JP5846438B2 - Polymer containing immobilized quaternary ammonium salt and method for producing the same - Google Patents

Description

In the present invention, quaternary ammonium immobilized on polystyrene that is easy to remove, insoluble in an organic solvent, and recoverable and reusable in general organic synthesis represented by production of epoxy compounds from olefins using hydrogen peroxide as an oxidizing agent. The present invention relates to a contained polymer and a production method thereof.

Quaternary ammonium salts, known as phase transfer catalysts, are frequently used in organic synthesis as reagents that initiate and accelerate the flow of reagents between aqueous and oil phases, and are used as agrochemical / pharmaceutical intermediates, resist materials, and plasticizers. It is a useful compound widely used in the production of various polymers such as adhesives and paint resins.

Among them, as a method for oxidizing an olefin to produce an epoxy compound with a low environmental load, a method using hydrogen peroxide as an oxidizing agent has attracted attention. A quaternary ammonium salt is used in order to efficiently bring hydrogen peroxide present in the aqueous phase into contact with the substrate present in the oil phase to advance the reaction (Non-patent Document 1).

However, the method according to Non-Patent Document 1 has a problem that the quaternary ammonium salt is mixed into the target product after the reaction and is difficult to remove. If the quaternary ammonium salt cannot be removed, it will lead to fatal performance deterioration of the target material, such as yellowing of the final product due to the mixed quaternary ammonium salt and deterioration of heat resistance and weather resistance. It is being considered.

For example, Patent Document 1 aims to provide a high-purity epoxy compound with a small amount of residual catalyst, and a compound having a carbon-carbon double bond in the presence of hydrogen peroxide, a quaternary ammonium salt, and a heteropolyacid. A method for producing an epoxy compound is described in which quaternary ammonium salt remaining in the reaction mixture is removed with activated carbon and a smectite-based substance after the oxidation reaction.

  In contrast, the quaternary ammonium salt to be used is fixed to the polymer and is not dissolved in the organic solvent, the target product or the raw material, thereby facilitating the removal of the quaternary ammonium salt after the reaction, and the quaternary ammonium salt in the product. Development of a catalyst in which a quaternary ammonium salt is immobilized for the purpose of hardly remaining in the catalyst has been advanced. (Patent Documents 2 and 3, Non-Patent Document 2).

For example, Patent Document 2 describes polystyrene-supported ammonium methyl sulfate with the object of obtaining a phase transfer catalyst that is very useful for various phase transfer reactions, particularly epoxidation reactions in a two-phase system.

Further, Patent Document 3 aims to provide a novel polymer-supported ammonium alkylsulfate and polymer-supported ammonium hydrogensulfate, a method for producing them, and a method for producing an epoxy compound using the same as a catalyst. Polymers having sulfates or ammonium hydrogen sulfate are described.

However, these quaternary ammonium salt-immobilized polymers lose the degree of freedom of the quaternary ammonium salt portion by immobilizing the quaternary ammonium salt to the polymer, and the performance as a phase transfer catalyst is significantly impaired. It is known. Actually, there are examples of highly selective reactions using a conventional quaternary ammonium salt-immobilized polymer in systems where epoxidation reaction of cyclic olefins or allylation of allyl alcohol is relatively easy. However, it cannot be applied to terminal olefins (Patent Documents 2 and 3, Non-Patent Document 3).

Furthermore, a conventional quaternary ammonium salt-immobilized polymer is prepared by quaternizing ammonium chloride of a polystyrene polymer having a commercially available benzylamine. In this method, a commercially available polymer having an amine is converted into a polymer. Due to the limited structure, it is not possible to produce an immobilized polymer with a high degree of freedom of the quaternary ammonium salt in which the carbon chain between the phenyl group of polystyrene and the nitrogen atom of the quaternary ammonium salt is elongated.

Therefore, it is a catalyst of a quaternary ammonium salt fixed to polystyrene, and contains a quaternary ammonium salt having a high degree of freedom in which the space between the polystyrene phenyl group and the nitrogen atom of the quaternary ammonium salt is controlled to 8 or more carbon atoms. In particular, there is a strong demand for a phase transfer catalyst that can be easily recovered while highly efficiently and selectively oxidizing various olefins including terminal olefins and a method for producing the same.

JP 2010-90032 A JP 2008-94899 A JP 2008-94916 A

K. Sato, Chem. Commun. 2003, 1977. M. Benaglia, Chem. Rev. 2003, 103, 3401. S. Ikegami, Tetrahedron 2004, 60, 4087.

The present invention has been made in order to solve the above-mentioned problems, and its object is to provide a polymer in which the number of carbon atoms between the quaternary ammonium salt and the phenyl group is 8 or more and the ammonium salt is developed outside the polymer. And a method of manufacturing the same.

The inventor paid attention to the effect of the carbon number between the phenyl group of polystyrene and the nitrogen atom of the quaternary ammonium salt on the reactivity, and increased the various olefins when the carbon number is more than a certain number. It has been found that it can be a phase transfer catalyst that can be epoxidized with high efficiency and selectivity.

Here, as the number of carbons between the phenyl group of polystyrene and the nitrogen atom of the quaternary ammonium salt, based on the knowledge of the quaternary ammonium salt highly active in the epoxidation reaction so far, the number of carbons is 8 or more apart. A bound quaternary ammonium salt (long-chain immobilized quaternary ammonium salt) was designed.

In the present invention, as part of the method for synthesizing the long-chain immobilized quaternary ammonium salt described above, a carboxylic acid (carboxyl-substituted quaternary ammonium salt) having a novel quaternary ammonium salt as a precursor was designed and synthesized.

The present invention has been developed by developing a method for producing an epoxy compound using a quaternary ammonium salt which is a carboxyl-substituted quaternary ammonium salt as a precursor and immobilized on a polymer using a Friedel-Crafts acylation reaction in polystyrene as a phase transfer catalyst. It came to be completed.

The long-chain immobilized quaternary ammonium hydrogensulfate according to the present invention for solving the above problems is represented by the general formula (1).

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示す。）

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer having 1 to 8 carbon atoms.)

  According to the present invention, it is possible to provide a long-chain-type immobilized quaternary ammonium hydrogen sulfate that can be used as a catalyst when performing an epoxidation reaction with high efficiency and high selectivity and that can be easily recovered and reused.

The long-chain immobilized quaternary ammonium halide according to the present invention for solving the above problems is represented by the general formula (2).

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

  According to the present invention, it is possible to provide a long-chain-type immobilized quaternary ammonium halide that can be used as a catalyst when performing an epoxidation reaction with high efficiency and high selectivity under weakly acidic conditions, and can be easily recovered and reused. It is.

The carboxyl-substituted quaternary ammonium salt according to the present invention for solving the above problems is represented by the general formula (3).

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

  According to the present invention, it is useful as a raw material for a long-chain immobilized quaternary ammonium salt that can be used as a catalyst for epoxidation reaction with high efficiency and high selectivity, and can be easily recovered and reused. In addition, a carboxyl-substituted quaternary ammonium salt useful as a surfactant having a carboxylic acid at the terminal and high hydrophilicity can be provided.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。） In order to solve the above problems, a method for producing a long-chain-type immobilized quaternary ammonium hydrogen sulfate represented by the general formula (1) according to the present invention comprises It is characterized by isolating and purifying a quaternary ammonium halide and reacting with sulfuric acid.

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示す。）

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer having 1 to 8 carbon atoms.)

  According to this invention, a long-chain type immobilized quaternary ammonium hydrogensulfate can be synthesized from a long-chain type immobilized quaternary ammonium halide with high efficiency and safety.

In order to solve the above-mentioned problems, a method for producing a long-chain immobilized quaternary ammonium halide represented by the general formula (2) according to the present invention comprises a carboxyl-substituted quaternary ammonium salt and polystyrene by a Friedel-Crafts reaction. It is made to react.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

  According to this invention, a long-chain type immobilized quaternary ammonium halide can be synthesized from a carboxyl-substituted quaternary ammonium salt with high efficiency and safety.

The method for producing a carboxyl-substituted quaternary ammonium salt represented by the general formula (3) according to the present invention for solving the above problems is represented by the ester represented by the general formula (4) and the general formula (5). It is characterized in that it is reacted with an amine, and the ester is converted into a carboxylate with sodium hydroxide and further converted into a carboxylic acid with hydrochloric acid.

（式中、Ｒ⁴はメチル基、エチル基またはプロピル基から選ばれるアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(In the formula, R ⁴ represents an alkyl group selected from a methyl group, an ethyl group, or a propyl group, n represents an integer of 1 to 8 carbon atoms, and X represents chlorine or bromine.)

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示す。）

(Wherein, R ^1, R ² and R ³ represents an alkyl group having 1 to 12 carbon atoms independently.)

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

  According to this invention, a carboxyl-substituted quaternary ammonium salt can be synthesized with high yield and safety from a commercially available amine and ester derivative.

A catalyst for epoxidation reaction of an olefin for solving the above-mentioned problems uses the general formula (1 ) .

Thereby, it can use suitably as a phase transfer catalyst with respect to the reaction of the two-phase system which requires various phase transfers, especially the epoxidation reaction in a two-phase system.

  In the polymer in which the quaternary ammonium salt according to the present invention is immobilized, the number of carbon atoms between the quaternary ammonium salt and the phenyl group is 8 or more, and the ammonium salt spreads outside the polymer. It is a very useful catalyst for the epoxidation reaction using hydrogen peroxide as an oxidizing agent, and the catalyst can be easily recovered and reused during the production of the epoxy compound.

  In the method for producing a polymer in which a quaternary ammonium salt is immobilized according to the present invention, the synthetic route using an amine as a starting material does not require an operation technique, and various amines can be easily applied. This is also effective in increasing the variation of the polymer in which the quaternary ammonium salt is immobilized.

  Hereinafter, the polymer containing the immobilized quaternary ammonium salt according to the present invention and the production method thereof will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

[Long-chain immobilized quaternary ammonium hydrogen sulfate according to the present invention]
The long chain-type immobilized quaternary ammonium hydrogen sulfate according to the present invention is a polymer containing a quaternary ammonium salt linked by a carbon chain having 8 or more carbon atoms immobilized on polystyrene.

Specifically, a long-chain type immobilized quaternary ammonium hydrogensulfate linked with a carbon chain having 8 or more carbon atoms immobilized on polystyrene represented by the general formulas (1) and (2) is provided. Can be mentioned.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示す。）

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer having 1 to 8 carbon atoms.)

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

[Carboxyl-substituted quaternary ammonium salt according to the present invention]
In the synthesis route of the long-chain immobilized quaternary ammonium bisulfate according to the present invention, a carboxyl-substituted quaternary ammonium salt is required on the way. Here, as a suitable carboxylic acid, for example, a carboxyl substitution in which the N atom represented by the general formula (3) and the carbonyl substituent are connected by a carbon chain having 8 or more carbon atoms including the carbonyl group. A quaternary ammonium salt is mentioned.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

The alkyl groups of R ¹ , R ² and R ³ are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl. Among them, a group having 8 to 12 carbon atoms is preferable because it has high reaction activity as a catalyst and is easily available. n is an integer of 1 to 8 carbon atoms, preferably an integer of 1 to 4. If it is within this range, the activity as a catalyst is high and the raw material is easily available. X represents bromine or chlorine, and chlorine is particularly preferred from the viewpoint of high activity as a catalyst and availability.

[Method for producing long-chain immobilized quaternary ammonium hydrogen sulfate]
A method for producing the long-chain immobilized quaternary ammonium hydrogen sulfate represented by the general formula (1) is as follows.

Sulfuric acid is allowed to act on the long-chain immobilized quaternary ammonium halide represented by the general formula (2). This reaction is preferably carried out in the presence of a reaction solvent. Although the reaction solvent in this case is not particularly limited, for example, an organic solvent such as benzene and toluene can be preferably used. These solvents can be used alone or in the form of a mixed solvent, if necessary.

The sulfuric acid used in this reaction is in the range of 1% to 100% by weight, preferably 30% to 60% by weight. When the sulfuric acid is within this range, it is preferable because highly efficient and reliable conversion from a halide to a hydrogen sulfate can be achieved.

The reaction temperature is in the range of 0 ° C to 100 ° C, preferably in the range of 20 ° C to 50 ° C. When the reaction temperature is within this range, the reaction proceeds promptly, and the ejection of the reaction solution and abnormal temperature increase can be suppressed, which is preferable from the viewpoint of safety during production.

Since the reaction time may be affected by the reaction temperature, it is difficult to determine it generally, but it is usually 4 to 12 hours.

Since this reaction is an anion species exchange reaction, the conversion rate is generally improved by repeating the above operation. In this case, it can be converted to hydrogen sulfate with higher efficiency by repeating the above operation 2 to 3 times.

The long-chain immobilized quaternary ammonium hydrogen sulfate thus produced is separated from the reaction solution after completion of the reaction, and is washed with an organic solvent such as acetone and then with water to remove excess adhering to the polymer. After removing the salt and organic solvent, it can be used for a useful application such as a catalyst by drying under reduced pressure.

[Method for producing long-chain immobilized quaternary ammonium halide]
The production method of the long-chain immobilized quaternary ammonium halide represented by the general formula (2) is as follows.

After carrying out a reaction for converting the carboxyl-substituted quaternary ammonium salt represented by the general formula (3) into the acid halide represented by the general formula (6), the Friedel-Crafts acylation reaction is carried out in the presence of a Lewis acid catalyst. By doing so, a long-chain type immobilized quaternary ammonium halide is synthesized.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示し、ｎは炭素数１〜８の整数を示し、Ｘは塩素又は臭素を示す。）

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

  An acid halide containing a quaternary ammonium salt represented by the general formula (6) is a chlorinating agent such as a carboxyl-substituted quaternary ammonium salt represented by the general formula (3) and oxalyl chloride represented by the general formula (7). Is synthesized.

This reaction is preferably carried out in the presence of an organic solvent. Although the reaction solvent in this case is not particularly limited, for example, a halogen-based organic solvent such as dichloromethane can be preferably used. These solvents can be used alone or in the form of a mixed solvent, if necessary. Moreover, although reaction advances immediately, Preferably it stirs at 10-40 degreeC for 1 to 5 hours.

The carboxylic acid halide containing the quaternary ammonium salt represented by the general formula (6) thus obtained is bonded to polystyrene by Friedel-Crafts acylation reaction.

  This reaction is preferably carried out in the presence of an organic solvent. Although the reaction solvent in this case is not particularly limited, for example, an organic solvent such as dichloromethane or dioxane can be preferably used. These solvents can be used alone or in the form of a mixed solvent, if necessary.

The catalyst used in this reaction is a Lewis acid, and for example, aluminum chloride is preferably used. The amount used is in the range of 1 to 100% by weight, preferably 5 to 40% by weight, based on the carboxylic acid halide containing the quaternary ammonium salt represented by the general formula (6) as the substrate. It is a range. When the amount used is within this range, the reaction proceeds rapidly and the reaction runaway is suppressed, so that the reaction can be performed reliably.

The reaction temperature is in the range of −10 ° C. to 100 ° C., preferably in the range of 0 ° C. to 40 ° C. When the reaction temperature is within this range, the reaction proceeds rapidly and the runaway reaction is suppressed, so that the reaction can be performed reliably.

Since the reaction time may be affected by the reaction temperature, it is difficult to determine it generally, but it is usually 12 to 24 hours.

The desired long chain type immobilized quaternary ammonium halide thus produced is separated from the reaction solution after the completion of the reaction, taken out, washed with water and an organic solvent, and free quaternary ammonium salt not supported on polystyrene. Is used after drying under reduced pressure.

[Method for producing carboxyl-substituted quaternary ammonium salt]
The production method of the carboxyl-substituted quaternary ammonium salt represented by the general formula (3) is as follows.

The halogen-substituted ester represented by the general formula (4) is allowed to act on the tertiary amine represented by the general formula (5) to produce an ester containing a quaternary ammonium salt. A carboxylic acid containing a quaternary ammonium salt is produced by converting to a carboxylate and further reacting with hydrochloric acid.

（式中、Ｒ⁴はメチル基、エチル基またはプロピル基から選ばれるアルキル基を示し、Ｘは塩素又は臭素を示す。）

(In the formula, R ⁴ represents an alkyl group selected from a methyl group, an ethyl group or a propyl group, and X represents chlorine or bromine.)

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に炭素数１〜１２のアルキル基を示す。）

(Wherein, R ^1, R ² and R ³ represents an alkyl group having 1 to 12 carbon atoms independently.)

  This reaction is preferably carried out in the presence of an organic solvent. Although the reaction solvent in this case is not particularly limited, for example, an organic solvent such as acetonitrile or dioxane can be preferably used. These solvents can be used alone or in the form of a mixed solvent, if necessary.

The reaction temperature is in the range of 10 ° C to 150 ° C, preferably in the range of 80 ° C to 120 ° C during the synthesis of the ester-substituted quaternary ammonium salt. Within this range, the reaction proceeds rapidly and the runaway reaction is suppressed, so that the reaction can be performed reliably.

When synthesizing the carboxyl-substituted quaternary ammonium salt, the temperature is in the range of 10 ° C to 100 ° C, preferably in the range of 20 ° C to 50 ° C. Within this range, the reaction proceeds rapidly and the runaway reaction is suppressed, so that the reaction can be performed reliably.

Since the reaction time may be affected by the reaction temperature, it is difficult to determine it generally, but it is usually 12 to 24 hours during the synthesis of the ester-substituted quaternary ammonium salt. In addition, it takes 2 to 5 hours during the synthesis of the carboxyl-substituted quaternary ammonium salt.

The carboxyl-substituted quaternary ammonium salt thus produced is separated from the reaction solution after completion of the reaction, washed with water and an organic solvent, and then dried under reduced pressure.

[Specific examples of long-chain immobilized quaternary ammonium hydrogen sulfate]
Specific examples of the long-chain immobilized quaternary ammonium hydrogen sulfate according to the present invention include compounds represented by the following chemical formulas (8) and (9), but the compounds are not limited to these compounds. Absent.

[Specific examples of long-chain immobilized quaternary ammonium halides]
Specific examples of the long-chain immobilized quaternary ammonium halide of the present invention include compounds represented by the following chemical formulas (10) and (11), but are not limited to these compounds.

[Specific examples of carboxyl-substituted quaternary ammonium salts]
Specific examples of the carboxyl-substituted quaternary ammonium salt of the present invention include compounds represented by the following chemical formulas (12) and (13), but are not limited to these compounds.

[Particle size of polystyrene]
The particle size of polystyrene constituting the long-chain immobilized quaternary ammonium salt according to the present invention is considered in terms of the ease of catalyst preparation, activity as a phase transfer catalyst, and separation and recovery from the reaction system. Then, 50-8000 micrometers, Preferably 100-3000 micrometers is preferable.

[Pore volume / pore diameter]
In general, the pore volume and pore diameter of polystyrene are such that if the pore diameter is small and the pore volume is large, the surface area becomes large and the efficiency per unit volume can be increased. Difficult to diffuse, causing efficiency to drop. However, the catalyst according to the present invention takes a certain distance from the pores of polystyrene and exhibits a behavior similar to that of a homogeneous catalyst, and therefore does not depend much on the pore area and the pore diameter. If it is in the range of the pore volume generally used, there is no problem, for example, in the range of 0.1 to 1.0 ml / g in the dry resin.

[Usage]
The compound according to the present invention can be used in various applications, and the scope thereof is not limited. A quaternary ammonium salt catalyst immobilized on polystyrene, which can be used as a phase transfer catalyst that can selectively epoxidize various olefins including terminal olefins with high efficiency and high selectivity, and can be easily separated from the target product. For example, it can be suitably used as a phase transfer catalyst for a two-phase reaction requiring various phase transfers, particularly an epoxidation reaction in a two-phase system. Further, the catalyst can be easily recovered and reused in the process of producing the epoxy compound.

  The present invention will be described more specifically by the following experimental examples. In addition, this invention is not limited to description of the following experiment examples, unless the summary is exceeded.

[Example 1: Production of ester-substituted methyl dioctyl ammonium salt]
To a 100 ml one-necked flask equipped with a stirrer and a Dimroth condenser, methyl 8-bromooctanoate (2.52 g, 10.0 mmol) and 26 ml of acetonitrile as a solvent were added, and methyl dioctylamine (2.56 g, 10.0 mmol) was added thereto. ) And heated for 19 hours. After ice cooling, the mixture was added to 30 ml of 1N hydrochloric acid and stirred for 10 minutes. Dichloromethane was added to the resulting mixture for extraction, dried over sodium sulfate, and then the product was separated and produced by column chromatography (methanol: chloroform = 1: 20) to obtain the desired 7- (carboxymethyl). 2.74 g of butyl dioctylmethylammonium bromide was obtained with an isolated yield of 54%.

[Example 2: Production of carboxyl-substituted methyl dioctyl ammonium salt]
To a 100 ml one-necked flask equipped with a stir bar and a Dimroth condenser, 7- (carboxymethyl) heptyldioctylmethylammonium bromide (2.74 g, 5.40 mmol), THF 19 ml, water 6 ml, and lithium hydroxide monohydrate ( 453 mg, 10.8 mmol) was added and stirred for 3 hours. Thereafter, 30 ml of 1N hydrochloric acid was added and the mixture was further stirred for 10 minutes. Dichloromethane was added to the resulting mixture for extraction, dried over sodium sulfate, and concentrated to obtain 1.80 g of the desired 7-carboxyheptyldioctylmethylammonium bromide in 71% isolated yield. .

[Example 3: Production of long-chain immobilized methyl dioctyl ammonium chloride (methyl dioctyl L8PS-QCl)]
To a 100 ml one-necked flask equipped with a stir bar and a calcium chloride tube, 7-carboxyheptyldioctylmethylammonium bromide (1.80 g, 3.76 mmol), dichloromethane 20 ml and oxalyl chloride 1.84 ml were added and stirred at room temperature for 1 hour. To a two-necked flask equipped with a stirrer, aluminum chloride (606 mg, 4.54 mmol) and 8 ml of dichloromethane were added and cooled to 0 ° C., and then the previously prepared mixture was added and stirred at 0 ° C. for 30 minutes. A polystyrene resin (manufactured by Tokyo Chemical Industry Co., Ltd., P1432, 438 mg) was added thereto and stirred at room temperature for 24 hours. The obtained solid was washed in turn with water, THF, and dichloromethane to obtain 613 mg of the desired long-chain immobilized methyl dioctyl ammonium chloride (methyl dioctyl L8PS-QCl). As a result of elemental analysis,
C, 79.3%, H, 9.51%, N, 1.45% (theoretical values: C, 79.5%, H, 9.25%, N, 1.43%) As a result, it was confirmed that polystyrene having 1 unit of quaternary ammonium salt bonded thereto per 4 units of styrene was synthesized.

[Example 4: Production of long-chain immobilized methyl dioctyl ammonium hydrogen sulfate (methyl dioctyl L8PS-QHSO ₄ )]
Methyldioctyl L8PS-QCl (500 mg, 0.52 mmol), 4 ml of toluene and 4 ml of 45% sulfuric acid were added to a 100 ml one-necked flask equipped with a stir bar and a calcium chloride tube, and stirred at room temperature for 12 hours. Toluene and suspended methyldioctyl L8PS-QCl were extracted, 4 ml of 45% sulfuric acid was added again, and the mixture was stirred at room temperature for 12 hours. Removed methyl dioctyl L8PS-QCl, toluene, washed successively with water, was subjected to vacuum drying, long-chain immobilized methylated dioctyl ammonium hydrogen sulfate (methyl dioctyl L8PS-QHSO ₄₎ was obtained 413mg of interest . As a result of elemental analysis,
C, 70.7%, H, 9.90%, N, 1.95%, S, 4.63% (theoretical value: C, 71.6%, H, 10.1%, N, 2.04) %, S, 4.66%), and it was confirmed that an immobilized quaternary ammonium hydrogen sulfate was synthesized as expected.

[Example 5: Epoxidation reaction of 1-octene using long-chain immobilized methyl dioctyl ammonium hydrogen sulfate (methyl dioctyl L8PS-QHSO ₄ )]
In a test tube equipped with a magnetic stir bar, sodium tungstate dihydrate (6.6 mg, 0.02 mmol), methyl dioctyl L8PS-QHSO ₄ (10.6 mg, 0.01 mmol), aminomethylphosphonic acid (1.1 mg, 0.01 mmol), 35% aqueous hydrogen peroxide solution (155 μL, 1.5 mmol) and 98% sulfuric acid (1.0 mg, 0.01 mmol) were added and stirred for 15 minutes. After the temperature was adjusted to 90 ° C., 1-octene (112 mg 1.0 mmol) was added, and the mixture was reacted at a stirring speed of 1000 rpm for 4 hours. When the organic layer separated from the aqueous layer was analyzed with a gas chromatograph, the conversion of 1-octene was 61%, the yield of 1,2-epoxyoctane was 61%, and the selectivity of 1,2-epoxyoctane was 99%. That was confirmed.

[Comparative Example 1: Epoxidation reaction of 1-octene using immobilized quaternary ammonium salt]
Sodium tungstate dihydrate (6.6 mg, 0.02 mmol) in a test tube equipped with a magnetic stir bar, methyl dioctyl ammonium synthesized in the same manner as in Japanese Patent Application Laid-Open Nos. 2008-94899 and 2008-94916 Immobilized quaternary ammonium salt with immobilized salt (7.6 mg, 0.01 mmol), aminomethylphosphonic acid (1.1 mg, 0.01 mmol), 35% aqueous hydrogen peroxide (155 μL, 1.5 mmol), 98% Sulfuric acid (1.0 mg, 0.01 mmol) was added and stirred for 15 minutes. After the temperature was adjusted to 90 ° C., 1-octene (112 mg, 1.0 mmol) was added, and the mixture was reacted at a stirring speed of 1000 rpm for 2 hours. When the organic layer separated from the aqueous layer was analyzed with a gas chromatograph, the conversion of 1-octene was 75%, the yield of 1,2-epoxyoctane was 55%, and the selectivity of 1,2-epoxyoctane was 73%. It was confirmed that.

[Example 6: Production of ester-substituted methyl dibutylammonium salt]
To a 100 ml one-necked flask equipped with a stirrer and a Dimroth condenser, methyl 8-bromooctanoate (2.52 g, 10.0 mmol) and 26 ml of acetonitrile as a solvent were added, and methyldibutylamine (1.44 g, 10.0 mol) was added thereto. ) And heated for 19 hours. After ice cooling, the mixture was added to 30 ml of 1N hydrochloric acid and stirred for 10 minutes. The resulting mixture was extracted by adding dichloromethane, dried over sodium sulfate, and then separated by column chromatography (methanol: chloroform = 1: 50) to produce the desired 7- (carboxymethyl). Thus, 2.23 g of butyl dibutylmethylammonium bromide was obtained with an isolated yield of 59%.

[Example 7: Synthesis of carboxyl-substituted methyldibutylammonium salt]
To a 100 ml one-necked flask equipped with a stir bar and Dimroth condenser, 7- (carboxymethyl) heptyldibutylmethylammonium bromide (2.23 g, 5.89 mmol), 21 ml THF, 7 ml water, and lithium hydroxide monohydrate ( (495 mg, 11.8 mmol) was added, and the mixture was stirred for 3 hours. Thereafter, 30 ml of 1N hydrochloric acid was added and the mixture was further stirred for 10 minutes. Dichloromethane was added to the resulting mixture for extraction, dried over sodium sulfate, and concentrated to obtain 1.24 g of the intended 7-carboxyheptyldibutylmethylammonium bromide in an isolated yield of 57%. .

[Example 8: Production of long-chain immobilized methyldibutylammonium chloride (methyldibutyl L8PS-QCl)]
To a 100 ml one-necked flask equipped with a stir bar and a Dimroth condenser, 7-carboxyheptyldibutylmethylammonium bromide (1.24 g, 3.38 mmol), 18 ml of dichloromethane and 1.45 ml of oxalyl chloride were added and stirred at room temperature for 1 hour. To a two-necked flask equipped with a stirrer, aluminum chloride (533 mg, 4.00 mmol) and 7 ml of dichloromethane were added and cooled to 0 ° C., and then the previously prepared mixture was added and stirred at 0 ° C. for 30 minutes. A polystyrene resin (manufactured by Tokyo Chemical Industry Co., Ltd., P1432, 357 mg) was added thereto and stirred at room temperature for 24 hours. The obtained solid was washed in turn with water, THF, and dichloromethane to obtain 413 mg of the desired long-chain immobilized methyldibutylammonium chloride (methyldibutyl L8PS-QCl). As a result of elemental analysis,
C, 84.8%, H, 8.13%, N, 0.82% (theoretical value: C, 85.9%, H, 8.69%, N, 1.14%) As a result, it was confirmed that polystyrene having 1 unit of quaternary ammonium salt bonded to 9 units of styrene was synthesized.

Example 9: Production of long-chain immobilized methylated dibutyl ammonium hydrogen sulfate (Mechirujibuchiru L8PS-QHSO _4)]
Methyldibutyl L8PS-QCl (500 mg, 0.29 mmol), 4 ml of toluene and 4 ml of 45% sulfuric acid were added to a 100 ml one-necked flask equipped with a stir bar and a calcium chloride tube, and stirred at room temperature for 12 hours. After extracting toluene and suspended methyldibutyl L8PS-QCl, 4 ml of 45% sulfuric acid was added again and stirred at room temperature for 12 hours. Removed Mechirujibuchiru L8PS-QCl, acetone, washed successively with water, was subjected to vacuum drying, long-chain immobilized methylated dibutyl ammonium hydrogen sulfate (Mechirujibuchiru L8PS-QHSO ₄₎ was obtained 323mg of interest . As a result of elemental analysis,
C, 83.0%, H, 7.87%, N, 0.84%, S, 1.41% (theoretical value: C, 83.9%, H, 8.24%, N, 0.87) %, S, 2.00%), and it was confirmed that an immobilized quaternary ammonium hydrogensulfate was synthesized as expected.

Claims (6)

A long-chain-type immobilized quaternary ammonium hydrogen sulfate represented by the general formula (1).

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer having 1 to 8 carbon atoms.) A long-chain immobilized quaternary ammonium halide represented by the general formula (2).

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.) A long-chain immobilized quaternary quaternary represented by the general formula (1), wherein the long-chain immobilized quaternary ammonium halide represented by the general formula (2) is isolated and purified and reacted with sulfuric acid. A method for producing ammonium hydrogen sulfate.

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.)

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer having 1 to 8 carbon atoms.) A process for producing a long-chain immobilized quaternary ammonium halide represented by the general formula (2), wherein a carboxyl-substituted quaternary ammonium salt and polystyrene are reacted by a Friedel-Crafts reaction .

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.) A general feature of reacting an ester represented by the general formula (4) with an amine represented by the general formula (5), converting the ester into a carboxylate with sodium hydroxide and further converting into a carboxylic acid with hydrochloric acid. A method for producing a carboxyl-substituted quaternary ammonium salt represented by formula (3).

(In the formula, R ⁴ represents an alkyl group selected from a methyl group, an ethyl group, or a propyl group, n represents an integer of 1 to 8 carbon atoms, and X represents chlorine or bromine.)

(Wherein, R ^1, R ² and R ³ represents an alkyl group having 1 to 12 carbon atoms independently.)

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 12 carbon atoms, n represents an integer having 1 to 8 carbon atoms, and X represents chlorine or bromine.) A catalyst for epoxidation reaction of an olefin using the compound according to claim 1.