JPS58118855A - Production of dioxazine compound - Google Patents

Abstract

PURPOSE:To produce the titled compd. of high quality in high yields, by condensing 3-amino-(9-ethyl) carbazole with chloranil in the presence of a basic org. compd. in an inert org. solvent and cyclizing the product. CONSTITUTION:A 3-amino-9-ethylcarbazole or 3-aminocarbazole of formula I(wherein R is H, ethyle) is condensed with chloranil in the presence of a basic org. compd. such as diethylamine as an acid acceptor on an inert org. solvent such as chlorobenzene. The product is cyclized in the presence of a cyclizing agent such as benzene-sulfonyl chloride by heating to produce a dioxazine compd. of formula II (wherein R is as defined above). The compds. are clear, fast violet pigments. By using the solvent-soluble basic org. compd. in place of known acid acceptors, yields and quality can be greatly improved.

Description

[Detailed description of the invention] The present invention is based on the formula (In the formula, R represents hydrogen or ethyl) The present invention relates to an improved method for producing a dioxazine compound shown in the following.

More specifically, 3-
Amino-9-ethercarbasole or 3-aminocarpazole and chloranyltra are condensed in an inert organic solvent in the presence of a basic organic compound as an acid binder, followed by ring-closing by heating in the presence of a ring-closing agent. The present invention relates to a method for producing a dioxazine compound having the following characteristics.

The compound in which R is an ethyl group in formula (1) corresponds to Color Indices Pigment Violet 231C, and has been used for various purposes as a vivid and robust purple pigment.

Conventionally, this compound is produced by condensing 3-amino-9-ethylcarpasol and chlorinyl in an inert solvent by adding an acid binder such as caustic soda or potash, soda or potassium carbonate, sodium bicarbonate or sodium acetate, and then converting it to a halide. For example, a common method has been to add a ring-closing agent such as toluenesulfonyl chloride, benzenesulfonyl chloride, or benzoyl chloride, heat the ring, close the ring, and separate the precipitated target product.

Since then, various improved manufacturing methods have been developed, such as JP-A-56-135.
Heating in a polar solvent as described in 556,
Ring-closing method, method using a phase transfer catalyst described in JP-A-56-141355, or JP-A-56-14
5951, a method in which a small amount of water is present has been proposed, but there are many industrially unsatisfactory points.

The present inventor discovered that in these conventional production methods, the acid binder commonly used in the previous condensation step is hardly soluble in the solvent, so the reaction is extremely uneven and does not proceed smoothly, resulting in poor yield and quality. In this invention, we have dramatically improved the yield and quality by using a basic organic compound soluble in a solvent in place of the known acid binder, making it an industrially extremely effective product. It has now been found that the desired dioxazine compounds can be advantageously produced.

The present invention will be explained in detail below.

Examples of basic organic compounds soluble in solvents used in the present invention include secondary amines such as diethylamine and dibutylamine, tertiary amines such as triethylamine, triplepyramine, tributylamine, triethanolamine, triisopropano-amine, etc. luagun, N,N-dimethylaniline, N,N-diethylaniline, etc., or nitrogen-containing cyclic compounds such as piperidine, piperazine, pyridine, N-ethylpiperidine, N-methylmorpholine, etc., and the amount added may be in an amount necessary to supplement the acid generated by the reaction, for example, 1.0 to 1.5 mol, preferably 1.0 to 1.5 mol, per 1 mol of the compound of formula (1).
It is 1 mole. Generally known methods can be applied except for changing the acid binder. 3-amino-9-ethylcarbazole or 3-aminocarbable, 2 moles and chloranil 1
Examples of solutions dissolved in inert solvents include chlorobenzene, dichlorobenzene (0-t m-*p-), tric-tetrabenzene ('+2°3-1l, 2.4-1,3.5-) and If a mixture of these, nitrobenzene, alkylbenzene or alkylnaphthalene is reacted in the presence of the above-mentioned basic organic compound at a reaction temperature of preferably 0 to 60°C for 1 to 5 hours, unreacted 3- The amino-9-ethyl carhasol or 3-aminocarbubble disappears and the condensation reaction is completed.

Then, as a ring-closing agent, sulfonic acid chlorides such as benzenesulfonyl chloride, toluenesulfonyl chloride, (Or p-)s methanesulfonyl chloride, or halides such as benzoic acid chloride, chlorol, dichloronaphthoquinone, etc. are added. Preferably, the ring-closing reaction is partially progressed after 1-5 hours at 60-220°C, but for example, 150-220°C is required for the ring-closing to be substantially completed.
It is necessary to heat it to 00°C.

The main raw materials used here, such as 3-amino-9-ethyl kaha salt chloranil and toluenesulfonyl chloride, as well as additives and solvents, were particularly purified. The product does not need to be of high purity, and the target product of high purity can be obtained extremely easily and in high yield without flowing an inert gas such as nitrogen gas during the reaction.

Although the dioxazine compound obtained in the present invention can be used as a pigment as it is, it is preferable to use it after grinding or kneading to finely disperse it and improving its quality characteristics using a conventional pigment preparation method.

Furthermore, since the target product can be obtained in high purity, when used in ink, paint, resin coloring, or pigment resin printing, it has better fastness to bleed, chemicals, and solvents than compounds with the same structure produced by known methods. It has excellent fluidity and gloss.

This will be specifically explained below by giving examples. Parts and parts are parts by weight and weight %.

Example 1 14.16 parts of chloranil was added to a solution of 1.0 parts of 3-amino-9-ethylcarbazole a, 280 parts of 0-dichlorobenzene, and 10.6 parts of triethylamine, and 20 to 35 parts of chloranil was added.
Incubate at ℃ for 2 hours.

Benzenesulfonyl chloride 11.9 parts 11. t17
The temperature is raised to 0°C and the reaction is carried out at 170-180°C for 2 hours.

Cool to 100°C, filter, and wash with 360 parts of 0-dichlorobenzene and then with 130 parts of methanol.

After washing with hot water and drying, use the following formula. 26.6 parts of a dioxazine compound represented by was obtained.

This product was confirmed to be the desired product by X-ray diffraction and E-R absorption spectrum.

90. from the raw material 3-amine, -9-ethylcarbazole
3, corresponding to a yield of 75.2% from chloranil.

Example 2 Aminoethylcarbasol 23.0 parts (3-amino form 21
・15 parts of chloranil and 10 parts of triethylamine in 250 parts of a solution of dichlorobenzene (88 parts of 〇, 10 parts of p-1, 2 parts of m- and mono-form) containing 0 parts, l-ag) form) -Add 6 parts and react at 20-30°C for 2 hours.

Toluenesulfonylchloride)” (M degree 85%) 12.
9 parts were dissolved in 30 parts of dichlorobenzene and heated to 170°C, and the above condensation reaction solution was added dropwise into this solution over 3 hours. React at 170-180°C for 1 hour. 100
After cooling to 0.degree. C., filtering, and washing with 360 parts of dichlorobenzene, the cake was steam distilled, filtered, washed with hot water, and dried to obtain 26.9 parts of the same dioxazine compound as in Example 1.

This is 87.9 from 3-amino-9-ethylcarbazole.
This corresponds to a yield of 72.1 from chloranil.

Comparative Example 1 21.0 parts of 3-amino-9-ethyl carpasol is dissolved in 400 parts of 0-dichlorobenzene, and 8.9 parts of anhydrous sodium acetate and 18.4 parts of chloranil are added at 50°C.

After keeping the temperature at 60 to 65°C for 2 hours, the temperature is raised to 116°C over 5 hours under reduced pressure. Return to normal pressure, add 10.5 parts of benzenesulfonyl chloride, and heat at 170 to 180°C.
Heat for an hour.

After adding 105 parts of 0-dichlorobenzene and hot filtration at 100°C, the same procedure as in Example 2 was performed to obtain 23.5 parts of the desired dioxazine compound.

The yield from 3-amino-9-ethylcarbazole is 〒9.
The yield from chloranil in 8 t is only 53.3 t.

Comparative Example 2 In order to improve the productivity of Comparative Example 1, the amount of solvent 〇-dichlorobenzene used was reduced from 400 parts to 220 parts, and 3
The reaction was carried out by adding 21.0 parts of -amino-9-ethylcarbasol and 23.0 parts of chloraniol, and adding 8.2 parts of sodium carbonate instead of 8.9 parts of sodium acetate as an acid binder.

Furthermore, 15.2 parts of p-toluenesulfonyl chloride was used in place of 5 parts of nibenzenesulfonyl chloride, and the reaction time was shortened to 8 hours, including the time required to raise the temperature.

After hot filtration at 100°C, the same procedure as in Example 1 yields 22·og of the desired dioxazine compound, which is 74·7% from 3-amino-9-ethercarbazole.
This corresponds to a yield of 40.0% from chloranil.

Example 3 The same procedure as in Example 1 was repeated except that 18.2 parts of 3-aminocarbubble was used instead of the raw material 3-amino-9-ethyl carhasol used in Example 1. 22.5 parts of a dioxazine compound represented by the following formula was obtained.

Example 4 Instead of 10.6 parts of triethylamine used in Example 1, 19.4 parts of tributylamine, 12.1 parts of N,N-dimethylaniline, 8.9 parts of piperidine, and 8 parts of N-ethylpiperidine were used. Or N-methylmorpholine 10.6
As a result of the same operation as in Example 1 with the addition of
The same dioxazine compound was obtained in high purity and yield.

Example 5 The same procedure as in Example 2 was carried out except that 7.7 parts of methanesulfonyl chloride was added instead of 12.9 parts of dichlorobenzene used in Example 2.

The desired dioxazine compound was obtained in comparable yield.

Example 6 The dioxazine compound obtained in Example 2 is converted into a pigment by a conventional method.

A total of 0.05 parts of the obtained pigment and 2 parts of titanium dioxide were mixed with 65 parts of vinyl chloride (trade name "Viniriki" - a product of Mitsubishi Monosanto Co., Ltd.), 32 parts of dioctyl 7 tallate, 2 parts of dibutyltin laurate, and 1 part of magnesium stearate. The mixture is mixed with 100 parts of a compound and uniformly melted at 0° C. using a heating roll.

When this was rolled in a press, a vivid purple colored PVC sheet was obtained, and its chemical resistance and bleed resistance were of the highest quality.

On the other hand, the dioxazine compound with the same structure obtained in Comparative Example 1 was made into a pigment by the same method and used for coloring vinyl chloride.
The hue was dirty and the fastness was lower than grade 1.

Patent applicant: Nippon Kayaku Co., Ltd.

Claims (1)

[Claims] (1) 3- represented by the formula (in the formula, R represents hydrogen or ethyl)
A formula characterized by condensing amino-9-ethylcarbazole or 3-aminocarpazole and chloranil in the presence of a basic organic compound as an acid binder in an inert organic solvent, followed by heating and ring-closing in the presence of a ring-closing agent. (In the formula, R represents the same meaning as above.) A method for producing a dioxazine compound represented by the following.