GB1583387A

GB1583387A - Preparation of reactive bisazo dyestuffs based on h acid

Info

Publication number: GB1583387A
Application number: GB3662677A
Authority: GB
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 1976-09-06
Filing date: 1977-09-01
Publication date: 1981-01-28
Also published as: FR2363608B1; DE2740152A1; JPS5331732A; FR2363608A1

Description

(54) PREPARATION DF REACTIVE BISAZO DYESTUFFS BASED ON H ACID (71) We, NIPPON KAYAKU KABUSHIKI KAISHA, a corporation organised and existing under the laws of Japan, of New Kaijo Buildings, 2-1, 1-chome, Marunouchi, Chiyoda-ku, Tokyo, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a process for the manufacture of bizazo dyes which, in their free acid form, are represented by the formula:

wherein one of A1 and A2 stands for H and the other stands for SO3H, one of B, and B2 stands for H and the other stands for SOBS.

Japanese Patent Provisional Publication No. 50022/74 discloses a process for the manufacture of the dyes of formula (I), which comprises condensing cyanuric chloride with equimolecular amount of sulfanilic acid or metanilic acid and one-half molecular amount of a bizazo compound of the formula:

in an arbitrary order.

The compounds of formula (IV) can be obtained by coupling 2 mol of a diazonium salt derived from 4-aminoacetanilide-3-sulfonic acid with 1 mol of H acid and hydrolysing the resulting product or by coupling 2 mol of a diazonium salt derived from 4-nitro-aniline-2sulfonic acid with 1 mol of H acid and reducing the resulting product with sodium sulfide.

However, in fact the former method can not be used for the industry, since the product contains a considerable amount of by-product which results due to the weakness of coupling power of a diazonium salt of 4-aminoacetanilide-3-sulfonic acid.

The latter method has a number of disadvantages: The reduction with sodium sulfide results in the production of hydrogen sulfide and Na2S203. Hydrogen sulfide is a deadly poison and it is not easy to remove hydrogen sulfide from the waste gas. In order to completely remove it an expensive and highly efficient equipment is needed.

As Na2S203 reacts with cyanuric chloride Na2S203 must be separated from the compound of formula (IV), and this is usually carried out as follows: First Na2S2O3 is hydrolysed with an acid into H2SO3 and sulfur which is removed by filtration. To the filtrate there is added sodium chloride and the compound of formula (IV) is precipitated, filtered and washed.

In this prior process equipment for absorbing hydrogen sulfide is required and furthermore a filtration stage of the solution, a salting-out and filtration stage of the filtrate and a washing stage of the press cake are necessary in order to remove sulfur.

Since the coupling power of the diazo component of an amino compound of formula (II) is weak, the compound of formula (I) has previously been obtained only in a low yield when an acidic coupling of an amino compound of formula (II) with H acid is employed. A red monoazo compound by-product of the formula:

is produced in considerable quantities along with the desired dark green bisazo dye, making it very difficult to obtain a good quality product.

According to the present invention, there is provided a process for the manufacture of bisazo dyes which, in their free acid form, are represented by the formula:

(t) wherein one of Al and A2 stands for H and the other stands for SOCH, one of B1 and B2 stands for H and the other stands for SO3H, which comprises coupling a diazonium compound derived from an amine of the formula:

wherein A, and A2 have the same meanings as given above, with 1-hydroxy-8aminonaphthol-3,6-disulfonic acid or its salt in an acidic medium in the presence of a coupling accelerator in the ortho position to the amino group and then coupling the monoazo compound thus obtained with a diazonium compound derived from an amine of the formula::

wherein B, and B2 have the same meanings as given above, in an alkaline medium.

In the process of this invention, since all stages of the first and second condensations of cyanuric chloride, diazotization and coupling can be carried out in the form of solution in a single batch, the invention is industrially efficient and very advantageous since it needs only a few stages and simple equipment.

The first acidic coupling of this invention is carried out by coupling a biazonium compound of an amine of formula (II) with H acid in the presence of a coupling accelerator in an acidic medium. Coupling accelerators for use in the acidic coupling reaction include acid amides (such as formamide, methylformamide, dimethyl formamide, acetamide, methyl acetamide, dimethyl acetamide). amidosulfonic acid, guanidine and its derivatives, methyl urea, urea, thiourea, glycol ether, alkyl glycol ether, polyglycol ether, and polyalkyl glycol ether. The most preferable are thiourea and urea. Moreover, although normally thiourea is easily substituted with an active chlorine or triazine, in the process of this invention surprisingly it works as an accelerator without any side reaction.

Without these coupling accelerators it takes very long time to complete the acidic coupling reaction and the quality and yield of the product are poor. The amount of coupling accelerator used can be varied to achieve the desired accelerating effect. For example, in the case of thiourea used as a coupling accelerator an amount of 0.2-10% (W/v) to the coupling solution is enough to achieve a desired accelerating effect, but a greater amount can be used. For urea 2-80% (W/v) of the coupling solution is required.

Neutralizing agents used in this invention may for example include sodium carbonate, sodium acetate, sodium primary phosphate and sodium secondary phosphate. They are used to adjust the acid coupling reaction mix to a desired pH value, for example 3.0-3.5.

After the first acidic coupling mentioned above the second alkaline coupling is carried out by a conventional method, that is: the resulting product obtained by the first acidic coupling is reacted with a diazonium salt of an amino compound of formula (III) at a preferred pH value, for example 7.0-8.5, in an alkaline medium containing sodium carbonate or sodium bicarbonate.

According to the process of this invention, when a diazonium salt of an amino compound of formula (II) is the same as that of formula (III), the dye of formula (I) is preferably obtained by adding 2 mole ratio of the diazonium salt of the amino compound to 1 mole ratio of H acid in the presence of a coupling accelerator in an acidic medium and after the end of the acidic coupling, subsequently coupling in an alkaline medium as mentioned above.

The dyes obtained by the process of this invention have good solubility and, when applied to cellulose fibres, show a dark green shade with very high fixation and build-up power in dip-dyeing and an excellent staining property on the adjacent undyed material during washing test in printing.

Following is a description by way of example only of methods of carrying the invention into effect.

In the examples parts and percent are by weight unless otherwise indicated.

Example 1 40.6 parts of aniline-3-sulfonic acid are dissolved in 200 parts of water at pH 7.0 and the solution is cooled down to 0.-5"C by adding 200 parts of ice. A small amount of Liponox RNA (a nonionic surface active agent made by Lion Oil Fatty Co.) and 44.1 parts of cyanuric chloride are added and the mixture is vigorously stirred. While being maintained at 0-5"C and at a pH of 6.0-7.0 by adding a 10% sodium carbonate solution, the mixture is stirred for about three hours until the completion of the reaction. A solution obtained by dissolving 43.2 parts of 1,4-diaminobenzene-2-sulfonic acid in 100 parts of water at pH 7.0 is then added to the said mixture over 15 minutes.Then, the pH is maintained at 6.0-6.5 by adding a 10% sodium carbonate solution and the temperature at 5-10"C if necessary, by adding ice and the mixture is stirred until the completion of the reaction (for 3-4 hours).

The condensation product solution thus obtained is cooled to 0-50C by adding ice and is mixed with 42 parts of a 40% sodium nitrile aqueous solution. The mixture is mixed with 50 parts of concentrated hydrochloric acid over 5 minutes and stirred at 0-10"C for 1 hour.

Then excess sodium nitrite is decomposed by adding sulfamic acid.

The viscous diazonium salt solution thus obtained is mixed with 50 parts of thiourea.

31.4 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved in 400 parts of water at pH 5.5-6.0.

The solution is dropwise added to the said diazonium salt solution over 20-30 minutes and stirred until the l-amino-8-naphthol-3,6-disulfonic acid disappears (for 8-10 hours), while maintaining 10-15"C and pH 3.0-3.5 by adding a 10% sodium carbonate solution.

Then the pH is adjusted to 8.0-8.5 with a sodium carbonate solution, stirring is carried out at 5-10"C for 2 hours and then further at room temperature overnight. During this time the pH is maintained at 8.0-8.5 with a sodium carbonate solution.

The solution is adjusted the pH to 6.5 by adding concentrated hydrochloric acid and salted to 20 % W/V with sodium chloride, the precipitate being filtered off.

The separated dye is dried in vacuo at 40"C. The yield of the dye is 85% with respect to the H acid which is the main starting material.

The dark-green dye obtained contains more than 1.95 atoms of hydrolysable chlorine per molecule. When applied to cellulose textile materials in conjunction with an acid-binding agent, the dye gives very high fixation, excellent build-up power in dyeing and excellent staining property in printing. In this example when aniline-4-sulfonic acid is used instead of aniline-3-sulfonic acid, a similar dye is obtained.

Example 2 24.4 parts of aniline-3-sulfonic acid are dissolved in 120 parts of water at pH 7.0, and 120 parts of ice are added to cool the mixture to 0-5"C. The solution is mixed with a small amount of Liponox RNA (a nonionic surface active agent made by Lion Oil & Fatty Co.) and 26.5 parts of cyanuric chloride and is then stirred well.

The mixture is stirred for about 3 hours until the end of the reaction, the temperature being maintained at 0-50C and the pH being maintained at 6.0-7.0 by the addition of a 10% sodium carbonate solution as necessary.

25.9 parts of 1,4-diaminobenzene-2-sulfonic acid are dissolved in 50 parts of water at pH 7.0. The solution is added to the mixture over 15 minutes. The pH is then adjusted to 6.0-6.5 by the addition of a 10% sodium carbohate solution and the mixture is stirred until the end of the reaction (3-4 hours), the temperature being maintained at 5-10"C, if necessary, by the addition of ice.

Ice is then added to the condensation product solution thus obtained to cool said product to 0-50C, and 25.2 parts of a 40% sodium nitrite aqueous solution are then added thereto.

To this mixture 30 parts of concentrated hydrochloric acid are added during 5 minutes and the mixture is stirred at 0-100C for 1 hour. Then excess sodium nitrite is decomposed by the addition of sulfamic acid. The diazonium salt solution thus obtained is mixed with 200 parts of urea. 31.4 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved in 400 parts of water at pH 5.5-6.0. The solution is added portionwise to the said diazonium salt solution over 20-30 minutes, the resulting mixture is stirred at 10-15DC, until the 1-amino-8naphthol-3,6-disulfonic acid disappears, (for 8-10 hours), to obtain monoazo solution, the pH being maintained at 3.0-3.5 by adding a 10% sodium carbonate solution.

Separately, a condensation product solution is obtained from 16.2 parts aniline-4-sulfonic acid, 17.6 parts of cyanuric chloride and 17.3 parts of 1,4-diaminobenzene-2-sulfonic acid by the same procedure as in said aniline-3-sulfonic acid. To the condensation product there are added 16-8 parts of a 40% sodium nitrite aqueous solution and a further 20 parts of concentrated hydrochloric acid over 5 minutes, and after stirring for 1 hour excess sodium nitrite is decomposed by the addition of sulfamic acid.

The diazonium salt solution thus obtained is added to the monoazo solution mentioned above, then the pH is adjusted to 8.0-8.5 by adding sodium carbonate solution.

The mixture is stirred for 2 hours at 5-100C while maintaining the same pH by the addition of sodium carbonate aqueous solution and further stirred overnight at room temperature.

The next day the pH is adjusted to 6.5 by adding concentrated hydrochloric acid. The mixture is salted to 30% W/V with sodium chloride, the precipitate is filtered off and dried at 40"C in vacuo.

Thus a dark-green dye is obtained in a yield of 80% with respect to the H acid. The dye contains more than 1.95 atoms of hydrolysable chlorine per molecule and has analogous dyeing properties to the dye obtained by using only aniline-3-sulfonic acid in place of aniline-3- and 4-sulfonic acid.

WHAT WE CLAIM IS: 1. A process for the manufacture of bisazo dyes which, in their free acid form, are represented by the formula:

wherein one of A, and A2 stands for H and the other stands for SO3H, one of B, and B2

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. The solution is adjusted the pH to 6.5 by adding concentrated hydrochloric acid and salted to 20 % W/V with sodium chloride, the precipitate being filtered off. The separated dye is dried in vacuo at 40"C. The yield of the dye is 85% with respect to the H acid which is the main starting material. The dark-green dye obtained contains more than 1.95 atoms of hydrolysable chlorine per molecule. When applied to cellulose textile materials in conjunction with an acid-binding agent, the dye gives very high fixation, excellent build-up power in dyeing and excellent staining property in printing. In this example when aniline-4-sulfonic acid is used instead of aniline-3-sulfonic acid, a similar dye is obtained. Example 2 24.4 parts of aniline-3-sulfonic acid are dissolved in 120 parts of water at pH 7.0, and 120 parts of ice are added to cool the mixture to 0-5"C. The solution is mixed with a small amount of Liponox RNA (a nonionic surface active agent made by Lion Oil & Fatty Co.) and 26.5 parts of cyanuric chloride and is then stirred well. The mixture is stirred for about 3 hours until the end of the reaction, the temperature being maintained at 0-50C and the pH being maintained at 6.0-7.0 by the addition of a 10% sodium carbonate solution as necessary. 25.9 parts of 1,4-diaminobenzene-2-sulfonic acid are dissolved in 50 parts of water at pH 7.0. The solution is added to the mixture over 15 minutes. The pH is then adjusted to 6.0-6.5 by the addition of a 10% sodium carbohate solution and the mixture is stirred until the end of the reaction (3-4 hours), the temperature being maintained at 5-10"C, if necessary, by the addition of ice. Ice is then added to the condensation product solution thus obtained to cool said product to 0-50C, and 25.2 parts of a 40% sodium nitrite aqueous solution are then added thereto. To this mixture 30 parts of concentrated hydrochloric acid are added during 5 minutes and the mixture is stirred at 0-100C for 1 hour. Then excess sodium nitrite is decomposed by the addition of sulfamic acid. The diazonium salt solution thus obtained is mixed with 200 parts of urea. 31.4 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved in 400 parts of water at pH 5.5-6.0. The solution is added portionwise to the said diazonium salt solution over 20-30 minutes, the resulting mixture is stirred at 10-15DC, until the 1-amino-8naphthol-3,6-disulfonic acid disappears, (for 8-10 hours), to obtain monoazo solution, the pH being maintained at 3.0-3.5 by adding a 10% sodium carbonate solution. Separately, a condensation product solution is obtained from 16.2 parts aniline-4-sulfonic acid, 17.6 parts of cyanuric chloride and 17.3 parts of 1,4-diaminobenzene-2-sulfonic acid by the same procedure as in said aniline-3-sulfonic acid. To the condensation product there are added 16-8 parts of a 40% sodium nitrite aqueous solution and a further 20 parts of concentrated hydrochloric acid over 5 minutes, and after stirring for 1 hour excess sodium nitrite is decomposed by the addition of sulfamic acid. The diazonium salt solution thus obtained is added to the monoazo solution mentioned above, then the pH is adjusted to 8.0-8.5 by adding sodium carbonate solution. The mixture is stirred for 2 hours at 5-100C while maintaining the same pH by the addition of sodium carbonate aqueous solution and further stirred overnight at room temperature. The next day the pH is adjusted to 6.5 by adding concentrated hydrochloric acid. The mixture is salted to 30% W/V with sodium chloride, the precipitate is filtered off and dried at 40"C in vacuo. Thus a dark-green dye is obtained in a yield of 80% with respect to the H acid. The dye contains more than 1.95 atoms of hydrolysable chlorine per molecule and has analogous dyeing properties to the dye obtained by using only aniline-3-sulfonic acid in place of aniline-3- and 4-sulfonic acid. WHAT WE CLAIM IS:

1. A process for the manufacture of bisazo dyes which, in their free acid form, are represented by the formula:

stands for H and the other stands for SO3H, which comprises coupling a diazonium compound derived from an amine of the formula:

wherein Al and A2 have the same meanings as given above, with 1-hydroxy-8- aminonaphthol-3 .6-disulfonic acid or its salt in an acidic medium in the presence of a coupling accelerator in the ortho position to the amino group and then coupling the monoazo compound thus obtained with a diazonium compound derived from an amine of the formula:

wherein B1 and B2 have the same meanings as given above, in an alkaline medium.

2. A process as claimed in claim 1 wherein the coupling accelerator is thiourea or urea.

3. A process as claimed in claim 1 or claim 2 wherein A1 and B1 are H, and A2 and B2 are SO3H.

4. A process as claimed in claim 1 and substantially as described in any one of the specific examples hereinbefore set forth.

5. Bisazo dyes whenever produced by the process claimed in any preceding claim or by an obvious chemical equivalent thereof.