WO2003051820A1 - Verfahren zur herstellung von 2-halogenacyl-3-amino-acrylsäure- derivaten - Google Patents

Verfahren zur herstellung von 2-halogenacyl-3-amino-acrylsäure- derivaten Download PDF

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Publication number
WO2003051820A1
WO2003051820A1 PCT/EP2002/013721 EP0213721W WO03051820A1 WO 2003051820 A1 WO2003051820 A1 WO 2003051820A1 EP 0213721 W EP0213721 W EP 0213721W WO 03051820 A1 WO03051820 A1 WO 03051820A1
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WIPO (PCT)
Prior art keywords
acid esters
acrylic acid
amino
haloalkyl
anhydrides
Prior art date
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Ceased
Application number
PCT/EP2002/013721
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German (de)
English (en)
French (fr)
Inventor
Norbert Lui
Thomas Brackemeyer
Peter Müller
Marielouise Schneider
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 AG
Bayer Chemicals AG
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Bayer AG
Bayer Chemicals AG
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Application filed by Bayer AG, Bayer Chemicals AG filed Critical Bayer AG
Priority to DE50214951T priority Critical patent/DE50214951D1/de
Priority to JP2003552708A priority patent/JP4301951B2/ja
Priority to AT02798321T priority patent/ATE501113T1/de
Priority to AU2002363862A priority patent/AU2002363862A1/en
Priority to EP02798321A priority patent/EP1458670B1/de
Publication of WO2003051820A1 publication Critical patent/WO2003051820A1/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C07D231/14—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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups

Definitions

  • the present invention relates to an improved process for the preparation of 2-haloacyl-3-amino-acrylic acid derivatives and pyrazole-4-carboxylic acid derivatives obtainable therefrom.
  • 2-haloacyl-3-amino-acrylic acid derivatives such as e.g. 2-Trifluoroacetyl-3-amino-acrylic acid esters are valuable intermediates in the production of substituted pyrazoles, which are used as fungicides, pesticides and herbicides.
  • EP-A 1 000 926 discloses a process for the preparation of 2-trihaloacetyl-3-amino-acrylic acid esters in which trihaloacetylacetates are substituted with ortho-formic acid derivatives.
  • the yields achieved in the reaction are only 61.8% and are not acceptable for industrial use.
  • c) can optionally be converted further to 3-haloalkyl-4-pyrazolecarboxylic acids by acidic or alkaline saponification.
  • 3-amino-acrylic acid esters are, for example and preferably, those of the general formula (I)
  • R 1 is C] -C 12 alkyl, C 6 -C 18 aryl or C 7 -C ⁇ 9 arylalkyl and
  • R 2 and R 3 each independently represent C] -C ⁇ 2 alkyl or C 7 -C] 9 arylalkyl.
  • R 1 is C] -C 4 alkyl, more preferably methyl or ethyl and R 2 and R 3 each independently preferably C ⁇ -C 4 alkyl, more preferably methyl or ethyl.
  • 3-amino-acrylic acid esters of the general formula (I) are 3- (N, N-dimethylamino) -acrylic acid methyl ester and 3- (N, N-diethylamino) -acrylic acid- ethyl esters of which 3- (N, N-dimethylamino) acrylic acid methyl ester are even more preferred.
  • the 3-amino-acrylic acid esters to be used can be prepared according to the literature or analogously thereto (EP-A 608 725).
  • alkyl is a straight-chain, cyclic, branched or unbranched alkyl radical which can optionally be further substituted by dC 6 alkoxy radicals such as, for example, methoxy or ethoxy.
  • dC 6 alkoxy radicals such as, for example, methoxy or ethoxy.
  • dC 4 - alkyl is methyl, ethyl, ethoxyethyl, n-propyl, isopropyl, n-butyl and tert-butyl, -C-C 8 alkyl; in addition for n-pentyl, cyclohexyl, n-hexyl, n-octyl or iso-octyl, C 1 -C 12 -alkyl in addition, for example for n-decyl and n-dodecyl.
  • alkoxy is a straight-chain, cyclic, branched or unbranched alkoxy radical which can optionally be further substituted by -C ⁇ alkoxy radicals such as, for example, methoxy or ethoxy.
  • -C 6 alkoxy is methoxy, ethoxy, 2-ethoxy-ethoxy, n-
  • aryl is, for example and preferably, carbocyclic aromatic radicals having 6 to 18 carbon atoms (C 6 -C 18 aryl), such as phenyl or naphthyl.
  • C ⁇ -C selected from the group of chlorine, fluorine, nitro, cyano, 4 alkyl such as methyl or ethyl, C] -C 4 -Acyl such as acetyl, -CC 4 alkoxy such as methoxy
  • C 6 -C -o-aryl radicals are phenyl, o-, m-, p-tolyl, o-, m-, p-anisyl and naphthyl for C 6 -C 18 -aryl in addition, for example, anthracenyl.
  • C 7 -C 13 arylalkyl is, for example, benzyl or the isomeric 1-methylbenzyls, and C -C 13 arylalkyl is also, for example, fluorenyl.
  • step a) of the process according to the invention haloalkyl carboxylic acid anhydrides are used.
  • haloalkylcarboxylic acid anhydrides are not only to be understood as meaning symmetrical anhydrides or mixed anhydrides of different haloalkylcarboxylic acids, but also mixed anhydrides of haloalkylcarboxylic acids with organic acids such as, for example, sulfonic acids or inorganic acids such as, for example, hydrohalic acids.
  • organic acids such as, for example, sulfonic acids or inorganic acids
  • hydrohalic acids such as, for example, hydrohalic acids.
  • the latter are often referred to as haloalkyl carboxylic acid halides.
  • haloalkylcarboxylic anhydrides used are, for example and preferably, those of the general formulas (Ha)
  • X for chlorine, bromine or iodine, preferably chlorine and
  • R 4 for chlorine, fluorine d-Cn-haloalkyl, Ci-Cu-alkyl, C 6 -C 18 aryl or C 6 - C ⁇ 9 arylalkyl, preferably chlorine, fluorine, trifluoromethyl, pentafluoroethyl, non-fluorobutyl and C ⁇ -C 4 alkyl, particularly preferably fluorine.
  • the haloalkylcarboxylic anhydrides used are furthermore, for example and preferably, those of the general formula (IIb)
  • radicals R 4 each independently have the same meaning and preferred ranges which have been given under the general formula (Ha).
  • the radicals R 4 are preferably identical in the general formula (IIb).
  • haloalkyl is, for example and preferably, a branched or unbranched, open-chain or cyclic alkyl radical which is substituted simply, repeatedly or completely by halogen atoms selected from the group consisting of chlorine and fluorine.
  • d-C ⁇ -haloalkyl is trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl and nonafluorobutyl.
  • haloalkyl carboxylic anhydrides are trifluoroacetic anhydride, trifluoroacetic acid chloride, trichloroacetic anhydride and
  • the molar ratio of haloalkyl carboxylic acid anhydrides to 3-amino-acrylic acid esters used can be, for example, 0.3 to 1.5, preferably 0.8 to 1.1, particularly preferably 0.95 to 1.05.
  • Suitable bases are, for example and preferably, tertiary nitrogen bases, carbonates, hydrides.
  • Tertiary nitrogen bases such as, for example, tertiary amines, substituted or unsubstituted pyridines and substituted or unsubstituted quinolines, are particularly preferably used.
  • Particularly preferred bases are pyridine, 2-, 3-, 4-picoline, 2,6-lutidine,
  • R 5 , R 6 and R 7 each independently of one another for C 1 -C 6 -alkyl, C -C 9 -
  • Arylalkyl or C 6 -C 8 aryl or two radicals together can also be part of a 5 to 8-membered N-heterocyclic radical, or all three radicals together part of an N-heterobicyclic or N-heterotri cyclic radical with 5 to 9 ring atoms can be per cycle which may also contain other heteroatoms such as oxygen.
  • A is C 2 -C 8 alkylene, such as for example and preferably 1,2-ethylene, 1,3 propylene, 2,3-butylene, 1, 2-cyclohexylene or C 6 -C ⁇ 8 arylene such examples Game 1, 2-phenylene can stand and
  • C 1 -C 8 alkyl, C 7 -C 9 arylalkyl or C 6 -C 8 aryl or two radicals together can also be part of a 5 to 8-membered N-heterocyclic ring or can be bridging between the two nitrogen atoms or all four leftovers together
  • Part of a bis-N-heterobicyclic or bis-N-heterotricyclic radical with 5 to 9 ring atoms per cycle can optionally also contain other heteroatoms such as oxygen.
  • bases of the general formula (purple) are trimethylamine
  • bases of the general formula (LTIb) are N, N, N, N-tetramethylethylenediamine, N, N-dimethyl-1,4-diazacyclohexane, N, N-diethyl-1,4-diazacyclohexane, 1,1 8-bis (dimethylamino) naphthalene, diazabicyclooctane (DABCO), diazabicyclononane (DBN) and diazabicycloundecane (DBU).
  • DABCO diazabicyclooctane
  • DBN diazabicyclononane
  • DBU diazabicycloundecane
  • Triethylamine is very particularly preferably used as the base.
  • the molar ratio of base to haloalkylcarboxylic anhydrides used can be, for example, 0.3 to 3, preferably 1.0 to 2.0, particularly preferably
  • reaction of the 3-amino-acrylic acid esters with haloalkyl carboxylic acid anhydrides in the presence of base can be carried out, for example, at temperatures from -30 to 120 ° C., preferably -10 to 20 ° C.
  • Suitable solvents are, for example, aliphatic or aromatic hydrocarbons, which can also be substituted by fluorine and chlorine atoms, ethers, such as THF or dioxane.
  • Fluorobenzene the isomeric chlorofluorobenzenes, dichloromethane, n-hexane, cyclohexane, methylcyclohexane, heptane, octane, iso-octane, petroleum ether, gasoline fractions, THF or dioxane, toluene is particularly preferred.
  • solvent for example, 50 to 1000 ml of solvent can be used per mole of 3-amino-acrylic acid derivative. This amount is preferably 100 to 600 ml. Larger amounts of solvent are not critical, but are uneconomical.
  • 3-aminoacrylic acid derivative and base are placed in a solvent and the haloalkylcarboxylic anhydride is added.
  • Working up can be carried out, for example, by optionally precipitating salts, e.g. separated by filtration, centrifugation or sedimentation and decanting and the reaction solution obtained in this way is either directly reacted further or to obtain the 2-haloacyl-3-amino-acrylic acid esters e.g. constricts to dryness.
  • optionally precipitating salts e.g. separated by filtration, centrifugation or sedimentation and decanting and the reaction solution obtained in this way is either directly reacted further or to obtain the 2-haloacyl-3-amino-acrylic acid esters e.g. constricts to dryness.
  • the 2-haloacyl-3-amino-acrylic acid derivatives can be further purified by distillation, but this is not necessary for use in the preparation of 3-haloalkyl-4-pyrazolecarboxylic acid esters.
  • 2-haloacyl-3-amino-acrylic acid esters of the general formula (IN) are obtained
  • R 2 and R 3 each independently have the same meaning and preferred ranges, which have been given under the general formula (I).
  • the 2-haloacyl-3-amino-acrylic acid derivatives produced in accordance with the invention are particularly suitable for the preparation of 3-haloalkyl-4-pyrazole carboxylic acid esters (step b).
  • the 2-haloacyl-3-amino-acrylic acid esters of the general formula (IV) can be reacted with hydrazines of the general formula (V), if appropriate in the presence of solvents, in 3-haloalkyl-4-pyrazolecarboxylic acid esters of the general Transfer formula (VI).
  • R is, for example and preferably, hydrogen, C 1 -C 2 alkyl, C 6 -C 18 aryl or C 7 -C 19 arylalkyl, particularly preferably d- C 4 alkyl.
  • Hydrazine, methylhydrazine and ethylhydrazine are very particularly preferably used, methylhydrazine being even more preferred.
  • R 1 has the same meaning and preferred ranges, which were given under the general formula (I) and
  • reaction is preferably carried out in the presence of solvent.
  • solvents are, for example and preferably, those which were specified above for carrying out step a).
  • step a) which is optionally obtained after removal of solids is used to prepare the compounds of the general formula (VI).
  • the reaction with hydrazine can be carried out, for example, and preferably at -30 to + 80 ° C, particularly preferably at -20 to 25 ° C and very particularly preferably at -10 to 10 ° C.
  • 3-haloalkyl-4-pyrazolecarboxylic acid derivatives can, if appropriate, in a manner known per se (Houben-Weyl, Methods of Organic Chemistry, 4th Edition,
  • volume E5, S 223ff. are converted, for example by acidic or alkaline saponification, into 3-haloalkyl-4-pyrazolecarboxylic acids of the general formula (VII), in the
  • R independently of this has the same meaning and preferred ranges which were given under the general formula (V) and M in the case of alkaline saponification for the cation of the base used or after acidification or in the case of acid saponification for hydrogen.
  • Alkaline saponification is preferred. This can be done in a manner known per se, for example by reaction with bases such as e.g. Alkali metal hydroxides such as e.g. Lithium, sodium or potassium hydroxide or their aqueous solutions.
  • bases such as e.g. Alkali metal hydroxides such as e.g. Lithium, sodium or potassium hydroxide or their aqueous solutions.
  • solvents are water, alcohols such as e.g. Methanol, ethanol and isopropanol, aromatic hydrocarbons such as e.g. Toluene, acetone, pyridine or mixtures of such solvents are suitable.
  • steps a) b) and c) are carried out without intermediate isolation in the same solvent, preferably aromatic hydrocarbons such as, for example, toluene, in order to prepare the compounds of the general formula (VII).
  • aromatic hydrocarbons such as, for example, toluene
  • the 2-haloacyl-3-amino-acrylic acid esters, 2-haloacyl-3-amino-acrylic acid esters and pyrazole-4-carboxylic acids or their salts prepared according to the invention are particularly suitable for use in a process for the preparation of medicaments and agrochemicals such as Fungicides, pesticides and herbicides.
  • the process according to the invention has the advantage that 2-haloacyl-3-amino-acrylic acid esters can be prepared in yields of over 95% from readily available substances.
  • Another advantage of the process according to the invention is that without isolation of the 2-haloacyl-3-aminoacrylic acid esters and without changing the solvent, substituted pyrazole-4-carboxylic acid esters or the acids can optionally be obtained in the form of their salts.
  • the product can also be used as a solution in toluene for further syntheses without further working up.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/EP2002/013721 2001-12-17 2002-12-04 Verfahren zur herstellung von 2-halogenacyl-3-amino-acrylsäure- derivaten Ceased WO2003051820A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE50214951T DE50214951D1 (de) 2001-12-17 2002-12-04 Verfahren zur herstellung von 2-halogenacyl-3-amino-acrylsäure- derivaten
JP2003552708A JP4301951B2 (ja) 2001-12-17 2002-12-04 ２−ハロゲンアシル−３−アミノ−アクリル酸−誘導体の製造方法
AT02798321T ATE501113T1 (de) 2001-12-17 2002-12-04 Verfahren zur herstellung von 2-halogenacyl-3- amino-acrylsäure- derivaten
AU2002363862A AU2002363862A1 (en) 2001-12-17 2002-12-04 Method for producing 2-halogenacyl-3-amino-acrylic acid derivatives
EP02798321A EP1458670B1 (de) 2001-12-17 2002-12-04 Verfahren zur herstellung von 2-halogenacyl-3-amino-acrylsäure- derivaten

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DE10161978.2 2001-12-17
DE10161978A DE10161978A1 (de) 2001-12-17 2001-12-17 Verfahren zur Herstellung von 2-Halogenacyl-3-amino-acrylsäure-derivate

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JP2007509850A (ja) * 2003-10-23 2007-04-19 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト ２−ジハロアシル−３−アミノ−アクリル酸エステルおよび３−ジハロメチル−ピラゾール−４−カルボン酸エステルの製造方法
EP2072497A1 (de) 2007-12-21 2009-06-24 Bayer CropScience AG Verfahren zum Herstellen von 2-Fluoracyl-3-amino-acrylsäure-Derivaten
WO2009135808A2 (de) 2008-05-05 2009-11-12 Basf Se Verfahren zur herstellung von 1,3,4-substituierten pyrazolverbindungen
EP2150536A1 (en) 2007-05-31 2010-02-10 Syngeta Participations AG Process for the production of pyrazoles
WO2009133179A3 (de) * 2008-05-02 2010-02-25 Basf Se Verfahren zur herstellung halogensubstituierter 2-(aminomethyliden)-3-oxobuttersäureester
EP2295411A1 (en) 2006-03-22 2011-03-16 F. Hoffmann-La Roche AG Pyrazoles as 11-beta-hsd-1
WO2011054732A1 (en) 2009-11-05 2011-05-12 Basf Se Process for preparing 1,3-disubstituted pyrazole compounds
WO2011054733A1 (en) 2009-11-05 2011-05-12 Basf Se Process for preparing aminale and their use for preparing 1,3-disubstituted pyrazole compounds
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EP2105434A4 (en) * 2006-12-28 2012-02-29 Mitsui Chemicals Agro Inc 2-FLUORED ACYL-3-AMINOACRYLONITRILE DERIVATIVE AND METHOD FOR THE PRODUCTION THEREOF
US8258335B2 (en) 2007-09-26 2012-09-04 Bayer Cropscience Ag Process for preparing 2-dihaloacyl-3-aminoacrylic acid derivatives
EP2263999A4 (en) * 2008-03-18 2012-11-07 Mitsui Chemicals Agro Inc METHOD FOR PRODUCING A FLUOROUS ACYL ACIDIC ACID DERIVATIVE, METHOD FOR THE PRODUCTION OF A FLUOROUS PYRAZOL CARBOXYLIC ACID DERIVATIVE AND METHOD FOR PRODUCING A FLUOROUS PYRAZOL CARBOXYLENE DERIVATIVE
US8314233B2 (en) 2008-05-02 2012-11-20 Basf Se Process for preparing 2-(aminomethylidene)-4,4-difluoro-3-oxobutyric esters
WO2012176717A1 (ja) * 2011-06-22 2012-12-27 セントラル硝子株式会社 ピラゾール化合物の製造方法
US8344157B2 (en) 2008-07-21 2013-01-01 Basf Se Process for preparing 1,3-disubstituted pyrazolecarboxylic esters
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US9856222B2 (en) 2014-06-11 2018-01-02 Bayer Cropscience Aktiengesellschaft Process for preparing 3,5-bis(haloalkyl)pyrazole derivatives via acylation of hydrazones
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WO2019224677A1 (en) 2018-05-21 2019-11-28 Pi Industries Ltd. Method for preparing substituted heterocyclic compounds
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