DE1235469B - Process for the preparation of monoazo dyes - Google Patents

Description

GERMAN

PATENT OFFICE

EDITORIAL

German class: 22 a - 1

Number:
File number:
Registration date:
Display day:

1,235,469
F 41706 IV c / 22 a
January 10, 1964
March 2 , 1967

It has been found that valuable new monoazo dyes are obtained if one is diazotized Cyananiline, which can have further cyano, halogen, alkyl and / or alkoxy groups, with a Azo component of the formula

alkylene —COO —R ₂

Process for the production of
Monoazo dyes

Applicant:

Paint factories Bayer Aktiengesellschaft,
Leverkusen

Named as inventor:

Dr. Winfried Kruckenberg, Leverkusen

NHOC - R

couples and thereby freely chooses the starting components of sulfonic acid and carboxylic acid groups. In the general formula (I), R denotes an alkyl radical containing 1 to 5 carbon atoms or the group - OR2 or -NH ₂ , R ₂ denotes the group - C _re H _2n +1, Ri denotes the group -C "H _{2n +} i, -C" _n H _2n OR ₂ , -C _re H _2n halogen or the group —alkylene — COOR ₂ , where “halogen” stands for a halogen atom, Rs is hydrogen, halogen, an alkyl or alkoxy radical, “alkylene” contains 2 to 4 carbon atoms Alkylene radical and η an integer from 1 to 5.

The coupling of the starting components is carried out in a manner customary per se, preferably in an acidic manner aqueous or organic-aqueous medium.

Suitable diazo components are, for. B. 4-cyananiline, 3-chloro-4-cyananiline, 3,4-dicyananiline, 2,6-dichloro - 4 - cyananiline, 2,5,6 - trichloro - 4 - cyananiline, 2 - cyano - 5 - chloroaniline, 2 - cyananiline, 2 - cyano-4,5,6-trichloroaniline, 2,4-dicyananiline, 2,4-dicyan-6-chloroaniline and 2,4-dicyan-6-methylaniline. Suitable coupling components of the formula (I) are, for. B. N-methyl-N- (2'-methoxy-5'-acetylaminophenyl) - β - amino - propionic acid methyl ester or ethyl ester, N-ethyl-N - (3'-propionylaminophenyl) - / i-aminopropionic acid methyl ester, - ethyl ester or propyl ester, N-methyl- or N-ethyl-N- (3'-acetylaminophenyl) - β - amino - propionic acid methyl ester or ethyl ester, N- (3'-acetylaminophenyl) -N- / i-carbomethoxyethyl - β - amino - propionic acid methyl ester, N - (2 '- methoxy - 5' - acetylaminophenyl) - N - β - carboethoxyethyl-ß-aminopropionic acid ethyl ester, N-ethyl-N - (2 '- ethoxy - 5' - acetylaminophenyl) - β - aminopropionic acid methyl ester, N - methyl - N - (2 '- ethoxy-5'-acetylaminophenyl) - / j-amino-propionic acid methyl ester, N - methyl - N - (3' - chloroacetylaminophenyl) - / j-propionic acid methyl ester, N-ethyl-N- ( 3'-methoxyacetylaminophenyl) - / i-arnino-propionic acid ethyl ester and N - propyl - N - (3 '- chloroacetylaminophenyl) - fl - amino - propionic acid methyl ester, N - (3' - carbo-

] ₅ methoxyaminophenyl) - N - ethyl - β - aminopropionic acid methyl ester, N - (3 '- ureidaphenyl) - β - aminopropionic acid methyl ester.

According to a variant of the preparation process, the new dyes can also be built up in such a way that, instead of a coupling component with one or two groups - alkylene -COOR _2, those azo components are used which contain one or two - alkylene - COOH groups and these after completion of the Coupling esterified with a lower aliphatic alcohol. Since this reaction is generally carried out in the presence of acidic catalysts, saponification of the NH - OCR group in the azo component can occur. However, the resulting NH ₂ group can subsequently be acylated again and converted into an NH - OCR group.

The new dyes correspond to the general formula

NHOC - R

where A is the radical of a cyanobenzene, which can have further cyano, halogen, alkyl and / or alkoxy groups, R, Ri, R ₂ , R ₃ and "alkylene" have the meaning already explained, and are free of sulfonic acid and carboxylic acid groups. They are sparingly or insoluble in water and are particularly suitable for dyeing and printing hydrophobic materials, especially for dyeing textile materials made from aromatic polyesters such as polyethylene terephthalates, aromatic polyesters made from terephthalic acid and 1,4-bishydroxy

709 51V471

methylcyclohexane, synthetic superpolyamides, cellulose esters and the like, especially on aromatic Polyesters and synthetic super polyamide fibers are dyeings with very good fastness properties, especially good wet fastness and sublimation fastness (for aromatic polyesters) and very good light fastness (for both types of fiber).

Compared to the dye of the formula known from Belgian patent 612

O ₂ N ~ ^ \ ^ ~ ^{N = N} ^

CN NHCOCH ₃

C ₂ H ₅

C ₂ H ₁ COOCH ₃

show the dyes of the formulas obtainable according to the invention

C ₂ H ₅

CN

/ ^ ²

^x C ₂ H ₄ COOCH ₃ and NHCOCH ₃

An = n / \ _n /

CN

C ₂ H ₅

NHCOCH ₃

CoH ₁ COOCH ₃

the advantage of the better lightfastness of the dyeings on super polyamide fabrics.
example

18 g of 2,4-dicyananiline are dissolved in 200 g of concentrated sulfuric acid and by adding 17 ml of nitrosylsulfuric acid (100 ml corresponds to 42 g of nitrite) are diazotized with stirring at 0 to 5 ° C. The diazonium salt solution is stirred into

The resulting dye corresponds to the formula a solution of 29 g of N- (3'-acetylaminophenyl) -N - β - carbomethoxyethyl - ß- amino - propionic acid methyl ester in dilute acid and poured into ice. The batch is then blunted with sodium hydroxide solution and finally with sodium acetate to pH 5.5 to 6, filtered off with suction, washed and dried.

NC

N =

= N

CN

C ₂ H ₄ COOCH ₃
^ C ₂ H ₄ COOCH ₃

NHOCCH ₃

The product is a dark powder that dissolves in an analogous manner from the corresponding organic solvents with a red color. the cyananiline diazo components and coupling components brought into a finer distribution by suitable means, the components in the following table dyes the dye synthetic superpolyamide-led dyes, the synthetic superpoly and polyethylene terephthalate fabrics in red color 4 ° amide fabrics and polyethylene terephthalate fabrics in tones with good sublimation -, wash and lightfastness. color the specified shades:

OCH ₃

N (C ₂ H ₄ COOCH ₃ ) ₂ bluish red
NHCONH ₂
OC ₂ H ₅

N (C ₂ H ₄ COOCH ₃ ) ₂ bluish red
NHCOCH ₃

CN

/ C ₂ H ₅

N _v strong reddish purple

^x C ₂ H ₄ COOCH ₃

NHCOOCH3

NC

■ N =

= N-

'C ₂ H ₅

C ₂ H ₄ COOCH ₃

NHCOCh ₂ OC ₂ H ₅ scarlet

Claims (1)

NC NC NC C ₂ H ₅ C ₂ H ₄ COOCH ₃ C ₂ H ₅ C ₂ HiCOOCH ₃ C ₂ H ₃ C ₂ H ₁ COOCH ₃ C ₂ H ₅
^x C ₂ H ₄ COOCH ₃ NHCOCH2OCH3 Scarlet fever Reddish orange Red Bluish red Claim: Process for the preparation of monoazo dyes, characterized in that one a diazotized cyananiline which has further cyano, halogen, alkyl and / or alkoxy groups can, with an azo component of the formula 35 alkylene - COO - R ₂ Tending alkyl radical or the group —OR ₂ or —NH ₂ , R _{2 represents} the radical —C _b Ho _b -I _j Ri the radical - C _b H _2b -1, -C _b H _2b OR ₂ , -C _b H _2b halogen or the group - alkylene - COOR ₂ , where "halogen" stands for a halogen atom, R _{3 stands} for hydrogen, halogen, an alkyl or alkoxy radical, "alkylene" means an alkylene radical containing 2 to 4 carbon atoms and η stands for a whole Number from 1 to 5, couples and thereby chooses the starting components free of sulfonic acid and carboxylic acid groups. 40 NHOC - R
wherein R contains 1 to 5 carbon atoms When the application was announced, a coloring table with explanations was displayed Considered publications:
Announced documents of the Belgian patent No. 634 612. 709 517/471 2.67 © Bundesdruckerei Berlin