JPH10195011A - Production of glyceryl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable efficient production of the subject compound that is useful as a raw material for surfactants with no formation of by-products, for example, aldehydes and ketones without bad smell and discoloration by reaction of a specific 1,3-dioxorane with a specific polyhydroxy compound. SOLUTION: The reaction of a compound of formula I (R<1> is a hydrocarbon group; R<2> and R<3> are each H or R<1> or they may incorporate to form a ring) with a compound of formula II affords a compound of formula III. This reaction is carried out by using an acid catalyst, for example, a protonic acid, a solid acid or a Lewis acid in an amount of 0.001-0.3 mole per mole of the compound of formula I at 50-150 deg.C under a pressure of 0.1-760mmHg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing glyceryl ether which is useful as a raw material for producing glycerin derivatives and surfactants.

[0002]

2. Description of the Related Art As a method for producing glyceryl ether, a method is known in which a 4-alkoxymethyl-1,3-dioxolane compound is hydrolyzed in the presence of an acid catalyst (JP-A-56-133281; 59-1106
No. 40, JP-B-63-24496, etc.). According to this hydrolysis method, glyceryl ether can be obtained in high yield. However, in the case of this hydrolysis method, there is a problem that ketones and aldehydes produced as by-products by the hydrolyzate of the dioxolane compound undergo aldol condensation to generate colored or odorous impurities. In addition, this hydrolysis method requires a large amount of a reaction solvent composed of a mixture of water and a lower alcohol, so that the separation and recovery of glyceryl ether from the reaction product and the separation and recovery of by-product ketones and aldehydes are costly. Includes issues such as

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an industrially advantageous method for producing glyceryl ether which does not require the use of a large amount of a reaction solvent and has no ketone or aldehyde by-product. I do.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, the following general formula (1)

Embedded image (Wherein R ¹ represents a hydrocarbon group, and R ² and R ³ represent a hydrogen atom or a hydrocarbon group, but R ² and R ³ may combine to form a ring). 1,3-dioxolane compound represented by the following general formula (2)

Embedded image (Wherein R ⁴ and R ⁵ may be the same or different and each represent a hydrogen atom, a hydroxymethyl group or a lower alkyl group), and reacted with a polyhydroxy compound represented by the following general formula ( 3)

Embedded image (Wherein R ¹ has the same meaning as described above).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the above-mentioned general formula (1) representing a reaction raw material used in the present invention, R ¹ represents a hydrocarbon group, wherein R ¹ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Is included. The aliphatic hydrocarbon group includes a linear or cyclic saturated or unsaturated group, and has 1 to 26, preferably 1 to 20, and more preferably 6 to 18 carbon atoms. Examples of such an aliphatic hydrocarbon group include, for example, methyl, ethyl, propyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl,
Hexadecyl, octadecyl, butenyl, hexenyl,
Linear alkyl or alkenyl groups such as oleyl;
Isopropyl, sec-butyl, t-butyl, 2-octyl, 2-decyl, 2-dodecyl, 2-tetradecyl,
a branched alkyl group or alkenyl group such as sec-butenyl and sec-hexenyl; a cycloalkyl group or cycloalkenyl group such as cyclohexyl and cyclohexenyl; On the other hand, as the aromatic hydrocarbon group,
Examples include an aryl group such as phenyl, p-tolyl and naphthyl, and an arylalkyl group such as benzyl and phenethyl.

R ² and R ³ in the general formula (1) are a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In this case, the aliphatic hydrocarbon group includes a straight chain. And branched or branched saturated or unsaturated aliphatic hydrocarbon groups. The aliphatic hydrocarbon group includes a chain and a cyclic one. The aliphatic hydrocarbon group has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Examples of such an aliphatic hydrocarbon group include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, octyl, decyl, 1-methylhexyl, 1-butylhexyl, propenyl, butenyl, hexenyl And the like. R ² and R ³
Are bonded to form a ring, the ring has 3 carbon atoms.
-10, preferably 4-8. As the ring in this case, cyclobutane, cyclopentane, cyclohexane,
Carbocycles such as cyclooctane can be mentioned. Examples of the aromatic hydrocarbon group include benzyl, phenyl, phenethyl, naphthyl and the like.

The 4-hydrocarbonoxymethyl-1,3-dioxolane compound represented by the general formula (1) can be produced, for example, by the following method. (1) A method in which an alcohol halide or a paratoluenesulfonic acid ester of an alcohol is reacted with a glycerin alkali metal alcoholate having a hydroxyl group protected by a ketone or an aldehyde. (2) A method of adding an aldehyde or ketone to glycidyl ether (JP-A-56-133281).

In the above general formula (2), which represents a polyhydroxy compound used as the other reaction raw material in the present invention,
R ⁴ and R ⁵ represent a hydrogen atom, a hydroxymethyl group or a lower alkyl group. R ⁴ and R ⁵ may be the same or different. In this case, the lower alkyl group includes methyl,
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as ethyl, propyl, isopropyl, butyl, sec-butyl and t-butyl. The polyhydroxy compound represented by the general formula (2) includes diols, triols and tetraols, and specific examples thereof include, for example, ethylene glycol, 1,2-propanediol, 1,2-
Butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,2-
Hexanediol, 2,3-hexanediol, 3,4
Diols such as -hexanediol, 3-methyl-1,2-butanediol, 3-methyl-1,2-pentanediol, 4-methyl-2,3-pentanediol; glycerin, 1,2,3-butane Triol, 1,2,3-
Triols such as pentanetriol and 4-methyl-1,2,3-pentanetriol; and tetraols such as meso-erythritol, DL-threitol, D-threitol and L-threitol. Preferably, glycerin is used.

In the present invention, glyceryl ether is obtained by reacting a 4-hydrocarbon oxymethyl-1,3-dioxolane compound represented by the general formula (1) with a polyhydroxy compound represented by the general formula (2). Manufactured by letting In this case, a 1,3-dioxolane compound represented by the following general formula (4) is generated as a by-product.

Embedded image (Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above) The glyceryl ether forming reaction is represented by the following formula.

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above)

[0010] The reaction is carried out in the presence of an acid catalyst,
The reaction temperature is 50-150 ° C, preferably 70-12.
0 ° C., and the reaction pressure is a pressure for keeping the reaction mixture in a liquid phase, and depending on the reaction temperature, 0.1 to 760 m
mHg, preferably 0.3 to 70 mmHg. The use ratio of the polyhydroxy mixture of the general formula (2) is 1 to 1 mol of the 1,3-dioxolane compound of the general formula (1).
The ratio is 5 mol, preferably 1 to 3 mol. The catalyst is used in an amount of 0.001 to 0.3 mol, preferably 0.1 mol, per 1 mol of the 1,3-dioxolane compound of the general formula (1).
008 to 0.1 mol.

[0011] Acid catalysts include protic acids, solid acids and Lewis acids. Specific examples thereof are as follows. (Protonic acid) p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, nitric acid, pyridinium paratoluenesulfonate and the like. (Solid acid) silica gel, alumina, montmorillonite,
Bentonite, kaolin, vermiculite, zeolite, heteropolyacid salt, silica complex, acid-type ion exchange resin, etc. (Lewis acid) Titanium tetrachloride, tin tetrachloride, aluminum chloride, lanthanoid metal salts of trifluoromethanesulfonic acid, and the like.

[0012]

According to the method of the present invention, the general formula (1)
Can be obtained in a very high yield, and the polyhydroxy compound of the general formula (2) used as a reaction raw material can be obtained by the following general formula (4)

Embedded image (Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above), which is converted into a 1,3-dioxolane compound which can be easily separated and recovered from the reaction product, and converts ketones and aldehydes. No by-products. Therefore, in the case of the present invention, problems such as coloring and odor caused by by-products of ketones and aldehydes by aldol condensate, and separation and recovery of by-product ketones and aldehydes from reaction products, which are defects of the conventional hydrolysis method, are obtained. Thus, the present invention is suitable as an industrial method for producing glyceryl ether. In addition, the general formula (4)
The by-product 1,3-dioxolane compound represented by the following formula is decomposed to give the following general formula (2)

Embedded image (Wherein R ⁴ and R ⁵ have the same meanings as described above), which is a reaction raw material for the 1,3-dioxolane compound of the general formula (1) Can be used as The decomposition reaction in this case can be carried out according to a conventionally known method, using an acid catalyst as described above.

[0013]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 (Synthesis of 2,2-dimethyl-1,3-dioxolan-4-methanol) A 1-liter three-necked flask equipped with a stirrer and a Dean-Stark trap was used as a reactor, and 237 g of acetone was added thereto. (4.09 mol), glycerin 1
00 g (1.09 mol) and low boiling petroleum ether 0.1.
3 liters were charged, 33.0 g (0.17 mol) of paratoluenesulfonic acid monohydrate was added, and the mixture was heated and stirred.
The reaction was carried out at the boiling point of the reaction solution for 25 hours while separating water produced by the reaction, and then cooled to room temperature, and then 3.0 g of anhydrous powdery sodium acetate was added to the reaction solution, followed by stirring for 30 minutes. Then, the solid matter was filtered off from the contents of the reactor, and the liquid matter after the filtration was distilled under reduced pressure at 60 ° C. or lower to remove petroleum ether and acetone. When the residual liquid after the distillation was distilled under reduced pressure at 11 mmHg, 2,2-dimethyl-1,3-dioxolan-4-methanol was 129 as a fraction at 80 to 81 ° C.
g were obtained.

Reference Example 2 (Synthesis of dodecyl p-toluenesulfonate) A 3-liter three-necked flask equipped with a stirrer and a thermometer was used as a reactor, and 186.3 g of dodecyl alcohol (1
1 mol), 316.4 g (4 mol) of pyridine and 1 liter of dichloromethane were charged and cooled to 0 ° C. Next, while stirring the contents of the reactor, 400.4 g (2.1 mol) of paratoluenesulfonyl chloride was added in four portions at 1-hour intervals, and the mixture was stirred for 12 hours while maintaining the temperature at 0 ° C., and then 1N 500 ml of hydrochloric acid was added, the organic layer was separated, and the aqueous layer was extracted twice with 300 ml of dichloromethane. The extract and the organic layer were combined, washed sequentially with 1 N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. The dichloromethane solution from which magnesium sulfate was filtered off was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography using a mixed solution of hexane and ethyl acetate (mixed weight ratio of 7: 3) as an eluent, to give dodecyl paratoluenesulfonate. 204.3 g (yield 60%) of the ester was obtained.

Reference Example 3 (2,2-dimethyl-4-dodecyloxymethyl-1,
Synthesis of 3-dioxolan) A 1-liter 3-neck flask equipped with a stirrer, a thermometer, a dropping funnel and a calcium chloride tube was used as a reactor, and 13 g of sodium hydride (0.1 g) was added thereto.
54 mol) and 300 ml of dry DMF, and the mixture was cooled to 0 ° C. while stirring to give 2,2-dimethyl-1,3-
59.47 g of dioxolan-4-metallur (0.45 g)
mol) was added dropwise over 30 minutes. After stirring until generation of gas was no longer observed, the temperature was raised to 60 ° C., and the mixture was heated and stirred for 1 hour. Next, 102.16 g of paratoluenesulfonic acid dodecyl ester dissolved in 250 ml of dry DMF
(0.3 mol) was added dropwise over 1 hour, and 10 minutes after the addition was completed.
After raising the temperature to 0 ° C. and reacting for 4 hours, the reaction solution was cooled to room temperature, and then DMF was distilled off under reduced pressure. Water 3
00 ml and 200 ml of ether were added, and the mixture was stirred for 15 minutes to separate an organic layer. The aqueous layer was extracted twice with 100 ml of ether. The extract and the organic layer were combined, washed sequentially with water and saturated saline, and dried over anhydrous sodium sulfate. After drying, sodium sulfate was filtered off and the residue concentrated under reduced pressure was purified by silica gel column chromatography using a mixed solution of hexane and ethyl acetate (mixing weight ratio: 5: 1) as an eluent.
63 g (70% yield) of dimethyl-4-dodecyloxymethyl-1,3-dioxolane was obtained.

Example 1 A 200 ml four-necked flask equipped with a stirrer and a distillation apparatus was used as a reactor, and the 2,2-dimethyl-4-dodecyloxymethyl-1,3-dioxolane 120 prepared in Reference Example 3 was added thereto. .19 g (0.4 mol), glycerin
84 g (0.4 mol) and paratoluenesulfonic acid 1
A hydrate (3.6 g, 20 mmol) was charged, and the pressure in the reactor was increased from normal pressure to 0.5 mm while stirring the reactor contents.
The pressure was reduced to Hg. Next, raise the temperature from room temperature to 80 ° C in 30 minutes.
The mixture was heated and stirred while distilling off 2,2-dimethyl-1,3-dioxolane-4-methanol. After 3 hours, the reaction was completed. The reaction was cooled to a temperature of 50 ° C., and the pressure in the reactor was increased. Normal pressure was applied. 100 ml of saturated aqueous sodium hydrogencarbonate and 100 ml of ethyl acetate were added to the reaction solution, and the mixture was stirred for 30 minutes to separate the organic layer. The aqueous layer was extracted twice with 100 ml of ethyl acetate.
And dried over anhydrous sodium sulfate. After drying, sodium sulfate was separated by filtration, and the residue concentrated under reduced pressure was purified by silica gel column chromatography (eluent: chloroform: methanol mixture weight ratio = 10: 1), and 98.9 g of 1-dodecylglyceryl ether was purified. (95% yield).

Example 2 In Example 1, 2-methyl-2-ethyl-4-dodecyloxymethyl-1,2,2-dimethyl-4-dodecyloxymethyl-1,3-dioxolane was used instead of 120.19 g. 125.8 g of 3-dioxolane (0.4 mo
Using l), 3.6 g of paratoluenesulfonic acid monohydrate
1.3 g (13 mmol) of sulfuric acid instead of (20 mmol)
An experiment was conducted in the same manner except that l) was used, and 95.8 g (yield 92%) of 1-dodecylglyceryl ether was obtained.

Example 3 In Example 1, instead of 36.84 g of glycerin, 30.44 g of 1,2-propanediol (0.4 m
ol) and the pressure in the reactor was increased from 0.5 mmHg to 2
An experiment was conducted in the same manner except that the pressure was changed to 0 mmHg, and 90.6 g of 1-dodecylglyceryl ether was obtained (yield: 87%).

Example 4 In Example 1, 2,2-dimethyl-4-octadecyloxymethyl-1,3-dioxolane was replaced by 120.19 g of 2,2-dimethyl-4-dodecyloxymethyl-1,3-dioxolane. 153.86 g of dioxolane (0.4 mo
The experiment was carried out in the same manner except that l) was used, and 104.8 g of 1-octadecylglyceryl ether was obtained (yield: 76).
%)Obtained.

Claims (3)

[Claims] [Claim 1] The following general formula (1) (Wherein R ¹ represents a hydrocarbon group, and R ² and R ³ represent a hydrogen atom or a hydrocarbon group, but R ² and R ³ may combine to form a ring). The 1,3-dioxolane compound represented by the following general formula (2): (Wherein R ⁴ and R ⁵ may be the same or different and each represent a hydrogen atom, a hydroxymethyl group or a lower alkyl group), and reacted with a polyhydroxy compound represented by the following general formula ( 3) (Wherein R ¹ has the same meaning as described above). 2. The following general formula (4) by-produced by the method of claim 1. (Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above) after decomposing into a hydroxy compound, which is reused as the hydroxy compound in claim 1 The method of claim 1. 3. The method according to claim 1, wherein the polyhydroxy compound represented by the general formula (2) is glycerin.