JPH0940593A - Method for producing ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of supplying an ether compound which can be widely used for a solvent, a cosmetic, a detergent composition, a lubricant, an emulsifier, and the like in a simple and high yield. An ether compound is obtained by reacting a hydroxy compound and a carbonyl compound in the presence of a Lewis acid such as BF ₃ complex in a hydrogen atmosphere using a catalyst.

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 capable of supplying an ether compound which can be widely used for a solvent, a cosmetic, a detergent composition, a lubricant, an emulsifier and the like in a simple and high yield.

[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
The use as an oil agent as a detergent composition or a new nonionic activator is also considered. 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 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. The dehydration reaction between alcohols with an acid is suitable for the synthesis of symmetrical ether compounds, but it is difficult to synthesize asymmetric ether compounds. In addition, olefin by-products are produced. In addition, in the synthesis by adding alcohol to olefin, the olefin compound is limited, and many are considerably expensive with the catalyst used.
Many of the olefins and 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.

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 are 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.

[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 easily supplied at a high yield has been desired.
Accordingly, an object of the present invention is to provide a production method capable of easily supplying an ether compound useful as a solvent, a cosmetic, a detergent composition, a lubricant, an emulsifier, and the like in a high yield.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted earnest studies on a simple and high-yield production method of an ether compound which can be generally used, and as a result, a hydroxy compound and a carbonyl compound have been obtained. When the compound is reacted with a catalyst in a hydrogen atmosphere, the presence of a Lewis acid in the reaction system makes it possible to obtain an ether compound in a single step and in a high yield, and to complete the present invention. Arrived That is, the present invention provides a method for producing an ether compound, which comprises reacting a hydroxy compound and a carbonyl compound in the presence of Lewis acid in a hydrogen atmosphere using a catalyst.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The Lewis acid used in the present invention may be any electron pair acceptor, for example, 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 COC
H ₃ (boron trifluoride-t-butyl methyl ether _{complex), BF 3 · CH 3 OH} ( boron trifluoride-methanol _{complex), BF 3 · CH 3 (} CH 2) 2 OH ( boron trifluoride-propanol Complex) such as BF ₃ complex, TiCl ₄ (titanium tetrachloride), SnCl
₄ (tin tetrachloride), AlCl ₃ (aluminum trichloride), TMSOTf
(Trifluoromethanesulfonic acid trimethylsilyl),
Ti (Oi-Pro) ₄ (Tetraisopropyl titanate), ZnCl
₂ (zinc dichloride), FeCl ₃ (iron trichloride), and the like, and particularly preferably BF ₃ · OEt ₂ (boron trifluoride / diethyl ether complex). The amount of these Lewis acids used is not particularly limited, but is preferably 0.01 to 20 times by mole, more preferably 0.1 to 10 times by mole, and still more preferably 0.5 to 5 times by mole with respect to the hydroxy compound used.

The catalyst used in the present invention includes:
It is not particularly limited as long as it has a hydrogenating ability, carbon, silica-alumina, alumina, silica, a palladium catalyst appropriately supported on a carrier such as zeolite, or palladium hydroxide, a palladium compound such as palladium oxide, carbon, Examples thereof include ruthenium, rhodium or platinum catalyst, ruthenium oxide, rhodium oxide, platinum oxide and the like, which are appropriately supported on a carrier such as alumina. Further, a catalyst such as iridium, osmium, rhenium or the like can be used. Among these catalysts, preferably a palladium catalyst, more preferably carbon, alumina silica, a palladium catalyst supported on alumina or silica, palladium hydroxide or palladium oxide, and particularly a palladium catalyst supported on carbon is preferable. . Moreover, these catalysts can be used as 1 type or a mixture of 2 or more types.

In the present invention, the catalyst is usually used by supporting it on a carrier such as carbon or alumina at a ratio of 1 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. If the catalyst is, for example, 5% by weight supported on the carrier, it is 0.1
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 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.

The hydroxy compound used in the present invention is, for example, a compound represented by the general formula (1) R _1- (OA) _n -OH (1) [wherein R ₁ is a straight chain or branched chain having 1 to 40 carbon atoms] An alkyl group or an alkenyl group is shown. A represents an alkylene group having 2 to 12 carbon atoms, and n A's may be the same or different. n shows the number of 0-30. ] The compound represented by this is mentioned.

Specific examples of the compound represented by the general formula (I) 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

[0014]

Embedded image

(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 alcohols, but the invention is not necessarily limited thereto.

Among these hydroxy compounds, aliphatic alcohols having 1 to 22 carbon atoms, particularly 6 to 22 carbon atoms, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve,
Butyl cellosolve, methyl carbitol, ethyl carbitol, isopropyl carbitol, butyl carbitol, or ethylene oxide adduct of aliphatic alcohol having 1 to 22 carbon atoms, especially 6 to 22 carbon atoms (average addition mole number of 0.1 to 2).
0) is preferable, and an aliphatic alcohol having 6 to 22 carbon atoms is more preferable. One or two of these hydroxy compounds
It can be used as a mixture of two or more species. Examples of the carbonyl compound used in the present invention include those represented by the general formula (2)

[0017]

Embedded image

[In the formula, R ₂ and R ₃ are hydrogen atoms and have 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 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, methyl n-heptyl ketone, methyl n-octyl ketone, methyl n-
Nonyl ketone, methyl n-decyl ketone, methyl n-undecyl ketone, methyl n-dodecyl ketone, methyl n
-Tetradecyl ketone, methyl n-hexadecyl ketone, methyl n-octadecyl ketone, diethyl ketone,
Ethyl-n-butyl ketone, di-n-propyl ketone,
Diisopropyl ketone, diisobutyl ketone, 2,6
Chain ketones such as 6-trimethylnonanone-4, 6-methyl-5-heptenone-2, cyclohexanone, 2-methylcyclohexanone, isophorone, cyclopentanone;
Methylcyclopentanone, hexylcyclopentanone,
Cyclic ketones such as cycloheptanone, formaldehyde,
Linear form such as paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, undecylaldehyde, dodecylaldehyde, hexadecylaldehyde, octadecylaldehyde, eicosylaldehyde, etc. Examples include, but are not limited to, aldehydes, branched aldehydes such as 2-ethylhexylaldehyde, 2-ethylbutyraldehyde, and methylheptadecylaldehyde.

Of these carbonyl compounds, a chain ketone having 1 to 12 carbon atoms, a cyclic ketone or an aldehyde is preferable, and acetone, methyl ethyl ketone, methyl isobutyl ketone (4-methyl-2-pentanone) or the like having 3 to 12 carbon atoms. 6 chain ketone, carbon number 1 to 12 such as formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, octyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde,
Further, 3 to 8 aliphatic aldehydes are particularly preferable, and acetone, methyl ethyl ketone, and methyl isobutyl ketone (4-methyl-2-pentanone) are particularly preferable.
These carbonyl 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 (molar ratio) = 50/1 to 1/50 is preferable, and particularly 10 / 1-1 / 1
0, and particularly preferably 5/1 to 1/5. If the hydroxy compound has a low molecular weight and can be easily removed by distillation or the like, the reaction is preferably performed using an excess of the hydroxy compound. Further, when the carbonyl compound has a low molecular weight and can be easily removed by distillation or the like, it is preferable to use an excess of the carbonyl compound for the reaction. 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, is reacted hydroxy compound and a carbonyl compound in a hydrogen atmosphere, the hydrogen pressure at that time is not particularly limited, usually 1~250kg / cm ^2, preferably from 1 to 100 kg / cm ² In particular, the effect of the present invention is 1 to
It is noticeable during the low pressure reaction of 30 kg / cm ² . Further, in the present invention, the reaction temperature when reacting the hydroxy compound and the carbonyl compound is not particularly limited, but is 10 to 200 ° C., preferably 15 to 100 ° C., and particularly 15 since the activity of this reaction is high.
It can be effectively reacted even at a low temperature of -50 ° C. The reaction time may be appropriately selected depending on the reaction temperature, hydrogen pressure, amount of Lewis acid added, amount of catalyst, etc., but usually 1 to 48
The time is preferably 1 to 18 hours.

In the present invention, the reaction may be carried out using a solvent which can be generally used in the reaction. As the solvent, any solvent can be used as long as it does not particularly adversely affect the reaction, and specific examples thereof include diethyl ether, tetrahydrofuran, hexane and the like. Further, in the present invention, the reaction may be carried out by adding a dehydrating agent such as anhydrous magnesium sulfate or anhydrous sodium sulfate for the purpose of removing water by-produced in the reaction system.

[0024]

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. In the examples,% is based on weight unless otherwise specified.

Example 1 10.7 g (0.05 mol) of tetradecyl alcohol and 4-methyl-2-pentanone were placed in a 100 ml flask equipped with a stir bar.
10 g (0.1 mol), 5% Pd-C (pH 3.8) 0.2 as a catalyst
g, 12 ml (0.1 mol) of boron trifluoride / diethyl ether complex as a Lewis acid was charged, and under a hydrogen atmosphere (normal pressure),
The mixture was stirred at room temperature for 18 hours. After completion of the reaction, the catalyst was removed by filtration, neutralized with saturated aqueous sodium bicarbonate solution, and then purified by silica gel column chromatography.
3-Dimethylbutyl tetradecyl ether 14.6 g (0.049
Mol) was obtained as a colorless transparent liquid. The isolation yield was 98%.

Comparative Example 1 Tetradecyl alcohol 10.7 g (0.05 mol) and 4-methyl-2-pentanone were placed in a 100 ml flask equipped with a stir bar.
10 g (0.1 mol), 5% Pd-C (pH 3.8) 0.2 as a catalyst
g was charged, and the mixture was stirred under a hydrogen atmosphere (normal pressure) at room temperature for 20 hours. After completion of the reaction, the catalyst was removed by filtration and the product was purified by silica gel column chromatography to obtain 1,3
0.15 g (0.5 mmol) of dimethylbutyl tetradecyl ether was obtained as a colorless transparent liquid. The isolation yield was 1%.

Examples 2 to 8 The hydroxy compound and carbonyl compound shown in Table 1 were
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 shown in Table 1 and the Lewis acid. The obtained product and its isolated yield are shown in Table 1.

Comparative Examples 2 to 8 The hydroxy compounds and carbonyl compounds shown in Table 2 were
In the presence of the catalyst shown in Table 2, the reaction was performed in the same manner as in Comparative Example 1 except for the reaction conditions shown in Table 2. The obtained product and its isolated yield are shown in Table 2.

[0029]

[Table 1]

[0030]

[Table 2]

Claims (7)

[Claims] 1. A method for producing an ether compound, which comprises reacting a hydroxy compound and a carbonyl compound in the presence of Lewis acid in a hydrogen atmosphere using a catalyst. 2. The hydroxy compound has the general formula (1) R _1- (OA) _n —OH (1) [wherein R ₁ represents a linear or branched alkyl or alkenyl group having 1 to 40 carbon atoms]. Show. A represents an alkylene group having 2 to 12 carbon atoms, and n A's may be the same or different. n shows the number of 0-30. ] The manufacturing method of the ether compound of Claim 1 which is a compound represented by these. 3. A carbonyl compound represented by the general formula (2): [In the formula, 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 manufacturing method of Claim 1 or 2 which is a compound represented by these. 4. The Lewis acid is a BF ₃ complex, titanium tetrachloride,
The method according to any one of claims 1 to 3, which is tin tetrachloride, aluminum trichloride, trimethylsilyl trifluoromethanesulfonate, tetraisopropyl titanate, zinc dichloride or iron trichloride. 5. The method according to claim 4, wherein the Lewis acid is BF ₃ .OEt ₂ (boron trifluoride / diethyl ether complex). 6. The method according to claim 1, wherein the Lewis acid is added in an amount of 0.01 to 20 times by mole with respect to the hydroxy compound. 7. The catalyst is carbon, alumina silica, 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.