JPH0995461A - Production of ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply produce an ether compound useful as a solvent, etc., from a carbonyl compound in a hydrogen atmosphere in one stage at a low cost by utilizing the availability of a symmetric type ether compound in high yield by using a catalyst. SOLUTION: Aliphatic aldehydes or ketones of formula I (R1 and R2 are each independently a 1-20C alkyl, etc.) are reacted by using a catalyst such as a palladium catalyst supported on carbon, etc., in a hydrogen atmosphere and the reaction is made to proceed while removing water formed as a by- product to the outside of the system and returning the unreacted raw materials discharged together with the water to the outside of the system thereinto to thereby afford the objective ether compound of formula II.

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 that can be easily and inexpensively supplied to a solvent, a cosmetic, a lubricant, a detergent composition, and the like, which can be used in a wide range.

[0002]

2. Description of the Related Art Conventionally, diethyl ether, dibutyl ether and the like have been used as solvents for ether compounds.
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. Further, the ether compound may be used as an oil agent as a detergent composition. Further, it can be used as a lubricant and the like. Expectations for the use of ether compounds are increasing for the above reasons as well, but the present situation is that truly useful ether compounds cannot be simply and inexpensively produced on an industrial level.

Examples of conventionally known methods used for the synthesis of ether compounds include, for example, synthesis from alcoholate and alkyl halide (Williamson synthesis method), synthesis from alcohol and ester compounds, acid between alcohols. The synthesis from the dehydration reaction by, the synthesis by addition of alcohol to olefin, etc. are general. However, in the synthesis from an alcoholate and an alkyl halide, an alcohol and an equivalent amount of metal (Na, K, etc.) or an alkali for forming the alcoholate are necessary, and further, after the reaction, a large amount of salt is generated. However, it is not industrially preferable. Further, in the synthesis from alcohol and ester compound, the ester compound is limited to dimethylsulfate, diethylsulfate, etc., methyl ether,
Although preferable for the synthesis of ethyl ether, it is difficult to synthesize an ether compound having more carbon atoms than these compounds. In the dehydration reaction between alcohols with an acid, an olefin is produced as a by-product, which is not preferable. Also,
In the synthesis by adding an alcohol to an olefin, the olefin compound is limited, and many of them are considerably expensive together with the catalyst to be used.
Many of the catalysts are difficult to recover and reuse, which is not industrially suitable.

Further, for example, Japanese Patent Application Laid-Open No. 48-33037 discloses the use of various monoethers, but it is clearly stated that the Williamson method is advantageous as a synthetic method thereof. 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 ether, there is a method for producing from ether and 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. See also J. Org. Chem., 26, 102.
6 (1961) discloses a method for synthesizing ethers by hydrogenolysis of various ketals, but this also mainly deals with lower alcohols having 6 or less carbon atoms, and there is no description of etherification of higher alcohols. None, not common. Further, in this reaction, there is also a disadvantage that the ketal must be once synthesized.

Recently, for example, Chem. Pharm. Bull.,
27, 2405 (1979), Chem. Lett., 743 (1985), a reduction method with triethylsilane using a strong acid as a catalyst was developed as a synthetic example of an ether compound using a higher alcohol. Various ether compounds have been synthesized from the compounds, but since strong acids, triethylsilane and the like are expensive, they are not industrially preferable methods.

[0007]

DISCLOSURE OF THE INVENTION As described 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. Therefore, an object of the present invention is to provide a production method capable of simply and inexpensively supplying an ether compound useful as a solvent, a cosmetic, a detergent composition, a lubricant and the like.

[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.
It was found that a symmetric ether compound can be obtained in a single step and in a high yield by reacting a carbonyl compound with a catalyst in a hydrogen atmosphere, and completed the present invention. That is, the present invention has the general formula (1)

[0009]

Embedded image

[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 method for producing an ether compound represented by the general formula (2), which comprises reacting a carbonyl compound represented by the formula (1) with a catalyst in a hydrogen atmosphere.

[0011]

Embedded image

[In the formula, R ₁ and R ₂ have the same meanings as described above. ]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The carbonyl compound used in the present invention is not particularly limited as long as it is a compound represented by the general formula (1), and specific examples thereof include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, pentylaldehyde, hexyl. Aldehyde, heptyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, hexadecyl aldehyde, octadecyl aldehyde, eicosyl aldehyde and other linear aldehydes, isobutyraldehyde, 2-ethylhexyl aldehyde, 2-ethyl butyl aldehyde ,
Branched aldehydes such as methylheptadecyl aldehyde, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, pinacolone, methyl-n-amyl ketone, methyl-n-hexyl ketone, diethyl. A chain ketone such as ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, diisobutyl ketone, 2,6,6-trimethylnonanone-4,6-methyl-5-heptenone-2, cyclohexanone, Examples thereof include cyclic ketones such as 2-methylcyclohexanone, isophorone, cyclopentanone, and cycloheptanone, but are not necessarily limited thereto.

Among these carbonyl compounds, aliphatic aldehyde having 1 to 20 carbon atoms, preferably 3 to 12 carbon atoms, symmetrical or asymmetric chain ketone having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, and 3 carbon atoms. -12, preferably 5-8 cyclic ketones are suitably used. These carbonyl compounds are
It can be used as one kind or as a mixture of two or more kinds.

In the present invention, the catalyst used when reacting the carbonyl compound is not particularly limited as long as it has a hydrogenating ability, but a palladium catalyst; a palladium compound such as palladium hydroxide or palladium oxide; ruthenium, Rhodium or platinum catalysts; ruthenium oxide, rhodium oxide, platinum oxide and the like can be mentioned. Further, a catalyst such as iridium, osmium, rhenium or the like can be used. These catalysts may be appropriately supported on a carrier such as carbon, alumina, silica-alumina, silica and zeolite. Among these catalysts, a palladium-based catalyst is preferable, more preferably carbon, alumina, silica Alumina or silica-supported palladium catalyst, palladium hydroxide or palladium oxide, and particularly carbon-supported palladium catalyst is preferable. .

In the present invention, the catalyst is usually used while being supported at a ratio of 2 to 10% by weight with respect to a carrier such as carbon or alumina, but may be used without being supported on the carrier. Also, a water-containing product of about 20 to 60% by weight may be used. If the catalyst is, for example, 5% by weight supported on the carrier, 0.1% of the carbonyl compound used.
It is preferred to use ~ 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. It is more preferably 0.5 to 5% by weight. The catalyst can be used in all pH ranges,
A catalyst having a pH of 8 to 2, and more preferably a pH of 7.5 to 3 is preferable. The pH of the catalyst here means ion-exchanged water.
It means the pH of an aqueous solution when 2 g of catalyst powder is dispersed in 30 g.

In the present invention, the carbonyl compound is reacted in a hydrogen atmosphere, but the hydrogen pressure is not particularly limited,
1 to 300 kg / cm ² is preferable, and 1 to 200 kg / cm ² is particularly preferable. Further, in the present invention, the reaction temperature when reacting the carbonyl compound is not particularly limited, 20 ~ 200 ℃
Is preferable, and 30 to 180 ° C. is particularly preferable. The reaction time is
It may be appropriately selected depending on the reaction temperature, hydrogen pressure, amount of catalyst and the like, but it is usually 1 to 24 hours, preferably 1 to 12 hours.

In this reaction, for the purpose of promoting the reaction, the reaction may be carried out while removing water by-produced by the reaction. As a method of removing water by-produced by the reaction, not only a method of removing water outside the reaction system but also a method of removing water with a dehydrating agent or the like in the reaction system can be used. Examples thereof include a method of removing water by carrying out a reaction in the presence of an agent, a method of removing water while circulating a gas such as hydrogen, and a method of removing water by azeotropic dehydration. Among these methods, a method of removing water by carrying out the reaction in the presence of a dehydrating agent,
Alternatively, a method of removing water from the system while circulating hydrogen is preferable, and particularly water produced as a by-product of the reaction is removed from the system while circulating hydrogen using a reactor equipped with a dehydration pipe,
In addition, a method is preferred in which the unreacted carbonyl compound that has come out of the system together with water is returned to the system.

In the method of removing water by carrying out the reaction in the presence of a dehydrating agent, the dehydrating agent used is
Magnesium sulfate, sodium sulfate, calcium sulfate,
Copper sulfate, inorganic salts such as calcium chloride, preferably their anhydrides, hydroxides such as calcium hydroxide, oxides such as magnesium oxide, crystalline zeolite such as molecular sieves, silica gel and the like, but not necessarily these. It is not limited to. Among these dehydrating agents, inorganic salt anhydrides and crystalline zeolite are preferable,
Particularly preferred are anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate, and molecular sieves. When using a dehydrating agent in the present invention, the amount used is not particularly limited, but 0.1 to 50 mol% relative to the carbonyl compound
Is preferable, and 1 to 30 mol% is more preferable.

In the method of removing water from the system while circulating hydrogen, the flow rate of hydrogen may be appropriately selected according to the reaction scale. For example, in the case of 1 liter scale, 0.01 to 30 liters / min. 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. The flow rate of hydrogen is 30 liters /
It is preferable that the amount is not more than min, since the amount of excess hydrogen can be adjusted and the amount of unreacted raw material carbonyl compounds and the like that are removed together with water is reduced. Further, the flow of hydrogen may be performed continuously or intermittently during the reaction,
Continuous flow is preferred in order to allow the reaction to proceed smoothly. In addition, the hydrogen circulated in the reaction system may be released to the atmosphere as it is, but in order to use hydrogen effectively, hydrogen that has come out of the system must be returned to the system again by a circulation line or the like. It is efficient and preferable to use the reaction while circulating and circulating. Furthermore, when useful components such as an unreacted carbonyl compound and a product are simultaneously removed from the system together with water, the unreacted carbonyl compound and the like are fractionally distilled, and water is removed by a separating or dehydrating agent, It is preferable to return it to the system again.

In the present invention, for the purpose of promoting the reaction, the reaction may be carried out by adding a lower alcohol such as methanol or ethanol, or the reaction may be carried out in the presence of a Lewis acid. The Lewis acid used here may be any electron pair acceptor, such as BF ₃ · OEt ₂ (boron trifluoride / diethyl ether complex), BF ₃ · 2CH ₃ CO ₂ H (boron trifluoride / acetic acid). _{complex), BF 3 · (CH 3} ) 3 COCH 3 ( boron trifluoride · t-butyl methyl ether complex), BF ₃ · CH
₃ OH (boron trifluoride-methanol complex), BF ₃ · CH ₃ (C
H ₂ ) ₂ OH (boron trifluoride-propanol complex), TiCl
₄ (titanium tetrachloride), SnCl ₄ (tin tetrachloride), AlCl ₃ (aluminum trichloride), TMSOTf (trimethylsilyl trifluoromethanesulfonate), Ti (Oi-Pro) ₄ (tetraisopropyl titanate), ZnCl ₂ (dichloride) Zinc chloride), FeCl ₃ (iron trichloride)
And the like, and particularly preferably BF ₃ · OEt ₂ . When a Lewis acid is used in the present invention, the amount used is not particularly limited, but is preferably relative to the carbonyl compound.
The molar amount is 0.01 to 20 times, more preferably 0.1 to 10 times, and most preferably 0.5 to 5 times.

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

[0023]

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 dibutyl ether CH ₃ (CH ₂ ) ₂ CH ₂ —O—CH ₂ (CH ₂ ) ₂ C
A 500 ml autoclave equipped with a H ₃ hydrogen gas introduction tube and a stirrer was charged with 284 g (4.0 mol) of n-butyraldehyde and 5.7 g of 5% Pd—C (pH 6.6) as a catalyst, and under a hydrogen pressure of 60 kg / cm ² , The mixture was stirred at 150 ° C for 8 hours.
After the reaction was completed, the catalyst was removed by filtration and further distilled (140
℃ / normal pressure), the target dibutyl ether 247g (1.9
Mol) was obtained as a colorless transparent liquid. The isolation yield was 90%.

Example 2 Synthesis of dihexyl ether CH ₃ (CH ₂ ) ₄ CH ₂ —O—CH ₂ (CH ₂ ) ₄ CH ₃ 250 g of n-hexylaldehyde was placed in a 500 ml autoclave equipped with a hydrogen gas introducing tube and a stirrer. (2.5 mol) and 5.0 g of 5% Pd-C (pH 6.6) as a catalyst were charged, and the mixture was stirred at 150 ° C. for 8 hours under a hydrogen pressure of 80 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (102 ° C /
50 Torr) to obtain the desired dihexyl ether 205 g (1.1
Mol) was obtained as a colorless transparent liquid. The isolation yield was 88%.

Example 3 Synthesis of dioctyl ether CH ₃ (CH ₂ ) ₆ CH ₂ —O—CH ₂ (CH ₂ ) ₆ CH ₃ 256 g of n-octylaldehyde was placed in a 500 ml autoclave equipped with a hydrogen gas introducing tube and a stirrer. (2.0 mol) and 5.1 g of 5% Pd-C (pH 3.8) as a catalyst were charged, and the mixture was stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (127 ° C
/3.5Torr) and the target dioctyl ether 215g
(0.89 mol) was obtained as a colorless transparent liquid. Isolated yield 8
It was 9%.

Example 4 Synthesis of didecyl ether CH ₃ (CH ₂ ) ₈ CH ₂ —O—CH ₂ (CH ₂ ) ₈ CH ₃ n-decyl aldehyde was placed in a 500 ml autoclave equipped with a hydrogen gas introduction tube and a stirrer. Charge 265 g (1.7 mol) and 5.3 g of 5% Pd-C (pH 6.6) as a catalyst under hydrogen pressure.
Stirring was performed at 150 ° C. for 8 hours under 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (142 ° C /
Perform 0.3 Torr to obtain the desired didecyl ether 215 g (0.72
Mol) was obtained as a colorless transparent liquid. The isolation yield was 85%.

Example 5 Synthesis of didodecyl ether CH ₃ (CH ₂ ) ₁₀ CH ₂ —O—CH ₂ (CH ₂ ) ₁₀ CH ₃ n-dodecyl aldehyde was placed in a 500 ml autoclave equipped with a hydrogen gas introducing tube and a stirrer. 276 g (1.5 mol) and 5.5 g of 5% Pd-C (pH 3.8) as a catalyst were charged, and the mixture was stirred at 150 ° C. for 8 hours under a hydrogen pressure of 120 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (165 ° C
/0.2 Torr), and the desired didodecyl ether 231g
(0.65 mol) was obtained as a white solid. The isolation yield was 87%.

Example 6 Synthesis of bis (1,3-dimethylbutyl) ether

[0030]

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500 equipped with a hydrogen gas inlet tube and a stirrer
250 g of methyl isobutyl ketone in ml autoclave
(2.5 mol), 5.0 g of 5% Pd-C (pH 3.8) as a catalyst
Was charged, and the mixture was stirred at 150 ° C. for 8 hours under a hydrogen pressure of 150 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (97 ° C / 50 Torr) was performed to obtain the desired bis (1,3
145 g (0.78 mol) of dimethylbutyl) ether were obtained as a colorless transparent liquid. The isolation yield was 62%.

Example 7 Synthesis of dicyclohexyl ether

[0033]

[Chemical 6]

500 equipped with a hydrogen gas inlet tube and a stirrer
245 g (2.5 mol) of cyclohexanone and 4.9 g of 5% Pd-C (pH 6.6) as a catalyst were charged in a ml autoclave, and the mixture was stirred at 150 ° C. for 8 hours under a hydrogen pressure of 150 kg / cm ² . After the completion of the reaction, the catalyst was removed by filtration, and the target dicyclohexyl ether (129 g, 0.71 mol) was obtained as a colorless transparent liquid by silica gel column chromatography. The isolation yield was 57%.

Example 8 Synthesis of didecyl ether Using exactly the same starting materials and catalysts as in Example 4, 2.7 g (0.02 mol) of anhydrous magnesium sulfate was added, and the same reaction and treatment as in Example 4 were carried out. Didecyl ether 228g
(0.77 mol) was obtained as a colorless transparent liquid. Isolation yield
It was 90%.

Example 9 Synthesis of bis (1,3-dimethylbutyl) ether Using the same raw materials and catalysts as in Example 6, 2.5 g (0.02 mol) of anhydrous magnesium sulfate was added, and the same reaction as in Example 6 was performed. Then, the same treatment was carried out to obtain 174 g (0.94 mol) of bis (1,3-dimethylbutyl) ether as a colorless transparent liquid. The isolation yield was 75%.

Example 10 Synthesis of dibutyl ether CH ₃ (CH ₂ ) ₂ CH ₂ —O—CH ₂ (CH ₂ ) ₂ CH ₃ 500 equipped with a hydrogen gas introduction tube, a stirrer and a cooling dehydration tube
284 g (4.0 g) of n-butyraldehyde in a ml autoclave.
Mol) and 5% Pd-C (pH 6.6) 8.5 g as a catalyst were charged, and under hydrogen pressure of 50 kg / cm ² , hydrogen flow rate 700 ml / min, 15
The mixture was stirred at 0 ° C. for 8 hours, water by-produced by the reaction was removed to the outside of the system, and n-butyraldehyde that had been out of the system together with water was returned to the inside of the system to carry out the reaction. After the reaction was completed, the catalyst was removed by filtration and further distilled (140 ° C / normal pressure),
247 g (1.9 mol) of the target dibutyl ether was obtained as a colorless transparent liquid. The isolation yield was 95%.

Example 11 Synthesis of dihexyl ether CH ₃ (CH ₂ ) ₄ CH ₂ —O—CH ₂ (CH ₂ ) ₄ CH ₃ Hydrogen gas introduction tube, stirrer and cooling dehydration tube 500
250 g of n-hexyl aldehyde in a ml autoclave
(2.5 mol), 7.5 g of 5% Pd-C (pH 6.6) as a catalyst
Was charged, hydrogen pressure was 50 kg / cm ² , hydrogen flow rate was 700 ml / min,
The mixture was stirred at 150 ° C. for 8 hours, water produced as a by-product of the reaction was removed to the outside of the system, and n-hexylaldehyde that had gone out of the system along with water was returned to the inside of the system to carry out the reaction. After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (102 ° C / 50 Tor)
r) was carried out to obtain 216 g (1.16 mol) of the desired dihexyl ether as a colorless transparent liquid. The isolation yield was 93%.

Example 12 Synthesis of dioctyl ether CH ₃ (CH ₂ ) ₆ CH ₂ —O—CH ₂ (CH ₂ ) ₆ CH ₃ 500 equipped with a hydrogen gas introduction tube, a stirrer and a cooling dehydration tube
256 g of n-octyl aldehyde in a 1 ml autoclave
(2.0 mol), 5% Pd-C (pH 3.8) as catalyst 7.7 g
Was charged, hydrogen pressure was 50 kg / cm ² , hydrogen flow rate was 800 ml / min,
The mixture was stirred at 150 ° C. for 8 hours, water by-produced by the reaction was removed to the outside of the system, and n-octyl aldehyde, which came out of the system together with water, was returned to the inside of the system to carry out the reaction. After the reaction was completed, the catalyst was removed by filtration, and further vacuum distillation (127 ° C / 3.5 Torr
r) was carried out to obtain 225 g (0.93 mol) of the desired dioctyl ether as a colorless transparent liquid. The isolation yield was 93%.

Example 13 Synthesis of didecyl ether CH ₃ (CH ₂ ) ₈ CH ₂ —O—CH ₂ (CH ₂ ) ₈ CH ₃ 500 equipped with a hydrogen gas introduction tube, a stirrer and a cooling dehydration tube
n-decylaldehyde 265 g (1.7
Mol), 8.0 g of 5% Pd-C (pH 6.6) as a catalyst was charged, and the hydrogen flow rate was 1 liter / min under a hydrogen pressure of 50 kg / cm ² .
The mixture was stirred at 150 ° C. for 8 hours, water produced as a by-product of the reaction was removed to the outside of the system, and n-decylaldehyde discharged from the system together with water was returned to the inside of the system to carry out the reaction. After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (142 ° C / 0.3 Torr)
The desired didecyl ether (233 g, 0.78 mol) was obtained as a colorless transparent liquid. The isolation yield was 92%.

Example 14 Synthesis of didodecyl ether CH ₃ (CH ₂ ) ₁₀ CH ₂ —O—CH ₂ (CH ₂ ) ₁₀ CH ₃ 500 equipped with a hydrogen gas introduction tube, a stirrer and a cooling dehydration tube
276 g of n-dodecyl aldehyde in a ml autoclave
(1.5 mol), 5% Pd-C (pH 3.8) as catalyst 8.3 g
Was charged under a hydrogen pressure of 60 kg / cm ² , and the hydrogen flow rate was 1 liter / m 2.
The mixture was stirred at 150 ° C. for 8 hours, water by-produced by the reaction was removed to the outside of the system, and n-dodecylaldehyde that had been out of the system together with water was returned to the inside of the system to carry out the reaction. After completion of the reaction, the catalyst was removed by filtration, and further vacuum distillation (165 ° C /
0.2 Torr) and 247 g (0.
70 mol) was obtained as a white solid. The isolation yield was 93%.

Example 15 Synthesis of bis (1,3-dimethylbutyl) ether

[0043]

[Chemical 7]

In a 500 ml autoclave equipped with a hydrogen gas introduction pipe, a stirrer and a cooling dehydration pipe, 250 g (2.5 mol) of methyl isobutyl ketone and 5% Pd-C (pH
3.8) Charge 10 g, hydrogen pressure 60 kg / cm ² , hydrogen flow rate 700 m
The mixture was stirred at l / min at 150 ° C. for 8 hours, water produced as a by-product of the reaction was removed to the outside of the system, and methyl isobutyl ketone, which was discharged with the water out of the system, was returned to the inside of the system for the reaction. After the reaction was completed, the catalyst was removed by filtration and further vacuum distillation (97 ° C
/ 50 Torr) to obtain 184 g (0.99 mol) of the target bis (1,3-dimethylbutyl) ether as a colorless transparent liquid. The isolation yield was 79%.

Example 16 Synthesis of dicyclohexyl ether

[0046]

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Cyclohexanone 2 was placed in a 500 ml autoclave equipped with a hydrogen gas introduction tube, a stirrer and a cooling dehydration tube.
45 g (2.5 mol), 5% Pd-C as catalyst (pH 6.6)
Charged 9.8g, under hydrogen pressure 60kg / cm ² , hydrogen flow rate 700ml / m
The mixture was stirred at 150 ° C. for 8 hours, water by-produced by the reaction was removed to the outside of the system, and cyclohexanone that came out of the system with water was returned to the inside of the system to carry out the reaction. After completion of the reaction, the catalyst was removed by filtration, and the target dicyclohexyl ether was further purified by silica gel column chromatography.
87 g (1.03 mol) was obtained as a colorless transparent liquid. The isolation yield was 82%.

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Claims (8)

[Claims] 1. A compound represented by the general formula (1): [In the formula, R ₁ and R ₂ represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, and 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 carbonyl compound represented by these is made to react using a catalyst in hydrogen atmosphere, The manufacturing method of the ether compound represented by General formula (2) characterized by the above-mentioned. Embedded image [In the formula, R ₁ and R ₂ have the same meanings as described above. ] 2. The carbonyl compound represented by the general formula (1) is an aliphatic aldehyde having 1 to 20 carbon atoms.
A method for producing the described ether compound. 3. The carbonyl compound represented by the general formula (1) is a symmetric or asymmetric chain ketone having 3 to 12 carbon atoms, or a cyclic ketone having 3 to 12 carbon atoms.
A method for producing the described ether compound. 4. The catalyst according to claim 1, wherein the catalyst is a palladium catalyst supported on carbon, alumina, silica alumina or silica, palladium hydroxide or palladium oxide.
The method for producing the ether compound according to any one of 1. 5. The method for producing an ether compound according to claim 1, wherein the reaction is carried out while removing water by-produced by the reaction. 6. The process for producing an ether compound according to claim 5, wherein water is removed by carrying out the reaction in the presence of a dehydrating agent. 7. The method for producing an ether compound according to claim 5, wherein water is removed to the outside of the system while circulating hydrogen. 8. The method for producing an ether compound according to claim 7, wherein the unreacted carbonyl compound represented by the general formula (1) which has been discharged from the system together with water is returned to the system.