JP2003002855A - Method for producing anthracene diether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially advantageous method for producing a high-purity anthracene diether in high yield. SOLUTION: This method for producing the anthracene diether is characterized by making an etherificating agent contained into an organic solvent and by adding an aqueous solution of an alkali salt of 9,10-anthracene diol into the organic solvent containing the etherificating agent to cause the etherification reaction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing anthracene diether. More specifically, a dialkoxyanthracene useful as a sensitizer for a photocurable composition using an energy ray such as an ultraviolet ray as a light source, particularly 9,1
The present invention relates to a method for producing dialkoxyanthracene such as 0-dipropoxyanthracene and 9,10-dibutoxyanthracene, and diaryloxyanthracene such as 9,10-diphenoxyanthracene.

[0002]

2. Description of the Related Art Conventionally, as a method for producing 9,10-dialkoxyanthracene, for example, U. Seitz et al., Synt.
As described in hesis, 686-688 (1986), a production method for reductive alkylation of an anthracene dione compound is known. The method described in this publication is a method of using hydrosulfite as a reducing agent and methyl iodide as an alkylating agent in a two-phase solvent system in which water and methylene chloride are mixed. However, according to the method described in this publication, there is concern about environmental pollution due to methylene chloride as a solvent, and it is hard to say that it is an industrially advantageous method such as using an expensive alkylating agent.

Further, Japanese Unexamined Patent Publication No. 2000-119208 describes a method for reductive alkylation of an anthracene dione compound in an alcohol medium using hydrosulfite as a reducing agent and diethyl sulfuric acid as an alkylating agent. . However, according to the experiments by the present inventors, when dipropoxyanthracene was synthesized by the method described in this publication, the use of dipropylsulfate or propylbromide as an alkylating agent resulted in a large number of by-products and the desired product. Dipropoxyanthracene could not be obtained. In addition, dibutoxyanthracene could not be obtained even when butyl bromide was used as the alkylating agent.

[0004]

Under the circumstances, the present inventors have found that dialkoxyanthracenes, particularly 9,1
As a result of intensive studies aimed at providing a method for industrially effectively producing anthracene diethers such as 0-dipropoxyanthracene and 9,10-dibutoxyanthracene, the present invention has completed the present invention. is there.

[0005]

In order to solve the above problems, in the present invention, in producing anthracene diether, an etherifying agent is contained in an organic solvent, and the etherifying agent-containing organic solvent contains 9,10 Provided is a method for producing anthracene diether represented by the following formula [I], which comprises reacting by adding an aqueous solution of an alkali salt of anthracene diol.

[0006]

[Chemical 2]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the manufacturing method according to the present invention,
The raw material is an alkali salt of a 10-anthracene diol compound. The alkali salt of a 9,10-anthracenediol compound is represented by the following formula [II] and can be obtained by reacting a 9,10-anthracenediol compound with an alkaline compound. The 9,10-anthracene diol compound is obtained by reducing the corresponding 9,10-anthracene dione compound. Examples of the alkaline compound include sodium hydroxide and potassium hydroxide. The alkali salt of the 9,10-anthracene diol compound is used as an aqueous solution when used in the etherification reaction.

[0008]

[Chemical 3]

As a method for reducing the 9,10-anthracenedione compound, (1) in a solvent such as alcohol,
Examples thereof include a method of reducing with hydrogen in the presence of a hydrogenation catalyst, and (2) a method of reducing with hydrosulfite in an aqueous medium. The above method (2) is preferable because the alkali salt of the 9,10-anthracenediol compound can be obtained as it is by reduction in the presence of an alkaline compound such as sodium hydroxide. Furthermore, (3) 9,10-anthracenedione is reduced with a solution of an alkaline compound of 1,4-dihydro-9,10-dihydroxyanthracene to produce an alkali salt of anthracene diol (JP-A-9-16982). (See Japanese Patent Publication), and the like. According to the method (3),
Since 1,4-dihydro-9,10-dihydroxyanthracene used for the reduction becomes anthracene diol,
It is preferable since it is not necessary to remove the reducing agent after use.

In the production method according to the present invention, an aqueous solution of an alkali salt of a raw material 9,10-anthracene diol compound is added to an organic solvent containing an etherifying agent and reacted. In the present invention, examples of the etherifying agent include an alkylating agent, an arylating agent, an allylating agent and the like described below. That is, examples of the alkylating agent include dialkyl sulfates such as diethyl sulfate and dipropyl sulfate, and alkyl halides such as ethyl bromide, propyl bromide and butyl bromide. As the arylating agent, bromobenzene, chlorobenzene, p-chlorotoluene, p-bromotoluene, m-bromotoluene, m-
Examples include aryl halides such as chlorotoluene, α-chloronaphthalene, α-bromonaphthalene, β-chloronaphthalene, β-bromonaphthalene. Examples of the allylating agent include allyl halides such as allyl bromide, allyl chloride and methallyl chloride. Other etherifying agents include 2-bromoethanol for hydroxyethylation and 2-bromoethyl methyl ether for methoxyethylation. The amount of these etherifying agents is preferably 2 times or more, and more preferably 2.5 to 4 times, relative to 1 mol of the alkali salt of the raw material 9,10-anthracene diol compound.

The organic solvent is not particularly limited as long as it dissolves the etherifying agent and is inert to the etherification reaction. Specifically, in addition to water-miscible organic solvents such as alcohols represented by methanol and ethanol, ethers represented by tetrahydrofuran, dimethylformamide, etc., water such as n-hexane, cyclohexane, benzene, toluene, xylene, etc. Examples thereof include poorly miscible organic solvents, and among them, the former water-miscible organic solvent is preferable. When an organic solvent having poor water miscibility is used, it is preferable to carry out the etherification reaction in the presence of a phase transfer catalyst such as tetrabutylammonium bromide. In this case, since the etherification reaction product is extracted into the organic solvent, the etherification reaction product can be easily separated, which is an industrially preferable method.

In the production method according to the present invention, the etherifying agent is contained in the organic solvent, and the alkali salt of the raw material 9,10-anthracenediol compound is used as an aqueous solution in the etherifying agent-containing organic solvent. Add
The etherification reaction is performed to obtain the target substance, anthracene diether. The order of addition of these raw materials is extremely important for the efficient progress of the etherification reaction. When the etherification agent-containing organic solvent is added to an aqueous solution of an alkali salt of a 9,10-anthracene diol compound by changing the order of addition, a side reaction proceeds and the yield of the target anthracene diether decreases. Is not preferred.

The temperature for carrying out the etherification reaction is 0 ° C. or higher at which the aqueous solution of the alkali salt of the 9,10-anthracene diol compound does not freeze, and the boiling point of the etherifying agent which is soluble in the solvent under normal pressure. It is preferable to carry out. When the temperature is 20 ° C. or lower, the etherification reaction is difficult to proceed, and when it is 80 ° C. or higher, the side reaction is easily promoted.

According to the production method of the present invention, the anthracene diether represented by the above formula [I] is obtained.
Examples of the alkyl group of the substituent R1 include an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
Specifically, a methyl group, an ethyl group, an n-propyl group, i
-Propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group and the like. Examples of the allyl group include allyl and 2-methylallyl, and examples of the aryl group include a phenyl group and o.
Examples include -tolyl group, m-tolyl group, p-tolyl group, naphthyl group and biphenyl group.

The hydroxyalkyl group includes 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methyl-2-hydroxyethyl group and 2-ethyl-2-hydroxyethyl group, and the alkoxyalkyl group has 2 groups. -Methoxyethyl group, 3-methoxypropyl group, 2
Examples include -ethoxyethyl group and 3-ethoxypropyl group.

The substituents R2 and R3 are inert to the etherification reaction of the method of the present invention, and specifically include C1 to C3 alkyl groups, alkoxy groups, amino groups and alkyl groups. In addition to an amino group and an alkylsulfonyl group, a halogen atom and the like can be mentioned.

Specific examples of the anthracene diether represented by the above formula [I] include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 9,10-.
Dialkoxyanthracene such as dipropoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2,3-diethyl-9,10-diethoxyanthracene, 9,10-
Diaryloxyanthracenes such as diphenoxyanthracene, 9,10-di (p-tolyloxy) anthracene, 9,10-dinaphthyloxyanthracene,
9,10-Diallyloxyanthracene, diallyloxyanthracene such as 9,10-di (2-methylallyloxy) anthracene, 9,10-di (2-hydroxyethoxy) anthracene, 9,10-di (2-methoxy) Ethoxy) anthracene and the like.

The anthracene diether represented by the above formula [I] obtained by the production method according to the present invention, particularly dialkoxyanthracene, is used as a sensitizer for a photocurable composition using an energy ray such as ultraviolet ray as a light source. It is useful.

[0019]

EXAMPLES Next, the present invention will be described in detail based on examples, but the present invention is not limited to the following description examples without departing from the gist thereof. In the following examples,% means% by weight unless otherwise specified.

Example 1 A three-necked flask having a capacity of 300 ml equipped with a stirrer, a thermometer, a heating jacket, a charging port, etc. was charged with 32 g of 30% sodium hydroxide aqueous solution and 57 g of water, and the mixture was stirred under stirring 9. 25 g of 10-anthracenedione was charged and suspended, and the air in the flask was replaced with nitrogen. While stirring the contents of the flask, 130 g of an aqueous solution of a sodium salt of 1,4-dihydro-9,10-dihydroxyanthracene (22% as the concentration of anthraquinone) was added, and the internal temperature was 85 to 90 ° C.
Was maintained for 4 hours to synthesize an aqueous sodium salt solution of 9,10-anthracenediol.

In an autoclave with a capacity of 1 liter equipped with a stirrer, a thermometer, a heating jacket, a charging port, etc., 300 g of dimethylformamide and 92 of propyl bromide were added.
A solution in which g was dissolved was charged, and the internal temperature was raised to 60 ± 5 ° C. and maintained. An aqueous solution of the sodium salt of 9,10-anthracenediol synthesized by the above method was continuously added to this autoclave with stirring over 1 hour.
After the continuous addition of the aqueous sodium salt solution of 9,10-anthracenediol was completed, the internal temperature was further raised to 70 ± 2 ° C. and maintained for 1 hour. Then, the internal temperature was cooled to 30 ° C. to precipitate the crystals of the product, the crystals were filtered, washed with 100 ml of methanol, and dried to obtain the product. The product has a melting point of 93 ° C. and an NMR spectrum of 9,1
It was confirmed to be 0-dipropoxyanthracene. The amount of the product was 48 g, and the yield based on the sodium salt of 9,10-anthracenediol was 60%.

Comparative Example 1 First, an aqueous solution of a sodium salt of 9,10-anthracenediol was synthesized by the method described in Example 1. Next, the autoclave used in the method described in Example 1 was charged with the aqueous solution of the sodium salt of 9,10-anthracene diol, and the internal temperature was raised to 60 ± 5 ° C. with stirring to maintain the odor. 92 g of propyl chloride was continuously added over 1 hour. After the continuous addition of propyl bromide was completed, the internal temperature was further raised to 70 ± 2 ° C. and maintained for 1 hour.
Then, the internal temperature was cooled to 30 ° C. to precipitate crystals, which was filtered and dried by the same procedure as in Example 1 to obtain a product. However, the product could not be confirmed as 9,10-dipropoxyanthracene in the NMR spectrum, and the melting point was 171 ° C.

Example 2 First, by the method described in Example 1, an aqueous solution of sodium salt of 9,10-anthracenediol was synthesized. Next, 300 g of dimethylformamide was added to the autoclave used in the method described in Example 1.
A solution having 108 g of butyl bromide dissolved therein was charged, and the internal temperature was raised to 60 ± 5 ° C. and maintained. In this autoclave,
With stirring, an aqueous solution of sodium salt of 9,10-anthracenediol synthesized by the method described in Example 1 was continuously added over 1 hour. After the continuous addition of the aqueous solution of the sodium salt of 9,10-anthracene diol was completed, the internal temperature was maintained at 70 ± 2 ° C. for 1 hour under stirring and aging. Then, the internal temperature was cooled to 30 ° C. to precipitate the crystals of the product, and the crystals were filtered and washed with methanol to obtain a dried product. The product had a melting point of 107 ° C. and was confirmed by NMR spectrum to be 9,10-dibutoxyanthracene. The amount of product is 59g, 9,1
The yield based on the sodium salt of 0-anthracene diol was 70%.

[0024]

As described above in detail, the present invention has the following particularly advantageous effects, and its industrial utility value is extremely large. 1. According to the production method of the present invention, the target anthracene diether can be industrially advantageously produced by using an industrially inexpensive alkyl halide or the like in addition to the dialkyl sulfuric acid as the etherifying agent. 2. According to the production method of the present invention, anthracene diether of high purity can be produced in high yield as compared with the conventional production method.

Claims (4)

[Claims] 1. When producing anthracene diether, an etherifying agent is contained in an organic solvent, and an aqueous solution of an alkali salt of a 9,10-anthracenediol compound is added to the etherifying agent-containing organic solvent for reaction. A process for producing anthracene diether represented by the following formula [I], characterized by: [Chemical 1] 2. The method for producing anthracene diether according to claim 1, wherein the organic solvent is selected from alcohol, tetrahydrofuran and dimethylformamide. 3. The method for producing anthracene diether according to claim 1, wherein the etherifying agent is selected from dialkyl sulfate, alkyl halide, aryl halide or allyl halide. 4. The anthracene according to any one of claims 1 to 3, wherein the etherification agent is in a range of 2.5 to 4 times with respect to 1 mol of the alkali salt of 9,10-anthracene diol. Method for producing diether.