DE2805304A1 - Azo dyes contg. benzisothiazole di:sulphonic acid gp. - give fast red to green-blue tints on polyamide(s), pelts etc. - Google Patents

Azo dyes contg. benzisothiazole di:sulphonic acid gp. - give fast red to green-blue tints on polyamide(s), pelts etc.

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DE2805304A1
DE2805304A1 DE19782805304 DE2805304A DE2805304A1 DE 2805304 A1 DE2805304 A1 DE 2805304A1 DE 19782805304 DE19782805304 DE 19782805304 DE 2805304 A DE2805304 A DE 2805304A DE 2805304 A1 DE2805304 A1 DE 2805304A1
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alkyl
beta
gamma
dyes
phenyl
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German (de)
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Heinz Dipl Chem Dr Eilingsfeld
Guenter Dipl Chem Dr Hansen
Guenther Dipl Chem Dr Seybold
Georg Zeidler
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BASF SE
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BASF SE
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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
    • 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)
    • C09B29/3634—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) from diazotized heterocyclic rings
    • 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
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0081—Isothiazoles or condensed isothiazoles
    • 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
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • 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
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/065—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group containing water solubilizing 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
    • C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
    • C09B29/28—Amino naphthols
    • C09B29/30—Amino naphtholsulfonic acid
    • 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
    • C09B29/3639—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 amino 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
    • C09B29/3656—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 amino-1,2-diazoles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

Acid azo dyes are claimed having the formula (I) in the free acid form, in which K is the residue of a coupling component. Typical coupling components K are in which R1 is H, Me, OMe or OEt; R2 is H, Cl, Me, Et, benzyl, sulphobenzyl, OMe, OEt. NHCO-C1-4 alkyl, acylamino or SO3H; R3 is H, 1-4C alkyl, 2-3C hydroxy- or dihydroxyalkyl, beta-sulphoethyl, gamma-sulphopropyl, beta-cyanoethyl, beta-hydroxy-gamma-chloropropyl, 1-4C alkoxyethyl, acetoxyethyl, beta-chloroethyl, gamma-amino or gamma-acetylaminopropyl, beta-carboxyethyl, beta-carbamoylethyl, benzyl, sulphobenzyl, phenylethyl, sulphophenylethyl or cyclohexyl; R4 is 1-4C alkyl, 2-3C hydroxyalkyl, beta-cyanoethyl, beta-chloroethyl, 1-4C alkoxyethyl, benzyl or sulphobenzyl; R5 is amino, acetylamino, chloracetylamino, phenoxyacetylamino, benzoylamino, chlorbenzoylamino or dichlorbenzoylamino; R6 is (chloro)methyl, phenyl, chlorophenyl or acetylamino; R7 is 1-8C alkyl, 2-3C hydroxyalkyl, phenyl-1-4C alkyl, cyclohexyl or phenyl; R8 is H or 1-3C alkyl; R9 is H, 1-4C alkyl, 1-4C alkoxy, 2-3C alkyl or hydroxyethyl or -propyl; R10 is (cyclo)alkyl or aryl or one R10 may be H; R11 is H, 1-4C alkoxy, benzyloxy or phenoxy-substd. 1-4C alkyl; X is CN or carbomoyl. (I) are red to green-blue dyes which are esp. useful for dyeing natural and synthetic polyamides, wool, pelts etc. The dyes have very high colour strength and give dyeings with very good resistance to light, moisture, sweat, seawater etc.

Description

Säurefarbstoffe Acid dyes

Die Erfindung betrifft Farbstoffe, die in Form der freien Säuren der allgemeinen Formel I entsprechen, in der K den Rest einer Kupplungskomponente bedeutet.The invention relates to dyes in the form of the free acids of the general formula I. correspond, in which K is the remainder of a coupling component.

Im einzelnen entspricht K z. B. einem Rest der Formeln wobei R1 Wasserstoff, Methyl, Methoxy oder Äthoxy, R2 Wasserstoff, Chlor, Methyl, Äthyl, Benzyl, Sulfobenzyl, Methoxy, Äthoxy, NHCO-C1- bis C4-Alkyl, Acylamino oder SO3H, R3 Wasserstoff, C1- bis C4-Alkyl, C2- oder C3-Hydroxy- oder Dihydroxyalkyl, ß-Sulfoäthyl, γ-Sulfopropyl, ß-Cyanäthyl, ß-Hydroxy-γ-chlorpropyl, C1- bis C4-Alkoxyäthyl, Acetoxyäthyl, ß-Chloräthyl, γ-Amino- oder γ-Acetylaminopropyl, ß-Carboxyläthyl, ß-Carbamoyläthyl, Benzyl, Sulfobenzyl, Phenyläthyl, Sulfophenyläthyl oder Cyclohexyl, R4 C1- bis C4-Alkyl, C2- oder C3-Hydroxyalkyl, ß-Cyanäthyl, ß-Chloräthyl, C1- bis C4-Alkoxyäthyl, Benzyl oder Sulfobenzyl, R5 Amins, Acetylamino, Chloraoetylamino, Phenoxyacetylamino, Benzoylamino, Chlorbensoylamino oder Dichlorbenzoylamino, R Methyl, Chlormethyl, Phenyl, Chlorphenyl oder Acetylamino, R7 C1- bis C8-Alkyl, C2- oder C3-Hydroxyalkyl, Phenyl-C1- bis C4-Alkyl, Cyclohexyl oder Phenyl, R8 Wasserstoff oder Ci bis C3-Alkyl, R9 Wasserstoff, C1 - bis C4-Alkyl, C1- bis C4-Alkoxy, C2 oder C3 Alkyl oder Hydroxyäthyl oder -propyl, die Reste R10 unabhängig voneinander gegebenenfalls substituiertes Alkyl, Cycloalkyl oder Aryl und einer der Reste auch Wasserstoff, R11 Wasserstoff, gegebenenfalls durch Ci" bis C4-Alkoxy, Benzyloxy oder Phenoxy substituiertes C1- bis C4-Alkyl, X Cyan oder Carbamoyl, m die Zahlen 0, 1 oder 2, n die Zahlen 1 oder 2 und p die Zahlen 0 oder 1 bedeuten.In detail, K z corresponds to. B. a remainder of the formulas where R1 is hydrogen, methyl, methoxy or ethoxy, R2 is hydrogen, chlorine, methyl, ethyl, benzyl, sulfobenzyl, methoxy, ethoxy, NHCO-C1- to C4-alkyl, acylamino or SO3H, R3 is hydrogen, C1- to C4-alkyl, C2- or C3-hydroxy- or dihydroxyalkyl, ß-sulfoethyl, γ-sulfopropyl, ß-cyanoethyl, ß-hydroxy-γ-chloropropyl, C1- to C4-alkoxyethyl, acetoxyethyl, ß-chloroethyl, γ-amino or γ- Acetylaminopropyl, ß-carboxylethyl, ß-carbamoylethyl, benzyl, sulfobenzyl, phenylethyl, sulfophenylethyl or cyclohexyl, R4 C1- to C4-alkyl, C2- or C3-hydroxyalkyl, ß-cyanoethyl, ß-chloroethyl, C1- to C4-alkoxyethyl, Benzyl or sulfobenzyl, R5 amine, acetylamino, chloroetylamino, phenoxyacetylamino, benzoylamino, chlorobensoylamino or dichlorobenzoylamino, R methyl, chloromethyl, phenyl, chlorophenyl or acetylamino, R7 C1 to C8 alkyl, C2 or C3yl hydroxyalkyl, C2 or C3yl hydroxyalkyl C4-alkyl, cyclohexyl or phenyl, R8 hydrogen or Ci to C3-alkyl, R9 hydrogen, C1- to C4-alkyl, C1- to C4-alkoxy, C2 ode r C3 alkyl or hydroxyethyl or propyl, the radicals R10 independently of one another optionally substituted alkyl, cycloalkyl or aryl and one of the radicals also hydrogen, R11 hydrogen, optionally C1 to C4 alkyl substituted by C1 "to C4-alkoxy, benzyloxy or phenoxy , X is cyano or carbamoyl, m is the number 0, 1 or 2, n is the number 1 or 2 and p is the number 0 or 1.

Acylaminoreste R2 sind beispielsweise Ci" bis C8-Alkylcarbonylamino, das noch durch Chlor, Hydroxy oder Carboxyl substituiert sein kann, gegebenenfalls substituiertes Benzoylamino oder C1- bis C4-Alkylaminocarbonylamino sowie Im einzelnen seien beispielsweise aufgeführt: NHCHO, NHCOCH3, NHCOC2H5, NHCOC3H7, NHCOC4H9, NHCOCH2Cl, NHCOCHCl2, NHCOCH2OH, NHCOCH2OCH3, NHCH2CH2COOH, NHCOCH=CH-COOH, NHCONH2, NHCONHCH3, NHCONHC3H7, NHCONHC4H9, NHCOC6H5, NHCOC6H4Cl, NHCOC6H4COOH oder NHCOC6H4SO3H.Acylamino radicals R2 are, for example, Ci "to C8-alkylcarbonylamino, which can also be substituted by chlorine, hydroxyl or carboxyl, optionally substituted benzoylamino or C1- to C4-alkylaminocarbonylamino as well Examples include: NHCHO, NHCOCH3, NHCOC2H5, NHCOC3H7, NHCOC4H9, NHCOCH2Cl, NHCOCHCl2, NHCOCH2OH, NHCOCH2OCH3, NHCH2CH2COOH, NHCOCH = CH-COOH, NHCONH2, NHCONHCH3, NHCONHC3H7, NHCONHC4H9, NHCOC6H5, NHCOC6H4Cl, NHCOC6H4COOH or NHCOC6H4SO3H.

Einzelne Alkyl- und Alkoxyalkylreste für R3 und R4 sind beispielsweise: CH3, C2H5, C3H7, C4H9, C2H4OCH3, C2H4OC2H5, C2H4OC3H7 oder C2H4OC4H7.Individual alkyl and alkoxyalkyl radicals for R3 and R4 are, for example: CH3, C2H5, C3H7, C4H9, C2H4OCH3, C2H4OC2H5, C2H4OC3H7 or C2H4OC4H7.

Pur R7 sind neben den bereits einzelnen genannten Resten zu erwähnen: CH3, C2H5, C3H7, C4H9, C5H11, C6H13, C8H17, C6H5CH2, C6H5C2H4, C6H5C3H6 oder C6H5C4H8.Pur R7 should be mentioned in addition to the individual residues already mentioned: CH3, C2H5, C3H7, C4H9, C5H11, C6H13, C8H17, C6H5CH2, C6H5C2H4, C6H5C3H6 or C6H5C4H8.

Reste R sind z. B.: gegebenenfalls durch Sauerstoff unterbrochenes und gegebenenfalls durch Hydroxy, Aryloxy, Ci - bis C8-Alkoxy, Cycloalkoxy, Aralkoxy oder Aroxy substituiertes Ci - bis C8-Alkyl, Allyl, Cycloalkyl, Phenyl-C1- bis C4-alkyl oder gegebenenfalls durch Methyl, Äthyl, Eydroxy, Methoxy, Äthoxy, Chlor oder Brom substituiertes Phenyl, wobei die Arylreste vom Substituenten R gegebenenfalls eine Hydroxysulfonylgruppe tragen können.Residues R are z. B .: possibly interrupted by oxygen and optionally by hydroxy, aryloxy, Ci - to C8-alkoxy, cycloalkoxy, aralkoxy or aroxy-substituted Ci - to C8-alkyl, allyl, cycloalkyl, phenyl-C1- to C4-alkyl or optionally by methyl, ethyl, hydroxy, methoxy, ethoxy, chlorine or bromine substituted phenyl, the aryl radicals of the substituent R optionally being one Can carry hydroxysulfonyl group.

Reste sind im einzelnen beispielsweise: CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, i-C4H9, C6H13, -CH2-CH=CH2, CH2CH2OH, (CH2)3OH, (CH2)4OH, (CH2)6OH, (CH2)2O(CH2)2OH, (CH2)3O(CH2)4OH, (CH2)3OC2H4OH, (CH2)3OC2H4OCH3, (CH2)3OC2H4OC2H5, (CH2)3O(CH2)6OH, (CH2)3OC2H4OCH(CH3)2, (CH2)3OC2H4OC4H9, (CH2)3OC2H4OCH2C6H5, (CH2)3OC2H4OC2H4C6H5, (CH2)3OC2H4OC6H5, CH2CE20CH3, CH2CH20C2H5, CH2CH20C3H7, CH2CH2OC4H9, CH2CH2OC6H5, (CH2)3OCH3, (CH2)3OC2H5, (CH2)3OC3H7, (CH2)3OC4H9, (CH2)3OC6H13, (CH2)3OC8H17, (CH2)3OCH2C6H5, (CH2)3OC2H4C6H5, (CH2)3OC6H5, und C6H4CH3 anstelle von C6H5.The individual radicals are, for example: CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, i-C4H9, C6H13, -CH2-CH = CH2, CH2CH2OH, (CH2) 3OH, (CH2) 4OH, (CH2) 6OH, (CH2) 2O (CH2) 2OH, (CH2) 3O (CH2) 4OH, (CH2) 3OC2H4OH, (CH2) 3OC2H4OCH3, (CH2) 3OC2H4OC2H5, (CH2) 3O (CH2) 6OH, (CH2) 3OC2H4OCH (CH3) 2 , (CH2) 3OC2H4OC4H9, (CH2) 3OC2H4OCH2C6H5, (CH2) 3OC2H4OC2H4C6H5, (CH2) 3OC2H4OC6H5, CH2CE20CH3, CH2CH20C2H5, CH2CH20C3H7, CH2CH2OC4H9, CH2CH2OC6H5, (CH2) 3OCH3, (CH2) 3OC2H5, (CH2) 3OC3H7, (CH2) 3OC4H9, (CH2) 3OC6H13, (CH2) 3OC8H17, (CH2) 3OCH2C6H5, (CH2) 3OC2H4C6H5, (CH2) 3OC6H5, and C6H4CH3 instead of C6H5.

C6H4CH3, C6H3(CH3)2, C6H4OCH3, C6H4OC2H5, C6H4OH, C6H4OCH2CH2OH, C6H4Cl, C2H4OCOCH3, C2H4OCOCH2COCH3, (C2H4O)2COCH3, (CH2)3OCOCH3 oder C2H4OCOC2H4-COOH. Sulfogruppenhaltige Reste 11 sind z. B.: CH2CH2SO3H, CH2CH2OSO3H, (CH2)3OSO3H, (CH2)4OSO3H, (CH2)2O(CH2)2OSO3H, (CH2)3O(CH2)2OSO3H, (CH2)3O(CH2)4SOS3H, (CH2)3OC2H4OCH2C6H4SO3H, (CH2)3OC2H4OC2H4C6H4SO3H, (CH2)3OC2H4OC6H4SO3H, CH2CH2OC6H4SO3H, (CH2)3OC6H4SO3H, (CH2)3OCH2C6H4SO3H, (CH2)3OC2H4C6H4SO3H, CH2C6H4SO3H, C2H4C6H4SO3H, Bevorzugte Reste R10 sind beispielsweise: Wasserstoff, CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, iso-C4H9, C6H13, CH2-CH2-OH, (CH2)3OH, (CH2)4OH, (CH2)6OH, (CH2)2O(CH2)2OH, (CH2)3O(CH2)2OH, (CH2)3O(CH2)4OH, (CH2)3O(CH2)6OH, CH2CH2OCH3, CH2CH2OC2H5, CH2CH2OC4H9, (CH2)3OCH3, (CH2)3OC2H5, (CH2)3OC3H7, (CH2)3OC4H9, (CH2)3OC6H13, (CH2)3OC2H4OCH3, (CH2)3OC2H4OC4H9, (CH2)3OC2H4OC4H9, CH2C6H5, C2H4C6H5, C C6H5, C6H4CH3, C6H3(CH3)2, C6H4OCH3, C6H4OC2H5, C6H4OC2H4OH, C6H4Cl, CH2CH2SO3H, CH2CH2OSO3H, (CH2)3OSO3H, (CH2)4OSO3H, (CH2)6OSO3H, (CH2)2O(CH2)2OSO3H, (CH2)3O(CH2)2OSO3H, (CH2)3O(CH2)4OSO3H, (CH2)3O(CH2)6SOS3H, (CH2)3OC6H4SO3H, (CH2)3OCH2C6H4SO3H, (CH2)3OC2H4C6H4SO3H, CH2C6H4SO3H, C2H4C6H4SO3H, C6H4SO3H, Zur Herstellung der Verbindungen der Formel I kann man eine Diazoniumverbindung des Amins der Formel II mit einer Kupplungskomponente der Formel III HK III umsetzen, K hat dabei die angegebene Bedeutung.C6H4CH3, C6H3 (CH3) 2, C6H4OCH3, C6H4OC2H5, C6H4OH, C6H4OCH2CH2OH, C6H4Cl, C2H4OCOCH3, C2H4OCOCH2COCH3, (C2H4O) 2COCH3, (CH2) 3OCOCH3 or C2H4OCOC2H4-COOH. Sulfo-containing radicals 11 are, for. E.g .: CH2CH2SO3H, CH2CH2OSO3H, (CH2) 3OSO3H, (CH2) 4OSO3H, (CH2) 2O (CH2) 2OSO3H, (CH2) 3O (CH2) 2OSO3H, (CH2) 3O (CH2) 4SOS3H, (CH2) 3OC2H4OCH2C6H4SO3H, (CH2) 3OC2H4OC2H4C6H4SO3H4, (CH4SO3H6) 3OCH2H6, (CH2H4H6) 3OCH2H2H6, CH2H4H6, CH2H4H6H6H4SO3H4 (CH2H4H6) 3H4SO3O (CH2) 4SOS3H, (CH2) 4SOS3H (CH2) 3O (CH2) 4SOS3H, (CH2H4H6) 3OCH4SO3H4O (CH2) 4SOS3H (CH2) 3O (CH2) 4SOS3H4H4SO3H4 CH2) 3OCH2C6H4SO3H, (CH2) 3OC2H4C6H4SO3H, CH2C6H4SO3H, C2H4C6H4SO3H, Preferred radicals R10 are, for example: hydrogen, CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, iso-C4H9, C6H13, CH2-CH2-OH, (CH2) 3OH, (CH2) 4OH, (CH2) 6OH, (CH2) 2O (CH2) 2OH, (CH2) 3O (CH2) 2OH, (CH2) 3O (CH2) 4OH, (CH2) 3O (CH2) 6OH, CH2CH2OCH3, CH2CH2OC2H5, CH2CH2OC4H9, (CH2) 3OCH3, (CH2) 3OC2H5, (CH2) 3OC3H7, (CH2) 3OC4H9, (CH2) 3OC6H13, (CH2) 3OC2H4OCH3, (CH2) 3OC2H4OC4H9, (CH2) 3OC2H4OC4H9, CH2C6H5, C2H4C6H5, C C6H5, C6H4CH3, C6H3 (CH3) 2, C6H4OCH3, C6H4OC2H5, C6H4OC2H4OH, C6H4Cl, CH2CH2SO3H, CH2CH2OSO3H, (CH2) 3OSO3H, (CH2) 4OSO3H, (CH2) 6OSO3H, (CH2) 2O (CH2) 2OSO3H, (CH2) 3O (CH2) 2OSO3H, (CH2) 3O (CH2) 4OSO3H, (CH2) 3O (CH2) 6SOS3H, (CH2) 3OC6H4SO3H , (CH2) 3OCH2C6H4SO3H, (CH2) 3OC2H4C6H4SO3H, CH2C6H4SO3H, C2H4C6H4SO3H, C6H4SO3H, To prepare the compounds of the formula I, a diazonium compound of the amine of the formula II can be used react with a coupling component of the formula III HK III, K has the meaning given.

Die Verbindung der Formel II erhält man durch Sulfonierung der Monosulfosäure der Formel oder des Amins der Formel mit ungefähr 20 dOigem Oleum bei ungefähr 20 bis 100 00. Einzelheiten der Herstellung sind im Beispielteil angegeben, in dem sich Angaben über Teile und Prozente, sofern nicht anders vermerkt, auf das Gewicht beziehen.The compound of the formula II is obtained by sulfonating the monosulfonic acid of the formula or the amine of the formula with about 20% oleum at about 20 to 100,000. Details of the preparation are given in the examples section, in which parts and percentages are by weight, unless otherwise stated.

Von besonderer technischer Bedeutung sind Verbindungen der Formel I a in der K1 ein Rest der Anilin-, Naphthalin-, Aminopyrazol- oder Pyridinreihe, d. h. im wesentlichen der Formeln Bevorzugte Reste sind dabei für: R2 Wasserstoff, Methyl, Chlor, Acylamino oder SO3H, R3 und R4 C1- bis C4-Alkyl, C2H4OH, CH2CHOHCH3, CH2CHOHCH2OH, CH2-CH2-OCOCH3, CH2CH2Cl, CH2CH2CN, CH2CHOHCH2Cl, CH2CH2OCH3, C2H4OC2H5, C3H6NHCOCH3 oder CH2C6H4SO3H, R1 Wasserstoff, Methoxy oder Methyl.Compounds of the formula I a are of particular industrial importance in K1 a radical from the aniline, naphthalene, aminopyrazole or pyridine series, ie essentially of the formulas Preferred radicals are: R2 hydrogen, methyl, chlorine, acylamino or SO3H, R3 and R4 C1- to C4-alkyl, C2H4OH, CH2CHOHCH3, CH2CHOHCH2OH, CH2-CH2-OCOCH3, CH2CH2Cl, CH2CH2CN, CH2CHOHCH2Cl, CH2CH2H6N, C3CH2OCH3 or CH2C6H4SO3H, R1 hydrogen, methoxy or methyl.

Bevorzugte Acylaminoreste R2 sind z. B.: COCH3, COCH2-OH, COCOOH, COCH2-CH2-COOH.Preferred acylamino radicals R2 are, for. E.g .: COCH3, COCH2-OH, COCOOH, COCH2-CH2-COOH.

R7 C2H5, C4H9, C6H5, -(CH2)3-C6H5, R8 H, CH3, R10 C2H4OH, C2H4OCH3, C2H4OC2H4OH, C3H6OCH3, C2H4C6H5, Die Farbstoffe der Formel I sind rot bis grunblau und eignen sich insbesondere zum Färben von natürlichen und synthetischen Polyamiden, wie Wolle, Polyamid-6 und -6,6, sowie Pelzen.R7 C2H5, C4H9, C6H5, - (CH2) 3-C6H5, R8 H, CH3, R10 C2H4OH, C2H4OCH3, C2H4OC2H4OH, C3H6OCH3, C2H4C6H5, The dyes of the formula I are red to green-blue and are particularly suitable for dyeing natural and synthetic polyamides, such as wool, polyamide-6 and -6,6, and furs.

Man erhält Färbungen mit sehr guten Echtheiten, von denen die Licht- und Naßechtheiten, wie Wasch-, Wasser-, Schweiß-, Walk-und Seewasserechtheiten hervorzuheben sind. Die Farbstoffe haben zudem eine sehr hohe Farbstärke. Bei den Pelzfärbungen ist die gute Bügelechtheit und Kombinierbarkeit zu Braun- und Schwarztönen hervorzuheben.The dyeings obtained have very good fastness properties, of which the light and to highlight wet fastness properties, such as wash, water, perspiration, milled and sea water fastnesses are. The dyes also have a very high color strength. With the fur dyes The good fastness to ironing and the ability to be combined with brown and black tones should be emphasized.

Beispiel 1 A. Herstellung der 3-Amino-2,1-benzisothiazol-5,7-disulfosäure a) 115 Teile 3-Amino-2,1-benzisothiazol-5-sulfosäure werden bei Raumtemperatur in 700 Teile Oleum (23 %ig) eingetragen und anschließend solange auf 60 °C erhitst, bis eine kleine Probe mit Eiswasser keine Fällung ergibt. Der Ansatz wird in 4 1 eisgekühltes Aceton vorsichtig eingerührt und das Produkt abgesaugt und mit Aceton säurefrei gewaschen. Ausbeute: 153 Teile # 99 %. Die 3-Amino-2,1-benzisothiazol-5,7-disulfosäure braucht nicht isoliert zu werden, sie kann auch in schwefelsaurer Lösung zu Farbstoffen weiterverarbeitet werden.Example 1 A. Preparation of 3-amino-2,1-benzisothiazole-5,7-disulfonic acid a) 115 parts of 3-amino-2,1-benzisothiazole-5-sulfonic acid are at room temperature in 700 parts of oleum (23%) entered and then heated to 60 ° C for as long as until a small sample with ice water shows no precipitation. The approach is shown in 4 1 Ice-cold acetone carefully stirred in and the product filtered off with suction and washed with acetone washed acid-free. Yield: 153 parts # 99%. 3-Amino-2,1-benzisothiazole-5,7-disulfonic acid does not need to be isolated, it can also form dyes in a sulfuric acid solution are further processed.

b) In gleicher Weise läßt sich die 3-Amino-2,1-benzisothiazol-5,7-disulfosäure durch Sulfierung des 3-Amino-2,1-benzisothiazols mit Oleum (23 %ig) gewinnen.b) 3-Amino-2,1-benzisothiazole-5,7-disulfonic acid can be used in the same way win by sulfating the 3-amino-2,1-benzisothiazole with oleum (23%).

Ausgehend von 150 Teilen gewinnt man 152 Teile Disulfosäure. Starting from 150 parts, 152 parts of disulfonic acid are obtained.

B. Farbstoffherstellung 31 Teile 3-Aminobenzisothiazol-5,7-disulfosäure werden in 100 Teilen Wasser gelöst, mit 10 Teilen 32 zeiger Salzsäure und 100 Teilen Eis versetst und danach mit einer Lösung von 6,9 Teilen Natriumnitrit diazotiert. Die Suspension des Diazoniumsalzes wird ca.B. Dye Preparation 31 parts of 3-aminobenzisothiazole-5,7-disulfonic acid are dissolved in 100 parts of water, with 10 parts of 32 pointer hydrochloric acid and 100 parts Ice set and then diazotized with a solution of 6.9 parts of sodium nitrite. The suspension of the diazonium salt is approx.

1 Stunde bei O - 5 0 gerührt, worauf man den Nitritüberschuß mit wenig Amidosulfonsäure zerstört. Danach gibt man eine wäßrige Lösung von 16,3 Teilen 3-(N,N-Diäthylamino)-methylbenzol in 100 Teilen Wasser und 11,5 Teilen 32 zeiger Salzsäure zu. Wach ca. 30 Minuten wird der pH-Wert des Reaktionsgemisches auf ca. 3 eingestellt und bis zum Ende der Kupplung weiter geruhrt. Anschließend wird der Farbstoff mit NaCl ausgesalzen, abgesaugt und bei 60 °c unter vermindertem Druck getrocknet. Man erhält ein dunkles Pulver der Formel das sich in Wasser mit rotstichig blauer Farbe löst und auf Polyamid 6, Pelzen und Wolle rotstichig blaue Färbungen von hohem Echtheitsniveau gibt.Stirred at 0.50 for 1 hour, after which the excess nitrite is destroyed with a little sulfamic acid. An aqueous solution of 16.3 parts of 3- (N, N-diethylamino) methylbenzene in 100 parts of water and 11.5 parts of 32 hydrochloric acid are then added. After about 30 minutes, the pH of the reaction mixture is adjusted to about 3 and stirring is continued until the coupling has ended. The dye is then salted out with NaCl, filtered off with suction and dried at 60 ° C. under reduced pressure. A dark powder of the formula is obtained which dissolves in water with a reddish blue color and gives reddish blue dyeings with a high level of fastness on polyamide 6, fur and wool.

analog dem Beispiel 1 werden die in der nachfolgenden Tabelle aufgeführten Farbstoffe mit ähnlichen coloristischen Eigenschaften hergestellt. Rr. ) Diazokomponente | Kupplungskomponente Farbton auf Polyamid 6 11 803 11 2 1103S1111 N0 11 blau, rotstichig 25 2 3 It S2E40H .. 0113 2115 011 4 , 2E5 violett 011 21140N 3 5 fl t C3H7 blau, rotstichig 011 37 011 6 .. t 49 ,. 04119 7 1, b oC2E5 violett 02115 8 .. CN'0 11 blau, rotstichig 2 5 Nr. iazokomponente Kupplungskomponente | Farbton auf Polyamid 6 so 9 4 9 C,H C1 H03S 11401 Violett 11112 2 4 02115 10 n C2E5 blau C2115 RHCOCH3 5 011 11 In 25 SHCOC2H5 5 0211 000011 12 ie 3 C2É4CN blau, rotstichig >=/ 2 4 13 n zu NH e blau 14 . g KE o CH3 25 5 n 8- e 2 5 16 fl 111102115 Nr. Diazokomponente Kupplungskomponente Farbton auf Polyamid 6 SO 11 17. 3 4 11035 NH-C3E60CH2 t blau, grünstichig 11112 16 lt i blau U 19 lt H2N 112N N' rot S 20 II lt hin (CH2)3 <) 011 30N 21 n hlt violett 11110 11 011 NHC,H, 2 4 CH 0N 22 ,. tNHC2E4OC2H4oH n NBC2H,C6H, 011 30N 23 " Ir 36°CE3 3 11110 1160011 11110311600113 Nr. Diazokomponente Kupplungskomponente Farbton auf Polyamid 6 SO,H CH, 24 4 S ß 3CE violett HO,S \J NHC2H, OCH, 11112 NHC3. 4OGH, 011 25 lt NEC2É40CH3 n NHC2H,OCK7 EC2E40C1I3 3eispiel 26 31 Teile 3-aminobenzisothiazol-5,7-disulfonsäure werden analog dem Beispiel 1 diazotiert. Anschließend fügt man zu der Suspension des Diazoniumsalzes eine neutrale Lösung von 31,3 Teilen 1-(4-Toluidino)-naphthalin-8-sulfonsäure in 300 Teilen Wasser zu. Der Ansatz wird dann mit Natriumacetat auf einen pH von 4 - 5 eingestellt und bis zum Ende der Kupplung weiter geruhrt. Der Farbstoff von der Zusammensetzang wird mit Natriumchlorid ausgesalzen, abgesaugt und bei 70 °C unter vermindertem Druck getrocknet. Er färbt Polyamid 6, Wolle sowie Pelz in echten, brillanten grünstichigen Blautönen.The dyes listed in the table below with similar coloristic properties are prepared analogously to Example 1. Rr.) Diazo component | Coupling component color on polyamide 6 11 803 11 2 1103S1111 N0 11 blue, tinged red 25th 2 3 It S2E40H .. 0113 2115 011 4, 2E5 purple 011 21140N 3 5 fl t C3H7 blue, red-tinged 011 37 011 6 .. t 49,. 04119 7 1, b oC2E5 purple 02115 8 .. CN'0 11 blue, reddish 2 5 No. iazo component coupling component | Color on polyamide 6 so 9 4 9 C, H C1 H03S 11401 purple 11112 2 4 02115 10 n C2E5 blue C2115 RHCOCH3 5 011 11 In 25 SHCOC2H5 5 0211 000011 12 ie 3 C2É4CN blue, reddish > = / 2 4 13 n to NH e blue 14th g KE o CH3 25th 5 n 8- e 2 5 16 fl 111102115 No. Diazo component, coupling component, color shade on polyamide 6 SUN 11 17. 3 4 11035 NH-C3E60CH2 t blue, greenish 11112 16 lt i blue U 19 according to H2N 112N N 'red S. 20 II according to there (CH2) 3 <) 011 30N 21 n holds purple 11110 11 011 NHC, H, 2 4 CH 0N 22,. tNHC2E4OC2H4oH n NBC2H, C6H, 011 30N 23 "Ir 36 ° CE3 3 11110 1160011 11110311600113 No. Diazo component, coupling component, color shade on polyamide 6 SO, H CH, 24 4 S ß 3CE purple HO, S \ J NHC2H, OCH, 11112 NHC3. 4OGH, 011 25 lt NEC2É40CH3 n NHC2H, OCK7 EC2E40C1I3 Example 26 31 parts of 3-aminobenzisothiazole-5,7-disulfonic acid are diazotized analogously to Example 1. A neutral solution of 31.3 parts of 1- (4-toluidino) -naphthalene-8-sulfonic acid in 300 parts of water is then added to the suspension of the diazonium salt. The batch is then adjusted to a pH of 4-5 with sodium acetate and stirring is continued until the coupling has ended. The color of the composition is salted out with sodium chloride, filtered off with suction and dried at 70 ° C under reduced pressure. It dyes polyamide 6, wool and fur in genuine, brilliant green-tinged shades of blue.

Die in der nachfolgenden Tabelle zusammengefaßten Farbstoffe lassen sich nach dem Beispiel 26 darstellen. Nr. Diazokomponente Kupplungskomponente Farbton auf Polyamid 6 SO 11 112N 27 1103S'3 110 blau, grünstichig X X X e 28 / 50311 OC 11 29 .t trNH2 SO SO 11 /0112 3 CH3 25 31 tI O 011 011 30N 32 l 1 bordo 11 011 011 33 II .CN 0 N1 011 05 Er. | Diazokomponente | Kupplungskomponente l Farbton auf Polyamid 6 SO? 011 34 -- - 11035 4 E4 9 0 11112 aTHC SO? SO 311 CR3c 35 \ 0 ß C2H40E t l 1 2 4 8031 The dyes summarized in the table below can be prepared according to Example 26. No. Diazo component, coupling component, color shade on polyamide 6 SO 11 112N 27 1103S'3 110 blue, greenish tinge XXX e 28 / 50311 OC 11 29 .t trNH2 SO SUN 11 / 0112 3 CH3 25th 31 tI O 011 011 30N 32 l 1 bordo 11 011 011 33 II .CN 0 N1 011 05 He. | Diazo component | Coupling component l color on polyamide 6 SO? 011 34 - - 11035 4 E4 9 0 11112 aTHC SO? SO 311 CR3c 35 \ 0 ß C2H40E t l 1 2 4 8031

Claims (4)

Patentansprüche 1. Säurefarbstoffe, die in Form der freien Säuren der allgemeinen Formel I entsprechen, in der K den Rest einer Kupplungskomponente bedeutet.Claims 1. Acid dyes in the form of the free acids of the general formula I correspond, in which K is the remainder of a coupling component. 2. Farbstoffe gemäß Anspruch 1 der Formel Ia in der K1 ein Rest der Anilin-, Naphthalin-, Aminopayrazol- oder Pyridinreihe, d.h. im wesentlichen der Formeln ist.2. Dyestuffs according to Claim 1 of the formula Ia in K1 a radical from the aniline, naphthalene, aminopayrazole or pyridine series, ie essentially of the formulas is. ). Verfahren zur Herstellung von Farbstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß man eine Diazoniumverbindung des Amins der Formel II mit einer Kupplungskomponente der Formel III-HK III umsetzt, K hat dabei die angegebenen Bedeutung.). Process for the preparation of dyes according to Claim 1, characterized in that a diazonium compound of the amine of the formula II with a coupling component of the formula III-HK III, K has the meaning given. 4. Verwendung der Farbstoffe gemäß Anspruch 1 zum Färben natürlicher oder synthetischer Polyamide sowie von Pelzen.4. Use of the dyestuffs according to Claim 1 for dyeing natural ones or synthetic polyamides as well as fur.
DE19782805304 1978-02-08 1978-02-08 Azo dyes contg. benzisothiazole di:sulphonic acid gp. - give fast red to green-blue tints on polyamide(s), pelts etc. Withdrawn DE2805304A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5175265A (en) * 1989-03-30 1992-12-29 Basf Aktiengesellschaft Azo dyes with a diazo component of the 4-amino-7-nitrobenzisothiazole series and a coupling compound from the aminopyrazole or hydroxypyridone series
US5532342A (en) * 1992-06-02 1996-07-02 Mitsubishi Chemical Corporation Azo metal chelate compound
CN111849194A (en) * 2020-07-27 2020-10-30 浙江青松轻纺股份有限公司 Benzisothiazole dye monomer compound, preparation method and application in hydrophobic fiber material dyeing

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5175265A (en) * 1989-03-30 1992-12-29 Basf Aktiengesellschaft Azo dyes with a diazo component of the 4-amino-7-nitrobenzisothiazole series and a coupling compound from the aminopyrazole or hydroxypyridone series
US5532342A (en) * 1992-06-02 1996-07-02 Mitsubishi Chemical Corporation Azo metal chelate compound
CN111849194A (en) * 2020-07-27 2020-10-30 浙江青松轻纺股份有限公司 Benzisothiazole dye monomer compound, preparation method and application in hydrophobic fiber material dyeing
CN111849194B (en) * 2020-07-27 2021-09-17 浙江青松轻纺股份有限公司 Benzisothiazole dye monomer compound, preparation method and application in hydrophobic fiber material dyeing

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