EP0904267A1 - Procede de production d'arylpyrazoles substitues - Google Patents

Procede de production d'arylpyrazoles substitues

Info

Publication number
EP0904267A1
EP0904267A1 EP97924956A EP97924956A EP0904267A1 EP 0904267 A1 EP0904267 A1 EP 0904267A1 EP 97924956 A EP97924956 A EP 97924956A EP 97924956 A EP97924956 A EP 97924956A EP 0904267 A1 EP0904267 A1 EP 0904267A1
Authority
EP
European Patent Office
Prior art keywords
general formula
chlorine
meanings given
stage
halogen
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Withdrawn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
EP97924956A
Other languages
German (de)
English (en)
Inventor
Reinhard Lantzsch
Thomas Himmler
Albrecht Marhold
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 CropScience AG
Original Assignee
Bayer 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 AG filed Critical Bayer AG
Publication of EP0904267A1 publication Critical patent/EP0904267A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07D231/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
    • C07C33/48—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts with unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C07C49/233—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
    • C07C49/235—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te

Definitions

  • the invention relates to a new process and new intermediates for the preparation of substituted arylpyrazoles, which as intermediates for
  • R represents hydrogen or halogen
  • R 2 represents cyano or halogen
  • R represents halogen, alkyl, haloalkyl or alkoxycarbonyl
  • R 4 represents optionally substituted alkyl
  • R, 1, r R> 2 and R have the meanings given above and
  • Z represents 1-hydroxy-isopropyl or trimethylsilyl
  • reaction auxiliaries optionally in the presence of one or more reaction auxiliaries and, if appropriate, in the presence of a diluent at temperatures between
  • X represents halogen or the grouping -O-CO-O-R
  • reaction auxiliaries optionally in the presence of one or more reaction auxiliaries and, if appropriate, in the presence of a diluent at temperatures between 0 ° C. and 150 ° C., and the arylalkynones of the general formula (VII) formed in this process in which
  • R, R .2, D R3 " and R have the meanings given above,
  • the process according to the invention preferably relates to the preparation of compounds of the formula (I) in which
  • R 1 represents hydrogen, FI uor or chlorine
  • R ⁇ stands for cyano, fluorine or chlorine
  • R represents halogen, C j -C 6 alkyl, C r C 6 haloalkyl or C ⁇ Q alkoxycarbonyl
  • R 4 represents C r C 6 alkyl optionally substituted by fluorine and / or chlorine
  • the process according to the invention relates in particular to the production of compounds of the formula (I) in which
  • R 1 represents hydrogen, fluorine or chlorine
  • R 2 represents cyano or chlorine
  • R 3 for fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxycarbonyl or
  • R 4 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine and / or chlorine
  • Formula (II) provides a general definition of the haloarenes to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I).
  • R 1 , R 2 and R 3 preferably or in particular have those meanings which are preferred or particularly preferred for R already in connection with the description of the compounds of the formula (I) according to the invention 1 , R 2 and R 3 have been given;
  • X preferably represents chlorine, bromine or iodine, in particular bromine or iodine.
  • the starting materials of the formula (II) are known and / or can be prepared by known processes (cf. J. Am. Chem. Soc. 81 (1959), 5643; J. Org.
  • halogenating agents e.g. Chlorine, bromine or iodine
  • a catalyst e.g. Iron
  • R 1 , R 2 and R have the meanings given above,
  • a hydrogen halide acid e.g. Hydrochloric acid (hydrogen chloride), hydrobromic acid (hydrogen bromide) or hydrogen iodide (hydrogen iodide), optionally in the presence of a catalyst, e.g. Copper (I) chloride, copper (I) bromide or copper (I) iodide, at temperatures between 0 ° C and 50 ° C.
  • a catalyst e.g. Copper (I) chloride, copper (I) bromide or copper (I) iodide
  • substituted alkynes to be used further as starting materials in the process according to the invention for the preparation of compounds of the formula (I) are known synthetic chemicals.
  • the first stage of the process according to the invention is carried out in the presence of one or more reaction auxiliaries.
  • palladium (optionally in the presence of a carrier material such as activated carbon), palladium complexes such as Palladium bis (triphenylphosphine) dichloride [bis (triphenylphosphine) palladium (II) dichloride] or tetrakis
  • triphenylphosphine palladium, as well as palladium salts, such as palladium (II) acetate or palladium (II) chloride ) optionally in the presence of triphenylphosphine and optionally in the presence of copper compounds, such as copper (I) chloride, copper (I) -bromide or copper (I) iodide, and - if necessary as further
  • Reaction aids - basic organic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N, N-
  • Suitable diluents for carrying out the process according to the invention are in particular inert organic solvents in all stages. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane , Cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dnsopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones, such as acetone, butanone or methyl isobutyl ketone, nitriles, such as
  • reaction temperatures can be varied within a substantial range. In general, temperatures between 50 ° C. and 150 ° C., preferably between 80 ° C. and 120 ° C.
  • the first stage of the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the first stage of the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar
  • 0.1 to 100 mmol, preferably 1.0 to 50 mmol, of a palladium complex, if appropriate 0.1 to 100 mmol, are generally used per mole of halogenars of the formula (II)
  • reaction components and reaction auxiliaries are mixed at room temperature and brought to the required temperature until the end of the reaction. action temperature heated
  • the work-up can be carried out in a conventional manner.For example, after the end of the reaction, the mixture is filtered and the solvent is carefully distilled off from the filtrate under reduced pressure, the reaction product remaining as a residue. However, it is also possible for the filtrate to be used directly for the further reaction in the second Level
  • the second stage of the process according to the invention is carried out using an alkali metal or alkaline earth metal hydroxide and / or an alkali metal or alkaline earth metal fluoride.
  • alkali metal or alkaline earth metal hydroxide include, for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium and Ba ⁇ um hydroxide and sodium, potassium, cesium and magnesium fluo ⁇ d preference, sodium hydroxide is used to carry out the second stage
  • a reaction auxiliary is preferably used.
  • Such are, in particular, basic organic nitrogen compounds, such as t ⁇ methylamine, t ⁇ ethylamine, t ⁇ propylamine, t ⁇ butylamine, ethyl-dnsopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine,
  • reaction temperatures can be varied within a wide range when carrying out the second stage of the process according to the invention. In general, temperatures between 0 ° C. and 150 ° C., preferably between 20 ° C. and 120 ° C.
  • reaction auxiliaries preferably 0.1 to 0.5 mol of alkali metal or alkaline earth metal hydroxide and optionally 1 to 100 mol, preferably 5 to 50 mol, of reaction auxiliaries
  • the filtrate from the first stage is mixed with an alkali metal or alkaline earth metal hydroxide at room temperature and the mixture is then heated to the required reaction temperature until the reaction has ended. for example by distillation under reduced pressure
  • Acidifying agents are generally defined by the formula (VI)
  • R 4 preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R 4 X 1 preferably represents fluorine, chlorine, bromine or the group -O-
  • the third stage of the process according to the invention is carried out in the presence of one or more reaction auxiliaries
  • reaction temperatures can be varied within a substantial range when the third stage of the process according to the invention is carried out. I think you work at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C
  • the third stage of the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the third stage of the process according to the invention under increased or reduced pressure - generally between 0.1 bar and 10 bar
  • acylating agent of the formula (VI) and, if appropriate, 0.01 are generally employed per mol of arylalkyne of the formula (V) up to 5.0 mol, preferably 0.1 to 2.5 mol, of reaction auxiliaries
  • arylalkyne of the formula (V) and reaction auxiliaries are mixed with a diluent and - preferably at a somewhat elevated temperature - the acylating agent is added.
  • the reaction mixture is then - preferably at elevated temperature and, if appropriate, at elevated pressure - until
  • the work-up can be carried out in the customary manner, for example by washing with dilute hydrochloric acid and then with water, separating off the organic phase and carefully distilling off the solvent therefrom under reduced pressure
  • reaction temperatures can be varied within a substantial range. In general, temperatures between 0 ° C. and 150 ° C., preferably between 20 ° C. and 120 ° C.
  • the fourth stage of the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the fourth stage of the process according to the invention under increased or reduced pressure - generally between 0.1 bar and 10 bar
  • 0.9 to 2.0 mol, preferably 1.0 to 1.5 mol, of hydrazine (hydrate) are generally employed per mol of arylalkinone of the formula (VII)
  • the reaction components are mixed with a suitable solvent at room temperature and the reaction mixture is heated until the end of the reaction, preferably on a water separator.
  • Working up can be carried out in a customary manner, for example by carefully distill off the solvent under reduced pressure
  • substituted arylpyrazoles of the formula (I) to be prepared by the process according to the invention can be used as intermediates for the preparation of herbicidally active compounds (cf. US 5281571)
  • a mixture of 2 g (20 mmol) triethylamine, 0.3 g (2 mmol) copper (I) - bromide, 3.4 g (20 mmol) (4-chloro-2-fluoro-5-methylphenyl) - eth ⁇ n and 15 ml of toluene are in an autoclave under argon for about 30 minutes at room temperature. temperature (approx. 20 ° C.) then 3.3 g (25 mmol) of tetrafluoroacetylchloride are introduced and the mixture is heated to 90 ° C. for approx. 12 hours after the autoclave has been closed. After cooling and opening the autoclave, the mixture is stirred with 2N hydrochloric acid and with water washed and then - first in a water jet vacuum, then in an oil pump vacuum - concentrated

Landscapes

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

Abstract

L'invention concerne un procédé de production d'arylpyrazoles substitués de formule générale (I), dans laquelle R?1, R2, R3 et R4¿ ont la signification mentionnée dans la description. L'invention concerne également de nouveaux intermédiaires pour la production desdits arylpyrazoles.
EP97924956A 1996-05-30 1997-05-20 Procede de production d'arylpyrazoles substitues Withdrawn EP0904267A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19621687A DE19621687A1 (de) 1996-05-30 1996-05-30 Verfahren zur Herstellung von substituierten Arylpyrazolen
DE19621687 1996-05-30
PCT/EP1997/002546 WO1997046534A1 (fr) 1996-05-30 1997-05-20 Procede de production d'arylpyrazoles substitues

Publications (1)

Publication Number Publication Date
EP0904267A1 true EP0904267A1 (fr) 1999-03-31

Family

ID=7795672

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97924956A Withdrawn EP0904267A1 (fr) 1996-05-30 1997-05-20 Procede de production d'arylpyrazoles substitues

Country Status (8)

Country Link
US (3) US6060605A (fr)
EP (1) EP0904267A1 (fr)
JP (1) JP2000514409A (fr)
CN (1) CN1096449C (fr)
AU (1) AU3027497A (fr)
BR (1) BR9709511A (fr)
DE (1) DE19621687A1 (fr)
WO (1) WO1997046534A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003024958A2 (fr) * 2001-09-18 2003-03-27 Onconova Therapeutics, Inc. Procedes de preparation de 1,5-diarylpyrazoles substitues en position 3
WO2003024400A2 (fr) 2001-09-18 2003-03-27 Onconova Therapeutics, Inc. Procede de preparation de 1,5-diarylpyrazoles
UA79804C2 (en) 2002-07-03 2007-07-25 Janssen Pharmaceutica Nv Cck-1 receptor modulators
JP2007521301A (ja) * 2003-07-02 2007-08-02 ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ Ｃｃｋ−１受容体モジュレーター

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2667316B1 (fr) * 1990-10-02 1994-09-16 Roussel Uclaf Nouveaux derives du benzofuranne, leur procede de preparation et leur application comme pesticides.
US5281571A (en) * 1990-10-18 1994-01-25 Monsanto Company Herbicidal benzoxazinone- and benzothiazinone-substituted pyrazoles
EP0659047A1 (fr) * 1992-09-09 1995-06-28 E.I. Du Pont De Nemours And Company Composes de benzene herbicides
KR100311921B1 (ko) * 1993-10-13 2002-10-31 스미또모 가가꾸 고오교오 가부시끼가이샤 톨란화합물,그의제조방법,이화합물을유효성분으로하는액정조성물및이액정조성물을사용하여이루어진액정소자
EP0648423A1 (fr) * 1993-10-14 1995-04-19 Ewa Lang Firma Organe support synthétique pour bayaux naturels plissés

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9746534A1 *

Also Published As

Publication number Publication date
DE19621687A1 (de) 1997-12-04
AU3027497A (en) 1998-01-05
WO1997046534A1 (fr) 1997-12-11
JP2000514409A (ja) 2000-10-31
US6433210B1 (en) 2002-08-13
CN1096449C (zh) 2002-12-18
US20020032337A1 (en) 2002-03-14
BR9709511A (pt) 1999-08-10
US6060605A (en) 2000-05-09
CN1220662A (zh) 1999-06-23
US6118031A (en) 2000-09-12

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