JPH0670067B2 - Method for producing dioxazine compound - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to an improved method for producing a dioxazine compound used as a dye, a pigment or a functional dye.

[Prior art]

Conventional formula [II] As a method of ring-closing a compound represented by the formula (wherein R represents an alkyl group having 1 to 4 carbon atoms) to obtain a dioxazine compound, a method of oxidative ring-closing using benzenesulfonyl chloride as an oxidizing agent is known. (See PB Report 65657). Also known is a method of ring closure using an organic acid such as P-toluene sulfonic acid (Japanese Patent Laid-Open No. S60-242242).
58-84857).

[Problems to be Solved by the Invention]

However, in the conventional method, the oxidant or the organic acid used for carrying out the ring-closing reaction is required to be 1 mol or more with respect to the compound of the general formula. More oxidants are used.
Therefore, after the completion of the ring-closure reaction, when the generated dioxazine compound is isolated, the reaction product of the oxidizing agent added and unreacted organic acid are entrapped in the generated dioxazine compound in a considerable amount, and the length of time during the filtration is long. There is a problem that it takes a long time and a large amount of organic solvent is required for cleaning. Further, when the amount of the organic solvent at the time of the washing step is insufficient, when using the produced dioxazine compound as a dye or particularly a pigment,
It is difficult to stabilize the quality including the hue, and there is a problem that it greatly affects the post-process.

[Means for solving the problem]

The present inventors have conducted diligent research in order to improve the drawbacks of the conventional method caused by the inclusion of an oxidizing agent in the dioxazine compound produced by ring-closing the compound of the general formula [II], which causes it. As a result, they have found that the above problems can be solved by using a small amount of an inorganic acid such as hydrochloric acid instead of the oxidizing agent or by using an inorganic acid such as hydrochloric acid and an oxidizing agent together. That is, the present invention is represented by the general formula [II] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms), the compound is subjected to a ring closure reaction by heating in an inert organic solvent in the presence of an inorganic acid or in the presence of an inorganic acid and an oxidizing agent. Characteristic general formula [I] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and
X ₁ and X ₂ are hydrogen atoms or Cl atoms, and X ₁ = X ₂ = Cl,
X ₁ ═Cl, X ₂ ═H and X ₁ ═X ₂ ═H each independently or as a mixture. ] It is a manufacturing method of the dioxazine compound shown by these. As the inert solvent in the present invention, chlorobenzene,
Dichlorobenzene, trichlorobenzene, a mixture thereof, nitrobenzene, an alkylbenzene having a boiling point of 110 ° C. or higher, or an alkylnaphthalene-based high-boiling solvent is used. Especially chlorobenzenes, nitrobenzene,
Alkylbenzenes are preferably used. Next, examples of the inorganic acid used in the present invention include hydrochloric acid, sulfuric acid, hydrobromic acid, phosphoric acid and the like, among which hydrochloric acid and sulfuric acid are preferably used. Further, the amount of the inorganic acid used may be a catalytic amount or more, but particularly, with respect to the compound of the general formula (II), 0.01 mol to 1.
Used in the range of 0 mol. Examples of the oxidizing agent used in combination with the inorganic acid include p-benzoquinone and its derivatives, o-benzoquinone and its derivatives, benzenesulfonyl chloride and its derivatives, and benzenesulfonic acid esters. Among them, p-benzoquinone, p-chloranil, tetracyanobenzoquinone, dicyano-dichlorobenzoquinone, o-chloranyl, p-toluninsulfonyl chloride, benzenesulfonyl chloride and the like are particularly preferable. The amount of the oxidizing agent used is in the range of 0.0001 to 1.0 mol, preferably 0.01 to 0.5 mol. The reaction temperature is usually 100 ° C or higher, and industrially 110 ° C to 200 ° C.
C., particularly preferably 130 to 180.degree. The heating time is usually 3 to 12 hours. When the reaction is complete, the crystals are separated by filtration and washed with the required amount of solvent. The desired dioxazine compound represented by the general formula [I] can be obtained in a high yield by sufficiently pressing and then drying.

【The invention's effect】

According to the present invention, the amount of the reaction accelerator used is smaller than that of the conventional method, so that the cost is low, and it is possible to shorten the filtration time and reduce the amount of solvent used, and as a result, the effort spent for solvent recovery and residue treatment. , Energy consumption is low, and effective manufacturing method for resource saving and energy saving has been established. Furthermore, since it has become possible to supply a dioxazine compound excellent in coloring power, gloss, transparency, etc. as a coloring agent such as a pigment, this industrial utility value is extremely large.

【Example】

Hereinafter, the present invention will be described in more detail with reference to Examples. In the text, parts and% represent parts by weight and% by weight. Example 1 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and further 36% hydrochloric acid 1.0 Parts were added, and the mixture was heated to 155-160 ° C. with stirring and heated at the same temperature for 5 hours. Then, it cooled to 120 degreeC and filtered at the same temperature. After completion of filtration of the reaction mass, the product was washed with 400 parts of o-dichlorobenzene preliminarily kept at 100 ° C., washed with 150 parts of methanol, then washed with 300 parts of water, squeezed, and the cake was taken out and dried. 51.0 parts of dioxazine compound (corresponding compound in which R in the general formula [I] is —C ₂ H ₅ ) were obtained. The elemental analysis values of the obtained compound are C; 71.0%, H; 4.1%, N;
It showed 9.7% and Cl; 9.0%. The reaction mass in the above operation can be filtered and washed in a short time, and the amount of the solvent used for the washing can be smaller than that in the conventional method. Example 2 2,5-Dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone (60 parts) was added to o-dichlorobenzene (400 parts), and 36% hydrochloric acid (2.5%) was added. Parts were added, and the mixture was heated to 165-170 ° C. with stirring and heated at the same temperature for 5 hours. Then, it cooled to 120 degreeC and filtered at the same temperature. After completion of filtration of the reaction mass, after washing with 400 parts of o-dichlorobenzene preliminarily kept at 100 ° C., washing with 150 parts of methanol, then washing with 300 parts of water, squeezing, removing the cake, and drying, 50.5 parts of dioxazine compound (R in the general formula [I] is C ₂ H ₅ ) were obtained. The elemental analysis values of the obtained compound are C; 70.5%, H; 4.0%, N; 9.6%, Cl; 10.0.
%showed that. The reaction mass in the above operation can be filtered and washed in a short time, and the amount of the solvent used for the washing can be smaller than that in the conventional method. Example 3 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and 78% sulfuric acid 2.0 was added. Part and tetracyanobenzoquinone (3.0 parts) are added, and the mixture is stirred at 155 to 160 ° C.
The temperature was raised to, and heated at the same temperature for 5 hours. Then 120 ℃
It was cooled to the same temperature and filtered at the same temperature. After the reaction mass filtration is completed,
After washing with 400 parts of o-dichlorobenzene which had been kept warm at 100 ° C. in advance, it was washed with 150 parts of methanol, then with 300 parts of water, squeezed, and the cake was taken out and dried to obtain 50.0 parts of the dioxazine compound ( In the general formula [I], R is
C ₂ H ₅ ) was obtained. The elemental analysis value of the obtained compound is C; 69.8.
%, H; 4.1%, N; 9.5%, Cl; 11.3%. The reaction mass in the above operation can be filtered and washed in a short time, and the amount of the solvent used for the washing can be smaller than that in the conventional method. Example 4 2,5-Dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone (60 parts) was added to o-dichlorobenzene (400 parts), and 36% hydrochloric acid (0.5%) was added. Parts were added, and the mixture was heated to 145-150 ° C. with stirring and heated at the same temperature for 12 hours. Then, it cooled to 120 degreeC and filtered at the same temperature. After completion of filtration of the reaction mass, after washing with 400 parts of o-dichlorobenzene preliminarily kept at 100 ° C., washing with 150 parts of methanol, then washing with 300 parts of water, squeezing, removing the cake, and drying, 51.0 parts of a dioxazine compound (R in the general formula [I] is C ₂ H ₅ ) was obtained. The elemental analysis values of the obtained compound are C; 72.0%, H; 4.1%, N; 9.8%, Cl; 8.5%
showed that. Filtration and washing in the above operation were easy, and the amount of washing solvent used was small. Example 5 2,5-Dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone (60 parts) was added to o-dichlorobenzene (400 parts), and 36% hydrochloric acid (1.0%) was added. Parts and p-chloranil 4 parts, and heated to 165-170 ° C. with stirring,
It heated at the same temperature for 12 hours. Then cool to 120 ° C,
It filtered at the same temperature. After the reaction mass filtration is completed, 10
After washing with 400 parts of o-dichlorobenzene kept at 0 ℃, 15
After washing with 0 part of methanol, followed by washing with 300 parts of water and pressing, the cake was taken out and dried to obtain 51.5 parts of a dioxazine compound (R in the general formula [I] is C ₂ H ₅ ).
The elemental analysis values of the obtained compound are C; 70.6%, H; 4.1%,
It showed N; 9.7% and Cl; 11.4%. Filtration and washing in the above operation were easy, and the amount of washing solvent used was small. Example 6 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of trichlorobenzene, and 1.0 part of 70% sulfuric acid was added. The temperature was raised to 190 to 200 ° C. with stirring, and the mixture was heated at the same temperature for 5 hours.
Then, it cooled to 120 degreeC and filtered at the same temperature. After completion of filtration of the reaction mass, washing with 400 parts of trichlorobenzene kept at 100 ° C. in advance, washing with 150 parts of methanol, then washing with 300 parts of water, squeezing, removing the cake, and drying to obtain 49.0 parts. To obtain a dioxazine compound (R in the general formula [I] is C ₂ H ₅ ). The elemental analysis values of the obtained compound were C; 71.0%, H; 4.1%, N; 10.0%, Cl; 8.5%. Filtration and washing in the above operation were easy, and the amount of washing solvent used was small. Example 7 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and 70% sulfuric acid 1.0% was added. Parts and 5.0 parts of p-benzenesulfonyl chloride were added, and the mixture was stirred at 165-
The temperature was raised to 170 ° C. and the mixture was heated at the same temperature for 5 hours. Then 120
It cooled to 0 degreeC and filtered at the same temperature. After completion of filtration of the reaction mass, o-dichlorobenzene 4 which was kept warm at 100 ° C in advance.
After washing with 00 parts, wash with 150 parts of methanol, then 300 parts
After washing with some water and pressing, the cake was taken out and dried. 51.0
Part of the dioxazine compound (R in the general formula [I] is —C ₂ H ₅ )
Got The elemental analysis values of the obtained compound are C; 71.0%, H;
It showed 4.1%, N; 9.7%, Cl; 10.8%. The reaction mass in the above operation can be filtered and washed in a short time, and the amount of the solvent used for the washing can be smaller than that in the conventional method. Example 8 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and 98% sulfuric acid 0.5% was added. Parts and 2 parts of o-chloranil, and heated to 165-170 ° C. with stirring,
It heated at the same temperature for 5 hours. Then cool to 120 ° C,
It filtered at the same temperature. After the reaction mass filtration is completed, 10
After washing with 400 parts of o-dichlorobenzene kept at 0 ℃,
After washing with 0 part of methanol and then with 300 parts of water and squeezing, the cake was taken out and dried. 51.0 parts of dioxazine compound (R in formula [I] is -C ₂ H ₅ ) were obtained. The elemental analysis values of the obtained compound are C; 71.0%, H; 4.1%, N; 9.7%,
Cl; 10.5% was shown. The reaction mass in the above operation can be filtered and washed in a short time, and the amount of the solvent used for the washing can be smaller than that in the conventional method. Example 9 2,5-Dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone (60 parts) was added to nitrobenzene (400 parts), and 36% hydrochloric acid (1.0 part) and benzoquinone were added.
2.0 parts was added, the temperature was raised to 155-160 ° C. with stirring, and the mixture was heated at the same temperature for 5 hours. Then it was cooled to 120 ° C. and filtered at the same temperature. After completion of filtration of the reaction mass, after washing with 400 parts of o-dichlorobenzene preliminarily kept at 100 ° C, washing with 150 parts of methanol, then washing with 300 parts of water, squeezing,
The cake was removed and dried. 51.0 parts of dioxazine compound (R in formula [I] is -C ₂ H ₅ ) were obtained. The elemental analysis values of the obtained compound are C; 71.0%, H; 4.1%, N; 9.5%, Cl; 10.
Showed 5%. The reaction mass in the above operation can be filtered and washed in a short time, and the amount of the solvent used for the washing can be smaller than that in the conventional method. Example 10 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to mesitylene 400.
In addition to 1.0 part, 1.0 part of 36% hydrochloric acid was added, and the mixture was stirred at 155-
The temperature was raised to 160 ° C and the mixture was heated at the same temperature for 5 hours. Then 120
It cooled to 0 degreeC and filtered at the same temperature. After completion of filtration of the reaction mass, o-dichlorobenzene 4 which was kept warm at 100 ° C in advance.
After washing with 00 parts, wash with 150 parts of methanol, then 300 parts
After washing with some water and pressing, the cake was taken out and dried. 51.0
Part of the dioxazine compound (R in the general formula [I] is —C ₂ H ₅ )
Got The elemental analysis values of the obtained compound are C; 71.0%, H;
It showed 4.1%, N; 9.7%, Cl; 9.0%. The reaction mass in the above operation can be filtered and washed in a short time, and the amount of the solvent used for the washing can be smaller than that in the conventional method. Comparative Example 1 (Prior Art) 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 400 parts of o-dichlorobenzene, and the mixture was heated. After warming, 19 parts of benzenesulfonyl chloride was added, the temperature was raised to 175 to 180 ° C, and the temperature was adjusted to 6
I kept it warm for an hour. After cooling to 120 ° C, the mixture was filtered at the same temperature.
Then, it was washed with 400 parts of o-dichlorobenzene which had been kept at 100 ° C. in advance. Then, it was further washed with 400 parts of the same 0-dichlorobenzene. Then 1
After washing with 50 parts of methanol and 800 parts of water, the cake was squeezed and the cake taken out was dried. 47.6 parts of dioxazine compound was obtained. The elemental analysis values of the obtained compound are C; 70.0%, H; 3.
It showed 8%, N; 9.6%, Cl; 11.5%, S; 0.3%. In the above operation, filtration of the reaction mass and washing with o-dichlorobenzene took a long time (about 1 hour). After the first washing with o-dichlorobenzene, 2
The elemental analysis values of the dioxazine compound obtained by performing the same treatment after washing with methanol without performing the second washing are C; 70.0%, H; 4.0%, N; 9.0%, Cl; 11.3%, S. ; 1.5%
The content of S was large and the cleaning was insufficient. Comparative Example 2 (Prior Art) 60 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone was added to 300 parts of o-dichlorobenzene, and P-toluenesulfonic acid 2
6 parts were added and the temperature was kept at 80 to 85 ° C. Separately add this suspension to 1
It was added to 100 parts of o-dichlorobenzene kept at 75 to 180 ° C. under stirring for 3 hours. After the addition was completed, the temperature was further kept at 175 to 180 ° C for 6 hours. Then, it cooled to 120 degreeC and filtered. Then, it was washed with 400 parts of o-dichlorobenzene which had been kept at 100 ° C. in advance. The same operation was repeated three times. Next, the cake was washed with 150 parts of methanol and 300 parts of water, squeezed, and the cake taken out was dried. 38.7 parts of dioxazine compound was obtained. The elemental analysis values of the obtained compound are C; 66.0%, H; 4.0%, N; 7.8%,
The Cl content was 6.5% and the S content was 3.3%. In the above operation, filtration of the reaction mass and washing with o-dichlorobenzene took a long time (about 2 hours). Reference Example (Use Example) 100 parts of the dioxazine compound obtained under the conditions of Example 1, Example 5 and Comparative Example 1 (washing with o-dichlorobenzene twice) were used, and the particle size of 300 mesh through was changed. Using 700 parts of common salt and 150 parts of ethylene glycol, with a double-armed experimental kneader, grind for 7 hours while maintaining 70-75 ° C, put the mass in 2,000 parts of warm water (80 ° C), and after stirring After filtering and washing with 4,000 parts of water, the cake was taken out and dried. Using this dried cake as a pigment, nitrocellulose to polyamide gravure ink was prepared and evaluated. At that time, the dioxazine compound obtained under the conditions of Comparative Example 1 was used as a standard for evaluation and the like. result

Claims (5)

[Claims] 1. General formula [II] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms), the compound is subjected to a ring closure reaction by heating in an inert organic solvent in the presence of an inorganic acid or in the presence of an inorganic acid and an oxidizing agent. Characteristic general formula [I] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and
X ₁ and X ₂ are hydrogen atoms or Cl atoms, and X ₁ = X ₂ = Cl,
X ₁ ═Cl, X ₂ ═H and X ₁ ═X ₂ ═H each independently or as a mixture. ] The manufacturing method of the dioxazine compound shown by these. 2. The method according to claim 1, wherein the inorganic acid is hydrochloric acid or sulfuric acid. 3. The oxidant is p-benzoquinone and its derivatives, o-benzoquinone and its derivatives, benzenesulfonyl chloride and its derivatives, or benzene sulfonic acid esters.
Method described in section. 4. The method according to claim 1, wherein the heating temperature is in the range of 110 ° C. to 200 °. 5. The inert organic solvent is chlorobenzene, dichlorobenzene, trichlorobenzene or a mixture thereof, nitrobenzene or alkylbenzenes having a boiling point of 110 ° C. or higher.
Method described in section.