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AU5357898A - Synthesis of fluorophenyl boranes - Google Patents

Synthesis of fluorophenyl boranes

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Publication number
AU5357898A
AU5357898A AU53578/98A AU5357898A AU5357898A AU 5357898 A AU5357898 A AU 5357898A AU 53578/98 A AU53578/98 A AU 53578/98A AU 5357898 A AU5357898 A AU 5357898A AU 5357898 A AU5357898 A AU 5357898A
Authority
AU
Australia
Prior art keywords
solvent
fluorophenyl
grignard reagent
reaction mixture
produced
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.)
Granted
Application number
AU53578/98A
Other versions
AU732314B2 (en
Inventor
Fredric Askham
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.)
Boulder Scientific Co
Original Assignee
Boulder Scientific Co
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Filing date
Publication date
Application filed by Boulder Scientific Co filed Critical Boulder Scientific Co
Publication of AU5357898A publication Critical patent/AU5357898A/en
Application granted granted Critical
Publication of AU732314B2 publication Critical patent/AU732314B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02Monocyclic aromatic halogenated hydrocarbons
    • C07C25/13Monocyclic aromatic halogenated hydrocarbons containing fluorine
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/093Preparation of halogenated hydrocarbons by replacement by halogens
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02Lithium compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02Boron compounds
    • C07F5/027Organoboranes and organoborohydrides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

SY THESIS OF FLUOROPHENYL BORANES
This application is a continuation of United States application Serial No. 08/754,622 filed 21 November 1996.
FIELD OF THE INVENTION
This invention relates to the synthesis of fluorophenyl boranes. More particularly, the invention relates to the synthesis of pentafluorophenyl boranes. BACKGROUND OF THE INVENTION
Prior art describes the production of tris- pentafluorophenyl borane from various starting materials. See, for example, United States patent 5,362,423 and Pohlmann, et al . , Z .Naturforschα . 20 b, 5-11 (1965) . Tris-pentafluorophenyl boranes are useful as catalyst or catalyst components in some types of olefin polymerization reactions.
SUMMARY OF THE INVENTION
Pursuant to the invention, a fluorophenyl Grignard compound is reacted in a non-interfering solvent with a boron trihalide to produce a borane.
DETAILED DESCRIPTION OF THE INVENTION
The fluorophenyl Grignard reagents useful in the invention have the formula RMgX, in which R is a fluorophenyl group, preferably a pentafluorophenyl group, and X is a halogen, preferably bromine or chlorine .
Boron trihalides useful on the invention have the formula BX3, in which X is a halide, bromine or chlorine or fluorine. The boron trihalides may be used per se or in the form of an etherate, e.g., BF3-OEt2.
Production of fluorophenyl Grignard reagents, specifically pentafluoro magnesium bromide, is described in Repress, et al . , J. Orαanometallic Chem. (1969) 18.:263-274 and Repress, et al . , J.Organometallic Chem. (1969) 18:191-195.
The invention may entail essentially the single step process in which the boron trihalide is combined with a pre-formed or existing solution of a fluorophenyl Grignard reagent in a non-interfering solvent .
Alternatively, the invention may be carried out in two steps in which the fluorophenyl Grignard reagent is first produced, for example, in a reaction mixture including an ether solvent and is thereafter reacted in a second step with the boron trihalide in a solvent which need not be an ether. The two-step method is preferably completed in a single solvent or a single reaction vessel in which the fluorophenyl Grignard reagent is first produced, for example, in an ether solvent and then reacted, if desired, after solvent exchange to provide a hydrocarbon solvent of the Grignard with the boron trihalide reactant .
In one preferred embodiment of the invention, hexafluoro benzene is first diluted with an ether, such as tetrahydrofuran. A ferrous chloride catalyst is added and the solution cooled in an ice bath. Ethyl magnesium bromide is added in solution in THF. The boron trihalide, in the laboratory in the form of the etherate, is added to the reaction mixture which is refluxed for a time sufficient to produce the desired fluorophenyl Grignard reagent . The hydrocarbon solvent is added, and the reaction mixture distilled to remove the THF.
In the embodiment of the invention conducted in a single solvent or reaction vessel, the fluorophenyl benzene, preferably hexafluoro benzene, and a catalyst, if appropriate, are dissolved in a solvent. The solution is cooled. A Grignard reagent, such as ethyl magnesium bromide, is added to the cooled solution at ambient temperature. In general, the reaction conditions for producing the fluorophenyl Grignard as described in the Repress, et al . references cited above may be utilized.
The boron trihalide, for example boron trifluoride etherate, is added by syringe to the reaction mixture containing the fluorophenyl Grignard in an amount sufficient under the conditions to provide the desired borane . After completion of the boron trihalide introduction, the mixture is stirred in an inert environment for a time sufficient to produce the desired tris-fluorophenyl borane. Sufficient reaction may be achieved by overnight refluxing. White solids begin to form during the first hour. The product may be recovered by conventional methods, such as distillation.
EXAMPLE 1 Hexafluoro benzene (66.5 mmol, 12.4 g) was diluted with 100 ml THF. FeCl2 (0.2 g, 1.6 mmol) was added, and the solution cooled to 0-5°C in an ice bath. A solution of EtMgBr (100 ml, 0.94 M in THF) was added over 30 minutes. After stirring for an additional 30 minutes, the ice bath was removed and BF3-OEt2 (1.9 ml, 15.6 mmol) was added by syringe, and the reaction mixture was refluxed overnight. Deoxygenated hydrocarbon solvent (Isopar E) was added, and the reaction mixture was distilled to remove THF. A portion of the sample was withdrawn and analyzed by 19F NMR which showed a (C6F5)B-THF adduct . The distillation was continued until THF was no longer present in aliquots of the hydrolyzed reaction mixture. Another 19F NMR spectrum was obtained showing (C6F5)3B free of THF.

Claims

CLAIMS :
1. A method for making a tris-fluorophenyl borane compound which comprises reacting a fluorophenyl Grignard reagent with a boron trihalide in a non- interfering solvent, wherein a reaction mixture containing a tris-fluorophenyl borane and said non- interfering solvent is produced.
2. A method which comprises reacting C6F5 MgBr or C 6 F 5 MgCl with BF3 or BC13 in a non-interfering solvent, wherein a reaction mixture containing (C6F5)3B and said non-interfering solvent is produced.
3. A process which comprises:
(i) providing a reaction vessel containing a first solution of a fluorophenyl Grignard reagent in an ether solvent,
(ii) exchanging said ether solvent for a solvent which is not an ether, wherein a second solution of said fluorophenyl Grignard reagent in said solvent which is not an ether is produced, and
(iii) adding a boron trihalide to said second solution for reaction with said fluorophenyl Grignard reagent, wherein a third solution of a fluorophenyl borane is produced.
4. The claim 3 process wherein the fluorophenyl Grignard reagent of step (i) is pentafluorophenyl magnesium bromine and said ether solvent is tetrahydrofuran; wherein the step (ii) solvent which is not an ether is benzene, toluene or xylene; wherein said boron trihalide added in step (iii) is BF3 or BF3 etherate; and wherein said fluorophenyl borane produced in step (iii) is pentafluorophenyl borane.
5. The claim 3 or claim 4 process further comprising :
(iv) isolating said fluorophenyl borane produced in step (iii) .
6. A method which comprises reacting C6F5 MgBr with BF3 or BF3 etherate in a non-interfering solvent wherein a reaction mixture containing C6F5B and said non-interfering solvent is produced.
7. The claim 6 method in which the non- interfering solvent is toluene.
8. The method which comprises:
(i) reacting hexafluorobenzene with a Grignard reagent in the presence of a catalyst to provide a first reaction mixture containing pentafluorophenyl Grignard reagent, and
(ii) adding a boron trihalide to said step (i) first reaction mixture, wherein boron trihalide reacts with said pentafluorophenyl Grignard reagent in said step (i) first reaction mixture to produce a second reaction mixture containing a (C6F5)3B.
AMENDED CLAIMS
[received by the International Bureau on 23 Apri l 1998 (23.04.98) ; original claims 1 and 2 cancel led ; original claims 4 and 6 amended ; remaining claims unchanged (3 pages) ]
3 . A process which comprises :
(i) providing a reaction vessel containing a first solution of a fluorophenyl Grignard reagent in an ether solvent ,
(ii ) exchanging said ether solvent for a solvent which is not an ether, wherein a second solution of said fluorophenyl Grignard reagent in said solvent which is not an ether is produced, and
(iii) adding a boron trihalide to said second solution for reaction with said fluorophenyl Grignard reagent , wherein a third solution of a fluorophenyl borane is produced .
4. The claim 3 process wherein the fluorophenyl Grignard reagent of step (i) is pentafluorophenyl magnesium bromide and said ether solvent is tetrahydrofuran; wherein the step (ii) solvent which is not an ether is benzene, toluene or xylene; wherein said boron trihalide added in step (iii) is BF3 or BF3 etherate; and wherein said fluorophenyl borane produced in step (iii) is pentafluorophenyl borane.
5. The claim 3 or claim 4 process further comprising :
(iv) isolating said fluorophenyl borane produced in step (iii) .
6. A method which comprises reacting C6F5 MgBr with BF3 or BF3 etherate in a non-interfering solvent wherein a reaction mixture containing (C6F5) 3B and said non-interfering solvent is produced.
7. The claim 6 method in which the non- interfering solvent is toluene.
8. The method which comprises:
(i) reacting hexafluorobenzene with a Grignard reagent in the presence of a catalyst to provide a first reaction mixture containing pentafluorophenyl Grignard reagent , and
(ii) adding a boron trihalide to said step (i) first reaction mixture, wherein boron trihalide reacts with said pentafluorophenyl Grignard reagent in said step (i) first reaction mixture to produce a second reaction mixture containing a (C6F5)3B.
AU53578/98A 1996-11-21 1997-11-19 Synthesis of fluorophenyl boranes Ceased AU732314B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US75462296A 1996-11-21 1996-11-21
US08/754622 1996-11-21
PCT/US1997/021071 WO1998022475A1 (en) 1996-11-21 1997-11-19 Synthesis of fluorophenyl boranes

Publications (2)

Publication Number Publication Date
AU5357898A true AU5357898A (en) 1998-06-10
AU732314B2 AU732314B2 (en) 2001-04-12

Family

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Family Applications (1)

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AU53578/98A Ceased AU732314B2 (en) 1996-11-21 1997-11-19 Synthesis of fluorophenyl boranes

Country Status (5)

Country Link
EP (1) EP0901495A4 (en)
AU (1) AU732314B2 (en)
CA (1) CA2243659A1 (en)
NZ (1) NZ331273A (en)
WO (1) WO1998022475A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL122004A0 (en) * 1996-10-25 1998-03-10 Nippon Catalytic Chem Ind Producing process of (fluoroaryl) borane compound and producing process of tetrakis (fluoroaryl) borate derivative
JPH1129576A (en) * 1997-07-04 1999-02-02 Nippon Shokubai Co Ltd Stabilizer of (fluorinated aryl)boron compound, stabilization and crystallization
WO2014085058A1 (en) 2012-11-27 2014-06-05 Albemarle Corporation Process for producing tetrakis(faryl)borate salts

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3080324A (en) * 1960-08-01 1963-03-05 Cincinnati Milling Machine Co Grignard reagents
DE3145286A1 (en) * 1981-11-14 1983-05-19 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING PENTAFLUORBENZYL ALCOHOL
US5510536A (en) * 1992-12-28 1996-04-23 Tosoh Akzo Corporation Production method of tris(pentafluorophenyl)borane using pentafluorophenylmagnesium derivatives prepared from pentafluorobenzene
US5600004A (en) * 1995-02-21 1997-02-04 Albemarle Corporation Process for preparing pentafluorophenyl compounds
WO1997014698A1 (en) * 1995-10-18 1997-04-24 The Dow Chemical Company Synthesis of perfluoroaryl-substituted compounds

Also Published As

Publication number Publication date
EP0901495A4 (en) 1999-06-09
AU732314B2 (en) 2001-04-12
EP0901495A1 (en) 1999-03-17
CA2243659A1 (en) 1998-05-28
NZ331273A (en) 2000-03-27
WO1998022475A1 (en) 1998-05-28

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