JPH08176059A - Production of quinones - Google Patents

Abstract

PURPOSE: To produce a quinone compound useful as a polymerization inhibitor, an unsaturated polyester stabilizer, intermediate for pharmaceuticals and agrochemicals, etc., in an easily separable state without causing a side reaction by oxidizing a hydroquinone compound in the presence of a small amount of a supported copper salt while repeatedly using the supported copper salt. CONSTITUTION: This quinone compound is produced by oxidizing (A) a hydroquinone compound with an oxygen-containing gas e.g. in an organic solvent in the presence of (B) a supported copper salt obtained e.g. by adding a bivalent copper salt (e.g. cupric sulfate, cupric halide or cupric acetate) and a carrier such as an inorganic carrier (e.g. alumina, silica gel or florisil) to a polar solvent capable of dissolving the copper salt (e.g. water or alcohol) and removing the solvent from the solution e.g. by evaporation. The amount of the component B is preferably 0.005-1.0 equivalent in terms of the copper salt based on 1 equivalent of the component A and the oxidation reaction is carried out preferably at 40-300 deg.C.

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 quinones, and more specifically, it can easily oxidize hydroquinones without side reaction to produce corresponding quinones.
The present invention relates to a method for producing quinones, which has a simple product isolation operation and is economically advantageous.

[0002]

BACKGROUND OF THE INVENTION Quinones are extremely useful compounds as intermediates for polymerization inhibitors, unsaturated polyester stabilizers, raw materials for aromatic polyester monomers, pharmaceuticals, agricultural chemicals, dyes and the like.

The method of oxidizing hydroquinones to obtain corresponding quinones is widely used because of easy availability of starting materials and high reaction yield. Conventionally, as a method of oxidizing hydroquinone to obtain quinone, for example, (1) a method of oxidizing hydroquinone with sodium chlorate using vanadium pentoxide as a catalyst with 2 wt% sulfuric acid as a medium (Organic Syntheses, Col.
Vol. II, P553 (1943)); (2) A method of oxidizing hydroquinone with sodium dichromate using sodium dichromate (Organic Syntheses, Co.
l. Vol. I, P482 (1941)); (3) A method of oxidizing hydroquinone with hydrogen peroxide solution using isopropyl alcohol as a medium (JP-A-5-79054), and the like. Generally, the method of (2) above is used. Has been adopted.

However, these methods have a problem that the oxidizing agent must be used in an amount of 1 equivalent or more with respect to the raw material hydroquinone, and that wastewater treatment such as heavy metal treatment and acidic waste liquid treatment must be performed. Therefore, it is not preferable as an industrial manufacturing method.

From this point of view, catalysis of the reaction has been studied, and a method of dissolving (a) copper (II) sulfate pentahydrate in 29% by weight of ammonia water and using it as a catalyst has been proposed so far. JP-A-62-81347); (b) Iron (III) -ethylenediaminetetracarboxylic acid complex 8
Method of dissolving in 0 wt% methanol water and using as a catalyst (Joshi et al., Tetrahedron Lett
ers, Vol. 35, P5083 (1994) and the like.

However, the above methods (a) and (b) require a complicated purification step such as separation and extraction of the reaction mixture, and are not preferable in terms of reaction operation as an industrial synthesis method. Further, in the method (a), 2-methyl-3
-While phytyl-1,4-naphthohydroquinone can be oxidized, industrially important hydroquinones such as p-hydroquinone can hardly be oxidized, its application range is narrow, and its generality is lacking. Furthermore, none of these methods has been put to practical use because of low yield and problems in the reaction operation.

[0007]

As described above in detail,
Conventionally known methods for producing quinones require 1) an oxidizing agent in an equimolar amount or more, 2) treatment of heavy metals or waste liquid treatment, and 3) purification steps of separation and extraction. 4) It is not preferable from an industrial point of view, such as a narrow application range and lack of generality. Therefore, from an industrial point of view, it is an important subject to develop a method for producing a quinone which is easy to isolate a product and is economically advantageous.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that hydroquinones are oxidized in the presence of a copper salt carrier in which a copper salt is supported on a carrier. The corresponding quinones can be produced by a simple method, and after the reaction is completed, the copper salt carrier can be separated from the product by a very simple operation such as filtration.
Further, if necessary, it can be easily purified by a known purification method such as a recrystallization method, a column chromatography, an adsorption method using activated carbon, and the copper salt-supported material used in this step proceeds even if the amount thereof is equal to or less than that of the hydroquinone. However, they have found that they can be used repeatedly if necessary, and have reached the present invention.

That is, the present invention provides a process for producing quinones, which is characterized in that hydroquinones are oxidized in the presence of a copper salt carrier. The hydroquinone used in the present invention is a general term for p-hydroquinone and derivatives thereof, and examples thereof include methyl-p-hydroquinone, chloro-p-hydroquinone and phenyl-p.
-Hydroquinone, trimethyl-p-hydroquinone,
Tetramethyl-p-hydroquinone, 2,6-tert
-Butyl hydroquinone, 1,4-dihydroxynaphthalene and the like can be mentioned. However, the hydroquinones are not limited to the compounds exemplified here.

The copper salt carrier used in the present invention is a carrier in which a copper salt is supported. As the copper salt, a divalent copper salt is preferably used. For example, copper (II) sulfate and copper halide ( II), copper acetate (II), copper nitrate (II) and the like. For example, CuSO ₄ , CuSO ₄ 5H ₂ O, Cu
F ₂ , CuCl ₂ , CuBr ₂ , Cu (OCOC
H ₃ ) ₂ , Cu (NO ₃ ) _{2 and the} like, but are not limited to the compounds exemplified here. Moreover, these can also be used together. Copper (II) sulfate, copper (II) halide and copper (II) acetate are preferable, and copper (II) sulfate is particularly recommended from an industrial viewpoint.

The carrier is not particularly limited as long as it can support a copper salt. Examples include alumina, silica gel, molecular sieve, florisil, celite, montmorillonite, activated clay, magnesium oxide, inorganic carriers such as barium oxide, polystyrene, polyethylene, organic carriers such as ion exchange resins, activated carbon and the like. ,
It is not limited to these compounds. Also, these may be used in combination. Of these, inorganic carriers are preferred, especially alumina, silica gel and florisil, with alumina being most recommended.

The preferred combination of the carrier and the copper salt is such that alumina supports copper (II) sulfate, alumina supports copper (II) acetate, and alumina supports copper (II) fluoride. In particular, it is recommended that alumina support copper (II) sulfate.

The method for preparing the copper salt carrier is not particularly limited, but in general, the copper salt is previously dissolved in a suitable solvent, the carrier is added thereto, and the amount of the solvent is not higher than the boiling point of the solvent. It can be prepared by stirring at temperature, distilling off the solvent and drying. The solvent is not particularly limited as long as it dissolves the copper salt, but polar solvents such as water, alcohols and nitriles are recommended, and water and / or alcohols are particularly preferable. The stirring temperature is not limited to room temperature, and there is no particular problem as long as it is not higher than the boiling point of the solvent used. Similarly, the stirring time is not particularly limited, but a range of 10 minutes to 1 hour is usually sufficient. Regarding the drying temperature, there is no particular problem as long as it is a temperature at which the solvent used can be removed, but if the temperature is too high, the activity of the carrier may be decreased or deactivated. It is preferable to set it slightly higher. Further, the drying may be carried out under atmospheric pressure, in air or in an atmosphere of an inert gas such as nitrogen or argon, or under reduced pressure.

The copper salt supporting rate of the copper salt carrier is not particularly limited, and 100 parts by weight or more of the copper salt can be supported with respect to 100 parts by weight of the carrier, but from the reaction rate and industrial viewpoint. It is recommended to support 0.1 to 50 parts by weight, especially 1 to 20 parts by weight, of copper salt with respect to 100 parts by weight of the carrier.

The oxidation reaction of the hydroquinone in the present invention can be carried out in the absence or presence of an organic solvent, but in the presence of an organic solvent, it is easy to separate the copper salt carrier after completion of the reaction. It is preferable to carry out. When an organic solvent is used, any of those that do not form a complex with a copper salt and do not react with hydroquinones can be used, for example, aliphatic hydrocarbons, aromatic hydrocarbons, esters,
It can be arbitrarily selected from ketones and the like. Among them, an organic solvent having a high boiling point is preferable in terms of reaction time because the reaction can be carried out at a high temperature and the reaction is completed in a short time. Usually, an organic solvent having a boiling point of 40 ° C or higher is used, but a low boiling point solvent is also used. Available, in which case it is advantageous to carry out the reaction under pressure. The aliphatic hydrocarbons and aromatic hydrocarbons include halogenated hydrocarbons.

Among the above-mentioned organic solvents, aliphatic hydrocarbons having 6 to 16 carbon atoms and optionally branched aliphatic hydrocarbons, and aromatic hydrocarbons having 6 to 16 carbon atoms. In 11, the aromatic hydrocarbons in which the halogen atom may be substituted are, as the esters, a carboxylic acid having 1 to 6 carbon atoms and an optionally branched alkyl group having 1 to 13 carbon atoms. The esters are preferably ketones having 3 to 13 carbon atoms and optionally branched.

Specific examples of these organic solvents include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and decalin, and aromatic hydrocarbons. Then chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, bromobenzene,
Examples of esters include m-dibromobenzene, o-dibromobenzene, p-dibromobenzene, benzonitrile, nitrobenzene, etc., and among the esters, propyl acetate, pentyl acetate, hexyl acetate, octyl acetate, dodecyl acetate, methyl propionate, methyl butyrate, methyl heptanoate. Butyl butyrate,
2-Ethylhexyl acetate and the like are 2-butanone, 2-hexane, 3-hexanone, 2-decanone, and 3 for ketones.
-Decanone, 4-decanone, 5-nonanone, methyl isobutyl ketone, methyl pentyl ketone, and the like, among them, the solubility of hydroquinones is excellent, and esters and ketones are preferable in that the reaction is completed in a short time, Esters are most preferred. The organic solvent that can be used in the present invention is not limited to the organic solvents exemplified here, and may be used in combination.

In carrying out the oxidation reaction of the present invention, the reaction temperature can be selected within an arbitrary range, but from an industrial viewpoint, it is 40 ° C.
The range of to 300 ° C. is preferable because the reaction is completed in a short time, and the range of 40 to 200 ° C. is particularly recommended. Also,
The reaction time depends on the reaction temperature and cannot be generally stated,
It ends in the range of 1 to 24 hours.

Further, in the production method of the present invention, the order of charging the respective raw materials is not limited, and the hydroquinones, the copper salt carrier and, if necessary, the organic solvent may be charged all at once in the beginning, or sequentially. Good. The charging ratio of the copper salt carrier used here varies greatly depending on the conditions at the time of the oxidation reaction and is not particularly limited, but from an industrial point of view, usually 1 mol of hydroquinone is 0.1% of copper salt in the copper salt carrier. A range of 005 to 10.0 equivalents is recommended. When an organic solvent is used, the amount thereof is not particularly limited, but it is 100 to 100 mol per 1 mol of hydroquinone.
A range of 5000 ml is recommended.

In the production method of the present invention, the oxidation reaction of hydroquinones can be carried out in an inert gas atmosphere or an oxygen-containing gas atmosphere. Also, an oxygen-containing gas may be introduced into the system during the oxidation reaction. In particular, when the oxidation reaction is carried out in an oxygen-containing gas atmosphere or while introducing an oxygen-containing gas, the copper salt carrier acts as an oxidation catalyst, and a relatively small amount used, for example, 1 mol of hydroquinone supports copper salt. It is particularly preferable because the oxidation reaction can be carried out in a used amount such that the copper salt in the body is 0.005 to 1.0 equivalent. When the reaction is carried out in an inert gas atmosphere, the copper salt carrier is used in a relatively large amount, for example, 1 to 10.0 equivalents of the copper salt in the copper salt carrier with respect to 1 mol of the hydroquinone. It is recommended to use the following amount, but after the reaction is completed, the filtered copper salt carrier is dispersed in an organic solvent and an oxygen-containing gas is introduced, which has the advantage that the oxidation activity can be regenerated. At this time, it may be carried out at room temperature, but it is preferable to carry out at a temperature of 50 ° C. or higher because it takes time to regenerate the oxidative activity. Examples of the oxygen-containing gas used here include a mixed gas of oxygen and an inert gas and air.

[0021]

EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples, but the present invention is not limited to these. The parts in the examples are parts by weight unless otherwise specified, and% is mol% based on the starting hydroquinone unless otherwise specified.

Example 1 Preparation of Copper Salt Carrier: In a 100 ml round bottom flask, 1.68 g of copper (II) sulfate pentahydrate and 50 ml of water were added to dissolve copper (II) sulfate pentahydrate. And then 10g of alumina
Was added, and the mixture was vigorously stirred at room temperature for 30 minutes. Then,
After distilling off the water with a tally evaporator, the mixture was kept at 150 ° C. for 7 hours.
After drying under reduced pressure for an hour, copper (II) sulfate-supported alumina carrying 10 parts of copper (II) sulfate per 100 parts of alumina was prepared and stored in a desiccator.

30 ml with stirrer and reflux condenser
In a round bottom flask of 0.110 g of p-hydroquinone
(1 mmol), the above copper (II) sulfate-supported alumina 0.3
51 g [copper (II) sulfate: 0.2 mmol] and 10 ml of hexyl acetate were added, the flask was immersed in a water bath at 140 ° C., and the reaction was carried out for 8 hours while blowing air into the reaction system.
After completion of the reaction, the reaction solution was cooled to room temperature and filtered. The filtration residue is washed twice with 30 ml of dichloromethane and 30 ml of acetone.
After washing twice with, the filtrate and the washing solution were combined and concentrated. By silica gel column chromatography (developing solvent, dichloromethane), 0.11 g (yield: 98%) of p-benzoquinone was obtained.

Example 2 Example 1 except that silica gel was used instead of alumina.
In the same manner as above, copper (II) sulfate-supported silica gel supporting 10 parts of copper (II) sulfate per 100 parts of silica gel was prepared.

Further, 0.351 g of this copper (II) sulfate-supported silica gel [copper (II) sulfate: 0.2 mmol] was added to 0.351 g of copper (II) sulfate-supported alumina [copper (II) sulfate:
0.2 mmol] in the same manner as in Example 1 except that p-benzoquinone (0.062 g, yield: 57) was used.
%) Was obtained.

Example 3 Example 1 except that Florisil was used instead of alumina.
In the same manner as above, copper (II) sulfate-supporting florisil supporting 10 parts of copper (II) sulfate with respect to 100 parts of florisil was prepared.

Further, 0.351 g of copper (II) sulfate-supporting Florisil [copper (II) sulfate: 0.2 mmol] was added to copper (II) sulfate-supporting alumina 0.351 g [copper (II) sulfate:
0.2 mmol] in the same manner as in Example 1 except that 0.11 g (yield: 98) of p-benzoquinone was used.
%) Was obtained.

Example 4 Alumina 100 was similarly prepared except that 1 g of copper (II) fluoride was used instead of 1.68 g of copper (II) sulfate pentahydrate.
Copper (II) fluoride-supported alumina supporting 10 parts of copper (II) fluoride was prepared.

Further, 0.223 g of this copper (II) fluoride-supported alumina [copper (II) fluoride: 0.2 mmol] was added to
0.351 g of copper (II) sulfate-supported alumina [copper sulfate (I
I): 0.2 mmol] in the same manner as in Example 1 except that 0.11 g of p-benzoquinone (yield:
98%).

Example 5 Instead of 1.68 g of copper (II) sulfate pentahydrate, copper acetate (I
I) Copper acetate (II) carrying 10 parts of copper acetate (II) per 100 parts of alumina in the same manner except that 1 g was used.
A supported alumina was prepared.

Further, this copper (II) acetate-supported alumina 0.
4 g [copper acetate (II): 0.2 mmol] was added to copper sulfate (I
I) Supported alumina 0.351 g [copper sulfate (II): 0.2
was used instead of [mmol] to obtain 0.105 g (yield: 97%) of p-benzoquinone in the same manner as in Example 1.

Example 6 Preparation of Copper Salt Carrier: In a 100 ml round bottom flask, 1 g of copper acetate and 100 ml of ethanol were added to dissolve copper acetate, 10 g of alumina was added, and the mixture was stirred at room temperature for 30 minutes. . Then, after distilling off ethanol, it was dried under reduced pressure at 100 ° C. for 7 hours to prepare copper acetate (II) -supported alumina carrying 10 parts of copper (II) acetate per 100 parts of alumina, and desiccation. It was stored in a table.

Further, this copper (II) acetate-supported alumina 0.
4 g [copper acetate (II): 0.2 mmol] was added to copper sulfate (I
I) Supported alumina 0.351 g [copper sulfate (II): 0.2
was used in the same manner as in Example 1 except that p-benzoquinone (0.092 g, yield: 85%) was obtained.

Example 7 10 ml of propyl acetate instead of 10 ml of hexyl acetate
In the same manner as in Example 1 except that the reaction was carried out in the same manner, 0.098 g (yield: 96%) of p-benzoquinone was obtained.

Example 8 Example 8 was repeated except that the reaction was carried out in 10 ml of methyl pentyl ketone instead of 10 ml of hexyl acetate.
0.78 g (yield: 76%) of p-benzoquinone was obtained.

Example 9 In the same manner as in Example 1 except that 10 ml of decalin was used instead of 10 ml of hexyl acetate, 0.047 g (yield: 46%) of p-benzoquinone was obtained.

Example 10 Preparation of copper salt carrier: In a 100 ml round bottom flask, 1.68 g of copper (II) sulfate pentahydrate and 50 ml of water were added to dissolve copper (II) sulfate pentahydrate. After that, 20g of alumina
Was added and stirred at room temperature for 30 minutes. Then, after distilling off the water with a rotary evaporator, it was dried under reduced pressure at 150 ° C. for 7 hours, and 5 parts of copper sulfate (I
Copper (II) sulfate-supported alumina supporting I) was prepared and stored in a desiccator.

30 ml with stirrer and reflux condenser
In a round bottom flask of 0.110 g of p-hydroquinone
(1 mmol), the above-mentioned copper (II) sulfate-supported alumina 0.6
7 g [copper (II) sulfate: 0.2 mmol] and 10 ml hexyl acetate were added, the flask was immersed in a water bath at 140 ° C., and the reaction was carried out for 8 hours while blowing air into the reaction system.
After completion of the reaction, the reaction solution was cooled to room temperature and filtered. The filter residue is washed twice with 30 ml of dichloromethane and then with acetone 3
After washing twice with 0 ml, the filtrate and the washing liquid were combined and concentrated. By silica gel column chromatography (developing solvent, dichloromethane), p-benzoquinone 0.1
03 g (yield: 95%) was obtained.

Example 11 Preparation of copper salt carrier: In a 100 ml round bottom flask, 1.68 g of copper (II) sulfate pentahydrate and 50 ml of water were added to dissolve copper (II) sulfate pentahydrate. And then 10g of alumina
Was added, and the mixture was vigorously stirred at room temperature for 30 minutes. Then,
After distilling off the water with a tally evaporator, the mixture was kept at 150 ° C. for 7 hours.
After drying under reduced pressure for an hour, copper (II) sulfate-supported alumina supporting 10 parts of copper (II) sulfate per 100 parts of alumina was prepared and stored in a desiccator.

30 ml with stirrer and reflux condenser
In a round bottom flask of 0.110 g of p-hydroquinone
(1 mmol), the above copper (II) sulfate-supported alumina 0.3
51 g [copper (II) sulfate: 0.2 mmol] and 10 ml of propyl acetate were added, the flask was immersed in a water bath at 100 ° C., and the reaction was carried out for 8 hours while blowing air into the reaction system.
After completion of the reaction, the reaction solution was cooled to room temperature and filtered. The filtration residue is washed twice with 30 ml of dichloromethane and 30 ml of acetone.
After washing twice with, the filtrate and the washing solution were combined and concentrated. Silica gel column chromatography (developing solvent, dichloromethane) gave 0.095 g (yield: 95%) of p-benzoquinone.

Example 12 p-Benzoquinone 0.09 was prepared in the same manner as in Example 11 except that the temperature of the water bath during the reaction was changed from 100 ° C to 80 ° C.
5 g (yield: 93%) was obtained.

Example 13 In a 30 ml round bottom flask equipped with a stirrer and a reflux condenser, 0.110 g (1 mmo of p-hydroquinone was added.
l), 10.534 g of copper (II) sulfate-supported alumina prepared in the same manner as in Example 11 [copper (II) sulfate: 6 mmol] and 20 ml of propyl acetate were added, and the flask was heated to 100 ° C.
It was immersed in a hot water bath and reacted for 8 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature and filtered. The filtration residue is washed twice with 30 ml of dichloromethane and 2 times with 30 ml of acetone.
After washing twice, the filtrate and the washing solution were combined and concentrated. By silica gel column chromatography (developing solvent, dichloromethane), 0.105 g of p-benzoquinone (yield:
97%).

Example 14 The amount of copper (II) sulfate-supported alumina used was changed from 0.351 g [copper (II) sulfate: 0.2 mmol] to 0.176 g [copper (II) sulfate: 0.1 mmol]. Example 1 except
In the same manner as in Example 1, 0.097 g (yield: 95%) of p-benzoquinone was obtained.

Example 15 The amount of copper (II) sulfate-supported alumina used was changed from 0.351 g [copper (II) sulfate: 0.2 mmol] to 0.088 g [copper (II) sulfate: 0.05 mmol]. Otherwise in the same manner as in Example 11, p-benzoquinone (0.096 g, yield: 94%) was obtained.

Example 16 The amount of copper (II) sulfate-supported alumina used was changed from 0.351 g [copper (II) sulfate: 0.2 mmol] to 0.053 g [copper (II) sulfate: 0.03 mmol]. Otherwise in the same manner as in Example 11, p-benzoquinone (0.066 g, yield: 65%) was obtained.

Comparative Example 1 Organic Syntheses, Col. Vo
l. The reaction was performed according to I, P482 (1941).

In a 2.5 liter flask, add 2 liters of water and p-
Add 100 g (0.91 mmol) of hydroquinone,
After dissolving at about 50 ° C., the solution was cooled to 20 ° C. and 100 g (54.4 ml) of concentrated sulfuric acid was slowly added. After cooling the mixture to 20 ° C. again, 140 g (0.47 mmol) of sodium dichromate dissolved in 65 ml of water
Was slowly added and stirred using a mechanical stirrer. Furthermore, an aqueous solution of sodium dichromate having the same concentration 9
0 ml was added to complete the reaction. About 10 reaction mixture
After cooling to ℃, suction filtration, the filtrate is benzene 150m
After extracting twice with l, p-benzoquinone obtained by filtration was placed in a 1 l beaker, and 500 ml of benzene and 300 ml of benzene used for extraction were added. Heat the mixture,
After completely dissolving p-benzoquinone, a small amount of calcium chloride was added, dried, and then filtered and concentrated to obtain p-
80 g (yield: 81%) of benzoquinone was obtained, but at the same time, an acidic waste liquid containing chromium that required treatment was generated.

Comparative Example 2 The reaction was carried out according to JP-A-62-81347.
At a temperature of 30 ° C., 5.0 g of p-hydroquinone was dissolved in 100 ml of hexane, and copper sulfate 5 was added to this hexane solution.
50 mg of water salt and 1.0 m of 29% by weight ammonia water
1 was added, and the hydrogen ion concentration was adjusted to 7.5 with diluted sulfuric acid.
25 ml of the prepared aqueous solution was added, and the mixture was stirred for about 1 minute. Then, at a temperature of 30 ° C., the mixture was stirred and mixed under air contact for 1 hour to react, and the reaction solution was allowed to stand for about 3 minutes and filtered. The reaction hardly proceeded and the filtration residue was unreacted p. -Was hydroquinone. Therefore, the reaction was tried under reflux with the boiling point of hexane (68.7 ° C.), but the reaction still did not proceed.

Example 17 Preparation of copper salt carrier: In a 100 ml round bottom flask, 1.68 g of copper (II) sulfate pentahydrate and 50 ml of water were added to dissolve copper (II) sulfate pentahydrate. And then 10g of alumina
Was added, and the mixture was vigorously stirred at room temperature for 30 minutes. Then,
After distilling off the water with a tally evaporator, the mixture was kept at 150 ° C. for 7 hours.
After drying under reduced pressure for an hour, copper (II) sulfate-supported alumina carrying 10 parts of copper (II) sulfate per 100 parts of alumina was prepared and stored in a desiccator.

30 ml with stirrer and reflux condenser
In a round bottom flask, add methyl-p-hydroquinone 0.1
24 g (1 mmol), 0.088 g of the above copper (II) sulfate-supported alumina [copper (II) sulfate: 0.05 mmol] and 10 ml of propyl acetate were added. Flask at 100 ° C
Was soaked in a hot water bath and allowed to react for 8 hours while blowing air into the reaction system. After the reaction was completed, the reaction solution was cooled to room temperature and filtered. The filtration residue was washed twice with 30 ml of dichloromethane and twice with 30 ml of acetone, and then the filtrate and the washing liquid were combined and concentrated. By silica gel column chromatography (developing solvent, dichloromethane), 0.115 g (yield: 94%) of methyl-p-benzoquinone was obtained.

Example 18 Methyl-p-hydroquinone 0.124 g (1 mmo
1) instead of tetramethyl-p-hydroquinone 0.
Tetramethyl-p-benzoquinone 0.161 was prepared in the same manner as in Example 17 except that 166 g (1 mmol) was used.
g (yield: 98%) was obtained.

Example 19 Methyl-p-hydroquinone 0.124 g (1 mmo
1,4-dihydroxynaphthalene 0.1 instead of l)
In the same manner as in Example 17 except that 60 g (1 mmol) was used, 0.153 g of 1,4-naphthoquinone (yield: 9
7%).

Example 20 Methyl-p-hydroquinone 0.124 g (1 mmo
Phenyl-p-hydroquinone 0.17 instead of l)
5 g (1 mmol) was used, and the amount of the copper (II) sulfate-supported alumina used was 0.088 g (0.05 mmol) to 0.
Example 1 except that the amount was changed to 176 g (0.1 mmol).
Phenyl-p-benzoquinone 0.17 in the same manner as 7.
5 g (yield: 95%) was obtained.

Example 21 Methyl-p-hydroquinone 0.124 g (1 mmo
2,6-di-tert-butyl-p-hydroquinone (0.222 g, 1 mmol) was used instead of l), and the amount of copper (II) sulfate-supported alumina used was 0.088 g (0.0
2,6-di-t was prepared in the same manner as in Example 17, except that the amount was changed from 5 mmol) to 0.176 g (0.1 mmol).
0.205 g (yield: 93%) of ert-butyl-p-benzoquinone was obtained.

Example 22 Methyl-p-hydroquinone 0.124 g (1 mmo
Instead of trimethyl-p-hydroquinone (0.
In the same manner as in Example 17, except that 152 g (1 mmol) was used and the amount of the copper (II) sulfate-supported alumina used was changed from 0.088 g (0.05 mmol) to 0.176 g (0.1 mmol), trimethyl was obtained. 0.146 g (yield: 97%) of -p-benzoquinone was obtained.

Example 23 Methyl-p-hydroquinone 0.124 g (1 mmo
Chloro-p-hydroquinone 0.145 instead of l)
g (1 mmol), and the amount of copper (II) sulfate-bearing alumina used is 0.088 g (0.05 mmol) to 0.5
Example 17 except that the amount was changed to 27 g (0.3 mmol).
Similarly to, 0.131 g of chloro-p-benzoquinone
(Yield: 92%) was obtained.

Example 24 Preparation of copper salt carrier: In a 100 ml round bottom flask, 1.68 g of copper (II) sulfate pentahydrate and 50 ml of water were added to dissolve copper (II) sulfate pentahydrate. And then 10g of alumina
Was added and the mixture was vigorously stirred at 50 ° C. for 30 minutes. Then, after water was distilled off with a rotary evaporator, it was dried under reduced pressure at 150 ° C. for 7 hours, and 10 parts of copper (II) sulfate was supported on 100 parts of alumina. Alumina was prepared and stored in a dessicator.

In a 2 liter round bottom flask equipped with a stirrer and a reflux condenser, 11.01 g of p-hydroquinone (10
0 mmol), the above copper (II) sulfate-supported alumina 8.78
g (5 mmol) and 1 liter of propyl acetate were added, the flask was immersed in a water bath at 100 ° C., and the reaction was carried out for 20 hours while blowing air into the reaction system. After the reaction was completed, the reaction solution was cooled to room temperature and filtered. The filtration residue is 300 m in dichloromethane
After washing twice with 1 times and twice with 300 ml of acetone, the filtrate and the washing solution were combined and concentrated. Silica gel column chromatography- (developing solvent, dichloromethane) gave p-
8.97 g (yield: 83%) of benzoquinone was obtained.

Example 25 The amount of p-hydroquinone used was 11.01 g (100 m).
mol) to 2.75 g (25 mmol) except that the reaction was carried out for 8 hours in the same manner as in Example 24. After completion of the reaction, the reaction solution was cooled to room temperature and filtered, and the filtration residue was twice added with 300 ml of dichloromethane. After washing twice with 300 ml of acetone, the filtrate and the washing solution are combined and concentrated, and p-
Obtained benzoquinone.

Then, the recovered copper (II) sulfate-supported alumina obtained by washing the filtration residue twice with 300 ml of dichloromethane and twice with 300 ml of acetone was used as it was, and 2.75 g (25 mmol) of p-hydroquinone was newly added. Was obtained in the same manner as above except that p-benzoquinone was obtained, and the same operation was repeated twice to obtain p-benzoquinone a total of 4 times. The total amount of p-benzoquinone obtained was 9.83 g (average yield: 91%).

[0061]

INDUSTRIAL APPLICABILITY According to the method of the present invention, the corresponding quinones can be produced by a simple method of oxidizing hydroquinones in the presence of a copper salt carrier in which a copper salt is supported on a carrier. After completion of the reaction, the copper salt carrier can be separated from the product by a very simple operation such as filtration, and the quinones can be produced economically. Moreover, the copper salt-supported material used in the present invention is an excellent production method from an industrial standpoint because the reaction proceeds even with an equivalent amount or less with respect to the hydroquinone and can be repeatedly used if necessary.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (19)

[Claims] 1. A method for producing quinones, which comprises oxidizing hydroquinones in the presence of a copper salt carrier. 2. The production method according to claim 1, wherein the copper salt carrier is a carrier in which a copper salt is supported on an inorganic carrier. 3. The method according to claim 2, wherein the copper salt is a divalent copper salt. 4. The inorganic carrier is one or more carriers selected from the group consisting of alumina, silica gel and florisil, and the divalent copper salt is copper (II) sulfate, copper (II) halide and copper acetate. The production method according to claim 3, which is one or more copper salts selected from the group consisting of (II). 5. The method according to claim 3, wherein the inorganic carrier is alumina, and the divalent copper salt is copper (II) sulfate. 6. The copper salt carrier is a carrier obtained by placing an inorganic carrier and a copper salt in a solvent in which the copper salt is dissolved, and then removing the solvent by evaporation. The manufacturing method according to any one of claims. 7. The production method according to claim 6, wherein the solvent that dissolves the copper salt is a polar solvent. 8. The method according to claim 7, wherein the polar solvent is water and / or alcohols. 9. The production method according to claim 1, wherein the copper salt carrier is a carrier supporting 1 to 20 parts by weight of the copper salt with respect to 100 parts by weight of the carrier. 10. The amount of copper salt in the copper salt carrier is 0.005-1 with respect to 1 equivalent of hydroquinone.
The manufacturing method according to any one of claims 1 to 9, wherein the production is performed in a range of 0.0 equivalent. 11. The production method according to claim 1, wherein the hydroquinone is oxidized in an organic solvent. 12. The method according to claim 11, wherein the organic solvent is an organic solvent having a boiling point of 40 ° C. or higher. 13. The method according to claim 11, wherein the organic solvent is a ketone and / or an ester having a boiling point of 40 ° C. or higher. 14. The production method according to claim 1, wherein the hydroquinones are oxidized in an oxygen-containing gas atmosphere. 15. The production method according to claim 14, wherein the hydroquinones are oxidized while blowing an oxygen-containing gas into a reaction system in an organic solvent. 16. A copper salt carrier having a copper salt carrier amount of 0.005-1.0 per 1 equivalent of hydroquinone.
16. The production method according to claim 14 or 15, wherein the production is performed in the range of 0 equivalent. 17. The production method according to claim 1, wherein the hydroquinones are oxidized at a temperature of 40 to 300 ° C. 18. The production method according to claim 1, wherein the hydroquinones are p-hydroquinones. 19. The method according to claim 1, wherein the reaction solution is filtered or the filtrate is concentrated after the oxidation reaction of the hydroquinones.