JP2761178B2 - Method for producing acylated aromatic compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an acylated aromatic compound, and to an acylated aromatic compound comprising an aromatic compound and an acylating agent in an efficient manner in the presence of a Lewis acid catalyst. The present invention relates to a method for producing a group III compound.

According to the present invention, quinizarin, 5,6,6
7,8-tetrafluoroquinizarin, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone, 1-amino-
Anthraquinone-based compounds such as 3-hydroxyanthraquinone can be efficiently produced.

[0003] These anthraquinones are useful for producing raw materials for pigments, dyes, medicines, agricultural chemicals, polymer materials and the like, or for producing hydrogen peroxide.

According to the present invention, an o-benzoylbenzoic acid compound can be produced from an aromatic compound and a phthalic anhydride compound.

[0005] An o-benzoylbenzoic acid compound is useful as an intermediate of anthraquinone compound or as an ultraviolet absorber.

According to the present invention, for example, a benzophenone compound, an acetophenone compound or the like can be produced from an aromatic compound and a carboxylic acid halide such as benzoyl chloride or acetyl chloride or a carboxylic anhydride such as acetic anhydride.

These benzophenone compounds and acetophenone compounds are useful as flavoring agents, solvents for cellulose and ester resins, raw materials for pharmaceutical synthesis, flavoring agents, and ultraviolet absorbers.

[0008]

2. Description of the Related Art A reaction for synthesizing an aromatic compound by alkylating an aromatic compound with an alkylating agent such as an alkyl halide or an olefin compound in the presence of a Lewis acid catalyst such as aluminum chloride, or The reaction of acylating with an acylating agent such as an acid chloride or an acid anhydride in the presence of a Lewis acid catalyst such as aluminum chloride to synthesize an acylated aromatic compound such as anthraquinone or an aromatic ketone is carried out by Friedel Crafts. Known as a reaction.

It is generally well known that in these alkylation reactions by the Friedel-Crafts reaction, a homogeneous reaction can be performed using a nitro compound such as nitrobenzene as a solvent. On the other hand, in the acylation reaction, the solvent itself often participates in the reaction, and examples of using the solvent for reasons such as causing an alkylation or heterogeneous reaction are used only in limited reactions.

In particular, quinizarin, 5,6,7,8-tetrafluoroquinizarin, 2-chloroanthraquinone, 2-chloroanthraquinone,
Methylanthraquinone, 2-ethylanthraquinone, 2
-The reaction temperature for producing anthraquinone-based compounds such as amylanthraquinone and 1-amino-3-hydroxyanthraquinone in one step requires a relatively high temperature, so that the explosive reaction between the nitro compound and aluminum chloride may occur. There was almost no use of an organic solvent due to the problem of occurrence or complicated side reactions such as heterogeneous reaction, and the problem of easy tar formation.

Therefore, in particular, in the method for producing dihydroxyanthraquinone from hydroquinone and phthalic anhydride, both the acylating agent and the aromatic compound are solid substances at room temperature.
-Crafts and related react
ions 3 Vol. 974-975 New York
k: Interscience Publishing 1965,
As described in JP-B-63-34141, aluminum chloride is appropriately mixed with sodium chloride and reacted under molten salt conditions. However, since these molten salts precipitate without melting at room temperature, there is a problem that a troublesome operation is required for their handling or intermediates, and separation from the target substance. This method was difficult to use as an industrial production method.

Alternatively, for example, as described in Dye Chemistry, Yutaka Hosoda, p. 552: Gihodo Shuppan, 1957, the synthesis of 2-chloroanthraquinone requires the conversion of phthalic anhydride and chlorobenzene first. It requires a two-step reaction of synthesizing o- (4-chloro) benzoylbenzoic acid in the presence of aluminum, isolating it, and then performing a dehydration reaction using fuming sulfuric acid. On page 562 of the same book, quinizarin is synthesized from phthalic anhydride and p-chlorophenol in concentrated sulfuric acid. However, concentrated sulfuric acid is troublesome to handle and has a problem in treating a large amount of waste liquid after use.

[0013]

SUMMARY OF THE INVENTION The present invention has been made by paying attention to the problem of the acylation reaction by the conventional Friedel-Crafts method.

That is, the present invention relates to an aromatic compound and a phthalic anhydride compound, for example, anthraquinone, quinizarin, 5,6,7,8-tetrafluoroquinizarin, 2-chloroanthraquinone, 2-methylanthraquinone , 2-ethylanthraquinone, 2-amylanthraquinone, 1-amino-3-hydroxyanthraquinone and the like have a problem as a solvent without isolating o-benzoylbenzoic acid as an intermediate. Providing a method that can perform a homogeneous reaction without using a molten salt or concentrated sulfuric acid, to obtain anthraquinones with high yield and high purity, and to eliminate troublesome operation by a reaction like the conventional method. It is intended to provide an industrially inexpensive manufacturing method that can be performed. The present invention also provides a method for producing a high-yield, high-purity acylated compound with few side reactions in all acylation reactions.

[0015]

The present invention relates to a method for producing an acylated aromatic compound, which comprises reacting an aromatic compound with an acylating agent in a nitrile solvent in the presence of a Lewis acid catalyst. is there.

That is, in the present invention, by reacting an aromatic compound with an acylating agent in the presence of a Lewis acid catalyst in a nitrile solvent, the catalyst, starting materials, The inventors have found that since the reaction product can be uniformly dissolved in a solvent, the side reaction is reduced without using a molten salt, and a uniform reaction can be performed at a high yield, thereby completing the present invention.

[0017]

According to the present invention, the reaction is carried out in the presence of a Lewis acid catalyst generally used in the Friedel-Crafts reaction, and these catalysts are generally used in the Friedel-Crafts reaction. Any Lewis acid catalyst can be used. For example, aluminum chloride, zinc chloride,
Examples include ferric chloride, aluminum bromide, tin chloride, antimony chloride, and titanium chloride. In the present invention, it is particularly preferable to use aluminum chloride.

The nitrile solvent used in the present invention includes, for example, aromatic nitriles such as benzonitrile, tolunitrile, and acetonitrile, and saturated fatty acid nitrile, and particularly preferably benzonitrile.

The method for producing an acylated aromatic compound of the present invention can be applied to any acylation reaction. As the acylating agent used at that time, for example, carboxylic acid halides such as acetyl chloride, malonyl chloride, benzoyl chloride, phthaloyl chloride, phthalic anhydride, naphthalene 1,2-dicarboxylic anhydride, maleic anhydride, succinic anhydride, anhydride Acid anhydrides such as acetic acid, and those carboxylic acids and acid anhydrides having a benzene ring on the ring of a halogen atom, a hydroxy group, an amino group, an alkyl group, an alkoxy group, a phenoxy group, an acyloxy group, an acylamino group, etc. Those having a substituent are mentioned. Examples of the aromatic compound include benzene, naphthalene, anthracene, phenanthrene, and compounds having an electron-donating group such as a hydroxy group, an amino group, an alkyl group, an alkoxy group, an acyloxy group, or an acylamino group on these rings.

By using these acylating agents and aromatic compounds, the present invention provides (1) a reaction of benzenes and acid anhydrides at a temperature of 50 to 100 ° C. to synthesize benzoyl organic acids; And maleic anhydride from β
-Synthesis of benzoylacrylic acid, synthesis of β-benzoylpropionic acid from benzene and succinic acid, synthesis of orthobenzoylbenzoic acids from benzenes and phthalic anhydrides, (2) aromatic compounds and phthalic anhydrides from 120 to 25
Reacting in a temperature range of 0 ° C. to synthesize anthraquinones;
For example, synthesis of anthraquinones from benzenes and phthalic anhydride, synthesis of 1-hydroxyanthraquinones from phenols and phthalic anhydrides, synthesis of quinizarins from hydroquinones and phthalic anhydrides, synthesis of quinizarins from phenols and phthalic anhydrides Synthesis of 3-amino-1-hydroxyanthraquinones, synthesis of 6,7-benz-1,2-dihydroxynaphthalenes from naphthalene 1,2-dicarboxylic anhydrides and hydroquinones or 1,4-dimethoxybenzenes , (3) reacting phenols with phthalic anhydrides to synthesize phenolphthalenes,
(4) Any acylation reaction such as synthesis of benzophenone compounds and acetophenone compounds by reacting benzenes with carboxylic acid halides such as benzoyl chloride and acetyl chloride or carboxylic anhydrides such as acetic anhydride in the range of 50 to 100 ° C. Can be applied to

In the course of these reactions, the present invention is effective for using the synthesis of anthraquinones from the aromatic compound of the group (2) and phthalic anhydride for the production of acylation in which a cyclization reaction is carried out in a single step. It is particularly preferable because it exerts an effect.

In particular, according to the present invention, an acylated aromatic compound as a target substance is represented by the following general formula (1):

[0023]

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(However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ may be each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxy group, an alkoxy group having 1 to 8 carbon atoms, or may be substituted Phenoxy group, acetyloxy group, benzoyloxy group, optionally substituted phenylthio group, amino group, alkylamino group having 1 to 8 carbon atoms, optionally substituted anilino group, optionally substituted Represents a dianilino group, an acetylamino group or a benzoylamino group. ) Is an anthraquinone compound represented by the formula:
The aromatic compound has the following general formula (2)

[0025]

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(Where R ¹ , R ² , R ³ and R ⁴ are
Each independently a hydrogen atom, a halogen atom, 1 to 8 carbon atoms
Alkyl groups, hydroxy groups, alkoxy groups having 1 to 8 carbon atoms, optionally substituted phenoxy groups, acetyloxy groups, benzoyloxy groups, optionally substituted phenylthio groups, amino groups, carbon atoms Represents an alkylamino group having 1 to 8 atoms, an anilino group which may be substituted, a dianilino group which may be substituted, an acetylamino group or a benzoylamino group. And an acylating agent represented by the following general formula (3)

[0027]

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(Where R ⁵ , R ⁶ , R ⁷ and R ⁸ are
Each independently a hydrogen atom, a halogen atom, 1 to 8 carbon atoms
Alkyl groups, hydroxy groups, alkoxy groups having 1 to 8 carbon atoms, optionally substituted phenoxy groups, acetyloxy groups, benzoyloxy groups, optionally substituted phenylthio groups, amino groups, carbon atoms Represents an alkylamino group having 1 to 8 alkyl groups, an anilino group which may be substituted, a dianilino group which may be substituted, an acetylamino group or a benzoylamino group, and X and Y each independently represent -OH or X; Y is bonded to -O-. ) Is preferably used for the production in which the phthalic acid compound is cyclized in one step.

In the general formula (1), R ¹ , R ² , R ³ ,
Examples of the halogen atom of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom and a chlorine atom are preferred. As an alkyl group having 1 to 8 carbon atoms,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, straight or branched pentyl, straight or branched hexyl, straight or branched heptyl, straight or Examples include a branched octyl group.

Examples of the optionally substituted phenoxy group include a phenoxy group, a 2-chlorophenoxy group,
2,6-dichlorophenoxy group, 3-chlorophenoxy group, 4-chlorophenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, Examples thereof include a 4-methylphenoxy group, a 2-methoxyphenoxy group, a 3-methoxyphenoxy group, and a 4-methoxyphenoxy group. Examples of the optionally substituted phenylthio group include a phenylthio group, a 2-chlorophenylthio group, a 2,6-dichlorophenylthio group,
Chlorophenylthio group, 4-chlorophenylthio group, 2
-Fluorophenylthio group, 3-fluorophenylthio group, 4-fluorophenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 3- Examples thereof include a methoxyphenylthio group and a 4-methoxyphenylthio group. As the anilino group which may be substituted,
For example, phenylamino, 2-chlorophenylamino, 2,6-dichlorophenylamino, 3-chlorophenylamino, 4-chlorophenylamino, 2-fluorophenylamino, 3-fluorophenylamino, 4-fluorophenylamino Group, 2-methylphenylamino group, 3-methylphenylamino group, 4-methylphenylamino group, 2-methoxyphenylamino group, 3
-Methoxyphenylamino group, 4-methoxyphenylamino group and the like.

In the general formula (2), R ¹ , R ² , R
A halogen atom in ³ and R ⁴ , an alkyl group having 1 to 8 carbon atoms, a hydroxy group, a phenoxy group which may be substituted, a phenylthio group which may be substituted, an amino group, which may be substituted The anilino group has the general formula (1)
Is the same as Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tertiary butoxy group, a linear or branched pentyloxy group,
A straight or branched hexyloxy group, a straight or branched heptyloxy group, a straight or branched octyloxy group are exemplified. Examples of the alkylamino group having 1 to 8 carbon atoms include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a tertiarybutylamino group,
Examples include a linear or branched pentylamino group, a linear or branched hexylamino group, a linear or branched heptylamino group, and a linear or branched octylamino group.

In the general formula (3), R ⁵ , R ⁶ , R
In ⁷ and R ^8, a halogen atom, 1-8 alkyl group carbon atoms, hydroxy group, a 1-8C alkoxy group having a carbon atom, an optionally substituted phenoxy group, acetyloxy group, benzoyloxy Group, an optionally substituted phenylthio group, an amino group, an alkylamino group having 1 to 8 carbon atoms, an optionally substituted anilino group,
The acetylamino group or the benzoylamino group is the same as R ¹ , R ² , R ³ and R ⁴ in the general formula (2).

A reaction example of synthesizing the acylated aromatic compound represented by the general formula (1) from the aromatic compound represented by the general formula (2) and the phthalic anhydride compound represented by the general formula (3) is described below. For example, anthraquinone is synthesized from benzene and phthalic anhydride; 1-chloroanthraquinone is synthesized from benzene and 3-chlorophthalic anhydride; 2-chloroanthraquinone is synthesized from benzene and 4-chlorophthalic anhydride. -Synthesis of 2-fluoroanthraquinone from benzene and 4-fluorophthalic anhydride-Synthesis of 2-fluoroanthraquinone from benzene and tetrachlorophthalic anhydride
Synthesis of 2,3,4-tetrachloroanthraquinone, from benzene and tetrafluorophthalic anhydride,
Synthesis of 2,3,4-tetrafluoroanthraquinone, 2-hydroxy-1,3,4-benzene and benzene and 4-hydroxy-3,5,6-trifluorophthalic anhydride
Synthesis of trifluoroanthraquinone, 2-hydroxy-1,3,3 from benzene and 4-acetyloxy-3,5,6-trifluorophthalic anhydride
Synthesis of 4-trifluoroanthraquinone, 2-hydroxy-1,2-hydroxy-1,4-benzoyloxy-3,5,6-trifluorophthalic anhydride
Synthesis of 3,4-trifluoroanthraquinone, 2-phenoxy-1,3,4-benzene and 4-phenoxy-3,5,6-trifluorophthalic anhydride
Synthesis of trifluoroanthraquinone;-Synthesis of 2-anilino-1,3,4-trifluoroanthraquinone from benzene and 4-anilino-3,5,6-trifluorophthalic anhydride; 6-dichloroanilino)-
3,5,6-trifluorophthalic anhydride and 2-
Synthesis of (2,6-dichloroanilino) -1,3,4-trifluoroanthraquinone, benzene and 4- (2,6-dimethylanilino)-
3,5,6-trifluorophthalic anhydride and 2-
Synthesis of (2,6-dimethylanilino) -1,3,4-trifluoroanthraquinone, 2-phenylthio-1,3,3 from benzene and 4-phenylthio-3,5,6-trifluorophthalic anhydride
Synthesis of 4-trifluoroanthraquinone;-Synthesis of 2-amino-1,3,4-trifluoroanthraquinone from benzene and 4-amino-3,5,6-trifluorophthalic anhydride;-Benzene and 4-acetyl From amino-3,5,6-trifluorophthalic anhydride, 2-amino-1,3,4-
Synthesis of trifluoroanthraquinone, 2-amino-1,3,4 from benzene and 4-benzoylamino-3,5,6-trifluorophthalic anhydride
-Synthesis of trifluoroanthraquinone,-Synthesis of 2-chloroanthraquinone from chlorobenzene and phthalic anhydride,-Synthesis of 2-methylanthraquinone from toluene and phthalic anhydride,-2-Ethylanthraquinone from ethylbenzene and phthalic anhydride. Synthesis of tertiary butylanthraquinone from tertiary butylbenzene and phthalic anhydride; Synthesis of n-amylanthraquinone from n-amylbenzene and phthalic anhydride; and Tertiary-amylbenzene and phthalic anhydride. Synthesis of 2 (tert-amyl) anthraquinone from catechol and phthalic anhydride; Synthesis of 2,3-dihydroxyanthraquinone from catechol and phthalic anhydride
Synthesis of hydroxyanthraquinone, 2 from benzoyloxybenzene and phthalic anhydride
-Synthesis of 5-hydroxy-2,3-dihydroxyanthraquinone from catechol and 3-chlorophthalic anhydride 6-chloro-2,3-dihydroxy from catechol and 4-chlorophthalic anhydride Synthesis of anthraquinone, • Synthesis of 2,3-dihydroxy-5,8-dichloroanthraquinone from catechol and 3,6-dichlorophthalic anhydride, • 2,3-Dihydroxy from catechol and 4,5-dichlorophthalic anhydride Synthesis of -6,7-dichloroanthraquinone, from catechol and tetrachlorophthalic anhydride,
Synthesis of 3-dihydroxy-5,6,7,8-tetrachloroanthraquinone; synthesis of 2,3-dihydroxy-5,6,7,8-tetrafluoroanthraquinone from catechol and tetrafluorophthalic anhydride; 2,3,6-trihydroxy-5,7,8-trifluoroanthraquinone is synthesized from 4-hydroxy-3,5,6-trifluorophthalic anhydride and catechol and 4-phenoxy-3,5 6-trifluorophthalic anhydride and 2,3-dihydroxy-6-
Synthesis of phenoxy-5,7,8-trifluoroanthraquinone, 2,3-dihydroxy-6-anilino-5,7,8- from catechol and 4-anilino-3,5,6-trifluorophthalic anhydride Synthesis of trifluoroanthraquinone, catechol and 4- (2,6-dichloroanilino)-
From 3,5,6-trifluorophthalic anhydride and 2,3-
Dihydroxy-6- (2,6-dichloroanilino)-
Synthesis of 5,7,8-trifluoroanthraquinone, Catechol and 4- (2,6-dimethylanilino)-
From 3,5,6-trifluorophthalic anhydride and 2,3-
Dihydroxy-6- (2,6-dimethylanilino)-
Synthesis of 5,7,8-trifluoroanthraquinone, 2,3-dihydroxy-6 from catechol and 4-phenylthio-3,5,6-trifluorophthalic anhydride
Synthesis of -phenylthio-5,7,8-trifluoroanthraquinone; 2,3-dihydroxy-6-amino-5,7,8 from catechol and 4-amino-3,5,6-trifluorophthalic anhydride -Synthesis of trifluoroanthraquinone,-2,3-dihydroxy- from catechol and 4-acetylamino-3,5,6-trifluorophthalic anhydride
Synthesis of 6-amino-5,7,8-trifluoroanthraquinone, catechol and 4-benzoylamino-3,5,6-
Synthesis of 2,3-dihydroxy-6-amino-5,7,8-trifluoroanthraquinone from trifluorophthalic anhydride; Synthesis of quinizarin from hydroquinone and phthalic anhydride; Hydroquinone and 3-chlorophthalic anhydride From 5
-Synthesis of chloroquinizarin, 6 from hydroquinone and 4-chlorophthalic anhydride
-Synthesis of chloroquinizarin,-Synthesis of 5,8-dichloroquinizarin from hydroquinone and 3,6-dichlorophthalic anhydride-6,7-Dichloroquiniza from hydroquinone and 4,5-dichlorophthalic anhydride Synthesis of phosphorus, • Synthesis of 5,6,7,8-tetrachloroquinizarin from hydroquinone and tetrachlorophthalic anhydride, • Synthesis of 5,6,7,8-tetrafluoroquinini from hydroquinone and tetrafluorophthalic anhydride Synthesis of zaline, 6-hydroxy-5 from hydroquinone and 4-hydroxy-3,5,6-trifluorophthalic anhydride
Synthesis of 7,8-trifluoroquinizarin, 6-phenoxy-5 from hydroquinone and 4-phenoxy-3,5,6-trifluorophthalic anhydride
Synthesis of 7,8-trifluoroquinizarin, 6-anilino-5,7,8 from hydroquinone and 4-anilino-3,5,6-trifluorophthalic anhydride
-Synthesis of trifluoroquinizarin, 6 from hydroquinone and 4- (2,6-dichloroanilino) -3,5,6-trifluorophthalic anhydride
Synthesis of-(2,6-dichloroanilino) -5,7,8-trifluoroquinizarin, hydroquinone and 4- (2,6-dimethylanilino) -3,5,6-trifluorophthalic anhydride And from 6
-(2,6-Dimethylanilino) -5,7,8-trifluoroquinizarin was synthesized. Hydroquinone and 4-phenylthio-3,5,6-
Trifluorophthalic anhydride and 6-phenylthio-
Synthesis of 5,7,8-trifluoroquinizarin;-Synthesis of 6-amino-5,7,8-trifluoroquinizarin from hydroquinone and 4-amino-3,5,6-trifluorophthalic anhydride;・ Hydroquinone and 4-acetylamino-3,5,6
-Trifluorophthalic anhydride and 6-amino-5
Synthesis of 7,8-trifluoroquinizarin,-Hydroquinone and 4-benzoylamino-3,5
6-trifluoro-5-phthalic anhydride and 6-amino-5
Synthesize 7,8-trifluoroquinizarin, ・ Synthesize quinizarin from 1,4-dimethoxybenzene and phthalic anhydride, ・ 1-hydroxy-4-methyl from 1-methoxy-4-methylbenzene and phthalic anhydride Synthesis of anthraquinone, Synthesis of 5-chloroquinizarin from 1,4-dimethoxybenzene and 3-chlorophthalic anhydride, Synthesis of 6-chloroquinizarin from 1,4-dimethoxybenzene and 4-chlorophthalic anhydride, 1 Synthesis of 5,8-dichloroquinizarin from 1,4-dimethoxybenzene and 3,6-dichlorophthalic anhydride; 6,7- from 1,4-dimethoxybenzene and 4,5-dichlorophthalic anhydride Synthesis of dichloroquinizarine, 5,6,7,8-tetrachloro-1,4-dimethoxybenzene and tetrachlorophthalic anhydride Synthesis of loroquinizarin, ・ Synthesis of 5,6,7,8-tetrafluoroquinizarin from 1,4-dimethoxybenzene and tetrafluorophthalic anhydride, ・ 1-methoxy-4-methylbenzene and tetrafluorophthalic anhydride And 1-hydroxy-4-methyl-
Synthesis of 5,6,7,8-tetrafluoroanthraquinone, 1,4-dimethoxybenzene and 4-hydroxy-
Synthesis of 6-hydroxy-5,7,8-trifluoroquinizarin from 3,5,6-trifluorophthalic anhydride; 1,4-dimethoxybenzene and 4-phenoxy-
6-phenoxy-5,7,8-trifluoroquinizarin is synthesized from 3,5,6-trifluorophthalic anhydride; 1,4-dimethoxybenzene and 4-anilino-3,
6-anilino-5,7,8-trifluoroquinizarin is synthesized from 5,6-trifluorophthalic anhydride, 1,4-dimethoxybenzene and 4- (2,6-dichloroanilino) -3, 5,6-trifluorophthalic anhydride and 6- (2,6-dichloroanilino) -5,7,
Synthesis of 8-trifluoroquinizarin, 6- (2,6-dimethyl) from 1,4-dimethoxybenzene and 4- (2,6-dimethylanilino) -3,5,6-trifluorophthalic anhydride Anilino) -5,7,
Synthesis of 8-trifluoroquinizarin, 1,4-dimethoxybenzene and 4-phenylthio-
6-phenylthio-5,7,8-trifluoroquinizarin is synthesized from 3,5,6-trifluorophthalic anhydride; 1,4-dimethoxybenzene and 4-amino-3,
5,6-trifluorophthalic anhydride and 6-amino-
Synthesis of 5,7,8-trifluoroquinizarin-Synthesis of 4-amino-1-hydroxyanthraquinone from 4-aminophenol and phthalic anhydride-Synthesis of 4-aminophenol and 3-chlorophthalic anhydride Synthesis of 4-amino-5-chloro-1-hydroxyanthraquinone; Synthesis of 4-amino-6-chloro-1-hydroxyanthraquinone from 4-aminophenol and 4-chlorophthalic anhydride; Synthesis of 4-amino-1-hydroxy-5,8-dichloroanthraquinone from toluene and 3,6-dichlorophthalic anhydride; 4-amino-1 from 4-aminophenol and 4,5-dichlorophthalic anhydride Synthesis of -hydroxy-6,7-dichloroanthraquinone, from 4-aminophenol and tetrachlorophthalic anhydride Amino-1-hydroxy-5,6,7,8
Synthesis of tetrachloroanthraquinone, 4-amino-1-hydroxy-5,6,7,8 from 4-aminophenol and tetrafluorophthalic anhydride
Synthesis of tetrafluoroanthraquinone, 4-aminophenol and 4-hydroxy-3,5,
6-trifluorophthalic anhydride and 4-amino-1,
Synthesis of 6-dihydroxy-5,7,8-trifluoroanthraquinone; 4-aminophenol and 4-phenoxy-3,5
6-trifluorophthalic anhydride and 4-amino-1-
Synthesis of hydroxy-6-phenoxy-5,7,8-trifluoroanthraquinone, 4-aminophenol and 4-anilino-3,5,6
-Synthesis of 4-amino-1-hydroxy-6-anilino-5,7,8-trifluoroanthraquinone from trifluorophthalic anhydride; 4-aminophenol and 4- (2,6-dichloroanilino)- Synthesis of 4-amino-1-hydroxy-6- (2,6-dichloroanilino) -5,7,8-trifluoroanthraquinone from 3,5,6-trifluorophthalic anhydride; 4-aminophenol And 4- (2,6-dimethylanilino) -3,5,6-trifluorophthalic anhydride to form 4-amino-1-hydroxy-6- (2,6-dimethylanilino) -5,7, Synthesis of 8-trifluoroanthraquinone, 4-aminophenol and 4-phenylthio-3,
5,6-trifluorophthalic anhydride and 4-amino-
Synthesis of 1-hydroxy-6-phenylthio-5,7,8-trifluoroanthraquinone; Synthesis of 4-amino-1-hydroxyanthraquinone from 4- (N-acetylamino) phenol and phthalic anhydride; Synthesis of 4-amino-1-hydroxyanthraquinone from (N-benzoylamino) phenol and phthalic anhydride, 4-amino-1 from 4- (N-acetylamino) -1-acetyloxybenzene and phthalic anhydride Synthesis of 4-hydroxyanthraquinone, 4- (N-benzoylamino) -1-benzoyloxybenzene and phthalic anhydride to synthesize 4-amino-1-hydroxyanthraquinone, 4- (N-acetylaminophenol) and 3 Chlorophthalic anhydride and 4-amino-5-chloro-1-hydroxyanthra Synthesis of quinone, 4-amino-1-hydroxy- from 4- (N-acetylaminophenol) and tetrachlorophthalic anhydride
Synthesis of 5,6,7,8-tetrachloroanthraquinone, 4-amino-1-hydroxy-5,6,7,8-tetrafluoro from 4- (N-acetylaminophenol) and tetrafluorophthalic anhydride Synthesis of anthraquinone.

The present invention is a process for producing an acylated aromatic compound, which comprises reacting an aromatic compound with an acylating agent in a nitrile solvent in the presence of a Lewis acid catalyst.

In the present invention, among the aromatic compounds, aqueous phthalic acid is easily dehydrated during the reaction and is converted into phthalic anhydride. Therefore, it is possible to use aqueous phthalic acid instead of phthalic anhydrides. I do not care.

The amount of the acylating agent based on the starting aromatic compound is in the range of 0.1 to 5 mol per 1 mol of the aromatic compound,
Preferably, it is used in the range of 0.8 to 1.5 mol.

The amount of the Lewis acid catalyst used in the present invention varies depending on the starting aromatic compound, the starting acylating agent and the type of the catalyst, and cannot be specified uniformly.
It is preferably used in an amount of 1 to 10 moles, particularly 3 to 8 moles per mole. That is, if the amount is too small, the reaction rate decreases, and if the amount is too large, the cost of waste liquid treatment increases, which is not preferable.

The amount of the nitrile solvent used can be up to 6 times the weight of the Lewis acid catalyst by weight. When the amount exceeds 6 times, no improvement in yield is observed, which is disadvantageous.

The reaction temperature in the present invention varies depending on the type of the starting aromatic compound, the starting acylating agent and the catalyst and cannot be uniformly defined, but is usually in the range of 0 to 300 ° C. In general, the higher the reaction temperature is, the higher the reaction rate is. However, if the reaction temperature is too high, a side reaction occurs to lower the product yield. Further, there arises a problem that the control of the reaction becomes difficult. For example, (1) The reaction temperature for synthesizing benzoyl organic acids from benzenes and acid anhydrides is preferably 50 to 150 ° C.
Range.

(2) The reaction temperature for synthesizing anthraquinones from an aromatic compound and phthalic anhydride is preferably in the range of 120 to 250 ° C.

(3) The reaction temperature for synthesizing phenolphthalenes from phenols and phthalic anhydrides is preferably in the range of 50 to 150 ° C.

(4) The reaction temperature for synthesizing a benzophenone compound or an acetophenone compound from benzene and a carboxylic acid halide or carboxylic anhydride is preferably in the range of 50 to 150 ° C.

On the other hand, the reaction time varies depending on the reaction temperature, but usually about 1 to 15 hours is sufficient.

[0044]

EXAMPLES The present invention will be described more specifically with reference to the following examples.

Example 1 Synthesis of 5,6,7,8-tetrafluoroquinizarine In a 300 cc four-necked flask, 20 g (0.091 mol) of 3,4,5,6-tetrafluorophthalic anhydride and 1 ,
15.1 g (0.109 mol) of 4-dimethoxybenzene
And 70 g (0.525 mol) of anhydrous aluminum chloride, and 150 cc of benzonitrile was added thereto while cooling with water.
For a minute. After that, it takes 190 to 196 ° C for about 2 hours.
The temperature was raised to 190 to 196 ° C. for about 3 hours.
After completion of the reaction, the mixture was cooled to room temperature, and the obtained homogeneous solution was gradually added to a mixed solution of about 250 cc of an aqueous hydrochloric acid solution and about 500 cc of methanol to precipitate. The precipitate was separated by filtration and washed with water to give 5,6,7,8-tetrafluoroquinizarin 2
5.9 g were obtained. Table 1 shows the results.

[0046]

[Table 1]

Examples 2 to 13 The following acylated aromatic compounds were prepared in the same manner as in Example 1 except that the starting materials, the charge ratio and the reaction time were changed as shown in Table 1. Was synthesized.
Table 1 shows the results.

Example 14 10 g of maleic anhydride was placed in a 300 cc four-necked flask.
(0.102 mol), 9.6 g (0.12 mol) of benzene and 50 g (0.375 mol) of anhydrous aluminum chloride
And add 100 cc of benzonitrile under water cooling to about 3
Stirred for 0 minutes. Thereafter, the temperature was raised to 80 to 85 ° C., and the reaction was carried out for about 5 hours. After completion of the reaction, the mixture was cooled to room temperature, and the obtained homogeneous solution was treated with about 200 cc of aqueous hydrochloric acid solution and about 300 cc of methanol.
The mixed solution of cc was poured little by little to precipitate. After the precipitate was separated by filtration, the precipitate was washed with water and β-benzoylacrylic acid 16.
7 g were obtained (yield 93.1 mol%).

Example 15 In Example 14, the maleic anhydride was replaced with succinic anhydride 1
The same operation as in Example 14 was carried out except that the amount was changed to 0 g (0.10 mol) to obtain 16.7 g of β-benzoylpropionic acid (yield 92.2 mol%).

Example 16 The procedure of Example 14 was repeated, except that maleic anhydride was replaced by 15 g (0.107 mol) of benzoyl chloride, to obtain 17.9 g of benzophenone (yield: 91. 7 mol%).

Example 17 In Example 14, the maleic anhydride was replaced with acetyl chloride 1
13.3 g of acetophenone was operated in the same manner as in Example 14 except that 11.9 g of 0 g (0.127 mol) benzene, the reaction temperature was 55 to 60 ° C., and the reaction time was changed to 12 hours.
Was obtained (yield: 87.2 mol%).

[0052]

According to the present invention, there is provided a method for producing an acylated compound having a high purity and a high yield with few side reactions in the acylation reaction. In particular, according to the present invention, an anthraquinone compound can be obtained from an aromatic compound and a phthalic anhydride compound by a solution reaction in which the reaction can be easily controlled without using a molten salt or using concentrated sulfuric acid as in the conventional method. Is provided in a single step with high yield, high purity and low cost.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 225/34 C07C 225/34 319/20 319/20 323/22 323/22 // C07B 61/00 300 C07B 61/00 300 (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 50/02-50/34 C07C 46/00 C07B 61/00 300 REGISTRY (STN) CA (STN)

Claims (2)

(57) [Claims] 1. The following general formula (2): (However, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxy group, an alkoxy group having 1 to 8 carbon atoms, An optionally substituted phenoxy group, an acetyloxy group, a benzoyloxy group, an optionally substituted phenylthio group, an amino group, an alkylamino group having 1 to 8 carbon atoms, an optionally substituted anilino group, Represents an optionally substituted dianilino group, an acetylamino group or a benzoylamino group) and an aromatic compound represented by the following general formula (3): (However, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxy group, an alkoxy group having 1 to 8 carbon atoms, Phenoxy group, acetyloxy group, which may be
A benzoyloxy group, an optionally substituted phenylthio group, an amino group, an alkylamino group having 1 to 8 carbon atoms, an optionally substituted anilino group, an optionally substituted dianilino group, an acetylamino group or Represents a benzoylamino group, and X and Y are each independently -OH or -O- wherein X and Y are bonded; Wherein the acylating agent is reacted in a nitrile solvent in the presence of a Lewis acid catalyst. (However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxy group An alkoxy group having 1 to 8 carbon atoms, a phenoxy group which may be substituted, an acetyloxy group, a benzoyloxy group, a phenylthio group which may be substituted, an amino group, an alkyl having 1 to 8 carbon atoms An amino group, an anilino group which may be substituted, a dianilino group which may be substituted, an acetylamino group or a benzoylamino group). 2. The method according to claim 1, wherein the Lewis acid catalyst is aluminum chloride.