JPH07118194A - Production of acylated aromatic compound - Google Patents

Abstract

PURPOSE:To obtain a acylated aromatic compound in a high purity and in a high yield in a state little in side reactions by reacting an aromatic compound with an acylating agent in the presence of a Lewis acid catalyst in a nitrile solvent. CONSTITUTION:An aromatic compound of formula I (R<1> to R<4> are H, halogen, 1-8C alkyl, hydroxy, 1-8C alkoxy, phenoxy, acetyloxy, benzoyloxy, phenylthio, amino, etc.,) is reacted with an acylating agent of formula II (R<5> to R<8> are the same as R<1> to R<4>, respectively; X,Y are -OH, or X and Y are combined to each other to form -O-) in the presence of a Lewis acid catalyst (e.g. aluminum chloride) in a nitrile solvent at 0-300 deg.C to obtain the compound of formula III. Anthraquinone compounds useful as raw materials for pigments, dyestuffs, medicines, agricultural chemicals, polymer materials, etc., are obtained from the aromatic compound and phthalic acid anhydride compounds. The reaction can homogeneously be performed without isolating an intermediate, o- benzoylbenzoic acis, and without using a fused salt and concentrated sulfuric acid.

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, which is an efficient method for producing an acylated aromatic compound from an aromatic compound and an acylating agent in the presence of a Lewis acid catalyst. The present invention relates to a method for producing a group compound.

According to the present invention, aromatic compounds and phthalic anhydride compounds are used, for example, quinizarin, 5, 6,
7,8-Tetrafluoroquinizarine, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone, 1-amino-
Anthraquinone compounds such as 3-hydroxyanthraquinone can be efficiently produced.

These anthraquinones are useful as raw materials in pigments, dyes, medicines, agricultural chemicals, polymeric materials, etc., or in the production of hydrogen peroxide.

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

The o-benzoylbenzoic acid type compound is useful as an intermediate of an anthraquinone type compound or as an ultraviolet absorber.

Further, 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 acid anhydride such as acetic anhydride.

These benzophenone compounds and acetophenone compounds are useful as a flavoring agent, a solvent for cellulose and ester resins, a raw material for synthesizing pharmaceuticals, a fragrance, and an ultraviolet absorber.

[0008]

2. Description of the Related Art Alkylation of 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 to synthesize an alkylated aromatic compound, or an aromatic compound The reaction to synthesize an acylated aromatic compound such as anthraquinone or an aromatic ketone by acylating it 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 is Friedel Crafts. It is known as a reaction.

It is generally well known that in the alkylation reaction by these Friedel-Crafts reaction, a homogeneous reaction can be carried out 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 are used only in a limited number of reactions because of causing alkylation or heterogeneous reaction.

Particularly from aromatic compounds and phthalic anhydride compounds, for example, quinizarine, 5,6,7,8-tetrafluoroquinizarine, 2-chloroanthraquinone, 2-
Methyl anthraquinone, 2-ethyl anthraquinone, 2
-The reaction temperature for producing the anthraquinone-based compound such as amylanthraquinone and 1-amino-3-hydroxyanthraquinone in a single step requires a relatively high temperature, so that an explosive reaction between a nitro compound and aluminum chloride may occur. There are almost no examples of using organic solvents because they have a problem of occurrence or a complicated side reaction such as a heterogeneous reaction and are liable to tar.

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

Alternatively, for example, as described in Dye Chemistry, Yutaka Hosoda, p. 552: Gihodo Publishing, 1957, first, in order to synthesize 2-chloroanthraquinone, first, chlorination was carried out from phthalic anhydride and chlorobenzene. 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. Also, 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 difficult to handle and has a problem in treating a large amount of waste liquid after use.

[0013]

The present invention has been made by focusing on the problems of the acylation reaction by the conventional Friedel-Crafts method.

That is, according to the present invention, an aromatic compound and a phthalic anhydride compound are used, for example, anthraquinone, quinizarin, 5,6,7,8-tetrafluoroquinizarin, 2-chloroanthraquinone, and 2-methylanthraquinone. , 2-ethylanthraquinone, 2-amylanthraquinone, 1-amino-3-hydroxyanthraquinone and other anthraquinone compounds have problems as a solvent without isolating intermediate o-benzoylbenzoic acid. By providing a method capable of performing a homogeneous reaction without using a molten salt or concentrated sulfuric acid, anthraquinones can be obtained in high yield and high purity, and a troublesome operation due to a reaction like a conventional method can be eliminated. The present invention provides an industrially possible and inexpensive manufacturing method. Further, the present invention also provides a method for producing a high-yield, high-purity acylated compound with few side reactions in any acylation reaction.

[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 and an acylating agent in the presence of a Lewis acid catalyst in a nitrile solvent, the catalyst, starting material and The present invention has been completed by discovering that the reaction product can be uniformly dissolved in a solvent, so that a side reaction can be reduced and a uniform reaction can be performed in a high yield without using a molten salt.

[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 thereof 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, benzonitriles, tolunitriles, aromatic nitriles such as acetonitrile and saturated fatty acid nitriles, and benzonitrile is particularly preferable.

The method for producing an acylated aromatic compound of the present invention can be applied to any acylation reaction. Examples of the acylating agent used at that time include carboxylic acid halides such as acetyl chloride, malonyl chloride, benzoyl chloride, and phthaloyl chloride, phthalic anhydride, naphthalene 1,2-dicarboxylic acid anhydride, maleic anhydride, succinic anhydride, and anhydrous. Acid anhydrides such as acetic acid, and halogen atoms, hydroxy groups, amino groups, alkyl groups, alkoxy groups, phenoxy groups, acyloxy groups, acylamino groups, etc. on the ring of those having a benzene ring in these carboxylic acids and acid anhydrides. The thing which has a substituent is mentioned. Examples of aromatic compounds 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, and an acylamino group on the ring thereof.

According to the present invention, by using these acylating agent and aromatic compound, (1) benzenes and acid anhydrides are reacted in a temperature range of 50 to 100 ° C. to synthesize benzoyl organic acids; And maleic anhydride from β
-Synthesis of benzoyl acrylic acid, synthesis of β-benzoyl propionic acid from benzene and succinic acid, synthesis of orthobenzoyl benzoic acid from benzene and phthalic anhydride, (2) 120 to 120% of aromatic compound and phthalic anhydride 25
Synthesis of anthraquinones by reaction in the temperature range of 0 ° C;
For example, synthesis of anthraquinones from benzenes and phthalic anhydride, synthesis of 1-hydroxyanthraquinones from phenols and phthalic anhydrides, synthesis of quinizarines from hydroquinones and phthalic anhydrides, 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) Reaction of phenols with phthalic anhydride to synthesize phenolphthalenes,
(4) Benzyl chloride, carboxylic acid halides such as acetyl chloride or carboxylic acid anhydrides such as acetic anhydride are reacted in the range of 50 to 100 ° C. to synthesize benzophenone compounds and acetophenone compounds, and all acylation reactions. Can be applied to.

Among these reactions, the present invention is effective for use in the production of acylation in which the synthesis of anthraquinones from the aromatic compounds of the group (2) and phthalic anhydride is carried out in a single step. It is particularly preferable because it exerts an action.

Particularly, in the present invention, the acylated aromatic compound which is a target substance is represented by the following general formula (1):

[0023]

[Chemical 4]

(However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ are 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 It represents a dianilino group, an acetylamino group or a benzoylamino group. ) Is an anthraquinone compound represented by
The aromatic compound is represented by the following general formula (2)

[0025]

[Chemical 5]

(However, R ¹ , R ² , R ³ and R ⁴ are
Each independently a hydrogen atom, a halogen atom, and 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 It represents an alkylamino group of the number 1 to 8, an optionally substituted anilino group, an optionally substituted dianilino group, an acetylamino group or a benzoylamino group. ) Is an aromatic compound represented by the following general formula (3)

[0027]

[Chemical 6]

(However, R ⁵ , R ⁶ , R ⁷ and R ⁸ are
Each independently a hydrogen atom, a halogen atom, and 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 A number 1 to 8 alkylamino group, an optionally substituted anilino group, an optionally substituted dianilino group, an acetylamino group or a benzoylamino group, wherein X and Y are each independently -OH or X; Y is bonded to form -O-. It is preferable to use it for the production in which the phthalic acid compound represented by the formula (1) is cyclized in one step.

R ¹ , R ² , R ³ in the general formula (1),
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 preferable. As the alkyl group having 1 to 8 carbon atoms,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or Examples include branched octyl groups.

Examples of the phenoxy group which may be substituted 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, 4-methylphenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group and the like can be mentioned. Examples of the optionally substituted phenylthio group include a phenylthio group, a 2-chlorophenylthio group, a 2,6-dichlorophenylthio group and a 3-
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 group, 2-chlorophenylamino group, 2,6-dichlorophenylamino group, 3-chlorophenylamino group, 4-chlorophenylamino group, 2-fluorophenylamino group, 3-fluorophenylamino group, 4-fluorophenylamino group. Group, 2-methylphenylamino group, 3-methylphenylamino group, 4-methylphenylamino group, 2-methoxyphenylamino group, 3
Examples include -methoxyphenylamino group and 4-methoxyphenylamino group.

R ¹ , R ² , R in the above general formula (2)
The halogen atom in ³ and R ⁴ , an alkyl group having 1 to 8 carbon atoms, a hydroxy group, an optionally substituted phenoxy group, an optionally substituted phenylthio group, an amino group, or an optionally 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-chain or branched hexyloxy group, a straight-chain or branched heptyloxy group, a straight-chain or branched octyloxy group can be mentioned. Examples of the alkylamino group having 1 to 8 carbon atoms include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, tert-butylamino group,
Examples thereof 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.

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

A reaction example in which the acylated aromatic compound represented by the general formula (1) is synthesized from the aromatic compound represented by the general formula (2) and the phthalic anhydride compound represented by the general formula (3). For example, anthraquinone is synthesized from benzene and phthalic anhydride, 1-chloroanthraquinone is synthesized from benzene and 3-chlorophthalic anhydride, and 2-chloroanthraquinone is synthesized from benzene and 4-chlorophthalic anhydride. , -Synthesis of 2-fluoroanthraquinone from benzene and 4-fluorophthalic anhydride- 1, -from benzene and tetrachlorophthalic anhydride
Synthesis of 2,3,4-tetrachloroanthraquinone, ・ 1, from benzene and tetrafluorophthalic anhydride
Synthesis of 2,3,4-tetrafluoroanthraquinone, 2-hydroxy-1,3,4-from benzene and 4-hydroxy-3,5,6-trifluorophthalic anhydride
Synthesis of trifluoroanthraquinone, 2-hydroxy-1,3 from benzene and 4-acetyloxy-3,5,6-trifluorophthalic anhydride
Synthesis of 4-trifluoroanthraquinone, 2-hydroxy-1, from benzene and 4-benzoyloxy-3,5,6-trifluorophthalic anhydride
Synthesis of 3,4-trifluoroanthraquinone, 2-phenoxy-1,3,4-from 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-Benzene and 4- (2,2 6-dichloroanilino)-
2-from 3,5,6-trifluorophthalic anhydride
Synthesis of (2,6-dichloroanilino) -1,3,4-trifluoroanthraquinone, benzene and 4- (2,6-dimethylanilino)-
2-from 3,5,6-trifluorophthalic anhydride
(2,6-Dimethylanilino) -1,3,4-trifluoroanthraquinone was synthesized, 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 Amino-3,5,6-trifluorophthalic anhydride and 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 tert-butylanthraquinone from tert-butylbenzene and phthalic anhydride, Synthesis of n-amylanthraquinone from n-amylbenzene and phthalic anhydride, Tertiary-amylbenzene and phthalic anhydride To 2 (tertiary-amyl) anthraquinone, -Synthesis of 2,3-dihydroxyanthraquinone from catechol and phthalic anhydride-2-from acetyloxybenzene and phthalic anhydride
Synthesis of hydroxyanthraquinone, 2 from benzoyloxybenzene and phthalic anhydride
-Synthesis of hydroxyanthraquinone-Synthesis of 5-chloro-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, 2, 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-Catechol 2,3,6-trihydroxy-5,7,8-trifluoroanthraquinone was synthesized from and 4-hydroxy-3,5,6-trifluorophthalic anhydride, catechol and 4-phenoxy-3,5, 2,3-Dihydroxy-6-from 6-trifluorophthalic anhydride
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)-
2,3-from 3,5,6-trifluorophthalic anhydride
Dihydroxy-6- (2,6-dichloroanilino)-
Synthesis of 5,7,8-trifluoroanthraquinone, catechol and 4- (2,6-dimethylanilino)-
2,3-from 3,5,6-trifluorophthalic anhydride
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-
2,3-dihydroxy-6-amino-5,7,8-trifluoroanthraquinone was synthesized from trifluorophthalic anhydride; -Quinizarine was synthesized from hydroquinone and phthalic anhydride-Hydroquinone and 3-chlorophthalic anhydride From 5
-Synthesis of chloroquinizarine, 6 from hydroquinone and 4-chlorophthalic anhydride
-Synthesis of chloroquinizarin, -Synthesis of 5,8-dichloroquinizarin from hydroquinone and 3,6-dichlorophthalic anhydride, -Hydroquinone and 4,5-dichlorophthalic anhydride from 6,7-dichloroquiniza Synthesis of phosphorus, -Synthesis of 5,6,7,8-tetrachloroquinizarin from hydroquinone and tetrachlorophthalic anhydride- 5,6,7,8-Tetrafluoroquinine from hydroquinone and tetrafluorophthalic anhydride Synthesis of Zarin, 6-hydroxy-5 from hydroquinone and 4-hydroxy-3,5,6-trifluorophthalic anhydride
Synthesis of 7,8-trifluoroquinizarine, 6-phenoxy-5, from hydroquinone and 4-phenoxy-3,5,6-trifluorophthalic anhydride
Synthesis of 7,8-trifluoroquinizarine, 6-anilino-5,7,8 from hydroquinone and 4-anilino-3,5,6-trifluorophthalic anhydride
-Synthesis of trifluoroquinizarine, 6 from hydroquinone and 4- (2,6-dichloroanilino) -3,5,6-trifluorophthalic anhydride
Synthesis of-(2,6-dichloroanilino) -5,7,8-trifluoroquinizarine, hydroquinone and 4- (2,6-dimethylanilino) -3,5,6-trifluorophthalic anhydride From to 6
Synthesis of-(2,6-dimethylanilino) -5,7,8-trifluoroquinizarine, hydroquinone and 4-phenylthio-3,5,6-
Trifluorophthalic anhydride and 6-phenylthio-
5,5,7,8-trifluoroquinizarine is synthesized, 6-amino-5,7,8-trifluoroquinizarine is synthesized 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-Amino-5, from 6-trifluorophthalic anhydride
Synthesis of 7,8-trifluoroquinizarine, -Synthesis of 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-chloroquinizarine from 1,4-dimethoxybenzene and 4-chlorophthalic anhydride, 1. Synthesis of 5,8-dichloroquinizarine from 3,4-dimethoxybenzene and 3,6-dichlorophthalic anhydride, 6,7-from 1,4-dimethoxybenzene and 4,5-dichlorophthalic anhydride Synthesis of dichloroquinizarine, 5,6,7,8-tetrahydro-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-trifluoroquinizarine from 3,5,6-trifluorophthalic anhydride, 1,4-dimethoxybenzene and 4-phenoxy-
Synthesis of 6-phenoxy-5,7,8-trifluoroquinizarine from 3,5,6-trifluorophthalic anhydride, 1,4-dimethoxybenzene and 4-anilino-3,
Synthesis of 6-anilino-5,7,8-trifluoroquinizarine 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-trifluoroquinizarine, 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-
Synthesis of 6-phenylthio-5,7,8-trifluoroquinizarine 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-trifluoroquinizarine-Synthesis of 4-amino-1-hydroxyanthraquinone from 4-aminophenol and phthalic anhydride-From 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, 4-Aminopheno- Of 4-amino-1-hydroxy-5,8-dichloroanthraquinone from bisphenol and 3,6-dichlorophthalic anhydride, 4-amino-1 from 4-aminophenol and 4,5-dichlorophthalic anhydride Synthesis of 4-hydroxy-6,7-dichloroanthraquinone, 4 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
-Synthesizing 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 from 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-
1-hydroxy-6-phenylthio-5,7,8-trifluoroanthraquinone is synthesized, 4-amino-1-hydroxyanthraquinone is synthesized from 4- (N-acetylamino) phenol and phthalic anhydride, 4- 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 hydroxy anthraquinone, -Synthesis of 4-amino-1-hydroxy anthraquinone from 4- (N-benzoylamino) -1-benzoyloxybenzene and phthalic anhydride, 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 Examples include 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 the presence of a Lewis acid catalyst in a nitrile solvent.

In the present invention, among the aromatic compounds, hydrous phthalic acid is easily dehydrated during the reaction and converted into phthalic anhydride. Therefore, even if hydrous phthalic acid is used instead of phthalic anhydrides. I do not care.

The amount of the acylating agent with respect to the raw material aromatic compound is in the range of 0.1 to 5 mol per mol of the aromatic compound,
It is preferably 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 raw material aromatic compound, the raw material acylating agent, the type of catalyst and the like, and cannot be uniformly defined.
It is preferably used in an amount of 1 to 10 times by mole, and particularly 3 to 8 times by 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 by weight based on the amount of the Lewis acid catalyst. If the amount exceeds 6 times, it is disadvantageous because the yield is not improved.

The reaction temperature in the present invention varies depending on the kinds of the starting aromatic compound, the starting acylating agent and the catalyst and cannot be specified uniformly, but it is usually in the temperature range of 0 to 300 ° C. Generally, the higher the reaction temperature, the higher the reaction rate. However, if the reaction temperature is too high, a side reaction occurs and the product yield decreases. Furthermore, the problem that control of reaction becomes difficult comes out. For example, (1) the reaction temperature for synthesizing benzoyl organic acid from benzene and acid anhydride is preferably 50 to 150 ° C.
Is the 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 anhydride 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 a carboxylic acid 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 about 1 to 15 hours is usually sufficient.

[0044]

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

Example 1 Synthesis of 5,6,7,8-tetrafluoroquinizarin In a 300 cc four-necked flask, 3,4,5,6-tetrafluorophthalic anhydride (20 g, 0.091 mol) and 1 were added. ，
4-dimethoxybenzene 15.1 g (0.109 mol)
And 70 g (0.525 mol) of anhydrous aluminum chloride were added, and 150 cc of benzonitrile was added under water cooling to about 30
Stir for minutes. After that, it takes about 2 hours to reach 190-196 ℃
The temperature was raised to 190 ° C.-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 poured into a mixed solution of about 250 cc of hydrochloric acid aqueous solution and about 500 cc of methanol for precipitation. The precipitate is filtered off and washed with water to give 5,6,7,8-tetrafluoroquinizarin 2
5.9 g was obtained. The results are shown in Table 1.

[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 charging ratio and the reaction time were changed as shown in Table 1. Was synthesized.
The results are shown in Table 1.

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

Example 15 In Example 14, 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 changed to 15 g (0.107 mol) of benzoyl chloride to obtain 17.9 g of benzophenone (yield 91. 7 mol%).

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

[0052]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for producing an acylated compound with a high yield and a high purity with less side reactions in the acylation reaction. In particular, according to the present invention, an anthraquinone compound is 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 as in the conventional method or using concentrated sulfuric acid. There is provided an inexpensive production method for carrying out a high yield, high purity and in a single step.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C07C 225/34 225/36 319/20 323/22 7419-4H // C07B 61/00 300

Claims (3)

[Claims] 1. A method for producing an acylated aromatic compound, which comprises reacting an aromatic compound and an acylating agent in a nitrile solvent in the presence of a Lewis acid catalyst. 2. An acylated aromatic compound is represented by the following general formula (1): (However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are 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, an optionally substituted phenoxy group, an acetyloxy group, a benzoyloxy group, an optionally substituted phenylthio group, an amino group, an alkyl having 1 to 8 carbon atoms An anthraquinone-based compound represented by an amino group, an optionally substituted anilino group, an optionally substituted dianilino group, an acetylamino group or a benzoylamino group, wherein the aromatic compound is represented by the following general formula (2) ) [Chemical 2] (However, R ¹ , R ² , R ³ and R ⁴ are 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, Optionally 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, Which represents an optionally substituted dianillino group, acetylamino group or benzoylamino group), and the acylating agent is represented by the following general formula (3): (However, R ⁵ , R ⁶ , R ⁷ and R ⁸ are 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, a substituent Optionally a 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, an optionally substituted dianilino group, an acetylamino group or It represents a benzoylamino group, and X and Y are each independently -OH or X and Y are combined to form -O-. The manufacturing method of Claim 1 which is a phthalic anhydride type compound shown by these. 3. The production method according to claim 1, wherein the Lewis acid catalyst is aluminum chloride.