JP2980296B2 - Method for producing dioxazine compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a compound. More specifically, the present invention relates to a method for producing a dioxazine compound useful as a functional dye in addition to a dye and a pigment.

[0002]

2. Description of the Related Art Conventionally, equation (2)

[0003]

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(Wherein R represents an alkyl group having 1 to 8 carbon atoms in the formula (2)), the compound represented by the formula (1)

[0005]

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In the formula (1), R represents an alkyl group having 1 to 8 carbon atoms, and X ₁ and X ₂ each independently represent a hydrogen atom or a chlorine atom. It is described in German Patent Specification 51 71 943 and British Patent Specification 385 565. Recently, P-
Ring closure using an organic acid such as toluenesulfonic acid (see JP-A-58-84857), and ring closure by heating in the presence of an inorganic acid or an inorganic acid and an oxidizing agent (JP-A-62-277388). No.).

[0007]

In the above-mentioned conventional methods, even if there are slight fluctuations in production conditions caused by fluctuations or changes in temperature, reaction time, reaction vessel, stirring method, etc., the yield and quality ( It is known that hue and gloss) change greatly. Furthermore, high yields cannot be expected due to the formation of many components other than the target substance due to side reactions during the ring closure reaction. In addition, a long time is required for filtration and a large amount of organic solvent is required for washing. Therefore, there is a need for solving these problems.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, they have found that the above problem can be solved by heating and closing the formula (2) under reduced pressure. That is, the present invention uses the formula (2)

[0009]

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(In the formula (1), R represents an alkyl group having 1 to 8 carbon atoms.) A compound represented by the formula:
Formula (1) characterized in that the ring is heated and closed under reduced pressure in the presence of an oxidizing agent.

[0011]

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(In the formula (1), R represents an alkyl group having 1 to 8 carbon atoms, and X ₁ and X ₂ each independently represent a hydrogen atom or a chlorine atom.) is there.

The present invention will be described in detail. In the present invention, as the inert organic solvent, chlorobenzene (monochlorobenzene, dichlorobenzene, etc.), alkylnaphthalene (methylnaphthalene, etc.), and nitrobenzene are used. The amount of these solvents to be used is 3 to 20 times by weight, preferably 5 to 10 times by weight, relative to the compound of the formula (2).

Next, examples of oxidizing agents that can be used in the production method of the present invention include 0-benzoquinone and its derivatives,
-Benzoquinone and its derivatives, benzenesulfonyl chloride and its derivatives, and benzenesulfonic acid esters. Among them, P-benzoquinone, P-chloranyl, P-toluenesulfonyl chloride, benzenesulfonyl chloride and the like are particularly preferable. These oxidizing agents are used in a molar ratio of 0.1 to 2.0, preferably 0.5 to 1.5, relative to the compound of the formula (2).

The degree of reduced pressure employed in the production method of the present invention is as follows:
It depends on the inert solvent used, but preferably 15
0 mmHg to 600 mmHg, more preferably 200 mmHg
Hg to 500 mmHg. Reaction temperature is 100
To 200 ° C, preferably 150 to 180 ° C, and the reaction time is usually 1 to 6 hours. When the reaction is completed, cool it down,
If necessary, after dilution with an organic solvent such as methanol, filtration is performed to separate the desired product. Thereafter, if necessary, washing is performed with a solvent.

The production method of the present invention uses the formula (2) as a starting material and the formula (3)

[0017]

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(In the formula (3), R represents an alkyl group having 1 to 8 carbon atoms.) And tetrachlorobenzoquinone in an inert organic solvent in the presence of an acid scavenger to condense the formula (2) A compound may be obtained, and the production method of the present invention may be applied without separating the compound. In the dioxazine compound of the formula (1) obtained by the production method of the present invention, X ₁ and X ₂ may both be a hydrogen atom or a chlorine atom,
One may be a hydrogen atom and the other may be a chlorine atom.

According to the production method of the present invention, a dioxazine compound having no change in the yield and quality (hue and gloss) can be obtained even if the temperature, reaction time, reaction vessel, stirring method and the like are changed or changed. Furthermore, the amount of the organic solvent used is small, and the washing is easy.

[0020]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, all percentages and parts are by weight.

EXAMPLE 1 20 parts of 2.5-dichloro-3.6-bis (9-ethyl-3-carbazolylamino) -1.4-benzoquinone were added to o
-In addition to 120 parts of dichlorobenzene, 6.5 parts of p-benzenesulfonyl chloride are further added as an oxidizing agent.
Heat to 160 ° C. while maintaining the degree of vacuum at 500 mmHg. React at the same temperature for 6 hours. During this period, the amount of o-dichlorobenzene distilled off is appropriately replenished. After completion of the reaction, 120
It cooled to ℃ and filtered at the same temperature. Next, 100
After washing with 80 parts of o-dichlorobenzene kept at
Wash sequentially with 0 parts methanol and 100 parts water. K
17.3 parts (yield 8
7.1%) of a dioxazine compound (compound of the general formula (1), wherein R is C ₂ H ₅ ).

Comparative Example 1 (Method described in JP-A-62-192385) 2.5-Dichloro-3.6-bis (9-ethyl-3-carbazolylamino) -1.4-benzoquinone 20 parts O
-In addition to 130 parts of dichlorobenzene, 6.5 parts of benzenesulfonyl chloride are further added as oxidizing agent. Then heat to 160 ° C. React at 160-165 ° C for 5 hours. After completion of the reaction, the mixture was cooled to 120 ° C. and filtered at the same temperature. Then, after washing with 250 parts of o-dichlorobenzene which was previously kept at 100 ° C., 50 parts of methanol, 10 parts
Wash sequentially with 0 parts of water. The cake was taken out and dried to obtain 15.8 parts (yield: 79.5%) of a dioxazine compound (compound of the formula (1) wherein R is C ₂ H ₅ ).

Example 2 20 parts of 3-amino-9-n-propylcarbazole were converted to o
Dissolve in 200 parts of dichlorobenzene, add 4.7 parts of sodium carbonate and add 14.3 parts of tetrachlorobenzoquinone at 25-30 ° C. When the reaction is carried out at the same temperature for 5 hours, 3-amino-9-n-propylcarbazole disappears. Next, 140 ° C. while maintaining a reduced pressure of 450 mmHg.
Heat up to Next, after returning to normal pressure, 8.5 parts of P-toluenesulfonyl chloride is added and the temperature is raised to 165 ° C. The reaction is completed when the temperature is maintained at 165 to 170 ° C. for 2 hours. After cooling to 120 ° C., the mixture was filtered at the same temperature. Next, o-dichlorobenzene 10 previously kept at 100 ° C.
After washing with 0 parts, it is sequentially washed with 60 parts of methanol and 80 parts of water. 23. removing the cake and drying;
9 parts (86.9% yield) of dioxazine compound (compound of formula (1) where R is C ₃ H ₇ ) was obtained.

Example 3 20 parts of 3-amino-9-ethylcarbazole was dissolved in 300 parts of nitrobenzene, and 11 parts of triethylamine was added. At 15 to 20 ° C., tetrachlorobenzoquinone 14.1 was added.
Add parts. When reacted at the same temperature for 5 hours, 3-amino-
9 Ethyl carbazole disappears. Next, the degree of decompression 200
The temperature is raised to 150 ° C. while maintaining mmHg. 10 parts of P-toluenesulfonyl chloride is added and the temperature is raised to 170 ° C. Next, the reaction is completed by returning to normal pressure and maintaining at 170 to 175 ° C. for 3 hours. After cooling to 120 ° C., the mixture was filtered at the same temperature. Then, after washing with 60 parts of nitrobenzene kept at 100 ° C. in advance, 20 parts of methanol, 80 parts
Wash successively with portions of water. The cake was taken out and dried to obtain 24.4 parts (yield: 87.0%) of a dioxazine compound (a compound of the formula (1) wherein R is C ₂ H ₅ ).

[0025]

According to the present invention, a production method has been found in which a dioxazine compound can be obtained in a very stable and high yield, and the amount of a solvent used for washing can be reduced as compared with the conventional method.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-62-277388 (JP, A) JP-A-64-16788 (JP, A) JP-A-58-118855 (JP, A) JP-A-58-118 52357 (JP, A) JP 41-17150 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 19/02 C09B 19/00 C07D 498/22

Claims (2)

(57) [Claims] (1) Formula (2) (Wherein, in the formula (2), R represents an alkyl group having 1 to 8 carbon atoms). A compound represented by the formula: (1) (In the formula (1), R represents an alkyl group having 1 to 8 carbon atoms, X ₁
And X ₂ each independently represent a hydrogen atom or a chlorine atom. For producing dioxazine compounds represented by the formula: 2. The pressure reduction degree is 150 mmHg to 600 mmHg.
The manufacturing method according to claim 1, wherein