GB1588372A - Waterinsoluble azodyes - Google Patents

Waterinsoluble azodyes Download PDF

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Publication number
GB1588372A
GB1588372A GB7481/78A GB748178A GB1588372A GB 1588372 A GB1588372 A GB 1588372A GB 7481/78 A GB7481/78 A GB 7481/78A GB 748178 A GB748178 A GB 748178A GB 1588372 A GB1588372 A GB 1588372A
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amino
methyl
hydrogen
phenyl
formula
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GB7481/78A
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Sanofi Aventis Deutschland GmbH
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Cassella AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/18—Azo 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
    • C09B29/3626—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O)
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/12—Disazo dyes from other coupling components "C"
    • C09B31/14—Heterocyclic components
    • C09B31/153—Heterocyclic components containing a six-membered ring with one nitrogen atom as the only ring hetero-atom
    • 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
    • C09B56/00—Azo dyes containing other chromophoric systems
    • C09B56/12—Anthraquinone-azo dyes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Polymerization Catalysts (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The new dyes conform to the formula I, wherein the substituents D, X, R1, R2 and R3 are each as defined in Claim 1. The new dyes are suitable in particular for dyeing and printing hydrophobic synthetic materials in high colour strength with excellent fastness properties. They are prepared by diazotising amines of the formula D-NH2 which are free of ionic groups and coupling with 3-cyano-6-hydroxy-2-pyridones of the formula III, which are likewise new compounds. <IMAGE>

Description

(54) IMPROVEMENTS IN OR RELATING TO WATER INSOLUBLE A2;0DYES (71) We, CASSELLA AKTIENGESELLSCHAFT, formerly Cassela Farbwerke Mainkur Aktiengesellschaft, a body corporate organised under' the laws of Germany of 526 Hanauer Landstrasse, 6 Frankfurt(Main) Fechenheim, Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement::- The present invention relates to valuable, new water-insoluble azo dyestuffs of the general formula I
wherein D denotes an optionally substituted pheny!, naphthyl, anthraquinonyl or heterocyclic radical which is free from groups conferring water-solubility, X and R, denote hydrogen or an alkyl group with 1 to 4-carbon atoms, R2 denotes hydrogen or an alkyl group with 1 to 8 carbon atoms and R3 denotes hydrogen, an alkyl group with 1 to 7 carbon atoms, an optionally substituted cycloalkyl group or a radical of the formula
wherein R4 represents an alkyl group with 1 to 8 carbon atoms or an optionally substituted cycloalkyl group and R5 and R8 represent an alkyl group with 1 to 4 carbon atoms, it also being possible for the alkyl groups R5 and R6, together with the nitrogen atom to which they are attached, to form, optionally with a further hetero-atom, a five-membered or six-membered heterocyclic ring.
The invention includes in particular water-insoluble azo dyestuffs of the general formula I wherein: (a) X is methyl, R, is hydrogen, R2 is hydrogen or methyl, and R3 is hydrogen, methyl or ethyl, or a radical of the formula
wherein each of R4, R5 and R6 is methyl, ethyl or n-butyl; or (b) D is a 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl-sulphonic acid 3-amino-phenyl ester, (4'-methyl-phenyl)-sulphonic acid 3amino-phenyl ester, 4-amino-benzophenone, 4-amino-4'-methoxy-benzophenone or dimethylsulphamic acid 3-amino-phenyl ester radical; or (c) D is a 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl-sulphonic acid 3-amino-phenyl ester, (4'-methyl-phenyl)-sulphonic acid 3amino-phenyl ester, 4-amino-benzophenone, 4-amino-4'-methoxybenzophenone or dimethylsulphamic acid 3-amino-phenyl ester radical, and X is methyl, R, is hydrogen, R2 is hydrogen or methyl, and R3 is hydrogen, methyl or ethyl, or a radical of the formula
wherein each of R4, R5 and R6 is methyl, ethyl or n-butyl.
The cycloalkyl radicals in R3 and R4 contain 3 to 8, preferably 5 or 6, carbon atoms, and can be monosubstituted or disubstituted by halogen, especially chlorine, optionally branched alkyl with 1 to 4 carbon atoms or optionally branched alkoxy with 1 to 4 carbon atoms.
All the alkyl or alkoxy groups can be straight-chain or branched.
The alkyl groups R5 and R8 can, together with the N atom to which they are bonded and optionally via a further hetero-atom, form the following 5-membered or 6-membered cyclic groups: I-pyrrolidinyl, l-piperazinyl, morpholino, thiomorpholino or piperidino. The l-piperazinyl radical can also be substituted in the 4-position by alkyl with 1 to 4 C atoms, so that, for example, 4-methyl- I-piperazinyl or 4-ethyl-1-piperazinyl radicals are also possible.
The new dyestuffs are obtainable by a process wherein an amine, which is free from ionic groups, of the general formula D-NH2 11 is diazotised and the diazotisation product is coupled with a 3-cyano-6-hydroxy-2pyridone of the general formula
wherein D, X, R1, R2 and R3 have the meanings indicated above. With regard to the formation of the disperse dyestuffs, or with respect to their colour yield, it can be advantageous to diazotise a mixture of two or more amines of the formula 11 and to couple the diazotisation products with one or more 3-cyano6-hydroxy-2-pyridones of the formula III, or to couple a diazotised amine of the formula 1I with two or more 3-cyano-6-hydroxy-2-pyridones of the formula Ill.
The invention includes in particular a process as specified in the last preceding paragraph but one wherein: (d) 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl- sulphuric acid 3-amino-phenyl ester, (4'-methyl-phenyl)-sulphonic acid 3-aminophenyl ester, 4-amino-benzophenone, 4-amino-4'-methoxy-benzophenone or dimethylsulphamic acid 3-amino-phenyl ester is used as the amine of the general formula II; or (e) a 3-cyano-6-hydroxy-2-pyridone of the general formula 111 in which X is methyl, Rl is hydrogen, R2 is hydrogen or methyl and R3 is hydrogen, methyl or ethyl or a radical of the formula
wherein each of R4, R5 and R6 is methyl, ethyl or n-butyl, is used; or (f) 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenylsulphonic acid 3-amino-phenyl ester, (4'-methyl-phenyl)-sulphonic acid 3-aminophenyl ester, 4-amino-benzophenone, 4-amino-4'-methoxy-benzophenone or dimethylsulphamic acid 3-amino-phenyl ester is used as the amine of the general formula II, and a 3-cyano-6-hydroxy-2-pyridone of the general formula III in which X is methyl, R, is hydrogen, R2 is hydrogen or methyl and R3 is hydrogen, methyl or ethyl or a radical of the formula
wherein each of R4, R5 and R6 is methyl, ethyl or n-butyl, is used.
It is possible for the dyestuffs of the formula I according to the invention and the starting compounds of the formula III to exist in tautomeric forms. Within the scope of the present invention, by the dyestuffs I according to the invention and the starting compounds III there are also to be understood the possible tautomers.
The invention also relates to the coupling components of the general formula III and processes for their manufacture.
The coupling components III can be manufactured, for example, analogously to the instructions of Bobbitt and Scola, J. Org. Chem. 25, 560 et seq., (1960), by condensation of a p-ketocarboxylic acid ester with a suitable N-substituted cyanoacetamide in the presence of alkali metal hydroxide, such as, for example, potassium hydroxide, in an alkanol, such as, for example, methanol or ethanol, at elevated temperature, for example at the reflux temperature. Alkanols which can be used are also glycol ethers, such as, for example, methylglycol, and it is also possible to use an alkali metal alcoholate, such as, for example, sodium methylate or sodium methylglycollate, instead of the alkali metal hydroxide. In this manufacturing procedure, the alkali metal salts of the coupling components of the formula III are formed. These alkali metal salts can be used directly for the coupling reaction.
The coupling components can also be manufactured by other different processes, such as are described, for example, in the monograph by Klingsberg "Pyridine and its Derivatives, Part Three", in particular on page 525 et seq. This monograph appeared within the series "The Chemistry of Heterocyclic Compounds" edited by Arnold Weissberger, published by Interscience Publishers, New York-London, 1962.
The N-substituted cyanoacetamides of the general formula VIII required for the manufacture of the coupling components of the general formula III can be manufactured by the following route:
wherein Rr, R2 and R3 have the meaning indicated above.An aldehyde of the general formula IV is melted together with an appropriately substituted amide of the general formula V in the presence of an alkali metal hydroxide, for example potassium hydroxide, at temperatures of about 40 to 1400C. The compound of the general formula VI thereby formed is reacted with cyanoacetamide in the presence of an acid, such as, for example, phosphoric acid, sulphuric acid or hydrochloric acid, and in an organic solvent which is suitable for distilling off azeotropically the water of reaction formed, such as, for example, methylene chloride, ethylene chloride or toluene. After distilling off the water of reaction azeotropically and, if appropriate, distilling off the organic solvent, the N-substituted cyanoacetamide of the formula VIII can be isolated.
The radicals D of the diazo components can, for example, be monosubstituted, disubstituted or trisubstituted by the following substituents: halogen, especially chlorine; cyano; nitro; trifluoromethyl; hydroxyl; alkyl, in particular with 1 to 6 C atoms; alkoxy, in particular with I to 6 C atoms; aryloxy, such as, for example, phenoxy; acyl, in particular with I to 7 C atoms (by acyl is understood the alkylcarbonyl radical formed from a carboxylic acid by removing the OH group; the alkylcarbonyl or acyl radical with 1 C atom is the formyl radical) or acyloxy, in particular with 2 to 7 C atoms; benzoyl; phenoxycarbonyl; alkoxycarbonyl, in particular with 2 to 8 C atoms; optionally N-monosubstituted or N,N-disubstituted carboxylic acid amide or sulphonic acid amide, possible substituents being, in particular, alkyl radicals with I to 8 C atoms or phenyl radicals; alkylsulphonyl, in particular with I to 4 C atoms; alkylsulphonylalkyl, in particular with 2 to 8 C atoms; alkylsulphonyloxy, in particular with 3 to 8 C atoms; arylsulphonyloxy; Nsubstituted and N,N-disubstituted aminosulphonyloxy; possible substituents being, in particular, alkyl radicals with I to 6 C atoms; and optionally substituted phenylazo.
Amines of the formula II which can be used are, for example: aniline, 2-, 3- or 4-aminotoluene, 2-, 3- or 4-amino-benzyl-dimethylamine, 4-amino-phenethyl-pdimethylamine, 4-amino-benzyl-N-piperidine, 3-amino-trifluoromethyl-benzene, 3or 4-amino-I ,2-dimethyl-benzene, 4-amino-n-butyl-benzene, 4-amino-n-hexylbenzene, 2-, 4- or 5-amino-1,3-dimethyl-benzene, 4-amino-I ,3,5-trimethyl-benzene, 2-, 3- or 4-amino-phenol, 2-, 3- or 4-amino-anisole 2-, 3- or 4-amino-phenetole, 2-, 3- or 4-amino-n-butoxy-benzene, 4-amino-iso-octyl-oxy-benzene, 2-, 3- or 4-amino diphenyl ether, 2-amino-I ,4-dimethoxy-benzene, 2-amino-l ,4-diethoxy-benzene, 2- amino-l,4-di-isopropoxy-benzene, 2-, 3- or 4-chloroaniline, 2-, 3- or 4bromoaniline, 2,3-, 2,4-, 2,5- or 3,4-dichloroaniline, 2,5-dibromoaniline, 2-, 3- or 4amino-dimethylamino- or -diethylamino-benzene, 2,4,5-, 2,4,6-, 3,4,5- or 3,4,6trichloroaniline, 3-, 4-, 5- or 6-chloro-2-amino-toluene, 4-chloro-3-amino-toluene, 2-chloro-4-amino-toluene, 5-chloro-2-amino-trifluoromethyl-benzene, 4,5- or 4,6dichloro-2-amino-toluene, 2,5- or 4,6-dichloro-3-amino-toluene, 2,5- or 3,5-dichloro-4-amino-toluene, 4,5,6-trichloro-2-amino-toluene, 4-chloro-2-amino- I ,3-di- methyl-benzene, 2-, 3- or 4-amino-benzyl-methyl-sulphone, 4-amino-phenylpropyl-methyl-sulphone, 6-chloro-3-amino-anisole, 2-chloro-4-amino-anisole, 2 chloro-4-amino-n-hexoxy-benzene, 3-chloro-4-amino-anisole, 2-, 3- or 4-nitroaniline, 2-nitro-4-amino-toluene, 3-nitro-4-amino-toluene, 4-nitro-2-aminotoluene, 2-ethyl-4-nitro-aniline, 5-nitro-2-amino-toluene, 5-nitro-4-amino-l ,3-dimethyl-benzene, 6-nitro-3-amino-anisole, 3-nitro-4-amino-anisole, 3-nitro-4amino-n-butoxy-benzene, 5-nitro-2-amino-phenethole, 2-nitro-4-aminophenethole, 3-nitro-4-amino-phenethole, 5-nitro-2-amino- I ,4-dimethoxy-benzene, 5-nitro-2-amino- 1 ,4-diethoxy-benzene, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 4-chloro-2-nitroaniline, 4-bromo-2-nitroaniline, 4,6-dichloro-2-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2,6-dibromo4-nitroaniline, 2,4-dinitroaniline, 6-chloro-2,4-dinitroaniline, 6-bromo-2,4-dinitroaniline, 2,4,6-trinitroaniline, 2-, 3- or 4-amino-benzonitrile, l-amino-2-cyano-5- chloro-benzene, 2-cyano-4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 4-cyano3-nitroaniline, 1-amino-2,4-dicyano-benzene, 1 -amino-2,6-dicyano-4-nitro- benzene, I -amino-2-chloro-4-methylsulphonyl-benzene, 2-methylsulphonyl-4nitroaniline, 2-iso-butylsulphonyl-4-nitroaniline, 4-methylsulphonyl-2-nitroanilme, 4-allylsulphonyl-2-nitroaniline, 4-phenylsulphonyl-2-nitroaniline, 2-, 3- or 4-arffino- benzaldehyde, 2-, 3- or 4-amino-diphenyl ether, 2-amino-4-chloro- or 4,4'-diçhloro- diphenyl ether, 2-, 3- or 4-amino-p-dimethylamino- or -p-diethyltamino- acetophenone, 2-, 3- or 4-amino-acetophenone, 4-amino-n-butyrophenone, 4amino-n-caprophenone, 4-amino-cu-ethyl-n-caprophenone, 2-amino-5-nitro-acetophenone, 2-, 3- or 4-amino-benzophenone, 2-, 3- or 4-amino-4'-methyl-, -4'-isopropyl-, -4'-n-butyl- or -4'-n-hexyl-benzophenone, 2-, 3- or 4-amino-2',4'-dimethylbenzophenone, 2-, 3- or 4-amino-4'-methoxy-benzophenone, 2-, 3- or 4-amino-4'chloro-benzophenone, 4-amino-5-nitro-benzophenone, 2-, 3- or 4-amino-benzoic acid methyl ester or ethyl ester, 2-, 3- or 4-amino-benzoic acid n-butyl ester, 2-, 3or 4-amino-benzoic acid n-decyl ester, 2-, 3- or 4-amino-benzoic acid iso-octyl ester, I-amino-benzene-3,5-dicarboxylic acid dimethyl ester or diethyl ester, 2-, 3or 4-amino-benzoic acid phenyl ester, 2-, 3- or 4-amino-benzoic acid 4'-tert.butylphenyl ester or 4'-isohexyl-phenyl ester, 2-, 3- or 4-amino-benzoic acid cyclohexyl ester, 2-, 3- or 4-amino-benzoic acid benzyl ester, 2-, 3- or 4-amino-benzoic acid A- methoxy-ethyl ester, 2-, 3- or 4-amino-benzoic acid p-ethoxy-ethyl ester, 2-, 3- or 4amino-benzoic acid p-iutoxy-ethyl ester, 2-, 3- or 4-amino-benzoic acid methyl aiglycdi ester, 2-, 3 orA-amino-benzoic acid ethyl-diglycol ester, 2-, 3- or 4-aminobenzoic acid methyl-triglycol ester, 2-, 3- or 4-amino-benzoic acid ethyl-triglycol ester, 2-, 3- or 4-amino-benzoic acid p-hydroxy-ethyl ester, 2-, 3- or 4-aminobenzoic acid p-acetoxy-ethyl ester, 2-, 3- or 4-amino-benzoic acid of-(ss'-hydroxy- ethoxy)-ethyl ester, 2-, 3- or 4-amino-benzoic acid phydroxy-propyl ester, 2-, 3- or 4-amino-benzoic acid y-hydroxy-propyl ester, 2-, 3- or 4-amino-benzoic acid - hydroxy-butyl ester, 2-, 3- or 4-amino-benzoic acid -hydroxy-hexyl ester, 4-nitroanthranilic acid methyl ester, 4-nitro-anthranilic acid iso-butyl ester, 4-nitroanthranilic acid methyldiglycol ester, 4-nitro-anthranilic acid p-methoxyethyl ester, 4-nitro-anthranilic acid p-butoxyethyl ester, 4-nitro-anthranilic acid methyldiglycol ester, 2-, 3- or 4-amino-benzoic acid amide, 2-, 3- or 4-amino-benzoic acid monomethylamide, 2-, 3- or 4-amino-benzoic acid iso-octylamide, 2-, 3- or 4amino-benzoic acid dimethylamide, 2-, 3- or 4-amino-benzoic acid ethyleneimide, 2-, 3- or 4-amino-benzoic acid iso-propylamide, 2-, 3- or 4-amino-benzoic acid nhexylamide, 2-, 3- or 4-amino-benzoic acid diethylamide, 2-, 3- or 4-amino-benzoic acid di-n-butylamide, 2-, 3- or 4-amino-benzoic acid morpholide, 2-, 3- or 4-aminobenzoic acid anilide, 2-, 3- or 4-amino-benzoic acid N-methylanilide, 2-, 3- or 4amino-benzoic acid N,N-dimethylhydrazide, 2-, 3- or 4-amino-benzoic acid ydimethylamino-propylamide, benzoic acid 2-, 3- or 4-amino-phenyl ester, 4'-tert.butyl-benzoic acid 2-, 3- or 4-amino-phenyl ester, 2',4',6'-trimethyl-benzoic acid 2-, 3- or 4-amino-phenyl ester, methyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, ethyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, p-chloroethyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, butyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, nhexyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, iso-octyl-sulphonic acid 2-, 3or 4-amino-phenyl ester, phenyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, 4'methyl-phenyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, 4'-n-butyl-phenylsulphonic acid 2-, 3- or 4-amino-phenyl ester, 4'-methoxy-phenyl-sulphonic acid 2-, 3- or 4-amino-phenyl ester, 4'-chloro-phenyl-sulphonic acid 2-, 3- or 4-aminophenyl ester, 2-, 3- or 4-amino-benzene-sulphonic acid phenyl ester, 2-, 3- or 4amino-benzene-sulphonic acid 4'-methyl-phenyl ester, 2-, 3- or 4-amino-benzenesulphonic acid 4'-n-butyl-phenyl ester, 2-, 3- or 4-amino-benzene-sulphonic acid 4'methoxy-phenyl ester, A-ethoxy-ethyl-sulphamic acid 2-, 3- or 4-amino-phenyl ester, dimethyl-sulphamic acid 2-, 3- or 4-amino-phenyl ester, ethyl-sulphamic acid 2-, 3- or 4-amino-phenyl ester, diethyl-sulphamic acid 2-, 3- or 4-amino-phenyl ester, di-n-butyl-sulphamic acid 2-, 3- or 4-amino-phenyl ester, cyclohexylsulphamic acid 2-, 3- or 4-amino-phenyl ester, 4-amino-phenyl-methyl-sulphone, 4amino-phenyl-n-butyl-sulphone, 4-amino-phenyl-iso-octyl-sulphone, 4-amino-diphenyl-sulphone, 2-, 3- or 4-amino-benzene-sulphonic acid amide, 2-, 3- or 4amino-benzene-sulphonic acid monomethylamide, 2-, 3- or 4-amino-benzenesulphonic acid iso-octylamide, 2-, 3- or 4-amino-benzene-sulphonic acid dimethylamide, 2-, 3- or 4-amino-benzene-sulphonic acid ethyleneimide, 2-, 3- or 4-aminobenzene-sulphonic acid diethylamide, 2-, 3- or 4-amino-benzene-sulphonic acid din-butylamide, 2-, 3- or 4-amino-benzene-sulphonic acid morpholide, 2-, 3- or 4amino-benzene-sulphonic acid cyclohexylamide, 2-, 3- or 4-amino-benzenesulphonic acid anilide, 2-, 3- or 4-amino-benzene-sulphonic acid N-methyl-anilide, I-methyl-2-amino-benzene-4-sulphonic acid amide, 1-methyl-2-amino-benzene-4- sulphonic acid n-hexylamide, I-methoxy-2-amino-benzene-4-sulphonic acid amide, I-methoxy-2-amino-benzene-4-sulphonic acid dimethylamide, 1-methoxy-2-amino- benzene-4-sulphonic acid di-n-butylamide, 1 -methoxy-2-amino-benzene-4- sulphonic acid N-methylanilide, l-chloro-2-amino-benzene-4-sulphonic acid dimethylamide, l-chloro-2-amino-benzene-5-sulphonic acid p-ethoxy-ethylamide, 1chloro-3-amino-benzene-4-sulphonic acid amide, 1-chloro-4-amino-benzene-2- sulphonic acid dimethylamide, 4-amino-benzene-phenylurethane, 2-, 3- or 4amino-acetanilide, 2-, 3- or 4-amino-phenoxyacetanilide, 2-, 3- or 4-amino-Nmethyl-acetanilide, I-amino-anthraquinone, I-amino-4- or -5-benzoylaminoanthraquinone, I-amino-4-chloro-anthraquinone, I -amino-naphthalene, I-amino5-ethoxy-naphthalene, 8-chloro-1 -amino-naphthalene, 2-amino-naphthalene, 2amino-naphthalene-6-sulphonic acid dimethylamide, 4-amino-azobenzene, 4amino-4'-hydroxy-azobenzene, 2',3-dimethyl-4-amino-azobenzene, 2,3'-dimethyl-4amino-azobenzene, 2,5-dirhethyl-4-amino-azobenzene, 2::methyl-5-methoxy-4- amino-azobenzene, 2',3-dimethoxy-4-amino-azobenzene, 4'-nitro-2,5-dimethoxy4-amino-azobenzene, 4'-nitro-2-methyl-5-methoxy-4-amino-azobenzene, I-phenylazo-4-amino-naphthalene, 2-amino-5-nitro-thiazole, 2-amino-4-methyl-5-nitrothiazole, 2-amino-6-nitro-benzthiazole, 2-amino-5-phenyl- I ,3,4-thiadiazole, 3 phenyl-5-amino- I ,2,4-thiadiazole, 4-amino-benz-l ,2,4-triazole, 2-amino-1,3,5- thiadiazole-4-methyl-thioether, 3-amino-5-nitro-2,1 -benzisothiazole, 3-amino-5nitro-7-chloro-2, I-benzisothiazole, 3-amino-7-nitro-2, I -benzisothiazole, 4-amino 7-nitro- I ,2-benzisothiazole, 4-amino-1,2-benzisothiazole and 3-amino-5-nitro- 1,2benzisothiazole.
Suitable coupling components of the formula III can contain, for example, hydrogen or a methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or tert.-butyl group in the X-position, hydrogen or a methyl, ethyl, n-propyl or n-, sec.- or iso-butyl group in the R1-position, hydrogen, a methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or tert.-butyl group, furthermore also the n- or iso-amyl, n-hexyl or iso-octyl group in the R2-position and hydrogen, a methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or tert.-butyl group, furthermore also the n- or iso-amyl, n-hexyl, a-ethyl-n-pentyl or cyclohexyl group in the R3-position.
The coupling components of the formula III can also contain, for example, the following groups in the R3-position: methoxy, ethoxy, n- or iso-propoxy, n- or isobutoxy, n- or iso-pentoxy, n- or iso-hexyloxy, iso-octyloxy, cyclohexyloxy, dimethylamino, diethylamino, methylethylamino, di-n-propylamino, di-n butylamino, morpholino or piperidino.
Dyestuffs and dyestuff mixtures of the formula I in which X denotes a methyl group, R1 denotes hydrogen, R2 denotes hydrogen or a methyl group and R3 denotes hydrogen, a methyl or ethyl group or the radicals
wherein R4, R5 and R6 denote a methyl, ethyl or n-butyl group, are preferred.
Dyestuffs and dyestuff mixtures of the formula I in which D denotes a 3nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl-sulphonic acid 3-amino-phenyl ester, 4'-methyl-phenyl-sulphonic acid 3-amino-phenyl ester, 4-amino-benzophenone, 4-amino-4'-methoxy-benzophenone or dimethylsulphamic acid 3-amino-phenyl ester radical are also preferred.
Dyestuffs of the general formula I in which both D and X, R1, R2 and R3 have the preferred meanings indicated above are of particular industrial interest.
Representatives of preferred dyestuffs are, for example:
The dyestuffs according to the invention are particularly suitable for dyeing and printing structures of synthetic materials, such as, for example, polyolefines, polyvinyl compounds, cellulose 2±acetate, cellulose triacetate and, in particular, polyester materials, for example polyethylene glycol terephthalate or analogous polymers. On these materials, they give deep yellow to red dyeings and prints with very good fastness properties by the customary dyeing and printing processes.
In addition to the very good fastness to light and heat-setting, the dyestuffs according to the invention have a very high tinctorial strength, a very good build-up capacity and a high pH stability, and furthermore also very good fastness properties during washing at 95"C, towards peroxides, acid and, in particular, alkaline perspiration, nitric oxides/off-gases and alkalis, coupled with fastness to boiling with sodium carbonate, with fastness to hypochlorite bleaching, under severe conditions, with fastness to rubbing and with fastness to Koratron treatment.
The fibre material mentioned is appropriately dyed with the dyestuffs according to the invention from an aqueous suspension in the presence of carriers between about 80--100"C, in the absence of carriers between about 1 10--140"C or by the so-called heat-setting process at about 18-230"C. The printing of the materials mentioned can be carried out by steaming the goods, which have been printed with the new dyestuffs, in the presence of a carrier at temperatures between about 80-I l00C or in the absence of a carrier at about 1 10--140"C, or by treating the printed goods according to the so-called heat-setting process at about 180--230"C.
The dyestuffs according to the invention are also suitable for dyeing the hydrophobic materials listed above from organic solvents and for bulk-dyeing.
Example 1.
a) 15.2 parts by weight of 2-methyl-4-nitroaniline are diazotised in 300 parts by weight of water, with the addition of 36 parts by, weight of 30% strength hydrochloric acid at 0 to +50C, with a solution of 7.7 parts by weight of sodium nitrite in 50 parts by weight of water. The filtered, clear diazo solution is then allowed to run into a solution of 26.7 parts by weight of sodium salt of l-(N-methyl formamido)-methylene-3-cyano-4-methyl.6-hydroxy-2-pyridone of the formula
in 400 parts by weight of water, 16.6 parts by weight of sodium hydroxide solution of 33"Be strength and 24.6 parts by weight of sodium acetate, and the reaction temperature is kept at 0 to +50C during the coupling reaction by adding 500 parts by weight of ice.After the coupling reaction has ended, the dyestuff which has formed is filtered off, washed with water until neutral and dried. It is a reddishtinged yellow powder, which dissolves in concentrated sulphuric acid to give a solution which is reddish-tinged yellow in colour.
b) 1.0 part by weight of the finely dispersed dyestuff of the formula
thus obtained is stirred into 2,000 parts by weight of water. The mixture is adjusted to a pH value of 5 with acetic acid and 4.0 parts by weight of ammonium sulphate and 2.0 parts by weight of a commercially available dispersing agent based on a naphthalenesulphonic acid/formaldehyde condensate are added.
100 parts by weight of a polyester fabric based on polyethylene glycol terephthalate are introduced into the dye liquor thus obtained and dyeing is carried out for I hour at 1300C.
After subsequent rinsing, reductive after-treatment with a 0.2% strength alkaline sodium dithionite solution for 15 minutes at 70--806C, rinsing and drying, a deep greenish-tinged yellow dyeing with very good coloristic properties, in particular a very good fastness to light and heat-setting, is obtained.
c) The coupling component required for the manufacture of the dyestuff according to paragraph a) is manufactured in the following way: 195.0 parts by weight of para-formaldehyde, 342.0 parts by weight of Nmethylformamide and 0.3 part by weight of caustic potash are stirred at 900C for 3 hours. A clear melt of N-methyl-N-methylol-formamide is obtained. 1,750.0 parts by weight of toluene, 420.0 parts by weight of cyanoacetamide and 5.2 parts by weight of 30% strength hydrochloric acid are added to this melt. First water is distilled off azeotropically and finally the toluene is distilled. N-Cyano-aceto-N'methyl-N'-formyl-diamino-methane of the formula
remains as a light yellow oil.
A solution of 30.0 parts by weight of sodium in 1,000.0 parts by weight of methylglycol is allowed to run into a solution of 155.0 parts by weight of Ncyanoaceto-N'-methyl-N'-formyl-diamino-methane in 140.0 parts by weight of acetoacetic acid ethyl ester at 600C, whilst stirring. The mixture is stirred for 4 hours at 600C and the methylglycol and the ethyl alcohol, which originates from the reaction, are then distilled off. The residue is stirred with 480.0 parts by weight of acetone and the sodium salt of l-(N-methyl-formamido)-methylene-3-cyano-4methyl-6-hydroxy-2-pyridone of the formula in paragraph a) which has formed is filtered off.
Example 2.
a) 24.9 parts by weight of phenylsulphonic acid 3-amino-phenyl ester of the formula
are diazotised, as described in Example la), with the addition of 108.0 parts by weight of 30% strength hydrochloric acid, and the diazotisation product is coupled with 26.1 parts by weight of l-(N-methoxycarbonyl)-amino-methylene-3-cyano-4.
methyl-6-hydroxy-2-pyridone of the formula
with the addition of 16.6 parts by weight of sodium hydroxide solution of 33 Bé strength and 73.8 parts by weight of sodium acetate.
The dyestuff which has formed is a reddish-tinged yellow powder which dissolves in concentrated sulphuric acid to give a solution reddish-tinged yellow in colour.
b) 30.0 parts by weight of the dyestuff of the formula
thus obtained are incorporated, in a finely divided form, into a printing paste which contains 45.0 parts by weight of carob bean flour, 6.0 parts by weight of sodium 3nitro-benzene-sulphonate and 3.0 parts by weight of citric acid per 1,000 parts by weight. On a polyester fabric, this printing paste gives, after printing, drying and fixing in a heat-setting frame for 45 seconds at 215"C, rinsing and finishing, as described in Example I b), paragraph 3, a deep greenish-tinged yellow print of very good coloristic properties, in particular of very good fastness to light and heatsetting.
c) On a triacetate fabric, the above printing paste gives, after printing, drying and fixing by pressure steaming for 15 minutes under 1.5 atmospheres gauge, rinsing and finishing, as described in Example Ib), paragraph 3, a greenish-tinged yellow print of very good fastness properties.
d) The coupling component required for the manufacture of the dyestuff according to paragraph a) is manufactured in the following way: 375.0 parts by weight of methyl carbamate, 160.0 parts by weight of paraformaldehyde and 0. I part by weight of potassium hydroxide are stired at l200C for 2 hours. A clear melt is obtained. 1,750.0 parts by weight of toluene, 420.0 parts by weight of cyanoacetamide and 5.7 parts by weight of 30% strength hydrochloric acid are now added to this melt and the water is then distilled off azeotropically. On cooling, the N-cyanoaceto-N'-methoxycarbonyl-diaminomethane of the formula NC-CH2-CO-NH-CH2-NII-CO-O-CH3 which has formed crystallises out in the form of colourless needles.
A solution of 120.0 parts by weight of potassium hydroxide in 80.0 parts by weight of methanol is slowly added dropwise, under reflux, to a solution of 35.0 parts by weight of N-cyanoaceto-N'-methoxycarbonyl-diamino-methane, 26.0 parts by weight of acetoacetic acid ethyl ester and 160.0 parts by weight of methanol. A clear yellow solution forms. The methanol is distilled off, the residue is dissolved in water, the solution is acidified with hydrochloric acid and the l-(N-methoxy carbonyl)-amino-methylene-3-cyano-4-methyl-6-hydroxy-2-pyridone of the formula in paragraph a) which has formed is filtered off.
Example 3.
a) 21.6 parts by weight of dimethylsulphamic acid 3-amino-phenyl ester of the formula
are diazotised in 150 parts by weight of glacial acetic acid with 34.2 parts by weight of 41.3% strength nitrosylsulphuric acid at +150C, whilst cooling externally. The clear diazo solution is then allowed to run into a solution of 26.7 parts by weight of l-(acetylamino)-methylene-3-cyano-4-methyl-6-hydroxy-2-pyridone of the formula
in 400.0 parts by weight of water and 120 parts by weight of sodium hydroxide solution of 33"Bt strength. The reaction temperature is kept at 0 to +50C during the coupling reaction by adding about 500 parts by weight of ice. After the coupling reaction has ended, the dyestuff which has formed is filtered off, rinsed with water and dried. It is a reddish-tinged yellow powder, which dissolves in concentrated sulphuric acid to give a solution which is reddish-tinged yellow in colour.
b) A fabric consisting of polyethylene glycol terephthalate is padded on a padder at 300C with a liquor which contains 30 parts by weight of the dyestuff of the formula
brought into a finely divided state, 1.0 part by weight of polyacrylamide with a K value of 120, ops part by weight of a polyglycol ether of oleyl alcohol and 968.5 parts by weight of water. After drying, the dyeing is fixed in a heat-setting frame for 60 seconds at 2100C. After subsequent rinsing and finishing, as described in Example Ib), paragraph 3, a deep greenish-tinged yellow dyeing of very good fastness properties, in particular of very good fastness to light and heat-setting, is obtained.
c) The coupling component required for the manufacture of the dyestuff is manufactured analogously to the instructions in Example I, paragraph c), using an equimolar amount of acetamide instead of N-methylformamide.
Example 4.
100 parts by weight of a polyester material are treated for 30 minutes at 121"C in 1,500 parts by weight of tetrachloroethylene in which 2.0 parts by weight of the dyestuff described in Example 2a) are dissolved.
The material is rinsed with warm and cold tetrachloroethylene and a strong greenish-tinged yellow dyeing of very good coloristic properties is obtained.
Similar greenish-tinged yellow dyeings of very good coloristic properties are obtained when the polyester material in the above example is replaced by 100 parts by weight of a triacetate material or a 2±acetate material and dyeing is carried out for 45 minutes at 1100C or for 45 minutes at 800C.
Further dyestuffs according to the invention, which are manufactured by coupling according to the instructions in Examples I to 3 and which give deep yellow to red dyeings or prints, also with very good coloristic properties, on polyester materials, are indicated in the table which follows. The dyestuffs to which the table relates are compounds having the formula
wherein D, X, R1, R2 and R3 have the specific meanings indicated below. No. D X Rl R2 R3
-C4H9(n) -H -H -H -CH3 -CH3 -CH3 -CH3 -CH3 -C4H9(n) -CH3 -CH3 -CH3 -H -C5H11(iso) -H -C4H9(iso) -H -C2H5 -CH3 -CH3 -H -C6H13(n) -CH3 -CH3 -H -CH3 -OC4H9(n) -CH3 -H -CH3 -CH3 -CH3 -H -CH3 -CH3 -C4H9(n) -H -CH3 -CH3 No.D X Rl R2 R3
CN 11 CHa -CH3 CHa OC5H,I(iso) 12OCH3 -C4H9(seC) -CH C2Hs -H CH3 13 eoc4Hqfn)-cH3 -CH3 CHa -H ;CHa C2H5 14 < CHa CHa -C4H9(n) +sCHt -rJ;eHZ- 01 15 < CHa CHa CHa Ct 16 to2 CHa CHa -CH,N'7N~ol, u 17 < xCH3 CH3 H H OCH3 2 \CH 18 CONH < CHa CHa -H OCaHs 19 -C, Ca H7 (n) -H CHa -H 20 -NH2 2 CHa -H Ca H7 (iso) CHa No.D X R1 R2 R3
21 O=C eC6H3 -CH3 -CH3 -H -OC4H(seC) CH3 22 e NOz CHa -H -H -N CHa 23 < CHa -CH3 -H -0C4H9(n) o- /CH3 'OS -N CH3 24 ~tk 3 CHa CHa CHa -CH3 OCH3 25 )\N=NN0 -CH1 -CH3 CHa -CH3 3 o 26 -CH, -H -CH, -H 26 CHa -H CHa -H 0 CL 27 tN\ CHa -H -H MOCHA 28 CHa CHa CHa -CH3 NOe C3C-N 29 II II -CH3 -H CH2 CHa -H OeN-C,s/C 5 30 "- CHa -H -CH3 -H No. D X Rl R2 Ra
CHa -H -CH3 -CH, WHAT WE CLAIM IS:1.A water-insoluble azo dyestuff of the general formula I
wherein D is an optionally substituted phenyl, naphthyl, anthraquinonyl or heterocyclic radical which is free from groups conferring water-solubility, X and R1 are the same or different and each is hydrogen or alkyl having I to 4 carbon atoms, R2 is hydrogen or alkyl having I to 8 carbon atoms and R3 is hydrogen, alkyl having I to 7 carbon atoms, an optionally substituted cycloalkyl group or a radical of the formula
wherein R4 is alkyl having I to 8 carbon atoms or an optionally substituted cycloalkyl group and R5 and R6 are the same or different and each is alkyl having I to 4 carbon atoms, or R5 and R8, together with the nitrogen atom to which they are attached, form, optionally with a further hetero atom, a five-membered or sixmembered heterocyclic ring.
2. A water-insoluble azo dyestuff according to Claim 1, wherein X is methyl, R, is hydrogen, R2 is hydrogen or methyl and R3 is hydrogen, methyl or ethyl or a radical of the formula
wherein each of R4, R5 and R6 is methyl, ethyl or n-butyl.
3. A water-insoluble azo dyestuff according to Claim 1 or Claim 2 wherein D is a 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl-sulphonic acid 3-amino-phenyl ester, (4'-methyl-phenyl)-sulphonic acid 3-amino-phenyl ester, 4-amino-benzophenone, 4-amino-4'-methoxy-benzophenone or dimethylsulphamic acid 3-amino-phenyl ester radical.
4. A water-insoluble azo dyestuff according to any of Claims 1 to 3, characterised in that D is a 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2nitroaniline, phenyl-sulphonic acid 3-amino-phenyl ester, (4'-methyl-phenyl)
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (22)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    No. D X Rl R2 Ra
    CHa -H -CH3 -CH, WHAT WE CLAIM IS:1. A water-insoluble azo dyestuff of the general formula I
    wherein D is an optionally substituted phenyl, naphthyl, anthraquinonyl or heterocyclic radical which is free from groups conferring water-solubility, X and R1 are the same or different and each is hydrogen or alkyl having I to 4 carbon atoms, R2 is hydrogen or alkyl having I to 8 carbon atoms and R3 is hydrogen, alkyl having I to 7 carbon atoms, an optionally substituted cycloalkyl group or a radical of the formula
    wherein R4 is alkyl having I to 8 carbon atoms or an optionally substituted cycloalkyl group and R5 and R6 are the same or different and each is alkyl having I to 4 carbon atoms, or R5 and R8, together with the nitrogen atom to which they are attached, form, optionally with a further hetero atom, a five-membered or sixmembered heterocyclic ring.
  2. 2. A water-insoluble azo dyestuff according to Claim 1, wherein X is methyl, R, is hydrogen, R2 is hydrogen or methyl and R3 is hydrogen, methyl or ethyl or a radical of the formula
    wherein each of R4, R5 and R6 is methyl, ethyl or n-butyl.
  3. 3. A water-insoluble azo dyestuff according to Claim 1 or Claim 2 wherein D is a 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl-sulphonic acid 3-amino-phenyl ester, (4'-methyl-phenyl)-sulphonic acid 3-amino-phenyl ester, 4-amino-benzophenone, 4-amino-4'-methoxy-benzophenone or dimethylsulphamic acid 3-amino-phenyl ester radical.
  4. 4. A water-insoluble azo dyestuff according to any of Claims 1 to 3, characterised in that D is a 3-nitroaniline, 2-methyl-4-nitroaniline, 4-methyl-2nitroaniline, phenyl-sulphonic acid 3-amino-phenyl ester, (4'-methyl-phenyl)
    sulphonic acid 3-amino-phenyl ester, 4-amino-benzophenone, 4-amino-4'methoxy-benzophenone or dimethylsulphamic acid 3-amino-phenyl ester radical and X is methyl, R, is hydrogen, R2 is hydrogen or methyl and Ra is hydrogen, methyl or ethyl or a radical of the formula
    wherein each of R4, R5 and R is methyl, ethyl or n-butyl.
  5. 5. A water-insoluble azo dyestuff according to any of Claims I to 4, of the formula
  6. 6. A water-insoluble azo dyestuff according to any of Claims I to 4, of the formula
  7. 7. A water-insoluble azo dyestuff according to any of Claims 1 to 4, of the formula
  8. 8. A water-insoluble azo dyestuff according to any of Claims I to 4, of the formula
  9. 9. A water-insoluble azo dyestuff substantially as described hereinbefore with particular reference to any of Examples I to 3 or any of the compounds numbered 1 to 315 in the accompanying Table.
  10. 10. Any of the water-insoluble azo dyestuff compounds of formula I specifically mentioned hereinbefore other than a compound as claimed in any of Claims 5 to 9.
  11. II. A process for the manufacture of water-insoluble azo dyestuffs of the general formula I as defined in any of Claims I to 8 comprising diazotisation of an amine, which is free from ionic groups, of the general formula II D-NH2 II wherein D has the same meaning as in Formula 1, and coupling of the diazotisation product with a 3-cyano-6-hydroxy-2-pyridone of the general formula III
    wherein X,. R1, R2 and R3 each have the same meaning as defined in formula I.
  12. 12. A process according to Claim 11, wherein a mixture of different amines of the general formula II as defined hereinbefore is diazotised and the diazotisation products are coupled with one or more 3-cyano-6-hydroxy-2-pyridones of the general formula III as defined hereinbefore.
  13. 13. A process according to Claim 11, wherein the amine of the general formula II as defined hereinbefore, after diazotisation, is coupled with two or more 3cyano-6-hydroxy-2-pyridones of the general formula III as defined hereinbefore.
  14. 14. A process according to any of Claims 11 to 13, wherein 3-nitroaniline, 2methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl-sulphonic acid 3-aminophenyl ester, (4'-methyl-phenyl)-sulphonic acid 3-amino-phenyl ester, 4-aminobenzophenone, 4-amino-4'-methoxy-benzophenone or dimethylsulphamic acid 3amino-phenyl ester is used as the amine of the general formula II.
  15. 15. A process according to any of Claims 11 to 14, wherein a 3-cyano-6hydroxy-2-pyridone of the general formula 111 in which X is methyl, R1 is hydrogen, R2 is hydrogen or methyl and R3 is hydrogen, methyl or ethyl or a radical of the formula
    wherein each of R4, R5 and R, is methyl, ethyl or n-butyl, is used.
  16. 16. A process according to any of Claws 11 to 15 wherein 3-nitroaniline, 2methyl-4-nitroaniline, 4-methyl-2-nitroaniline, phenyl-sulphonic acid 3-aminophenyl ester, (4'-methyl-phenyl)-sulphonic acid 3-amino-phenyl ester, 4-aminobenzophenone, 4-amino-4'-methoxy-benzophenone or dimethyl-sulphamic acid 3amino-phenyl ester is used as the amine of the general formula 11, and a 3-cyano-6hydroxy-2-pyridone of the general formula 111 in which Xis methyl, R, is hydrogen, R2 is hydrogen or methyl and Ra is hydrogen, methyl or ethyl or a radical of the formula
    wherein each of R4, R5 and R8 is methyl, ethyl or n-butyl, is used.
  17. 17. A process for the manufacture of a water-insoluble azo dyestuff according to Claim I substantially as described hereinbefore with particular reference to any of Examples I to 3.
  18. 18. A water-insoluble azo dyestuff when prepared by a process according to any of claims 11 to 17.
  19. 19. A process for dyeing or printing a hydrophobic synthetic material, wherein is used a dyestuff of the general formula 1 as defined hereinbefore in any of Claims I to 9.
  20. 20. A process for dyeing or printing a polyolefines, cellulose 21-acetate, cellulose triacetate of polyester material, wherein is used a dyestuff of the general formula I as defined hereinbefore in any of Claims I to 9.
  21. 21. A process for dyeing or printing a hydrophobic synthetic material substantially as described hereinbefore with particular reference to any of Examples I to 4.
  22. 22. A hydrophobic synthetic material which has been dyed or printed by a method according to any of Claims 19 to 21.
GB7481/78A 1977-02-26 1978-02-24 Waterinsoluble azodyes Expired GB1588372A (en)

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DE19772708418 DE2708418A1 (en) 1977-02-26 1977-02-26 HYDRO-INSOLUBLE AZO DYES AND PROCESS FOR THEIR PRODUCTION, AS WELL AS THEIR COUPLING COMPONENTS AND PROCESS FOR PRODUCING THE COUPLING COMPONENTS

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FR (1) FR2381807A1 (en)
GB (1) GB1588372A (en)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4772292A (en) * 1985-02-21 1988-09-20 Cassella Aktiengesellschaft Mixture of yellow disperse dyestuffs containing pyridone disazo dye

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DE3024857A1 (en) * 1980-07-01 1982-02-04 Bayer Ag, 5090 Leverkusen ANTHRACHINONAZO COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE

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CH552661A (en) * 1968-11-12 1974-08-15 Ciba Geigy Ag PROCESS FOR PRODUCING NEW AZO DYES.
BE786947A (en) * 1971-07-29 1973-01-29 Ciba Geigy NITROGEN COMPOUNDS, PROCESS FOR THE PREPARATION AND THEIR USE

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4772292A (en) * 1985-02-21 1988-09-20 Cassella Aktiengesellschaft Mixture of yellow disperse dyestuffs containing pyridone disazo dye

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JPS53106729A (en) 1978-09-18
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IT1158655B (en) 1987-02-25
NL7801886A (en) 1978-08-29
CH632292A5 (en) 1982-09-30
FR2381807A1 (en) 1978-09-22
DE2708418A1 (en) 1978-08-31
BR7801127A (en) 1978-10-10
BE864317A (en) 1978-08-24

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