DE2203262A1 - Disazo dyes - Google Patents

Description

PATENTANWXLTI DR.-INQ. H. FINCKE DIPL.-ING. H. BOHR DIPL.-1NQ. S. STAEQER

β ΜύΝΟΗΕΝ β, 24th YEAR. 1972

to 31

Folder 22783 - Dr.K / P ICI Case Dd. 23640

IMPERIAL CHEMICAL INDUSTRIES LIMITED London, United Kingdom

Disazo dyes

Priority: February 25, 1971 - Great Britain

The invention relates to new disazo dyes, the ice Reactive dyes for dyeing cellulose textiles / materials are useful.

According to the invention, disazo dyes of the formula

(D

209837 / 1U7

proposed, in which R _{1 stands} for Ii, Cl, NO ₂ or SO »H and H _{2 stands} for Cl, NO ₂ or SO ₅ H, where at least one of the symbols R ₁ and R _{2 stands} for SO ₅ H, and in which further either X is H, Z is SO ₅ H and Y is a group of the formula

NN f ^ r * ⁼ \ to \

ι ι UJ ^ k < ² >

"^ N

where R, H or CH, R _{4 is} a 4 ^f -hitro-2,2 ^f -disulfostilben-4-yl or a disulfonaphthyl radical and the benzene nucleus A is represented by CH ₅ , OCH ₅ , NHCOCH ₅ or NHCONH ₂ may be substituted, or X represents a group of the formula (2), one of the symbols Y and Z represents H and the other of the symbols represents SO ₅ H.

According to the invention, a process for the preparation of the new dyes is also proposed, which is carried out by that one cyanuric chloride with one mole of a compound of the formula

(3)

and with one mole of a compound of the formula

209837 / 1U7

converts, v / obei R ₁ , R ₂ , R., and R. have the meanings given above, the benzene nucleus A can be substituted as in formula (2) and either X stands for H, Y _{1 stands} for NH ₂ and Z _{1 stands} for SO ^ H or X _{1 stands} for NH ₂ and one of the symbols Y ₁ and Z ₁ stands for H and the other of the symbols stands for SO ^ H.

The above process can be carried out in general by stirring da.3 cyanuric chloride with an aqueous solution of one of the compounds of formula (3) or (4) until the replacement of one chlorine atom is largely over, and then adding the second compound and stirring continues until a second chlorine atom has reacted. The first stage is preferably carried out at a temperature between 0 and 10 ^° C. and the second stage at a temperature between 30 and 50 ^° C. It is preferred to add an acid binding agent to neutralize hydrogen chloride released during the reaction. In particular, it is preferred to add the acid binding agent at a rate such that the pH of the reaction medium is maintained between 5 and 7.

The compounds of the formula (3) can be obtained by that you get the diazonium of 4-amino-4'-nitrestilbene-2,2'-disulfonic acid or a naphthylarain disulfonic acid with an amine the formula

209837/1147

• · ■ 4 ·· 4 · * ■

(5)

couples, where R _{5 is} H or CH, and the benzene nucleus A can be substituted as in formula (2).

Examples of naphthylamine disulfonic acids that can be used are 1-naphthylamines, 7- _f 3,6-, 3,8-, 4,6-, 4,7-, 5,7- vßia 6,8-disulfonic acid and 2-faphthylarain-1,5-, 5,6-, 3,7-, 4,8-, 5,7- and 6,8-disulfonic acid

Examples of amines of the formula (5) that can be used are aniline, N-methylaniline, m-toluidine, 2,5 - dimethylaniline, Oresidin, N-methyl-m-toluidine, o-anisidine, m - anisidine, 2,5-di- raethoxyaniline, ra-aminophenyl urea and m-aminoacetanilide.

The compounds of the formula (4) can be obtained by adding 1-amino-8-naphthol ~ 3,6 ~ or 4,6-disulfonic acid or 2-Amino-5-naphthol-1,7-disulfonic acid with the diazonium salt of a Aminophenols of the formula

R ₂

wherein R ^ and Rg have the meanings given above, coupled and treated the monoazo compound obtained with a copper salt. Examples of aminophenols of the formula (6), the

209837 / 1U7

Can be used are 2-aminophenol-4-sulfonic acid or -4,6-disulfonic acid, 6-nitro-2-aminophenol-4-sulfonic acid, 4-nitro-2-aminophenol-6-sulfonic acid, 6-chloro-2-aminophenol-4-sulfonic acid and 4-chloro-2-eminophenol-6-sulfonic acid.

Examples of copper salts that can be used are Copper sulfate, copper acetate or their amine derivatives of, for example Ammonia, pyridine or ethanolamine.

The new dyes can from the reaction mixture in which they have been produced, are isolated by customary measures, and preferably by - that they are salted out and filtered off, but also, for example, by direct drying of the entire condensation mixture, for example by spray drying. Optionally, diluents such as urea, sodium chloride and / or sucrose can be added before drying will.

The new disazo dyes are useful for dyeing cellulose textile materials, for example of textile materials that contain natural or regenerated cotton. For coloring this The new dyes are preferred to textile materials either by a dyeing or a printing process on the cellulosic textile materials applied, with a treatment with an acid beforehand during or after the application of the dye binding means, such as e.g. Sodium hydroxide, sodium carbonate or Sodium bicarbonate. Alternatively, if the If a heating stage is used, then one can also be used Substance such as sodium trichloroacetate can be used converted into an acid-binding agent during heating will. When the new disazo dyes are applied in this way to cellulosic textile materials, in particular from dye baths with large liquid ratios, then react the new disazo dyes with cellulose, whereby they in

209837 / 1U7

strong reddish brown to oratnge-brown hues can be established, the light very good fastness to wet treatments and _t, especially against Bleichbehendlungen possess.

Among the classes of dyes defined above, those who in which X stands for a group of the formula (2), good over-dyeing fastness in washing tests, whereas those Dyes in which Y represents the group of the formula (2) can be built up into deeper shades. Under this latter Klesse give those dyes in which R, stands for CH%, better fastness to over-dyeing in washing tests.

Accordingly, a preferred class of new dyes is represented by the formula

in which the symbols R ₁ , R ₂ and R, have the meanings given above and the benzene ring A can be substituted _{by CH ,, OCH ,, KHCOCH * or NHCONH 2.}

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

example 1

A solution of 6.47 parts of the trisodium salt of 1: 1 Kupferkoräplexea of 6-amino-2- (2 ^I -hydroxyphenylazo) -1-naphthol ~ 3.5 ^»l 5 trisulfoneäure in 100 parts of water Rait a pH of 7 is currencies -

209837 / 1U7

* ♦ # * fc

Added over half an hour to a stirred suspension of 1.95 parts of cyanuric chloride in 20 parts of acetone, 20 parts of water and 20 parts of ice. The pH value is kept at 5 to 6 by the occasional addition of an 8 # aqueous sodium hydroxide solution, and the resulting solution is ^{stirred for a further hour at a temperature of 0 to 5 °} C. in order to bring the reaction to completion. The solution is then filtered.

The filtrate is stirred at a temperature of 20 to 25 ° O, and a solution of 5.62 parts of disodium ^{salsea of 4- (4 w} -methylaminophenylazo) -4'-nitrostilbene-2,2'-disulfonic acid in 400 parts of water admitted. The temperature is raised to 35 to 40 ⁰ C, and the pH is maintained by addition of a 1 st 8 # aqueous sodium hydroxide solution to 1. The reaction solution is stirred for a further 17 hours at 35 to 40 ^° C., the pH is adjusted to 6 again, and the dye is isolated by adding sodium chloride. The filter cake is redissolved in 300 parts of water and precipitated by adding 30 parts of sodium chloride. The product is filtered, washed with acetone and dried at 40 ⁰ C.

The dye thus obtained contains 1.0 hydrolyzable atom Chlorine per molecule. If he is exposed to a treatment with an acid binding agent on cellulosic fabrics is applied, then the dye gives orange-brown shades with very good fastness to washing and light and bleaching.

In the following table are further examples of the invention Described dyes which are obtained in a manner similar to that in Example 1 by adding cyanuric chloride with the copper complex of the aminoazo compound obtained from the diazo and Coupling components of columns II and III is obtained, and

209837/1147

Χ ·: "" ::: 220326 *

with the aminoazo compound, the aua the diazo and coupling components of columns IV and V is obtained, condensed. The shades obtained with the dyes are in the column specified.

209837/1147

.1
at
game II
Diazo component III
Coupling component IV
Diazo component V
Clutch
component VI
hue 2 2-Ajninophenol-4-
sulfonic acid 2-aaino-5-naphthol-
1,7-dieulfonic acid 2-naphthylamine
4,8-disulfonic acid N-methylaniline reddish
Brown 3 6-chloro-2 ~ amino-
phenol-4-sulfone
Diacid 1,8-aminonaphthol
3,6-di-sulfonic acid - 4-amino-4'-nitro-
β ^^ βη-2,2'-α1-
sulfonic acid ti Brown 4th 2 ~ aminophenol ~ 4,6-
sulfonic acid η η dd U 5 η 2-amino-5-naphthol-
1,7-di-sulfonic acid H If orange
Brown . 6th η 1? 2-naphthylarain-
4,8-disulfonic acid m-toluidine η 7th « 1,8 amine naphthol
3,6-disulfonic acid η « reddish
Brown 8th 6-chloro-2-amirso-
phenol ~ 4-aulfonic acid N η η It 9 6-N itro ~ 2- aininopheno
4-sulfonic acid i- 2-amino-5-naphthol-
1,7-disulfonic acid dd η orange-
Brown .10 2-aminophenol-4-
sulfonic acid Il
L,. η m-aminopheny1-
harnatoff ti

ro ro ο co

ro ο to oe ο

I.
At-
epiel II
Diazo component III
Coupling component IV
Slide component V
Coupling
component VI
hue 11 6-nitro-2-amino
phenol-4-eulfone-
säui-e 1-Ainlno- 8-naphthol-
3 c 6-disulfone & ure 2-naphthylamine
k , S-disulfonic acid m-aminopheny1-
h ame t off red-brown 12th 2-arainophenol-4 .6-
dieulfonic acid it ι: Il It 13th 6-nitro-2-ani.inopheno
4-sulfonic acid i- 2 ~ amino- ^ - naphthol-
1,7-dieulfona acid 4-amino-ii · ~ nitro-
stilbene-2,2'-di-
βulfonic acid N-methyl aniline orange
Brown 14th η 1-amino-8-naphthol-
4,6-di-sulfonic acid η N-methyl-m-
toluidine red-brown 15th 6-chloro-2-andno-
phenol-ll-eulfone-
sSlure 2-amino-5-naphthol
1,7-disulfonic acid η N-ethylaniline orange
Brown Ii 2-Aniinop] lienol-4 _S 6-
sulfonic acid ti 2-naphthylsBJin-
1 _s 5-dlsulfonefture 2,5-diniethoxy
aniline η IT » M. 1-naphthylamine
4 χ 8-dieulfonic acid m-Arainoaoet-
anilide ir
η 18th : H
• N 1-naphthylamine
3,6-disulf oneflure N-methylaniline Il 19th 2-aminophenol-4-
sulfoneSur 1-Aeino-8-naphthol-
3 * 6-dieulfonstur * •
2-NaphthylaBin-
4,8-diaulfonic acid m-toluidine red-brown

Ca) fO

I.
at
game II
Diazo component III
Coupling component IV
Diaeocoaponente V
Clutch
component VI
hue 20th 2-aminophenol-4-
sulfonic acid 1-amino-8-naphthol-
4,6-di-sulfonic acid 2-naphthylarain-
6,8-disulfonic acid ra-aminoacet-
anilide red-brown 21st 4-chloro-2-amino-
phenol-6-eulfone-
atture 1-amino-3-naphthol-
3,6-disulfonic acid 2-naplithylamine
5 j, 7-disulfonic acid 2,5-dimethyl
anilide η 22nd N η i-naphthylamine
4,6-disulfonic acid N-methyl-m-
toluidine η 23 2-aninophenol-4,6-
disulfonic acid 2-amino-5-naphthol-
1,7-disulfonic acid 2-naphthylamine
3,7-di-sulfonic acid 2-methoxy-5-
methylaniline organge-
Brown 24 6-nitro-2-amino
phenol-4-sulfone
acid 1-Aeino-8-naphthol-
4,6-di-sulfonic acid 1-naphthylamine
4,7-di-sulfonic acid N-methyl-m-
toluidine red-brown 25th 4-nitro-2-amino
phenol-6-suliOn-
• acid η 2-naphthylamine
3,6-disulfonic acid m-aminophenyl
harnatoff

Claims (7)

Claims NO ₂ or and R ₂ for wherein R _{1 stands} for H, Cl, KO ₂ or SO, H and R _{2 stands} for Cl, SO, H, where at least one of the symbols SO, H is, and in which either X is H, Z is SO, H and Y stands for a group of the formula R, (2) where R * is H or CH, R. is a 4 ^! ~ Nitro-2,2' ~ dlsulfostilben-4-yl or an Eisulfonaphthylradikal means and the benzene nucleus A through CH, OCH .., NHCOCHr or substi can be tuiert, or X stands for a group of the formula (2), one of the symbols Y and Z stands for H and the other of the symbols stands for SO ₃ H. 209837 / 1U7 ΐ> Hfl · ■ * · * - 13 - 2. Dyestuffs according to Claim 1 of the general formula wherein R .., R «and R. have the meanings given in claim 1 and the benzene ring A can be substituted by CH ,, OCH ,, NHCOCH, or NHCONHp. 3. Dyestuffs according to claim 1 or 2, wherein R _{2 is} SO ₅ H and stands for H or SO ^ H 4. Dyestuffs according to one of claims 1 to 3, wherein R. is 4 -'-nitro-2,2'-disulfostilben-4-yl, R _{5 is} CH, and the benzene ring A is unsubstituted. 5. Dyestuffs according to one of claims 1 or 3, wherein R, is 4,6-disulfonaphth-2-yl, R, is H and the benzene nucleus contains a single substituent selected _{from CH 1, NHCOCH 4 and NHCONH 2} is. 6. Process for the preparation of disazo dyes according to Claim 1, characterized in that cyanuric chloride is mixed with one mole of a compound of the formula N = N R; (35) 209837 / 1U7 • · - 14 - and with one mole of a compound of the formula Gu N = N (4) reacted, where R ^, R ₂ , R ~ and R. have the meanings given in claim 1, the benzene nucleus A can be substituted as in formula (2) and either X _{1 is} H, Y _{1 is} NH « stands and Z stands for SO ₅ H or stands for NHp and one of the symbols Y ₁ and Z ₁ stands for H and the other of the symbols stands for SO ₅ H. 7. Use of the dyes according to one of claims 1 to together with a treatment with an acid-binding agent for dyeing cellulosic textile materials. PATENTANWXlTf VlAHQ.H. f 1!. 'CKE, DIPLMNO. H. K) H * DlPL-INS S. STASUt 209837/1147