JPH0848905A - Production of mixture of dioxadine compounds - Google Patents

Abstract

PURPOSE:To produce a dioxazine mixture having a low content of by-products and a high purity in a short filtration time in high yields by subjecting a specified compound and a 3-aminocarbazole derivative to a cyclization reaction by heating under specified conditions. CONSTITUTION:A mixture of at least two compounds selected from among quinone compounds (A) represented by formula I (wherein X is a halogeno; and (n) is 0-4) and compounds (B) represented by formula II (wherein Z1 and Z2 are each OH or amino; X is halogeno; and (m) is 0-4) (when a mixture of A with B is used, either (n) or (m) is an integer except 0) is condensed with a 3-aminocarbazole derivative represented by formula III (wherein R is H or a 1-8C alkyl) in the presence of an acid binder (e.g. soda ash) in an inert organic solvent (e.g. o-dichlorobenzene), and the product is subjected to a cyclization reaction by heating in the presence of a cyclizing agent (e.g. p-toluenesulfonyl chloride) to obtain a mixture of at least two member selected from among nonhalogeno-, monohalogenoand dihalogeno-dioxadines represented by formula IV (wherein Y1 and Y2 are each a halogeno or H).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved process for producing a mixture of dioxazine compounds represented by the following formula (4) used as a dye and pigment, and a coloring material containing the same.

[0002]

2. Description of the Related Art A dioxazine compound represented by the following formula (4) is produced by condensing 9-alkyl-3-aminocarbazole represented by the following formula (3) and chloranil in an inert solvent in the presence of an acid binder to close the ring. Has been done (PB Report 656
57, Japanese Patent Publication No. 60-11986, Japanese Patent Laid-Open No. 58-1188.
55 mag. ). Further, in particular, in order to obtain X in the formula (4) described below as a mixture of chlorine and hydrogen atoms, a method of ring closure in the presence of an organic acid or the like is known (JP-A-58-8485).
7).

[0003]

However, when a mixture of the following formula (4) is produced by the above-mentioned production method using an organic acid, a large amount of by-products are produced and it takes a long time to filter out, and solvent washing is difficult. Furthermore, the yield was extremely low and the productivity was poor.

[0004]

Means for Solving the Problems The inventors of the present invention independently prepared a mixture (1) or a mixture (2) of a quinone compound having a small number of halogen atoms in place of chloranil which has been used so far, when producing a mixture of dioxazine compounds. Or by mixing and using, there are few by-products, the filtration time is short,
It has been found that a higher yield can be obtained. That is, the present invention relates to formula (1) (1)

[0005]

Embedded image

(In the formula, X represents a halogen atom, and n is 0 to
Indicates an integer of 4. ) And the formula (2)

[0007]

[Chemical 6]

(In the formula, Z ₁ and Z ₂ each represent a hydroxyl group or an amino group, X represents a halogen atom, and m represents 0 to 4).
Represents the integer. ) A mixture of two or more kinds of compounds selected from the compounds represented by the formula (when a mixture of the compound of the formula (1) and the compound of the formula (2) is used, one of n and m is other than 0; Is an integer) is given by the formula (3)

[0009]

[Chemical 7]

After condensation with a 3-aminocarbazole derivative represented by the formula (wherein R represents hydrogen or an alkyl group having 1 to 8 carbon atoms) in an inert organic solvent in the presence of an acid binder, the ring is closed. Formula (4), characterized in that the cyclization is performed by heating in the presence of an agent

[0011]

Embedded image

(Wherein Y ₁ and Y ₂ each independently represent a halogen atom or a hydrogen atom, and R is the same as defined above), a non-halogenodioxazine compound, a monohalogenodioxazine compound and a dihalogenodioxazine compound. A method for producing a mixture of two or more dioxazine compounds selected from the above, (2) a coloring material containing the mixture of the compounds of formula (4), which is synthesized by the method described in (1) above. .

In the present invention, a mixture of two or more compounds selected from the quinone compound represented by the above formula (1) and the compound represented by the above formula (2) is, for example, benzoquinone, monohalogenobenzoquinone, A quinone compound represented by the formula (1) such as dihalogenobenzoquinone, trihalogenobenzoquinone, tetrahalogenobenzoquinone,
And hydroquinone, monohalogenohydroquinone, dihalogenohydroquinone, trihalogenohydroquinone, tetrahalogenohydroquinone, p-aminophenol, p-
Two or more compounds selected from compounds represented by formula (2) such as amino-monohalogenophenol, p-amino-dihalogenophenol, p-amino-trihalogenophenol, p-amino-tetrahalogenophenol It is a mixture of. As a preferable mixture, for example, a mixture of 2 to 4 kinds of quinone compounds represented by the formula (1), or 2 to 4 kinds of quinone compounds represented by the formula (2).
There are four types of mixture. When a mixture of the compound of formula (1) and the compound of formula (2) is used, a mixture of compounds in which both n and m are 0 gives only a non-halogenodioxazine compound. One is 0
It is preferred to use compounds that are integers other than.

In the above formulas (1), (2) and (4),
Examples of the halogen atom of X, Y ₁ and Y ₂ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. Further, the above formulas (3) and (4)
In, R is an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like can be mentioned, but ethyl group is preferable. In the formula (2), Z ₁ and Z ₂ each represent a hydroxyl group or an amino group, but preferably both are hydroxyl groups, or one is a hydroxyl group and the other is an amino group.

Examples of the quinone compound of the above formula (1) used in the present invention include p-benzoquinone and chloro-p-
Benzoquinone, bromo-p-benzoquinone, dichloro-
Examples thereof include p-benzoquinone, dibromo-p-benzoquinone, trichloro-p-benzoquinone, tribromo-p-benzoquinone, tetrachloro-p-benzoquinone and tetrabromo-p-benzoquinone. Examples of the compound represented by the formula (2) include p-aminophenol,
p-hydroquinone, chloro-p-aminophenol, chloro-p-hydroquinone, dichloro-p-aminophenol, dichloro-p-hydroquinone, trichloro-p-
Aminophenol, trichloro-p-hydroquinone, tetrachloro-p-aminophenol, tetrachloro-p
-Hydroquinone, bromo-p-aminophenol, bromo-p-hydroquinone, dibromo-p-aminophenol, dibromo-p-hydroquinone, tribromo-p-aminophenol, tribromo-p-hydroquinone, tetrabromo-p-aminophenol, tetrabromo -P-
Examples include hydroquinone.

To carry out the method of the present invention, for example, the following may be carried out. That is, a mixture of two or more compounds selected from the quinone compound represented by the above formula (1) and the compound represented by the above formula (2), for example, the above formula (1)
2 to 4 kinds of quinone compounds are mixed at an arbitrary ratio, added to an inert solvent containing the compound of the formula (3), and condensed in the presence of an acid binder to obtain the compound of the formula (5).

[0017]

[Chemical 9]

A compound of the formula (wherein R, Y ₁ and Y ₂ are the same as above) is prepared. At this time, the mixture of the quinone compound of the formula (1) in an arbitrary ratio to 1.0 mol of the compound of the formula (3) has a 0.3 to 1.0 molar ratio, preferably 0.4 to 0.7.
It is a molar ratio. The mixing ratio is, for example, when non-halogenobenzoquinone is used, 0.1 to 10 parts by weight of halogenobenzoquinone per 1 part by weight of the compound, for example, when halogenobenzoquinone is used, di, tri, and trihalogenobenzoquinone are added to 1 part by weight. Alternatively, about 0.1 to 10 parts by weight of tetrahalogenobenzoquinone and about 0.1 to 10 parts by weight of tri- or tetrahalogenobenzoquinone are suitable for 1 part by weight of dihalogenobenzoquinone. It is needless to say that a mixture of the compound represented by the formula (2) in any ratio (mixing ratio is the same as above) may be used instead of the quinone compound, and the compound of the formula (1) and the formula (2) may be used. A mixture of the compounds of) may be used.

Examples of the acid binder include inorganic compounds such as sodium hydrogen carbonate, sodium carbonate and potassium carbonate, sodium hydroxide and potassium hydroxide, salts of organic acids such as sodium acetate and potassium acetate, and bases such as pyridine, piperidine and triethylamine. Organic compounds and the like can be used. The acid binder is used in an amount of 0.1 to 10 mol ratio, preferably 0.2 to 3 mol ratio, based on the compound of formula (3).

The reaction time is 0.5 to 10 hours, preferably 1 to 5 hours. The reaction temperature is 0 to 100 ° C, preferably 30 to 60 ° C. As the inert solvent used in the reaction, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, dibromobenzene, chloronaphthalene, chlorotoluene, dichlorotoluene, and bromotoluene, xylene, mesitylene, ethylbenzene, In addition to trimethylbenzene, diethylbenzene, butylbenzene, and alkylated aromatics such as methylnaphthalene and dimethylnaphthalene, nitrobenzene, alkanes such as decane, undecane, dodecane, decene, undecene, and dodecene, alkenes, and the like can be given. These can be used alone or in combination. The amount of this solvent used is 5 to 40 times by weight, preferably 10 to 20 times the amount of the compound of the above formula (3).

Subsequently, the reaction solution containing the ring-closing precursor represented by the above formula (5) obtained by the above method is heated to add a ring-closing agent, and the ring-closing reaction is carried out at a high temperature. At this time, it is also possible to heat while reducing the pressure. Reaction temperature is 100-200
℃, preferably 150-180 ℃, the reaction time is 0.5
~ 6 hours. When the reaction is completed, the reaction mixture is cooled and, if necessary, diluted with an organic solvent such as methanol and then filtered to separate the target product. Thereafter, if necessary, the product is washed with a solvent or the like and dried to obtain the desired product. The ring-closing precursor represented by the formula (5) may of course be isolated from the reaction solution containing it and then subjected to the ring-closing reaction.

Examples of the ring-closing agent used here are benzenesulfonyl chloride, toluenesulfonyl chloride,
Chlorobenzenesulfonyl chloride, nitrobenzenesulfonyl chloride and other sulfonic acid halides, benzoyl chloride and other acid chlorides, chloranil, dichloronaphthoquinone and other halides, benzenesulfonic acid, p-
Examples thereof include organic acids such as toluenesulfonic acid, and particularly preferred are benzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, chlorobenzenesulfonyl chloride and the like. The addition amount is 0.1 to 2 molar ratio with respect to the compound of the formula (3),
It is preferably used in a molar ratio of 0.5 to 1.5.

The target product obtained by the above method is two or more kinds of dioxazine compounds selected from the non-halogenodioxazine compounds represented by the above formula (4), monohalogenodioxazine compounds and dihalogenodioxazine compounds. Is a mixture of. Specifically, for example, a mixture of a non-halogenodioxazine compound and a monohalogenodioxazine compound, a mixture of a non-halogenodioxazine compound and a dihalogenodioxazine compound, a mixture of a monohalogenodioxazine compound and a dihalogenodioxazine compound, etc. Examples thereof include a mixture of three kinds of compounds, and a mixture of three kinds of a non-halogenodioxazine compound, a monohalogenodioxazine compound and a dihalogenodioxazine compound. According to the method of the present invention, it is possible to control the hue of the dioxazine dye as a mixture, and there are few by-products, the filtration time is short, the solvent washing is easy, the purity is high, and the mixture of the dioxazine compounds is high in yield. Can be manufactured.

[0024]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples,% and parts are% by weight
And parts by weight are shown.

Example 1 8 parts of 3-amino-9-ethylcarbazole and X is chlorine,
3 parts of a quinone compound (1) in which n is 2, X is chlorine, 3 parts of a quinone compound (1) in which n is 3, 2 parts of soda ash, o-
Mix 80 parts of dichlorobenzene and stir at 30-65 ° C. Then depressurize and remove water to 140-150
The temperature is raised to 0 ° C, 5 parts of p-toluenesulfonyl chloride is added at the same temperature, and the mixture is stirred at 165 to 175 ° C for 5 hours. After completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain a mixture of 9.4 parts of dioxazine compounds (in the formula (4), R is an ethyl group and Y is Y). A mixture of chlorine and hydrogen) was obtained. This compound is a mixture of dioxazine compounds by elemental analysis, infrared absorption spectrum, mass spectrum and the like (a non-halogenodioxazine compound in which R is an ethyl group in formula (4) and both Y ₁ and Y ₂ are hydrogen atoms, Y _A monochlorodioxazine compound in which _one of Y ₁ and Y ₂ is a hydrogen atom and the other is a chlorine atom, and a mixture of three dioxazine compounds of the same chlorodioxazine compound in which both Y ₁ and Y ₂ are chlorine atoms)
It has been confirmed that is generated.

Example 2 8 parts of 3-amino-9-ethylcarbazole and 3 parts of a quinone compound (1) in which n is 0, 3 parts of a quinone compound (1) in which X is chlorine and n is 4, soda ash 2 And 80 parts of o-dichlorobenzene are mixed and stirred at 30 to 65 ° C. p-
Toluene sulfonyl chloride 5 parts was added and 165-17
Stir at 5 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain a mixture of 9.3 parts of dioxazine compounds (in the formula (4), R is an ethyl group and Y is Y). A mixture of chlorine and hydrogen) was obtained. This is a mixture of dioxazine compounds (R in formula (4) is an ethyl group, Y ₁ , Y ₂
Non halogenoalkyl diacetic benzoxazine compounds both are hydrogen atoms, while the hydrogen atoms of Y _1, Y _2, monochrome distearate oxazine compound other is a chlorine atom, both of Y _1, Y ₂ is a chlorine atom Jikuroruji It was confirmed that a mixture of three dioxazine compounds of oxazine compounds) was produced.

Examples 3 to 8 According to Example 1, using a mixture of quinone compound (1) or compound (2) with different mixing ratio, the same mixture (4) of dioxazine compounds as in Example 1 was obtained. It was The results are shown in Table 1.

[0028]

Table 1 Table 1 Examples Raw material mixture Yield (parts) Example 3 (1) X = Cl, n = 22 2 parts 9.4 (1) X = Cl, n = 4 4 parts Example 4 (1) n = 0 1 part 9.3 (1) X = Cl, n = 2 2 parts (1) X = Cl, n = 4 3 parts Example 5 (1) n = 0 2 parts 9.1 (1) X = Cl, n = 3 4 parts Example 6 (1) n = 0 1 part 9.5 (1) X = Cl, n = 45 parts Example 7 (1) n = 0 3 parts 9.3 (1) ) X = Br, n = 4 3 parts Example 8 (2) X = Cl, m = 2 9.2 Z ₁ = NH ₂ , Z ₂ = OH 3 parts (2) X = Cl, m = 4 Z ₁ = OH, Z ₂ = OH 3 parts

Example 9 To 22 parts of the dioxazine compound obtained in Example 1 was added 33 parts of ethylene glycol and 150 parts of ground salt, and a dispersion pigment was formed with a kneader. When the obtained pigment is stirred and mixed with an ink varnish with a high speed mixer to form an ink, it has excellent gloss and tinting strength. When the vinyl chloride resin was colored, a clear vinyl chloride sheet excellent in dispersibility, having a large coloring power, was obtained.

[0030]

According to the method of the present invention, a mixture of dioxazine compounds can be easily produced with a small amount of by-products, a short filtration time, and a high yield.

Claims (2)

[Claims] 1. A formula (1): (Wherein X represents a halogen atom and n represents an integer of 0 to 4) and a quinone compound represented by the formula (2): (Wherein Z ₁ and Z ₂ each represent a hydroxyl group or an amino group, X represents a halogen atom, and m represents an integer of 0 to 4) and two or more compounds selected from the compounds (When using a mixture of the compound of the formula (1) and the compound of the formula (2), one of n and m is an integer other than 0), and the compound of the formula (3) (Wherein R represents hydrogen or an alkyl group having 1 to 8 carbon atoms) and the 3-aminocarbazole derivative are condensed in an inert organic solvent in the presence of an acid binder, and then a ring-closing agent is present. The formula (4) is characterized in that the ring is closed by heating under (In the formula, Y ₁ and Y ₂ each independently represent a halogen atom or a hydrogen atom, and R is the same as the above.), Among the non-halogenodioxazine compounds, monohalogenodioxazine compounds and dihalogenodioxazine compounds. A method for producing a mixture of two or more selected dioxazine compounds. 2. A coloring material containing a mixture of compounds of formula (4) synthesized by the method according to claim 1.