GB2221471A - Fibre-reactive disazo dyestuffs containing two chlorotriazine rings linked by piperazine - Google Patents

Description

FIBRE-REACTIVE DISAZO DYESTUFFS Case 150-5267 This invention relates to

disazo compounds containing heterocyclic fibre- reactive groups, processes for their preparation and their use as fibre- reactive dyestuffs.

More particularly, this invention provides compounds of formula I in free acid or salt form cl H cl N-,,,-N - HO ' 2TH N \-NH OH H (I) N = N N N =N N = N COOH H so 3 H so 3 H so 3 H so 3 H H COOH 1 The invention further provides a process for the preparation of compounds of formula I comprising reacting one mole of two different compounds of formula II H N-, H N N=N W COOH { so 3 H SO 3 H H cl (II) or two moles of the same compound of formula II in free acid or salt form with one mole of piperazine.

This reaction may be carried out by known methods suitably at between room temperature and slightly elevated temperature.

- 2 Case 150-5267 The compounds of formula I may be isolated in accordance with known methods, for example by conventional salting out with alkali metal salts, filtering and drying optionally in vacuo.

Conversion from free acid form to single or mixed salt form or vice versa or interconversion between salt forms may be performed by conventional means.

Compounds of formula I may be prepared for use as dyestuffs in salt form in which the cations used are non-chromophoric cations capable of forming water soluble salts. Suitable cations are those conventional in the field of fibre-reactive dyestuffs, such as, for example alkali metal cations or unsubstituted or substituted ammonium cations, e.g. lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methyl- or ethylammonium, mono-, di- and triethanolammonium cations. Preferably the cations are sodium.

The starting compounds of formula II can be made using known starting compounds, for example, by alkaline coupling one mole of the diazonium compound of the amine of formula III H - - - NH 2 COOH H (III) with 1 mole of a compound of formula IV HO NR - R X so 3 H so 3 H IV (IV) in which R. is hydrogen, a removable protecting group, e.g., the acetyl group, or R. is 2,4-dichloro triazin-6-yl, and followed by Case 150-5267 a) in the case where R,, is hydrogen, reacting with cyanuric chloride using a molar ratio of 1:1, and b) in the case where R,, is a protecting group, removing the protecting group and reacting the resulting primary amino group with cyanuric chloride using a molar ratio of 1:1.

The compounds of formula I and mixtures thereof are useful as fibrereactive dyestuffs for dyeing or printing hydroxy group- or nitrogencontaining organic substrates. Preferred substrates are leather and fibre material containing or consisting of natural or synthetic polyamides and, particularly, of natural or regenerated cellulose such as cotton, viscose and spun rayon. The most preferred substrate is textile material containing or consisting of cotton.

Dyeing or printing is carried out by known methods conventional in the fibre-reactive dyestuff field. Preferably, the compounds of formula I are applied by exhaust dyeing.

It is an advantage of the present invention that dyeing with the compounds of formula I is not temperature dependent in the 60-120C dyeing temperature range. Therefore, dyeing may be effected almost equally well at 80C as at 1001C without any essential loss of fixation yield, and dyeings of practically the same colour strength are obtained.

The compounds of this invention are compatible with other fibre-reactive dyestuffs; they may be applied per se or in combination with appropriate fibre-reactive dyestuffs of the same class having analogous dyeing properties, e.g., fastness properties, extent of ability to exhaust from the dyebath onto the fibre etc. The dyeings obtained with such combination mixtures have good fastness properties and are comparable to those obtained with a single dyestuff.

Case 150-5267 The compounds of formula I show high exhaust and fixation yields. Any unfixed dyestuff can be easily washed off the substrate. The build-up power of the compounds is also good. The dyeings and prints obtained show good fastness properties, especially with respect to dry and wet light fastness properties and general wet fastnesses such as fastness to washing, water, sea water and sweat. They are also resistant to oxidative influences, e.g., chlorinated water, hypochlorite bleach and peroxide- or perborate- containing wash fluids.

In particular, the dyeings obtained with the compounds of formula I have a surprisingly high acid stability, for example, a dyeing when contacted with dilute acetic acid, only shows a slight staining of the undyed accompanying fabric.

The invention will now be illustrated by the following examples. In the examples all parts and percentages are by weight unless indicated to the contrary. All temperatures are in degrees Centigrade.

EXAMPLE 1 parts of 30% hydrochloric acid and 200 parts of ice are added to 27 parts of 4-aminobenzoic acid which are suspended in 200 parts of water. 50 parts of a 4N sodium nitrite solution are added dropwise at 00 over a period of 15 minutes and a brown suspension results. Any excess nitrite is decomposed with ca. 5 parts of 10% sulphamic acid. The resulting suspension is added dropwise over a period of 20 minutes to a solution of 67 parts of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid and 35 parts of calcined soda in 200 parts of water. During the addition.,the temperature of the reaction mixture is kept at 00 by adding ice. Simultaneously, the pE of the mixture is kept at 8.5 for ca. one hour by the addition of a 20% soda solution. When no diazonium compound is detectable any longer, the solution is neutralised (pH 7) by adding 30 parts of 10% hydrochloric acid, followed by 300 Case 150-5267 parts of sodium chloride. Stirring is effected overnight. A monoazo compound of the formula 1b HO 2 HOOC --0- N = N 1 - (1b) so 3 H so 3 H precipitates out and the precipitate is filtered and dried.

The monoazo compound of formula 1h is redissolved in 2000 parts of water and added to a suspension of 45 parts of cyanuric chloride in 700 parts of a mixture of water and ice. This suspension is stirred at 51 for approximately three hours at a constant pH of 6-7 maintained by the addition of 95 parts of a 20X soda solution. 8 parts of piperazine are added to the resultant mixture, and the mixture is stirred for ca. 20 hours at room temperature. To complete the reaction, the mixture is stirred for a further eight hours at 401. Subsequently, the pH of the reaction mixture is adjusted to 7.5 by the addition of 15 parts of disodium hydrogenphosphate. The resulting dyestuff which precipitates out on adding 600 parts by volume of sodium chloride is of the formula 1.

cl cl IN-, z, HO NH N N OH N= N HOOC N = N N N N=N COOH so 3 H so 3 H so 3 R so 3 H (1a) in sodium salt form.

On drying a dark red-powder results which is readily soluble in water.

Case 150-5267 The dyestuff dyes cotton a brilliant bluish red shade. These dyeings show good general fastness properties, e.g., good light and wet fastnesses, particularly good wet light fastness and high resistance to oxidative influences and acid hydrolysation.

EXAMPLES 2 AND 3 By analogy with the method described in Example 1 and using appropriate starting compounds, compounds of formula 2. and 3.

N -, cl cl HO NH N N -NH OH (2.) N - N.1.It = Y N=N N N 1 1 \-i f)_ 1 p1-1It" GOOH so 3 H so 39 so 3 H so 3 H cl cl t -, 7, HO NH -y N _ NH OH N = r---\ 5-14 HOOC N = N N N N=N so 3 H so 3 H so 3 a so 3 H COOR (3a) can be prepared.

COOH The dyestuffs of Examples 2 and 3 are obtained in sodium salt f orm.

These dyestuffs in salt form may be applied to natural or regenerated cellulose fibres, and particularly to cotton fabrics, conventional exhaust dyeing methods. Bluish red dyeings showing good V Case 150-5267 fastness properties are obtained.

APPLICATION EXAMPLE A parts of mercerized cotton fabric are added to a dyebath consisting of 1000 parts of water, 20 parts of Glauber's salt (calcined), 2.5 parts of sodium carbonate (calcined) and 1 part of the sodium salt of l- nitrobenzene-3-sulphonic acid. The bath is heated to 40, then 1 part of the compound of formula 1. of Example 1 is added. The temperature is raised to 980 over 45 minutes. During this time, 20 parts of Glauber's salt (calcined) are added after 15 minutes and a further 20 parts of Glauber's salt ' (calcined) are added after a further 15 minutes. At the - end of this time 7.5 parts of sodium carbonate (calcined) are added. Dyeing is continued at the boil for 45 to 60 minutes. Subsequently, the dyed fabric is removed from the liquor, rinsed with running hot water, and washed at the boil for 15 minutes in 500 parts of demineralised water in the presence of 0.25 parts of a commercially available anion-active detergent. After rinsing and drying a bluish red cotton dyeing with good light and wet fastness properties is obtained.

APPLICATION EXAMPLE B 1 Part of the compound of formula 1. of Example 1 is dissolved in 2000 parts of water. 100 Parts of cotton fabric are added and the temperature of the dyebath is raised to 80 over 10 minutes. 100 Parts of Glauber's salt (calcined) are added and 20 parts of sodium carbonate (calcined) are added over 30 minutes. Dyeing is continued for one hour at 801. Subsequently, the dyed fabric is rinsed with cold running water and then with hot water, and is washed as in Application Example A. After rinsing and drying, a bluish red cotton dyeing is obtained having good fastness properties.

Case 150-5267 APPLICATION EXAMPLE c A printing paste consisting of parts of the compound of formula 1, of Example 1 100 parts of urea 340 parts of water 500 parts of a 4% sodium alginate thickener, and 20 parts of sodium carbonate 1000 parts total is applied to cotton fabric by a conventional printing method.

The printed fabric is dried and fixed in steam at 102-104 for 4-8 minutes. It is then rinsed with cold and hot water, washed at the boil (according to the method described in Application Example A) and dried. The resulting bluish red print shows good general fastness properties.

In Application Examples A to C, an appropriate amount of the compound of formula 2. or 3. of Example 2 or 3 may be employed in place of that of the compound of formula 1,. In all cases, bluish red dyeings (Examples A and B) or prints (Example C) are obtained having good fastness properties.

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Claims (7)

1. What is claimed is

   Case 150-5267 1. A compound of the formula I in free acid or salt form cl cl H HO NH N N ', \-NH OR H 111 11: =N N = N N N N = N - COOH H so 3 H so 3 H so 3 H so 3 H H COOR
2. 2. A compound of formula I according to Claim 1 in which the carboxy group on each terminal phenyl group is in the paraposition relative to the azo group.
3. 3. A compound of formula I according to Claim 1 in which the carboxy group on each terminal phenyl group is in the meta-position relative to the azo group.
4. 4. A compound of formula I according to Claim 1 in which the carboxy group on one terminal phenyl group is bound in the meta- and the carboxy group on the other terminal phenyl group is in the para-position relative to the azo group.
5. 5. A process for the preparation of a compound of the formula I as defined in Claim 1 which comprises reacting one mole of two different compounds of formula II cl H N-, 1,40 NH--'7 N N.=1\ N = N cl COOH H SO 3 H so 3 H (II) Case 150-5267 or two moles of the same compound of formula II (in free acid or salt form) with one mole of piperazine.
6. 6. A process for dyeing or printing a hydroxy group-or nitrogencontaining organic substrate, which comprises applying a compound according to Claim 1 to the substrate.
7. 7. A process according to Claim 6 for the dyeing or printing of leather or textile material or fibres of natural or synthetic polyamides or natural or regenerated cellulose.

   I Published 1990 at The Patent Office.StateI.Iouse.66 71 High Hol.born. LondonWC1R4TP-F'artherc6ples maybe obtainedfrom The PatentOtrice. Sales Branch. St Mary Cray. Orpington. Kent BR5 ULD Printed by Multiplex techniques lid. St Mary Cray, Kent, COn. V87