DE27948C - Process for the preparation of dyes by the action of the anhydrides of organic acids on the halogen salts of primary, secondary and tertiary aromatic amines - Google Patents

Description

IMPERIAL

PATENT OFFICE.

This method concerns the representation of dyes through the action of the anhydrides organic acids to the halogen salts of primary, secondary and tertiary aromatic Amines in closed vessels with or without the use of condensation agents.

What is new is the formation of the dyes by heating the halogen salts of aromatic bases with the anhydrides of organic acids even without the use of condensation agents such as Zn Cl ₂ , Al ₂ Cl _e etc. to temperatures which do not exceed ^{200 ° C.}

If aniline, hydrochloric acid aniline is heated _{in a closed vessel to a temperature of 150 to 200 ° C for 12 hours with the ι Y 2} times to double the weight of acetic anhydride, a thick, brown-yellow melt is obtained, which shows a green-yellow fluorescence. When poured into water, this melt separates a brownish-yellow resin that does not dissolve in hot water, but dissolves easily in dilute hydrochloric acid. If this resin is heated with dilute sodium hydroxide solution, no aniline is obtained, which is proof that no acetanilide is formed in the melt. The base, obtained by boiling with sodium hydroxide solution, which looks dark brown, gives the original water-insoluble salt with hydrochloric acid. If, on the other hand, the resin is boiled for a long time with dilute sulfuric acid, acetic acid escapes, and the base precipitated by excess soda now gives, with hydrochloric acid, a yellow salt which is very easily soluble in water and becomes colorless in concentrated hydrochloric acid.

So in my process the hydrochloric acid acetyl derivative of a yellow dye is formed, which can easily be converted into the dye by boiling with dilute sulfuric acid running. By simultaneous use of condensation agents, such as. B. completely anhydrous zinc chloride, aluminum chloride etc., the action is accelerated somewhat, however, this application is not required. By replacing the aniline with other aromatic ones Bases such as B. toluidine, xylidine, naphthylamine, etc., are dyes of very obtained different nuances. The hydrochloric acid salts can then be replaced by the corresponding bromo- or hydroiodic acid salts are replaced.

In this process, the acetic anhydride can also by its homologues, such as. B. Valeric anhydride, as well as the mixed anhydrides of the fatty acid series, such as. B. Propionic anhydride. Likewise, the anhydrides of the aromatic series, as well as the mixed anhydrides of these and those consisting of the acid residues more aromatic and the fatty acids, such as. B. Acetbenzoic anhydride, can be used.

An example explains the representation of the dyes.

For example, dye made from hydrochloric aniline: 12 kg of hydrochloric aniline are ^{heated to 180 to 200 °} C. for 12 hours with 18 kg of acetic anhydride in a suitable autoclave.

The melt obtained in this way is then poured into five times the amount of water.

pour. Here the dye is for the most part deposited as a red-yellow resin, while the mother liquor still contains some dye and some unaffected aniline salt. The separated resin is now in a suitable retort with five times the amount Water containing 20 to 30 pCt. Contains sulfuric acid, cooked until there is none in the distillate Acetic acid finds more. The solution is then allowed to cool, filtered, and finally oversaturated with soda or caustic soda. The precipitated base is with a little hydrochloric acid and Dissolved water, the dye by precipitating with common salt and by dissolving in a weakly saline solution Ultimately, the water is kept pure. When powdered, it forms a yellow powder similar to the Jaune d'or and dyes silk, wool and cotton a splendid green-yellow.

The mechanism of the reaction in this process is with the anhydrides of the fatty series simply that 2 molecules of the hydrochloric acid salt of the base to 1 molecule of the anhydride act with splitting off of 3 molecules of water, whereby the dye is then formed. It works a little differently Procefs with the aromatic anhydrides. Here are 2 molecules of the acidic salt of the Base to 1 molecule of anhydride in such a way that only 1 molecule of water is formed and 1 molecule the hydrate of the anhydride used is formed and then a triphenylmethane derivative is formed or forms a homologue thereof. The following equations explain the Procefs:

1) 2 QH ₅ NH ₂ .HC / + £ j | £ g> O = C ₁₁ H ₁₆ N ₂ . 2 HC / + 3 H ₂ O

, \ ₀ η WNH.

2) 2 C ₆ H ₅ jv ± / ₂ .

= C ₁₉ H ₁₂ -NH ₂ .2 HCl

"" / CO ₂ H + H ₂ O

c ₆ # * ^ jv _O

The following acids - anhydrides and bases are used:

I. Anhydrides.

1. acetic anhydride,

2. butyric anhydride,

3. acetic acid butyric anhydride,

4. benzoic anhydride,

5. Paranitrobenzoic anhydride.

II. Bases,
ι. Aniline,

2. toluidine,

3. xylidine,

4. Diphenylamine,

5. Monomethylamine !,

6. Monoethy! Aniline,

7. dimethylaniline,

8. diethylaniline,

9. metaphenylenediamine;
10. Metatolylenediamine.

With the acid anhydrides mentioned above, the following combinations have proven to be technical proven valuable.

A. Dyes from acetic anhydride due to the action of the halogen salts of:

1. Aniline, yellow dye (soluble in water),

2. Toluidine (Para-, Ortho-), yellow dye (water-soluble),

3. Xylidine (Para-, Meta-, Ortho-), yellow dye (water-soluble),

4. Metaphenylenediamine, brown-yellow dye (water-soluble),

5. Metatoluylenediamine, brown dye (water soluble),

6. Diphenylamine, yellow dye (soluble in fuel).

B. dyes from butyric anhydride, by the action of the halogen salts of:

1. Aniline, orange-yellow dye (soluble in water),

2. Toluidine (ortho-, para), orange-yellow dye (water-soluble),

3. Xylidine (ortho-, para-, meta-), orange-yellow dye (water-soluble),

4. Metaphenylenediamine, brown dye (water soluble),

5. Metatoluylenediamine, brown dye (water soluble),

6. Diphenylamine, yellow dye (soluble in fuel).

C. Colorants from Acetbutyric Acid

anhydride
by the action of the halogen salts of:

1. Aniline, yellow dye (soluble in water),

2. Toluidine (ortho-, para), yellow dye (water-soluble),

3. Xylidine (ortho-, para-, meta-), yellow dye (water-soluble),

4. Metaphenylenediamine, brown-yellow dye (water-soluble),

5. Metatoluylenediamine, brown dye (water soluble),

6. Diphenylamine, yellow dye (soluble in fuel).

D. Dyes from benzoic anhydride due to the action of the halogen salts of:

ι. Aniline, reddish-blue dye (water-soluble),

2. Toluidine (ortho-), reddish-blue dye (water-soluble),

3. Xylidine (Para-, Meta-), reddish-blue dye (water soluble),

4. Diphenylamine, green dye (soluble in fuel),

5. methyl aniline, green dye (water soluble),

6. Ethylaniline, green dye (water-soluble),

7. Dimethylaniline, green dye (water soluble),

8. Diethylaniline, green dye (water soluble),

9.Methyldiphenylamine, green dye (soluble in fuel),

10. Ethyldiphenylamine, green dye (soluble in fuel).

E. Paranitrobenzoic acid dyes

anhydride
by the action of the halogen salts of:

1. aniline, paranitrodiamidotriphenylcarbinol,

2. toluidine, paranitrodiamidoditolylphenylcarbinol,

3. xylidine, paranitrodiamidodixylylphenylcarbinol,

4. Diphenylamm, Paranitrodiamidopentaphenylcarbinol,

5. methylaniline, paranitrodiamidodimethyltriphenylcarbinol,

6. ethylaniline, paranitrodiamidodiethyltriphenylcarbinol,

7. Dimethylaniline, Paranitrodiamidötetramethyltriphenylcarbinol,

8. Diethylaniline, Paranitrodiamidotetraäthyltriphenylcarbinol,

9. methyldiphenylamine, paranitrodiamidodimethylpentaphenylcarbinol,

10. Ethyldiphenylamine, paranitrodiamidodiethylpentaphenylcarbinol.

The bodies in this last row are all gas-soluble green dyes, but they are are valuable only in that they are easily removed by suitable reducing and oxidizing agents can be converted into the corresponding rosanilines.

Claims (1)

Patent claim: Representation of dyes through the action of the anhydrides of organic acids on the halogen salts primary, secondary and tertiary aromatic amines in closed vessels, with or without the use of condensation agents.