DE298852C - - Google Patents

Description

In the introduction to patent specification 116640 the following statement can be found: Even those distinguished by their special coupling energy Aminonaphtholdisulfonic acid K does not combine with the diazo compounds of the aminosalicylic acids in acidic solution to form uniform o-aminazo dyes. «Friedländer comments on this patent specification in the note (advances in tar paint production, Vol. V, p. 519): While diazosalicylic acid and K acid in acidic solution not smoothly and combined in practically insufficient yield ”.

It has now been found that, contrary to these statements, it is possible under certain circumstances Conditions from the diazosalicylic acids or their core substitution products and the i-Amino-S-oxynaphthalene-4 · 6-disulfonic acid uniform To produce o-aminoazo dyes in good yield. The procedure persists in that the components are expediently in acidic solution at a moderately elevated temperature at 30 to 40 ° C, allowed to act on each other.

Example I.

15.3 parts of 4-amino-i-oxybenzene-2-carboxylic acid are dissolved in water with the addition of 5.3 parts of sodium carbonate and an aqueous solution Mixed solution of 6.9 parts of sodium nitrite. This mixture is divided into 55 parts Run in 2 percent hydrochloric acid and 200 parts of water. When the diazotization is complete, there are an aqueous solution of 35 parts of the acidic sodium salt of i-amino-8-oxynaphthalene-4 Add 6-disulfonic acid and heat the mixture to 35 to 40 ° C while stirring, until the dye formation is complete. Then heat up higher, neutralize with 16 parts Sodium carbonate and salt out the dye.

Example II.

The aminooxybenzenecarboxylic acid is diazotized as in Example I and then added to the Diazo compound is an aqueous solution of 35 parts to which 8.2 parts of sodium acetate are added of the acid sodium salt of i-amino-8-oxynaphthalene-4 6-disulfonic acid is added and the procedure continues as in Example I.

The o-aminoazo dye obtained according to these examples forms a dark brown powder, which dissolves in water with a yellowish brown color. This solution is made by soda brownish fox-red, colored dark red-violet by hydrochloric acid. In concentrated sulfuric acid the dye dissolves with a red-violet color. '. ·.; ■

The 6-amino-i-oxybenzene-2-carboxylic acid behaves in the same way as 4-amino-i-oxybenzene-2-carboxylic acid and the substitution products of these two acids, e.g. B. the sulfoaminosalicylic acids, the nitroaminosalicylic acids, the amino-o- and amino-m-cresotinic acid, etc.

Example III.

An aqueous solution of 17.5 parts of the sodium salt to which 6.9 parts of sodium nitrite were added of 6-amino-i-oxybenzene-2-carboxylic acid

is left in no parts of 10 percent hydrochloric acid come in. When the diazotization is complete, 35 parts of the acidic sodium salt are added of i-amino-8.-Qxynaph.thalin-4 · 6-disulfonic acid added and continued, as in the first example indicatedqjjsi. ' ■; .; _; ;. · ...

Example IV.

27.7 parts of the sodium salt of 4-amino-6-sulfo-i-oxybenzene-2-carboxylic acid are diazotized with 6.9 parts of nitrite and 75 parts of a 20 percent hydrochloric acid in the manner indicated in Example 1, and the resulting compound is coupled diazo compound with 35 parts of the acid sodium salt of i-amino-8-oxynaphthalene-4 · 6-disulfonic acid at 40 to 50 ⁰ C. If the dye formation terminated, neutralizing the reaction mixture with 21.5 parts of sodium carbonate, and separates the dye in a known Way off.

Example V.

22 parts of the sodium salt of 6-nitro-4-amino-i-oxybenzene-2-carboxylic acid are, as described in Example III, diazotized and with 35 parts of the acidic sodium salt of i-amino-8-oxynaphthalene-4 · 6-disulfonic acid coupled at 30 to 50 ° C. After dye formation is complete is neutralized with 16 parts of sodium carbonate and the dye deposited in the usual way.

Example VI.

In the preparation of the dye p-aminoocresotinic acid - azo - aminooxynaphthalene disulfonic acid K from 16.7 parts of 4-amino-i-oxy-6-methylbenzene-2-carboxylic acid proceed exactly according to the ways given in the first or second example. In the table below some reactions of the new dyes are listed.

Dye off coloring the
water
solution the soda "
alkaline
solution ¹ the salt
acidic
solution the solution
in conc.
sulfur
acid i-Amino-8-oxynaphthalene-4x6-disulfonic acid
and diazotized yellowish
Brown fuchsin red dark red-
violet red-violet i. 4-amino-i-oxybenzene-2-carboxylic acid bluish red purple red the same violet 2. 6-Amino-i-oxybenzene-2-carboxylic acid fuchsin red red-violet the same purple red 3. 6-Amino-4-sulfo-i-oxybenzene-2-carboxylic acid. Red fuchsin red bluish
violet the same 4. 4-Amino-6-sulfo-i-oxybenzene-2-carboxylic acid. yellow-brown the same purple red the same 5.4-Amino-i-oxy-6-methylbenzene-2-carboxylic acid orange Red Brown the same 6. 4-Amino-i-oxy-5-methylbenzene-2-carboxylic acid Red bordeaux violet-
Brown fuchsin red 7. 6-Nitro-4-amino-i-oxybenzene-2-carboxylic acid.

The above-mentioned o-aminoazo dyes from i-amino-S-oxynayhthalene ^ -ö-disulfonic acid have proven to be technically useful intermediates for the production of new azo dyes, insofar as they are at the coupling with diazo and tetrazo compounds previously unknown, valuable dyes deliver.

Claims (1)

Patent-An saying:
Process for the preparation of o-aminoazo dyes, consisting in that. the diazo compounds of o- or p-aminosalicylic acid, sulfoaminosalicylic acids, nitroaminosalicylic acids, amino-o- or amino-m-kresosinic acid to i-amino-8-oxynaphthalene-4 · 6-disulphonic acid; in acidic solution at moderate Elevated temperature, expediently at 30 to 40 ° C, can act.