DE2545827A1 - DISAZO DYES - Google Patents

Description

Folder 23850 - Dr. K / by ICI Case Dd 27335

IMPERIAL CHEMICAL INDUSTRIES LTD, London, "United Kingdom

Disazo dyes

Priority: 10/14/74 _r Great Britain

The invention relates to disazo dyes and to their application to textile materials.

According to the invention there are water-soluble disazo dyes suggested that in the form of the free acids the general formula:

609818/1083

N = N-E

have, wherein the ring B optionally by sulfonic acid and / or Hydroxyl groups can be substituted and E stands for a radical of one of the following formulas:

wherein ß is a hydrogen atom or an optionally substituted one Represents an alkyl or optionally substituted aryl radical;

2
R represents a hydrogen atom or an optionally substituted alkyl radical and R ^ and R each independently represent a hydrogen atom or a lower alkyl, lower alkoxy, halogen or acylamino radical; or

(OH).

wherein R represents a hydrogen atom or an alkyl, acyl or aryl radical which is optionally substituted by alkyl, alkoxy, halogen, hydroxy or acylamino, ρ has a value of O ₁ 1 or 2, with the restriction that the total number of Sulphonic acid groups in the dye does not exceed 3, and m has a value of 0 or 1.

- 2 809818/1083

The terms "lower alkyl" and "lower alkoxy" used in this Description used refer to alkyl and alkoxy groups having 1 to 4 carbon atoms.

The hydroxyl group in ring A can be in relation to the sulfonic acid group and are in any position to the azo group.

1 2 substituents that may be present on the alkyl groups R and R are halogen atoms and cyano, carboxy, hydroxy, Acyloxy and alkoxycarbonyl groups. Substituents that may be present on the aryl groups R are halogen atoms and alkyl, alkoxy, hydroxy and acylamino groups.

The preferred dyes contain two sulfonic acid groups.

The dyes according to the invention can be prepared by adding a primary amine of the formula:

SO H

OH

diazotized, the resulting diazo compound with an aminonaphthalene the formula:

wherein the ring B is optionally replaced by sulfonic acid and / or hydroxyl groups may be substituted, couples and finally diazotized the aminomonoazo compound and the obtained Diazo compound with a coupling containing amino groups

609818/1083

one of the following formulas couples: (D

NR ¹ R ²

1 2 -5 4

wherein R, R, R and R have the meanings given above

own; or (II)

wherein R, m and ρ have the meanings given above.

Suitable aminophenolsulfonic acids for use in The preparation of the dyes according to the invention are 3-aminophenol-4-sulfonic acid and 4-aminophenol-3-sulfonic acid.

Suitable aminonaphthalenes for use in the preparation of the dyes according to the invention are a-naphthylamine, 1-aminonaphthalene- »-6- and -7-sulfonic acid and 1-Amino - ^ - hydroxynaphthalene-V-sulfonic acid.

Suitable coupling components of the formula (I) are aniline, F, N-dimethylaniline, N, N-diethylaniline, N-ethyl-N-ß-hydroxyethylaniline, N, N-bis-ß-hydroxyethylaniline, N-ethyl-N-benzylaniline, o-toluidine, o-anisidine, cresidine, 2,5-dimethoxyaniline, N-ethyl-N-benzyl-m-toluidine, N-ethyl-N-ß-chloro-

609818/1083

ethyl-rm-toluidine, N-ethyl-N-ß-cyanoethylaniline, N, N-diethyl-3-methoxyaniline, ^ N-diethyl ^ -chloroaniline, N-ethyl-N-ßacetoxyethylaniline, Ν, Ν-bis-ß- acetoxyethyl-m-toluidine, Ν, Ν-bis-ß-ethoxycarbonylethylaniline, Ν, Ν-bis-ß-methoxycarbonylethylaniline, 3 · ■ · acetylamino-N, N-diethylaniline, 3-acetylamino-N-ethylaniline, 3- N-ß-cyanoethylaniline, 3-ac e tylamino-N, N-bis-ß-hydroxyäthylani1In, 3-Benζoy1amino-Ν, ΙΤ-diethylaniline, 3-benzoylamino-N, N-bis-ß-cyanoethylaniline, 3-benzoylamino- N-ß-hydroxyethylaniline, 3-benzoylaminol-benzyl-N-ethylaniline, 5-acetylamino-2-metlloxy-N-ethylaniline, 5-acetylamino-2-methyl-N, N-bis-ß-cyanoethylaniline, 5-acetylamino- 2-methyl-N-ß-llydroxyätllyl-N-ethylaniline, 5-acetylamino-2-methyl-IT-ß-cyanoethyl-N-ethylaniline, 5-acetylamino-2-methyl-N-benzyl-IT-ätb.ylaniline, 5-acetylamino-2-methoxy-N-ß-hydroxyethyl-rr-ethylaniline, 5-acetylamino-2-methoxy-li-ß-cyanoethylaniline, 5-acetylamino-2-metb.oxy-N, N-diethylaniline, 5- Acetylamino-2-methoxy-N, N-bis-ß-hydroxyethylaniline, 5-benzoylamino-2-methyl-N-ethylaniline _ί 5-benzoylamino-2-methyl-IT-ß-cyanoethylaniline, 5-benzoylamino-2-methyl-II, N-diethylaniline, 5-benzoylamino-2-methoxy-H ' , N-bis-ß-cyanoethylaniline, 5-benzoylamino-2-methoxy-N-ßh.ydroxyäthyl-N-ethylaniline, 5-benzoylamino-2-methoxy-N-ßcyanoäthyl-N-ethy! Aniline, ^ -Benzoylamino-2 -methoxy-N-benzyl-N-ethylaniline, 3-acetylamino-N-ethyl-N-ß-acetoxyethylaniline, 3-acetylamino-N, N-bis-ß-acetoxyätnylaniline, 5-acetylamino-2-methyl-N, N -bis-ß-acetoxyäth.ylaniline ^ 5-benzoylamino-2-methoxy-N, N-bis-ß-acetoxyätliylanilin, ^ -acetylamino-N _t N-bis-ß-ethoxycarbonylethylaniline, 3-acetylamino-N-ethyl-N -ß-ethoxycarbonylethylaniline ,, 3-acetylamino-N-ethyl-N-ß-carboxyethylaniline _t 5-acetylamino-2-methoxy-N, N-bis-ß-ethoxycarbonylethylaniline, 5-acetylamino-2-Tnetlioxy-N-ß carb'oxyethylaniline, 5-acetylamino-2-methoxy-N-ß-methoxyethoxycarbonylethylaniline, 5-benzoylamino-2-methoxy-N-ß-carboxyethylaniline, 3-acetylamino-N-ß-chloroethylaniline, 3-acetylamino-1 -bis-ß-cb.loroäthylan iline, 5-acetylamino-

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2-chloro-N-ethylaniline and iJ-acetylamino ^ -chloro-N-ethyl-N-ß-hydroxyethylanil in.

Suitable coupling components of the formula (II) are N-ethyl-a-naphthylamine, N-phenyl-ct-naphthylamine, N- (4- methylphenyl) -a-naphthylamine, N- (4-methoxyphenyl) -a-naphthylamine and N-phenyl-1-naphthylamine-8-sulfonic acid.

The reactions necessary to form the dyes according to the invention can be carried out using the conditions set out in the technical literature are described in detail. Similarly, the dyes can be isolated by known methods. Like it in the case of other dyes which contain sulfonic acid groups, it is often expedient to use the dyes in To isolate and use the form of their water-soluble salts, in particular in the form of their alkali metal or Ammonium salts and especially in the form of their sodium salts. It should be noted that the invention relates both to the free acids and to their salts.

The dyes according to the invention are particularly suitable for application to polyamide textile materials, such as Hylon-66, , Nylon-6 and nylon-11, any well known Methods for applying acidic dyes to such materials can be used. The dyes result red, navy blue and other dyeings with a high fastness to wet treatments and to light.

The invention is illustrated by the following examples, in which all parts and percentages are by weight are expressed.

example 1

To a solution of 18 parts of 3-aminophenol-4-sulfonic acid in

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250 parts of water are added at 0-5 ° C. with stirring, 15 parts of 36% strength hydrochloric acid and 26 parts of 13.8% strength sodium nitrite solution. After stirring for 15 minutes at 0-5 ° C., the diazo solution is at 0-5 ° C to a solution of 12 parts of a mixture of 1-naphthylamine-6- and -7-sulfonic acid in 500 parts of water and 5 parts of 33% sodium hydroxide solution was added. the coupling solution is 1 st stirred at 0-5 ⁰ C and the pH is then raised to 4.5 by adding sodium hydroxide solution, potassium chloride is added to a concentration of 15% and the precipitated product is filtered off and dried.

10 parts of a 13.8% strength sodium nitrite solution are added to a solution of 6.7 parts of the above amino monoazo dye in 200 parts of water and 1 part of 33% strength sodium hydroxide solution. The stirred solution is cooled to 0-5 ° C. and then 3 parts of 36% hydrochloric acid are added. After a 3 continuous stirring st at 0-5 ⁰ G, a solution of 3.5 parts of N-benzyl-N-ethylaniline in 20 parts of dimethylformamide is added at 0-5 ° G, the addition of 8 parts of sodium acetate whereupon connects. The coupling solution is stirred at 0-5 ⁰ 1 st G, and then potassium chloride is added to a concentration of 10% was added. The precipitated disazo dye is filtered off and dried.

When applied to nylon from a weakly acidic dye bath then becomes a maroon coloration with very good fastness to wet treatments and in relation to receiving light.

Further dyes according to the invention can be prepared by adding those in the second column of the following Aminophenolsulfonic acids indicated in the table and diazotized with the aminonaphthalenes indicated in the third column couples and then diazotized the resulting aminomonoazo compounds again and with the in the four-

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Coupling components specified in the th column. When these dyes are used under neutral or weakly acidic conditions are applied to nylon, then the colors listed in the fifth column are obtained, the have good fastness to washing and to light.

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example Aminophenol
sulfonic acid Aminonaphthalene Coupling component hue 2 3-aminophenol-4—
sulfonic acid Mixture of 1-amino
naphthalene-6 and
-7-sulfonic acid N-ethyl-N-benzyl-m-tolui-
din chestnuts
Brown 3 Il Il F, N-bis-ß-hydroxyethyl
aniline ti 4th ti Il N, N-diethyl-3-methoxy-
aniline reddish-
marine
blue 5 It . ti N, N-diethyl-3-chloro-
aniline chestnuts
Brown 6th 4-aminophenol-3-
sulfonic acid ti N-ethyl-N-ß-acetoxyethyl
aniline ti 7th Il It 3-acetylamino-N, N-diethyl-
aniline reddish-
marine
blue 8th 3-aminophenol-4-
sulfonic acid 1-aminonaphthalene
6-sulfonic acid 3-acetylamino-N-ß-cyano-
ethylaniline ti 9 Il It 3-benzoylamino-N, N-
diethylaniline dd 10 It 1-aminonaphthalene
7-sulfonic acid 5-acetylamino-2-ynethyl
N-ß-hydroxyethyl-N-
ethylaniline marine
blue 11 Il ti 5-acetylamino-2-methoxy-
W-ethylaniline greenish-
marine
blue

example

12 13

14 15

Aminophenol sulfonic acid

3-amino.phenol-4-sulfonic acid

^ • -aminophenolesulfonic acid

16 Il 17th It 18th 3-aminophenol-4-
sulfonic acid 19th Il 20th Il 21 "1

Aminonaphtha1ine

1-aminonaphthalene

Mixture of 1-aminonaphthalene-6- and -7-sulfonic acid

1-aminonaphthalene 6-sulfonic acid

1-aminonaphthalene-5-sulfonic acid

1-aminonaphthalene-7-sulfonic acid

Coupling component

W- ( 3-sulfobenzyl ) -N-ethyl aniline

5-benzoylamino-2-methoxy-N-benzyl-N-ethylaniline

5-Benzoylamino-2-methyl-N ₇ N-bis-ß-hydroxyethyl aniline

I-Acetylamino-N-ethyl-N-ß-acetoxyethylaniline

3-acetylamino-N, N-bis-ßethoxycarbonylethylaniline

3- ^ acetylamino-N-ethyl-N-ß-carboxyethylaniline

5-Benzoylamino -? - methoxy-N-ethylaniline

5-acetylamino-2-methoxy-Ν, Ν-bis-ß-ethoxycarbonyl- ethylaniline

5-acetylamino-2-methoxy-N-ß-carboxyethylaniline

5-acetylamino-2-methoxy-N-ß-methoxyethoxycarbonyl äthy! aniline

hue

maroon

greenish marine blue

navy blue

reddish navy blue

navy blue

greenish navy blue

navy blue

cn - £ - cn oo

NJ) -J

example Aminophenol
sulfonic acid Arainonaphthalene Coupling component hue 22nd 3-aminophenol-4-
sulfonic acid 1-aminonaphthalene
7-sulfonic acid 5-acetylamino ~ 2-chloro-N-
ethylaniline reddish-
marine
blue 23 4-aminophenol-3-
sulfonic acid Mixture of 1-amino
naphthalene-6 and
-7-sulfonic acid N-Ä thy 1 - ot-napht hy 1 ainin marine
blue 24 It Il N-phenyl-a-naphthylamine reddish-
marine
blue 25th ti ti N- (4-methylphenyl) - <* -
naphthylamine marine
blue 26th 3-aminophenol-4-
sulfonic acid 1-amino-5-hydroxy
naphthalene-7-sulfone
acid Il greenish-
marine
blue 27 Il α-naphthylamine N-phenyl-Ö-naphthylamine-
8-sulfonic acid marine
blue 28 Il Mixture of 1-amino
naphthalene-6 and
-7-sulfonic acid N- (4-Με thoxyphenyl) -Ä-
naphthylamine It 29 Il π N-ethyl-a-naphthylamine dd 30th Il Il N-phenyl-a-naphthylamine reddish-
marine
blue

Claims (3)

PATENT CLAIMS: 1. Water-soluble disazo dyes, which are in the form of the free Acid the general formula: N - E have, in which the ring B is optionally replaced by sulfonic acid and / or hydroxyl groups can be substituted and E stands for a radical of one of the following formulas: (D wherein R is a hydrogen atom or an optionally substituted one Alkyl or optionally substituted aryl radical P.
represents; R is a hydrogen atom or an optionally substituted ■ χ Μ tes alkyl radical and R ^ and R each independently from each other a hydrogen atom or a lower alkyl, Represent lower alkoxy, halogen or acylamino radical; or - 12 609818/1083 NHR ⁵ (OH). wherein R is a hydrogen atom or an alkyl, acyl or Represents aryl radical which is optionally substituted by alkyl, alkoxy, halogen, hydroxy or acylamino, ρ is a Value, of 0, 1 or 2, with the restriction that the The total number of sulfonic acid groups in the dye does not exceed 3, and m has a value of 0 or 1. 2. Dyestuffs according to Claim 1, characterized in that they have two sulfonic acid groups. 3. Process for the preparation of the dyes according to Claim 1, characterized in that a primary amine is used the formula: diazotized, the slide compound obtained with a Aminonaphthalene of the formula: - 13 809818/1083 wherein the ring B is optionally replaced by sulfonic acid and / or hydroxyl groups can be substituted, couples and then the. obtained aminomonoazo compound diazotized and with an amino group-containing coupling component of one of the following formulas: 12 3 4 wherein ß, R * R and R are those given in claim 1 Have meanings; or (II) (SO_H) 3 P wherein R, m and ρ have the meanings given in claim 1 own. Use of the dyestuffs according to Claim 1 for dyeing polyamide textile materials. 609818/1083 - 14. -