JP3083236B2 - Method for producing 3,3'-dichloroindanthrone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art 3,3'-Dichloroindanthrone is
Color index since ancient times, C.I. I. Bat Blue 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. 2,413,514.
), A method of condensing chlorinated aminoanthraquinone such as 1,3-dichloro-2-aminoanthraquinone, a method of chlorinating indanthrone, and the like.

Among them, a method widely practiced industrially is a method of chlorinating indanthrone, specifically, a method of chlorinating in an inert solvent such as benzene, and a method of chlorinating a small amount of manganese dioxide in sulfuric acid. And chlorination (Yoshi Hosoda, theoretical dye chemistry).

The compounds obtained by these chlorinations have the formula (1)

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

[0006]

The inventors of the present invention chlorinated indanthrone according to the conventional method, and then reduced the indanthrone. After the reduction, the reaction solution was discharged into water. However, there are problems such as clogging, and long filtration time and washing time, which are not industrially very advantageous.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, after reducing the azine compound, the reaction solution was discharged into water, and then an anionic surfactant was added to the discharged solution. As a result, the present inventors have found that the fine crystals become larger, and thus completed the present invention.

That is, the present invention provides a compound of the formula (1)

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

[0009]

Embedded image Is a method for producing 3,3′-dichloroindanthrone, which comprises discharging a reaction solution after reduction into water and then adding an anionic surfactant to the discharged solution.

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 sulfuric acid and reduced using a reducing agent such as aluminum powder, iron, iron halide or iron sulfate. After completion of the reduction, the reaction solution is gradually discharged into water, and then an anionic surfactant is added, followed by filtration and washing to obtain 3,3′-dichloroindanthrone.

The anionic surfactant which can be used in the method of the present invention is not particularly limited. Examples thereof include a sulfonate of an alkylcarboxylic acid derivative, a sulfonate of an alkylbenzenesulfonic acid derivative, an α-olefin sulfonate, Surfactants that are oil-soluble, water-soluble, and have strong penetrating power, such as condensates of naphthol, formalin, and sodium sulfite, and condensates of cresol, phenol, formalin, and sodium sulfite. Particularly, the following general formula (3) having excellent acid resistance

[0012]

Embedded image (R is a linear or branched alkyl group of C ₁ ~C _30, C ₁ ~
And a C ₃₀ linear or branched polyalkyl ether group. )) Is preferred.

In the method of the present invention, the anionic surfactant is used in an amount of 0.1 to 30% by weight based on the azine compound to be reduced.
Preferably 1-5% by weight, more preferably 2-3% by weight
Add within the range. If the addition amount of the anionic surfactant is too small, the crystal form may remain fine,
If it is too large, it is effective, but not economically preferable.

The temperature at which the anionic surfactant is added in the method of the present invention is not particularly limited.
Particularly, 20 to 35 ° C. is preferable.

In the method of the present invention, the amount of water discharged from the reduced reaction solution is such that the sulfuric acid concentration after the discharge is 10 to 50% by weight, preferably 20 to 40% by weight. If the sulfuric acid concentration after discharge is too high, crystallization tends to be difficult.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Incidentally,% in the examples is% by weight.
Is shown.

Example 1 179 g of 98% sulfuric acid was added to the following formula (1)

[0018]

Embedded image Was charged into a reactor and heated to 50 ° C. Aluminum powder 1.1 in it
g, calcol 0.6 g, soybean oil 0.6 g mixed solution in 1
It was charged over a period of time, and a reduction reaction was performed at 50 ° C. for 1 hour. After the reduction, the reaction solution was gradually discharged into 800 cc of water. The mixture was stirred for 1 hour while maintaining the temperature of 70 to 80 ° C. due to the heat generated at that time, then cooled to around 30 ° C., and charged with 1.2 g of Neocol P (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., an anionic surfactant). . Then, it is filtered and washed,
Wet cake 1 containing 44 g of dichloroindanthrone
57.2 g were obtained.

Observation of the crystals with an optical microscope revealed that crystals having a particle size of 159 μm as shown in FIG. 1 were obtained.
In addition, the filtration time was reduced to 1/6 as compared with Comparative Example 1.

Example 2 Anionic surfactant Neocol P (Daiichi Kogyo Seiyaku)
Was performed in the same manner as in Example 1 except that 0.8 g was used. Crystals having the same particle size as in Example 1 were obtained, and the filtration time and the washing time were the same as in Example 1.

Comparative Example 1 The same operation as in Example 1 was carried out except that Neocol P (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., anionic surfactant) was not added, and 3,3′-dichloroindanthrone was discharged. Floated on the surface as fine crystals, and the subsequent filtration rate was also very slow. Observing the crystal with an optical microscope,
It was found that a crystal having a particle size of 52.9 μm as shown in FIG. 2 was obtained.

[0022]

According to the method of the present invention, the crystal form of 3,3'-dichloroindanthrone can be obtained in a large size, so that the filterability is good and the filtration time and washing time can be shortened. This is also an efficient and very useful method.

[Brief description of the drawings]

FIG. 1 is an optical micrograph of the crystal obtained in Example 1, wherein the black part is a crystal of 3,3′-dichloroindanthrone. (Approximately 200 times magnification)

FIG. 2 is an optical micrograph of the crystal obtained in Comparative Example 1, and the black part is a crystal of 3,3′-dichloroindanthrone. (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 (3)

(57) [Claims] (1) Formula (1) (Formula 1) Is reduced in sulfuric acid to obtain a compound of formula (2) 3. The method for producing 3,3′-dichloroindanthrone according to claim 1, wherein after the reduction, the reaction liquid is discharged into water, and then an anionic surfactant is added to the discharged liquid. 2. An anionic surfactant represented by the formula (1): 2. The method according to claim 1, wherein the compound is added in an amount of 0.1 to 30% by weight based on the weight of the compound.
The described method. 3. The method according to claim 1, wherein the anionic surfactant is a sulfonate of an alkyl carboxylic acid derivative.