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EP1240127A1 - Production de trifluoromethylacetophenones - Google Patents

Production de trifluoromethylacetophenones

Info

Publication number
EP1240127A1
EP1240127A1 EP00975941A EP00975941A EP1240127A1 EP 1240127 A1 EP1240127 A1 EP 1240127A1 EP 00975941 A EP00975941 A EP 00975941A EP 00975941 A EP00975941 A EP 00975941A EP 1240127 A1 EP1240127 A1 EP 1240127A1
Authority
EP
European Patent Office
Prior art keywords
general formula
group
aromatic ring
process according
acidification
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Withdrawn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
EP00975941A
Other languages
German (de)
English (en)
Inventor
Hans-Dieter Schneider
Urs Gysel
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 EP1240127A1 publication Critical patent/EP1240127A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups

Definitions

  • the present invention relates to a method for preparation of trifluoromethylacetophenones, specifically, 3-trifluoromethylacetophenone.
  • the present invention provides a process for producing the trifluoromethylacetophenones in high yield and purity and employs readily available starting materials. Furthermore, the described process has advantages with respect to environmental protection.
  • the process of the present invention comprises the two steps of (a) reacting a trifluoromethylbenzoyl halide with a cyclic secondary amine in the presence of aqueous base to form a cycloalkyl-trifluoromethylbenzamide and (b) addition of a methyl Grignard reagent to said benzamide followed by acidification with aqueous acetic acid to form the product.
  • a trifluoromethylbenzoyl halide with a cyclic secondary amine in the presence of aqueous base to form a cycloalkyl-trifluoromethylbenzamide
  • a methyl Grignard reagent to said benzamide followed by acidification with aqueous acetic acid to form the product.
  • the present invention provides a process for the preparation of trifluoromethylacetophenones of the general formula I
  • Hal is a halogen atom selected from the group consisting of fluorine, chlorine, bromine, and iodine, with a cyclic secondary amine of the general formula
  • A is C 3 -C 7 -alkylene bridge which may be interrupted by a oxygen or sulfur atom in the presence of an aqueous base, used as an acid acceptor, resulting in the formation of a cycloalkyl-trifluoromethylbenzamide of the general formula IV
  • the process is used to produce 3-trifluoromethylacetophenone.
  • the cyclic secondary amine of formula III specifically contributes to the high yield and purity of the trifluoromethylacetophenone so produced.
  • the cyclic secondary amine typically denotes pyrrolidine, piperidine either unsubstituted or substituted in 2, 3 or 4 position by lower alkyl like methyl or ethyl, or preferably is morpholine or thiomorpholine.
  • the reactions of both steps (a) and (b) are typically carried out at moderate temperatures, ranging from about room temperature (+20°C to 25°C) to about +60°C.
  • the trifluoromethylbenzoyl halide reactants are known. Particularly useful in the practice of the present invention is 3-trifluoromethylbenzoyl chloride.
  • the bases useful as an acid acceptor are sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, calcium carbonate, calcium hydroxide, zinc oxide, calcium oxide and mixtures thereof in aqueous solution at concentrations of about 5-70%.
  • the cyclic amine may be any of those within the above-defined formula III and mixtures of one or more thereof, but are not limited to given examples.
  • Particularly useful in the process of the present invention are piperidine and morpholine.
  • the process of the invention is carried out in an inert solvent such as an ether like diethylether, ethylmethylether, tert.butyl-methylether, tetrahydrofuran, dioxane and the like.
  • Grignard reagents used for the present invention are the Grignard reagents which employ methyl as the alkyl substituent. Typical are l-Mg-CH 3 , Br-Mg-CH 3 and CI-Mg-CH 3 .
  • Acidification is preferably accomplished with acetic acid.
  • acidification reagents such as hydrochloric acid, sulfuric acid and ammonium chloride may also be employed in the process of the present invention.
  • the high purity products of the present invention facilitate the handling as intermediates for the production of the important agricultural fungicide trifloxystrobin.

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

Cette invention concerne un nouveau procédé permettant la préparation de trifluorométhylacétophénones représentés par la formule générale (I), dans laquelle le groupe CF3 peut être placé en position 2 ou 3 relativement à l'acétyle. Ce procédé comprend les étapes suivantes : (a) on fait réagir un halogénure de trifluorométhylbenzoyle représenté par la formule générale (II), dans laquelle le groupe CF3 situé sur le noyau aromatique peut être placé en position 2 ou 3 relativement à l'acétyle et Hal est un atome d'halogène sélectionné dans le groupe constitué par le fluor, le chlore, le brome et l'iode, avec une amine secondaire cyclique représentée par la formule générale (III), dans laquelle A est un pont alkylène C3-C7 qui peut être interrompu par un atome d'oxygène ou de soufre en présence d'une base aqueuse, utilisé en tant qu'accepteur d'acide, de manière à former un cycloalkyl-trifluorométhylbenzamide représenté par la formule générale (IV) dans laquelle la position du groupe CF3 sur le noyau aromatique et A sont tels que définis ci-avant, puis (b) on ajoute un réactif de Grignard préparé avec du méthyle à ce cycloalkyl-trifluorométhylbenzamide, et on procède à une acidification avec un réactif d'acidification aqueux afin de former le trifluorométhylacétophénone représenté par la formule (I).
EP00975941A 1999-12-14 2000-10-27 Production de trifluoromethylacetophenones Withdrawn EP1240127A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9929562.8A GB9929562D0 (en) 1999-12-14 1999-12-14 Organic compounds
GB9929562 1999-12-14
PCT/EP2000/010596 WO2001044152A1 (fr) 1999-12-14 2000-10-27 Production de trifluoromethylacetophenones

Publications (1)

Publication Number Publication Date
EP1240127A1 true EP1240127A1 (fr) 2002-09-18

Family

ID=10866309

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00975941A Withdrawn EP1240127A1 (fr) 1999-12-14 2000-10-27 Production de trifluoromethylacetophenones

Country Status (11)

Country Link
EP (1) EP1240127A1 (fr)
JP (1) JP2003517029A (fr)
KR (1) KR20020056943A (fr)
CN (1) CN1409697A (fr)
AU (1) AU1388901A (fr)
BR (1) BR0016320A (fr)
GB (1) GB9929562D0 (fr)
HK (1) HK1052926A1 (fr)
IL (1) IL149713A0 (fr)
MX (1) MXPA02005873A (fr)
WO (1) WO2001044152A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI518076B (zh) * 2008-04-09 2016-01-21 杜邦股份有限公司 製備雜環化合物之方法
JP5211876B2 (ja) * 2008-06-11 2013-06-12 セントラル硝子株式会社 高純度２’−トリフルオロメチルプロピオフェノンの製造方法
CN104478792B (zh) * 2014-12-26 2016-10-05 西华大学 一种具有抑菌活性的化合物及其水溶性液剂的制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9808447D0 (en) * 1998-04-18 1998-06-17 Zeneca Ltd Process
US5969188A (en) * 1999-01-05 1999-10-19 Nipa Hardwicke, Inc. Process for producing trifluoromethylacetophenones

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0144152A1 *

Also Published As

Publication number Publication date
JP2003517029A (ja) 2003-05-20
CN1409697A (zh) 2003-04-09
BR0016320A (pt) 2002-08-27
KR20020056943A (ko) 2002-07-10
AU1388901A (en) 2001-06-25
MXPA02005873A (es) 2003-01-28
HK1052926A1 (zh) 2003-10-03
GB9929562D0 (en) 2000-02-09
IL149713A0 (en) 2002-11-10
WO2001044152A1 (fr) 2001-06-21

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