JP3025754B2 - Method for producing ether compound - Google Patents

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 easily and inexpensively supply an ether compound which 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. Also, the ether compound is
Use as an oil agent as a detergent composition or as a new nonionic surfactant is also conceivable. Further, it can be used for a lubricant, an emulsifier, and the like. Expectations for the use of ether compounds are increasing for the above reasons, but at present it is not possible to produce truly useful ether compounds on an industrial level simply and inexpensively.

[0003] 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. However, in the synthesis from an alcoholate and an alkyl halide, a metal (Na, K, or the like) equivalent to an alcohol for forming the alcoholate or an alkali is required, and after the reaction, a large amount of a salt is generated along with the reaction. However, it is not industrially preferable. For the synthesis from alcohol and ester compounds, the ester compounds are limited to dimethyl sulfate, diethyl sulfate, etc., and methyl ether,
Although preferred for the synthesis of ethyl ether, it is difficult to synthesize ether compounds having more carbon atoms than these compounds. The dehydration reaction with an acid between alcohols is suitable for synthesizing a symmetric ether compound, but it is difficult to synthesize an asymmetric ether compound. 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.

[0004] 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.

[0005] In addition, as a method for synthesizing an ether, there is a method for producing an ether from 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 use only lower alcohols such as methanol, ethanol and propyl alcohol, and do not describe higher alcohols having more than 6 carbon atoms. Also, J. Org. Chem., 26, 102
6 (1961) discloses a method for synthesizing ethers by hydrogenolysis of various ketals, but also on lower alcohols having 6 or less carbon atoms. Not common. Further, in this reaction, there is also a disadvantage that the ketal must be once synthesized.

In recent years, as an example of synthesis of an ether compound using a higher alcohol, a reduction method using 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 acids, triethylsilane and the like may be expensive, and are not industrially preferable.

[0007]

SUMMARY OF THE INVENTION As mentioned above,
Although the ether compound is expected to be used, it is difficult to produce the ether compound and cannot be used for general purposes. Therefore, a method for producing the ether compound which can be supplied simply and inexpensively has been desired. Accordingly, an object of the present invention is to provide a production method capable of supplying an ether compound useful as a solvent, a cosmetic, a detergent composition, a lubricant, an emulsifier and the like simply and inexpensively.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a simple and inexpensive method for producing general-purpose ether compounds.
Hydroxy compound and carbonyl compound under a hydrogen atmosphere,
In carrying out the reaction using a catalyst, it was found that by performing the reaction while removing water by-produced by the reaction, an ether compound was obtained in one step and in a high yield, and the present invention was completed. Was. That is, the present invention provides a method for producing an ether compound by reacting a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst, wherein the reaction is carried out while removing water by-produced by the reaction. It provides a manufacturing method.

[0009]

Embodiments of the present invention will be described below in detail. In the present invention, the reaction is carried out while removing water by-produced by the reaction.In the present invention, removing water by-produced by the reaction means not only removing water outside the reaction system but also the reaction. The case where water is removed by a dehydrating agent or the like in the 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 distilling water by azeotropic dehydration, and the like, and a method of removing water while flowing a gas such as hydrogen. A method such as a removing method may be used. Among these methods, a method of removing water by performing a reaction in the presence of a dehydrating agent or a method of removing water while flowing hydrogen is preferable, and particularly, a method of flowing hydrogen using a reactor equipped with a dehydrating tube. A preferred method is to remove water produced as a by-product of the reaction outside the system while performing the reaction, and to return unreacted raw materials that have come out of the system together with the water to the inside of the system.

In the method of removing water by performing a reaction in the presence of a dehydrating agent, the dehydrating agent used includes a so-called drying agent used for drying a liquid. Generally, the expression of the dehydrating ability of a dehydrating agent is based on physical adsorption, chemical adsorption or chemical reaction of water. However, the dehydrating agent used in the present invention is not particularly limited in the mechanism of the dehydrating ability, and the dehydrating ability or water absorbing ability Any one may be used as long as it substantially removes water produced as a by-product of the reaction and allows the desired etherification reaction to proceed rapidly.
Among the dehydrating agents, it is not preferable to use a strong acid or a strong alkali as it is, which substantially dissolves a reaction other than dehydration ability, for example, dissolves a catalyst or causes a dimerization reaction to carbonylation. Needless to say, even strong alkalis can be used if they are 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 anhydrides thereof, hydroxides such as calcium hydroxide, and oxides. Examples thereof include oxides such as magnesium, crystalline zeolites such as molecular sieves, and silica gel, but are not necessarily limited thereto. Among these dehydrating agents, anhydrides of inorganic salts and crystalline zeolites are preferred, and anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate, and molecular sieves are particularly preferred.

In the present invention, the amount of the dehydrating agent used is not particularly limited, but may be 0.1 to 0.1 with respect to the hydroxy compound used.
50 mol% is preferable, and 1 to 30 mol% is more preferable. Such a method of removing water by performing a reaction in the presence of a dehydrating agent is very preferable because a special reaction device is not required and water can be easily removed simply by adding a dehydrating agent.

In the present invention, water produced as a by-product of the reaction can be removed from the reaction system by distilling it off. The method for distilling water is not particularly limited, and examples thereof include a method such as azeotropic dehydration. At this time, a method of distilling off water together with unreacted raw materials is preferable.
After the distillation, it is preferable that water and unreacted raw materials are separated, and the unreacted raw materials are returned to 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 of performing the reaction and distilling off water stepwise, such as performing azeotropic dehydration and performing the reaction again, may be used. 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 the present invention in which water is removed by azeotropic dehydration to carry out the reaction, as the azeotropic solvent to be used, not only a carbonyl compound or a hydroxy compound as a reaction raw material but also a solvent having no adverse effect on the reaction is used. You may. 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 a solvent that does not adversely affect the reaction is used, 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, it is also possible to remove water by-produced by the reaction out of the reaction system while flowing 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, it is preferable that the flow rate of hydrogen is 30 liter / min or less, since the amount of the raw material hydroxy compound or carbonyl compound removed together with water is reduced. However, even in this case, useful components such as unreacted raw materials and products such as hydroxy compounds and carbonyl compounds that are removed together with water are removed, for example, by fractional distillation, liquid separation or removal of water by a dehydrating agent, and then into the reaction system again. The reaction can be carried out without delay by returning or adding a raw material in an amount corresponding to the amount removed. 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 to the atmosphere as it is. However, in order to use hydrogen effectively, the hydrogen that has come out of the system must be recirculated through a circulation line or the like. It is efficient and preferable to return the mixture to circulation and use it for the reaction while circulating. Such a method of removing water while circulating hydrogen is particularly preferable because it has the advantage that there is no reagent to be added, that hydrogen and water can be easily separated, and that post-treatment is simple.

In the present invention, the hydroxy compound is reacted with the carbonyl compound while removing water by-produced by the reaction. The hydroxy compound used in the present invention is represented by the general formula (1) R _1- (OA) _n —OH (1) wherein R ₁ represents a linear or branched alkyl group or alkenyl group having 1 to 40 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. A represents an alkylene group having 2 to 12 carbon atoms, and n A's may be the same or different. n is 0
Indicates the number of ~ 30. ] The compound represented by this is mentioned.

Specific examples of the compound represented by the general formula (1) include methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, and n-heptyl alcohol. 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-octyld Sill alcohol, 2-decyl tetradecyl alcohol, 2- (1,3,3-trimethyl-butyl) -5,7,7- trimethyl-octyl alcohol,
Next formula

[0019]

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(Where a and b are a + b = 14, and a = b
= Having a distribution having a peak at 7), saturated branched alcohols such as methyl-branched isostearyl alcohol, 2-tetradecyloctadecyl alcohol, 2-hexadecyleicosyl alcohol, 9-octadecenyl alcohol, and farnesyl alcohol , Abiethyl alcohol,
Alkenyl alcohols such as oleyl 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, Monoethers of ethylene glycol such as ethylene glycol monohexyl ether, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monoisopropyl ether (isopropyl carbitol), diethylene glycol monobutyl ether (butyl carbitol) ) Triethylene glycol monoethers such as diethylene glycol monoethers, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monohexyl ether, triethylene glycol monododecyl ether, and triethylene glycol monotetradecyl ether 1,4-butanediol monohexyl ether, 2-methyl-1,3-propanediol monooctyl ether, 1,6-pentanediol monohexyl ether, 2,2′-dimethylpropanediol monooctyl ether, 3-methyl Monoalkylene glycol monoethers such as -1,5-pentanediol monohexyl ether; ethylene oxide and propylene oxide of the above alcohol; Examples include butylene oxide adducts, cyclopentanol, cyclohexanol, and cycloheptanol, but are not necessarily limited thereto.

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 an ethylene oxide or / and propylene oxide adduct of an aliphatic alcohol having 1 to 22 carbon atoms, particularly 6 to 22 carbon atoms (average mole number 0.1 to 0.1) 20), a cycloalkanol having 5 to 8 carbon atoms is preferable, and an aliphatic alcohol having 6 to 22 carbon atoms, cyclohexanol is more preferable. These hydroxy compounds can be used alone or as a mixture of two or more. As the carbonyl compound used in the present invention, general formula (2)

[0022]

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Wherein R ₂ and R ₃ are each a hydrogen atom, having 1 to 20 carbon atoms.
And R ₂ and R ₃ may be the same or different. Further, a cyclic structure in which R ₂ and R ₃ are bonded may be used. ] The compound represented by this is mentioned.

Specific examples of the compound represented by the general formula (2) include acetone, methyl ethyl ketone, 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 and 6-methyl-5-heptenone-2, cyclohexanone, 2-
Cyclic ketones such as methylcyclohexanone, isophorone, cyclopentanone and cycloheptanone, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde,
Examples include linear aldehydes such as undecylaldehyde, dodecylaldehyde, hexadecylaldehyde, octadecylaldehyde, and eicosylaldehyde, and branched aldehydes such as isobutylaldehyde, 2-ethylhexylaldehyde, 2-ethylbutyraldehyde, and methylheptadecylaldehyde. However, the present invention is not necessarily limited to these.

Among these carbonyl compounds, a chain ketone having 1 to 12 carbon atoms, an aldehyde having 1 to 12 carbon atoms or a cyclic ketone having 5 to 8 carbon atoms is preferable.
A chain ketone having 3 to 6 carbon atoms such as methyl ethyl ketone and methyl isobutyl ketone (4-methyl-2-pentanone); and a carbon atom having 1 carbon atom such as formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, isobutyraldehyde, octylaldehyde, dodecylaldehyde To 12 and more preferably 3 to 8 cyclic ketones such as aliphatic aldehydes and cyclohexanone, and more preferably acetone, methyl ethyl ketone and 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 production method of the present invention, the charge ratio of the hydroxy compound to the carbonyl compound is not particularly limited, but usually the hydroxy compound / carbonyl compound (molar ratio) is preferably 30/1 to 1/30, particularly preferably 20/1/30. 1-1 / 2
0, more preferably 10/1 to 1/10. 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. In addition, if the hydroxy compound has a large molecular weight and solidifies at room temperature or the like, it is preferable to use an excess of the carbonyl compound and react all the hydroxy compounds that are difficult to remove. If the molar ratio of the hydroxy compound / carbonyl compound is out of the above range, the yield is not significantly affected, but it is not economical.

In the present invention, the catalyst used in the reaction between the hydroxy compound and the carbonyl compound is not particularly limited as long as it has a hydrogenating ability. Palladium catalysts; palladium compounds such as palladium hydroxide and palladium oxide Ruthenium, rhodium or platinum catalysts; ruthenium oxide, rhodium oxide, platinum oxide and the like; Further, a catalyst such as iridium, osmium, rhenium or the like can be used. These catalysts
It may be appropriately supported on a carrier such as carbon, alumina, silica alumina, silica, and zeolite. Among these catalysts, preferably a palladium-based catalyst, more preferably carbon, alumina, palladium catalyst supported on silica alumina or silica, palladium hydroxide or palladium oxide, particularly preferably a palladium catalyst supported on carbon .

In the present invention, the catalyst is usually used while being supported at a ratio of 2 to 10% by weight based on a carrier such as carbon or alumina, but it may be used without being supported on the carrier. Further, it may be a water-containing product of about 20 to 60% by weight. If the catalyst is, for example, 5% by weight supported on a carrier, the catalyst is 0.1% based on the hydroxy compound used.
It is preferred to use up to 10% by weight. 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 can be used in all pH ranges,
Preferably, the catalyst has a pH of 8 to 2, more preferably 7.5 to 3. The pH of the catalyst referred to here is ion-exchanged water.
It refers to the pH of the aqueous solution when 2 g of the catalyst powder is dispersed in 30 g.

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, and may be either pressurization or atmospheric pressure, and is 1 (atmospheric pressure) to 300 kg / cm. ² is preferable, and 1 (atmospheric pressure) to 200 kg / cm ² is particularly preferable. In the present invention, the reaction temperature when reacting the hydroxy compound with the carbonyl compound is not particularly limited, but is preferably from 10 to 200 ° C, particularly preferably from 30 to 180 ° C. The reaction time may be appropriately selected depending on the reaction temperature, hydrogen pressure, amount of catalyst, and the like, but is usually 1 to 24 hours, preferably 1 to 12 hours.

In the reaction of the present invention, the reaction may be carried out using a solvent which does not adversely affect the reaction in some cases. Examples of the solvent having no adverse effect on the reaction include, but are not necessarily limited to, hydrocarbon solvents such as hexane, heptane and octane. When a solvent which does not adversely affect the reaction is used, the amount of the solvent used is not particularly limited, but is preferably 0.5 to 2 times the volume of the reaction solution.

[0031]

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 Production of 1,3-dimethylbutyltetradecyl ether

[0033]

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500 equipped with a hydrogen gas inlet tube and a stirring device
107 g of tetradecyl alcohol in a ml autoclave
(0.5 mol), 100 g (1.0 mol) of 4-methyl-2-pentanone, 2.1 g of 5% Pd-C (pH 6.6) as a catalyst, and 8.6 g (0.07 mol) of anhydrous magnesium sulfate as a dehydrating agent, and a hydrogen pressure of 100 kg The mixture was stirred at 150 ° C. for 5 hours under / cm ² . After completion of the reaction, the catalyst and magnesium sulfate were removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Further, distillation under reduced pressure (143 ° C./1 Torr) was performed to obtain 148 g (0.49 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless transparent liquid. The isolation yield was 99%.

Comparative Example 1 Example 1 except that no anhydrous magnesium sulfate was added.
In the same manner as in the above, 109 g (0.37 mol) of 1,3-dimethylbutyltetradecyl ether was obtained as a colorless transparent liquid.
The isolation yield was 73%.

Examples 2 to 7 Hydroxy compounds and carbonyl compounds shown in Table 1 were used.
The reaction was carried out in the same manner as in Example 1 except for the reaction conditions shown in Table 1 in the presence of the catalyst and the dehydrating agent shown in Table 1. Table 1 shows the obtained products and their isolation yields.

Comparative Examples 2 to 7 The hydroxy compounds and carbonyl compounds shown in Table 2 were
The reaction was carried out in the presence of the catalyst shown in Table 2 in the same manner as in Comparative Example 1 except for the reaction conditions shown in Table 2. Table 2 shows the obtained products and their isolation yields.

[0038]

[Table 1]

[0039]

[Table 2]

Example 8 Preparation of dicyclohexyl ether

[0041]

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500 equipped with a hydrogen gas inlet tube and a stirrer
147 g (1.5 mol) of cyclohexanone, 100 g (1.0 mol) of cyclohexanol, 5 g of 5% Pd-C (pH 6.6) as a catalyst, 13 g (0.1 mol) of anhydrous magnesium sulfate as a dehydrating agent were charged into a 100 ml autoclave, and hydrogen pressure was 100 kg.
The mixture was stirred at 180 ° C. for 7 hours under / cm ² . After the completion of the reaction, the autoclave was cooled to room temperature, hydrogen in the autoclave was evacuated, and the autoclave was opened. After removing the catalyst and magnesium sulfate from the reaction solution by filtration, analysis was performed by gas chromatography. As a result, the apparent conversion of cyclohexanol was 97%, and the yield of dicyclohexyl ether was 95%.

Comparative Example 8 Example 8 except that anhydrous magnesium sulfate was not added.
In the same manner as in the above, dicyclohexyl ether was obtained. As a result, the apparent conversion of cyclohexanol was 81%, and the yield of dicyclohexyl ether was 78%.

Example 9 Production of 1,3-dimethylbutyltetradecyl ether

[0045]

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500 equipped with a hydrogen gas inlet tube and a stirrer
80 g of tetradecyl alcohol (0.
37 mol), 150 g (1.5 mol) of 4-methyl-2-pentanone, 1.6 g of 5% Pd-C (pH 4.0) as a catalyst, and the first stage at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ² . The reaction was performed. After the completion of the first-stage reaction, the catalyst was removed by filtration, and the filtrate was dried in a 500 ml
A mixture of 4-methyl-2-pentanone and water, which was charged into a flask and distilled off by azeotropic distillation, was separated and separated by a dehydrating reflux tube to remove water. Next, the azeotropic dehydration end solution and the catalyst were returned to the autoclave again, and the hydrogen pressure was reduced to 100 kg / cm ² for 15 minutes.
The second stage reaction was performed at 0 ° C. for 7 hours. After the completion of the second-stage reaction, the catalyst was removed by filtration, and excess 4
-Methyl-2-pentanone was removed. Further vacuum distillation
(143 ° C./1 Torr) to obtain 107 g (0.36 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless transparent liquid. The isolation yield was 97%.

Comparative Example 9 80 g (0.37 mol) of tetradecyl alcohol was placed in a 500 ml autoclave equipped with a hydrogen gas inlet tube and a stirring device.
-Methyl-2-pentanone 150 g (1.5 mol) and 1.6 g of 5% Pd-C (pH 4.0) as a catalyst were charged at a hydrogen pressure of 100 g.
The reaction was performed at 150 ° C. for 15 hours under kg / cm ² . After the reaction,
The catalyst was removed by filtration and the excess 4-methyl-
2-Pentanone was removed. Further, distillation under reduced pressure (143 ° C / 1
Torr) to obtain 86 g (0.29 mol) of the desired 1,3-dimethylbutyltetradecyl ether as a colorless transparent liquid. The isolation yield was 78%.

Example 10 Production of 1,3-dimethylbutylhexadecyl ether

[0049]

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90 g (0.37 mol) of hexadecyl alcohol, 4-methyl-2-pentanone 1 in a 500 ml autoclave equipped with a hydrogen gas inlet tube, a stirrer and a dehydrating reflux device.
50 g (1.5 mol), 5% Pd-C (pH 4.0) as a catalyst
Charge 1.8 g, and perform azeotropic dehydration, hydrogen pressure 20 kg / cm
Stirring was performed at 150 ° C. for 12 hours under ² . The mixture of 4-methyl-2-pentane and water distilled off by azeotropic distillation during the reaction is separated into layers by a fractionating tube in a dehydrating reflux apparatus, and only 4-methyl-2-pentane is continuously autoclaved. Refluxed. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure.
Further, distillation under reduced pressure (145 ° C./0.3 Torr) was performed to obtain the desired 1,3
-115 g (0.35 mol) of dimethylbutylhexadecyl ether were obtained as a colorless and transparent liquid. The isolation yield was 95%.

Comparative Example 10 90 g (0.37 mol) of hexadecyl alcohol, 150 g (1.5 mol) of 4-methyl-2-pentanone and 500 g of a catalyst were placed in a 500 ml autoclave equipped with a hydrogen gas inlet tube and a stirrer.
% Pd-C (pH 4.0) 1.8 g, hydrogen pressure 20 kg / cm ²
Under stirring at 150 ° C. for 12 hours. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Distillation under reduced pressure (145 ℃ / 0.3Torr)
To obtain the desired 1,3-dimethylhexadecyl ether
75 g (0.23 mol) were obtained as a clear, colorless liquid. The isolation yield was 62%.

Examples 11 to 13 Hydroxy compounds and carbonyl compounds shown in Table 3 were used.
The reaction was carried out in the presence of the catalyst shown in Table 3 in the same manner as in Example 10 except for the reaction conditions shown in Table 3. The products obtained and their isolation yields are shown in Table 3 together with the results of Examples 9 and 10.

Comparative Examples 11 to 13 The hydroxy compounds and carbonyl compounds shown in Table 4 were
The reaction was carried out in the presence of the catalyst shown in Table 4 in the same manner as in Comparative Example 10 except for the reaction conditions shown in Table 4. The products obtained and their isolation yields are shown in Table 4 together with the results of Comparative Examples 9 and 10.

[0054]

[Table 3]

[0055]

[Table 4]

Example 14 Production of 1,3-dimethylbutyltetradecyl ether

[0057]

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5 equipped with a hydrogen gas inlet tube and a stirring device
Tetradecyl alcohol 5 in a 00 ml autoclave
3.5 g (0.25 mol), 4-methyl-2-pentanone 100
g (1.0 mol), 5% Pd-C (pH 6.6) 1.1 as a catalyst
g under hydrogen pressure of 20 kg / cm ² and hydrogen at 0.2 liter /
The mixture was stirred at 150 ° C. for 8 hours while continuously flowing at min. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Further, distillation under reduced pressure (143 ° C./1 Torr) was performed to obtain 71 g (0.24 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless transparent liquid. The isolation yield was 95%.

Comparative Example 14 The procedure of Example 14 was repeated except that hydrogen was not passed continuously, and 1,3-dimethylbutyltetradecyl ether 45 was used.
g (0.15 mol) was obtained as a colorless transparent liquid. The isolation yield was 60%.

Examples 15 to 25 The hydroxy compounds and carbonyl compounds shown in Tables 5 and 6 were combined with the catalysts shown in Tables 5 and 6 in the presence of the catalysts shown in Tables 5 and 6.
The reaction was carried out in the same manner as in Example 14 except for the reaction conditions shown in. The products obtained and their isolation yields are shown in Tables 5 and 6 together with the results of Example 14.

COMPARATIVE EXAMPLES 15-25 Comparative examples 14 and 25 were prepared by combining the hydroxy compounds and carbonyl compounds shown in Tables 7 and 8 in the presence of the catalysts shown in Tables 7 and 8 except for the reaction conditions shown in Tables 7 and 8. The reaction was performed in the same manner. The products obtained and their isolation yields are shown in Tables 7 and 8 together with the results of Comparative Example 14.

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

Example 26 Preparation of 1,3-dimethylbutyltetradecyl ether

[0067]

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In a 500 ml autoclave equipped with a hydrogen gas inlet tube, a stirrer and a reflux dehydration tube, 53.5 g (0.25 mol) of tetradecyl alcohol, 4-methyl-2-pentanone
100 g (1.0 mol), 5% Pd-C (pH 6.
6) was charged 1.6g, hydrogen pressure 8 kg / cm ² under hydrogen 700 ml / m
The mixture was stirred at 150 ° C. for 7 hours while continuously flowing in. In addition, the water by-produced by the reaction was removed to the outside of the system, and 4-methyl-2-pentanone which came out of the system simultaneously with the water was refluxed into the system. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Further, distillation under reduced pressure (143 ° C./1 Torr) was performed to obtain the desired 1,3-
73.8 g (0.248 mol) of dimethylbutyltetradecyl ether were obtained as a colorless transparent liquid. The isolation yield was 99%.

Comparative Example 26 21.6 g (0.073 mol) of 1,3-dimethylbutyltetradecyl ether was mixed with a colorless transparent liquid in the same manner as in Example 26, except that a reflux dehydration tube was not attached and hydrogen was not passed continuously. As obtained. The isolation yield was 29%.

Examples 27 to 37 The hydroxy compounds and carbonyl compounds shown in Tables 9 and 10 were combined with the catalysts shown in Tables 9 and 10 in the presence of the catalysts shown in Tables 9 and 10.
The reaction was carried out in the same manner as in Example 26 except for the reaction conditions shown in. The products obtained and their isolation yields are shown in Tables 9 and 10 together with the results of Example 26.

Comparative Examples 27 to 37 The hydroxy compounds and carbonyl compounds shown in Tables 11 and 12 were used in the presence of the catalysts shown in Tables 11 and 12 in the presence of the catalysts shown in Tables 11 and 12.
The reaction was carried out in the same manner as in Comparative Example 26 except for the reaction conditions shown in 12. The obtained products and their isolation yields are shown in Tables 11 and 12 together with the results of Comparative Example 26.

[0072]

[Table 9]

[0073]

[Table 10]

[0074]

[Table 11]

[0075]

[Table 12]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07B 61/00 300 C07B 61/00 300 (72) Inventor Katsumi Kita 1334 Minato, Wakayama-shi, Wakayama Prefecture Kao Corporation Laboratory (56) Reference Document JP-A-60-11438 (JP, A) JP-A-6-321837 (JP, A) JP-A-59-167530 (JP, A) JP-A-7-133272 (JP, A) (58) Field (Int. Cl. ⁷ , DB name) C07C 41/01 CA (STN) REGISTRY (STN)

Claims (15)

(57) [Claims] 1. A method for producing an ether compound by reacting a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst having a hydrogenating ability, while performing the reaction while removing water by-produced by the reaction. A method for producing a characteristic ether compound. 2. The process according to claim 1, wherein the water is removed by carrying out the reaction in the presence of a dehydrating agent. 3. The method according to claim 2, wherein the dehydrating agent is an inorganic salt, oxide, hydroxide, crystalline zeolite or silica gel having a dehydrating ability. 4. The method according to claim 3, wherein the dehydrating agent is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate, or molecular sieve. 5. The production method according to claim 2, wherein the amount of the dehydrating agent added is 0.1 to 50 mol% based on the hydroxy compound. 6. The process according to claim 1, wherein water produced as a by-product of the reaction is removed by distillation. 7. The method according to claim 6, wherein water is distilled off by azeotropic dehydration. 8. The method according to claim 6, wherein water is distilled off together with unreacted raw materials.
Or the production method according to 7. 9. The method according to claim 1, wherein water produced as a by-product of the reaction is removed by flowing hydrogen. 10. The production method according to claim 9, wherein unreacted raw materials that have come out of the system together with water are returned to the system. 11. A hydroxy compound represented by the general formula (1) R _1- (OA) _n -OH (1) wherein R ₁ is a linear or branched alkyl or alkenyl group having 1 to 40 carbon atoms, Alternatively, it represents a cycloalkyl group having 3 to 12 carbon atoms. A represents an alkylene group having 2 to 12 carbon atoms, and n A's may be the same or different. n is 0
Indicates the number of ~ 30. Wherein the compound is represented by the formula:
The production method according to any one of claims 10 to 10. 12. The method according to claim 12, wherein the hydroxy compound is an aliphatic alcohol having 1 to 22 carbon atoms, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, isopropyl carbitol, butyl carbitol, or one carbon atom. ~ 22 aliphatic alcohol ethylene oxide or / and propylene oxide adducts (average addition moles 0.1 to 20),
The method according to claim 11, which is a cycloalkanol having 5 to 8 carbon atoms. 13. A carbonyl compound represented by the general formula (2): [Wherein, R ₂ and R ₃ represent a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, and R ₂ and R ₃ may be the same or different. Further, a cyclic structure in which R ₂ and R ₃ are bonded may be used. The method according to any one of claims 1 to 12, which is a compound represented by the formula: 14. The method according to claim 13, wherein the carbonyl compound is a chain ketone having 1 to 12 carbon atoms, an aliphatic aldehyde or a cyclic ketone having 5 to 8 carbon atoms. 15. A palladium catalyst supported on carbon, alumina, silica alumina or silica,
It is palladium hydroxide or palladium oxide.
15. The production method according to any one of items 14 to 14.