JPS593491B2 - Method for manufacturing triphenodioxazine dye - Google Patents

Description

Detailed Description of the Invention The present invention is based on the following general formula (I) (wherein, X is a chlorine atom or a bromine atom, and Y is (0R')N
OR group, R' represents a C,~4 alkylene group, R represents a C,~4 alkyl group, and n is 1 or 2.

A triphenodioxazine dye represented by the formula (wherein X, R, R', and n have the same meanings as in the general formula (1) above) can be obtained in a good yield.

However, for reference, let me explain (the above general formula (1)
), when Y is a hydrogen atom, the ring-closing reaction is generally
Requires acidic condensing agent. The acidic condensing agent promotes the desired ring-closing reaction and at the same time carries out the ring-closing reaction of the compound represented by the ether linkage of the alkoxy group in the general formula (1) in an organic medium.
) (wherein, X, R, R/ and n have the same meanings as in the general formula (I) above).

To explain the present invention in detail, x in the general formula (1) includes halogen atoms such as chlorine atom and bromine atom.

Further, as a specific example of the alkoxy group represented by (0R')NOR, 0CH2CH20CH2CH20C4H9
(n) etc. The present invention is carried out as follows.

That is, the ring-closing reaction is carried out by heating the compound represented by the general formula (1) in an organic solvent at 1000C or higher, preferably 130 to 250C, in the presence or absence of an acidic condensing agent. In this case, as in the present invention, Y in the general formula (1) is (0R'). In the case of 0R group,
The ring-closing reaction proceeds easily even in the absence of an acidic condensing agent, and suitable organic solvents for use in the reaction of the following general formula include benzene, which may be halogenated and/or nitrated as the case may be. Examples of aromatic hydrocarbons include toluene, xylene, monochlorobenzene, o-dichlorobenzene, trichlorobenzene, nitrobenzene, o-nitrotoluene, naphthalene, α-chloronaphthalene, and α-methylnaphthalene.

In addition to these, quinoline, picoline, N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, sulfolane, etc. can also be used. Examples of acidic condensing agents include acid chlorides of carboxylic acids and sulfonic acids, such as benzoyl chloride, benzenesulfonyl chloride, p-toluenesulfonyl chloride, as well as thionyl chloride, phosphorus pentachloride, hydrochloric acid, hydrobromic acid, acetic anhydride, and p-toluenesulfonyl chloride. Examples include toluenesulfonic acid, or metal chlorides such as aluminum chloride or zinc chloride.

The progress of the reaction can be monitored by, for example, thin layer chromatography.

After the completion of the ring-closing reaction, the desired reaction product generally precipitates as crystals by cooling, so it is sufficient to collect the crystals. When the target product has a high solubility in the reaction medium, the target product can be separated out by adding a solvent such as methanol that has a low dissolving power to the target product.

The triphenodioxazine dye obtained by the method of the present invention is itself a new dye, and has an excellent affinity for polyethylene terephthalate and cellulose acetate, and is a very vivid red color with excellent light fastness. Gives tonal dyeing.

The compound represented by the above general formula (1) is a tetrahalogeno p-benzoquinone and the following general formula (l) (wherein R, R', Y, and n are the same as in the above general formula (1)). It can be obtained by condensing anilines represented by

EXAMPLES The present invention will be explained in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 2 g of the compound represented by the following structural formula was reacted in 20 ml of nitrobenzene under reflux for 10 hours, and after cooling, the precipitate was collected by filtration to obtain 1.0 g of a pure dioxazine compound represented by the following structural formula.
I got it.

This product is a reddish-brown crystal with a melting point of 296-298°C, and the elemental analysis results agreed well with the calculated values as shown below.

Example 2 The product has the following structural formula (i) and the following structural formula (t).This product is a reddish-brown crystal with a melting point of 241 to 243°C, and the elemental analysis results were in good agreement with the calculated values as shown below.

Reference example The following structural formula results (support: silica gel, developing solvent: benzene:ethyl acetate = 3:1), 3,10-dialkoxy-
Many fluorescent red spots characteristic of 6,13-dihalogenotriphenodioxazines appeared.

When this product was dissolved in concentrated sulfuric acid, it developed a blue color characteristic of triphenodioxazines. It is clear from these results that the reddish brown crystals obtained are a mixture of triphenodioxazine compounds.

Also, as a result of measuring the mass spectrum of this material, m/e-
Jmo V4,772,770,730,728,726,7
24,722,686,684,682,680,67
A peak was detected at 8,676,674.

Claims (1)

[Claims] 1 The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula,
is a chlorine atom or a bromine atom, Y is a (OR')_nOR group,
R' represents a C_1-_4 alkylene group, R represents a C_1-_4 alkyl group, and n is 1 or 2. ) The following general formula (II) is characterized by carrying out a ring-closing reaction in an organic medium. There are mathematical formulas, chemical formulas, tables, etc. (II) (wherein, n has the same meaning as in the general formula (I).) A method for producing a triphenodioxazine dye represented by the formula (I).