JPH10330381A - Production of triarylborane amine complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject complex useful as a soil preventing agent for a ship bottom boating material, etc., by a new method for converting an alkali metal salt of a tetraarylborate into a triarylborane with an acid and then reacting an amine therewith. SOLUTION: This method of producing a triarylborane amine complex is to react an alkali metal salt of a tetraarylborate of the formula: M<+> [BAr4 ]<-> (Ar is an aryl; M is an alkali metal) (e.g. sodium tetraphenylborate) with an inorganic acid or an organic acid in an ether-based solvent (e.g.; dioxane) singly or in a mixed solvent of the above solvent with a hydrocarbon-based solvent to obtain a triarylborane of the formula: BAr3 , then react the obtained compound with a primary to tertiary amine of the formula: NR<1> R<2> R<3> (R<1> to R<3> are each H, an alkyl, etc.), (e.g.; ethylamine) or an aromatic amine of the formula (R<4> to R<6> are each H, an aryl, etc.), (e.g.; pyridine). As the above-mentioned inorganic acid or organic acid, hydrochloric acid is preferable. Further, as the objective complex, e.g. pyridinetriphenylborane is cited.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for industrially and advantageously producing a triarylboraneamine complex useful as an antifouling component such as a ship bottom paint or a fishing net treating agent.

[0002]

2. Description of the Related Art The following method is known as a method for synthesizing a triarylboraneamine complex.

Conventional method 1 A method of preparing an anhydrous ether solution of triarylborane by dropping an anhydrous ether solution of phenylmagnesium into an anhydrous ether solution of boron trifluoride and reacting the resulting solution with an amine (Berichte, Vol. 57, No. 57) Page 813 1924
Year).

Conventional method 2 A caustic soda adduct of triphenylborane is synthesized by the reaction of sodium phenyl and orthoborates (US Pat. No. 4,468,815), and an amine is added to an aqueous solution of the caustic soda adduct of triphenylborane. For obtaining a triarylboraneamine complex (Japanese Patent Laid-Open No. 8-31)
No. 1074).

[0005]

In the case of the conventional method 1, the molar ratio between the aryl magnesium halide and the boron halide needs to be 3: 1. It is known that when the dropping of the arylmagnesium halide is fast, the yield of triarylborane decreases due to the formation of tetraarylborate ions.

Further, in the case of the conventional method 2, since the metallic sodium used in the reaction reacts violently in the presence of water and generates heat, there is a risk of ignition in the presence of a flammable organic solvent. Therefore, handling a large amount on an industrial scale has a problem of increasing the risk of fire.

Therefore, development of a new arylborane complex has been desired instead of these techniques. An object of the present invention is to provide a novel method for producing a triarylboraneamine complex that meets such needs.

[0008]

In order to solve these problems, a method for producing a triarylboraneamine complex in high yield was studied. As a result, the present invention has been made. That is, the feature of the present invention is that, as shown in the following reaction formula, the first step, that is, the formula (1) in an ether-based solvent alone or in a mixed solvent obtained by adding a hydrocarbon-based solvent thereto. A) reacting an alkali metal salt of a tetraaryl borate represented by formula (2) with an inorganic or organic acid of (2) to obtain a triaryl borane represented by formula (3);
Then, as a second step, the reaction liquid containing the arylborane is mixed with amines, that is, a primary amine to a tertiary amine represented by the formula (5), or an aromatic amine represented by the formula (6). The present invention relates to a method for producing a triarylboraneamine complex represented by the formula (4), which is characterized by reacting.

[0009]

Embedded image [Wherein, M represents an alkali metal, and Ar represents an aryl group. Amine refers to a tertiary to tertiary amine represented by the formula (5) or an aromatic amine represented by the formula (6). ]

Embedded image (Wherein, R ¹ to R ³ are the same or different and each represents hydrogen, a cycloalkyl group, an alkyl group, an aralkyl group, R ⁴
To R ⁶ are the same or different and represent a hydrogen, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogen atom. )

In the formula (1), M is an alkali metal,
Specific examples are lithium and sodium.

In equations (1), (3) and (4), A
r is an aryl group, and specific examples include a phenyl group, p
-Tolyl group, m-tolyl group, mesityl group, xylyl group,
Examples include a biphenyl group, a naphthyl group, a pentafluorophenyl group, a p-chlorophenyl group, and an o-chlorophenyl group.

The inorganic acid (2) used in the present invention includes, for example, hydrochloric acid, dilute sulfuric acid, hydrogen bromide and the like.
As the organic acid, toluenesulfonic acid, trifluoroacetic acid and the like can be used, and hydrochloric acid is particularly preferable.

The ether solvents used in the present invention include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like. These may be used alone, but hydrocarbon solvents such as benzene,
It may be used as a mixed solvent to which toluene, xylene and the like are added.

Specific examples of the compound of the general formula (1) include
Examples thereof include sodium tetraphenyl borate, lithium tetraphenyl borate, sodium tetra-m-tolyl borate, lithium tetraphenyl borate, and lithium tetra-m-tolyl borate.

In the above formula (5), R ¹ , R ² and R ³ may be the same or different and are hydrogen, alkyl, cycloalkyl or aralkyl. R ⁴ , R ⁵ ,
R ⁶ is the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group or a halogen atom. In Formula (5) or Formula (6), the alkyl group is an alkyl group having 1 to 30 carbon atoms, the cycloalkyl group is a cycloalkyl group having 3 to 7 carbon atoms, and the alkoxy group is , Having 1 to 1 carbon atoms
An aryl group refers to an unsubstituted phenyl group, or an phenyl group substituted by one or more of an alkyl group, an alkoxy group, and a halogen atom; Is fluorine, chlorine, bromine and iodine, and the aralkyl group is a benzyl group, a phenethyl group, a phenylpropyl group and the like.

As a specific example of the formula (5), ethylamido
Alkyls such as propylamine and propylamine (C 1-7) A
Min, octylamine, dodecylamine, dioctylua
Min, phenethylamine, benzylamine, dibenzyl
Amines and the like.

Further, specific examples of the general formula (6) include pyridine, 4-methylpyridine, 2,4-dichloropyridine and the like. And the target compound of formula (4)
Examples of octylamine triphenylborane, dioctylamine triphenylborane, dodecylamine triphenylborane, octylamine tri (p-tolyl) borane, hexylamine tri (m-tolyl) borane, heptylamine tri (m- Tolyl) borane, pyridinetriphenylborane, 4-methylpyridinetri (m-
Tolyl) borane, 2,4-dichloropyridine triphenyl borane, phenethylamine triphenyl borane, and the like.

[0018]

Next, a specific method for carrying out the present invention will be described.

Method for synthesizing compound (raw material) of formula (1) The lithium or sodium salt of the tetraarylborate of formula (1) used in the present invention is a known compound,
It is easily synthesized by the reaction of boron trifluoride ether complex with arylmagnesium.

First Step [Synthesis of Compound of Formula (3)] In the present invention, first, a lithium salt or a sodium salt of a tetraarylborate of the formula (1) is converted to an ether solvent alone or a hydrocarbon. The compound is dissolved in a mixed solvent to which a system solvent has been added, and an inorganic or organic acid of the compound (2) in an equimolar amount to the compound of the formula (1) is added dropwise to the solution while maintaining the temperature at 40 ° C. or lower. The triarylborane of 3) is produced.

Second Step [Synthesis of Compound of Formula (4)] Next, the reaction mixture is mixed with a primary amine to a tertiary amine of formula (5).
When the primary amine or the aromatic amine of the formula (6) alone or dissolved in the same solvent as the solvent used in the first step is added dropwise, the triarylboraneamine complex of the formula (4) is formed. At this time, if crystals precipitate,
The crystals are filtered, washed sufficiently with water to remove excess amine and by-product alkali metal salts, and dried to obtain the desired compound of formula (4). When the product is dissolved in the organic layer, the aqueous layer is separated and removed, and after washing with water to remove salts, the organic solvent is distilled off to obtain the desired formula. (4) A compound is obtained.

[0022]

Next, examples of the present invention will be described. However, the present invention is not limited to the following examples.

Example 1 A 4-diameter flask equipped with a mechanical stirrer, a thermometer and a dropping funnel and purged with nitrogen was charged with sodium tetraphenylborate (34.2 g, 0.1 mol), and tetrahydrofuran (100 ml) and toluene (50 m2).
l) was added and dissolved. 10% hydrochloric acid (3
(6.5 ml, 0.1 mol) was added dropwise at 40 ° C. or lower over 1 hour. After the addition, the mixture was stirred for 1 hour. Then, octylamine (12.9 g, 0.1 m
ol) was added dropwise at room temperature over 30 minutes. After dropping, stirring was continued at room temperature for another 2 hours to ripen. After aging, the aqueous layer was separated and removed, and washed sufficiently with water to remove salts in the organic layer. By distilling off the solvent from the organic layer, 35 g of white crystals of octylamine triphenylborane were obtained.
(Yield 95%) was obtained.

EXAMPLE 2 Sodium tetraphenylborate (34.2 g, 0.1 mol) was charged into a 4-diameter flask equipped with a mechanical stirrer, a thermometer, and a dropping funnel and purged with nitrogen, and tetrahydrofuran (100 ml) and toluene (50 m2).
l) was added and dissolved. 10% hydrochloric acid (3
6.2 ml, 0.1 ml) was added dropwise at 40 ° C. or lower over 1 hour. After the addition, the mixture was stirred for 1 hour. Thereafter, the reaction solution was stirred while dodecylamine (18.5 g, 0.1 mol
A solution of l) in toluene (100 ml) was added dropwise at room temperature over 30 minutes. After dropping, continue stirring at room temperature for another 2 hours,
Matured. After aging, the aqueous layer was separated and removed, and washed sufficiently with water to remove salts in the organic layer. By distilling off the solvent from the organic layer, 40.6 g (yield 90%) of white crystals of dodecylamine triphenylborane were obtained.

Example 3 Sodium tetra-p-tolyl borate (38.4 g, 0.1 mol) was charged into a 4-diameter flask equipped with a mechanical stirrer, a thermometer, and a dropping funnel and purged with nitrogen.
Tetrahydrofuran (100 ml) and toluene (50 m
l) was added and dissolved. 10% hydrochloric acid (3
(6.5 ml, 0.1 mol) was added dropwise at 40 ° C. or lower over 1 hour. After the addition, the mixture was stirred for 1 hour. Thereafter, the reaction solution was stirred while dodecylamine (18.5 g, 0.1 mol
A solution of l) in toluene (100 ml) was added dropwise at room temperature over 30 minutes. After dropping, continue stirring at room temperature for another 2 hours,
Matured. After aging, the aqueous layer was separated and removed, and washed sufficiently with water to remove salts in the organic layer. The solvent was distilled off from the organic layer to obtain 42.0 g (yield: 93%) of white crystals of dodecylamine tri-p-tolylborane.

Example 4 A 4-diameter flask equipped with a mechanical stirrer, a thermometer and a dropping funnel and purged with nitrogen was charged with sodium tetraphenylborate (34.2 g, 0.1 mol), and tetrahydrofuran (100 ml) and toluene (50 m2) were added.
l) was added and dissolved. 10% hydrochloric acid (3
(6.5 ml, 0.1 mol) was added dropwise at 40 ° C. or lower over 1 hour. After the addition, the mixture was stirred for 1 hour. Thereafter, pyridine (7.9 g, 0.1 mol) was added dropwise at room temperature over 30 minutes while stirring the reaction solution. After dropping, stirring was continued at room temperature for another 2 hours to ripen. After aging, the aqueous layer is separated and removed,
Washing was carried out sufficiently to remove salts in the organic layer. By distilling off the solvent from the organic layer, 30.5 g (92% yield) of white crystals of pyridinetriphenylborane were obtained.

Example 5 A 4-diameter flask equipped with a mechanical stirrer, a thermometer and a dropping funnel and purged with nitrogen was charged with sodium tetraphenylborate (34.2 g, 0.1 mol), and tetrahydrofuran (100 ml) and toluene (50 ml) were added.
l) was added and dissolved. 10% hydrochloric acid (3
(6.5 ml, 0.1 mol) was added dropwise at 40 ° C. or lower over 1 hour. After the addition, the mixture was stirred for 1 hour. Thereafter, cyclohexylamine (9.9 g, 0.1
mol) was added dropwise over 30 minutes at room temperature. After dropping, stirring was continued at room temperature for another 2 hours to ripen. After aging, the aqueous layer was separated and removed, and washed sufficiently with water to remove salts in the organic layer. By distilling off the solvent from the organic layer, white crystals of cyclohexylamine triphenylborane are obtained.
2.4 g (95% yield) were obtained.

Example 6 A 4-diameter flask equipped with a mechanical stirrer, a thermometer and a dropping funnel and purged with nitrogen was charged with sodium tetraphenylborate (34.2 g, 0.1 mol), and tetrahydrofuran (100 ml) and toluene (50 m2).
l) was added and dissolved. 10% hydrochloric acid (3
(6.5 ml, 0.1 mol) was added dropwise at 40 ° C. or lower over 1 hour. After the addition, the mixture was stirred for 1 hour. Thereafter, while stirring the reaction solution, phenethylamine (12.1 g, 0.1 m
ol) was added dropwise at room temperature over 30 minutes. After dropping, stirring was continued at room temperature for another 2 hours to ripen. After aging, the aqueous layer was separated and removed, and washed sufficiently with water to remove salts in the organic layer. By distilling off the solvent from the organic layer, 34.5 g of white crystals of phenethylamine triphenylborane were obtained.
(96% yield) was obtained.

[0029]

Industrial Applicability According to the method of the present invention, a triarylboraneamine complex, which is useful as an active ingredient such as a ship bottom paint and a fishing net antifouling agent, can be industrially easily and advantageously produced.

Claims (1)

[Claims] 1. An inorganic or organic acid of (2) is reacted with an alkali metal salt of a tetraarylborate of the formula (1) in an ether solvent alone or in a mixed solvent of an ether solvent and a hydrocarbon solvent. Forming a triarylborane of the formula (3), followed by reacting a primary amine to a tertiary amine of the formula (5) or an aromatic amine of the formula (6). And a method for producing a triarylboraneamine complex of the formula (4). Embedded image (In the formula, Ar represents an aryl group, and M represents an alkali metal.) (In the formula, R ^{1 to} R ³ are the same or different and represent hydrogen, cycloalkyl group, alkyl group, or aralkyl group.) (In the formula, R ^{4 to} R ⁶ are the same or different and represent hydrogen, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogen atom.)