F0RM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention - "FIBRE REACTIVE BISAZO REACTIVE COLORANTS, MIXTURES OF REACTIVE COLORANTS, PRODUCTION AND USE THEREOF"
2. Applicants)
(a) NAME : COLOURTEX INDUSTRIES LIMITED
(b) NATIONALITY : An Indian Company
(c) ADDRESS : Survey No 91, Paikee Bhestan, Navasari-Surat Road, Surat - 395 023,
Gujarat (India)
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:

FIELD OF INVENTION
The present invention relates to compounds of the formula (1)

The present invention further relates to intermediates used in the preparation of formula (1) a process for the preparation of the compounds of the formula (1). These dyes can be applied as single dye or as mixture or in combination with other compatible dyestuffs for dyeing a wide variety of fibre materials selected from, cellulose, polyamide or protein fibres and yield dyeings having good allround properties such as excellent washing fatness, low contact staining.
BACKGROUND OF THE INVENTION
The presently known state of the art dyes for deep red, red-brown and rubine shades are Bisazo reactive dyes based on 2-amino-5-naphthol-7-sulfonic acid as coupling agent, which have been published in the US patent No. 6,537,332 and in the US patent No. 6,011,140. Patent No. 6,01 1,140 describes reactive dyes of the formula

wherein n is 1 or 2, Gl is hydrogen or hydroxyl, G2 is hydrogen or hydroxysulfonyl, G3 is hydrogen or arylazo, Rl is hydrogen or hydroxysulfonylmethyl, R2 is hydrogen or hydrqXysulfonylmethyl, and D is a

radical of a diazo or tetraazo component having in each case at least one anchor radical of the formula SO2-Y, wherein Y is vinyl or substituted ethyl, and their use for dyeing or printing hydroxyl-containing or nitrogenous organic substrates, and naphthylamines as intermediates.
Patent No. 6,537,332 discloses reactive colorants and mixtures of reactive colorants that are suitable for dyeing a wide variety of fibre materials, especially cellulosic fibre materials, and yield dyeings having good all-round properties.
Reaction path for preparation of the intermediates which yield N-substituted derivatives of 2-amino-5-naphthol-7-sulfonic acid are known from "The Complete Technology book on dyes & dye intermediates". Reactions which yield B-amino derivatives of carboxylic acid derivatives, such as esters, acids or nitriles are known from Tetrahedron 2004, 60, 383-387 and from Letters in Organic Chemistry 2007, 4, 54-59, and from the US patent application No. 2 759 913.
However, these colorants of the state of the art have certain disadvantages, such as poor fixation yields, limited build-up, limited wash and contact fastness, especially with regard to staining on adjacent fibres such as cotton, viscose, wool, polyester or nylon, and limited solubility in high concentrations.
There is a need for novel dyes with better build-up and higher fixation yields on cellulose containing textile fibres, in particular cotton and regenerated cellulose fibres, and improved technical properties, especially related to wash fastness, contact fastness, perspiration fastness and high solubility in dyeing applications such as exhaust or continuous dyeing, in order to achieve economical dyeing of high quality.
OBJECT OF INVENTION
It is an object of the present invention to provide Bisazo dyes based on derivatives of N-substituted 2-amino-5-naphthol-7-sulfonic acid, of the respective formula

(1), with higher fixation yields, superior build-up, improved dyeing and fastness properties with regard to washing and contact fastness to water and acid as well as alkaline perspiration.
It is another object of the present invention to provide bisazodyes which can be applied as single dye or as mixture, or in combination with other compatible dyestuffs containing vinylsulfone and/or heterocyclic reactive groups, preferably applied in dichromatic or trichromatic combinations, to achieve very deep shades, and excellent fastness properties.
It is another object of the present invention to provide novel intermediates for the preparation of Bisazo dyes.
It is yet another object of the invention to provide process steps for the preparation of intermediates for the preparation of Bisazo dyes.
SUMMARY OF INVENTION
According to an aspect of the present invention there is provided Bisazo dyes of the formula (1) and salts thereof

wherein
R1 is a radical of the formula -W-Q wherein
W is C1-C6 Alkylene, which can be substituted by hydroxy,

Q is a carboxylic acid or inorganic acid radical, or a derivative of carboxylic acid or inorganic acid selected , from the series -COOH, -CN, -COOR3, -CONH2, -CONHR2-, -CONR2R3-, -SO3H, a carbonyl radical of the formula -CO-R2, or a radical -O-CO-R3 , -OS03H , -SS03H, -OPO3H, which form together with W an organic or inorganic acid ester, wherein R2 andR3 are independent from each other C1-C4 Alkyl, which may be further substituted by Sulfo, Sulfato, or Hydroxy, or R2 and R3 form together a 5-or 6 ring N-heterocyclic ring such as morpholino, pyrollidino, or piperidino; provided that when Q is Sulfo, W is not methylene; D1 and D2 are independently of each other are selected from a radical of the formula (2a), (2b) or (2c), containing a vinylsulfone fibre reactive group,

wherein
Y is is -CH=CH2, or -CH2CH2-L in which L is a leaving group which is
eliminated in alkaline medium such as Sulfato, Halogen, Acetato,
Thiosulfato, or Phosphato,
R2 is C1-CrAlkyl, C1-C4-Alkoxy, Carboxy, Halogen, hydroxyl, preferably
methoxy or methyl,
n2 is 0,1 or 2,
n3 is 0,1 or 2,
m is 0, 1 or 2,
B is -CO-NR3-W2- or -NR3-CO- w-,
wherein
W2is methylene,-(CH2)2-3, 1,3-phenylen, 1,4-phenyIen,
R3 is hydrogen, or methyl,

and in case ofwhen m=2, the radicals R2 may have identical or different
meanings,
Or
a radical of the formula (3a) or (3b), containing a fibre reactive group is of a the heterocyclic type,

wherein
R4 is hydrogen or methyl, Z is a pyrimidinyl radical containing leaving groups of the series fluoro, chloro, or methylsulfonyl, and optionally additional substituents such as methyl, chloro, and cyano, or a or triazinyl radical radical of the formula

wherein
XI is a leaving group from the series chloro, fluoro, or Pyridinyl which may
be substituted by Carboxy,
X2 is chloro, cyanamino, NHQ1, NQ1Q2, -NH-ary1, NR'-ary0-S02Y, -NR"-
alk0-S02Y! N(alko-S02Y)2 or

wherein

ary0 is 1,3-phenylen or 1,4-phenylen, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo, R' is hydrogen, methyl, or ethyl, alko is 1,2-efhylen, 1,3-propylen or -(CH2)2-0-(CH2)2-, R'' is hydrogen, methyl, or phenyl,
aryi is phenyl which may be substituted independent from each other by 1 -2 substituents sulfo, methyl, methoxy, chloro, bromo, carboxy or nitro, Q1 is C1-C3-Alkyl, which may be substituted independent from each other by 1 -2 substituents hydroxy, sulfo, sulfate, or aceteto,
Q2 has one of the meanings of O1, preferably Q2 has the same meaning as Qi, or Q2 forms together with N and Q1 a 5 or 6- membered heterocyclic ring, such as morpholino, piperidiono or pyrrolidino and Y has one of the above defined meanings; Or a radical of the formula

wherein Hal is Chloro or Bromo.
According to another aspect of the invention there is provided mixtures of bisazo dyestuffs of formula (1) with at least one dyestuff of the formula (la), (lb), (lc), (Id), (le), (If), (lg), (lh), (li), (lj) and (Ik), wherein the ratio of formula (1) to the sum of the dyestuffs (la) to (Ik) is 99:1 to 25:75.
According to yet another aspect of the invention, there is provided intermediates of bisazo dyestuffs of the formula

According to yet another aspect of the invention there is provided a process for manufacturing the intermediates of formula (7).
DETAILED DESCRIPTION
The dyestuffs of the present invention have the formula (1)

Wherein
Ri is a radical of the formula -W-Q wherein
W is C1-C6 alkylene, which can be substituted by hydroxy,
Q is a radical of a carboxylic acid or inorganic acid, or a derivative of a
carboxylic acid or an inorganic acid, from the series -COOH, -CN, -COOR3, -
CONH2, -CONHR2-, -CONR2R3-, -SO3H, a carbonyl radical of the formula -
CO-R2, or a radical -O-CO-R3 , -OSO3H , -SSO3H, -OPO3H, which form
together with W an organic or inorganic acid ester, wherein R2 and R3,
independently of each other, are C1-C4 alkyl, which may be further substituted by
sulfo, sulfato, or hydroxy, or R2 and R3 form together a 5-or 6 ring N-heterocyclic
ring such as morpholino, pyrollidino, or piperidino.
In preferred radicals of R\,
W is -CH2 -, -(CH2)2 , -CH2-CH(CH3)-, -CH(CH3)- CH2-, and
Q is -COOH, -CN, -CONH2, -S03H, and-OS03H.
In particular, preferred radicals W are -(CH2) - and -(CH2)2 -.

In particular, preferred radicals Q are COOH and SO3H.
D1 and D2 are independently of each other a benzene or naphthyl radical, which
are substituted by fibre reactive groups, containing at least one fibre reactive
group in both D1 and D2, preferably one fibre reactive group in both D1 and D2,
wherein the fibre reactive groups, independently of each other, are of the
vinylsulfone type or heterocyclic type, in particular of the halogenpyrimidinyl or
halogentriazinyl reactive group, or of the acrylamide type which is substituted by
halogen. In case the fibre reactive group is of the vinylsulfone type, it also
includes fi-ethylsulfone substituted in B-position by a leaving group removable
under alkaline medium.
In case the fibre reactive group is of heterocyclic type, it is preferably of
halogenpyrimidinyl or the halogentriazinyl type.
Di is a radical of the formula (2a), (2b) or (2c), (2d) or (2e) containing at least one
vinylsulfone fibre reactive group,

wherein
Y is -CH=CH2, or -CH2CH2-L wherein L is a leaving group which is eliminated
in alkaline medium such as sulfato, halogen, acetato, thiosulfato, or phosphato,
preferably L is sulfato or chloro, and more preferably
S02Y is -S02CH2CH2OS03H or -S02CH=CH2,

R.2 is C1-C4-alkyl, C1-C4-alkoxy, carboxy, halogen, hydroxyl, preferably methoxy
or methyl,
n2 is 0,1 or 2, preferably 0 or 1,
n3 is 0,1 or 2, preferably 0 or 1,
m is 0, 1 or 2,
B is -CO-NR3-W2- or -NR3-CO- W2-,
wherein W2 is methylene, -(CH2)2-3, 1, 3-phenylene, 1,4-phenylene, or a radical of
the formula -(CH2)2-0-(CH2)2-, and R3 is hydrogen or methyl or phenyl or -
(CH2)2-3S02Y, where Y has one of the above defined meanings, and in case m=2,
the radical R2 may have identical or different meanings.
The benzene ring B1 carries 0-2 identical or different substituents of C1-C3-
alkoxy, preferably methoxy, Ci-C3-alkyl, more preferably methyl, carboxy,
halogen, or hydroxyl,
Ui is hydroxyl or has one of the meanings of Y; preferably Ui is hydroxyl, vinyl
or 6-sulfatoethyl.
Further D1 is also a radical of the formula (3a) or (3b), containing a fibre reactive
group of a heterocyclic type,

wherein
R4 is hydrogen or methyl, preferably hydrogen,
Z is a pyrimidinyl radical containing leaving groups of the series fluoro, chloro,
or methylsulfonyl, and optionally additional substituents such as methyl, chloro,
and cyano, wherein Z is preferably 2,4-difluoro-pyrimidinyl- , 5-chloro-2,4-
difluoro-pyrimidinyl, or 2,4,5-trichloro-pyrimidinyI, or Z is a triazinyl radical of
the formula (4)

wherein
X1 is a leaving group from the series chloro or fiuoro, or pyridinyl which may be
substituted by carboxy,
X2 is chloro, cyanamino, NHQ1, NQ1Q2, -NH-aryl, NR'-ary0-S02Y, -NR"-aIk0-
S02Y, N (alko-S02Y)2 or

wherein
ary0 is 1,3-phenylene or 1,4-phenylene, which may be substituted by methyl,
methoxy, carboxy, chloro, or sulfo,
R' is hydrogen, methyl, or ethyl,
alkois 1,2-ethylen, l,3-propylenor-(CH2)2-0-(CH2)2-,
R' 'is hydrogen, methyl, or phenyl,
aryi is phenyl which may be substituted independently of each other by 1 -2
substituents sulfo, methyl, methoxy, chloro, bromo, carboxy or nitro, preferably
aryi is 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl or 2,5-disulfophenyl-,
Qi is Ci-C3-alkyl, which may be substituted independently of each other by 1-2
substituents hydroxy, sulfo, sulfato, or acetato, preferably Qj is methyl, ethyl, J3-
hydroxyethyl, B-sulfoethyl or B-sulfatoethyl,
Q2 has one of the meanings of Q1, preferably Q2 has the same meaning as Q1, or
Q2 forms together with N and Q1 a 5 or 6- membered heterocyclic ring, such as
morpholino, piperidiono or pyrrolidino, and Y has one of the above defined
meanings,
Furthermore D1 is a radical of the formula


wherein Hal is halogen, chloro or bromo , preferably bromine, D2 has, independently of the meaning of D1, one of the meanings of D1.
The dyestuffs wherein the radical WQ is CH2SO3H, in case D1 and D2 are radicals of the formula (2a), are already known from prior art and are hence excluded from the scope of the present invention.
The dyestuffs wherein the radical WQ is CH2SO3H, in case D1 is a radical of the formula (2a) wherein n2 is 2, m is 0, and D2 a radical of the formula (3 a), wherein Z is a radical of the formula,

are also excluded since these dyes are already disclosed in prior art.
As C1-C6alkylene for the radical W there come into consideration, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butyIene, 1,5-pentylene, 1,6-hexylene, 2-hydroxy-l,2-ethylene, 3-hydroxy-1,3-propylene, 2-hydroxy-1,2-propylene, 4-hydroxy-l,4-butylene, 3-hydroxy-1,3-butylene , 5-hydroxy- 1,5-pentylene , 6-hydroxy-l,6-hexylene , wherein position "1" is the chemical bond linked with the amino group of formula (1).
Examples for preferred radicals W are methylene, 1,2-ethylene, 1,3-propylene and 1,2-propylene.

Examples for radicals Q are COOH, CN, COOC2H5, COOCH3j CONH2, -CONHCH3-, -CONHC2H5- -CONH(CH2)2OH, -CONH(CH2)3OH, CONH(CH2)2S03H, -CON(CH3)(CH2)2S03H, -CONH(CH2)2OS03H CON(CH3)2, -CON(C2H5)2, -CON[(CH2)2OH]2, radicals of the formula

SO3H, COCH3, COC2H5 , -O-CO-CH3 , -0-CO-C2H5 , -0-CO-C3H7 , -O-CO-C4H9, OSO3H , -SSO3H or -OP03H.
Examples for radicals W-Q are -CH2-COOH, -CH2CH2-COOH, -CH(CH3)-CH2-COOH, -CH2-CH(CH3)-COOH, -(CH2)3-COOH, -(CH2)4-COOH, -(CH2)5-COOH, -(CH2)6-COOH, -CH2CH2-S03H, -CH2CH2-0-S03H, -CH2CH2-S-S03H, -CH2CH2-0-P03H, -CH2.-CN, -CH2CH2-CN, -CH(CH3>CH2-CN, -CH2-CH(CH3)-CN,-(CH2)3-CN, -(CH2)4-CN, -(CH2)5-CN,-(CH2)6-CN, -CH2CH2-CONH2, -CH2CH2-CO NH-CH3, -CH2CH2-CO NH-C2H5,-CH2CH2-CO N(CH3)2j -CH(CH3)-CH2-CONH2 , -CH2-CH(CH3)-CONH2 , -(CH2)3-CONH2;, -(CH2)4-CONH2, -(CH2)5-CONH2 ,- (CH2)6-CONH2 ,-CH2CH2-COCH3, -CH2CH2-COC2H5, -CH2CH2-COOCH3, -CH2CH2-COOC2H5) -CH2CHrCOOCH2-C6H5, -CH2CH2-CO-N(CH3)-CH2CH2-S03H,-CH(CH3)CH2-CO-N(CH3)-CH2CH2-S03H Preferred radicals for W-Q are -CH2-COOH, -CH2CH2-COOH, -CH(CH3)-CH2-COOH,-CH2CH(CH3)-COOH, -CH2CH2-S03H and -CH2CH2-OS03H.
Examples for radicals (2a) are
4-(2'-sulfatoethyl)sulfonyl-phenyl,
3-(2'-sulfatoethyl)sulfonyl-phenyl,
2-methoxy-5-(2'-sulfatoethyl)sulfonyl-phenyl,
2,5-dimethoxy-4-(2'-sulfatoethyl)sulfonyl-phenyl,
2-methoxy-5-methyl-4-(2'-sulfatoethyl)sulfonyl-phenyl,
4-vinyIsulfonyI-phenyl,

3-vinylsulfonyl-phenyl,
2-methoxy-5-vinylsulfonyl-phenyI,
2,5-dimethoxy-4-vinylsulfonyl-phenyl,
2-methoxy-5-methyl-4-vinylsulfonyl-phenyl,
4-(2r-chloroethyl)sulfonyl-phenyl,
3-(2'-chloroethyl)sulfonyl-phenyl5
2-methoxy-5-(2'-chloroethyl)sulfonyl-phenyl,
2,5-dimethoxy-4-(2'-chloroethyl)sulfonyl-phenyl?
2-methoxy-5-methyl-4-(2'-chloroethyl)sulfonyl-phenyl,
Examples for radicals (2b) are
6-(J3-sulfatoethylsulfonyl)-napth-2-yl>
6-(J3-sulfatoethylsulfonyl)-l-sulfo-napth-2-yl,
8-(B-sulfatoethylsulfonyl)-napth-2-yl,
8-(fi-sulfatoethylsulfonyl)-6-sulfo-napth-2-yl,
5-(C-sulfatoethylsulfonyl)-napth-2-yl,
5-(ft-sulfatoethylsulfonyl)-1 -sulfonapth-2-yl,
Examples for radicals (2c) are
4- [2-(2 '-sulfatoethylsulfonyl)-ethyl]amidocarbonyl-phenyl,
4-[3-(2'-sulfatoethylsulfonyl)-propyl] amidocarbonyl -phenyl,
3-[2-(2'-sulfatoethylsulfonyl)-ethyl] amidocarbonyl -phenyl,
3-[3-(2'-sulfatoethyIsulfonyl)-propyl] amidocarbonyl -phenyl,
4- [3-(2 '-sulfatoethylsulfonyl)-phenyl]amidocarbonyl-phenyl,
3- [3-(2'-sulfatoethylsulfonyl)-phenyl]amidocarbonyl-phenyl,
4- [4-(2 '-sulfatoethylsulfonyl)-phenyl]amidocarbonyl-phenyl,

3- [4-(2'-sulfatoethyIsulfonyl)-phenyl]arnidocarbonyl-phenyl,
4- [3-(2'-sulfatoethylsulfonyl)-phenyl]carbonylamido-phenyl,
4- [3-(2'-sulfatoethylsulfonyl)-phenyl]carbonylamido-l-sulfo-phenyl,
3- [3-(2 '-sulfatoethylsulfonyl)-phenyl]carbonylarnido-phenyl,
3- [3-(2 '-su!fatoethylsulfonyl)-phenyf]carbonylamido- 1-sulfo-phenyl,


Examples for radicals (2d) and (2e) are
Examples for radicals (3b) are
5-[2 ',4 '-difluoipyrimidinyljaminomethylen-1 -sulfo-napth-2-yl,
5-[5 'chlor-2 ',4 '-difIuorpyrimidinyl]aminomethylen-1 -suIfo-napth-2-yI,
Examples for radicals Z in radicals (3a) are 2,4-difiuorpyrimidinyl,
5-chlor-2,4-difluorpyrimidinyl,
2,4,5-trichlorpyrimidinyl,
5-chlor-2-fluor-4-methyl-pyrimidinyl,
5-chlor-2-methylsulfonyl-4-methyl-pyrimidinyl,
5-cyano-2,4-dichlor-pyrimidinyl,
2,4-dichlortriazinyl,
2-chlor-4-aminotriazinyl,
2-chlor-4-{3'-sulfophenyl}aminotriazinyl,
2-chlor-4-{4'-sulfophenyl}aminotriazinyl,
2-chlor-4-{2 ',5 '-disulfophenyl}aminotriazinyl,
2-chlor-4-{2',4'-disulfophenyl}aminotriazinyl,
2-fluor-4-{2'-J3-sulfatoethylsulfonyl-ethyl}aminotriazinyl,
2-fluor-4-{3'-B-sulfatoethylsulfonyl-propyl}aminotriazinyl,
2-chlor-4-{2'-fi-sulfatoethylsulfonyl-ethyl}aminotriazinyl,

2-chlor-4-{2'-B-chlorethylsulfonyl-ethyl}aminotriazinyl,
2-chlor-4-bis{2'-6-chlorethylsulfonyl-ethyl}aminotriaziny],
2-chlor-4-bis {3 '-fi-chlorethylsulfonyl-propyl} aminotriazinyl,
2-fluor-4-[methyl- {2 '-B-sulfatoethylsulfonyl-ethyl} ]aminotriazinyl,
2-fluor-4-[phenyl-{2'-B-sulfatoethylsulfonyl-ethyl}]aminotriazinyl,
2-chlor-4-{3'-fi-sulfatoemylsulfonyl-propyl}aminotriazinyI,
2-chlor-4-{4'-B-sulfatoethylsulfonyl-phenyl}aminotriazinyl,
2-chlor-4- {3' -B-sulfatoethylsulfonyl-phenyl} aminotriazinyl,
2-chJor- 4-[ethyI -{3 '-i3-sulfatoethylsulfony/-pheny]}]-aminotriazinyl,
2-chlor-4-[ethyl-{4'-B-sulfatoethylsulfonyl-phenyl}]-aminotriazinyl.
Such radicals (3 a) and their manufacturing are known from many publications and patents.
Preferred structures of formula (1) are dyes of the formula (5a), (5b) or (5c)

wherein
Ri'is -CH2-COOH, -CH2CH2-COOH, -CH(CH3)-CH2-COOH, -CH2-CH(CH3)-
COOH, -CH2CH2-CN, -CH2CH2-CONH2, -CH2CH2-S03H and -CH2CH2-

OS03H, and in particular, especially preferred radicals Rf are -CH2-COOH , -CH2CH2-COOH and -CH2CH3-S03H, the benzene rings(6a) and (6b)

may additionally carry 1 or 2 substituents of sulfa, methoxy or methyl groups, wherein in particular preferred are benzene rings (6a) which carry as substituents methyl, methoxy , and benzene rings (6b) which carry no substituent or 1 sulfo group,
V is -S02CH=CH2, S02-CH2CH2-OS03H or S02-CH2CH2-C1,
V has, independent of the radical V, one of the meanings of the radical V,
Z] is one of the following radicals

wherein
X1' is chloro or fluoro,
X2' ischloro, B-sulfoethylamino, morpholino or cyanamino,
Q1' is methyl, ethyl, n-propyl, B-hydroxyethyl, B-sulfoethyl or B-sulfatoethyl,
Q2' has one of the meanings of Q1, preferably Q2 has the same meaning as Q3\,
Y' is -CH=CH2, -CH2CH2OS03H or -CH2CH2C1.
Preferably V and V are vinylsulfonyl or B-sulfatoethylsulfonyl located in meta or para position to the azo link.
In particular, especially preferred dyestuffs of the formula (5a) are structures of the formula (5a') and (5a")

wherein,
Y is -CH=CH2 or -CH2CH2-OS03H,
R, is -(CH2)2-COOH or -(CH2)2-S03H.
In particular, especially preferred radicals D2 are
In particular, especially preferred radicals Di are



The present invention includes mixtures of dyestuffs of formula (1) with at least one dyestuff of the formula (la), (lb), (lc), (Id), (le), (If), (Ig), (lh), (if), (Ij) and (Ik), wherein
the ratio of the components of these mixtures (l):(la) is 99:1 to 30:70,
preferably 80:20 to 55:45;
the ratio of the components of the mixtures (l):(lb) is 99:1 to 85:15,
preferably 96:4 to 92:8;
the ratio of the components of the mixtures (!):(!c) is 99:1 to 85:15,
preferably 96:4 to 92:8;
the ratio of the components of the mixtures (l):(ld) is 99:1 to 90:10,
preferably 99:1 to 95:5;
the ratio of the components of the mixtures (l):(le) is 99:1 to 90:10,
preferably 99:1 to 95:5;
the ratio of the components of the mixtures (l):(lf) is 99:1 to 90:10,
preferably 99:1 to 95:5;
the ratio of the components of the mixtures (l):(lg) is 99:1 to 85:15,
preferably 99:1 to 94:6;
the ratio of the components of the mixtures (l):(lh) is 99:1 to 85:15,
preferably 99:1 to 94:6;
the ratio of the components of the mixtures (l):(li) is 99:1 to 85:15,
preferably 99:1 to 94:6;
the ratio of the components of the mixtures (l):(lj) is 99:1 to 85:15,
preferably 99; 1 to 94:6;

the ratio of the components of the mixtures (l):(lk) is 99:1 to 90:10,
preferably 99:1 to 95:5, and wherein the mixtures may contain several dyestuffs of (la) to (Ik), provided that the ratio of (1) to the sum of the dyestuffs (la) to (Ik) is 99:1 to 25:75, preferably 99:1 to 4.0:60.



wherein R1, D1 and D2 have one of the above defined meanings.
Of the above mixtures, preferred are mixtures of the compounds of formula (1) and compounds of formula (la) wherein Dl and D2 have one of the meanings of the radical (2a) and the ratio of the components of these mixtures is (l):(la) is 90:10 to 60:40.
Especially preferred mixtures of the compounds of formula (1) and compounds of formula (la) are mixtures of (5a') with (la') wherein Dl and D2 have one of the meanings of the radical (2a) and the ratio of the mixing components is 90:10 to 60:40.
Also especially preferred mixtures of the compounds of formula (1) and compounds of formula (la) are mixtures of (5a") with (la") wherein Dl and D2 have one of the meanings of the radical (2a) and the ratio of the mixing components is 90:10 to 60:40.

The dyestuff mixtures may be obtained as reaction mass from synthesis in a one pot azo coupling reaction or by physical mixing of the compounds, preferably as reaction mass from synthesis, and applied without further purification, or purified by isolation, such as salting out from sodium or potassium chloride or sulphate solution, by reverse osmosis treatment or purified at the stage of the intermediate synthesis by crystallization or precipitation from aqueous medium, preferably from acidic solution.
The dyestuffs of the formula (la), (le), (If), (li) and (lj) are already known. The dyestuffs of the formula (lb), (lc), (Id), (lg), (lh) and (Ik) are new compounds, and are also included as single dyestuff components in the present invention, excluding dyestuffs (lb) wherein Ri is CH2SO3H and Dl is a radical of the formula (2a) since it is known from prior art. The compounds (la) to (Ik) may be formed as byproducts in the manufacturing of the dyestuffs of the present invention, or added to the mixtures after separate manufacturing operation. The present invention includes intermediates of the formula

Wherein, W and Q have one of the above specified meanings. W is C2-C6 alkylene, which can be substituted by hydroxy Q has one of the above specified meanings.

The invention also includes mixtures of the compounds of the formula (7) with compounds of the formula (7a) in the ratio 100:0 to 30:70, preferably 99:1 to
55:45.

The compound of the formula (7) wherein W is methylene and Q is carboxy, is already known, and therefore excluded from the invention. The compound of the formula (7) wherein W is methylene and Q is sulfo, is already known, and therefore excluded from the invention.
Examples for intermediates of formula (7) are
3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanoic acid,
2-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanoic acid,
3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butanoic acid,
3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanenitrile,
2-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanenitrile,
3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butanenitrile,
3-({5'-hydroxy-7'-sulfo} naphth-2'-yI} amino) propanamide,
2-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanamide,
3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butanamide,
N-methyl-3-({5'-hydroxy-7'-sulfo}naphth-2'-yl}amino)propanamide, N-methyl-2-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanamide, N-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butanamide, N,N-dimethyl-3 -({ 5 '-hydroxy-7 '-sulfo} naphth-2 '-yl} amino)propanamide, N,N-dimethyl-2-methyl-3-({5'-hydroxy-7'-sulfo}naphth-2'-yl}amino) propanamide,

N,N-dimethyl-3-({5'-hydroxy-7'-sulfo}naphth-2'-yI}amino)butanamide,
N-(fl-hydroxyethyI)-3 -({5 '-hydroxy-7 '-sulfo} naphth-2 '-yl} amino)propanamide,
N-(B-hydroxyethyl)-2-methyl-3-({5 '-hydroxy-7'-sulfo} naphth-2'-yl} amino)
propanamide,
N-(B-hydroxyethyl)-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butanamide,
N-(B-sulfoethyl)-3-({5'-hydroxy-7'-sulfo}naphth-2'-yl}amino)propanamide,
N-(B-sulfoethyl)-2-methyl-3-({5 '-hydroxy-7'-sulfo} naphth-2'-yl} amino)
propanamide,
N-(B-sulfoethyl)-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butanamide,
N-methyl-N-(B-sulfoethyl)-3-({5'-hydroxy-7'-sulfo}naphth-2'-yl}amino)
propanamide,
N-methyl -N-(B-sulfoethyl)-2-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl}
amino) propanamide,
N-methyl- N-(B-sulfoethyl)-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino)
butanamide,
3-({5'-hydroxy-7'-sulfo}naphth-2'-yl}amino)propanoic acid ethyl ester,
2-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanoic acid ethyl
ester,
3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butanoic acid ethyl ester,
3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanoic acid methyl ester,
2-methyl-3-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) propanoic acid methyl
ester,
3-({5'-hydroxy-7'-sulfo}naphth-2'-yl}amino)butanoic acid methyl ester,
4-({5 '-hydroxy-7 '-sulfo} naphth-2 '-yl}amino)butane-2-one,
4-({ 5 '-hydroxy-7 '-sulfo} naphth-2 '-yl} amino)pentane-2-one,
3-methyl-4-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) butane-2-one,
2-({5'-hydroxy-7'-sulfo}naphth-2'-yl}amino)ethane sulfonic acid,
2-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) ethyl hydrogen sulfate,
2-({5'-hydroxy-7'-sulfo} naphth-2'-yl} amino) ethyl dihydrogen phosphate,
2-({5'-hydroxy-7'-sulfo} naphth-2'-yl}amino)ethyl hydrogen thiosulfate,


Examples for particularly preferred intermediates of formula (7) are
The invention also covers the manufacturing process of the new intermediates of formula (7) wherein -W-Q has one of the above described meanings. The intermediates of the formula (7) are prepared according to reaction path (8a) by reacting 2-amino-naphthol-7-sulfonic acid with a compound of the formula hal-W-Q, wherein hal is chloro or bromo and W and Q have one of the above meanings, at a temperature of 40-80 °C, and pH of 2-9, preferably 3-5,

(8a) or, according to reaction path (8b), by reacting 2-amino-5-naphthol-7-sulfonic
acid with a primary amine of the formula H2N-W-Q in the presence of a catalyst
such as sodium bisulphite, under reaction conditions typical for the Bucherer
reaction, at a temperature of 60-130°C, preferably 80-99°C, and pH of 2-9,
preferably 3-6,


Or, according to reaction path (8c), by reacting 2-amino-5-naphthol-7-sulfonic acid with a,ii -unsaturated compounds of the formula (9) , wherein R5 and R6 are independently of each other hydrogen or methyl, and Q has one of the above meanings, at conditions typical for a Michael addition, a temperature of 60-100 °C, and pH of 2-9, preferably 3-7,

which yields compounds of the formula (7) wherein the radical W-Q has the meaning of the radical (9a)

Or, according to reaction path (8d), by reacting 2-amino-5-naphthol-7-sulfonic acid with a primary amine of the formula H2N-W-OH in presence of a catalyst such as sodium bisulphite, at a temperature of 60-130°C, preferably 80-99°C, and pH of 2-9, preferably 3-6, followed by esterification, by using typical reagents for synthesis of sulfuric acid or phosphoric acid esters, to yield a compound of the formula (7) wherein Q is sulfato or phosphate

Concerning mixtures of (7) and (7a), these mixtures are obtained by the above synthesis procedures according to routes (8a), (8b), (8c) or (8d) depending on the

stoichiometry of reagents and reaction conditions of the manufacturing procedures, such mixtures are obtained.
Reactions of the reaction path (8b) which yield N-substituted derivatives of 2-amino-5-naphthol-7-sulfonic acid are known from "The Complete Technology book on dyes & dye intermediates", NIIR, exemplified for the manufacturing of 2-phenylamino-5-naphthol-7-sulfonic acid.
Reactions of the reaction path (8c) which yield J3-amino derivatives of carboxylic acid derivatives, such as esters, acids or nitriles are known from Tetrahedron 2004, 60, 383-387 and from Letters in Organic Chemistry 2007, 4, 54-59, and from the US patent application No. 2 759 913.
Examples for compounds hal-W-Q are
2-chloroacetic acid, 3-chloropropionic acid, 2-chloropropionic acid, 4-
chlorobutyric acid, 3-chlorobutyric acid, 2-chlorobutyric acid, 2-bromoacetic acid,
3-bromopropionic acid, 2-bromopropionic acid, 4-bromobutyric acid, 3-
bromobutyric acid, 2-bromobutyric acid, 2-chloroacetic acid methyl ester, 3-
chloropropionic acid methyl ester, 2-chloroacetic acid ethyl ester, 3-
chloropropionic acid ethyl ester, 2-chloroacetic acid iso-propyl ester, 3-
cbJoropropionic acid iso-propyl ester.
Examples for compounds H2N-W-Q are
2-sulfoethylamin, 2-sulfopropylamin, 3-aminopropionic acid, 2-aminopropionic
acid, 4-aminobutyric acid, 3-aminobutyric acid, 2-aminobutyric acid.
Examples for compounds H2N-W-OH are 2-Aminoethanol, 3-aminopropanol, 2-
aminopropanol, 4-aminobutanol, 3-aminobutanol.
Examples for compounds R5-CH=C(R4)-Q of the formula (9) are acrylic acid,
acrylonitrile, acrylamide, acrylic acid ethyl ester, acrylic acid methyl ester, acrylic
acid n-propyl ester, acrylic acid iso-propyl ester, crotonic acid, methacrylic acid,
crotonic acid ethyl ester, methacrylic acid ethyl ester, cro tonic acid methyl ester,

methacrylic acid methyl ester, N-methyl-acrylamide, N,N-dimethyl-acrylamide , N-ethyl-acrylamide, N,N-diethyl-acrylamide, N-ft-sulfoethyl-acrylamide, N-6-hydroxyethyl-acrylamide, N,N-bis(fi-hydroxyethyl)-acrylamide, vinyl-methyl-ketone, vinyl-ethyl-ketone.
The inventive products of the formula (1) are subsequently prepared by azo coupling of coupling components of the formula (7) according to reaction path (10a) with freshly prepared diazonium salts of the formula D1-N2+ and D1-N2+, which are made in the usual way from the aromatic amines D1-NH2, and D2-NH2 in acidic conditions by use of sodium nitrite and acid, e.g. hydrochloric or sulfuric acid,

wherein the radicals D1 and D2 independent of each other have one of the above described meanings, wherein the first coupling is carried out at a temperature of 0-25°C, preferably 0-15 °C, at pH 0.5 - 2, preferably 1-1.5, and the second coupling is carried out at a pH of 5-7, preferably 6-6,8, at a temperature of 0-25°C, preferably 0-15 °C.
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.

Example 2
Example 3
In particular, examples for preferred dyes of the present invention are Example 1




Example 4

Example 5

Example 6

Example 7




Example 8
Example 9
Example 10

Application
The present invention provides a process for dyeing from aqueous bath and printing of fibre materials 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 method,
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 dye 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.
Coloration in deep shades is often a challenge, especially when high fastness to
washing, contact and perspiration is concerned. All known dyes have limitations
in this respect.
The present dyes are of red to rubine colour, and are especially suitable for dyeing
in deep shades such as deep red, rubine, dark brown, burgundy, and black shades,
applied as single dye or as mixture in the present invention, or in combination
with other compatible dyestuffs containing vinylsulfone and/or heterocyclic
reactive groups, preferably applied in dichromatic or trichromatic combinations,
while exhibiting superior properties in coloration technology compared to known
mixtures of state of the art, with regard to achieving very deep shades, and
excellent fastness properties.
Examples of suitable alkali used for fixation include alkali hydroxide, alkali
carbonate, alkali silicate, of which sodium hydroxide, sodium carbonate, sodium
silicate are preferred.
The amount of dye applied in the dye bath can vary according to the desired depth
of shade, generally an amount of 0.01 to 10 % per weight of fabric is suitable, and
in particular 0.2 to 8% per weight of fabric is preferred.

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 the 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 9-11, and at a temperature of 40-90°C, preferably 45-65 °C.
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 is
dischargeable and can be applied in discharge printing.
Experimental part:
The following examples illustrate the invention which are however does not limit the scope of the invention.
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.
Examples for intermediates of the present invention: Intermediate Example A (path 8a):
To a solution of 24 parts per weight of 2-amino-naphthoI-7-sulfonic acid ("J-acid") in 500 parts per volume of water is charged 10 parts per weight of chloro acetic acid, and the reaction mixture is heated and stirred for 4 h at a temperature of 60-70 °C while the pH value is adjusted to pH 6-7. Hydrochloric acid is added to adjust to pH 1. The reaction mass is filtered and the compound of the formula


is obtained as solution in the mother liquor which is directly used for coupling as described in the examples 1 and 5.
Intermediate Example B (route Sb)
To a solution of 24 parts per weight of 2-amino-naphthol-7-sulfonic acid ("J-acid") in 500 parts per volume of water is charged 26 parts per weight of 2-Sulfoethylamin, 12 parts per weight of sodium buisulfite, and the reaction mixture is stirred for 30 h at a temperature of 95-98 °C while the pH value is adjusted to pH 6.5. Finally hydrochloric acid is added to adjust to pH 1. The reaction mass is filtered and the compound of the formula

is obtained which is used as wet cake for coupling as described in example 4.
Intermediate Example C (path 8b)
To a solution of 24 parts per weight of 2-amino-naphthol-7-sulfonic acid ("J-acid") in 60 parts per volume of water is charged 13 parts per weight of B-alanine, 10 parts per weight of sodium bisulfite, and the reaction mixture is stirred for 30 h at a temperature of 95-98 °C while the pH value is adjusted to pH 7 . Caustic soda 33% solution is added to adjust to pH 7, while the product precipitates. The reaction mass is filtered and the compound of the formula.


Alternative synthesis procedure for Intermediate Example C (path 8c -1 step method)
To a solution of 24 parts per weight of 2-amino-naphthoI-7-sulfonic acid ("J-acid") in 500 parts per volume of water is charged 8 parts per weight of acrylic acid, and the reaction mixture is stirred for 2 h at a temperature of 60-70 °C while the pH value is adjusted to pH 6-7. Hydrochloric acid is added to adjust to pH 1. The reaction mass is filtered and the compound of intermediate C, 2-(fi-Carboxyethyl)amino-naphthol-7-sulfonic acid is obtained as solution in the mother liquor which directly used for coupling as described in the examples 2 and 3.
Alternative synthesis procedure for intermediate C (path 8c - 2step method)
To a solution of 24 parts per weight of 2-amino-naphthol-7-sulfonic acid ("J-acid") in 500 parts per volume of Water is charged, 7 parts per weight of acrylonitrile. 9 parts per weight of sodium hydroxide the reaction mixture is stirred for 30-hrs at a temperature of 60-70 °C, followed by addition of further 15 parts per weight of sodium hydroxide, and mixture is stirred for at temperature 90 c for 4-hrs. Finally the product is isolated as described above.
Example D (path 8c)

is obtained as solution in the mother liquor which directly used for coupling as described in example 24.
To a solution of 24 parts per weight of 2-amino-naphthol-7-sulfonic acid ("J-acid") in 500 parts per volume of water is charged 9,5 parts per weight of methacrylic acid, and the reaction mixture is stirred for 2 h at a temperature of 60-70 °C while the pH value is adjusted to pH 6-7. Hydrochloric acid is added to adjust to pH 1. The reaction mass is filtered and the compound of the formula

Example E (path 8c):
To a solution of 24 parts per weight of 2-amino-naphthol-7-sulfonic acid ("J-acid") in 500 parts per volume of Water is charged, 7 parts per weight of Acrylonitrile. The reaction mass is stirred for 6 h at pH 6-7. The compound of the formula

is obtained which is used without further isolation as outlined in example 6. Further examples:



Examples for dvestuffs of the present invention : Example 1:
To a dispersion of 36 parts per weight of 2-Sulfo-4-B-Sulfatoefhylsulfonyl-aniline in 500 parts per volume of water is charged 6.9 parts per weight of sodium nitrite, and 25 parts per weight of hydrocn/oric acid, 32% grade 6y weignt, at a temperature of 0 °C. After stirring the reaction mass for 30 min. a freshly prepared diazonium salt is obtained, and charged slowly over a period of 1 h to the intermediate mother liquor as described in example A, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloride acid, and temperature is raised to 5-10 °C. The diazonium salt is charged to the extent until the first coupling stage is completed. In a separate vessel, 31 parts per weight of 2-Methoxy-5-6-Sulfatoethylsulfonyl-aniline is dispersed in 500 parts per volume of water, then 7 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of 0-5 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained. This diazonium salt is charged slowly over a period of 1 h to the

reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10qC. The diazonium salt is charged to the extent until the second coupling stage is completed. The dye stuff of the formula

rubine, (λmax= 533 rim) is obtained. The dyestuff is isolated in the usual manner by spray drying. The dyestuff provides dyeing on cotton in very deep rubine shades and exhibit excellent build-up in very deep shades, and good wash fastness.
Example 2:
To a dispersion of 56 parts per weight of 4-fi-SulfatoethylsulfonyI-aniline in 500 parts per volume of water is charged 14 parts per weight of sodium nitrite, and 30 parts per weight of hydrochloric acid, 36% grade by weight, at a temperature of 0 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained as fine dispersion, and then 31 parts per weight of the intermediate compound C as wet cake, prepared as described in example C, is charged into the reaction mass containing the diazonium salt, while during that time the pH value is kept < 1 by adding further diluted hydrochloric acid, at a temperature of 0-5°C. The reaction mass is stirred for 4 hrs at pH 1 and 0-5°C to carry out the Ist coupling stage. Then the pH value is raised to pH 5-5.5 by adding portion wise

sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5°C. The reaction mass is stirred for 1 more hours. The dyestuff of the formula

red-brown (λmax- 506 nm) is obtained. The dyestuff is isolated in the usual manner by spray drying. The dyesruff provides dyeing on cotton in deep red-brown shades and exhibit good build-up in very deep shades, and good wash fastness
Example 3:
To a dispersion of 36 parts per weight of 2-Sulfo-4-JJ-Sulfatoethylsulfonyl-aniline in 1200 parts per volume of water is charged 6.9 parts per weight of sodium nitrite, and 22 parts per weight of hydrochloric acid, 32% grade by weight, at a temperature of 0 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained. To this is then added 31 parts of the intermediate C, and the reaction mass is stirred for 4 hours at pH 1. Then slowly the temperature is raised to 5-10 °C. In a separate vessel, 28 parts per weight of 4-J3-Sulfatoethylsulfonyl-amline is dispersed in 500 parts per volume of water, then 6.9 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of 0-5 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained as fine dispersion. This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH

value is adjusted to pH 5.5-6.0 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The diazonium salt is charged to the extent until the second coupling stage is completed, The dyestuff of the formula

Carmine (λmax= 510 nm) is obtained. The dyestuff is isolated in the usual manner by spray drying. The dyestuff provides dyeing on cotton in deep carmine red shades and exhibit good build-up in very deep shades, and good wash fastness.
Example 4:
To a dispersion of 36 parts per weight of 2-Sulfo-4-B-Sulfatoethylsulfonyl-aniline in 500 parts per volume of water is charged 6.9 parts per weight of sodium nitrite, and 20 parts per weight of hydrochloric acid, 32% grade by weight, at a temperature of 0 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained. After the diazotization is completed, 35.2 parts of intermediate compound B is added into the reaction mass containing the diazonium compound at a temperature of 0-5*c. Stir for 4 hours at <1 pH. In a separate vessel, 28 parts per weight of 4-fi-Sulfatoethyls\ilfonyl-aniline is dispersed in 600 parts per volume of water, then 6.9 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of 0-5 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained as fine dispersion.

This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The diazonium salt is charged to the extent until the second coupling stage is completed. The dyestuff of the formula

red-brown (λmax= 504) is obtained. The dyestuff is isolated in the usual manner by spray drying. The dyestuff provides dyeing on cotton in deep red shades and exhibit good build-up in very deep shades, and good wash fastness.
Example 5:
To a dispersion of 36 parts per weight of 2-Sulfo-4-B-Sulfatoethylsulfonyl-aniline in 550 parts per volume of water is charged 7.0 parts per weight of sodium nitrite, and 23 parts per weight of hydrochloric acid, 32% grade by weight, at a temperature of 0 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained, and charged slowly over a period of 1 h to the intermediate mother liquor as described in example A, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloric acid, and temperature is raised to 5-10 °C. The diazonium salt is charged to the extent until the first coupling stage is completed. In a separate vessel, 32.5 parts per weight of 2-Methoxy-5-methyl-4-B-SulfatoethylsuIfonyl-aniline is dispersed in 600 parts per volume of water, then 6.9 parts per weight of sodium nitrite, and 22.5 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of

0-5 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained as fine dispersion. This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.5-7.2 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5°C. The diazonium salt is charged to the extent until the second coupling stage is completed.
The dyestuff of the formula

is obtained. The dyestuff is isolated in the usual manner by spray drying. The dyestuff provides dyeing on cotton in deep rubine shades and exhibit good buildup in very deep shades, and good wash fastness.
Example 6:
To a diazonium salt of 36 parts per weight of 2-Sulfo-4-B-Sulfatoethylsulfonyl-aniline in 500 parts per volume of water, prepared in the usual manner, is charged slowly over a period of 1 h to the intermediate mother liquor as described in example E, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloric acid, and temperature is raised to 5-10 °C. The diazonium salt is charged to the extent until the first coupling stage is completed.

In a separate vessel, 31 parts per weight of 2-Methoxy-5-fl-Sulfatoethylsulfonyl-aniline is diazotized in the usual manner and charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The diazonium salt is charged to the extent until the second coupling stage is completed.
The dyestuff of the formula

Rubine (7,max= 535)
is obtained. The dyestuff is isolated in the usual manner by spray drying. The dyestuff provides dyeing on cotton in deep rubine shades and exhibit good buildup in very deep shades, and good wash fastness
Examples 7-39


Ex. Rl Dl D2 Shade,
NO. Comm
ents
7 -CH2-CH2- 4-B-Sulfatoethyl-sulfonyl- 3-Sulfatoethyl- Red
COOH phenylen sulfonyl-phenylen brown
8 -CH2-CH2- 4-B-Sulfatoethyl-sulfonyl- 2-methoxy-5- Red/
COOH phenylen methyl-
4-Sulfatoethyl-
sulfonyl-phenylen Rubine
9 -CH2-CH2- 4-JJ-Sul fatoethyl -sulfonyl - 2,5-dimethoxy- 4- Violet
COOH phenylen Sulfatoethyl-sulfonyl-phenylen
10 -CH2-CH2- 4-ft-SuIfatoethyl-sulfonyl- 2-Methoxy- 4- Rubine
COOH phenylen Sulfatoethyl-sulfonyl-phenylen
11 -CH2-CH2- 2-suIfo-5-fi-SulfatoethyI- 4-SulfatoethyI- Red
COOH sulfonyl-phenylen sulfonyl-phenylen brown
12 -CH2-CH2- 2-sulfo -4-fi-SulfatoethyI- 2-methoxy-5- Rubine
COOH sulfony] -phenyl en Sulfatoethyl-sulfonyl-phenylen
13 -CH2-CH2- 2-sulfo -4-B-SuIfatoethyl- 2-methoxy-5- Rubine
COOH sulfonyl-phenylen methyl-
4-Sulfatoethyl-
sulfonyl-phenylen
14 -CH2-CH2- 4-Vinylsulfonyl-phenylen 4-Sulfatoethyl- Red
COOH sulfonyl-phenylen brown
15 -CH2-CH2- 4-Vinylsulfonyl-phenylen 4-Vinylsulfonyl- Red
COOH phenylen brown
16 -CH2-CH2- 2-Sulfo-4-Vinylsulfonyl- 4-Sulfatoethyl- Red
COOH phenylen sul fonyl-phenyl en brown

17 -CH2-CH2- 2-Sulfo-4-Vinylsulfonyl- 4-Vinylsulfonyl- Red
COOH phenylen phenylen brown
18 -CH2-CH2- 2-sulfo -4-fi-SulfatoethyI- 4-6-Chloroethyl- Red
COOH sulfonyl-phenylene sulfonyl -phenyl ene brown
19 -CH2-CH2-CN 2-sulfo-4-fl-Sulfatoethyl- 4-Sulfatoethyl- Red
20 sulfonyl-phenylen sulfonyl-phenylene brown

-(CH2)3-CN 2-su]fo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red
sulfonyl-phenylene sulfony 1 -phenyl ene brown
21 -CH2-CH;>- 2-sulfo-4-fl-Sulfatoethyl- 4-Sulfatoethyl- Red
COCH3 sulfonyl-phenylene sulfonyl-phenylene brown
22 -CH2-CH2- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red
COOCH3 sulfonyl-phenylene sulfonyl-phenylene brown
23 -CH2-CH2- 2-suIfo-4-fi-SuIfatoethyI- 4-SulfatoethyI- Red
COOC2H5 sul fony 1-phenylene sulfonyl-pheny 1 ene brown
24 -CH(CH3)-CH2- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red '
COOCH3 sul fony 1 -phenyl ene sulfonyl-phenylene brown
IS -CH2-CH(CH3) 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red
COOH sulfonyl-phenylene sul fony 1-phenylene brown
26 -CH2-CH(CH3)- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red
COO CH3 sulfonyl-phenylene sulfonyl-phenylene brown
27 -CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red
sulfonyl-phenylene sulfonyl-phenylene brown
28 -CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red
sulfonyl-phenylene sulfonyl-phenylene brown
29 -CH2-COOH 2-sulfo-4-fi-SulfetoethyI-sulfonyl-phenylene 2-methoxy-5-methyl-4- Rubine
Sulfatoethyl-

sulfonyl-phenylene
30 -CH2-COOH 2-sulfo-4-B-Sulfatoethyl-sulfonyl-phenylene 2,5-methoxy- 4-
Sulfatoethyl-
sulfonyl-phenylene Purple
31 -CH2-CH2-S03H 4-B-Sulfatoethyl-sulfonyl- 4-G-Sulfatoethyl- Red
phenylen sulfonyl-phenylene brown
32 -CH2-CH2-S03H 2-Sulfo-4-fi-Sulfato ethyl-sulfonyl-phenylen 2-methoxy-5-methyl-4-Sulfatoethyl-sulfonyl-phenylene Rubine
33 -CH2-CH2-SO3H 2-Sulfo-4-B-Sulfato ethyl-
sulfonyl-phenylen 2-methoxy-5-Sulfatoethyl-sulfonyl-phenylene Rubine
34 -CH2-CH2-S03H 2-SuIfo-4-β-Sulfato ethyl-sulfonyl-phenylene 2-chloro-4-
Sulfatoethyl-
sulfonyl-phenylene Rubine
35 -CH2-CH2- 2-Sulfo-4-β-Sulfato ethyl- 4-B-Sulfoto ethyl- Red
CONH2 sulfonyl-phenylene sulfonyl-phenylene brown
36 -CH2-CH2- 2-Sulfo-4-β-Sulfato ethyl- 4-B-Sulfato ethyl- Red
CONH(CH3) sul fonyl-phenylece sulfonyl-phenylene brown
37 -CH2-CH2- 2-Sulfo-4-B-Sulfato ethyl- 4-B-Sulfato ethyl- Red
CONH- sulfonyl-phenylerie sulfonyl-phenylene brown
CH2CH2OH
38 -CH2-CH2- 2-Sulfo-4-6-Sulfato ethyl- 4-B-Sulfato ethyl- Red
CONH-CH2CH2SO3H sulfonyl-phenylene sulfonyl-phenylene brown


Example 40:
Example 3 is repeated, however, instead of using the intermediate compound A. 33.8 parts per weight of the intermediate compound M is used. The dyestuff of the formula

Red brown (λmax= 510) is obtained. The dyestuff is isolated in the usual manner by spray drying. The dyestuff provides dyeing on cotton in deep red brown shades and exhibit good build-up in very deep shades, and good wash fastness
Example 41:
To a dispersion of 36 parts per weight of 2-Sulfo-4-B-Sulfatoethylsulfonyl-aniline in 500 parts per volume of water is charged 6.9 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 36% grade by weight, at a temperature of 0°C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained, and charged slowly over a period of 1 h to the intermediate prepared as described in example B, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloric acid, and temperature is raised to 5-10°C, The diazonium salt is charged to the extent until the first coupling stage is completed. In a separate vessel, 31 parts per weight of 1-Sulfo-6-{B-Sulfatoethyl}sulfonyl-2-naphthylamin is dispersed in 750 parts per volume of water, then 7 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 36% grade by weight, are charged at a temperature of 0-

5°C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained. This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.5-7.3 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The diazonium salt is charged to the extent until the second coupling stage is completed. The dyesruff of the formula

Red (λmax= 525 nm) is obtained which dyes on cotton in very deep rubine shades and exhibit excellent build-up in very deep shades, and good wash fastness.

Ex. Rl Dl p2 Shade
No. ■" .'..
42 -CH2-CH2- 4-B-Sulfato ethyl-sulfonyl- 6-Sulfatoethyl-sulfonyl- red
SO3H phenylene naphth-2-ylene
43 -CH2-CH2- 2-suIfo- 4-B-Sulfato ethyl- 1-Sulfo- 6-Sulfatoethyl- red
SO3H sulfonyl-phenylene sulfonyl-naphth-2-ylene
44 -CH2-CH2- 4-B-Sulfato ethyl-sulfonyl- 6-Sulfo- 8-Sulfatoethyl- red
SO3H phenylene sulfonyl-naphth-2-ylene

45 -CH2-CH2- 2-sulfo-4-B-Sulfato ethyl- 8-Sulfatoethyl-sulfonyl- red
S03H sulfonyl-phenylene naphth-2-ylene
46 -CH2-COOH 4-B-SuIfato ethyl-sulfonyl-phenylene 1-Sulfo- 6-SuIfatoethyI-sulfonyl-naphth-2-ylene red
47 -(CH2)2- 4-B-Sulfato ethyl-sulfonyl- 1-Sulfo- 6-Sulfatoethyl- red
COOH phenylene sulfonyl-naphth-2-ylene
48 -(CH2)r 1-Sulfo- 6-Sulfatoethyl- 1-Sulfo- 6-Sulfatoethyl- red
COOH sulfonyl-naphth-2-y]ene sulfonyl-naphth-2-ylene
49 -(CH2)2- 1-Sulfo- 6-Sulfatoethyl- 2-methoxy-5- red
COOH sulfonyl-naphth-2-ylene Sulfatoethyl-sulfonyl-phenylene
50 -(CH2)2- 1-Sulfo- 6-Sulfatoethyl- 2 -methoxy- 5 -methy 1- red
COOH sulfonyl-naphth-2-ylene 4-Sulfatoethyl-sulfonyl-phenylene
Example 51:
To a dispersion of 36 parts per weight of 2-Sulfo-4-B-Sulfatoethylsulfonyl-aniline in 500 parts per volume of water is charged 6.9 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, at a temperature of 0 °C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained, and charged slowly over a period of 1 h to the intermediate solution as described in example A, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloric acid, and temperature is raised to 5-10 °C. The diazonium salt is charged to the extent until the first coupling stage is completed.
In a separate vessel, 18.4 parts per weight of cyanuric chloride is dispersed by means of a dispersing aid under vigorous stirring in 500 parts per volume of water, and 300 parts per weight of crushed ice. At a temperature of 0-5 °C, a solution of 28.1 parts per weight of 4-6-Sulfatoethylsulfonyl-aniline. previously

dissolved at pH 4.5 and 20-25 °C in 400 parts per volume of water by portion-wise addition of 60 parts per volume of sodium carbonate, is charged, while stirring. pH falls below 1, then pH is raised to pH 4-4.5 by dosing a diluted 10% solution of sodium carbonate. Stirring is maintained in this range for 2 h. Then 29.6 parts per weight of 1, 3-diaminobenzoI-6-suIfonic acid, dissolved in 600 parts per volume of water at pH 6.5, is added. pH is raised to pH 6.5 with sodium carbonate 10% solution. The reaction mass is stirred for 6 h at 40-50 °C at pH 6.5 while pH is adjusted with sodium carbonate 10% solution. Then 6.9 parts per weight of sodium nitrite, and 23 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of 0-5 °C. After stirring the reaction mass for 60 min, a freshly prepared diazonium salt is obtained. This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.6 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5°C. The diazonium salt is charged to the extent until the second coupling stage is completed.
Red ( Xmax= 520 run )
The dyestuff of the formula


is obtained which dyes on cotton in very deep red shades and exhibit excellent build-up in very deep shades, and good wash fastness.
Example 52:
To a dispersion of 28 parts per weight of 4-fl-Sulfatoethylsulfonyl-aniline in 500 parts per volume of water is charged 6,9 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, at a temperature of 0°C. After stirring the reaction mass for 30 min, a freshly prepared diazonium salt is obtained, andcharged slowly over a period of 1 h to the intermediate solution of example B, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloric acid, and temperature is raised to 5-10°C. The diazonium salt is charged to the extent until the first coupling stage is completed. In a separate vessel, 29.6 parts per weight of 1, 3-diaminobenzol-6-sulfonic acid is dissolved in 600 parts per volume of water at pH 6.5. 0.75 parts per weight of sodium dihydrogen phosphate x 12 H2O and 0.75 parts per weight of disodium hydrogen phosphate x 2 H2O is added. Then 15 parts per volume of 2, 4, 6-trifluorpyrimidin is charged under stirring at 15-20 °C. The reaction mass is heated to 50°C, and stirred for 6 h at pH 6.5 while pH is adjusted with sodium carbonate solution. Then the solution is clarified, then 7 parts per weight of sodium nitrite, and 25 parts per weight of hydrochloric acid, 32% grade by weight, are charged at a temperature of 0-5 °C. After stirring the reaction mass for 60 min, a freshly prepared diazonium salt is obtained.
This diazonium salt is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.6 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 0-5°C. The diazonium salt is charged to the extent until the second coupling stage is completed. The dyestuff of the formula


Red (Xmax= 525 nm) is obtained which dyes on cotton in very deep red shades and exhibit excellent build-up in very deep shades, and good wash fastness.

Exam R1 Dl D2 -q Shad
ple e
Nr.
53 -(CH2)2- 4-B-Sulfatoethyl-sulfonyl- 5-[2',4'-dichloro-triazin- Red
COOH phenylene 6'-yl] amino-2-sulfo-phenylene
54 -CH2-COOH 2-suIfo-4-fl-SuIfatoethyI-sul fonyl-phenylene 5-[5'-chloro-2',4'-
difluoro-pyrimidin-6'-yl]
amino-2-sulfo-phenylene .Red
55 -(CH2)2- 4-B-Sulfatoethyl-sulfonyl- 5-[2'-chloro-4'-{3"- Red
S03H phenylene sulfophenyljamino-triazin-6'-yl] amino-2-sulfo-phenylene
56 -(CH2)2- 4-B-SulfatoethyI-sulfonyl- 5-[2'-chloro-4'-{2"- Red
COOH phenylene hydroxyethyl} amino -triazin-6'-yl] amino-2-sulfo-phenylene
57 -(CH2)2- 4-B-Sulfatoethyl-sulfonyl- 5-[2'-fluoro-4'-{3"-ft- Red
COOH phenylene sulfatoethylsulfonyl-

propyl }amino-triazin-6'- J
yl] amino-2-sulfo-phenylene
58 -CH2-COOH 2-sulfo-4-ß-Sulfatoethyl-sulfonyl-phenylene 5-[2'-fluoro-4'-{2"-ß-sulfatoethylsulfonyl-ethyl} amino-triazin-6'-yl] amino-2-sulfo-phenylene Red
59 CH2-COOH 2-su]fo-4-J3-Sulfatoethyl-sulfonyl-phenylene 5-[2'-fluoro-4'-N-methyl-{2"-iJ-sulfatoethylsulfonyl-ethyl) -amino-triazin-6 '-yl] amino-2-sulfo-phenylene Red
60 CH2-COOH 2-suIfo-4-6-SuIfatoethyI-sulfonyl-phenylene 5-[2'-fIuoro-4'-N-phenyl-{2"-ß-sulfatoethylsulfonyl-ethyl} -amino-triazin-6 '-yl] amino-2-sulfo-phenylene Red
61 -(CH2)2-S03H 4-vinylsulfonyl-phenylene 4-[2'-chIoro-4'-{3"-sulfophenyl} ami no-triazin-6'-yl] amino-2-sulfo-phenylene Red
62 -(CH2)2-COOH 4-vinylsulfonyl-phenylene 5-[2',4',5'-trichloro-pyrimidin-6'-yl] amino-2-sulfo-phenylene Red
63 -(CH2)2- 2-sulfo-4-G-Sulfatoethyl- 4-[2',4',5'-trichloro- Red
S03H sulfonyl-phenylene pyrimidin-6'-yl] amino-2-sulfo-phenylene

Example 64:
5-Aminomethylen-2-amino-naphthalene-l -sulfonic acid is condensed with 2,4,6-trifluorotriazine according to EP 526792 at pH 3-4 and 0-5°, and diazotised in the usual manner by means of sodium nitrite and hydrochloric acid at pH 1 and 0-5°C, and then coupled first coupling stage of example 3 at pH 6.5 and 0-5°C. The dyestuff of the formula

Red (>^max= 530 nm) is obtained which dyes on cotton in very deep red shades and exhibit excellent build-up in very deep shades, and good wash fastness.
Examples for dyestuff mixtures Example 65;
56.2 parts per weight of 4-ft-Sulfatoethylsulfonyl-aniline is diazotized in the usual manner in 500 parts per volume of water using 14 parts per weight of sodium nitrite, at pH 0.5-1.5 and a temperature of 0-5 °C. The freshly prepared diazonium salt is charged slowly to the intermediate mother liquor as described in example C, containing per weight 20.7 parts of example C, and added 7.9 parts per weight of 2-amino-naphthol-7-sulfonic acid, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloric acid, and temperature is raised to 5-10 °C. Approximately half the volume of the diazonium salt is

charged until the first coupling stage is completed. Then the remaining diazonium salt dispersion is charged slowly over a period of 1 h to the reaction mass obtained from first coupling stage, while during that time the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The diazonium salt is charged to the extent until the second coupling stage is completed. A mixture of the dyes of the formula is obtained

in the ratio 66.7%: 33.3%.
The dyestuff composition is isolated in the usual manner, by spray drying. The dyestuff composition provides on cotton deep red brown shades and exhibit good build-up in deep shades, and good wash fastness.
Example 66:
36.1 parts per weight of 2-Sulfo-4-J3-Sulfatoethylsulfonyl-aniline is diazotized in the usual manner in 500 parts per volume of water using 14 parts per weight of sodium nitrite, at pH 0.5-1.5 and a temperature of 0-5°C. The freshly prepared diazonium salt is charged slowly to the intermediate mother liquor as described in

example B, containing per weight 22 parts of example B, and added 7.2 parts per weight of 2-amino-naphthol-7-sulfonic acid, while during that time the pH value is adjusted to pH 1-1.5 by adding further diluted hydrochloric acid, and temperature is raised to 5-10°C. After the first coupling stage is completed, a freshly prepared solution of the diazonium salt of 28.1 parts per weight of 4-ß-Sulfatoethylsulfonyl-aniline, prepared in the same manner as in example 65, is charged slowly to the reaction mass while during charging the pH value is adjusted to pH 6.2-6.7 by adding portion wise sodium carbonate and sodium bicarbonate, and the temperature is maintained at 5-10°C. The reaction mass is stirred until the coupling is completed. A mixture of the dyes of the formula is obtained

in the ratio 70% : 30%.
The dyestuff composition is isolated in the usual manner, by spray drying. The
dyestuff composition provides on cotton deep red shades and exhibit excellent
build-up in very deep shades, and good wash fastness.
The mixtures of the following table examples are made by azo coupling of
mixtures of the underlying coupling components

Example
Dyestuff(l) Dyestuff(la) Shade
67 60% dye of example 31 40% Orange 1 Red brown
68 70% dye of example 3 30% Scarlet 1 Red brown
69 56% dye of example 3 44% Scarlet 2 Red brown
70 80% dye of example 4 20% Scarlet 1 Red brown
71 75% dye of example 10 25% Rubine 1 Rubine
72 77% dye of example 5 23% Rubine 2 Rubine
The following dyes have been used in the table examples in the mixtures



Comparative examples
The following dye stuffs are used as comparative examples:
Scarlet 1, Rubine 2, Carmine 1 and Orange 2 are known from JSDC Coloration
Technologies 125 (2009), 216. Scarlet 3 is known from US 6,011,140, example
34.
Comparative dyestuffs Orange 1 is known from US6537332, example 27, Scarlet
1 and Scarlet 2 are known from US6537332, example 87/88.

In the following table advantages of the dyestuffs of the present invention are illustrated.
In the table, DIN EN ISO105-C03 is 60 °C washing fastness and C9A fastness is Color Fastness to Wet Light according to specification of Marks & Spender. All fastness tests are obtained from dyeing in 1/1 standard depth with dyes of the present invention of formula in comparison with structural similar known dyestuffs. In the fastness test, the staining of adjacent cotton and polyamide fabric is assessed. On the assessment scale used, 5 denotes to no staining whatsoever and 1 denotes to substantial staining.
Fixation yield refers to the degree of fixation on cotton relative to the total amount of dyestuff applied in the dye bath in exhaust dyeing, carried out according to the dyeing examples 1 and 2, in % owf (in parts "of weight fabric") as mentioned in the table. The method for assessment of fixation yield is according to the published procedure as described in Dyes and Pigments, 21 (1993), 23 wherein the dyestuff concentration in the dyebath was applied at the same concentration.

Table: Comparative examples

Example Dyestuff of present Comparative Advantage of
invention Dyestuff dyestuff of the present invention
73 Example 2, Orange 1, Significantly improved
Rl,R2=H,n2=0, WQ= CH2CH2COOH staining on CO/PA : 3 / 3-4 Rl, R2=H, n2=0,
WQ = H
staining on CO/PA : 2 / 2-3 Wash fastness, much less staining on CO and PA adjacent fibre material,
C9A fastness: 3-4 C9A fastness: 2-3 significantly higher
fixation yield (3% owf): 70% fixation yield (3% owf): 50% fixation yield, significantly higher
C9A fastness
74 Example 3, Rl,R2=H,n2=l
WQ= CH2CH2COOH staining on CO/PA : 4 / 4 C9A fastness: 3-4 fixation yield (3% owf}: 75% Scarlet 1 , RI,R2=H,n2=l WQ = H
staining on CO/PA : 3-4 / 3-4
C9A fastness: 3
fixation yield (3% owf): 70% Significantly improved
Wash fastness, much
less staining on CO and
PA adjacent fibre
material
higher fixation yields
higher C9A fastnesses
75 Example 4, Rl,R2=H,n2=] WQ= CH2CH2S03H
staining on CO/PA : 4-5 / 4-5

C9A fastness: 3-4
fixation yield (3% owf): 78 %
76 Example 5, Rubine 2, Significantly improved
Rl=OCH3, R2=€H3, n2=l WQ= CH2COOH staining on CO / PA :4/4 Rl=OCH3, R2=CH3,n2=l
WQ = H
staining on CO / PA : 2-3 / 3 Wash fastness, much less staining on CO and PA adjacent fibre material
fixation yield (3% owf): 80 % fixation yield (3% owf): 75% higher fixation yields

77 Example 12, Carmine 1,
R1=0CH3, R2=H,n2=l WQ = CH2CH2COOH Rl-OCH3, R2=H, n2=l WQ = CH2S03H Significantly higher fixation yields
fixation yield (3% owf): 79% fixation yield (3% owf): 69%
78 Example 33 Carmine 1
Rl=OCH3JR2=H,n2=l WQ = CH2CH2S03H Rl=OCH3, R2=H,n2=l WQ = CH2S03H Significantly higher
fixation yields
Superior build-up (see
fixation yield (2% owf) = 76 % fixation yield (2% owf) = 69% chart below)
79 Example 4 Orange 2
Rl,R2=H,n2=l R],R2=H, n2=l higher fixation yields
WQ = CH2CH2S03H WQ = CH2S03H
fixation yield (3% owf): 76% fixation yield (3% owf): 72%


The table shows that fastnesses and fixation yields of the dyes of the present invention are superior compared to similar dyes of the closest state of the art. This is surprising given the structural similarity of the dyes.
Dyeing example 1:
100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dye bath containing 800 parts of water, 50 parts per weight of sodium chloride, and 3 parts per weight of the dyestuff of example 3. 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 red dye with excellent fastness to washing and very low contact staining is obtained.
Dyeing Example 2:
100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a dye bath containing 1000 parts of water, 50 parts per weight of sodium chloride, and 5 parts per weight of the dyestuff of example 4. 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 ml of sodium hydroxide solution 50% 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 deep red dye with excellent fastness to washing and very low contact staining 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, 50 parts per weight of the dyestuff of example 1,

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. A deep red dye with excellent fastness to washing and very low contact staining is obtained.


We claim:
1. Bisazo dyes of the formula (1) and salts thereof
wherein
R1 is a radical of the formula -W-Q wherein
W is C1-C6 Alkylene, which can be substituted by hydroxy,
Q is a carboxylic acid or inorganic acid radical, or a derivative of
carboxylic acid or inorganic acid selected from the series -COOH, -CN, -
COOR3, -CONH2, -CONHR2-, -CONR2R3-, -SO3H, a carbonyl radical
of the formula -CO-R3, or a radical -O-CO-R3 , -OSO3H , -SS03H, -
OPO3H, which form together with W an ester, wherein R2 and R3 are
independent from each other C1-C4 Alkyl, which may be further substituted
by Sulfo, Sulfato, or Hydroxy, or R2 and R3 form together a 5-or 6 ring N-
heterocyclic ring such as morpholino, pyrollidino, or piperidino, provided
that when Q is Sulfo, W is not methylene;
D1and D2 independent of each other are selected from
a radical of the formula (2a), (2b) or (2c) containing a vinylsulfone fibre
reactive group,


wherein
Y is -CH=CH2, or -CH2CH2-L in which L is a leaving group such as
Sulfato, Halogen, Acetato, Thiosulfato, or Phosphate,
R2 is C1-C4-Alkyl. C1-C4-Alkoxy, Carboxy, Halogen, hydroxyl, preferably
methoxy or methyl,
n2 is 0,1 or 2,
n3 is 0,1 or 2,
m is 0, 1 or 2,
B is -CO-NR3-W2- or -NR3-CO- W2-,
wherein
W2 is methylene,-(CH2)2-3, 1,3-phenylen, 1,4-phenylen,
R3 is hydrogen, or methyl, and when m=2, the radicals R2 may have identical or different meanings, Or
a radical of the formula (3a) or (3b), containing a fibre reactive group of the heterocyclic type,

(3a) (3b)
wherein
R4 is hydrogen or methyl, Z is a pyrimidinyl radical containing leaving groups of the series fluoro, chloro, or methylsulfonyl, and optionally additional substituents such as methyl, chloro, and cyano or a triazinyl radical of the formula


wherein
XI is a leaving group from the series chloro, fluoro, or Pyridinyl which may
be substituted by Carboxy;
X2 is chloro, cyanamino, NHQt, NQ1Q2, -NH-aryi, NR'-ary0-S02Y, -NR"-
alk0-S02Y, N(alko-S02Y)2or

wherein
ary0 is 1,3-phenylen or 1,4-phenylen, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo, R' is hydrogen, methyl, or ethyl, alko is 1,2-ethylen, 1,3-propylen or-(CH2)2-0-(CH2)2-, R" is hydrogen, methyl, or phenyl, aryi is phenyl which may be substituted independent from each other by 1 -2 substituents sulfo, methyl, methoxy, chloro, bromo, carboxy or nitro, Qi is Ci-C3-Alkyl, which may be substituted independent from each other by 1-2 substituents hydroxy, sulfo, sulfato, or acetato, Q2 has one of the meanings of Q1, preferably Q2 has the same meaning as Q1 or Q2 forms together with N and QI a 5 or 6- membered heterocyclic ring, such as morpholino, piped diono or pyrrolidino and Y has one of the above defined meanings; Or a radical of the formula

wherein Hal is Chloro or Bromo. 2. Bisazo dyes as claimed in claim 1 wherein W is selected from -CH2 -,

-(CH2)2, -CH2-CH(CH3)-, -CH(CH3)- CH2- and Q is selected from -COOH, -CN, -CONH2, -SO3H, and-OS03H.
3. Bisazo dyes as claimed in claim 2 wherein W is -(CH2)2 and Q is selected from -COOH or -S03H.
4. Bisazo dyes as claimed in any one of the preceding claims wherein Y is Vinyl, B-Sulfatoefhylsulfonyl, or B-chloroethylsulfonyl.
5. Bisazo dyes as claimed in any one of the preceding claims, wherein Rl is -CH2-COOH, -(CH2)2-COOH or -(CH2)2-S03H;

D2 is a radical of the formulae

Dl is a radical of the formulae
6. Bisazo dyes as claimed in any one of the preceding claims, wherein compound of formula (1) is preferably of the formula


wherein n2 is 0 or 1;
Y is -CH=CH2: or -CH2CH2-OS03H; Rl is -(CH2)2-COOH or -(CH2)2-S03H. 7. Bisazo dyes as claimed in any one of the claims 1-5, wherein compound of formula (1) is of the formula

wherein
n2 is 0 or 1;
Y is -CH=CH2or -CH2CH2-OS03H;
Rl is -(CH2)2-COOH or -(CH2)2-S03H.
8. Bisazo dyes as claimed in any one of the claims 6 and 7 wherein when n2 is 1, Rl is -(CH2)2-S03H.
9. Bisazo dyes as claimed in any one of the claims 6 and 7, wherein when n2 is 0 or l,Rlis-(CH2)2-COOH.
10. Bisazo dyes as claimed in any one of the claims 1-4, wherein D1 and D2 independent of each other, have at least one of the radicals of the formula (3a)


wherein R4 is hydrogen and the radical Z has one of the meanings

wherein XI is chloro or fluoro;
X2 is chloro, cyanamino, NHQ,, NQ1Q2, -NH-ary,, NR'-ary0-S02Y, -NH-(CH2)2-0 -(CH2)2 -S02Y, -NR"-(CH2)2.3-S02Y, or N[(CH2)2.3-S02Y]2 Wherein ary0 is 1,3-phenylen or 1.4-phenylen, aryi is 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl or2,5-disuIfophenyl; Qi is methyl, ethyl, B-hydroxyethyl, fl-sulfoethyl or JJ-sulfatoethyl; Q2 has one of the meanings of Q1; R' is hydrogen, methyl or ethyl;
R" is hydrogen, methyl or phenyl, Y is Vinyl, B-Sulfatoethyl, or B-chloroethyl, Hall is chloro or fluoro, Hal2 is chloro or fluoro; X3 is hydrogen or chloro. 11. Bisazo dyes as claimed in any one of the claims 1-4, wherein compound of formula (1) is preferably of the formula (5 a) or (5b)


(5a) (5b)
wherein,
the benzene rings A and B may additionally carry J or 2 substituents of sulfo, methoxy or methyl groups; Rl is -CH2-COOH, -(CH2)2-COOH or -(CH2)2-S03H; V and V independent of each other is selected from -SO2CH=CH2 or S02-CH2CH2-OS03H. 12. Bisazo dyes as claimed in any one of the claims 1-4, wherein compound of formula (1) is preferably of the formula (5 c)

wherein
V is Vinylsulfonyl or B-Sulfatoethylsulfonyl and the nucleus B carries 0-1 sulfo groups; Rl is -(CH2)2-COOH or -(CH2)2-S03H; Zl is a radical of the formula


wherein
XI' is Chloro or Fluoro; X2' is chloro, ß-Sulfoethylamino, morpholmo or
Cyanamino; Ql' is methyl, ethyl, ß-hydroxyethyl, 13-sulfoethyl or B-
sulfatoethyl; Q2' has one of the meanings of Ql; Y' is -CH=CH2, -
CH2CH2OSO3H or -CH2CH2CI.
13. Bisazo dyes as claimed in any one of the preceding claims wherein the salts of formula (1) are preferably alkali metal and alkaline earth metal salts, and are preferably in the form of their sodium, potassium or lithium salts.
14. Mixtures of bisazo dyestuffs of formula (1) as defined in claim 1 with at least one dyestuff of the formula (la), (lb), (lc), (Id), (le), (If), (lg), (lh), (li), (lj) and (Ik), wherein the compounds 1(a) to l(k) have the formula

wherein R\, Dj and D2 have one of the above defined meanings; and the ratio of the components of the mixtures (l):(la) is 99:1 to 30:70, preferably 99:1 to 55:4;
the ratio of the components of the mixtures (l):(lb) is 99:1 to 85:15, preferably 99:1 to 92:8;
the ratio of the components of the mixtures (l):(lc) is 99:1 to 85:15, preferably 99:1 to 92:8;
the ratio of the components of the mixtures (l):(ld) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (l):(le) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (l):(lf) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (l):(lg) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (l):(lh) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (l):(li) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (l):(lj) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (l):(lk) is 99:1 to 90:10, preferably 99:1 to 95:5. 15. Mixtures of bisazo dyestuffs of formula (1) with at least one dyestuff of the formula (la), (lb), (lc), (Id), (le), (If), (lg), (lh), (li), (lj) and (Ik) as

claimed in claim 14 wherein the ratio of formula (1) to the sum of the dyestuffs (la) to (Ik) is 99:1 to 25:75, preferably 99:1 to 40:60.
16. Bisazo dye mixtures as claimed in claim 14 and claim 15, wherein Dl and D2
in formula (I) and formula (la) has one of the meanings of the radical (2a) and
the ratio of the components of the mixtures (l):(la) is 90:10 to 30:70.
17. Bisazo dye mixtures as claimed in claim 16, wherein the ratio of the
components of these mixtures is (1): (la) 90:10 to 60:40.
18. Intermediates of the formula

wherein W has one of the meanings as specified in claim 1, excluding methylene and Q has one of the meanings as specified in claim 1.
19. Intermediates as claimed in claim 18, wherein W is -(CH2)2, -CH2-CH(CH3)-or -CH(CH3)- CH2- and Q is -COOH or -S03H .
20. A process for manufacturing the intermediates of formula (7) by
8a) reacting 2-amino-naphthol-7-suIfonic acid with a compound of the formula hal-W-Q, wherein hal is chloro or bromo and W and Q have one of the meanings as specified in claim 1, at a temperature of 40-80°C, and pH of 2-9, preferably 3-5,

Or,
8b) by reacting 2-amino-5-naphthol-7-sulfonic acid with a primary amine of the formula H2N-W-Q in the presence of a catalyst such as sodium bisulphite, under reaction conditions typical for the Bucherer reaction, at a

temperature of 60-130°C, preferably 80-99°C, and pH of 2-9, preferably 3-6,

Or,
8c) by reacting 2-amino-5-naphthol-7-sulfonic acid with a, B -unsaturated compounds of the formula (9) . wherein R5 and R$ are independently of each other hydrogen or methyl, and Q has one of the above meanings, at a temperature of 60-100°C, and pH of 2-9, preferably 3-7,

which yields compounds of the formula (7) wherein the radical W-Q has the meaning of the radical (9a)

Or,
8d) by reacting 2-amino-5-naphthoI-7-sulfonic acid with a primary amine of the formula H2N-W-OH in presence of a catalyst such as sodium bisulphite, at a temperature of 60-130°C, preferably 80-99°C, and pH of 2-9, preferably 3-6, followed by esterification, by using typical reagents for synthesis of sulfuric acid or phosphoric acid esters, to yield a compound of the formula (7) wherein Q is sulfato or phosphate

The process for manufacturing the intermediates of formula (7) by following the process route (8a) as claimed in claim 20 wherein W is CH2 and hal is chloro.
22. The process for manufacturing the intermediates of formula (7), by following the process route (8b) as claimed in claim 20, wherein W is CH2CH2 and Q is sulfo or carboxy.
23. The process for manufacturing the intermediates of formula (7) by following the process route (8c) as claimed in claim 20, wherein Q is carboxy and W is CH2CH2.
24. A process for dyeing and printing fibre materials which comprises treating the fibre materials with a dye of the formula (1) as claimed in claim (1).
25. The process as claimed in claim 24, wherein the fibre material is selected from, cellulose, polyamide or protein fibres preferably cotton or regenerated cellulose, viscose or Lyocell, a polyamide fibre, nylon 6 or nylon 66 or a protein fibre, wool or silk.