AU732314B2 - Synthesis of fluorophenyl boranes - Google Patents
Synthesis of fluorophenyl boranes Download PDFInfo
- Publication number
- AU732314B2 AU732314B2 AU53578/98A AU5357898A AU732314B2 AU 732314 B2 AU732314 B2 AU 732314B2 AU 53578/98 A AU53578/98 A AU 53578/98A AU 5357898 A AU5357898 A AU 5357898A AU 732314 B2 AU732314 B2 AU 732314B2
- Authority
- AU
- Australia
- Prior art keywords
- fluorophenyl
- solvent
- solution
- ether
- 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.)
- Ceased
Links
- -1 fluorophenyl boranes Chemical class 0.000 title claims description 18
- 229910000085 borane Inorganic materials 0.000 title description 6
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000007818 Grignard reagent Substances 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BUEBLNVFMGQFGA-UHFFFAOYSA-N fluoro(phenyl)boron Chemical compound F[B]C1=CC=CC=C1 BUEBLNVFMGQFGA-UHFFFAOYSA-N 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- QXALIERKYGCHHA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)borane Chemical compound BC1=C(F)C(F)=C(F)C(F)=C1F QXALIERKYGCHHA-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- AMQDBUIQKQUCKY-UHFFFAOYSA-M magnesium;1,2,3,4,5-pentafluorobenzene-6-ide;bromide Chemical compound [Mg+2].[Br-].FC1=[C-]C(F)=C(F)C(F)=C1F AMQDBUIQKQUCKY-UHFFFAOYSA-M 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 description 12
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 125000001207 fluorophenyl group Chemical group 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- JJXBITPDOUWVAI-UHFFFAOYSA-N Bc1ccc(F)c(F)c1F Chemical compound Bc1ccc(F)c(F)c1F JJXBITPDOUWVAI-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229910052731 fluorine Chemical group 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/02—Monocyclic aromatic halogenated hydrocarbons
- C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- 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
Landscapes
- 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
1A SYNTHESIS OF FLUOROPHENYL BORANES 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 The discussion of the background to the invention herein is included to explain the context of the invention. This is not to be taken as an admission that any of the material referred to was published, known or part of the common general knowledge in Australia as at the priority date of any of the claims.
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.Naturforschq. 20 b, 5-11 (1965). Tris-pentafluorophenyl boranes are useful as catalyst or catalyst or components in some types of olefin polymerization reactions.
SUMMARY OF THE INVENTION According to the present invention there is provided a process which includes: 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.
Accordingly, a fluorophenyl Grignard compound is reacted in a non-interfering solvent with a boron trihalide to produce a borane.
Also disclosed herein is a method which includes reacting C 6
F
5 MgBr with
BF
3 or BF 3 etherate in a toluene wherein a reaction mixture containing (C 6
F
5 3
B
Sand said non-interfering solvent is produced.
MR W:\mary\MMHNODEL53578a.doc 1B Further disclosed herein is a method which includes: 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 first reaction mixture wherein boron trihalide reacts with said pentafluorophenyl Grignard reagent in said step first reaction mixture to produce a second reaction mixture containing a (C 6
F
5 3
B.
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 o MR W:\maryMMHNODEL\53578a.doc WO 98/22475 PCT/US97/21071 -2group, and X is a halogen, preferably bromine or chlorine.
Boron trihalides useful on the invention have the formula BX 3 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,
BF
3 *OEt 2 Production of fluorophenyl Grignard reagents, specifically pentafluoro magnesium bromide, is described in Repress, et al., J.Organometallic 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 WO 98/22475 PCT/US97/21071 -3exchange 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 WO 98/22475 PCT/US97/21071 -4borane. 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. FeC1 2 (0.2 g, 1.6 mmol) was added, and the solution cooled to 0-5 0 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 minutes, the ice bath was removed and BF 3 *OEt 2 (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 9
F
NMR which showed a (C 6 Fs)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 (C 6 Fs) 3
B
free of THF.
Claims (5)
1. A process which includes: 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.
2. The process of claim 1 wherein the fluorophenyl Grignard reagent of step is pentafluorophenyl magnesium bromide and said ether solvent is 15 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 BF 3 or BF 3 etherate; and wherein said fluorophenyl borane produced in step (iii) is pentafluorophenyl borane.
3. The process of claim 1 or 2, further including: (iv) isolating said fluorophenyl borane produced in step (iii).
4. A fluorophenyl borane solution produced by the method of any preceding claim.
5. A process according to claim 1, substantially as herein described with reference to the Example. DATED: 29 January 2001 PHILLIPS ORMONDE FITZPATRICK LIA Patent Attorneys for: S. BOULDER SCIENTIFIC COMPANY MR W:\mary\MMHNODEL\53578a.doc
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 AU5357898A (en) | 1998-06-10 |
| AU732314B2 true AU732314B2 (en) | 2001-04-12 |
Family
ID=25035609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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)
| 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 |
| CN107522724B (en) | 2012-11-27 | 2019-08-16 | 阿尔比马尔公司 | The method for generating four (fluoro aryl) borates |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0604963A1 (en) * | 1992-12-28 | 1994-07-06 | Tosoh Akzo Corporation | Production method of tris(pentafluorophenyl)borane using pentafluorophenylmagnesium derivatives prepared from pentafluorobenzene |
| WO1997014698A1 (en) * | 1995-10-18 | 1997-04-24 | The Dow Chemical Company | Synthesis of perfluoroaryl-substituted compounds |
Family Cites Families (3)
| 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 |
| US5600004A (en) * | 1995-02-21 | 1997-02-04 | Albemarle Corporation | Process for preparing pentafluorophenyl compounds |
-
1997
- 1997-11-19 EP EP97950624A patent/EP0901495A4/en not_active Withdrawn
- 1997-11-19 AU AU53578/98A patent/AU732314B2/en not_active Ceased
- 1997-11-19 NZ NZ331273A patent/NZ331273A/en unknown
- 1997-11-19 CA CA 2243659 patent/CA2243659A1/en not_active Abandoned
- 1997-11-19 WO PCT/US1997/021071 patent/WO1998022475A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0604963A1 (en) * | 1992-12-28 | 1994-07-06 | Tosoh Akzo Corporation | Production method of tris(pentafluorophenyl)borane using pentafluorophenylmagnesium derivatives prepared from pentafluorobenzene |
| WO1997014698A1 (en) * | 1995-10-18 | 1997-04-24 | The Dow Chemical Company | Synthesis of perfluoroaryl-substituted compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2243659A1 (en) | 1998-05-28 |
| NZ331273A (en) | 2000-03-27 |
| EP0901495A4 (en) | 1999-06-09 |
| AU5357898A (en) | 1998-06-10 |
| EP0901495A1 (en) | 1999-03-17 |
| WO1998022475A1 (en) | 1998-05-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) | ||
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |