WO2013018057A2 - Fibre reactive bisazo reactive colorants, mixtures of reactive colorants, production and use thereof - Google Patents

Fibre reactive bisazo reactive colorants, mixtures of reactive colorants, production and use thereof Download PDF

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Publication number
WO2013018057A2
WO2013018057A2 PCT/IB2012/053966 IB2012053966W WO2013018057A2 WO 2013018057 A2 WO2013018057 A2 WO 2013018057A2 IB 2012053966 W IB2012053966 W IB 2012053966W WO 2013018057 A2 WO2013018057 A2 WO 2013018057A2
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Prior art keywords
formula
mixtures
radical
sulfo
methyl
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PCT/IB2012/053966
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French (fr)
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WO2013018057A3 (en
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Pankaj Desai
Christian Schumacher
Ashit VASHI
Nikhil Desai
Jay Patel
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Colourtex Industries Limited
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Priority to IN382MUN2014 priority Critical patent/IN2014MN00382A/en
Publication of WO2013018057A2 publication Critical patent/WO2013018057A2/en
Publication of WO2013018057A3 publication Critical patent/WO2013018057A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411—Azo dyes
    • C09B62/4415—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0047—Mixtures of two or more reactive azo dyes
    • C09B67/005—Mixtures of two or more reactive azo dyes all the reactive groups being not directly attached to a heterocyclic system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0055—Mixtures of two or more disazo dyes
    • C09B67/0057—Mixtures of two or more reactive disazo dyes
    • C09B67/0059—Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system

Definitions

  • 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.
  • G1 is hydrogen or hydroxyl
  • G2 is hydrogen or hydroxysulfonyl
  • G3 is hydrogen or arylazo
  • R1 is hydrogen or hydroxysulfonylmethyl
  • R2 is hydrogen or hydroxysulfonylmethyl
  • D is a radical of a diazo or tetraazo component having in each case at least one anchor radical of the formula S0 2 -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.
  • Ri is a radical of the formula -W-Q wherein
  • W is Ci-C 6 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, -COOR 3 , -CONH 2 , - CONHR2-, -CONR2R3-, -SO3H, a carbonyl radical of the formula -CO-R 2 , or a radical -O-CO-R3 , -OSO 3 H , -SSO 3 H, -OPO 3 H , which form together with W an organic or inorganic acid ester, wherein R 2 and R 3 are independent from each other C1-C4 Alkyl, which may be further substituted by Sulfo, Sulfato, or Hydroxy, or R 2 and R 3 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;
  • Di and D 2 are independently of each other are selected from a radical of the formula (2a), (2b) or (2c), containing a vinylsulfone fibre reactive group,
  • R 2 is CrC 4 -Alkyl, CrC 4 -Alkoxy, Carboxy, Halogen, hydroxyl, preferably methoxy or methyl,
  • n 2 0, 1 or 2
  • n 3 0, 1 or 2
  • n 0, 1 or 2
  • B is -CO-NR 3 -W 2 - or -NR 3 -CO- W 2 -,
  • W 2 is methylene, -(CH 2 ) 2 . 3 , 1 ,3-phenylen, 1 ,4-phenylen,
  • R 3 is hydrogen, or methyl
  • radicals R 2 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,
  • R 4 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
  • X1 is a leaving group from the series chloro, fluoro, or Pyridinyl which may be substituted by Carboxy,
  • X2 is chloro, cyanamino, NHQi , NQ 1 Q 2 , -NH-aryi , NR ' -ary 0 -S0 2 Y, -NR " -alk 0 -S0 2 Y, N(alk 0 -S02Y) 2 or
  • ary 0 is 1 ,3-phenylen or 1 ,4-phenylen, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo,
  • FT is hydrogen, methyl, or ethyl
  • alk o is 1 ,2-ethylen, 1 ,3-propylen or -(CH 2 ) 2 -0-(CH 2 ) 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 CrC 3 -Alkyl, which may be substituted independent from each other by 1 -2 substituents hydroxy, sulfo, sulfato, or acetato,
  • Q 2 has one of the meanings of Qi , preferably Q 2 has the same meaning as Qi , or Q 2 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
  • Figurel provides graphical representation to show Build-Up comparison of example 33 vs Carmine 1 : K/S vs %owf dye concentration
  • the dyestuffs of the present invention have the formula (1 )
  • Ri is a radical of the formula -W-Q wherein
  • W is Ci-C 6 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, -COOR 3 , -CONH 2 , -CONHR 2 -, - CONR2R3-, -SO3H, a carbonyl radical of the formula -CO-R 2 , or a radical -O-CO-R3 , - OSO 3 H , -SSO 3 H, -OPO 3 H, which form together with W an organic or inorganic acid ester, wherein R 2 and R 3 , independently of each other, are C1-C4 alkyl, which may be further substituted by sulfo, sulfato, or hydroxy, or R 2 and R 3 form together a 5-or 6 ring N- heterocyclic ring such as morpholino, pyrollidino, or piperidino.
  • W is -CH 2 -, -(CH 2 ) 2 , -CH 2 -CH(CH 3 )-, -CH(CH 3 )- CH 2 -, and
  • Q is -COOH, -CN, -CONH 2 , -S0 3 H, and -OS0 3 H .
  • preferred radicals W are -(CH 2 ) - and -(CH 2 ) 2 - .
  • preferred radicals Q are COOH and S0 3 H.
  • D- and D 2 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 D and D 2 , preferably one fibre reactive group in both D- and D 2 , 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.
  • the fibre reactive group is of the vinylsulfone type, it also includes ⁇ -ethylsulfone substituted in ⁇ -position by a leaving group removable under alkaline medium.
  • 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,
  • R 2 is CrC 4 -alkyl, Ci -C 4 -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 ,
  • n 0, 1 or 2
  • B is -CO-NR 3 -W 2 - or -NR 3 -CO- W 2 - ,
  • the benzene ring carries 0-2 identical or different substituents of Ci-C 3 -alkoxy, preferably methoxy, C C 3 -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 ⁇ - sulfatoethyl.
  • R 4 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-pyrimidinyl, or Z is a triazinyl radical of the formula (4)
  • Xi is a leaving group from the series chloro or fluoro, or pyridinyl which may be substituted by carboxy
  • X 2 is chloro, cyanamino, NHQi , NQ 1 Q 2 , -NH-aryi , NR ' -ary 0 -S0 2 Y, -NR " -alk 0 -S0 2 Y, N (alk 0 -S0 2 Y) 2 or
  • ary 0 is 1 ,3-phenylene or 1 ,4-phenylene, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo,
  • FT is hydrogen, methyl, or ethyl
  • alk o is 1 ,2-ethylen, 1 ,3-propylen or -(CH 2 ) 2 -0-(CH 2 ) 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 CrC 3 -alkyl, which may be substituted independently of each other by 1 -2 substituents hydroxy, sulfo, sulfato, or acetato, preferably Qi is methyl, ethyl, ⁇ - hydroxyethyl, ⁇ -sulfoethyl or ⁇ -sulfatoethyl,
  • Q 2 has one of the meanings of Qi , preferably Q 2 has the same meaning as Qi , or
  • Q 2 forms together with N and Qi a 5 or 6- membered heterocyclic ring, such as morpholino, piperidiono or pyrrolidino, and Y has one of the above defined meanings,
  • Di is a radical of the formula
  • D 2 has, independently of the meaning of Di , one of the meanings of Di .
  • the dyestuffs wherein the radical WQ is CH 2 S0 3 H, in case and D 2 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 CH 2 S0 3 H, in case D- is a radical of the formula (2a) wherein n2 is 2, m is 0, and D 2 a radical of the formula (3a) , wherein Z is a radical of the formula,
  • Ci-C 6 alkylene 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-butylene, 1 ,5- pentylene, 1 ,6-hexylene, 2-hydroxy-1 ,2-ethylene, 3-hydroxy-1 ,3-propylene, 2-hydroxy-1 ,2- propylene, 4-hydroxy-1 ,4-butylene, 3-hydroxy-1 ,3-butylene , 5-hydroxy-1 ,5-pentylene , 6- hydroxy-1 ,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.
  • radicals Q are COOH, CN, COOC 2 H 5 , COOCH 3 , CONH 2 ,
  • radicals W-Q are -CH 2 -COOH, -CH 2 CH 2 -COOH, -CH(CH 3 )-CH 2 -COOH, CH 2 -CH(CH 3 )-COOH, -(CH 2 ) 3 -COOH, -(CH 2 ) 4 -COOH, -(CH 2 ) 5 -COOH, -(CH 2 ) 6 -COOH, CH 2 CH 2 -S03H, -CH 2 CH 2 -0-S03H, -CH 2 CH 2 -S-S03H, -CH 2 CH 2 -0-P03H, -CH 2 _-CN, - CH 2 CH 2 -CN, -CH(CH 3 )-CH 2 -CN, -CH 2 -CH(CH 3 )-CN,-(CH 2 ) 3 -CN, -(CH 2 ) 4 -CN, -(CH 2 ) 5 -CN,- (CH 2 ) 6 -CN,
  • Preferred radicals for W-Q are -CH 2 -COOH, -CH 2 CH 2 -COOH, -CH(CH 3 )-CH 2 -COOH,- CH 2 CH(CH 3 )-COOH, -CH 2 CH 2 -S0 3 H and -CH 2 CH 2 -OS0 3 H.
  • radicals (2a) are examples for radicals (2a).
  • radicals (2b) are examples for radicals (2b).
  • radicals 2d) and (2e) are examples of radicals 2d).
  • radicals (3b) are examples for radicals (3b).
  • radicals Z in radicals (3a) are examples of radicals Z in radicals (3a).
  • FV is -CH 2 -COOH, -CH 2 CH 2 -COOH, -CH(CH 3 )-CH 2 -COOH, -CH 2 -CH(CH 3 )-COOH, - CH 2 CH 2 -CN, -CH 2 CH 2 -CONH 2 , -CH 2 CH 2 -S0 3 H and -CH 2 CH 2 -OS0 3 H, and in particular, especially preferred radicals FV are -CH 2 -COOH , -CH 2 CH 2 -COOH and -CH 2 CH 2 -S0 3 H, the benzene rings(6a and (6b)
  • sulfo may additionally carry 1 or 2 substituents of sulfo, 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 has, independent of the radical V, one of the meanings of the radical V,
  • Z- is one of the following radicals
  • ⁇ is chloro or fluoro
  • X 2 ' is chloro, ⁇ -sulfoethylamino, morpholino or cyanamino
  • Qi ' is methyl, ethyl, n-propyl, ⁇ -hydroxyethyl, ⁇ -sulfoethyl or ⁇ -sulfatoethyl,
  • Q 2 ' has one of the meanings of Qi , preferably Q 2 has the same meaning as Qi ,
  • V and V are vinylsulfonyl or ⁇ -sulfatoethylsulfonyl located in meta or para position to the azo link.
  • especially preferred dyestuffs of the formula (5a) are structures of the formula (5a ' ) and (5a " )
  • Ri is -(CH 2 ) 2 -COOH or -(CH 2 ) 2 -S0 3 H.
  • the present invention includes mixtures of dyestuffs of formula (1 ) with at least one dyestuff of the formula (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g), (1 h), (1 i), (1j) and (1 k), wherein the ratio of the components of these mixtures (1 ):(1 a) is 99:1 to 30:70, preferably
  • the ratio of the components of the mixtures (1 ):(1 b) is 99:1 to 85:15, preferably 96:4 to 92:8;
  • the ratio of the components of the mixtures (1 ):(1 c) is 99:1 to 85:15, preferably 96:4 to 92:8; the ratio of the components of the mixtures (1 :(1 d) is 99:1 to 90:10, preferably 99:1 to 95:5;
  • the ratio of the components of the mixtures (1 :(1 e) is 99:1 to 90:10, preferably 99:1 to 95:5;
  • the ratio of the components of the mixtures (1 :(1 f) is 99:1 to 90:10, preferably 99:1 to 95:5;
  • the ratio of the components of the mixtures (1 :(1 g) is 99:1 to 85:15, preferably 99:1 to 94:6;
  • the ratio of the components of the mixtures (1 :(1 h) is 99:1 to 85:15, preferably 99:1 to 94:6;
  • the ratio of the components of the mixtures (1 :(1 i) is 99:1 to 85:15, preferably 99:1 to 94:6;
  • the ratio of the components of the mixtures (1 :(1j) is 99:1 to 85:15, preferably 99:1 to 94:6;
  • the ratio of the components of the mixtures (1 :(1 k) is 99:1 to 90:10, preferably 99:1 to 95:5, and
  • the mixtures may contain several dyestuffs of (1 a) to (1 k), provided that the ratio of (1 ) to the sum of the dyestuffs (1 a) to (1 k) is 99:1 o 25:75, preferably 99:1 to 40:60.
  • R 1 ; D-i and D 2 have one of the above defined meanings.
  • Especially preferred mixtures of the compounds of formula (1 ) and compounds of formula (1 a) are mixtures of (5a ' ) with (1 a ' ) wherein D1 and D2 have one of the meanings of the radical (2a) and the ratio of the mixing components is 90:10 to 60:40.
  • mixtures of the compounds of formula (1 ) and compounds of formula (1 a) are mixtures of (5a “ ) with (1 a " ) wherein D1 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 (1 a), (1 e), (1 f), (1 i) and (1j) are already known.
  • the dyestuffs of the formula (1 b), (1 c), (1 d), (1 g), (1 h) and (1 k) are new compounds, and are also included as single dyestuff components in the present invention, excluding dyestuffs (1 b) wherein Ri is CH 2 S0 3 H and D1 is a radical of the formula (2a) since it is known from prior art.
  • the compounds (1 a) to (1 k) may be formed as byproducts in the manufacturing of the dyestuffs of the present invention, or added to the mixtures after separate manufacturing operation.
  • Th resent invention includes intermediates of the formula
  • W and Q have one of the above specified meanings.
  • W is C 2 -C 6 alkylene, which can be substituted by hydroxy
  • 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 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,
  • reaction path (8b) by reacting 2-amino-5-naphthol-7-sulfonic acid with a primary amine of the formula H 2 N-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,
  • a catalyst such as sodium bisulphite
  • reaction path (8c) by reacting 2-amino-5-naphthol-7-sulfonic acid with ⁇ . ⁇ -unsaturated compounds of the formula (9) , wherein R 5 and R 6 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,
  • reaction path (8d) by reacting 2-amino-5-naphthol-7-sulfonic acid with a primary amine of the formula H 2 N-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 phosphato. 2. esterification
  • reaction path (8c) which yield ⁇ -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-sulfoethylamin 2-sulfopropylamin, 3-aminopropionic acid, 2-aminopropionic acid, 4- aminobutyric acid, 3-aminobutyric acid, 2-aminobutyric acid.
  • Examples for compounds H 2 N-W-OH are 2-Aminoethanol, 3-aminopropanol, 2- aminopropanol, 4-aminobutanol, 3-aminobutanol.
  • 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 D N 2 + and D N 2 + , which are made in the usual way from the aromatic amines D NH ⁇ and D 2 -NH 2 in acidic conditions by use of sodium nitrite and acid, e.g. hydrochloric or sulfuric acid,
  • 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.
  • the present invention provides a process for dyeing from aqueous bath and printing of fibre materials with the dyes of the present invention.
  • 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.
  • 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.
  • 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.
  • alkali used for fixation examples 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.
  • 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.
  • 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 9-1 1 , 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.
  • the dyeing obtained with the dyes of the present invention is dischargeable and can be applied in discharge printing.
  • J-acid 2-amino-naphthol-7-sulfonic acid
  • chloro acetic acid 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 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
  • J-acid 2-amino-naphthol-7-sulfonic acid
  • ⁇ -alanine 10 parts per weight of sodium bisulfite
  • 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.
  • J-acid 2-amino-naphthol-7-sulfonic acid
  • methacrylic acid 9-amino-naphthol-7-sulfonic acid
  • J-acid 2-amino-naphthol-7-sulfonic acid
  • 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.
  • reaction mass is stirred for 4 hrs at pH 1 and 0-5 °C to carry out the 1 st 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 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
  • 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.
  • 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 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.
  • 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 is isolated in the usual manner by spray drying.
  • the dyestuff provides dyeing on cotton in deep rubine shades and exhibit good build-up in very deep shades, and good wash fastness.
  • Rubine k 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 build-up in very deep shades, and good wash fastness
  • 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 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
  • 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 ' ⁇ . The diazonium salt is charged to the extent until the second coupling stage is completed.
  • 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.
  • 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.
  • 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.
  • 5-Aminomethylen-2-amino-naphthalene-1 -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.
  • diazonium salt 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.
  • 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.
  • 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.
  • Scarlet 3 is known from US 6,01 1 ,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.
  • 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.
  • WQ CH 2 COOH
  • WQ H CO and PA staining on CO / PA : 4 staining on CO / PA : adjacent fibre material
  • 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 ⁇ ' ⁇ , 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.
  • 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.

Abstract

Bisazo dyes based on derivatives of N-substituted 2-amino-5-naphthol-7-sulfonic acid of formula (1) wherein R is a radical of the formula -W-Q wherein W is C1-C6 Alkylene, which can be substituted by hydroxyl group, D1 and D2 are independently of each other a benzene or naphthyl radical, which are 10 substituted by fibre reactive groups, containing at least one fibre reactive group in both D1 and D2, wherein the fibre reactive groups are independent from each other of the vinylsulfone type, of a heterocyclic type, in particular of the halogenpyrimidinyl or halogentriazinyl reactive group, or of the acrylamide type which is substituted by halogen, which can be applied as single dye or as mixture or in combination with other compatible 1 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.

Description

FIBRE REACTIVE BISAZO REACTIVE COLORANTS, MIXTURES OF REACTIVE COLORANTS, PRODUCTION AND USE THEREOF
FIELD OF INVENTION
The present invention relates to compounds of the formula (1 )
Figure imgf000003_0001
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. 6,01 1 ,140. Patent No. 6,01 1 ,140 describes reactive d es of the formula
Figure imgf000003_0002
wherein n is 1 or 2, G1 is hydrogen or hydroxyl, G2 is hydrogen or hydroxysulfonyl, G3 is hydrogen or arylazo, R1 is hydrogen or hydroxysulfonylmethyl, R2 is hydrogen or hydroxysulfonylmethyl, and D is a radical of a diazo or tetraazo component having in each case at least one anchor radical of the formula S02-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 β-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
Figure imgf000005_0001
(1 )
wherein
Ri is a radical of the formula -W-Q wherein
W is Ci-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 , -OSO3H , -SSO3H, -OPO3H , which form together with W an organic or inorganic acid 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;
Di 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,
Figure imgf000006_0001
(2a) (2b) (2c)
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 CrC4-Alkyl, CrC4-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 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,
Figure imgf000006_0002
(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 or triazinyl radical radical of the formula
Figure imgf000007_0001
wherein
X1 is a leaving group from the series chloro, fluoro, or Pyridinyl which may be substituted by Carboxy,
X2 is chloro, cyanamino, NHQi , NQ1Q2, -NH-aryi , NR'-ary0-S02Y, -NR"-alk0-S02Y, N(alk0-S02Y)2 or
Figure imgf000007_0002
wherein
ary0 is 1 ,3-phenylen or 1 ,4-phenylen, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo,
FT 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 CrC3-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 Qi , 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
Figure imgf000007_0003
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 (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g), (1 h), (1 i), (1j) and (1 k), wherein the ratio of formula (1 ) to the sum of the dyestuffs (1 a) to (1 k) is 99:1 to 25:75.
According to yet another aspect of the invention, there is provided intermediates of bisazo dyestuffs of the formula
Figure imgf000008_0001
According to yet another aspect of the invention there is provided a process for
manufacturing the intermediates of formula (7).
DESCRIPTION OF FIGURE
Figurel provides graphical representation to show Build-Up comparison of example 33 vs Carmine 1 : K/S vs %owf dye concentration
DETAILED DESCRIPTION
The dyestuffs of the present invention have the formula (1 )
Figure imgf000008_0002
(1 )
Wherein
Ri is a radical of the formula -W-Q wherein
W is Ci-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 Ri ,
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 S03H.
D- 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 D and D2, preferably one fibre reactive group in both D- 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 β-ethylsulfone substituted in β-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,
Figure imgf000009_0001
(2a) (2b) (2c)
Figure imgf000009_0002
(2d) (2e)
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,
R2 is CrC4-alkyl, Ci -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
Figure imgf000010_0001
carries 0-2 identical or different substituents of Ci-C3-alkoxy, preferably methoxy, C 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 β- sulfatoethyl.
Further Di is also a radical of the formula (3a) or (3b), containing a fibre reactive group of a heterocyclic type,
Figure imgf000010_0002
(3a) (3b)
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-pyrimidinyl, or Z is a triazinyl radical of the formula (4)
Figure imgf000010_0003
wherein Xi is a leaving group from the series chloro or fluoro, or pyridinyl which may be substituted by carboxy,
X2 is chloro, cyanamino, NHQi , NQ1Q2, -NH-aryi , NR'-ary0-S02Y, -NR"-alk0-S02Y, N (alk0-S02Y)2 or
Figure imgf000011_0001
wherein
ary0 is 1 ,3-phenylene or 1 ,4-phenylene, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo,
FT 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 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 CrC3-alkyl, which may be substituted independently of each other by 1 -2 substituents hydroxy, sulfo, sulfato, or acetato, preferably Qi is methyl, ethyl, β- hydroxyethyl, β-sulfoethyl or β-sulfatoethyl,
Q2 has one of the meanings of Qi , preferably Q2 has the same meaning as Qi , or
Q2 forms together with N and Qi a 5 or 6- membered heterocyclic ring, such as morpholino, piperidiono or pyrrolidino, and Y has one of the above defined meanings, Furthermore Di is a radical of the formula
Figure imgf000011_0002
wherein Hal is halogen, chloro or bromo , preferably bromine, D2 has, independently of the meaning of Di , one of the meanings of Di . The dyestuffs wherein the radical WQ is CH2S03H, in case 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 CH2S03H, in case D- is a radical of the formula (2a) wherein n2 is 2, m is 0, and D2 a radical of the formula (3a) , wherein Z is a radical of the formula,
SO,H
S02 \— o— SO3H
are also excluded since these dyes are already disclosed in prior art.
As Ci-C6 alkylene 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-butylene, 1 ,5- pentylene, 1 ,6-hexylene, 2-hydroxy-1 ,2-ethylene, 3-hydroxy-1 ,3-propylene, 2-hydroxy-1 ,2- propylene, 4-hydroxy-1 ,4-butylene, 3-hydroxy-1 ,3-butylene , 5-hydroxy-1 ,5-pentylene , 6- hydroxy-1 ,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, COOCH3, 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 f the formula
Figure imgf000012_0001
S03H, COCH3, COC2H5 , -0-CO-CH3 , -0-CO-C2H5 , -0-CO-C3H7 , -O-CO-C4H9 , OS03H -SSQ3H or -OPQ3H.
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)2, -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, -CH2CH2-COOCH2-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- vinylsulfonyl-phenyl,
3- vinylsulfonyl-phenyl,
2-methoxy-5-vinylsulfonyl-phenyl,
2,5-dimethoxy-4-vinylsulfonyl-phenyl,
2- methoxy-5-methyl -4-vinylsulfonyl-phenyl,
4- (2'-chloroethyl)sulfonyl-phenyl,
3- (2'-chloroethyl)sulfonyl-phenyl,
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-(B-sulfatoethylsulfonyl)-napth-2-yl,
6-(3-sulfatoethylsulfonyl)-1 -sulfo-napth-2-yl,
8-(B-sulfatoethylsulfonyl)-napth-2-yl,
8-(B-sulfatoethylsulfonyl)-6-sulfo-napth-2-yl,
5- (B-sulfatoethylsulfonyl)-napth-2-yl,
5-(B-sulfatoethylsulfonyl)-1 -sulfo-napth-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'-sulfatoethylsulfonyl)-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'-sulfatoethylsulfonyl)-phenyl]amidocarbonyl-phenyl,
4- [3-(2'-sulfatoethylsulfonyl)-phenyl]carbonylamido-phenyl,
4- [3-(2'-sulfatoethylsulfonyl)-phenyl]carbonylamido-1 -sulfo-phenyl,
3- [3-(2'-sulfatoethylsulfonyl)-phenyl]carbonylamido-phenyl,
3- [3-(2'-sulfatoethylsulfonyl)-phenyl]carbonylamido-1 -sulfo-phenyl,
Examples for radicals 2d) and (2e) are
Figure imgf000014_0001
Examples for radicals (3b) are
5-[2',4'-difluorpyrimidinyl]aminomethylen-1 -sulfo-napth-2-yl, 5-[5'chlor-2',4'-difluorpyrimidinyl]aminomethylen-1 -sulfo-napth-2-yl,
Examples for radicals Z in radicals (3a) are
2,4-difluorpyrimidinyl,
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'-3-sulfatoethylsulfonyl-ethyl}aminotriazinyl,
2-fluor-4-{3'-B-sulfatoethylsulfonyl-propyl}aminotriazinyl,
2-chlor-4-{2'-B-sulfatoethylsulfonyl-ethyl}aminotriazinyl,
2-chlor-4-{2'- -chlorethylsulfonyl-ethyl}aminotriazinyl,
2-chlor-4-bis{2'- -chlorethylsulfonyl-ethyl}aminotriazinyl,
2-chlor-4-bis{3'-B-chlorethylsulfonyl-propyl}aminotriazinyl,
2-fluor-4-[methyl-{2'- -sulfatoethylsulfonyl-ethyl}]aminotriazinyl,
2-fluor-4-[phenyl-{2'- -sulfatoethylsulfonyl-ethyl}]aminotriazinyl,
2-chlor-4-{3'- -sulfatoethylsulfonyl-propyl}aminotriazinyl,
2-chlor-4-{4'-B-sulfatoethylsulfonyl-phenyl}aminotriazinyl,
2-chlor-4-{3'-B-sulfatoethylsulfonyl-phenyl}aminotriazinyl,
2-chlor- 4-[ethyl -{3'-B-sulfatoethylsulfonyl-phenyl}]-aminotriazinyl,
2-chlor- 4-[ethyl -{4'-B-sulfatoethylsulfonyl-phenyl}]-aminotriazinyl.
Such radicals (3a) and their manufacturing are known from many publications and patents. Preferred structures of formula (1 ) are dyes of the formula (5a), (5b) or (5c)
Figure imgf000015_0001
(5a) (5b)
Figure imgf000016_0001
wherein
FVis -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 FV are -CH2-COOH , -CH2CH2-COOH and -CH2CH2-S03H, the benzene rings(6a and (6b)
Figure imgf000016_0002
(6a) (6b)
may additionally carry 1 or 2 substituents of sulfo, 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-CI,
V has, independent of the radical V, one of the meanings of the radical V,
Z- is one of the following radicals
Figure imgf000017_0001
wherein
ΧΓ is chloro or fluoro,
X2 ' is chloro, β-sulfoethylamino, morpholino or cyanamino,
Qi ' is methyl, ethyl, n-propyl, β-hydroxyethyl, β-sulfoethyl or β-sulfatoethyl,
Q2 ' has one of the meanings of Qi , preferably Q2 has the same meaning as Qi ,
Y' is -CH=CH2, -CH2CH2OS03H or -CH2CH2CI.
Preferably V and V are vinylsulfonyl or β-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")
Figure imgf000018_0001
(5a') (5a") wherein,
Y is -CH=CH2 or -CH2CH2-OS03H,
Ri is -(CH2)2-COOH or -(CH2)2-S03H.
In particular, especially preferred radicals D are
Figure imgf000018_0002
In particular, especially preferred radicals D2 are
Figure imgf000018_0003
The present invention includes mixtures of dyestuffs of formula (1 ) with at least one dyestuff of the formula (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g), (1 h), (1 i), (1j) and (1 k), wherein the ratio of the components of these mixtures (1 ):(1 a) is 99:1 to 30:70, preferably
80:20 to 55:45;
the ratio of the components of the mixtures (1 ):(1 b) is 99:1 to 85:15, preferably 96:4 to 92:8;
the ratio of the components of the mixtures (1 ):(1 c) is 99:1 to 85:15, preferably 96:4 to 92:8; the ratio of the components of the mixtures (1 :(1 d) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (1 :(1 e) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (1 :(1 f) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (1 :(1 g) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (1 :(1 h) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (1 :(1 i) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (1 :(1j) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (1 :(1 k) is 99:1 to 90:10, preferably 99:1 to 95:5, and
wherein the mixtures may contain several dyestuffs of (1 a) to (1 k), provided that the ratio of (1 ) to the sum of the dyestuffs (1 a) to (1 k) is 99:1 o 25:75, preferably 99:1 to 40:60.
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000020_0001
Figure imgf000020_0002
wherein R1 ; D-i 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 (1 a) wherein D1 and D2 have one of the meanings of the radical (2a) and the ratio of the components of these mixtures is (1 ):(1 a) is 90:10 to 60:40.
Especially preferred mixtures of the compounds of formula (1 ) and compounds of formula (1 a) are mixtures of (5a') with (1 a') wherein D1 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 (1 a) are mixtures of (5a") with (1 a") wherein D1 and D2 have one of the meanings of the radical (2a) and the ratio of the mixing components is 90:10 to 60:40.
Figure imgf000021_0001
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 (1 a), (1 e), (1 f), (1 i) and (1j) are already known. The dyestuffs of the formula (1 b), (1 c), (1 d), (1 g), (1 h) and (1 k) are new compounds, and are also included as single dyestuff components in the present invention, excluding dyestuffs (1 b) wherein Ri is CH2S03H and D1 is a radical of the formula (2a) since it is known from prior art. The compounds (1 a) to (1 k) may be formed as byproducts in the manufacturing of the dyestuffs of the present invention, or added to the mixtures after separate manufacturing operation.
Th resent invention includes intermediates of the formula
Figure imgf000021_0002
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.
Figure imgf000022_0001
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'-yl} 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'-yl}amino)butanamide,
N-(B-hydroxyethyl)-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 preferre
Figure imgf000023_0001
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,
Figure imgf000024_0001
(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,
Figure imgf000024_0002
(8b)
Or, according to reaction path (8c), by reacting 2-amino-5-naphthol-7-sulfonic acid with □.β -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,
Figure imgf000024_0003
(8c)
which yields compounds of the formula (7) wherein the radical W-Q has the meaning of the radical (9a)
Figure imgf000024_0004
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 phosphato.
Figure imgf000025_0001
2. esterification
Q = OS03H, OP03H,..
(8d) 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 β-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- chloropropionic 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, crotonic acid methyl ester, methacrylic acid methyl ester, N- methyl-acrylamide, Ν,Ν-dimethyl-acrylamide , N-ethyl-acrylamide, N,N-diethyl-acrylamide, Ν-β-sulfoethyl-acrylamide, Ν-β-hydroxyethyl-acrylamide, N,N-bis(B-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 D N2 + and D N2 +, which are made in the usual way from the aromatic amines D NH^ and D2-NH2 in acidic conditions by use of sodium nitrite and acid, e.g. hydrochloric or sulfuric acid,
Figure imgf000026_0001
(10a) wherein the radicals D-\ 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.
In particular, examples for preferred dyes of the present invention are
Figure imgf000027_0001
Figure imgf000027_0002

Figure imgf000028_0001
Example 4
Figure imgf000028_0002
Example 5
Figure imgf000028_0003
Exam le 6
Figure imgf000029_0001
Example 8
COOH
Figure imgf000029_0002
Figure imgf000030_0001
Example 10
Figure imgf000030_0002
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 9-1 1 , 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-naphthol-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
Figure imgf000032_0001
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 8b)
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
Figure imgf000033_0001
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 β-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.
Figure imgf000033_0002
Alternative synthesis procedure for Intermediate Example C (path 8c - 1 step 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 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-(B-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)
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
Figure imgf000034_0001
is obtained as solution in the mother liquor which directly used for coupling as described in example 24.
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 com ound of the formula
Figure imgf000034_0002
is obtained which is used without further isolation as outlined in example 6.
Further examples:
Figure imgf000035_0001
Figure imgf000036_0001
Examples for dvestuffs of the present invention :
Example 1 :
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 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-B-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 5-10 °C. The diazonium salt is charged to the extent until the second coupling stage is completed.
The dyestuff of the formula H03S0 H— COOH
Figure imgf000037_0001
rubine, kmax= 533 nm)
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-B-Sulfatoethylsulfonyl-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 1 st 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 H
Figure imgf000038_0001
red-brown kmax= 506 nm)
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 3:
To a dispersion of 36 parts per weight of 2-Sulfo-4-B-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-B-Sulfatoethylsulfonyl-aniline 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
Figure imgf000039_0001
Carmine kmax= 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-B-Sulfatoethylsulfonyl- 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
Figure imgf000040_0001
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-Sulfatoethylsulfonyl-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
Figure imgf000041_0001
Rubine kmax= 532)
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 build-up 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-B-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
Figure imgf000042_0001
Rubine kmax= 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 build-up in very deep shades, and good wash fastness
Figure imgf000043_0001
Figure imgf000043_0002
-CH2-CH2- 4-Vinylsulfonyl-phenylen 4-Sulfatoethyl- Red COOH sulfonyl-phenylen brown
-CH2-CH2- 4-Vinylsulfonyl-phenylen 4-Vinylsulfonyl- Red COOH phenylen brown
-CH2-CH2- 2-Sulfo-4-Vinylsulfonyl- 4-Sulfatoethyl- Red COOH phenylen sulfonyl-phenylen brown
-CH2-CH2- 2-Sulfo-4-Vinylsulfonyl- 4-Vinylsulfonyl- Red COOH phenylen phenylen brown
-CH2-CH2- 2-sulfo -4-β- 4-B-Chloroethyl- Red COOH Sulfatoethyl-sulfonyl- sulfonyl-phenylene brown phenylene
-CH2-CH2-CN 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red sulfonyl-phenylen sulfonyl-phenylene brown
-(CH2)3-CN 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-CH2- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red COCH3 sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-CH2- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red COOCH3 sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-CH2- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red COOC2H5 sulfonyl-phenylene sulfonyl-phenylene brown
-CH(CH3)-CH2- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red COOCH3 sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-CH(CH3)- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red COOH sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-CH(CH3)- 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red COO CH3 sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 4-Sulfatoethyl- Red sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 2-methoxy-5- Rubin sulfonyl-phenylene methyl-4- e
Sulfatoethyl- sulfonyl-phenylene
-CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 2,5-methoxy- 4- Purple sulfonyl-phenylene Sulfatoethyl- sulfonyl-phenylene
-CH2-CH2-SO3H 4-B-Sulfatoethyl- 4-B-Sulfatoethyl- Red sulfonyl-phenylen sulfonyl-phenylene brown
-CH2-CH2-SO3H 2-Sulfo-4-B-Sulfato 2-methoxy-5- Rubin ethyl-sulfonyl-phenylen methyl- e
4-Sulfatoethyl- sulfonyl-phenylene
-CH2-CH2-SO3H 2-Sulfo-4-B-Sulfato 2-methoxy-5- Rubin ethyl-sulfonyl-phenylen Sulfatoethyl- e sulfonyl-phenylene
-CH2-CH2-SO3H 2-Sulfo-4-B-Sulfato 2-chloro-4- Rubin ethyl-sulfonyl-phenylene Sulfatoethyl- e sulfonyl-phenylene
-CH2-CH2- 2-Sulfo-4-B-Sulfato 4-B-Sulfato ethyl- Red CONH2 ethyl-sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-CH2- 2-Sulfo-4-B-Sulfato 4-B-Sulfato ethyl- Red CONH(CH3) ethyl-sulfonyl-phenylene sulfonyl-phenylene brown
-CH2-CH2- 2-Sulfo-4-B-Sulfato 4-B-Sulfato ethyl- Red
CONH- ethyl-sulfonyl-phenylene sulfonyl-phenylene brown CH2CH2OH
-CH2-CH2- 2-Sulfo-4-B-Sulfato 4-B-Sulfato ethyl- Red CONH- ethyl-sulfonyl-phenylene sulfonyl-phenylene brown CH2CH2SO3H 39 2-Sulfo-4-B-Sulfato 4-B-Sulfato ethyl- Red
ethyl-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
Figure imgf000046_0001
Red brown ( max= 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 'Ό. The diazonium salt is charged to the extent until the second coupling stage is completed.
The dyestuff of the formula
Figure imgf000047_0001
Red ( max= 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.
Figure imgf000047_0002
47 -(CH2)2- 4-B-Sulfato ethyl-sulfonyl- 1 -Sulfo- 6-Sulfatoethyl- red
COOH phenylene sulfonyl-naphth-2- ylene
48 -(CH2)2- 1 -Sulfo- 6-Sulfatoethyl- 1 -Sulfo- 6-Sulfatoethyl- red
COOH sulfonyl-naphth-2-ylene 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-methyl- 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- β-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-diaminobenzol-6-sulfonic 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.
The dyestuff of the formula
oso3H
Figure imgf000049_0001
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-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, 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 H20 and 0.75 parts per weight of disodium hydrogen phosphate x 2 H20 is added. Then 1 5 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
Figure imgf000050_0001
Red ( max= 525 nm )
is obtained which dyes on cotton in very deep red shades and exhibit excellent build-up very deep shades, and good wash fastness.
Figure imgf000050_0002
-(CH2)2- 4-B-Sulfatoethyl- 5-[2'-chloro-4'-{3"- Red S03H sulfonyl-phenylene sulfophenyljamino- triazin-6'-yl] amino-2- sulfo-phenylene
-(CH2)2- 4-B-Sulfatoethyl- 5-[2'-chloro-4'-{2"- Red COOH sulfonyl-phenylene hydroxyethyljamino- triazin-6'-yl] amino-2- sulfo-phenylene
-(CH2)2- 4-B-Sulfatoethyl- 5-[2'-fluoro-4'-{3"-B- Red COOH sulfonyl-phenylene sulfatoethylsulfonyl- propyljamino-triazin- 6'-yl] amino-2-sulfo- phenylene
-CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 5-[2'-fluoro-4'-{2"-B- Red sulfonyl-phenylene sulfatoethylsulfonyl- ethyl}amino-triazin-6'- yl] amino-2-sulfo- phenylene
CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 5-[2'-fluoro-4'-N- Red sulfonyl-phenylene methyl-{2"-B- sulfatoethylsulfonyl- ethyl}-amino-triazin-6'- yl] amino-2-sulfo- phenylene
CH2-COOH 2-sulfo-4-B-Sulfatoethyl- 5-[2'-fluoro-4'-N- Red sulfonyl-phenylene phenyl-{2"-B- sulfatoethylsulfonyl- ethyl}-amino-triazin-6'- yl] amino-2-sulfo- phenylene
-(CH2)2- 4-vinylsulfonyl- 4-[2'-chloro-4'-{3"- Red S03H phenylene sulfophenyl} amino- triazin-6'-yl] amino-2- sulfo-phenylene
62 -(CH2)2- 4-vinylsulfonyl- 5-[2',4',5'-trichloro- Red
COOH phenylene pyrimidin-6'-yl] amino- 2-sulfo-phenylene
63 -(CH2)2- 2-sulfo-4-B-Sulfatoethyl- 4-[2',4',5'-trichloro- Red
S03H sulfonyl-phenylene pyrimidin-6'-yl] amino- 2-sulfo-phenylene
Example 64:
5-Aminomethylen-2-amino-naphthalene-1 -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
Figure imgf000052_0001
Red kmax= 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-B-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
Figure imgf000053_0001
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-B-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- β-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 d es of the formula is obtained
Figure imgf000054_0001
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 (1 ) Dyestuff ( 1 a) 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 53
Figure imgf000055_0001
Comparative examples
The following dyestuffs 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 6,01 1 ,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.
Carmine 1 ,
Orange 2
Figure imgf000056_0001
Scarlet 3
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
Figure imgf000058_0001
Example Dyestuff of present Comparative Advantage of invention Dyestuff dyestuff of the present invention
73 Example 2, Orange 1 , Significantly
R1 , R2=H, n2=0, R1 , R2=H, n2=0, improved Wash fastness, much WQ= CH2CH2COOH WQ = H
less staining on staining on CO/PA : 3 / staining on CO/PA : 2 / CO and PA
3-4 2-3 adjacent fibre material,
C9A fastness: 3-4 C9A fastness: 2-3
significantly fixation yield (3% owf): fixation yield (3% owf): higher fixation
70% 50% yield, significantly higher C9A fastness
74 Example 3,
R1 , R2=H, n2=1
Significantly WQ= CH2CH2COOH Scarlet 1 ,
improved Wash staining on CO/PA : 4 / R1 , R2=H, n2=1 fastness, much
4 WQ = H less staining on
CO and PA
C9A fastness: 3-4
adjacent fibre fixation yield (3% owf): staining on CO/PA : 3- material
75% 4 / 3-4 higher fixation yields
75 Example 4, C9A fastness: 3
R1 , R2=H, n2=1 fixation yield (3% owf): higher C9A
WQ= CH2CH2SO3H 70% fastnesses staining on CO/PA : 4-5
/ 4-5 C9A fastness: 3-4
fixation yield (3% owf):
78 %
Example 5, Rubine 2 , Significantly R1 =OCH3, R2=CH3, R1 =OCH3, R2=CH3, improved Wash fastness, much n2=1 n2=1
less staining on
WQ= CH2COOH WQ = H CO and PA staining on CO / PA : 4 staining on CO / PA : adjacent fibre material
/ 4 2-3 / 3
higher fixation fixation yield (3% owf): fixation yield (3% owf): yields
80 % 75%
Example 12, Carmine 1 ,
R1 =OCH3, R2=H, n2=1 R1 =OCH3, R2=H, Significantly higher fixation WQ = CH2CH2COOH n2=1
yields fixation yield (3% owf): WQ = CH2S03H
79% fixation yield (3% owf):
69%
Example 33 Carmine 1
R1 =OCH3, R2=H, n2=1 R1 =OCH3, R2=H, Significantly higher fixation WQ = CH2CH2S03H n2=1
yields fixation yield (2% owf) = WQ = CH2S03H Superior build-up 76 % fixation yield (2% owf) (see chart below)
= 69%
Example 4 Orange 2
R1 , R2=H, n2=1 R1 , R2=H, n2=1 higher fixation yields WQ = CH2CH2S03H WQ = CH2S03H
fixation yield (3% owf): fixation yield (3% owf):
76% 72% The table and figure 1 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 ΘΟ'Ό, 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.

Claims

CLAIM:
1 . Bisazo dyes of the formula (1 ) and salts thereof
Figure imgf000061_0001
(1 )
wherein
Ri is a radical of the formula -W-Q wherein
W is Ci-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 , -OSO3H , -SSO3H, -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;
D- and D2 independent of each other are selected from
a radical of the formula (2a), (2b) or (2c) containing a vinylsulfone fibre reactive group,
Figure imgf000061_0002
(2a) (2b) (2c)
wherein
Y is -CH=CH2, or -CH2CH2-L in which L is a leaving group such as Sulfato, Halogen, Acetato, Thiosulfato, or Phosphato,
R2 is CrC4-Alkyl, CrC4-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,
Figure imgf000062_0001
(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
Figure imgf000062_0002
wherein
X1 is a leaving group from the series chloro, fluoro, or Pyridinyl which may be substituted by Carboxy;
X2 is chloro, cyanamino, NHQ1 , NQ1Q2, -NH-aryi , NR'-ary0-S02Y, -NR"-alk0-S02Y, N(alk0-S02Y)2 or
Figure imgf000062_0003
wherein
ary0 is 1 ,3-phenylen or 1 ,4-phenylen, which may be substituted by methyl, methoxy, carboxy, chloro, or sulfo, FT is hydrogen, methyl, or ethyl, alk0 is 1 ,2-ethylen, 1 ,3- propylen or -(CH2)2-0-(CH2)2-, R" is hydrogen, methyl, or phenyl,
Figure imgf000063_0001
is phenyl which may be substituted independent from each other by 1 -2 substituents sulfo, methyl, methoxy, chloro, bromo, carboxy or nitro, Qi is CrC3-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 Qi , 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
Figure imgf000063_0002
wherein Hal is Chloro or Bromo.
2. Bisazo dyes according to 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 according to claim 2 wherein W is -(CH2)2 and Q is selected from -COOH or -SO3H.
4. Bisazo dyes according to any one of the preceding claims wherein Y is Vinyl, β- Sulfatoethylsulfonyl, or β-chloroethylsulfonyl.
5. Bisazo dyes according to any one of the preceding claims, wherein R1 is -CH2-COOH, -(CH2)2-COOH or -(CH2)2-S03H ;
D1 is a radical of the formulae
Figure imgf000064_0001
D2 is a radical of the formulae
Figure imgf000064_0002
6. Bisazo dyes according to any one of the preceding claims, wherein compound of formula (1) is preferably of the formula
Figure imgf000064_0003
wherein
n2 is 0 or 1;
Yis-CH=CH2, or-CH2CH2-OS03H;
R1 is -(CH2)2-COOH or -(CH2)2-S03H.
7. Bisazo dyes according to any one of the claims 1-5, wherein compound of formula (1) is of the formula
Figure imgf000065_0001
wherein
n2 is 0 or 1 ;
Y is -CH=CH2 or -CH2CH2-OS03H;
R1 is -(CH2)2-COOH or -(CH2)2-S03H.
8. Bisazo dyes according to any one of the claims 6 and 7 wherein when n2 is 1 ,
R1 is -(CH2)2-S03H.
9. Bisazo dyes according to any one of the claims 6 and 7, wherein when n2 is 0 or 1 , R1 is -(CH2)2-COOH.
10. Bisazo dyes according to any one of the claims 1 -4, wherein D- and D2 independent of each other, have at least one of the radicals of the formula (3a)
Figure imgf000065_0002
(3a)
wherein R4 is hydrogen and the radical Z has one of the meanings
Figure imgf000065_0003
wherein
X1 is chloro or fluoro;
X2 is chloro, cyanamino, NHQ1 , NQiQ2, -NH-aryi , 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 or 2,5-disulfophenyl; Qi is methyl, ethyl, β-hydroxyethyl, β-sulfoethyl or β-sulfatoethyl;
Q2 has one of the meanings of Q1 ;
FT is hydrogen, methyl or ethyl;
R" is hydrogen, methyl or phenyl, Y is Vinyl, β-Sulfatoethyl, or β-chloroethyl, Hah is chloro or fluoro, Hal2 is chloro or fluoro;
X3 is hydrogen or chloro.
1 1 . Bisazo dyes according to any one of the claims 1 -4, wherein compound of formula (1 ) is preferably of the formula (5a) or (5b)
Figure imgf000066_0001
(5a) (5b)
wherein, the benzene rings A and B may additionally carry 1 or 2 substituents of sulfo, methoxy or methyl groups;
R1 is -CH2-COOH, -(CH2)2-COOH or -(CH2)2-S03H;
V and V independent of each other is selected from -S02CH=CH2 or S02-CH2CH2- OS03H.
12. Bisazo dyes according to any one of the claims 1 -4, wherein compound of formula (1 ) is preferably of the formula (5c)
Figure imgf000067_0001
wherein
V is Vinylsulfonyl or β-Sulfatoethylsulfonyl and the nucleus B carries 0-1 sulfo groups; R1 is -(CH2)2-COOH or -(CH2)2-S03H; Z1 is a radical of the formula
Figure imgf000067_0002
Figure imgf000067_0003
wherein Χ is Chloro or Fluoro; X2' is chloro, β-Sulfoethylamino, morpholino or Cyanamino; Q1' is methyl, ethyl, β-hydroxyethyl, β-sulfoethyl or β-sulfatoethyl; Q2' has one of the meanings of Q1 ; Y' is -CH=CH2, -CH2CH2OS03H or -CH2CH2CI.
13. Bisazo dyes according to 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 (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j) and (1k), wherein the compounds 1(a) to 1(k) have the formula
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000069_0002
wherein R1 ; D-\ and D2 have one of the above defined meanings; and
the ratio of the components of the mixtures (1 ):(1 a) is 99:1 to 30:70, preferably 99:1 to 55:4;
the ratio of the components of the mixtures (1 ):(1 b) is 99:1 to 85:15, preferably 99:1 to 92:8;
the ratio of the components of the mixtures (1 ):(1 c) is 99:1 to 85:15, preferably 99:1 to 92:8;
the ratio of the components of the mixtures (1 ):(1 d) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (1 ):(1 e) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures ( ) :( f ) is 99:1 to 90:10, preferably 99:1 to 95:5;
the ratio of the components of the mixtures (1 ):(1 g) is 99:1 to 85:15, preferably 99:1 to 94:6; the ratio of the components of the mixtures (1 ):(1 h) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (1 ):(1 i) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures (1 ):(1j) is 99:1 to 85:15, preferably 99:1 to 94:6;
the ratio of the components of the mixtures ( 1 ) : ( 1 k) 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 (1 a), (1 b), (1 c), (1 d), (1 e), (1 f), (1 g), (1 h), (1 i), (1j) and (1 k) according to claim 14 wherein the ratio of formula (1 ) to the sum of the dyestuffs (1 a) to (1 k) is 99:1 to 25:75, preferably 99:1 to 40:60.
16. Bisazo dye mixtures according to claim 14 and claim 15, wherein D1 and D2 in formula (1 ) and formula (1 a) has one of the meanings of the radical (2a) and the ratio of the components of the mixtures (1 ):(1 a) is 90:10 to 30:70.
17. Bisazo dye mixtures according to claim 16, wherein the ratio of the components of these mixtures is (1 ): (1 a) 90:10 to 60:40.
18. Intermediates of the formula
Figure imgf000070_0001
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 according to 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-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 meanings as specified in claim 1 , at a temperature of 40-80 °C, and pH of 2-9, preferably 3-5,
Figure imgf000071_0001
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,
Figure imgf000071_0002
Or,
8c) by reacting 2-amino-5-naphthol-7-sulfonic acid with α, β -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 a temperature of 60-100°C, and pH of 2-9, preferably 3-7,
Figure imgf000071_0003
which yields compounds of the formula (7) wherein the radical W-Q has the meaning of the radical (9a)
Figure imgf000071_0004
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 phosphato.
Figure imgf000072_0001
Q = OS03H, OP03H,...
21 . The process for manufacturing the intermediates of formula (7) by following the process route (8a) according to 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) according to 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) according to 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 ) according to claim (1 ).
25. The process according to 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.
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