JP4952084B2 - 1,4-Dihydro-anthracene derivative and process for producing the same - Google Patents

Description

  The present invention relates to a 1,4-dihydro-anthracene derivative and a method for producing the same. The above compound according to the present invention is a novel compound, and is useful as, for example, a polymer raw material, a polymer additive, a photopolymerization sensitizer and the like.

  The polymer is required to have various functions depending on its use, and examples of the function include ultraviolet absorption ability and flame retardancy. For example, sun rays are often used to promote health, but it is known that erythema is caused by excessively exposing the skin to sun rays. It is also known that such a phenomenon is mainly caused by so-called UV-B rays having a wavelength of 280 to 320 nm. Therefore, for the purpose of preventing the occurrence of such burn symptoms, it has been proposed to blend an ultraviolet absorber having absorption in the UV-B region (Patent Document 1).

  In general, polymers are required to have flame retardancy, but at present, phosphorus compounds and halogen compounds are frequently used as flame retardants. However, dephosphorization and dehalogenation are demanded in consideration of health and the environment, and it is known to introduce an aromatic ring into a polymer skeleton for imparting flame retardancy (for example, Patent Document 2).

  As described above, various bicyclic and tricyclic aromatic compounds have been proposed as additives for enhancing the function of the polymer, but electronically while the skeleton is tricyclic similar to anthracene. A compound having a bicyclic structure similar to naphthalene and having a hydroxyl group that can be incorporated into a polymer is not known.

  On the other hand, in photocationic polymerization, it is known that 9,10-dialkoxyanthracene compounds act as sensitizers of photocationic polymerization initiators. For example, alicyclic epoxy using an iodonium salt as a polymerization initiator. It is known to use 9,10-dimethoxyanthracene or the like for the polymerization of compounds (Patent Document 3).

Japanese Patent Publication No.59-39404 Japanese Patent No. 3153875 JP 11-279212 A

  An object of the present invention is to have a 1,4-dihydro-9,10-anthracene structure which has an ultraviolet absorbing ability required for a polymer and is useful as a raw material, an additive or a sensitizer corresponding to flame retardancy. It is to provide a compound and a method for producing the compound.

  The inventors of the present invention studied a method for producing a 1,4-dihydro-9,10-anthracene compound having a hydroxyl group that can be industrially produced at low cost, and 1,4-dihydro in the presence of an alkaline compound. It has been found that a novel 1,4-dihydro-anthracene derivative can be easily obtained by reacting a -9,10-anthracenediol compound with an epoxy compound, and the present invention has been completed.

  That is, the first gist of the present invention resides in a 1,4-dihydro-anthracene derivative represented by the following formula (I).

In formula (I), R ¹ and R ² represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxymethyl group, an allyloxymethyl group, and an aryloxymethyl group, May be different. In the formula (I), X represents any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and an alkenyl group.

  The second gist of the present invention is that, in the presence of an alkaline compound, a 1,4-dihydroanthracene-9,10-diol compound represented by the following formula (II) and an epoxy compound represented by the following (III): The method for producing a 1,4-dihydro-anthracene derivative according to claim 1, wherein the reaction is performed.

  In the formula (II), X represents any one selected from the group of a hydrogen atom, a halogen atom, an alkyl group, and an alkenyl group. In the formula (III), R represents a hydrogen atom, an alkyl group, an alkoxymethyl group, Any one selected from the group of an allyloxymethyl group and an aryloxymethyl group is shown.

  The 1,4-dihydro-anthracene derivatives of the present invention are used as raw materials and additives for ultraviolet absorbing polymers, raw materials and additives for non-halogen / non-phosphorous flame retardant polymers, sensitizers for photocationic polymerization initiators, etc. Useful. Moreover, this compound can be easily obtained industrially by reacting 1,4-dihydroanthracene-9,10-diol with an epoxy compound in the presence of an alkaline compound.

  The 1,4-dihydro-anthracene derivative of the present invention is a compound represented by the general formula (I).

In formula (I), R ¹ and R ² represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxymethyl group, an allyloxymethyl group, and an aryloxymethyl group, May be different. In formula (I), X represents any one selected from the group consisting of a hydrogen atom, a chlorine atom, an alkyl group, and an alkenyl group.

Examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, and a propyl group. Examples of the alkoxymethyl group include a methoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Examples of the allyloxymethyl group include an allyloxymethyl group and a methallyloxymethyl group, and examples of the aryloxymethyl group include a phenyloxymethyl group and a p-tolyloxymethyl group. Examples of the alkyl group represented by X include a methyl group and a 4-methylpentyl group, and examples of the alkenyl group include a 4-methyl-3-pentenyl group. Moreover, as a halogen atom represented by X, a chlorine atom, a fluorine atom, etc. are mentioned, for example.

  Specific examples of the 1,4-dihydro-anthracene derivative of the present invention include those shown in the following groups (a) to (e).

(A) 1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene, 1,4-dihydro-9,10-bis (2-hydroxypropoxy) anthracene, 1,4-dihydro-9,10 -Bis (2-hydroxybutoxy) anthracene, 1,4-dihydro-9,10-bis (2-hydroxy-3-methoxypropoxy) anthracene, 1,4-dihydro-9,10-bis (2-hydroxy-3) -Butoxypropoxy) anthracene, 1,4-dihydro-9,10-bis (2-hydroxy-3-allyloxypropoxy) anthracene, 1,4-dihydro-9,10-bis (2-hydroxy-3-phenoxypropoxy) ) Anthracene.

(B) 2-methyl-1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene, 2-methyl-1,4-dihydro-9,10-bis (2-hydroxypropoxy) anthracene, 2 -Methyl-1,4-dihydro-9,10-bis (2-hydroxybutoxy) anthracene, 2-methyl-1,4-dihydro-9,10-bis (2-hydroxy-3-methoxypropoxy) anthracene, 2 -Methyl-1,4-dihydro-9,10-bis (2-hydroxy-3-butoxypropoxy) anthracene, 2-methyl-1,4-dihydro-9,10-bis (2-hydroxy-3-allyloxy) Propoxy) anthracene, 2-methyl-1,4-dihydro-9,10-bis (2-hydroxy-3-phenoxypropoxy) anthracene, etc. A.

(C) 2-chloro-1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene, 2-chloro-1,4-dihydro-9,10-bis (2-hydroxypropoxy) anthracene, 2 -Chloro-1,4-dihydro-9,10-bis (2-hydroxybutoxy) anthracene, 2-chloro-1,4-dihydro-9,10-bis (2-hydroxy-3-methoxypropoxy) anthracene, 2 -Chloro-1,4-dihydro-9,10-bis (2-hydroxy-3-butoxypropoxy) anthracene, 2-chloro-1,4-dihydro-9,10-bis (2-hydroxy-3-allyloxy) Propoxy) anthracene, 2-chloro-1,4-dihydro-9,10-bis (2-hydroxy-3-phenoxypropoxy) anthracene, etc. A.

(D) 2- (4-methylpentyl) -1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene, 2- (4-methylpentyl) -1,4-dihydro-9,10- Bis (2-hydroxypropoxy) anthracene, 2- (4-methylpentyl) -1,4-dihydro-9,10-bis (2-hydroxybutoxy) anthracene, 2- (4-methylpentyl) -1,4- Dihydro-9,10-bis (2-hydroxy-3-methoxypropoxy) anthracene, 2- (4-methylpentyl) -1,4-dihydro-9,10-bis (2-hydroxy-3-butoxypropoxy) anthracene 2- (4-methylpentyl) -1,4-dihydro-9,10-bis (2-hydroxy-3-allyloxypropoxy) anthracene, 2- ( - methylpentyl) a 1,4-dihydro-9,10-bis (2-hydroxy-3-phenoxypropoxy) anthracene.

(E) 2- (4-Methyl-3-pentenyl) -1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene, 2- (4-methyl-3-pentenyl) -1,4- Dihydro-9,10-bis (2-hydroxypropoxy) anthracene, 2- (4-methyl-3-pentenyl) -1,4-dihydro-9,10-bis (2-hydroxybutoxy) anthracene, 2- (4 -Methyl-3-pentenyl) -1,4-dihydro-9,10-bis (2-hydroxy-3-methoxypropoxy) anthracene, 2- (4-methyl-3-pentenyl) -1,4-dihydro-9 , 10-bis (2-hydroxy-3-butoxypropoxy) anthracene, 2- (4-methyl-3-pentenyl) -1,4-dihydro-9,10-bis (2-hydroxy-) - allyloxy propoxy) anthracene, 2- (4-methyl-3-pentenyl) -1,4-dihydro-9,10-bis (2-hydroxy-3-phenoxypropoxy) anthracene.

  A typical structural formula is shown below.

  The 1,4-dihydro-anthracene derivative of the present invention is obtained by reacting the 1,4-dihydroanthracene-9,10-diol compound represented by the above formula (II) with the epoxy compound represented by the above (III). Can be obtained.

  In the formula (II), X represents any one selected from the group of a hydrogen atom, a chlorine atom, an alkyl group, and an alkenyl group. In the formula (III), R represents a hydrogen atom, an alkyl group, an alkoxymethyl group, Any one selected from the group of an allyloxymethyl group and an aryloxymethyl group is shown. These specific examples are the same as the specific examples described in the formula (I).

  1,4-Dihydroanthracene-9,10-diol compound is generally obtained by isomerization of 1,4,4a, 9a-tetrahydro-9,10-anthraquinone compound obtained by Diels-Alder reaction of naphthoquinone and substituted butadiene. I can do it.

  An acid or alkali is used as the isomerization catalyst. Examples of the acid include sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid and the like. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine, piperidine and pyridine. When an alkali is used as an isomerization catalyst for a 1,4,4a, 9a-tetrahydro-9,10-anthraquinone compound, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used. An aqueous solution of an alkali metal salt of a 1,4-dihydroanthracene-9,10-diol compound is obtained, and this aqueous solution can also be used as a reaction raw material. In addition, the usage-amount of an isomerization catalyst is 0.1 to 10 weight% normally as a ratio with respect to a 1,4,4a, 9a-tetrahydro-9,10-anthraquinone compound, Preferably it is 0.5 to 5 weight%. . When the amount of the isomerization catalyst used is less than 0.1% by weight, the reaction rate is slow, and when it exceeds 10% by weight, a side reaction occurs and the purity of the target product is lowered.

  Specific examples of the epoxy compound include ethylene oxide, propylene oxide, butylene oxide, methyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether.

  Examples of the alkaline compound used in the reaction of the 1,4-dihydroanthracene-9,10-diol compound and the epoxy compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, magnesium hydroxide, and hydroxide. In addition to alkaline earth metal hydroxides such as calcium, sodium carbonate and sodium hydrogen carbonate are listed. Also, organic bases such as triethylamine, trimethylamine, methylamine, ethylamine, pyridine, piperidine and the like can be used. These alkaline compounds may be used as they are or as an aqueous solution. In particular, when an aqueous solution of an alkali metal hydroxide is used as an isomerization catalyst for a 1,4,4a, 9a-tetrahydro-9,10-anthraquinone compound, 1,4-dihydroanthracene-9,10-diol is used. Since an aqueous solution of the sodium salt or potassium salt of the compound is obtained, it can be used as it is for the reaction with the epoxy compound, which is very convenient. The usage-amount of said alkaline compound is 0.2-3 times mole normally as a ratio with respect to a 1, 4- dihydroanthracene-9,10-diol compound, Preferably it is 0.5-1 times mole. When the amount of the alkaline compound used is less than 0.2 mol, the reaction rate is slow, and when it exceeds 3 mol, a side reaction occurs and the purity of the target product is lowered.

  Solvents used for the reaction of the 1,4-dihydro-9,10-anthracenediol compound and the epoxy compound include alcohols such as methanol, ethanol, propyl alcohol, ethylene glycol, and propylene glycol, dimethylformamide, diethylformamide, Examples include amide solvents such as dimethylacetamide, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, water-soluble ethers such as tetrahydrofuran and dioxane, and amine solvents such as pyridine and piperidine. Moreover, these mixed solvents can also be used. Although the amount of the solvent used depends on the type, the concentration of the 1,4-dihydro-9,10-anthracenediol compound is usually 5 to 20% by weight. Even when the 1,4-dihydro-9,10-anthracenediol compound is not completely dissolved and becomes a slurry, the reaction proceeds without problems.

  The reaction temperature of the 1,4-dihydro-9,10-anthracenediol compound and the epoxy compound depends on the kind and amount of alkali to be added and other conditions, but is usually 0 to 80 ° C., preferably 20 to 60 ° C. It is. When the reaction temperature is less than 0 ° C., the reaction takes too much time, and when it exceeds 80 ° C., the epoxy compound decomposes and the yield decreases. The reaction time is usually 0.5 to 5 hours, and the reaction pressure is 0.2 to 0.5 MPa.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.

Example 1 (Synthesis of 1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene):
In a 200 ml glass autoclave equipped with a thermometer and a stirrer, 25 ml of water was placed under a nitrogen atmosphere, and 4.2 g (20 mmol) of 1,4,4a, 9a-tetrahydroanthraquinone was dispersed therein, and sodium hydroxide was added. 1.8 g (44 mmol) was added, and the mixture was stirred at 80 ° C. for 1 hour. A red solution of the sodium salt of 1,4-dihydro-9,10-anthracenediol formed. The reaction solution was cooled to room temperature, 40 ml of methanol was added, and 9 g (150 mmol) of ethylene oxide was injected over 15 minutes so that the pressure did not exceed 0.3 Pa. After stirring for 5 hours at room temperature, 20 ml of water was added to the resulting slurry reaction product, and the mixture was stirred well and filtered with suction. After thoroughly washing with water and drying, 4.2 g of white yellow powder was obtained. ^{From 1} H-NMR, IR, and mass spectrum, it was confirmed that the obtained compound was 1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene. These measurement data are shown below. The melting point was 203-204 ° C. The yield was 70 mol%.

¹ H-NMR (CDCl ₃ , 270 MHz): δ 2.30 (m, 2H), 3.57 (s, 4H), 4.10 (s, 8H), 6.02 (s, 2H), 7.47 (M, 2H), 8.10 (m, 2H)

IR (KBr, cm ⁻¹ ): 3400, 3030, 2975, 2860, 1585, 1450, 1392, 1350, 1330, 1260, 1080, 1056, 1025, 978, 882, 758, 660, mass spectrum: (EI-MS ) M / z = 300 (M ⁺ )

Example 2 (Synthesis of 1,4-dihydro-9,10-bis (2-hydroxypropoxy) anthracene):
A 200 ml three-necked flask equipped with a thermometer and a stirrer was charged with 25 ml of water under a nitrogen atmosphere, and 4.2 g (20 mmol) of 1,4,4a, 9a-tetrahydroanthraquinone was dispersed therein, and sodium hydroxide 1 0.8 g (44 mmol) was added and stirred at 80 ° C. for 1 hour. A red solution of the sodium salt of 1,4-dihydro-9,10-anthracenediol formed. Next, the reaction solution was cooled to room temperature, 40 ml of methanol was added, and then 10 g (170 mmol) of propylene oxide was added. Crystals gradually precipitated as the reaction progressed. After stirring at room temperature for 5 hours, 20 ml of water was added to the resulting slurry-like reaction product, stirred well, and then suction filtered. After thoroughly washing with water and drying, 4.5 g of white-yellow powder was obtained. ^{From 1} H-NMR, IR, and mass spectrum, it was confirmed that the obtained compound was 1,4-dihydro-9,10-bis (2-hydroxypropoxy) anthracene. These measurement data are shown below. The melting point was 163-165 ° C. The yield was 65 mol%.

¹ H-NMR (CDCl ₃ , 270 MHz): δ 1.30 (d, J = 7 Hz, 6H), 2.70 (d, J = 4 Hz, 2H), 3.55 (s, 4H), 3.85 ( m, 4H), 4.37 (m, 2H), 6.00 (s, 2H), 7.47 (m, 2H), 8.07 (m, 2H)

IR (KBr, cm ⁻¹ ): 3320, 2960, 2860, 1675, 1590, 1448, 1320, 1280, 1060, 1008, 962, 934, 857, 760, 692, 644, mass spectrum: (EI-MS) m / Z = 328 (M ⁺ )

Example 3 (Synthesis of 1,4-dihydro-9,10-bis (2-hydroxybutoxy) anthracene):
A 200 ml three-necked flask equipped with a thermometer and a stirrer was charged with 25 ml of water under a nitrogen atmosphere, and 4.2 g (20 mmol) of 1,4,4a, 9a-tetrahydroanthraquinone was dispersed therein, and sodium hydroxide 1 0.8 g (44 mmol) was added, and the mixture was stirred at 80 ° C. for 1 hour. A red solution of the sodium salt of 1,4-dihydro-9,10-anthracenediol formed. Next, the reaction solution was cooled to room temperature, 40 ml of methanol was added, and then 10.8 g (150 mmol) of butylene oxide was added. After heating to an internal temperature of 44 ° C. and stirring for 4 hours, 40 ml of water was added to the resulting slurry reaction product, and the mixture was stirred well and suction filtered. After thoroughly washing with water and drying, 4.5 g of white-yellow powder was obtained. ^{From 1} H-NMR, IR, and mass spectrum, it was confirmed that the obtained compound was 1,4-dihydro-9,10-bis (2-hydroxybutoxy) anthracene. These measurement data are shown below. The melting point was 160-162 ° C. The yield was 67 mol%.

¹ H-NMR (CDCl ₃ , 270 MHz): δ 1.08 (t, J = 8 Hz, 6H), 1.68 (dq, J ₁ = 8 Hz, J ₂ = 8 Hz, 4H), 2.78 (d, J = 4 Hz, 2H), 3.55 (s, 4H), 3.88 (m, 4H), 4.13 (m, 2H), 6.00 (s.2H), 7.48 (m, 2H) , 8.07 (m, 2H)

IR (KBr, cm ⁻¹ ): 3400, 2960, 2930, 2870, 1590, 1455, 1392, 1350, 1330, 1260, 1180, 1122, 1070, 1024, 980, 945, 908, 760, 662, 640, mass Spectrum: (EI-MS) m / z = 356 (M ⁺ )

Example 4 (Synthesis of 1,4-dihydro-9,10-bis (2-hydroxy-3-butoxypropoxy) anthracene):
A 200 ml three-necked flask equipped with a thermometer and a stirrer was charged with 25 ml of water under a nitrogen atmosphere, and 4.2 g (20 mmol) of 1,4,4a, 9a-tetrahydroanthraquinone was dispersed therein, and sodium hydroxide 1 0.8 g (44 mmol) was added, and the mixture was stirred at 80 ° C. for 1 hour. A red solution of the sodium salt of 1,4-dihydro-9,10-anthracenediol formed. Next, the reaction solution was cooled to room temperature, 40 ml of methanol was added, and then 13 g (100 mmol) of butyl glycidyl ether was added. After stirring for 4 hours at an internal temperature of 44 ° C., 40 ml of water was added to the resulting slurry reaction product, and the mixture was stirred well and suction filtered. After thoroughly washing with water and drying, 3.5 g of white-yellow powder was obtained. ^{From 1} H-NMR, IR, and mass spectrum, it was confirmed that the obtained compound was 1,4-dihydro-9,10-bis (2-hydroxy-3-butoxypropoxy) anthracene. These measurement data are shown below. The melting point was 109-110 ° C. The yield was 40 mol%.

¹ H-NMR (CDCl ₃ , 270 MHz): δ 0.95 (t, J = 8 Hz, 6H), 1.45 (m, 4H), 1.60 (m, 4H), 2.70 (d, J = 4 Hz, 2H), 3.53 (s, 4H), 3.55 (t, J = 6 Hz, 4H), 3.72 (d, J = 6.5 Hz, 4H), 4.01 (d, J = 6 Hz, 4H), 4.30 (m, 2H), 6.00 (s, 4H), 7.46 (m, 2H), 8.09 (m, 4H)

IR (KBr, cm ⁻¹ ): 3400, 2950, 2930, 2860, 1590, 1460, 1450, 1390, 1350, 1330, 1260, 1118, 1060, 982, 760, 660, mass spectrum: (EI-MS) m / Z = 472 (M ⁺ )

Evaluation Example 1:
An alicyclic epoxy compound (UVR-6105 manufactured by DOW) is used as a monomer, and 2 parts by weight of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (“IRGACURE250” manufactured by Ciba Specialty) 1 part by weight of 1,4-dihydro-9,10-bis (2-hydroxyethoxy) anthracene synthesized in Example 1 was mixed to prepare a photocurable composition. This composition was applied on a polyester film (“Lumirror” manufactured by Toray Industries Inc.) with a bar coater so that the film thickness was 12 μm. Next, the surface was irradiated with light using a high-pressure mercury lamp. The light irradiation time “tack free time” during which tackiness disappeared was 2.8 minutes.

Evaluation Example 2:
Evaluation in Evaluation Example 1 except that 1 part by weight of 1,4-dihydro-9,10-bis (2-hydroxypropoxy) anthracene synthesized in Example 2 was used instead of the compound synthesized in Example 1. As a result of evaluation in the same manner as in Example 1, the light irradiation time “tack free time” was 2.7 minutes.

Evaluation Example 3:
In Evaluation Example 1, instead of the compound synthesized in Example 1, 1.5 parts by weight of 1,4-dihydro-9,10-bis (2-hydroxybutoxy) anthracene synthesized in Example 3 was used. As a result of evaluation in the same manner as in Evaluation Example 1, the light irradiation time “tack free time” was 2.4 minutes.

Evaluation Example 4:
In Evaluation Example 1, instead of the compound synthesized in Example 1, 1.5 weight of 1,4-dihydro-9,10-bis (2-hydroxy-3-butoxypropoxy) anthracene synthesized in Example 4 was used. As a result of evaluating in the same manner as in Evaluation Example 1 except that the light irradiation time “tack free time” was 3.5 minutes.

Evaluation Example 5 (Comparative Example):
In Evaluation Example 1, except that the compound synthesized in Example 1 was not added, a photocuring composition was prepared in the same manner as in Evaluation Example 1, and a curing time was obtained by irradiation with a high-pressure mercury lamp. It did not cure after 20 minutes of irradiation.

  The 1,4-dihydro-anthracene derivative of the present invention is a novel compound, and is useful as a raw material for a polymer (or oligomer) in which an alcoholic hydroxyl group such as polyester, polyurethane, or polyether can be a reactive group. Further, it is a useful compound as a raw material for ultraviolet absorbing polymer, a sensitizer for a photocationic polymerization initiator, and the like.

Claims (5)

1,4-dihydro-anthracene derivative represented by the following formula (I).
(In Formula (I), R ¹ and R ² represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxymethyl group, an allyloxymethyl group, and an aryloxymethyl group, and both are the same. In the formula (I), X represents any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, and an alkenyl group. The 1,4-dihydro-anthracene derivative according to claim ^1, wherein R ¹ and R ² are alkyl groups. The 1,4-dihydroanthracene-9,10-diol compound represented by the following formula (II) is reacted with the epoxy compound represented by the following (III) in the presence of an alkaline compound. A process for the preparation of the described 1,4-dihydro-anthracene derivatives.
(In the formula (II), X represents any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group and an alkenyl group. In the formula (III), R represents a hydrogen atom, an alkyl group and an alkoxymethyl group. , An allyloxymethyl group, or an aryloxymethyl group.   The production method according to claim 3, wherein the epoxy compound is ethylene oxide, propylene oxide, butylene oxide, butyl glycidyl ether or phenyl glycidyl ether.   The production method according to claim 3 or 4, wherein an aqueous solution of an alkali metal salt thereof is used as the 1,4-dihydroanthracene-9,10-diol compound.