JPS5819700B2 - Method for producing new azopyrazolium dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel azopyrazolium dyes that can be used for dyeing acrylonitrile polymer or copolymer fibers, as well as processes for the production of such dyes.

The present invention is based on the formula (wherein R1 and R2 each represent the same alkyl group having 1 to 4 carbon atoms, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 represents an alkyl group having 1 to 4 carbon atoms. group, a cyanalkyl group having 1 to 4 carbon atoms, an alkane (1 to 5C) dioylimide alkyl group (1 to 4C), and Y is a hydrogen atom, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, or Represents acylamino, Z is a hydrogen atom or has 1 to 1 carbon atoms
2 represents an alkoxy group, and X represents a monovalent anion).

Alkyl groups have 1 to 4 carbon atoms, preferably 1
The individual atoms contain two carbon atoms.

Alkane groups have 1 to 5 carbon atoms, preferably 2
Contains 5 carbon atoms.

Acyl groups contain 1 to 5, preferably 2 carbon atoms.

Alkoxy groups contain one or two carbon atoms.

The monovalent anion may be, for example, chloride, sulfomethylate, zinc chloride or half-anionic sulfate.

The present invention provides dyes having the general formula (wherein R3, R4, Y and Z have the same meanings as above) by treating with an alkylating agent a dye having the formula (
The method for producing the dye of I) is included.

The alkylation treatment may be carried out in organic solvents, for example benzene hydrocarbons or chlorinated derivatives thereof, dimethylformamide or chloroform.

Examples of alkylating agents that may be used are: alkyl rogenides, alkylarylsulfonates, alkylsulfonates and especially methyl or ethyl salts.

The process may be carried out in excess of alkylating agent.

Dyes of formula (II) are, for example, 3(5)-phenyl-4-nitro-5(3)-
It may be produced by coupling a diazo derivative of aminopyrazole and a substituted aniline having the general formula.

3(5)-phenyl-4-nitro-5(3)-aminopyrazole is new and 3(5)-phenyl-5(3)
-It may be produced by reacting acetyl nitrate with acylaminopyrazole.

Acetyl nitre) is 3(5)-phenyl-5(3)
- can be prepared in the absence of aminopyrazole and then placed in an acetic acid solution of the latter.

It can also be prepared in situ in glacial acetic acid or acetic anhydride medium.

The aminopyrazole of formula (■) is preferably a low molecular weight organic acid,
For example, formic acid, acetic acid and propionic acid diazotize in the presence of propionic acid or concentrated mineral acids, such as sulfuric acid, hydrochloric acid and phosphoric acid.

The present invention also includes a process for dyeing acrylonitrile polymer or copolymer fibers, or polyester or polyamide fibers modified with acid groups, with dyes of formula (I) by conventional dyeing methods known in the art.

Fibers, especially acrylonitrile fibers, are dyed in a very vivid bluish-red color and exhibit extremely high tinting strength.

Light fastness is very good. The fibers are dyed with dye cations.

The anion does not have any dyeing role and may be replaced by another anion, for example to improve the solubility of the dye.

The invention is illustrated by the following examples, in which the middle parts of the examples are parts by weight.

Example 1 84 parts of 3(5)-phenyl-4-nitro-5(3)-aminopyrazole are dissolved in 100 parts of glacial acetic acid.

370 parts of acetic anhydride are added successively and then, after 30 minutes, cooled and 42 parts of fuming nitric acid in 300 parts of glacial acetic acid are added.

When the addition was complete, the mixture was stirred for 48 hours and diluted with a mixture of ice and water to give 3(5)-phenyl-4-nitro5.
(3) -Precipitate acetylaminopyrazole.

Pass the mixture through your mouth and dry. F: recrystallized in trobenzene at 264°C) Analysis C11H1ON403] Calculated value C53.65% H4.09% N22.75%
Analysis value 53.68 4.18 22.444
The nitration at the C4-H position was determined by nuclear magnetic resonance spectroscopy.
[hexadeute
6.9 ppm in dimethyl sulfoxide
, internal reference
[compared to tetramethylsilane] was hydrolyzed at the boiling point in a 6N hydrochloric acid solution to liberate the base.

8.16 parts of 3(5)-phenyl-4-nitro-5(3)-aminopyrazole are dissolved in 50 parts of concentrated sulfuric acid.

A solution of 3.2 parts of sodium nitrite dissolved in 30 parts of concentrated sulfuric acid is added to this solution and cooled to 0°C to 5°C.

Stir the solution for 30 minutes. The sulfuric acid solution of the diazo derivative thus obtained is added sequentially to a solution of 76 parts of diethylanili in 100 parts of water and 3 parts of concentrated sulfuric acid.

Sequentially bring the pH to 4 and couple.

The precipitated dye is filtered, washed with water and dried.

3 parts of the above dye are placed in 8 parts of methyl sulfuric acid.

This mixture was heated at 80°C until the test sample was completely dissolved in the water.
and then left to come to room temperature, 10 parts of water are added and the mixture is stirred at 65° C. for 30 minutes.

Sodium chloride and zinc chloride are added to the dye, precipitated, filtered and dried.

The obtained 1,2-dimethyl-3-phenyl-4-nitro-5-(4-diethylaminophenylazo)pyrazolium zinc chloride salt is very well soluble in water.

This dye dyes acrylonitrile polymer and copolymer fibers in a bright bluish-red color and is particularly resistant to light and extremely fast.

The staining experiment was conducted as follows.

Add 123 d of water to the dyeing container and 1.25% aqueous solution of a condensate derivative of oleylamine and 7 molecules of ethylene oxide.
I put d.

Raise the temperature to 40℃ and add 5 d of warm water with 1 d of ordinary acetic acid.
A pre-caulked solution consisting of 12.5 to 10% of the dye was introduced.

2.5 I of the fabric to be dyed were added and the temperature was gradually increased from 40° C. to boiling temperature in 2 hours per portion and kept at that temperature for 1 hour.

The fabric was then rinsed and dried.

An example analogous to Example 2 using the same diazo derivative and another coupling compound is shown in the following table.

The present invention includes the following aspects.

(1) A method for producing a dye according to claim 1, characterized in that alkylation is carried out with a methyl or ethyl salt.

(2. Acrylonitrile polymer or copolymer fiber dyed with the dye of formula (I) as shown in claim 1,
Alternatively, polyester or polyamide fibers modified with acid groups.

(3) with the formula 3(5) ~ phenyl4-nitro5(3)-
Aminopyrazole.

○ indicates the maximum absorption wavelength of the dye obtained in the above example

Claims (1)

[Claims] Formula 1: (In the formula, R4 and R2 each represent the same alkyl group having 1 to 4 carbon atoms, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 has a carbon number of 1 to 4. represents an alkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms, an alkane (1 to 5 C) dioylimide alkyl group (1 to 4 C), and Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a carbon number Represents 1 to 4 alkoxy or anrulamino, Z is a hydrogen atom or has 1 carbon number
~2 alkoxy group, X represents a monovalent anion) 3(5)-phenyl-4-
A diazo derivative of ditro-5(3)-aminopyrazole is coupled with an aniline having the formula: A method for producing the above-mentioned dye, which comprises subjecting it to a chemical treatment.