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WO1994008931A1 - Procede et intermediaires pour la preparation de substitues 2-phenyl-5-(3-phenoxyphenyl)-1,1,1-trifluoropentanes substitues - Google Patents

Procede et intermediaires pour la preparation de substitues 2-phenyl-5-(3-phenoxyphenyl)-1,1,1-trifluoropentanes substitues Download PDF

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Publication number
WO1994008931A1
WO1994008931A1 PCT/EP1993/002843 EP9302843W WO9408931A1 WO 1994008931 A1 WO1994008931 A1 WO 1994008931A1 EP 9302843 W EP9302843 W EP 9302843W WO 9408931 A1 WO9408931 A1 WO 9408931A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
suitable solvent
preparation
reacted
meanings given
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.)
Ceased
Application number
PCT/EP1993/002843
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English (en)
Inventor
Heinrich Franke
Klaus-Dieter Graske
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 Pharma AG
Original Assignee
Schering 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 Schering AG filed Critical Schering AG
Priority to AU51778/93A priority Critical patent/AU5177893A/en
Publication of WO1994008931A1 publication Critical patent/WO1994008931A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/295—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing hydroxy or O-metal groups

Definitions

  • This invention relates to a new process and new intermediates for the preparation of substituted 2-phenyl- 5-(3-phenoxyphenyl) -1, 1,l-trifluoropentanes of general formula I
  • R l is fluorine, chlorine, methoxy, difluoromethoxy, ethoxy or trifluoroethoxy
  • R 2 and R 3 independently of each other, are hydrogen or fluorine.
  • the preparations described in this document have the disadvantage that they comprise many reaction stages.
  • a further disadvantage is that one of the reaction stages comprises a Wittig reaction in which a large amount of triphenylphosphine oxide is formed as by-product.
  • W is hydrogen or halogen
  • X is hydrogen or fluorine
  • Q is a group -(CF 2 ) n R 1 , in which R 1 is hydrogen, fluorine or chlorine and n is 1 or 2, and Z is halogen, C 1 -c 6 -alkyl, c 1 -C 6 -alkoxy, halo-C [ -c 6 -alkyl or halo- C 1 -C 6 -al oxy.
  • This process also proceeds via a ittig reaction.
  • the object of the invention is thus to provide a process with a smaller number of steps and which also avoids the Wittig reaction.
  • R 3 has the meaning given in formula I
  • acetylene in which R 3 has the meaning given in formula I, is reacted with acetylene in a suitable solvent with a strong base, in which the acetylene is deprotonated before the reaction,
  • R 1 , R 2 and R 3 have the meaning given in general formula I is reacted with the halogenating agent in a suitable solvent, optionally using a base and finally
  • R 1 , R 2 and R 3 have the meaning given in general formula I and Hal is chlorine or bromine is catalytically hydrogenated in a suitable solvent, optionally with the addition of an acid binding agent, or
  • R 1 and R 2 have the meanings given in general formula I, is reacted with acetylene and a strong base or with sodium acetylide in a suitable solvent.
  • the reaction step a) is suitably carried at a temperature of between -78°C at room temperature, in which as the base, there can be used for example sodium amide, sodium hydride or a Grignard reagent and as the solvent there can be used for example an ether, such as diethyl ether, a hydrocarbon, such as toluene, or liquid ammonia.
  • the base there can be used for example sodium amide, sodium hydride or a Grignard reagent
  • the solvent there can be used for example an ether, such as diethyl ether, a hydrocarbon, such as toluene, or liquid ammonia.
  • phase transfer catalysed ethynylation is also possible, using concentrated alkali metal hydroxide as a base.
  • the reaction step b) is suitably carried out at a temperature of between -78 ⁇ C and 0°C, in which as the base, there can be used for example n-butyllithium and as the solvent, there can be used for example an ether, such as diethyl ether or tetrahydrofuran, or a hydrocarbon, such as hexane or toluene.
  • the base there can be used for example n-butyllithium
  • the solvent there can be used for example an ether, such as diethyl ether or tetrahydrofuran, or a hydrocarbon, such as hexane or toluene.
  • the reaction stage c) is suitably carried out at a temperature between 0 ⁇ C and 120°C in which there can be used, as halogenating agent for example thionyl chloride, phosphorus tribromide or concentrated hydrobromic acid, as the base for example pyridine or imidazole and as the solvent for example a hydrocarbon, such as toluene, a halogenated hydrocarbon, such as chloroform or dichloromethane, an ether, such as diethyl ether or tetrahydrofuran, a nitr x.e , such as acetonitrile, or an amide, such as dimethylforma ide.
  • This reaction step can also be carried out without a solvent.
  • Reaction step d) is suitably carried out at a temperature between room temperature and 200°C, under a hydrogen partial pressure of 1-150 bar.
  • catalyst for the catalytic hydrogenation there is preferably used palladium on active charcoal.
  • solvents it is preferable to use an alcohol, such as methanol or ethanol, or acetic acid.
  • acid binding agent sodium acetate is preferred.
  • the reaction step e) is suitably carried out at a temperature between -78°C and room temperature.
  • Suitable bases are for example Grignard reagents.
  • solvent there can be used ethers, such as diethyl ether or hydrocarbons, such as toluene or xylene.
  • Reaction step f) is suitably carried out at a temperature between -78 ⁇ C and room temperature.
  • Suitable bases include for example n-butyllithium, Grignard reagents, sodium hydride or sodium amide.
  • Suitable solvents include for example ethers, such as diethyl ether, hydrocarbons such as toluene or hexane, nitriles such as acetonitrile, or liquid ammonia.
  • the invention also includes diols of general formula V
  • reaction steps a)-c) can be combined.
  • the aldehyde of general formula II can be reacted with sodium acetamide in tetrahydrofuran. Without working up, an equivalent of n-butyllithium and then the ketone general formula I can be added. Then this can be worked up with water to the diol of general formula II or can be further converted with a halogenating agent directly into the allene of general formula VI, in which optionally acetonitrile or di ethylformamide can be added.
  • a reaction sequence can also begin with a ketone of general formula IV in which, after the addition of butyllithium, the aldehyde of general formula II is added.
  • the compounds of general formula I have one chiral centre, whereas the compounds of general formula V and VI have two.
  • the invention includes all enantiomers and diastereoisomers, as well as their mixtures.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Nouveau procédé de préparation de 2-phényl-5-(3-phénoxyphényl)-1,1,1-trifluoropentanes substitués de formule (I). Dans cette formule, R1 représente fluor, chlore, méthoxy, difluorométhoxy, éthoxy ou trifluoroéthoxy, et R2 et R3 représentent indépendamment hydrogène ou fluor, l'invention décrivant également des intermédiaires permettant de préparer ces composés.
PCT/EP1993/002843 1992-10-15 1993-10-14 Procede et intermediaires pour la preparation de substitues 2-phenyl-5-(3-phenoxyphenyl)-1,1,1-trifluoropentanes substitues Ceased WO1994008931A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU51778/93A AU5177893A (en) 1992-10-15 1993-10-14 Process and intermediates for the preparation of substituted 2-phenyl-5-(3-phenoxyphenyl)-1,1,1-trifluoropentanes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4235228 1992-10-15
DEP4235228.2 1992-10-15

Publications (1)

Publication Number Publication Date
WO1994008931A1 true WO1994008931A1 (fr) 1994-04-28

Family

ID=6470812

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002843 Ceased WO1994008931A1 (fr) 1992-10-15 1993-10-14 Procede et intermediaires pour la preparation de substitues 2-phenyl-5-(3-phenoxyphenyl)-1,1,1-trifluoropentanes substitues

Country Status (7)

Country Link
CN (1) CN1090838A (fr)
AU (1) AU5177893A (fr)
IL (1) IL107161A0 (fr)
MX (1) MX9306388A (fr)
TW (1) TW247903B (fr)
WO (1) WO1994008931A1 (fr)
ZA (1) ZA937677B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6133279A (en) * 1996-06-26 2000-10-17 Chugai Seiyaku Kabushiki Kaisha Therapeutic agents for renal diseases and organ preservatives
WO2012150207A1 (fr) 2011-05-04 2012-11-08 Bayer Cropscience Ag Utilisation de dérivés d'esters de l'acide cyclopropancarboxylique pour lutter contre les insectes résistants aux insecticides
WO2012150206A2 (fr) 2011-05-04 2012-11-08 Bayer Cropscience Ag Nouveaux dérivés d'esters de l'acide cyclopropane utilisés comme pesticides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115819662B (zh) * 2022-12-18 2023-09-12 四川轻化工大学 一种含氟环氧树脂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0233834A1 (fr) * 1986-01-22 1987-08-26 Schering Aktiengesellschaft Dérivés de trifluorométhylalcanes insecticides
GB2187452A (en) * 1986-03-04 1987-09-09 Ici Plc Insecticidal fluoroalkyl benzene derivatives
EP0279531A2 (fr) * 1987-02-17 1988-08-24 Imperial Chemical Industries Plc Procédé et intermédiaires pour la fabrication de composés actives comme insecticides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0233834A1 (fr) * 1986-01-22 1987-08-26 Schering Aktiengesellschaft Dérivés de trifluorométhylalcanes insecticides
GB2187452A (en) * 1986-03-04 1987-09-09 Ici Plc Insecticidal fluoroalkyl benzene derivatives
EP0279531A2 (fr) * 1987-02-17 1988-08-24 Imperial Chemical Industries Plc Procédé et intermédiaires pour la fabrication de composés actives comme insecticides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
H. UNEME ET AL: "SYNTHESIS OF NON-ESTER PYRETHROIDS HAVING A 1-FLUORO-1-METHYLETHYL GROUP USING 1,2-MIGRATION OF AN ARYL GROUP", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 65, no. 9, September 1992 (1992-09-01), TOKYO JP, pages 2401 - 2410 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6133279A (en) * 1996-06-26 2000-10-17 Chugai Seiyaku Kabushiki Kaisha Therapeutic agents for renal diseases and organ preservatives
WO2012150207A1 (fr) 2011-05-04 2012-11-08 Bayer Cropscience Ag Utilisation de dérivés d'esters de l'acide cyclopropancarboxylique pour lutter contre les insectes résistants aux insecticides
WO2012150206A2 (fr) 2011-05-04 2012-11-08 Bayer Cropscience Ag Nouveaux dérivés d'esters de l'acide cyclopropane utilisés comme pesticides

Also Published As

Publication number Publication date
ZA937677B (en) 1994-05-24
CN1090838A (zh) 1994-08-17
AU5177893A (en) 1994-05-09
MX9306388A (es) 1994-05-31
TW247903B (fr) 1995-05-21
IL107161A0 (en) 1993-12-28

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