JPH09316017A - Production of ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply and easily produce an ether compound useful as a solvent, etc., in high yield. SOLUTION: This ether compound is produced by proceeding a reaction of a hydroxy compound with a carbonyl compound in a hydrogen atmosphere under a catalyst while removing a formed water as a by-product with the proviso that at least one kind of hydroxy and carbonyl compounds is a polyfunctional compound. A polyfunctional alcohol used in the reaction has 2-10 hydroxy groups and polyfunctional carbonyl compound is a 2-20C compound having 2-10 carbonyl groups. The catalyst is a palladium catalyst, etc., supported on a carbon, etc. The water formed as a by-product is preferably distilled off with an unreacted raw material and the unreacted raw material is preferably separated from the water and returned to the reaction system.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a method for producing an ether compound. More specifically, the present invention relates to a method for producing an ether compound, which can be easily and inexpensively supplied with a high yield of an ether compound that can be widely used in solvents, cosmetics, detergent compositions, lubricants, emulsifiers and the like.

[0002]

2. Description of the Related Art Conventionally, as ether compounds, diethyl ether, dibutyl ether, diethylene glycol diethyl ether and the like have been used as solvents. However, at present, those having a higher molecular weight or asymmetric type are hardly used because of difficulty in synthesis. Particularly, as an oil agent that can be blended into cosmetics and the like, ether compounds are becoming more useful because they are less sticky and do not hydrolyze as compared with ester oil agents that are currently widely used.

[0003] Further, the use of ether compounds as an oil agent as a detergent composition or as a new nonionic activator is also conceivable. Furthermore, it can be used as a solvent, a lubricant, an emulsifier, etc. Expectations for the use of ether compounds are increasing for the reasons described above, but the present situation is that truly useful ether compounds cannot be produced at a high yield in a simple and inexpensive manner.

[0004] Conventionally used methods for synthesizing ether compounds include, for example, synthesis from alcoholates and alkyl halides (Williamson synthesis method), synthesis from alcohols and ester compounds, and acid synthesis between alcohols. , And synthesis by addition of an alcohol to an olefin.

[0005] However, in the synthesis from an alcoholate and an alkyl halide, an alcohol and an equivalent of metal (Na, K, etc.) or an alkali are required to form the alcoholate. Is produced, which is not industrially preferable. In addition, for the synthesis from alcohol and ester compounds, the ester compound is limited to dimethyl sulfate, diethyl sulfate, etc., which is preferable for the synthesis of methyl ether and ethyl ether, but an ether compound having more carbon atoms than these compounds is synthesized. It is difficult to do.

[0006] The dehydration reaction with an acid between alcohols is suitable for the synthesis of a symmetrical ether compound, but the synthesis of an asymmetrical ether compound is difficult. In addition, in the synthesis by addition of alcohol to olefins, the number of olefin compounds is limited, and many of them are quite expensive together with the catalyst to be used. Furthermore, it is difficult to recover and reuse both olefins and catalysts. Not suitable.

[0007] For example, Japanese Patent Application Laid-Open No. 48-33037 discloses the use of various monoethers, and it is specified that the Williamson method is advantageous as a synthesis method. However, as mentioned above, the Williamson method is not preferred on an industrial level. Further, the use of ether compounds is disclosed in JP-A-48-5941 and U.S. Pat. No. 4,092,254, but most of them also use the Williamson method.

In addition, as a method for synthesizing an ether, there is a method for producing an ether from an alcohol and a carbonyl compound. For example, J. Chem. Soc., 5598 (1963), Chem. Commun., 422
(1967) describes a method for synthesizing an ether compound in an alcohol-excess system under a hydrogen atmosphere at normal pressure and using an acidic catalyst. However, all of them have a large excess of alcohol, and only use of lower alcohols such as methanol, ethanol and propyl alcohol, and higher alcohols or polyhydric alcohols having more than 6 carbon atoms are not described. Also, J. Or
g. Chem., 26, 1026 (1961) discloses a method for synthesizing ethers by hydrogenolysis reaction of various ketals, and this also relates to lower alcohols having 6 or less carbon atoms, There is no description of etherification of alcohol or polyhydric alcohol, and it is not common. Further, in this reaction, there is also a disadvantage that the ketal must be once synthesized.

In recent years, as a synthetic example of an ether compound using a higher alcohol, a reduction method with triethylsilane using a strong acid as a catalyst has been developed, and various ether compounds have been synthesized from a higher alcohol and various carbonyl compounds ( Chemistry letters, P.743-746, 1985), strong acid, triethylsilane and the like are sometimes expensive, and therefore they are not industrially preferable methods.

Further, US Pat. No. 5,446,210 describes a method for producing a polyol ether by reacting at least one polyol and at least one carbonyl compound at high temperature in the presence of a hydrogenation catalyst. Has been done. However, with this method, the yield is low and it is not possible to obtain a polyol ether in a high yield.

[0011]

DISCLOSURE OF THE INVENTION As described above,
An ether compound, particularly an ether compound having two or more ether bonds, cannot be used for general purpose because it is difficult to manufacture although its use is expected, and a method for producing an ether compound that can be supplied at a high yield simply and inexpensively. Was desired. Therefore, an object of the present invention is to provide an ether compound having two or more ether bonds, which is useful as a solvent, a cosmetic, a detergent composition, a lubricant, an emulsifier, etc., in a high yield simply and inexpensively. It is to provide a manufacturing method that can.

[0012]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have earnestly studied a method for producing an ether compound having two or more ether bonds in a high yield in a simple and inexpensive manner. By using a polyvalent hydroxy compound or a polyvalent carbonyl compound as a raw material and carrying out the reaction while removing water by-produced by the reaction, it is possible to have two or more ether bonds in one step and in a high yield. They have found that an ether compound can be obtained, and have completed the present invention.

That is, according to the present invention, a polyvalent compound is used as at least one of a hydroxy compound and a carbonyl compound, and the hydroxy compound and the carbonyl compound are reacted under a hydrogen atmosphere with a catalyst to produce an ether compound. The present invention provides a method for producing an ether compound, which comprises reacting while removing by-produced water.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. In the present invention, a polyvalent compound is used as at least one of the hydroxy compound or the carbonyl compound when the ether compound is produced by reacting the hydroxy compound with the carbonyl compound in a hydrogen atmosphere using a catalyst. Examples of the method include a method of reacting a polyhydric alcohol or its derivative with a monovalent carbonyl compound, a method of reacting a monovalent hydroxy compound with a polyvalent carbonyl compound, and a method of reacting a polyhydric alcohol or its derivative with a polyvalent carbonyl compound. There is a method of reacting.

Examples of the polyhydric alcohol or its derivative used in the present invention include compounds having 2 to 10 hydroxyl groups, specifically, diols having 2 to 20 carbon atoms, glycerin, trimethylolethane and trimethylol. Examples thereof include propane, pentaerythritol, sugar, and alkylene oxide adducts thereof. Of these, diols having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, glycerin or ethylene oxide adducts thereof are particularly preferable.

Examples of the polyvalent carbonyl compound used in the present invention include compounds having 2 to 10 carbonyl groups, and specific examples thereof include chain or cyclic dicarbonyl compounds having 2 to 20 carbon atoms. To be Among these, a chain dicarbonyl compound having 2 to 10 carbon atoms and cyclohexanedione are particularly preferable.

In the present invention, the monovalent carbonyl compound to be reacted with the polyhydric alcohol or its derivative is represented by the general formula (1)

[0018]

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[In the formula, R ¹ and R ² are hydrogen atoms and have 1 to 20 carbon atoms.
Of R ¹ and R ² may be the same or different. Further, it may have a cyclic structure in which R ¹ and R ² are bonded. ] The compound represented by this is mentioned.

Specific examples of the compound represented by the general formula (1) include acetone, methyl ethyl ketone and methyl-n-.
Propyl ketone, methyl isopropyl ketone, methyl-
n-butyl ketone, methyl isobutyl ketone (4-methyl-2-pentanone), pinacolone, methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisopropyl ketone , Diisobutyl ketone, 2,
Chain ketones such as 6,6-trimethylnonanone-4,6-methyl-5-heptenone-2, cyclohexanone, 2-
Cyclic ketones such as methylcyclohexanone, isophorone, cyclopentanone, cycloheptanone, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde,
Examples include linear aldehydes such as undecyl aldehyde, dodecyl aldehyde, hexadecyl aldehyde, octadecyl aldehyde and eicosyl aldehyde, and branched aldehydes such as isobutyraldehyde, 2-ethylhexyl aldehyde, 2-ethyl butyraldehyde and methyl heptadecyl aldehyde. However, it is not necessarily limited to these.

Of these carbonyl compounds, chain ketones having 1 to 12 carbon atoms, aliphatic aldehydes or cyclic ketones having 5 to 8 carbon atoms are preferable, and acetone, methyl ethyl ketone, methyl isobutyl ketone (4-methyl-2
-Pentanone) etc., chain ketone having 3 to 6 carbon atoms, formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, isobutyraldehyde, octyl aldehyde, dodecyl aldehyde, etc.
Further, cyclic ketones such as aliphatic aldehydes of 3 to 8 and cyclohexanone are particularly preferable, and further acetone, methyl ethyl ketone, methyl isobutyl ketone (4-methyl-
2-pentanone) is particularly preferred. These carbonyl compounds can be used alone or as a mixture of two or more.

In the present invention, the monovalent hydroxy compound to be reacted with the polyvalent carbonyl compound is represented by the general formula (2) R ³ — (OA) _n —OH (2) [wherein R ³ has 1 carbon atom (s)] Is a linear or branched alkyl group or alkenyl group having ˜40, or a cycloalkyl group having 3 to 12 carbon atoms. A represents an alkylene group having 2 to 3 carbon atoms, and n A's may be the same or different. n is 0
~ 200, preferably 0 ~ 30. ] The compound represented by this is mentioned.

Specific examples of the compound represented by the general formula (2) include methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-. Octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecyl alcohol, n-hexadecyl alcohol, n- Linear saturated alcohols such as octadecyl alcohol and n-eicosyl alcohol, isopropyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol, 2-hexyldecyl alcohol, 2-heptylundecyl alcohol, 2-octylde Sill alcohol, 2-decyl tetradecyl alcohol, 2- (1,3,3-trimethyl-butyl) -5,7,7- trimethyl-octyl alcohol,
Next formula

[0024]

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(Where a and b are a + b = 14 and a = b
A saturated branched alcohol such as 2-tetradecyl octadecyl alcohol, 9-octadecenyl alcohol, farnesyl alcohol, abiethyl alcohol, oleyl alcohol, etc. Alkenyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monoisopropyl ether (isopropyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve),
Ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether and other ethylene glycol monoethers, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monoisopropyl ether (isopropyl carbitol), diethylene glycol Diethylene glycol monoethers such as monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monohexyl ether, triethylene glycol monododecyl ether, triethylene glycol monotetradecyl ether, etc. Of triethylene glycol Noethers, 1,4-butanediol monohexyl ether, 2-methyl-1,3-propanediol monooctyl ether, 1,6-pentanediol monohexyl ether, 2,2′-dimethylpropanediol monooctyl ether, 3 -Methyl-1,
Examples include alkylene glycol monoethers such as 5-pentanediol monohexyl ether, ethylene oxide, propylene oxide or butylene oxide adducts of the above alcohol, cyclopentanol, cyclohexanol, cycloheptanol, and the like.
It is not necessarily limited to these.

Among these hydroxy compounds, aliphatic alcohols having 1 to 22 carbon atoms, especially 6 to 22 carbon atoms, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve,
Butyl cellosolve, methyl carbitol, ethyl carbitol, isopropyl carbitol, butyl carbitol, or ethylene oxide, propylene oxide or a mixed adduct of ethylene oxide and propylene oxide of an aliphatic alcohol having 1 to 22 carbon atoms, especially 6 to 22 ( A cycloalkanol having an average added mole number of 0.1 to 20) and a carbon number of 5 to 8 is preferable. These hydroxy compounds can be used alone or as a mixture of two or more.
In the production method of the present invention, the charging ratio of the hydroxy compound and the carbonyl compound is not particularly limited, but usually, the hydroxy compound / carbonyl compound (equivalent ratio) = 30/1
To 1/30 are preferred, especially 20/1 to 1/20, more particularly 10
/ 1-1 / 10 is preferable. If the hydroxy compound has a low molecular weight and can be easily removed, it is preferable to use the hydroxy compound in excess to react all of the carbonyl compound. Also, the hydroxy compound has a large molecular weight,
Further, if it solidifies at room temperature or the like, it is preferable to use the carbonyl compound in excess and to react all hydroxy compounds that are difficult to remove. Even if the equivalent ratio of the hydroxy compound / carbonyl compound is outside the above range, the yield is not significantly affected, but it is not economical.

In the present invention, it is necessary to carry out the reaction while removing the water by-produced by the reaction. In the present invention, removing the water by-produced by the reaction means that water is removed from the reaction system. Of course, the case of removing water by a dehydrating agent or the like in the reaction system is also included. Specific methods for removing water include a method of removing water by performing a reaction in the presence of a dehydrating agent, a method of removing water while passing a gas such as hydrogen, and a method of removing water by azeotropic dehydration. And the like. Among these methods, a method of removing water by carrying out a reaction in the presence of a dehydrating agent, or a method of removing water while circulating hydrogen is preferable, and hydrogen is circulated using a reactor equipped with a dehydration tube. A method is preferred in which water by-produced by the reaction is removed to the outside of the system while the reaction is being carried out, and unreacted raw materials that have come out of the system together with water are returned to the inside of the system.

In the method of removing water by carrying out the reaction in the presence of a dehydrating agent, the dehydrating agent used includes a so-called desiccant used for drying a liquid. Generally, the dehydration ability of the dehydrating agent is based on physical adsorption, chemical adsorption or chemical reaction of water, but the dehydrating agent used in the present invention is not particularly limited by the mechanism of manifesting the dehydrating ability, and the dehydrating ability or water absorbing ability is not limited. Any of those which have the above-mentioned properties, and which substantially remove water by-produced by the reaction and rapidly proceed with the intended etherification reaction can be used.
Incidentally, among the dehydrating agents, it is not preferable to use a strong acid or a strong alkali as it is, which is a reaction substantially other than the dehydrating ability, such as dissolving a catalyst or causing a dimerization reaction to carbonylation. It goes without saying that, even with strong alkali, it can be used if devised so as not to come into direct contact with the reaction system.

Preferred dehydrating agents used in the present invention include inorganic salts such as magnesium sulfate, sodium sulfate, calcium sulfate, copper sulfate and calcium chloride, preferably their anhydrides, hydroxides such as calcium hydroxide and oxidation. Examples thereof include oxides such as magnesium, crystalline zeolites such as molecular sieves, silica gel, and the like, but are not limited thereto. Among these dehydrating agents, anhydrous inorganic salts and crystalline zeolite are preferable, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate and molecular sieve are more preferable, and anhydrous magnesium sulfate is particularly preferable.

In the present invention, the amount of the dehydrating agent used is not particularly limited, but is 0.1 to 0.1% with respect to the hydroxy compound used.
50 equivalent% is preferable, and 1 to 30 equivalent% is more preferable. The method of removing water by carrying out the reaction in the presence of such a dehydrating agent is very preferable because no special reaction apparatus is required and the water can be simply removed by adding the dehydrating agent.

Further, in the present invention, water by-produced by the reaction can be removed to the outside of the reaction system while circulating a gas such as hydrogen. The flow rate of hydrogen used in the present invention may be appropriately selected according to the scale of the reaction.
0.01 to 30 liters / mi on a 0.5 to 1 liter scale
n is preferable, and 0.01 to 10 liter / min is more preferable. By setting the flow rate of hydrogen to 0.01 liter / min or more, water is easily removed from the system, and the reaction speeds up. Further, when the flow rate of hydrogen is 30 liter / min or less, the amount of unreacted raw material such as hydroxy compound or carbonyl compound which is removed together with water is reduced, which is preferable. However, even in this case, unreacted raw materials such as a hydroxy compound and a carbonyl compound which are removed together with water are returned to the reaction system again after the water is removed by, for example, fractional distillation or a dehydrating agent, so that the reaction is performed without delay. be able to. In addition, the flow of hydrogen may be performed continuously or intermittently during the reaction, but continuous flow is preferable in order to make the reaction proceed smoothly.

Further, the hydrogen circulated in the reaction system may be released into the atmosphere as it is, but in order to effectively use the hydrogen, the hydrogen discharged from the system is re-introduced into the system through a circulation line or the like. It is efficient and preferable to use it for the reaction while returning to circulation and circulating. Such a method of removing water while circulating hydrogen is very preferable because it has the advantage that there is no reagent to be added, hydrogen and water can be easily separated, and post-treatment is simple.

Further, in the present invention, water by-produced by the reaction can be removed outside the reaction system by distilling off. The method for distilling off water is not particularly limited, but examples thereof include azeotropic dehydration. At this time, a method in which water is distilled off together with the unreacted raw materials is preferable.
After the distillation, it is preferable to separate water and unreacted raw materials and return the unreacted raw materials into the reaction system. As a method of azeotropic dehydration,
For example, using an azeotropic dehydration apparatus, not only a method of continuously performing the reaction and the distillation of water, but also, for example, once the reaction is performed,
A method in which the reaction and water are distilled off in stages, such as azeotropic dehydration and then the reaction may be performed again. It is preferable to carry out the reaction continuously to make the reaction proceed smoothly. In order to perform dehydration efficiently, azeotropic dehydration may be performed while flowing hydrogen.

In the method of carrying out the reaction by removing water by azeotropic dehydration according to the present invention, the azeotropic solvent used is not only a carbonyl compound or a hydroxy compound as a reaction raw material, but also a solvent which does not adversely affect the reaction. May be. When azeotropic dehydration is performed using a solvent having no adverse effect on the reaction, preferred solvents used include, but are not necessarily limited to, toluene, xylene, benzene and the like. When using a solvent that does not adversely affect the reaction at all, the amount of the solvent used is not particularly limited, but is preferably 1 to 2 times the volume of the reaction solution.

In the present invention, the catalyst used when reacting the hydroxy compound and the carbonyl compound is a palladium catalyst appropriately supported on a carrier such as carbon, silica-alumina, zeolite, alumina, silica, or palladium hydroxide, Examples thereof include a palladium compound such as palladium oxide, ruthenium, rhodium or a platinum catalyst, ruthenium oxide, rhodium oxide, platinum oxide and the like, which are appropriately supported on a carrier such as carbon and alumina. Further, a catalyst such as iridium, osmium, rhenium or the like can be used. Among these catalysts, preferably a palladium-based catalyst, more preferably carbon, silica-alumina, a palladium catalyst supported on alumina or silica, palladium hydroxide or palladium oxide, and particularly a palladium catalyst supported on carbon is preferred. .

In the present invention, the catalyst is usually used by supporting it on a carrier such as carbon or alumina in a proportion of 2 to 10% by weight, but it may be used as it is without supporting it on the carrier. Also, a water-containing product of about 20 to 60% by weight may be used. The catalyst is preferably used in an amount of 0.1 to 10% by weight based on the hydroxy compound or carbonyl compound used, if the catalyst is, for example, 5% by weight supported on the carrier. If the amount is less than 0.1% by weight, the reaction proceeds, but the reaction is unfavorably slow. When the amount is more than 10% by weight, the reaction is fast, but on the contrary, a side reaction proceeds, which is not preferable. More preferably, it is 0.5 to 5% by weight. The catalyst is all p
Although it can be used in the H region, a catalyst having a pH of 8 or less is preferable. The pH of the catalyst as used herein refers to the pH of an aqueous solution obtained by dispersing 2 g of the catalyst powder in 30 g of ion-exchanged water.

In the present invention, the hydroxy compound and the carbonyl compound are reacted in a hydrogen atmosphere, but the hydrogen pressure is not particularly limited, preferably 1 to 300 kg / cm ² , and 1 to 20 kg.
0 kg / cm ² is particularly preferred. In the present invention, the reaction temperature when reacting the hydroxy compound and the carbonyl compound is not particularly limited, but is preferably 10 to 200 ° C, and 50
~ 180 ° C is particularly preferred. The reaction time may be appropriately selected depending on the reaction temperature, hydrogen pressure, amount of catalyst, etc., but is usually 1 to 24.
The time is preferably 1 to 12 hours.

[0038]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Synthesis of 1,6-hexanediol diisopropyl ether

[0040]

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500 equipped with a hydrogen gas inlet tube and a stirrer
47 g of 1,6-hexanediol in a ml autoclave
(0.4 mol), acetone 232 g (4 mol), 5 as a catalyst
% Pd-C (pH 6.4) 0.94 g, anhydrous magnesium sulfate 28 g (0.23 mol) as a dehydrating agent were charged, and hydrogen pressure was 70 kg / c.
The mixture was stirred at 150 ° C. for 7 hours under m ² . After the reaction was completed, the catalyst and magnesium sulfate were removed by filtration, and excess acetone was removed under reduced pressure. Further, the product was purified by silica gel column chromatography to obtain 79 g (0.39 mol) of the target 1,6-hexanediol diisopropyl ether as a colorless transparent liquid. The isolation yield was 98% (based on 1,6-hexanediol).

Examples 2 to 4 A polyvalent hydroxy compound and a monovalent carbonyl compound shown in Table 1 were prepared in the same manner as in Example 1 except for the reaction conditions shown in Table 1 in the presence of the catalyst and dehydrating agent shown in Table 1. To react. The obtained product and its isolated yield are shown in Table 1. The isolated yield is based on the hydroxy compound.

[0043]

[Table 1]

Examples 5 to 9 A monovalent hydroxy compound and a polyvalent carbonyl compound shown in Table 2 were prepared in the same manner as in Example 1 except for the reaction conditions shown in Table 2 in the presence of the catalyst and dehydrating agent shown in Table 2. To react. The obtained product and its isolated yield are shown in Table 2. The isolated yield is based on the carbonyl compound.

[0045]

[Table 2]

Note) * 1: P represents the average number of moles of ethylene oxide added.

Example 10 Isopropylpolyoxyethylene (P = 4.3) Synthesis of glycerin

[0048]

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500 equipped with a hydrogen gas inlet tube and a stirrer
In an autoclave of ml, polyoxyethylene (P = 4.3) glycerin 99g (0.15mol), acetone 133g (2.3mol), 5% Pd-C (pH 3.8) 2.0g as a catalyst, anhydrous magnesium sulfate 16g (0.13m) as a dehydrating agent. Mol), and the mixture was stirred at 150 ° C. for 10 hours under a hydrogen pressure of 100 kg / cm ² . After the reaction was completed, the catalyst and magnesium sulfate were removed by filtration, and excess acetone was removed under reduced pressure. Further, low boiling components were completely removed by steaming to obtain 110 g of desired isopropyl polyoxyethylene (P = 4.3) glycerin as a colorless transparent liquid. Hydroxyl value before reaction [255 (KOH
mg / g)] and the hydroxyl value after the reaction [26 (KOH mg / g)], the etherification rate was 76%.

Example 11 The polyvalent hydroxy compound shown in Table 3 and the monovalent carbonyl compound were reacted in the presence of the catalyst and dehydrating agent shown in Table 3 in the same manner as in Example 10 except for the reaction conditions shown in Table 3. Let
The obtained product and its etherification rate are shown in Table 3.

[0051]

[Table 3]

Example 12 Synthesis of 1,4-butanediol bis (1,3-dimethylbutyl) ether

[0053]

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18 g (0.2 mol) of 1,4-butanediol and 200 g of methyl isobutyl ketone were placed in a 500 ml autoclave equipped with a hydrogen gas introduction pipe, a stirrer and a cooling dehydration pipe.
(2 mol), 2 g of 5% Pd-C (pH 7.1) as a catalyst
Was charged, under a hydrogen pressure of 3 kg / cm ² , a hydrogen flow rate of 300 ml / min,
The mixture was stirred at 105 ° C for 10 hours. During this period, the water by-produced by the reaction was removed to the outside of the system, and the unreacted methyl isobutyl ketone that had gone out of the system with water was returned to the inside of the system. After completion of the reaction, the catalyst was removed by filtration, and excess methyl isobutyl ketone was removed under reduced pressure. Furthermore, it was purified by silica gel column chromatography to obtain the desired 1,4-
50.6 g (0.196 mol) of butanediol bis (1,3-dimethylbutyl) ether was obtained as a colorless transparent liquid.
The isolation yield was 98% (based on 1,4-butanediol).

Examples 13 to 15 A polyvalent hydroxy compound shown in Table 4 and a monovalent carbonyl compound were reacted in the presence of the catalyst shown in Table 4 in the same manner as in Example 12 except for the reaction conditions shown in Table 4. It was The obtained product and its isolated yield are shown in Table 4. The isolated yield is based on the hydroxy compound.

[0056]

[Table 4]

Examples 16 to 17 The monovalent hydroxy compound shown in Table 5 and the polyvalent carbonyl compound were reacted in the presence of the catalyst shown in Table 5 in the same manner as in Example 12 except for the reaction conditions shown in Table 5. It was The products obtained and their isolated yields are shown in Table 5. The isolated yield is based on the carbonyl compound.

[0058]

[Table 5]

Example 18 Synthesis of 1,9-nonanediol diisopropyl ether

[0060]

[Chemical 6]

500 equipped with hydrogen gas inlet tube and stirrer
48 g (0.3 g of 1,9-nonanediol) in a ml autoclave
Mol), 174 g of acetone (3 mol), 5% P as a catalyst
Charged 4 g of d-C (pH 7.1) under hydrogen pressure of 10 kg / cm ² ,
The reaction was carried out at 100 ° C for 10 hours at a hydrogen flow rate of 250 ml / min.
After the reaction was completed, the catalyst was removed by filtration, and excess acetone was removed under reduced pressure. Further, the product was purified by silica gel column chromatography to obtain 72.5 g (0.297 mol) of the target 1,9-nonanediol diisopropyl ether as a colorless transparent liquid. The isolation yield is 99% (1,9-
Nonanediol standard).

Example 19 Synthesis of triethylene glycol bis (2-methyl) propyl ether

[0063]

[Chemical 7]

500 equipped with hydrogen gas inlet tube and stirrer
30 g of triethylene glycol (0.2
Mol), 144 g of isobutyraldehyde (2 mol) and 2.2 g of 5% Pd-C (pH 6.4) as a catalyst were charged, and the reaction was carried out at 110 ° C. for 10 hours under a hydrogen pressure of 10 kg / cm ² under a hydrogen flow rate of 250 ml / min. went. After the reaction is completed, the catalyst is removed by filtration,
Excess isobutyraldehyde was removed under reduced pressure. Furthermore, the product was purified by silica gel column chromatography to obtain the target triethylene glycol bis (2-methyl)
51.4 g (0.196 mol) of propyl ether was obtained as a colorless transparent liquid. The isolation yield was 98% (based on triethylene glycol).

Example 20 106 g of 3-methyl-1,5-pentanediol was placed in a 500 ml autoclave equipped with a hydrogen gas introducing tube and a stirrer.
(0.9 mol), 1,4-cyclohexanedione 101 g (0.9
Mol) and 7 g of 5% Pd-C (pH 7.1) as a catalyst, and under hydrogen pressure of 3 kg / cm ² , hydrogen flow rate of 300 ml / min, 1
The reaction was carried out at 00 ° C for 10 hours. After the reaction was completed, the catalyst was removed by filtration to obtain 180 g of a product. When this product was subjected to GPC (gel permeation chromatography) measurement, a peak of a compound having a molecular weight of about 230 to 1500 was observed. The main peak is about 345, and IR and ¹ H-N
From the results of MR, it was found to be a mixture of compounds represented by the following formula.

[0066]

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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsumi Kita 1334 Minato Minato, Wakayama City, Wakayama Kao Research Institute

Claims (7)

[Claims] 1. When a polyvalent compound is used as at least one of a hydroxy compound or a carbonyl compound and a hydroxy compound and a carbonyl compound are reacted with each other in a hydrogen atmosphere using a catalyst to produce an ether compound, a by-product is produced by the reaction. A process for producing an ether compound, which comprises reacting while removing water. 2. The polyhydric alcohol or its derivative is
The method according to claim 1, which is a compound having 2 to 10 hydroxyl groups. 3. The method according to claim 1, wherein the polyvalent carbonyl compound is a chain or cyclic compound having 2 to 10 carbonyl groups and having 2 to 20 carbon atoms. 4. The catalyst is carbon, silica-alumina, a palladium catalyst supported on alumina or silica, palladium hydroxide or palladium oxide.
The production method according to any one of claims 1 to 4. 5. The production method according to claim 1, wherein water is removed by carrying out the reaction in the presence of a dehydrating agent. 6. The production method according to claim 1, wherein water is removed from the system while circulating hydrogen. 7. The production method according to claim 6, wherein the unreacted raw material that has come out of the system together with water is returned to the system.