Reactive azo dyes with an aminonaphthalenesulf onic acid coupling component and intermediates therefor

The present invention relates to novel reactive dyes of the for ^¬ mula I

where

n is 1 or 2 ,

G ¹ is hydrogen or hydroxyl,

G ² is hydrogen or hydroxysulfonyl,

G ³ is hydrogen or a radical of the formula

E R ¹ is hydrogen or hydroxysulfonylmethyl,

R ² is hydrogen or hydroxysulfonylmethyl, and

D is, when n is 1, a radical of the formula

R4

E or, when n is 2, a radical of the formula

where the ring A may be benzofused, R ³ , R ⁴ and R ⁵ are each independently of the others hydrogen, Cχ-C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or hydroxysulfonyl, E is hydrogen, a heterocyclic anchor radical or a anchor radical of the aliphatic series, Y is vinyl or a radical of the formula C ₂ H ₄ -Q, where Q is an alkali-detachable group, and T is a bridge member,

with the proviso that at least one hydroxysulfonylmethyl group shall be present in the molecule and that dyes of the formula

where n, D and G ² are each as defined above, shall be excluded,

to their use for dyeing or printing hydroxyl-containing or ni¬ trogenous organic substrates and to naphthylamines as intermedi' ates therefor.

The above-excluded dyes and intermediates are known from prior patent application WO 9610610.

It is an object of the present invention to provide novel reactive dyes derived from phenyl- or naphthalene-azo-naphthalene dyes. The novel dyes shall have an advantageous application property profile.

We have found that this object is achieved by the reactive dyes of the formula I defined at the beginning.

The novel reactive dyes of the formula I are each indicated in the form of the free acid, but salts thereof are also encompassed by the claims, of course.

Suitable cations are derived from metal or ammonium ions. Metal ions are in particular the lithium, sodium or potassium ions. Ammonium ions for the purposes of the present invention are sub¬ stituted or unsubstituted ammonium cations. Substituted ammonium cations include for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkyl-ammoniu cations or cations derived from nitrogenous five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium or piperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted prod- ucts. Alkyl is generally to be understood as meaning straight- chain or branched Cι-C ₂ o~alkyl which may be substituted by 1 or 2 hydroxyl groups and/or interrupted by from 1 to 4 oxygen atoms in ether function.

jAny alkyl or alkylene herein can be straight-chain or branched.

Any substituted alkyl herein generally contains 1 or 2 substitu¬ ents.

Any substituted phenylene herein contains for example, unless otherwise stated, Cχ-C ₄ -alkyl, Ci-C ₄ -alkoxy, halogen, hydroxysulfonyl, sulfamoyl or mono- or di-Cι-C -alkylsulfamoyl as substituents. Substituted phenylene then generally contains from 1 to 3, preferably 1 or 2, substituents.

R ³ , R ⁴ and R ⁵ are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, fluorine, chlorine or bromine.

Q is an alkali-detachable group . Such groups include for example chlorine , bromine, Cι-C ₄ -alkylsulfonyl , phenyl sulfonyl , OS0 ₃ H, SSO ₃ H, OP (0) (OH) ₂ , Cι-C ₄ -alkylsulfonyloxy, subs ti tuted or unsubstituted phenylsulfonyloxy, Cι-C ₄ -alkanoyloxy, Cι~C ₄ -dialkyl - amino or a radical of the formula

where L ¹ , L ² and L ³ are each independently of the others Cι-C ₄ - alkyl or benzyl and An® is in each case one equivalent of an anion. Suitable anions include for example fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methane- sulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate.

Ancnor radical-. undergo substitutive or additive reactions with the hydroxyl or nitrogenous groups of the substrates to be treated.

The fact that the anchor radical reacts substitutively with the relevant groups in the substrates, for example with the hydroxyl groups of cellulose, means that the leaving groups or atoms (eg. fluorine or chlorine) in the anchor radical are replaced by the hydroxyl groups of the cellulose as per the following scheme:

Cl

X ^{^} X ₊ HO- (cellulose) N O— (cellulose)

N :N

The fact that the anchor radical reacts additively with the rele¬ vant groups in the substrates, for example with the hydroxyl groups of cellulose, means that the hydroxyl groups of the cellu- lose are added to the anchor radical as per the following scheme:

-S0 ₂ -CH=CH ₂ + HO— (cellulose) -S0 ₂ -CH ₂ -CH ₂ -O— (cellulose)

Heterocyclic anchor radicals E include for example halogen-con¬ taining radicals derived from the following basic heterocyclic species: 1, 3, 5-triazine, quinoxaline, phthalazine, pyrimidine or pyridazine or the 2-alkylsulfonylbenzothiazole radical.

The following are particularly suitable heterocyclic radicals:

where

X is hydrogen or Cι-C ₄ -alkyl,

Hal is fluorine or chlorine,

U ¹ is hydrogen or nitro, and

U ² and U ³ are each independently of the other hydrogen, Cι-C ₆ -alkyl with or without substitution by hydroxyl, halogen, cyano, hydroxysulfonyl or a radical of the formula -S0 ₂ -Y, where Y is as defined above, and with or without interruption by one or two oxygen atoms in ether function or nonadjacent imino or Cι-C -alkylimino groups, or

U ² and U ³ are together with the nitrogen atom joining them together pyrrolidinyl, piperidinyl, orpholinyl, piperazinyl or N- (Cι-C ₄ -alkyl)piperazinyl,

or else U ² may also be a radical of the formula

-#

in which case the rings B and K may each be singly or doubly hydroxysulfonyl-substituted and/or benzofused and ring K may independently be monosubstituted or disubstituted by chlo- rine, nitro, Cι~C -alkyl, Cι-C ₄ -alkoxy, cyano, carboxyl, acetylamino, hydroxysulfonylmethyl or a radical of the formula CH ₂ -S0 ₂ -Y, S0 ₂ -Y, NH-CO-Y or NU ² -CO-NU ² -Z-S0 ₂ -Y, where Y and U ² are each as defined above and Z is C ₂ -C ₆ -alkylene with or without substitution by hydroxyl, chlorine, cyano, carboxyl, Cι-C -alkoxycarbonyl, Cχ-C -alkanoyloxy or sulfato and with or without interruption by 1 or 2 oxygen atoms in ether function or nonadjacent imino or Cι-C ₄ -alkylimino groups.

Aliphatic anchor radicals E include for example acryloyl, mono-, di- or trichloroacryloyl, mono-, di- or tribromoacryloyl, -CO- CCl=CH-COOH, -CO-CH=CCl-COOH, 2-chloropropionyl,

1, 2-dichloropropionyl, 1, 2- ibromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl, 2, 3, 3-tri- fluoro-2-chlorocyclobutylcarbonyl, 2,2,3, 3-tetrafluoro- cyclobutylcarbonyl, 2, 2 , 3, 3-tetrafluorocyclobutylsulfonyl,

2- (2,2, 3, 3-tetrafluorocyclobutyl)acryloyl, 1- or 2-alkyl- or 1- or 2-aryl-sulfonylacryloyl, such as 1- or 2-methylsulfonyl- acryloyl, or a radical of the formula S0 ₂ -Y, W ¹ -S0 ₂ -Y, CONX- W -S0 ₂ -Y or NXCONX-W ² -S0 ₂ -Y, where X and Y are each as defined above, W ¹ is Cι-C ₄ -alkylene and W ² is Cι-C ₄ -alkylene or substituted or unsubstituted phenylene.

W ¹ and W ² are each for example CH ₂ , (CH ₂ ) , (CH ) ₃ , (CH ₂ ) ₄ , CH(CH ₃ )CH ₂ or CH (CH ₃ )CH(CH ₃ ) .

W ² may further be for example 1,2-, 1,3- or 1, 4-phenylene.

T in the formula I is a bridge member. Suitable bridge members conform for example to the formula

NX- NX NX CO- NX CO or S0 ,

where p is 0 or 1 and Hal, W ² , X and Z are each as defined above.

Particularly suitable bridge members are radicals of the formula

Hal

N-"^;N

-XN- NX- CO or S0 ₂ ,

of which CO and S0 are preferred.

When n is 2, D preferably conforms to the formula

_ _ _T _Q_ _S02- ,

where E, Y and- T are each as defined above,

Preference is given to reactive dyes of the formula I where R ³ , R ⁴ and R ⁵ are each hydrogen.

Preference is further given to reactive dyes of the formula I where E is hydrogen, a anchor radicals of the 1,3, 5-triazine se¬ ries or a radical of the formula S0 -Y, where Y is as defined above.

Preference is further given to reactive dyes of the formula I where T is a radical of the formula CO or S0 ₂ when n is 2.

Preference is further given to reactive dyes of the formula I where n is 1.

Preference is further given to reactive dyes of the formula I where the ring A is not benzofused.

Preference is further given to reactive dyes of the formula Ia

where n and D are each as defined above.

Preference is further given to reactive dyes of the formula lb

where n, D, G ² and R ¹ are each as defined above.

Preference is further given to reactive dyes of the formula Ic

where n, D and R ² are each as defined above.

Preference is further given to reactive dyes of the formula Id

where G ³ is a radical of the formula

^E and n, D, the ring A, E, R ³ , R ⁴ , R ⁵ and Y are each as defined above.

Particular preference is given to reactive dyes of the formula I where E is hydrogen or a radical of the formula S0 ₂ -Y, where Y is as defined above.

Particular preference is further given to reactive dyes of the formula I, in particular of the formulae I a-d, where the radical of the formula S0 ₂ -Y is disposed ortho to the azo group.

The novel reactive dyes of the formula I are obtainable in a con¬ ventional manner.

For example, an aniline of the formula lla or lib

where the ring A, R ³ , R ⁴ , R ⁵ , E, Y and T are each as defined above, can be diazotized or tetraazotized in a conventional manner and coupled with aminonaphthalene of the formula III

where G ¹ , G ² , R ¹ and R ² are each as defined above.

The anilines of the formula lib are obtainable in a conventional manner, for example as described in prior patent application DE-A-195 08 311.

The present invention further provides naphthylamines of the for¬ mula III

where

G ¹ is hydrogen or hydroxyl,

G ² is hydrogen or hydroxysulfonyl.

R ¹ is hydrogen or hydroxysulfonylmethyl, and

R ² is hydrogen or hydroxysulfonylmethyl

witn tne proviso that at least one hydroxysultonylmethyl group shall be present in the molecule, and that naphthylamines of the formula

where G ² is as defined above, shall be excluded.

Preference is given to naphthylamines of the formulae Ilia to IIIC

SO ₃ H

where G ² , R ¹ and R ² are each as defined above.

The novel naphthylamines of the formula III are obtainable in a conventional manner.

For example, a naphthylene derivative of the formula IV

where G ¹ and G ² are each as defined above, can be reacted in a basic medium with the addition product of an alkali metal bisulfite with formaldehyde, eg. formaldehyde sodium bisulfite of the formula HOCH ₂ S0 ₃ Na.

By partial hydrolysis in the alkaline region the hydroxysulfonyl- amino group can also be converted back into the free amino group.

The novel reactive dyes of the formula I are advantageously use¬ ful for dyeing or printing hydroxyl-containing or nitrogenous or- ganic substrates. Such substrates include for example leather or fiber material predominantly comprising natural or synthetic polyamides or natural or regenerated cellulose. The novel dyes are preferably useful for dyeing and printing textile material based on wool and in particular on cotton. The dyeings obtained have red shades.

Cellulose-based substrates in particular are dyed with a very high yield of fixation in strong dyeings having very good light- fastness and also excellent wetfastness properties, such as wash, chlorine bleach, peroxide bleach, alkali, seawater or perspira¬ tion fastness properties.

The Examples which follow illustrate the invention.

Example 1

a) 149 g (0.5 mol) of 2-aminonaphthalene-5-sulfonic acid were suspended in 750 ml of water and dissolved by adding sodium hydroxide solution. 106 g (0.75 mol) of formaldehyde sodium bisulfite were added at pH 6.5 a little at a time and the

mixture was stirred .at 60°C for 4 h. 200 g of sodium chloride were added to precipitate the product of the formula

to obtain 449 g (0.4 mol) of a moist paste.

15 g (0.05 mol) of 4- (2-sulfatoethylsulfonyDaniline were suspended in 200 ml of ice-water, admixed with 15 ml of ION hydrochloric acid and diazotized at 0-5°C by the dropwise addition of 15 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5°C for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 56 g (0.05 mol) of the compound described under a) , and the reaction solution was held at a pH of from 2.5 to 3 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was adjusted to 5-5.5 with so¬ dium carbonate. 300 ml of methanol and 2 1 of acetone were added to obtain 27 g (0.044 mol) of the scarlet dye of the formula

λ _ma x (water) :483 nm.

The following- dyes were obtained in a similar manner:

Example 2

(water) :495 nm

Example 3

x (water) : 514 nm

Example 4

Example 5

ter):514 nm

Example 6

a) 207 g (0.5 mol) of 2-amino-8-hydroxynaphthalene-3,6-disul- fonic acid were suspended in 750 ml of water and dissolved by adding sodium hydroxide solution. 176.5 g (1.25 mol) of form¬ aldehyde sodium bisulfite were added at pH 8.5 a little at a time and the mixture was stirred at 60°C for 20 h. 350 g of potassium chloride were added to precipitate the product of the formula

to obtain 523 g of a moist paste.

b) 523 g of the compound prepared under a) were suspended in 800 ml of water and admixed with 75 ml (1.35 mol) of aqueous sodium hydroxide solution and stirred at 80°C for 7 h. After the reaction had ended, a pH of 3 was set with dilute hydro¬ chloric acid and the dye was salted out with 300 g of potas¬ sium chloride to obtain 182.5 g (0.35 mol) of a beige solid of the formula

c) 25 g (0.05 mol) of 3- (2-sulfatoethylsulfonyl)aniline-4,6-di- sulfonic acid were suspended in 200 ml of ice-water, admixed with 15 ml of ION hydrochloric acid and diazotized at 0-5°C by the dropwise addition of 15 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at from 0 to 5°C for 3 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 26 g (0.05 mol) of the compound described under b) , and the reaction solution was held at a pH of from 2.5 to 3 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was ad¬ justed to 5-5.5 with sodium bicarbonate. Precipitation with a methanol/ acetone mixture yielded 38.3 g (0.044 mol) of a reddish violet dye of the formula

λ _max (water):544 nm.

The following dyes were obtained in a similar manner:

Example 7

λ _ma (water):529 nm

Example 8

Example 9

Example 10

a) 129 g (0.5 mol) of 2-amino-8-hydroxynaphthalene-6-sulfonic acid were suspended in 750 ml of water and dissolved with sodium hydroxide solution. 176.3 g (1.25 mol) of formaldehyde sodium bisulfite were added a little at a time at pH 8-8.5 and the mixture was stirred at 60°C for 9 h. After the reac¬ tion had ended, the product was precipitated with 300 g of sodium chloride to obtain 447 g (0.41 mol) of a beige solid of the formula

b) 15 g (0.05 mol) of 2- (2-sulfatoethylsulfonyDaniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5°C by the dropwise addition of 15 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5°C for

2 hours, -the small _. excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 55 g (0.05 mol) of the compound described under a) , and the reaction solution was held at a pH of from 2.5 to 3 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was adjusted to 5-5.5 with sodium bicarbonate. Precipitating with the methanol/acetone mixture yielded 37.9 g (0.047 mol) of a reddish violet dye of the formula

λ _max (water):542 nm.

The fol lowing dyes were obtained in a similar manner :

Example 11

Example 12

Example 13

ter): 537 nm

Example 14

26 nm

Example 15

a) 129 g (0.5 mol) of 2-amino-8-hydroxynaphthalene-6-sulf onic acid were suspended in 750 ml of water and dissolved with sodium hydroxide solution. 176.3 g (1.25 mol) of formaldehyde sodium bisulfite were added a little at a time at pH 8-8.5 and the mixture was stirred at 60°C for 9 h. After the reaction had ended, 137.5 ml (2.5 mol) of 50 % strength by weight sodium hydroxide solution were added and the mixture

was heated- at 90°C for 1.5 h. Thereafter it was adjusted to pH 5 with dilute hydrochloric acid, and the precipitate was filtered off. The paste was suspended in 800 ml of water and admixed with 100 ml of saturated aqueous sodium chloride solution to obtain 208 g (0.358 mol) of a moist paste of the formula

b) 13.5 g (0.045 mol) of 2- (2-sulfatoethylsulfonyl)aniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5°C by the dropwise addition of 13.5 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5 ^c C for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 31 g (0.045 mol) of the compound prepared under a), and the reaction solution was held at a pH of from 3.5 to 4 with sodium acetate. After the reaction had ended, the reaction mixture was warmed to room temperature, and the pH was adjusted to 5-5.5 with sodium bicarbonate. The product was precipitated by adding 100 g of sodium chloride to obtain 34 g (0.041 mol) of a red dye of the formula

r _nax (water) : 522 nm.

The following dyes were obtained in a similar manner :

Example 16

Example 17

Example 18

Example 19

a) 386 g (1.5 mol) of 2-amino-5-hydroxynaphthalene-7-sulfonic acid were suspended in 2250 ml of water and dissolved with sodium hydroxide solution. 318 g (2.25 mol) of formaldehyde sodium bisulfite were added at pH 5 and the mixture was stirred at 60°C for 4 h. After the reaction had ended, the resulting product of the formula

was not isolated but used as a coupling component in solu¬ tion.

14.5 g (0.05 mol) of 3- (2-sulfatoethylsulfonyl)aniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5°C by dropwise addi¬ tion of 15 ml of 23 % strength by weight aqueous sodium ni¬ trite solution with stirring. After stirring at 0-5°C for 3 hours, the small excess of nitrous acid was destroyed with sulfamic acid.

106 ml (0.053 mol) of the solution described under a) were admixed with ice and adjusted to pH 3 with dilute hydrochlo¬ ric acid. The diazonium salt solution was added dropwise to this solution while a pH of 2.5-3 was maintained with sodium acetate. After the reaction had ended, the mixture was warmed to room temperature and the pH was adjusted to 5-5.5 with sodium bicarbonate. The dye was precipitated by adding 150 g of potassium chloride and 50 g of sodium chloride. Filtration left 37.5 g (0.048 mol) of a scarlet dye of the formula

The following dyes were obtained in a similar manner:

Example 20

Example 21

Example 22

a) 2 1 (1.0 mol) of the solution described in Example 19a) were adjusted to pH 8.5 with sodium hydroxide solution and heated to 60°C. At that temperature, 70.5 g (0.05 mol) of formalde¬ hyde sodium bisulfite were added and the mixture was stirred at 60°C for 2 hours. After the reaction had ended, the re¬ sulting compound of the formula

was not isolated but used in solution as coupling component.

b) 14.5 g (0.05 mol) of 3- (2-sulfatoethylsulfonyl) aniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5°C by dropwise addi¬ tion of 15 ml of 23 % strength by weight aqueous sodium ni¬ trite solution with stirring. After stirring at 0-5°C for 3 hours, the small excess of nitrous acid was destroyed with sulfamic acid.

112 ml (0.053 mol) of the solution described under a) were admixed with ice and adjusted to pH 3 with dilute hydrochlo¬ ric acid. The diazonium salt solution was added dropwise to this solution while a pH of 2.5-3 was maintained with sodium acetate. After the reaction had ended, the mixture was warmed to room temperature and the pH was adjusted to 5-5.5 with sodium bicarbonate. The dye was precipitated by adding 200 g of sodium chloride. Filtration left 47.8 g (0.045 mol) of a scarlet dye of the formula

The following dyes were obtained in a similar manner :

Example 23

Example 24

Example 25

a) 1.05 1 (0.5 mol) of the solution described in Example 22 a) were heated to 60°C and admixed a little at a time at that reaction temperature with a total of 137.5 ml (2.5 mol) of 50 % strength by weight sodium hydroxide solution. After the reaction had ended, the pH was adjusted to 5 with dilute hydrochloric acid and 200 g of sodium chloride were added to isolate 497 g (0.33 mol) of moist paste of the formula

b) 14.5 g (0.05 mol) of 3- (2-sulfatoethylsulfonyl)aniline were suspended in 200 ml of ice-water, admixed with 20 ml of ION hydrochloric acid and diazotized at 0-5°C by the dropwise addition of 15 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5°C for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. To this solution were added 74 g (0.05 mol) of the compound prepared under a) and the reaction solution was held at pH 3.5-4 with sodium acetate. After the reaction had ended, the mixture was warmed to room temperature and the pH was adjusted to 5-5.5 with sodium bicarbonate. Precipitating with a methanol/ethanol mixture yielded 35.1 g (0.042 mol) of the dye of the formula

The following dye was obtained in a similar manner:

Example 26

Example 27

35.3 g (0.075 mol) of 3- (2-sulfatoethylsulfonyl)aniline-4, 6-di- sulfonic acid were suspended in 300 ml of ice-water, admixed with 30 ml of ION hydrochloric acid and diazotized at 0-5°C by dropwise addition of 22.5 ml of 23 % strength by weight aqueous sodium nitrite solution with stirring. After stirring at 0-5 ^* C for 2 hours, the small excess of nitrous acid was destroyed with sulfamic acid. 70 ml (0.035 mol) of the solution described in Example 19 a) were admixed with ice and adjusted to pH 3 with dilute hydrochloric acid. Half the diazonium salt solution was added dropwise to this solution while the pH was held within the range from 2.5 to 3 with sodium acetate. After the coupling in the ortho position to the amino group was complete, the pH was raised to 5-5.5 and the rest of the diazonium salt solution was added dropwise. Precipitating with methanol/ethanol mixture yielded 50.3 g (0.034 mol) of a scarlet dye of the formula

HO3S N

SOC ₂ H OS0 ₃ H λ _max (water) :490 nm

The following dyes were obtained in a similar manner:

Example 28

λm _a x (water): 510 nm

Example 29

SO ₂ C H ₄ 0SO ₃ H

λmax (water): 494 nm

Example 30

Example 31

_m a (water) :500 nm Example 32

λm _a x (water) :495 nm Example 33

λmax (water) :492 nm

Example 34

Example 35

Example 36

λma (water) :490 nm