JPH06247981A - Production of tetrakis (pentafluorophenyl) borate derivative using pentafluorophenyl alkali metal salt prepared from pentafluorobenzene - Google Patents

Abstract

PURPOSE:To produce a tetrakis(pentafluorophenyl)borate derivative as an important intermediate of cocatalyst in preparing a cation complex polymerization catalyst in high yield from inexpensive pentafluorobenzene. CONSTITUTION:Pentafluorobenzene expressed by the formula C6HF5 in an amount of 1 equivalent is made to react with 0.5-1.5 equivalent organometallic compound expressed by the general formula RM in an ether-based solvent, a hydrocarbon-based solvent or a mixed solvent of this ether-based solvent with the hydrocarbon-based solvent at -120 to 80 deg.C to afford a pentafluorophenyl alkali metal salt expressed by the formula C6H5M and 1 equivalent boron compound expressed by the formula BX3 is made to react with >=3.7 equivalent of the pentafluorophenyl metal compound expressed by the formula C6H5M to produce the objective tetrakis(pentafluorophenyl)borate derivative expressed by the formula (C6F5)4BM.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing a tetrakis (pentafluorophenyl) borate derivative using pentafluorobenzene. The boron derivative obtained in the present invention is a very useful substance as an intermediate of a cocatalyst for cationic complex polymerization.

[0002]

2. Description of the Related Art In recent years,
The number of academic literatures or patents for the study of polymerization reactions using a tetrakis (pentafluorophenyl) borate derivative and a cyclopentadienyl transition metal complex, a so-called metallocene derivative, to generate a cation complex and catalyzing this has been remarkably increasing. For example, Macromol. Chem. Rapid Commu
n., 2 , pp 663-667 (1991). However, in the conventional production of tetrakis (pentafluorophenyl) borate derivatives, relatively expensive pentafluorobenzene bromide has been used as a starting material for the source of pentafluorophenyl group.

According to the method, pentafluorobenzene bromide is subjected to a bromine-metal exchange reaction using an organometallic compound such as butyllithium to generate pentafluorophenyllithium, and boron trichloride or boron trifluoride is used as a starting material for a boron source. Etc. to synthesize directly or to react pentafluorobromobenzene with magnesium to generate a Grignard reagent such as pentafluorophenylmagnesium bromide and similarly react with boron trichloride or boron trifluoride as a starting material for the boron source. Then, tris (pentafluorophenyl) borane was synthesized and then reacted with pentafluorophenyllithium to produce tetrakis (pentafluorophenyl) borate derivative (J. Organometallic Che).
m., 2 , 245-250 (1964)).

Pentafluorobenzene bromide can be obtained by brominating pentafluorobenzene, but if the tetrakis (pentafluorophenyl) borate derivative can be produced directly from pentafluorobenzene, the production process can be reduced by one step, and therefore it is available. It becomes easier and the price of the starting material is reduced. In addition, there are already published documents in which pentafluorobenzene is used as a starting material to generate and react pentafluorophenyllithium or pentafluorophenylmagnesium bromide (J. Che.
m. Soc., 166 (1959), Synthesis of Fluoroorganic C
ompounds p.141, J. Org. Chem., 29, 2385 (1964) and
ibid, 31 , 4229 (1966)), and no application to the production of tetrakis (pentafluorophenyl) borate derivatives.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, the present inventors have changed pentafluorobenzene from pentafluorobenzene bromide used as a starting material to the production of a tetrakis (pentafluorophenyl) borate derivative to pentafluorobenzene. By changing the method, the present invention has been reached by examining various methods for synthesizing the relatively expensive pentafluorobenzene bromide as a starting material by eliminating the bromination step of pentafluorobenzene.

That is, the gist of the present invention lies in the formula [I]
With respect to 1 equivalent of pentafluorobenzene represented by
By reacting 0.5 to 1.5 equivalents of the organometallic compound represented by the formula [II] at −120 to 80 ° C. in an ether solvent, a hydrocarbon solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent, A pentafluorophenyl alkali metal salt represented by the formula [III] is generated to produce 3.7 equivalents or more of the boron compound represented by the formula [IV] per 1 equivalent.
[I] a method for producing a tetrakis (pentafluorophenyl) borate derivative represented by the formula [VII] by reacting a pentafluorophenyl metal compound represented by the formula [VII], or 1 equivalent of pentafluorobenzene represented by the formula [I] By reacting 0.5 to 1.5 equivalents of the organometallic compound represented by the formula [II] in an ether solvent, a hydrocarbon solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent at -120 to 80 ° C. The pentafluorophenyl alkali metal salt represented by the formula [III] is generated to generate 0.8 equivalent or more of the pentafluorophenylborane represented by the formula [VIII]. The present invention relates to a method for producing a tetrakis (pentafluorophenyl) borate derivative represented by the formula [VIII] by reacting a fluorophenyl metal compound.

[0007]

The present invention will be described in detail below. The ether solvent referred to in the present invention is diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether,
Diisoamyl ether, 1,2-dimethoxyethane,
1,2-diethoxyethane, di-2-methoxyethyl ether, tetrahydrofuran, tetrahydropyran,
1,4-dioxane and the like are shown.

The hydrocarbon solvent used in the present invention is pentane, isopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, n-paraffin or petroleum ether. Saturated hydrocarbons such as benzene, toluene, o-xylene, m-
Xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-
Aromatic hydrocarbons such as trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, propylbenzene and butylbenzene, and mixtures thereof are shown.

Next, in the formula [II] of the present invention, the functional groups which do not influence the reaction include a methyl group, an ethyl group,
Propyl group, isopropyl group, propenyl group, 2-isopropenyl group, allyl group, butyl group, sec-butyl group,
tert-butyl group, isobutyl group, pentyl group, sec-pentyl group, tert-pentyl group, neo-pentyl group, isopentyl group, sec-isopentyl group, hexyl group, sec
-Hexyl group, isohexyl group, sec-isohexyl group, cyclohexyl group, phenyl group, benzyl group, o-
A tolyl group, m-tolyl group, p-tolyl group, methoxymethyl group, methylthiomethyl group, 2-dimethylaminoethyl group, o-anis group, m-anis group, p-anis group, trimethylsilylmethyl group, etc., Examples of the organometallic compound represented by the formula [II] include methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, isopentyllithium, sec. -Pentyl lithium, tert-pentyl lithium, sec-isopentyl lithium, hexyl lithium, isohexyl lithium, sec-hexyl lithium, cyclohexyl lithium, phenyl lithium, o
-Tolyllithium, m-tolyllithium, p-tolyllithium, trimethylsilyllithium, phenylsodium, o-tolylsodium, m-tolylsodium, p
-Tolyl sodium, butyl lithium / potassium tert-
Butoxide or butyl lithium / sodium tert-
Butoxide and the like are preferable, and isopropyllithium, sec-butyllithium, tert-butyllithium, sec-pentyllithium, tert-pentyllithium, sec-isopentyllithium, sec- having strong basicity and hardly affecting the reaction Examples include hexyl lithium and cyclohexyl lithium.

Next, examples of the boron compound represented by the formula [V] in the present invention include boron trifluoride, boron trichloride, boron tribromide, boron triiodide, trimethylboric acid, triethylboric acid, Examples thereof include tripropyl boric acid, triisopropyl boric acid, tributyl boric acid, trimethylene borate, tris (dimethylamino) boron, tris (diethylamino) boron, tripyrrolidinoboron, tripiperidinoboron and trimorpholinoboron. Further, a complex such as a boron trifluoride diethyl ether complex, a boron trifluoride dibutyl ether complex, a boron trifluoride dimethyl sulfide complex, a boron trichloride diethyl ether complex or a boron trichloride dibutyl ether complex is also included in this category.

A specific manufacturing method will be sequentially described below. The pentafluorobenzene represented by the formula [I] is dissolved in an ether solvent, a hydrocarbon solvent or a mixed solvent thereof. 0.5 to 1.5 equivalents of the organometallic compound represented by the formula [II] is reacted with this solution in the range of -120 to 80 ° C with respect to 1 equivalent of pentafluorobenzene.

In this reaction, when the pentafluorophenyl alkali metal salt represented by the formula [III] is generated, the pentafluorobenzene represented by the formula [I] is used to generate the formula [II].
If the amount of the organometallic compound represented by is too small, a large amount of unreacted pentafluorobenzene remains, and if it is used in excess, it is produced by the halogen-metal exchange with the fluorine of the pentafluorophenyl metal salt represented by the formula [III]. It is desirable to use 0.8 to 1.20 equivalents of the organometallic compound represented by the formula [II] because it may react, and the reaction temperature is -80 ° C.
If it is too low, the reaction progresses very slowly, and if it is higher than 0 ° C., the side reaction progresses extremely fast, and in any case, the yield becomes very low. Therefore, it is desirable to react in the range of -80 to 0 ° C. The reaction mixture starts at 5 minutes at the same temperature.
A pentafluorophenyl alkali metal salt represented by the formula [III] is prepared by reacting for 120 minutes. .

The pentafluorophenyl alkali metal salt represented by the formula [III] produced here is C ₆ F ₅ Li, C
₆ F ₅ Na, a C ₆ F ₅ K.

The amount of the pentafluorophenyl alkali metal salt used is 4 equivalent as the theoretical amount when the boron compound represented by the formula [IV] is used in the reaction, but it is shown here.
If the amount is less than 3.7 equivalents, the yield of the tetrakis (pentafluorophenyl) borate derivative is remarkably reduced, so use of 3.7 equivalents or more is desirable.

Further, tris (pentafluorophenyl)
When borane is used as a boron compound in the reaction, the theoretical amount is 1 equivalent, but when the amount is less than 0.7 equivalent shown here, the yield of the tetrakis (pentafluorophenyl) borate derivative is remarkably reduced, so use of 0.7 equivalent or more is recommended. desirable.

When the temperature for mixing the pentafluorophenyl alkali metal salt and the boron compound is lower than −100 ° C., the reaction progresses extremely slowly, and therefore a temperature higher than this is desirable, and when it is higher than 0 ° C., the side reaction progresses extremely. Since it becomes faster and the yield becomes very low in any case, a temperature below this is desirable.

If the reaction temperature is lower than -100 ° C, the reaction progresses very slowly, and if it is higher than 0 ° C, unreacted pentafluorophenyl alkali metal salt is decomposed, so that -100 to 0 ° C.
It is desirable to react at ℃.

[0018]

【The invention's effect】

INDUSTRIAL APPLICABILITY According to the present invention, a tetrakis (pentafluorophenyl) borate derivative, which is an important intermediate of a co-catalyst in preparing a cationic complex polymerization catalyst, is prepared from a cheaper pentafluorobenzene instead of pentafluorobenzene bromide. The effect of the present invention is great in that it can provide a method for producing a tetrakis (pentafluorophenyl) borate derivative in a high yield via a pentafluorophenyl alkali metal salt.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention does not exceed the gist thereof, and the following examples do not impose any limitation.

The reaction yield is determined by ¹⁹ F-NMR for the amount of tetrakis (pentafluorophenyl) borate derivative produced using pentafluorotoluene as an internal standard substance, or N, N-dimethylanilinium chloride or tributyl chloride. after induction by exchanging pair cation of N, N- dimethylanilinium or tributylammonium tetrakis (pentafluorophenyl) borate with ammonium, calculated based on the dry weight of the crystals, pentafluorotoluene as an internal standard ¹⁹
Purity was measured by F-NMR.

Example 1 A 100 ml glass three-necked flask was equipped with a 50 ml glass dropping funnel, a temperature resistor and a septum rubber, and the system was sufficiently replaced with nitrogen. The flask is charged with 5 g (29.8 mmol) of pentafluorobenzene and 30 ml of diethyl ether, and the solution is cooled to -65 ° C. Then, the internal temperature of a 16.1 wt% tert-butyllithium pentane solution (12.3 g, 29.8 mmol) charged in a dropping funnel was adjusted to −
Add dropwise while keeping the temperature below 55 ° C. After completion of dropping
Stir at 65 to -55 ° C to prepare pentafluorophenyllithium. To the prepared solution of pentafluorophenyl lithium was added 1 mol / L hexane solution of boron trichloride (7.45 mL, 7.45 mmol) at -65 to -55 ° C, stirred at the same temperature for 30 minutes, and then warmed to room temperature and reacted. Diethyl ether was distilled off from the mixture, and the organic layer was washed with 20 mL of water three times. After combining the aqueous layers, 1.1 equivalents of an aqueous solution of N, N-dimethylanilinium chloride with respect to the boron source is reacted with the aqueous layer to precipitate white crystals. The obtained crystals were filtered, washed with water and then vacuum dried to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in a yield of 92.3%. ^The purity was measured by ¹ H and ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance.
It was over 98wt%.

Example 2 Pentafluorobenzene (4.
40g, 26.2mmol) and a solution of diethyl ether (50ml)
20 wt% tert-butyllithium / pentane solution (7.98
g, 25.0 mmol) while the temperature of the reaction solution is kept at -55 to -65 ° C, and after completion of the dropwise addition, the reaction solution is stirred for about 0.5 hour while keeping the temperature at -25 to -50 ° C. Then, a 20.0 wt% tris (pentafluorophenyl) borane / toluene solution (63.8 g, 25.0 mmol) was mixed while maintaining the temperature of the reaction solution at -25 to -40 ° C, and the mixture was stirred at the same temperature for 30 minutes, and then allowed to reach room temperature. Diethyl ether was distilled off from the solution of lithium tetrakis (pentafluorophenyl) borate obtained by heating, and the organic layer was washed with 20 mL of water three times. After combining the aqueous layers, 1.1 equivalents of an aqueous solution of N, N-dimethylanilinium chloride with respect to the boron source is reacted with the aqueous layer to precipitate white crystals. The obtained crystals were filtered, washed with water and then vacuum dried to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in a yield of 97.3%. ^The purity was measured by ¹ H and ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance and found to be 98 wt% or more.

(Example 3) Pentafluorobenzene (4.
40g, 26.2mmol) and a solution of diethyl ether (50ml)
20 wt% sec-butyllithium / hexane solution (7.98
g, 25.0 mmol) while the temperature of the reaction solution is kept at -55 to -65 ° C, and after completion of the dropwise addition, the reaction solution is stirred for about 0.5 hour while keeping the temperature at -25 to -50 ° C. Then, a 20.0 wt% tris (pentafluorophenyl) borane / toluene solution (63.8 g, 25.0 mmol) was mixed while maintaining the temperature of the reaction solution at -25 to -40 ° C, and the mixture was stirred at the same temperature for 30 minutes, and then allowed to reach room temperature. Diethyl ether was distilled off from the solution of lithium tetrakis (pentafluorophenyl) borate obtained by heating, and the organic layer was washed with 20 mL of water three times. After combining the aqueous layers, 1.1 equivalents of an aqueous solution of N, N-dimethylanilinium chloride with respect to the boron source is reacted with the aqueous layer to precipitate white crystals. The obtained crystals were filtered, washed with water and then vacuum dried to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in a yield of 96.1%. ^The purity was measured by ¹ H and ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance.
That was all.

Example 4 A 100 ml glass three-necked flask was equipped with a 50 ml glass dropping funnel, a temperature resistor and a septum rubber, and the system was sufficiently replaced with nitrogen. The flask is charged with 5 g (29.8 mmol) of pentafluorobenzene and 30 ml of diethyl ether, and the solution is cooled to -65 ° C. Thereafter, the internal temperature of the 16.1 wt% tert-butyllithium pentane solution (12.3 g, 29.8 mmol) charged in the dropping funnel was −
Add dropwise while keeping the temperature below 55 ° C. After completion of dropping
Stir at 65 to -55 ° C to prepare pentafluorophenyllithium. To the prepared solution of pentafluorophenyl lithium was added 1 mol / L hexane solution of boron trichloride (7.45 mL, 7.45 mmol) at -65 to -55 ° C, and the mixture was stirred at the same temperature for 30 minutes and then warmed to room temperature. After filtering the produced lithium chloride, the yield of the solution of the obtained lithium tetrakis (pentafluorophenyl) borate determined by ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance was 94.3%.

(Example 5) Pentafluorobenzene (1
After cooling a solution of 5.8 g, 100.0 mmol) and diethyl ether (100 ml) to −40 ° C., 25 wt% tert-butyllithium / pentane solution (22.5 g, 88.0 mmol) was added at −30 to −40 ° C.
Stir for 22 hours. After that, 1.0 mol / L boron trichloride /
Add a hexane solution (21.0 ml, 21.0 mmol) at -40 ° C and warm to room temperature over 2 hours. Diethyl ether was distilled off from the obtained solution of lithium tetrakis (pentafluorophenyl) borate, and the organic layer was washed with 30 mL of water three times. After combining the water layers, add 1.1 to the boron source in the water layer.
When an equivalent amount of an aqueous solution of tributylammonium chloride is reacted, white crystals are precipitated. The crystals obtained were filtered, washed with water, and then vacuum dried to obtain tributylammonium tetrakis (pentafluorophenyl) borate.
Obtained in 95.2%. ^The purity was measured by ¹ H and ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance and found to be 98 wt% or more.

(Example 6) Pentafluorobenzene (1
After cooling the solution of 4.8 g, 88.0 mmol) and diethyl ether (100 ml) to -40 ℃, add 20 wt% butyllithium / hexane solution (28.1 g, 87.7 mmol) and stir at -30 to -40 ℃ for 10 hours. To do. Then, boron trifluoride diethyl ether complex (2.84 g, 20.0 mmol) is added at -40 ° C, and the temperature is raised to room temperature over 2 hours. After stirring at room temperature overnight, toluene (200 ml) is added, and then diethyl ether and hexane are distilled off by heating, and toluene is also distilled off by heating to an extent of recovering about 30% of the charged amount. After filtering the precipitated lithium fluoride and concentrating and drying toluene, lithium tetrakis (pentafluorophenyl) borate was obtained with a yield of 51%.

Example 7 Pentafluorobenzene (1
After cooling a solution of 4.8 g, 88.0 mmol) and diethyl ether (100 ml) to −40 ° C., 24 wt% tert-butyllithium / pentane solution (23.4 g, 87.7 mmol) was added to −30 to −40 ° C.
Stir for 10 hours. Then, boron trifluoride diethyl ether complex (2.84 g, 20.0 mmol) is added at -40 ° C, and the temperature is raised to room temperature over 2 hours. After stirring overnight at room temperature, toluene (20
(0 ml) is added, and diethyl ether and hexane are distilled off by heating, and then toluene is further distilled off by heating to the extent that about 30% of the charged amount is recovered. The precipitated lithium fluoride was filtered and then toluene was concentrated to dryness to obtain lithium tetrakis (pentafluorophenyl) borate in a yield of 68%.

Example 8 Pentafluorobenzene (1
After cooling the solution of 5.1 g, 90.0 mmol) and diethyl ether (100 ml) to −40 ° C., 20 wt% sec-butyllithium / hexane solution (28.2 g, 88.0 mmol) was added to −30 to −40 ° C.
Stir for 10 hours. Then, boron trifluoride diethyl ether complex (2.84 g, 20.0 mmol) is added at -40 ° C, and the temperature is raised to room temperature over 2 hours. After stirring overnight at room temperature, toluene (20
(0 ml) is added, and diethyl ether and hexane are distilled off by heating, and then toluene is further distilled off by heating to the extent that about 30% of the charged amount is recovered. After filtering the precipitated lithium fluoride and concentrating toluene to dryness, lithium tetrakis (pentafluorophenyl) borate was obtained with a yield of 65%.

Example 9 Pentafluorobenzene (1
A solution of 4.8 g, 88.0 mmol) and diethyl ether (100 ml) was cooled to -40 ° C, and a 15 wt% butyl sodium / hexane solution (47.0 g, 88.0 mmol) was added to the mixture at -30 to -40 ° C for 1 hour.
Stir for hours. Then, boron trifluoride diethyl ether complex (2.84 g, 20.0 mmol) is added at -40 ° C, and the temperature is raised to room temperature over 2 hours. Diethyl ether was distilled off from the obtained sodium tetrakis (pentafluorophenyl) borate solution, and the organic layer was washed with 20 mL of water three times. After combining the aqueous layers, 1.1 equivalents of an aqueous solution of N, N-dimethylanilinium chloride with respect to the boron source is reacted with the aqueous layer to precipitate white crystals. The obtained crystals were filtered, washed with water and then vacuum dried to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in a yield of 86.1%. ^The purity was measured by ¹ H and ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance and found to be 98 wt% or more.

(Example 10) Pentafluorobenzene (1
After cooling a solution of 6.8 g, 100.0 mmol) and dibutyl ether (100 ml) to -40 ° C, a 20 wt% sec-butyllithium / hexane solution (28.2 g, 88.0 mmol) was added to -30 to -40 ° C.
Stir for 2 hours. Then, boron trifluoride diethyl ether complex (2.84 g, 20.0 mmol) is added at -40 ° C, and the temperature is raised to room temperature over 2 hours. After stirring overnight at room temperature, octane (200
ml) is added, and diethyl ether and hexane are distilled off by heating, and then octane is further distilled off by heating until about 30% of the charged amount is recovered. After filtering the precipitated lithium fluoride and concentrating and drying octane, lithium tetrakis (pentafluorophenyl) borate was obtained with a yield of 67.3%.

(Example 11) Pentafluorobenzene (1
4.8g, 88.0mmol) and diisopropyl ether (100ml)
Solution was cooled to -40 ℃, then 18wt% sec-butyllithium / hexane solution (31.3g, 88.0mmol) was added at -30 ℃.
Stir at -40 ℃ for 0.5 hours. Then, add 1mol / L boron trichloride / hexane solution (20mL, 20.0mmol) to -40 ℃.
The temperature is raised to room temperature over 2 hours. Diisopropyl ether was distilled off from the obtained solution of lithium tetrakis (pentafluorophenyl) borate to remove the organic layer.
Wash 3 times with 20 mL of water. After combining the aqueous layers, 1.1 equivalents of an aqueous solution of N, N-dimethylanilinium chloride with respect to the boron source is reacted with the aqueous layer to precipitate white crystals. The obtained crystals were filtered, washed with water and then vacuum dried to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in a yield of 95.1%. ¹ H and
^The purity was measured by ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance and found to be 98 wt% or more.

(Example 12) Pentafluorobenzene (1
A solution of 4.8 g, 88.0 mmol) and diethyl ether (100 ml) was cooled to -40 ° C, 15 wt% tert-butyllithium / pentane solution was added, and the mixture was stirred at -30 to -40 ° C for 30 hr. Then, trimethylboric acid (2.08g, 20.0mmol) was added to -40 ° C.
The temperature is raised to room temperature over 2 hours. After stirring overnight at room temperature, octane (200 ml) was added, diethyl ether was distilled off, and the organic layer was washed 3 times with 20 mL of water. After combining the water layers, add 1.1 equivalents of N, N-chloride to the boron source in the water layer.
White crystals are precipitated when an aqueous solution of dimethylanilinium is reacted. The obtained crystals were filtered, washed with water, and then vacuum dried to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in a yield of 83.2%.
Got with. Purity was measured by ¹ H and ¹⁹ F-NMR using pentafluorotoluene as an internal standard substance.
It was more than wt%.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiichi Kaji 1-1-1, 31, Miyanoe, Shinnanyo-shi, Yamaguchi Prefecture Ishinshin Dormitory (72) Kenji Ishimaru 1-1-1, 31, Shinnanyo, Yamaguchi Prefecture Ishinshin Dormitory

Claims (2)

[Claims] 1. With respect to 1 equivalent of pentafluorobenzene represented by the following formula [I] C ₆ HF ₅ [I],
0.5 to 1.5 equivalents of the general formula [II] RM [II] (wherein M represents an alkali metal ion, R represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group influences the reaction. Reacting in an ether solvent, a hydrocarbon solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent at -120 to 80 ° C. The following general formula [I
II] C ₆ F ₅ M [III] (wherein M represents an alkali metal ion) to generate a pentafluorophenyl alkali metal salt, and the following general formula [IV] BX ₃ [IV] [ In the formula, X is halogen or the following general formula [V] OR [V] (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group has a function not affecting the reaction. Or a group represented by the following general formula [VI] NRR ′ [VI] (wherein R and R ′ are the same or different hydrogen or have 1 to 10 carbon atoms). 20 hydrocarbon groups, which may include a functional group that does not influence the reaction, and R and R ′ may be bonded to each other to form a ring). And may form a 1: 1 complex with an ether solvent. ] With respect to 1 equivalent of the boron compound represented by the formula, 3.7 equivalent or more of the pentafluorophenyl metal compound represented by the formula [III] is reacted to give the following general formula [VII] (C ₆ F ₅ ) ₄ BM [VII ] (In formula, M shows an alkali metal ion.) The method of manufacturing the tetrakis (pentafluorophenyl) borate derivative represented by this. 2. A method of formula [II] in the same manner as in the method of claim 1.
I] of the pentafluorophenyl alkali metal salt is generated to produce 0.8 equivalents or more of 1 equivalent of trispentafluorophenylborane represented by the following formula [VIII] (C ₆ F ₅ ) ₃ B [VIII]. A method for producing a tetrakis (pentafluorophenyl) borate derivative represented by the formula [VII] (C ₆ F ₅ ) ₄ BM [VII] by reacting a pentafluorophenyl metal compound represented by the formula [III].