JPH11310544A - Production of glyceryl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a high purity glyceryl ether, capable of producing the glyceryl ether in a high yield and in the high conversion of a raw material alcohol compound. SOLUTION: This method for producing a glyceryl ether comprises reacting an alcohol compound with an α-epihalohydrin in the presence of an acid catalyst containing an aluminum compound of the general formula: Al(R<1> -SO3 )1 (R<2> )m (R<3> )n [R<1> exhibits a hydrocarbon group which may have a substituent; R<2> is a hydrocarbon group which may have a substituent, a hydrocarbonoxy group which may have a substituent, or a halogen atom; R<3> is an aromatic hydrocarbonoxy group which may have a substituent; (l), (m) and (n) are each a number of 0-3 so as to give a relation of the equation: (l)+(m)+(n)=3 wherein (l) is not zero], treating the reaction product with an alkali to produce the ring-closed product, and subsequently hydrolyzing the product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing glyceryl ether with high selectivity and high yield.

[0002]

2. Description of the Related Art As a method for producing glyceryl ether,
A method in which alcohols and α-epihalohydrin are condensed and ring-closed with an alkali in the presence of a phase transfer catalyst to carry out further hydrolysis, and a method in which alcohols and α-epihalohydrin are reacted in the presence of an acid catalyst to form halohydrin. There has been known a method in which a ring is closed with an alkali after being converted into an ether, and this is hydrolyzed.

[0003]

However, the former requires an excessive use of α-epihalohydrin in order to avoid further addition of alcohols to the glycidyl ether produced as an intermediate. In the latter case, when the acid catalyst is a Bronsted acid such as sulfuric acid, the conversion of the raw material alcohols is low, and when the acid catalyst is a highly active Lewis acid catalyst such as boron trifluoride or tin tetrachloride, The excess reaction of α-epihalohydrin to the intermediate halohydrin ether tends to occur, and in order to avoid this, it is necessary to use alcohols in sufficient excess with respect to α-epihalohydrin. Further, when a metal chloride such as aluminum chloride, tin chloride, or iron chloride is used as the Lewis acid catalyst, there is also a problem that the catalyst is deactivated by alcoholysis and a generated free chlorine group reacts with α-epihalohydrin. Further, there is another problem that a hydrophilic solvent or a phase transfer catalyst must be used in order to efficiently perform ring closure of the halohydrin ether with an alkali.

[0004] Accordingly, the present invention provides a high conversion of alcohols, a high yield of a halohydrin ether intermediate, a high efficiency of the subsequent ring closure reaction, and a high yield of a glycidyl ether intermediate. It is an object of the present invention to provide a method for producing glyceryl ether with high yield.

[0005]

The present invention provides the following general formula (1):

[0006]

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[Wherein, R ¹ represents a hydrocarbon group which may have a substituent, and R ² may be a hydrocarbon group which may have a substituent or may have a substituent. It represents an aliphatic hydrocarbon oxy group or a halogen atom, and R ³ represents an aromatic hydrocarbon oxy group which may have a substituent. l, m and n each represent a number of 0 to 3 such that 1 + m + n = 3, but 1 does not become 0). In the presence of an acid catalyst containing an aluminum compound represented by the formula (1), alcohols and α-epihalohydrin And then reacting with an alkali treatment to close the ring and hydrolyze it to provide a method for producing glyceryl ether.

The present invention also relates to a method of reacting an alcohol with an α-epihalohydrin in the presence of (A) an aluminum alkoxide and (B) a phenol and / or a sulfonic acid, followed by an alkali treatment to effect ring closure. A process for producing glyceryl ether, which hydrolyzes glyceryl ether.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), the optionally substituted hydrocarbon group represented by R ¹ may be a hydroxyl group, an alkoxyl group or an alkyl group optionally substituted by a halogen atom. Group or alkenyl group; alkyl group,
Examples thereof include a hydroxyl group, an alkoxyl group, and an aryl group optionally substituted with a halogen atom. Here, the alkyl group which may have a substituent has 1 carbon atom.
-36 linear or branched alkyl groups, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, Undecyl group, dodecyl group,
Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 2-ethylhexyl, 3,5
-Dimethylhexyl group and the like. Examples of the alkenyl group which may have a substituent include a linear or branched alkenyl group having 2 to 36 carbon atoms, and specific examples thereof include a vinyl group, a propenyl group, an oleyl group, and a linole group. No. Examples of the aryl group which may have a substituent include a phenyl group and a naphthyl group. Examples of the alkoxyl group which may be substituted with these alkyl group, alkenyl group and aryl group include those having 1 to 1 carbon atoms.
36 straight or branched chain alkoxyl groups, specific examples of which include methoxyl, ethoxyl, propoxyl, isopropoxyl, pentyloxy, hexyloxy, heptyloxy, octyloxy, Nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy Group, 2-ethylhexyloxy group, 3,5-dimethylhexyloxy group and the like. Examples of the halogen atom which may be substituted with the alkyl group, the alkenyl group and the aryl group include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. Examples of the alkyl group which may be substituted with the aryl group include the same linear or branched one having 1 to 36 carbon atoms as described above.

Of these R ¹ , the above-mentioned optionally substituted alkyl, alkenyl, phenyl and naphthyl groups, and the above-mentioned optionally substituted alkyl, phenyl and naphthyl groups Is preferable, and among these,
Examples of the alkyl group which may have a substituent include a methyl group and a trifluoromethyl group, and examples of the phenyl group which may have a substituent include a phenyl group, a chlorophenyl group, a methylphenyl group, and an ethyl group. A phenyl group, a propylphenyl group, a butylphenyl group, a dodecylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a propoxyphenyl group, a butoxyphenyl group and a hydroxyphenyl group may be a naphthyl group which may have the above substituent. And a hydroxynaphthyl group are particularly preferred. Most preferred as R ¹ is a hydroxyphenyl group.

[0011] In the general formula (1), as the hydrocarbon group which may have a substituent group represented by R ^2, provides the same as those listed above R ^1, a polyoxyalkylene group as a substituent Ones having. Examples of the aliphatic hydrocarbon oxy group which may have a substituent represented by R ² include a hydroxyl group, an alkoxyl group, a polyoxyalkylene group or an alkoxyl group or an alkenyloxy group which may be substituted with a halogen atom. No. Here, as the alkoxyl group which may have a substituent, the alkoxyl group as a substituent and a halogen atom, the same as those described above can be mentioned. Further, the alkenyloxy group which may have a substituent has 2 to 2 carbon atoms.
36 linear or branched alkenyloxy groups are mentioned, and specific examples thereof include a propenyloxy group, an oleyloxy group, a linoloxy group and the like. Among these aliphatic hydrocarbonoxy groups which may have a substituent, an alkoxyl group and an alkenyloxy group, particularly an alkoxyl group, are preferred. Further, R ² may be a halogen atom. In this case, the halogen atom is preferably a chlorine atom or a bromine atom. Most preferred as R ² are isopropoxyl and isobutoxyl.

In the general formula (1), examples of the optionally substituted aromatic hydrocarbonoxy group represented by R ³ include those substituted with an alkyl group, a hydroxyl group, an alkoxyl group or a halogen atom. A good aryloxy group is mentioned, and specific examples thereof are particularly preferably a phenoxyl group, a hydroxyphenoxyl group, a chlorophenoxyl group, a dichlorophenoxyl group, a trichlorophenoxyl group, and a naphthoxyl group.

Specific examples of the aluminum compound (1) include the following compounds.

[0014]

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[0015]

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The aluminum compound (1) is obtained, for example, by reacting a sulfonic acid with a trialkylaluminum, trialkoxyaluminum or aluminum trihalide (halogen: chlorine or bromine) to form an alkyl group of the trialkylaluminum, It is produced by partially or completely substituting an alkoxyl group or a halogen group of aluminum trihalide with the sulfonic acids, and further substituting the remaining alkyl group, alkoxyl group or halogen group with an appropriate alcohol or phenol. . The substitution reaction with sulfonic acids and the substitution reaction with alcohols and phenols are performed by heating in a solvent such as a hydrocarbon or alcohol.

Aluminum compound (1) used in the present invention
Among them, the most preferred are those synthesized from aluminum triisopropoxide or aluminum triisobutoxide and p-phenolsulfonic acid, that is, the compounds (a), (b), (c), (k) and (L).

In the process for producing glyceryl ether of the present invention, by using an acid catalyst containing the above aluminum compound (1), particularly at the stage of producing a halohydrin ether intermediate, a metal chloride such as aluminum chloride or iron chloride is used. As in the case of using as a catalyst, there is no catalyst deactivation due to alcoholysis, and there are few side reactions such as polymerization of raw material epihalohydrin and excessive addition to halohydrin ether,
The reaction can proceed with high yield.

The alcohol used in the present invention is not particularly limited, but for example, the following general formula (2)

[0020]

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Wherein R ⁴ represents a saturated or unsaturated linear or branched hydrocarbon group having 1 to 36 carbon atoms, A ¹ represents an alkylene group having 2 to 4 carbon atoms, and p represents Indicates the number from 0 to 100. ] Are represented. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol,
In addition to aliphatic saturated alcohols such as dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, 2-ethylhexanol and 3,5-dimethylhexanol, oleyl alcohol And aliphatic unsaturated alcohols such as linole alcohol and alkylene oxide adducts thereof. The alkylene oxide adduct is preferably an ethylene oxide adduct (A ¹ is ethylene in the general formula (2)), and the number of moles added (p in the general formula (2)) is preferably from 0 to 20. ,
As the alcohols, those to which no alkylene oxide is added (p = 0 in the general formula (2)) are preferable.
Further, R ⁴ preferably has ⁴ to 22 carbon atoms, and more preferably 4 to 18 carbon atoms.

The α-epihalohydrin used in the present invention includes α-epichlorohydrin, α-epibromohydrin, and α-epiiodohydrin. Hydrin is preferred.

The reaction between alcohols and α-epihalohydrin may be carried out in the same manner as in normal halohydrin etherification, except that the aluminum compound (1) is used as an acid catalyst. That is, α-epihalohydrin is used in an amount of 0.5 to 1.5 mole times, preferably 0.6 to 1.5
The aluminum compound (1) is used in an amount of 0.001 to 0.1 mole, preferably 0.005 to 0.05 mole, based on the alcohol.
0-150 ° C, preferably 70-120 ° C, 0.5-
It is good to do for 10 hours.

All of the above reactions are carried out in the presence of an aluminum alkoxide (A) and a phenol and / or sulfonic acid (B) in place of the acid catalyst containing the aluminum compound (1). In this case also, the aluminum compound (1)
The same good results as those obtained by using are obtained. this is,
It is presumed that the reaction of (A) aluminum alkoxide with (B) phenols and / or sulfonic acids produces an aluminum compound (1), which acts as an acid catalyst.

That is, by reacting an alcohol with epihalohydrin in the presence of (A) aluminum alkoxide and (B) phenols and / or sulfonic acids, the corresponding halohydrin ether can be obtained in high yield.

The aluminum alkoxide (A) used herein may be any of mono-, di- and trialkoxides, but more preferably trialkoxides, and the alkoxyl group has 1 to 4 carbon atoms. Some are preferred. More specifically, examples of the aluminum trialkoxide include aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, and aluminum triisobutoxide, and aluminum triisopropoxide and aluminum triisobutoxide are particularly preferable. These may be commercially available products, or may be a mixture of a mono-, di-, or trialkoxide compound obtained by reacting an aluminum trihalide or a trialkylaluminum with an alcohol. In this case as well, it is preferable to select conditions that increase the content of the trialkoxide compound.

(B) The phenols may be those having a phenolic hydroxyl group which may be substituted with a halogen atom, such as phenol, chlorophenol, dichlorophenol, 2,4,6-trichlorophenol, -Naphthol, 2-naphthol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, binaphthol and the like.

(B) As the sulfonic acids, R ¹ SO ₃ H
In the above, for example, as R ¹ , an alkyl group or an alkenyl group optionally substituted by a hydroxyl group, an alkoxyl group or a halogen atom; an aryl optionally substituted by an alkyl group, a hydroxyl group, an alkoxyl group or a halogen atom And those having a group. These alkyl groups and the like are the same as those described above. More specifically, methanesulfonic acid, trichloromethanesulfonic acid, benzenesulfonic acid or naphthalenesulfonic acid which may be substituted with an alkyl group or a hydroxyl group having 1 to 12 carbon atoms, and preferably 2,
Examples include 4,6-trichlorophenolsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, phenolsulfonic acid, dodecylbenzenesulfonic acid, and naphthalenesulfonic acid, and phenolsulfonic acid is particularly preferred.

Among these, the most preferable combination is a case where aluminum triisopropoxide or aluminum triisobutoxide is used as (A) and p-phenolsulfonic acid is used as (B).

As described above, when the reaction is carried out in the presence of (A) aluminum alkoxide and (B) phenols and / or sulfonic acids, the ratio of the raw materials used, the reaction temperature and the reaction time are determined by using the aluminum compound (1). This is the same as in the case of using an acid catalyst. The amount of (A) aluminum alkoxide and (B) phenols and / or sulfonic acids used is such that (A) aluminum alkoxide is 0.001 to 0.1 times by mole, especially 0.002 to 0 times the amount of alcohols. 0.05 mole times, (B) phenols and / or sulfonic acids are 1.0 to 3.0 mole times, especially 2.0 to 2.0 mole times, relative to (A) aluminum alkoxide.
It is preferable that the amount is 3.0 mole times.

When the aluminum compound (1) or (A) aluminum alkoxide, (B) phenols and / or sulfonic acids are added in the form of an aqueous solution or hydrate, the reaction can be carried out as it is, It is preferable to remove water from the system in accordance with the above because both the reaction rate and the yield increase.

In order to produce glyceryl ether from halohydrin ether obtained by the above reaction via glycidyl ether, an alkali is added without removing the catalyst from the reaction mixture, and the ring is closed by a dehydrohalogenation reaction. A hydrolysis reaction may be performed. Here, the ring closure reaction and the hydrolysis reaction can be separately performed, or may be performed simultaneously.

When the ring-closing reaction and the hydrolysis reaction are separately performed, after the ring-closing reaction is completed, the remaining raw material alcohols and epihalohydrin, as well as by-products, can be separated by known separation and purification means.
Specifically, it can be removed by distillation, washing, recrystallization, column chromatography or the like, but the next hydrolysis reaction may be carried out without removal. As by-products, in the halohydrin etherification reaction, α-epihalohydrin is excessively added to the halohydrin ether intermediate, and further, a glycidyl ether derivative subjected to ring closure by the alkali of the ring closure reaction, and an alcohol at the 2-position of epihalohydrin Addition of ring-opened isomers of halohydrin ether, polymer of epihalohydrin and glycidyl ether derivative obtained by subjecting the polymer to ring-closing reaction, salts produced as a by-product of ring-closing reaction, and glycidyl ether formed by ring-closing reaction remain Examples thereof include a dialkyl product reacted with an alcohol, a polymer polymerized between glycidyl ethers formed, a cross-reaction product between these compounds, and a reaction product of these compounds with glycidyl ether.

Examples of the alkali used in the ring closure reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. Sodium and potassium hydroxide are preferred. Further, it is preferable to use 1.0 to 4.0 mole times, particularly 1.0 to 2.5 mole times of the alkali with respect to the charged amount of epihalohydrin, and it is preferable to add the alkali as, for example, a 10 to 50% aqueous solution. preferable. The reaction temperature is preferably from 40 to 110 ° C, and the reaction is preferably performed for several hours.

Glyceryl ether can be obtained by hydrolyzing the glycidyl ether obtained as described above by a known method. Specifically, hydrolysis can be performed directly with an aqueous solution of an acid or an alkali, and glycidyl ether is reacted with a carboxylic acid to form α.
-A method of leading to glycerol esters and hydrolyzing them, the hydrolysis of glycidyl ethers to fatty acid mono and / or
Or a method in an aqueous solution of a polycarboxylate (Japanese Patent Laid-Open No.
No. 9-86307), a method in which a carbonyl compound is added to glycidyl ether to lead to a 1,3-dioxolane compound, which is hydrolyzed (JP-A-56-1332).
No. 81), a glycidyl ether is reacted with a carboxylic anhydride in the presence of a catalyst to give a diester compound,
A method of hydrolyzing it (JP-A-58-134049) and a method of reacting glycidyl ether with benzyl alcohol in the presence of a base and hydrolyzing it in the presence of a metal catalyst (JP-A-62-84036) JP-A-5-32578, a method in which phosphoric acid or activated clay is used as an acid catalyst for the hydrolysis reaction of glycidyl ether, and N, N-substituted amide is added as a solvent. Is used as a solvent (JP-A-6-25053), a method of performing a hydrolysis reaction of glycidyl ether in the presence of a tertiary amine (JP-A-7-53431), and the like. To obtain glyceryl ether.

Specifically, for example, Japanese Patent Application Laid-Open No. 49-8630
When the hydrolysis reaction is carried out in an aqueous solution of an aliphatic mono- and / or polycarboxylic acid salt (hereinafter simply referred to as carboxylic acid) according to JP-A-7, the carboxylic acid is not particularly limited, Examples thereof include carboxylic acids having a saturated or unsaturated linear or branched hydrocarbon group having 1 to 36 carbon atoms. Examples of such carboxylic acids include acetic acid, octanoic acid, lauric acid, stearic acid, triacontanic acid, 2-ethylhexanoic acid, 3,5-dimethylhexanoic acid, succinic acid, lauryl succinic acid, citric acid and the like. In addition to saturated carboxylic acids, unsaturated carboxylic acids such as oleic acid and linoleic acid may be mentioned, but carboxylic acids having 1 to 22 carbon atoms are preferred from the viewpoint of easy handling, and carboxylic acids having 1 to 18 carbon atoms are particularly preferred. preferable. These can be used in an amount of 0.001 to 10 molar equivalents relative to glycidyl ether, but from the viewpoint of reaction rate and cost, 0.01
It is preferable to use from 1 to 1 molar equivalent, particularly from 0.03 to 0.
It is preferred to use 2 molar equivalents.

Examples of the alkali include, but are not particularly limited to, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. Sodium oxide or potassium hydroxide is preferred. These can be used in an amount of 0.01 to 10 molar equivalents based on the carboxyl group of the carboxylic acid to be used, but from the viewpoint of the reaction rate and selectivity, it is particularly preferable to use 0.1 to 1 molar equivalent.

Although the amount of water used is not particularly limited, it can be used in an amount of 1 to 100 molar equivalents relative to glycidyl ether. Especially from the viewpoint of reaction selectivity and productivity,
10 molar equivalents are preferred.

The hydrolysis reaction using this carboxylic acid is as follows:
The reaction can be carried out at 50 ° C. to 250 ° C. under normal pressure or under pressure.
It is preferable to carry out the reaction at a temperature of 200C for 0.1 to 30 hours.

For example, it is used when a carbonyl compound is added to glycidyl ether described in JP-A-56-133281 to produce a 1,3-dioxolane compound, and a hydrolysis reaction is carried out according to a method of hydrolyzing the compound. Examples of the carbonyl compound include common ketones and aldehydes. More specifically, aliphatic ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, dipropyl ketone, ethyl propyl ketone, methylhexyl ketone or cyclic ketones such as cyclobutanone, cyclopentanone, cyclohexanone, cyclooctanone, acetophenone , Aromatic ketones such as benzophenone, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, octyl aldehyde, cyclic aldehydes such as cyclopentyl aldehyde and cyclohexyl aldehyde,
And aromatic aldehydes such as benzaldehyde and naphthyl aldehyde. Lower carbonyl compounds having a small number of carbon atoms are preferred from the viewpoint of ease of post-treatment, and those having 6 or less carbon atoms are particularly preferred.

As an acid catalyst for synthesizing a dioxolane from a glycidyl ether and a carbonyl compound, the reaction proceeds as long as there is an excess of the carbonyl compound even if not used, but either a protonic acid or a Lewis acid can be used. . Protic acids include mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and fatty acids, and organic acids such as paratoluenesulfonic acid. Lewis acids include boron trifluoride etherate complex, boron trifluoride acetic acid complex, Boron fluoride phenol complex, aluminum chloride, aluminum bromide, zinc chloride, tin tetrachloride, antimony chloride, titanium tetrachloride,
Silicon tetrachloride, ferric chloride, ferric bromide, cobaltous chloride, cobaltous bromide, zirconium chloride, boron oxide, acidic activated alumina, aluminum compound (1) and the like can be mentioned.

As the reaction solvent, any solvent which does not affect the reaction can be used, but aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and aromatic hydrocarbons such as benzene, xylene and toluene can be used. And hydrocarbon solvents such as cyclic hydrocarbons such as cyclopentane and cyclohexane.

In the step of producing dioxolanes from the glycidyl ether, the carbonyl compound is used in an amount of 1 to 30 molar equivalents, preferably 2 to
15 molar equivalents, particularly preferably 4 to 10 molar equivalents,
In the presence of 0.001 to 0.2 molar equivalents, preferably 0.01 to 0.1 molar equivalents of the above acid catalyst based on glycidyl ether, at 0 to 70 ° C, preferably 0 to 60 from the viewpoint of reaction selectivity. C., particularly preferably at 20 to 50.degree.

When the reaction is carried out under the above conditions, the dioxolane is usually obtained in a high yield of 90% or more. If necessary, the dioxolane can be purified by a known method such as distillation, but without purification. It can be used as it is for the next hydrolysis reaction.

The dioxolane can be hydrolyzed by a known method. More specifically, mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, paratoluenesulfonic acid, benzenesulfonic acid, and the like can be used. It can be achieved by heating in water using a proton acid catalyst such as an organic acid such as acetic acid. The amount of the acid catalyst to be used is not particularly limited, but 0.01 to 2N is sufficient.
0.5 is preferred.

In order to improve the solubility of dioxolanes in water, water-soluble organic solvents such as lower alcohols such as methanol, ethanol and isopropanol, and TH
It is preferable to add F, dioxane, etc., and carry out at 50 to 100 ° C.

The glyceryl ether obtained as described above can be isolated and purified by known separation and purification means, specifically, distillation, washing, recrystallization, column chromatography and the like.

[0048]

Example 1 117 g of octyl alcohol, 3.61 g of aluminum triisopropoxide and 9.40 g of p-phenolsulfonic acid were placed in a 1-L eggplant-shaped flask and heated to 100 ° C. while stirring. Further under reduced pressure (6.67 kPa)
After stirring for 1 hour, 100 g of epichlorohydrin was added to 30
Minutes, and the mixture was stirred for 3 hours. The reaction mixture is brought to 50 ° C.
The mixture was cooled to 50 ° C., and while maintaining the temperature at 50 ° C., 400 mL of a 48% aqueous sodium hydroxide solution was added dropwise over 1 hour. After stirring for 3 hours, 200 mL of water was added to separate layers. After removing the aqueous layer, the mixture was further washed twice with 300 mL of water to obtain 200 g of crude octyl glycidyl ether. 175 g of this crude octyl glycidyl ether, 110 g of water, 7.
1 g and 0.71 g of sodium hydroxide were put in a 2 L autoclave, the temperature was raised to 157 ° C. with stirring, and the mixture was stirred for 5 hours. This was extracted with 500 mL of ethyl acetate, washed twice with 300 mL of water, and the solvent was distilled off.
g of crude monooctyl glyceryl ether was obtained. Purification was performed by distillation under reduced pressure (53 to 67 Pa, 120 to 123 ° C.) to obtain 124 g of monooctyl glyceryl ether. Purity was more than 99% by GLC. The overall yield based on octyl alcohol was 75%.

200 MHz ¹ H-NMR (deuterated chloroform, internal standard; TMS) 0.9 ppm (3H, triplet,-(CH ₂ ) ₇ CH ₃ ) 1.2-1.5 ppm (10 H, overlapping broad peaks) _{, -CH 2 CH 2 (C H} 2) 5 CH 3) 1.58ppm (2H, _{triplet, -CH 2 C H 2 (CH} 2) 5 CH 3) 3.45ppm (4H, complex multiplet, - _{C H 2 OC H 2 -)} 3.63ppm (2H, _{quartet, -C H 2 OH) 3.85ppm (} 1H, complex _{multiplet, -CH 2 C H (OH)} CH 2 OH)

Example 2 175 g of crude octyl glycidyl ether obtained in the same manner as in Example 1, 110 g of water, 21.3 g of lauric acid
And 2.1 g of sodium hydroxide were placed in a 500 mL four-necked flask, and heated to 100 ° C. while stirring. After stirring for 6 hours, the resulting reaction mixture was subjected to reduced pressure (5.3
After removing water at 100 ° C. and reduced pressure distillation (5 kPa).
(3 Pa, 120-123 ° C.) to obtain 127 g of monooctyl glyceryl ether. Purity was more than 99% by GLC. The total yield based on octyl alcohol was 77%.

Example 3 158 g of isoamyl alcohol, 3.61 g of aluminum triisopropoxide and 9.40 g of p-phenolsulfonic acid were placed in a 1-L eggplant-shaped flask, and the temperature was raised to 90 ° C. while stirring. Further under reduced pressure (26.7 kPa) 1
After stirring for an hour, the temperature was raised to 100 ° C., 170 g of epichlorohydrin was added dropwise over 30 minutes, and the mixture was stirred for 3 hours. The reaction mixture was cooled to 50 ° C. and maintained at 50 ° C. for 4 hours.
800 mL of an 8% aqueous sodium hydroxide solution was added dropwise over 1 hour, and after stirring for 3 hours, 400 mL of water was added and the layers were separated. After removing the aqueous layer, the mixture was further washed twice with 500 mL of water to obtain 280 g of crude isoamyl glycidyl ether. The obtained crude isoamyl glycidyl ether 140
g, 140 g of water, 7.64 g of lauric acid and 2.14 g of sodium hydroxide were placed in a 2 L autoclave, the temperature was raised to 157 ° C. with stirring, and the mixture was stirred for 5 hours. This was extracted with 500 mL of ethyl acetate, and further extracted with 300 mL of water.
After washing twice, the solvent was distilled off to obtain 157 g of crude monoisoamyl glyceryl ether. Vacuum distillation (267 Pa,
114-115 ° C) to obtain 103 g of monoisoamyl glyceryl ether. The overall yield based on isoamyl alcohol was 71%. ¹ H-NMR
(200 MHz), the disappearance of the proton signal at δ = 2.60 and 2.80 (methylene on the epoxy ring) was recognized, and the compound was identified. Purity was more than 99% by GLC.

Example 4 190 g of n-amyl alcohol, 3.61 g of aluminum triisopropoxide and 9.40 g of p-phenolsulfonic acid were placed in a 1-L eggplant-shaped flask, and the temperature was raised to 90 ° C. while stirring. Further under reduced pressure (26.7 kPa) 1
After stirring for an hour, the temperature was raised to 100 ° C., 165 g of epichlorohydrin was added dropwise over 30 minutes, and the mixture was stirred for 3 hours. After removing excess alcohol at 100 ° C. under reduced pressure (53 Pa), the reaction mixture was cooled to 50 ° C., transferred to a 2 L autoclave, and treated with a 48% aqueous solution of potassium hydroxide 21%.
4.3 g was dripped in one hour, and 10.7 g of lauric acid was further added.
And heated to 160 ° C. while stirring. After stirring for 5 hours, the mixture was cooled to room temperature. From the resulting reaction mixture,
After removing water at 100 ° C. under reduced pressure (53 Pa), the precipitated salt was removed by filtration, and further distilled under reduced pressure (267P).
a, 114-115 ° C.) to obtain 222 g of monoamyl glyceryl ether. The overall yield based on epichlorohydrin was 77%.

200 MHz ¹ H-NMR (deuterated chloroform, inner standard; TMS) 0.9 ppm (3H, triplet,-(CH ₂ ) ₇ CH ₃ ) 1.2-1.5 ppm (4H, overlapping broad peaks) _{, -CH 2 CH 2 (C H} 2) 2 CH 3) 1.58ppm (2H, _{triplet, -CH 2 C H 2 (CH} 2) 5 CH 3) 3.45ppm (4H, complex multiplet, - _{C H 2 OC H 2 -)} 3.63ppm (2H, _{quartet, -C H 2 OH) 3.85ppm (} 1H, complex _{multiplet, -CH 2 C H (OH)} CH 2 OH)

Example 5 50 mL of toluene, 3.6 of aluminum isopropoxide
0 g and 9.21 g of p-phenolsulfonic acid in 100 parts
The mixture was placed in a 4-mL four-necked flask, and stirred for 3 hours while introducing nitrogen using a Dean-Stark trap while introducing nitrogen. The solvent was distilled off to obtain 9.6 g of an aluminum compound (1) (a) as a pale yellow solid. Confirmation was made by IR. Confirmation of ν _OH = 3281 cm ⁻¹ (phenolic hydroxyl group) Confirmation of disappearance of ν _CH = 2800 to 3000 cm ⁻¹ ( _CH stretching derived from isopropyl group)

270 g of isostearyl alcohol and 5.44 g of the aluminum compound (1) (a) were placed in a four-necked flask, and the temperature was raised to 95 ° C. while stirring under nitrogen. 92.5 g of epichlorohydrin was added dropwise over 1 hour, and the mixture was stirred for 3 hours. Then cool to 50 ° C, 48%
After 83.3 g of an aqueous sodium hydroxide solution was added dropwise over 1 hour, the mixture was stirred at 80 ° C. for 3 hours. The reaction mixture was separated by adding 200 mL of water, and the aqueous layer was removed. 293 g of the obtained crude isostearyl glycidyl ether was added to acetone 365
g and 9 g of boron trifluoride etherate were dropped into the 2 L four-necked round bottom flask over 2 hours while cooling so as to keep the temperature at 20 to 30 ° C. After reacting for 1 hour, the reaction mixture was poured into a large amount of a diluted aqueous solution of sodium bicarbonate to neutralize the mixture. After adding ether and stirring, the mixture was allowed to stand and separated to separate an ether layer. After adding sodium sulfate to remove water and removing the solid by filtration, the solvent was distilled off from the filtrate at room temperature under reduced pressure (133 Pa).

298 g of the obtained 2,2-dimethyl-4-isostearyloxymethyl-1,3-dioxolane was charged into a 5 L four-necked round bottom flask, and 800 mL of ethanol and 800 mL of 0.1N sulfuric acid were added thereto. The temperature was raised to 80 ° C. while stirring. After reacting for 10 hours, the mixture was cooled to room temperature, allowed to stand, separated, and an oil layer was taken out. The aqueous layer was extracted twice with 300 mL of ether, and the residual oil was neutralized by adding an aqueous sodium bicarbonate solution together with the oil layer.
Separate the layer to remove the aqueous layer, and reduce the pressure (13.3 Pa) to 100
Drying at 3 ° C. for 3 hours gave 273 g of α-monoisostearyl glyceryl ether. The total yield based on isostearyl alcohol was 79%, and the purity was 99% or more based on GLC.

[0057]

According to the present invention, glyceryl ether used in various applications such as solvents, cosmetics, detergents, emulsifiers, humectants, lubricants and oils can be used with a high conversion of raw material alcohol and high yield. Can be manufactured with high purity.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tomohito Kitsuki 1334 Minato, Wakayama City, Wakayama Prefecture Inside Kao Research Institute

Claims (5)

[Claims] 1. The following general formula (1): [Wherein, R ¹ represents a hydrocarbon group which may have a substituent, and R ² represents a hydrocarbon group which may have a substituent or an aliphatic hydrocarbon which may have a substituent. R ³ represents a hydrogen oxy group or a halogen atom, and R ³ represents an aromatic hydrocarbon oxy group which may have a substituent. l, m and n each represent a number of 0 to 3 such that 1 + m + n = 3, but 1 does not become 0). In the presence of an acid catalyst containing an aluminum compound represented by the formula (1), alcohols and α-epihalohydrin And then reacting with an alkali to close the ring and hydrolyze it to produce glyceryl ether. 2. In the formula (1), R ¹ is a hydroxyl group, an alkoxyl group or an alkyl or alkenyl group which may have a halogen atom as a substituent, or an alkyl group, a hydroxyl group or an alkoxyl group as a substituent. Or an aryl group optionally having a halogen atom, wherein R ² is a hydroxyl group, an alkoxyl group, a polyoxyalkylene group or an alkyl group, an alkenyl group, an alkoxyl group which may have a halogen atom, or An alkenyloxy group, or an alkyl group as a substituent, a hydroxyl group, an alkoxyl group, or an aryl group which may have a halogen atom, wherein R ³ represents an alkyl group, a hydroxyl group, an alkoxyl group, or a halogen atom as a substituent; Aryloxy group which may be possessed The method for producing glyceryl ether according to claim 1, wherein 3. An alcohol is reacted with α-epihalohydrin in the presence of (A) an aluminum alkoxide and (B) phenols and / or sulfonic acids, and then the ring is closed by an alkali treatment to hydrolyze the ring. A method for producing glyceryl ether. 4. The process for producing glyceryl ether according to claim 3, wherein (A) is an aluminum trialkoxide. 5. A method according to claim 1, wherein (B) is phenol or naphthol optionally substituted with a halogen atom,
The method for producing glyceryl ether according to claim 3 or 4, wherein the alkyl group or hydroxyl group is benzenesulfonic acid or naphthalenesulfonic acid which may be substituted.