DE1794398A1 - MONOAZO CONNECTIONS, THEIR PRODUCTION AND USE - Google Patents

Description

SANDOZ A.G IW ^ w '*, Case 150-1933 / A

, _{S! R 35}

Monoazo compounds , their production and use

It was found _Λ is that the monoazo compounds of the formula I

.CH CH -R CN 2 2 ^R 4

where R, chlorine or cyano,

R is hydrogen, chlorine or bromine and R_ and R. chloroacetoxy, cyanoacetoxy, hydroxyacetoxy,

• J TE

Methoxyacetoxy, methoxycarbonyloxy or ethoxycarbonyloxy mean,

excellent as disperse dyes, for dyeing or printing of fibers or threads or materials made from them made of fully or semi-synthetic, hydrophobic, high molecular weight organic substances.

The diazo components of the formula are preferred

.-CN

and

R ₅ Cl

V 'where Rg is hydrogen or bromine. The new compounds are prepared by diazotizing an amine of the formula

0 "N- \ O / ~ ^NH

7th
\
R ₂

509819/1053

- 2 - Case 150-1933 / A

and coupling the obtained diazomium compound with an amin the formula

CH CH -R

Diazotization and coupling are carried out according to well-known methods carried out.

The dyes produced in this way are generally converted into coloring preparations before they are used. To do this, they are crushed, until the average particle size is about 0.01 to 10 microns, and especially about 0.1 to 5 microns. That Comminution can take place in the presence of dispersants or fillers take place. For example, the dried dye is mixed with a dispersant, optionally in the presence of fillers, ground or kneaded in paste form with a dispersant and then in a vacuum or by atomization dried. With the preparations obtained in this way, after adding more or less water, in so-called dye, pad or print long or short liquors. When dyeing in a long liquor one generally applies up to to about 20 g of dye per liter, when dyeing in a short liquor up to about 80 g per liter, when padding up to about 150 g per liter, preferably 0.1 to 100 g per liter, and when printing up to about 150 g per kilogram of printing paste. That The liquor ratio can be chosen within wide limits, e.g. between about 1: 3 and 1: 200, preferably between 1: 3 and 1:80.

The dyes are excellent for molded bodies made of fully synthetic or semisynthetic ones from aqueous suspension high molecular weight. Fabrics on. They are particularly suitable for dyeing, padding or printing Fibers, threads or fleeces, woven or knitted fabrics

5 0 9 819/1053

- 3 - Case 150-1933 / A

linear, aromatic polyesters, as well as cellulose-2 1/2 acetate or cellulose triacetate. Also synthetic polyamides, polyolefins, acrylonitrile polymerisation products and Polyvinyl compounds can be colored with them. Particularly valuable colorations are obtained on linear, aromatic polyesters. These are generally polycondensation products from terephthalic acid and glycols, especially ethylene glycol.

It is dyed according to methods known per se. Polyester fibers can be dyed in the presence of carriers at temperatures between about 80 ° and 125 ° C or in the absence of carriers under pressure at about 100 ° to 140 ⁰ C by the exhaust method. Further, they can with the aqueous dispersions of the novel dyes padding, padding or printing, and the impregnation obtained fix at about 140 ° to 230 ⁰ C, for example with the aid of steam, contact heat or hot air. In particularly favorable temperature range between 180 ° and 220 ⁰ C, the dyes diffuse rapidly into the polyester fiber and not sublimate again, even if these high temperatures a longer time to act leaves. This avoids annoying soiling of the dyeing equipment. Cellulose-2 1/2 acetate is preferably dyed between about 65 ° and 80 ⁰ C and cellulose triacetate at temperatures up to about 115 ° C, the most favorable pH range is between 2 and 9, and particularly 4 to 8

Usually the usual dispersants are added, which are preferred are anionic or non-ionic and can also be used in a mixture with one another. About 0.5 g Dispersants per liter of dye preparation are often sufficient, but larger amounts can also be used, e.g. up to about 3 g per liter can be used. Amounts in excess of 5g usually do not result in any further advantage. Known anionic dispersants which are suitable for the process,

RriQR 1 Q / 1 η S3 ■■ · ■; ■■

- 4 - Case 150-1933 / A

are for example condensation products from naphthalenesulfonic acids and formaldehyde, especially dinaphthylmethane disulphonates, esters of sulphonated succinic acid, Turkish red oil and alkali salts of sulfuric acid esters of fatty alcohols, e.g. sodium lauryl sulfate or sodium cetyl sulfate, Sulphite cellulose waste liquor or its alkali salts, soaps or alkali sulphates of monoglycerides of fatty acids. Examples of known and particularly suitable nonionic Dispersants are addition products of about 3-40 mol of ethylene oxide with alkylphenols, fatty alcohols or fatty amines and their neutral sulfuric acid esters.

The usual thickening agents are used in padding and printing use, e.g. modified or unmodified natural products, for example alginates, British gum, Gum arabic, crystal gum, locust bean gum, tragacanth, Carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides or Polyvinyl alcohol.

The dyeings obtained are extraordinarily fast, for example outstandingly heat-setting, subliming, pleating, smoke gas, over-dyeing, dry cleaning, chlorine and wet fast, for example water, washing and perspiration fast. The etchability and reserve of wool and cotton are good. The lightfastness is excellent, even in light colored bins, so that the new dyes are also very suitable as mixing components for the production of pastel-colored fashion shades. The dyes are temperatures up to at least 220 ⁰ C and especially at 80 ° verkoch-Uend resistant to reduction by * to 140 ⁰ C. This resistance is not adversely affected either by the liquor ratio or by the presence of dye accelerators.

5098 19/10 53

Case 150-1933 / A

In the following example, the parts mean parts by weight that Temperatures are given in degrees Celsius.

Be is ρ ie 1

6.9 parts of powdered sodium nitrite are added to 120 parts of concentrated sulfuric acid at 60-70 ° with vigorous stirring given. The mixture is stirred for a further 10 minutes at 60 °, then cooled 10 ° and adds 100 parts of glacial acetic acid and then 16.3 parts of 2-amino-5-nitrobenzonitrile and 100 parts of glacial acetic acid at 10-20 ° to. The mixture is stirred for a further 2 hours and the diazoniuro salt obtained is poured solution to a mixture of 35 parts of di- [ß- (methoxyacetoxy) ethyl] amino-3-cyanobenzene 100 parts of glacial acetic acid, 150 parts of ice and 10 parts of aminosulfonic acid. the Coupling is completed in a buffered medium (pH 3-4). The dye obtained is filtered off, washed free of acid and dried. It dyes synthetic fibers in red tones with excellent fastness properties.

The table below shows further dyes of the formula which can be prepared analogously to the procedure of Example 1 1 and the nuances of their coloration on polyester fiber material specified.

Tabel

E.g.
No. ^R l V ^R 3 V Nuance on
Polyester fiber
material 2 -CN H -0-COCH ₂ Cl -0-COCH ₂ Ci Red 3 do. H -0-COCH ₂ CN -0-COCH ₂ CN do. 4th Cl Cl -0-CO-O-CH ₃ -0-CO-O-CH ₃ Brown 5 do. do. -0-COO-C ₂ H ₅ -0-CO-OC ₀ H do. 6th -CN Br -0-COCH ₂ OH -0-COCH ₂ OH Red 509 8 9/1053

Claims (9)

Claims 1. The monoazo compounds of the formula CH CH ₉ -R (D, CH ₂ CH ₂ -R ₄ wherein R, chlorine or cyano, R is hydrogen, chlorine or bromine and R and R. chloroacetoxy, cyanoacetoxy, hydroxyacetoxy, Methoxyacetoxy, methoxycarbonyloxy or ethoxycarbonyloxy mean. 2. Process for the preparation of the monoazo compounds of the formula 1 according to claim 1, characterized in that an amine of the formula II (II) diazotized and with a compound of formula III CH cn -K (IU) CH CH -R ₄ CN clutch. 509819/1053 - 7 - Case 150-1933 / A 3. The compound 2-cyano-4-nitro-2'-cyano-4 '- [bis- (methoxyacetoxyethyl) -amino] -1,1'-azobenzene, according to claim 4. The compound 2-cyano-4-nitro-2'-cyano-4 '- [bis- (chloroacetoxyethyl) -amino] -1,1'-azobenzene, according to Claim.il. 5. The compound 2-cyano ~ 4 ~ nitro-2'-cyano-4 '- {bis - (cyano- acetoxyethyl) amino] -1,1'-azobenzene, according to claim 6. The compound 2,6-dichloro-4-nitro-2'-cyano-4 .'- [bis- (cyancarbonyloxyethyl) -amino] -1,1'-azobenzene, according to claim 7. The compound 2,6-dichloro-4-nitro-2'-cyano-4 '- [bis- (ethoxycarbonyloxyethyl) -amino-1,1'-azobenzene, according to claim 8. The compound 2-cyano-4-nitro-6-bromo-2'-cyano-4 '- [bis (hydroxyacetoxyethyl) amino] -1.1 ^! -azobenzene, according to claim 1. 9. Use of the monoazo dyes of the formula 1 according to Claim 1, for dyeing or printing fibers or threads or materials made therefrom from fully or semi-synthetic, hydrophobic, high molecular weight organic substances. 3700 / HW / FE 509819/1053