USRE38325E1 - Method for the production of tetrakis (pentafluorophenyl) borates - Google Patents

Method for the production of tetrakis (pentafluorophenyl) borates Download PDF

Info

Publication number
USRE38325E1
USRE38325E1 US10/050,869 US5086902A USRE38325E US RE38325 E1 USRE38325 E1 US RE38325E1 US 5086902 A US5086902 A US 5086902A US RE38325 E USRE38325 E US RE38325E
Authority
US
United States
Prior art keywords
pentafluorophenyl
formula
tetrakis
compound
solvent
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.)
Expired - Lifetime
Application number
US10/050,869
Inventor
Terry E. Krafft
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
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 Boulder Scientific Co filed Critical Boulder Scientific Co
Priority to US10/050,869 priority Critical patent/USRE38325E1/en
Application granted granted Critical
Publication of USRE38325E1 publication Critical patent/USRE38325E1/en
Anticipated expiration legal-status Critical
Assigned to ANTARES CAPITAL LP, AS AGENT reassignment ANTARES CAPITAL LP, AS AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOULDER SCIENTIFIC COMPANY, LLC
Assigned to BOULDER SCIENTIFIC COMPANY, LLC reassignment BOULDER SCIENTIFIC COMPANY, LLC CERTIFICATE OF CONVERSION FROM A DELAWARE OR NON-DELAWARE CORPORATION TO A DELAWARE LIMITED LIABILITY COMPANY PURSUANT TO SECTION 18-214 OF THE LIMITED LIABILITY COMPANY ACT Assignors: BOULDER SCIENTIFIC COMPANY
Expired - Lifetime legal-status Critical Current

Links

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 System
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides

Definitions

  • This invention relates to the synthesis of tetrakis (pentafluorophenyl) borates by reaction of a tetrafluoroborate salt with a pentafluorophenyl compound.
  • the invention provides a method for the production of tetrakis (pentafluorophenyl) borates by reacting a tetrafluoroborate salt with pentafluorophenyl magnesium halide in a non-interfering solvent.
  • Pentafluorophenyl magnesium halides are known. See, e.g., Respess, et al., J. Organometal. Chem. (1969) 18:263-274 and Respess, et al., J. Organometal. Chem. (1969) 19:191-195.
  • Pentafluorophenyl magnesium halides useful in the invention have the formula C 6 F 6 MgX in which X is a halogen, e.g., iodine, chlorine or bromine, preferably bromine.
  • Tetrafluoroborate salts useful in the invention have the formula QBF 4 in which Q is sodium, lithium or potassium, preferably sodium.
  • the reaction between the Grignard and the tetrafluoroborate salt may be conducted in any non-interfering solvent.
  • Typical solvents have the formula R—O—R′ in which the R and R′ are the same or different aliphatic hydrocarbon groups having 2-10 carbon atoms. Ethyl ether is preferred.
  • the reaction is appropriately conducted at a temperature of 0° C. to 100° C., preferably at 30° C. to 35° C.
  • the tetrafluoroborate salt is added to the Grignard solution in stoichiometric amounts or in such greater or lesser amount as may be deemed appropriate. In the preferred practice of the invention the tetrafluoroborate salt is added in an amount more than 15% of stoichiometric. Preferably the reaction mixture is refluxed to expedite the reaction.
  • a reaction vessel is changed with 0.25 mol of C 6 H 5 MgBr and 0.056 mol of NaBF 4 in an ethyl ether solvent.
  • the reaction mixture is refluxed overnight under nitrogen.
  • the reaction mixture was processed to recover 24.4 g of brown solids. Apparent yield 62.1%.
  • Example I was repeated using NaBF 4 ground by pestle and mortar and a 36 hour reflux time. Yield: 62.2% of a product having a tetrakis (pentafluorophenyl) borate purity of about 60% as indicated by 19 F NMR.

Abstract

A process for preparing tetrakis (pentafluorophenyl) borate is described that involves reaction of a pentafluorophenyl magnesium halide with an alkali metal tetrafluoroborate.

Description

This application is a continuation-in-part of Ser. No. 09/077,999 filed Jun. 15, 1998, now abandoned, which is the 35 U.S.C. §371 counterpart of application PCT/U.S.96/16390 filed Oct. 15, 1996.
FIELD OF THE INVENTION
This invention relates to the synthesis of tetrakis (pentafluorophenyl) borates by reaction of a tetrafluoroborate salt with a pentafluorophenyl compound.
BACKGROUND OF THE INVENTION
It is known to produce tetrakis (pentafluorophenyl) borates by reaction of boron trihalide with pentafluorophenyl lithium or pentafluorophenyl magnesium halide and by reaction of tris (pentafluorophenyl) boron with pentafluorophenyl lithium. See generally, published European patent application No. 0 604 961 A2 and U.S. Pat. No. 5,473,036. Such borates are important intermediates in the synthesis of catalysts used in combination with metallocene polymerization catalysts.
SUMMARY OF THE INVENTION
The invention provides a method for the production of tetrakis (pentafluorophenyl) borates by reacting a tetrafluoroborate salt with pentafluorophenyl magnesium halide in a non-interfering solvent.
DETAILED DESCRIPTION OF THE INVENTION
Pentafluorophenyl magnesium halides (Grignards) are known. See, e.g., Respess, et al., J. Organometal. Chem. (1969) 18:263-274 and Respess, et al., J. Organometal. Chem. (1969) 19:191-195. Pentafluorophenyl magnesium halides useful in the invention have the formula C6F6MgX in which X is a halogen, e.g., iodine, chlorine or bromine, preferably bromine.
Tetrafluoroborate salts useful in the invention have the formula QBF4 in which Q is sodium, lithium or potassium, preferably sodium.
The reaction between the Grignard and the tetrafluoroborate salt may be conducted in any non-interfering solvent. Typical solvents have the formula R—O—R′ in which the R and R′ are the same or different aliphatic hydrocarbon groups having 2-10 carbon atoms. Ethyl ether is preferred. The reaction is appropriately conducted at a temperature of 0° C. to 100° C., preferably at 30° C. to 35° C.
The tetrafluoroborate salt is added to the Grignard solution in stoichiometric amounts or in such greater or lesser amount as may be deemed appropriate. In the preferred practice of the invention the tetrafluoroborate salt is added in an amount more than 15% of stoichiometric. Preferably the reaction mixture is refluxed to expedite the reaction.
EXEMPLIFICATION OF THE INVENTION EXAMPLE I
A reaction vessel is changed with 0.25 mol of C6H5MgBr and 0.056 mol of NaBF4 in an ethyl ether solvent. The reaction mixture is refluxed overnight under nitrogen. The reaction mixture was processed to recover 24.4 g of brown solids. Apparent yield 62.1%.
19F NMR peaks established the presence of tetrakis (pentafluorophenyl) borate in an amount corresponding to approximately 50% of the total product of the reaction.
EXAMPLE II
Example I was repeated using NaBF4 ground by pestle and mortar and a 36 hour reflux time. Yield: 62.2% of a product having a tetrakis (pentafluorophenyl) borate purity of about 60% as indicated by 19F NMR.

Claims (7)

I claim:
1. A method for the production of tetrakis (pentafluorophenyl) borate which comprises reacting a pentafluorophenyl compound having the formula C6F5MgX in which X is a halide with an alkali metal salt of tetrafluoroborate in a non-interfering solvent.
2. The claim 1 method in which the pentafluorophenyl compound is C6F5MgBr and said alkali metal salt is NaBF4.
3. The claim 1 or claim 2 method in which said solvent has the formula R—O—R′ in which R and R′ are the same or different aliphatic hydrocarbon groups having 2 to 10 carbon atoms.
4. The claim 1 or claim 2 method in which said solvent is ethyl ether.
5. A method which comprises reacting a compound having the formula C6F5MgX in which X is a halide with a compound having the formula QBF4 in which Q is sodium, lithium or potassium,
said reaction being conducted at a temperature of 0° C. to 100° C. in a solvent being the formula R—O—R′ in which R and R′ are the same or different aliphatic hydrocarbon groups having 2 to 10 carbon atoms to produce a reaction mixture containing a tetrakis (pentafluorophenyl) borate and
recovering said tetrakis (pentafluorophenyl) borate from said reaction mixture.
6. The claim 5 method in which C6H5MgBr is reacted with NaBF4 in ethyl ether.
7. The claim 5 method in which the compound having the formula C6H5MgX and compound QBF4 are reacted in an amount which is more than 15% of the stoichiometric amount.
US10/050,869 1999-07-14 2002-01-18 Method for the production of tetrakis (pentafluorophenyl) borates Expired - Lifetime USRE38325E1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/050,869 USRE38325E1 (en) 1999-07-14 2002-01-18 Method for the production of tetrakis (pentafluorophenyl) borates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/353,156 US6096928A (en) 1999-07-14 1999-07-14 Method for the production of tetrakis (pentafluorophenyl) borates
US10/050,869 USRE38325E1 (en) 1999-07-14 2002-01-18 Method for the production of tetrakis (pentafluorophenyl) borates

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/353,156 Reissue US6096928A (en) 1999-07-14 1999-07-14 Method for the production of tetrakis (pentafluorophenyl) borates

Publications (1)

Publication Number Publication Date
USRE38325E1 true USRE38325E1 (en) 2003-11-18

Family

ID=23387989

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/353,156 Ceased US6096928A (en) 1999-07-14 1999-07-14 Method for the production of tetrakis (pentafluorophenyl) borates
US10/050,869 Expired - Lifetime USRE38325E1 (en) 1999-07-14 2002-01-18 Method for the production of tetrakis (pentafluorophenyl) borates

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/353,156 Ceased US6096928A (en) 1999-07-14 1999-07-14 Method for the production of tetrakis (pentafluorophenyl) borates

Country Status (1)

Country Link
US (2) US6096928A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002356930A1 (en) * 2001-12-13 2003-06-30 Exxonmobil Chemical Patents Inc. Partially fluorinated naphthyl-based borates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5488169A (en) * 1992-12-28 1996-01-30 Tosoh Akzo Corporation Method of producing tetrakis(pentafluorophenyl)borate derivatives using pentafluorophenylmagnesium derivatives
US5600005A (en) * 1992-06-23 1997-02-04 Idemitsu Kosan Co., Ltd. Process for producing tetrakisflorophenylborate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5600005A (en) * 1992-06-23 1997-02-04 Idemitsu Kosan Co., Ltd. Process for producing tetrakisflorophenylborate
US5488169A (en) * 1992-12-28 1996-01-30 Tosoh Akzo Corporation Method of producing tetrakis(pentafluorophenyl)borate derivatives using pentafluorophenylmagnesium derivatives

Also Published As

Publication number Publication date
US6096928A (en) 2000-08-01

Similar Documents

Publication Publication Date Title
Oshiki et al. Stereospecific reduction of menthyloxyphosphine-boranes with one-electron reducing agents
WO2014185020A1 (en) Novel tetraaryl borate compound and method for producing same
HU226471B1 (en) Direct ortho-metalation process for the synthesis of 5-(2-substituted-phenyl)-tetrazol derivatives
JPH08253485A (en) Production of pentafluorophenyl compound
EP0582114B1 (en) Process for preparing metallocenes
USRE38325E1 (en) Method for the production of tetrakis (pentafluorophenyl) borates
JPH08253486A (en) Production of pentafluorophenyl compound
Brauer et al. Stabilization of tris (trifluoromethyl) borane in complexes with primary, secondary and tertiary amines. Crystal and molecular structure of (CF3) 3B· NHEt2 and (CF3) 3B· NH2Et
EP0866794B1 (en) Method for the production of tetrakis (pentafluorophenyl) borates
JP3708131B2 (en) Method for producing tetrakis borate (pentafluorophenyl)
US4045494A (en) Method for preparing triogranophosphines
Zavitsas et al. Kinetics of free radical brominations. Effect of ring substitution on the strength of benzyl carbon-hydrogen bonds
NZ323123A (en) Method for the production of tetrakis (pentafluorophenyl) borates by reaction of a tetrafluoroborate salt with a pentafluorophenyl compound
CA2240513A1 (en) Method for the production of tetrakis(pentafluorophenyl) borates
US20040019231A1 (en) Preparation of mixed-halogen halo-silanes
US3397241A (en) Process for the economical preparation of br3 organoboron compounds
US3928370A (en) Process for making dialkyl pyridylphosphates
JP2001048885A (en) Production of grignard reagent and new grignard reagent
JP3751713B2 (en) Method for producing triarylborane phosphine complex
JPH09295984A (en) Production of tetrakis(pentafluorophenyl) borate derivative using pentafluorophenylmagnesiium derivative
US3421844A (en) Method of producing highly pure halogen compounds of gallium and indium
JPS62132893A (en) Production of tetraorganophosphonium tetraaryl borate
JPS6145996B2 (en)
JPH10330381A (en) Production of triarylborane amine complex
JPH01113397A (en) Production of phosphane

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: ANTARES CAPITAL LP, AS AGENT, ILLINOIS

Free format text: SECURITY INTEREST;ASSIGNOR:BOULDER SCIENTIFIC COMPANY, LLC;REEL/FRAME:049619/0182

Effective date: 20190628

Owner name: BOULDER SCIENTIFIC COMPANY, LLC, VIRGINIA

Free format text: CERTIFICATE OF CONVERSION FROM A DELAWARE OR NON-DELAWARE CORPORATION TO A DELAWARE LIMITED LIABILITY COMPANY PURSUANT TO SECTION 18-214 OF THE LIMITED LIABILITY COMPANY ACT;ASSIGNOR:BOULDER SCIENTIFIC COMPANY;REEL/FRAME:049624/0023

Effective date: 20190627