JPH0326226B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula (In the formula, R represents hydrogen or ethyl.) This invention relates to an improved method for producing a dioxazine compound represented by the following formula.

For more details, please refer to the formula (In the formula, R represents hydrogen or ethyl.) 3-amino-9-ethylcarbazole or 3-aminocarbazole and chloranil,
A formula characterized by condensation in the presence of a basic organic compound as an acid binder in an inert organic solvent, 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 shown in the following.

The compound in which R is an ethyl group in formula () corresponds to Color Index Pigment Purple 23, and has been used as a bright and robust purple pigment for various purposes.

Traditionally, this compound has been prepared by condensing 3-amino-9-ethylcarbazole and chloranil 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 adding a halide such as toluene. The general method was to add a ring-closing agent such as sulfonyl 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-
135556, a method of ring-closing by heating in a polar aprotic solvent, a method using a phase transfer catalyst described in JP-A-56-141355, or JP-A-Sho.
56-145951, 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 prepared.

The present invention will be explained in detail below.

The solvent-soluble basic organic compounds used in the present invention include secondary amines such as diethylamine and dibutylamine, tertiary amines such as triethylamine, tripropylamine, tributylamine, triethanolamine, triisopropanolamine, N,N-dimethylaniline,
Examples include N,N-diethylaniline, etc., or nitrogen-containing cyclic compounds such as piperidine, piperazine, pyridine, N-ethylpiperidine, N-methylmorpholine, etc., and the amount added is sufficient to supplement the acid generated by the reaction. Only the necessary amount is required, for example, 1.0 to 1.5 mol per 1 mol of the compound of formula (),
Preferably it is 1.0 to 1.1 mol. Generally known methods can be applied except for changing the acid binder. That is, 2 moles of 3-amino-9-ethylcarbazole or 3-aminocarbazole and 1 mole of chloranil are dissolved in an inert solvent such as chlorobenzene, dichlorobenzene (o-, m-, p-), trichlorobenzene (1,2,3- . If the reaction is carried out at the reaction temperature for 1 to 5 hours, unreacted 3-amino-9-ethylcarbazole or 3-
The aminocarbasol disappears and the condensation reaction is completed.

Next, benzenesulfonyl chloride, toluenesulfonyl chloride (o-, p
-), sulfonic acid chlorides such as methanesulfonyl chloride or benzoic acid chlorides,
Add a halide such as chloranil or dichloronaphthoquinone, preferably at 60 to 220°C for 1 to 5 minutes.
Time reacts. The amount added is 0.5 to 1 mol, preferably 0.5 to 0.7 mol, per 1 mol of the compound of formula []. Part of the ring-closing reaction is also progressing in parallel with the condensation reaction in the previous stage, but it is necessary to heat the reaction mixture to, for example, 150 to 200°C in order to substantially complete the ring-closing reaction.

The main raw materials used here, 3-amino-9-ethylcarbazole, chloranil, toluenesulfonyl chloride, and other 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 % represent parts by weight and % by weight.

Example 1 21.0 parts of 3-amino-9-ethylcarbazole, o
-280 parts of dichlorobenzene, triethylamine
Add 14.76 parts of chloranil to 10.6 parts of solution,
Incubate for 2 hours at ~35°C.

Add 11.9 parts of benzenesulfonyl chloride
The temperature was raised to 170°C, and the reaction was carried out at 170-180°C for 2 hours.
It is cooled to 100 DEG C., filtered and washed with 360 parts of o-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 IR absorption spectrum.

From the raw material 3-amino-9-ethylcarbazole
90.3%, corresponding to a yield of 75.2% from chloranil.

Example 2 23.0 parts of aminoethyl carbazole (3-amino form
15 parts of chloranil and 10.6 parts of triethylamine were added to 250 parts of dichlorobenzene (88% o-form, 10% p-form, 2% m- and mono-form) solution containing 21.0 parts of 1-amino form, 2.0 parts of 1-amino form). React at 20-30°C for 2 hours.

Toluenesulfonyl chloride (purity 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. Cool to 100℃ and dichlorobenzene 360
After washing the cake in a
After washing with hot water and drying, 25.9 parts of the same dioxazine compound as in Example 1 was obtained.

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

Comparative Example 1 21.0 parts of 3-amino-9-ethylcarbazole was
-Dissolve in 400 parts of dichlorobenzene and add 8.9 parts of anhydrous sodium acetate and 18.4 parts of chloranil at 50°C.

After keeping the temperature at 60-65°C for 2 hours, the temperature was raised to 115°C over 5 hours under reduced pressure. Return to normal pressure, add 10.5 parts of benzenesulfonyl chloride, and heat to 170-180℃.
Heat for 8 hours.

After adding 105 parts of o-dichlorobenzene and heating at 100°C, the same procedure as in Example 2 was performed to obtain 23.5 parts of the target dioxazine compound. 3-
Yield from amino-9-ethylcarbazole is 79.8
% yield from chloranil is only 53.3%.

Comparative Example 2 In order to improve the productivity of Comparative Example 1, the solvent o-
The amount of dichlorobenzene used was reduced from 400 parts to 220 parts, and the amount of 3-amino-9-ethylcarbazole was reduced to 21.0 parts.
The reaction was carried out by adding 23.0 parts of chloranil and 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 instead of 10.5 parts of benzenesulfonyl chloride, and the reaction time was increased to 8.0 parts, including the time required to raise the temperature.
time was shortened.

After heating at 100°C, 22.0 parts of the target dioxazine compound was obtained by operating in the same manner as in Example 1, which corresponds to a yield of 74.7% from 3-amino-9-ethylcarbazole and 40.0% from chloranil. .

Example 3 3-aminocarbazole was used instead of the raw material 3-amino-9-ethylcarbasol used in Example 1.
The procedure is the same as in Example 1 except that part 18.2 is used. Dioxazine compound represented by the following formula 22.5 parts were obtained.

Example 4 In place of 10.6 parts of triethylamine used in Example 1, 19.4 parts of tributylamine, 12.7 parts of N,N-dimethylaniline, 8.9 parts of piperidine, 11.8 parts of N-ethylpiperidine, or N-methylmorpholine were used.
As a result of adding 10.6 parts and operating in the same manner as in Example 1, the same dioxazine compound as in Example 1 was obtained with high purity and high yield.

Example 5 The same procedure as in Example 2 was carried out except that nitrobenzene was used as a solvent instead of the dichlorobenzene used in Example 2, and 7.7 parts of methanesulfonyl chloride was added instead of 12.9 parts of toluenesulfonyl chloride.

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.

0.05 part of the obtained pigment and 2 parts of titanium dioxide were mixed with 65 parts of vinyl chloride (trade name "Vinica" - a product of Mitsubishi Monsanto), 32 parts of dioctyl phthalate, 2 parts of dibutyltin laurate, and 1 part of magnesium stearate.
Mix with a compound consisting of 100 parts in total and melt uniformly at 170°C with 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, but the hue was dirty and the fastness was lowered by grade 1 or higher.

Claims (1)

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