DE1644376B - Dispersion dyes of the Monoazo series, their manufacture and use - Google Patents

Description

The invention relates to 2,5-dihalo-4-dialkylaminosulfonyl - 4 '- (N -cyanoalkyl-N-alkyl) -amino-1,1 '-azobenzene dyes, their colorations on fibers or threads and those made from them Textile materials made from fully synthetic or semi-synthetic hydrophobic, high molecular organic Fabrics have excellent fastness properties.

The new dyes correspond to the formula

IO

NSO ₂ -

N = N

O) CH ₂ CHCN

R-7

wherein R ₁ , R ₂ and R ₆ independently of one another denote an alkyl radical having 1 to 4 carbon atoms, R ₃ and R ₄ independently of one another denote a chlorine or bromine atom and R ₅ and R ₇ denote independently of one another a hydrogen atom or a methyl group.

The dyes are produced by diazotizing an amine of the formula

25th

^ NSO ₂ ^> - NH ₂ R ₄

(Π)

and coupling the resulting compound with a compound of the formula

35

(III)

CH ₂ CHCN

R ₇ Suitable amines of the formula (II) are, for. B .:

I-amino ^ -brom ^ -diethylaminosulfonyl-

5-bromobenzene,
l-amino ^ -bronM-dipropylaminosulfonyl-

5-bromobenzene,
l-Amino ^ -chloM-dipropylaminosulfonyl-

5-chlorobenzene,
l-Aniino ^ -chloM-dimethylaminosulfonyl-

5-chlorobenzene,
l-Amino ^ -chloM-diethylaminosulfonyl-

5-chlorobenzene,
l-amino ^ -chloM-dibutylaminosulfonyl-

5-chlorobenzene,
l-Amino ^ -bronM-dimethylaminosulfonyl-5-bromobenzene.

As coupling components of the formula (III), for. B. Consider:

N-ethyl-N-cyanoethylaniline,

N-Ä thy l-N-ß-cyanpropylanil in, N-ethyl-N-cyanoethyl-m-toluidine, N-ethyl-N-jS-cyanopropyl-m-toluidine, N-methyl-N-cyanoethylaniline, N-propyl-N-cyanoethylaniline, N-butyl-N-cyanoethylaniline,

N-butyl-N-0-cyanopropylaniline, N-butyl-N '/ S -cyanopropyl-m-toluidine.

40

45

5 °

55

60

65 In general, the coupling takes place in acidic, optionally with z. B. an alkali acetate (to about pH 4) buffered medium with cooling, preferably at 0 to 5 ⁰ C, instead.

It is particularly advantageous to use the new To convert dyes into dye preparations before they are used. Processing to dye preparations takes place in well known manner, e.g. B. by grinding in the presence of dispersants and / or fillers. With the preparations, optionally dried in a vacuum or by atomization, can after adding more or less water in so-called long or short liquor colors, padding or print.

The dyes are extremely well absorbed from aqueous suspension on fibers or threads and the textile materials made from them made of fully synthetic or semi-synthetic, hydrophobic, high molecular weight organic substances. Especially suitable are acetate for dyeing, padding or printing textile material aps linear aromatic polyesters, and cellulose-2 _^1/2 cellulose triacetate and synthetic polyamides.

One dyes or prints according to known, z. B. the method described in French patent 1,445,371. The dyeings of orange to scarlet red shade obtained have very good all-round fastness properties; in particular, they are outstandingly thermosetting, subliming, pleating, ozone and smoke gas fast. The wet fastness properties are also very good, ζ. B. the water, perspiration and wash fastness. The reserve of wool and cotton and the lightfastness should also be emphasized. The dyes are extremely resistant to the effects of the various permanent pressing processes. They are also hydrolysis and reduction resistant at temperatures up to about 220 ^° C. and especially up to 140 ^° C. and acid and alkali resistant over a wide range.

These resistances are neither by the liquor ratio nor by the presence of Dye accelerators adversely affected.

Compared to the dyes known from US Pat. No. 3,050,516, those according to the invention have Dyes have better drawing and build-up properties and better wash fastness on fibers made of synthetic polyamides and cellulose triacetate.

In the French patent 1 226 501 dyes of a similar structure are described. A comparison the closest comparable dyes from this patent on the one hand and from the present one Invention, on the other hand, has shown that the dyes from the French patent specification are inferior Have fastness to washing, fastness to dry cleaning or fastness to rubbing.

The parts mentioned in the examples are parts by weight and the percentages are percentages by weight. the Temperatures are given in degrees Celsius.

example 1

7 parts of sodium nitrite are added to 155 parts of sulfuric acid at 70 ° and then at 15 ° to 20 ° 100 parts of glacial acetic acid and 26.9 parts of 1-amino-2,5-dichlorobenzene-4-sulfonic acid dimethylamide. After 2 hours, the diazonium salt solution obtained is poured onto 100 parts of water and 400 parts of ice. You destroy that excess sodium nitrite by Ζμβ ^ ε of 5 parts Aminosulfonic acid and filtered clear. To the filtrate

a solution of 17.4 parts of N-ethyl-N-cyanoethylaniline is left Glacial acetic acid pour in in SO parts. Dip coupling is made by blunting with sodium acetate finished, the dye was filtered off, washed acid-free and dried. Recrystallized from alcohol-dioxane the dye is obtained in pure form and dyes polyester fibers in orange tones with good ones General fastnesses.

Example 2

26.9 parts of 1-amino-2,5-dichlorobenzene-4-sulfonic acid dimethylamide are stirred in finely powdered form in 56 parts of water and 0.5 part of 30% sodium hydroxide solution for one hour. Then is added 60 parts of 30% hydrochloric acid, 45 parts of glacial acetic acid and 27 parts of ice are added and the mixture at -5 to +5 ⁰ C 30 ml of 4N sodium nitrite solution are slowly added dropwise. After 3 hours, the excess sodium nitrite is destroyed by adding aminosulfonic acid and the solution is filtered until clear. A solution of 18.8 parts of N-ethyl-N- / 3-cyanopropylaniIin in 50 parts of glacial acetic acid is allowed to flow into the filtrate. The coupling is complete after 2 hours, the dye is filtered off, washed free of acid and dried. You can ays. Recrystallize alcohol — dioxane. The dye stains polyester fibers in orange shades with good fastness properties.

Staining instructions

S 7 parts of the dye obtained according to Example 1 are mixed with 4 parts of dinaphthylmethandisulfonsaurem Sodium, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate in a ball mill Ground to a fine powder for 48 hours. 1 part of the dye preparation obtained in this way is used in 3000 parts Water, which is 3 parts of a 30% solution of a highly sulfonated castor oil and 20 parts of an emulsion of a chlorinated benzene, dispersed. 100 parts of polyester fiber fabric are brought at 20 to 25 ° one, heats the bath to 95 to 100 ° in about 30 minutes and colors at 95 to 100 ° for 1 hour. The The material to be dyed is taken out of the bath, rinsed, 15 minutes at 70 ° with a 0.1% solution of a Soaped alkylphenyl polyglycol ethers, rinsed again and dried. An orange color is obtained with excellent fastness properties.

The following table contains further dyes of the formula (I); they are based on that described in Example 1 Way made.

at
game R. R ₂ R ₃ fc R ₅ R ₆ R ₇ Nuance on
polyester 3 -CH ₃ -CH ₃ -Cl -Cl - H -CH ₃ TJ orange 4th -CH ₃ -CH ₃ -Cl -Cl - H -C ₃ H ₇ - H orange 5 -CH ₃ -CH ₃ -Cl -Cl - H C ₄ H ₉ - H orange 6th -C ₂ H ₅ -C ₂ H ₅ -Cl -Cl - H C ₄ H ₉ - H orange 7th -C ₂ H ₅ -C ₂ H ₅ -Cl -Cl - H -C ₂ H ₅ - H orange 8th -C ₂ Hs -C ₂ H ₅ - Br - Br - H -C ₂ H ₅ - H orange 9 -C ₂ H ₅ -C ₂ H ₅ - Br - Br - H -CH ₃ - H orange 10 -C ₂ H ₅ -C ₂ H ₅ - Br - Br -CH ₃ -C ₂ H ₅ - H Scarlet fever 11th -CH ₃ -CH ₃ - Br -Br TT -C ₂ H ₅ - H orange 12th -CHa -CHa -Cl -Cl - H -C ₂ H ₅ CH ₃ orange 13th -CH ₃ -CH ₃ - Br - Br - H C ₂ H ₅ -CH ₃ orange 14th -CHa -CH ₃ - Br - Br - H -CH ₃ - H orange 15th -CH ₃ -CH ₃ -Br - Br - H -C ₃ H ₇ - H orange 16 ^ CH ₃ -CH ₃ - Br - Br - H C ₄ H ₉ - H orange 17th -CHa -CH ₃ -Cl -Cl - H -CH ₃ -CH ₃ orange 18th -CH ₃ -CHa -Cl -Cl - H -C ₃ H ₇ -CH ₃ orange 19th -CH ₃ -CH ₃ -Cl -Cl - H C ₄ H ₉ -CH ₃ orange 20th -CH ₃ -CH ₃ - Br - Br TT -CH ₃ -CH ₃ orange 2} -CHa -CH ₃ - Br - Br -H -C ₂ H ₅ -CHa orange 22nd -CHa -CHa - Br - Br TJ -C ₃ H ₇ -CH ₃ orange 23 -CH ₃ -CH ₃ - Br - Br - H C ₄ H ₉ -CH ₃ orange 24 -CH ₃ -CH ₃ - C! -Cl -CH ₃ -CH ₃ -CH ₃ Scarlet fever 25th -CH ₃ -CH ₃ - C | -Cl -CH ₃ -C ₂ H ₅ -CH ₃ Scarlet fever 26th CH ₃ -CH ₃ -Cl -Cl CH ₃ -C ₃ H ₇ -CHa Scarlet fever 27 -CH ₃ -CHa -Cl -Cl -CH ₃ CH ₃ - H Scarlet fever 28 CH3 -CH ₃ -C! . -Cl -CHa -C ₂ H ₅ - H Scarlet fever 29 -CH ₃ -CH ₃ -Cl -Cl -CHa -CaH ₇ TJ Scarlet fever 30th -CH ₃ ~~~ CH3 -Cl -Cl -CHa C ₄ H ₉ - H Scarlet fever 31 -C ₃ H ₇ -C ₃ H, -Cl -Cl - H -CH ₃ TJ orange 32 C4H9 C4H9 —Ci -Cl -H -C ₂ H ₅ | _I * orange 33 C ₃ H, -C ₃ H, - Br - Br - H C ₂ H ₅ TT orange

Claims (3)

-C3H75R31 644376RjR * 6R7Nuance onC4Hy— Br-CH3— ΗPolyesterC4Hy— Br continuation— Η-CH3— ΗOrangeBei— Br— Η-CH3-CH3Orange game-C3H7R * Claims: Orange34C4Hy— Br35C4 Br .y— Br36C4Hy— Br36C4Hy— 1. Dyes of the formula NSO ₂ R, N = N R ₄ . ^R 6 CH ₂ CHCN
R ₇ wherein R ₁ , R ₂ and R ₆ independently of one another denote an alkyl radical having 1 to 4 carbon atoms, R ₃ and R ₄ independently of one another denote a chlorine or bromine atom and R ₅ and R ₇ denote independently of one another a hydrogen atom or a methyl group. 2. Process for the preparation of dyes of the formula NSO, R ₄ R. NSO ₂ NH, R ₄ N = N wherein R ₁ , R ₂ and R _{6 are} independently an alkyl radical having 1 to 4 carbon atoms, R ₃ and R _{4 are} independently a chlorine or bromine atom and R ₅ and R _{7 are} independently a hydrogen atom or a methyl group, characterized in that one Amine of the formula 40 (II) R ₆ CH ₂ CHCN R ₇ diazotized and with a compound of the formula CH ₂ CHCN clutch. ' ^R 7 3. Process for dyeing, padding or printing fibers or threads and those made from them Textile materials made from fully synthetic or semi-synthetic, hydrophobic, high molecular weight Organic substances, characterized in that dyes of the formula (I) according to Claim 1 are used.