DE272437C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

CLASS 22 «. GROUP

FARBENFABRIKEN vorm. FRIEDR. BAYER & CO. in LEVERKUSEN b. COIN a. Rh.

Process for the preparation of fflonoazo dyes. Addendum to patent 268791.

Patented in the German Empire on October 16, 1912. Longest duration: May 1, 1927.

The main patent is a process Protected for the representation of mordant dyes, which consists in the fact that the diazo compounds the aminoacidylaminosalicylic acids, their homologues and substitution products, combined with azo dye components.

It has now been found that dyes are obtained with very similar properties when one considers the aminoacidyl compounds in the process of the main patent of the aminosalicylic acids by their aminobenzimidazole or p-aminophenylazimino derivatives replaced.

The aminobenzimidazole derivatives not previously described in the literature have the following general formula:

(I)

COOH (2)

C ₁₁ H / - N -

-NH,

XC = N '

X = H, alkyl, aryl; In addition, hydrogen atoms in the salicylic acid nucleus can be replaced by halogen, alkyl or sulfo groups.

For their representation one deals with the

_χ ΟΗ (ι)

/ COOH (2)

C ₆ H / - (4)

by condensation of aminosalicylic acids with dinitrochlorobenzene and subsequent Reduction of readily available 2 · 4-diaminophenylaminosalicylic acids successively with acidylating and saponifying agents, e.g. B.

H ₂ N '

2 4-diaminodiphenyl-p-aminosalicylic acid,

, OH COOH

HN

NH - CHO-

HCO-HN '

Diformyl product,

H ₃ -

OH COOH

-N-

-NH ₉

r /

CH = N '

5-amino-i · 4'-oxy-3'-carboxyphenylbenzimidazo] (Aminobenzimidazole-p-aminosalicylic acid ethers).

An analogous product arises from the diacety! Derivative

.OH COOH

-N-

-NH ₉

r /

CH _Z - C

5-Amino-i · 4'-oxy-3'-carboxyphenyl-2-methylbenzimidazoI (aminomethylbenzimidazole-p-aminosalicylic acid).

The products are powders that are very sparingly soluble in water, which turn out to be corrosive and Carbonate alkalis dissolve with the formation of the corresponding salts. As far as they have no sulfo group contain, they also form easily soluble salts with mineral acids.

The ρ-aminophenylazimino derivatives of aminosalicylic acids, which have also not yet been described are made from the 2 · 4 - dinitrophenylaminosalicylic acids in an analogous manner obtained as for the corresponding derivatives of 2-naphthylamine-5 · 7-disulfonic acid in patent specification 214658, e.g. B. according to the following scheme:

OH

/ COOH ■ .Η / - NH

NO.

■ NO, - ~

C ₁₁ H

β "3

OH COOH

I N = N

-NH *

Example 1. 259 parts of 2x4-diaminophenyl-o-aminosalicylic acid are refluxed with 400 parts of formic acid (go percent) for 4 hours. 50 The solution is precipitated with water and filtered off from the precipitated. The fixed sub

, OH COOH

_t H _s

-N- is boiled for saponification with 600 parts of water and 200 parts of hydrochloric acid (19 ¹ Z ₂ ⁰ Be.) Until everything has gone into solution. The 5-amino-i · 2'-oxy-3'-carboxyphenylbenzimidazole (aminobenzimidazole - ο - aminosalicylic acid) of the formula:

-NH ₉

CH =

becomes very sparingly soluble from the solution by neutralizing the hydrochloric acid with soda amorphous precipitation precipitated. You can also use the hydrochloric acid solution by

precipitate the hydrochloric acid salt with table salt.

269 parts of 5-amino-i.2'-oxy-3'-carboxyphenylbenzimidazole (Aminobenzimidazole-o-aminosalicylic acid) with 69 parts of nitrite and the necessary amount of hydrochloric acid is diazotized. The solution of the diazo compound is left on while stirring in an ice-cold solution of 246 parts of i-naphtol mixed with 250 parts of soda - 4 - Sodium sulphate pour in. The coupling is finished after a short time. Of the Almost completely precipitated dye forms a dark red powder after filtering off and drying. The pressure with chromium acetate on Cotton is a yellowish red, resistant to soap and chlorine; Chromed on wool one red of a similar shade.

OH (i) / COOH (2) // SO ₃ H (6) C ₆ H / -

Used instead of i-naphthol-4-sulfonic acid the 2-naphthol-5 · 7-disulfonic acid, this gives a reddish-tinged orange; Acetyl-i · 8-aminonaphtol-3 6-disulfonic acid gives a very bluish red.

The aminobenzimidazole derivatives which can be prepared in a manner similar to that indicated above p-aminosalicylic acid and aminocresotinic acids give dyes that differ only slightly in shade and properties from those of o-aminosalicylic acid.

Example 2.

363 parts of 5-amino-1 · 4'-oxy-3'-carboxy-5'-sulfophenyl - 2 - methylbenzimidazole (aminomethylbenzimidazole-p-aminosulfosalicylic acid)

NH ₁ ,

CH ^ -C = N '

(Obtained in an analogous manner from 2 · 4-diaminophenyl-p-aminosulfosalicylic acid by treatment with acetic anhydride and saponification) are diazotized with 69 parts of nitrite. the Diazo compound is left in an ice-cold solution of 405 parts of the disodium salt Acetyl -1 · 8 - aminonaphtol - 3 · 6-disulfonic acid pour in with stirring and add gradually 300 parts of sodium bicarbonate. The coupling will soon be over. The one by salting out The isolated dye forms a dark red powder after drying, which dissolves in water dissolves with blue-red paint. With chromium acetate on cotton you get a nice red-violet, real against soap and chlorine.

Example 3.

350 parts of 5-amino-1 x 4'-oxy-3'-carboxy-5'-sulf ophenylaziminobenzene (p - aminophenyl - 4-aziminosulfosalicylic acid, prepared from 2 · 4-dinitrophenyl- ρ - aminosulfosalicylic acid by converting it into the nitroamino compound, Conversion with nitrous acid into the nitroazimino compound and reduction of the same) are diazotized with 69 parts of sodium nitrite. The diazo compound is left on Stir in an ice-cold solution of 405 parts of disodium salt to which 280 parts of soda are added of acetyl-i · 8-aminonaphthol-4 · 6-disulfonic acid. The coupling is over soon. The dye is salted out. When dry it represents a brownish red powder, which dissolves in water with a yellowish red color. The print on cotton with chromium acetate is a yellowish red.

Acetyl-i · 8-aminonaphthol-4 · 6-disulfonic acid can of course by other coupling components of the benzene and naphthalene series can be replaced, whereby the most diverse nuances are obtained.

The dyes from the ρ-aminophenylazimino compound the homologous salicylic acid and its substitution products differ only slightly from the products from the Aminophenyl-i-aziminosulfonic acid.

Claims (1)

Patent claim: Modification of the method of representation protected by the main patent 268791 of azo dyes, characterized in that the aminoacidyl compounds of the aminosalicylic acids, their Homologues and substitution products here by the aminobenzimidazole or p-aminophenylazimino compounds the same replaced.