WO1997014698A1 - Synthesis of perfluoroaryl-substituted compounds - Google Patents

Synthesis of perfluoroaryl-substituted compounds Download PDF

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Publication number
WO1997014698A1
WO1997014698A1 PCT/US1996/015794 US9615794W WO9714698A1 WO 1997014698 A1 WO1997014698 A1 WO 1997014698A1 US 9615794 W US9615794 W US 9615794W WO 9714698 A1 WO9714698 A1 WO 9714698A1
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perfluoroaryl
compound
pentafluorophenyl
tris
contacting
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PCT/US1996/015794
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French (fr)
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Kevin A. Frazier
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The Dow Chemical Company
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    • 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 perfluoroaryl-substituted compounds, particularly tris pentafluorophenyl borane.
  • Tris pentafluorophenyl borane is known to be useful as a co-catalyst for Ziegler- o Natta type polymerizations.
  • Ziegler-Natta type catalyst systems are useful in the polymerization of olefins, such as polymerization of ethylene to polyethylene. See, for example, U.S. Patent No. 5,296,433 to Siedle et al.
  • Tris pentafluorophenyl borane is known to be prepared from pentafluorophenyl magnesium derivatives. See, for example, J. L. W. Pohlmann and F.E. Brinckmann, "Preparation 5 and Characterization of Group III Derivatives " Z. Naturforschg, 20 b, 5- 11 (1965). Such pentafluorophenyl magnesium derivatives can be produced using pentaf luorobromobenzene as a starting material, as described, for example, in J. Organometal. Chem., 11 (1968) 619-622. An efficient method to produce tris pentafluorophenyl borane from alternative starting materials is desired.
  • the present invention is a method of making perfluoroaryl-substituted compounds from perfluoroaryl compounds, particularly preparation of tris pentafluorophenyl borane from hexafluorobenzene.
  • the method comprises contacting a perfluoroaryl compound with an organomagnesium reagent under conditions such that a perfluoroaryl magnesium compound is formed; and contacting the perfluoroaryl magnesium compound with a trihalide 0 compound of a Group IIIA element to form a tris perfluoroaryl-substituted compound.
  • Group IIIA elements include boron, aluminum, gallium, indium, and thallium; boron is preferred.
  • the reaction with the organomagnesium reagent is preferably carried out in the presence of a catalyst.
  • the resulting compounds are known to be useful catalysts for polymerization. 5
  • the reaction of the present invention will be described with specific reference to tris pentafluorophenyl borane, however, one of skill in the art will be able to synthesize other perfluoroaryl-substituted compounds following the method described herein by substituting appropriate reagents.
  • the first step of this reaction is described herein specifically with reference to a perf luorobenzene starting material; in light of the disclosure herein, this metalation step can be readily carried out using other perfluoroaryl compounds such as decafluorobiphenyl, octafluorotoluene, octafluoronaphthalene, and decaf luoroanthracene. See, for example, J. Organometal. Chem., 18 (1969) 263-274 which is herein fully incorporated by reference.
  • this specification describes the second step of this reaction specifically with respect to a boron trihalide reagent, in light of the disclosure herein, this second step can be readily carried out using the product of step one and trihalides of other Group IIIA elements. See for example, Z. Naturforschg, 20 b, 5-11 (1965) 5-11 which is herein fully incorporated by reference.
  • producing tris pentafluorophenyl borane from hexafluorobenzene involves a metalation reaction followed by a displacement reaction which may be represented generally as follows:
  • RMgX represents an organomagnesium reagent including compounds wherein R is C1-C10 alkyl or C6-C10 aryl; preferably, C1-C10 alkyl; and more preferably, C1 -C3 alkyl.
  • R is C1-C10 alkyl or C6-C10 aryl; preferably, C1-C10 alkyl; and more preferably, C1 -C3 alkyl.
  • halogen such as fluorine, chlorine, bromine or iodine
  • C1-C10 alkyl or C6-C10 aryl preferably, X is a halogen or C1-C10 alkyl; more preferably, chlorine, fluorine, bromine, or C1-C3 alkyl; and, most preferably, chlorine, fluorine, or bromine.
  • the organomagnesium reagent (R gX) is preferably an alkyl magnesium halide; most preferably, ethyl magnesium bromide or ethyl magnesium chloride.
  • catalyst may be added in a sufficient amount to accelerate the rate of reaction.
  • the amount of catalyst is greater than 0.2 mole percent relative to hexafluorobenzene; more preferably, greater than 1 mole percent relative to hexafluorobenzene.
  • the amount of catalyst is less than 5 mole percent relative to hexafluorobenzene; more preferably, the amount of catalyst is 2 mole percent
  • the catalyst comprises an inorganic salt, preferably an inorganic salt which is a mild Lewis acid; representative catalysts include CoCI2, FeCl2, NiCI2, Cui, TiCl4, AgCI, PdCI2, or RhCI3. More preferably, the catalyst comprises CoCI2, or FeCI2; most preferably, CoCI2.
  • Suitable boron trihalides include BF3, BBr3, BCI3, BI3, and boron trifluoride
  • boron trihalides include those that are comparatively less sensitive to decomposition and to undesired side reactions under experimental conditions.
  • the boron trihalide is preferably BF3 or BF3.Et20; most preferably, BF3.Et20.
  • the entire reaction is completed in the same solvent.
  • the solvent chosen should be inert to the reaction such that the solvent does not significantly and 5 undesirably interact with the reactants.
  • Representative examples of such solvents include ether-type reaction solvents such as tetrahydrofuran, tetrahyd ropy ran, 1 ,4-dioxane, 1,2- dimethoxyethane, 1 ,2-diethoxyethane, butyl ether, and di-2-methoxyethyl ether, and mixtures thereof.
  • Tetrahydrofuran (THF) is a preferred solvent.
  • hexafluorobenzene and a catalyst are dissolved in a solvent.
  • the hexafluorobenzene solution is cooled, for example, in an ice bath.
  • the temperature at which each step in the reaction is carried out depends on the specific reactants and solvent employed. In general for both reaction steps, temperatures from -25° C to about the reflux temperature of the solvent may be employed.
  • temperatures from -25° C to about the reflux temperature of the solvent may be employed.
  • the solution is cooled and 5 solvent is preferably maintained below ambient temperature. Temperatures of 0° C to 10° C are preferred during organomagnesium reagent addition and trihalide reagent addition. More preferably, an ice bath is used resulting in a temperature of 0° C.
  • the pressure at which the reaction takes place is not critical; ambient pressure is suitable.
  • an organomagnesium reagent (RMgX) is slowly added to the hexafluorobenzene solution.
  • the mole ratio of organomagnesium reagent to hexafluorobenzene is from 0.25: 1 to 3 : 1 ; preferably, from 1.9: 1 to 2.5: 1 ; more preferably, 2: 1.
  • the solution is advantageously stirred during addition and for a sufficient time period after complete addition of the organomagnesium reagent to ensure complete reaction to the pentafluorophenyl magnesium compound. Typically, sufficient reaction is achieved in less than about 30 minutes. This reaction is advantageously carried out under an inert atmosphere, such as a nitrogen atmosphere.
  • the pentafluorophenyl magnesium compound of step one may then be o converted to tris pentafluorophenyl borane by reaction with a boron trihalide as follows. While the resulting pentafluorophenyl magnesium compound solution is cooled, a boron trihalide is added.
  • the mole ratio of boron trihalide to hexafluorobenzene is preferably from 0.1 : 1 to 0.5: 1 ; more preferably, 0.30: 1 to 0.35: 1 ; and most preferably, 0.33 : 1.
  • the 5 reaction is preferably stirred in an inert environment, for example, under nitrogen, for a sufficient time to produce tris pentafluorophenyl borane; this stirring may be conducted at ambient temperature. Typically, sufficient reaction is achieved in 12 to 18 hours.
  • Example 1 To make a tris heptafluoronaphthyl borane product (m/e 770), the steps of Example 1 were followed substituting octafluoronaphthalene (1.22 g, 4.5 mmol) for hexafluorobenzene, and changing the amount of ether to 3.0 mL, 9 mmol and the amount of trifluoride etherate to 0.18 mL, 1.5 mmol.

Abstract

Perfluoroaryl-substituted compounds are prepared from perfluoroaryl compounds, particularly tris pentafluorophenyl borane is prepared from hexafluorobenzene. The method comprises contacting a perfluoroaryl compound with an organomagnesium reagent in the presence of a catalyst to form a perfluoroaryl magnesium compound, and contacting the perfluoroaryl magnesium compound with a trihalide element to form a tris perfluoroaryl-substituted compound.

Description

SYNTHESIS OF PERFLUOROARYL-SUBSTITUTED COMPOUNDS
This application claims the benefit of the October 18, 1995 filing date of U.S. Provisional Application No. 60/005,552 and the September 6, 1996 filing date of U.S. Application No. 08/709,058.
This invention relates to the synthesis of perfluoroaryl-substituted compounds, particularly tris pentafluorophenyl borane.
Tris pentafluorophenyl borane is known to be useful as a co-catalyst for Ziegler- o Natta type polymerizations. Ziegler-Natta type catalyst systems are useful in the polymerization of olefins, such as polymerization of ethylene to polyethylene. See, for example, U.S. Patent No. 5,296,433 to Siedle et al.
Tris pentafluorophenyl borane is known to be prepared from pentafluorophenyl magnesium derivatives. See, for example, J. L. W. Pohlmann and F.E. Brinckmann, "Preparation 5 and Characterization of Group III Derivatives " Z. Naturforschg, 20 b, 5- 11 (1965). Such pentafluorophenyl magnesium derivatives can be produced using pentaf luorobromobenzene as a starting material, as described, for example, in J. Organometal. Chem., 11 (1968) 619-622. An efficient method to produce tris pentafluorophenyl borane from alternative starting materials is desired. U.S. Patent No. 5,362,423 to Ikeda describes the alternative use of 0 a pentafluorobenzene starting material to produce pentaf luorophenylmagnesium derivatives, which are disclosed in column 1, lines 10- 16 to be useful intermediates for boron derivatives such as tris pentafluorophenyl borane. A more cost effective starting material is desired.
Synthesis of tris pentafluorophenyl borane efficiently and cost effectively from a commercially available solvent, hexafluorobenzene, has been discovered. 5 The present invention is a method of making perfluoroaryl-substituted compounds from perfluoroaryl compounds, particularly preparation of tris pentafluorophenyl borane from hexafluorobenzene. The method comprises contacting a perfluoroaryl compound with an organomagnesium reagent under conditions such that a perfluoroaryl magnesium compound is formed; and contacting the perfluoroaryl magnesium compound with a trihalide 0 compound of a Group IIIA element to form a tris perfluoroaryl-substituted compound. Group IIIA elements include boron, aluminum, gallium, indium, and thallium; boron is preferred. The reaction with the organomagnesium reagent is preferably carried out in the presence of a catalyst.
The resulting compounds are known to be useful catalysts for polymerization. 5 The reaction of the present invention will be described with specific reference to tris pentafluorophenyl borane, however, one of skill in the art will be able to synthesize other perfluoroaryl-substituted compounds following the method described herein by substituting appropriate reagents. For example, the first step of this reaction is described herein specifically with reference to a perf luorobenzene starting material; in light of the disclosure herein, this metalation step can be readily carried out using other perfluoroaryl compounds such as decafluorobiphenyl, octafluorotoluene, octafluoronaphthalene, and decaf luoroanthracene. See, for example, J. Organometal. Chem., 18 (1969) 263-274 which is herein fully incorporated by reference. Similarly, although this specification describes the second step of this reaction specifically with respect to a boron trihalide reagent, in light of the disclosure herein, this second step can be readily carried out using the product of step one and trihalides of other Group IIIA elements. See for example, Z. Naturforschg, 20 b, 5-11 (1965) 5-11 which is herein fully incorporated by reference.
In accordance with the present invention, producing tris pentafluorophenyl borane from hexafluorobenzene involves a metalation reaction followed by a displacement reaction which may be represented generally as follows:
Figure imgf000004_0001
Figure imgf000004_0002
wherein
RMgX represents an organomagnesium reagent including compounds wherein R is C1-C10 alkyl or C6-C10 aryl; preferably, C1-C10 alkyl; and more preferably, C1 -C3 alkyl. On both the organomagnesium reagent and the pentafluorophenyl magnesium compound, X
5 represents a halogen (such as fluorine, chlorine, bromine or iodine) or C1-C10 alkyl or C6-C10 aryl; preferably, X is a halogen or C1-C10 alkyl; more preferably, chlorine, fluorine, bromine, or C1-C3 alkyl; and, most preferably, chlorine, fluorine, or bromine. The organomagnesium reagent (R gX) is preferably an alkyl magnesium halide; most preferably, ethyl magnesium bromide or ethyl magnesium chloride.
•J Q Although catalyst may not be necessary, catalyst may be added in a sufficient amount to accelerate the rate of reaction. Preferably, the amount of catalyst is greater than 0.2 mole percent relative to hexafluorobenzene; more preferably, greater than 1 mole percent relative to hexafluorobenzene. Preferably, the amount of catalyst is less than 5 mole percent relative to hexafluorobenzene; more preferably, the amount of catalyst is 2 mole percent
15 relative to hexafluorobenzene.
The catalyst comprises an inorganic salt, preferably an inorganic salt which is a mild Lewis acid; representative catalysts include CoCI2, FeCl2, NiCI2, Cui, TiCl4, AgCI, PdCI2, or RhCI3. More preferably, the catalyst comprises CoCI2, or FeCI2; most preferably, CoCI2. Suitable boron trihalides include BF3, BBr3, BCI3, BI3, and boron trifluoride
20 etherate (BF3.Et20). Preferred boron trihalides include those that are comparatively less sensitive to decomposition and to undesired side reactions under experimental conditions. The boron trihalide is preferably BF3 or BF3.Et20; most preferably, BF3.Et20.
Preferably, the entire reaction is completed in the same solvent. The solvent chosen should be inert to the reaction such that the solvent does not significantly and 5 undesirably interact with the reactants. Representative examples of such solvents include ether-type reaction solvents such as tetrahydrofuran, tetrahyd ropy ran, 1 ,4-dioxane, 1,2- dimethoxyethane, 1 ,2-diethoxyethane, butyl ether, and di-2-methoxyethyl ether, and mixtures thereof. Tetrahydrofuran (THF) is a preferred solvent.
Turning more specifically to the procedure for carrying out the method of the
30 present invention, hexafluorobenzene and a catalyst are dissolved in a solvent. The hexafluorobenzene solution is cooled, for example, in an ice bath. The temperature at which each step in the reaction is carried out depends on the specific reactants and solvent employed. In general for both reaction steps, temperatures from -25° C to about the reflux temperature of the solvent may be employed. Preferably, before grignard is added, the solution is cooled and 5 solvent is preferably maintained below ambient temperature. Temperatures of 0° C to 10° C are preferred during organomagnesium reagent addition and trihalide reagent addition. More preferably, an ice bath is used resulting in a temperature of 0° C. The pressure at which the reaction takes place is not critical; ambient pressure is suitable. Once cooled to a desired temperature, an organomagnesium reagent (RMgX) is slowly added to the hexafluorobenzene solution. Typically, the mole ratio of organomagnesium reagent to hexafluorobenzene is from 0.25: 1 to 3 : 1 ; preferably, from 1.9: 1 to 2.5: 1 ; more preferably, 2: 1. The solution is advantageously stirred during addition and for a sufficient time period after complete addition of the organomagnesium reagent to ensure complete reaction to the pentafluorophenyl magnesium compound. Typically, sufficient reaction is achieved in less than about 30 minutes. This reaction is advantageously carried out under an inert atmosphere, such as a nitrogen atmosphere.
The pentafluorophenyl magnesium compound of step one may then be o converted to tris pentafluorophenyl borane by reaction with a boron trihalide as follows. While the resulting pentafluorophenyl magnesium compound solution is cooled, a boron trihalide is added. The mole ratio of boron trihalide to hexafluorobenzene (more the perfluoroaryl starting material employed) is preferably from 0.1 : 1 to 0.5: 1 ; more preferably, 0.30: 1 to 0.35: 1 ; and most preferably, 0.33 : 1. After complete boron trihalide addition, the 5 reaction is preferably stirred in an inert environment, for example, under nitrogen, for a sufficient time to produce tris pentafluorophenyl borane; this stirring may be conducted at ambient temperature. Typically, sufficient reaction is achieved in 12 to 18 hours.
The resulting product may be recovered by conventional methods such as distillation. 0 This invention will be further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details should not be construed to unduly limit the invention. EXAMPLE 1
Under a nitrogen atmosphere, hexafluorobenzene (2.33 g, 12.5 mmol) was 5 dissolved in tetrahydrofuran (THF) (15 mL) containing anhydrous cobalt (II) chloride
(approximately 25 mg). The resulting slurry, in which the CoCI2 did not completely dissolve, was cooled to 0°C in an ice bath. Ethyl magnesium chloride, 3 M in ether (8.33 mL, 25 mmol) was added slowly via syringe to the cooled slurry. The mixture was stirred about 15 minutes after complete addition of ethyl magnesium chloride. 0 Boron trifluoride etherate (0.51 mL, 4.17 mmol) was added by syringe and the cooling bath was removed. The reaction was stirred overnight under a nitrogen atmosphere. A white solid began to form within about one hour. After complete reaction, the white solid was allowed to settle, and the supernatant THF containing the borane product was removed. Mass spectrometric analysis of the THF solution showed a major product at mass to charge 5 (m/e) 512, which corresponds to the mass of the desired tris pentafluorophenyl borane. EXAMPLE 2
To make a tris heptafluoronaphthyl borane product (m/e 770), the steps of Example 1 were followed substituting octafluoronaphthalene (1.22 g, 4.5 mmol) for hexafluorobenzene, and changing the amount of ether to 3.0 mL, 9 mmol and the amount of trifluoride etherate to 0.18 mL, 1.5 mmol.

Claims

WHAT IS CLAIMED IS:
1. A method of making tris perfluoroaryl-substituted compounds, comprising the steps of:
(a) contacting a perfluoroaryl compound with an organomagnesium reagent under conditions such that a perfluoroaryl magnesium compound is formed; and
(b) contacting the perfluoroaryl magnesium compound with a trihalide compound to form the tris perfluoroaryl-substituted compound.
2. The method of claim 1 wherein the perfluoroaryl compound comprises hexafluorobenzene.
3. The method of claim 1 wherein the perfluoroaryl compound comprises octafluoronaphthalene.
4. The method of claim 1 wherein the conditions of step (a) include a reaction temperature below ambient temperature.
5. The method of claim 1 wherein step (a) is carried out in the presence of a catalyst.
6. The method of claim 5 wherein the catalyst comprises CoCI2, FeCI2, NiCI2, Cui, TiCl4, AgCI, PdCI2, or RhCI3
7. A method of making tris pentafluorophenyl borane, comprising the steps o :
(a) contacting hexafluorobenzene with an organomagnesium reagent in the presence of a catalyst to form a pentafluorophenyl magnesium compound; and
(b) contacting the pentafluorophenyl magnesium compound with a boron trihalide compound to form the tris pentafluorophenyl borane.
8. The method of claim 7 wherein the boron trihalide compound is boron trifluoride or boron trifluoride etherate.
9. The method of claim 7 wherein the pentafluorophenyl magnesium compound comprises a pentafluorophenyl magnesium halide. Q 10. A method of making tris pentafluorophenyl borane comprising the steps of:
(a) contacting hexafluorobenzene with ethyl magnesium bromide in the presence of a catalyst to form a pentafluorophenyl magnesium halide; and
(b) contacting the pentafluorophenyl magnesium halide with a boron trihalide 5 compound selected from the group consisting of boron trifluoride and boron trifluoride etherate to form the tris pentafluorophenyl borane.
PCT/US1996/015794 1995-10-18 1996-10-02 Synthesis of perfluoroaryl-substituted compounds WO1997014698A1 (en)

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US555295P 1995-10-18 1995-10-18
US60/005,552 1995-10-18
US70905896A 1996-09-06 1996-09-06
US08/709,058 1996-09-06

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Cited By (3)

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WO1999006412A1 (en) * 1997-08-01 1999-02-11 The Dow Chemical Company Perfluoronaphthyl substituted boron containing catalyst activator
EP0901495A1 (en) * 1996-11-21 1999-03-17 Boulder Scientific Company Synthesis of fluorophenyl boranes
US6218488B1 (en) 1998-03-04 2001-04-17 Exxon Mobil Chemical Patents Inc. Polymerization process for olefin copolymers using bridged hafnocene compounds

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RESPESS W L ET AL: "New synthesis of perfluoroaromatic Grignard reagents", J. ORGANOMETAL. CHEM. (JORCAI);69; VOL.18 (2); PP.263-74, WRIGHT-PATTERSON AIR FORCE BASE;AIR FORCE MATER. LAB.; OHIO, XP000612755 *
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0901495A1 (en) * 1996-11-21 1999-03-17 Boulder Scientific Company Synthesis of fluorophenyl boranes
EP0901495A4 (en) * 1996-11-21 1999-06-09 Boulder Scient Co Synthesis of fluorophenyl boranes
AU732314B2 (en) * 1996-11-21 2001-04-12 Boulder Scientific Company Synthesis of fluorophenyl boranes
WO1999006412A1 (en) * 1997-08-01 1999-02-11 The Dow Chemical Company Perfluoronaphthyl substituted boron containing catalyst activator
AU748095B2 (en) * 1997-08-01 2002-05-30 Northwestern University Perfluoronaphthyl substituted boron containing catalyst activator
US6635597B1 (en) * 1997-08-01 2003-10-21 Northwestern University Perfluoronaphthyl substituted boron containing catalyst activator
US6218488B1 (en) 1998-03-04 2001-04-17 Exxon Mobil Chemical Patents Inc. Polymerization process for olefin copolymers using bridged hafnocene compounds

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