CA2243545C - Tetrakis-pentafluorophenyl borates from pentafluorophenyl grignard reagents - Google Patents
Tetrakis-pentafluorophenyl borates from pentafluorophenyl grignard reagents Download PDFInfo
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- CA2243545C CA2243545C CA002243545A CA2243545A CA2243545C CA 2243545 C CA2243545 C CA 2243545C CA 002243545 A CA002243545 A CA 002243545A CA 2243545 A CA2243545 A CA 2243545A CA 2243545 C CA2243545 C CA 2243545C
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- pentafluorophenyl
- ether
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- tetrakis
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- -1 pentafluorophenyl grignard reagents Chemical class 0.000 title claims abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000002904 solvent Substances 0.000 claims abstract description 51
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 150000004820 halides Chemical class 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 109
- 150000004795 grignard reagents Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 21
- 239000007818 Grignard reagent Substances 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- AMQDBUIQKQUCKY-UHFFFAOYSA-M magnesium;1,2,3,4,5-pentafluorobenzene-6-ide;bromide Chemical group [Mg+2].[Br-].FC1=[C-]C(F)=C(F)C(F)=C1F AMQDBUIQKQUCKY-UHFFFAOYSA-M 0.000 claims description 12
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011877 solvent mixture Substances 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 125000002221 trityl group Chemical class [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OJJVPGJEBAZOIF-UHFFFAOYSA-N (2,3,4,5-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC(F)=C(F)C(F)=C1F OJJVPGJEBAZOIF-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- FPPYBBOIFQGHHZ-UHFFFAOYSA-M Fc1c(F)c(F)c([Mg]Cl)c(F)c1F Chemical compound Fc1c(F)c(F)c([Mg]Cl)c(F)c1F FPPYBBOIFQGHHZ-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000008896 Opium Substances 0.000 description 1
- JOXNNISDIMLBKW-UHFFFAOYSA-M [Br-].[Mg+2].B(OC1=C(C(=C(C(=C1F)F)F)F)F)([O-])O Chemical compound [Br-].[Mg+2].B(OC1=C(C(=C(C(=C1F)F)F)F)F)([O-])O JOXNNISDIMLBKW-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960001027 opium Drugs 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
Pentafluorophenyl Grignard reagents are reacted with a boron trihalide in a non-ethereal solvent such as toluene to produce a tetrakis-pentafluorophenyl borate magnesium halide.
Description
TETRAKIS-PENTAFLUOROPHENYL BORATES
FROM PENTAFLUOROPHENYL GRIGNARD REAGENTS
This application is s continuation of United States Patent No. 6,231,790 issued 15 May 2001.
FIELD OF THE INVENTION
The invention relates to novel Grignard reagents for the production of tetrakis-pentafluorophenyl borate magnesium halides and to the conversion of such halides to different tetrakis-pentafluoorphnenyl salts having borate anions useful in metallocene olefin polymerization catalysts.
BACKGROUND OF THE INVENTION
Combinations of an activating ration and a weekly coordinating borate anion are used as components of metallocene olefin polymerization catalysts.
Procedures for preparation of the borate anion portion of such combinations are described in the prior art.
See European patent applications Nos. 505,972 and 505,997, Japanese published patent application No. 63-238057, and PCT International Application No. 94/00459.
Grignard reactions are conventionally conducted in an ether solvent. United States patent 5,473,036 describes the reaction of a fluorophenyl Grignard with a boron trihalide in an ether solvent to produce a magnesium halide salt of a tetrakis-fluorophenyl borate. The patent states: "The ether is needed to solubilize the Grignard reagent, fluorophenyl magnesium bromide" (Col. 2, 11. 1-2). The magnesium halide is converted by ration exchange to a different tetrakis-fluorophenyl borate salt to provide a borate anion useful in metallocene catalyst synthesis.
SUI~iARY OF THE INVENTION
One aspect of this invention provides solutions of Grignard reagents in solvents which are not an ether, in particular, hydrocarbon solvents.
Pursuant to another aspect of the invention, a pentafluorophenyl magnesium halide is reacted with a boron trihalide in a solvent which is not an ether to produce a tetrakis-pentafluorophenyl magnesium halide.
The magnesium halide may be converted by reaction with a suitable ration, such as substituted ammonium, trityl or onium ration, to a compound comprising a weakly coordinating borate anion and an activating ration.
In accordance with an aspect of the invention, there is provided a method for preparing a hydrocarbon solution of a Grignard reagent, wherein said Grignard reagent comprises pentafluorophenyl magnesium halide, said method comprising:
(i) providing a solution of said Grignard reagent in an ether;
(ii) adding a hydrocarbon solvent to said solution, whereby a reaction mixture is produced;
- 2a (iii)removing said ether from said step (ii) reaction mixture; and (iv) treating said reaction mixture with a boron trihalide to produce a tetrakis-pentafluorophenyl borate magnesium halide.
In accordance with another aspect of the invention, there is provided a methyl cyclohexane or toluene solution of a Grignard reagent wherein said solution contains no free ether.
l0 In accordance with a further aspect of the invention, there is provided a toluene solution of pentafluorophenyl magnesium bromide or chloride wherein said solution contains no free ethyl ether.
In accordance with another aspect of the invention, there is provided a method which comprises:
(i) reacting a boron trihalide with a solution in a solvent which contains no free ether of a pentafluorophenyl magnesium bromide or chloride wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
In accordance with a further aspect of a invention, there is provided a method which comprises (i) providing a first solution of C6F5 MgBr in ethyl ether;
- 2b -(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii) removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) optionally isolating said C6F5 MgBr from said third solution.
In accordance with another aspect of the invention, there is provided a method which comprises (i) providing a first solution of C6F5 MgBr in ethyl ether;
(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii) removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) reacting BF3 with said C6F5 MgBr in said third solution to produce tetrakis (C6F5)B MgBr; and (v) subjecting said tetrakis (C6F5) B MgBr to a cation exchange reaction to produce a different tetrakis pentafluorophenyl borate salt which has an anion useful as a metallocene polymerization catalyst component.
In accordance with a further aspect of the invention, there is provided a Grignard reagent in solution in a solvent wherein said solvent contains no free ether.
- 2c -In accordance with another aspect of the invention, there is provided a pentafluorophenyl magnesium bromide or chloride in solution in a solvent wherein said solvent contains no free ethyl ether.
In accordance with a further aspect of the invention, there is provided a method which comprises:
i) reacting a boron trihalide with a solution of a pentafluorophenyl magnesium bromide or chloride in solution in a solvent that contains no free ethyl ether, wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
DEFINITIONS
Ether-A compound having the formula ROR, Ar-O-Ar or R-O-Ar in which R is alkyl and Ar is aryl.
Non-ethereal solvent A solvent which is not an ether.
FROM PENTAFLUOROPHENYL GRIGNARD REAGENTS
This application is s continuation of United States Patent No. 6,231,790 issued 15 May 2001.
FIELD OF THE INVENTION
The invention relates to novel Grignard reagents for the production of tetrakis-pentafluorophenyl borate magnesium halides and to the conversion of such halides to different tetrakis-pentafluoorphnenyl salts having borate anions useful in metallocene olefin polymerization catalysts.
BACKGROUND OF THE INVENTION
Combinations of an activating ration and a weekly coordinating borate anion are used as components of metallocene olefin polymerization catalysts.
Procedures for preparation of the borate anion portion of such combinations are described in the prior art.
See European patent applications Nos. 505,972 and 505,997, Japanese published patent application No. 63-238057, and PCT International Application No. 94/00459.
Grignard reactions are conventionally conducted in an ether solvent. United States patent 5,473,036 describes the reaction of a fluorophenyl Grignard with a boron trihalide in an ether solvent to produce a magnesium halide salt of a tetrakis-fluorophenyl borate. The patent states: "The ether is needed to solubilize the Grignard reagent, fluorophenyl magnesium bromide" (Col. 2, 11. 1-2). The magnesium halide is converted by ration exchange to a different tetrakis-fluorophenyl borate salt to provide a borate anion useful in metallocene catalyst synthesis.
SUI~iARY OF THE INVENTION
One aspect of this invention provides solutions of Grignard reagents in solvents which are not an ether, in particular, hydrocarbon solvents.
Pursuant to another aspect of the invention, a pentafluorophenyl magnesium halide is reacted with a boron trihalide in a solvent which is not an ether to produce a tetrakis-pentafluorophenyl magnesium halide.
The magnesium halide may be converted by reaction with a suitable ration, such as substituted ammonium, trityl or onium ration, to a compound comprising a weakly coordinating borate anion and an activating ration.
In accordance with an aspect of the invention, there is provided a method for preparing a hydrocarbon solution of a Grignard reagent, wherein said Grignard reagent comprises pentafluorophenyl magnesium halide, said method comprising:
(i) providing a solution of said Grignard reagent in an ether;
(ii) adding a hydrocarbon solvent to said solution, whereby a reaction mixture is produced;
- 2a (iii)removing said ether from said step (ii) reaction mixture; and (iv) treating said reaction mixture with a boron trihalide to produce a tetrakis-pentafluorophenyl borate magnesium halide.
In accordance with another aspect of the invention, there is provided a methyl cyclohexane or toluene solution of a Grignard reagent wherein said solution contains no free ether.
l0 In accordance with a further aspect of the invention, there is provided a toluene solution of pentafluorophenyl magnesium bromide or chloride wherein said solution contains no free ethyl ether.
In accordance with another aspect of the invention, there is provided a method which comprises:
(i) reacting a boron trihalide with a solution in a solvent which contains no free ether of a pentafluorophenyl magnesium bromide or chloride wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
In accordance with a further aspect of a invention, there is provided a method which comprises (i) providing a first solution of C6F5 MgBr in ethyl ether;
- 2b -(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii) removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) optionally isolating said C6F5 MgBr from said third solution.
In accordance with another aspect of the invention, there is provided a method which comprises (i) providing a first solution of C6F5 MgBr in ethyl ether;
(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii) removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) reacting BF3 with said C6F5 MgBr in said third solution to produce tetrakis (C6F5)B MgBr; and (v) subjecting said tetrakis (C6F5) B MgBr to a cation exchange reaction to produce a different tetrakis pentafluorophenyl borate salt which has an anion useful as a metallocene polymerization catalyst component.
In accordance with a further aspect of the invention, there is provided a Grignard reagent in solution in a solvent wherein said solvent contains no free ether.
- 2c -In accordance with another aspect of the invention, there is provided a pentafluorophenyl magnesium bromide or chloride in solution in a solvent wherein said solvent contains no free ethyl ether.
In accordance with a further aspect of the invention, there is provided a method which comprises:
i) reacting a boron trihalide with a solution of a pentafluorophenyl magnesium bromide or chloride in solution in a solvent that contains no free ethyl ether, wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
DEFINITIONS
Ether-A compound having the formula ROR, Ar-O-Ar or R-O-Ar in which R is alkyl and Ar is aryl.
Non-ethereal solvent A solvent which is not an ether.
Isolated, crystalline Grignard reagents are typically compounds coordinated with a Lewis base, usually the ether solvent in which the reagent is prepared. Such coordinated ethers are an integral part of the Grignard and do not function as solvents.
Similarly, ethers coordinated with boron halide, e.g., BX3~OEt2 in which X is a halide, do not function as solvents in the methodology of this invention.
Although such boron trihalide ether complexes are useful as a matter of convenience in the laboratory practice of the invention, boron halides per ,sue are to be used commercially.
Non-interfering solvent A solvent which does not interfere with the reaction between a pentafluorophenyl Grignard reagent, e.g., pentafluorophenyl magnesium chloride or bromide, and a boron trihalide.
Grianard reagent Any art recognized compound which functions as a Grignard reagent. For the purposes of this invention, Grignard reagents have the formula RMgX (excluding any coordinated Lewis base such as an ether) in which X is a halogen, preferably chlorine or bromine and R is a straight or branched chain acyclic or cyclic two to eight carbon atom aliphatic hydrocarbon or a two to eight carbon atom ' 25 aromatic hydrocarbon group which may be substituted with, in r alia, a halogen. Representative aliphatic W0 98/22470 PCTlUS97/21232 - -hydrocarbons include methyl, propyl, isopropyl, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl and methyl cyclohexyl groups. Representative aromatic groups include phenyl, tolyl, xylenyl groups which may be halogen or otherwise substituted.
Preferred Grignard reagents for one embodiment of this invention are fluorophenyl, in particular, pentafluorophenyl magnesium halides. A particularly preferred Grignard reagent is pentafluorophenyl magnesium bromide.
DESCRIPTION OF THE PREFERRED EMEODIMENTS
An important aspect of this invention provides solutions of Grignard reagents in non-ethereal solvents. A first solution of the Grignard in an ether, usually ethyl ether, is prepared. A non-ethereal solvent, preferably a hydrocarbon solvent, is then added, and ether is removed to provide a second solution of the Grignard reagent in the non-ethereal solvent.
The relative proportions of the ethereal and non-ethereal solvents are chosen to maintain the Grignard reagent in solution not only in the mixed solvent but also in the non-ethereal solvent after the ether , component of the mixed solvent is removed. In general, both of the ethereal and non-ethereal components may ' WO 98!22470 PCT/US97l21232 -constitute 30~ to 70~ by volume of the initial solvent mixture.
The ether component of the solvent mixture may have the formula R-O-R', in which R and R' are the same or different two to five or more carbon atom alkyl groups. Diethyl ether is preferred. Dipropyl, diisopropyl, dibutyl and diisobutyl ether solvents are also appropriate.
The non-interfering, non-ethereal solvent component is preferably a five to eight carbon atom, acyclic or cyclic, aliphatic, or six to nine carbon atom aromatic hydrocarbon. Representative hydrocarbon solvents include normal or iso pentane, hexane, heptane, octane, cyclohexane, methyl cyclohexane, benzene, toluene and xylene.
A preferred embodiment provides a method for producing a solution in a hydrocarbon solvent, e.g., toluene, of the Grignard reagent (C6F5) MgX in which X
is a halogen, preferably chlorine or bromine.
Pursuant to that embodiment, a solution of pentafluorophenyl magnesium halide in a solvent mixture including an ether and a non-interfering, non-ethereal, preferably hydrocarbon, solvent is provided. The ether component of the solvent mixture is then removed to ' 25 provide a solution of pentafluorophenyl magnesium halide Grignard in the non-ethereal solvent. The Grignard is then reacted with a boron trihalide to produce a tetrakis-pentafluorophenyl borate magnesium halide in solution in the non-ethereal solvent.
Typically, an ethyl ether solution of from about 0.5 to 2.0 molar in pentafluorophenyl magnesium bromide Grignard reagent is utilized in the first step of the method. The non-interfering, non-ethereal solvent is combined with the solution of the Grignard reagent in an amount sufficient to maintain the pentafluorophenyl borate magnesium halide produced in subsequent steps in solution.
Preferably, the ether component of the original solvent mixture is removed under vacuum, e.g., about 30 Toor, until the pot temperature rises to from 20° to 40°C, preferably 30°C. Ether removal provides a non-ethereal solution of the Grignard. Boron trihalide, which for laboratory purposes, may be in the form of an ether complex, e.g., BF3~OEt2, is added, preferably by injection, to the non-ethereal solution of the Grignard. A spontaneous temperature rise to about 40°C
to 60°C typically occurs, whereupon external heat is applied and a reaction temperature of 50° to 100°C, preferably 85°C to 90°C, is established and maintained for a time period, usually of one to four hours, appropriate to substantially complete the production of the desired tetrakis-pentafluorophenyl borate magnesium _7_ halide. In a typical reaction, this halide may comprise more than 95~ of the fluorine containing reaction products.
The tetrakis borate reaction product may optionally be isolated and reacted with a salt, such as chloride, containing an appropriate ration, such as ammonium, trityl or onium, to provide by ration exchange a compound comprising a weakly coordinating borate and an activating ration useful in the preparation of metallocene olefin polymerization catalysts. Representative ammonium salts contain, as the ration portion, R3NH+, where R can be phenyl (Ph) which is either unsubstituted or substituted (e. g., with such alkyl groups as lower alkyl, namely, ethyl and/or ethyl). Such ammonium salts may be exemplified by triethyl ammonium chloride or phenyldimethyl ammonium chloride. The corresponding trityl salts have a ration of the formula PH3C+, whereas the opium salts can contain a ration of the formula PHZI*.
The route for forming the ammonium and onium-containing products involves the reaction of the intermediate in water with the selected salt to precipitate the desired combination of weakly coordinating boron-containing anion and activating ration. The route for forming the trityl-containing products uses a hydrocarbon solvent medium (e. g., _g_ toluene) in which the byproduct salt is insoluble but ' the borate anion-cation is soluble.
PLE I
Pentafluorophenyl magnesium bromide (250 ml, 2.025 M in Et20) and dry, deoxygenated toluene (500 ml) were combined in a 1 1. flask which had previously been purged with nitrogen. Diethyl ether was removed under vacuum (~ 30 Torr) until the pot temperature rose to 32°C. At this point, 3 ml of the solution was withdrawn by syringe and hydrolyzed by addition to 30~
aqueous HC1 at 0°C in a closed test tube to insure that volatile materials are not lost.
Analysis by gas chromatography showed about a 1:3 ratio of Et20: C6FSH which indicates a 1 : 3 ratio of Et20: C6FSMgBr in solution before hydrolysis .
The solvent stripping was continued until an additional 100 ml of toluene had been removed. Another 3 ml aliquot was hydrolyzed and analyzed by gas chromatography as above with the same result (1:3 Et20:C6F5H). These results indicate that at this point, no free Et20 remained in solution (i.e., Et20 is no longer a component of the solvent system). All Et20 is tightly bound to the magnesium of the Grignard reagent. , BF3~OEt2 (7.0 ml) was then injected causing a spontaneous temperature rise to 50°C. External heat was applied and the reaction temperature was maintained WO 98/22470 PCTIiTS97/21232 -_g_ at 85-90°C. for a time sufficient to drive the reaction to completion. After cooling to room temperature, an aliquot was withdrawn and analyzed by 19F NMR. This showed tetrakis pentafluorophenyl borate magnesium bromide to comprise >g5% of the fluorine containing products.
This magnesium salt, optionally after isolation, may be reacted in known manner by cation exchange to provide a compound having an anion useful in a metallocene catalyst. Use of pentafluorophenyl magnesium chloride yields a similar result.
EXAMPLE II
Example I is repeated with the exception that pentafluorophenyl magnesium bromide is added to a preformed mixture of ethyl ether and toluene containing about 30% to 70% toluene.
EXAMPLE III
Example I is repeated with the exception that methyl cyclohexane is substituted for toluene.
Similarly, ethers coordinated with boron halide, e.g., BX3~OEt2 in which X is a halide, do not function as solvents in the methodology of this invention.
Although such boron trihalide ether complexes are useful as a matter of convenience in the laboratory practice of the invention, boron halides per ,sue are to be used commercially.
Non-interfering solvent A solvent which does not interfere with the reaction between a pentafluorophenyl Grignard reagent, e.g., pentafluorophenyl magnesium chloride or bromide, and a boron trihalide.
Grianard reagent Any art recognized compound which functions as a Grignard reagent. For the purposes of this invention, Grignard reagents have the formula RMgX (excluding any coordinated Lewis base such as an ether) in which X is a halogen, preferably chlorine or bromine and R is a straight or branched chain acyclic or cyclic two to eight carbon atom aliphatic hydrocarbon or a two to eight carbon atom ' 25 aromatic hydrocarbon group which may be substituted with, in r alia, a halogen. Representative aliphatic W0 98/22470 PCTlUS97/21232 - -hydrocarbons include methyl, propyl, isopropyl, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl and methyl cyclohexyl groups. Representative aromatic groups include phenyl, tolyl, xylenyl groups which may be halogen or otherwise substituted.
Preferred Grignard reagents for one embodiment of this invention are fluorophenyl, in particular, pentafluorophenyl magnesium halides. A particularly preferred Grignard reagent is pentafluorophenyl magnesium bromide.
DESCRIPTION OF THE PREFERRED EMEODIMENTS
An important aspect of this invention provides solutions of Grignard reagents in non-ethereal solvents. A first solution of the Grignard in an ether, usually ethyl ether, is prepared. A non-ethereal solvent, preferably a hydrocarbon solvent, is then added, and ether is removed to provide a second solution of the Grignard reagent in the non-ethereal solvent.
The relative proportions of the ethereal and non-ethereal solvents are chosen to maintain the Grignard reagent in solution not only in the mixed solvent but also in the non-ethereal solvent after the ether , component of the mixed solvent is removed. In general, both of the ethereal and non-ethereal components may ' WO 98!22470 PCT/US97l21232 -constitute 30~ to 70~ by volume of the initial solvent mixture.
The ether component of the solvent mixture may have the formula R-O-R', in which R and R' are the same or different two to five or more carbon atom alkyl groups. Diethyl ether is preferred. Dipropyl, diisopropyl, dibutyl and diisobutyl ether solvents are also appropriate.
The non-interfering, non-ethereal solvent component is preferably a five to eight carbon atom, acyclic or cyclic, aliphatic, or six to nine carbon atom aromatic hydrocarbon. Representative hydrocarbon solvents include normal or iso pentane, hexane, heptane, octane, cyclohexane, methyl cyclohexane, benzene, toluene and xylene.
A preferred embodiment provides a method for producing a solution in a hydrocarbon solvent, e.g., toluene, of the Grignard reagent (C6F5) MgX in which X
is a halogen, preferably chlorine or bromine.
Pursuant to that embodiment, a solution of pentafluorophenyl magnesium halide in a solvent mixture including an ether and a non-interfering, non-ethereal, preferably hydrocarbon, solvent is provided. The ether component of the solvent mixture is then removed to ' 25 provide a solution of pentafluorophenyl magnesium halide Grignard in the non-ethereal solvent. The Grignard is then reacted with a boron trihalide to produce a tetrakis-pentafluorophenyl borate magnesium halide in solution in the non-ethereal solvent.
Typically, an ethyl ether solution of from about 0.5 to 2.0 molar in pentafluorophenyl magnesium bromide Grignard reagent is utilized in the first step of the method. The non-interfering, non-ethereal solvent is combined with the solution of the Grignard reagent in an amount sufficient to maintain the pentafluorophenyl borate magnesium halide produced in subsequent steps in solution.
Preferably, the ether component of the original solvent mixture is removed under vacuum, e.g., about 30 Toor, until the pot temperature rises to from 20° to 40°C, preferably 30°C. Ether removal provides a non-ethereal solution of the Grignard. Boron trihalide, which for laboratory purposes, may be in the form of an ether complex, e.g., BF3~OEt2, is added, preferably by injection, to the non-ethereal solution of the Grignard. A spontaneous temperature rise to about 40°C
to 60°C typically occurs, whereupon external heat is applied and a reaction temperature of 50° to 100°C, preferably 85°C to 90°C, is established and maintained for a time period, usually of one to four hours, appropriate to substantially complete the production of the desired tetrakis-pentafluorophenyl borate magnesium _7_ halide. In a typical reaction, this halide may comprise more than 95~ of the fluorine containing reaction products.
The tetrakis borate reaction product may optionally be isolated and reacted with a salt, such as chloride, containing an appropriate ration, such as ammonium, trityl or onium, to provide by ration exchange a compound comprising a weakly coordinating borate and an activating ration useful in the preparation of metallocene olefin polymerization catalysts. Representative ammonium salts contain, as the ration portion, R3NH+, where R can be phenyl (Ph) which is either unsubstituted or substituted (e. g., with such alkyl groups as lower alkyl, namely, ethyl and/or ethyl). Such ammonium salts may be exemplified by triethyl ammonium chloride or phenyldimethyl ammonium chloride. The corresponding trityl salts have a ration of the formula PH3C+, whereas the opium salts can contain a ration of the formula PHZI*.
The route for forming the ammonium and onium-containing products involves the reaction of the intermediate in water with the selected salt to precipitate the desired combination of weakly coordinating boron-containing anion and activating ration. The route for forming the trityl-containing products uses a hydrocarbon solvent medium (e. g., _g_ toluene) in which the byproduct salt is insoluble but ' the borate anion-cation is soluble.
PLE I
Pentafluorophenyl magnesium bromide (250 ml, 2.025 M in Et20) and dry, deoxygenated toluene (500 ml) were combined in a 1 1. flask which had previously been purged with nitrogen. Diethyl ether was removed under vacuum (~ 30 Torr) until the pot temperature rose to 32°C. At this point, 3 ml of the solution was withdrawn by syringe and hydrolyzed by addition to 30~
aqueous HC1 at 0°C in a closed test tube to insure that volatile materials are not lost.
Analysis by gas chromatography showed about a 1:3 ratio of Et20: C6FSH which indicates a 1 : 3 ratio of Et20: C6FSMgBr in solution before hydrolysis .
The solvent stripping was continued until an additional 100 ml of toluene had been removed. Another 3 ml aliquot was hydrolyzed and analyzed by gas chromatography as above with the same result (1:3 Et20:C6F5H). These results indicate that at this point, no free Et20 remained in solution (i.e., Et20 is no longer a component of the solvent system). All Et20 is tightly bound to the magnesium of the Grignard reagent. , BF3~OEt2 (7.0 ml) was then injected causing a spontaneous temperature rise to 50°C. External heat was applied and the reaction temperature was maintained WO 98/22470 PCTIiTS97/21232 -_g_ at 85-90°C. for a time sufficient to drive the reaction to completion. After cooling to room temperature, an aliquot was withdrawn and analyzed by 19F NMR. This showed tetrakis pentafluorophenyl borate magnesium bromide to comprise >g5% of the fluorine containing products.
This magnesium salt, optionally after isolation, may be reacted in known manner by cation exchange to provide a compound having an anion useful in a metallocene catalyst. Use of pentafluorophenyl magnesium chloride yields a similar result.
EXAMPLE II
Example I is repeated with the exception that pentafluorophenyl magnesium bromide is added to a preformed mixture of ethyl ether and toluene containing about 30% to 70% toluene.
EXAMPLE III
Example I is repeated with the exception that methyl cyclohexane is substituted for toluene.
Claims (14)
1. A method for preparing a hydrocarbon solution of a Grignard reagent, wherein said Grignard reagent comprises pentafluorophenyl magnesium halide, said method comprising:
(i) providing a solution of said Grignard reagent in an ether;
(ii) adding a hydrocarbon solvent to said solution, whereby a reaction mixture is produced;
(iii)removing said ether from said step (ii) reaction mixture; and (iv) treating said reaction mixture with a boron trihalide to produce a tetrakis-pentafluorophenyl borate magnesium halide.
(i) providing a solution of said Grignard reagent in an ether;
(ii) adding a hydrocarbon solvent to said solution, whereby a reaction mixture is produced;
(iii)removing said ether from said step (ii) reaction mixture; and (iv) treating said reaction mixture with a boron trihalide to produce a tetrakis-pentafluorophenyl borate magnesium halide.
2. The method of claim 1 in which said hydrocarbon solvent is an aliphatic, straight or branched chain hydrocarbon having 5 to 8 carbon atoms or a cyclic hydrocarbon having 5 to 8 carbon atoms or an aromatic hydrocarbon having 6 to 9 carbon atoms.
3. The method of claim 1 or claim 2, in which said liquid hydrocarbon solvent is normal or iso pentane, hexane, heptane, or octane, or benzene, toluene or xylene.
4. The method of claim 1 or claim 2, in which said hydrocarbon solvent is added in step (ii) in an amount selected to maintain said Grignard reagent in solution in said hydrocarbon solvent.
5. The method of claim 1, 2 or 3, in which said hydrocarbon solvent is added in step (ii) in an amount which provides a mixed hydrocarbon and ether solvent containing from 30% to 70% by volume of said hydrocarbon solvent and correspondingly 70% to 30% by volume of said ether solvent.
6. The method of claim 1 or claim 2, in which said Grignard reagent is a pentafluorophenyl magnesium bromide or chloride, said ether utilized in step (i) is diethyl ether, and said hydrocarbon solvent added in step (ii) is methyl cyclohexane or toluene.
7. A toluene solution of pentafluorophenyl magnesium bromide or chloride wherein said solution contains no free ethyl ether.
8. A method which comprises:
(i) reacting a boron trihalide with a solution in a solvent in which contains no free ether of a pentafluorophenyl magnesium bromide or chloride wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
(i) reacting a boron trihalide with a solution in a solvent in which contains no free ether of a pentafluorophenyl magnesium bromide or chloride wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
9. The method of claim 8 further comprising:
(ii) isolating said tetrakis-pentafluorophenyl borate magnesium bromide or chloride produced in step (i), and (iii)subjecting said tetrakis-pentafluorophenyl borate magnesium bromide isolated in step (ii) to a ration exchange reaction to produce a tetrakis pentafluorophenyl borate which has an anion useful as a metallocene olefin polymerization catalyst component.
(ii) isolating said tetrakis-pentafluorophenyl borate magnesium bromide or chloride produced in step (i), and (iii)subjecting said tetrakis-pentafluorophenyl borate magnesium bromide isolated in step (ii) to a ration exchange reaction to produce a tetrakis pentafluorophenyl borate which has an anion useful as a metallocene olefin polymerization catalyst component.
10. The method of claim 8 or claim 9, in which said solvent is toluene.
11. A method which comprises:
(i) providing a first solution of C6F5 MgBr in ethyl ether;
(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii)removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) optionally isolating said C6F5 MgBr from said third solution.
(i) providing a first solution of C6F5 MgBr in ethyl ether;
(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii)removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) optionally isolating said C6F5 MgBr from said third solution.
12. A method which comprises:
(i) providing a first solution of C6F5 MgBr in ethyl ether;
(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii) removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) reacting BF3 with said C6F5 MgBr in said third solution to produce tetrakis (C6F5)B MgBr; and (v) subjecting said tetrakis (C6F5)B MgBr to a cation exchange reaction to produce a different tetrakis pentafluorophenyl borate salt which has an anion useful as a metallocene polymerization catalyst component.
(i) providing a first solution of C6F5 MgBr in ethyl ether;
(ii) adding toluene to provide a second solution of said C6F5 MgBr in a mixture of said ethyl ether and toluene;
(iii) removing the ether from said second solution wherein a third solution of C6F5 MgBr in toluene is formed; and (iv) reacting BF3 with said C6F5 MgBr in said third solution to produce tetrakis (C6F5)B MgBr; and (v) subjecting said tetrakis (C6F5)B MgBr to a cation exchange reaction to produce a different tetrakis pentafluorophenyl borate salt which has an anion useful as a metallocene polymerization catalyst component.
13. A pentafluorophenyl magnesium bromide or chloride in solution in a solvent wherein said solvent contains no free ethyl ether.
14. A method which comprises:
(i) reacting a boron trihalide with a solution of a pentafluorophenyl magnesium bromide or chloride in solution in a solvent that contains no free ethyl ether, wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
(i) reacting a boron trihalide with a solution of a pentafluorophenyl magnesium bromide or chloride in solution in a solvent that contains no free ethyl ether, wherein a tetrakis-pentafluorophenyl borate magnesium bromide or chloride is produced.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/751,985 US6231790B1 (en) | 1996-11-19 | 1996-11-19 | Tetrakis-pentafluorophenyl borates from pentafluorophenyl grignard reagents |
| US08/751,985 | 1996-11-19 | ||
| PCT/US1997/021232 WO1998022470A1 (en) | 1996-11-19 | 1997-11-19 | Tetrakis-pentafluorophenyl borates from pentafluorophenyl grignard reagents |
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