DE2244541A1 - AZO DYES - Google Patents

Description

PATENTANWXLTi
DR.-INQ. H. PINOKE DIPL.-ING. H. BOHR DIPL.-ΙΝΘ. S. STAEQER

Fariruh · 40 <0

Folder 22986 - Dr. K. Case Dd 2429 *

8 MUNICH O. "J f. SEP. 1972

MOll.r.tro «. 31

Imperial Chemical Industries Ltd «London» Great Britain

Azo dyes

Priority: 10.

- Great Britain

The invention relates to new azo dyes that as green reactive dyes for dyeing cellulose textile materials suitable.

It has been found that green reactive dyes with a very good fastness to light and to washing and bleaching treatment, which also produce very good deep shades when dyeing from salt-containing alkaline dye baths,

309811/1074

ORIGINAL INSPECTED

can thereby be obtained if: nan certain copper complex monoazoamino compounds and certain amino compounds are valid with the help of a chloro-s-tria3iE linkage group connected.

According to the invention, dyes of the formula 0 become Cu 0

(D

suggested where

m and η independently represent 0 or 1, R represents H or CH,

the ring A can be further _{substituted by SO 5} H and / or NOp

can and

R _{1 is} a group of the formula

-NH -4 { \ V-CH-CH ^ / 7- NO _D (2)

SO, H

or - NR ₂ -H ₃ -NNH ₄ (3)

is where

Rp is H or CH,

R ₃ for a 1,4-Naphthalinradlkal which by SO ₃ H and / or

OCH ₇ substituted ka & ij, or for a 1,4-phenylene radical,

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which by CH ₅ , OCH ₅ , Cl, SO ₅ H ₇ CO _? H, MCOM ₂ or KHCOR _{5 may be} substituted kasai, in which R, - ~ H or alkyl ra. ". T is up to 3 carbon atoms, ucd

R ₂ ^ stands for a sulfopheayl or sulfonaphthyl group, which in the form of phenyl riter through chloro, nitro, acetylamino, methoxy, methyl, 4'-nitro, 2'-sulfophenylvinyl, 4 -'-nitro-2'-sulfoanilino or carboxy substituted ssin can «

According to the invention there is also a method of manufacture of the new dyes proposed, which is carried out by adding cyanuric chloride with 1 mol of an amino compound the formula

HHR

and with 1 mole ^ -i

or an amino compound of the formula

- N - F - S ₅ - KHR ₂

converts, where the symbols m, n, R _t R ₂ , R, and have the meanings given.

(5)
the above

The method according to the invention you came ixi zweckmäßi.ger manner be carried out by that maxx a suspension of Cyanurchlorida in an aqueous "medium zimechst with the first of the amino compounds at a temperature from 0 to 5 ⁰ C stirred until a chlorine atom of Cyanurc? .IlorJds. _v uwd reacted to this

309811/1074

BAD ORlGINAL.

22-5-1

the second aiainoverhinder increases and the reaction in one slightly higher temperature * usually io Boreich from 40 to 45 ° C. continues until a swaites chlorine atom of cyanuric chloride responded. The condensations are preferably carried out at a pH of 6 to 7, with an acid-binding Agent is added to neutralize the hydrochloric acid formed during the reaction. When the reaction is over then the new dyes can be isolated by the usual techniques used for the isolation of water-soluble ones Reactive dyes are known, for example by salting out and filtration or by spray drying the reaction mixture, in which the dye has been produced. If necessary, stabilizers can be added, such as mixtures of alkali metal hydrogen phosphates.

The compounds of the formula (4) used in the above process can be prepared in that mar, a Naphthylamine sulfonic acid of the formula

(6)

diazotized and with an aminonaphtholsulfonic acid formula

(SO ₅ H) _n

(7)

30981 1/1074

couples, where the symbols R and η the Be given above Have interpretations, whereupon the obtained azo. compound in aqueous solution with a copper salt, for example Copper sulfate or copper acetate, in the presence an oxidizing agent such as an alkali metal per oxides, percarbonates, perborates, organic peracids, acyl peroxides. Air in the presence of an oxygen transfer catalyst, such as anthraquinone-2- * sulfonic acid, but preferably hydrogen peroxide, converts *

As examples of liaphthyläminsulfonsäuren of the formula (6) the following should be mentioned: 2-naphthylamine-4,8-disulfonic acid and

, 8-disulfonic acid.

Examples of aminonaphthols of formula (7) are as follows: ■
2-amino-5-naphthol-7-sulfonic acid,
2-amino-8-naphthol-6-sulfonic acid _t
2-methylamino ~ 5-naphthol-7-sulfonic acid,

J ^ e- and -4,6-disulfonic acid,

naphthol-y-surf on acid, 2-Amlno-5-naphthol-1,5-disulfonic acid and 2-amino-8-naphthol-3,6-disulfonic acid.

The compounds used in the above process d © r formula (5) can be obtained by reacting sulfonated aminoazobenzene or diazotising a aniline or Naphthylaminaulfonsäure which may be further substituted _s and with a coupled, in the p-position of the benzene amine or naphthalene series. Examples of Dlazo components are the following:

309811/1074

Aniline-o-, m- and p-sulfonic acid, 2 ~ aminotoluene-4 ~ and -5-sulfonic acid, 2 ~ aminoanisole-4- and -5-sulfonic acid, aniline-2,4-, 2,5- and 3 , 5- <sulfonic acid, 4-nitro-4'-aminostilbea-2,2'-disulfonic acid, 4-amino-4'-nitrodiphenylamine-2,3-disulfonic acid, 1-aminonaplithalin-5- and -6-sulfonic acid , 2-aminonaphthalene-1,5- »4 _t 8- and 6,8-disulionic acid and 2-alinillolaphthalene-3, 6,8- and 4,6,8- triaulphonic acid.

Examples of coupling components are the following:

Aniline,

o- and m-anisidine, anthranilic acid.

o ~ and m-toluidine, 2,5-dimethoxyaniline, Cresidin,

m-aminoacetanilide, o-aminophenylurea, 1 ~ aminonaphthalene-6, 7- and 8-sulfonic acid, 1-aminonapnthalin-6,8-disulfonic acid, H-ethylaniline, N-methyl-o-anisidine and N-O-hydroxyethyl-m-toluidine.

The new reactive dyes are suitable for dyeing cellulosic textile materials, which contain or consist of natural or regenerated cellulose. For coloring such Materials, the new dyes are preferably applied either by a printing or by a dyeing process the cellulosic textile material applied, together with an acid-binding agent such as caustic soda or

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22U541

Sodium carbonate, phosphate, silicate or bicarbonate. The acid binding gown can be applied to the cellulosic textile material be applied before, during or after the application of the dye. The new dyes are particularly suitable for application from salty alkaline dye baths, in which an unusually high proportion of the attached dye reacts with the fiber «As a result, strong green tones are obtained on the textile material have excellent fastness to light and wet treatments, in particular washing and bleaching treatments.

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

example 1

A solution of 8 parts of the tetrasodium salt of the copper complex of 8-amino-1,1'-dihydroxy ~ 2,2'-e-eonaphthalene-3 »4 't 6,8'-tetrasulfonic acid in 200 parts of ice-cold water to a suspension of 1.85 parts of cyanuric chloride in 40 parts Water at 0 to 5 ° C. is added, and the mixture is stirred for 2 h at 0 to 5 ° C., the pH being adjusted by adding 5 parts 2N sodium carbonate solution is maintained at 6.0 to 6.5.

Then a solution of 5.03 parts of the disodium salt of 4-nitro-4 X is - (IJ ^ll -methylaminophenylazo) stilbene-2,2 '-disulf oneäure added in 100 parts of water, and the mixture is heated to 4Q ^e C and 18 st stirred at 40 ⁰ C, the pH being maintained by the addition of 5 parts of 6 to 2n Natriuacarbonatlösuiig. 7 ,

30981 1/1074

22U541

Then ^ίι Ο parts of salt are added, and the mixture is ^{cooled 2 et to 15 0} C and stirred and then filtered, whereupon the residue on the filter with 15%? Brine and is dried at 4O ⁰ C.

The product obtained in this way dyes cellulose textile materials from salt-containing alkaline dye baths in green shades that show excellent fastness to washing and bleaching and to light.

Example 2

A solution of 5 "10 parts of the copper complex of 6-nitro-6 * -amino-1,1 ^l -dihydroxy-2,2 ^l -azonaphthalene-3 ^l » 4 _t 5 ', 8-tetraeulfonic acid in 250 parts of water is obtained Cooled 0 to 5 ⁹ C and the pH is adjusted to 7. A solution of 1.25 parts of cyanuric chloride in 15 parts of acetone is then added, and the pH is kept at 6 to 6.5 by adding 2N sodium carbonate solution. The reaction is sin 2 st, and the solution is then diluted with 15O parts of water, heated at 3O ⁰ C and freed by filtration from überschüBSigem cyanuric chloride. Then 3 × 4 parts of 4-nitro-4 '- (4 "-methylaminophenylazo) ethylben-2,2'-disulfonic acid are added, whereupon the solution is etched for 3 hours at a pH of 6 to ^U b, the pH is maintained by adding 2N sodium carbonate solution. the solution is further stirred and allowed to cool, salted out dry with 10% (w / v) sodium chloride, filtered and the residue on the filter at 35 to 4O ⁰ C is dried. the in this A dyestuff obtained in this manner dyes cotton from an alkaline bath at 8O ⁰ O in green shades which are fast to washing and also to light etc.d bleaching solutions.

30S8MM07 £

In the following table are further according to the invention Dye examples given, which are obtained by that one cyanuric chloride with 1 mole of the copper complex Aminoazoverbinduag and specified in the other column 1 mol of the amine indicated in the third column condensed. <

30981 1/1074

O (D OO

3sp.

6 7 8

10 11

6-Amifio ~ 6'-nitro-1,1 · -hydroxy-2,2 · - azonaphthalene-3,4 · ** 5,8'-tetrasulfonic acid

5-methylamino-6 '-ait ro-1,1 * -dihydroxy-2,2'-azonaphthalene-3, ^' , »- trisulfonic acid

- do - -

8-Amino-1,1'-dihydroxy-2,2-azonaphthalene-3,4 ', 6 “8'-tetrasulfonic acid

- do -

- do -

8-Amino-1,1'-dihydroxy-2,2 · -azonaphthalenes ^, 6 ', 8'-tetrasulfonic acid

- do -

- do -

4-Amino-4'-aitrosti It en-2,2'-disulfonic acid

2- (4'-Amino-2'-methylphenylazo) naphthalene- ^ - _f 8-disulphonous acid

2- (4'-Amino-2'-ute idophenyla zo) naphthalene-3,6,8-trisulfonic acid

- do -

4-Amino-4 '-nitrostilben-2,2' -disulf oleic acid

2- (4'-Amino-2'-methylphenylazo) naphthalene- j 4 _T 8-diaulfonic acid j

- do 4-amino-4'-nitrostilbene-2,2'-disulfonic acid

2- (4'-Amino-2 · -ureidophenylazo jnaphthalene-3,6,8-trisulfonic acid

8-amino-6'-nitro-1,1'-dihydroxy-2,2 '

asonapiJ.tnaiin-3,4 '* 6,8' -tstrasulf on- ! acid

- do -

- do 2- (H- '-amino-2' -ureidophenylazo) naphthalene-3,6,8-tri8ulfonic acid

2- (4'-Amino-2 '-laethylphenylazo) naphthalene-4 · _s 8-disulfonic acid

4-Amino-4'-nitrostilboia-2,2'-disulfonic acid

Claims (3)

22A45A1 Claims Dyes of the formula < ^S0 3 ^H) m ta and η independently of one another represent O or 1, H is H or CH, the ring A can be further substituted _{by SO 35} H and / or NO ₂ can and H ^ for a group of Forael HO ₁ S Y = J - ⁽²⁾ 8O ₅ R approx -HBχ - R, '- R - N - fy (3) stands! worl η H ₂ for H or OH, otebt, ' R ₇ , for <* in 1 _f i »-Kephthft3inra'iikal v / elcliee by SO, H and / or : * D <i if 11 / < 0 22445A1 OCH, or for a 1,4-phenylene radical * which can be substituted by CEU, OCH ₅₁ Cl, SO ₅ H, CO ^ H, MCONH ₂ or NHCORn, in which Rc-H or alkyl with up to 3 carbon atoms , stands, and R ^ stands for a sulfophenyl or sulfonaphthyl group, which in the case of phenyl further by chloro, nitro, acetylamino, Methoxy, methyl, V-nitro-2'-sulfophenylvinyl, 4'-nitro-2-sulfoanilino or carboxy may be substituted. 2. A method for producing the dyes i; ach claim 1, characterized in that cyanuric chloride is mixed with 1 mol of an amino compound of the formula NHR and with 1 mol ^ -nitro ~ 4 ^l -aminostilbene-2,2'-disulfonaiiurö or an amino compound of the formula - N - N - R ₅ - NHR ₂ (5) converts, where the symbols m, n, R, R ₂ * R ₅ and R ^ have the meanings given in claim 1. 3. Use of the dyes according to Claim 1 together with an acid-binding agent for printing or dyeing cellulose textiles. ΜΤΜΤΑΝΜβΠ 309811/1074