JPS62277388A - Production of dioxazine compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as dyes, pigments, etc. by using a small amount of a reaction promoter at a low cost, by subjecting a specific benzoquinone derivative to cyclization reaction while heating in an inert organic solvent in the presence of an inorganic acid, etc. CONSTITUTION:A compound expressed by formula I (R represents 1-4C alkyl) [example; 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoqu-inone, etc.] is cyclized in an inert organic solvent (preferably chlorobenzene, dichlorobenzene, trichlorobenzene or nitrobenzene, or alkylbenzene with >=110 deg.C boiling point) in the presence of an inorganic acid (preferably hydrochloric acid or sulfuric acid) or both the inorganic acid and an oxidizing agent (preferably p- benzoquinone, etc.) while heating preferably at 110-200 deg.C to obtain the aimed compound expressed by formula II (X, and X2 represent H or Cl).

Description

[Detailed description of the invention]

3. Detailed description of the invention

[Industrial application field]

The present invention relates to an improved method for producing dioxazine compounds used as dyes, pigments, functional pigments, etc.

[Conventional technology]

Conventionally, a method for obtaining a dioxazine compound by ring-closing a compound represented by general formula (II) (wherein R represents an alkyl group having 1 to 4 carbon atoms) uses benzenesulfonyl chloride as an oxidizing agent. A method of oxidation opening using PB (Refer to PB Rev. 65657) is known. Furthermore, a method of ring-closing using an organic acid such as P-)luenesulfonic acid is also known (JP-A-58-8485I
).

[Problems to be solved by the invention]

However, in the conventional method, the oxidizing agent or organic acid used to carry out the ring-closing reaction is required to be at least 1 mol per mole of the compound of the general formula. Furthermore, more oxidizing agents are used. Therefore, when the generated dioxazine compound is isolated after the completion of the ring-closing reaction, a considerable amount of reactants of the added oxidizing agent and unreacted organic acids are entangled in the generated dioxazine compound, and it takes a long time to filter it out. There are problems in that it takes time and also requires a large amount of organic solvent used for cleaning. In addition, if the amount of organic solvent during the washing process is insufficient, it will be difficult to stabilize the quality, including the hue, when using the generated dioxazine compound as a dye or especially a pigment.
The problem was that it had a large impact on subsequent processes.

[Means to solve the problem]

The present inventors have discovered that an oxidizing agent or the like is incorporated into a dioxazine compound produced by ring-closing the compound of general formula (II),
In order to improve the drawbacks of conventional methods caused by this, we have conducted intensive research and found that by using a small amount of an inorganic acid such as hydrochloric acid instead of an oxidizing agent, or by using an inorganic acid such as hydrochloric acid and an oxidizing agent together. We have found that the above problem can be solved by this method. That is, the present invention provides a method for preparing a compound represented by the general formula [■] (wherein R represents an alkyl group having 1 to 4 carbon atoms) in an inert organic solvent in the presence of an inorganic acid or in the presence of an inorganic acid and an oxidizing agent. General formula (I) characterized in that the ring-closing reaction is carried out by heating in the presence of
represents an alkyl group, xl and x2 are hydrogen atoms or C1 atoms, and X1=X2=Cj! , L=C
1, L=H and X, =X2=H each individually or as a mixture. ) is a method for producing a dioxazine compound shown in In the present invention, the inert solvent includes chlorobenzene,
Dichlorobenzene, trichlorobenzene, mixtures thereof, nitrobenzene, alkaline benzenes having a boiling point of 110° C. or higher, or alkylnaphthalene-based high boiling point solvents are used. In particular, chlorobenzenes, nitrobenzenes, and alkylbenzenes are preferably used. Next, examples of inorganic acids used in the present invention include hydrochloric acid, sulfuric acid,
Examples include hydrobromic acid and phosphoric acid, among which hydrochloric acid and sulfuric acid are preferably used. Further, the amount of the inorganic acid used may be at least a catalytic amount, but it is particularly used in the range of 0.01 mol to 1.0 mol relative to the compound of general formula (I[). Examples of the oxidizing agent used in combination with the inorganic acid include p-benzoquinone and its derivatives, 0-benzoquinone and its derivatives, benzenesulfonyl chloride and its derivatives, and benzenesulfonic acid esters. Among them, p-benzoquinone, p-chloranil,
Preferred are tetracyanobenzoquinone, dicyano-dichlorobenzoquinone, 0-chloranil, p-toluninsulfonyl chloride, benzenesulfonyl chloride, and the like. The amount of oxidizing agent used is in the range of 0.0001 to 1.0 mol, preferably 0.1 to 0.5 mol. The reaction temperature is usually 100°C or higher, industrially 110°C.
-200°C, particularly preferably 130°C - 180°C. The heating time is usually 3 to 12 hours. After the reaction is completed, the crystals are separated by filtration and washed with the required amount of solvent. By sufficiently squeezing and drying, the desired dioxazine compound represented by the general formula [■] can be obtained in high yield.

【Effect of the invention】

Compared to conventional methods, the present invention uses a small amount of reaction accelerator, making it less expensive, and also shortens filtration time and reduces the amount of solvent used.As a result, the labor required for solvent recovery and residue treatment is reduced. , an effective manufacturing method that consumes less energy and saves resources and energy has been established. Furthermore, it has become possible to supply dioxazine compounds with excellent coloring power, gloss, transparency, etc. as colorants for pigments, and their industrial utility value is extremely large.

【Example】

The present invention will be described in more detail with reference to Examples below. Hustle. 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 0
- In addition to 400 parts of dichlorobenzene, 1.0 part of 36% hydrochloric acid was added, the temperature was raised to 155 to 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 the reaction mass filtration was completed, the mixture was washed with 400 parts of 0-dichlorobenzene kept at 100°C in advance, washed with 150 parts of methanol, and then washed with 300 parts of methanol.
After washing and squeezing with 50% water, the cake was taken out and dried. 51
．． In 0 parts of the dioxazine compound (general formula CI), R is -C
2)1. The corresponding compound) was obtained. The elemental analysis values of the obtained compound were: C: 1.0%, H: 4.1%,
N: 9.7%, C1: 9.0%. Filtration and washing of the reaction mass in the above operation can be performed in a short time, and the amount of solvent used for washing can be reduced compared to conventional methods. Example 2 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 2.5 parts of 36% hydrochloric acid were added, and the temperature was raised to 165 to 170°C with stirring, and heated at the same temperature for 5 hours. Then, it was cooled to 120°C and filtered at the same temperature. After the reaction mass filtration was completed, the mixture was washed with 400 parts of 0-dichlorobenzene kept at 100°C in advance, washed with 150 parts of methanol, and then washed with 300 parts of methanol.
After washing with 50% water and squeezing, the cake was taken out and dried to obtain a 50.5N dioxazine compound (general formula CI).
(middle R is C2H5) was obtained. The elemental analysis values of the obtained compound were as follows: C: 0.5%, H: 4.0%, N: 9.6.
%,Cj! ; showed 10.0%. Filtration and washing of the reaction mass in the above operation can be performed in a short time, and the amount of solvent used for washing can be reduced compared to conventional methods. Example 3 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 2.0 parts of 78% sulfuric acid and 3.0 parts of tetracyanobenzoquinone were added, and the temperature was raised to 155 to 160 °C with stirring, and at the same temperature
heated for an hour. Then, it was cooled to 120°C and filtered at the same temperature. After the reaction mass filtration was completed, after washing with 400 parts of 0-dichlorobenzene kept at 100°C,
After washing with 0 parts of methanol, then washing with 300 parts of water, and pressing, the cake was removed and dried.
0 parts of a dioxazine compound (R in general formula (1) is C2H
5) was obtained. The elemental analysis values of the obtained compound were C; 69.8%, H;
4.1%, N; 9.5%, Cj! ; IIJ% was shown. Filtration and washing of the reaction mass in the above operation can be performed in a short time, and the amount of solvent used for washing can be reduced compared to conventional methods. Example 4 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 0.5 part of 36% hydrochloric acid was added, and the temperature was raised to 145 to 150°C with stirring, and heated at the same temperature for 12 hours. Then, it was cooled to 120°C and filtered at the same temperature. After the reaction mass filtration was completed, it was washed with 400 parts of 0-dichlorobenzene kept at 100°C in advance, then washed with 150 parts of methanol, and then washed with 30 parts of methanol.
After washing with 0 parts of water and pressing, the cake was taken out and dried to obtain 51.0 parts of a dioxazine compound (general formula CI
) where R was CzHs) was obtained. The elemental analysis values of the obtained compound were: C: 72.0%, H: 4.1%, N: 9.8%
, C18.5%. Filtration and washing in the above operation were easy, and the amount of washing solvent used was small. Example 5 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 1.0 part of 36% hydrochloric acid and 4 parts of p-chloranil were added, and while stirring,
The temperature was raised to 5 to 170°C, 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 the reaction mass filtration was completed, the cake was washed with 400 parts of O-dichlorobenzene kept at 100°C in advance, washed with 150 parts of methanol, then washed with 300 parts of water, and after being squeezed, the cake was taken out and dried. 51.5 parts of a dioxazine compound (general formula 1"I) in which R is C2H5) was obtained. The elemental analysis values of the obtained compound were: C; 70.6%; H;
4.1%, N; 9.7%, Cj! ; showed 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 processed into 400 parts of trichlorobenzene, and further 70% sulfuric acid 1
．． Add 0 parts and raise the temperature to 190-200°C while stirring,
It was heated at the same temperature for 5 hours. Then cooled to 120°C,
It was filtered at the same temperature. After the reaction mass filtration is completed, 1
After washing with 400 parts of trichlorobenzene kept at 00°C, washing with 150 parts of methanol, then washing with 300 parts of water, and after squeezing, the cake was taken out and dried.
49.0 parts of a dioxazine compound (R in general formula (1) is C2)Is was obtained. The elemental analysis values of the obtained compound were: C: 71.0%, H: 4.1%, N: 10.0%, C
It showed 18.5%. The filtration and washing involved in the above operations were easy, and the amount of washing solvent used was small. Example 7 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-pentuquinone 6011B
In addition to 400 parts of O-dichlorobenzene, an additional 70%
1.0 part of sulfuric acid and p-benzenesulfonyl chloride5.
0 part was added and the temperature was raised to 165-170°C while stirring.
It was heated at the same temperature for 5 hours. The mixture was then cooled to 120°C and filtered at the same temperature. After the reaction mass filtration was completed, the cake was washed with 400 parts of O-dichlorobenzene previously kept at 100°C, washed with 150 parts of methanol, and then washed with 300 parts of water, compressed, and then the cake was taken out and dried. 51.
OR dioxazine compound (R in general formula (1) is -C2
H3) was obtained. The elemental analysis value of the obtained compound is C; 7
1.0%, H; 4.1%, N; 9.7%, C1'; 10
．． It showed 8%. Filtration and washing of the reaction mass in the above operation can be performed in a short time, and the amount of solvent used for washing can be reduced compared to conventional methods. Example 8 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, 0.5 part of 98% sulfuric acid and 2 parts of 0-chloranil were added, and while stirring,
The temperature was raised to 5 to 170°C, and the mixture was heated at the same temperature for 5 hours. The mixture was then cooled to 120°C and filtered at the same temperature. After completion of reaction mass filtration, O-
After washing with 400 parts of dichlorobenzene, washing with 150 parts of methanol, and then washing with 300 parts of water and pressing, the cake was taken out and dried. 51.0 parts of a dioxazine compound (R in general formula (1) is -C2H5) was obtained. The elemental analysis values of the obtained compound were: C: 71.0%, H: 4.1%
, N: 9.7%, Cj2: IQ, 5%. Filtration and washing of the reaction mass in the above operation can be performed in a short time, and the amount of solvent used for washing can be reduced compared to conventional methods. Example 9 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 400 parts of nitrobenzene, and further 1.0 parts of 36% hydrochloric acid was added.
part and 2.0 parts of benzoquinone, and while stirring, 155~
The temperature was raised to 160°C and heated at the same temperature for 5 hours. The mixture was then cooled to 120°C and filtered at the same temperature. After the reaction mass filtration was completed, the cake was washed with 400 parts of 0-dichlorobenzene kept at 100° C., then washed with 15011E methanol, and then washed with 300 parts of water, compressed, and then the cake was taken out and dried. 51.0 parts of a dioxazine compound (R in the general formula [■] is -C28%) was obtained. The elemental analysis values of the obtained compound were: C: 71.0%, H: 4.1%, N: 9.5%, C
It showed 110.5%. Filtration and washing of the reaction mass in the above operation can be performed in a short time, and the amount of solvent used for washing can be reduced compared to conventional methods. Example 10 60 parts of 2.5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 400 parts of mesitylene, and 1.5 parts of 36% hydrochloric acid was added. OB was added, and the temperature was raised to 155 to 160°C while stirring, and heated at the same temperature for 5 hours. The mixture was then cooled to 120°C and filtered at the same temperature. After the reaction mass filtration is completed, the temperature is 100°C in advance.
After washing with 400 parts of 0-dichlorobenzene kept warm at
After washing with 50 parts of methanol and then 300 parts of water and pressing, the cake was taken out and dried. 51.0 parts of a dioxazine compound (R in general formula [I] is -C2H5) was obtained. The elemental analysis value of the obtained compound was C; 71.0%
, H; 4.1%, N; 9.7%, Cj! showed 9.0%. Filtration and washing of the reaction mass in the above operation can be performed in a short time, and the amount of solvent used for washing can be reduced compared to conventional methods. Comparative example 1 (known example) 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 0
- In addition to 400 parts of dichlorobenzene, after raising the temperature, add 19 parts of benzenesulfonyl chloride,
The temperature was raised to ℃ and kept at the same temperature for 6 hours. After cooling to 120°C, it was filtered at the same temperature. Then, preheat to 100℃
Washing was performed using 400 parts of 0-dichlorobenzene that had been kept warm. Then, it was further washed using 400 parts of the same 0-dichlorobenzene. Thereafter, the cake was washed with 150 parts of methanol and 800 parts of water, then squeezed, and the taken out cake was dried. 47.6 parts of dioxazine compound were obtained. The elemental analysis values of the obtained compound were: C: 70.0%, H: 3.8%, N
; 9.6%, C111.5%, S: 0.3%. In the above operation, it took a long time (about 1 hour) to filter the reaction mass and wash it with 0-dichlorobenzene. In addition, after the first washing with 0-dichlorobenzene, 2
The elemental analysis value of the dioxazine compound obtained by performing the same treatment after washing with methanol without performing the second washing is as follows.
C: 70.0%, H: 4.0%, N: 9.0%, C11
1.3%, S; shows 1.5%, with a high content of 8 minutes,
Cleaning was insufficient. Comparative Example 2 (Known Example) 60 parts of 2,5-dichloro-3,6-bis(9-ethyl-3-carbazolylamino)-1,4-benzoquinone was added to 0
In addition to 300 parts of -dichlorobenzene, 26 parts of P-)luenesulfonic acid was added, and the mixture was kept at 80 to 85°C. This suspension was added to 100 parts of 0-dichlorobenzene, which had been separately kept at a temperature of 175 to 180°C, while stirring for 3 hours. After addition, further heat to 175-180℃
It was kept warm for 6 hours. Thereafter, it was cooled to 120°C and filtered. Next, it was washed using 400 parts of 0-dichlorobenzene that had been kept at 100°C in advance. The same operation was performed three more times. Then 150 parts of methanol, 3
After washing with 0.00 parts of water, the cake was squeezed and the taken out cake was dried. A dioxazine compound of 38 parts was obtained. The elemental analysis values of the obtained compound were: C: 66.0%, H: 4.0%, N;
7.8%, Cj2: 6.5%, S: 3.3%, and 8 minutes were common. In the above operation, it took a long time (about 2 hours) to filter the reaction mass and wash it with 0-dichlorobenzene. Reference Example (Usage Example) Dioxazine compounds obtained under the conditions of Example 1, Example 5, and Comparative Example 1 (washed twice with o-dichlorobenzene) each having a particle size of 100 parts and 300 mesh through. 700 parts of common salt and 150 parts of ethylene glycol were ground for 7 hours while maintaining a temperature of 70 to 75°C using a double-armed experimental Ni-Goo, and the mass was poured into 2,000 parts of warm water (80°C) and stirred. After that, it is filtered and 4,000
After washing with 100 ml of water, the cake was taken out and dried. Using this dried cake as a pigment, a nitrocellulose-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. Results * Specific surface area is determined by gas adsorption method using BET method * 7 Coloring power is determined by using a standard sample of 10096 and varying the amount of sample added in the ink to show the same coloring power * Gloss is determined by JISLO 804: Judgment was made according to the gray scale for discoloration and fading, and the difference in the number 4 color chart was 2. The difference in the number 4 to 5 color charts was 1. *Transparency was determined according to the same method as gloss. that's all

Claims (5)

[Claims] (1) General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [I] (In the formula, R is the number of carbon atoms) represents an alkyl group of 1 to 4, 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 alone or as a mixture. ) A method for producing a dioxazine compound shown in (2) The method according to claim 1, wherein the inorganic acid is hydrochloric acid or sulfuric acid. (3) The oxidizing agent is p-benzoquinone and its derivatives, o
- The method according to claim 1, characterized in that it is benzoquinone and its derivatives, benzenesulfonyl chloride and its derivatives, or benzenesulfonic acid esters. (4) The method according to claim 1, wherein the heating temperature is in the range of 110°C to 200°C. (5) the inert organic solvent is chlorobenzene, dichlorobenzene, trichlorobenzene or a mixture thereof;
2. The method according to claim 1, wherein nitrobenzene or an alkylbenzene having a boiling point of 110° C. or higher is used.