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

Definitions

• the present invention relates to a novel method for producing tris (pentafluorophenyl) borane.
• Tris (pentafluorophenyl) borane is a compound useful as a co-catalyst for enhancing the activity of a meta-mouth catalyst used in a cationic complex polymerization reaction.
• the methods (1) and (2) use expensive bromopentafluorene benzene as a raw material.
• the methods (3) and (4) use less expensive pentafluorene benzene, but the pentafluorene benzene has a flash point. Low (1 3 ° C), a 2 Ru compound Yosu careful handling.
• pentafluorophenylmagnesium bromide is used.
• removal of magnesium by-products from the compound is complicated. Operation was necessary, and there was a disadvantage of inefficiency. Disclosure of the invention
• the present invention has been made in order to solve the above-mentioned problem, and is represented by the following formula 1 with pentafluorobenzene and benzene in an ether solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent.
• the compound is reacted with an organometallic compound to form a pentafluorophenyl metal represented by the following formula 2, and then expressed in an ether-based solvent or a mixed solvent of an ether-based solvent and a hydrocarbon-based solvent by the formula 2
• a method for producing tris (pentafluorophenyl) borane which comprises reacting a pentafluorophenyl metal to be reacted with a boron compound represented by the following formula 3.
• R a hydrocarbon group having 1 to 10 carbon atoms.
• X in the formula may be the same or different and is a halogen atom or an alkoxy group, respectively.
• the ether-based solvent a known or well-known ether-based solvent is employed. , 1,2-Jetoxetane, 2,2′-dimethoxyethoxyethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like are preferred.
• the ether solvent is preferably a dialkyl ether, particularly diisopropyl ether, getyl ether, di ( n -propyl) ether or di (n-ether). (Butyl) ether is preferred.
• hydrocarbon-based solvent examples include known or well-known hydrocarbon-based solvents, and any of an aliphatic hydrocarbon-based solvent and an aromatic hydrocarbon-based solvent can be employed.
• Aliphatic hydrocarbon solvents include n-pentane, isopentane, ⁇ -hexane, cyclohexane, n-heptane, n-octane, n-nonane, n-decane, n-pentane, n-dodecane, n- Preferred are tridecane, n-tetradecane, ⁇ -pentadecane, ⁇ -hexadecane, or a mixture of aliphatic hydrocarbons obtained as a petroleum fraction.
• aromatic hydrocarbon solvents examples include benzene, toluene, ⁇ -xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5 —Trimethylbenzene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene or “fc ert-butylbenzene” is preferred.
• R in the organometallic compound (formula 1) represents a hydrocarbon group having 1 to 10 carbon atoms.
• R is preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably R is an alkyl group having 4 to 10 carbon atoms.
• the alkyl group may have a straight-chain structure, a branched structure, or a ring structure, and preferably has a branched structure or a ring structure.
• M represents an alkali metal atom, and is preferably a lithium atom, a sodium atom, or a potassium atom.
• organometallic compound (formula 1) are preferably the following: methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium Butyllithium, n-pentyllithium, isopentyllithium, 2-methylbutyllithium, 1-methylbutyllithium, 1-ethylpropyllithium, 1,1-dimethylpropyllithium, 2,2-dimethylpropyllithium, n- Hexyllithium, isohexyllithium, 1-methylpentyllithium, 1-ethylbutyllithium, cyclohexyllithium, phenyllithium, o-tolyllithium, m-tolyllithium, p-tolyllithium, phenylnadium , O-tolyl
• an organometallic compound having strong basicity and hardly causing a side reaction is preferable.
• isopropyllithium, sec-butyllithium, tert-butyllithium, 2-methylbutyllithium, 1,1-dimethylpropyllithium, 2,2-dimethylpropyllithium, 1-methylbutyllithium, 1-ethylpropyllithium, 1-methylpentyllithium, 1-ethylbutyllithium, or cyclohexyllithium is preferred, and sec-butyllithium is particularly preferred. Lithium is preferred.
• X in the boron compound (Formula 3) may be the same or different in the formula, and represents a halogen atom or an alkoxy group, respectively.
• X is preferably the same.
• the octogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom or a fluorine atom is preferable.
• the alkoxy group an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group shown in the following specific examples is preferable.
• Examples of the boron compound (formula 3) include boron trifluoride, boron trichloride, boron tribromide, boron triiodide, trimethoxy boron, triethoxy boron, tripropoxy boron, triisopropoxy boron, and tributoxy. Boron and the like are preferable, and boron trifluoride or boron trichloride is particularly preferable.
• the boron compound (Formula 3) may form a complex with an ether solvent or a thioether solvent.
• the ether solvent may be a complex with the same solvent as the solvent used for the reaction or a complex of a different compound.
• Examples of the complex with the ether-based solvent include boron trifluoride dimethyl ether complex, boron trifluoride dibutyl ether complex, boron trichloride dimethyl ether complex, and boron trichloride dibutyl ether complex.
• Examples of the complex with a solvent include a boron trifluoride dimethylthioether complex and a boron trifluoride dimethylthioether complex.
• an ether-based solvent or a mixed solvent of an ether-based solvent and a hydrocarbon-based solvent hereinafter collectively referred to as a reaction solvent.
• a reaction solvent an ether-based solvent or a mixed solvent of an ether-based solvent and a hydrocarbon-based solvent
• pentafluorobenzene C 6 F 5 C 1
• an organometallic compound formula 1
• Pentafluorobenzene is an inexpensive compound and has no flash point, making it easy to handle and excellent in practicality.
• the reaction solvent in the reaction of the first step is preferably a mixed solvent of an ether solvent and a hydrocarbon solvent, more preferably a mixed solvent of an ether solvent and an aliphatic hydrocarbon solvent, and particularly preferably a dialkyl ether and an aliphatic solvent.
• a mixed solvent with a hydrocarbon solvent is preferred.
• the mixing ratio in the mixed solvent is arbitrary, and the amount of the hydrocarbon solvent is preferably an excess amount (more than 50% by volume) with respect to the amount of the ether solvent. It is preferable to use a mixed solvent of 0.1 to 1% by volume.
• the reaction is preferably carried out by dissolving pentafluorene benzene in a reaction solvent to obtain a pentafluorobenzene solution, and then dropping an organometallic compound into the solution.
• the amount of the organometallic compound is preferably 0.5 to 1.5 times the equivalent of pentafluorobenzene. If the amount of the organometallic compound is too small, a large amount of unreacted pentafluorobenzene remains unreacted, and if the amount of the organometallic compound is too large, halogen-metal exchange is also performed on the fluorine atoms in the pentafluorophenyl metal formed. Reaction may occur. Therefore, the amount of the organometallic compound is preferably 0.8 to 1.2 times equivalent to that of chlorobenzene.
• the reaction between the pentafluorobenzene and the organometallic compound (formula 1) is preferably carried out at a temperature between 120 ° C. and + 80 ° C.
• the reaction temperature is preferably 180 ° C or higher, and the reaction temperature is preferably 0 ° C or lower to suppress side reactions.
• the reaction temperature is preferably from 180 ° C to 0 ° C, and more preferably from 140 ° C to 120 ° C in view of the yield.
• the reaction time is preferably from 5 ° C to 120 minutes.
• M in the pentafluorophenyl metal is the same as M in Formula 1.
• the crude reaction product containing the penfluorofluorofunyl metal (Formula 2) is usually used as it is in the next reaction. If the reaction product is heated to a high temperature, a side reaction of pentafluorophenyl metal may occur, so the reaction product is preferably kept at -20 eC or lower.
• a pentafluorophenyl metal (formula 2) and a boron compound (formula 3) are reacted in the second step.
• the reaction is preferably carried out by adding a boron compound (formula 3) to a crude reaction product containing a pentafluorophenyl metal (formula 2) and mixing.
• the theoretical amount of pentafluorophenyl metal (formula 2) consumed in the reaction is 3 times the molar amount of the boron compound (formula 3), but the boron compound (formula 3) is converted to pentafluorophenyl metal (formula 2). If the molar ratio is less than 2.1 times, the yield of the desired tris (pentafluorophenyl) borane is remarkably reduced. If the molar ratio exceeds 3.9 times, undesired tetrakis (pentafluorophenyl) borane is not obtained. Nil) Borate formation becomes prominent.
• the amount of the boron compound (formula 3) should be 2.1 to 3.9 times the amount of the pen-fluorofluorometal (formula 2). And more preferably 2. to! -2.9 times.
• the reaction temperature between the pentafluorofunyl metal (formula 2) and the boron compound (formula 3) is preferably from -80 ° C to 0 ° C.
• the reaction time is preferably 0.5 to 50 hours. In an actual reaction, it is preferable to carry out the reaction while raising the reaction temperature from 14 CTC to around 30 ° C. within 0.5 to 50 hours.
• reaction solvent used in the reaction of the second step.
• the same reaction solvent as used in the reaction in the first step can be used.
• a mixed solvent of a hydrocarbon solvent and an ether solvent is preferable as the reaction solvent, and the amount of the hydrocarbon solvent is preferably an excess amount (more than 50% by volume) with respect to the amount of the ether solvent. It is preferable to use a mixed solvent in which the amount of the ether-based solvent is 0.01 to 1% by volume based on the amount of the hydrocarbon-based solvent.
• the amount of the reaction solvent is also preferably about the same as in the first step, preferably 1 to 100 times, more preferably 10 to 50 times the volume of pentafluorobenzene.
• tris (pentafluorophenyl We sulfonyl) borane [B (C 6 F 5) a] is produced.
• the tris (pentafluorophenyl) borane may be a complex in which an ether solvent is coordinated, but from the viewpoint of the activity of the cocatalyst, tris (pentafluorophenyl) in which the ether solvent is not coordinated. Borane is preferred.
• the ether solvent may be an ether solvent as a reaction solvent or a boron compound (Formula 3) used in the reaction. And other ether-based solvents.
• an ether solvent is coordinated to tris (pentafluorobenzene) borane, it can be removed if necessary. In the case of removing, it is preferable to remove in a post-treatment step. Can be removed.
• Post-treatment of the reaction product is preferably performed by a method of distilling off the reaction solvent and volatile components under reduced pressure, and then diluting with a hydrocarbon solvent again.
• hydrocarbon-based solvent examples include known or well-known hydrocarbon-based solvents, and any of aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, and mixtures thereof can be employed.
• Aliphatic hydrocarbon solvents include n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, n-octane, n-nonane, n-decane, n-pentane, n-dodecane, n- Preferred are tridecane, n-tetradecane, n-pentadecane, or n-hexadecane.
• aromatic hydrocarbon solvents examples include benzene, toluene, o-xylene, m-ki Silene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, propylbenzene, or butylbenzene is preferred.
• a mixture of the aliphatic hydrocarbon solvent and the aromatic hydrocarbon solvent a petroleum fraction having a boiling point of about 40 to 200 ° C can be used.
• the amount of the hydrocarbon solvent used in the post-treatment is tris (pentafluoro).
• the weight is preferably 10 to 300 times the theoretical yield of (phenyl) borane, and particularly preferably 20 to 100 times the weight in consideration of solubility. If insolubles are present in the hydrocarbon solution of (pentafluorophenyl) borane, it is preferable to remove it by filtration.
• Pentafluorobenzene (11.38 g) was dissolved in diisopropyl ether (100 ml). After cooling this solution to ⁇ 40, a solution of 0.97 M sec-butyllithium in cyclohexane / hexane (57.9 ml) was added at a reaction temperature of ⁇ 40 ° C. to 130 ° C. It was added dropwise while adjusting to C. After stirring at 14 CTC to 130 ° C for 1 hour to obtain pentafluorophenyllithium, a 1 M solution of boron trichloride in hexane (19.5 ml) was added dropwise at the same temperature. .
• Example 2 The reaction was carried out in the same manner as in Example 1 except that diisopropyl ether in Example 1 was changed to getyl ether to obtain an isoper E solution of tris (pentafluorophenyl) borane. A portion of this solution was concentrated, and the yield of tris (pentafluorophenyl) borane was calculated to be 4.27 g (46% yield).
• Example 2 The reaction was carried out in the same manner as in Example 1 except that diisopropyl ether in Example 1 was changed to a mixed solvent of hexane (140 ml) and diisopropyl ether (0.28 ml), and tris (pentafluorophenyl) was used. ) A borane in Isopar E solution was obtained. A portion of this solution was concentrated, and the yield of tris (pentafluorofluorophenyl) borane was calculated to be 7.96 g (81% yield).
• tris (pentachlorofluorophenyl) borane can be synthesized in two steps using inexpensive and easy-to-handle fluorobenzene benzene as a starting material.
• This synthesis method is a practically excellent method because it has a high yield without using special reagents, reaction conditions, and reaction equipment.
• the product, tris (pentafluorophenyl) borane is a very important compound as a cocatalyst for cationic complex polymerization. Even when an ether solvent is coordinated with the product, the ether solvent can be easily removed by the post-treatment method of the present invention to obtain a highly active cocatalyst.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=15814114

Family Applications (1)

Country Status (2)

Families Citing this family (1)

Citations (4)

• 1998
  • 1998-06-12 JP JP16552898A patent/JP2000001492A/ja not_active Withdrawn
• 1999
  • 1999-06-03 WO PCT/JP1999/002974 patent/WO1999064427A1/ja not_active Ceased

Patent Citations (4)

Also Published As

Similar Documents

Legal Events