DE61950C - Process for the preparation of trisazo dyes. (2 - Google Patents

Description

IMPERIAL

PATENT OFFICE.

In patent no. 57331 and its first addition No. 61949 describes a process for the preparation of trisazo dyes, which, depending on whether the diazo compounds of the mixed dyes listed there: tetrazodiphenyl or respectively. Tetrazoditolyl + ι mol. Salicylic acid respectively. o-oxy-p-toluic acid - \ - 1 mol of a -. naphthylamine the various Naphtolsulfosäuren or Dioxynaphtalinsulfosäuren act läfst, green-black to graubis or leads Russian green Producten.

These dyes are sparingly soluble and can therefore only be used in an alkaline soap bath be colored.

Technically extremely valuable dyes are obtained if the mixed dyes mentioned are obtained from tetrazodiphenyl or. Tetrazoditolyl + 1 mol. Salicylic acid (or cresol carboxylic acid) + 1 mol. A - Naphthylamine initially sulfated before further diazotization.

In this way, easily soluble intermediate products are obtained which, after diazotization and after combining with amines, phenols, their sulfo and carboxylic acids, give mixed tetrazo dyes, which can be used both in an alkaline soap bath and in a neutral bath with the addition of table salt unheated cotton able to stain directly. The new products obtained in this way also provide nuances that are essentially different from those not treated, e.g. B. the dye, which is obtained by sulphuring the tetrazo compound: tetrazodiphenyl - \ - salicylic acid + α-naphthylamine, by further diazotizing and coupling with salicylic acid, turns yellow-red, while the analogous dye containing α- naphthylamine as the third component provides an excellent dark dark brown .

The procedure for representing these dyes is as follows:

The mixed dyes from 1 mol. Tetrazo compound, ι mol. Salicylic acid respectively. Cresolcarboxylic acid and 1 mole of a- naphthylamine are mixed with 4 parts of fuming sulfuric acid of 20 pCt. Anhydride content sulphated with cooling, these sulphured products dissolved in alkali, mixed with the calculated amount of nitrite, cooled, and diazotized by acidification with hydrochloric acid. Diazotization is complete after 12 hours of standing. It is filtered off, and the diazo compound obtained by introducing it into the alkaline solution of a phenol, its sulfo or carboxylic acids or into the acetic acid solution of an amine or diamine, respectively. their sulfonic acids are used to produce the new dyes. The further processing of the reaction mixture takes place in the usual way.

The following should serve to explain the procedure in more detail:

I. Representation of the diazo compound of the sulphured intermediate product from tetrazodiphenyl, Salicylic acid and α-naphthylamine.

48.7 kg of the mixed salicylic acid-a-naphthylamine tetrazodiphenyl dye are slowly dissolved in 200 kg of fuming sulfuric acid of 20 pCt. Anhydride content between ⁰ ° and 30 0 entered. As soon as a sample of it dissolves clearly in alkali, the sulphurisation mixture is poured onto ice, the dyestuff acid which has separated out is filtered off and dissolved in alkali.

It is allowed to cool, 7 kg of sodium nitrite are added and the mixture is acidified with hydrochloric acid. To Diazotization is complete after standing for 12 hours; the diazo product formed separates due to its poor solubility.

II. Yellow-brown dye composed of the above diazo compound and salicylic acid.

The filtered diazo compound with a nitrite content of 7 kg obtained by the above process is entered in an alkaline solution of 16 kg of salicylic acid by soda in ice cold. the Coupling of the dye is slow and only takes place after standing for 12 hours accomplished. The resulting dye dyes unheated cotton yellow-red.

III. Black-brown dye of the diazo compound I and a-naphthylamine.

Läfst to the 7 kg nitrite corresponding diazo compound I at an acetic acid solution of 16 kg a-naphthylamine act, is obtained after 1 standing for 2 hours, heating at 50 ⁰ and basifying a cotton deep black brown coloring dye.

IV. Gray-black dye from the diazo compound I and a, - naphthol monosulfonic acid (Nevile-Winther).

When the diazo compound I acts on an alkaline solution of 25 kg of a-naphthol monosulfonic acid (Nevile-Winther) a gray-black coloring product is obtained.

V. Russian green dye from the diazo compound I and dioxynaphthalene monosulfonic acid S.

30 kg of dioxynaphthalene monosulfonate of soda. in acetic acid solution deliver in completely analogous Way with the diazo connection I a very beautiful Russian green.

In general, it is characteristic of the dyes that can be prepared by the above process, that the differences in nuances are only due to the use made in the last place arriving dye components are conditioned. A notable difference between the corresponding benzidine and tolidine dyes do not exist.

The following table shows the nuances of the trisazo dyes obtained in the above manner compiled:

I. m - phenylenediamine Benz
+ Salicylic acid
+ α-naphthylamine
(sulfated unc
4th
Brown black Color c
idin
4- o-oxy-p-toluyl-
acid
4-α-naphthylamine
. diazotized)
Brown black } ff from
ToI
4- salicylic acid
4-α-naphthylamine
(sulfated unc
4th
Brown black din
4- o-oxy-p-toluyl-
acid
4 - «- naphthylamine
J diazotized)
Brown black 2. m -tolylenediamine grey black grey black grey black black-brown 3 · α-naphthylamine Brown black Brown black Brown black Brown black 4th ß-naphthylamine Brown black Brown black Brown black Brown black 5 · m - phenylenediaminesulfonic acid greenish black greenish black greenish black grey black 6th α - naphthoic acid Brown black red-brown red-brown red-brown 7 · β-naphtylamine monosulfonic acid
(Brönner) light brown Brown Brown Brown 8th. Ethyl - β - naphthylamine monosulfonic acid dark brown red-brown red-brown dark brown 9- ß-naphthylamine disulfonic acid G. light brown light brown light brown light brown 10. phenol yellow-red yellow-red yellow-red yellow-red II. Resorcinol Brown black dark brown Brown black Brown black 12th Salicylic acid yellow-red yellow-red yellow-red yellow-red ! 3- 0 - oxy - ρ - toluic acid yellow-red yellow-red yellow-red brownish yellow

ΐ4 α - naphtol Benz
+ Salicylic acid
+ «-Naphtylamine
(sulfated unc
H
greenish black Dye
idin
-4- ce-oxy-p-toluyl-
acid
+ «-Naphtylamine
diazotized)
greenish black off off
ToI
+ Salicylic acid
+ a-naphthylamine
(sulfated unc
H
greenish black idin
+ o-oxy-p-toiuyl-
acid
■ + ■ ce-naphthylamine
I diazotized)
greenish black > 5 ß-naphtol grey black grey black grey black Gray ΐ6. a. - Naphtol monosulfonic acid (N evil e-
Winther) grey black blue gray gray-green Gray ^ι 7- α - naphthol monosulfonic acid (C1 e ν e) grey black grey black gray-green gray-green ΐ8. β - naphthol monosulfonic acid (S c häff e r) grey black grey black brown-gray grey black I ₉ . ß-naphthol- S-monosulfonic acid (2 - 7) gray-green gray-green green grey gray-green 20th a. - Naphthol disulfonic acid S (patent 40571) grey black grey black grey black grey black 21. a - Naphtol - ε - disulfonic acid (Patent 45776) greenish black greenish black greenish black greenish black 22nd Amidonaphtol monosulfonic acid G. grey black grey black blue-gray blue-gray 23- ι ■ 8-dioxynaphthalene Gray Gray light gray Gray 24- ι · 8-Dioxynaphthalene-ct-monosulfo-
acid S russian green russian green russian green russian green ² 5 α - naphtholecarboxylic acid red-brown red-brown red-brown red-brown 26th β - naphtholecarboxylic acid (melting point 216 °) Gray light gray Gray Gray 2 ₇ . ι · 8 - Dioxynaphthalene monocarboxylic acid gray-green gray-green gray-black grey black

Claims (1)

Patent claim: Innovation in the process for the preparation of trisazo dyes, consisting in the fact that one of 1 mol. Tetrazodiphenyl or tetrazoditolyl with 1 mol. Salicylic acid or o-oxy-p-toluic acid and 1 mole of a-naphthylamine The mixed dyes obtained are first sulfated and then by the method of Main patent diazotized and allows the following dye components to act: tn-phenylenediamine, m-tolylenediamine, a-naphthylamine, ß-naphthylamine, m-phenylenediamine sulfonic acid, a-naphthoic acid, β - naphtylamine mono- sulfonic acid (Brönner), ethyl-ß-naphthylamine monosulfonic acid, β - naphthylamine disulfonic acid G, phenol, resorcinol, salicylic acid, o-oxy-p-toluic acid, α-naphtol, ß-naphtol, α-naphtol monosulfonic acid (Nevile-Winther), a-naphtol monosulfonic acid (Cleve), ß-naphtol monosulfonic acid (Schäffer), ß-naphthol-i-monosulfonic acid (2-7), a-naphthol disulfonic acid S (Patent No. 40 5 71), α-naphthol-ε-disulfonic acid (Patent No. 45776), Amidonaphthol monosulfonic acid G, 1x8-dioxynaphthalene, i. 8-Dioxynaphthalene-tt-monosulfonic acid S, α-naphtholecarboxylic acid, β-naphtholecarboxylic acid (Mp. 216 °), ι · 8 - dioxynaphthalene monocarboxylic acid.