EP0777704A1 - Naphtholactam dyes - Google Patents
Naphtholactam dyesInfo
- Publication number
- EP0777704A1 EP0777704A1 EP95929798A EP95929798A EP0777704A1 EP 0777704 A1 EP0777704 A1 EP 0777704A1 EP 95929798 A EP95929798 A EP 95929798A EP 95929798 A EP95929798 A EP 95929798A EP 0777704 A1 EP0777704 A1 EP 0777704A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- optionally substituted
- alkyl
- hydrogen
- formula
- naphtholactam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/06—Peri-condensed systems
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/06—Naphtholactam dyes
Definitions
- the present invention relates to new naphtholactam derivatives of the formula I.
- R 1 is hydrogen, optionally substituted C 1 -C 6 -alkyl
- R 2 and R 3 each independently of one another hydrogen, Ci-C ⁇ -alkanoyl, optionally substituted benzoyl, optionally substituted C 2 -C 4 alkyl, optionally substituted C 2 -C 4 alkenyl, optionally substituted C 2 -C 4 alkynyl, Halogen, nitro, sulfamoyl, hydroxy, mercapto, Ci-Cg-alkoxy, optionally substituted phenoxy, Ci-C ⁇ -alkylthio, optionally substituted phenylthio,
- R ⁇ hydrogen or together with R 3 a radical of the formula
- R 5 is hydrogen or Ci-C ⁇ -alkyl
- R 6 cyano, carbamoyl, -C 4 -C mono- or dialkylcarbamoyl, carboxyl or -C -C 4 alkoxycarbonyl and R 7 substituted -CC alkyl, C5 -CC alkyl, which is optionally substituted and can be interrupted by 1 to 3 oxygen atoms in ether function, 1 to 3 sulfur atoms or 1 to 3 imino or -C 4 alkylimino groups , or benzoyl mean
- the object of the present invention was to provide new naphtholactam dyes which are distinguished by advantageous performance properties.
- the new dyes should have high color strength and brilliance and have good usage properties.
- Alkenyl groups can be straight-chain or branched.
- the substituents can be, for example, cyclohexyl, phenyl, C 1 -C 4 -alkylphenyl, C 1 -C 4 -alkoxyphenyl, halophenyl, C 1 -C 3 -alkanoyloxy, C ⁇ -Ci 3 - alkoxycarbonyl, C ⁇ -C ⁇ alkoxycarbonyloxy 3, wherein the alkyl chain of the three last-mentioned radicals optionally interrupted by from 1 to 3 oxygen atoms in ether function and / or substituted by phenyl or phenoxy, cyclohexyloxy, phenoxy, halogen, hydroxy or cyano can be considered.
- the alkyl radicals generally have 1 or 2 substituents.
- alkyl radicals occur in the formulas mentioned above which are interrupted by oxygen atoms in ether function, sulfur atoms or imino or C 1 -C 4 -alkylimino groups, unless otherwise noted, preference is given to those alkyl radicals, each having 1 or 2 oxygen atoms, in ether function , Sulfur atoms or imino or -CC 4 alkylimino groups are interrupted.
- substituents such as Ci-C ⁇ -alkyl, Ci-Cs-alkoxy, nitro or halogen can be used as substituents especially chlorine or bromine.
- the phenyl radicals generally have 1 to 3 substituents.
- alkenyl radicals occur in the abovementioned formula I, substituents such as phenyl, C 1 -C 3 alkoxycarbonyl, cyano and hydroxy can be used.
- the alkenyl radicals generally have a substituent.
- Alkinyl ⁇ radicals have come into consideration, as a rule a substituent on: If I substituted alkynyl radicals appearing in the abovementioned formula, then c ⁇ i c may have as substituents for example, hydroxyl, phenyl,..
- Suitable radicals R 1 and R 5 are, for example, methyl or, like radicals R 2 and R 3 , ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
- R 1 and R 5 are also, like R 7 , pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.
- R 7 radicals are furthermore, for example, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, (The above names are isooctyl, isononyl, isodecyl and isotridecyl Trivial names and derive from the alcohols obtained after the oxo synthesis - cf. Ullmanns Encyclopedia of Industrial Chemistry, 5th Edition, Vol. AI, pages 290 to 293, and Vol.
- R 1 , R 2 , R 3 and R 7 are furthermore 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 3-ethoxycarbonylpropyl, 2- or 3-butoxycarbonylpropyl,
- 2- or 3-cyanopropyl 4-cyanobutyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2- or 3-acetyloxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 4-hydroxybutyl, 2-cyclohexyloxyethyl, 2- or 3-cyclohexyloxypropyl, 2- or 4-cyclohexyloxybutyl, phenoxymethyl, 2-phenoxyethyl, 2- or 3-phenoxypropyl, 2- or 4-phenoxybutyl, 2-cyclohexylethyl, 2- or 3-cyclohexylpropyl or benzyl, 1- or 2-phenylethyl, 2-chloroethyl, 2- or 3-chloropropyl or 2- or 4-chlorobutyl.
- R 1 are also, for example, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, 2-, 3- or 4-methylphenyl, 2, 4-dimethylphenyl, 2-,
- R 2 and R 3 are, for example, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, isopentanoyl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, benzoyl, 2-, 3- or 4-methylbenzoyl, 2-, 3rd - or 4-methoxybenzoyl, 2-, 3- or 4-chlorobenzoyl, allyl,
- R 6 radicals are, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, mono- or dimethylcarbamoyl, mono- or
- Diethylcarbamoyl mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl or N-methyl-N-ethylcarbamoyl.
- Naphtholactam derivatives of the formula I in which R 1 is hydrogen are preferred. Naphtholactam derivatives of the formula I in which R 2 is hydrogen are also preferred.
- Ci-C ⁇ -alkylthio, phenylthio or R 3 and R 4 together form a radical of the formula
- Naphtholactam derivatives of the formula I in which R 6 is cyano are also preferred.
- Naphtholactam dyes of the formula I in which R 7 is C 6 -C 1 alkyl, in particular C 7 -Ci 3 alkyl, Cs -C 1 alkyl which is interrupted by 1 or 2 oxygen atoms in ether function, or phenylethyl are particularly preferred.
- Naphtholactam derivatives of the formula Ia are also particularly preferred.
- X 1 is hydrogen, C 2 -C 4 -alkanoyl, benzoyl, halogen, nitro, Ci-Ce-alkyl hio or phenylthio,
- X 2 is hydrogen or together with X 1 is a radical of the formula
- X 3 Cs-Ci 3 alkyl which is optionally substituted by phenoxy and can be interrupted by 1 to 3 oxygen atoms in ether function, or phenylethyl.
- the naphtholactam derivatives of the formula I according to the invention can be obtained by methods known per se.
- Z 1 is oxygen or sulfur
- Z 2 -CC 4 alkyl and An ⁇ are the equivalent of an anion (for example halide, methosulfate or ethosulfate) and R 1 , R 2 , R 3 and R 4 each have the abovementioned meaning own, with a pyridone of formula III
- R 5 , R 6 and R 7 each have the abovementioned meaning, condense. If Z 1 is oxygen, the presence of a condensation agent is required. This is not necessary for compounds in which Z 1 is sulfur or which obey the formula Ib.
- Suitable condensing agents are e.g. Phosphorus halides, such as phosphorus pentachloride, phosphorus trichloride, phosphorus oxide trichloride or phosphorus oxide tribromide.
- Phosphorus halides such as phosphorus pentachloride, phosphorus trichloride, phosphorus oxide trichloride or phosphorus oxide tribromide.
- the use of phosphorus oxychloride is preferred.
- the reaction can be carried out in a diluent, e.g. Glycol ether, such as methyl glycol, ethyl glycol, methyl diglycol or ethyl diglycol, ⁇ -butyrolactone, dichloroethane, chlorobenzene, dichlorobenzene, nitrobenzene or dioxane or in an excess of condensing agent.
- a diluent e.g. Glycol ether, such as methyl glycol, ethyl glycol, methyl diglycol or ethyl diglycol, ⁇ -butyrolactone, dichloroethane, chlorobenzene, dichlorobenzene, nitrobenzene or dioxane or in an excess of condensing agent.
- diluents are also suitable for the reaction of the naphtholactams without a condensing agent.
- pyridine N, N-dimethylformamide or N-methylpyrolidone.
- the naphtholactam derivatives of the formula I according to the invention are advantageously suitable for dyeing or printing textile materials. These are, for example, fibers or fabrics made of cellulose esters or polyesters, but also made of polyamides, or mixed fabrics made of polyesters and cellulose fibers. This gives dyeings or prints with high fastness to heat setting, high color strength and high brilliance as well as good fastness to use.
- the naphtholactam derivatives according to the invention are furthermore advantageously suitable for the thermal transfer from a support to a paper coated with plastic by means of an energy source (see e.g. EP-A-416 434).
- CH CH-C 6 H 5 ( ⁇ m ax: 558 nm, in CH 2 C1 2 )
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
- Plural Heterocyclic Compounds (AREA)
- Paper (AREA)
Abstract
The invention concerns naphtholactam derivatives of formula (I), in which: R1 represents hydrogen, optionally substituted C¿1?-C6 alkyl, C5-C6 cycloalkyl or substituted phenyl; R?2 and R3¿ represent hydrogen, C¿1?-C8 alkanoyl, optionally substituted benzoyl, optionally substituted C2-C4 alkyl, optionally substituted C2-C4 alkenyl, optionally substituted C2-C4 alkinyl, a halogen, nitro, sulphamoyl, optionally substituted hydroxy, optionally substituted mercapto, C1-C6 alkylsulphonyl or optionally substituted phenylsulphonyl; R?4¿ represents hydrogen or, with R3, a group of formula (II); R5 represents hydrogen or C¿1?-C6 alkyl; R?6¿ represents cyano, carbamoyl, C¿1?-C4 mono- or dialkylcarbamoyl, carboxyl or C1-C4 alkoxycarbonyl; and R?7¿ represents substituted C¿1?-C4 alkyl, optionally substituted C5-C13 alkyl or benzoyl. Also disclosed is the use of these derivatives for dyeing or printing textiles.
Description
NaphtholactamfarbstoffeNaphtholactam dyes
Beschreibungdescription
Die vorliegende Erfindung betrifft neue Naphtholactamderivate der Formel IThe present invention relates to new naphtholactam derivatives of the formula I.
in derin the
R1 Wasserstoff, gegebenenfalls substituiertes Cι-C6-Alkyl,R 1 is hydrogen, optionally substituted C 1 -C 6 -alkyl,
C5-C7-Cycloalkyl oder gegebenenfalls substituiertes Phenyl,C 5 -C 7 cycloalkyl or optionally substituted phenyl,
R2 und R3 unabhängig voneinander jeweils Wasserstoff, Ci-Cβ-Alkanoyl, gegebenenfalls substituiertes Benzoyl, gegebenenfalls substituiertes C2-C4-Alkyl, gegebenenfalls substituiertes C2-C4-Alkenyl, gegebenenfalls substituiertes C2-C4-Alkinyl, Halogen, Nitro, Sulfamoyl, Hydroxy, Mercapto, Ci-Cg-Alkoxy, gegebenenfalls substituiertes Phenoxy, Ci-Cβ-Alkylthio, gegebenenfalls substituiertes Phenylthio,R 2 and R 3 each independently of one another hydrogen, Ci-Cβ-alkanoyl, optionally substituted benzoyl, optionally substituted C 2 -C 4 alkyl, optionally substituted C 2 -C 4 alkenyl, optionally substituted C 2 -C 4 alkynyl, Halogen, nitro, sulfamoyl, hydroxy, mercapto, Ci-Cg-alkoxy, optionally substituted phenoxy, Ci-Cβ-alkylthio, optionally substituted phenylthio,
Ci-Cδ-Alkylsulfonyl oder gegebenenfalls substituiertes Phenyl- sulfonyl,Ci-C δ- alkylsulfonyl or optionally substituted phenylsulfonyl,
Rή Wasserstoff oder zusammen mit R3 einen Rest der FormelR ή hydrogen or together with R 3 a radical of the formula
R5 Wasserstoff oder Ci-Cβ-Alkyl,R 5 is hydrogen or Ci-Cβ-alkyl,
R6 Cyano, Carbamoyl, Cι-C4-Mono- oder Dialkylcarbamoyl, Carboxyl oder Cι-C4-Alkoxycarbonyl und
R7 substituiertes Cι-C -Alkyl, C5-Cι -Alkyl, das gegebenenfalls substituiert ist und durch 1 bis 3 Sauerstoffatome in Ether- funktion, 1 bis 3 Schwefelatome oder 1 bis 3 Imino- oder Cι-C4-Alkyliminogruppen unterbrochen sein kann, oder Benzoyl bedeuten,R 6 cyano, carbamoyl, -C 4 -C mono- or dialkylcarbamoyl, carboxyl or -C -C 4 alkoxycarbonyl and R 7 substituted -CC alkyl, C5 -CC alkyl, which is optionally substituted and can be interrupted by 1 to 3 oxygen atoms in ether function, 1 to 3 sulfur atoms or 1 to 3 imino or -C 4 alkylimino groups , or benzoyl mean
sowie deren Verwendung zum Färben oder Bedrucken von textilen Materialien.and their use for dyeing or printing textile materials.
Aus der DE-A-2 611 665 sowie der US-A-4 096 145 sind bereits Farbstoffe auf Basis von ähnlichen Naphtholactamderivaten be¬ kannt. Es hat sich jedoch gezeigt, daß die dort beschriebenen Produkte noch Mängel in ihren anwendungstechnischen Eigenschaften aufweisen.Dyes based on similar naphtholactam derivatives are already known from DE-A-2 611 665 and US-A-4 096 145. However, it has been shown that the products described there still have defects in their application properties.
Aufgabe der vorliegenden Erfindung war es, neue Naphtholactam- farbstoffe bereitzustellen, die sich durch vorteilhafte anwendungstechnische Eigenschaften auszeichnen. Insbesondere sollten die neuen Farbstoffe hohe Farbstärke und Brillanz auf- weisen und über gute Gebrauchseigenschaften verfügen.The object of the present invention was to provide new naphtholactam dyes which are distinguished by advantageous performance properties. In particular, the new dyes should have high color strength and brilliance and have good usage properties.
Demgemäß wurden die eingangs näher bezeichneten Naphtholactam¬ derivate der Formel I gefunden.We have found that this object is achieved by the naphtholactam derivatives of the formula I described at the outset.
Alle in den obengenannten Formeln auftretenden Alkyl- oderAll alkyl or in the formulas mentioned above
Alkenylgruppen können sowohl geradkettig als auch verzweigt sein.Alkenyl groups can be straight-chain or branched.
Wenn in den obengenannten Formeln substituierte Alkylreste auf¬ treten, so können als Substituenten z.B. Cyclohexyl, Phenyl, C;-Cή-Alkylphenyl, Cι-C4-Alkoxyphenyl, Halogenphenyl, Cι~Cι3-Alka- noyloxy, Cχ-Ci3-Alkoxycarbonyl, Cι-Cι3-Alkoxycarbonyloxy, wobei die Alkylkette der drei letztgenannten Reste gegebenenfalls durch 1 bis 3 Sauerstoffatome in Etherfunktion unterbrochen und/oder durch Phenyl oder Phenoxy substituiert ist, Cyclohexyloxy, Phen- oxy, Halogen, Hydroxy oder Cyano in Betracht kommen. Die Alkyl¬ reste weisen dabei in der Regel 1 oder 2 Substituenten auf.If substituted alkyl radicals occur in the formulas mentioned above, the substituents can be, for example, cyclohexyl, phenyl, C 1 -C 4 -alkylphenyl, C 1 -C 4 -alkoxyphenyl, halophenyl, C 1 -C 3 -alkanoyloxy, Cχ-Ci 3 - alkoxycarbonyl, Cι-Cι alkoxycarbonyloxy 3, wherein the alkyl chain of the three last-mentioned radicals optionally interrupted by from 1 to 3 oxygen atoms in ether function and / or substituted by phenyl or phenoxy, cyclohexyloxy, phenoxy, halogen, hydroxy or cyano can be considered. The alkyl radicals generally have 1 or 2 substituents.
Wenn in den obengenannten Formeln Alkylreste auftreten, die durch Sauerstoffatome in Etherfunktion, Schwefelatome oder Imino- oder Cι-C4-Alkyliminogruppen unterbrochen sind, so sind, sofern nicht anders vermerkt, solche Alkylreste bevorzugt, die jeweils durch 1 oder 2 Sauerstoffatome, in Etherfunktion, Schwefelatome oder Imino- oder Cι-C4-Alkyliminogruppen unterbrochen sind.If alkyl radicals occur in the formulas mentioned above which are interrupted by oxygen atoms in ether function, sulfur atoms or imino or C 1 -C 4 -alkylimino groups, unless otherwise noted, preference is given to those alkyl radicals, each having 1 or 2 oxygen atoms, in ether function , Sulfur atoms or imino or -CC 4 alkylimino groups are interrupted.
Wenn in den obengenannten Formeln substituierte Phenylreste auf¬ treten, so können als Substituenten, sofern nicht anders ver¬ merkt, z.B. Ci-Cβ-Alkyl, Ci-Cs-Alkoxy, Nitro oder Halogen, dabei
insbesondere Chlor oder Brom, in Betracht kommen. Die Phenylreste weisen dabei in der Regel 1 bis 3 Substituenten auf.If substituted phenyl radicals occur in the abovementioned formulas, unless otherwise noted, substituents such as Ci-Cβ-alkyl, Ci-Cs-alkoxy, nitro or halogen can be used as substituents especially chlorine or bromine. The phenyl radicals generally have 1 to 3 substituents.
Wenn in der obengenannten Formel I substituierte Alkenylreste auftreten, so können als Substituenten z.B. Phenyl, Cι-Cι3-Alkoxy- carbonyl, Cyano und Hydroxy in Betracht kommen. Die Alkenylreste weisen dabei in der Regel einen Substituenten auf.If substituted alkenyl radicals occur in the abovementioned formula I, substituents such as phenyl, C 1 -C 3 alkoxycarbonyl, cyano and hydroxy can be used. The alkenyl radicals generally have a substituent.
Wenn in der obengenannten Formel I substituierte Alkinylreste auftreten, so können als Substituenten z.B. Hydroxy, Phenyl, ci~c:3"Alkoxycarbonyl und Cyano in Betracht kommen. Die Alkinyl¬ reste weisen dabei in der Regel einen Substituenten auf. 3 "alkoxycarbonyl and cyano The Alkinyl¬ radicals have come into consideration, as a rule a substituent on: If I substituted alkynyl radicals appearing in the abovementioned formula, then c ~ i c may have as substituents for example, hydroxyl, phenyl,..
Geeignete Reste R1 und R5 sind z.B. Methyl oder weiterhin, wie auch Reste R2 und R3, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl oder tert-Butyl.Suitable radicals R 1 and R 5 are, for example, methyl or, like radicals R 2 and R 3 , ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
Reste R1 und R5 sind weiterhin, wie auch Reste R7, z.B. Pentyl, Isopentyl, Neopentyl, tert-Pentyl, Hexyl oder 2-Methylpentyl.R 1 and R 5 are also, like R 7 , pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.
Reste R7 sind weiterhin z.B. Heptyl, 1-Ethylpentyl, Octyl, 2-Ethylhexyl, Isooctyl, Nonyl, Isononyl, Decyl, Isodecyl, Unde- cyl, Dodecyl, Tridecyl, Isotridecyl, (Die obigen Bezeichnungen Isooctyl, Isononyl, Isodecyl und Isotridecyl sind Trivialbezeich- nungen und stammen von den nach der Oxosynthese erhaltenen Alko¬ holen - vgl. dazu Ullmanns Encyclopedia of Industrial Chemistry, 5th Edition, Vol. AI, Seiten 290 bis 293, sowie Vol. A 10, Seiten 284 und 285), 2-Propoxyethyl, 2-Isopropoxyethyl, 2-Butoxyethyl, 2- oder 3-Ethoxypropyl, 2- oder 3-Propoxypropyl, 2- oder 3-Buto- xypropyl, 2- oder 4-Methoxybutyl, 2- oder 4-Ethoxybutyl, 2- oder 4-Propoxybutyl, 3, 6-Dioxaheptyl, 3, 6-Dioxaoctyl, 4,8-Dioxanonyl, 3, 7-Dioxaoctyl, 3, 7-Dioxanonyl, 4,7-Dioxaoctyl, 4, 7-Dioxanonyl, 2- oder 4-Butoxybutyl, 4, 8-Dioxadecyl, 3, 6, 9-Trioxadecyl, 3, 6, 9-Trioxaundecyl, 3, 6, -Trioxadodecyl, 4,11-Dioxapentadecyl, 6-Phenoxy-4-oxahexyl, 3-Phenoxy-4-oxahexyl, 2- oder 3-Ethylthio- propyl, 2- oder 4-Methylthiobutyl, 2- oder 4-Ethylthiobutyl, 2-Dimethylaminopropyl, 4-Aza-4-methylpentyl, 2-Ethylaminopropyl, 4-Azahexyl, 2-Diethylaminopropyl, 4-Aza-4-ethylhexyl, 5-Azahexyl, 5-Aza-5-methylhexyl, 5-Azaheptyl, 5-Aza-5-ethylheptyl, 3,6-Diaza- heptyl, 3, 6-Diaza-6-methylheptyl oder 3, 6-Diaza-3, 6-dimethyl- heptyl.R 7 radicals are furthermore, for example, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, (The above names are isooctyl, isononyl, isodecyl and isotridecyl Trivial names and derive from the alcohols obtained after the oxo synthesis - cf. Ullmanns Encyclopedia of Industrial Chemistry, 5th Edition, Vol. AI, pages 290 to 293, and Vol. A 10, pages 284 and 285), 2- Propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3, 6-dioxaheptyl, 3, 6-dioxaoctyl, 4,8-dioxanonyl, 3, 7-dioxaoctyl, 3, 7-dioxanonyl, 4,7-dioxaoctyl, 4, 7-dioxanonyl, 2- or 4 -Butoxybutyl, 4, 8-dioxadecyl, 3, 6, 9-trioxadecyl, 3, 6, 9-trioxaundecyl, 3, 6, -trioxadodecyl, 4,11-dioxapentadecyl, 6-phenoxy-4-oxahexyl, 3-phenoxy- 4-oxahexyl, 2- or 3-ethylthiopropyl, 2- or 4-methylthiobut yl, 2- or 4-ethylthiobutyl, 2-dimethylaminopropyl, 4-aza-4-methylpentyl, 2-ethylaminopropyl, 4-azahexyl, 2-diethylaminopropyl, 4-aza-4-ethylhexyl, 5-azahexyl, 5-aza-5 -methylhexyl, 5-azaheptyl, 5-aza-5-ethylheptyl, 3,6-diaza-heptyl, 3, 6-diaza-6-methylheptyl or 3, 6-diaza-3, 6-dimethyl-heptyl.
Reste R1, R2, R3 und R7 sind weiterhin 2-Methoxycarbonylethyl, 2-Ethoxycarbonylethyl, 2- oder 3-Methoxycarbonylpropyl, 2- oder 3-Ethoxycarbonylpropyl, 2- oder 3-Butoxycarbonylpropyl,R 1 , R 2 , R 3 and R 7 are furthermore 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 3-ethoxycarbonylpropyl, 2- or 3-butoxycarbonylpropyl,
4-Methoxycarbonylbutyl, 4-Ethoxycarbonylbutyl, 2-Methoxycarbonyl- oxyethyl, 2-Ethoxycarbonyloxyethyl, 2- oder 3-Methoxycarbonyloxy-
propyl, 2- oder 3-Ethoxycarbonyloxypropyl, 2- oder 4-Methoxycar- bonyloxybutyl, 2- oder 4-Ethoxycarbonyloxybutyl, 2-Cyanoethyl,4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2- or 3-methoxycarbonyloxy- propyl, 2- or 3-ethoxycarbonyloxypropyl, 2- or 4-methoxycarbonyloxybutyl, 2- or 4-ethoxycarbonyloxybutyl, 2-cyanoethyl,
2- oder 3-Cyanopropyl, 4-Cyanobutyl, 2-Acetyloxyethyl, 2-Propio- nyloxyethyl, 2- oder 3-Acetyloxypropyl, 2-Hydroxyethyl, 2- oder 3-Hydroxypropyl, 4-Hydroxybutyl, 2-Cyclohexyloxyethyl, 2- oder 3-Cyclohexyloxypropyl, 2- oder 4-Cyclohexyloxybutyl, Phenoxy- methyl, 2-Phenoxyethyl, 2- oder 3-Phenoxypropyl, 2- oder 4-Phen- oxybutyl, 2-Cyclohexylethyl, 2- oder 3-Cyclohexylpropyl oder Ben- zyl, 1- oder 2-Phenylethyl, 2-Chlorethyl, 2- oder 3-Chlorpropyl oder 2- oder 4-Chlorbutyl .2- or 3-cyanopropyl, 4-cyanobutyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2- or 3-acetyloxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 4-hydroxybutyl, 2-cyclohexyloxyethyl, 2- or 3-cyclohexyloxypropyl, 2- or 4-cyclohexyloxybutyl, phenoxymethyl, 2-phenoxyethyl, 2- or 3-phenoxypropyl, 2- or 4-phenoxybutyl, 2-cyclohexylethyl, 2- or 3-cyclohexylpropyl or benzyl, 1- or 2-phenylethyl, 2-chloroethyl, 2- or 3-chloropropyl or 2- or 4-chlorobutyl.
Reste R1 sind weiterhin z.B. Cyclopentyl, Cyclohexyl, Cycloheptyl, Phenyl, 2-, 3- oder 4-Methylphenyl, 2, 4-Dimethylphenyl, 2-,R 1 are also, for example, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, 2-, 3- or 4-methylphenyl, 2, 4-dimethylphenyl, 2-,
3- oder 4-Methoxyphenyl, 2, 4-Dimethoxyphenyl, 2-, 3- oder 4-Chlorphenyl oder 2, 6-Dichlorphenyl.3- or 4-methoxyphenyl, 2, 4-dimethoxyphenyl, 2-, 3- or 4-chlorophenyl or 2, 6-dichlorophenyl.
Reste R2 und R3 sind z.B. Formyl, Acetyl, Propionyl, Butyryl, Iso- butyryl, Pentanoyl, Isopentanoyl, Hexanoyl, Heptanoyl, Octanoyl, 2-Ethylhexanoyl, Benzoyl, 2-, 3- oder 4-Methylbenzoyl, 2-, 3- oder 4-Methoxybenzoyl, 2-, 3- oder 4-Chlorbenzoyl, Allyl,R 2 and R 3 are, for example, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, isopentanoyl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, benzoyl, 2-, 3- or 4-methylbenzoyl, 2-, 3rd - or 4-methoxybenzoyl, 2-, 3- or 4-chlorobenzoyl, allyl,
Methallyl, Styryl, 2-Methoxycarbonylprop-l-en-l-yl, 2-Ethoxycar- bonylprop-1-en-l-yl, 2- (2-Ethylhexyloxycarbonyl)prop- 1-en-l-yl, 2-Tridecyloxycarbonylprop-l-en-l-yl, 2-Isotridecyloxy- carbonylprop-1-en-l-yl, Ethinyl, Prop-1-in-l-yl, Prop-l-in-3-yl, 3-Hydroxyprop-l-in-l-yl, But-1-in-l-yl, But-2-in-l-yl, Methyl- thio, Ethylthio, Propylthio, Isopropylthio, Butylthio, Isobutyl- thio, Pentylthio, Hexylthio, Phenylthio, 2-Methylphenylthio, 2-Methoxyphenylthio, 2-Chlorphenylthio, Methoxy, Ethoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy, sec-Butoxy, Pentyloxy, Isopentyl- oxy, Neopentyloxy, tert-Pentyloxy, Hexyloxy, 2-Methylpentyloxy, Phenoxy, 2-, 3- oder 4-Methylphenoxy, 2-, 3- oder 4-Methoxyphen- oxy, Fluor, Chlor, Brom, Methylsulfonyl, Ethylsulfonyl, Propyl- sulfonyl, Isopropylsulfonyl, Butylsulfonyl, Isobutylsulfonyl sec-Butylsulfonyl, Pentylsulfonyl, Isopentylsulfonyl, Neopentyl- sulfonyl, Hexylsulfonyl, Phenylsulfonyl, 2-Methylphenylsulfonyl, 2-Methoxyphenylsulfonyl oder 2-Chlorphenylsulfonyl.Methallyl, styryl, 2-methoxycarbonylprop-l-en-l-yl, 2-ethoxycarbonylprop-1-en-l-yl, 2- (2-ethylhexyloxycarbonyl) prop-1-en-l-yl, 2-tridecyloxycarbonylprop -l-en-l-yl, 2-isotridecyloxy-carbonylprop-1-en-l-yl, ethynyl, prop-1-in-l-yl, prop-l-in-3-yl, 3-hydroxyprop-l -in-1-yl, but-1-in-1-yl, but-2-in-1-yl, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, hexylthio, phenylthio, 2 -Methylphenylthio, 2-methoxyphenylthio, 2-chlorophenylthio, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy, 2-methylpentyloxy, phenoxy, 2-, 3- or 4-methylphenoxy, 2-, 3- or 4-methoxyphenoxy, fluorine, chlorine, bromine, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl sec-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neop Hexylsulfonyl, phenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl or 2-chlorophenylsul fonyl.
Reste R6 sind z.B. Methoxycarbonyl, Ethoxycarbonyl, Propoxy- carbonyl, Isopropoxycarbonyl, Butoxycarbonyl, Isobutoxycarbonyl, sec-Butoxycarbonyl, Mono- oder Dimethylcarbamoyl, Mono- oderR 6 radicals are, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, mono- or dimethylcarbamoyl, mono- or
Diethylcarbamoyl, Mono- oder Dipropylcarbamoyl, Mono- oder Diiso- propylcarbamoyl, Mono- oder Dibutylcarbamoyl oder N-Methyl-N- ethylcarbamoyl.Diethylcarbamoyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl or N-methyl-N-ethylcarbamoyl.
Bevorzugt sind Naphtholactamderivate der Formel I, in der R1 Was¬ serstoff bedeutet.
Weiterhin bevorzugt sind Naphtholactamderivate der Formel I, in der R2 Wasserstoff bedeutet.Naphtholactam derivatives of the formula I in which R 1 is hydrogen are preferred. Naphtholactam derivatives of the formula I in which R 2 is hydrogen are also preferred.
Weiterhin bevorzugt sind Naphtholactamderivate der Formel I, in der R3 Wasserstoff, C2-C4-Alkanoyl, Benzoyl, Halogen, Nitro,Naphtholactam derivatives of the formula I in which R 3 is hydrogen, C 2 -C 4 -alkanoyl, benzoyl, halogen, nitro,
Ci-Cδ-Alkylthio, Phenylthio oder R3 und R4 zusammen einen Rest der FormelCi-Cδ-alkylthio, phenylthio or R 3 and R 4 together form a radical of the formula
bedeuten. mean.
Weiterhin bevorzugt sind Naphtholactamderivate der Formel I, in der R5 Wasserstoff oder Methyl, insbesondere Wasserstoff bedeutet,Also preferred are naphtholactam derivatives of the formula I in which R 5 is hydrogen or methyl, in particular hydrogen,
Weiterhin bevorzugt sind Naphtholactamderivate der Formel I, in der R6 Cyano bedeutet.Naphtholactam derivatives of the formula I in which R 6 is cyano are also preferred.
Weiterhin bevorzugt sind Naphtholactamderivate der Formel I, in der R7 C5-Cχ3-Alkyl, das gegebenenfalls durch Phenoxy substituiert ist und durch 1 bis 3 Sauerstoffatome in Etherfunktion unterbro¬ chen sein kann, oder Phenylethyl bedeutet.Also preferred are naphtholactam derivatives of the formula I in which R 7 is C 5 -Cχ 3 alkyl, which is optionally substituted by phenoxy and can be interrupted by 1 to 3 oxygen atoms in ether function, or phenylethyl.
Besonders bevorzugt sind Naphtholactamfarbstoffe der Formel I, in der R7 C6-Cι -Alkyl, dabei insbesondere C7-Ci3-Alkyl, Cs-Cι -Alkyl, das durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen ist, oder Phenylethyl bedeutet.Naphtholactam dyes of the formula I in which R 7 is C 6 -C 1 alkyl, in particular C 7 -Ci 3 alkyl, Cs -C 1 alkyl which is interrupted by 1 or 2 oxygen atoms in ether function, or phenylethyl are particularly preferred.
Weiterhin besonders bevorzugt sind Naphtholactamderivate, die der Formel IaNaphtholactam derivatives of the formula Ia are also particularly preferred
gehorchen, in der
X1 Wasserstoff, C2-C4-Alkanoyl, Benzoyl, Halogen, Nitro, Ci-Ce-Alkyl hio oder Phenylthio, obey in the X 1 is hydrogen, C 2 -C 4 -alkanoyl, benzoyl, halogen, nitro, Ci-Ce-alkyl hio or phenylthio,
X2 Wasserstoff oder zusammen mit X1 einen Rest der FormelX 2 is hydrogen or together with X 1 is a radical of the formula
X3 Cs-Ci3-Alkyl, das gegebenenfalls durch Phenoxy substituiert ist und durch 1 bis 3 Sauerstoffatome in Etherfunktion unter¬ brochen sein kann, oder Phenylethyl bedeuten.X 3 Cs-Ci 3 alkyl, which is optionally substituted by phenoxy and can be interrupted by 1 to 3 oxygen atoms in ether function, or phenylethyl.
Die erfindungsgemäßen Naphtholactamderivate der Formel I können nach an sich bekannten Methoden erhalten werden.The naphtholactam derivatives of the formula I according to the invention can be obtained by methods known per se.
Beispielsweise kann man ein Naphtholactam der Formel Ila oder IlbFor example, a naphtholactam of the formula Ila or Ilb
in der Z1 Sauerstoff oder Schwefel, Z2 Cι-C4-Alkyl und AnΘ das Äquivalent eines Anions (z.B. Halogenid, Methosulfat oder Etho¬ sulfat) bedeuten und R1, R2, R3 und R4 jeweils die obengenannte Bedeutung besitzen, mit einem Pyridon der Formel IIIin which Z 1 is oxygen or sulfur, Z 2 -CC 4 alkyl and An Θ are the equivalent of an anion (for example halide, methosulfate or ethosulfate) and R 1 , R 2 , R 3 and R 4 each have the abovementioned meaning own, with a pyridone of formula III
in der R5, R6 und R7 jeweils die obengenannte Bedeutung besitzen, kondensieren.
Wenn Z1 Sauerstoff bedeutet, ist die Anwesenheit eines Kondensati¬ onsmittels erforderlich. Bei Verbindungen, in denen Z1 Schwefel bedeutet oder die der Formel Ib gehorchen, ist dies nicht erfor¬ derlich.in which R 5 , R 6 and R 7 each have the abovementioned meaning, condense. If Z 1 is oxygen, the presence of a condensation agent is required. This is not necessary for compounds in which Z 1 is sulfur or which obey the formula Ib.
Geeignete Kondensationsmittel sind z.B. Phosphorhalogenide, wie Phosphorpentachlorid, Phosphortrichlorid, Phosphoroxidtrichlorid oder Phosphoroxidtribromid. Die Verwendung von Phosphoroxidtri- chlorid ist bevorzugt.Suitable condensing agents are e.g. Phosphorus halides, such as phosphorus pentachloride, phosphorus trichloride, phosphorus oxide trichloride or phosphorus oxide tribromide. The use of phosphorus oxychloride is preferred.
Man kann die Umsetzung in einem Verdünnungsmittel, z.B. Glykol- ether, wie Methylglykol, Ethylglykol, Methyldiglykol oder Ethyl- diglykol, γ-Butyrolacton, Dichlorethan, Chlorbenzol, Dichlor- benzol, Nitrobenzol oder Dioxan oder auch in einem Überschuß an Kondensationsmittel, durchführen.The reaction can be carried out in a diluent, e.g. Glycol ether, such as methyl glycol, ethyl glycol, methyl diglycol or ethyl diglycol, γ-butyrolactone, dichloroethane, chlorobenzene, dichlorobenzene, nitrobenzene or dioxane or in an excess of condensing agent.
Bei der Umsetzung der Naphtholactame ohne Kondensationsmittel eignen sich ebenfalls die obengenannten Verdünnungsmittel, zu¬ sätzlich sind noch z.B. Pyridin, N,N-Dimethylformamid oder N-Me- thylpyrolidon zu nennen.The above-mentioned diluents are also suitable for the reaction of the naphtholactams without a condensing agent. To name pyridine, N, N-dimethylformamide or N-methylpyrolidone.
Die erfindungsgemäßen Naphtholactamderivate der Formel I eignen sich in vorteilhafter Weise zum Färben oder Bedrucken von texti- len Materialien. Dies sind beispielsweise Fasern oder Gewebe aus Celluloseestern oder Polyestern, aber auch aus Polyamiden, oder Mischgewebe aus Polyestern und Cellulosefasern. Man erhält dabei Färbungen oder Drucke mit hoher Thermofixierechtheit, hoher Farb¬ stärke und hoher Brillanz sowie guten Gebrauchsechtheiten.The naphtholactam derivatives of the formula I according to the invention are advantageously suitable for dyeing or printing textile materials. These are, for example, fibers or fabrics made of cellulose esters or polyesters, but also made of polyamides, or mixed fabrics made of polyesters and cellulose fibers. This gives dyeings or prints with high fastness to heat setting, high color strength and high brilliance as well as good fastness to use.
Um einen günstigen Farbaufbau zu erreichen, kann es in manchen Fällen von Vorteil sein, Mischungen der Naphtholactamderivate der Formel I untereinander zum Färben zu verwenden.In order to achieve a favorable color build-up, it can be advantageous in some cases to use mixtures of the naphtholactam derivatives of the formula I with one another for dyeing.
Die erfindungsgemäßen Naphtholactamderivate eignen sich weiterhin vorteilhaft für die thermische Übertragung von einem Träger auf ein mit Kunststoff beschichtetes Papier mittels einer Energie¬ quelle (s. z.B. EP-A-416 434).The naphtholactam derivatives according to the invention are furthermore advantageously suitable for the thermal transfer from a support to a paper coated with plastic by means of an energy source (see e.g. EP-A-416 434).
Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
Beispiel 1example 1
Zu einem Gemisch aus 150 ml γ-Butyrolacton, 8,2 g (0,03 mol) 4-Benzoylnaphtholactam und 7,3 g (0,037 mol) 1- (4-0xahexyl)- 3-cyano-6-hydroxypyrid-2-on wurden unter Rühren bei 80°C 8,2 ml (0,90 mol) Phosphoroxidtrichlorid zugetropft. Man rührte 6 h bei 120°C, destillierte anschließend bei 0,5 bis 0,7 mbar und 50 bis
54°C γ-Butyrolacton und Phosphoroxidtrichlorid ab, tropfte dann bei dieser Temperatur langsam und unter Rühren 70 ml Ethanol zu, kühlte auf Raumtemperatur ab und rührte die resultierende Mischung 2 h bei Raumtemperatur. Dann wurde der Farbstoff ab- filtriert, mit Petrolether gewaschen und getrocknet. Man erhielt 7,5 g (54 %) des Farbstoffes der FormelTo a mixture of 150 ml of γ-butyrolactone, 8.2 g (0.03 mol) of 4-benzoylnaphtholactam and 7.3 g (0.037 mol) of 1- (4-0xahexyl) -3-cyano-6-hydroxypyrid-2- 8.2 ml (0.90 mol) of phosphorus oxide trichloride were added dropwise with stirring at 80.degree. The mixture was stirred at 120 ° C. for 6 h, then distilled at 0.5 to 0.7 mbar and 50 to From 54 ° C γ-butyrolactone and phosphorus oxychloride, 70 ml of ethanol were slowly added dropwise at this temperature while stirring, and the mixture was cooled to room temperature and the resulting mixture was stirred at room temperature for 2 hours. The dye was then filtered off, washed with petroleum ether and dried. 7.5 g (54%) of the dye of the formula were obtained
CO-C6H5 CO-C 6 H 5
in Form roter Kristalle.in the form of red crystals.
(Fp.: 128 bis 135°C; λmax: 278 ran, 548 nm, in CH2C12)(Fp .: 128 to 135 ° C; λ max : 278 ran, 548 nm, in CH 2 C1 2 )
Beispiel 2Example 2
Zu einem Gemisch aus 150 ml γ-Butyrolacton, 6,1 g (0,03 mol) 4-Chlornaphtholactam und 8,2 g (0,037 mol) l-(2-Ethyl- hexyl) -3-cyano-6-hydroxypyrid-2-on wurden unter Rühren bei 80°C 8,2 ml (0,09 ml) Phosphoroxidtrichlorid zugetropft. Man rührte 1,5 h bei 100°C, destillierte anschließend bei 0,5 bis 0,7 mbar und 50 bis 54°C γ-Butyrolacton und Phosphoroxidtrichlorid ab, tropfte dann bei dieser Temperatur langsam und unter Rühren 80 ml Ethanol zu, kühlte auf Raumtemperatur ab und rührte dieseTo a mixture of 150 ml of γ-butyrolactone, 6.1 g (0.03 mol) of 4-chloronaphtholactam and 8.2 g (0.037 mol) of l- (2-ethylhexyl) -3-cyano-6-hydroxypyride- 2-one, 8.2 ml (0.09 ml) of phosphorus oxide trichloride were added dropwise with stirring at 80 ° C. The mixture was stirred at 100 ° C. for 1.5 h, then γ-butyrolactone and phosphorus oxide trichloride were distilled off at 0.5 to 0.7 mbar and 50 to 54 ° C., then 80 ml of ethanol were slowly added dropwise at this temperature, with stirring, and the mixture was cooled to room temperature and stirred this
Mischung 2 h bei Raumtemperatur. Dann wurde der Farbstoff ab¬ filtriert, mit Petrolether gewaschen und getrocknet. Man erhielt 5,0 g (38,4 %) eines Farbstoffs der FormelMix for 2 hours at room temperature. The dye was then filtered off, washed with petroleum ether and dried. 5.0 g (38.4%) of a dye of the formula were obtained
in Form roter Kristalle.in the form of red crystals.
(Fp. : 212 bis 216°C; « : 520 nm, 560 nm, in CH2C12)
Beispiel 3(Mp: 212 to 216 ° C; «: 520 nm, 560 nm, in CH 2 C1 2 ) Example 3
a) Man vereinigte 5 g (0,02 mol) 4-Bromnaphtholactam, 2,3 ga) Combine 5 g (0.02 mol) of 4-bromonaphtholactam, 2.3 g
(0,022 mol) Styrol, 3,9 g (0,21 mol) Tributylamin, 0,052 g (0,0002 mol) Triphenylphosphin und 0,0022 g (0,00001 mol)(0.022 mol) styrene, 3.9 g (0.21 mol) tributylamine, 0.052 g (0.0002 mol) triphenylphosphine and 0.0022 g (0.00001 mol)
Palladiumacetat unter Stickstoffatmosphäre und erhitzte die Mischung 4 h unter Rühren auf 150°C. Nach Abkühlen auf Raum¬ temperatur wurde die Mischung in 1200 ml Aceton unter Erwär¬ men gelöst und der Katalysator abfiltriert. Die Lösung wurde anschließend langsam bei Raumtemperatur eingeengt, wobei ein Feststoff auskristallisierte. Man erhielt 4,16 g (77 %) eines gelben Produkts der FormelPalladium acetate under a nitrogen atmosphere and heated the mixture to 150 ° C. with stirring for 4 h. After cooling to room temperature, the mixture was dissolved in 1200 ml of acetone with heating and the catalyst was filtered off. The solution was then slowly concentrated at room temperature, a solid crystallizing out. 4.16 g (77%) of a yellow product of the formula were obtained
CH=CH-C6H5 CH = CH-C 6 H 5
b) 1,48 g der unter a) erhaltenen Verbindung wurden analog Bei¬ spiel 2 mit 1,47 g l-Hexyl-3-cyano-6-hydroxypyrid-2-on kon¬ densiert. Man erhielt 2,34 g (90 %) der Verbindung der Formelb) 1.48 g of the compound obtained under a) were condensed analogously to Example 2 with 1.47 g of l-hexyl-3-cyano-6-hydroxypyrid-2-one. 2.34 g (90%) of the compound of the formula were obtained
CH=CH-C6H5 (λmax : 558 nm, in CH2C12 )
CH = CH-C 6 H 5 (λ m ax: 558 nm, in CH 2 C1 2 )
Beispiel 4Example 4
8,4 g (0,05 mol) Naphtholactam und 11,6 g (0,05 mol) l-Heptyl-3-cyano-6-hydroxypyrid-2-on wurden bei 50°C 15 min in 35 ml 1,2-Dichlorethan gerührt. Danach ließ man 10 ml Phosphor¬ oxidtrichlorid zutropfen und rührte weitere 2 h bei 80°C. Danach wurde bei Raumtemperatur überschüssiges Phosphoroxidtrichlorid zerstört und gleichzeitig das Produkt gefällt. Es wurde über Nacht bei Raumtemperatur nachgerührt, abgesaugt und mit Methanol gewaschen. Man erhielt 8,71 g (45,2 %) eines Produkts der Formel8.4 g (0.05 mol) of naphtholactam and 11.6 g (0.05 mol) of l-heptyl-3-cyano-6-hydroxypyrid-2-one were at 35 ° C in 35 ml of 1.2 for 15 min -Dichloroethane stirred. Thereafter, 10 ml of phosphorus oxide trichloride were added dropwise and the mixture was stirred at 80 ° C. for a further 2 h. Excess phosphorus oxide trichloride was then destroyed at room temperature and the product was precipitated at the same time. The mixture was stirred overnight at room temperature, suction filtered and washed with methanol. 8.71 g (45.2%) of a product of the formula were obtained
Fp.: 212°C; λmax 507 nm, 544 nm, in CH2C12)Mp: 212 ° C; λ max 507 nm, 544 nm, in CH 2 C1 2 )
In analoger Weise können die im folgenden aufgeführten Naphtho- lactamderivate erhalten werden.The naphtholactam derivatives listed below can be obtained in an analogous manner.
Claims
1. Naphtholactamderivate der Formel I1. Naphtholactam derivatives of the formula I.
in derin the
R1 Wasserstoff, gegebenenfalls substituiertes Cι-C6-Alkyl, C5~C7-Cycloalkyl oder gegebenenfalls substituiertes Phenyl,R 1 is hydrogen, optionally substituted C 1 -C 6 -alkyl, C 5 ~ C7-cycloalkyl or optionally substituted phenyl,
R2 und R3 unabhängig voneinander jeweils Wasserstoff,R 2 and R 3 are each independently hydrogen,
Ci-Cß-Alkanoyl, gegebenenfalls substituiertes Benzoyl, gegebenenfalls substituiertes C2~C -Alkyl, gegebenenfalls substituiertes C2-C4-Alkenyl, gegebenenfalls substituier¬ tes C2-C4-Alkinyl, Halogen, Nitro, Sulfamoyl, Hydroxy, Mercapto, C:-C6-Alkoxy, gegebenenfalls substituiertes Phenoxy, Ci-Cε-Alkylthio, gegebenenfalls substituiertes Phenylthio, Ci-Cδ-Alkylsulfonyl oder gegebenenfalls sub- stituiertes Phenylsulfonyl,Ci-C ß alkanoyl, optionally substituted benzoyl, optionally substituted C 2 -C 4 alkyl, optionally substituted C 2 -C 4 alkenyl, optionally substituted C 2 -C 4 alkynyl, halogen, nitro, sulfamoyl, hydroxy, Mercapto, C: -C 6 -alkoxy, optionally substituted phenoxy, Ci-Cε-alkylthio, optionally substituted phenylthio, Ci-C δ -alkylsulfonyl or optionally substituted phenylsulfonyl,
R4 Wasserstoff oder zusammen mit R3 einen Rest der FormelR 4 is hydrogen or together with R 3 is a radical of the formula
R5 Wasserstoff oder Cι-C6-Alkyl,R 5 is hydrogen or -CC 6 alkyl,
R6 Cyano, Carbamoyl, Cχ-C4-Mono- oder Dialkylcarbamoyl, Carboxyl oder Cι~C4-Alkoxycarbonyl und R7 substituiertes Cι-C4-Alkyl, Cs-Cι3-Alkyl, das gegebenen¬ falls substituiert ist und durch 1 bis 3 Sauerstoffatome in Etherfunktion, 1 bis 3 Schwefelatome oder 1 bis 3 Imino- oder Cι-C4-Alkyliminogruppen unterbrochen sein kann, oder Benzoyl bedeuten.R 6 cyano, carbamoyl, Cχ-C 4 mono- or dialkylcarbamoyl, carboxyl or Cι ~ C 4 alkoxycarbonyl and R 7 substituted C 1 -C 4 -alkyl, Cs-C 3 -alkyl, which is optionally substituted and interrupted by 1 to 3 oxygen atoms in ether function, 1 to 3 sulfur atoms or 1 to 3 imino or C 1 -C 4 -alkylimino groups can be, or mean benzoyl.
2. Naphtholactamderivate nach Anspruch 1, dadurch gekennzeich¬ net, daß R1 Wasserstoff bedeutet.2. Naphtholactam derivatives according to claim 1, characterized gekennzeich¬ net that R 1 is hydrogen.
3. Naphtholactamderivate nach Anspruch 1, dadurch gekennzeich¬ net, daß R2 Wasserstoff bedeutet.3. Naphtholactam derivatives according to claim 1, characterized gekennzeich¬ net that R 2 is hydrogen.
4. Naphtholactamderivate nach Anspruch 1, dadurch gekennzeich¬ net, daß R3 Wasserstoff, C2~C4-Alkanoyl, Benzoyl, Halogen, Nitro, Cι-C6-Alkylthio, Phenylthio oder R3 und R4 zusammen einen Rest der Formel4. Naphtholactam derivatives according to claim 1, characterized gekennzeich¬ net that R 3 is hydrogen, C 2 ~ C 4 alkanoyl, benzoyl, halogen, nitro, -C-C 6 alkylthio, phenylthio or R 3 and R 4 together a radical of the formula
bedeuten.mean.
5. Naphtholactamderivate nach Anspruch 1, dadurch gekennzeich¬ net, daß R5 Wasserstoff oder Methyl bedeutet.5. Naphtholactam derivatives according to claim 1, characterized gekennzeich¬ net that R 5 is hydrogen or methyl.
6. Naphtholactamderivate nach Anspruch 1, dadurch gekennzeich¬ net, daß R6 Cyano bedeutet.6. Naphtholactam derivatives according to claim 1, characterized gekennzeich¬ net that R 6 is cyano.
Naphtholactamderivate nach Anspruch 1, dadurch gekennzeich¬ net, daß R7 C5-Cι3-Alkyl, das gegebenenfalls durch Phenoxy substituiert ist und durch 1 bis 3 Sauerstoffatome in Ether¬ funktion unterbrochen sein kann, oder Phenylethyl bedeutet.Naphtholactam derivatives according to Claim 1, characterized in that R 7 is C 5 -C 3 alkyl, which is optionally substituted by phenoxy and can be interrupted by 1 to 3 oxygen atoms in ether function, or phenylethyl.
Naphtholactamderivate nach Anspruch 1, dadurch gekennzeich¬ net, daß R7 C6-Cι3-Alkyl, Cs-C:3-Alkyl, das durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen ist, oder Phenylethyl bedeutet . 9. Naphtholactamderivate nach Anspruch 1, die der Formel IaNaphtholactam derivatives according to Claim 1, characterized in that R 7 is C 6 -C 3 alkyl, Cs-C: 3 alkyl which is interrupted by 1 or 2 oxygen atoms in ether function, or phenylethyl. 9. Naphtholactam derivatives according to claim 1, which of the formula Ia
gehorchen, in derobey in the
15 X: Wasserstoff, C2-C4-Alkanoyl, Benzoyl, Halogen, Nitro, C:-C6-Alkylthio oder Phenylthio,15 X : hydrogen, C 2 -C 4 alkanoyl, benzoyl, halogen, nitro, C: -C 6 alkylthio or phenylthio,
X2 Wasserstoff oder zusammen mit X1 einen Rest der FormelX 2 is hydrogen or together with X 1 is a radical of the formula
25 X3 C5-Ci3-Alkyl, das gegebenenfalls durch Phenoxy substi¬ tuiert ist und durch 1 bis 3 Sauerstoffatome in Ether¬ funktion unterbrochen sein kann, oder Phenylethyl bedeu¬ ten.25 X 3 C 5 -Ci 3 alkyl, which is optionally substituted by phenoxy and can be interrupted by 1 to 3 oxygen atoms in ether function, or mean phenylethyl.
30 10. Verwendung der Naphtholactamderivate gemäß Anspruch 1 zum Färben oder Bedrucken von textilen Materialien.30 10. Use of the naphtholactam derivatives according to claim 1 for dyeing or printing textile materials.
3535
4040
45 45
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4429548 | 1994-08-19 | ||
DE4429548A DE4429548A1 (en) | 1994-08-19 | 1994-08-19 | Naphtholactam dyes |
PCT/EP1995/003112 WO1996006137A1 (en) | 1994-08-19 | 1995-08-04 | Naphtholactam dyes |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0777704A1 true EP0777704A1 (en) | 1997-06-11 |
Family
ID=6526153
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95929798A Ceased EP0777704A1 (en) | 1994-08-19 | 1995-08-04 | Naphtholactam dyes |
Country Status (12)
Country | Link |
---|---|
US (1) | US5929245A (en) |
EP (1) | EP0777704A1 (en) |
JP (1) | JPH10504588A (en) |
CN (1) | CN1158629A (en) |
AU (1) | AU3342695A (en) |
BR (1) | BR9508728A (en) |
CA (1) | CA2198028A1 (en) |
DE (1) | DE4429548A1 (en) |
MX (1) | MX9701263A (en) |
MY (1) | MY132078A (en) |
TW (1) | TW416954B (en) |
WO (1) | WO1996006137A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7279678B2 (en) * | 2005-08-15 | 2007-10-09 | Schlumber Technology Corporation | Method and apparatus for composition analysis in a logging environment |
WO2019078513A1 (en) | 2017-10-17 | 2019-04-25 | 에스에프씨 주식회사 | Merocyanine-based compound and biomolecular labeling dye, kit and contrast agent composition comprising same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2025427A1 (en) * | 1970-05-25 | 1971-12-09 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | 2,6-dihydroxy-3-oxo-pyridine cpds prodn- from 2,6-dihydroxy cpds, - starting materials for dyes and pesticides |
DE2611665A1 (en) * | 1976-03-19 | 1977-09-22 | Basf Ag | NAPHTHOLACTAM DERIVATIVES |
DE2705108A1 (en) * | 1977-02-08 | 1978-08-10 | Basf Ag | Orange-blue naphtho-lactam derivs. - used as fast dyes for polyester textiles and transparent dyes for plastics |
DE3929698A1 (en) * | 1989-09-07 | 1991-03-14 | Basf Ag | TRIAZOLOPYRIDINE DYES AND A METHOD FOR THERMAL TRANSFER OF METHINE DYES |
-
1994
- 1994-08-19 DE DE4429548A patent/DE4429548A1/en not_active Withdrawn
-
1995
- 1995-08-04 CN CN95195185.8A patent/CN1158629A/en active Pending
- 1995-08-04 JP JP8507739A patent/JPH10504588A/en active Pending
- 1995-08-04 US US08/776,596 patent/US5929245A/en not_active Expired - Fee Related
- 1995-08-04 CA CA002198028A patent/CA2198028A1/en not_active Abandoned
- 1995-08-04 AU AU33426/95A patent/AU3342695A/en not_active Abandoned
- 1995-08-04 BR BR9508728A patent/BR9508728A/en not_active Application Discontinuation
- 1995-08-04 WO PCT/EP1995/003112 patent/WO1996006137A1/en not_active Application Discontinuation
- 1995-08-04 MX MX9701263A patent/MX9701263A/en unknown
- 1995-08-04 EP EP95929798A patent/EP0777704A1/en not_active Ceased
- 1995-08-18 TW TW084108619A patent/TW416954B/en not_active IP Right Cessation
- 1995-08-19 MY MYPI95002446A patent/MY132078A/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9606137A1 * |
Also Published As
Publication number | Publication date |
---|---|
US5929245A (en) | 1999-07-27 |
WO1996006137A1 (en) | 1996-02-29 |
CA2198028A1 (en) | 1996-02-29 |
DE4429548A1 (en) | 1996-02-22 |
AU3342695A (en) | 1996-03-14 |
MY132078A (en) | 2007-09-28 |
MX9701263A (en) | 1997-05-31 |
JPH10504588A (en) | 1998-05-06 |
TW416954B (en) | 2001-01-01 |
BR9508728A (en) | 1997-11-11 |
CN1158629A (en) | 1997-09-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0534296A1 (en) | Azo dyes with a quinoline-type coupling component | |
EP0787169B1 (en) | Methine and azo dye-containing dye mixtures | |
EP0791034B1 (en) | Methine and azamethine dyes made from trifluoromethylpyridones | |
EP0591736B1 (en) | Use of pyridine dyes for textiles, mixtures of dyes containing pyridine dyes, and triazolopyridine dyes with a thienyl radical | |
EP0640116B1 (en) | Azo dyes with an acetalised diazo component from the thiophene o r thiazol series | |
EP0773976B1 (en) | Azo dyes having a coupling component from the aminothiazole series | |
WO1996006137A1 (en) | Naphtholactam dyes | |
EP0291853B1 (en) | Thienon compounds | |
EP0944673B1 (en) | Trifluormethylpyridone based indolenine methine dyes | |
WO1997047690A1 (en) | Dye mixtures | |
EP0524401B1 (en) | Thiazolazo dyestuffs with a coupling component of the diphenylamine series | |
EP0742811B1 (en) | Method for preparing pyridine dyes | |
DE19650958A1 (en) | Indolenine methine dye, used for dyeing, printing and diffusion transfer | |
DE19533026A1 (en) | Dye mixtures containing methine and anthraquinone dyes | |
EP0736575B1 (en) | Azamethine dyes with heterocyclic side groups | |
DE4339270A1 (en) | 5=Nitro-1,2-2=benzoisothiazole azo dyes useful for dyeing textile or thermal transfer | |
DE2610674C3 (en) | Styryl dyes, processes for their preparation and their use for dyeing or printing synthetic organic fiber materials | |
EP0691382B1 (en) | Thiazolomethine dyes | |
EP0796297B1 (en) | Methine dyes based one formylaminopyridones | |
WO1998037150A1 (en) | Trifluoromethyl-substituted azo dyes | |
EP0569759A1 (en) | Benzisothiazol and benzothiphenazo dyes with a coupling component of the aniline series | |
DE4440486A1 (en) | Azamethine dyes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19970217 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE FR GB GR IT LI |
|
17Q | First examination report despatched |
Effective date: 19991123 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 20010205 |