DES0036906MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: December 22, 1953. Advertised on May 24, 1956

GERMAN PATENT OFFICE

The subject of the present patent is a process for the production of monoazo dyes, which are based on cellulose ester fibers, synthetic polyamide fibers and polyester fibers in pure ruby red, ^ pull up violet, blue and red-brown tones and their colorations are distinguished by excellent Can be etched as well as characterized by very good fastness to light, washing, perspiration and sublimation. from The monoazo dyes, which color in violet and blue tones, are of particular importance, since after the previously known processes etchable and at the same time lightfast disperse dyes not produced can be.

Compared to the dyes known from US Pat. No. 2,576,037, which acetate rayon in yellow, orange and scarlet tones, the monoazo dyes of the present stand out Invention through deeper tones and better lightfastness of their dyeings on acetate artificial silk out.

The new monoazo dyes are obtained when 1 mol of the diazo compound from a i-Amino-4-nitrobenzene-6-sulfonic acid fluoride of the composition

O, N

NE

wherein χ is hydrogen, halogen, alkyl, trifluoromethyl or alkoxy, with 1 mol of a sulfonic acid

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and benzene series tertiary amine free of carboxyl groups.

The ι - amino - 4 - nitrobenzene - 6 - sulfonic acid fluoride, which are used to produce the diazo compounds can be further insoluble in water on the aryl nucleus carry making substituents.

In particular, compounds are used which are in the 3-position by fluorine, chlorine, Bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, etc. are substituted. These starting products are new and can, for example, by reacting the corresponding sulfonic acid chlorides in aqueous suspension with a hydrofluoric acid salt.

Amines in the composition are used as azo components

CH ₉ -Z

y y

for use in which y is, for example, hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, Acetylamino and trifluoroacetylamino and ζ ζ. Β. Hydrogen, methyl, ethyl, propyl, oxymethyl, Oxyethyl, oxypropyl, oxybutyl, dioxyethyl, methoxymethyl, methoxy-oxy-ethyl, dimethoxyethyl, cyano, Cyanomethyl, difluoromethyl, trifluoromethyl, difluoroethyl, Trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, acetyl, propionyl, acetonyl, methylsulfonyl, methylsulfonylmethyl, Ethylsulfonylmethyl, carbamidomethyl, carbomethoxymethyl, carbethoxymethyl, acetoxymethyl ' and means propionoxymethyl.

The coupling of the diazo compounds with the azo components is carried out in a conventional manner, preferably in acidic medium. The precipitated monoazo dyes are filtered and washed and dried.

Processing on dye preparations can be carried out in a wide variety of ways. For example, the dried dye with a suitable dispersant, optionally in the presence of fillers, ground or in paste form with a Dispersant kneaded. and then dried in vacuo or by sputtering.

The following examples illustrate the invention. Parts are understood to mean parts by weight, and the percentages mean percentages by weight.

SO -D ■ · 1

example 1

7.6 parts of sodium nitrite are introduced into 90 parts of pure sulfuric acid at 60 ° within ι hour. The resulting solution is cooled to 10 °, at 10 ° with 100 parts of concentrated acetic acid and then with 22 parts of i-amino ^ -nitrobenzene-o-sulfonic acid fluoride added, whereupon 100 parts of concentrated acetic acid are again added. After 1 hour the excess nitrite is blunted with 5 parts of urea and the diazotization mass is made up to 250 parts Ice off. They are now combined with one of 19 parts of N-oxethyl-N-cyanoethyl-aminobenzene, 200 parts Water, 20 parts of 30% hydrochloric acid and 100 parts of ice-made mixture. The new dye begins to drop out soon; it is isolated after some time by filtration. After washing and Drying gives a dark red powder; this crystallizes from ethanol in blue-red rectangles Leaflets with a melting point of 175 to 177 °. The new monoazo dye gives acetate rayon a ruby red color Tones of excellent light, washing, sweat, gas, fume and sublimation fastness. the Dyes on synthetic polyamide fibers are somewhat more yellowish and also have excellent properties Fastness to washing, perspiration, smoke gas and sublimation.

Example 2

44 parts of i-amino-4-nitrobenzene-6-sulfonic acid fluoride are introduced into 350 parts of pure sulfuric acid. The resulting solution is heated to 60 ° and at this temperature 14 parts of sodium nitrite are added. After completion of the diazotization, the mass is discharged onto 500 parts of water and 1000 parts of ice, so that the temperature remains below 5 ^0th Combine the diazo suspension with a solution of 33 parts of N-ethyl-N-oxa-ethyl-aminobenzene, 400 parts of water, 40 parts 3o ° / ₀ hydrochloric acid and 400 parts of ice. The coupling to the new dye occurs quickly; it is worked up in the usual way. It crystallized from ethanol in violet rectangular flakes of melting point 162 to 164 ⁰ and dyes Acetatkunstseide pure purple and blaustichigrot polyamide fibers.

The diazo compound of i-amino-4-nitrobenzene-6-sulfonic acid fluoride is coupled in a corresponding manner

with N, N-dioxyethylaminoberizole or N-butyl-N-oxäthylaminobenzene or N-ethyl-N-oxybutylaminobenzene or N-ethyl-N-carbamidoethyl-aminobenzene or N-methyl-N-oxyethyl-aminobenzene or N, N-dimethylaminobenzene or N, N-diethylaminobenzene to dyes soluble in violet ethanol,

with N-ethyl-N-cyanoethyl-aminobenzene to one dye soluble in ethanol with a ruby red color,

with i- (N-ethyl-N-glyceryl-amino) -2-methoxy-5-methylbenzene to a dye soluble in ethanol with a violet color,

with ι- (N, N-dioxyethyl-amino) -3-chlorobenzene to a soluble in ethanol with a red-violet color Dye,

with i- (N, N-dioxethyl-amino) -3-methoxybenzene or i- (N-ethyl-N-carbamidoethyl-amino) -3-methylbenzene or 1 - (N, N - dioxäthylamino) - 3 - methylbenzene or i -_ (N-methyl-N-oxäthylamino) -3-methylbenzene to dyes soluble in violet ethanol,

with i- (N-ethyl-N-oxybutyl-amino) -3-methylbenzene or ι - (N - butyl - N - oxäthyl - amino) - 3-methylbenzene, or ι - (N - ethyl - N - oxäthyl - amino) - 2 - methoxy-5-methylbenzene to dyes soluble in blue-violet ethanol,

with i- (N, N-dioxethyl-amino) -2-methoxy-5-trifluoroacetyl-aminobenzene or i- (N-Ethyl-N-oxäthylamino) -2-methoxy-5-acetylaminobenzene or i- (N-Ethyl-N-oxäthyl-amino) - 2-methoxy-5-trifluoroacetylaminobenzene or 1 - (N -Ethyl- N- glyceryl -amino) -

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2-methoxy-5-acetylaminobenzene or i- (N-ethyl-N-glyceryl-amino) -2-methoxy-5-trifluoroacetylamino above zol to dyes soluble in blue in ethanol

and with a compound of the presumed composition ι - (N - cyanoethyl - N - oxäthyl - amino) 3-acetylaminobenzene to a dye soluble in ethanol with a red-violet color.

The last-mentioned azo component is new and is obtained when the one melting at 109 to 111 ° Intermediate compound from i-amino-3-acetylaminobenzene and acrylonitrile reacts with ethylene oxide.

Example 3

17.5 parts of i-Amino ^ -chloro ^ ö-nitrobenzene-sulfonic acid fluoride are stirred at 60 ° in 180 parts of 96 ° / _o sulfuric acid and diazotized with 5 parts of anhydrous sodium nitrite. After some time, the mixture is allowed to cool and it is poured onto 750 parts of ice and 250 parts of water, the excess nitrous acid is blunted with sulfamic acid and the diazo solution is combined with a solution of 16.5 parts of ι- (N, N-dioxäthyl- amino) -2-methoxy-5-methylbenzene in 10 parts of 3O ° / ₀ hydrochloric acid and 100 parts of water. The new dye precipitates, is filtered, washed acid-free and dried. It dissolves in ethanol with a violet color and, after recrystallization in ethanol, melts at 162 to 165 ^° . He dyes acetate silk in lightfast violet tones.

The diazo compound of the i-amino-chloro-chloro-nitrobenzene-δ-sulfonic acid fluoride is coupled in a similar manner with N-cyanoethyl-N-oxäthyl-aminobenzene to a dye soluble in ethanol with a red-brown color,.

with N-ethyl-N-oxäthyl-aminobenzene to an in Ethanol with violet-brown color soluble dye,

with i- (N - ethyl-N-oxäthyl-amino) -3-methylbenzoi and with i- (N, N-diethyl-amino) -3-methylbenzene to form dyes which are soluble in ethanol with a brown-violet color,

with i- (N-cyanoethyl-N-ethyl-amino) -3-methylbenzene to a dye soluble in ethanol with a brownish-red color,

with ι - (N - butyl - N - oxäthyl - amino) - 2 - methoxy - 5-methylbenzene to a dye soluble in alcohol with a purple color

and with i- (N, N-dioxäthyl-amino) -2-methoxy-5-acetylaminobenzene to a dye soluble in ethanol with a blue-gray color.

The corresponding dyes from diazotized i-amino ^ -methoxy ^ -nitrobenzene-o-sulfonic acid fluoride undi- (N-ethyl-N-oxethyl-amino) -3-methylbenzene or ι- (N, N-dioxethyl-amino) -2-methoxy-5-methylbenzene or i- (N, N-Dioxäthyl-amino) -2-methoxy-5-acetylaminobenzene dissolve with red-brown or violet or greenish blue color in ethanol.

Dyes soluble in ethanol with a violet color are also obtained by coupling, i-diazo-2-fluoro-4 -nitrobenzene - 6 - sulfonic acid fluoride or 1 - diazo 2-bromo-4-nitrobenzene-6-sulfonic acid fluoride or i-diazo-2 - trifluoromethyl - 4 - nitrobenzene - 6 - sulfonic acid fluoride with i- (N, N-dioxethyl-amino) -2-methoxy-5-methylbenzene.

Example 4

44 parts of i-amino ^ -nitrobenzene-o-sulfonic acid fluoride are diazotized as in Example 2, poured onto ice water and treated with a solution of 40 parts of i- (N-difluoroethyl-N-oxethyl-amino) -3-methylbenzene in 90 parts of 3O ° / ₀ coupled hydrochloric acid. After the dye has been separated off in the usual manner, a dye is obtained which dyes acetate rayon in very genuine red-violet shades.

Corresponding dyes from i-diazo-4-nitrobenzene-6-sulfonic acid fluoride and i- (N-trifluoroethyl-N-oxäthylamino) - 3 - methylbenzene or N - difluoroethyl - N - ox ethyl aminobenzene or N-trifluoroethyl-N-oxäthylaminobenzene have similar properties, but dye acetate rayon and polyamide fibers somewhat more yellowish.

From i-diazo-4-nitrobenzene-6-sulfonic acid fluoride and those compiled in the table below Azo components are prepared using the procedures outlined in the previous examples received further dyes.

Azo component . Melting point Solution color
in ethanol Hue of at
game i- (N-cyanoethyl-N-oxethyl-amino) -3-methylbenzene Colorations on
AjCetat- i- (N-Ethyl-N-oxethyl-amino) -3-methylbenzene 178 to 180 ° Red-violet rayon 5 i- (N, N-Dipxäthyl-amino) -2-methoxy-5-Met.hylbenzol 187 to 189 ° violet Red-violet 6th i- (N, N-dimethyl-amino) -3-methyrbenzene i68 ° violet violet 7th i- (N, N-diethyl-amino) -3-methylbenzene 222 to 225 ° violet violet 8th i- (N-cyanoethyl-N-ethyl-amino) -3-methylbenzene 192 to 194 ° violet violet 9 i- (N-methoxyethyl-N-ethyl-amino) -3-methylbenzene 227 to 229 ° Red-violet violet IO i- (N-glyceryl-N-ethyl-amino) -3-methylbenzene 168 to 170 ⁰ Red-violet Red-violet II i- (N-Butyl-N-oxäthyl-amino) -2-methoxy- 189 to 190 ° violet Red-violet 12th 5-methylbenzene violet 13th i- (N, N-dioxethyl-amino) -3-acetylaminobenzene 62 to 66 ° Reddish blue ι - (N, N-Dioxäthyl-amino) ^ -methoxy-S-acetyl- 190 ° violet Reddish blue aminobenzene violet 15th 204 ° blue Pure blue

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Claims (1)

S 36906 IVb / 22 a PATENT CLAIM: Process for the preparation of monoazo dyes, characterized in that ι Mol the diazo compound from an i-amino-4-nitrobenzene-6-sulfonic acid fluoride the composition SO ₂ F O ₂ N- NH, wherein χ is hydrogen, halogen, alkyl, trifluoromethyl or is alkoxy, with 1 mol of a sulfonic acid and carboxyl group-free tertiary Benzene series amine couples. References: U.S. Patent No. 2,576,037. 609 527/506 5.56