FIELD OF INVENTION

The resent invention relates to compounds of the formula (1 )

(1 )

The present invention further relates to a process for the preparation of the compounds of the formula (1 ) and intermediates used for manufacturing of dyestuffs of the formula (1 ).

BACKGROUND OF THE INVENTION

Today's requirements in reactive dyes for coloration of cellulose fibres are high colour yield and good build-up with excellent fastness. The presently known dyes for medium to dark shades are mostly azo dyes, often with two identical or different chromophores built in one molecule, containing several reactive groups of the vinylsulfone types or mixed bifunctional groups such as vinylsulfone and monochlorotriazine. Such know dyes of state of the art are described in the patent applications US 5,548,071 , US 4,485,041 , EP 478,503, EP 776,947, and EP 775,732 or EP 626,429.

EP 623.655 describes dyes of the general formula

X

A

n.— R N wherein D1 is a radical of a dye chromophore, X is halogen, substituted pyridine or optionally substituted amino, hydroxyl, alkoxy or alkylthio - preferably halogen, and D is a radical of the formula

wherein Z is benzene or naphthalene radical carrying a fibre reactive group of the vinylsulfonyl type.

EP 957,137 describes mixtures of d es of the general formulae (1 ) and (2)

where M is hydrogen, ammonium, an alkali metal or the equivalent of an alkaline earth metal, R1 is hydrogen or sulfo, R2 is hydrogen or sulfo, X1 and X2 are each fluorine, chlorine, amino, which may be mono- or disubstituted by lower alkyl or optionally substituted aryl and one of the radicals possesses a group of the formula -S02-Y1 or - S02-Y2, where Y1 and Y2 are each vinyl or ethyl substituted in the beta -position by an alkali-eliminable grouping, or X1 and X2 are each optionally substituted morpholino or pyrimidino, cyanoamino, hydroxyl, lower alkoxy or optionally substituted aryloxy and where the groups -S02-Y1 and -S02-Y2 are attached to the benzene nucleus meta or para to the azo or amino group.

However, these dyes have certain disadvantages and limitations such as limited build-up, low fixation yields, low solubility, poor washing and contact fastness, as well as ecological disadvantages. The present invention discloses novel fibre-reactive dyes which are suitable for dyeing from aqueous bath and printing of fibre materials containing cellulose, polyamide or protein fibre materials, and blends containing such fibre materials.

The dyes of the present invention carrying two reactive groups of the vinylsulfone type overcome these limitations have excellent fixation yield and excellent build-up. They can achieve very deep shades with very good fastness to washing, water, acid and alkaline perspiration (contact fastness).

OBJECT OF THE INVENTION

It is an object of the present invention to provide novel fibre-reactive and water soluble yellow, orange, brown and red dyes carrying two vinylsulfone reactive groups which are in the form of free acid of the formula (1 ) or the salts thereof.

It is another object of the present invention to provide water soluble dyestuffs to achieve very deep shades with better fastness to washing, and contact fastness to water, acid and alkaline perspiration.

It is yet another object of the present invention to provide a process for the preparation of the dyestuffs of the formula (1 ).

SUMMARY OF THE INVENTION

According to one aspect of the invention there is provided Water soluble dyestuffs having two vinylsulfone reactive groups in the form of free acid of the formula (1 ) and salts thereof

(1 ) wherein

X is -NHCN, -NHR, -N (CH ₃ ) R, -O- R, or - or X is a heterocyclic radical of the formula — W

wherein W has one of the meanings of R,

wherein R is selected from C1 -C6-Alkyl, which is substituted by at least one sulfo, sulfato, phosphate, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy;

R _a is Hydrogen or C1 -C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo,

R _b has one of the meanings of R _a ,

is a radical of the benzene or naphthalene series which is substituted by amino, hydroxy, Acylamino, Ureido, C1 -C3 alkoxy, C1 -C3 alkyl, halogen, nitro or carboxy groups and is optionally further substituted by 1 or 2 Sulfo groups;

K ₂ has one of the meanings of K _{1 ;}

is a benzene or naphthalene radical which is non-substituted or substituted by one or more substituents selected from sulfo, C1 -C4 alkyl, C1 -C4 alkoxy or halogen,

D2 has one of the meanings of D1 ,

Y is Vinyl or CH2CH2-L in which L is a leaving group selected from groups such as sulfato, acetato, halogen, such as chloro or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,

wherein dyestuffs of the formula (1 ) in which X is NHCN, K1 and K2 are both 8-hydroxy- 3,6-disulfo-napth-1 -yl and Y0 ₂ S-Di and D ₂ S0 ₂ Y are both either 4-( β- sulfatoethylsulfonyl)phenyl- or 2-sulfo-4-(B-sulfatoethyl-sulfonyl) phenyl are excluded. According to another aspect of the invention, there is provided novel intermediates of formula (5) X

(so ₃ H)

(SO3H)

(5)

According to another aspect of the invention, there is provided a process for manufacturing dyestuffs of the formula (1 ), by azo coupling reaction of diazotized and Y0 ₂ S- D ₂ NH ₂ followed by coupling with components of the formula (5).

According to another aspect of the invention, there is provided a process for manufacturing dyestuffs of the formula (1 ), by step-wise condensing monoazo dyestuffs of the formula NHRa and Y0 ₂ S-D ₂ N=N-K2NHR _b with compounds of the formula Hal ₂ cyX ,wherein Hal is chloro or fluoro , cy is 1 ,3,5-triazinyl and X has one of the above meanings.

According to another aspect of the invention, there is provided a process for manufacturing asymmetrical dyestuffs of the formula (1 ), by first synthesizing an intermediate of the formula Y0 ₂ S-D ₁ N=N-K1 NR _a -cyXHal, then condensing with K2NR _b and finally coupling with diazotized Y0 ₂ S-D ₂ NH ₂ .

According to another aspect of the invention, there is provided a process for manufacturing asymmetrical dyestuffs of the formula (1 ) by condensing a compound of the formula Y0 ₂ S- DiN=N-K1 NR _a -cyHal- NRb-K2-N=N-D2-S02Y with a compound of the formula HX, in aqueous solution at pH values and temperatures which are common for condensations and azo couplings of halogenated triazine compounds.

DETAILED DESCRIPTION

The dyestuffs of the present invention are water soluble yellow, orange, brown and red dyestuffs carrying two vinylsulfone reactive groups which are in the form of the free acid of the formula 1 )

(1 ) wherein

is a radical of the benzene or naphthalene series which is substituted by amino, hydroxy, acylamino, ureido, and optionally further substituted by 1 or 2 sulfo groups, and optionally substituted by CrC ₃ -alkoxy, CrC ₃ alkyl, halogen, nitro, or carboxy.

K ₂ has independently of the meaning of Ki one of the meanings of K _{1 ;}

X is -NHCN, -NHR, -N(CH ₃ ) R, -O- R , or -S- R wherein R is CrC ₆ -alkyl, preferably CrC ₃ , which is substituted by at least one sulfo, sulfato, phosphato, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy, or a heterocyclic radical of the formula

wherein W has one of the meanings of R, preferably β-sulfatoethyl, and in particular, X is preferably cyanamino, 2-sulfoethylamino, N-methyl- 2-sulfoethyl- amino, 2-sulfatooethylamino, carboxymethylthio, carboxyethyloxy or a radical of the formula

R _a is hydrogen or CrC ₄ -alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo, preferably R _a is hydrogen or methyl,

R _b has independently of R _a one of the meanings of R _a

Y is vinyl or CH ₂ CH ₂ L, wherein L is a leaving group which is split off under alkaline conditions, such as sulfato, acetato, halogen, such as chloro or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy, preferably Y is vinyl or β-sulfatoethyl, is a benzene or naphthalene radical of the formula (2a) or (2b) which may be non- substituted or substituted by one or more substituents sulfo, Ci -C ₄ -alkyl, Ci-C ₄ -alkoxy, or halogen,

wherein R ₃ is preferably methoxy, methyl, chloro or bromo, n is 0, 1 or 2, and m is 0 or 1 , and in case n=2 the radicals R ₃ may have identical or different meanings, and in case (2b) m is 0 or 1 .

D ₂ has independently of the meaning of Di one of the meanings of Di .

Suitable radicals Y include vinyl, 2-sulfatoethyl, 2-chloroethyl, 2-bromoethyl, 2- acetoxyethyl, 2-phenoxyethyl, 2-phosphatoethyl, 2-thiosulfatoethyl. Preferably Y is vinyl or 2-sulfatoethyl.

The dyestuffs of the formula (1 ) wherein X is NHCN, Ki and K ₂ are both 8-hydroxy-3,6- disulfo-napth-1 -yl and Y0 ₂ S-Di and D ₂ S0 ₂ Y are both either 4-(β- sulfatoethylsulfonyl)phenyl- or 2-sulfo-4-(B-sulfatoethyl-sulfonyl)phenyl- are excluded. Preferably formula (2a) in D1 independent of D2 is one of the following radicals

wherein Y is Vinyl or β-sulfatoethyl

Preferably formula (2b) in D1 independent of D2 is one of the following radicals

wherein Y is Vinyl or β-sulfatoethyl. K NR _a - is preferably a radical of the formula (3a), (3b) or (3c) of the benzene or series or a radical (4) of the naphthalene series,

(3a) (3b) (3c)

wherein

R ₀ is hydrogen or methyl, preferably hydrogen

Ri is hydrogen, methyl, or ethyl, preferably hydrogen,

R ₂ is amino or methyl,

r is 0-1 ,

Preferably K ₂ -NR _b has independently of K NR _a one of the meanings of K NR _a, wherein the radicals R ₀ , Ri , R2 and r have one of the above meanings. Preferably formula (3a) is one of the following radicals

Preferably formula (3b) is the following radical Preferably formula (3c) is one of the followin radicals

Preferably formula (4) is ne of the following radicals

Examples of suitable radicals X include cyanamino, sulfomethylamino-, 2- sulfoethylamino, N-methyl-2-sulfoethylamino, 3-sulfopropylamino-, 2-sulfato-ethylamino-,

3- sulfato-propylamino, 2-carboxyethylamino, carboxymethylthio-, 2-carboxyethylthio , 2- carboxyethyloxy-, carboxymethyloxy-, 2-phosphatoethylamino, 2-thiosulfoethylamino, 3- phosphatopropylamino, 3-thiosulfopropylamino.

Examples for preferred radicals D ₁ S0 ₂ Y and D ₂ S0 ₂ Y in formula (1 ) are

4- (2 ^' -sulfatoethylsulfonyl)phenyl,

2-sulfo-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

3-(2 ^' -sulfatoethylsulfonyl)phenyl,

2-sulfo-5-(2 ^' -sulfatoethylsulfonyl)phenyl,

2-(2 ^' -sulfatoethylsulfonyl)phenyl,

2-methoxy-5-(2 ^' -sulfatoethylsulfonyl)phenyl, 2-methoxy-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

4-methoxy-3-(2 ^' -sulfatoethylsulfonyl)phenyl,

2-chloro-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

2,6-dichloro-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

2-brom-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

2,6-dibromo-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

2.5- dimethoxy-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

2-methoxy-5-methyl-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

4- methyl-5-(2 ^' -sulfatoethylsulfonyl)phenyl,

2.6- dimethyl-4-(2 ^' -sulfatoethylsulfonyl)phenyl,

6-(2 ^' -sulfatoethylsulfonyl)napth-2-yl,

5- (2 ^' -sulfatoethylsulfonyl)napth-2-yl,

8-(2 ^' -sulfatoethylsulfonyl)napth-2-yl,

1 -sulfo-6-(2 ^' -sulfatoethylsulfonyl)napth-2-yl,

6- sulfo-8-(2 ^' -sulfatoethylsulfonyl)napth-2-yl,

Preferred radicals and -NRb-K ₂ -N=N-D2-S0 ₂ Y in formula (1 ) are, independently of each other, radicals of the formula

11

wherein the reactive group β-sulfatoethylsulfonyl is drawn in the form of its sulfuric acid form but can likewise be the alkali metal salt thereof, especially sodium salt, or it can be in the form of vinylsulfonyl to which it is easily converted upon exposure to alkaline medium, and the sulfo groups are drawn in the form of its sulfuric acid form as well, but can likewise be the alkali metal salt thereof, especially sodium salt. This illustration form is used in all further structures drawn of preferred embodiments or preferred radicals

The dyes can be symmetrical (K _{1 =} K ₂ and D _{1 =} D ₂ ) or asymmetrical (Ki<>K ₂ and/or D ₁ oD ₂ ). Of the dyes in the present invention, such dyes are especially preferred which contain in each of the radicals D ₁ -N=N-K ₁ and K ₂ -N=N-D ₂ at least one sulfo group.

In particular, especially preferred dyestuffs for dyes of the present invention are the dyestuffs of the formula (1 .1 ), (1 .2), (1 .3), (1 .4), (1 .5) and (1 .6)

wherein

R1 is hydrogen or methyl, preferably hydrogen,

R2 ^' is methyl or amino,

X is Cyanamino, N(CH3)-CH ₂ CH ₂ -S0 ₃ H , NH-CH ₂ CH ₂ -S0 ₃ H, S-CH ₂ -COOH, 0-( CH ₂ ) ₂ - COOH, or a radical of the formula

Y is Vinyl or β-sulfatoethyl.

Furthermore, of the dyestuffs (1.1) to (1.6) such dyestuffs containing at least one sulfo group in the radicals and K ₂ NR _b are especially preferred.

Of the structures (1.1) the dyes of the formula (1.1a), (1.1. b) and (1.1. c) are especially preferred.

YO ₂ S

(1.1. a)

In particular, examples for dyes of the present invention are the following dyestuffs

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

5

15 Example 13

Example 14

Example

Example 16

Example 17

Example 18

Example 19

22 Example 24

Example 25 The novel dyestuffs can be in the form of the free acid or their salts, preferably in the form of the salts, especially the alkali metal and alkaline earth metal salts, and in particular in the form of their sodium, potassium or lithium salts. The novel dyestuffs are preferably used in the form of their alkali metal salts for dyeing and printing fibre materials.

Intermediates of the formula (5)

wherein the radicals Q1 and Q2 are independent from each other amino or hydroxy, preferably amino, Ro is hydrogen or methyl, preferably hydrogen, and X has one of the meanings as defined above, are also part of the present invention. These intermediates are suitable as coupling components in the manufacturing of the dyestuff of the present invention.

Especially preferred are intermediates of the formula (5) wherein Q is amino and X Cyanamino, N(CH3)-CH ₂ CH ₂ -S0 ₃ H , NH-CH ₂ CH ₂ -S0 ₃ H, S-( CH ₂ )i_ ₂ -COOH, 0-( CH ₂ ) COOH, or a radical of the formula

Manufacturing:

The present invention also relates to different processes for manufacturing of the novel dyestuffs of formula (1 ) (wherein cyX stands for 2-X-4, 6-triazinyl-) such as:

a) A process for manufacturing dyestuffs of the formula (1 ), by azo coupling reactions of diazotized Y0 ₂ S-D ₁ NH ₂ and Y0 ₂ S-D ₂ NH ₂ on coupling components of the formula (5).

b) A process for manufacturing dyestuffs of the formula (1 ),by step-wise condensing monoazo dyestuffs of the formula NHR _a and Y0 ₂ S-D ₂ N=N- K2NHR _b with compounds of the formula Hal ₂ cyX ,wherein Hal is chloro or fluoro , cy is 1 ,3,5-triazinyl and X has one of the above meanings,

c) A process for manufacturing dyestuffs of the formula (1 ), in case of asymmetrical dyes by first synthesizing an intermediate of the formula NR _a -cyXHal, then condensing with K2NRb and finally coupling with diazotized YO2S-D2NH2.

d) A process for manufacturing dyestuffs of the formula (1 ) in case of asymmetrical dyes by condensing a compound of the formula NR _a -cyHal- NRb- K2-N=N-D2-S02Y with a compound of the formula HX, in aqueous solution at pH values and temperatures which are common for condensations and azo couplings of halogenated triazine compounds.

The dyes of the present invention can be preferably prepared by different methods involving the following steps:

a) In case D _{1 =} D ₂ , by first preparing the coupling component KrNR _a -cyX-NR _b -K ₂ , then coupling with freshly diazotized YC^S-D Nh^ at pH 1 -8 and at a temperature of 0-40 °C, preferably pH 3-7 and at a temperature of 0-25 °C,

b) In case D ₁ oD ₂ , by preparing the K NR _a -cyX-hal wherein hal is CI or F , then couple with freshly diazotized Y0 ₂ S-Di-NH _a at pH 1 -8 and at a temperature of 0-40 °C, preferably pH 3-7 and at a temperature of 0-25 °C which will yields the intermediate monoazo dye Y02S-Di-N=N-KrNR _a -cyX-cl, then condensation with either K ₂ NRb, followed by coupling with YO ₂ S-D ₂ NH ₂ at pH 1 -8 and at a temperature of 0-40 °C, preferably pH 3-7 and at a temperature of 0-25 °C, or alternatively by condensation with K ₂ NR _b -N=N-D ₂ S0 ₂ Y at pH 4-7 and a temperature of 40-90 °C.

c) By coupling first freshly diazotized Y0 ₂ S-Di-NH ₂ at pH 1 -8 and at a temperature of 0- 40 °C, preferably pH 3-7 and at a temperature of 0-25 ^< Ό, with K ₁ -NHR ₁ to yield the monofunctional monoazo dye to yield Y0 ₂ S-D ₁ -N=N-K ₁ -NR _a -cyX-Hal which is finally reacted with another monofunctional dye K ₂ -NHR ₂ -N=N-D ₂ -S02Y to yield the product Y0 ₂ S-Di-N=N-Ki- NR _a -cyX-K ₂ -NR _b -N=N-D ₂ -S02Y , wherein Ki and K ₂ as well as and D ₂ have different or identical meanings.

d) By coupling first freshly diazotized Y0 ₂ S-D NH ₂ at pH 1 -8 and at a temperature of 0- 40 °C, preferably pH 3-7 and at a temperature of 0-25 ^< Ό, with K NHR _a to yield the monofunctional monoazo dye then reacted in two steps with cyXhal ₂ and K ₂ NHR ₂ , in 1 st step at pH 2-7 and at a temperature of 0-5 °C and in 2 ^nd step at pH 3-7 and at a temperature of 30-85 °C to yield a secondary coupling component of the formula Y02S-DrN=N-Ki-NR _a -cyX-NRb-K ₂ which is finally coupled with freshly diazotized H ₂ N-D ₂ -S0 ₂ Y to yield the product -cyX- K2-NR ₂ -N=N-D ₂ -S02Y, wherein Ki and K ₂ as well as Di and D ₂ have different or identical meanings.

e) By preparing the compound -cy(hal)-K ₂ -NR _b -N=N-D ₂ -S0 ₂ Y wherein hal is chloro or fluoro, and replacing by the substituent X in the last step at pH 4-8 and at a temperature of 30-95 °C

In route (A) the coupling component KrNR _a -cyX-NR _b -K ₂ is prepared in the following alternative methods

(A1 ) Condensation of 2,4,6-trichlorotriazine with HX at a temperature of 0-5 °C and pH 2-7, followed by 2 ^nd condensation with K NHR _a at a temperature of 20-60 °C and pH 4-7, and subsequently 3 ^rd condensation with NHR _b -K ₂ , HX at a temperature of 40-95 °C and pH 5- 7.

(A2) Condensation of 2,4,6-trichlorotriazine with K NHR _a at a temperature of 0-5 °C and pH 2-7, followed by 2 ^nd condensation with NHR _b -K _2. at a temperature of 20-60 °C and pH 4-7, which will yield K NR _a cyCI-NR _b K ₂ and subsequently 3 ^rd condensation with HX at a temperature of 40-95 °C and pH 5-7.

(A3) condensation of 2, 4, 6-trichlorotriazine with K NHR _a at a temperature of 0-5 °C and pH 2-7, followed by 2 ^nd condensation with HX. at a temperature of 20-60 °C and pH 4-7, which will yield K NR _a cyX-CI and subsequently 3 ^rd condensation with NHR _b -K ₂ at a temperature of 40-95 °C and pH 5-7

(A4) condensation of 2,4,6-trifluorotriazine with HX at a temperature of -5-10 °C and pH 2- 7, followed by 2 ^nd condensation with K NHR _a at a temperature of 0-15 °C and pH 4-7, and subsequently 3 ^rd condensation with NHR _b -K _2, HX at a temperature of 20-60 °C and pH 5- 7.

(A5) condensation of 2,4,6-trifluorotriazine with K NHRi at a temperature of -5-10°C and pH 2-7, followed by 2 ^nd condensation with NHR ₂ -K ₂ at a temperature of 0-15 °C and pH 4-7, which will yield K NR _a cyF-NR _b K ₂ and subsequently 3 ^rd condensation with HX at a temperature of 20-60 °C and pH 5-7.

(A6) condensation of 2,4,6-trifluorotriazine with K NHRi at a temperature of -5-10°C and pH 2-7, followed by 2 ^nd condensation with HX at a temperature of 0-15 °C and pH 4-7, which will yield K NR _a cyX-F and subsequently 3 ^rd condensation with NHR ₂ -K ₂ at a temperature of 20-60 °C and pH 5-7.

In route (B) the coupling component the K1 -NR _a -cyX-Hal is prepared as described under A3 or A6. The diazotization of the aromatic amines D NH ₂ and D ₂ NH ₂ used in the methods a) to e) are carried out by generally known methods, in presence of acid, in particular hydrochloric acid or sulfuric acid, and sodium nitrite at a temperature of -5 to 25 °C, preferably at a temperature of 0-5 °C.

Examples for compounds of the formula KrNHR _a and K ₂ -NHR _b are

1 ,3-diamino-benzene, 4-sulfo-1 ,3-diamino-benzene, 4-methyl-1 ,3- diaminobenzene, 2,4- disulfo-1 ,3-diamino-benzene, 1 -hydroxy-3-amino-benzene, 1 -amino-3- acetylaminobenzene, 1 -amino-3-ureido-benzene, 4-sulfo-1 -amino-3-acetylaminobenzene 1 -hydroxy-8-amino-3,6-disulfo-naphthalin, 1 -hydroxy-8-amino-3,5-disulfo-naphthalene, 1 - hydroxy-6-amino-3-sulfo- naphthalene, 1 -hydroxy-7-amino-3-sulfo- naphthalene

Aromatic amines of the formula D NH ₂ and D ₂ -NH ₂ are known form various publications, such as the German patent applications Nos. 1.278.041 , 1 .276.842, 1 .150.163, 1 .126.542, 1 .153.029.

Examples for such diazo compounds of the aromatic amines of the formula Di-NH ₂ and D ₂ -NH ₂ are

4-(2 ^' -sulfatoethylsulfonyl)phenylamine,

2- sulfo-4-(2 ^' -sulfatoethylsulfonyl)phenylamine

3- (2 ^' -sulfatoethylsulfonyl)phenylamine,

2-sulfo-5-(2 ^' -sulfatoethylsulfonyl)phenylamine,

2-(2 ^' -sulfatoethylsulfonyl)phenylamine,

2-methoxy-5-(2 ^' -sulfatoethylsulfonyl)phenylamine,

2-methoxy-4-(2 ^' -sulfatoethylsulfonyl)phenyl amine,

4- methoxy-3-(2 ^' -sulfatoethylsulfonyl)phenyl amine,

2-chloro-4-(2 ^' -sulfatoethylsulfonyl)phenylamine,

2,6-dichloro-4-(2 ^' -sulfatoethylsulfonyl)phenylamine

2-bromo-4-(2 ^' -sulfatoethylsulfonyl)phenylamine,

2,6-dibromo-4-(2 ^' -sulfatoethylsulfonyl)phenylamine

2.5- dimethoxy-4-(2 ^' -sulfatoethylsulfonyl)phenylamine,

2-methoxy-5-methyl-4-(2 ^' -sulfatoethylsulfonyl)phenylamine,

4- methyl-5-(2 ^' -sulfatoethylsulfonyl)phenylamine

2.6- dimethyl-4-(2 ^' -sulfatoethylsulfonyl)phenylamine,

6-(2 ^' -sulfatoethylsulfonyl)napth-2-yl-amine,

5- (2 ^' -sulfatoethylsulfonyl)napth-2-yl-amin, 8-(2 ^' -sulfatoethylsulfonyl)napth-2-yl-amin,

1 -sulfo-6-(2 ^' -sulfatoethylsulfonyl)napth-2-aminyl-,

6-sulfo-8-(2 ^' -sulfatoethylsulfonyl)napth-2-yl-amin,

The novel dyestuffs can be in the form of the free acid or in the form of their salts. They are preferably in the form of the salts, especially the alkali metal and alkaline earth metal salts, and in particular in the form of their sodium, potassium or lithium salts. The novel dyestuffs are preferably used in the form of their alkali metal salts for dyeing and printing fibre materials. Application

The present invention further provides a process for dyeing from aqueous bath and printing of fibre materials containing hydroxyl and/or amino groups with the dyes of the present invention. In particular, cellulose, natural cellulose fibres such as cotton, linen or hemp, especially cotton, and regenerated cellulose such as viscose or Lyocell, polyamide fibres such as nylon 6, nylon 6.6 or protein fibres such as wool or silk are preferred fibre materials.

The dyes are also suitable for dyeing and printing of fibre blends containing the mentioned cellulose, polyamide or protein fibre materials.

The dyes of the invention can be applied to and fixed on the fibre material in various ways, in particular in the form of aqueous dye solutions and print pastes. They are suitable for known application techniques which are established for the application of reactive dyes, in particular exhaust method, padding methods, whereby the material is impregnated with aqueous, salt containing or salt free solutions of the dyes, and fixed after alkali treatment or in presence of alkali with or without heating, and printing methods, conventional or digital (ink jet) printing. After fixing, the dyeing and prints are rinsed and thoroughly washed with cold or hot water containing auxiliary agents such as detergents or surfactants that promote the wash-off of unfixed portions. Examples for suitable alkali used for fixation include alkali hydroxide, alkali carbonate, alkali silicate, of which sodium hydroxide, sodium carbonate, sodium silicate are in particular preferred. The amounts wherein the dyes are applied in the dye baths can vary according to the desired depth of shade, generally amounts of 0.01 to 10 % per weight of fabric are suitable, in particular 0.2 to 8%.

The dye bath may contain additions of auxiliaries such as inorganic salt, preferably sodium chloride or sodium sulfate, to support the exhaustion of the dyes onto the fibre material, and in padding process urea, and in printing applications thickening pastes such as alginate thickenings.

In exhaust dyeing process, the preferred procedure is dyeing from an aqueous batch, in presence of 20-100 g/L salt, sodium chloride or sodium sulfate, and a liquor ratio of 1 :2 to 1 :50, preferably 1 :3 to 1 :30, at a dye bath pH of 7-13, preferably 9-1 1 , and a temperature of 40-90, preferably 45-65 ^< Ό.

The dyeing obtained with the dyes of the present invention has excellent fixation yield and excellent build-up. The obtained dye-fibre bond is of high stability not only in the acid but also in the alkaline range, also good light fastness and very good wash fastness, even in deep shades, as well as good contact fastness to water, and perspiration.

Moreover, the dyeing obtained with the dyes of the present invention are dischargeable and can be applied in discharge printing.

Examples for dvestuffs of present invention :

The following examples illustrate the invention.

Parts are given, unless specified otherwise, in parts per weights, such as grams.

The relationship between the parts by weight quoted in the examples and parts by volume is the same as between kilogram and liters. The percentages are by weight unless stated otherwise. Example 1 :

In 2000 parts by volume of water and 500 parts of ice is charged 184 parts per weight of 1 ,3,5-Trichlorotriazine. To this dispersion is added 140 parts per weight of N-methyl- taurine. While the reaction mass is stirred at 0-5 °C, the pH value falls down and is held at pH 1 .5-2 by constantly dosing diluted 20% soda ash solution. This procedure will yield the primary condensation product 2-(N-B-Sulfoethyl) amino-4,6-dichlorotriazine. The reaction mass is stirred for 3 h. To this is then added 376 parts per weight of 1 ,3-Phenylendiamine- sulfonic acid and the reaction is conducted at pH 5-6 and stirred for several hrs at a temperature of 30-40 °C, maintained by constantly dosing 20% soda ash solution, to yield the coupling component of the following formula

Then 562 parts by weight of freshly diazotized 4-(B-sulfatoethylsulfonyl) phenylamine suspension - diazotized in the usual manner using sodium nitrite and hydrochloric acid at 0-5 °C and pH 1 -1 .5 in 3000 parts per volume of water is charged to the solution of the coupling component. The azo coupling is carried out within 3 hrs at pH 5-6 and 0-5 °C to yield a yellow d estuff of the formula

Golden Yellow (λ max 412 nm)

The dyestuff is isolated by adding potassium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades. Example 2:

In 2000 parts by volume of water and 500 parts of ice is charged 184 parts per weight of 1 ,3,5-Trichlorotriazine. To this dispersion is added 42 parts per weight of Cyanamide. While the reaction mass is stirred at 0 °C, the pH value is maintained at pH 8-8.5 by constantly dosing diluted 10% soda ash solution. This procedure will yield the primary condensation product 2-Cyanamino-4,6-dichlorotriazin. The reaction mass is stirred for 3 hrs. To this is then added 216 parts per weight of 1 ,3-Phenylendiamine, and the reaction is conducted at pH 7-8 and a temperature of 35-45 ^< Ό for 1 hr, then temperature is increased to 70-80 °C and pH is maintained in the range 7-8. This procedure will yield the coupling component of the following formula

The reaction slurry is filtered, washed with warm water. Then the wet cake is dispersed in 2000 parts per volume of water, to which is charged 722 parts by weight of freshly diazotized 2-Sulfo-4-(B-sulfatoethylsulfonyl)phenylamine in 2000 parts per volume of water. Cou lin is carried out at pH 5-6 and 0-5 °C to yield a dyestuff of the formula

Orange-brown (λ max 465 nm)

The dyestuff is isolated by spray drying in the usual manner. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Example 3:

In 2000 parts by volume of water and 500 parts of ice is charged 184 parts per weight of 1 , 3, 5-Trichlorotriazine. To this dispersion is added 42 parts per weight of Cyanamide. While the reaction mass is stirred at 0°C, the pH value is maintained at pH 8-8.5 by constantly dosing diluted 10% soda ash solution. This procedure will yield the primary condensation product 2-Cyanamino-4, 6-dichlorotriazin. The reaction mass is stirred for 3 hrs. To this is then added 376 parts per weight of 1 , 3-Phenylendiamin-4-sulfonic acid and the reaction is conducted at pH 6 and a temperature of 45-50 °C, to yield the coupling component of the structure

Then 562 parts by weight of freshly diazotized 4-(B-sulfatoethylsulfonyl) phenylamine, as suspension in 1500 parts per volume of water, is charged to the solution of the coupling component. Cou ling is carried out at pH 5-6 and 0-5 °C to yield a dyestuff of the formula

Golden Yellow (λ max 416 nm)

The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Comparative example 1 :

The d estuff of the formula

is already known from EP 623.655, example 80, and prepared accordingly. Strength as K S value At 1 °o Of At 3% of Dyestuff of example 3 45 89

Comparative example 1 28 47

The comparison of comparative dye 1 vs example 3 of the present invention surprisingly exhibits superior colour strength although one fibre reactive group has been removed.

Example 4:

In 2000 parts by volume of water and 500 parts of ice is charged 184 parts per weight of 1 ,3,5-Trichlorotriazine. To this dispersion is added 42 parts per weight of Cyanamide. While the reaction mass is stirred at Ο'Ό, the pH value is held at pH 8 by constantly dosing diluted 10% soda ash solution. This procedure will yield the primary condensation product 2-Cyanamino-4,6-dichlorotriazin. The reaction mass is stirred for 2 h. To this is then added 188 parts per weight of 1 ,3-Phenylendiamin-4-sulfonic acid and the reaction is conducted at pH 6 and a temperature of 45-50 °C, to yield the secondary condensation product. Then 281 parts by weight of freshly diazotized 4-(B-sulfatoethylsulfonyl) phenylamine suspension in 1200 parts per volume of water is charged to the solution of the coupling component. Coupling is carried out at pH 5-6 and 0-5 °C which will yield the intermediate dyestuff of the formula

To this reaction mass is added 108 parts by weights of 1 , 3-Phenylendiamine, and stirred at 35-40 °C and pH 5-6. Finally the last coupling step is carried out by charging 361 parts by weight of freshly diazotized 2-Sulfo-4-(B-sulfatoethylsulfonyl)phenylamine, prepared in the usual manner, in 1000 parts per volume of water to yield a dyestuff of the formula

Golden yellow (λ max 414nm)

The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Example 4b:

In 2000 parts by volume of water 480 parts per weight of monoazo dyestuff of the formula

is prepared in the usual manner from azo coupling of 4-(β- sulfatoethylsulfonyl)phenylamine onto 1 ,3-Phenylendiamine sulfonic acid, is condensed with 190 parts per weight of 2-Cyanamino-4,6-dichlorotriazine, prepared as in example 2, at a temperature of 40 °C over a period of 3 hrs at pH 7.

To this is added 480 parts er weight of the monoazo dyestuff of the formula

which is prepared in the usual manner from azo coupling of 2-Sulfo-4-(B- sulfatoethylsulfonyl) phenylamine onto 1 ,3-Phenylendiamine, and the tertiary condensation is carried out at 80 °C at pH 8 over a period of 3 hrs. The dyestuff of the formula

Golden yellow (436 is obtained. The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Example 5:

In 2000 parts by volume of water 480 parts per weight of monoazo dyestuff of the formula

which is prepared in the usual manner from azo coupling of 4-(β- sulfatoethylsulfonyl)phenylamine onto 1 ,3-Phenylendiamine sulfonic acid , is condensed with 273 parts per weight of 2-(N-B-sulfoethyl)amino-4,6-dichlorotriazin, prepared as in example 1 , at a temperature of 40-45 °C over a period of 3 hrs at pH 5-5.5. To this is added 602 parts per weight of the monoazo d estuff of the formula

which is prepared in the usual manner from azo coupling of 2-Sulfo-4-(B- sulfatoethylsulfonyl) phenylamine onto 3-Aminophenyl urea, and the tertiary condensation is carried out at 70-75 °C at pH 6-6.5 over a period of 3 hrs. The dyestuff of the formula

Golden yellow (λ max 430nm) is obtained. The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Example 6:

In 2000 parts by volume of water 600 parts per weight of monoazo dyestuff of the formula

which is prepared in the usual manner from azo coupling of 2-Sulfo-4-(B- sulfatoethylsulfonyl) phenylamine onto 3-aminophenylurea, is condensed with 273 parts per weight of 2-(N-B-sulfoethyl)amino-4,6-dichlorotriazine, prepared as in example 1 , at a temperature of 40-45 °C over a period of 3 hrs at pH 5-5.5. Then temperature is raised to 70-75 °C and the reaction is continued under stirring at pH 6-6.5 over a period of 3 hrs to complete the tertiary condensation. The dyestuff of the formula

Golden yellow (λ max 432 nm) is obtained. The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Example 7:

In 2000 parts by volume of water, 190 parts per weight of 2-Cyanamino-4, 6-dichlorotriazin is prepared as in example 2. To this is then added 244 parts per weight of 2, 4- diaminotoluene, and the reaction is conducted at pH 8-8.5 and a temperature of 80 °C for 3hr. This procedure will yield the cou ling component of the following formula

The reaction slurry is filtered, washed with warm water. Then the wet cake is dispersed in 2000 parts per volume of water, to which is charged 722 parts by weight of freshly diazotized 2-Sulfo-4-(B-sulfatoethylsulfonyl) phenylamine in 2000 parts per volume of water. The azo coupling is carried out at pH 6.5-7 and 0-5 °C over a period of 4h. The dyestuff of the formula

Orange (λ max 488 nm)

is obtained. The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades. The following table illustrates more examples of the formula which can be prepared in a similar manner as in examples 1 -6 by using the respective intermediate compounds.

Examples 8-29:



Example 30:

530 parts per weight of the dyestuff of the formula

dissolved in 4000 parts per volume of water, is condensed under vigorous stirring with 140 parts per weight of 1 ,3,5-trifluorotriazine at 0-2 °C and pH 3.5-4.5 by dosing diluted sodium carbonate solution, then 125 parts per weight of taurine is added and the secondary condensation is carried out at a temperature of 0-5 °C and a pH value of 6-7. The reaction mass is stirred for 2 h. Then 1 ,3-Phenylendiamin sulfonic acid is added to the reaction mass, and the pH value is adjusted to pH 4-5 and a temperature of 60-70 °C. The reaction mass is stirred for 2 h. Finally 280 parts by weight of freshly diazotized 4-(B-sulfato- ethylsulfonyl) phenylamine suspension - diazotized in the usual manner using sodium nitrite and hydrochloric acid at 0-5°C and pH 1 -1.5 - in 1000 parts per volume of water is charged to the solution of the coupling component. The azo coupling is carried out within 3 hrs at pH 5-6 and 0-5°C to yield an orange dyestuff of the formula

Orange (λ max 435 nm)

The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades. The following table illustrates more examples which can be prepared in a similar manner as in example 30 by using the respective intermediate compounds.

Example 35:

In 2000 parts by volume of water, 190 parts per weight of 2-Cyanamino-4,6-dichlorotriazin is prepared as in example 2. To this is then added 188 parts per weight of 1 ,3- diaminophenylen sulfonic acid, and the reaction is conducted at pH 5-5.5 and a temperature of 30-35°C for 3hr. To this is added a solution of 238 parts per weight of 2- amino-5-hydroxy-naphthalene -7-sulfonic acid (J acid) in 1500 parts per weight of water, and the condensation is carried out at pH 8-8.5 and a temperature of 70-80 °C over a period of 3 hrs.

This procedure will yield the coupling component of the following formula

in a separate vessel, 562 parts by weight of 4-(B-sulfatoethylsulfonyl) phenylamine is freshly diazotized in the usual manner using sodium nitrite and hydrochloric acid at 0-5°C and pH 1 -1 .5 in 1500 parts per volume of water, and the diazonium salt suspension is charged to the solution of the coupling component. The azo Coupling is carried out within 3 hrs at pH 5-5.5 and 0-5 °C which will a orange dyestuff of the formula

Orange (λ max 432 nm)

The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades

Example 36:

In 2000 parts by volume of water, 190 parts per weight of 2-Cyanamino-4,6-dichlorotriazin is prepared as in example 2. To this is then added 188 parts per weight of 1 ,3- diaminophenylen sulfonic acid, and the reaction is conducted at pH 5-5.5 and a temperature of 30-35°C for 3hr. To this is added a solution of 320 parts per weight of 1 - amino-8-hydroxy-naphthalene -3,6-disulfonic acid (H acid) in 2500 parts per weight of water, and the condensation is carried out at pH 8-8.5 and a temperature of 70-80 °C over a period of 3 hrs. This procedure will yield the coupling component of the following formula

In a separate vessel, 562 parts by weight of 4-(B-sulfatoethylsulfonyl)phenylamine is freshly diazotized in the usual manner using sodium nitrite and hydrochloric acid at 0-5°C and pH 1 -1 .5 in 1500 parts per volume of water, and the diazonium salt suspension is charged to the solution of the coupling component. The azo coupling is carried out within 4 hrs at pH 5-5.5 and 0-5 °C which will a red dyestuff of the formula

Red (λ max The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

The following table illustrates more examples which can be prepared in a similar manner as in example 35-36 by using the respective intermediate compounds.

Example 42:

In 3000 parts per volume of water 320 parts per weight of 8-Hydroxy-4,6-Disulfo-3-amino naphthalene is dissolved at pH 6, and then reacted with 184 parts per weight of 1 ,3,5- Trichlorotriazine at a pH 1 .5-2 and a temperature of 0-5 °C. 239 parts per weight of 8- Hydroxy-6-Sulfo-3-amino naphthalene is added and the secondary condensation is carried out at pH 4-5 and a temperature of 35°C. Finally, 125 parts per weight of taurin (β- Sulfoethylamine) is added, and the tertiary condensation is carried out at 60 °C and a pH of 6-7. To this is added a freshly diazotised fine dispersion of 580 parts per weight of 4-(β- sulfatoethylsulfonyl)phenylamine at 0-5 °C and a pH of 6-7. This yields the dyestuff of the formula

Orange (λ max = 460 nm)

The dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Example 43:

The dyestuff of example 2 of the US patent application 4.485.041 is reacted with N-methyl- taurine at a pH value of 6-7 and a temperature of 60-65 °C. This yields the dyestuff of the formula

Red (λ max = 525 The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

The following table illustrates more examples which can be prepared in a similar manner as in examples 34-35 by using the respective intermediate compounds.

Example 58:

26 parts per weight of the N-Hydroxyethylpiperazine is charged in 40 parts per weight of sulfuric acid 100% followed by addition of 65% oleum. The reaction mass is stirred for 1 h, and drown on 70 parts per weight of methanol and 37 parts per weight of ice water. 37 parts per weight of N-Sulfatoethylpiperazine is obtained.

Ice and 33 parts per weight of Cyanuric chloride is added while the primary condensation takes place during 1 -2 h at 0-5°C at pH 1 -2.

Then 66 parts per weight of 1 ,3-Phenylendiamine-sulfonic acid is added, and the reaction mass is stirred for 6h at 20 °C at pH 5-6. The reaction is heated to 60-65 °C to complete the reaction. The intermediate coupling component of the formula

is obtained.

Then 99 parts by weight of 4-(B-sulfatoethylsulfonyl)phenylamine suspension is diazotized in the usual manner using sodium nitrite and hydrochloric acid at 0-5 °C and pH 1 -1 .5, in 500 parts per volume of water is charged to the solution of the coupling component . The azo Coupling is carried out at pH 5-6 and 0-5 °C to yield a yellow dyestuff of the formula

Reddish Yellow (λ max = 416)

The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

The following table illustrates more examples which can be prepared in a similar manner as in example 58 by using the respective intermediate compounds.

Example 66:

92 parts by weight of thioglycolic acid is condensed with cyanuric chloride at pH 2-3 in 3 hrs at a temperature of 0-5°C. To this is added 36 parts per weight of 1 , 3- Phenylendiamine-sulfonic acid and the reaction is carried out at pH 8-9 and a temperature of 40-50 °C. Then 56 parts by weight of freshly diazotized 4-(B-sulfatoethylsulfonyl) phenylamine, as suspension in 300 parts per volume of water, prepared in the usual manner, is charged to the solution of the coupling component. Coupling is carried out at pH 5-6 and 0-5 °C to yield a dyestuff of the formula

Golden yellow (λ max 414nm)

The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

The following table illustrates more examples which can be prepared in a similar manner as in example 66 by using the respective intermediate compounds.

Example 76:

In 2000 parts by volume of water and 500 parts of ice is charged 184 parts per weight of 1 , 3, 5-Trichlorotriazine. To this dispersion is added 90 parts per weight of 3- Hydroxypropionic acid. While the reaction mass is stirred at 0-10°C, the pH value is held at pH 8-9 by constantly dosing diluted 20% soda ash solution. This procedure will yield the primary condensation product 2-(B-hydroxy) amino-4, 6-dichlorotriazin. The reaction mass is stirred for 3 h. To this is then added 376 parts per weight of 1 ,3-Phenylendiamine- sulfonic acid and the reaction is conducted at pH 5-6, temperature is allowed to increase gradually and stirred for several hrs at a temperature of 30-40 °C, maintained by constantly dosing 10% soda ash solution, to yield the coupling component of the following formula

Then 562 parts by weight of freshly diazotized 4-(B-sulfatoethylsulfonyl) phenylamine suspension - diazotized in the usual manner using sodium nitrite and hydrochloric acid at 0-5 °C and pH 1 -1 .5 in 1500 parts per volume of water is charged to the solution of the coupling component. The azo Coupling is carried out within 3 hrs at pH 5-6 and 0-5°C to yield a yellow dyestuff of the formula

Golden yellow (λ max 418 nm)

The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

The following table illustrates more examples which can be prepared in a similar manner as in example 76 by using the respective intermediate compounds.

83 -0- Red

(CH ₂ )

2 ^"

COO

H

Example 84

In 2000 parts by volume of water, 190 parts per weight of 2-Cyanamino-4, 6-dichlorotriazin is prepared as in example 2. To this is then added 218 parts per weight of 3-aminophenol and the reaction is conducted at pH 5-5.5 and a temperature of 30-35 °C for 3hr, then temperature is increased to 70-80 °C and the condensation is carried out at pH 8-8.5 over a period of 3 hrs.

The coupling component of the following formula is obtained

Then 562 parts by weight of freshly diazotized 2-sulfo -4-(B-sulfatoethylsulfonyl) phenylamine suspension - diazotized in the usual manner using sodium nitrite and hydrochloric acid at 0-5°C and pH 1 -1 .5 - in 1500 parts per volume of water is charged to the solution of the coupling component . The azo Coupling is carried out within 3 hrs at pH 5-6 and 0-5 °C which will a yellow dyestuff of the formula

The dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.

Dyeing example 1 :

100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dyebath containing 800 parts of water, 50 parts per weight of sodium chloride, and 3 parts per weight of the dyestuff of example 1. After 30 min at 60°C, 15 parts per weight of sodium carbonate is added, and the dyeing temperature is maintained at 60 °C for another 45 min. The dyed fabric is then rinsed in a fresh bath of 2000 parts warm water, neutralized by adding 1 part per weight of acetic acid, and soaped in another fresh bath of 2000 parts of water in presence of a conventional detergent for 5 min. at 95 °C, and dried. A golden yellow dye with good fastness properties is obtained. Dyeing Example 2:

100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dyebath containing 1000 parts of water, 50 parts per weight of sodium chloride, and 5 parts per weight of the dyestuff of example 3. After 30 min at 60°C, 10 parts per weight of sodium carbonate is added, the dyeing temperature is maintained at 60 °C for 15 min, then 2 parts per volume of sodium hydroxide 50% solution is added, then dyeing temperature is maintained at 60 °C for another 30 min. The dyed fabric is then rinsed and soaped in the same manner as outlined in dyeing example 1. A golden yellow dye with good fastness properties is obtained. Dyeing Example 3:

100 parts per weight of cotton fabric is padded with a padding liquor, applying a liquor pickup of 70% per weight of fabric, in a freshly prepared padding liquor containing 1000 parts of water, 25 parts per weight of the dyestuff of example 2, 30 parts per weight of sodium carbonate and 10 parts per weight of sodium hydroxide 50% solution. The padded fabric is then rolled, covered to keep it wet, and stored for a period of 16 to 24 h. Finally the fabric is rinsed and soaped in the same manner as outlined in dyeing example 1 . An orange dye with good fastness properties is obtained.