JP3322281B2 - Method for producing ether compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ether compound, and more particularly to a method for efficiently producing a useful ether compound having a wide range of uses as a solvent, a lubricating oil and the like by hydrogenating an acetal or a ketal compound. About the method.

[0002]

2. Description of the Related Art Methods for producing ether compounds from acetal compounds and ketal compounds are described in, for example, Experimental Chemistry Lecture Vol. 20 (4th edition, Maruzen), which describes a combination of an acid and an alkali metal hydride, a silicon reagent, and diborane. A method using such a method is shown. However, these reactions are not preferable as an industrial production method because stoichiometric amounts of very expensive alkali metal hydride, diborane, and silicon reagent are used as hydrogenating agents. Further, a method combining an acid catalyst and catalytic hydrogenation is known. W. L. Howard
[J. Org. Chem. 26, 1026 (196
According to 1)], it has been reported that ether was produced by catalytic hydrogenolysis of ketal with a catalyst in which rhodium was supported on alumina in the presence of hydrochloric acid. US Patent No. 40
No. 88700 describes cyclic acetal 1,3-
A method for producing an ether compound by catalytic hydrogenolysis of dioxolanes with a platinum or rhodium catalyst in the presence of a Lewis acid such as boron trifluoride or aluminum trichloride is disclosed. However, in these production methods, hydrochloric acid, boron trifluoride, aluminum trichloride and the like are used. Therefore, when an ordinary apparatus is used, corrosion thereof becomes a problem and a special treatment is required, which is not preferable.

[0003] Therefore, as a method not using an acid, for example, JP-A-58-4739 and JP-A-58-17.
No. 7929 proposes a method for producing an ether compound by hydrogenating and decomposing acetal with a palladium catalyst supported on carbon. In this method, since no acid is used, there is no problem of corrosion of the apparatus, but the conversion of the raw acetal was not satisfactory. That is, an operation of separating the product and the raw material and recycling the raw material is required, which is not preferable. Further, when the produced ether cannot be separated and purified by distillation or the like, acetal remains in the product. Acetals generally lack stability, particularly hydrolysis resistance, and the resulting aldehydes cause oxidation, reduction, polycondensation, etc., which significantly impairs the properties of the product, causing a problem. Therefore, its application range must be narrow. As described above, a method for producing an ether compound from an acetal or ketal compound having sufficient reaction activity, good selectivity, and causing no apparatus corrosion or the like has not been found yet, and its development is strongly desired. ing.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has sufficient reaction activity, has excellent selectivity, and does not cause corrosion of equipment. It is an object of the present invention to provide a method for producing an ether compound.

[0005]

Means for Solving the Problems The present inventors have found that a solid catalyst having an acid property and a hydrogenating ability can meet the above-mentioned object, and have completed the present invention. That is,
The present invention relates to a compound of the formula (I)

[0006]

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Wherein R ¹ and R ² each represent a hydrocarbon group or a hydrocarbon group containing ethereal oxygen in the main chain and / or side chain, and R ³ , R ⁴ and R ⁵ represent hydrogen, hydrocarbon Represents a hydrogen group or a hydrocarbon group containing etheric oxygen in the main chain and / or side chain, and R ^{1 to} R ⁵ may be the same or different. Reacting the acetal or ketal compound of formula (II) or (III) with hydrogen in the presence of a solid catalyst having acidity and hydrogenation ability

[0008]

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[Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same as above. And a method for producing an ether compound represented by the formula:

In the method of the present invention, an acetal compound or a ketal compound represented by the above general formula (I) is used as a starting material. In the above general formula (I), R
¹ and R ² each represent a hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a formula:

[0011]

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[Wherein, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m represents an integer of 1 to 500. And a hydrocarbon group containing etheric oxygen in the main chain and / or side chain. R ³ , R ⁴ and R ⁵ are each hydrogen or the same as R ¹ and R ² described above;

[0013]

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[Wherein, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m represents an integer of 1 to 500. ] And so on.
In the present invention, by reacting the acetal or ketal compound represented by the general formula (I) with hydrogen in the presence of a solid catalyst having acidity and hydrogenation ability,
General formula (II) or (III)

[0015]

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[Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same as above. Is obtained. The acetal or ketal compound represented by the general formula (I) includes a compound represented by the general formula (IV)

[0017]

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[In the formula, R ⁶ and R ⁷ each represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing ethereal oxygen, and n represents an integer of 1 to 500. In this case, a compound represented by the general formula (V) or (VI)

[0019]

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Wherein R ⁶ , R ⁷ and n are the same as above. Is obtained. The compound represented by the general formula (IV) includes a compound represented by the general formula (IX)

[0021]

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Wherein R ⁶ and n are as defined above. In such a mixture, the resulting ether compound is a compound of the general formula (V) or a compound of the general formula (V) and a compound of the formula (VI). It becomes a mixture. Further, as the acetal and ketal compounds represented by formula (I), the general formula ^{(VII) R 8 CH (OR} 9) 2 ··· (VII) wherein, R ⁸ and R ⁹ are each 1 to carbon atoms Represents 20 hydrocarbon groups. ] Are also preferably used. In this case, the ether compound represented by the general formula (VII
I) R ⁸ CH ₂ OR ⁹ (VIII) wherein R ⁸ and R ⁹ are the same as above. Is obtained.

The method of the present invention comprises:Hydrogenation catalyst and solid acid catalyst
Catalyst or metal with hydrogenation ability combining two types of
-Loaded solid acid catalystIs used. Hydrogenation catalyst
There are no particular restrictions on various commonly used
Hydrogenation catalysts can be used, such as nickel
Gold such as metal, palladium, rhodium, platinum, ruthenium
Genus alone or those containing these as main components, above
Metal catalyst component supported on activated carbon, alumina, diatomaceous earth, etc.
Catalyst, Raney nickel, Raney cobalt, etc.
-Type catalysts are particularly effective. Particularly as solid acid catalysts,
There is no restriction, use various commonly used things
For example, activated clay, acid clay, various zeora
Site, ion exchange resin, silica-alumina, heteropoly
Acids and the like are particularly effective. Also,Metals with hydrogenation ability
As a solid acid catalyst carryingFor example, various Zeoli
Nickel, palladium, rhodium, platinum, ruthenium
A catalyst supporting a catalyst or the like is particularly effective.

The amount of the catalyst suitable for carrying out the process of the present invention is 0.1 to 50% by weight of the hydrogenation catalyst based on the reaction substrate.
The solid acid catalyst is 0.1 to 50% by weight.
50% by weight. If the amount is less than 0.1% by weight, the reaction does not proceed sufficiently, and if it exceeds 50% by weight, the amount of the catalyst becomes too large with respect to the raw material, and there is a disadvantage that productivity is lowered. In the present invention, the acetal or ketal compound represented by the general formula (I) is reacted with hydrogen in the presence of the above-described catalyst, and the molar ratio of hydrogen gas to the acetal or ketal compound is 1:10 to 200: It is preferred to make contact as 1. When the molar ratio is lower than the above range, the reaction does not proceed sufficiently, and when the molar ratio is higher than the above range, the productivity is lowered.

The reaction conditions suitable for carrying out the hydrogenation reaction according to the method of the present invention include a reaction temperature of 10-2.
50 ° C., hydrogen gas partial pressure 1 to 200 kg / cm ² , reaction time is 0.1 to 10 hours for a batch type reaction, and weight hourly space velocity (WHS) of a reaction solution for a reaction in a liquid phase flow system.
V) = 0.01 to 100 / hr, and the gas space velocity (GHSV) of hydrogen gas = 100 to 10000 / hr. Furthermore, the reaction can be performed without using a solvent,
Any solvent that is stable under the reaction conditions may be used. Examples of the solvent that can be used include hydrocarbon solvents such as hexane, heptane, and octane.

By the reaction as described above, the acetal or ketal compound represented by the above general formula (I) is converted from the acetal or ketal compound into -OR which constitutes the acetal or ketal.
^{The 1} or —OR ² group is eliminated and replaced with a hydrogen atom to produce an ether compound represented by the general formula (II) or (III). In this reaction, even when any of R ^{1 to} R ⁵ represents a hydrocarbon group containing ethereal oxygen,
It has been found that hydrogen does not act on the etheric oxygen but acts exclusively on the acetal or ketal oxygen portion. After completion of the reaction, the reaction mixture can be separated from the catalyst by usual filtration or decantation. The separated catalyst can be reused without special treatment. The product can be made into a product by performing operations such as distillation, extraction, washing, and drying as necessary.

[0027]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. Catalyst Preparation Example 1 Raney Nickel (manufactured by Kawaken Fine Chemical Company, trade name M
100T (water-containing state) was placed in a flask, and 100 g of absolute ethanol was added thereto and mixed well. afterwards,
The Raney nickel was allowed to settle by standing, and the supernatant was removed by decantation. The above operation was performed five times on Raney nickel remaining in the flask.

Catalyst Preparation Example 2 Zeolite (manufactured by Tosoh Corporation, trade name: HSZ330HUA)
20 g was put into a 100 ml eggplant-shaped flask,
And the pressure was reduced by an oil rotary vacuum pump for 1 hour. After cooling to room temperature, the pressure was adjusted to normal pressure with dry nitrogen. Catalyst Preparation Example 3 20 g of activated clay (manufactured by Wako Pure Chemical Industries) was placed in a 100 ml eggplant-shaped flask, placed in a 150 ° C. oil bath, and evacuated with an oil rotary vacuum pump for 1 hour. After cooling to room temperature, the pressure was adjusted to normal pressure with dry nitrogen.

Example 1 In a 1 liter autoclave made of SUS-316L, 100 g of acetaldehyde diethyl acetal, 100 g of n-heptane, Raney nickel prepared in Catalyst Preparation Example 1
3.0 g (in the wet state of ethanol) and 3.0 g of the zeolite prepared in Catalyst Preparation Example 2 were charged. Hydrogen was introduced into the autoclave to a hydrogen pressure of 10 kg / cm ² , stirred for about 30 seconds, and then depressurized. Hydrogen was introduced again into the autoclave to adjust the hydrogen pressure to 10 kg / cm ² ,
After stirring for 0 seconds, the pressure was released. After that, the hydrogen pressure was increased to 30k
g / cm ² and the temperature was raised to 130 ° C. in 30 minutes with stirring. The reaction was performed at 130 ° C. for 2 hours and 30 minutes. Reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure was increased and the pressure decreased due to the temperature increase, and the reaction was carried out while maintaining the hydrogen pressure at 30 kg / cm ² by appropriately reducing and increasing the pressure. After the completion of the reaction, the pressure was reduced to 20 ° C., and then reduced to normal pressure. The reaction liquid was subjected to qualitative and quantitative analysis by gas chromatography. The conversion of acetaldehyde diethyl acetal was 94.9% and the selectivity for diethyl ether was 68.3%.

Example 2 100 g of propionaldehyde diethyl acetal was added to a 1 liter autoclave made of SUS-316L,
100 g of octane, 6.0 g of Raney nickel prepared in Catalyst Preparation Example 1 (in the wet state of ethanol) and 6.0 g of zeolite prepared in Catalyst Preparation Example 2 were charged. Hydrogen was introduced into the autoclave to a hydrogen pressure of 10 kg / cm ² , stirred for about 30 seconds, and then depressurized. Hydrogen was again introduced into the autoclave to a hydrogen pressure of 10 kg / cm ² , stirred for about 30 seconds, and then depressurized. Thereafter, the hydrogen pressure was adjusted to 30 kg / cm ^2, and 130 ° C. for 30 minutes while stirring.
The temperature rose. The reaction was carried out at 130 ° C. for 1 hour and 30 minutes. Reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure was increased and the pressure was decreased due to the temperature rise, and the reaction was carried out by adjusting the hydrogen pressure to 30 kg / cm ² by appropriately reducing and increasing the pressure. After the completion of the reaction, the pressure was reduced to 20 ° C., and then reduced to normal pressure. The reaction liquid was subjected to qualitative and quantitative analysis by gas chromatography. The conversion of propionaldehyde diethyl acetal was 97.0%, and the selectivity for ethyl n-propyl ether was 72.0%.

Example 3 (1) Preparation of Raw Materials In a 5-liter glass flask equipped with a dropping funnel, a condenser and a stirrer, 1,000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of boron trifluoride diethyl ether complex were placed. 2500 g of ethyl vinyl ether was put into the dropping funnel and dropped over 2 hours and 30 minutes. During this time, the reaction started and the temperature of the reaction solution rose, but was kept at about 25 ° C. while cooling in an ice water bath. After completion of the dropwise addition, the mixture was stirred for 5 minutes, the reaction mixture was transferred to a washing tank, and washed three times with 1000 ml of a 5% aqueous sodium hydroxide solution, and further washed three times with 1,000 ml of water. Using a rotary evaporator, the solvent and unreacted raw materials were removed under reduced pressure to obtain 2833 g of a product. Of this one
FIG. 1 shows the ¹ H-NMR spectrum. From this spectrum diagram, it was found that the product had the structures of the following formulas (A) and (B). The kinematic viscosity of the product is 100
It was 5.18 cSt at 40 ° C and 38.12 cSt at 40 ° C.

[0032]

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The ratio of the number of molecules is (A) :( B) = 4.
5: 1 and the average value of n was 5.6. (2) In a 1-liter autoclave made of SUS-316L, 200 g of the oligomer prepared in (1) above, 6.0 g of Raney nickel prepared in Catalyst Preparation Example 1 (in a wet state of ethanol), and prepared in Catalyst Preparation Example 2 6.0 g of zeolite were charged. After introducing hydrogen into the autoclave to a hydrogen pressure of 10 kg / cm ² and stirring for about 30 seconds,
Depressurized. Hydrogen was again introduced into the autoclave to a hydrogen pressure of 10 kg / cm ² , stirred for about 30 seconds, and then depressurized. After performing this operation one more time, the hydrogen pressure was increased to 25%.
and kg / cm ^2, the temperature of the mixture reached 140 ° C. for 30 minutes. The reaction was performed at 140 ° C. for 2 hours. Reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition,
The reaction was carried out by adjusting the hydrogen pressure to 25 kg / cm ² by appropriately reducing and increasing the pressure to increase the pressure due to the temperature rise and decrease the pressure due to the reaction. After the completion of the reaction, the reaction mixture was cooled to room temperature and then reduced to normal pressure. After adding 100 ml of hexane, the mixture was allowed to stand for 30 minutes to precipitate the catalyst, and the reaction solution was removed by decantation. The hexane solution was combined with the reaction solution, and filtered using a filter paper. The catalyst was reused in Example 5. Hexane, water and the like were removed under reduced pressure using a rotary evaporator. The yield was 162 g. Its ¹ H-NMR spectrum is shown in FIG. From this spectrum diagram, the raw material acetal is represented by the formula (C)

[0034]

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(Et represents an ethyl group), and the conversion is 100.
%Met. The kinematic viscosity was 4.90 cSt at 100 ° C. and 29.50 cSt at 40 ° C. In addition, the ethyl vinyl ether oligomer of the above formula (B) was also an ether compound represented by the above formula (C).

Example 4 In a 1 liter autoclave made of SUS-316L, 200 g of the oligomer prepared in Example 3 (1), 20 g of Raney nickel prepared in Catalyst Preparation Example 1 (in a wet state of ethanol) and Catalyst Preparation Example 2 20 g of the zeolite prepared in the above. Hydrogen was introduced into the autoclave to a hydrogen pressure of 7 kg / cm ² , stirred for about 30 seconds, and then depressurized. After performing this operation once more, the hydrogen pressure was reduced to 7 kg.
/ Cm ² and the temperature was raised to 130 ° C. in 30 minutes with stirring. The reaction was performed at 130 ° C. for 2 hours and 30 minutes. Reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure was increased and the pressure was decreased due to the temperature rise. The reaction was carried out by appropriately reducing and increasing the pressure to adjust the hydrogen pressure to 7 kg / cm ² . After the completion of the reaction, the reaction mixture was cooled to room temperature and then reduced to normal pressure. The reaction mixture was filtered, and water and the like were removed from the solution portion under reduced pressure using a rotary evaporator. The yield was 160 g. As a result, the same ether compound as that obtained in Example 3 (2) was obtained as the raw material acetal, and the conversion was 100%. The kinematic viscosity is 4.77 cSt at 100 ° C. and 30.27 cS at 40 ° C.
t.

Example 5 200 g of the oligomer produced in Example 3 (1) was placed in an autoclave in which the catalyst remained in Example 3 (2), and the reaction was carried out in the same manner as in Example 3 (2). Yield 164
g. Thus, the raw material acetal was obtained in Example 3.
The same ether compound as obtained in (2) was obtained, and its conversion was 100%. The kinematic viscosity is 100 ° C
Was 4.93 cSt and 29.13 cSt at 40 ° C.

Example 6 (1) Preparation of raw materials Example 3 (1) was repeated except that acetaldehyde diethyl acetal was 450 g, boron trifluoride diethyl ether complex was 4.5 g, and ethyl vinyl ether was 2800 g. The reaction was carried out in the same manner as in (1). The yield was 3175 g. The structure of this is the third embodiment.
Same as (1). However, the kinematic viscosity is 6.
79 cSt, 40.degree. C., 59.68 cSt, the ratio of the number of molecules was (A) :( B) = 8: 1, and the average value of n was 6.8. (2) In a 1-liter autoclave made of SUS-316L, 200 g of the oligomer prepared in (1) above, 10 g of Raney nickel prepared in Catalyst Preparation Example 1 (in a wet state of ethanol), and activated clay prepared in Catalyst Preparation Example 3 15g was put. Hydrogen was introduced into the autoclave to a hydrogen pressure of 10 kg / cm ² , stirred for about 30 seconds, and then depressurized. Hydrogen was introduced again into the autoclave to a hydrogen pressure of 10 kg / cm ² , stirred for about 30 seconds, and then depressurized. After performing this operation once more, the hydrogen pressure was increased to 30 kg.
/ Cm ² and the temperature was raised to 150 ° C. in 40 minutes with stirring. The reaction was performed at 150 ° C. for 1 hour. Reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure increase due to the temperature increase, the pressure decrease due to the reaction is timely decompression,
The reaction was carried out by adjusting the hydrogen pressure to 30 kg / cm ² by pressurization. After the completion of the reaction, the reaction mixture was cooled to room temperature and then reduced to normal pressure. The reaction mixture was filtered, and water and the like were removed from the solution portion under reduced pressure using a rotary evaporator. Yield 1
The weight was 58 g. As a result, the same ether compound as that obtained in Example 3 (2) was obtained as the raw material acetal,
Its conversion was 100%. The kinematic viscosity is 100
It was 7.06 cSt at 40 ° C and 57.32 cSt at 40 ° C.

Example 7 A 1-liter autoclave made of SUS-316L was prepared.
200 g of oligomer produced in Example 3 (1), catalyst preparation
10 g of the zeolite prepared in Example 2 and Pd / C (Pd
(5% loading: manufactured by Wako Pure Chemical Industries, Ltd.). Oat crepe
Hydrogen is introduced into the chamber and hydrogen pressure is 7kg / cm^TwoAnd about
After stirring for 30 seconds, the pressure was released. Again in the autoclave
Hydrogen is introduced into the reactor and hydrogen pressure is 7kg / cm^TwoAnd about 30 seconds
After stirring for a while, the pressure was released. This operation was performed once more
Then, the hydrogen pressure is 7kg / cm^Two30 minutes with stirring
To 120 ° C. The reaction was performed at 120 ° C. for 7 hours.
Reaction occurred during and after heating, and hydrogen pressure decreased.
Was done. In addition, pressure increase due to temperature rise, pressure due to reaction
Decrease and reduce the pressure as needed to increase the hydrogen pressure to 7 kg / cm ^TwoTo
The reaction was performed with adjustment. After the completion of the reaction, the resultant was cooled to room temperature.
Thereafter, the pressure was reduced to normal pressure. The reaction mixture is filtered and the solution
Use a rotary evaporator to remove water, etc. under reduced pressure.
I left. The yield was 167.2 g. As a result,
Acetal is the same ether as obtained in Example 3 (2).
The compound was obtained and its conversion was 100%. Ma
The kinematic viscosity is 5.28 cSt at 100 ° C, and at 40 ° C
It was 32.93 cSt.

Example 8 In a 1-liter autoclave made of SUS-316L, 200 g of the oligomer prepared in Example 3 (1), 20 g of the zeolite prepared in Catalyst Preparation Example 2 and Ru / C (Ru
5% supported: manufactured by Wako Pure Chemical Industries, Ltd.). Hydrogen was introduced into the autoclave to a hydrogen pressure of 30 kg / cm ² ,
After stirring for about 30 seconds, the pressure was released. Hydrogen was introduced again into the autoclave to a hydrogen pressure of 30 kg / cm ² ,
After stirring for 0 seconds, the pressure was released. After this operation was performed once more, the hydrogen pressure was adjusted to 30 kg / cm ^2, and the mixture was stirred for 3 hours.
The temperature was raised to 130 ° C. in 0 minutes. The reaction was performed at 130 ° C. for 1 hour. Reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure increase due to the temperature rise and the pressure decrease due to the reaction are reduced and pressurized as appropriate to increase the hydrogen pressure to 30 kg / c.
The reaction was performed after adjusting to m ² . After the completion of the reaction, the reaction mixture was cooled to room temperature and then reduced to normal pressure. The reaction mixture was filtered, and water and the like were removed from the solution portion under reduced pressure using a rotary evaporator. The yield was 156 g. This allows
As the starting acetal, the same ether compound as that obtained in Example 3 (2) was obtained, and its conversion was 100%. The kinematic viscosity is 5.18 cSt at 100 ° C.
It was 31.53 cSt at 0 ° C.

Example 9 A 2-liter autoclave made of SUS-316L was charged with N.
15 g of i-diatomaceous earth and 350 g of hexane were charged. After replacing the inside of the autoclave with hydrogen, the hydrogen pressure was increased to 30 kg.
/ Cm ² . The temperature was raised to 150 ° C. for 30 minutes with stirring, and the catalyst was activated for 30 minutes. After cooling, the oligomer 30 prepared in Example 3 (1) was placed in an autoclave.
0 g and 15 g of the zeolite of Catalyst Preparation Example 2 were added. Hydrogen was introduced into the autoclave, and the hydrogen pressure was 30 kg / cm ²
After stirring for about 30 seconds, the pressure was released. Hydrogen was introduced again into the autoclave, and the hydrogen pressure was adjusted to 30 kg / cm ² .
After stirring for about 30 seconds, the pressure was released. After this operation was performed once more, the temperature was increased to 130 ° C. in 30 minutes with stirring at a hydrogen pressure of 30 kg / cm ^2, and the reaction was carried out at 130 ° C. for 1 hour. Reaction occurred during and after the heating, and a decrease in hydrogen pressure was observed. In addition, the pressure increase due to the temperature rise and the pressure decrease due to the reaction are reduced and pressurized as appropriate to increase the hydrogen pressure to 30 kg / c.
m ² and the reaction was carried out. After completion of the reaction, the reaction mixture was cooled to room temperature and then reduced in pressure to normal pressure. The reaction mixture was filtered, and hexane, water and the like were removed from the solution under reduced pressure using a rotary evaporator. The yield was 240 g. As in Example 3, the conversion of the starting acetal was 100%. The kinematic viscosity was 5.38 cSt at 100 ° C and 33.12 cSt at 40 ° C.

[0042]

According to the method of the present invention, an ether compound can be produced from an acetal compound or a ketal compound at a high conversion and a high selectivity. Can be used. Further, according to the method of the present invention, even when the acetal or ketal is exclusively hydrogenated and the raw acetal or ketal compound has a hydrocarbon group containing etheric oxygen, the etheric oxygen portion remains as it is, and the acetal or ketal bond is left. Changes to an ether bond.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a raw acetal oligomer produced in Example 3 (1).

FIG. 2 shows ^{one of} the ether compounds produced in Example 3 (2).
It is an H-NMR spectrum figure.

Continuation of the front page (72) Inventor Nobuaki Shimizu 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd. (56) References JP-A-1-102039 (JP, A) JP-A-61-33238 (JP, A) JP-A-61-249940 (JP, A) JP-A-57-128648 (JP, A) US Patent 4,088,700 (US, A) US Patent 2,590,598 (US, A) L. Howard et al. , J. et al. Org. Chem. , 1961, No. 1; 26, p. 1026-1028 M.P. Verzele et al. J., J .; Chem. Soc. , 1963, p. 5598-5600 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 43/04 C07C 41/28 C08C 19/00-19/44 C08F 6/00-246/00 B01J 21 / 00-38/74 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) [In the formula, R ¹ and R ² each represent a hydrocarbon group or a hydrocarbon group containing ethereal oxygen in the main chain and / or side chain, and R ³ , R ⁴ and R ⁵ each represent a hydrogen, a hydrocarbon group or Represents a hydrocarbon group containing etheric oxygen in the main chain and / or side chain. The acetal or ketal compound represented by the formula (1) is hydrogenated with a solid acid catalyst (aluminum chloride).
(Excluding aluminum ) or a solid acid catalyst (aluminium chloride) supporting a metal capable of hydrogenation
Formula which comprises reacting with hydrogen in the presence of excluding arm) (II) or (III) ## STR2 ## Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as above. ] The manufacturing method of the ether compound shown by this. 2. An acetal or ketal compound represented by the general formula (I) is converted to a compound represented by the general formula (IV): Wherein R ⁶ and R ⁷ each represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group containing ethereal oxygen;
They may be the same or different, R ⁶ may be the same or different for each structural unit, and n represents an integer of 1 to 500. A compound represented by the general formula (V):
Or (VI) Wherein R ⁶ , R ⁷ and n are the same as above. The method for producing an ether compound according to claim 1, which is a compound represented by the formula: 3. An acetal or ketal compound represented by the general formula (I) is represented by the general formula (VII): R ⁸ CH (OR ⁹ ) ₂ ... (VII) wherein R ⁸ and R ⁹ each represent carbon Represents a hydrocarbon group of the formulas 1 to 20, which may be the same or different. Wherein the resulting ether compound is represented by the general formula (VIII): R ⁸ CH ₂ OR ⁹ ... (VIII) wherein R ⁸ and R ⁹ are as defined above. The method for producing an ether compound according to claim 1, which is a compound represented by the formula: