DE606039C - Process for the production of azo dyes - Google Patents

Description

Process for the preparation of azo dyes It has been found that new, valuable azo dyes are obtained by using diazo compounds with compounds of the general formula in which R1 and R2 are hydrogen, alkyl or aryl, or their Desmotropes are coupled. Compounds of this type are, for example, 2,4-dioxypyridine and -picoline, the N-alkyloxypyridones and -picolons.

Those from these coupling components and sulfonated or unsulfonated Azo dyes obtainable from diazo compounds are generally yellow, orange, brown or red. Those produced using dianotated o-oxyun.d o-alkoxyamines Dyes can be removed by treating them with metal donating agents, such as chromium or copper compounds, in substance or on the fiber in metal-containing dyes convict. The dyes are generally good lightfast and stand out, as far as they are sufficiently soluble in water, through an excellent leveling ability, large capacity and often good washfastness.

The azo dyes obtainable according to the present invention draw ahead of the already known, using oxyquinolines as a coupling component Azo dyes produced in particular by the fact that they are a considerably better Have equalizing power.

Example 95 parts of aniline are dianotized in the customary manner and the resulting solution of the diazo compound is added with stirring to an alkaline soda solution of 142 parts of 2,4-dioxypicoline (cf. reports from the German Chemical Society, vol. 31, p. 771 ff.). The yellow dye obtained can e.g. B. are used to color paints, wax preparations and oils as well as acetate silk.

Similar dyes are obtained if the diazo compounds are used as the diazo component used by toluidines, xylidines, aminonaphthalenes or aminoazobenzene. Instead of des 2, q.-Dioxypicolins can be. the 2, q.-dioxypyridine (see reports of the German i shy Chemical Society, Vol. 31, p. 1687) use which greenish yellow dyes, or N-methyl-4-oxy-2-picolon (F. 225 bis 226 ° C with decomposition, produced for example by heating for 2 hours 1 mole of 6-MethS # 1-pyronone with about 2 moles of methylamine in aqueous solution to 130.degree and subsequent acidification), which gives reddish yellow tones.

Further suitable coupling components are N-ethyl-4-oxy-2-picolon (mp 198 ° C, made from 6-methylpyronone and ethylamine) and N-butyl-4-oxy-2-picolon (oil, made from 6-methylpyronone and butylamine). EXAMPLES 140 parts of i-amino-3-nitrobenzene are diazotized in the customary manner and the resulting solution of the diazo compound is added to a soda-alkaline solution of 142 parts of 2,4-dioxypicoline. A yellow dye is obtained which can be used as a pigment for the paint industry and for dyeing acetate silk. The dye prepared in an analogous manner by coupling with the N-methyl-4-oxy-2-picolon mentioned in Example -i has a somewhat reddish cast.

The following table lists some other dyes produced with the help of nitrated amines and their color shades. - Diazo compound from 2, q.-dioxypicolin N-methyloxy pichlone i-Amino-2-nitrobenzene ............ c ................... reddish yellow orange i-Amino-4-nitrobenzene ................................ reddish yellow orange x-amino-2,4-dinitrobenzene. . . . . . . . . . . . . :. . . . . . . . . . . . . . yellow brown dark brown i-methyl-4-amino-3-nitrobenzene ........................ yellow-orange red-orange i-Amino-2-methoxy-5-nitrobenzene ...................... red-orange red x-Amino-2-chloro-4-nitrobenzene .......................... red brown-yellow i-Amino-2-chlorobenzene ................................ yellow yellow i-amino-2,5-dichlorobenzene. . . . . . . . . . . . . . . . . . . . . . . . . . . . yellow yellow 4,4 @ -diamino-3,3'-dichlorodiphenyl. . . . . . . . . . . . . . . . . . . . . yellow reddish yellow Example 3 22o parts of i-methyl-3-amino-6-chlorobenzene-4-sulfonic acid are diazotized and coupled with 142 parts of 2,4-dioxypicoline in an alkaline soda solution. After salting out, a yellow dye is obtained which dyes wool in bright yellow and very even tones. The corresponding, using 2; The dye made with q.-dioxypyridine has a greener cast, while the dye made with N-methyl-4-oxy-2-picolon has a slightly reddish cast.

The dyes can be coated with barium salts in the usual way and make beautiful, bright yellow pigments.

Dyes with similar properties are obtained when using i-amino-4-chlorobenzene-3-sulfonic acid, i-amino-2-methylbenzene-4-sulfonic acid, i-aminonaphthalene-2-sulfonic acid, i-aminonaphthalene-5- or - 7 or. -8-sulfonic acid, 2-aminonaphthalene-3 or. -6- or -8-sulfonic acid, 2-aminonaphthalene-5, 7- or -6,8- or -q., 8-disulfonic acid or i-aminonaphthalene-4, 7-disu-ifonic acid as diazo components .

Example 4 267 parts of i-amino-2-methoxynaphthalene-6-sulfonic acid become diazotized and coupled with 150 parts of 2,4-dioxypicoline in a soda-alkaline solution. The dye obtained by salting out colors the animal fibers very evenly Orange red.

If the dye is treated in the usual way with chromium-releasing agents Agents, such as chromium formate, under conditions where the methyl radical is split off takes place, a chromium-containing dye is obtained, the wool very evenly colors purple-red.

The table below contains additional ones produced in an analogous manner Dyes, indicating the colorations that come with these dyes or those made from them chromium complex compounds produced on wool are available.

Example s Acetate silk is dyed in the usual way with i 1 / o aminoazobenzene. The fiber is then diazotized and developed with a weakly alkaline solution of 2,4-dioxypicoline. The orange coloration obtained has good lightfastness and excellent washfastness. In a similar way you can pre-dye Acetatsei, de with other aminoazo compounds and z. B. develop with 2,4-dioxypyridine or N-methyl-4-oxy-2-picolon. . The colorations obtained are yellow, red to purple. Coloring on wool of the color of the chrome fabric comp @ ex- link 1-Amino-2-methoxy-5-chlorobenzene-3-sulfonic acid r 2, 4-Dioxypicolin yellow pink i-Amino-2-methoxy-5-methylbenzene-4-sulfonic acid @r 2, 4-dioxy-golden yellow Bordeaux picoline i-Amino-2-methoxybenzene-5-sulfonic acid r 2, 4-Dioxypicolin ...... yellow yellow-red i-Amino-2-methoxy-4-nitrobenzene-5-sulfonic acid> - 2, 4-Dioxypicolin golden yellow red i-Amino-2-methoxybenzene-5-sulfonic acid -> - N-methyl 4-oxy-2-picolon yellow red i-Amino-2-methoxy-5-chlorobenzene-3-sulfonic acid r N-methyl-4-oxy- yellow pink 2-picolon. Example 6 226 parts of r-oxy-2-amino-4-chlorobenzene-6-sulfonic acid are diazotized and coupled with 13o parts of 2,4-dioxypicoline in an alkaline soda solution. The dye obtained dyes wool in very uniform yellow-brown shades. Its chrome compound, which is produced by re-chrome plating on the fiber or by chrome plating in substance, gives very even, genuine Bordeaux tones.

The table below contains further azo dyes with 2,4-dioxypicoline as a coupling component and the shades on wool that can be obtained with them or with their chromium compounds. Shade on wool Diazo component of the dye of the chrome connection i-Oxy-2-aminobenzene-4,6-disulfonic acid. . . . . . . . . . . . . . . . . yellow-brown red i-Oxy-2-amino-6-nitrobenzene-4-sulfone, # acid ............... violet red i-Oxy-2-amino-4-nitrobenzene-6-sulfonic acid ............... brown-red yellow-red i-Amino-2-oxy-6-nitronaphthalene-4-sulfonic acid. . . . . . . . . . . brown marron i-Amino-2-oxynaphthalene-4-sialfonic acid 2. . . . . . . ,. . . . . . . . . orange red The dyes prepared in a corresponding manner with 2,4-dioxypyridine, N-methyl-4-oxy-2-picolon or N-ethyl-4-oxy-2-picolon as coupling components have similar properties and nuances.

Example? 37o parts of 4,4'-diaminostilbene-2, 2'-disulfonic acid tetrazotized and with 29o parts of N-methyl-4-oxy-2-picolon in a soda-alkaline solution coupled. The dye obtained gives red shades on cotton.

The table below contains further azo dyes formed from N-methyl-4-oxy-2-picolon and other diazo compounds, with details of the dyeings on cotton that can be obtained with them. Diazo or tetrazole component coloring cotton Dehydrothiotoluidinsulfonic acid _........................................ yellow-orange 4,4'-Diaminodiphenyl-5, 5'-disulfonic acid ................................ orange 4. 4'-Diamino-3, 3'-dimethoxydiphenyl-5, 5'-disulfonic acid. . . . . . . . . . . . . . . . . Red orange 4,4'-diaminodiphenylurea-5, 5'-disulfonic acid. . . . . . . . . . . . . . . . . . . . . . . : orange Similar colorations are obtained with azo dyes in which the diazo or diazo dyes mentioned. Tetrazo components and N-ethyl-4-oxy-2-picolon or 2,4-dioxypyridine or 2,4-dioxypicoline are used as coupling components, or if the tetrazo compounds mentioned are used with only 1 mole of an N-alkylated oxypyridone or 2, q.-Dioxypyridine or 2, 4-Dioxypicohn and r moles of another couplable compound, z. B. 2-oxynaphthalene, z-oxy-q.-methylbenzene, acetoacetic acid anili.d or 2-oxynaphthalene-6-sulfonic acid.

Example 8 137 parts of r-aminobenzene-2-carboxylic acid are diazotized and coupled with r25 parts 2, q.-Dioxypicolin in a soda-alkaline solution. The through Salting out of the deposited dye produces yellow dyeings on wool from an acid bath. By treating the dye with chromium-releasing agents, a chromium-containing one is obtained Dye that provides orange tones with high fastness properties on wool. r-Aminobenzene-2-carboxylic acid-5-sulfonic acid as a diazo component provides a dye of similar properties.

When using r-oxy-2-amino-4, 6-dinitrobenzene as the diazo component a dye is obtained which, from an acid bath, produces brown-red dyeings on wool. When the dye is treated with chromium-releasing agents, the color tone changes hardly, but the fastness properties are significantly improved.

Claims (1)

PATENT CLAIMS Process for the production of azo dyes, characterized in that diazo compounds are compounds of the general formula in .der R1 and R = hydrogen, alkyl or aryl, or their Desmotropen couples.