DE127447C - - Google Patents

Description

IMPERIAL

PATENT OFFICE,

The monoazo dyes obtained from diazotized amidonaphthol sulfonic acids and toluenediaminesulfonic acid are used

(CH ₃ NH ₂ NH ₂ H -.SO ₅ = 1: 2: 6: 4;

If diazo compounds act, two places in the molecule come into consideration where they intervene can: either in the benzene residue or in the naphthalene residue. Dyes more similar Compositions are described in patent 84546, claim 2; their constitution is not to be seen from the information given there.

But as can be seen from the content of patent 84292 and additions and patent 109161, combine monoazo dyes of the formula

A S- azo-m-diamine

(AS = amidonaphthol sulfonic acid) in the action of diazo compounds always in the phenylene radical. The same constitution

\ rn - diamine - AS

(D = diamine, X = any component), is therefore also included in the polyazo dyes obtained according to the information in patent 84546, claim 2. If you now use their sulfonic acids in place of the meta-diamines, z. For example, toluenediaminesulfonic acid, which expression in the following is always to be understood as meaning the acid of the above composition, one could assume that dyes obtained in this way also have the constitution

D ^{/ X}

^ Toluenediaminesulfonic acid- AS

have, since the said toluenediaminesulfonic acid is just as easy as m-phenylene or m-Toluylenediamine combined with 2 mol. Diazo compound.

Contrary to expectations, however, the monoazo dyes (AA - azo - toluylenediamine sulfonic acid) do not combine in the phenylene radical, but in the naphthalene radical, so one obtains dyes, giving way to the constitution

/ X
\ A S - azo - toluenediaminesulfonic acid

comes to. That the combination really takes place in the naphthalene residue can best be seen from the fact that the trisazo dyes of the formula γ-

D \ "a ο by diazotizing and combining with

Toluylenediaminesulfonic acid in its behavior and its properties are identical to the trisazo dyes, which from the intermediate products D ^/

by union with the

Monoazo dyes A S-azo- toluenediaminesulfonic acid can be obtained. Accordingly, the use of toluenediaminesulfonic acid instead of meta-diamines gives the monoazo dyes prepared from them a completely different behavior towards diazo compounds, and polyazo dyes of the constitution can be obtained directly from monoazo dyes (AS-azo - toluenediaminesulphonic acid)

, X
\ 4 S- azo-toluenediaminesulfonic acid

get what according to the information of the patents 48297 and additions and those of the patent 109161 could not be foreseen. It is coming accordingly also the dyes of the present

the patent has a different constitution than the dyes of patent 84546, claim 3.

If tetrazo compounds are allowed to act on monoazo dyes ( aa - azo - toluenediaminesulfonic acid) in alkaline solution, intermediate products coupled in the naphthalene residue are first obtained, which then combine with another molecule of the same or a different monoazo dye or a molecule of an amine, phenol, amidophene - and carboxylic acids combine to form valuable dyes. They dye cotton without staining, have great color strength, in spite of easy solubility, good fastness to soap, and go easily and evenly on the fiber; they show much bluer respectively. Greener nuances than the dyes of patent 84546. Furthermore, most of the dyes in this group are etched with bisulfite zinc dust as well as with pure white tin salt. They can be diazotized and developed on the fiber or combined with diazo compounds, and produce far more beautiful greener or bluer, more valuable shades than the dyes of patent 84546.

So far, the monoazo dyes were made from 2: S-amidonaphthol-δ-sulfonic acid, 2: 8-amidonaphthol-3 : 6-disulfonic acid and 2: 5-amidonaphthol-7-sulfonic acid and toluenediaminesulfonic acid investigated in more detail in this direction.

Examples:

I. Dyestuff from benzidine - \ - 2 mol. Of the monoazo dyestuff as amidonaphthol monosulphonic acid G -J- toluenediaminesulphonic acid 1: 2: 6: 4.

18.4 kg of benzidine are used in a known manner converted into the tetrazo compound and this into an alkaline to the end by soda held solution of 103.6 kg sodium salt of the monoazo dye from amidonaphthol monosulfonic acid G -J- Toluenediaminesulfonic acid 1: 2: 6: 4 (obtainable in a known manner by combining of diazotized amidonaphthol monosulphonic acid with toluenediaminesulphonic acid 1: 2: 6: 4 in soda-alkaline or better acetic acid solution). After 24 hours it is The formation of the dye is complete, the temperature is raised to about 80 to 90 ° and it is precipitated with salt; after this Cooling is filtered, pressed and dried. The dye represents a black, faint shiny metallic powder, which easily dissolves in water with a dark brown color and dyes cotton deep black without staining.

If tolidine or dianisidine is used instead of benzidine, something is obtained greener dyes.

II. Dye from benzidine -J- 1 mol. Monoazo dye -J- 1 mol. Amidonaphthol disulfonic acid H.

The tetrazo compound obtained from 18.4 kg of benzidine one leaves in a strongly alkaline soda solution of 51.8 kg sodium salt of the monoazo dye from amidonaphtol monosulfonic acid G + toluenediaminesulfonic acid 1: 2: 6: 4; the intermediate product is formed immediately and is for the most part as a black precipitate deposited. A solution of 34.1 kg of the acidic sodium salt of 1: 8-amidonaphthol disulfonic acid is added H, dye formation occurs rapidly, which ends after 12 hours is. It is warmed up, precipitated with salt, and the dye is filtered off. The same puts dried is a gray-black powder, which is easily mixed with dark blue-black in water Dye dissolves and dyes cotton greenish black-blue without staining. Tolidine and dianisidine accordingly provide greener dyes. With ι: 8-amidonaphthol-4-monosulfonic acid is obtained one slightly greener nuances. The other periamidonaphthol sulfonic acids give similar dyes.

Amidonaphthol monosulfonic acid G and 2: 8-amidonaphthol-3: 6-disulfonic acid produce black dyes. When using the equivalent amount of the monoazo dye from 1: 8-amidonaphthol disulphonic acid H -J- a - naphthylamine instead of Η-acid, a dark gray product is obtained. If the monoazo dye from 2: 8-amidonaphthol-3: 6-disulfonic acid H -J-toluenediaminesulfonic acid 1: 2: 6: 4 is used in the first place, almost identical, only slightly more soluble, dyes are obtained.

III. Dye from benzidine -j- 1 mol. Monoazo dye from (2: 8-amidonaphtol "3: 6-disulfonic acid -J- toluenediaminesulfonic acid 1: 2: 6: 4)

and ι mol. α-naphthylamine.

The tetrazo compound obtained from 18.4 kg of benzidine is made in a soda-alkaline solution with 61.1 kg sodium salt of the monoazo dye 2: 8-amidonaphthol "3: 6-disulfonic acid and toluenediamine sulfonic acid 1: 2: 6: 4 combined to form an intermediate product; a solution of 14.3 kg of α-naphthylamine is added to this in the necessary solution Amount of hydrochloric acid dissolved. The dye formation begins immediately and is completed after 24 hours. It is warmed up, covered with salt, filtered and dried. The dye thus obtained stains unheated cotton dark brown purple.

If the equivalent amount of ß -naphtol is used instead of α-naphtylamine, a blue-violet dye is obtained.

IV. Dye from benzidine -J- 1 mol. Of the monoazo dye from (amidonaphtol monosulfonic acid G -J- toluenediaminesulfonic acid 1: 2: 6: 4)

-J- ι: 4-naphthol sulfonic acid.

That from 18.4 kg of benzidine and 51 kg of monoazo dye Intermediate product obtained in a soda-alkaline solution is poured into a soda-alkaline solution Flow in a solution of 24.6 kg 1: 4 naphthol sulfonic acid soda; the immediately beginning coloring

The formation of the substance ends after 12 hours. The dye becomes after being heated with salt pleases. It dyes unheated cotton purple.

If the naphthol sulfonic acid is replaced by equivalent amounts of the following substances, dyes with the following nuances are obtained:
m-phenylenediamine or m-

Toluylenediamine black-brown,

Toluenediamine sulfonic acid. black-brown,

a-naphthylamine violet brown,

ß-naphtol black-violet,

1: 6- and ι: 7-naphthyl-

aminesulfonic acid (mixture) gray-black,
2: 6- naphthylamine sulfonic acid red-violet,

2: 6-dioxynaphthalene gray-black,

1: 8- dioxynaphthalene -3: 6-

disulfonic acid greenish black,

2: 3-Dioxynaphthalene - 6 -

sulfonic acid purple black.

V. Dye from benzidine -f- 2 mol. Of the monoazo dye (2: 5-Amidonaphthol-7-monosulfuric acid-j-Toluenediaminesulfonic acid 1: 2: 6: 4).

18.4 kg of benzidine are converted into the tetrazo compound in a known manner and this is converted into a solution of 103.0 kg of sodium salt of the monoazo dye from 2: 5-amidonaphthol-7 monosulfonic acid - \ - toluenediaminesulfonic acid 1: 2: 6, which is kept alkaline until the end: 4 (obtained in a known manner by combining diazotized 2: 5-amidonaphthol-7-monosulphonic acid with toluenediaminesulphonic acid in acetic acid solution). The dye formation is complete after 24 hours, the mixture is warmed to 80 to 90 ^° C. and precipitated with salt; after cooling, it is filtered, pressed and dried. The dye is a blackish, metallic shimmering powder, which easily dissolves in water with a blue color and dyes cotton blackish indigo blue.

VI. Dye from benzidine -f- 1 mol. Of the monoazo dye from (2: 5-amidonaphthol-7-monosulfonic acid - \ - toluenediaminesulfonic acid 1: 2: 6: 4) -f- 1 mol. Amidonaphthol monosulfonic acid G.
The tetrazo compound obtained from 18.4 kg of benzidine is allowed to run into a strongly alkaline soda solution of 51.8 kg of the sodium salt of the monoazo dye from 2: 5-amidonaphthol-7-nionosulfonic acid-f-toluenediaminesulfonic acid 1: 2: 6: 4; the intermediate product forms immediately and will separate out as a black precipitate. If a solution, corresponding to 23 kg of amidonaphthol monosulfonic acid G, is now added, dye formation occurs rapidly, which is complete after 12 hours. One warmed to 80 ⁰ C. on, coincides with salt and filtered off the dye. When dried, it is a blackish powder, which easily dissolves in water with a reddish-blue color and dyes cotton black-blue without staining.

If, in this example, the benzidine is replaced by 21.2 kg of tolidine or 24.4 kg of dianisidine, so you get slightly bluer nuances.

VII. Dye from benzidine + 1 mol. 1: 5-naphthol sulfonic acid -j- 1 mol. of the monoazo dye from (2: 5 - amidonaphthol-7-monosulfonic acid -j- Toluenediaminesulfonic acid 1: 2: 6: 4). The tetrazo compound prepared from 18.4 kg of benzidine if you run into a soda-alkaline solution of 24.6 kg 1: 5 - naphtholsulfosaurem Pour in baking soda. After the formation of the intermediate product has ended, a solution is added of 51.8 kg of the sodium salt of the monoazo dye from 2: 5-amidonaphthol-7-monosulfonic acid and toluenediaminesulfonic acid 1: 2: 6: 4. The formation of the dye has ended after 24 hours. Warm up, fall with salt and dry. The dye thus obtained stains unheated Cotton reddish black-blue.

Claims (1)

Sponsorship claim: Process for the representation of nouns Polyazo dyes, consisting in that one Monoazo dyes made from β-diazonaphthol sulfonic acids and toluenediaminesulfonic acid (CH ₃ : NH ₂ : NH ₂ : S O ₃ H = 1: 2: 6: 4; combined with a paradiamine to form the intermediate product and the intermediate products thus obtained with another molecule of the same or another monoazo dye or a molecule of an amine, phenol or amidophenols or their sulfo or carboxylic acids combined to form dyes, or vice versa.