EP2046720A2 - Derives des nitrobenzole ainsi que procede pour la preparation de tels nitrobenzoles et alkylaniline - Google Patents

Derives des nitrobenzole ainsi que procede pour la preparation de tels nitrobenzoles et alkylaniline

Info

Publication number
EP2046720A2
EP2046720A2 EP07786008A EP07786008A EP2046720A2 EP 2046720 A2 EP2046720 A2 EP 2046720A2 EP 07786008 A EP07786008 A EP 07786008A EP 07786008 A EP07786008 A EP 07786008A EP 2046720 A2 EP2046720 A2 EP 2046720A2
Authority
EP
European Patent Office
Prior art keywords
halogen
alkyl
hydrogen
formula
prop
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07786008A
Other languages
German (de)
English (en)
Inventor
Alexander Straub
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer CropScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP2046720A2 publication Critical patent/EP2046720A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/34—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • 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
    • C07C209/70—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 by reduction of unsaturated amines
    • 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
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to a process for the preparation of nitrobenzene derivatives and aniline derivatives, which are important as intermediates for fungicidally effective alkylanilides.
  • Alkyl nitrobenzenes can be converted to alkylanilines by reduction of the nitro group and have hitherto been used e.g. by the nitration of alkylaromatics (EP-A-824099; WO-A-03074491) or the reaction of nitrobenzene derivatives with Grignard reagents (J. Org. Chem. 1980, 45, 522).
  • Alkenyl nitrobenzenes e.g. l- (2-Nitrophenyl) -1,3-butadiene have hitherto only been accessible via the complicated route shown in Scheme (I) (see US Pat. No. 2,626,960).
  • the alkylanilines which are unbranched in the 1 'position should be obtainable with improved selectivities in high purities and yields.
  • R 1 is hydrogen, halogen, -CR '(CF 3 ) 2 , wherein R' is selected from H, F or an O-Ci. 4 alkyl group and preferably is hydrogen, s I is the substituent R 1 is preferably in the meta or para position, more preferably in the 4-position (para to the NO 2 group) of the aromatic
  • R 2 is i-propyl, cyclopropyl, ethyleneyl or t-butyl, characterized in that 2-halonitrobenzenes of the formula (II)
  • R 1 has the above meaning
  • X is a halogen atom, preferably Cl or Br, particularly preferably Cl, with alkenes of the formula (HI)
  • a second embodiment of the invention relates to nitrobenzene derivatives according to the general formula (IV)
  • R hydrogen, halogen, -CR '(CF 3) 2, wherein R' is selected from H, F, or -0-Ci -4 - alkyl;
  • halogens includes elements selected from the group consisting of fluorine, chlorine, bromine and iodine, with fluorine, chlorine and bromine being preferred and chlorine and bromine being particularly preferably used.
  • Optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
  • C 1 -C 4 -alkyl encompasses the largest range defined herein for an alkyl radical.
  • this definition includes the meanings methyl, ethyl, n-, iso-propyl, n-, iso-, sec- and t-butyl.
  • the compounds of the invention may be prepared as mixtures of various possible isomeric forms, particularly stereoisomers, e.g. E and Z, threo and erythro, as well as optical isomers, but optionally also of tautomers. Both the E and the Z isomers, as well as the threo and erythro, and the optical isomers, any mixtures of these isomers, as well as the possible tautomeric forms claimed.
  • the coupling of the halonitrobenzene (II) and the alkene (III) can be carried out in the presence of a transition metal or noble metal catalyst, preferably in the presence of a palladium catalyst.
  • the noble metal catalyst is used in a ratio of 10.0 to 0.001 mol%, preferably 2.0 to 0.01 mol%, particularly preferably 1.0 to 0.1 mol%. % used.
  • the Heck-analogous implementation of the coupling step is preferably carried out in the presence of an inorganic or organic base.
  • organic bases are diethylamine, dipropylamine, diisopropylethylamine, dibutylamine, dicyclohexylamine, piperidine, triethylamine, tripropylamine, tributylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,4-diazabicyclo [ 2.2.2] octane (DABCO).
  • inorganic bases are potassium acetate, sodium acetate, potash, soda, potassium t-butylate, sodium t-butylate, sodium t-amylate, with triethylamine, tributylamine, sodium acetate and potassium acetate are preferably used.
  • the coupling step according to the invention can be carried out with or without the addition of ligands.
  • ligands triarylphosphines, diarylalkylphosphines, diarylphosphines, e.g. Tri (o-tolyl) phosphine, triphenylphosphine, diphenylcycloalkylphosphines, di- and tri-
  • BINAP Dicyclohexylphosphine, diadamanylbutylphosphine, trialkyl phosphites and BINAP
  • dialkylphosphines 2,2'-bis (diphenylphosphino) -1,1'-binaphthalene) dialkylphosphines, dialkylarylphosphines, trialkylphosphines, diaryl (dialkylamino) phosphines and arylbis (dialkylamino) phosphines and
  • BINAP 2,2'-bis (diphenylphosphino) -1,1'-bi- naphthalene) and tri (o-tolyl) phosphine
  • Triphenylphosphine, diphenyl-menthyl-phosphine, diphenyl-neomenthylphosphine, BINAP are particularly preferably used.
  • the ligands are added to the reaction mixture in the amount necessary for the desired molar ratio.
  • the reaction mixture can either be a ligand-free precursor of the catalyst, such as a palladium salt such as PdCl 2 or Pd (OAc) 2 , or a complex already contained the ligand, such as dichloro-bis (triphenylphosphine) palladium (II) or tetrakis (triphenyl- Phosphine) -palladium (O), to which in addition an appropriate amount of the same or another ligand is added until the desired molar ratio is set.
  • a ligand-free precursor of the catalyst such as a palladium salt such as PdCl 2 or Pd (OAc) 2
  • a complex already contained the ligand such as dichloro-bis (triphenylphosphine) palladium (II) or tetrakis (triphenyl- Phosphine) -palladium (O), to
  • the coupling step according to the invention is preferably carried out in a solvent or solvent mixture.
  • suitable solvents are, for example, N, N Dialkylalkanamides such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide; Ketones such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone; Nitriles, such as acetonitrile and butyronitrile; Ethers such as dimethoxyethane (DME), tetrahydrofiirane (THF), 2-methyl-TKF and dioxane; Alcohols, such as methanol, ethanol, n-propanol, isopropanol and isoamyl alcohol; Water; Ethylene carbonate or propylene carbonate.
  • N, N Dialkylalkanamides such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide
  • Ketones such as
  • the coupling step is carried out in the presence of water.
  • triarylphosphines can be used, which are preferably 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, aryl 4 PX (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.
  • the proportion of reactants to solvent can be varied within a wide range.
  • the proportion of reactants is 5 to 75 wt .-%, particularly preferably 10 to 50 wt .-%, based on the mixture of solvent and reactants.
  • reactants in this context includes the 2-halonitrobenzenes, the alkenes, the Pd complex, the ligands and the bases.
  • R 1 represents hydrogen, halogen, -CR '(CF 3) 2, wherein R' is selected from H, F, or an O-CI_ 4 alkyl group and preferably hydrogen and
  • R 5 is -CH 2 CH 2 -t-Bu, -CH 2 CH 2 -i-prop, -CHrCHz-cyclopropyl, and the
  • Substituent R 1 is preferably in the meta or para position, more preferably in the 4 position (para to the NO 2 group) of the aromatic;
  • R 1 is hydrogen, halogen, -CR '(CF 3 ) 2 , wherein R' is selected from H, F or an O-Ci_ 4 alkyl group and is preferably hydrogen, and the substituent R 1 preferably in meta or para position, more preferably in the 4 position (para to
  • a further aspect of the present invention relates to a process for the preparation of the compounds of the formula (XII)
  • R 1 is hydrogen, halogen, -CR '(CF 3 ) 2 , wherein R' is selected from H, F or 0-C 1-4 alkyl, and
  • R 7 is CH 2 CH 2 -t-Bu, -CH 2 CH 2 -i-prop,
  • R 1 is hydrogen, halogen, -CR '(CF 3 ) 2 , wherein R' is selected from H, F or 0-C 4 -alkyl, and
  • the reaction conditions of the hydrogenation are known in the art and in the prior art, for. In Becker, HGD et al., Organikum (1976), Interdruck, Leipzig.
  • the hydrogenation in the liquid and / or gas phase is particularly preferably carried out in the presence of suitable hydrogenation catalysts.
  • suitable hydrogenation catalysts Pd / C, PtO 2 and Raney nickel are suitable as catalysts.
  • the hydrogenation is usually carried out with hydrogen pressures of 1 to 100 bar, preferably 2 to 30 bar, more preferably 5 to 10 bar and at temperatures in the range of 0 to 150 0 C, preferably 10 to 100 0 C and particularly preferably 15 to 50 0 C. carried out.
  • the hydrogenation with hydrogenation reagents the z. B. selected from Zn, Fe, SnCh, Sn and dithionite.
  • the hydrogenation can be carried out in the presence of an acid.
  • Suitable sources of hydrogen are also formates and hydrazine.
  • R 1 is hydrogen, halogen, -CR '(CFs) 2 , wherein R' is selected from H, F or OC). 4 alkyl and preferably hydrogen, and the substituent R 1 is preferably in the meta or para position, more preferably in the 4 position (para to N ⁇ 2 group) of the aromatic is;
  • R 1 represents hydrogen, halogen, -CR '(CF 3) 2, wherein R' is selected from H, F, or 0-C] - 4 alkyl and is preferably hydrogen, and the substituent R 1 is preferably in meta or para position, more preferably in the 4 position (para to the NO 2 group) of the aromatic,
  • the cyclopropanation is carried out by Simmons-Smith reaction with dihalomethane and zinc and / or copper or diethylzinc.
  • the reaction conditions of the cyclopropanation are known to those skilled in the art and are known in the art, e.g. in Org. React. 1973, 20, pp. 1-131.
  • the cyclopropanation can also be carried out by carbene addition with diazomethane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé permettant la production de dérivés de nitrobenzène et des dérivés d'aniline, qui peuvent être utilisés en tant que produits intermédiaires pour des alkylanilides à action fongicide.
EP07786008A 2006-07-14 2007-07-12 Derives des nitrobenzole ainsi que procede pour la preparation de tels nitrobenzoles et alkylaniline Withdrawn EP2046720A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006033091A DE102006033091A1 (de) 2006-07-14 2006-07-14 Verfahren zum Herstellen von in 1'-Stellung unverzweigten Alkenylnitrobenzolderivaten
PCT/EP2007/006176 WO2008006574A2 (fr) 2006-07-14 2007-07-12 Procédé permettant la production de alkylnitrobenzoles et d'alkylanilines non ramifiés en position 1',à partir de nitotoluoles

Publications (1)

Publication Number Publication Date
EP2046720A2 true EP2046720A2 (fr) 2009-04-15

Family

ID=38645672

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07786008A Withdrawn EP2046720A2 (fr) 2006-07-14 2007-07-12 Derives des nitrobenzole ainsi que procede pour la preparation de tels nitrobenzoles et alkylaniline

Country Status (7)

Country Link
US (1) US20110237836A1 (fr)
EP (1) EP2046720A2 (fr)
JP (2) JP2009543763A (fr)
CN (1) CN101489977A (fr)
BR (1) BRPI0714411A2 (fr)
DE (1) DE102006033091A1 (fr)
WO (1) WO2008006574A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785200B2 (en) 1998-11-12 2014-07-22 Life Technologies Corporation Transfection reagents
US10195280B2 (en) 2014-07-15 2019-02-05 Life Technologies Corporation Compositions and methods for efficient delivery of molecules to cells

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023008401A1 (fr) * 2021-07-30 2023-02-02 東レ・ファインケミカル株式会社 Procédé de production d'un composé aromatique ayant un groupe éthynyle

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2626960A (en) * 1950-04-05 1953-01-27 Hoffmann La Roche 1, 4-dioxo-5-(nitrophenyl)-1, 4, 4a, 5, 8, 8a-hexahydro-naphthalenes
DE4421730C1 (de) * 1994-06-22 1995-11-23 Hoechst Ag Verfahren zur Herstellung von aromatischen Olefinen unter Katalyse von Palladacyclen
JP3982879B2 (ja) * 1996-08-15 2007-09-26 三井化学株式会社 置換カルボン酸アニリド誘導体およびこれを有効成分とする植物病害防除剤
MXPA06004308A (es) * 2003-10-23 2006-06-05 Bayer Cropscience Ag Isopentilcarboxanilidas para la lucha contra los microorganismos indeseables.
JP4565927B2 (ja) * 2004-01-30 2010-10-20 川研ファインケミカル株式会社 炭素−炭素結合を生成するＨｅｃｋ反応用パラジウム触媒
US7501510B2 (en) * 2004-03-26 2009-03-10 The University Of Hong Kong Thiourea compositions and uses thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008006574A3 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785200B2 (en) 1998-11-12 2014-07-22 Life Technologies Corporation Transfection reagents
US9358300B2 (en) 1998-11-12 2016-06-07 Life Technologies Corporation Transfection reagents
US10195280B2 (en) 2014-07-15 2019-02-05 Life Technologies Corporation Compositions and methods for efficient delivery of molecules to cells
US10792362B2 (en) 2014-07-15 2020-10-06 Life Technologies Corporation Compositions and methods for efficient delivery of molecules to cells
US11872285B2 (en) 2014-07-15 2024-01-16 Life Technologies Corporation Compositions and methods for efficient delivery of molecules to cells

Also Published As

Publication number Publication date
CN101489977A (zh) 2009-07-22
WO2008006574A3 (fr) 2008-03-20
JP2009543763A (ja) 2009-12-10
BRPI0714411A2 (pt) 2013-03-12
US20110237836A1 (en) 2011-09-29
JP2013173751A (ja) 2013-09-05
DE102006033091A1 (de) 2008-01-24
WO2008006574A2 (fr) 2008-01-17

Similar Documents

Publication Publication Date Title
EP2700630B1 (fr) Procédé de fabrication de biphényles substitués
JP5107267B2 (ja) 置換ビフェニルの製造法
EP3024836B1 (fr) Procédé amélioré de fabrication de biphénylanilides chlorés et de biphénylanilines
EP1856024B1 (fr) Procede de fabrication de biphenyls substitues
EP1303525A1 (fr) Nouveaux ligands de phosphane, leur production et leur utilisation dans des reactions catalytiques
EP2398764B1 (fr) Procédé de fabrication de 2-aminobiphenylènes
EP2046754B1 (fr) Procede destine à produire des aklylanilides à partir de derives d'halogenobenzenes
EP2046720A2 (fr) Derives des nitrobenzole ainsi que procede pour la preparation de tels nitrobenzoles et alkylaniline
EP1963251B1 (fr) Procede pour la fabrication des amines
DE60010682T2 (de) Verfahren zur herstellung von zwischenprodukten für pestizide
EP0056154B1 (fr) Procédé de préparation d'acides 2.2-diméthyl-3-vinyl-cyclopropane-carboxyliques et leurs esters
EP0039810A1 (fr) Procédé de préparation de 2-trifluorométhylaniline
EP0397042B1 (fr) Préparation d'isoquinoléines
EP2043995A1 (fr) Procede pour la preparation de derives alcenylnitrobenzene non ramifies en position 1'
EP0682008A1 (fr) Chloro-2 trifluoro-3,4,5 benzènes et procédé pour leur préparation
DE10107227A1 (de) Verfahren zur Herstellung von 4-substituierten 2-Alkyl- und 2-Alkoxylbiphenylen
EP0696576A2 (fr) Procédé pour la préparation d'amino-2-aryl-2-éthanols et leurs intermédiaires
DE10134160A1 (de) Verfahren zur Herstellung von Mono-Propargylaminen
JP2010500304A (ja) フェロセニルビホスフィンリガンドを含むパラジウム複合体の存在下での芳香族アミン類の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090216

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130806

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BAYER INTELLECTUAL PROPERTY GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20150310