GB2066283A

GB2066283A - Fibre-reactive dyestuffs

Info

Publication number: GB2066283A
Application number: GB8040437A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1979-12-20
Filing date: 1980-12-17
Publication date: 1981-07-08
Also published as: MY8600696A; HK31884A; DE3046451A1; FR2472002A1; IT8050316A0; GB2066283B; FR2472002B1; ES8303501A1; JPS56100860A; BE904409Q; BR8008409A; ES498022A0; CH643873A5; IT1142199B; KE3635A

Abstract

The present invention relates to compounds of formula I, <IMAGE> in which R1 is hydrogen or sulpho, either R2 is hydrogen, alkyl or hydroxyalkyl, and R3 is alkyl, hydroxyalkyl, HO3-alkyl, HOOC-alkyl or phenyl optionally substituted by up to three substituents from the group consisting of sulpho, carboxy, halogen, alkyl and alkoxy, or, R2 and R3, together with the nitrogen atom form a 6-membered heterocyclic ring optionally containing a further heteroatom, with the proviso that when -NR2R3 is p-sulphoaniline, R1 is hydrogen, R4 is hydrogen or C1-4alkyl, and Hal is fluorine, chlorine or bromine, salts thereof, and mixtures of such compounds which compounds and mixtures are useful as fibre reactive dyestuffs.

Description

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

Accordingly, the present invntion provides compounds of formula

in which R1 is hydrogen or sulpho, either R2 is hydroyen, C14alkyl or 2-, 3-or 4-hydroxyC2~4alkyl, and R3is cl-4alkyl 2-, 3-or 4-hydroxyC24alkyl, HO3S-C,~4alkyl, HOOC-C, 4alkyl or phenyl optionally substituted by up to three substituents selected from the group consisting of sulpho, carboxy, halogen, C,~4alkyi and C, 4alkoxy, or, R2 and R3, together with the nitrogen atom form a 6-membered heterocyclic ring optionally containing a further heteroatom, with the proviso that when -NR2R3 is p-sulphoanilino, R, is hydrogen, R4 is hydrogen or C, 4alkyl, and Hal is fluorine, chlorine or bromine, salts thereof, and mixtures of such compounds.

R, is preferably hydrogen. When R, is hydrogen the sulpho group in ring A is preferably in the 4- or 5-position, especially the 4-position. When R, is sulpho the two sulpho groups are preferably in the 4,6-positions.

Any alkyl as R2 and/or R3 is preferably methyl or ethyl, especially methyl. Any hydroxyalkyl as R2 and/or R3 is preferably hydroxyethyl or hydroxypropyl, especially hydroxyethyl.

Any sulpho- or carboxy-substituted alkyl as R3 preferably contains 1 or 2 carbona atoms, most preferably 2 carbon atoms.

Any alkyl and alkoxy substituents on the phenyl radical as R preferably contain 1 or 2 carbon atoms, and are more preferably methyl or methoxy. Any halogen substituent on the phenyl as is fluorine, chlorine or bromine, with chlorine or bromine, especially chlorine, being preferred.

Any substituted phenyl radical as R2 is preferably substituted by one or two substituents, more preferably 1 or 2 substituents selected from the group consisting of sulpho, carboxy, chlorine, methyl and methoxy. More preferably any substituted phenyl as R3 is 3- or 4-sulphenyl optionally further substituted by chlorine, methyl, methoxy, carboxy or sulpho, especially methyl or sulpho, the further substituent is preferably in the 2-position with the sulpho group in the 4or 5-position.

When R2 and R3 together with the nitrogen atom form a 6-membered heterocyclic ring they preferably form a piperidine or morpholine ring R2 is preferably R2, where R2 is hydrogen, methyl, ethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl or together with the nitrogen atom and R3' forms a piperidine or morpholine ring.

More preferably R2 is Run', where R'.' is hydrogen, methyl or 2-hydroxyethyl, with hydrogen being most preferred.

R, is preferably R4, where R; is methyl, ethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, sulphoor carboxy-C, 2alkyl or phenyl optionally substituted by 1 or 2 substituents selected from the group consisting of sulpho, carboxy, chlorine, methyl and methoxy. More preferably R3 is R3', where R31' is methyl. 2-hydroxyethyl, sulpho- or carboxyethyl, phenyl. 3- or 4-sulphophenyl optionally further substituted by chlorine, methyl, methoxy, carboxy or sulpho.

Even more preferably R3 is R", where B3111 is 2-hydroxyethyl, phenyl, 3- or 4-sulphophenyl, 2- methyl-4-sulphophenyl or 2,5-disulphophenyl.

Still more preferably B3 is R3v, where R3lv is 2-hydroxyethyl, 3- or 4- sulphophenyl, 2-methyl4-sulphophenyl or 2.5-disulphophenyi. Most preferably B3 is B3', where B3 is 3- or 4sulphophenyl, 2-methyl-4-sulphophenyl or 2,5-disulphophenyl.

Alkyl as R4 is preferably methyl or ethyl, especially methyl.

R4 is preferably R4, where R4' is hydrogen or methyl, especially hydrogen.

Hal is preferably fluorine or chlorine, most preferably chlorine.

Preferred compounds of formula I are (1) those wherein R, and the sulpho group in ring A are in the above preferred positions; (2) those wherein R4 is B41, especially hydrogen; (3) those wherein Hal is fluorine or chlorine; (4) those wherein R, is B; and R3 is R3'; (5) those of (4) wherein R2 is R',' and R3 is R3'; (6) those of (5) wherein R3 is R3"; (7) those of (6) where R2 is hydrogen and R3 is R3lV; (8) those of (1) to (7) wherein Hal is chlorine; (9) those of (1) to (8) wherein when R3 is sulphophenyl B1 is hydrogen; (10) those of (1) to (8) in which Rl is hydrogen; (11) those of formula la.

and salts thereof.

The cations of the sulpho group and carboxy groups of the compounds, when in salt form, are not critical and may be any of those non-chromophoric cations conventional for fibre-reactive dyestuffs, for example alkali metal cations and unsubstituted or substituted ammonium cations, such as lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium. Preferred cations are alkali metal and ammonium with sodium being especially preferred.

The present invention still further provides a process for the production of a compound of formula 1, comprising reacting a compound of formula II

or a salt thereof, or a mixture of such compounds, with a compound of formula Ill RyN R2R3 Ill in which either Rx is a radical of formula (a)

and Ry is hydrogen or Ry is a radical of formula (a) and Rx is hydrogen.

The preferred process is one in which Ry is a radical of formula (a).

The condensation may be effected in accordance with known methods, preferably in a weakly acid to weakly alkaline medium. The reaction temperature may be between room temperature and 65"C. Suitable acid binding agents include sodium carbonate, sodium bicarbonate, sodium hydroxide and triethylamine.

The compounds of formula II and Ill where Rx and Ry are hydrogen are either known or may be prepared by known methods. Similarly the compounds of formulae li and III wherein Bx and Ry signify a radical of formula (a) may be prepared in accordance with known methods by condensing the corresponding compound wherein Rx resp. Ry is hydrogen with cyanuric halide.

The condensation reation may be effected in accordance with known methods as described above for the reaction of the compound of formula II with the compound of formula Ill However, owing to the ease with which the first halogen atom is replaced, the reaction may be conducted at a lower temperature, preferably at a temperature between O and 5,C.

The compounds of formula I are isolated in accordance with known methods, e.g. by salting out, filtering and drying in vacuo.

The compounds of formula I and mixtures thereof are useful as fibre reactive dyestuffs for dyeing and printing hydroxy group-containing or nitrogen-containing organic substrates. Preferred substrates are leather and textile materials comprising or consisting of natural or synthetic polyamides such as wool, silk and nylon and natural regenerated cellulose such as cotton, viscose or spun rayon.

The dyes may be employed in dyebaths or in printing pastes for dyeing or printing according to known methods. The dyes may also be employed in conjunction with other dyestuffs.

The dyestuffs give a good dye yield, have good build-up power and have good fixation properties in particular they give a good fixation yield.

The dyeings and prints obtained have good wetfastness such as wash-, sweat-, water- and chlorine-fastness. The dyeings are resistant to peroxide bleaches and possess good lightfastness.

In printing, the sharpness of the contours, the ability to remove unbound dyestuff by washing and the paste stability are noteworthy. In padding processes the solubility of the dyes and the stability of padding liquor are good as in the fastness of the dyeings obtained and the ability to remove unbound dyestuff.

The following Examples further serve to illustrate the present invention. In the Examples all parts are by weight and the temperatures are in degrees Centigrade.

EXAMPLE 1 94.5 Parts 2-amino-1-hydroxybenzene-4-sulphonic acid are stirred in 300 parts water and after the addition of 1 5 parts 30% hydrochloric acid are diazotized with 1 27 parts 4N sodium nitrite solution at O to 5" in a period of 60 minutes.

167.5 Parts 1-amine-8-hydroxy-naphthalene-3,6-disulphonic acid are stirred in 625 parts water and are dissolved at pH 6.5 by the addition of sodium hydroxide solution. After the addition of 50 parts sodium bicarbonate and 46 parts sodium chloride and ice thereto, the diazonium solution is added dropwise at 3 to 6" over 90 minutes. The coupling mixture is stirred for 6 hours at 3 to 6" and subsequently the temperature is allowed to rise to 20 . The monoazo compound obtained is salted out at pH 7 by the addition of 310 parts sodium chloride and is filtered.

The dyestuff is stirred in 900 parts water and 45 parts 30% sodium hydroxide solution. 420 Parts of a one molar copper sulphate solution are added dropwise at 50 to 60 over a period of 2 to 3 hours, the pH being maintained at 5 with 30% sodium hydroxide solution.

84.5 Parts sulphanilic acid are dissolved in 553 parts water at pH 7. This solution is added dropwise at O to 5"C within an hour to a mixture of 87.5 parts cyanuric chloride and 140 parts water/ice mixture. The pH is kept at 3 to 4 with a 20% soda solution.

The sulphanilic acid - cyanuric chloride condensate is added dropwise to the solution of the coppered monoazo compound and the reaction temperature is gradually increased to 40 to 45 .

The pH is held at 5 to 6 with 20% soda solution. The pH is then adjusted to 7 and the solution is made clear with some activated charcoal. The dye is finally salted out at 40 with 800 parts sodium chloride, filtered at 30 and dried. The dye which is of formula

gives dyeings and prints, of reddish-violet shades with good fastness on natural and regenerated cellulose. (Aeraax (H20) 552 nm) EXAMPLE 2 86.5 Parts sulphanilic acid are dissolved in 500 parts water with the addition of aqueous sodium hydroxide and diazotized as described in Example 1.A filtered solution of 189.5 parts of the potassium salt of 1-acetylamino-8-hydroxynaphthalene-3,6-disulphonie acid in 750 parts water is cooled and adjusted to pH 6.5. The diazotized suspension is pumped into this solution in an hour at 8 , whereby the pH is maintained at 6.5 with a soda solution. The dyestuff formed, for the most part precipitates from the solution. The solution is diluted to 3000 parts by volume with water and the whole is stirred overnight at room temperature.

To the dye suspension is added 500 parts of a 1-molar copper sulphate solution and 50 parts sodium acetate. At 1 5' 90 parts sodium perborate are shaken in over a period of 2 hours, subsequently 40 parts of a 30sub hydrogenperoxide solution are added dropwise in 1 hour. The reaction temperature is gradually raised to 40 and the mixture is stirred at 40 for 3 hours. The copper containing dye is salted out at room temperature with 500 parts sodium chloride and 2500 parts methanol, and filtered off. The paste obtained is stirred after having being adjusted to 1000 parts by volume with water. The splitting off of the acetyl group is effected by hydrolysis for 4 hours at 60t with 50 parts solid sodiumhydroxide.The whole is adjusted to pH 5 and the product is isolated with 225 parts sodium chloride and filtered at 40 .

The paste product is again adjusted to 1000 parts by volume with water and stirred.

Approximately, 50 parts cyanuric chloride are shaken in portionwise and condensation is effected for 5 hours at O to 5"C, the pH being kept at 5 with soda solution.

56.1 Parts 1-amino-2-methylbenzene-4-sulphonic acid in 450 parts water are added dropwise at 60 within approximately 4 hours to the dyestuff solution thus obtained. The pH is kept at 5 with soda solution. The dyestuff gradually precipitates. The pH is adjusted to 6.5 and the dye is filtered off.

The filtered dye is dissolved in 1 500 volume parts water at 50 . The solution is filtered clear with the addition of some activated charcoal, subsequently the dye is salted out with 1 50 parts sodium chloride filtered and dried. The product of formula

(Amax (H2O) 560nm) gives dyeings and prints on natural and regenerated cellulose in bluish-violet shades with good fastnesses.

In analogy with the procedure of Examples 1 or 2 further compounds given in Tables 1 and 2 may be prepared. The compounds correspond to formula I, wherein R4 is hydrogen and the other symbols are given in the Tables. The dyestuffs are also obtained in the sodium salt form and they give dyeings and prints of the indicated shades on natural and regenerated cellulose whereby a = reddish-violet and b = bluish-violet.

Table 1

l3;lSi3n) r jBai R2 R3 J 3 4 H C1 H cH3 a 4 4 a C1 H -cu2CH2oH a 5 4 H Cl -CH2cH2oH -CHZCHZOH a 6 4 H C1 CH3 4 a 7 4 H F H S03Na a 8 4 H C1 H SO3Na a SO a 9 4 H C1 H t S03Na a CH3 10 4 H C1 CH3 -CH2CH2SO3Na a 11 4 a F H -CH2CH20H a 12 5 H ci H CH3 b 13 5 H C1 H -CH2Cll2OH I b 14 5 H Cl H 42 b SO3Na 15 5 N F H tS03Na b 16 4 503Na(6) Cl H do. 3 b i7 H X, Cl H do. b 18 4 do. Cl H CH3 b 19 4 do. C1 -CH2CH20II -CH2CH2OH b b 20 4 do. C1 H A 4 do. Cl H 03Na b 22 4 do. Cl b b Table 2

I- < . oositon No. lof So 3 R Hal -NR2R in rind A in ring A 23 4 H ci 1 / CIt2c'i \a12- 2 a 24 5 II ci do. b 24 cll2--cu 25 4 H C1 -U O CH2CH2/ a cN2-cH;,,, 26 4 S03a(6) C1 do. b EXAMPLE A 2 Parts of the dye of Example 1 are dissolved in 100 parts warm water (ca. 40 ) to which 10 parts urea have been added. 30 Parts 10% sodium carbonate and 0.5 parts sodium salt of 1nitrobenzene-3-sulphonic acid are added thereto. Spun rayon fabric is impregnated with this solution (take-up 75% of dry weight).After drying, the fabric is steamed for 5 to 10 minutes at 102", rinsed and soaped at the boil for 1 5 minutes. After drying a reddish-violet dyeing with good fastnesses is obtained.

EXAMPLE B 2 Parts of the dyestuff of Example 7 are dissolved in 50 parts water and 20 parts urea at 20 .

After the addition of 1 5 parts 10% sodium carbonate the solution is made up of 100 parts by volume. The solution is padded onto 20 parts cotton fabric (take-up 80% of the dry weight).

After intermediate drying the fabric is steamed at 103 for 10 minutes, rinsed, soaped at the boil, rinsed again and dried. A reddish-violet dyeing with good fastnesses is obtained.

EXAMPLE C Mercerised cotton satin is printed in accordance with known methods with a printing paste containing: 25 parts dye of Example 1 100 parts urea 440 parts water 400 parts 4% sodium alginate 10 parts sodium salt of 1 -nitrobenzene-3-sulphonate 25 parts sodium bicarbonate.

The printed textile is steamed for 4-8 minutes at 102-104"C and then cold- and hot- rinsed.

After hot-soaping followed by rinsing and drying, a reddish-violet print with good light- and wetfastness is obtained.

Claims

1. A compound of formula I

in which R, is hydrogen or sulpho, either R2 is hydrogen, C,~4alkyl or 2-, 3- or 4-hydroxyC2~4alkyl, and R3 is Ci 4alkyl, 2-, 3- or 4- hydroxyC2~4alkyl, HO3S-C1 4alkyl, HOOC-C,~4alkyl or phenyl optionally substituted by up to three substituents selected from the group consisting of sulpho, carboxy, halogen, C1 4alkyl and C1 4alkoxy, or, R2 and R3, together with the nitrogen atom form a 6-membered heterocyclic ring optionally containing a further heteroatom, with the proviso that when -NR2R3 is p-sulphoanilino, Rains hydrogen, R4 is hydrogen or C1 4aIkyl, and Hal is fluorine, chlorine or bromine, salts thereof, and mixtures of such compounds.

2. A compound according to Claim 1, in which R2 is R2,, where R2' is hydrogen, methyl, ethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl or together with the nitrogen atom and R3' forms a piperidine or morpholine ring and R3 is B3', where R3' is methyl, ethyl, 2-hydroxyethyl, 2- or 3hydroxypropyl, sulpho- or carboxy-C,~2aikyl or phenyl optionally substituted by 1 or 2 substituents selected from the group consisting of sulpho, carboxy, chlorine, methyl and methoxy.

3. A compound according to Claim 1 or Claim 2, in which R2 is R2', where R2' is hydrogen, methyl or 2-hydroxyethyl and R3 is R3', where R3" is methyl or 2-hydroxyethyl, sulpho- or carboxyethyl, phenyl, 3- or 4- sulphophenyl optionally further substituted by chlorine, methyl, methoxy, carboxy or sulpho.

4. A compound according to any one of Claims 1 to 3, in which, when R1 is sulpho, the sulpho groups in ring A are in the 4,6-positions and when R1 is hydrogen the sulpho group is in the 4- or 5-position.

5. A compound according to any one of the preceding Claims, in which R4 is hydrogen or methyl.

6. A compound according to any one of the preceding Claims, in which Hal is fluorine or chlorine.

7. A compound according to any one of the preceding Claims, in which Hal is chlorine.

8. A compound according to any one of the preceding Claims, in which R3 is R3", where R3" is 2-hydroxyethyl, phenyl, 3- or 4-sulphophenyl, 2-methyl-4-sulphophenyl or 2,5-disulphophenyl.

9. A compound according to any one of the preceding Claims, in which R2 is hydrogen and R3 is RB', where R3iV is 2-hydroxyethyl, 3- or 4-sulphophenyl, 2-methyl-4- sulphophenyl or 2,5disulphophenyl.

10. A compound according to any one of the preceding Claims, in which, when R3 is sulphophenyl, R, is hydrogen.

11. A compound according to any one of the preceding Claims, in which R1 is hydrogen.

1 2. A compound of formula la

in which R3' is 3- or 4-sulphophenyl, 2-methyl-4-sulphophenyl or 2,5-disulphophenyl, or a salt thereof.

1 3. A compound of formula

in salt form.

14. A compound according to any one of Examples 2 to 26 in salt form.

1 5. A process for the production of a compound of formula I as defined in Claim 1, comprising reacting a compound of formula 11,

or a salt thereof, or a mixture of such compounds, with a compound of formula III RyNR2R3 Ill in which either R, is a radical of formula (a)

and Ry is hydrogen or Ryis a radical of formula (a) and Rx is hydrogen.

16. A process according to Claim 15, in which Ry is a radical of formula (a).

1 7. A process for the production of a compound of formula I, substantially as hereinbefore described with reference to any one of Examples 1 to 26.

1 8. A compoound of formula I whenever obtained by a process according to any one of Claims 15 to 17.

1 9. A process for dyeing or printing hydroxy group- or nitrogen-containing organic substrates comprising applying a compound according to any one of Claims 1 to 14 or 18 thereto, as dyeing or printing agent.

20. A process according to Claim 19, in which the substrate consists of or comprises cotton, viscose or spun rayon.

21. A process for dyeing or printing hydroxy group- or nitrogen-containing organic substrates substantially as hereinbefore described with reference to any one of Examples A, B and C.

22. Dyed or printed substrates whenever obtained by a process according to any one of Claims 19 to 21.