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WO1997039003A1 - Preparation de tris-(pentafluorophenyl) borane - Google Patents

Preparation de tris-(pentafluorophenyl) borane Download PDF

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Publication number
WO1997039003A1
WO1997039003A1 PCT/US1997/005483 US9705483W WO9739003A1 WO 1997039003 A1 WO1997039003 A1 WO 1997039003A1 US 9705483 W US9705483 W US 9705483W WO 9739003 A1 WO9739003 A1 WO 9739003A1
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WO
WIPO (PCT)
Prior art keywords
pentafluorophenyl
group
metal
borane
contacting
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/US1997/005483
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English (en)
Inventor
David R. Wilson
Robert E. Lapointe
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Publication of WO1997039003A1 publication Critical patent/WO1997039003A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides

Definitions

  • the present invention relates to a process for preparing tris(pentafluorophenyl)borane.
  • Tris(pentafluorophenyl)borane is a strong Lewis acid having many useful industrial applications.
  • the compound is useful as a catalyst activator in combination with metallocene catalysts in Ziegler-Natta polymerizations.
  • an improved process for preparing tris(pentafluorophenyl)borane comprising: a) forming a pentafluorophenyl metal compound wherein the metal is selected from Group 11 or 12; b) contacting the (pentafluorophenyl) metal compound from step a) with a boron halide compound to form tris(pentafluorophenyl)borane; and c) recovering the resulting tris(pentafluorophenyl)borane.
  • the initial step a) is performed by decarboxylation of a metal pentafluorobenzoate wherein the metal is selected from Group 11 or 12.
  • the decarboxylation is preferably conducted by heating the metal pentafluorophenyl benzoate, preferably in a hydrocarbon liquid at a temperature from 100 to 500°C, optionally under reduced pressure. It has been discovered that the decarboxylation process can be carried out in high yield by the use of such hydrocarbon liquids. The alternative, prior art decarboxylation process utilizing sublimation under vacuum is difficult to practice in an industrial setting and yields are poor. On the other hand, the use of ethereal solvents requires a solvent change thereby complicating the synthesis and is therefor not desired.
  • the improved process for preparing tris(pentafluorophenyl)borane disclosed herein most preferably comprises the steps of: a1) forming a Group 11 or 12 metal pentafluorobenzoate by contacting pentafluorobenzoic acid with a Group 11 or 12 metal oxide or hydroxide under neutralization conditions and, optionally, dehydration conditions, or by contacting a Group 1 or 2 metal salt of pentafluorobenzoic acid with a Group 11 or 12 metal halide compound; a2) forming a (pentafluorophenyl) Group 11 or 12 metal compound by decarboxylation of the Group 11 or 12 metal pentafluorobenzoate; b) contacting the (pentafluorophenyl) Group 11 or 12 metal compound from step a2) with a boron halide compound to form tris(pentafluorophenyl)borane; and c) recovering the resulting tris(pentafluorophenyl)borane
  • Preferred Group 11 or 12 metal oxides and hydroxides for use herein include zinc, copper, cadmium and mercury compounds. Highly preferred metal oxides and hydroxides are zinc and copper oxides and hydroxides. The most highly preferred metal oxides and hydroxides are zinc hydroxide or zinc oxide.
  • Preferred Group 11 or 12 metal halides for use herein include zinc, copper, cadmium and mercury compounds. Highly preferred metal halides are zinc and copper halides. The most highly preferred metal halide is zinc chloride. Preferred Group 1 or 2 metal salts include lithium, sodium, potassium and magnesium compounds.
  • Step a1) is preferably conducted in the presence of a solvent or diluent at a temperature from 0 to 150°C, more preferably from 25 to 100°C.
  • a preferred diluent is water. Any suitable pressure may be employed from 0.00001 to 1000 Mpa.
  • the water used as a diluent or generated in step a1 ) may be removed (dehydration) by evaporation or by use of azeotropic distillation techniques, including reduced pressure, if desired.
  • the decarboxylation reaction, step a2) can be conducted in the absence of a solvent or diluent, that is by sublimation, preferably under reduced pressure at temperatures of greater than 175°C, preferably greater than 190°C, most preferably greater than 200°C.
  • o aliphatic or alicyclic or aromatic hydrocarbons especially octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, decahydronaphthalene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, diethylbenzene, diethyltoluene, triethylbenzene, triisopropylbenzene, and mixtures thereof.
  • Step b) may be conducted in the same diluent as was used for step a), or if no diluent was employed for step a), a diluent preferably is used for step b).
  • Hydrocarbon diluents are preferred, but other solvents, for example ethers, may also be used provided that the solvents do not adversely affect either the starting materials or the product.
  • ether diluents generally gives results inferior to the embodiment using hydrocarbon diluents.
  • strongly coordinating ethers such as tetrahydrofuran have been found to produce the best yields.
  • the resulting adducts may be "cracked" to remove ether by contacting the complexes with a strong Lewis acid, especially AICI3 or BCI3.
  • Preferred boron halide compounds are boron trihalides, preferably boron trichloride.
  • Step b) is preferably conducted at a temperature from 0 to 150°C, more preferably from 25 to 100°C. Any suitable pressure may be employed from 0.00001 to 1000 Mpa.
  • the same diluent is utilized in steps a2) and b).
  • Merely increasing the temperature and optionally the pressure, and periodically or continuously venting the reactor can be utilized in the subsequent decarboxylation process.
  • Reduced or elevated pressures from 0.001 atmosphere to 100 atmospheres (0.0001 to 10 Mpa) and removal of CO 2 from the reactor such as by venting the same are desirably employed.
  • the final recovery of tris(pentafluoro-phenyl)borane can be accomplished merely by decanting the solution of the reaction product from insoluble byproducts or coproducts or incompletely-reacted insoluble starting materials, by filtering or by a solvent exchange.
  • the solvent may be readily removed by evaporation.
  • the presence of the hydrocarbon diluent is highly desirable and recovery of the final product in a neat form is not necessary.
  • Zinc pentafluorobenzoate Zn(C 6 F 5 COO) 2
  • Zinc pentafluorobenzoate (0.50 g) was slurried in 10 mL of tridecane and the mixture was heated for several days after which time most of the solid has dissolved and the slurry had darkened. By observing the 19 F NMR spectrum, the reaction was deemed to be complete and to have formed the desired product. The bis(pentafluorophenyl)zinc was divided into two volumes for further use. Tris(pentafluorophenyl)borane, (C 6 F 5 ) 3 B

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

La présente invention, qui concerne un procédé de préparation de tris-(pentafluorophényl) borane comporte plusieurs opérations: (a) former un composé (pentafluorophényl) métal dans lequel le métal appartient au groupe 11 ou 12, puis (b) mettre en contact le composé (pentafluorophényl) métal issu de l'opération (a) avec un composé d'halogénure de bore pour former le tris-(pentafluorophényl) borane, et (c) récupérer le tris-(pentafluorophényl) borane résultant.
PCT/US1997/005483 1996-04-15 1997-04-02 Preparation de tris-(pentafluorophenyl) borane Ceased WO1997039003A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US1545596P 1996-04-15 1996-04-15
US60/015,455 1996-04-15
US1582196P 1996-04-18 1996-04-18
US60/015,821 1996-04-18

Publications (1)

Publication Number Publication Date
WO1997039003A1 true WO1997039003A1 (fr) 1997-10-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/005483 Ceased WO1997039003A1 (fr) 1996-04-15 1997-04-02 Preparation de tris-(pentafluorophenyl) borane

Country Status (1)

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WO (1) WO1997039003A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0604963A1 (fr) * 1992-12-28 1994-07-06 Tosoh Akzo Corporation Procédé de préparation de tris(pentafluorophényl)borane utilisant un derivé magnésien de pentafluorophényl preparé à partir de pentafluorobenzine
EP0604962A1 (fr) * 1992-12-28 1994-07-06 Tosoh Akzo Corporation Procédé de préparation de tris(pentafluorophényl)borane utilisant un sel alcalin de pentafluorophényl préparé à partir de pentafluorobenzine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0604963A1 (fr) * 1992-12-28 1994-07-06 Tosoh Akzo Corporation Procédé de préparation de tris(pentafluorophényl)borane utilisant un derivé magnésien de pentafluorophényl preparé à partir de pentafluorobenzine
EP0604962A1 (fr) * 1992-12-28 1994-07-06 Tosoh Akzo Corporation Procédé de préparation de tris(pentafluorophényl)borane utilisant un sel alcalin de pentafluorophényl préparé à partir de pentafluorobenzine

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