US3341513A - Disperse monoazo dyestuffs - Google Patents

Disperse monoazo dyestuffs Download PDF

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US3341513A
US3341513A US300670A US30067063A US3341513A US 3341513 A US3341513 A US 3341513A US 300670 A US300670 A US 300670A US 30067063 A US30067063 A US 30067063A US 3341513 A US3341513 A US 3341513A
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phenyl
acid
methyl
hydroxybenzene
ester
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Hans E Wegmuller
Bossard Werner
Voltz Jacques
Favre Francois
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Novartis AG
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JR Geigy AG
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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
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/30—Preparation of azo dyes from other azo compounds by esterification of —COOH or —SO3H groups
    • 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
    • C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
    • C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
    • C09B29/366—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles containing hydroxy-1,2-diazoles, e.g. pyrazolone
    • 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
    • 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
    • C09B31/143—1,2-Diazoles
    • C09B31/147—Pyrazoles

Definitions

  • the present application concerns new, water-dispersible azo dyestuffs, processes for the production thereof, processes for the dyeing of organic hydrophobic material using the new dyestuffs and, as industrial product, the materials dyed with the aid of these dyestuffs.
  • A represents unsubstituted phenyl or lower alkylphenyl, trifiuoromethylphenyl, lower alkoxyphenyl, lower alkanoylaminophenyl, benzoylaminophenyl, nitrophenyl, cyan-ophenyl, fluorophenyl, chlorophenyl, bromophenyl, lower alkylcarbonylphenyl, benzoylphenyl, carbamylphenyl, mono-N-lower alkyl-carbamylphenyl, di-(N-lower alkyl) carbamylphenyl, N lower alkyl-N-phenyl-carbamylphenyl, piperidino (1)-carbonylphenyl, morpholino (l)-carbonylphenyl, lower alkoxycarbonylphenyl, phenoxy-carbonyl-phenyl or benzyloxy-carbamyl-phen
  • B represents hydrogen, alkyl with from 1 to 6 carbon atoms, cycloalkyl with from 5 to 6 carbon atoms, hydroxyalkyl with from 1 to 4 carbon atoms, cyanoalkyl with from 1 to 4 carbon atoms, alkoxyalkyl with a total of from 3 to 6 carbon atoms the alkyl moiety of which radicals contains at least 2 carbon atoms, phenyl-lower ,alkyl, lower alkyl-phenyl-lower alkyl, chloro-phenyl-lower alkyl, bromo-phenyl-lower alkyl, phenyl, lower alkylphenyl, chloro-phenyl, bromo-phenyl, lower alkoxyphenyl, lower alkanoylamino-phenyl, naphthyl, lower alkyl-naphthyl, chloro-naphthyl or bromo-naphthyl, and
  • R represents one of the following radicals: primary alkyl with from 4 to 10 carbon atoms, secondary alkyl with from 4 to 10 carbon atoms, phenyl, lower alkylphenyl, lower alkoXy-phenyl, chloro-phenyl, bromophenyl, lower alkanoylamino phenyl, hydroxy-lower alkybphenyl, carbamyl-phenyl, mono-N-lower alkylcarbamyl phenyl, di (N-lower alkyl)carbamyl-phenyl, lower .alkoxy carbonylphenyl, nitrophenyl, di (lower alky1)-arnino-phenyl, phenoXy-phenyl, lower alkyl-phenoxyphenyl, lower alkoXy-phenoxy-phenyl or pyridyl- (3) radicals; while cyclohexyl, chloro-phenoxy-phenyl, bromo-phenoxy-phen
  • Dyestuffs according to the invention are also useful for the dyeing of synthetic polyamide fibers such as nylon or of Perlon which dyeings are distinguished by their good fastness properties, among them fastness to washing (alkali, water, sea water, etc.) and to light and sublimation.
  • Dyestuffs of Formula I are also suited for use in dyeing acetate rayon, polyester fibers, polyamide fibers such as nylon and the like, in the mass, prior to spinning (dope dyeing) and also as pigments in lacquers and paints, because of their good solubility in organic solvents such as acetone, chloroform and the like.
  • Polyester fibers are dyed with aqueous dispersions of dyestuffs according to the invention preferably at temperatures of over C. under pressure. Dyeing can also be performed, however, at the boiling point of the dyebath in the presence of carriers such as phenylpenol, polychlorobenzene compounds or similar auxiliaries, or by the foulard process after which the dyeing is thermofixed at -210" C.
  • the drawing power of the dyestuffs can be still further improved by mixing two or more monoazo dyestuffs according to the invention.
  • Dyestuffs according to the invention are distinguished by good affinity to hydrophobic polyesters fibers, particularly to polyglycol terephthalates and, depending on their composition, produce on these fibers greenish yellow to reddish yellow dyeiugs of good colour strength which have very good fasteness to washing, sublimation, light, perspiration and cross-dyeing.
  • vegetable and animal fibers, particularly cotton are very well reserved by the dyestuffs according to the invention. They can also be dyed evenly with the usual commercial carriers.
  • '9 A is one of the radicals of the formulas S
  • X represents hydrogen, lower alkyl, lower alkoxy, Cl,
  • Br, F, or --NO X represents hydrogen, Cl, Br, CF or lower alkoxy-carbonyl, each of X and X independently, represents hydrogen,
  • B represents phenyl, lower alkyl-phenyl, chloro-phenyl, bromo-phenyl, lower alkoxy-phenyl, lower alkanoylamino-phenyl, naphthyl, lower alkyl-naphthyl, chloro-naphthyl, or bromo-naphthyl,
  • HO- J I I (SOBOR) Y2 Yr r N is (1v) wherein Y represents hydrogen, lower alkyl, lower alkoxy, or hydroxy-lower alkoxy,
  • Y represents hydrogen, lower alkyl, lower alkoxy, hydroxy-lower alkoxy, chlorine, bromine, fluorine or trifluoromethyl
  • B represents phenyl, lower alkyl-phenyl, chloro-phenyl
  • R represents phenyl, lower alkyl-phenyl, lower alkoxyphenyl, chl'oro-phenyl, bromo-phenyl, hydroXy-lower alkyl-phenyl, lower alkanoylamino-phenyl, lower alkoxy-carbonyl-phenyl, carbamyl-phenyl, monoand di- (N-lower alkyl)-carbamyl-phenyl, or pyridyl-(3).
  • novel dyestuffs according to the invention are produced by coupling the diazonium compound of an amine of the formula chlorine, bromine, lower alkyl A-NH (V with a coupling component of the formula OH-GCH3 Holt i of which two reactants either the diazo compound or the coupling component contains a substituent SO OR, bonded directly to an aromatic (benzene or naphthalene) nucleus; A, B and R in Formulas VI and VII having the above given meanings.
  • B in Formula VII is either an aliphatic or a cycloaliphatic radical such as the methyl, ethyl, propyl, isopropyl, butyl, methoxypropyl, or cyanoethyl group or the cyclohexyl radical.
  • B is an araliphatic radical, it is, for example, the benzyl group; when it is an aromatic radical, it is, for example, an unsubstituted or a substituted phenyl or naphthyl radical.
  • the radical -OR represents, for example, an alkoxy group which is derived from nor sec. butanol, or from a primary or secondary amyl or hexyl alcohol, or it is a cycloalkoxy group, e.g. the cyclohexyloxy radical, or an unsubstituted or substituted aryloxy group which is derived, e.g.
  • a hydroxynaphthalene such as a l-hydroxyor 2-hydroxy-naphthalene or preferably from a monohydroxybenzene such as phenol, an alkyl-, alkoxy-, or hydroxyalkyl-hydroxybenzene, or an aryloXy-, halogeno-, dialkyl-amino-, N- al-kyl-N-phenylamino-, alkoxycarbonyl-, carbamyl, or alkanoylamino-hydroxybenzene, i.e. it is derived, for example, from 2-, 3- or 4-methylor 2-, 3- or 4-ethyll-hydroxybenzene or technical mixtures thereof, from 3,4- or 2,4-di methyl-, 4-sec.
  • substituents of the benzene ring of A are: aliphatic groups such as methyl, trifluoromethyl, ethyl, propyl or isopropyl groups, alkoxy groups such as methoxy, ethoxy or butoxy groups, acylamino, especially lower alkanoylamino groups such as acetylamino, or benzoylamino groups, particularly however, electrophilic substituents such-asnitro groups, the trifluoromethyl or cyano groupsmentioned above, halogens, in particular fluorine, chlorine or bromine, keto groups such as acetyl, propionyl or benzoyl groups, and, when the substituent SO -OR is at the B-moiety, carboxylic acid ester groups such as the carbomethoxy, carboethoxy, carboisopropoxy, carbobutoxy, or carbophenoxy group, or unsubstituted or substituted carbamyl or sulfamyl
  • ring A contains an arylazo group
  • the latter is preferably a phenylazo group the benzene ring of which is unsubstituted or contains the substituents previously mentioned.
  • the rings of that radical are either unsubstituted or substituted, for example, by halogens such as chlorine or bromine, particularly in a position adjacent to the bond to the pyrazolene nucleus as well as by lower alkyl or alkoxy groups or acylamino, especially lower alkanoylamino groups.
  • Dyestuffs of Formula I substituted at the benzene ring of A by an arylazo group produce more reddish yellow dyeings; when A does not contain an arylazo group, very pure, more. greenish yellow dyeings are obtained.
  • diazonium compounds of amines of Formula VI usable according to the invention contain the characteristic SO OR group, then these are, for example, esters of the alcohols, naphthols and, particularly, phenols mentioned above in the discussion of the group RO-, which are derived, forexample, from l-aminobenzene-Z, -3- or -4-sulphonic acid, 2-alkyl-l-aminobenzeneor 2-halogenl-aminobenzene- -4- or 5-sulphonic acids, 3-alkyl-l-aminobenzene-j l-sulfonic acid, 4-alkyl-l-aminobcnzeneor 4- halogen-l-aminobenzene- Z-sulphonic acids, or 2,5-dichloro-l-aminobenzene-4-sulphonic acid, 3,4-dichloro-laminobenzene-6-sulfonic acid and 2-chloro-3-1nethyl-l-amin
  • Coupling components of Formula VII usable according to the invention which contain the SO OR group as defined are esters of the hydroxyl compounds mentioned with, e.g. lphenyl-3-methyl-pyrazol-5-one, 2'-, -3'- or -4- sulphonic acid, 1-(4'-methyl-phenyl)-3 methyl-pyrazole- 5-one-3'-sulphonic acid, 1 (2-chloro-phenyl)-3-methylpyrazol-5-one-5'-sulphonic acid, 1-(2',5'-di-chlorophenyl)- 3-methyl-pyrazol-5-one-4'-sulphonic acid.
  • Amines of Formula VI containing sulphonic acid ester groups are obtained, for example, by reacting the desired alcohol, naphthol or phenol with the corresponding nitrobenzene sulphonic acid chloride or bromide and then reducing the nitro group to the amino group.
  • Sulfonic acid ester substituted pyrazolones of Formula VII which serve as coupling components for producing dyestuffs according to the invention are produced by esterification of the corresponding starting compound of the formula wherein B has the above given meaning, with the corresponding hydroxylated compound of the formula wherein R has the meaning given above, reduction of the nitro group of the resulting nitro ester to the corresponding amino ester, conversion to the hydrazino ester and condensation of thelatter with an acetoacetic acid ester.
  • Examples of amines of Formula VI free from the characteristic sulphonic acid ester group which are used according to the invention are l-amino-Z-nitrobenzene, 1-amino-2 nitro-4-methyl-benzene, 1-amino-2-nitro-4-methoxyor 4-ethoxy-benzene, 1-amino 2-nitro-4-chloro-,
  • Examples of coupling components of Formula II without the defined SO OR group are 3-methyl-pyrazol-5- one, 1,3-dimethyl-pyrazol-5-one, 3-methyl-pyrazol-5-one which are substituted in l-position by ethyl, propyl, isopropyl, ,e-hydroxyethyl, ,B-cyanoethyl, cyclohexyl, benzyl, phenyl, 2'-methyl-phenyl, 3-methyl-phenyl, 4'-methylphenyl, 2'-methoXy-phenyl, 3-methoxy-pehnyl, 4'-methoxy-phenyl, 2'-chloro-phenyl, 4'-chloro-phenyl, 2',4-dichloro phenyl, 2,4' dibromo-phenyl, 3'-acetyl-aminophenyl or 4-acetyl-amino-phenyl.
  • the coupling is performed in mineral acid or, preferably, in weakly acid solution advantageously, while gradually bulfering the acid, e.g., with alkali metal salts of carbonic acid or low fatty acids.
  • a suitable diazonium compound can also be coupled simultaneously with a mixture of two or more coupling components which are usable according to the invention.
  • a modification of the process for the production of azo dyestuffs consists in condensing an azo compound of formula wherein A represents a phenyl radical which can also contain phenyl azo groups,
  • B represents hydrogen or an aliphatic, cycloaliphatic
  • X represents chlorine or bromine and the SO -X group is directly bound to an aromatic, carbocyclic nucleus
  • R represents an alkyl radical containing at least 4 carbon atoms or a cycloalkyl radical or an unsubstituted or a substituted aryl radical
  • the starting materials of the Formula VIII are obtained, for example, by coupling the diazonium compound of an amine of Formula V1 with a coupling component of Formula VII, one of which components contains the sulfonic acid group, directly bound to an aromatic, carbocyclic nucleus, and converting the azo dyestuff sulfonic acid so obtained to the corresponding sulfonic acid chloride, or bromide, for example by means of a phosphorus halide or thionyl chloride, without or in the presence of a tertiary nitrogen base and an inert solvent or diluent.
  • Suitable amines of Formula VI and of coupling components of Formula VII are the l-aminobenzenes or 3-methyl-pyrazol-5-ones respectively or the sulfonic acids of these compounds mentioned in the first process, as well as Z-nitro-l-aminobenzene 4-sulfonic acid, 4-nitro-l-amino-benzene-Z-sulfonic acid, 5 chloro-2-nitro-1-amino-benzene-4-sulfonic acid, 4-amino-azobenZene-4-sulfonic acid, 2-methyl-4- amino-azobenzene-4-sulfonic acid and 2-methyl-4-aminoaZobenzene-3'-sulfonic acid.
  • organic hydroxyl compounds of Formula IX which are to be reacted with the sulfonic acid chlorides or bromides of Formula VIII are those mentioned in the illustration of RO.
  • the condensation of compounds of Formula VIII with the hydroxyl compounds of Formula IX to form esters of Formula I is performed advantageously at a raised temperature, optionally in aqueous, organic or aqueous/ organic solution.
  • Suitable organic solvents for this purpose are those which are miscible with water, e.g., lower alkanols, especially methanol or ethanol, lower aliphatic ketones such as acetone or methylethyl ketone, or ether alcohols such as ethylene glycol monomethyl or monoethyl ether, or those which are not miscible with water, e.g., unhalogenated or halogenated aromatic hydrocarbons such as benzene, toluene, xylenes, chlorobenzene or dichlorobenzenes.
  • the hydroxyl compounds to be reacted such as the hydroxyalkyl, hydroxycycloalkyl or hydroxyaryl compounds, are advantageously used in the form of their metal salts such as the sodium or potassium
  • EXAMPLE 1 34.4 parts of 1-phenyl-3-methyl-pyrazole-5-one-3'-sulphonic acid-(4"-methylphenyl)-ester are dissolved in 100 parts of dimethyl formamide and the solution is poured into 400 parts of water and 6 parts of cetyl polyglycol ether while stirring quickly.
  • the diazonium salt solution of 17.3 parts of l-amino-2-chloro-4-nitro-benzene is added dropwise at 05 to the fine dispersion and then the free mineral acid is buttered by the addition of sodium acetate.
  • the precipitate formed is filtered oif, washed with a great deal of water and dried in vacuo at 60-70.
  • the coupling product is a red-orange powder, the composition of which corresponds to the formula Milled with a condensation product of naphthalene sulphonic acids and formaldehyde, the dyestufr so obtained dyes polyglycol terephthalate fibres such as Dacron in vivid yellow shades from aqueous dispersion, if necessary in the presence of carriers such as o-phenylphenol.
  • the dyeings have excel-. lent fastness to washing, sublimation and light.
  • the 1-phenyl-3-methyl-pyrazole-5-one 3' sulphonic acid- (4"-methylphenyl)-ester used for the coupling is ob-v tained for example by reacting 1-nitrobenzene-3-sulphonic acid chloride with p-cresol, reducing the nitro group to the amino group, converting the l-aminobenzene-Bf-sul: phonic acid-(4-methylphenyl)-ester into the corresponding hydrazine and condensing the 1-hydrazino-benzene-3- sulphonic acid-(4"-methylphenyl)-ester with acetoacetic acid methyl ester.
  • EXAMPLE 2 After milling with a condensation product of naphthalene sulphonic acids and formaldehyde, it dyes polyglycol terephthalate fibres such as Dacron in reddish yellow shades from an aqueous dispersion, sometimes in the presence of o-phenylphenol. The dyeings have excellent fastness to washing, light and sublimation.
  • the 1-phenyl-3-methyl-pyrazole-5-one 4 sulphonic acid phenyl ester used as starting material is obtained by reacting l-nitrobenzene-3-sulphonic acid chloride with phenol, reducing the nitro group to the amino group, converting the amine into 1-hydrazino-benzene 3 sulphonic acid phenyl ester and condensing this with acetoacetic acid methyl ester.
  • Dyestuffs having similar properties are obtained if, instead of the 33.0 parts of 1-phenyl-3-me-thyl-pyrazole-5- one-4-sulphonic acid phenyl ester, the equivalent amounts of 1-phenyl-3-methylpyrazole-5-one-4 sulphonic acid- (2"- methylphenyl)-ester, l-phenyl-3 methylpyrazole one-4-sulpho'nic acid-(3"-methylphenyl) ester, l-phenyl- 3-rnethylpyrazole-5-one-4'-sulphonic acid-(4" methylphenyl)-ester or 1-phenyl-3-methylpyrazole 5 one 4'- sulphonic acid (2" chlorophenyl) ester, 1 phenyl- 3-methylpyrazole 5 one 3 sulphonic acid (2"- methy1phenyl)-ester or 1-phenyl-3-methylpyrazole S-one- 3-sulphonic acid phenyl ester, 1-phen
  • the solution of the diazonium salt so obtained is then poured into a slurry of 36.5 parts of 1-(2'-chlorophenyl)-3-methylpyrazole-5-one-5'-sulphonic acid- (4-methylphenyl) -ester and 120 parts of crystallised sodium acetate in 150 parts of dirnethyl formamide and 1500 parts of ice water whereupon the yellow azo dyestulf of the formula precipitates.
  • the pH of the coupling solution is maintained at 4-5 by the simultaneous addition dropwise of sodium hydroxide solution.
  • the dyestufi is filtered off, washed neutral with Water and dried in vacuo at 60-70".
  • the l-(2'-cl1lorophenyl) 3-methylpyrazole-5-one-5'- sulphonic -acid-(4"-methylphenyl)-ester used as coupling component is obtained analogously to the coupling component mentioned in Example 2 starting from 4-nitro-2- chlorobenzenes-S-sulphonic acid chloride and p-cresol.
  • the dyeings have excellent fastness to washing, rubbing and sublimation.
  • benzene 3--. 1-amlno-4-nitro- 1-phenyl-3-methy1pyrazole-5- Yellow. 10 benzene. one-3-sulphonic acid-(3- methylphenyD-ester.
  • EXAMPLE 4 15.1 parts of 1-arnino-2-nitro-4-methylbenzene are diazotised in the usual way and coupled with 28.8 parts of 1-(2-chlorophenyl) 3 methylpy-razole-5-one-3-sul phonic acid.
  • the dyestuff so obtained is dried, and converted with phosphorus oxychloride in an inert solvent in the presence of catalytic amounts of pyridine; into the" corresponding sulphonic acid chloride.
  • the product so obtained has the formula L N NO: HO LN
  • the dyeings are fast to washing, sublimation and light.
  • EXAMPLE 5 then cooled to room temperature and the yellow dyestufl. corresponding to the formula is filtered olf and washed with a lot of water.
  • the product when dried in vacuo at 60-70 is a yellow powder.
  • the dyeings are 20 fast to washing and sublimation.
  • O1 C1ON N H OH; Do.
  • a solution of 38.0 parts of 1-(2-chlo1 ophenyl)-3-methylpyrazole-5-one-5'-su1phonic acid-(2"-1 nethyl- 01 CH8 phenyl)-ester in 125 parts of dimethyl formamide is added dropwise at 0-5 to the clear diazonium salt solution, and the mineral acid is buffered by the addition of sodium aceis filtered off, washed with water, dried in vacuo at 6070 and milled with a mixture of a condensation product of naphthalene-Z-sulphonic acid with formaldehyde and a lignin sulphonate.
  • the dyestuff is a yellow powder which dyes polyglycol terephthalate fibres in pure greenish yellow shades from an aqueous dispersion if necessary in the presence of a carrier such as o-phenylphenol.
  • the dyeings have very good fastness to washing, rubbing, light and sublimation.
  • the 1-(2'-chlorophenyl)-3-methylpyrazole-5-0ne-5'-sulphonic acid-(2"-methylphenyl)-ester used as coupling component is obtained, for example, by reacting l-nitro- 2-chlorobenzene-5-sulphonic acid chloride with o-cresol, reducing the nitro group to the amino group, converting the 1-amino-2chloro-5-sulphonic acid (2"-methylphenyl)- ester into the corresponding hydrazine and condensing this with acetoacetic acid methyl ester.
  • EXAMPLE 7 l N02 HO- l O 3 C a is filtered off and washed with a lot of water. After drying solvents, e.g. chloroform of acetone.
  • the dyestuff can be used for the dyeing of lacquers, e.g. nitro lacquers or stoving lacquers, and for the dyeing of acetyl cellulose in the mass. Acetyl cellulose dyed therewith in the spinning mass has a pure yellow shade and has good wet fastness and very good light fastness properties.
  • the 1 phenyl 3-methyl-4-(2"-nitro-4"-chloro-pheny1- azo)-pyrazole-5-one-3-sulphonic acid chloride used as starting material is obtained by coupling diazotised 1- amino-Z-nitro-4-chlorobenzene with 1-phenyl-3-methylpyrazole-5-one-3'-sulphonic acid and reacting the dry dyestutf sulphonic acid with phosphorus oxychloride in chlorobenzene in the presence of catalytic amounts of pyridine.
  • EXAMPLE 8 17.3 parts of 1-amino-4-nitro-2chlorobenzene are diazotised analogously to Example 1 and coupled with 25.4 parts of 1 phenyl 3 methylpyrazole-5-one-3'-sulphonic acid. The dried dyestutf so obtained is converted into the corresponding sulphonic acid chloride with phosphorus oxychloride in an inert solvent in the presence of catalytic amounts of pyridine.
  • the dyeings are fast to washing, sulphonic acid chlorides given in column 2 of the folrubbing and have excellent fastness to sublimation. lowing Table V are condensed with equivalent amounts of Similar dyestuffs are obtained under the conditions the hydroxyaryl compounds given in column 3.
  • NO:-C -N N u CH a I V I 4-methyl-l-hydroxybenzene D0.
  • EXAMPLE with water and dried in vacuo. It corresponds to the 1-aminobenzene-3-sulphonic acid is diazotised in the known manner and coupled with l-phenyl-B-rmethylpyrazole-S-one. The dried azo dyest'ufi is converted into the corresponding dyestufi acid chloride in chlorobenzene with phosphorus oxychloride in the presence of a little pyridine as catalyst.
  • the dyeings are fast to washing, rubbing and light.
  • Dyestuifs having similar properties are obtained if, instead of Z-methyl-l-hydroxybenzene in the above example, the equivalent amount of 4-methyl-1-hydroxy- 34 benzene, 2-chloro-l-hydroxybenzene, 2,-4 dichloro-l-hydroxybenzene, B-methoxy-l-hydroxybenzene or 4-t.butyll-hydroxybenzene is used.
  • CHzCHzCN EIQMMPLE 11 ride in an inert solvent such as chlorobezene in the presence of catalytic amounts of pyridine. 24 parts of sodium carbonate and 11 parts of 4-amyl-l hydr-oxybenzene are added to a suspension of 12 parts of this acid chloride 75 in a mixture of 150 parts of water and 50 parts of ethanol,
  • the dyeings have good dyeing properties.
  • N N'- IE-CEa 4-methyl-l-hydroxybenzene
  • N N ILL-CH3 2-methyl-l-hydroxybenzene Greenish yellow

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CH925862A CH428031A (de) 1962-08-02 1962-08-02 Verfahren zur Herstellung von in Wasser schwerlöslichen Azofarbstoffen

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549612A (en) * 1967-11-06 1970-12-22 Du Pont Cationic aryl monoazo and disazo - 3 - substituted - 1 - aminomethylpyrazolone dyes
US3988310A (en) * 1968-08-17 1976-10-26 Bayer Aktiengesellschaft Reactive dyestuffs containing a substituted 1-methyl or 1-ethyl pyrazolyl radical
US5669967A (en) * 1996-05-30 1997-09-23 Engelhard Corporation Pigment compositions
US5746821A (en) * 1995-02-13 1998-05-05 Engelhard Corporation Pigment compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549612A (en) * 1967-11-06 1970-12-22 Du Pont Cationic aryl monoazo and disazo - 3 - substituted - 1 - aminomethylpyrazolone dyes
US3988310A (en) * 1968-08-17 1976-10-26 Bayer Aktiengesellschaft Reactive dyestuffs containing a substituted 1-methyl or 1-ethyl pyrazolyl radical
US5746821A (en) * 1995-02-13 1998-05-05 Engelhard Corporation Pigment compositions
US5669967A (en) * 1996-05-30 1997-09-23 Engelhard Corporation Pigment compositions

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DE1444686B2 (de) 1973-02-15
ES290509A1 (es) 1964-02-16
GB1025059A (en) 1966-04-06
DE1444686A1 (de) 1968-10-10
AT244477B (de) 1966-01-10
CH428031A (de) 1967-01-15
AT245130B (de) 1966-02-10
DE1444686C3 (de) 1973-11-22

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