyl having 1 to 7 fluorine, chlorine and / or
  • Bromine atoms, R 12 3 alkyl or Ci-C is 3 -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms, hydrogen, halogen, C r C,
  • Hal is chlorine, bromine or iodine
  • R 2 is hydrogen
  • R 3 is hydrogen or the group A-CO- or a protective group, or R 2 and R 3 together represent a protective group,
  • R 1 and A have the meanings given above, reacted with ethene, (2) in a second stage, the ethenyl aniline compounds of the formula (III) thus obtained
  • R 2 is hydrogen and R 3 is a protecting group, or
  • R 2 and R 3 together represent a protecting group
  • R 1 , X 1 and X 2 have the meanings given above, the protective group is split off on the nitrogen, and
  • A has the abovementioned meanings and Y is halogen or hydroxyl, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
  • Hal, A, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , X 1 and X 2 have the above preferred, particularly preferred and very particularly preferred meanings Y is preferably chlorine or hydroxyl.
  • the first to fourth stages of method B correspond to the first to fourth stages of the method A according to the invention and are carried out as described above.
  • the carboxylic acid derivatives of the formula (VIII) to be used as starting materials in carrying out the process A according to the invention in the fifth stage are known and / or can be prepared by known processes (cf., WO 03/066609, WO 03/066610, cf. EP-A 0 545 099, EP-A 0 589 301, EP-A 0 589 313 and US 3,547,917).
  • Suitable diluents for carrying out the fifth step of process B according to the invention are all inert organic solvents. These include, preferably, aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as
  • the fifth step of process B according to the invention is optionally carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor all customary inorganic or organic bases are suitable. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, lithium diisopropylamide, sodium methoxide, sodium ethoxide, potassium tert-butoxide , Sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium bicarbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-Methyhnorpholine, N,
  • the fifth step of process B according to the invention is optionally carried out in the presence of a suitable condensing agent.
  • a suitable condensing agent all condensing agents conventionally used for such amidation reactions are suitable.
  • acid halide biidners such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride
  • Anhydridtruckner such as ethyl chloroformate, Chlorameisenklame- ethyl ester, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride
  • Carbodiimides such as N, N'-dicyclohexylcarbodiimide (DCC), other conventional condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-caprotyldidnazole, 2-eth
  • the fifth step of process B according to the invention is optionally carried out in the presence of a catalyst.
  • a catalyst examples which may be mentioned are 4-dimethylaminopyridine, 1-hydroxybenzotriazole or dimethylformamide.
  • reaction temperatures can be varied in carrying out the fifth step of the process B according to the invention in a wider range.
  • the reaction is carried out at temperatures of from 0 ° C. to 150 ° C., preferably at temperatures of from 0 ° C. to 80 ° C.
  • Step 1 N-r (4-fluoro-2-vinyl) phenyllacetamide
  • the filtrate is mixed with 0.5 g pyrocatechol and evaporated at 3, 5 -5mm / 58 ° C heating bath temperature.
  • the residue is stirred four times with 4 l of toluene at 8O 0 C and sucked hot over a 3 cm high layer of silica gel.
  • the filtrate is evaporated to 1.2 1, cooled with stirring to 0 0 C and filtered off with suction.
  • the residue is superficially stirred with 480 ml of methylcyclohexane and filtered with suction. This is repeated with 400 ml of methylcyclohexane. - -
  • the target product is obtained in 74% yield (versus standard) and 93% purity with a melting point of 1 10-112 0 C.
  • Second embodiment with 0.25 mol% Pd catalyst and triphenylphosphine To a mixture of 7.65 g (33 mmol) of N- (2-bromo-4-fluorophenyl) acetamide and 6.68 g (66 mmol) of triethylamine in 55 ml DMF is added 86.56 mg (0.33 mmol) of triphenylphosphine and 18.52 mg (0.083 mmol) of palladium (II) acetate and stirred in an autoclave at an ethene pressure of 30 bar for 16 hours at 110 0 C.
  • Step 2 ⁇ -f 2- (3,4-dichlorocyclohexa-2,4-dien-1-yl) -4-fluorophenylacetamide
  • Catalyst preparation 1 eq of MoO3 and 0.5 eq of NaVO3 are added to water at a rate of about 85 percent. Phosphoric acid and cook for 8 hours. After acidification with conc. HCl is extracted with ether, the ethereal phase evaporated and the residue dried in a drying oven. The catalyst (H 5 [PMo I oV 2 O 4O ], is dissolved in methanol, treated with the appropriate amount of activated carbon and evaporated.
  • Step 5 N- (3'4'-Dichloro-5-fluorobiphenyl-2-yl) -3- (difluoromethvn-1-methyl-7H-pyrazole-4-carboxamide

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PCT/EP2007/002720 2006-04-07 2007-03-28 Verfahren zum herstellen von biphenylaminen über vinylaniline WO2007115685A1 (de)

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JP2013503118A (ja) * 2009-08-31 2013-01-31 バイエル・クロップサイエンス・アーゲー 置換ビフェニル類を調製するためのテトラアリールボレートプロセス
CN108440312A (zh) * 2018-05-04 2018-08-24 江苏科技大学 一种2-(3,4)-二氯苯基-4-氟苯胺的制备方法

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CN102348675B (zh) 2009-03-09 2014-10-01 巴斯夫欧洲公司 制备取代2-硝基联苯的方法
CN106103404B (zh) * 2014-01-17 2017-11-24 迈克斯(如东)化工有限公司 联苯化合物的制备及应用
EP3416949A1 (en) * 2016-02-18 2018-12-26 Solvay Sa Process for the manufacture of carboxamides

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WO2003070705A1 (de) * 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Disubstituierte pyrazolylcarboxanilide
WO2006024388A1 (de) * 2004-08-27 2006-03-09 Bayer Cropscience Ag Verfahren zum herstellen von biphenylaminen

Patent Citations (2)

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WO2003070705A1 (de) * 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Disubstituierte pyrazolylcarboxanilide
WO2006024388A1 (de) * 2004-08-27 2006-03-09 Bayer Cropscience Ag Verfahren zum herstellen von biphenylaminen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013503118A (ja) * 2009-08-31 2013-01-31 バイエル・クロップサイエンス・アーゲー 置換ビフェニル類を調製するためのテトラアリールボレートプロセス
CN108440312A (zh) * 2018-05-04 2018-08-24 江苏科技大学 一种2-(3,4)-二氯苯基-4-氟苯胺的制备方法

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