JP3083248B2 - Method for producing 3,3'-dichloroindanthrone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to vat dyes 3,3 '.
The invention relates to a method for producing dichloroindanthrone.

[0002]

2. Description of the Related Art 3,3'-Dichloroindanthrone is
Color index since ancient times, C.I. I. Battoburu over 6
This compound is useful as a blue-based dye having good fastness to chlorine.

[0003] Conventionally, as a method for producing 3,3'-dichloroindanthrone, for example, a method in which a bromine atom of a bromide of indanthrone is replaced with a chlorine atom (US Pat.
No. 413,483, U.S. Pat. No. 2,413,51.
No. 4), a method of condensing chlorinated aminoanthraquinone such as 1,3-dichloro-2-aminoanthraquinone, a method of chlorinating indanthrone, and the like are known.

[0004] Among them, a method widely practiced industrially is a method of chlorinating indanthrone. Specifically, a method of chlorinating indanthrone obtained by condensing 1-aminoanthraquinone by the action of an alkaline condensing agent in sulfuric acid, and a method of chlorinating in sulfuric acid using manganese dioxide as a catalyst (Toyo Hosoda, Theory Manufacturing) Dye chemistry) or a method of chlorination in an inert solvent such as nitrobenzene. The compounds obtained by these chlorinations are:
Formula (1)

[0005]

Embedded image (Hereinafter, referred to as an azine compound), which can be reduced using aluminum powder or ferrous sulfate heptahydrate to produce the desired 3,3′-dichloroindanthrone. it can.

[0006]

According to the conventional method, the present inventors chlorinated indanthrone and then reduced it to obtain 3,3'-dichloroindanthrone as a fine-particle dye, and confirmed the quality. However, it has been found that there is a problem in dyeability (especially, heat resistance, high-concentration filterability, insufficient dyeing density in padding dyeing), and an improved method thereof has been desired.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, after reducing the azine derivative, a method of dropping water or an aqueous solution of sulfuric acid at a high temperature to the reaction solution is adopted. The present inventors have found that the crystal form of 3,3'-dichloroindanthrone is changed, and the quality of the desired fine particle dye of 3,3'-dichloroindanthrone is improved, thereby completing the present invention. That is, the present invention provides a compound represented by the formula (1)

[0008]

Embedded image Is reduced in an aqueous sulfuric acid solution to obtain a compound of formula (2)

[0009]

Embedded image In the method for producing
A method for producing 3,3'-dichloroindanthrone, which comprises dropping water or an aqueous solution of sulfuric acid after the temperature is reduced to 0 ° C.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In a specific embodiment of the present invention, for example, an azine compound is dissolved in an aqueous solution of sulfuric acid and reduced using a reducing agent such as aluminum powder, iron, iron halide or iron sulfate. After completion of the reduction, the temperature of the reaction solution is raised to 80 to 180 ° C., and water or an aqueous solution of sulfuric acid is added dropwise thereto.
-Dichloroindanthrone can be obtained.

In the method of the present invention, the sulfuric acid which dissolves the azine compound is usually 98% by weight in which the azine compound is easily dissolved.
However, any concentration may be used as long as the azine compound is dissolved. Preferably, 96% by weight or more is used. The amount used is usually 4.0 to 20.0 times by weight, preferably 4.0 to 7.0 times the weight of the azine body of the raw material.
Use 0 weight times.

The reducing agent used for the reduction is preferably an inorganic reducing agent such as aluminum powder, iron, iron halide or iron sulfate. The amount of the reducing agent is usually 0.1 mol based on the azine compound as a raw material. To 5.0 molar ratio, preferably 0.
It is used in the range of 5 to 2.0 molar ratio.

The reduction reaction is usually carried out at a temperature of 30 ° C. to 80 ° C., preferably 30 ° C. to 50 ° C. After completion of the reduction, the reaction solution is heated to 80 to 180 ° C, preferably 135 to 140 ° C.
Keeping warm and adding water or sulfuric acid aqueous solution
Crystal modification of 3'-dichloroindanthrone is performed.

The crystal form of the target compound synthesized by a conventional method is an amorphous square crystal, but is converted into a needle-like crystal form by the above operation. Thereafter, the reaction solution is 10-
After allowing to cool to 60 ° C., preferably about 30 ° C., filtration and washing are performed to obtain 3,3′-dichloroindanthrone.

In the method of the present invention, water or an aqueous solution of sulfuric acid is added dropwise to the reaction solution after completion of the reduction at a high temperature, but an aqueous solution of sulfuric acid is preferred. The concentration of the sulfuric acid aqueous solution is usually 4
Those having 0 to 50% by weight are preferred.

In the method of the present invention, the time for dropping the aqueous sulfuric acid solution or water into the reduction reaction solution is usually 1 to 10 hours, and the time for dropping the aqueous sulfuric acid solution is preferably 4 to 5 hours. 5 to 9 hours are preferred.

If the dropping time is short, crystal transformation of 3,3'-dichloroindanthrone is possible, but the crystal diameter tends to be small, and the quality of the finely divided dye tends to be deteriorated.

In the method of the present invention, the sulfuric acid concentration after dropping an aqueous solution of sulfuric acid or water into the reduction reaction solution is 50 to 95.
%, Preferably 65 to 90% by weight, more preferably 80 to 85% by weight.

In the method of the present invention, the temperature at which the aqueous solution of sulfuric acid or water is dropped into the reduction reaction solution is 80 to 180 ° C., preferably 120 to 170 ° C., and more preferably 130 to 15 ° C.
0 ° C is good. If the dropping temperature is low, the crystal transformation may not occur, and the quality of the finely divided dye tends to deteriorate.

[0020]

The present invention will be further described with reference to the following examples.
In addition,% in an Example shows a weight%.

Example 1 (Synthesis Example 1) 348 g of 98% sulfuric acid and 99.4 g of azine-form wet cake (containing 50 g of azine form and 49.4 g of aqueous sulfuric acid) were charged into a reactor and dissolved. While purging the reactor with nitrogen, ferrous sulfate heptahydrate therein.
7 g was charged over 30 minutes, the temperature was raised to 80 ° C., and a reduction reaction was performed at the same temperature for 1 hour. 25% fuming sulfuric acid 1 after reduction
62.5 g was charged, and the mixture was further stirred at the same temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 140 ° C., and 50% sulfuric acid was added dropwise over 5 hours to adjust the sulfuric acid concentration of the reaction solution to 85%, thereby depositing crystals. The mixture was stirred at the same temperature for 1 hour and allowed to cool to 30 to 40 ° C. After filtration and washing, 89.5 g of a wet cake containing 43.9 g of 3,3′-dichloroindanthrone was obtained.
Observation of the crystals with an optical microscope revealed needle-like crystals as shown in FIG. 1, and the crystal grain size was about 63 μm.

(Example 1 of Fine Particle Dye) The wet powder of the dye synthesized in Synthesis Example 1 and the auxiliary were dispersed according to the following formulation, atomized, and spray-dried to obtain a fine dye. The atomization was performed using a six-cylinder sand grinder (manufactured by Igarashi Machine Manufacturing Co., Ltd.) at 1500 rpm. p. It took 18 hours to atomize at m and to atomize to a practical level. The finely divided dye obtained as described above had a high dyeing concentration by the padding method and also had other good physical properties. Hereinafter, the conditions for forming fine particles in the examples are the same, and the staining results are shown in Table 1.

Dispersion formula 50.4 g (asDry 24.7 g) of bulk powder wet cake obtained in Synthesis Example 1 Vanirex RNAP (lignin-based surfactant, manufactured by Nippon Paper Industries Co., Ltd.) 9.3 g Labelin WP (anion-based interface) Activator, Daiichi Kogyo Seiyaku Co., Ltd.) 4.8 g Neocol P (anionic surfactant, Daiichi Kogyo Seiyaku Co., Ltd.) 0.4 g Water 66.0 g

Example 2 (Synthesis Example 2) 220 g of 98% sulfuric acid and 99.4 g of an azine-form wet cake (containing 50 g of azine-form and 49.4 g of aqueous sulfuric acid) were charged into a reactor and dissolved. The reactor was heated to 50 ° C. while purging with nitrogen. Next, 1.4 g of aluminum powder was charged over 1 hour, and a reduction reaction was carried out at 50 ° C. for 1 hour. Thereafter, the temperature of the reaction solution was raised to 140 ° C., and 50% sulfuric acid was added dropwise over 5 hours to bring the sulfuric acid concentration of the reaction solution to 85% to precipitate crystals. Stir for 1 hour at the same temperature 3
It was allowed to cool to 0-40 ° C. After filtration and washing, 81.3 g of a wet cake containing 44.3 g of 3,3′-dichloroindanthrone was obtained. Observation of the crystals with an optical microscope revealed needle-like crystals similar to those in FIG. 1 and a crystal grain size of about 60 μm.

(Example 2 of Fine Particle Dye) In the same manner as in Fine Particle Dye Example 1, the wet powder cake obtained in Synthesis Example 2 was atomized. It took 16 hours to atomize to a practical level.

Example 3 (Synthesis Example 3) After the reduction reaction, the reaction solution, which was the same as in Synthesis Example 1 until the charging of 25% fuming sulfuric acid, was heated to 80 ° C.
157.2 g of sulfuric acid was dropped over 1 hour to adjust the sulfuric acid concentration of the reaction solution to 85% to precipitate crystals. The mixture was stirred at the same temperature for 1 hour and allowed to cool to 30 to 40 ° C. Filter and wash
74.0 g of a wet cake containing 45.6 g of 3'-dichloroindanthrone was obtained. Observation of the crystals with an optical microscope revealed that the crystals had the same crystal shape as that of FIG.

Example 4 (Synthesis Example 4) 176 g of 98% sulfuric acid and 72.7 g of an azine-type wet cake (containing 40 g of an azine-type and 32.7 g of aqueous sulfuric acid) were charged into a reactor and dissolved. The temperature in the reactor was raised to 50 ° C. while purging with nitrogen. Next, 1.1 g of aluminum powder was charged over 1 hour, and a reduction reaction was carried out for 1 hour. Thereafter, the temperature of the reaction solution was raised to 140 ° C., water was added dropwise over 1 hour, and the sulfuric acid concentration of the reaction solution was reduced to 85%.
To precipitate crystals. Stir for 1 hour at the same temperature, 30
The mixture was allowed to cool to 、 40 ° C., and filtered and washed to obtain 38.4 g of 3,3′-dichloroindanthrone. When the crystals were observed with an optical microscope, needle-like crystals similar to those in FIG. 1 were obtained, and the crystal grain size was about 20 μm.

Example 5 (Synthesis Example 5) 176 g of 98% sulfuric acid and 72.7 g of an azine-type wet cake (containing 40 g of azine-type and 32.7 g of aqueous sulfuric acid) were charged into a reactor and dissolved. The temperature in the reactor was raised to 50 ° C. while purging with nitrogen. Next, 1.1 g of aluminum powder was charged over 1 hour, and a reduction reaction was carried out for 1 hour. Thereafter, the temperature of the reaction solution was raised to 140 ° C., and 40% sulfuric acid was added dropwise over 1 hour to adjust the sulfuric acid concentration of the reaction solution to 70% to precipitate crystals. Stir at the same temperature for 1 hour, allow to cool to 30-40 ° C, filter and wash
-41.6 g of dichloroindanthrone were obtained. When the crystals were observed with an optical microscope, needle-like crystals were obtained, and the crystal grain size was about 15 μm.

Example 6 (Synthesis Example 6) 348 g of 98% sulfuric acid and 99.4 g of an azine-type wet cake (containing 50 g of an azine-type and 49.4 g of aqueous sulfuric acid) were charged into a reactor and dissolved. The temperature in the reactor was raised to 50 ° C. while purging with nitrogen. Then ferrous sulfate
60.7 g of heptahydrate was charged over 30 minutes, the temperature was raised to 80 ° C., and a reduction reaction was performed for 1 hour. Thereafter, 162.5 g of 25% fuming sulfuric acid was added to the reaction solution, and the mixture was further stirred for 1 hour. Thereafter, the temperature of the reaction solution was raised to 140 ° C., and water was added dropwise over 3 hours to adjust the sulfuric acid concentration of the reaction solution to 70% to precipitate crystals. The mixture was stirred at the same temperature for 1 hour, allowed to cool to 30 to 40 ° C., filtered and washed to obtain 52.2 g of 3,3′-dichloroindanthrone. Observing the crystal with an optical microscope,
Acicular crystals were obtained, and the crystal grain size was about 20 μm.

Comparative Example 1 (Comparative Synthesis Example 1) 208.8 g of 98% sulfuric acid and 61.7 g of an azine-type wet cake (30 g of azine-type and sulfuric acid water 3
1.7 g) was charged to the reactor and dissolved. While the inside of the reactor was purged with nitrogen, 36.4 g of ferrous sulfate heptahydrate was charged therein over 30 minutes, the temperature was raised to 80 ° C., and a reduction reaction was performed at the same temperature for 1 hour. After the reduction, 97.5 g of 25% fuming sulfuric acid was charged, and the mixture was further stirred at the same temperature for 1 hour. Thereafter, the reaction solution was cooled to 70 ° C.
The reaction solution is discharged at 50 ° C. or lower. After filtration and washing, 193.3 g of a wet cake containing 29.9 g of 3,3′-dichloroindanthrone was obtained. Observation of the crystal with an optical microscope revealed that the crystal had a square crystal shape as shown in FIG.

(Comparative Example 1 of Fine Particle Dye) In the same manner as in Example 1 of fine particle dye, the wet base cake of the dye prepared in Comparative Synthesis Example 1 and an auxiliary agent are dispersed, atomized, and spray-dried to obtain fine dye. I got The atomization time was as long as 28 hours. The finely divided dye obtained as described above had a low dyeing concentration by the padding method and had other poor physical properties. Table 1 shows the results of the staining.

Comparative Example 2 (Comparative Synthesis Example 2) 352 g of 98% sulfuric acid and 150.4 g of an azine-type wet cake (80 g of azine-type and 70.degree.
4 g) was charged to the reactor and dissolved. The reactor was heated to 50 ° C. while purging with nitrogen. 2.2 g of aluminum powder was charged therein over 1 hour, and the temperature was kept at 50 ° C.
For 1 hour. After the reduction, the reaction solution was gradually discharged into 1500 g of water. 70-80 due to heat generated at that time
Stir for 1 hour while maintaining the temperature of ° C. Filter and wash at 50-60 ° C, 3,3'-dichloroindanthrone
289.7 g of a wet cake containing 7 g were obtained. Observation of the crystal with an optical microscope revealed that the crystal had a square crystal shape similar to that of FIG.

(Comparative Example 2 of Fine Dye) In the same manner as in Fine Example 1 of the dye, the wet cake of the raw powder of the dye prepared in Comparative Synthesis Example 2 and an auxiliary agent are dispersed, finely divided, and spray-dried to form the finely divided dye. I got The atomization time was as long as 30 hours. The finely divided dye obtained as described above had a low dyeing concentration by the padding method and had other poor physical properties. Table 1 shows the results of the staining.

[0034]

[Table 1]

Note) a) A dye obtained by dissolving a fine particle dye in water, adding sodium hydroxide and hydrosulfite, dyeing a cotton thread in a reducing atmosphere, performing post-treatment, and checking the concentration. b) Observation of the staining concentration via the following route.

[0036]

C) A specified amount of the finely divided dye and hot water are mixed,
After natural filtration, the filtration time is measured. d) Fine particle dye dried at 110 ° C for 3 hours and subjected to a particle size test.

[0038]

According to the method of the present invention, the quality of the finely divided dye can be improved by transforming the crystal form of 3,3'-dichloroindanthrone into a completely different crystal form. That is, by reducing the azine compound and then dropping water or an aqueous solution of sulfuric acid at a high temperature, the desired 3,3 ′ is obtained by crystal modification of 3,3′-dichloroindanthrone.
The quality of the finely divided dye of dichloroindanthrone is improved, and the method of the present invention is industrially extremely useful.

[Brief description of the drawings]

FIG. 1 is an optical micrograph of a crystal of 3,3′-dichloroindanthrone synthesized in Synthesis Example 1. (Approximately 200 times magnification)

2 is an optical micrograph of a crystal of 3,3′-dichloroindanthrone synthesized in Comparative Example 1. FIG. (Approximately 200 times magnification)

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 241/46 C09B 5/56 CA (STN) CAOLD (STN)

Claims (2)

(57) [Claims] (1) Formula (1) (Formula 1) Is reduced in an aqueous sulfuric acid solution to obtain a compound of the formula (2) In the method for producing
A method for producing 3,3'-dichloroindanthrone, which comprises dropping water or an aqueous solution of sulfuric acid into the reaction solution after the temperature is reduced to 0 ° C. 2. The method according to claim 1, wherein the concentration of sulfuric acid after the addition of water or an aqueous sulfuric acid solution to the reaction solution after the reduction is 50 to 95%.