JPH08311074A - Method for producing triphenylborane amine complex compound - Google Patents

Abstract

(57) Abstract: An industrially advantageous method for producing a triphenylborane amine complex has been desired. The subject can be achieved by reacting a sodium hydroxide addition product or a potassium hydroxide addition product of triphenylborane with an amine in an aqueous solution to produce a corresponding triphenylborane amine complex. Since this method uses water as a solvent, it is inexpensive, there is no risk of fire and the reaction can be carried out in air. Further, since the raw material is a sodium hydroxide adduct of triphenylborane, etc., it is stable and can be handled safely.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a triphenylborane amine complex which is useful as an active ingredient such as a fishing net antifouling agent, a ship bottom paint, an industrial antiseptic / antifungal agent, or an animal repellent.

[0002]

2. Description of the Related Art Berichte No. 57
Vol. B, page 813 (1924), a solution of triphenylborane in anhydrous ether was prepared and reacted with amines such as methylamine, ethylamine, n-propylamine and pyridine under a nitrogen stream to give a compound of general formula (I ), A method for synthesizing various triphenylborane amine complexes is described.

US Pat. No. 3,211,679 describes
Other methods for producing triphenylborane-dodecylamine complex, triphenylborane-n-tetradecylamine complex, and the like, and JP-A-62-277307 disclose the production of pyridine-tris (4-fluorophenyl) boron. Each law is disclosed, but the content is the same as that of Berichte.

All of these are production methods suitable only for laboratory scale synthesis, and have some industrial difficulties. For example, the use of expensive and highly flammable ethers, the reaction having to be accomplished under a stream of nitrogen, and the starting material triphenylborane being a flammable solid, therefore, in large quantities on an industrial scale. Handling is dangerous.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an industrially advantageous method for producing a triphenylborane amine complex.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive research conducted by the present inventors in order to overcome the above-mentioned drawbacks of the conventional method for producing a triphenylborane amine complex, industrially advantageous triphenylborane is obtained. The inventors have found a method for synthesizing an amine complex and completed the present invention. That is, the present invention provides the compound of formula (II-a)

[0007]

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Sodium hydroxide adduct of triphenylborane represented by or formula (II-b)

[0009]

[Chemical 9]

A potassium hydroxide adduct of triphenylborane represented by the general formula (III-a)

[0011]

[Chemical 10]

(Wherein R ¹ represents an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an aralkyl group), or a primary amine represented by the general formula (III-b).

[0013]

[Chemical 11]

(In the formula, R ² , R ³ and R ⁴ are the same or different and each represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, a halogen, an alkoxy group, an alkenyl group or an aralkyl group. ) And a pyridine compound represented by the formula (I) are reacted in an aqueous solution.

[0015]

[Chemical 12]

(In the formula, ← X is

[0017]

[Chemical 13]

Or

[0019]

Embedded image

Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. ) Relates to a method for producing a triphenylborane amine complex.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, an alkyl group is an alkyl having 1 to 30 carbon atoms, a halogen is chlorine, bromine, fluorine or iodine, and a halogen-substituted alkyl group is 1 to 3 carbon atoms. 1 carbon atom substituted by halogen
To 4 alkyl, a cycloalkyl group is a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group is an alkoxy group having 1 to 8 carbon atoms, and an alkenyl group is 2 to 2 carbon atoms. 8 alkenyl groups, an aryl group is phenyl or phenyl substituted by halogen, alkyl, alkoxy, alkenyl, nitro, amino, and an aralkyl group is benzyl, phenethyl, phenylpropyl or halogen, alkyl, aralkyl,
Benzyl substituted with alkenyl, nitro, amino, phenethyl, phenylpropyl and the like.

The sodium hydroxide adduct or potassium hydroxide adduct of triphenylborane used in the method of the present invention has the formula

[0023]

[Chemical 15]

Or

[0025]

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The aqueous solution of sodium hydroxide or potassium hydroxide is added dropwise to, for example, a xylene solution of triphenylborane to form an aqueous phase, which is usually supplied in the form of an aqueous solution.

Even if an aqueous solution of sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or the like is used instead of the aqueous solution of sodium hydroxide or potassium hydroxide, the sodium hydroxide adduct or hydroxide of triphenylborane can be used. Potassium adducts can be produced.

According to the method of the present invention, the desired triphenylborane complex of the formula (I) can be added to an aqueous solution of triphenylborane with a sodium hydroxide or potassium hydroxide adduct of the formula (III-a). It is produced by dropping a primary amine or a pyridine compound of (III-b). The reaction proceeds at room temperature or under heating. Also,
When the amine is a solid at room temperature, an aqueous solution of triphenylborane sodium hydroxide or potassium hydroxide adduct can be added dropwise to the heated and melted amine to obtain the desired product.

Since the obtained complex is insoluble in water, it is immediately separated. When the separated complex crystallizes, it may be collected by filtration, washed with water, and dried. If it does not crystallize, it is extracted with an organic solvent such as toluene or xylene, washed with water, dried over anhydrous magnesium sulfate or the like, and the solvent is distilled off under reduced pressure to obtain an oily complex. The reaction temperature may be room temperature, but can be changed from 0 ° C. to 80 ° C. if necessary. The reaction time is 3
0 minutes to 2 days.

Since the method for producing the triphenylborane amine complex of the present invention uses water as a solvent, it is inexpensive, there is no danger of fire, and the reaction can be carried out in air. Further, since the raw material is sodium hydroxide adduct or potassium hydroxide adduct of triphenylborane, it is stable and can be handled safely.

[0031]

EXAMPLES Examples will be shown below, but the present invention is not limited thereto.

Example 1 Triphenylborane-n-pro
Pyramine complex A mechanical stirrer, cooling tube, dropping funnel, thermometer equipped with a 1 liter four-necked flask, triphenylborane sodium hydroxide adduct aqueous solution (reagent of Tokyo Kasei; sodium triphenylborane hydroxide) 461.0 g of adduct content (9.6%) was added and stirring was started. When 10.8 g of n-propylamine (a reagent of Kishida Chemical Co., Ltd.) was slowly added dropwise at room temperature (20 ° C.) over 30 minutes, crystals were immediately precipitated. The reaction was allowed to proceed by stirring at room temperature for 3 hours. After the crystals are collected by suction filtration, the crystals are washed with water to remove unreacted n with sodium hydroxide.
-Propylamine was removed. 42.2g when dried
White crystals having a melting point of 107.4 to 108.4 ° C. (yield 90%) were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 2 Triphenylborane-n-butyl
Ruamine complex A mechanical stirrer, a condenser, a dropping funnel, and a 1-liter four-necked flask equipped with a thermometer were charged with 560% of the aqueous solution of the sodium hydroxide adduct of triphenylborane.
0 g was added and stirring was started. N-butylamine (reagent of Tokyo Kasei Co., Ltd.) 1 for 4 hours at room temperature (20 ° C.)
Crystals were immediately precipitated when 0.8 g was slowly added dropwise. The reaction was allowed to proceed by stirring at room temperature for 3 hours and 30 minutes. The crystals were collected by suction filtration and washed with water to remove sodium hydroxide and unreacted n-butylamine. When dried, 56.3 g (94% yield) melting point 109.5-1
White crystals having a temperature of 11.5 ° C. were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 3 Triphenylborane-n-hex
To a 1 liter four-necked flask equipped with a silamine complex mechanical stirrer, a condenser, a dropping funnel, and a thermometer, 500 ml of the sodium hydroxide adduct aqueous solution of triphenylborane was added.
0 g was added and stirring was started. N-hexylamine (reagent of Tokyo Kasei Co., Ltd.) 1 at room temperature (20 ° C.) for 2 hours
When 9.0 g was slowly added dropwise, a white oil separated from the aqueous solution. The mixture was stirred as it was at room temperature for 2 hours, and the reaction was allowed to proceed, whereby a white oil was crystallized. The crystals were collected by suction filtration and washed with water to remove sodium hydroxide and unreacted n-hexylamine. When dried, 53.5 g (yield 92%) of white crystals having a melting point of 81.3 to 85.7 ° C were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 4 Triphenylborane-n-octane
A liter amine complex mechanical stirrer, a condenser, a dropping funnel, and a thermometer were attached to a 1-liter four-necked flask containing 500 ml of the aqueous solution of the sodium hydroxide adduct of triphenylborane.
0 g was added and stirring was started. N-octylamine (reagent of Tokyo Kasei Co., Ltd.) 2 at room temperature (20 ° C.) over 1 hour
When 6.5 g was slowly added dropwise, a white oil separated from the aqueous solution. The mixture was stirred as it was at room temperature for 2 hours, and the reaction was allowed to proceed, whereby a white oil was crystallized. The crystals were collected by suction filtration and washed with water to remove sodium hydroxide and unreacted n-octylamine. When dried, 58.0 g (yield 92%) of white crystals having a melting point of 79.0 to 80.5 ° C. were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 5 Triphenylborane-n-dode
22.0 g of n-dodecylamine (reagent of Kishida Chemical Co., Ltd.) was put in a 500 ml four-necked flask equipped with a silamine complex mechanical stirrer, a cooling tube, a dropping funnel, and a thermometer.
After the stirring was started, the four-necked flask was placed in a water bath at 45 ° C to melt the n-dodecylamine. Subsequently, with the four-necked flask still in the water bath, 359.1 g of the above-mentioned triphenylborane sodium hydroxide adduct aqueous solution was added.
It dripped over a period of minutes. Immediately after the dropping was completed, a white oil separated from the aqueous solution. After completion of the dropping, the water bath was removed and stirring was continued for 5 hours to allow the reaction to proceed. White oil is about 4
Crystallization occurred when stirring was continued for a period of time. The crystals were collected by suction filtration and washed with water to remove sodium hydroxide and unreacted n-dodecylamine. When dried, 43.1 g (yield 99%) of white crystals having a melting point of 60.5 to 61.3 ° C. were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 6 Triphenylborane-n-octane
Tadecylamine complex 65.8 g of n-octadecylamine (a reagent of Kishida Chemical Co., Ltd.) was put into a 1-liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a dropping funnel, and a thermometer. The one-necked flask was placed in a 70 ° C. water bath to melt n-octadecylamine. Then, with the four-necked flask kept in a water bath, the above-mentioned aqueous solution of triphenylborane sodium hydroxide adduct 768.3.
g was added dropwise over 1 hour. After the dropping, remove the water bath,
Stirring was continued for 2 hours to allow the reaction to proceed. About 30 minutes after the completion of the dropping, a white oil separated from the aqueous solution. Then, after another hour, a white oil crystallized. The crystals were collected by suction filtration and washed with water to remove sodium hydroxide and unreacted n-octadecylamine. 122.1 g (98% yield) melting point 63.0-6 when dried
White crystals having a temperature of 4.0 ° C. were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 7 Triphenylborane-Secondary Bu
A liter amine complex mechanical stirrer, a condenser, a dropping funnel, and a thermometer were attached to a 1-liter four-necked flask, and the aqueous solution of the sodium hydroxide adduct of triphenylborane was added to the flask.
0 g was added and stirring was started. Next, at room temperature (20 ° C), 5
16.2 g of secondary butylamine (reagent of Tokyo Kasei Co., Ltd.) was added dropwise over a period of time. After completion of dropping, stirring was continued for 7 hours and 30 minutes in order to proceed the reaction. About 1 after starting stirring
Crystals started to precipitate in time. At the end of stirring, precipitation of a large amount of crystals was confirmed. The crystals were collected by suction filtration and washed with water to remove sodium hydroxide and unreacted secondary butylamine. When dried, 49.0 g (yield 82%) of white crystals having a melting point of 111.0 to 112.5 ° C. were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 8 Triphenylborane-2-ethyi
Ruhexylamine complex A 500 ml four-necked flask equipped with a mechanical stirrer, a cooling tube, a dropping funnel, and a thermometer was charged with the sodium hydroxide adduct aqueous solution of triphenylborane 203.
8 g was added and stirring was started. 2-ethylhexylamine (Kishida Chemical Co., Ltd.) at room temperature (20 ° C.) for 30 minutes
10.4 g of the above reagent) was added dropwise thereto, and then the mixture was stirred at room temperature for 4 hours and 30 minutes to allow the reaction to proceed. When the stirring was stopped, the target substance separated as a white oil. After extracting the oil with toluene, the toluene layer was washed with water to remove unreacted 2-ethylhexylamine with sodium hydroxide. Anhydrous magnesium sulfate was added to the toluene layer for drying, and then toluene was distilled off under reduced pressure to obtain 25.4 g (yield 99%) of a pale yellow transparent oil. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 9 Triphenylborane-pyridine
A 500 ml four-necked flask equipped with a complex mechanical stirrer, a cooling tube, a dropping funnel, and a thermometer was charged with 200% of the sodium hydroxide adduct aqueous solution of triphenylborane.
0 g was added and stirring was started. Pyridine (reagent of Kishida Chemical Co., Ltd.) 5.4 g at room temperature (20 ° C.) over 2 hours
When was slowly added dropwise, crystals immediately precipitated. The reaction was allowed to proceed by stirring at room temperature for 6 hours. The crystals were collected by suction filtration and washed with water to remove sodium hydroxide and unreacted pyridine. When dried, 13.1 g (yield 60%) of white crystals having a melting point of 210 ° C. (decomposition) were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product.

Example 10 In the same manner as in Example 1, methylamine complex, ethylamine complex, isopropylamine complex, n-hexadecylamine complex, cyclohexylamine complex, benzylamine complex, 4-methylpyridine complex, 3,5 -It was confirmed that a triphenylborane amine complex such as a dichloropyridine complex can be synthesized. That is, a triphenylborane-primary amine complex and a triphenylborane-substituted pyridine complex were synthesized by this synthetic method.

The melting points of the compounds synthesized according to Example 10 are shown below. Methylamine complex 205.4 to 209.5 ° C (decomposition) Ethylamine complex 167.0 to 174.0 ° C (decomposition) Isopropylamine complex 154.0 to 161.0 ° C n-hexadecylamine complex 63.0 to 65. 5 ° C (decomposition) cyclohexylamine complex 181.0-183.5 ° C benzylamine complex 176.0-181.0 ° C 4-methylpyridine complex 135.0-145.0 ° C 3,5-dichloropyridine complex 112.0 ~ 115.0 ° C

[0043]

INDUSTRIAL APPLICABILITY By the method of the present invention, a triphenylborane amine complex can be produced industrially easily and advantageously. The triphenylborane amine complex produced by the method of the present invention is a compound useful as an active ingredient such as a fishing net antifouling agent, a ship bottom paint, an industrial antiseptic fungicide or an animal repellent.

Front page continuation (72) Inventor Eiji Shibuya 2-6-9 Hirano-cho, Chuo-ku, Osaka City, Osaka Prefecture Yoshitomi Pharmaceutical Co., Ltd. Chemicals Division (72) Inventor Kazuki Katsuyama 1-6-7 Yushima, Bunkyo-ku, Tokyo No. Yoshitomi Pharmaceutical Co., Ltd.Tokyo Branch Office Chemicals Division

Claims (1)

[Claims] (1) Formula (1) A sodium hydroxide adduct of triphenylborane represented by or And a potassium hydroxide adduct of triphenylborane represented by the general formula: (In the formula, R ¹ is an alkyl group, a halogen-substituted alkyl group,
A cycloalkyl group, an aryl group, an alkenyl group and an aralkyl group are shown. ) A primary amine represented by or (In the formula, R ² , R ³ and R ⁴ are the same or different and are hydrogen;
An alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, a halogen, an alkoxy group, an alkenyl group and an aralkyl group are shown. ) And a pyridine compound represented by the formula (I) are reacted in an aqueous solution. (In the formula, ← X is Or [Chemical 7] Where R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. The manufacturing method of the triphenyl borane amine complex represented by these.