JPH10195067A - Production of 4-hydroxymethyl-1,3-dioxolane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a raw material for surfactant, etc., without necessitating the removal of water by distillation causing the increase in cost by reacting hydrated glycerol with a specific carbonyl compound in the presence of an acid catalyst in a reaction solvent having a boiling point lower than a specific level. SOLUTION: The objective compound of the formula II is produced by reacting a hydrated glycerol having a water-content of 1-20wt.% or an aqueous solution of glycerol containing 30-80wt.% of glycerol with a carbonyl compound of the formula I (R<1> and R<2> are each H or a hydrocarbon group) in the presence of an acid catalyst in a reaction solvent having a boiling point of <=150 deg.C and lower than the boiling point of the carbonyl compound. The amount of the carbonyl compound is 1.1-4.0mol based on 1mol of glycerol and that of the acid catalyst is 0.01-5.0wt.% based on glycerol. The reaction temperature is 30-135 deg.C and the reaction system is maintained at a temperature to cause the evaporation and removal of the reaction solvent and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a 4-hydroxymethyl-1,3-dioxolane compound useful as a raw material for producing a glycerin derivative or a surfactant.

[0002]

2. Description of the Related Art A method for producing a 4-hydroxymethyl-1,3-dioxolane compound by a condensation reaction of glycerin and a carbonyl compound in the presence of an acid catalyst is known (Japanese Patent Publication No. 6-15540). JP-A-6-32
1931). This condensation reaction is a reaction that generates condensed water, and it is necessary to remove water from the reaction system in order for the reaction to proceed smoothly. Prior to this, it was considered essential to remove the water in advance. Therefore, in water-containing glycerin, prior to subjecting it to a condensation reaction, dehydration by distillation is repeated to evaporate and remove water contained in glycerin (Japanese Patent Publication No. 6-15540). However, the removal of water from such hydrated glycerin by a special distillation operation requires a large amount of cost, which causes an increase in product cost.

[0003]

The present invention relates to a method for producing a 4-hydroxymethyl-1,3-dioxolane compound by a condensation reaction of glycerin and a carbonyl compound, wherein hydrous glycerin is used as a reaction raw material without dehydration. It is an object of the present invention to provide a method capable of performing such operations.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, according to the present invention, a water-containing glycerin containing 1 to 20% by weight of water or a glycerin aqueous solution containing 30 to 80% by weight of glycerin, and the following general formula (1)

Embedded image (Wherein, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group)
And a reaction solvent having a boiling point of 150 ° C. or lower and having a boiling point lower than the boiling point of the carbonyl compound is heated in the presence of an acid catalyst. Wherein the water contained in is removed together with the reaction solvent by evaporation

Embedded image (Wherein, R ¹ and R ² have the same meanings as described above), and a method for producing a 4-hydroxymethyl-1,3-dioxolane compound represented by the formula: According to the present invention,
Hydrated glycerin containing 1 to 20% by weight of water or 30
A glycerin aqueous solution containing ８０80% by weight of glycerin;
The following general formula

Embedded image (Wherein, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group)
A mixture comprising a carbonyl compound having a boiling point of 150 ° C. or higher represented by the formula: wherein the mixture is heated under reduced pressure in the presence of an acid catalyst, and water contained in the reaction mixture is removed by evaporation. A method for producing a 4-hydroxymethyl-1,3-dioxolane compound represented by the formula: Furthermore, according to the present invention, a glycerin aqueous solution containing 1 to 20% by weight of water or a glycerin aqueous solution containing 30 to 80% by weight of glycerin is represented by the following general formula (1):

Embedded image (Wherein, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group)
A reaction mixture consisting of a carbonyl compound having a boiling point of 150 ° C. or lower represented by
There is provided a method for producing a 4-hydroxymethyl-1,3-dioxolane compound represented by the general formula (2), wherein water contained in the reaction mixture is removed by evaporation.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The carbonyl compound used in the present invention is represented by the above general formula (1). R ¹ and R ² in the general formula (1) may be the same or different and represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group in this case includes
Aliphatic hydrocarbon groups and aromatic hydrocarbon groups are included.
The aliphatic hydrocarbon group includes a chain or cyclic alkyl group. Examples of such an aliphatic hydrocarbon group include an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms. The aromatic hydrocarbon group includes an aryl group and an arylalkyl group. Aryl groups include phenyl, tolyl, naphthyl and the like. Examples of the arylalkyl group include benzyl, phenerti, naphthylmethyl and the like. The carbonyl compound of the general formula (1) includes an aldehyde compound and a ketone compound. Specific examples of the aldehyde compound include, for example, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, capraldehyde, octylaldehyde, cyclohexylaldehyde, benzaldehyde and the like. Examples of the ketone compound include dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone, dipropyl ketone, methyl butyl ketone, ethyl butyl ketone, methyl cyclohexyl ketone, cyclohexanone, acetophenone, benzophenone and the like.

[0006] In the present invention, an acid catalyst is used.
Examples of the acid catalyst include sulfuric acid and organic sulfonic acids such as paratoluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid.

The raw material glycerin used in the present invention is hydrated glycerin containing 1 to 20% by weight, preferably 5 to 20% by weight of water based on the total amount of water and glycerin, or based on the total amount of water and glycerin. And glycerin in 30-8
A glycerin aqueous solution containing 0% by weight, preferably 50 to 80% by weight. Glycerin containing such water is different from highly viscous glycerin containing no water,
The viscosity is greatly reduced, and when the carbonyl compound, the reaction solvent, the catalyst, and the like are added and stirred and mixed, the stirring and mixing are easy. Therefore, by using glycerin containing water as a reaction raw material, uniform mixing of the reaction mixture is facilitated, and an enhanced reaction efficiency can be achieved.

In one method for carrying out the method of the present invention, a reactor is charged with aqueous glycerin or an aqueous glycerin solution, a carbonyl compound, a reaction solvent and an acid catalyst. In this case, the kind of the carbonyl compound is not particularly limited, and any of a low boiling point and a high boiling point can be used. The use ratio of the carbonyl compound is 1.1 to 4.0 mol, preferably 1.5 to 2.0 mol, per 1 mol of glycerin.
5 mole ratio. The use ratio of the acid catalyst is 0.01 to 5.0% by weight, preferably 0.1% by weight, based on glycerin.
~ 3.0 wt%.

As the reaction solvent, any solvent having a boiling point of 150 ° C. or lower, preferably 120 ° C. or lower, more preferably 100 ° C. or lower and inert to the reaction can be used. Hydrogen, dialkyl ether and the like are used. Specific examples include petroleum ether, hexane, pentane, octane, isooctane, toluene,
Examples include benzene and xylene. These can be used alone or in the form of a mixture. The reaction solvent is
Those having a boiling point lower than the boiling point of the carbonyl compound to be used, preferably those having a boiling point lower by about 5 to 20 ° C are used. The amount of the reaction solvent used is 100 to 3000 parts by weight, preferably 200 to 20 parts by weight, per 100 parts by weight of water contained in aqueous glycerin or an aqueous glycerin solution.
The ratio is 00 parts by weight.

The reaction mixture charged in the reactor as described above is heated under stirring. The heating temperature in this case is 30 to 135 ° C., preferably 50 to 110 ° C., but is appropriately determined in relation to the reaction solvent. That is, the mixture is heated to a temperature at which water contained in the reaction mixture is removed by evaporation together with the reaction solvent. As the reaction pressure, normal pressure or reduced pressure is used, and it is appropriately selected so that the heating temperature is within the above-mentioned reaction temperature range. As the reaction device, a device having a structure in which a distillation column is provided on a reaction vessel can be preferably used so that a mixture of water and a reaction solvent is predominantly removed. By the heating operation as described above, water in the reaction mixture is smoothly removed to the outside of the reaction system. As a result, the condensation reaction between glycerin and the carbonyl compound proceeds smoothly. The end point of the reaction is based on the point at which the distillation of water stops. The reaction time mainly depends on the amount of water contained in the aqueous glycerin or the aqueous glycerin solution, but is about 3 to 30 hours.

After the completion of the condensation reaction, an alkaline substance is added to the reaction solution to neutralize the acid catalyst, and the neutralized salt is filtered off.
The 1,3-dioxolane compound is separated and collected.

In another method for carrying out the present invention, a carbonyl compound having a boiling point of 150 ° C. or higher is used, and a reaction mixture containing no reaction solvent or a reaction solvent having a boiling point of 150 ° C. or higher is used. Is heated under reduced pressure to prevent the carbonyl compound contained in the reaction mixture from distilling out of the reaction system, and water is selectively distilled out of the reaction system. The reaction pressure is lower than normal pressure,
At a reaction temperature, the pressure is low enough to evaporate off water in the reaction mixture, and is usually 1 to 300 mmHg, preferably 20 to 200 mmHg. As the heating temperature, a temperature in the range of 30 to 135C, preferably 50 to 110C is selected. When a reaction solvent is used, the use ratio of the reaction solvent is 100 to 3000 parts by weight, preferably 200 to 20 parts by weight, per 100 parts by weight of water contained in the aqueous glycerin or the aqueous glycerin solution as a reaction raw material.
The ratio is 00 parts by weight. By heating under reduced pressure as described above, water in the reaction mixture is smoothly removed to the outside of the reaction system. As a result, the condensation reaction between glycerin and the carbonyl compound proceeds smoothly.

In yet another method for practicing the present invention, the reaction mixture is heated without using a reaction solvent,
The water in the reaction mixture is evaporated off together with the carbonyl compound. In this case, the carbonyl compound used is 150 ° C.
Or less, preferably 130 ° C. or less, more preferably 110 ° C.
It has a boiling point of not more than ° C., and its use amount is such that even if it is evaporated and removed from the reaction system together with water, a sufficient amount required for the reaction remains in the reaction system. Generally, 3 parts per 100 parts by weight of aqueous glycerin or glycerin aqueous solution is used.
The ratio is at least 00 parts by weight, preferably 1000 to 5000 parts by weight. The reaction temperature in this method is 50-17.
0 ° C, preferably 80 to 150 ° C. The reaction pressure is
At the reaction temperature is a pressure at which water in the reaction mixture is smoothly evaporated out of the system together with the carbonyl compound,
Normal or reduced pressure conditions are used. As mentioned above,
Water in the reaction mixture is smoothly removed to the outside of the reaction system, and the condensation reaction between glycerin and the carbonyl compound proceeds smoothly.

[0014]

Next, the present invention will be described in more detail with reference to examples. The products described below were analyzed by gas chromatography using a capillary column having a diameter of 0.32 mm and a length of 5 m (trade name: Ultra 2 manufactured by Hewlett-Packard Company). In this case, the composition ratio of each component was determined by the peak area% of the gas chromatograph of each component. Further, as a sample for gas chromatograph measurement, a sample in which acetic anhydride and pyridine were previously added and reacted by heating to acetylate a hydroxyl group was used.

Example 1 (2-Methyl-2-ethyl-1,3-dioxolan-4)
-Synthesis of ethanol) A 500 ml four-necked flask equipped with a stirrer, a thermometer, a Dean-Stark trap, a reflux condenser and a calcium chloride tube was used as a reactor, and 118 g of glycerin containing 15% by weight of water and methyl ethyl ketone were used. 157.0 g (2.18 mol), sulfuric acid 1 g
(0.2 mmol) and 200 ml of hexane. The mixture was heated and reacted at a temperature of 80 to 85 ° C. for 26 hours while stirring the inside of the flask. By heating in this case, water in the reaction mixture was smoothly distilled out of the system together with low boiling point methyl ethyl ketone. After completion of the reaction, the mixture was cooled to 50 ° C., and neutralized by adding 2.6 g (0.03 mol) of sodium hydrogen carbonate. After stirring at 50 ° C. for 1 hour, the reaction product was filtered through a filter paper with a fold. Was concentrated under reduced pressure to obtain 156.9 g of a brown colored oily substance. When this was analyzed, it contained 153 g (yield: 96%) of the title compound and 2.35 g of glycerin.

Example 2 (Synthesis of 2,2-dimethyl-1,3-dioxolan-4-methanol) 3 equipped with a stirrer, thermometer, Dean-Stark trap, reflux condenser and calcium chloride tube
A 0 ml four-necked flask was used as a reactor, and 73.6 g of a 50% by weight glycerin aqueous solution and 71.25 acetone
g (1.23 mol), 0.94 g (4.9 mmol) of paratoluenesulfonic acid monohydrate and petroleum ether 11
0 ml was charged. Temperature 5 while stirring inside the flask
Heat reaction was performed at 0 ° C. for 24 hours. By heating in this case, water in the reaction mixture was smoothly removed by evaporation together with petroleum ether having a low boiling point. After completion of the reaction, the mixture was cooled to room temperature, neutralized by adding 0.43 g (5.1 mmol) of sodium hydrogen carbonate, and stirred at room temperature for 1 hour. Then, the same operation as in Example 1 was performed to obtain 37.9 g of the title compound (yield: 84). 44.2 g) and 4.88 g of glycerin.

Example 3 In Example 1, high boiling methyl octyl ketone was used as the carbonyl compound, high boiling butyl benzene was used as the reaction solvent, and the reaction temperature was about 65 ° C.
The experiment was performed in the same manner except that a reduced pressure of about 50 mmHg was used as the reaction pressure. Also in this case, the water in the reaction mixture was smoothly evaporated and removed, and the condensation reaction also proceeded smoothly.

An experiment was conducted in the same manner as in Example 3 except that no reaction solvent was used. In this case as well, water in the reaction mixture was smoothly evaporated and removed, and the condensation reaction proceeded smoothly.

Example 4 An experiment was conducted in the same manner as in Example 1, except that the amount of methyl ethyl ketone was changed to 3540 g without using a reaction solvent. Also in this case, the water in the reaction mixture was smoothly evaporated and removed, and the condensation reaction also proceeded smoothly.

[0020]

According to the present invention, hydrated glycerin or an aqueous glycerin solution can be used as a raw material for the reaction, so that a 4-hydroxymethyl-1,3-dioxolane compound can be produced at low cost.

Claims (6)

[Claims] 1. A glycerin aqueous solution containing 1 to 20% by weight of water or a glycerin aqueous solution containing 30 to 80% by weight of glycerin, and the following general formula (1): (Wherein, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group)
And a reaction solvent having a boiling point of 150 ° C. or lower and a boiling point lower than the boiling point of the carbonyl compound, and heating the mixture in the presence of an acid catalyst. The water contained therein is removed by evaporation together with the reaction solvent. The following general formula (2): (Wherein, R ¹ and R ² have the same meanings as described above). 2. The ratio of the reaction solvent in the reaction mixture is 0.5 parts by weight per 1 part by weight of aqueous glycerin or an aqueous glycerin solution.
The method of claim 1 wherein the amount is from about 20 to 20 parts by weight. 3. A glycerin aqueous solution containing 1 to 20% by weight of water or a glycerin aqueous solution containing 30 to 80% by weight of glycerin, and the following general formula (1): (Wherein, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group)
Wherein a mixture comprising a carbonyl compound having a boiling point of 150 ° C. or higher is heated under reduced pressure in the presence of an acid catalyst, and water contained in the reaction mixture is removed by evaporation. 2) (Wherein, R ¹ and R ² have the same meanings as described above). 4. The method of claim 3, wherein said reaction mixture contains said reaction solvent having a boiling point of 150 ° C. or less. 5. A glycerin aqueous solution containing 1 to 20% by weight of water or a glycerin aqueous solution containing 30 to 80% by weight of glycerin, and the following general formula (1): (Wherein, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group)
A reaction mixture consisting of a carbonyl compound having a boiling point of 150 ° C. or lower represented by
The water contained in the reaction mixture is removed by evaporation. The following general formula (2): (Wherein, R ¹ and R ² have the same meanings as described above). 6. The process according to claim 1, wherein the proportion of the carbonyl compound in the reaction mixture is at least 1.1 mol per mol of glycerin.