JPH1129562A - Production of 3-chloromethyl-3-alkyloxetane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method producing 3-chloromethyl-3-alkyloxetane in a short reaction time and in excellent yield. SOLUTION: In the process producing 3-chloromethyl-3-alkyloxetane by carrying out the dehydrochlorination or decoxychlorination reaction of 1,1-bis(chloromethyl)-1-hydroxymethylalkane or their carboxylic acid ester, the reaction is carried out in an aqueous solution or aqueous suspension of an alkaline compound in the presence of an aniontc ton exchange resin having ammonium group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a 3-chloromethyl-3-alkyloxetane (hereinafter referred to as "OXC").
OXC is useful as an intermediate material of an oxetane compound which is a monomer capable of ring-opening polymerization.

[0002]

2. Description of the Related Art As a method for producing OXC, 1,1 or 1 in an alcohol solvent diluted with alcohol or water is used.
After reacting bis (chloromethyl) -1-hydroxymethylpropane or its acetate with potassium hydroxide, the precipitated inorganic salt was removed by filtration, the solvent was distilled off, and further distilled under reduced pressure. To obtain 3-chloromethyl-3-ethyloxetane, or after the above reaction, adding water to dissolve the inorganic salt, and extracting with an organic solvent,
A method of obtaining 3-chloromethyl-3-ethyloxetane by distillation under reduced pressure after distilling off the organic solvent by distillation (Japanese Patent Publication No.
No. 10342) is known. However, these methods require a step of filtering off an inorganic salt or extracting with an organic solvent in order to obtain a target substance.In addition, in order to recover and reuse the alcohol as a reaction solvent, the reaction is carried out. The present inventors have found that a step of removing generated water to some extent is necessary, and from these points, it has not reached an industrially satisfactory level.

Accordingly, the present inventors have proposed a method for producing OXC having a short reaction time and high yield by dehydrochlorination of 1,1-bis (chloromethyl) -1-hydroxymethylalkane or its carboxylic acid ester. It has been proposed to carry out the reaction or deacidification reaction in an aqueous solution or suspension of an alkaline compound in the presence of a phase transfer catalyst. The catalyst is recovered and dissolved
It was found that there was room for improvement upon reuse.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to produce OXC with a short reaction time and a high yield, and to easily recover and reuse the catalyst to be used. It is to provide a method.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that 1,1-bis (chloromethyl) -1-hydroxymethylalkane or a carboxylic acid ester thereof can be obtained. By performing the dehydrochlorination reaction or deacidification reaction in an aqueous solution or suspension of an alkaline compound in the presence of an anion exchange resin having an ammonium group, the reaction time is short and the yield is high.
It has been found that C can be produced and that the anion exchange resin to be used can be easily recovered and reused, and the present invention has been completed. That is, the present invention produces 3-chloromethyl-3-alkyloxetane by subjecting 1,1-bis (chloromethyl) -1-hydroxymethylalkane or its carboxylic acid ester to a dehydrochlorination reaction or a deacidification reaction. Wherein the reaction is performed in an aqueous solution or suspension of an alkaline compound in the presence of an anion exchange resin having an ammonium group. is there.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The 1,1-bis (chloromethyl) -1-hydroxymethylalkane of the present invention can be obtained by chlorinating various trimethylolalkanes with hydrogen chloride or the like. Due to the availability and industrial handling, 1,1-bis (chloromethyl) -1-hydroxymethylethane and 1,1
-Bis (chloromethyl) -1-hydroxymethylpropane is preferred. Also, 1,1-bis (chloromethyl)-
Carboxylic acid esters of 1-hydroxymethylalkane,
For example, esters with acetic acid, propionic acid, butyric acid, benzoic acid and the like can be used as a raw material. Among them, esters of acetic acid and propionic acid are preferable from the viewpoint of easy availability and industrial handling.

The aqueous solution or aqueous suspension of an alkaline compound in the present invention is obtained by dissolving or suspending an alkali metal hydroxide or the like in water. Examples of the alkaline compound used include sodium hydroxide, potassium hydroxide, and the like. Examples thereof include lithium hydroxide, calcium hydroxide, sodium carbonate, and sodium hydrogencarbonate. Of these, sodium hydroxide and potassium hydroxide are preferable because a sufficient conversion can be obtained in a short time. When 1,1-bis (chloromethyl) -1-hydroxymethylalkane is used as a raw material, the alkali is preferably used in an amount of 1 to 2 mol per 1 mol of the raw material. When using, raw material 1
It is preferred to use 2 to 3 moles per mole. The concentration of the alkali in the aqueous solution or suspension of the alkali is preferably 1 to 60% by weight, more preferably 5 to 25% by weight.
% By weight.

The anion exchange resin having an ammonium group according to the present invention is an anion exchange resin which is insoluble in an aqueous solution or aqueous suspension of the above-mentioned alkaline compound and 1,1-bis (chloromethyl) -1-hydroxymethylalkane as a raw material. If it is, it is not particularly limited, but examples thereof include Amberlyst A-26 manufactured by Organo Corporation and Diaion PA-306 manufactured by Mitsubishi Chemical Corporation, which are polystyrene resins having an ammonium group.

The amount of the anion exchange resin used is not limited at all, and can be arbitrarily selected depending on the kind of the raw material, the reaction temperature and the reaction system. Is an anion exchange resin with respect to 1,1-bis (chloromethyl) -1-hydroxymethylalkane or a carboxylic acid ester thereof, which is 0.01%.
Preferably, it is used in an amount of at least% by weight. Further, the anion exchange resin used in the reaction can be separated and recovered from the reaction solution by an easy operation such as filtration, and can be reused without a special purification step.

The reaction in the present invention can be carried out not only under normal pressure but also under reduced pressure and increased pressure. The reaction temperature is preferably in the range of 40 to 110 ° C, more preferably 60 to 100 ° C. If the reaction temperature is higher than 110 ° C., the production of by-products may increase and the yield may decrease. On the other hand, if the reaction temperature is lower than 40 ° C., the reaction rate becomes slow, and a sufficient raw material conversion rate can be obtained. There is a risk of disappearing. The reaction time is determined by the starting materials used, the reaction temperature, and the reaction form described below.However, the reaction time is determined in consideration of the conversion rate in the reaction while tracking the reaction materials by gas chromatography or the like. do it.

The above reaction can be carried out in any of a batch system, a semi-batch system and a continuous system. Specific examples of these reaction systems are described below, but are not limited to these systems.

1) Batch type 1,1-bis (chloromethyl) -1-hydroxymethylalkane or a carboxylic acid ester thereof, an aqueous solution or suspension of an alkaline compound and an anion exchange resin having an ammonium group are placed in a reactor. The reaction is carried out while charging and heating and stirring. After completion of the reaction, the anion exchange resin is removed by a method such as filtration, and then separated into an organic phase and an inorganic phase.
In this method, an inert solvent insoluble in water may be used, and examples of the inert solvent include toluene, xylene, hexane, chlorobenzene, methyl-t-butyl ether, and methyl isobutyl ketone.

An aqueous or aqueous suspension of 1,1-bis (chloromethyl) -1-hydroxymethylalkane or a carboxylic acid ester thereof, an alkaline compound and an anion exchange resin having an ammonium group are charged into a reactor, and heated and stirred. Then, while distilling OXC to be produced together with water, the reaction is allowed to proceed until OXC is no longer distilled. The distillate is cooled and separated into an organic phase and an aqueous phase. The separated aqueous phase can be reused.

2) Continuous type 1,1-from the top of the reaction tower filled with an anion exchange resin
An aqueous solution or aqueous suspension of bis (chloromethyl) -1-hydroxymethylalkane or a carboxylic acid ester thereof and an alkaline compound is supplied, the reaction is carried out under heating, and the reaction solution flowing out from the lower part of the column is separated into an organic phase and water. Separate into phases.

[0015] Further, utilizing the method of the above 1), a semi-batch system in which any of the raw materials is continuously supplied, or both raw materials and the anion exchange resin are continuously supplied, and the inorganic salt is supplied from the reactor. It can also be carried out as a continuous system in which an aqueous solution or suspension of an alkaline compound containing an anion exchange resin is withdrawn at a fixed ratio. Further, after reacting to some extent by the method of 1), the method of 1) may be combined. The anion exchange resin used for the reaction was
After separation by filtration or the like, it can be used again for the reaction.

From the organic phase composed of OXC obtained by the above-mentioned reaction, distillation operation, which is a general separation method, is used.
OXC of high purity can be obtained.

[0017]

The present invention will be described below in detail with reference to examples.

Example 1 51 g of 1,1-bis (chloromethyl) -1-hydroxymethylpropane (0.3 mol, hereinafter referred to as "BCP"), 75 g of a 20% by weight aqueous solution of NaOH (NaOH)
0.38 mol) and 40 g of Amberlyst A-26 (anion exchange resin) manufactured by Organo Co., Ltd.
Charge into a 0 ml glass reactor and stir while stirring.
The mixture was heated to 0 ° C. and reacted for 8 hours. After the reaction is over, 1
After adding 00 ml of methylene chloride and filtering the ion exchange resin, it was separated into an organic phase and an aqueous phase.

The contents of 3-chloromethyl-3-ethyloxetane (hereinafter referred to as "EOXC") and BCP in the organic phase were quantified by gas chromatography analysis, and the BCP conversion and the EOXC selectivity were determined. Table 1 shows the results. The BCP conversion and EOXC selectivity were calculated by the following equations. All percentages in the following formula are on a molar basis. BCP conversion (%) = (1−unreacted BCP ÷ prepared BC)
P) × 100 EOXC selectivity (%) = EOXC generated (BCP charged)
-Unreacted BCP) x 100

Example 2 After collecting the anion exchange resin used in Example 1, the reaction was carried out for 8 hours in the same manner as in Example 1 except that the resin was used as it was.
After completion of the reaction, the same analysis as in Example 1 was performed to determine the BCP conversion and the EOXC selectivity. Table 1 shows the results.

Example 3 51 g of BCP (0.30 mol), 180 g of a 10% by weight aqueous solution of NaOH (0.45 mol as NaOH) and 30 g of Amberlyst A-2 manufactured by Organo Corporation
7 (anion exchange resin) was charged into a 500 ml glass reactor, and heated with stirring under normal pressure until distillation was observed. The distillate was cooled by a condenser and captured in a receiver. The reaction was carried out for 3 hours until the distillation of the organic matter disappeared. In addition, the temperature of the reaction liquid changed in 102-105 degreeC. The distillate is separated into an organic phase and an aqueous phase,
5.6 g of an organic phase and 79.1 g of an aqueous phase were obtained. The content of EOXC and BCP in the distilled organic phase and the content of BCP in the liquid remaining in the reactor were analyzed in the same manner as in Example 1 to determine the BCP conversion and the EOXC selectivity. Table 1 shows the results.

Example 4 Example 1 was repeated except that 150 g of a 10% by weight aqueous solution of NaOH (0.38 mol as NaOH) was used and Amberlite IRA-401 manufactured by Organo Corporation was used as an anion exchange resin. The reaction was performed for 8 hours in the same manner as described above. After completion of the reaction, the same analysis as in Example 1 was performed to determine the BCP conversion and the EOXC selectivity. Table 1 shows the results.

Example 5 40 g of an acetate ester of BCP (0.19 mol, hereinafter,
The reaction was carried out for 8 hours in the same manner as in Example 1, except that 95 g of a 20% by weight aqueous NaOH solution (0.48 mol as NaOH) was used as a raw material, and 95 g of a 20% by weight aqueous solution of NaOH was used.
After completion of the reaction, the same analysis as in Example 1 was performed to determine the BCPE conversion and the EOXC selectivity. Table 1 shows the results.

Example 6 Using 47 g of 1,1-bis (chloromethyl) -1-hydroxymethylethane (0.3 mol, hereinafter referred to as “BCE”) as a raw material, 150 g of a 10% by weight aqueous solution of NaOH ( Except for using 0.38 mol of NaOH)
The reaction was carried out for 8 hours in the same manner as in Example 1. After completion of the reaction, the same analysis as in Example 1 was performed, and 3-chloromethyl-3-methyloxetane (hereinafter, referred to as “MOXC”) and BCE as a raw material were quantified, and the BCE conversion and the MOXC selectivity were determined. Table 1 shows the results.

Comparative Example 1 The reaction was carried out for 8 hours in the same manner as in Example 1 except that no anion exchange resin was used. After completion of the reaction, the same analysis as in Example 1 was performed to determine the BCP conversion and the EOXC selectivity. Table 1 shows the results.

Comparative Example 2 A reaction was carried out for 3 hours in the same manner as in Example 2 except that no anion exchange resin was used. The temperature of the reaction solution was 102
で 104 ° C. The distillate was separated into an organic phase and an aqueous phase to obtain 32 g of an organic phase and 112 g of an aqueous phase. After completion of the reaction, the same analysis as in Example 1 was performed to determine the BCP conversion and the EOXC selectivity. Table 1 shows the results.

[0027]

[Table 1]

[0028]

According to the present invention, an aqueous solution or aqueous alkali suspension of 1,1-bis (chloromethyl) -1-hydroxymethylalkane and / or a carboxylic acid ester thereof and an alkaline compound is used as a raw material. Methyl-3-alkyloxetane can be produced in a short time and with high yield.

Claims (1)

[Claims] 1. Production of 3-chloromethyl-3-alkyloxetane by subjecting 1,1-bis (chloromethyl) -1-hydroxymethylalkane or a carboxylic acid ester thereof to a dehydrochlorination reaction or a deacidification reaction. A process for producing 3-chloromethyl-3-alkyloxetane, wherein the reaction is carried out in an aqueous solution or suspension of an alkaline compound in the presence of an anion exchange resin having an ammonium group.