JP2002037751A - Method for producing 9,10-dietherified anthracene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a 9,10-dietherified anthracene derivative from an anthracene compound, capable of omitting a catalyst recovery process and simply producing the derivative in a high yield. SOLUTION: The anthracene compound is reduced with a dithionite into a leuco compound, which is reacted with an alkylsulfonic acid ester or its derivative to give the 9,10-dietherified anthracene derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a 9,10-dietherified anthracene derivative which is also useful as a photosensitizer. More specifically, the present invention relates to a method for reducing anthraquinones with dithionite to form a leuco compound. The present invention relates to a method for producing a 9,10-dietherified anthracene derivative by reacting an alkylsulfonic acid ester as an alkylating agent.

[0002]

2. Description of the Related Art A method for producing an anthracene derivative by reducing quinones such as anthraquinone to synthesize an aromatic compound such as anthracene has long been known. For example, JPShaefer is J.Org.Chem., 25,2027
In (1916), a method using Sn-Hg in hydrochloric acid, ELMa
Rtin, J. Am. Chem. Soc., 58, 1438 (1936), reports a process using Zn-Cu in an aqueous sodium hydroxide solution. Regarding the reduction using a metal, K. Ts
uda, E. Ohki, S. Nozoe et al. report a method using Zn in J. Org. Chem., 28, 786 (1963), and a reduction method using Zn in Japanese Patent Publication No. 7-108893. AJ Fatiadi and WFSager have described the method using metal salts in the literature "Orga
nic Syntheses ”, Coll. Vol. V, p. 595 (1973)
The process using nCl2.2H2O was described by JR Hanson and S. Mehta in J. Chem. Soc., C, 1969, 2349.
Report on the manufacturing method. On the other hand, HCBrown et al., Israel J. Chem., 1,430
(1963), LiAlH (O-tC4H9) 3, J. Am. Chem. Soc., 87, 5614 (1965).
The production method using (OCH3) 3 is described in J. Am. Chem. Soc., 88, 1458.
(1966) describes the production method using LiAlH4 and J. Am.
m. Soc., 88, 1458 (1966) reports on the production method using AlH3. Also GSPanson and CE
Weill, J. Org. Chem., 22, 120 (1957), reports a process using NaBH4.

[0003]

With respect to the method for producing an anthracene derivative, when an organic chemical reaction is carried out, heavy metals are not often used in ordinary synthesis.
In the reduction reaction, heavy metals such as Zn, Cu, Sn and Cr described above are often used. After completion of the reaction, these heavy metals are rarely contained in the target compound. However, after completion of the reaction, these heavy metals must be recovered and discarded. Since these heavy metals easily generate ions harmful to living organisms and the environment in the natural environment, special treatment is required when disposing them. In the case of metal hydride complex compounds, lithium aluminum hydride and sodium aluminum hydride react violently with water to generate hydrogen, and if they remain excessively after the reaction, hydrogen is generated when they come into contact with water. With danger. Also, sodium borohydride and lithium borohydride are generally expensive. Also, borane reduction using borane or diborane can be used to reduce quinones to synthesize an aromatic compound, but the reaction of borane reduction in this case is very slow, There is a high possibility that cost performance is not suitable for producing an aromatic compound.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have reduced anthraquinones with dithionite to form leuco bodies, and then converted alkylsulfonates into alkyl groups. By reacting as an agent, a method for easily obtaining an anthracene derivative having a desired structure was successfully established. That is, the present invention provides a method for producing a 9,10-dietherified anthracene derivative, comprising: [1] reducing anthraquinones with a dithionite, followed by reacting an alkylsulfonic acid ester as an alkylating agent; 2] Anthraquinones of the formula (1)

[0005]

Embedded image

Wherein R1, R2, R3, R4, R5,
R6, R7 and R8 each independently represent a hydrogen atom, C1
To C12 alkyl, fluorine, chlorine, bromine, cyano, phenyl, cyclohexyl, hydroxyl, benzyl, cyclohexylmethyl, 1-naphthyl, 2-naphthyl, 2-hydroxyethyl, 3 −
Hydroxypropyl group, 4-hydroxybutyl group, -O
-R9, -CO-R9 or -S-R9 (R9 is Cl to
An alkyl group up to C8, a phenyl group, a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group or a 4-hydroxybutyl group is there. ). The method for producing a 9,10-dietherified anthracene derivative according to [1], which is a compound represented by the formula [2], wherein the alkylsulfonic acid ester used as an alkylating agent is a compound represented by the formula (2):

R10SO ₃ A (2)

(Wherein R10 is a methyl group, an ethyl group or a trifluoromethyl group, and A is C1
A straight-chain or branched alkyl group up to C18,
Hydroxyethyl group, 3-hydroxypropyl group, 4-
Hydroxybutyl, phenyl, benzyl, cyclohexyl, benzoyl, allyl, 1-naphthyl, 2-naphthyl, 4-tert-butylcyclohexyl, 4-methyl-3-pentenyl,-(CH ₂ ) _{L
X, - ((CH 2)} m O) n Y, - (CH (CH 3) CH 2
O) _n Y,-(CH ₂ ) _m O (CH ₂ ) _n OY (where m ≠ n),-(CH ₂ ) _l -SZ- (where X is a fluorine atom, a chlorine atom , A bromine atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group or a 2-naphthyl group, and Y is a C1-C12 alkyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl A phenyl group, a benzyl group, a 2-phenylethyl group, a cyclohexyl group, a cyclohexylmethyl group, a benzoyl group, an allyl group, a 1-naphthyl group or a 2-naphthyl group, and Z is a C1-C12 alkyl group. , Phenyl group, benzyl group, 2-phenylethyl group, cyclohexyl group, cyclohexylmethyl group,
A benzoyl group, an allyl group, a 1-naphthyl group or a 2-naphthyl group, l is an integer of 1 to 8, m is 2
An integer of 1 to 4, and n is an integer of 1 to 4. ). The method for producing a 9,10-dietherified anthracene derivative according to [1] or [2], wherein the alkylsulfonic acid ester represented by the formula (2) Wherein A is a C1-C4 linear or branched alkyl group or a 2-methoxyethyl group, the 9,10-dietherified anthracene derivative according to any one of [1] to [3]. [5] An anthraquinone represented by the formula (1)
The method for producing a 9,10-dietherified anthracene derivative according to any one of [1] to [4], which is -ethylanthraquinone; [6] the dithionite is sodium dithionite. The present invention relates to a method for producing a 9,10-dietherified anthracene derivative according to any one of [1] to [5].

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The 9,10-dietherified anthracene derivative obtained by the present invention can be represented by, for example, the following formula (3).

[0010]

Embedded image

Wherein R1, R2, R3, R4, R5,
R6, R7 and R8 each independently represent a hydrogen atom, C1
To C12 alkyl, fluorine, chlorine, bromine, cyano, phenyl, cyclohexyl, hydroxyl, benzyl, cyclohexylmethyl, 1-naphthyl, 2-naphthyl, 2-hydroxyethyl, 3 −
Hydroxypropyl group, 4-hydroxybutyl group, -O
-R9, -CO-R9 or -S-R9 (R9 is Cl to
Any of alkyl groups up to C8, phenyl group, benzyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, 2-hydroxyethyl group, 3-hydroxypropyl group or 4-hydroxybutyl group is there. A is a linear or branched C1-C18 alkyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, phenyl group, benzyl group, cyclohexyl group, benzoyl group, allyl group, 1-naphthyl, 2-naphthyl, 4-tert-butylcyclohexyl group, 4-methyl-3-pentenyl group _{,, - (CH 2) l X} , - ((CH
_{2) m O) n Y,} - (CH (CH 3) CH 2 O) n Y, - (C
H ₂ ) _m O (CH ₂ ) _n OY (where m ≠ n),
_{- (CH 2) l -S-} Z- ( wherein, X is fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a cyclohexyl group, 1-
A naphthyl group or a 2-naphthyl group,
Y is a C1-C12 alkyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a phenyl group, a benzyl group, a 2-phenylethyl group,
A cyclohexyl group, a cyclohexylmethyl group, a benzoyl group, an allyl group, a 1-naphthyl group or a 2-naphthyl group, and Z is a C1-C12 alkyl group;
A phenyl group, a benzyl group, a 2-phenylethyl group, a cyclohexyl group, a cyclohexylmethyl group, a benzoyl group, an allyl group, a 1-naphthyl group or a 2-naphthyl group, 1 is an integer of 1 to 8, m is Integer of 2-4, n is an integer of 1-4. ). )

In the above formula (3), examples of the C1 to C12 alkyl group for R1 to R8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-alkyl group.
Butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 2-ethyl-hexyl, n-
Nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl group, and the like.
Examples of —OR 9 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group,
-Pentoxy group, isopentoxy group, n-hexoxy group, isohexoxy group, n-heptoxy group, isoheptoxy group, n-octoxy group, isooctoxy group, 2-ethylhexoxy group, phenoxy group, phenylmethyloxy group, cyclohexoxy group, cyclohexylmethyl Oxy group, 1-naphthoxy group, 2-naphthoxy group, 2-hydroxyethoxy group, 3-hydroxypropoxy group, 4-
And a hydroxybutoxy group. Examples of -CO-R9 include a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an isopropylcarbonyl group, an n-butylcarbonyl group, an isobutylcarbonyl group, a tert-butylcarbonyl group, an n-pentylcarbonyl group, Pentylcarbonyl group, n-hexylcarbonyl group, isohexylcarbonyl group, n-heptylcarbonyl group, isoheptylcarbonyl group, n-octylcarbonyl group, isooctylcarbonyl group, 2-ethylhexylcarbonyl group, phenylcarbonyl group, phenylmethylcarbonyl Group, cyclohexylcarbonyl group, cyclohexylmethylcarbonyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, 2-hydroxyethylcarbonyl group, 3-hydroxypropylcarbo Group, such as 4-hydroxybutyl group and the like. As -SR9, for example, a methylthio group,
Ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-
Butylthio group, n-pentylthio group, isopentylthio group, n-hexylthio group, isohexylthio group, n-heptylthio group, isoheptylthio group, n-octylthio group, isooctylthio group, 2-ethylhexylthio group,
Examples include phenylthio, phenylmethylthio, cyclohexylthio, cyclohexylmethylthio, 1-naphthylthio, 2-naphthylthio, 2-hydroxyethylthio, 3-hydroxypropylthio, and 4-hydroxybutylthio.

In the substituent A of the above formula (3),
Specific examples of the linear or branched alkyl group up to C18 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t
tert-butyl group, n-pentyl group, isopentyl group,
n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-
Ethyl-hexyl group, n-nonyl group, isononyl group, n
-Decyl group, isodecyl group, n-dodecyl group, isododecyl group, n-octadecyl group, isooctadecyl group and the like. Further, - specific examples of (CH _{2) l} X is
For example, a fluoromethyl group, a chloromethyl group, a bromomethyl group, a benzyl group, a cyclohexylmethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group,
2-phenylethyl group, 2-cyclohexylethyl group,
2- (1-naphthyl) ethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bromopropyl group, 3
-Phenylpropyl group, 3-cyclohexylpropyl group, 3- (1-naphthyl) propyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group,
-Phenylbutyl group, 4-cyclohexylbutyl group, 4
-(1-naphthyl) butyl group, 5-fluoropentyl group, 5-chloropentyl group, 5-bromopentyl group, 5
-Phenylpentyl group, 5-cyclohexylpentyl group, 5- (1-naphthyl) pentyl group, 6-fluorohexyl group, 6-chlorohexyl group, 6-bromohexyl group, 6-phenylhexyl group, 6-cyclohexylhexyl group , 6- (1-naphthyl) hexyl group, 7-fluoroheptyl group, 7-chloroheptyl group, 7-bromoheptyl group, 7-phenylheptyl group, 7-cyclohexylheptyl group, 7- (1-naphthyl) heptyl group , 8-fluorooctyl, 8-chlorooctyl, 8-bromooctyl, 8-phenyloctyl, 8-cyclohexyloctyl, 8- (1-naphthyl) octyl and the like. - Specific examples of _{((CH 2) m O)} n Y , for example, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n- Butoxyethyl group, 2-isobutoxyethyl group, 2-n-hexoxyethyl group, 2-isohexoxyethyl group, 2-n-octoxyethyl group, 2
-Isooctoxyethyl group, 2-n-desoxyethyl group, 2-n-dodesoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- (3-hydroxypropoxy) ethyl group, 2- (4-hydroxybutoxy) ) Ethyl group, 2-phenoxyethyl group, 2-benzyloxyethyl group, 2- (2-phenylethoxy) ethyl group, 2-cyclohexoxyethyl group, 2-cyclohexylmethoxyethyl group, 2-benzoyloxyethyl group, -Allyloxyethyl group, 2- (1-naphthoxy) ethyl group, 2
-(2-naphthoxy) ethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-butoxypropyl group, 3-n-hexoxypropyl group, 3-n-octoxypropyl group, 3- ( 2-hydroxyethoxy) propyl group, 3- (4-hydroxybutoxy) ethyl group, 3
-Phenoxypropyl group, 3-benzyloxypropyl group, 3- (2-phenylethoxy) propyl group, 3-cyclohexoxypropyl group, 3-benzoyloxypropyl group, 3-allyloxypropyl group, 3- (1-naphthoxy ) Propyl, 4-methoxybutyl, 4-ethoxybutyl, 4-n-butoxybutyl, 4-n-hexoxybutyl, 4-n-octoxybutyl, 4-
(2-hydroxyethoxy) butyl group, 4- (4-hydroxybutoxy) butyl group, 4-phenoxybutyl group,
4-benzyloxybutyl group, 4- (2-phenylethoxy) butyl group, 4-cyclohexoxybutyl group, 4-
Benzoyloxybutyl, 4-allyloxybutyl, 4- (1-naphthoxy) butyl, 2- (2-methoxyethoxy) ethyl, 2- (2-ethoxyethoxy) ethyl, 2- (2-n -Butoxyethoxy) ethyl group, 2- (2-n-hexoxyethoxy) ethyl group,
2- (2-n-octoxyethoxy) ethyl group, 2-
(2- (2-hydroxyethoxy) ethoxy) ethyl group, 2- (2- (4-hydroxybutoxy) ethoxy)
An ethyl group, a 2- (2-phenoxyethoxy) ethyl group,
2- (2-cyclohexoxyethoxy) ethyl group, 2-
(2-benzoyloxyethoxy) ethyl group, 2- (2
-Allyloxyethoxy) ethyl group, 2- (2- (1-
Naphthoxy) ethoxy) ethyl group, 3- (3-methoxypropoxy) propyl group, 3- (3-ethoxypropoxy) propyl group, 3- (3-n-butoxypropoxy)
Propyl group, 3- (3-n-hexoxypropoxy) propyl group, 3- (3-n-octoxypropoxy) propyl group, 3- (3- (2-hydroxyethoxy) propoxy) propyl group, 3- ( 3- (4-hydroxybutoxy) propoxy) propyl group, 3- (3-phenoxypropoxy) propyl group, 3- (3-cyclohexoxypropoxy) propyl group, 3- (3-benzoyloxypropoxy) propyl group, (3-allyloxypropoxy) propyl group, 3- (3- (1-naphthoxy) propoxy) propyl group, 4- (4-methoxybutoxy) butyl group, 4- (4-ethoxybutoxy) butyl group, 4-
(4-n-butoxybutoxy) butyl group, 4- (4-n
-Hexoxybutoxy) butyl group, 4- (4-n-octoxybutoxy) butyl group, 4- (4- (2-hydroxyethoxy) butoxy) butyl group, 4- (4- (4-hydroxybutoxy) butoxy ) Butyl group, 4- (4-phenoxybutoxy) butyl group, 4- (4-cyclohexoxybutoxy) butyl group, 4- (4-benzoyloxybutoxy) butyl group, 4- (4-allyloxybutoxy) butyl group , 4- (4- (1-naphthoxy) butoxy) butyl group, 2- (2- (2-methoxyethoxy) ethoxy) ethyl group, 2- (2- (2-ethoxyethoxy) ethoxy) ethyl group, 2- (2- (2-n-butoxyethoxy) ethoxy) ethyl group, 2- (2- (2-n
-Hexoxyethoxy) ethoxy) ethyl group, 2- (2
-(2-n-octoxyethoxy) ethoxy) ethyl group, 2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethyl group, 2- (2- (2- (4-hydroxybutoxy)) Ethoxy) ethoxy) ethyl group, 2
-(2- (2-phenoxyethoxy) ethoxy) ethyl group, 2- (2- (2-cyclohexoxyethoxy) ethoxy) ethyl group, 2- (2- (2-benzoyloxyethoxy) ethoxy) ethyl group, 2 -(2- (2-allyloxyethoxy) ethoxy) ethyl group, 2- (2- (2
-(1-naphthoxy) ethoxy) ethoxy) ethyl group,
3- (3- (3-methoxypropoxy) propoxy) propyl group, 3- (3- (3-ethoxypropoxy) propoxy) propyl group, 3- (3- (3-n-butoxypropoxy) propoxy) propyl group, 3- (3- (3-
(2-hydroxyethoxy) propoxy) propoxy)
Propyl group, 3- (3- (3-phenoxypropoxy)
Propoxy) propyl group, 3- (3- (3-cyclohexoxypropoxy) propoxy) propyl group, 3- (3
-(3-allyloxypropoxy) propoxy) propyl group, 3- (3- (3- (1-naphthoxy) propoxy) propoxy) propyl group, 4- (4- (4-methoxybutoxy) butoxy) butyl group, -(4- (4-ethoxybutoxy) butoxy) butyl group, 4- (4- (4
-N-butoxybutoxy) butoxy) butyl group, 4-
(4- (4- (2-hydroxyethoxy) butoxy) butoxy) butyl group, 4- (4- (4-phenoxybutoxy) butoxy) butyl group, 4- (4- (4-cyclohexoxybutoxy) butoxy) butyl Group, 4- (4- (4
-Allyloxybutoxy) butoxy) butyl group, 4-
(4- (4- (1-naphthoxy) butoxy) butoxy)
Butyl group, 2- (2- (2- (2-methoxyethoxy))
Ethoxy) ethoxy) ethyl group, 2- (2- (2- (2
-Ethoxyethoxy) ethoxy) ethoxy) ethyl groups,
2- (2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethoxy) ethyl group, 2- (2-
(2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl group, 3- (3- (3- (3-methoxypropoxy) propoxy) propoxy) propyl group, 3- (3
-(3- (3-ethoxypropoxy) propoxy) propoxy) propyl group, 3- (3- (3- (3- (3- (2-hydroxyethoxy) propoxy) propoxy) propoxy) propyl group, 3- (3- (3 -(3-phenoxypropoxy) propoxy) propoxy) propyl group, 4-
(4- (4- (4-methoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4-ethoxybutoxy) butoxy) butoxy) butyl group, 4- (4- (4
-(4- (2-hydroxyethoxy) butoxy) butoxy) butoxy) butyl group, 4- (4- (4- (4- (4-phenoxybutoxy) butoxy) butoxy) butyl group and the like. Specific examples of — (CH (CH ₃ ) CH ₂ O) _n Y include, for example, a 2-methoxy-1-methylethyl group,
2-ethoxy-1-methylethyl group, 1-methyl-2-
n-propoxyethyl group, 2-n-butoxy-1-methylethyl group, 2-n-hexoxy-1-methylethyl group, 1-methyl-2-n-octoxyethyl group, 2-n
-Desoxy-1-methylethyl group, 2-n-dodesoxy-1-methylethyl group, 2- (2-hydroxyethoxy) -1-methylethyl group, 2- (3-hydroxypropoxy) -1-methylethyl group , 2- (4-hydroxybutoxy) -1-methylethyl group, 1-methyl-2-phenoxyethyl group, 2-benzyloxy-1-methylethyl group, 1-methyl-2- (2-phenylethoxy) ethyl Group, 2-cyclohexoxy-1-methylethyl group,
2-cyclohexylmethoxy-1-methylethyl group, 2
-Benzoyloxy-1-methylethyl group, 2-allyloxy-1-methylethyl group, 1-methyl-2- (1-
Naphthoxy) ethyl group, 1-methyl-2- (2-naphthoxy) ethyl group, 2- (2-methoxy-1-methylethoxy) -1-methylethyl group, 2- (2-ethoxy-1
-Methylethoxy) -1-methylethyl group, 2- (2-
(2-methoxy-1-methylethoxy) -1-methylethoxy) -1-methylethyl group, 2- (2- (2-ethoxy-1-methylethoxy) -1-methylethoxy)-
1-methylethyl group, 2- (2- (2- (2-methoxy-1-methylethoxy) -1-methylethoxy) -1-
Methylethoxy) -1-methylethyl group, 2- (2-
(2- (2-ethoxy-1-methylethoxy) -1-methylethoxy) -1-methylethoxy) -1-methylethyl group and the like. _{- (CH 2) m O (} CH 2) n OY
(In this case, m ≠ n) is, for example, a 2- (3-methoxypropoxy) ethyl group,
(3-ethoxypropoxy) ethyl group, 2- (3-n-
Propoxypropoxy) ethyl group, 2- (3-isopropoxypropoxy) ethyl group, 2- (3-n-butoxypropoxy) ethyl group, 2- (3-n-hexoxypropoxy) ethyl group, 2- (3- n-octoxypropoxy) ethyl group, 2- (3-n-desoxypropoxy) ethyl group, 2- (3-n-dodeoxypropoxy) ethyl group, 2- (3- (2-hydroxyethoxy) propoxy ) Ethyl group, 2- (3- (3-hydroxypropoxy) propoxy) ethyl group, 2- (3- (4-hydroxybutoxy) propoxy) ethyl group, 2- (3-phenoxypropoxy) ethyl group, 2- ( 3-benzyloxypropoxy) ethyl group, 2- (3- (2-phenylethoxy) propoxy) ethyl group, 2- (3-cyclohexoxypropoxy) ethyl Group, 2- (3-cyclohexyl-methoxypropoxy) ethyl group, 2- (3-benzoyloxy propoxy) ethyl group, 2- (3-allyloxy propoxy) ethyl group, 2- (3- (1-naphthoxy)
Propoxy) ethyl group, 2- (3- (2-naphthoxy)
Propoxy) ethyl group, 2- (4-methoxybutoxy)
Ethyl group, 2- (4-ethoxybutoxy) ethyl group, 2
-(4-n-butoxybutoxy) ethyl group, 2- (4-
(2-hydroxyethoxy) butoxy) ethyl group, 2-
(4-phenoxybutoxy) ethyl group, 2- (4-allyloxybutoxy) ethyl group, 2- (4- (1-naphthoxy) butoxy) ethyl group, 3- (2-methoxyethoxy) propyl group, 3- ( 2-ethoxyethoxy) propyl group, 3- (2-n-butoxyethoxy) propyl group,
3- (2- (2-hydroxyethoxy) ethoxy) propyl group, 3- (2-phenoxyethoxy) propyl group,
3- (2-allyloxyethoxy) propyl group, 3-
(2- (1-naphthoxy) ethoxy) propyl group, 3-
(4-methoxybutoxy) propyl group, 3- (4-ethoxybutoxy) propyl group, 3- (4-n-butoxybutoxy) propyl group, 3- (4- (2-hydroxyethoxy) butoxy) propyl group, 3 -(4-phenoxybutoxy) propyl group, 3- (4-allyloxybutoxy) propyl group, 3- (4- (1-naphthoxy) butoxy) propyl group, 4- (2-methoxyethoxy) butyl group, 4- (2-ethoxyethoxy) butyl group, 4- (2
-N-butoxyethoxy) butyl group, 4- (2- (2-
Hydroxyethoxy) ethoxy) butyl group, 4- (2-
Phenoxyethoxy) butyl group, 4- (2-allyloxyethoxy) butyl group, 4- (2- (1-naphthoxy)
Ethoxy) butyl group, 4- (3-methoxypropoxy)
Butyl group, 4- (3-ethoxypropoxy) butyl group,
4- (3-n-butoxypropoxy) butyl group, 4-
(3- (2-hydroxyethoxy) propoxy) butyl group, 4- (3-phenoxypropoxy) butyl group, 4-
(3-allyloxypropoxy) butyl group, 4- (3-
(1-naphthoxy) propoxy) butyl group and the like. Specific examples of — (CH ₂ ) ₁ —S—Z include, for example, methylthiomethyl, ethylthiomethyl, n-propylthiomethyl, isopropylthiomethyl, n-
Butylthiomethyl group, isobutylthiomethyl group, ter
t-butylthiomethyl group, n-hexylthiomethyl group,
n-octylthiomethyl group, n-decylthiomethyl group,
n-dodecylthiomethyl group, phenylthiomethyl group, phenylmethylthiomethyl group, phenylethylthiomethyl group, cyclohexylthiomethyl group, cyclohexylmethylthiomethyl group, benzoylthiomethyl group, allylthiomethyl group, (1-naphthyl) thiomethyl group , (2-naphthyl) thiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-propylthioethyl group, 2
-Isopropylthioethyl group, 2-n-butylthioethyl group, 2-isobutylthioethyl group, 2-tert-butylthioethyl group, 2-n-hexylthioethyl group, 2
-N-octylthioethyl group, 2-n-decylthioethyl group, 2-n-dodecylthioethyl group, 2-phenylthioethyl group, 2-phenylmethylthioethyl group, 2-phenylethylthioethyl group, 2- Cyclohexylthioethyl group, 2-cyclohexylmethylthioethyl group, 2-
Benzoylthioethyl group, 2-allylthioethyl group, 2
-(1-naphthyl) thioethyl group, 2- (2-naphthyl) thioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-propylthiopropyl group, 3-isopropylthiopropyl group, 3- n-butylthiopropyl group, 3-isobutylthiopropyl group, 3-
tert-butylthiopropyl group, 3-n-hexylthiopropyl group, 3-n-octylthiopropyl group, 3-
n-decylthiopropyl group, 3-n-dodecylthiopropyl group, 3-phenylthiopropyl group, 3-phenylmethylthiopropyl group, 3-phenylethylthiopropyl group, 3-cyclohexylthiopropyl group, 3-cyclohexylmethylthiopropyl Group, 3-benzoylthiopropyl group, 3-allylthiopropyl group, 3- (1-naphthyl) thiopropyl group, 3- (2-naphthyl) thiopropyl group, 4-methylthiobutyl group, 4-ethylthiobutyl group, -N-propylthiobutyl group, 4-isopropylthiobutyl group, 4-n-butylthiobutyl group, 4-isobutylthiobutyl group, 4-tert-butylthiobutyl group, 4-n-hexylthiobutyl group, 4 -N-octylthiobutyl group, 4-n-decylthiobutyl group, 4-n-
Dodecylthiobutyl group, 4-phenylthiobutyl group, 4
-Phenylmethylthiobutyl group, 4-phenylethylthiobutyl group, 4-cyclohexylthiobutyl group, 4-cyclohexylmethylthiobutyl group, 4-benzoylthiobutyl group, 4-allylthiobutyl group, 4- (1-naphthyl) thiobutyl Group, 4- (2-naphthyl) thiobutyl group, 5-methylthiopentyl group, 5-ethylthiopentyl group, 5-n-butylthiopentyl group, 5-n-hexylthiopentyl group, 5-n-octylthiopentyl Group,
5-n-decylthiopentyl group, 5-n-dodecylthiopentyl group, 5-phenylthiopentyl group, 5-cyclohexylthiopentyl group, 5- (1-naphthyl) thiopentyl group, 6-methylthiohexyl group, 6- Ethylthiohexyl group, 6-n-butylthiohexyl group, 6-n-
Hexylthiohexyl group, 6-n-octylthiohexyl group, 6-n-decylthiohexyl group, 6-n-dodecylthiohexyl group, 6-phenylthiohexyl group, 6-
Cyclohexylthiohexyl group, 6- (1-naphthyl)
Thiohexyl group, 8-methylthiooctyl group, 8-ethylthiooctyl group, 8-n-butylthiooctyl group, 8
-N-hexylthiooctyl group, 8-n-octylthiooctyl group, 8-n-decylthiooctyl group, 8-n-
Dodecylthiooctyl, 8-phenylthiooctyl and the like can be mentioned.

Further, specific examples of the 9,10-dietherified anthracene derivative represented by the above formula (3) obtained by the present invention include, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10
Di (n-propoxy) anthracene, 9,10-di (n-butoxy) anthracene, 9,10-diisobutoxyanthracene, 9,10-di (n-hexoxy) anthracene, 9,10-di (n-octoxy) ) Anthracene, 9,10-di (2-ethylhexoxy) anthracene, 9,10-di (n-desoxy) anthracene,
9,10-di (n-dodeoxy) anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-
9,10-di (n-propoxy) anthracene, 9.1
0-di (n-butoxy) -2-ethylanthracene,
9,10-diisobutoxy-2-ethylanthracene,
2-ethyl-9,10-di (n-hexoxy) anthracene, 2-ethyl-9,10-di (n-octoxy) anthracene, 2-ethyl-9,10-di (2-ethylhexoxy) anthracene, 10-di (n-desoxy) -2-ethylanthracene, 9,10-di (n-dodesoxy) -2-ethylanthracene, 9,10-difluoromethoxyanthracene, 2-ethyl-9,10-
Difluoromethoxyanthracene, 9,10-dichloromethoxyanthracene, 2-ethyl-9,10-dichloromethoxyanthracene, 9,10-dibromomethoxyanthracene, 2-ethyl-9,10-dibromomethoxyanthracene, 9, 10-diphenoxyanthracene, 2-ethyl-9,10-diphenoxyanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 9,
10-dicyclohexylmethoxyanthracene, 9.1
0-dicyclohexylmethoxy-2-ethylanthracene, 9,10-di (1-naphthyl) methoxyanthracene, 2-ethyl-9,10-di (1-naphthyl) methoxyanthracene, 9,10-di (2-naphthyl) Methoxyanthracene, 2-ethyl-9,10-di (2-naphthyl) methoxyanthracene, 9,10-di (2-fluoroethoxy) anthracene, 2-ethyl-9,10-
Di (2-fluoroethoxy) anthracene, 9,10-
Di (4-phenylbutoxy) anthracene, 2-ethyl-9,10-di (4-phenylbutoxy) anthracene, 9,10-di (8-cyclohexyloctoxy) anthracene, 2-ethyl-9,10-di ( 8-cyclohexyloctoxy) anthracene, 9,10-di (2-
Methoxyethoxy) anthracene, 2-ethyl-9,1
0-di (2-methoxyethoxy) anthracene, 9.1
0-di (2-ethoxyethoxy) anthracene, 2-ethyl-9,10-di (2-ethoxyethoxy) anthracene, 9,10-di (2-n-butoxyethoxy) anthracene, 9,10-di (2 -N-butoxyethoxy)
-2-ethylanthracene, 9,10-di (2- (2-
Hydroxyethoxy) ethoxy) anthracene, 2-ethyl-9,10-di (2- (2-hydroxyethoxy)
Ethoxy) anthracene, 9,10-di (2-phenoxyethoxy) anthracene, 2-ethyl-9,10-di (2-phenoxyethoxy) anthracene, 9,10-
Di (2- (2-methoxyethoxy) ethoxy) anthracene, 2-ethyl-9,10-di (2- (2-methoxyethoxy) ethoxy) anthracene, 9,10-di (2
-(2-ethoxyethoxy) ethoxy) anthracene,
2-ethyl-9,10-di (2- (2-ethoxyethoxy) ethoxy) anthracene, 9,10-di (2-methoxy-1-methylethoxy) anthracene, 2-ethyl-9,10-di (2 -Methoxy-1-methylethoxy)
Anthracene, 9,10-di (2-ethoxy-1-methylethoxy) anthracene, 2-ethyl-9,10-di (2-ethoxy-1-methylethoxy) anthracene,
9,10-di (2-phenoxy-1-methylethoxy)
Anthracene, 2-ethyl-9,10-di (2-phenoxy-1-methylethoxy) anthracene, 9,10-
Di (2- (2-hydroxyethoxy) -1-methylethoxy) anthracene, 2-ethyl-9,10-di (2-
(2-hydroxyethoxy) -1-methylethoxy) anthracene, 9,10-di (2- (4-methoxybutoxy) ethoxy) anthracene, 2-ethyl-9,10-
Di (2- (4-methoxybutoxy) ethoxy) anthracene, 9,10-di (2- (4-ethoxybutoxy) ethoxy) anthracene, 2-ethyl-9,10-di (2
-(4-ethoxybutoxy) ethoxy) anthracene,
9,10-di (4- (2-methoxyethoxy) butoxy) anthracene, 2-ethyl-9,10-di (4-
(2-methoxyethoxy) butoxy) anthracene,
9,10-di (4- (2-ethoxyethoxy) butoxy) anthracene, 2-ethyl-9,10-di (4-
(2-ethoxyethoxy) butoxy) anthracene, 2
-Tert-butyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 1-phenylthio-9,10-di (2-methoxyethoxy) anthracene, 2-dodecyl-9,10
-Di (2-methoxyethoxy) anthracene, 2-stearyl-9,10-di (2-methoxyethoxy) anthracene, 2,4-dimethyl-9,10-di (2-methoxyethoxy) anthracene, 1-chloro- 9,10-di (2-methoxyethoxy) anthracene, 2-chloro-
9,10-di (2-methoxyethoxy) anthracene,
9,10-di (methylthiomethoxy) anthracene,
9,10-di (ethylthiomethoxy) anthracene,
9,10-di (n-propylthiomethoxy) anthracene, 9,10-di (n-butylthiomethoxy) anthracene, 9,10-di (n-hexylthiomethoxy) anthracene, 9,10-di (n- Octylthiomethoxy)
Anthracene, 9,10-di (n-decylthiomethoxy) anthracene, 9,10-di (n-dodecylthiomethoxy) anthracene, 9,10-di (phenylthiomethoxy) anthracene, 9,10-di (cyclohexylthio) Methoxy) anthracene, 9,10-di ((1-naphthyl) thiomethoxy) anthracene, 9,10-di (2-methylthioethoxy) anthracene, 9,10-
Di (2-ethylthioethoxy) anthracene, 9,10
-Di (2-n-propylthioethoxy) anthracene,
9,10-di (2-n-butylthioethoxy) anthracene, 9,10-di (2-n-hexylthioethoxy)
Anthracene, 9,10-di (2-n-octylthioethoxy) anthracene, 9,10-di (2-n-decylthioethoxy) anthracene, 9,10-di (2-n-
Dodecylthioethoxy) anthracene, 9,10-di (2-phenylthioethoxy) anthracene, 9,10
-Di (2-cyclohexylthioethoxy) anthracene, 9,10-di (2- (1-naphthyl) thioethoxy) anthracene, 9,10-di (3-methylthiopropoxy) anthracene, 9,10-di (3-ethyl Thiopropoxy) anthracene, 9,10-di (3-n-butylthiopropoxy) anthracene, 9,10-di (3
-N-hexylthiopropoxy) anthracene, 9.1
0-di (3-n-octylthiopropoxy) anthracene, 9,10-di (3-phenylthiopropoxy) anthracene, 9,10-di (4-methylthiobutoxy) anthracene, 9,10-di (4-ethyl Thiobutoxy)
Anthracene, 9,10-di (4-n-butylthiobutoxy) anthracene, 9,10-di (4-n-hexylthiobutoxy) anthracene, 9,10-di (4-n-
Octylthiobutoxy) anthracene, 9,10-di (4-phenylthiobutoxy) anthracene, 9,10
-Di (6-methylthiohexoxy) anthracene, 9,
10-di (6-ethylthiohexoxy) anthracene,
9,10-di (6-n-butylthiohexoxy) anthracene, 9,10-di (6-n-hexylthiohexoxy) anthracene, 9,10-di (6-n-octylthiohexoxy) anthracene 9,10-di (6-phenylthiohexoxy) anthracene, 9,10-di (8
-Methylthiooctoxy) anthracene, 9,10-di (8-ethylthiooctoxy) anthracene, 9,10
-Di (8-n-butylthiooctoxy) anthracene,
9,10-di (8-n-hexylthiooctoxy) anthracene, 9,10-di (8-n-octylthiooctoxy) anthracene, 9,10-di (8-phenylthiooctoxy) anthracene, -Ethyl-9,10-di (methylthiomethoxy) anthracene, 2-ethyl-
9,10-di (ethylthiomethoxy) anthracene, 2
-Ethyl-9,10-di (n-propylthiomethoxy)
Anthracene, 9,10-di (n-butylthiomethoxy) -2-ethylanthracene, 2-ethyl-9,10
-Di (n-hexylthiomethoxy) anthracene, 2-
Ethyl-9,10-di (n-octylthiomethoxy) anthracene, 9,10-di (n-decylthiomethoxy)
-2-ethylanthracene, 9,10-di (n-dodecylthiomethoxy) -2-ethylanthracene, 2-ethyl-9,10-di (phenylthiomethoxy) anthracene, 9,10-di (cyclohexylthiomethoxy) -2
-Ethylanthracene, 2-ethyl-9,10-di ((1-naphthyl) thiomethoxy) anthracene,
Ethyl-9,10-di (2-methylthioethoxy) anthracene, 2-ethyl-9,10-di (2-ethylthioethoxy) anthracene, 2-ethyl-9,10-di (2-n-propylthioethoxy) ) Anthracene, 9,
10-di (2-n-butylthioethoxy) -2-ethylanthracene, 2-ethyl-9,10-di (2-n-hexylthioethoxy) anthracene, 2-ethyl-9,
10-di (2-n-octylthioethoxy) anthracene, 9,10-di (2-n-decylthioethoxy) -2
-Ethylanthracene, 9,10-di (2-n-dodecylthioethoxy) -2-ethylanthracene, 2-ethyl-9,10-di (2-phenylthioethoxy) anthracene, 9,10-di (2- Cyclohexylthioethoxy) -2-ethylanthracene, 2-ethyl-9,10
-Di (2- (1-naphthyl) thioethoxy) anthracene, 2-ethyl-9,10-di (3-methylthiopropoxy) anthracene, 2-ethyl-9,10-di (3-
Ethylthiopropoxy) anthracene, 9,10-di (3-n-butylthiopropoxy) -2-ethylanthracene, 2-ethyl-9,10-di (3-n-hexylthiopropoxy) anthracene, 2-ethyl- 9,10
-Di (3-n-octylthiopropoxy) anthracene, 2-ethyl-9,10-di (3-phenylthiopropoxy) anthracene, 2-ethyl-9,10-di (4
-Methylthiobutoxy) anthracene, 2-ethyl-
9,10-di (4-ethylthiobutoxy) anthracene, 9,10-di (4-n-butylthiobutoxy) -2
-Ethylanthracene, 2-ethyl-9,10-di (4
-N-hexylthiobutoxy) anthracene, 2-ethyl-9,10-di (4-n-octylthiobutoxy) anthracene, 2-ethyl-9,10-di (4-phenylthiobutoxy) anthracene, 2-ethyl -9,10-
Di (6-methylthiohexoxy) anthracene, 2-ethyl-9,10-di (6-ethylthiohexoxy) anthracene, 9,10-di (6-n-butylthiohexoxy) -2-ethylanthracene, 2-ethyl-9,10
-Di (6-n-hexylthiohexoxy) anthracene, 2-ethyl-9,10-di (6-n-octylthiohexoxy) anthracene, 2-ethyl-9,10-di (6-phenylthiohexene) Soxy) anthracene, 2-ethyl-9,10-di (8-methylthiooctoxy) anthracene, 2-ethyl-9,10-di (8-ethylthiooctoxy) anthracene, 9,10-di (8-n -Butylthiooctoxy) -2-ethylanthracene, 2-
Ethyl-9,10-di (8-n-hexylthiooctoxy) anthracene, 2-ethyl-9,10-di (8-n
-Octylthiooctoxy) anthracene, 2-ethyl-9,10-di (8-phenylthiooctoxy) anthracene, 2-tert-butyl-9,10-di (2-methylthioethoxy) anthracene, 2-tert- Butyl-9,10-di (2-ethylthioethoxy) anthracene, 2-tert-butyl-9,10-di (2-n-
(Butylthioethoxy) anthracene, 2-tert-butyl-9,10-di (2-n-hexylthioethoxy)
Anthracene, 2-tert-butyl-9,10-di (2-n-octylthioethoxy) anthracene, 2-
tert-butyl-9,10-di (2-n-decylthioethoxy) anthracene, 2-tert-butyl-9,
10-di (2-n-dodecylthioethoxy) anthracene, 2-tert-butyl-9,10-di (2-phenylthioethoxy) anthracene, 2-tert-butyl-9,10-di (2-cyclohexylthio) Ethoxy) anthracene, 2-tert-butyl-9,10-di (2
-(1-naphthyl) thioethoxy) anthracene, 2-
tert-butyl-9,10-di (3-methylthiopropoxy) anthracene, 2-tert-butyl-9,1
0-di (3-ethylthiopropoxy) anthracene, 2
-Tert-butyl-9,10-di (3-n-butylthiopropoxy) anthracene, 2-tert-butyl-
9,10-di (3-n-hexylthiopropoxy) anthracene, 2-tert-butyl-9,10-di (3-
n-octylthiopropoxy) anthracene, 2-te
rt-butyl-9,10-di (3-phenylthiopropoxy) anthracene, 2-tert-butyl-9,10
-Di (4-methylthiobutoxy) anthracene, 2-t
tert-butyl-9,10-di (4-ethylthiobutoxy) anthracene, 2-tert-butyl-9,10-
Di (4-n-butylthiobutoxy) anthracene, 2-
tert-butyl-9,10-di (4-n-hexylthiobutoxy) anthracene, 2-tert-butyl-
9,10-di (4-n-octylthiobutoxy) anthracene, 2-tert-butyl-9,10-di (4-phenylthiobutoxy) anthracene, 2,3-dimethyl-9,10-di (2- Methylthioethoxy) anthracene, 9,10-di (2-ethylthioethoxy) -2,3
-Dimethylanthracene, 9,10-di (2-n-butylthioethoxy) -2,3-dimethylanthracene,
2,3-dimethyl-9,10-di (2-phenylthioethoxy) anthracene, 2,3,6,7-tetramethyl-9,10-di (2-methylthioethoxy) anthracene, 2-methoxy-9, 10-di (2-methylthioethoxy) anthracene, 9,10-di (2-ethylthioethoxy) -2-methoxyanthracene, 2-methylcarbonyl-9,10-di (2-methylthioethoxy) anthracene, 9,10 -Di (2-ethylthioethoxy)-
2-methylcarbonylanthracene, 9,10-di (2
-Methylthioethoxy) -1-phenylthioanthracene, 9,10-di (2-ethylthioethoxy) -1-phenylthioanthracene, and the like.

Among the 9,10-dietherified anthracene derivatives represented by the above formula (3), preferred examples of preferable compounds include, for example, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 2-ethyl-9,10-di (n-propoxy) anthracene, 9,10-di (n-butoxy)-
2-ethylanthracene, 9,10-diisobutoxy-
2-ethylanthracene, 2-ethyl-9,10-difluoromethoxyanthracene, 2-ethyl-9,10-
Diphenoxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 9,10-dicyclohexylmethoxy-2-ethylanthracene, 9,10-di (2-methoxyethoxy) anthracene, 2-ethyl-
9,10-di (2-methoxyethoxy) anthracene,
2-ethyl-9,10-di (2-ethoxyethoxy) anthracene, 2-ethyl-9,10-di (2-phenoxyethoxy) anthracene, 2-tert-butyl-
9,10-dimethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,4-dimethyl-9,10-di (2-methoxyethoxy) anthracene, 2-chloro-9,10-di ( 2-methoxyethoxy) anthracene, 2-ethyl-9,10-di (2-
Methylthioethoxy) anthracene, 2-ethyl-9,
10-di (2-ethylthioethoxy) anthracene, 2
-Ethyl-9,10-di (2-phenylthioethoxy)
Anthracene, 2-tert-butyl-9,10-di (2-methylthioethoxy) anthracene, 2-ter
t-butyl-9,10-di (2-ethylthioethoxy)
Anthracene, 2-tert-butyl-9,10-di (2-phenylthioethoxy) anthracene and the like can be mentioned. Among them, a particularly preferable compound is, for example, 2-ethyl-9,10-. Dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di (n-butoxy) -2-ethylanthracene, 2-ethyl-9,10-di (2-methoxyethoxy) anthracene, 2- Ethyl-9,10-di (2-ethylthioethoxy) anthracene and the like can be mentioned.

Next, specific examples of the anthraquinone compound represented by the formula (1) used in the present invention include, for example, unsubstituted anthraquinone, 1-methylanthraquinone,
-Ethylanthraquinone, 1-n-propylanthraquinone, 2-n-propylanthraquinone, 1-isopropylanthraquinone, 2-isopropylanthraquinone, 1-n-butylanthraquinone, 2-n-butylanthraquinone, 1-isobutylanthraquinone, 2-isobutyl Anthraquinone, 2-tert-butylanthraquinone, 1-n-pentylanthraquinone, 2-n-
Pentyl anthraquinone, 1-isopentyl anthraquinone, 2-isopentyl anthraquinone, 1-n-hexyl anthraquinone, 2-n-hexyl anthraquinone, 1-isohexyl anthraquinone, 2-isohexyl anthraquinone, 1-n-heptyl anthraquinone,
2-n-heptylanthraquinone, 1-n-octylanthraquinone, 2-n-octylanthraquinone, 1-
n-nonylanthraquinone, 2-n-nonylanthraquinone, 1-n-decylanthraquinone, 2-n-decylanthraquinone, 1-n-dodecylanthraquinone, 2
-N-dodecylanthraquinone, 1-methoxyanthraquinone, 2-methoxyanthraquinone, 1-ethoxyanthraquinone, 2-ethoxyanthraquinone, 1-phenoxyanthraquinone, 2-phenoxyanthraquinone, 2- (2-hydroxyethyl) anthraquinone,
-Chloranthraquinone, 2-chloroanthraquinone,
2-cyanoanthraquinone, 1,2-dimethylanthraquinone, 1,3-dimethylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2,4-dimethylanthraquinone, 2,5-dimethylanthraquinone, 2,6 -Dimethylanthraquinone,
3,4-dimethylanthraquinone, 1,2-diethylanthraquinone, 1,3-diethylanthraquinone, 1,
4-diethylanthraquinone, 2,3-diethylanthraquinone, 2,4-diethylanthraquinone, 2,5-
Diethylanthraquinone, 2,6-diethylanthraquinone, 3,4-diethylanthraquinone, 1,2,3-
Trimethylanthraquinone, 1,2,4-trimethylanthraquinone, 2,3,6,7-tetramethylanthraquinone, 1-fluoroanthraquinone, 2-fluoroanthraquinone, 1-cyanoanthraquinone, 2-cyanoanthraquinone, 2-phenylanthraquinone, 1 -Benzylanthraquinone, 2-benzylanthraquinone,
1- (1-naphthyl) anthraquinone, 1-methylcarbonylanthraquinone, 2-methylcarbonylanthraquinone, 1-ethylcarbonylanthraquinone, 2-ethylcarbonylanthraquinone, 1-phenylcarbonylanthraquinone, 2-phenylcarbonylanthraquinone, 1-methylthioanthraquinone, 2-methylthioanthraquinone, 1-ethylthioanthraquinone, 2-
Examples thereof include ethylthioanthraquinone, 1-phenylthioanthraquinone, and 2-phenylthioanthraquinone.

When the anthraquinone represented by the formula (1) is reduced to a leuco form by using a dithionite, the anthraquinone is first added to an aqueous alkali solution with stirring. As the aqueous alkali solution used at this time, an aqueous alkali metal salt solution is preferable. Aqueous solution,
An aqueous solution of an inorganic alkali metal salt such as an aqueous solution of an alkali metal carbonate such as an aqueous solution of sodium carbonate or an aqueous solution of potassium carbonate can be given. Further, the concentration of the aqueous alkali solution is preferably 10 to 50% by weight of the alkali metal salt with respect to water, and more preferably 20 to 30% by weight. Further, the amount of the anthraquinone to be charged is preferably 3 to 20 parts, more preferably 10 to 15 parts with respect to 100 parts of the aqueous alkali solution.

For the purpose of acclimating the anthraquinone to the aqueous alkali solution and further promoting the reduction reaction, an alcohol is added before the anthraquinone is added to the aqueous alkali solution. As alcohols, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-
Examples thereof include butanol, ethylene glycol, diethylene glycol, and triethylene glycol, and more preferred alcohols are methanol and ethanol. The ratio of adding alcohols is preferably in a weight ratio of alcohol: alkali aqueous solution = 90: 10 to 10:90, and more preferably 80:20 to 50:50.

After the addition of the anthraquinones, dithionite is added to reduce the anthraquinones. Examples of the dithionite used at this time include lithium dithionite, sodium dithionite, potassium dithionite and the like. From the viewpoint of solubility in water and the like, sodium dithionite (hydro Preference is given to using sodium sulfite). The dithionite is preferably used in an amount of 1.0 to 5.0 moles, more preferably 1.4 to 1.6 moles, per mole of anthraquinones. .

When dithionite is added to reduce anthraquinones to obtain a leuco compound, nitrogen gas or the like may be blown into the reaction solution to dissolve dissolved oxygen in advance. Further, the reaction temperature is preferably in the range of 10 to 100C, more preferably in the range of 30 to 50C. The reaction time is usually preferably from 0.5 to 24 hours, more preferably from 1 to 4 hours.

The anthraquinones are reduced with a dithionite to form a leuco body, and then an alkylsulfonic acid ester represented by the formula (2) is gradually added and reacted. When the desired alkyl sulfonic acid ester is a solid such as a wax, it can be used after being diluted with a solvent not involved in the reaction system. Examples of the solvent that does not participate in the reaction system include aromatic hydrocarbon compounds such as toluene and xylene, ethers such as diethyl ether and isopropyl ether, aliphatic hydrocarbon compounds such as n-hexane and cyclohexane, methanol, ethanol, isopropanol, and the like. Alcohols and the like. Further, when the desired alkyl sulfonic acid ester represented by the formula (2) is used after being diluted with a solvent, the dilution ratio is usually from 1 to 99 w%, preferably from 40 to 80 w%.

The amount of the alkylsulfonic acid ester represented by the formula (2) is preferably 1.0 to 8.0 mol, more preferably 3.0 mol, per 1.0 mol of anthraquinone. It is good to make it 5.0 mol. The temperature at the time of charging the alkyl sulfonic acid esters is 20 ° C.
The temperature is preferably 80 ° C., and more preferably 40 ° C. to 75 ° C. The reaction temperature after charging the alkylsulfonic acid ester represented by the formula (2) is 20 ° C to 100 ° C.
C., preferably 30 to 80C. The reaction time is preferably 1 to 120 hours, and more preferably 2 to 24 hours. The pH of the reaction solution during the reaction is preferably 9 or more. When the pH of the reaction solution is 9 or less, the progress of the reaction is significantly slowed down, or raw materials that cannot be completely reduced remain. It is good to adjust so that.

After the reaction, if unreacted leuco remains, it can be removed by the following treatment. That is, the obtained reaction product is added to, for example, a 5% by weight aqueous solution of sodium dithionite while stirring. At this time, the amount of the 5% by weight aqueous solution of sodium dithionite is 5 to 100 parts by weight, preferably 1 part by weight, based on the theoretical amount of the obtained 9,10-dietherified anthracene derivative.
0 to 30 parts by weight. After stirring for 1 hour, the crystals were filtered off, and usually 5 to 10 parts by weight of a 5% by weight aqueous sodium dithionite solution based on the theoretical amount of the obtained 9,10-dietherified anthracene derivative, and then usually 20 to 10 parts by weight The crystals are washed with 50 parts by weight of water, and usually with 2 to 5 parts by weight of methanol, and then dried to obtain the desired 9.1.
A 0-dietherified anthracene derivative is obtained.

The obtained 9,10-dietherified anthracene derivative may be dried as it is, or may be recrystallized using an organic solvent. Examples of organic solvents that can be used for recrystallization include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and n-butyl acetate, and aromatics such as toluene and xylene. Compounds can be mentioned. These organic solvents may be used alone or in combination of two or more.

The alkyl sulfonic acid ester represented by the formula (2) is prepared by mixing an alcohol with any of methanesulfonic acid halide, ethanesulfonic acid halide or trifluoromethanesulfonic acid halide and adding an alkali compound. Desired alkyl sulfonic acid esters can be synthesized and used. Alternatively, the desired alkyl sulfonic acid esters are synthesized by mixing alcohols in advance with an alkali compound and adding any of methanesulfonic acid halide, ethanesulfonic acid halide or trifluoromethanesulfonic acid halide to use. Is possible. As the halide, chloride or bromide is preferable. In the case of monohydric alcohol, the charged amount of the halide relative to the alcohol is preferably 0.9 to 2.0 mol, more preferably 1.0 to 1.2 mol, per 1.0 mol of the alcohol. In the case of dihydric alcohols, it is preferable to add 0.5 to 1.2 mol of halides to 1.0 mol of alcohols, more preferably 0.9 to 1.0 mol. Good. If the alcohols do not easily react with the halides, the alcohols may be converted into alcoholates with lithium hydride, sodium hydride, potassium hydride, or the like before reacting with the halides. The reaction is preferably performed at -50 to 20C. The reaction time is 1 to 30 hours, and the more preferable reaction time is 2 to 15 hours.

As the alkali compound used in the esterification reaction, for example, sodium hydroxide, potassium hydroxide,
Alkali metal compounds such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, etc., monoethylamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, n-butylamine, n-dibutylamine, n-tributylamine, isobutylamine, diisobutyl Amine, n-pentylamine, dipentylamine, tripentylamine, 2-ethylbutylamine, n-heptylamine, 2-ethylhexylamine, dioctylamine, cyclohexylamine, dicyclohexylamine, aniline, monomethylaniline, dimethylaniline, diethylaniline, o -Toluidine, pyridine, α-picoline, β-picoline, γ
Organic amines such as -picoline, 2,4-lutidine, 2,6-lutidine, quinoline, morpholine and ethylmorpholine.

The amount of these alkali compounds to be charged is preferably 1.0 to 10.0 mol, more preferably 2.0 to 4.0 mol, per 1.0 mol of alcohols. These alkali compounds may be used as they are or as an aqueous solution.
The content of the alkali compound is preferably 10 to 50% by weight relative to water, and most preferably 20 to 30% by weight. In addition, when adding an alkali compound, when using as it is, without using it as an aqueous solution, it is good to charge it little by little, and when using as an aqueous solution, it is preferable to dripping gradually. During the charging of the alkali compound, the liquid temperature is preferably maintained at 0 to 50C, more preferably at 10 to 20C.

After the completion of the reaction, the alkali compound is neutralized with an acid, washed with water, filtered and washed with water at a temperature of 20 ° C. or lower, or separated and extracted with a solvent to obtain a desired alkyl sulfone. Obtain acid esters. When the alkylsulfonic acid esters are taken out by solvent extraction, examples of organic solvents that can be used include toluene, xylene, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and isobutyl acetate. Dibutyl, methyl isobutyl ketone and the like can be mentioned. After extraction with these organic solvents, the solvent is removed and dried to obtain a desired alkylsulfonic acid ester.

The alcohols used in the esterification reaction include, for example, methanol, ethanol, n
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, isobutyl alcohol, tert-
Butyl alcohol, n-pentyl alcohol, isopentyl alcohol, n-hexyl alcohol, isohexyl alcohol, n-heptyl alcohol, isoheptyl alcohol, n-octyl alcohol, isooctyl alcohol, n-nonyl alcohol, isononyl alcohol, n- Decyl alcohol, isodecyl alcohol, n
-Dodecyl alcohol, isododecyl alcohol, n-
Stearyl alcohol, isostearyl alcohol, 2
-Fluoroethanol, benzyl alcohol, cyclohexyl alcohol, cyclohexyl methanol, 4-t
tert-butylcyclohexanol, 4-methyl-3-
Pentenyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisopentyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono -N-hexyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene Glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, 1-butoxyethoxypropanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene Glycol monomethyl ether, 2-methylthioethanol, 2-ethylthioethanol, 2-n
-Propylthioethanol, 2-isopropylthioethanol, 2-n-butylthioethanol, 2-isobutylthioethanol, 2-tert-butylthioethanol, 2-n-octylthioethanol, 2-n-dodecylthioethanol, -Phenylthioethanol, 2-
Phenylethylthioethanol, 2-cyclohexylthioethanol, 4-methylthiobutanol, 4-ethylthiobutanol, 4-n-butylthiobutanol, 4-
Monohydric alcohols such as phenylthiobutanol, 6-ethylthiohexanol, 6-phenylthiohexanol, 8-ethylthiooctanol, 8-phenylthiooctanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, Dipropylene glycol,
Examples thereof include dihydric alcohols such as trimethylene glycol.

Specific examples of the alkylsulfonic acid esters represented by the formula (2) include, for example, methyl methanesulfonate, ethyl methanesulfonate, methanesulfonic acid-
n-propyl, isopropyl methanesulfonate, n-butyl methanesulfonate, isobutyl methanesulfonate, n-pentyl methanesulfonate, isopentyl methanesulfonate, n-hexyl methanesulfonate, isohexyl methanesulfonate, methanesulfone Acid-n-
Heptyl, isoheptyl methanesulfonate, n-octyl methanesulfonate, isooctyl methanesulfonate, n-nonyl methanesulfonate, isononyl methanesulfonate, n-decyl methanesulfonate, isodecyl methanesulfonate, methanesulfonate- n-dodecyl, isododecyl methanesulfonate, n-stearyl methanesulfonate, isostearyl methanesulfonate,
Methanesulfonic acid- (2-fluoroethyl), benzyl methanesulfonic acid, cyclohexyl methanesulfonic acid,
Cyclohexylmethyl methanesulfonate, cyclohexylethyl methanesulfonate, methanesulfonic acid- (4-
tert-butylcyclohexyl), methanesulfonic acid- (4-methyl-3-pentenyl), methanesulfonic acid- (2-hydroxyethyl), methanesulfonic acid- (2
-Methoxyethyl), methanesulfonic acid- (2-ethoxyethyl), methanesulfonic acid- (2-n-propoxyethyl), methanesulfonic acid- (2-isopropoxyethyl), methanesulfonic acid- (2-n- Butoxyethyl), methanesulfonic acid- (2-isobutoxyethyl), methanesulfonic acid- (2-isopentoxyethyl), methanesulfonic acid- (2-phenoxyethyl),
Methanesulfonic acid- (2-benzoxyethyl), methanesulfonic acid- (2-n-hexoxyethyl), methanesulfonic acid- (2-methoxymethoxyethyl), methanesulfonic acid- (2- (2-hydroxyethoxy) ethyl ), Methanesulfonic acid- (2- (2-methoxyethoxy) ethyl), methanesulfonic acid- (2- (2-ethoxyethoxy) ethyl), methanesulfonic acid- (2- (2
-N-butoxyethoxy) ethyl), methanesulfonic acid- (3-fluoropropyl), methanesulfonic acid- (3
-Hydroxypropyl), methanesulfonic acid- (3-methoxypropyl), methanesulfonic acid- (3-ethoxypropyl), methanesulfonic acid- (3-phenoxypropyl), methanesulfonic acid- (3-benzoxypropyl), Methanesulfonic acid- (3- (2-methoxyethoxy) propyl), methanesulfonic acid- (3- (2-ethoxyethoxy) propyl), methanesulfonic acid- (4-
(Fluorobutyl), methanesulfonic acid- (4-hydroxybutyl), methanesulfonic acid- (4-methoxybutyl), methanesulfonic acid- (4-ethoxybutyl), methanesulfonic acid- (4-phenoxybutyl), methanesulfone Acid-(4- (2-methoxyethoxy) butyl),
Methanesulfonic acid- (4- (2-ethoxyethoxy) butyl), methanesulfonic acid- (2-methylthioethyl), methanesulfonic acid- (2-ethylthioethyl),
Methanesulfonic acid- (2-n-propylthioethyl),
Methanesulfonic acid- (2-isopropylthioethyl),
Methanesulfonic acid- (2-n-butylthioethyl), methanesulfonic acid- (2-isobutylthioethyl), methanesulfonic acid- (2-tert-butylthioethyl),
Methanesulfonic acid- (2-n-octylthioethyl),
Methanesulfonic acid- (2-n-dodecylthioethyl),
Methanesulfonic acid- (2-phenylthioethyl), methanesulfonic acid- (2-phenylethylthioethyl), methanesulfonic acid- (2-cyclohexylthioethyl),
Methanesulfonic acid- (4-methylthiobutyl), methanesulfonic acid- (4-ethylthiobutyl), methanesulfonic acid- (4-n-butylthiobutyl), methanesulfonic acid- (4-phenylthiobutyl), methane Sulfonic acid-
(6-ethylthiohexyl), methanesulfonic acid- (6
-Phenylthiohexyl), methanesulfonic acid- (8-
Ethylthiooctyl), methanesulfonic acid- (8-phenylthiooctyl), methyl ethanesulfonate, ethyl ethanesulfonate, isopropyl ethanesulfonate, n-butyl ethanesulfonate, isobutyl ethanesulfonate, ethanesulfonic acid- ( 2-fluoroethyl), benzyl ethanesulfonate, cyclohexyl ethanesulfonate,-(2-hydroxyethyl) ethanesulfonate,
Ethanesulfonic acid- (2-methoxyethyl), ethanesulfonic acid- (2-ethoxyethyl), ethanesulfonic acid- (2-phenoxyethyl), ethanesulfonic acid- (3
-Methoxypropyl), ethanesulfonic acid- (2-ethylthioethyl), methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, isopropyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, isobutyl trifluoromethanesulfonate, Trifluoromethanesulfonic acid- (2-
Fluoroethyl), benzyl trifluoromethanesulfonate, cyclohexyl trifluoromethanesulfonate,
Trifluoromethanesulfonic acid- (2-hydroxyethyl), trifluoromethanesulfonic acid- (2-methoxyethyl), trifluoromethanesulfonic acid- (2-ethoxyethyl), trifluoromethanesulfonic acid- (2-
Phenoxyethyl), trifluoromethanesulfonic acid-
(3-methoxypropyl), trifluoromethanesulfonic acid- (2-ethylthioethyl) and the like.

[0031]

The present invention will be described in more detail with reference to the following examples. In addition, this invention is not limited only to the following.

Example 1 Synthesis of 2-Ethyl-9,10-dimethoxyanthracene In a 200 mL four-necked flask, 50.0 g of a 30% aqueous sodium hydroxide solution was added.
0.0 g and 11.8 g of 2-ethylanthraquinone
Was added thereto and dispersed by stirring in a nitrogen stream. Further, 13.1 g of sodium dithionite was added to this solution,
The temperature was raised and the reaction was carried out at 40 to 45 ° C for 2 hours. The solution in which the yellow powder was dispersed turned into a dark red solution. next,
To this solution, 22.0 g of methyl methanesulfonate was added dropwise over 2 hours while paying attention to heat generation. After the dropwise addition of methyl methanesulfonate, the mixture was stirred at 40 to 45 ° C for 6 hours. After cooling, the reaction solution was poured into 300 mL of a 5 w% aqueous solution of sodium dithionite while stirring, and the unreacted leuco body was removed by filtration. The obtained cake is sufficiently washed with water, stirred and washed in methanol, filtered, washed with a small amount of methanol, and dried to obtain 9.0 g of desired 2-ethyl-9,10-dimethoxyanthracene (yield). 67.7%). 2-ethyl-9,10 obtained
-Dimethoxyanthracene was a fluorescent yellow powder having a purity of 98.1% (high performance liquid chromatography: area percent) and a melting point of 118 ° C. The analysis data of the obtained compound are shown below.

(A) Mass * 1: m / e = 266 (b) NMR * 2: (a) 4.14 ppm 6 H (b) 2.86 to 2.92 ppm 2 H (c) 1.37-1 0.43 ppm 3 H (c) UV-Vis * 3 (λmax * 4): 425 nm (ε * 5): Table 1 (d) Elemental analysis: Table 2

* 1: Mass is an abbreviation for mass spectrum.
The same applies to the following embodiments. * 2: NMR is an abbreviation for proton nuclear magnetic resonance spectrum.
CDCl3 solvent tetramethylsilane standard. * 3: UV-Vis is an abbreviation for ultraviolet-visible absorption spectrum. * 4: λ is the wavelength, λmax is the abbreviation of the maximum absorption wavelength. * 5: ε is an abbreviation for molar extinction coefficient.

Table 1 Peak wavelength (nm) ε 221 14210 250 67000 259 67430 341 2650 360 5220 381 7100 401 6000

Table 2 Element Actual value (% by weight) Calculated value (% by weight) C 81.21 81.16 H 6.83 6.83

Example 2 Synthesis of methanesulfonic acid- (2-methoxyethyl) 1100.0 g of a 25 w% aqueous sodium hydroxide solution was placed in a 2 L four-necked flask and cooled to 5 to 10 ° C. with stirring. To this solution was added 2-methoxyethanol 150.0
g of methanesulfonic acid chloride.
7.1 g was added dropwise over 2 hours while taking care that the temperature of the reaction solution did not exceed 15 ° C. After the dropwise addition of methanesulfonic acid chloride, the mixture was further stirred at 15 ° C. or lower for 4 hours, and 100 g of water cooled to 15 ° C. or lower was added to the solution. The remaining organic layer was washed twice with 300 g of water, dried over anhydrous magnesium sulfate and filtered, and methanesulfonic acid- (2-
(Methoxyethyl) 275.0 g (90.5% yield) was obtained. The obtained methanesulfonic acid- (2-methoxyethyl) was a pale yellow transparent liquid having a specific gravity of 1.27 (25 ° C.), and the purity was 98.0% (high-performance liquid chromatography: area percent). . Table 3 shows the results of the elemental analysis.

Table 3 Element Actual value (% by weight) Calculated value (% by weight) C 31.14 31.15 H 6.56 6.55 S 20.87 20.80

Example 3: 2-ethyl-9,10-di (2
Synthesis of -methoxyethoxy) anthracene To a 200 mL four-necked flask was added 50.0 g of a 30 w% aqueous sodium hydroxide solution, and ethanol 6
0.0 g and 11.8 g of 2-ethylanthraquinone
Was added thereto and dispersed by stirring in a nitrogen stream. Further, 13.1 g of sodium dithionite was added to this solution,
The temperature was raised and the reaction was carried out at 40 to 45 ° C for 2 hours. The solution in which the yellow powder was dispersed turned into a dark red solution. next,
The temperature of this solution was raised to 70 ° C., and 34.7 g of methanesulfonic acid- (2-methoxyethyl) synthesized in Example 2 was obtained.
Was added dropwise over 2.0 hours while paying attention to heat generation. After dropwise addition of methanesulfonic acid- (2-methoxyethyl), the mixture was stirred at 70 to 75 ° C for 1 hour. After cooling, the same post-treatment as in Example 1 was carried out to obtain the desired 2-ethyl-
12.0 g (yield 67.8%) of 9,10-dimethoxyanthracene was obtained. The obtained 2-ethyl-9,10-
Dimethoxyanthracene was a fluorescent yellow powder, having a purity of 98.2% (high performance liquid chromatography: area percent) and a melting point of 52 ° C. The analysis data of the obtained compound are shown below.

(A) Mass: m / e = 354 (B) NMR: (a) 8.13 to 8.35 ppm 4 H (b) 7.32 to 7.47 ppm 3 H (c) 4.30 to 4 0.33 ppm 4 H (d) 3.83 to 3.88 ppm 4 H (e) 3.55 ppm 6 H (f) 2.85 to 2.91 ppm 2 H (g) 1.35 to 1.39 ppm 3 H (c ) UV-Vis (λmax): 420 nm (ε): Table 4 (d) Original analysis: Table 5

Table 4 Peak wavelength (nm) ε 221 15700 252 75000 259 80800 360 6180 381 8170 400 7220

[0042]
Table 5 Element Actual measured value (% by weight) Calculated value (% by weight) C 74.53 74.54 H 7.40 7.41

Synthesis Examples of Other Anthracene Derivatives Using Alkyl Sulfonates Esters of alkyl sulphonates were synthesized in the same manner as in Example 2 and further in the same manner as in Examples 1 and 3. The following anthracene derivative can be synthesized by reacting a compound obtained by reducing an anthraquinone derivative with a dithionite and an alkylsulfonic acid ester.

2-ethyl-9,10-dimethoxyanthracene 2-ethyl-9,10-diethoxyanthracene 9,10-di (n-butoxy) -2-ethylanthracene 2-ethyl-9,10 -Di (2-methoxyethoxy)
Anthracene 2-ethyl-9,10-di (2-ethylthioethoxy) anthracene 2-ethyl-9,10-di (4-t-butylcyclohexyloxy) anthracene 2-ethyl-9,10-di ( 4-methyl-3-pentenyloxy) anthracene 2-ethyl-9,10-dibenzyloxyanthracene 2-tert-butyl-9,10-diethoxyanthracene 2-phenylthio-9,10-dimethoxyanthracene 1 -Chloro-9,10-dimethoxyanthracene 2-dodecyl-9,10-dimethoxyanthracene 2,4-dimethyl-9,10-di (2-hydroxyethyloxy) anthracene 2-ethyl-9,10-di (2-n-butyloxyethyloxy) anthracene

[0045]

As is evident from the above results, the use of dithionite for the reduction of anthraquinones and the further reaction of alkyl sulfonates with
It has become possible to easily synthesize an anthracene derivative having a desired structure. Further, since the synthesis method of the present invention does not use a metal-based reducing agent, the step of recovering the catalyst can be omitted, which is useful as an industrial production method.

Claims (6)

[Claims] 1. A process for producing a 9,10-dietherified anthracene derivative, comprising reducing anthraquinones with a dithionite and reacting an alkylsulfonic acid ester as an alkylating agent. 2. An anthraquinone represented by the formula (1): (Wherein, R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a hydrogen atom, a C1-C12 alkyl group, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a phenyl group, a cyclohexyl group , Hydroxyl, benzyl, cyclohexylmethyl, 1-naphthyl, 2-naphthyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, -OR9, -C
O-R9 or -S-R9 (R9 is a C1-C8 alkyl group, phenyl group, benzyl group, cyclohexyl group, cyclohexylmethyl group, 1-naphthyl group, 2-naphthyl group, 2-hydroxyethyl group, 3-hydroxyethyl group, Either a hydroxypropyl group or a 4-hydroxybutyl group). The method for producing a 9,10-dietherified anthracene derivative according to claim 1, which is a compound represented by the formula: 3. An alkylsulfonic acid ester used as an alkylating agent is represented by the formula (2) R10SO ₃ A (2) wherein R10 is any one of a methyl group, an ethyl group and a trifluoromethyl group; Is a C1-C18 linear or branched alkyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, phenyl group, benzyl group, cyclohexyl group,
A benzoyl group, an allyl group, 1-naphthyl, 2-naphthyl, 4-tert-butylcyclohexyl group, 4-methyl-3-pentenyl _{group, - (CH 2) 1 X} , - ((CH
_{2) m O) n Y,} - (CH (CH 3) CH 2 O) n Y, - (C
H ₂ ) _m O (CH ₂ ) _n OY (where m ≠ n),
— (CH ₂ ) ₁ —S—Z (wherein X is any one of a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a cyclohexyl group, a 1-naphthyl group and a 2-naphthyl group, and Y is A C12 alkyl group, a 2-hydroxyethyl group,
3-hydroxypropyl group, 4-hydroxybutyl group,
A phenyl group, a benzyl group, a 2-phenylethyl group, a cyclohexyl group, a cyclohexylmethyl group, a benzoyl group, an allyl group, a 1-naphthyl group or a 2-naphthyl group, and Z represents a C1 to C12 alkyl group; Group, benzyl group, 2-phenylethyl group, cyclohexyl group, cyclohexylmethyl group, benzoyl group,
An allyl group, a 1-naphthyl group or a 2-naphthyl group, 1 is an integer of 1 to 8, m is an integer of 2 to 4, n
Is an integer of 1 to 4. ). 9. The compound according to claim 1 or 2, which is a compound represented by the formula:
A method for producing a 10-dietherified anthracene derivative. 4. The alkyl sulfonic acid ester represented by the formula (2), wherein A is a C1-C4 linear or branched alkyl group or a 2-methoxyethyl group. 9, 10 according to any one of
-A method for producing a dietherified anthracene derivative. 5. An anthraquinone represented by the formula (1):
The method for producing a 9,10-dietherified anthracene derivative according to any one of claims 1 to 4, which is 2-ethylanthraquinone. 6. The method for producing a 9,10-dietherified anthracene derivative according to any one of claims 1 to 5, wherein the dithionite is sodium dithionite.