DE2119745A1 - Azo cationic dyes - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENT LAWYERS 8 MUNICH 8O, MAUERKIRCHERSTR. 48

Dr. Berg Dipl.-tng. Stapf, 8 Mönchen 80, MauerkircherstraBe 45 *

Attorney file 20 837

Your sign Your writing «» Our sign »Date 22i ΑρΤϋ 1971

Ugine Kuhlmann, Paris / France

Azo cationic dyes

The invention relates to new cationic azo dyes which are used for coloring fibers based on acrylonitrile polymers or copolymers can be used.

In French patent 1,497 1 ^ 9 are (4-arylazo or 3-arylazo-benzenesulfonamidoalkyl) trialkylammonium dyes described. These dyes deliver 'on acrylic fibers of various origins, for example

Hn / ci 109847/1638

(WlI) 48 * 272 (»8272) 487043 (987043) 483310 (983310) telegram ·! lERGSTAPFPATENT MOnditR TElEX 05 24 560 IERO d Banki Bayernch · Vmiixbank Mönche «4531OB PottidMcki Munich 453 43

on the commercially available under the names "Crylor" and "Courtelle" ;, Parb nuances (shades) that are of one type of fiber on the other hand are not even. One such dye that dyes "Crylor" fibers red dyes "Courtelle" fibers orange (see, for example, the dyes of Examples 3, 4j 5 and 6). The lack of uniformity in the colors is a significant disadvantage for the dyer, as he cannot rely on the fact that different ones are used Batches of fibers are dyed in a uniform shade (shade).

It has now been found that it is possible to acrylic fibers of various origins shades excellent uniformity to achieve ₃ when de die.se on the erf indungs geraäßen new cationic azo dyes Ball applying common formula:

N t = N - R > n 9 ^R l - N ^R 2
^R 3 , -NH ( CH ₂

XO (I)

in which R is the remainder of a coupler of the formula RH, R ^, ^ * ^R 3 which is free of sulfonic acid or carboxylic acid groups, and is the same or different alkyl groups with low molecular weight, preferably methyl or ethyl groups, η the number

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2 or 3 and X is a monovalent anion or its equivalent mean. The anion X has no influence on the dyeing. It does not take part in the combination with the fiber, -it can be a mineral or organic anion and, if desired, by known methods against a other anion can be exchanged.

The couplers of the formula RH can belong to the series of aromatic amines; Examples of this are the primary, secondary or tertiary arylamines, optionally substituted on the nucleus, in particular the benzene arylamines. Both Couplers RH can also be hydroxyl compounds, for example Phenols, enolizable ketone compounds, for example Pyrazolones, compounds with a reactive methylene group, for example Indo1derivate act.

The * dyes of the formula I according to the invention can be prepared be by in an aqueous medium a compound of the formula RH with the diazo derivative of a chlorinated Couples o-aminosulfonamides of the general formula:

SO ₂ NH (CH ₂ ) _n - N - R ₂ X θ (II)

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in which R-, Rp, R ,, η and X have the meanings given above own = «

The amines of formula II can be conveniently prepared by converting from a chlorinated o-nitrobeneol sulfochloride goes out that one with an N, N-dialkylalkylenediamine in aqueous medium or in an organic solvent, optionally in the presence of an acid neutralizing agent Condensed by means. A quaternization treatment is then carried out with an alkylating agent, which can replace the solvent. Optionally, you can also in an aqueous medium or in an organic Solvent work. The nitro group is then reduced using known methods. For quaternization suitable alkylating agents are e.g. B. the alkyl sulfates, the alkyl halides, the alkyl aryl sulfonates.

Ψ The color shades (tones) obtained with the dyes of the invention have in addition to the advantage of excellent uniformity Feiner the property that they are agile and stable, especially to light.

The following examples are intended to illustrate the invention without, however, restricting it thereto. The specified

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numbered parts are _3, unless otherwise stated, based on weight,

example 1

In a well-stirred suspension of 25 parts of 2-nitro-4-chloro-benzenesulfonyl chloride in 150 parts of chlorobenzene and 1 part dimethylformamide leads to 25 parts diethylaminoethylamine to exceed a ^ without the temperature of 30 ⁰ C. One brings within a period of about one

_o holds
At 100 ° C. for one hour, keep this temperature upright for one hour, allow to cool, separate the settling product by decanting, take it up with warm water, remove the last traces of chlorobenzene with steam and allow the product to harden. After drying, 30 parts of 2-nitro-4-chloro-1-sulfonamido-N- (diethylaminoethyl) benzene are obtained. For analysis purposes, this product can be recrystallized in heptane. It is obtained in the form of white crystals, mp 77-78 ° C.

Analysis for C ₁₂ H ₁ Q ₃₁ J.

Calcd .: C 42.9 H 5.36 Cl 1O ₃ 58 N 12.51 S found: 43.3 5.44 10.1 12.6 9.37

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Within half an hour the mixture is heated 6 ₃ 7 parts of this compound in 5 parts of dimethyl sulfate at 80-90 ° C and then 30 parts of water. The mixture is stirred until a clear solution is obtained. In this way, a solution of (4-chloro-2-nitro-benzenesulfonamidoethyl) diethylmethylammonium sulfomethylate is obtained, which is stirred into a suspension which has previously been brought to the boil, 10 parts of iron powder and 50 parts of water, over a period of 10 minutes 1 part contains acetic acid. The mixture is heated under reflux for one hour, the medium is made slightly alkaline by adding sodium carbonate, filtered while warm, the iron hydroxide sludge is washed out, filtered off with suction, then the piltrate is acidified with 5 parts by volume of 2 η hydrochloric acid.

This solution is cooled to 5 ° C. by adding ice and a 1 η solution of sodium nitrite is added over the course of 10 minutes until an excess of nitrite remains for about 10 minutes. 15 ₅ 8 parts by volume of this solution are used. The solution of the diazo derivative thus obtained is mixed with a solution of 2.8 parts of N-diethyl-mtoluidine in 40 parts of water, to which 2 parts by volume of 10 η hydrochloric acid are added. Over a period of about half an hour, 25 parts by volume of a 25 % sodium acetate solution are added and the mixture is stirred for about

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For two hours, filter off the precipitated dye, suction it off and dry it at a moderate temperature. This gives 7 ₉ 6 parts of a dye of the fibers on Acrylnitrilpolymerisat- _s or -misehpolymerisatbasis in a strong scarlet hue colors, the resistance excellent general properties, particularly excellent lightfastness, having. The hue obtained is also outstandingly uniform regardless of the origin of the acrylic fiber used.

In the following Table I a number of examples of dyes of the formula III is summarized with the same diazo derivative and different couplers were made.

Table I.

Example RH color of ge no. colored acrylic fibers

2 N-dimethylaniline orange

3 N-Ethyl-N-Zsuccinimidoathyl T-m-Orange toluidine

4 N-ethyl-N-zsuccinimidoathyiy-aniline orange

5 N-Ethyl-N- / Syanäthoxyäthyl7-m-tolui- _{Schar h} din

ο 3-methyl-5-pyrazolone green-yellow

7 '' 2-methyl-indole yellow

8 phenol pale yellow

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example 9

In a suspension of 25 parts of 2-nitro-4-chloro-benzenesulfo-chloride in 75 parts of water, stirring is carried out over the course of 15 minutes a mixture of 15 parts of diethylaminopropylamine and 100 parts by volume of a 2 η sodium carbonate solution a ₃ without. the temperature of 25 ° C is exceeded. The mixture is stirred for two hours at 20 to 25 ⁰ C, then heated for one hour at 40 ⁰ C. The mixture is cooled, filtered, washed _s with water and dried at a moderate temperature the precipitate obtained. 27 parts of 2-nitro-4-chloro-1-sulfonamido-II- (diethylaminopropyl) benzene, mp 80.degree.-81.degree. C., are obtained. For the analysis, the product is crystallized in hexane at ₃ F. 83 - 84 ⁰ C. Analysis for C ₁₃ Ii ₂₀ Cl N ₃ O ^ S:

calc .: C 44 _S 6 H 5.72 N 12.0 S S ₁ IG found : 45.3 5.9 11.9 9.5 %.

Following the procedure of Example 1, it is then quaternized, reduced, _3- diazotized and finally coupled with N-diethyl-m-toluidine. A dye is obtained which dyes acrylic fibers with a scarlet shade of very similar hue and dyeing properties.

In the following Table II are examples of dyes

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of the general formula IV indicated in an analogous manner with other RH couplers.

CH ₃ Cl ^θ (IV)

I ₅ NH- (CH ₀ ), -N =

Table Il

Example RH shade of the

No. . colored

Acrylic fibers

10 N-ethyl-N-cyanoethyl-m-toluidine orange

11 N-ethyl-N-cyanoethyl-m-chloroaniline golden orange

12 N-Ethyl-N-ZiuecinimidoathylZ-m- _{Reddish orange} toluidm

13 3-methyl-5-pyrazolone green yellow IM l-PhBnyl-3-methyl-5-pyrazolone yellow

15 2-methylindole yellow

16 2-phenylindole golden yellow

Example 17

By replacing in Example 9, 3-diethylamino-propylamine by the equivalent amount of dimethylaminopropylamine, obtained under the same conditions, the 2-nitro-M-chlorl-sulfonamido-N- (dimethylaminopropyl) benzene, melting at 93-94 ⁰ C .

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- ίο -

Analyze for C ₁₁ H ₁₆ Cl N ₃ O ₂ JS

calc .: C 4l _s 05 H 4 _S 97 N 13.06 S 9.96 found . : 41.4 5 _a 2O 12 ₃ 6, 10.2 y

In the following Table III a series of examples of dyes of the formula V is compiled ₃ which were prepared from this intermediate product by the process described in Example 1.

= N-R

SO ₂ NH- (CH ₂ )

- N = (CH,)
->

Cl

(V)

example Table III

RH

Color of the colored acrylic fibers

N-diethyl-m-toluene

N ~ ethyl-N- / succinimidoethyl7-mtoluidine

N-ethyl-N-eyanethyl-m-toluidine 2-methylindole

Scarlet reddish orange

orange
yellow

If the 2-nitro-4-chlorobenzenesulfonyl chloride in Examples I ₅ 9 _{3 17 is replaced by its isomer s,} the 2-nitro = 5-chloro benzenesulfochloride, the intermediate products are obtained

of the following formula:

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SO ₂ NH (CH ₂ ) _n - N -

(VI)

F.

2 C ₂ H ₅ 76 - 75 ° C 3 CH, 87 - 77 ° C 3 C H - 8S ⁰ C

If these new intermediates are used in the processes described in the preceding examples, dyes of the formula VII are obtained which have analogous coloring properties and resistance properties.
In the following Table IV is a number of examples
this type summarized.

= N-R

SO ₂ - NH - (CH ₂ ) _n

-NO.

Cl

(VII)

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η R ₁ , Table IV Hue that
colored
Acrylic fibers orange orange example
Mr. 2 C ₂ H R ₂ MH Scharlaeürot yellow yellow 21st « It I ₅ ϊΓ-bioethyl-m-toIuidine Zteoberrofe Green yellow Green yellow 22nd ti dd IT-S thy I -M- C s uc c inimida -
äthy 1) -ia-t ο lui din orange scarlet 23 IV 11 N-At hy / 1-K- cyanaafchyl-m-
t-oluidine yellow N-Ethyl-N-ZsuccinimidoathylZ-
m-toluidine ~ Vermilion ~ vermilion 24 it dd 2-methylindole Green yellow N-ethyl-N-cyanoethyl-m-
toluidine 25th 3 / TTT * 3-meth> ylpyrazolone scarlet 2-methylindole 26th . It It Kf-diethyl-ra-toluidine N-ethyl-N- / succinimidoethyl? -
m-toluidine ~ ZliTtiberrot 3-methylpyrazolone 27 ti dd N-ethyl-N-cyanoethyl-m-
toluidine 28 It It 2-methylindole 29 dd Il 3-methylpyrazolone 30th It C ₂ H ₅ N-diethyl-m-toluidine 31 Il It 32 It dd 33 ti Il 34 ti It 35

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Claims (1)

Patent claims 1. Procedure Cl for the production from Dyes the general formula - R ^^ SO ₂ NH- (CH Φ ^ R ₁
2 ⁾ n ~~ ^N C ~ ^R 2
^R 3 θ
X (D in which R is the remainder of a coupler without sulfonic acid and carboxylic acid groups a R ₁ , Rg, R, identical or different alkyl groups with low molecular weight ;, η is the number 2 or 3 and X is a monovalent anion or its equivalent, characterized in _{that 3} a coupler free of sulfonic acid and carboxylic acid groups is coupled in an aqueous medium with the diazo derivative of an amine of the general formula oi - t- I »^ ^R i SO ₂ NH- (OHj) _n - N ^: - R ₂ X ⁹ (II) ^R 3 in which R. ₃ Rp, R ₅₅ η and X have the meanings given above. 1Ü9847 / 1638 2, dyes, characterized by the general formula (l) N ' N - R η -N- θ X so ₂ NH- (CH ₂ : ^ ^R l -R ₂ in which R is the remainder of a coupler without sulfonic acids and
Carboxylic acid groups, R ^, Rp ₅ R- ^ the same or different alkyl groups with low molecular weight ₃ denote number 2 or 3 and X is a monovalent anion or its equivalent, . Compounds characterized by the general formula (II) NH ₂ (CH ₂ ) _n 9 y. ^R l SO ₂ NH - - N R ₂ R, 3
in which R ₁ , R ₉ , R _x , η and X are those specified in claim 2 X c. j Have meanings. 4. Dyed fibers based on acrylonitrile polymers or acrylonitrile polymers, characterized in that they are with the dyes according to claim 2 are colored. 1Ü9847 / 1638