JPH11228466A - Production of polyhydroxyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially and simply and efficiently produce the subject compound by bringing a compound in which specific hydroxyl groups of a polyhydric alcohol are protected with a ketal or an acetal into contact with steam and carrying out the deprotection of the compound in the presence of an acidic catalyst. SOLUTION: A compound having a structure in which two hydroxyl groups of a polyhydric alcohol represented by formula I [R<1> and R<2> are each H, a 1-22C alkyl or the like; X is R<3> O (R<3> is H, a 1-23C aliphatic hydrocarbon group, a 1-22C aliphatic acyl or the like) or a halogen; A is a 2-4C alkylene; (n) is 0-100] or its derivative are protected with a ketal or an acetal is brought into contact with steam in the presence of an acidic catalyst (e.g. an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as p- toluenesulfonic acid) and deprotected (deketalized or deacetalized) to produce the objective compound represented by formula II. The deprotection is carried out at 10-120 deg.C under atmospheric pressure or 0.13-66.6 kPa by adding the acidic catalyst in an amount of 0.0001-0.5 wt.% based on the compound represented by formula I thereto while blowing the steam into the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a simple and efficient method for producing a polyhydroxyl compound by deprotecting a compound in which a specific hydroxyl group of a polyhydric alcohol or a derivative thereof is protected with a ketal or an acetal. Things.

[0002]

2. Description of the Related Art A specific hydroxyl group of a compound having a plurality of hydroxyl groups is protected by ketalization or acetalization, and the remaining hydroxyl groups are modified and derivatized, if necessary. Protecting and synthesizing the desired polyhydroxyl compound is a well-known method commonly performed in the field of organic chemistry.

Here, the deprotection (deketalization and deacetalization) is usually carried out by hydrolyzing a mixture containing an excess of water and, if necessary, a solvent for homogenizing the reaction system under an acid catalyst. After that, the acid catalyst is neutralized, and the ketone or aldehyde derived from the generated protecting group is distilled off under reduced pressure together with excess water and solvent, and if necessary, the precipitated salt is filtered off to remove the deprotected polyketone. This is carried out by obtaining a dihydric alcohol (for example, in JP-A-6-145341,
The pH of the mixture was adjusted to 1.0 with 0% aqueous hydrochloric acid and stirred at 60 ° C. for 1 hour, then the pH of the mixture was adjusted to 6.5 with 50% sodium hydroxide, 100 ° C., 1
A method is disclosed in which ketones produced by heating at 3.33 kPa or less for 1 hour are distilled off together with water, and precipitated salts are filtered off).

[0004] However, the above-mentioned method has a drawback that the yield for preparation is low due to the use of excess water and, if necessary, a solvent, and the productivity is poor when considering industrial production. It is desirable to use as little water and solvent as possible. In addition, in the method using an excess of water as described above, when a compound having a hydrolyzable group such as an ester group is deprotected, hydrolysis of the ester group or the like is simultaneously caused during the deprotection reaction, It is inevitable that undesired decomposition products are produced.

In the method using excess water as described above, a step of removing the generated ketone or aldehyde, excess water, solvent and the like under reduced pressure after deprotection is required, and industrial production is required. In consideration of this, simplification of the process is desired.

Further, in the above method, since the acid used is diluted in an aqueous solution system and used, when the water used is excessive, an amount of an acid catalyst corresponding to the excess is necessary, and the acid is formed by neutralizing this. The salt may be contained as an impurity, and it is desired that the amount of salt used in industrial production be low in terms of cost.

[0007] Accordingly, an object of the present invention is to provide an industrially simple method for deprotecting a compound in which a specific hydroxyl group of a polyhydric alcohol or a derivative thereof is protected by a ketal or an acetal without using excessive water and a solvent. To provide an efficient method.

[0008]

Means for Solving the Problems The present inventors have conventionally carried out a deprotection (deketalization, deacetalization) step carried out in a reaction system using an excess of water while contacting with water vapor. Similarly, they have found that deprotection is possible and that the above-mentioned problems can be solved, and the present invention has been completed. That is, the present invention provides a compound represented by the general formula (I):

[0009]

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[In the formula, R ¹ and R ² are the same or different and each is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or a total of which may be substituted with an alkyl group. an aryl group having 6 to 30 carbon atoms, R ¹
And R ² may together form a ring. X is R ³ O-
Represents a group or a halogen atom, R ³ is a hydrogen atom,
Straight-chain or branched-chain saturated or unsaturated aliphatic hydrocarbon group having 1 to 23 carbon atoms, aliphatic acyl group having 1 to 22 carbon atoms, or substituted with alkyl group or acyl group, or protected with ketal or acetal. Glyceryl group. A represents an alkylene group having 2 to 4 carbon atoms;
May be the same or different. n is a number from 0 to 100 indicating the average number of added moles of the alkylene oxide. However, when n is 0, X is not HO-. A compound having a structure in which two hydroxyl groups of a polyhydric alcohol or a derivative thereof represented by the following formula is protected by a ketal or an acetal (deketalization or deacetalization), and then represented by the general formula (II):

[0011]

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[Wherein, X, A and n have the above-mentioned meanings. A process for producing a polyhydroxyl compound represented by the general formula (1), wherein the polyhydroxyl compound is deprotected by contacting with water vapor under an acid catalyst.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the protected compound represented by the general formula (I) used as a raw material in the present invention, R ¹ and R ² are the same or different and each represents a hydrogen atom, a linear or branched carbon atom. An alkyl group or alkenyl group of the formulas 1 to 22, or a total carbon number of 6 to 3 which may be substituted with an alkyl group.
It represents an aryl group of 0, and R ¹ and R ² may together form a ring, but is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

X represents a group represented by R ³ O— or a halogen atom; R ³ represents a hydrogen atom, a linear or branched C 1-23
A saturated or unsaturated aliphatic hydrocarbon group, an aliphatic acyl group having 1 to 22 carbon atoms, or a glyceryl group which may be substituted with an alkyl group or an acyl group or protected with a ketal or acetal, Numbers 1 to 18
Or an aliphatic acyl group having 1 to 22 carbon atoms.

A represents an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group. n represents an average number of added moles of alkylene oxide of 0 to 10
Although it is a number of 0, it is preferably a number of 0 to 30.

The synthesis of the compound represented by the general formula (I)
For example, when the polyhydric alcohol derivative is a glycerin derivative, two of the three hydroxyl groups of glycerin are replaced by the general formula (III)

[0017]

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[Wherein, R ¹ and R ² have the same meanings as described above. ]
Ketalized or acetalized with a ketone or aldehyde represented by the general formula (IV)

[0019]

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[Wherein R ¹ and R ² have the same meanings as above. ]
A 1,3-dioxolane compound represented by the following formula is obtained, and then, if necessary, an alkylene oxide is added in the presence of a catalyst, and the compound is further added with a compound represented by the general formula (V) R ⁴ COOR ⁵ (V) , R ⁴ represents a hydrogen atom or a residue obtained by removing a CO group from an aliphatic acyl group having 1 to 22 carbon atoms, and R ⁵ represents a residue obtained by removing an R ⁴ COO group from a hydrogen atom, a lower alkyl group or an oil or fat. Is shown. Or a fatty acid lower alkyl ester or a fat or oil represented by the general formula (VI) R ⁶ -Y (VI) wherein R ⁶ is a linear or branched chain It represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 23 carbon atoms, and Y represents halogen. By reacting an alkyl halide, epichlorohydrin, alkyl glycidyl ether or the like represented by the formula (1) to carry out etherification.

Here, glycerin is reacted with a ketone or aldehyde represented by the general formula (III) to form a ketal or an acetal to protect a hydroxyl group, and to form a compound represented by the general formula (I
The method for obtaining the 1,3-dioxolane compound represented by V) is a well-established process in the field of organic chemistry. Usually, these reactions are carried out in an acid catalyst and a solvent, and the solvent is azeotropically distilled. Helps to remove water generated during the reaction and create an equilibrium relationship, which facilitates ketal or acetal formation.

The ketone or aldehyde represented by the general formula (III) used in the above reaction includes ketones such as acetone, methyl ethyl ketone and cyclohexanone, and aldehydes such as formaldehyde and acetaldehyde.

Here, the 1,3-formula represented by the general formula (IV)
As the dioxolane compound, for example, commercially available 2,2-dimethyl-dioxolane-4-methanol (general name: solketal) can be used as it is.

The alkylene oxide optionally added to the 1,3-dioxolane represented by the general formula (IV) obtained as described above includes alkylene oxides having 2 to 4 carbon atoms, specifically, Examples thereof include ethylene oxide, propylene oxide, and butylene oxide. One or more of these may be added, and when two or more are added, their addition state may be random or block.

As a catalyst used in the alkylene oxide addition reaction, an alkali metal compound or an alkaline earth metal compound selected from hydroxides, oxides, organic acid salts or alcoholates of alkali metals or alkaline earth metals is used. Is preferred.

The fatty acid represented by the general formula (V) used for esterifying the 1,3-dioxolane represented by the general formula (IV) or the alkylene oxide adduct thereof obtained as described above, As fatty acid lower alkyl esters or fats and oils, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
Examples thereof include saturated or unsaturated fatty acids having 1 to 22 carbon atoms such as isostearic acid, methyl, ethyl and propyl esters of these fatty acids, and fats and oils containing these fatty acids as constituent components. The reaction conditions for the esterification are not particularly limited, and the esterification can be carried out using an enzyme having an esterification activity, in addition to the method using a normal base catalyst.

The general formula (I) obtained as described above
The halogenated alkyl represented by the general formula (VI) used for etherifying 1,3-dioxolane represented by V) or an alkylene oxide adduct thereof has an alkyl group having 1 to 23 carbon atoms. Chloride,
And bromide. Other examples of the etherification reagent include epoxy compounds such as epichlorohydrin, alkyl glycidyl ethers having an alkyl group having 1 to 23 carbon atoms, and acyl glycidyl ethers having an acyl group having 1 to 22 carbon atoms. The reaction conditions for the etherification are not particularly limited, and the etherification can be performed using a usual phase transfer catalyst.

In the present invention, the compound represented by the general formula (I) obtained as described above is deprotected (deketalization, deacetalization) while contacting with steam in the presence of an acid catalyst. Perform Examples of the acid catalyst used here include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as paratoluenesulfonic acid and benzenesulfonic acid.

As a typical method for deprotection in the present invention, an acid catalyst is used in an amount of 0.0001 to 0.5% by weight, preferably 0.005 to 0.5% by weight, based on the compound represented by the general formula (I).
0.2% by weight, 10 ° C to 120 ° C, preferably 30 ° C
At a reaction temperature of 100 ° C. to 100 ° C., at normal pressure, or
6.66 kPa, preferably 1.33 to 13.33 kP
The process is carried out while blowing steam under the reduced pressure of a, and the ketone or aldehyde generated by the deprotection is simultaneously distilled out of the system. The amount of steam blown per hour is preferably 0.1 to 100 parts by weight per 100 parts by weight of the raw material,
-20 parts by weight is more preferable, and 1-10 parts by weight is further preferable. Further, the total amount of steam blown up to the completion of the reaction is preferably 1 to 100 parts by weight, more preferably 2 to 60 parts by weight, and still more preferably 5 to 40 parts by weight based on 100 parts by weight of the raw material.

The raw material to be deketalized has an ester group or the like, and from the viewpoint of suppressing hydrolysis, the water content in the reaction system is preferably 5% by weight or less, more preferably 3% by weight or less, further preferably 1% by weight or less. % By weight or less.

When steam is blown in at normal pressure, the ketone or aldehyde generated after the reaction may be removed and water may be removed. After completion of the reaction, if necessary, removal operations such as neutralization of the catalyst, adsorption treatment, and filtration are performed to obtain a deprotected polyhydroxyl compound represented by the general formula (II). By performing such a method, a polyhydroxyl compound having two adjacent hydroxyl groups and having only the α-position derivatized can be obtained.

[0032]

According to the deprotection of the present invention, it is not necessary to add excessive water, solvent, etc., and only a small change in volume is required by introducing steam. (Yield), and the step of removing excess water, solvent, etc. is unnecessary, and the number of steps is reduced, which is advantageous as an industrial production method.

Further, since the reaction can be carried out with a low catalytic amount, the amount of salts produced by performing post-treatments such as neutralization of the acid used can be reduced, and a high-quality target product can be obtained. Furthermore, since deprotection is possible under mild reaction conditions,
The deprotection reaction can be performed while suppressing the decomposition of other functional groups (hydrolysis of an ester group, etc.), and a good quality compound with few impurities can be obtained.

[0034]

The percentages in the following examples are by weight unless otherwise specified.

Example 1 (a) Esterification Reaction Methyl caprylate 237. was placed in a 2 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dehydrating cooler.
4 g (1.5 mol) and 2,2-dimethyl-1,3-dioxolan-4-methanol (general name: solketal) 59
After charging 4 g (4.5 mol) and 16.6 g of a 28% methanol solution of sodium methylate, the temperature was raised to 170 ° C. while removing generated methanol, and an esterification reaction was carried out for 5 hours. 97% conversion.

The reaction solution was cooled to 80 ° C., 33.2 g of Kyoward 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, the mixture was treated for 1 hour, and the catalyst was removed by filtration.
At 140 to 150 ° C. to give 1,3-dioxolancaprylic acid ester 25 represented by the following formula (VII):
8.7 g were obtained. 73% yield. Gas chromatography purity 98%.

[0037]

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(B) Deketalization reaction To 150 g (0.58 mol) of 1,3-dioxolancaprylic ester of the formula (VII) obtained in the above reaction was added 0.3 g of paratoluenesulfonic acid monohydrate. (1.58 × 1
0 ^-3 mol) were charged, 40 ° C., at 2.67 kPa, and introduced into the reaction system 2-4% of water vapor with respect to a 1,3-Lanka prills ester per hour, to produce ketone (acetone) After performing a deketalization reaction for 8 hours while removing excess water vapor out of the system, the catalyst was neutralized with an aqueous solution of N / 2 potassium hydroxide, and 2.67 kPa,
After dehydration at 60 ° C. for 0.5 hour, 125.5 g (0.5 g) of caprylic acid monoglyceride represented by the following formula (VIII)
7 mol). The yield in this deketalization reaction is 99
%Met. Acid value 0.2 (calculated value 0), saponification value 254
(Calculated value 257). As a result of analyzing the product by gas chromatography, the area percentage of caprylic acid monoglyceride was 92%. Further, the charging yield of the target product obtained with respect to the raw materials charged in the deketalization reaction was 83.6%.

[0039]

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Example 2 (a) Esterification reaction Instead of methyl caprylate, 300 g of methyl laurate was used.
An esterification reaction was carried out in the same manner as in Example 1 except that (1.4 mol) was used. 97% conversion. After the same post-treatment as in Example 1, vacuum distillation was performed at 170 to 185 ° C. at 0.40 kPa to obtain 339.0 g of 1,3-dioxolan laurate represented by the following formula (IX). . Yield 72%. Gas chromatography purity 94%.

[0041]

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(B) Deketalization reaction Example 1 was repeated except that 150 g (0.48 mol) of 1,3-dioxolan laurate ester represented by the formula (IX) obtained by the above reaction was used as a raw material. Similarly, a deketalization reaction was performed to obtain 130.4 g (0.48 mol) of lauric acid monoglyceride represented by the following formula (X). The yield in this deketalization reaction was 99%. Acid value 0.3
(Calculated value 0), saponification value 205 (calculated value 204). As a result of analyzing the product by gas chromatography, the area percentage of lauric acid monoglyceride was 93%.
The yield of the target product obtained with respect to the raw materials charged in the deketalization reaction was 86.9%.

[0043]

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Example 3 (a) Ketalization reaction 230.3 g of glycerin was placed in a 2 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and dehydrating cooler.
(2.5 mol) and 270.4 g of methyl ethyl ketone
(3.75 mol) and 4.77 g of paratoluenesulfonic acid
(0.025 mol) and 109.7 g of heptane,
The reaction was carried out at a temperature of 75 to 98 ° C. for 16 hours while removing water produced by the reaction. Next, heptane and excess methyl ethyl ketone were distilled off under reduced pressure.
Vacuum distillation was performed at 0 to 85 ° C. to obtain 310.7 g (2.13 mol) of glycerin ketal represented by the following formula (XI). Yield 85%.

[0045]

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(B) Ethylene oxide addition reaction In a 3.5 liter autoclave, 300.0 g of the glycerin ketal represented by the formula (XI) obtained by the above reaction was added.
(2.05 mol) and 0.56 g of potassium hydroxide (0.0
1 mol), and after dehydration at 2.67 kPa and 110 ° C., the temperature was raised to 165 ° C. Thereafter, at the same temperature, 542 g (12.3 mol) of ethylene oxide was applied under a pressure of 0.29.
The reaction was carried out while maintaining the pressure at ~ 0.49 MPa.

After aging at the same temperature for 0.5 to 1 hour,
℃, KYOWARD 600S (Kyowa Chemical Co., Ltd.)
4.5 g (8 weight times KOH) and 4.00 kP
a for 1 hour under reduced pressure to neutralize the catalyst and remove unreacted ethylene oxide, followed by filtration.
800.0 g (1.95 mol) of an ethylene oxide adduct of glycerin ketal represented by I) was obtained. Yield 9
5%.

[0048]

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(C) Esterification reaction In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dehydrating cooler, the formula (XI) obtained by the above reaction was added.
238.4 g (0.58 mol) of ethylene oxide adduct of glycerin ketal represented by I) and caprylic acid 1
26.5 g (0.88 mol) and immobilized lipase (No.
After charging 8.4 g of vozym 435, Novo Nordisk Bioindustry Co., Ltd., 0.67 kP
a) The reaction was carried out for 8 hours while removing water generated at 40 ° C. Conversion rate 98%.

After removing the immobilized lipase from the reaction solution by filtration, the temperature was raised to 170 ° C. at 0.67 kPa, and excess caprylic acid was distilled off under reduced pressure.
Caprylic acid was removed by introducing 36.5 g of steam at 0 ° C., and caprylic acid ester of ethylene oxide adduct of glycerine ketal represented by the following formula (XIII) 289.
5 g (0.54 mol) were obtained. Yield 93%.

[0051]

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(D) Deketalization reaction Paratoluenesulfonic acid was added to 150 g (0.28 mol) of a caprylic ester of ethylene oxide adduct of glycerine ketal represented by the formula (XIII) obtained by the above reaction.
0.3 g (1.58 × 10 ⁻³ mol) of water salt was charged and 80
At 2.67 kPa at a temperature of 2.67 kPa, 2 to 4% of steam based on the caprylate of ethylene oxide adduct of glycerin ketal is introduced into the reaction system per hour, and the generated ketone (methyl ethyl ketone) and excess steam are added to the system. A deketalization reaction was carried out for 8 hours while removing to the outside to obtain 132.4 g (0.27 mol) of α-polyoxyethylene glycerin monocaprylate represented by the following formula (XIV). The yield in this deketalization reaction was 98%. Acid value 0.2 (calculated value 0), saponification value 115.2
(Calculated value 116). As a result of analyzing the product by gas chromatography, the area percentage of α-polyoxyethylene monocaprylate was 91%. Further, the charging yield of the target product obtained with respect to the raw materials charged in the deketalization reaction was 88.3%.

[0053]

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Example 4 (a) Etherification reaction 2 equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser
Octyl chloride 32 in a 4-liter four-neck flask
7.1 g (2.2 mol) and 264.3 g solketal
(2.0 mol) and 127.0 g (0.4 mol) of tetrabutylammonium bromide (TBAB), and then 785 g of a 48% aqueous potassium hydroxide solution at 80 ° C.
(6.8 mol) was added dropwise over 30 minutes, and the temperature was raised to 95 ° C. to carry out an etherification reaction for 10 hours. Then water 300
g was added to dissolve the generated salt, and the separated lower layer was removed. 300 g of cyclohexane was added thereto, followed by washing with 2 L of water. Then, cyclohexane and excess octyl chloride were distilled off under reduced pressure, and 415.4 g of glycerin ketal octyl ether represented by the following formula (XV) was obtained.
(1.7 mol). Yield 85%.

[0055]

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(B) Deketalization reaction The reaction was carried out at a reaction temperature of 80 ° C., using 150 g (0.61 mol) of the glycerin ketal octyl ether represented by the formula (XV) obtained in the above reaction as a raw material. A deketalization reaction was carried out in the same manner as in Example 1 to obtain 122.1 g (0.61 mol) of octylglyceryl ether represented by the following formula (XVI). The yield in this deketalization reaction was 98%. Acid value 0.3 (calculated value 0), hydroxyl value 545 (calculated value 549). As a result of analyzing the product by gas chromatography, the area percentage of octyl glyceryl ether was 98%. The yield of the target product obtained with respect to the raw materials charged in the deketalization reaction is 8%.
It was 1.4%.

[0057]

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Example 5 (a) Etherification reaction Instead of the solketal, the formula (X) obtained in (b) of Example 3 was used.
II) except that 410.5 g (1.0 mol) of an ethylene oxide adduct of glycerin ketal represented by
The same etherification reaction as in Example 4 was carried out, and the compound represented by the following formula (XVII)
470.4 g (0.9 mol) of an octyl ether of an ethylene oxide adduct of glycerin ketal represented by the following formula was obtained. 90% yield.

[0059]

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(B) Deketalization reaction Using 150 g (0.29 mol) of octyl ether of an ethylene oxide adduct of glycerin ketal represented by formula (XVII) obtained by the above reaction as a raw material,
The deketalization reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at a temperature of 13 ° C. to obtain 133.2 g (0.28 mol) of octylglyceryl ether ethoxylate represented by the following formula (XVIII). The yield in this deketalization reaction was 98%. Acid value 0.2 (calculated value 0), hydroxyl value 237 (calculated value 239.5). As a result of analyzing the product by gas chromatography, the area percentage of octylglyceryl ether ethoxylate was found to be 95%. The yield of the target product obtained with respect to the raw materials charged in the deketalization reaction was 88.8%.

[0061]

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Example 6 (a) Epoxidation reaction In a 1-liter four-necked flask equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube and reflux condenser, 370.1 g (4.0 mol) of epichlorohydrin was added. 2.3 g (0.01 mol) of triethylbenzylammonium chloride and N
52.0 g (1.3 mol) of aOH was charged and 35 to 40
Glycerin ketal 14 obtained in Example 3 (a)
6.2 g (1.0 mol) was added dropwise over 1.5 hours, followed by aging for 4.5 hours. The generated salt was removed by filtration, and excess epichlorohydrin was distilled off under reduced pressure. Then, 133.6 g (0.66 mol) of an epoxidized glycerin ketal represented by the following formula (XIX) was obtained by distillation under reduced pressure.

[0063]

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(B) Ketalization reaction 1 equipped with a stirrer, thermometer, dropping funnel and reflux condenser
In a 4-liter 4-liter flask, add methyl ethyl ketone 16
7.3 g (2.3 mol) and 0.65 g (0.0046 mol) of boron trifluoride ethyl ether complex were charged, and epoxidized glycerin ketal represented by the formula (XIX) obtained by the above reaction was added thereto. 116.3 g (0.57 mol) was added dropwise at room temperature over 2 hours. After further aging at 30 ° C. for 1 hour, the catalyst was neutralized with an aqueous NaOH solution, and excess methyl ethyl ketone was distilled off under reduced pressure. ) Got. Yield 99%.

[0065]

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(C) Deketalization reaction Using 137.0 g (0.5 mol) of a ketalized product of diglycerin represented by the formula (XX) obtained by the above reaction as a raw material,
The deketalization reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 80 ° C., to obtain 81.4 g (0.49 mol) of diglycerin represented by the following formula (XXI). The yield in this deketalization reaction was 98%. Acid value 0.4 (calculated value 0), hydroxyl value 1345 (calculated value 1350). As a result of analyzing the product by gas chromatography, the area percentage of diglycerin was 92%. Further, the charging yield of the target product obtained with respect to the raw materials charged in the deketalization reaction was 59.4%.

[0067]

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Example 7 (a) Glyceryl Etherification Reaction Example 3 was carried out in a 2 liter four-necked flask equipped with a stirrer, thermometer, dropping funnel, nitrogen gas inlet tube and reflux condenser.
146.2 g of the glycerin ketal obtained in (a) above
(1.0 mol) and 3.4 g (0.02 mol) of tetramethyl-1,6-diaminohexane were charged and stirred and mixed under a nitrogen gas flow. Next, 93.1 g (0.5 mol) of octyl glycidyl ether was added dropwise at 100 ° C. over 2 hours. After the dropwise addition, the mixture was aged at a reaction temperature of 130 to 140 ° C. for 6 hours, and 200 g of ion-exchanged water was added. After collecting the upper layer by liquid separation,
After the excess glycerin ketal was distilled off under reduced pressure, the mixture was further distilled under reduced pressure to obtain 149.5 g of octylglyceryl ether of glycerin ketal represented by the following formula (XXII).
(0.45 mol). Yield 90.0%.

[0069]

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(B) Deketalization reaction 133.0 g of octylglyceryl ether of glycerin ketal represented by the formula (XXII) obtained by the above reaction was used as a raw material.
(0.4 mol), and a deketalization reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at a reaction temperature of 80 ° C.
XIII) 109.1 g of octyl diglycerin represented by
(0.39 mol). The yield in this deketalization reaction was 98%. Acid value 0.2 (calculated value 0), hydroxyl value 300 (calculated value 605). As a result of analyzing the product by gas chromatography, the area percentage of octyldiglycerin was 93%. Further, the charging yield of the target product obtained with respect to the raw materials charged in the deketalization reaction was 82%.

[0071]

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Example 8 (a) Ketalization reaction 139.1 g (1.5 mol) of epichlorohydrin was placed in a 2-liter four-necked flask equipped with a stirrer, thermometer, dropping funnel, nitrogen gas inlet tube and reflux condenser. And acetone 47
9.1 g (3.25 mol) and 0.69 g (0.5% of epichlorohydrin) of a boron trifluoride ethyl ether complex were charged, reacted at 40 ° C., and confirmed that the raw material epichlorohydrin disappeared in 3 hours. It was confirmed by gas chromatography. Next, excess acetone used was distilled off under reduced pressure, and 100 g of a 5% aqueous potassium carbonate solution and ion-exchanged water 2
After the reaction product was washed with 20 g of water, dehydration under reduced pressure was performed, and the following formula was used.
165.7 g (1.0 mol) of a ketalized product of 3-chloro-1,2-propanediol represented by (XXIV) was obtained. Yield 73.3%.

[0073]

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(B) Deketalization reaction 67.8 ketalized product of 3-chloro-1,2-propanediol represented by the formula (XXIV) obtained by the above reaction as a raw material.
g (0.45 mol), and a deketalization reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at a reaction temperature of 80 ° C. 47.3 g (0.43 mol) of propanediol were obtained. The yield in this deketalization reaction was 95%. Acid value 0.4 (calculated value 0), hydroxyl value 1010 (calculated value 1015). As a result of analyzing the product by gas chromatography, the area percentage of 3-chloro-1,2-propanediol was 91%. Further, the charging yield of the target product obtained with respect to the raw materials charged in the deketalization reaction was 69.8%.

[0075]

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Comparative Example 1 (a) Deketalization Reaction The 1,3-formula represented by the formula (VII) obtained in (a) of Example 1
To 150 g (0.58 mol) of dioxolan caprylate, 525 g of ethanol and 262.5 g of ion-exchanged water
And 0.15 g of concentrated hydrochloric acid, and after performing a deketalization reaction for 2 hours while refluxing at 80 ° C., neutralize the catalyst with an aqueous solution of N / 2 potassium hydroxide, and heat at 2.67 kPa and 60 ° C. for 5 hours. The ethanol was distilled off under reduced pressure and dehydrated to obtain caprylic acid monoglyceride 12 represented by the formula (VIII).
4.3 g (0.57 mol) were obtained. The yield in this deketalization reaction was 98%. Acid value 0.3 (calculated value 0), saponification value 218 (calculated value 257). As a result of analyzing the product by gas chromatography, glycerin (5%) and caprylic acid (4%) were generated by hydrolysis of the ester, and the area percentage of caprylic acid monoglyceride was 85%. Further, in such a usual deketalization reaction, since the amount of the solvent and water used is large, the charging yield of the target product obtained with respect to the charged raw material is 13.3.
%Met.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 43/13 C07C 43/13 D 67/297 67/297 69/30 69/30 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Kaoru Ohmae 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Research Center

Claims (1)

[Claims] 1. A compound of the general formula (I) [Wherein, R ¹ and R ² are the same or different and each have a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a total of 6 carbon atoms which may be substituted with an alkyl group. And 30 to 30 aryl groups, and R ¹ and R ² may together form a ring. X represents a group or a halogen atom represented by R ³ O-, R ³ is a hydrogen atom, a straight-chain or branched-chain saturated or unsaturated aliphatic hydrocarbon group having a carbon number of 1 to 23, 1 to 22 carbon atoms A glyceryl group which may be substituted with an aliphatic acyl group, an alkyl group or an acyl group, or protected with a ketal or acetal. A represents an alkylene group having 2 to 4 carbon atoms, and n A's may be the same or different. n is a number from 0 to 100 indicating the average number of added moles of the alkylene oxide. Where n is 0
Then X is not HO-. A compound having a structure in which the two hydroxyl groups of the polyhydric alcohol or a derivative thereof represented by the above formula is protected by a ketal or an acetal (deketalization and deacetalization) to obtain a compound represented by the general formula (II): [Wherein, X, A and n have the above-mentioned meanings. In producing the polyhydroxyl compound represented by
A method for producing a polyhydroxyl compound, wherein deprotection is performed by contacting with water vapor.