DE591494C - Process for the production of water-insoluble azo dyes - Google Patents

Description

GERMAN EMPIRE

ISSUED ON
JANUARY 22, 1934

REICH PATENT OFFICE

PATENT LETTERING

CLASS 22 a GROUP

Society for Chemical Industry in Basel in Basel, Switzerland

Patented in the German Empire on October 8, 1932

It has been found that very valuable new dyes are obtained if Arylides of 2, 3-oxynaphthoic acids with diazotized aryl or aralkyl ethers of 5 o-aminophenols couples the at least one carboxylic acid ester group in the o-aminophenol radical contain. In this way, yellowish-tinged scarlet to blue-red dyes are formed. On the fiber become the same Color tones achieved, which are characterized by extraordinary luminosity and excellent fastness properties, especially chlorine and moisture fastness.

The diazo components used here have compared to the o-aminophenolaryl ethers in the o-aminophenol radical contain a carboxylic arylide group, the important advantage of easier diazotization. In addition, the coupling capacity the diazotized carboxylic acid ester is significantly larger than that of the carboxylic acid ry Ii de, so that much more extensive colorations are obtained on the fiber will.

The diazo components in question here can be, for. B. in general are produced by reducing the condensation products, which are formed from compounds, such as the alkyl, aralkyl or aryl esters of a-nitro-i-chlorobenzene - ^ - or -5-carboxylic acid, with phenol and its core substitution products, such as 2-, 4- and 3-methyl-i-oxybenzene, 2-, 4- and 3-chloro-i-oxybenzene, Chlorocresols, dichlorophenols, 1,4-, 1,3- or i, 2-dioxybenzene monoalkyl ethers, i-Oxy ^ -methoxy ^ -chlorobenzene, naphthols, also benzyl alcohol. You can also condense the 2-nitro-i-chlorobenzene "4- or -5-carboxylic acid with the phenols mentioned, esterification and reduction of the compounds obtained will. Such compounds can also be obtained in other ways, e.g. B. by condensation of suitable o-nitrophenol carboxylic acid esters, such as i-oxy-2-nitrobenzene-4-carboxylic acid methyl, -äthyl-, -propyl-, -butly-, -atnyl- or -phenylester, with Benzyl chloride and reducing the condensation product.

50 B is ρ ie 1 ι

25.7 parts of ethyl ester of 2-amino-i, i'-diphenylether-4-carboxylic acid are diazotized as usual. The clear diazo solution obtained is converted into a solution consisting of 31.3 parts of 2- (2 ', 3'-oxynaphthoylamino) naphthalene, 95 parts of 30 percent sodium hydroxide solution, 15 parts of sodium acetate and 3000 parts of water entered. The resulting dye precipitates immediately. The Red Precipitate is filtered and dried.

B e i s ρ i e 1 2

Cotton yarn is dissolved by dissolving 5 g of the i- (2 ', 3'-oxynaphthoylamino) -2-methoxy-5-methylbenzene in 300 ecm of hot water with the addition of 10 ecm ßoprozentiger sodium hydroxide, 10 ecm Turkish red oil and diluting the approach ι 1 prepared solution primed. It is then wound off and developed in a solution blunted with sodium acetate, containing 2 g of diazotized ethyl ester of 4'-chloro-2-amino-i, i'diphenylether-4-carboxylic acid per liter. The result is a very pure alizarin red of very, good detergent, chlorine,

* 5 Fastness to touch and light.

B e i s ρ i e 1 3

Cotton yarn is mixed with a solution containing 7 g of i- (2 ', 3'-Oxynaphthoylamino) -4-ethoxybenzene, 14 ecm 30 percent sodium hydroxide solution and contains 10 ecm Turkish red oil per liter, impregnated, well wound and in a diazo solution truncated with sodium acetate, the 2 g of the ethyl ester of 2 ', 5'-dichloro-2-amino-i, i'-diphenylether-4-carboxylic acid contains, developed, rinsed and soaped in the liter. A very pure scarlet color of excellent color is obtained Authenticity properties.

Example 4

Cotton yarn is mixed in a liquor ratio of ι: 25 with a solution of 5 g i- (2 ', 3'-oxy- ·· ■■ naphthoylamino) naphthalene, 10 ecm 30 percent sodium hydroxide solution, 10 ecm Turkish red oil, 5 ecm 40 percent formaldehyde solution per liter at 25 Impregnated to 30 ⁰ C, well wound and then in a truncated solution containing 2 g of diazotized ethyl ester of 4'-chloro-2-amino-i, i'-diphenylether-4-carboxylic acid per liter,

developed. This is followed by rinsing and soaping. A very pure alizarin red is obtained Dye of excellent wash, chlorine, touch and lightfastness.

Example 5

Cotton yarn is mixed with a by dissolving 7 g of the i- (2 ', 3'-oxynaphthoylamino-2-methoxybenzene in 300 ecm hot water with the addition of 14 ecm 3O percent sodium hydroxide solution, 10 ecm Turkish red oil and diluting the batch to 1 1 prepared Solution primed. Then you wind off and develop in one with sodium acetate truncated solution containing 2 g of diazotized methyl ester of 4'-chloro-2-amino-i, i'-Diphenylether-5-carboxylic acid per liter. A very pure scarlet color is obtained Coloring of excellent fastness properties.

Similar scarlet colorations are obtained e.g. B. with the i- (2 ', 3'-oxynaphthoylamino) -4-methylbenzene, the i- (2 ', 3'-Üxynaphthoylamino) -4-methoxybenzene and the 2,3-oxynaphthoylaminobenzene.

Red colorations are obtained with i- (2 ', 3'-0xynaphthoylamino) -4-chlorobenzene, i- (2 ', 3'-oxynaphthoylamino) -naphthalene, 2 - (2', 3'-oxynaphthoylamino) -naphthalenundi- (2 ', 3'-0xynaphthoylamino) -4-ethoxybenzene.

In these examples, the methyl ester of 4'-chloro-2-amino-i, i'-diphenyl ether-5-carboxylic acid is replaced by the corresponding ethyl ester, - so one obtains similar scarlet to red colorations with excellent fastness properties.

In the following compilation, the hue will follow a number of others the present process on cotton or rayon made from regenerated cellulose available dyes:

Diazo component Coupling component ! ■ 'arbton Red Ethyl ester of 2-amino-i, i ^'j diphenyl- ι- (2 ', 3' -oxynaphthoylamino) -2-meth- ether-4-carboxylic acid oxybenzene Scarlet fever the same ι - (2 ', 3' - Oxynaphthoylamino) -naph thalin Scarlet fever the same i- (2 ', 3'-oxynaphthoylamino) -2, 5-di- methoxybenzene Red the same ι - (2 ', 3'- oxynaphthoylamino) - 2 - me- ethyl 4-methoxybenzene alizarin red the same i- (2 ', 3'-oxynaphthoylamino) -2-chloro- ■ benzene Red the same _N i- (2 ', 3'-oxynaphthoylamino) -3-chloro- benzene Scarlet fever the same ι - (2 ', 3'- Oxynaphthoylamino) - 2 -me- ethyl-5-ch 1 orbenzene

Diazo component Coupling component hue 5 Ethyl ester of 2'-chloro-2-amino-i, i'-di-
phenyl ether-4-carboxylic acid ι - (2 ', 3' - Oxynaphthoylamino) - naph
thalin Scarlet fever the same i- (2 ', 3'-oxynaphthoylamino) -4-meth-
oxybenzene yellow scarlet 10 the same i- (2 ', 3'-oxynaphthoylanlino) -2-meth-
oxybenzene Red the same 2- (2 ', 3'-oxynaphthoylamino) -naph
thalin Scarlet fever 15th the same. i- (2 ', 3'-oxynaphthoylamino) -2-chloro-
benzene Red the same i- (2 ', 3'-oxynaphthoylamino) -3-me-
ethylbenzene Scarlet fever ; 20th Ethyl ester of 3'-methyl-2-amino-
i, ι'-diphenylether-4-carboxylic acid i- (2 ', 3'-oxynaphthoylamino) -2-meth-
oxybenzene scarlet the same i- (2 ', 3'-oxynaphthoylamino) -2-meth-
oxy-5-chlorobenzene Scarlet fever 25th the same i- (2 ', 3'-oxynaphthoylamino) -2-meth-
oxy-5-methylbenzene Scarlet fever Ethyl ester of 4'-chloro-2-amino-i, i'-di-
phenyl ether-4-carboxylic acid ι- (2 ', 3'-Oxynaphthoylamino) -4-eth-
oxybenzene Scarlet fever the same 2,3-Oxynaphthoylaminobenzene Scarlet fever 30th the like. ι - (2 ', 3' - Oxynaphthoylamino) - 2 -me-
ethyl-4-chlorobeiizole Red the same ;; 2 - {2 ', 3' - oxynaphthoylamino) - naph
thalin Scarlet fever 35 the same i- (2 ', 3'-oxynaphthoylamino) -2, 4-di-
methylbenzene red ■ the like. i- (2 ', 3'-oxynaphthoylamino) -2, 5-di-
methylbenzene Red 40 the same i- (2 ', 3'-oxynaphthoylamino) -2, 5-di-'
methoxybenzene alizarin red the like. i- (2 ', 3'- oxynaphthoylamino) - 2 - ether-
oxy-5-methylbenzene alizarin red 45 Ethyl ester of 4'-methyl-2-amino-
i, ι'-diphenylether-4-carboxylic acid i- (2 ', 3'-oxynaphthoylamino) -naph
thalin alizarin red the same i- (2 ', 3'-oxynaphthoylamino) -4-eth-
oxybenzene Scarlet fever 50 the same i- (2 ', 3'-oxynaphthoylamino) -2-meth-
oxybenzene Scarlet fever the same ι - (2 ', 3' - Oxynaphthoylamino) - 2 - me-
ethyl-4-methoxybenzene Red 55 the same ι- (2 ', 3'-oxynaphthoylamino) -3-me-
ethylbenzene Red the same i- (2 ', 3'-oxynaphthoylamino) -3-chloro-
benzene Red 6 ο also - ' i- (2 ', 3'-oxynaphthoylamino) -4-chloro-
benzene Red

Diazo component Coupling component hue 5 . Ethyl ester of 4 '- methyl - 2 - amino
i, 1'-diphenylether-4-carboxylic acid i- ^(2;, 3'-oxynaphthoylamino) -2-meth- ■
oxy-5-chlorobenzene Scarlet fever the same i- (2 ', 3'-oxynaphthoylamino) -2, 4-di-
methylbenzene alizarin red IO the same i- (2 ', 3'-oxynaphthoylamino) -2, 5-di--
methylbenzene Red Ethyl ester of 2 ', 5'-dichloro-2-amino
i, ι'-diphenylether-4-carboxylic acid i- (2 ', 3'-oxynaphthoylamino) -naph
thalin Red the same 2,3-Oxynaphthoylaminobenzene Scarlet fever 15th the same 2- (2 ', 3'-oxynaphthoylamino) -2-naph-
thalin Scarlet fever the same ι - (2 ', 3'-Oxynaphthoylamino) -4-me-
ethylbenzene Scarlet fever 20th the same i- (2 ', 3'-oxynaphthoylamino) -3-chloro-
benzene Scarlet fever Ethyl ester of 2'-methyl-2-amino-
i, ι'-diphenylether-4-carboxylic acid i- (2 ', 3'-oxynaphthoylamino) -2-chloro-
benzene / Red 25th ) the same i- (2 ', 3'-oxynaphthoylamino) -2, 4-di-
methylbenzene Scarlet fever the same i- (2 ', 3'-oxynaphthoylamino) -2-meth-
oxy-5-methylbenzene sqharlach 30th Methyl ester of 2-amino-i, i'-diphe-
nylon-4-carboxylic acid ι - (2 ', 3' - Oxynaphthoylamino) - 2 -me-
ethyl 4-chlorobenzene Red the same ι - (2 ', 3' - Oxynaphthoylamino) - 3 - ni-
trobenzene deep red 35 the same i- (2'-, 3'-oxynaphthoylamino) -2-chloro-
benzene Red the same i- (2 ', 3'-oxynaphthoylamino) -2-meth-
oxy-5-chlorobenzene Red 40 the same ι - (2 ', 3' - Oxynaphthoylamino) - 2 -me-
ethylbenzene Red the same ι - (2 ', 3' - Oxynaphthoylamino) -3 -me-
ethylbenzene alizarin red 45 the same i- (2 ', 3'-oxynaphthoylamino) -4-mc-
tliylbenzene Red the same ι - (2 ', 3' - Oxynaphthoylamino) -meth-
oxy-5-methylbenzene alizarin red the same i- (2 ', 3'-oxynaphthoylamino) -2-eth-
oxy-5-methylbenzene Scarlet fever 50 the same 2, 3-Oxynaphthoylaminobenzol Red the same i- (2 ', 3' -oxynaphthoylamino) -4-chloro-
benzene Scarlet fever 55 the same ι - (2 ', 3' - Oxynaphthoylamino) -naph
thalin alizarin red Methyl ester of 2'-methyl-2-amino
i, ι'-diphenylether-4-carboxylic acid 2,3-Oxynaphthoylaminobenzene Red 6ο the same i- (2 ', 3'-oxynaphthoylamino) -4-chloro-
benzene Scarlet fever

Claims (1)

Diazo component Coupling component hue Red 5 Methyl ester of 2'-methyl-2-amino
i, i'-Diphenylether-4-carboxylic acid ι - (2 '', 3 '- Oxynaphthoylamino) - 2 -me-
ethylbenzene Red the same ι - (2 ', 3' - Oxynaphthoylamino) - 4 -me-
ethylbenzene Red 10 the same ι - (2 ', 3' - Oxynaphthoylamino) - 2 -me-
tnyl-4-methoxybenzene alizarin red Methyl ester of 4 '- chloro - 2 - amino
i, ι'-diphenylether-4-carboxylic acid ι - (2 ', 3' - Oxynaphthoylamino) - 3 -me-
ethylbenzene alizarin red '5 the same i- (2 ', 3'-oxynaplithoylamino) -2-meth-
oxy-3-chlorobenzene Red the same ι - (2 ', 3' - Oxynaphthoylamino) - 2 - me-
ethyl 5-chlorobenzene Red 20th the same i- (2 ', 3'-oxynaphthoylamino) -2-meth-
oxy-5-methylbenzene If the above-mentioned diazo components are replaced by z. B. the isopropyl ester or the n-butyl ester of 4'-chloro-2-amino-i, i'-diphenylether-4-carboxylic acid, dyes are obtained _; which have the same purity and the same properties of purity. Very pure dyes are also produced when benzyl, phenyl, tolyl, methoxy or ethoxyphenyl esters are used instead of esters of aliphatic alcohols. Similar results are obtained in piece dyeing or in printing. The dyes can also be made on other fibers such as silk, rayon, of course the procedures given in the preceding examples accordingly the information in the relevant literature must be changed. If one wishes to make the dyes of the present invention on wool, one will with advantage that from the British patent specification 310 258 or the French patent 734 189 known regulations. Ρατενϊλν Proverb: Process for the preparation of water-insoluble azo dyes ^ characterized in that arylides of 2, 3-oxynaphthoic acids with diazotized aryl. Or Aralkyläthern of 2-amino-i-oxy benzene or its substitution products are coupled, which still contain a Carbonsäureestergruppc in the 4- or 5-position _v.