DE2055962A1 - Basic nitro dyes free from sulfonic acid groups, their production and use - Google Patents

Description

Dp: -ι -, -: ■ ■ - · - ■ ·!

D *. V S-: r .... -r-.k

Dr. P. ν ...:. Dr. O Gudel

6 Frar.t.'cf -..- ί .. Cf. iiscnenheixner "Str.

SA! Γ Β O Z AG. ? asel / Switzerland

Case 150-3112

Basic nitro dyes free from sulfonic acid groups, their production and use

The invention relates to basic sulfonic acid groups Nitro dyes that are excellent for dyeing, padding and printing on textile material made from acrylonitrile polymers or copolymers or contains such.

The new dyes correspond to the formula

NO,

nh

SO ₀ -NXYN

v Μ

1 G9822 / 2ÜL

wherein R is an optionally substituted aromatic carbocyclic or aromatic heterocyclic

Rest,
R is hydrogen or an optionally substituted one

Hydrocarbon residue,
X is the direct bond or an optionally substituted divalent radical,

Y is an optionally substituted alkylene radical which can be interrupted by heteroatoms

and Rp and R each represent a hydrogen atom or an optional substituted hydrocarbon radical mean

and the aromatic ring B can be further substituted, for example by a fused-on, optionally substituted one Phenyl radical,

and the radicals Rg and R ^ together with the neighboring N atom can form a saturated or partially saturated heterocycle.

The dyes of the formula (I) can be obtained by using a compound of the formula

(II) with a compound of the formula

10 9 8 2 2/2051 _BA D

-3 -

(Ill),

wherein Hal represents a halogen atom, condenses.

The dyes of the formula (I) can also be obtained when you have a compound of the formula

₀
\ R

RN = N- ^ B ^ -KH- / ~ VsO ₂ -NXYA (IV)

wherein A is the acid residue of an ester, with a Ver binding the formula

H-Nf ² (V)

implements.

Good dyes conform to the formula

-n-y-n <^

wherein the ring D can be further substituted,

109822/2051

They are also used for dyeing or printing synthetic polyamides or synthetic polyesters which have been modified by acidic groups. Such polyamides are known, for example, from Belgian patent specification 706.104. The corresponding polyesters are known from the USA, Patents 3.OI8.272 or 3.379.723.

Dyeing is in general particularly advantageous in aqueous, neutral or acid medium at temperatures of 6O-1OO ° C or at temperatures above 100 ⁰ C under pressure. Here, even colorations are obtained even without the use of retarders.

Mixed fabrics, which contain a polyacrylonitrile fiber content, can be colored very well. Those dyes which have good solubility in organic solvents are also used for coloring natural plastic masses or dissolved or undissolved plastic or natural resin masses suitable. It has been shown that it is also advantageous to use mixtures of two or more of the new dyes or can use mixtures with other cationic dyes; i.e. they are easy to combine. They are also used for coloring of plastic masses or of leather or for dyeing paper.

109822/2051

Mari obtains level dyeings with good lightfastness and good wet fastness properties, especially on acrylonitrile polymers or copolymers !!, but also on other substrates,

The new dyes can be converted into dye preparations. The processing, e.g. into stable liquid or solid coloring preparations, can be carried out in a generally known manner, e.g. by grinding or granulating or then also dissolving in suitable solvents, optionally with the addition of an auxiliary, e.g. a stabilizer.

In any case, halogen is preferably bromine, fluorine or iodine However, to understand chlorine.

Hydrocarbon radicals are, for example, optionally substituted Alkyl, such as cyeloalkyl radicals, or optionally substituted ones Aryl residues, e.g. cyclohexyl, alkyl cyclohexyl or phenyl residues.

Alkyl radicals, for example straight-chain or branched alkyl radicals, usually contain 1 to 12 or 1 to 6 and preferably 1, 2, 5 or 4 carbon atoms. If these radicals are substituted, they contain in particular halogen atoms, hydroxyl or cyano groups or aryl radicals, such as, for example, phenyl radicals; In such cases, alkyl stands for an aralkyl radical, for example a benzyl radical.

10 9 8 2 2/2051 _ßA0 ORIGINAL

Alkoxyx'este contain, for example, L to 6 and preferably; I, 2 or 3 carbon atoms.

Alkylene radicals may be straight or branched and for example by halogen atoms, hydroxyl or ¹ Cyangruppcn be substituted; they can contain 1 to 6 and preferably from 1 to "j> carbon atoms.

They can be interrupted, for example, by nitrogen, oxygen or sulfur atoms.

Divalent radicals can be, for example, optionally substituted hydrocarbon radicals, such as alkylene, alkenylene, phenylene or cyclohexylene radicals or divalent bridge members, like -S-, -O- -N- etc.

R ₀ and R-, together with the neighboring N atom, can be hetero- ² 3

form cycles, e.g. a pyrrolidine, piperidine, morpholine, Aziridine or piperazine ring.

All residues of an aromatic character, e.g. aromatic-carboeyclic, such as rings B and / or D, or aromatic-heterocyclic radicals, for example aryl radicals, e.g. phenyl, naphthyl, or tetrahydronaphthyl or pyridyl, quinolyl or Tetrahydroquinolyl radical, substituents can, in particular not

1 Π 9 H 2 2 /? 0 B 1 BAD ORIGINAL

carry water-solubilizing substances, e.g. halogen atoms, Nitro, amino, cyano, rhodan, hydroxyl, alkyl, alkoxy, Trjfluoroalkyl, ■ trichloroalkyl, phenyl, phenyloxy, alkyl, amino-, dia] kylaniino-. Acyl, acyloxy, acylamino, e.g. Urethane, alkylsulfonyl, arylsulfonyl, sulfonic acid amides Alkylsulfonic acid amide, dialkyl sulfonic acid amide, aryl sulfonic acid amide group, Arylazo, e.g. phenylazo, diphenylazo, naph-

I thylazo, etc.

But you can also carry the -COOH group.

The radicals A are preferably those of the hydrohalic acids j A is preferably chlorine or bromine. Further acid residues A are, for example, those of Sulfuric acid, a sulfonic acid or hydrogen sulfide.

The reaction of a compound of the formula (II) with a compound of the formula (III) can be carried out by methods I known per se, for example in an inert solvent, if appropriate with the addition of an alkaline compound, e.g. alkali metal hydroxides or carbonates, and, if necessary, at elevated temperatures and under pressure.

ßAD

10 9 8 2 2/2051

The reaction of a compound of formula (IV) with a compound of formula (V) can also be done by known methods, for example in an organic solvent and at temperatures from -50 ⁰ C to +250 ⁰ C, advantageously at -1O ° C bjs +120 ⁰ C. US Pat. No. 2,834,793 includes the dye of the formula

VnH- / VsO ₂ -NH-C H ₆ -N (CH) ₂ (a)

known for coloring polyacrylonitrile. It is surprising that the dyes of the formula (I), also colored on polyacrylonitrile, are more strongly colored than the dye of the formula (a).

In the following examples, the parts are parts by weight and the temperatures are given in degrees Celsius.

109822/2051 ORIGINAL BATHROOM

Example 1

With stirring, 19.7 parts of 4-amino-1,1'-azobenzenes 39.3 parts of 4-chloro-3-nitrobenzene-1-sulfonic acid 3'-dimethyl-n-propylamide are added to 250 parts of water at 95 ° chlorine hydrate and 30 parts of ground calcium carbonate entered. The mixture is stirred for 3 hours. The reaction mass is then mixed with hydrochloric acid and cooled to room temperature. The yellow dye is precipitated by adding sodium chloride, collected on a filter, washed with a saline solution and dried. Purified by ümkristallisation from 8o $ strength ethyl alcohol, you get the new dye in reddish yellow crystals with a melting point of 235-236 ^0th With this dye, polyacrylonitrile fibers can be dyed in reddish yellow, lightfast and wetfast shades.

For the preparation of the ^ -Chlor-J-nitro-benzene-l- sulfonic acid-jj '-dimethylamino-n-propylamide-Ehlorwydrats are 61.5 parts, ^ • "chlorine - ^ - nitrobenzene-l-sulfonic acid chloride at 60? In 400 parts of 1,2-dichlorobenzene are dissolved and 20 parts of 3-dimethylamine-n-propylene are added at the same temperature.

It takes about -> - 4 hours and a reaction temperature of 6ö · the reactant mass is allowed to cool to room temperature and the precipitated yellow crystals are collected ^ -Chlor-J-nitrobenzene-l ^ sulfonic acid-3'-dlmethylahiino-n-. propylamide chlorohydrate on a filter. Recrystallized, 2nd B .; Aue n ^ butanol, it contains the compound in 187-188. '

"1- 09822/2051 _ _ßAD ORIGINAL

Very similar, equally excellent dyes are obtained if, in the above example, the 39 * 3 parts ^/ i-chloro-3-ni trobenzene-1-sulfonic acid-3'-dimethylamino-n-propylamide chlorohydrate, for example, by the equivalent amount of hydrochloric acid salt of 4-chloro-3-nitrobenzene-1-sulfonic acid-2'-diethylamino-ethylamide, 4-chloro-3-nitrobenzene-1-sulfonic acid-2'-di- (2 "-hydroxyethyl) -amino- propylamide, 4-chloro-3-nitrobenzene-1-sulfonic acid-4 "-diethylaminobenzylamide or 4-chloro-3-nitroberi ;. ' _J ol-l-sulfonic acid-i * f-methylpiperaztd replaced, and otherwise as in the example. 1 proceeds.

Example 2

With stirring, in 250 parts of V / water at 95 °, 19.7 parts of 4-aminoazobenzene, 28 parts of 4-chloro-3-nitrobenzene-1-sulfonic acid-2'-hydroxy-ethylamide (prepared from 4-chloro-3- nitrobenzenesulfonic acid chloride and 2-hydroxyethylamine) and 20 parts of calcium carbonate entered. The reaction vessel is then mixed with hydrochloric acid and cooled to room temperature. The crystalline, yellow dye is filtered off, washed with water, dried and purified by recrystallization. 20.5 parts of the product thus obtained are dissolved in 28ö parts Dimethylforma * mld, treated with 7,9.Teilen thionyl chloride and the mixture stirred at 50 JJÖ- Buns ^0th Duroh dilution with water, the resulting, halogen-containing yellow dye is precipitated, filtered off, washed out with water and dried. 8.6 parts of this halogen-containing compound / ^ 4 ^tt -Phenylazo) -diphenylaniin-2 ~ ftitro-4-sulfonic acid «2 ^1M -chloräthylamic | / are in 100 parts of dioxane

.ΙΟ »Λ» '"a' BAO ORIGINAL

dissolved and mixed with 5 parts of J) Line thy ι ami η and the mixture stirred for several hours at 60 °. After all, the Reaction mass diluted with hydrochloric acid and the new, yellow dye salted out as chlorohyerate.

Purified by recrystallization and ground, one obtains a rototiohi g-yellow powder the polyacrylonitrile fibers from aqueous IÄSsung colors in very real yellow tones.

Dyeing Preference I

20 parts of the dye from Example 1 are mixed with 80 parts Dextrin mixed in a ball mill for 48 hours. 1 Part of the preparation obtained in this way is mixed with 1 part of 40% acetic acid made into a paste, pour 200 parts of demineralized water over the porridge and boil briefly. One dilutes with 7OOO Parts of demineralized water, add 2 parts of glacial acetic acid and goes into the bath at 60 ° with 100 parts of polyacrylonitrile fabric. You can add the material beforehand for 10 to 15 minutes

60 ° in a bath, consisting of 8000 parts of water and 2 parts " Pre-treat glacial acetic acid.

The mixture is heated to 98-100 ⁰ within 30 minutes, boiled for 11/2 hours and rinsed. A reddish yellow dyeing with good lightfastness and good wetfastnesses is obtained.

T0 9 8 2 2/20 & i

BAD OBlGlNAU

Claims (1)

Claims 1. Sulfonic acid group-free basic nitro dyes of the formula NO ₂ f ~~ \ } r ~ <\ ι ¹ / ^B o RN = N- / B V-NH - # ySO _p -NXY-Ii ^ ^ (i), wherein R see an optionally substituted aromatic arboc.y el i or aromatic-heterocyclic radical,
JL hydrogen or an optionally substituted one Hydrocarbon residue, X is the direct bond or an optionally substituted one divalent remainder, Y is an optionally substituted alkylene radical of ^ can be interrupted by heteroatoms, and Rp and R ^ each represent a hydrogen atom or an optional substituted hydrocarbon radical and the aromatic ring B can be further substituted and the radicals R _p and R together with the adjacent nitrogen atom can form a saturated or partially saturated heterocycle. BATH ORIGINAL 109822/2051 2. Sulfonsäuregruppenfrele nitro dyes according to claim 1 that of the formula (VI) correspond,
wherein the ring D can be substituted by pus. ^. Process for the preparation of basic sulforxic acid groups Nitro dyes of the formula (I) according to claim 1, characterized in that a compound of the formula with a compound of the formula Hai- / Vso -nxyn; ² (in), where Hai means a halogen atom, condensed. BATH ORIGINAL 109822/2051 2 O 5 b 9 G 2 4. Process for the preparation of basic sulfonic acid groups Nitro dyes of the formula (I) according to claim Ij, characterized in that a compound of the formula NU ₀ 'VSO ₀ -HXYA (IV), where A is the acid rent one, ester means with a ver binding the formula HN ' ² (V) implements. 5. Use of the molding materials of the formula (I) according to claim 1 for dyeing, padding or printing fibers, Threads or textiles made therefrom, which consist of or contain acrylonitrile polymers or acrylonitrile polymers. 6. Use of the dyestuffs of the formula (I) according to patent claim 1 for dyeing, padding or printing fibers, Threads or textiles made therefrom, which are made of synthetic polyamides or synthetic polyesters, which by acidic groups are modified, exist or contain such. 1 0 9 B 2 2/2 0 5 1 ^ßAD 7 · Use of the dyes of the formula (I) according to patent claim 1. for dyeing plastics, leather and paper 8. The padded colored according to claims 5 and 6 or printed textiles. 9. The material dyed or printed according to claim 7. The patent attorney (Dr. V. Schnie ^ f-Kowarzik) BATH 109822 / 2OE1