JPS609058B2 - Manufacturing method of monoazo dye - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing monoazo dyes. More specifically, the present invention is based on the general formula [1] (where RI represents a hydrogen atom, a lower alkyl group, a substituted or unsubstituted phenyl group, and R2 represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, an aralkyl group). or allyl group, and R3 represents a hydrogen atom or a methyl group. However, the purpose of levering, according to the method of the invention, is the general formula

[0] (wherein R2 and R3 have the same meanings as in the above general formula [1]), the general formula [m]
This is achieved by coupling a diazonium salt of 2-amino-5-nitrothiazole represented by the following formula (wherein RI has the same meaning as in the general formula [1]). The present invention will be explained in more detail. In the monoazo dye represented by the general formula [1] shown above, R
In addition to hydrogen atoms, I includes lower alkyl groups such as methyl, ethyl, propyl, and butyl, phenyl, and substituted phenyl groups, and when it is a substituted phenyl group, p-chlorophenyl group, Monosubstituted phenyl groups such as m-chlorophenyl group, p-fromophenyl group, and p-cyanophenyl group are preferred. In the compound of formula [1], RI is preferably methyl or hydrogen, more preferably hydrogen. In addition to a hydrogen atom and an allyl group, R2 includes a methyl group, a lower alkyl group such as an ethyl group, a propyl group, and a butyl group, an aralkyl group such as a benzyl group and an 8-phenylethyl group, a hydroxy group, an alkoxy group, a sia/group, Halogen atom, alkoxycarbonyl group, acyloxy group, alkoxycarbonyloxy group, furyl group, tetrahydrofuryl group,
Substituted lower alkyl groups having a substituent such as a morpholino group, a carbamoyl group, and an N-alkyl-substituted carbamoyl group are mentioned. As specific examples of lower alkyl groups having these substituents, those having a hydroxy group include B-hydroxyethyl group, 6-hydroxypropyl group, 3-y-dihydroxypropyl group, Q-hydroxymethyl-8- Examples include hydroxyethyl group, y-hydroxybutyl group, and 8-(3'-hydroxyethoxy)ethyl group. As the lower alkyl group having an alkoxy group, an acyloxy group, an alkoxycarbonyloxy group, a furyl group, or a tetrahydrofuryl group, the hydroxy group of the lower alkyl group having a hydroxy group mentioned above can be used as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. group, 8-methoxyshetoxy group, 6-ethoxyshetoxy group, 8-butoxyshetoxy group, furfuryloxy group, tetrahydrofurfuryloxy group, acetoxy group, propionyloxy group, benzoyloxy group, methoxycarbonyloxy group Examples include those converted to a group, an ethoxycarbonyloxy group, a ptoxycarbonyloxy group, and the like. cyano group, halogen atom,
As the lower alkyl group having an alkoxycarbonyl group, furyl group, tetrahydrofuryl group, morpholyl group, carbamoyl group, N-alkyl substituted carbamyl group, 8
-Cyanoethyl group, 8-chloroethyl group, 6-bromoethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 6-methoxycarbonylethyl group, 8-ethoxycarbonylethyl group, 8-propoxycarbonylmethyl group thyl group, 8-butoxycarbonylethyl group, 6-(8'-methoxyshethoxycarbonyl)ethyl group, 8-(B'-ethoxyshethoxycarbonyl)ethyl group, 8-furfuryloxycarbonylethyl group, 3- Tetrahydrofurfuryloxycarbonylethyl group, furfuryl group, tetrahydrofurfuryl group, morpholinoethyl group, 8-carbamoylethyl group, 8-(N-methylcarbamoyl)ethyl group, B-(N
-ethylcarbamoyl)ethyl group, 8-(N.N-dimethylcarbamoyl)ethyl group, 3-(N.N-dimethylcarbamoyl)ethyl group, and the like. Further, R3 represents a hydrogen atom or a methyl group. In the present invention, diazotization and coupling can be carried out by known methods. The diazotization of the 2-amino-5-nitrothiazole represented by the above general formula [m] can be carried out using, for example, nitrosyl sulfuric acid at a concentration of 20 oo or less, preferably -5 to 500. At this time, good results can be obtained by adding an organic acid such as acetic acid or propionic acid, or phosphoric acid. Coupling this diazonium salt with the general formula

It may be added to a solution of the 8-aminoquinoline represented by [0] in an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid, or an organic acid such as acetic acid or propionic acid at a temperature of 2000 or less, preferably at -5 to 5°C. This coupling reaction is preferably carried out in a matrix of 5 or less and can be carried out in the presence of an alkali metal salt of acetic acid or propionic acid, preferably sodium acetate, as a buffer, if desired. After completion of the coupling, the desired monoazo dye represented by the general formula [1] can be easily obtained by pouring into ice water, removing the precipitate from an oven, washing with water, and drying. The dye represented by the general formula [1] obtained by the present invention is itself a novel compound and is suitable for dyeing various synthetic fiber materials, especially polyester fibers, but it is suitable for dyeing polyacrylonitrile fibers, triacetate fibers, etc. It is possible to change the color of synthetic fibers made of synthetic or semi-synthetic polymeric substances, such as fibers, diacetate fibers, polyamide fibers, polyurethane fibers, etc., into clear tones with good fastness. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 2-amino-5-nitrothiazole 14.5 hours
At 5°C, nitrosyl sulfuric acid (95% sulfuric acid)
Prepared by melting sodium nitrate (7.0 yen)
, 150% of acetic acid and 30% of propionic acid were gradually added to the mixture, and the mixture was left at the same temperature for 3 hours. Add 2.0 liters of urea to this, and add 81 (y) of this diazo solution.
-methoxypropyl)aminoquinoline was added dropwise at 0-5*°C to a 15M solution of 75% acetic acid and 15M propionic acid. After rinsing at the same temperature for 3 hours, the precipitate was poured into 800 g of ice water and collected in a furnace, washed with water and dried to obtain a pale blue powder represented by the following structural formula. The max of this product was 61 blood (acetone). High temperature dyeing of polyester fibers using this dye (1300
0), a vivid blue dyed cloth was obtained. Example 2
0-5 2-amino-5-nitrothiazole 14.59
At the same temperature, 87% nitrosyl sulfuric acid (prepared by dissolving 80% sodium nitrite in 80% 95% sulfuric acid) was gradually added to a mixture consisting of 120% acetic acid and 50% 86% phosphoric acid. I stayed there for 3 hours. To this was added 2.0 mm of urea, and the diazo solution was mixed with 2.3 mm of 2-methyl-8-(y-methoxypropyl)aminoquinoline.
The mixture was added dropwise at 0 to 5° C. to 300° C. of an ice-water solution of hydrochloric acid.
At the same temperature, sodium acetate was gradually added to make it weakly acidic, and the mixture was heated for 5 hours.The precipitate was poured into 500 g of ice water and collected in an oven, washed with water and dried to obtain a blue powder represented by the following structural formula. . The maximum content of this product was 613n (acetone). High temperature dyeing of polyester fibers using this dye (130q
o) As a result, a bright blue beam cloth was obtained. Example 3
Monoazo dyes shown in Table 1 below were obtained by the operating method according to Example 1 or 2. The table also shows the color tones of dyed fabrics obtained when polyester fibers were dyed using the obtained dyes using the high temperature dyeing method. Table-1

Claims (1)

[Claims] 1 General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R^2 represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, an aralkyl group, or an allyl group, R^3
represents a hydrogen atom or a methyl group. ) to the 8-aminoquinolines represented by the general formula [III]
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydrogen atom, a lower alkyl group, or a substituted or unsubstituted phenyl group.) Diazonium of 2-amino-5-nitrothiazoles General formula [I] which is characterized by coupling salt ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2 and R^3 are the general formula [I]
I] and [III] have the same meaning. ) A method for producing monoazo dyes.