EP0530208A1 - Procede de production de alpha-fluorstyrols - Google Patents

Procede de production de alpha-fluorstyrols

Info

Publication number
EP0530208A1
EP0530208A1 EP91907846A EP91907846A EP0530208A1 EP 0530208 A1 EP0530208 A1 EP 0530208A1 EP 91907846 A EP91907846 A EP 91907846A EP 91907846 A EP91907846 A EP 91907846A EP 0530208 A1 EP0530208 A1 EP 0530208A1
Authority
EP
European Patent Office
Prior art keywords
fluorostyrene
preparation
reaction
group
carried out
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Withdrawn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
EP91907846A
Other languages
German (de)
English (en)
Inventor
Walter Heitz
Arno Knebelkamp
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.)
Hoechst AG
Original Assignee
Hoechst 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 Hoechst AG filed Critical Hoechst AG
Publication of EP0530208A1 publication Critical patent/EP0530208A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons

Definitions

  • the present invention relates to a method for
  • the first stage produces ⁇ , ⁇ -difluoroethylbenzene, from which ⁇ -fluorostyrene can be obtained by pyrolysis at 400 ° C.
  • Bromine fluoride generated in situ added to styrene, and in a second step with elimination of hydrogen bromide, ⁇ -fluorostyrene formed in 63% yield.
  • the addition of bromine fluoride to substituted olefins takes place with high regioselectivity.
  • Bromine fluoride is not used directly for synthesis, but must be e.g. from N-bromoacetamide and
  • Hydrogen fluoride can be generated in absolute ether. Another disadvantage is the generally difficult handling and toxicity of interhalogen compounds. Palladium-catalyzed coupling reactions of fluorovinyl
  • Zinc compounds with aryl iodides were described in 1986 by Heinze and Burton (P.L. Heinze, D.J. Burton, J. Fluorine
  • Styrene derivatives react.
  • the object of the present invention was therefore a
  • the invention thus relates to a process for the preparation of ⁇ -fluorostyrenes by reacting halogen aromatics with fluoroolefins in the presence of a palladium catalyst, via a one-step reaction which is characterized by good
  • halogenated aromatics preferably bromo- or iodoaryls
  • fluoroolefins with palladium catalysis in an organic water-miscible solvent.
  • Bases can be added to the reaction mixture, preferably secondary or tertiary amines and the reaction carried out at a temperature between 50 and 180 ° C.
  • reaction product is followed by a
  • Vacuum distillation separated and has purities of over 95% with preparative yields of 30 to 80%.
  • a halogen-substituted aromatic (I) is preferably a bromine- or iodine-substituted aromatic, with a
  • Palladium catalyst to be converted to an ⁇ -fluorostyrene The halogen aromatic can be substituted in the ortho, meta or para position, in particular in the meta or para position, the radical R being a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a
  • Dialkylamino group an aryl radical or a fused aryl or heteroaryl ring, a hydroxy or
  • X halogen, especially bromine or iodine
  • Z hydrogen, fluorine, chlorine.
  • the catalyst systems used for the process according to the invention are preferably palladium, palladium acetate,
  • Solvents especially acetonitrile, dimethylformamide, methanol, dioxane, which in addition to
  • Palladium catalyst so-called cocatalysts can be added.
  • Suitable reaction temperatures for this process are in the range from 50 to 180 ° C., preferably in the range from 100 to 130 ° C.
  • the ⁇ -fluorostyrenes according to the invention can be easily calibrated to polymers with defined
  • Refractive index for example, use as a cladding material for optical fibers or similar materials that have high optical requirements.
  • Halogen atom on the aromatic and a fluorine atom on the olefin is split off, and not as expected
  • biphenyl and stilbene can also be used
  • Styrene formation is preferred (yields up to 80%), while stilbene formation predominates at lower pressures.
  • halogen aromatics bromo- or iodarenes are preferably used.
  • polycyclic aromatics and heteroaromatics e.g. Benzene, naphthalene, quinoline or pyridine.
  • ortho substituents in particular bulky groups, have a negative effect on the course of the reaction because of their steric hindrance.
  • di-, tri- or tetrasubstituted may be suitable, where two fluorine atoms must be on the same carbon atom so that ⁇ -fluorostyrenes are formed as reaction products.
  • olefins which are only monosubstituted, styrenes are obtained since the fluorine atom on the
  • Olefin is split off. So styrene and stilbene are obtained from iodobenzene and vinyl fluoride. In contrast, ß-fluorostyrenes are formed with olefins which carry the halogen atoms on two different carbon atoms.
  • the yields of the process according to the invention can be increased further by adding the olefin coupling component in excess; preferred is e.g. an excess of 2.5 equivalents of olefin, particularly preferably larger excesses.
  • Reactor are continuously fed back while the reaction product is separated from the reaction mixture.
  • Such a method is particularly advantageous from an economic and ecological point of view.
  • reaction is preferably carried out in a polar solvent, for example particularly preferred
  • Secondary and tertiary amines are used as bases, trialkylamine being particularly preferred, but also inorganic acetates and carbonates can also be used.
  • Possible catalyst systems that are suitable for the claimed process are e.g. elementary palladium,
  • Triarylphosphine / palladium complexes but likewise all catalysts or catalyst systems which are suitable for the Heck reaction can also be used here, the concentrations between 0.01-10 mol%,
  • Catalyst should lie.
  • the ⁇ -fluorostyrene obtained according to the invention is characterized by a high purity, so that e.g. with yourself
  • Moisture affinity and low flammability are thermally and chemically very stable and they have special surface properties.
  • Poly ( ⁇ -fluorostyrene) has, like some others
  • Fluoropolymers have a low refractive index, what this
  • the autoclave was heated to 115 ° C. in an oil bath and this temperature was maintained for about 18 hours.
  • the main product was obtained by vacuum distillation as a clear, colorless liquid with a boiling point of

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

Un procédé permet de produire de l'alpha-fluorstyrol à partir de fluoroléfines. Un aromate halogène (I) est converti en un alpha-fluorostyrol (III) avec un éthylène (II) à substitution de fluor en présence d'un catalyseur en palladium. R peut représenter un atome d'hydrogène, un atome d'halogène, un groupe C1-C4-alkyle, un groupe C1-C5 alkoxyle, un groupe amine, alkylamine ou dialkylamine, un reste aryle ou un noyau aryle ou hétéroaryle annelé, un groupe hydroxyle ou hydroxyalkyle, un groupe trifluorométhyle ou perfluoralkyle, ou un groupe nitro.
EP91907846A 1990-04-26 1991-04-24 Procede de production de alpha-fluorstyrols Withdrawn EP0530208A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4013305 1990-04-26
DE4013305A DE4013305A1 (de) 1990-04-26 1990-04-26 Verfahren zur herstellung von (alpha)-fluorstyrol

Publications (1)

Publication Number Publication Date
EP0530208A1 true EP0530208A1 (fr) 1993-03-10

Family

ID=6405131

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91907846A Withdrawn EP0530208A1 (fr) 1990-04-26 1991-04-24 Procede de production de alpha-fluorstyrols

Country Status (5)

Country Link
US (1) US5313001A (fr)
EP (1) EP0530208A1 (fr)
JP (1) JPH0720888B2 (fr)
DE (1) DE4013305A1 (fr)
WO (1) WO1991016286A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5382718A (en) * 1993-09-16 1995-01-17 E. I. Du Pont De Nemours And Company Cyclofluoroalkylated fullerene compounds
DE69825639T2 (de) * 1997-01-08 2005-08-11 Albemarle Corp. Reinigungsverfahren für Arylcarbonsäuren
US6096920A (en) * 1997-01-08 2000-08-01 Albemarle Corporation Preparation of carboxylic compounds and their derivatives
DE19712388A1 (de) * 1997-03-25 1998-10-01 Studiengesellschaft Kohle Mbh Verfahren zur Synthese von aromatisch substituierten Olefinen
DE19843012A1 (de) * 1998-09-21 2000-03-23 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von Olefinen
JPWO2009011364A1 (ja) * 2007-07-18 2010-09-24 旭硝子株式会社 電子線、ｘ線またはｅｕｖ光を用いたリソグラフィー法に用いられるレジスト組成物
JP5562069B2 (ja) * 2009-03-05 2014-07-30 国立大学法人大阪大学 有機フッ素化合物の合成方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2752400A (en) * 1953-06-26 1956-06-26 Gen Electric Method for preparing phenyltrifluoroethylene
JPS609013B2 (ja) * 1982-01-29 1985-03-07 株式会社東芝 ２−クロロ−１，２−ジフルオロビニル基を有するベンゼン誘導体の製造方法
JPS58174335A (ja) * 1982-04-07 1983-10-13 Toshiba Corp β−クロロ−α，β−ジフルオロスチレン誘導体の製造方法
JPS6413036A (en) * 1987-07-06 1989-01-17 Mitsubishi Chem Ind Dimerization of aromatic halogen compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9116286A1 *

Also Published As

Publication number Publication date
US5313001A (en) 1994-05-17
JPH05502034A (ja) 1993-04-15
WO1991016286A1 (fr) 1991-10-31
JPH0720888B2 (ja) 1995-03-08
DE4013305A1 (de) 1991-10-31

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