GB2127840A

GB2127840A - Chloro-triazinyl monoazo compounds

Info

Publication number: GB2127840A
Application number: GB08324170A
Authority: GB
Inventors: Werner Koch
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1982-09-13
Filing date: 1983-09-09
Publication date: 1984-04-18
Also published as: JPH0522738B2; BE904411Q; GB2127840B; FR2532943A1; HK91686A; MY8700164A; IT8348959A0; FR2532943B1; SG30789G; CH655734A5; KE3886A; DE3331861A1; IT1170482B; GB8324170D0; JPS5966459A; DE3331861C2

Abstract

The present invention provides compounds of the formula, <IMAGE> in which either R1 is hydrogen or hydroxy-C2-3alkyl, and R2 is hydroxy-C2-3alkyl, or, R1 is hydrogen or 2-cyanoethyl, and R2 is -CH2CH2OCH2CH2OH, and mixtures of such compounds, which compounds are in free acid or salt form, and are useful for dyeing or printing hydroxy group- or nitrogen- containing organic substrates, especially leather and textiles containing or consisting of natural or synthetic polyamides or of natural or regenerated cellulose; the most preferred substrate is textile material containing or consisting of cotton.

Description

SPECIFICATION Improvements in or relating to organic compounds - The present invention relates to chloro-triazinyl monoazo compounds, their preparation and use as fibre-reactive dyestuffs.

More particularly, this invention provides compounds which, in the free acid form, correspond to formula I,

in which either R, is a hydrogen or hydrnxy-C23alkyl, and R2-is hydroxy-C2~3alkyl or, R, is hydrogen or 2-cyanoethyl, and R2 is -CH2CH20CH2CH20H, and mixtures of such compounds, which compounds are in free acid or salt form.

In any hydrnxysubstkuted alkyl group the hydroxy group is bound to a carbon atom other than to the C,-atom; Preferred compounds of formula I are those in which any hydroxyalkyl as R1 and/or R2 is 2hydroxyethyl. More preferred are compounds of formula I, where R, is hydrogen or 2-hydroxyethyl and R2 is 2-hydroxyethyl. Most preferred is the compound, wherein R1 is hydrogen and R2 is 2-hydroxyethyl.

Preferred mixtures of compounds of formula I are those in which in a compound AR1 is hydrogen and R2 is 2-hydroxyethyl, and in a compound B R, and R2 are both 2-hydroxyethyl, Preferably, these mixtures contain the compounds A and B in a molar ratio range of from 90:10 to 10:90, more preferably 75:25 to 25:75: The cations of the sulpha groups when the compounds of formula I are in salt form may be any of those nori-chromophoric cations common in the chemistry of reactive dyestuffs. Examples of suitable cations are'alkali metal cations and unsubstituted or substituted ammonium ions, such as lithium, sodium, potassium, ammonium, mono-, di-, tri and tetra-methylammonium, triethylammonium and mono-, di-and-tri-ethanolammonium.

The preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.

TheEpresent invention further provides a process for the preparation of the compounds of formula I comprising reacting the following components: -the diazotized amino compound of formula II,

-the coupling component of formula Ill,

- cyanuric chloride, and - a compound of formula IV, HNR,R2 IV or a mixture thereof, which components must be present in the corresponding stoichiometric molar ratio to obtain a compound of formula I - by coupling and condensing in any desired order.

More particularly, it is preferred to prepare the compounds of formula I by condensing a compound of formula V,

in free acid or salt form, with a compound of formula IV HNR,R2 IV or a mixture thereof.

Diazotization and coupling reaction may be effected in conventional manner. The replacement of the chlorine atoms in cyanuric chloride by separate condensation steps may be effected in accordance with conventional methods, e.g., the replacement of the first chlorine atom may be carried out at temperatures of from 0 to 1 OOC, preferably atO0 to 500The replacement of the second chlorine atom may be effected at temperatures of from 200 up to 550C in an alkaline medium.

The compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali metal salt, filtering and drying in a vacuo. Depending on the reactionand isolation-conditions a compound of formula l-is obtained in free acid or preferably salt form or even mixed salt forms containing, for example, one or more of the above mentioned cations. It may be converted from free acid form to a salt form or mixture of salt forms or vice versa or from one salt form to another by conventional means.

The starting materials, compounds of formula Il, Ill and IV, are either known or may be prepared in accordance with known methods from available starting material.

The compounds of formula I and mixtures thereof which are preferably in salt form, are useful as reactive dyestuffs for dyeing or printing hydroxy group- or nitrogen-containing organic substrates.

Preferred substrates are leather and textiles containing or consisting of natural or synthetic polyamides such as wool, silk and nylon, 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 effected in accordance with known methods. Since the compounds of formula I exhaust well from the dyebath they are suitable for all conventional dyeing processes using the exhaust dyeing method. They may be applied according to conventional methods per se or in combination with appropriate other fibre-reactive dyestuffs having analogous dyeing properties and, since they are well compatible, also in important three component dye mixtures. The dyeing obtained with such combination mixtures have good fastness properties and do not show catalytic fading.

Since the reactivity of the compounds of formula I to the substrate is not temperature dependent in the usual dyeing temperature ranges dyeing may be effected equally well at 1000C as at 800C without any loss of fixation yield, even in some cases the fixation yield will be increased at 1 00 C.

Evidently, the dyestuffs of the present invention are hydrolysis resistant at high temperatures and passing over the dyeing temperature will not be critical to the fixation yield.

Advantageously, a dyeing temperature at about 1000C may be applied because dyestuffs migrate better at high temperatures thus giving more even.dyeings.

Furthermore, the compounds of this invention are notably well soluble in water, even in electrolyte-containing dyeing liquors. The dyeings obtained with the compounds of formula I show good light fastness and wet fastness properties, e.g., wash-, water- and sweat-fastness. Further, they have good fastness to chlorinated water, peroxide and perborate-containing wash liquors.

The following examples further serve to illustrate the invention. In the examples all parts and percentages are by weight or volume and the temperatures are in degrees Centrigrade.

EXAMPLE 1 75.8 Parts 2-aminonaphthalene-4,8-disulphonic acid are diazotized in accordance with known methods. To the resulting diazo suspension a solution 34.3 parts 2-amino-I -methoxy-4-methylbenzene in a mixture of water and hydrochloric acid are added dropwise, and coupling is effected whilst gradually adding a total amount of 42.5 parts sodium bicarbonate with stirring. After four hours the resulting monoazo dyestuff is isolated by heating the reaction mixture to 600C and adding hydrochloric acid up to pH 1. The dyestuff which precipitates is filtered and washed with a solution of a mixture of water, sodium chloride and 30% hydrochloric acid.

The thus obtained product is stirred in 1000 parts water and completely dissolved by the addition of ca. 25 parts 30% sodium hydroxide solution to give a medium with pH 8. This solution is stirred overnight. After the addition of 500 parts ice the temperature is reduced to - I . Subsequently, 46 parts cyanuric chloride are added, the condensation reaction starts at about 70. The reaction is completed in approximately two hours whereby the temperature is raised to 300 for the last hour.

For the next condensation step 1 9.8 parts monoethanol diluted with 50 parts water are added to the reaction mixture within 5 minutes whereby the pH rises to 11.2. Stirring is effected for 1 5 minutes and the temperature is then elevated to 500. After a further 20 minutes stirring the pH falls to 7 and stirring is continued for approximately three hours. Then, further 2 parts monoethanolamine diluted with water are added and stirring is continued until a pH of ca. 8.8 is reached which remains unchanged.

The product is isolated by portionwise adding of 300 parts sodium chloride, filtering and drying in a vacuo at 600 C. The thus obtained dyestuff which in form of the free acid corresponds to the formula

is highly soluble in water and dyes cotton in yellow shades. The dyeings show good light fastness and wet fastness properties.

Ln analogy with the method described in Example 1 but using instead of monoethanolamine the corresponding amount of other mono or disubstituted amines or a mixture of such amines further compounds-of formula I are obtained-which are listed in the following Table. These dyes or mixtures of dyes-also give yellow dyeings on cotton.

Example No. R1 R2 2 -CH2CH2OH -CH2CHOH 3 -CH2CH2CN -CH2CH2-OCH2CH2OH 4 H do.

5 -CH2CH2OH 75% by weight 5 -CH2CH2OH do. | 25% by weight The preparation of a dye mixture containing different groups -NR1R2, e.g., the mixture of Example 5,. may be carried out by stepwise reaction first with 3/4 mole equivalent of monoethanolamine and second with 1/4 mole equivalent of diethanolamine but using a 30% excess of the last component. This condensation is effected-at 400 and pH during ten hours.

In accordance with the reaction and isolation-conditions as described the dyestuffs of Examples 1 to 5-are obtained in the sodium salt form. They may, depending on the reaction-/isolation-conditions or by reacting the sodium salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms containing one or more cations indicated in the description hereinbefore.

In the following examples the application of the dyestuffs of this invention is illustrated.

APPLICATION EXAMPLE A To a dyebath consisting of 1000 parts water, 20 parts Glauber's salt (calcinated), 2.5 parts sodium carbonate (calcinated) and 1 part of the sodium salt of 1 -nitrobenzene-3-sulphonic acid 50 parts mercerized cotton fabric are added. The bath is heated to 400, then 1 part of the dye of Example 1 is added. The temperature is raised to 980 within 45 minutes; during this time 20 parts Glauber's salt (calcinated) are added after 1 5 minutes and again 20 parts Glauber's salt (calcinated) are added after further 15 minutes. At the end of this time 7.5 parts sodium carbonate (calcinated) are added. Dyeing is continued at the boil for 45 to 60 minutes. Subsequently, the dyed fabric is rinsed hot and soaped at the boil for 20 minutes in 500 parts water and 0.5 parts sodiumalkylsulphonate.After rinsing and drying a yellow cotton dyeing with good fastness properties is obtained.

APPLICATION EXAMPLE B To a dyebath consisting of 1000 parts water, 60 parts Glauber's salt (calcinated), 1 5 parts sodium carbonate (calcinated) and 1 part of the sodium salt of 1 -nitrobenzene-3-sulphonic acid 50 parts of cotton fabric are added. The bath is heated to 600. Subsequently 1.5 parts of the dye of Example 1 are added. The temperature is kept at 600 for 1 5 minutes and is then raised to 980 within 30 minutes.

Dyeing is continued for 45-60 minutes at 980. The dyed fabric is rinsed hot and soaped according to the method given in Application Example A. After rinsing and drying a yellow cotton dyeing is obtained having good fastness properties.

APPLICATION EXAMPLE C 1 Part of the dyestuff of Example 1 is dissolved in 2000 parts water. 100 Parts cotton fabric are added and the temperature of the dyebath is raised to 800 with 10 minutes. 100 parts Glauber's salt (calcinated) are added and 30 minutes thereafter, 20 parts sodium carbonate (calcinated). Dyeing is continued for one hour at 800. Subsequently, the dyed fabric is rinsed cold, then hot, and is soaped according to the method given for Application Example A. After rinsing and drying a yellow cotton dyeing is obtained having good fastness properties.

Similarly, the dyes or mixtures of Example 2 to 5 may be employed to dye cotton in accordance with the method given for Application Example A, B or C.

Claims

1. A compound of formula I,

and mixtures thereof, in which either R, is hydrogen or hydroxy C2~3alkyl, and R2 is hydroxy-C2~3alkyl, or R, is hydrogen or 2-cyanoethyl, and R2is-CH 2CH2OCH2CH2OH, which compounds and mixtures are- in free acid or salt form.

2. A compound or mixture according to Claim 1, wherein R1 is hydrogen or 2-hydroxyethyl and R2 is 2-hydroxyethyl.

3. A compound according to Claim 1, wherein R, is hydrogen and R2 is 2-hydroxyethyl, which compound is in free acid or salt form.

4. A mixture according to Claim 2, consisting of compound A which is a compound of formula I wherein R, is hydrogen and R2 is 2-hydroxyethyl, and of compound B which is a compound of formula I wherein R1 and R2 are both 2-hydroxyethyl.

5. A mixture according to Claim 4, containing the compounds A and B in molar ratio range from 90:10 to 10:90.

6. A mixture according to Claim 5, wherein said molar ratio range is of from 75:25 to 25:75.

7. A compound or mixture according to any one of Examples 2 to 5.

8. A process for the preparation of a compound of formula I as defined in Claim 1, or a mixture thereof, comprising reacting the following components: -the diazotized amino compound of formula II,

-the coupling component of formula III,

- cyanuric chloride, and - a compound of formula IV, HNR,R2 IV or a mixture thereof, wherein R, and R2 are as defined in Claim 1, which components must be present in the corresponding stoichiometric molar ratio range to obtain a compound of formula I - by coupling and condensing in any desired order.

9. A process according to Claim 8, to prepare a compound of formula I by condensing a compound of formula V,

in a free-acid or salt form, with a compound of formula IV, HNR,R2 IV wherein R, and R2 are as defined in Claim 1, or a mixture thereof.

10. A process for the preparation of a compound of formula I, as defined in Claim 1, or a mixture therepf, substantially as hereinbefore described with reference to any. one of Examples 1 to 5.

1 A;compound of formula I or a mixture thereof, whenever obtained by a process according to any dne of Claims 8 to 10.

12. A process for dyeing or printing hydroxy group- or nitrogen-containing organic substrates comprising åpplying a compound of formula I- or a mixture thereof according to any one of Claim 1 to 7 or 11. as dyeing or printing agent.

1 3. A process according to Claim 12, wherein said substrate is leather or a textile containing or consisting of natural or regenerated cellulose.

14. A process according to Claim 13, wherein said substrate is a textile containing or consisting of cotton.

1 5. Dyed or printed substrates whereverobtained by a process according-to any one of Claims 12 to 14.