WO2015062929A1 - Colorants acides, procédé pour les produire, et leur utilisation - Google Patents

Colorants acides, procédé pour les produire, et leur utilisation Download PDF

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Publication number
WO2015062929A1
WO2015062929A1 PCT/EP2014/072630 EP2014072630W WO2015062929A1 WO 2015062929 A1 WO2015062929 A1 WO 2015062929A1 EP 2014072630 W EP2014072630 W EP 2014072630W WO 2015062929 A1 WO2015062929 A1 WO 2015062929A1
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Prior art keywords
amino
carbamoyl
monocycloalkyl
sulfamoyl
monoalkyl
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PCT/EP2014/072630
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English (en)
Inventor
Roxana Barbieru
Sivamurugan Vajiravelu
Wei Tian LOH
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Dystar Colours Distribution Gmbh
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Priority claimed from EP20130190654 external-priority patent/EP2868710A1/fr
Priority claimed from EP20130190657 external-priority patent/EP2868712A1/fr
Application filed by Dystar Colours Distribution Gmbh filed Critical Dystar Colours Distribution Gmbh
Publication of WO2015062929A1 publication Critical patent/WO2015062929A1/fr

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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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/50—Tetrazo dyes
    • C09B35/56—Tetrazo dyes of the type

Definitions

  • Acid dyes process for the production thereof and their use
  • the present invention relates to the technical field of dyestuffs for dyeing and printing of hydroxyl- and/or carboxamido-containing material.
  • Acid dyes with pyridine couplers are known from the prior art and can be used as colorants in different applications, see for example US 3,959,250, US 5,468,848 and WO 2007/045825.
  • Acid dyes with bridging groups are known from prior art and can be used as colorants in different applications, see for example GB 1 ,331 ,445, DE 34 16 327, US 3,979,378, US 5,543,259, US 2009/207287, WO 2010/000780 and CN 101337925.
  • the known dyes have a number of technical disadvantages, which require improvement.
  • One such disadvantage is, that many of them are comprising heavy metals such as Cu, Cr or Ni. Such heavy metals are critical from a toxicological as well as an environmental point of view and shall thus be excluded.
  • dyes of formula (1 ) show highly advantageous properties over the known dyes. These include high tinctorial strength with high brilliance as well as high fastness properties such as wash, contact and light fastness on the materials mentioned above, on blends containing them as well as on microfibres.
  • dyes of formula (1 ) are substantially heavy metal free and provide dyeings that are levelled. Metals may only be present as counter ions and are selected from the groups of alkali and earth alkali metals, which do not have such effects as heavy metals.
  • the present invention is directed to dyes of formula (I) and mixtures thereof
  • Y 1 is formula (lla)
  • Y 2 is formula (Ilia)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independent of each other is hydrogen, alkyi, alkoxy, halogen, trifluoronnethyl or SO3M whereby at least two of them are SO3M
  • R 9 , R 10 , R 1 1 , R 12 , R 13 , R 14 , R 15 and R 16 independent of each other is hydrogen, alkyi, substituted alkyi, alkyi chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyi, heterocycloalkyi, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsul
  • R 17 and R 20 independent of each other is hydrogen, alkyi, alkenyl, cycloalkyi, trifluoromethyl, aryl, heteroaryl, heterocycloalkyi, carbamoyl, N-monocycloalkyl-carb- amoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarba- moyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, ⁇ , ⁇ -dicycloalkyl-sulf
  • R 18 and R 21 independent of each other is cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, alkylsulfonyl, halogen, alkyl sulfonic acid or SOsM,
  • R 19 and R 22 independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or
  • R 24 and R 30 independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, sulfonylalkyl or halogen,
  • R 23 and R 29 independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or
  • alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkyl- ureido and phenylureido,
  • R 25 , R 26 , R 27 , R 28 , R 31 , R 32 , R 33 , R 34 independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkyl- thioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocyclo- alkylalkyl
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, the dyes of formula (I) have two to six sulfonic acid groups
  • bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R 25 , R 26 , R 27 and R 28 , respectively can be positioned ortho or para to R 24 , meaning that when the amino rest bearing the substituents R 25 and R 26 is positioned ortho to R 24 , the amino rest bearing the substituents R 27 and R 28 is positioned para to R 24 , and vice versa;
  • AlkyI groups appearing in this invention may be straight-chain or branched and are (Ci-Ci2)-alkyl groups, preferably (Ci-C8)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl.
  • alkoxy groups which accordingly are preferably (Ci-C8)-alkoxy, for example methoxy and ethoxy
  • thioalkoxy groups which are preferably (Ci-Cs)- thioalkoxy, for example -SCH3 or -SC2H5.
  • Cycloalkyi groups are preferably (C3-C8)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl.
  • the term cycloalkyi comprises for the purpose of the present invention substituted cycloalklyl groups and unsatured cycloalkyi groups as well. A preferred group of this type is cyclopentenyl.
  • Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis(hydroxyalkyl)amino, monoalkyl-mono- (hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Alkenyl groups may be straight-chain or branched and are preferably (C2-C6)-g roups for example vinyl and allyl.
  • alkenyl comprises for the purpose of the present invention alkynyl groups as well, for example ethynyl and propargyl.
  • Aryl groups are preferably phenyl or naphthyl.
  • the terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl.
  • Preferred substituents are alkyl, cycloalkyi, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono- (hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Heteroaryl groups are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1 ,3,4-thiadiazole, furane, oxazole, benzoxazole or isoxazole.
  • heteroayl comprises the above groups in unsubstituted as well as in substituted form.
  • Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, mono- alkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetra- hydrofuran or piperazine.
  • heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form.
  • Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, amino- carbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.
  • Halogen is preferably chlorine, bromine or fluorine.
  • M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(Ci- C 4 )-alkylammonium.
  • Y 1 is (lla) and Y 2 is (Ilia)
  • Y 1 is (Mb) and Y 2 is (lllb) and also those structures, wherein Y 1 is (lla) and Y 2 is (lllb) or Y 1 is (Mb) and Y 2 is (Ilia) form preferred embodiments of the present invention.
  • One preferred embodiment of the present invention are dyes of formula (1 ) and mixtures thereof
  • X is oxygen or sulphur
  • Y 1 is (Mb)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M whereby at least two of them are SO3M,
  • R 9 , R 10 , R 1 1 , R 12 , R 13 , R 14 , R 15 and R 16 independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyi, heterocycloalkyi, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, -SO3H or alkylureido,
  • R 24 and R 30 independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, sulfonylalkyl or halogen,
  • R 23 and R 29 independent of each other is hydrogen, alkyl, cycloalkyi, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, the dyes of formula (1 ) have two to six sulfonic acid groups
  • bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R 25 , R 26 , R 27 and R 28 , respectively can be positioned ortho or para to R 24 , meaning that when the amino rest bearing the substituents R 25 and R 26 is positioned ortho to R 24 , the amino rest bearing the substituents R 27 and R 28 is positioned para to R 24 , and vice versa;
  • R 1 a , R 2a , R 5a and R 6a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
  • R 9a , R 10a , R 13a and R 14a independent of each other is hydrogen, (Ci-C )-alkyl, (Ci- C 4 )-alkoxy, halogen, trifluoromethyl, -SO3M or (Ci-C 4 )-acylamino,
  • R 24a and R 30a independent of each other are cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
  • R 23a and R 29a independent of each other is unsubstituted, linear or branched (Ci-C 4 ) alkyl, unsubstiuted (C5-C7) cycloalkyi, substituted (C5-C7) cycloalkyi with one or more substituents preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, R 25 3j R 26a R 27 3j R 28 3j R 3i 3j R 32 3j R 33a a nd R 34a independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino- hydroxy-alkyl, al
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
  • Especially preferred dyes of formula (1 a) are dyes of the formula (1 aa) and mixtures thereof
  • R 1aa and R 6aa is SO 3 M and R 2aa and R 5aa is hydrogen
  • R 1aa and R 6aa is hydrogen and R 2aa and R 5aa is SO 3 M,
  • R 9aa , R 10aa , R 13aa and R 14aa independent of each other is hydrogen, methyl, halogen, - SO3M or acetylamino
  • R 24aa and R 30aa independent of each other is cyano or carbonamide
  • R 25aa , R 26aa R 27aa , R 28aa , R 31 aa , R 32aa , R 33aa and R 34aa independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2- methylbutyl, 1 -ethyl propyl, 1 ,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3- methoxypropyl, 2-fluoroethyl
  • M is hydrogen, sodium, potassium, lithium or ammonium.
  • Examples of especially preferred dyes of formula (1 aa) are the compounds of formulae (1 aa 1 to 1 aa 440 ) and mixtures thereof as shown in Table 1 , wherein R 23aa and R 29aa is methyl:
  • R 1 b , R 2b , R 3b , R 4b , R 5b , R 6b , R 7b and R 8b independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M, R 9b , R 10b , R 13b and R 14b independent of each other is hydrogen, (Ci-C )-alkyl, (Ci- C 4 )-alkoxy, halogen, trifluoromethyl, -SO3M or (Ci-C 4 )-acylamino,
  • R 24b and R 30b independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl,
  • R 23b and R 29b independent of each other is unsubstituted, linear or branched (Ci-C 4 )- alkyl, unsubstiuted (Cs-CzJ-cycloalkyl or substituted (Cs-CzJ-cycloalkyl with one or more substituents preferably selected from the group consisting of: methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, R 25b_ R 26b R 27b_ ⁇ >28 ⁇ ⁇ >3 ⁇ ⁇ ⁇ >32 ⁇
  • R 33b a nd R 34b independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl,
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
  • Especially preferred dyes of formula (1 b) are dyes of formula (1 bb) and mixtures thereof
  • R 1 bb and R 7bb is SO 3 M and R 3bb , R 4bb , R 5bb and R 8bb is hydrogen,
  • R 3bb and R 5bb is SO 3 M and R 1 bb , R 4bb , R 7bb and R 8bb is hydrogen,
  • R 4bb and R 8bb is S0 3 M and R 1 bb , R 3bb , R 5bb and R 7bb is hydrogen,
  • R 9bb , R 10bb , R 13bb and R 14bb independent of each other is hydrogen, methyl, halogen, - SO3M or acetylamino,
  • R 23bb and R 29bb is met yl
  • R 25bb j R2 6bb R 27 bbj R 28 bbj R 3i bb j R 32 bbj R 33bb and R 34bb independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2- methylbutyl, 1 -ethyl propyl, 1 ,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-nnethoxyethyl , 3- methoxypropyl, 2-fluoro
  • M is hydrogen, sodium, potassium, lithium or ammonium.
  • Examples of especially preferred dyes of formula (1 bb) are the compounds of the formulae (1 bb 1 to 1 bb 660 ) and mixtures thereof, which are shown in Table 2 and wherein R 23bb and R 29bb is methyl:
  • R 1c , R 2c , R 3c , R 4c , R 5c , R 6c , R 7c and R 8c independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
  • R 9c , R 10c , R 13c and R 14c independent of each other is hydrogen, (Ci-C )-alkyl, (Ci-C )- alkoxy, halogen, trifluoromethyl, -SO3M or (Ci-C 4 )-acylamino ,
  • R 24c and R 30c independent of each other is cyano, carbamoyl, substituted carbamoyl, sulfonylalkyl or alkoxycarbonyl
  • R 23c and R 29c independent of each other is unsubstituted, linear or branched (Ci-C 4 )- alkyl, unsubstiuted (Cs-CzJ-cycloalkyl or substituted (Cs-CzJ-cycloalkyl with one or more substituents preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, R 25c , R 26c R 27c , R 28c , R 31c , R 32c , R 33c and R 34c independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cycl
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
  • Especially preferred dyes of formula (1 c) are dyes of formula (1 cc) and mixtures thereof
  • R 1cc and R 5cc is SO 3 M and R 4cc and R 8cc is hydrogen
  • R 1cc and R 5cc is hydrogen and R 4cc and R 8cc is SO 3 M,
  • R 9cc , R 10cc , R 13cc and R 14cc independent of each other is hydrogen, methyl, halogen, - SO3M or acetylamino, R 24cc and R 30cc independent of each other is cyano or carbamoyl,
  • R 25 ⁇ R 26cc R 27c Cj R 28 ⁇ R 3i ⁇ R 32 ⁇ R 33cc a nd R 34cc independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2- methylbutyl, 1 -ethyl propyl, 1 ,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3- methoxypropyl, 2-fluoroethyl, 2-chloroethyl,
  • M is hydrogen, sodium, potassium, lithium or ammonium.
  • Examples of especially preferred dyes of formula (1 cc) are the compounds of formulae (1 cc 1 to 1 cc 624 ) and mixtures thereof as are shown in Table 3, wherein R 23cc and R 29cc is methyl:
  • Another preferred embodiment of the present invention are dyes of formula (2)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independent of each other is hydrogen, alkyi, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 independent of each other is hydrogen, alkyi, substituted alkyi, alkyi chain interrupted by one or two heteroatoms selected from the group consisting of oxygen and sulphur, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino
  • R 18 and R 21 independent of each other is cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, alkylsulfonyl, halogen, alkyl sulfonic acid or SOsM,
  • R 19 and R 22 independent of each other is hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation
  • the dyes of formula (2) have two to six sulfonic acid groups.
  • Particularly preferred dyes of the present invention are those of formula (2a)
  • R 1 a , R 2a , R 3a , R 4a , R 5a , R 6a , R 7a and R 8a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,
  • R 9a , R 10a , R 13a and R 14a independent of each other is hydrogen, (Ci-C )-alkyl, (Ci- C 4 )-alkoxy, halogen, trifluoromethyl, SO3M or (Ci-C 4 )-acylamino,
  • R 17a and R 20a independent of each other is hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyi, carbamoyl, sulfamoyl, amino, N- acylamino, ureido, alkylureido, phenylureido, N-monoalkylannino, N,N-dialkyl-amino, N-arylamino, ⁇ , ⁇ -diarylamino, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N,N- dicycloalkylamino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, hydroxy- alkylsulfonylalkyl or
  • alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur
  • R 18a and R 21 a independent of each other is cyano, carbamoyl or alkoxycarbonyl,
  • R 19a and R 22a independent of each other is unsubstituted, linear or branched (Ci-C 4 )- alkyl, unsubstiuted (Cs-CzJ-cycloalkyl or substituted (Cs-CzJ-cycloalkyl with one or more substituents preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, and
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.
  • R 1 a and R 6a is SO 3 M and R 2a and R 5a is hydrogen
  • R 1 a and R 6a is hydrogen and R 2a and R 5a is SO 3 M
  • R 3a , R 4a , R 7a and R 8a is hydrogen
  • R 9a , R 10a , R 13a and R 14a independent of each other is hydrogen, methyl, halogen, - SO3M or acetylamino,
  • R 17a and R 20a independent of each other is methyl, ethyl, butyl, n-propyl, n-butyl, n- pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methyl- cyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1 -ethyl propyl, 1 ,2-dimethylpropyl, tert- butyl, 3-methylbutyl, pentene-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, allyl, 2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoro- ethyl, 2-chloroethyl, 3-chloropropy
  • R 19a and R 22a is methyl
  • M is hydrogen, sodium, potassium, lithium or ammonium.
  • Examples of preferred dyes of formula (2a) are the compounds of formulae (2a 1 to 2a 878 ) as shown in Table 4, wherein R 3a , R 4a , R 7a , R 8a is hydrogen and R 19a and R 22a is methyl:
  • the present invention also provides a process for the production of the dyes of formula (I) and mixtures thereof comprising the steps:
  • step b) reacting the diazonium salt obtained in step a) with the compounds of formula (4) and (5)
  • step c) reacting the diazonium salts obtained in step c) with the compounds selected from the group consisting of formula (7), (8), (9), (10), (1 1 ) and (12) or mixtures thereof
  • the diazotization of the compound of formula (3) and (6), respectively can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.
  • the coupling reaction of the diazonium salts obtained by diazotization of the compound of the formula (3) onto the compounds of formulae (4) and (5) as well as the coupling reaction of the the diazonium salts obtained by diazotization of the compound of the formula (6) onto the compounds of formulae (7), (8), (9), (10), (1 1 ) and (12) can likewise be performed by known methods. In such reactions stochiometric amounts may be taken or the diazonium compound may be used at a surplus of 5 to 10 %.
  • the compounds of formula (3) are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art such as the methods disclosed in DE140613C.
  • the pyridines of formula (7), (8), (9) and (10) in which R 24 and R 30 represent cyano are commercially available or can be synthesized via methods disclosed in the literature such as DE2230392. Through analogy, all the diamino pyridines that are used in this invention can be synthesized with the protocol.
  • the obtained pyridines can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridines of formula (7), (8), (9) and (10) in which R 24 and R 28 represent carbonamide or by hydrolysis and further esterification to form pyridines, in which R 24 and R 28 represent alkoxycarbonyl.
  • the pyridones of formula (1 1 ) and (12) in which R 18 and R 21 represent cyano are commercially available or can be synthesized via methods disclosed in the literature such as US 2004/006234 A1 .
  • all the pyridone nitriles used in this invention can be synthesized using the protocol.
  • the obtained pyridone nitriles can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridones of formula (1 1 ) and (12) in which R 18 and R 21 represent carbonamide or by hydrolysis and further esterification to form pyridones of formula (1 1 ) and (12) in which R 18 and R 21 represent alkoxycarbonyl.
  • the above-mentioned derivatization reactions can be carried out in alkaline or acidic media, preferably in acidic media using strong inorganic acids such as sulfuric acid or hydrochloric acid gaseous or solution, acidic resins or chlorotrimethylsilane or other suitable acid catalyst in the presence of the corresponding alcohol.
  • the reactions are advantageously carried out under inert atmosphere at temperatures in the range from 40 °C to 150 °C.
  • the above mentioned derivatization reactions can be undertaken as a final step after the synthesis of the corresponding dyes with pyridine nitriles.
  • the dyes of the present invention can be used alone or as a mixture with other dyes according to the present invention and/or other substances.
  • a chemical composition comprising one or more dye(s) as described above is also an aspect of the present invention.
  • a chemical composition consisting of two or more dyes as described above forms another preferred aspect of the present invention.
  • an aqueous solution for dying comprising one or more dye(s) as described above forms an aspect of the present invention.
  • the dyes of the present invention are suitable for dyeing and printing of natural, manufactured regenerated, modified or synthetic hydroxyl- amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for acid dyes.
  • the present invention also is directed to a process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with a dye as described above.
  • Still another aspect of the present invention is/are: Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) of the present invention either in chemically and/or physically bound form.
  • the above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet.
  • woven fabric such as paper and leather
  • films such as nylon films
  • a bulk mass for example composed of polyamide and polyurethane
  • fibers for example cellulose fibers.
  • the fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of hanks or wound packages.
  • the dyes of the present invention and their salts and/or mixtures can be used as a single dyeing colorant in dyeing or printing processes or can be part of a di-, tri- or multi-component combination colorant in dyeing or in printing compositions.
  • the di-, tri- or multi-component shade dyeings show similar fastness level as compared to dyeing performed with a single colorant component.
  • Dyes of the present invention and their salts or mixtures are highly compatible with other known and/or commercially available acid dyes and they can be used together with such dyes of related chromophores and similar technical performance to obtain specific hues. Similar technical performance includes: comparable build-up, comparable fastness properties and comparable exhaustion rates during dyeings.
  • the dyes according to the invention can be applied to the materials mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes. This applies to both, dyeing and printing processes.
  • the material to be dyed is introduced into the bath at a temperature of about 40 °C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98 °C.
  • the dyeings can also be carried out at the boil or in a sealed dyeing apparatus at temperatures of up to 106 °C. Since the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.
  • the dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing.
  • the dyes of the present invention need to be formulated in aqueous inks.
  • An Ink for digital textile printing comprising a dye of the present invention is another aspect of the present invention.
  • the inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 to 50 % by weight, more preferably from 0.5 to 30 % by weight and most preferably from 1 to 15 % by weight, based on the total weight of the ink. If desired the inks may contain further dyes used in digital printing in addition to the one or more dyes of the present invention.
  • a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte.
  • Useful electrolytes include for example lithium nitrate and potassium nitrate.
  • the inks of the present invention may include organic solvents at a total level of 1 to 50 % by weight and preferably 5 to 30 % by weight.
  • Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5-pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6- hexanediol, 1 ,2,6-hexanetriol, 1 ,2-octanediol, polyalkylene
  • the inks of the present invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1 .5 to 40.0 mPas in a temperature range from 20 to 50 °C.
  • Preferred inks have a viscosity of 1 .5 to 20 mPas and particularly preferred inks have a viscosity of 1 .5 to 15 mPas.
  • Useful viscosity moderators include rheological additives, for example:
  • polyvinylcaprolactam polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
  • the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mlM/m, which are adapted if necessary as a function of the process used (thermal or piezo technology).
  • Useful surface-active substances include for example: all surfactants, preferably nonionic surfactants, butyldiglycol, 1 ,2-hexanediol.
  • the inks of the present invention may further comprise customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.
  • the inks may be prepared in a conventional manner by mixing the components in water.
  • the inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind.
  • pretreated materials such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind.
  • Blend fabrics for example blends of cotton, silk, wool with polyester fibers or polyamide fibers can similarly be printed.
  • auxiliaries In contrast to conventional textile printing, where the printing ink already contains all necessary chemicals, in digital or inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.
  • the pretreatment of the textile substrate for example cellulose and regenerated cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor prior to printing.
  • an aqueous alkaline liquor prior to printing.
  • thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans.
  • pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.
  • 1 part of the dye 1 a 95 of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5.5 using acetic acid (80 %).
  • the dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6,6 fabric. The temperature was raised to 120 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material.
  • the polyamide-6,6 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained gave orange to red shades with very good light and wet fastness and also good levelness in the fibre.
  • 100 parts of polyamide-6 material were padded with a 1000 parts 50 °C liquor solution that consisted of 40 parts of the dye 1 a 95 , 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 815 parts of water.
  • the material was rolled up and placed into a steaming chamber at 85 to 98 °C for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried.
  • the dyeings obtained gave orange to red shades with very good light and wet fastness and also good levelness in the fibre.
  • 1 part of the dye 1 a 95 of this invention was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were added.
  • the pH was then adjusted to 4.5 using acetic acid (80 %).
  • the dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 90 °C and removal of the dyed material.
  • the wool fabric was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained gave orange to red shades with very good light and wet fastness and also good levelness in the fibre.
  • Example 3 3 parts of the dye 1 a 95 of this invention dissolved in 82 parts of deionized water were added into the dyebath with 15 parts of diethylene glycol at 60 °C. On cooling, an orange to red printing ink was obtained.
  • the printing ink can be used for ink jet printing on paper, polyamide or wool textiles.
  • the intermediate precipitate obtained 4,4'-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2'-disulfo- nic acid, was filtered off with suction and washed with organic solvent and dried. 15.22 g of the dried intermediate, 5,5'-Bis-(4-amino-2,5-dimethyl-phenylazo)-2,2'- ureylene-bis-benzenesulfonic acid, were then dissolved in water at slightly acidic pH to give a complete reddish orange solution. Ice was added to the solution and when the temperature reached 10 to 15 °C, 10.1 ml of 5N sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8 °C when the mixture was added dropwise into concentrated HCI with ice. A violet suspension formed and reaction mixture was completed in 90 mins.
  • the reaction mixture was used in the next step as described below.
  • 1 part of the dye 2a 3 of this invention was dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5 using acetic acid (80%). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98 °C over the course of 50 minutes and then dyeing is carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material. The polyamide-6 fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.
  • levelling assistant based on condensation product of a higher aliphatic amine and ethylene oxide
  • 1 part of the dye 2a 3 of this invention was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were added.
  • the pH was then adjusted to 4.5 using acetic acid (80 %).
  • the dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 90 °C and removal of the dyed material.
  • the wool fabric was washed with hot and cold water, soaped and then spun and dried. The orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.
  • 1 part of the dye 2a 3 of this invention was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate, and 1 parts of a wetting agent (anionic) was added. 100 parts of bleached cotton knitted fabric were added to this solution.
  • the dye bath was then heated up to 98 °C with a gradient of 2 °C/min, then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80 °C. At 80 °C the dyeing was continued for another 20 minutes.
  • the dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried.
  • the orange dyeings obtained have very good light and wet fastness and also good levelness in the fibre.
  • the orange printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Colorants de formule (1), leur procédé de production et leur utilisation.
PCT/EP2014/072630 2013-10-29 2014-10-22 Colorants acides, procédé pour les produire, et leur utilisation WO2015062929A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP20130190654 EP2868710A1 (fr) 2013-10-29 2013-10-29 Colorants d'acide dépourvus de métaux, procédé pour leur production et leur utilisation
EP13190657.0 2013-10-29
EP20130190657 EP2868712A1 (fr) 2013-10-29 2013-10-29 Colorants d'acide dépourvus de métaux, procédé pour leur production et leur utilisation
EP13190654.7 2013-10-29

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WO2015062929A1 true WO2015062929A1 (fr) 2015-05-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11945785B2 (en) 2021-12-30 2024-04-02 Biomea Fusion, Inc. Pyrazine compounds as inhibitors of FLT3

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE140613C (fr)
GB1331445A (en) 1970-03-31 1973-09-26 Ici Ltd Azo dyestuffs
DE2230392A1 (de) 1972-06-22 1974-01-31 Cassella Farbwerke Mainkur Ag Substituierte pyridinverbindungen und verfahren zu ihrer herstellung
US3959250A (en) 1973-02-10 1976-05-25 Cassella Farbwerke Mainkur Aktiengesellschaft Bisazo dyestuffs of the 2,6-diaminopyridine
US3979378A (en) 1970-01-31 1976-09-07 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Water-soluble azo dyes having a substituted 2-hydroxypyridone (6) coupling component
DE3416327A1 (de) 1984-05-03 1985-11-07 Basf Ag, 6700 Ludwigshafen Farbsalze sulfonsaeuregruppenhaltiger polyazofarbstoffe
US5468848A (en) 1993-06-28 1995-11-21 Bayer Aktiengesellschaft Basic azo dyestuffs of the 3-cyano-2,4,6-triamino pyridine series
US5543259A (en) 1993-12-13 1996-08-06 Xerox Corporation Developer compositions
US20040006234A1 (en) 2002-06-27 2004-01-08 Xerox Corporation Process for preparing substituted pyridone compounds
WO2007045825A2 (fr) 2005-10-22 2007-04-26 Fujifilm Imaging Colorants Limited Colorants azoiques jaunes pour impression a jet d'encre
US20090000511A1 (en) * 2006-09-29 2009-01-01 Seiko Epson Corporation Ink set, ink cartridge, inkjet recording method, and recorded matter
CN101337925A (zh) 2007-07-04 2009-01-07 住友化学株式会社 偶氮化合物或其盐
US20090207287A1 (en) 2008-01-24 2009-08-20 Yoshiko Miya Colored photosensitive composition, and color filter array and solid image pickup device using the same
WO2010000780A1 (fr) 2008-07-02 2010-01-07 Clariant International Ltd Colorants acides
US20120050382A1 (en) * 2010-08-26 2012-03-01 Yasuhiro Tanaka Ink jet ink composition, ink jet recording method, ink cartridge, recording unit, and ink jet recording apparatus
EP2457956A1 (fr) * 2010-11-30 2012-05-30 Kemira Oyj Colorants azoïques

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE140613C (fr)
US3979378A (en) 1970-01-31 1976-09-07 Badische Anilin- & Soda-Fabrik Aktiengesellschaft Water-soluble azo dyes having a substituted 2-hydroxypyridone (6) coupling component
GB1331445A (en) 1970-03-31 1973-09-26 Ici Ltd Azo dyestuffs
DE2230392A1 (de) 1972-06-22 1974-01-31 Cassella Farbwerke Mainkur Ag Substituierte pyridinverbindungen und verfahren zu ihrer herstellung
US3959250A (en) 1973-02-10 1976-05-25 Cassella Farbwerke Mainkur Aktiengesellschaft Bisazo dyestuffs of the 2,6-diaminopyridine
DE3416327A1 (de) 1984-05-03 1985-11-07 Basf Ag, 6700 Ludwigshafen Farbsalze sulfonsaeuregruppenhaltiger polyazofarbstoffe
US5468848A (en) 1993-06-28 1995-11-21 Bayer Aktiengesellschaft Basic azo dyestuffs of the 3-cyano-2,4,6-triamino pyridine series
US5543259A (en) 1993-12-13 1996-08-06 Xerox Corporation Developer compositions
US20040006234A1 (en) 2002-06-27 2004-01-08 Xerox Corporation Process for preparing substituted pyridone compounds
WO2007045825A2 (fr) 2005-10-22 2007-04-26 Fujifilm Imaging Colorants Limited Colorants azoiques jaunes pour impression a jet d'encre
US20090000511A1 (en) * 2006-09-29 2009-01-01 Seiko Epson Corporation Ink set, ink cartridge, inkjet recording method, and recorded matter
CN101337925A (zh) 2007-07-04 2009-01-07 住友化学株式会社 偶氮化合物或其盐
US20090207287A1 (en) 2008-01-24 2009-08-20 Yoshiko Miya Colored photosensitive composition, and color filter array and solid image pickup device using the same
WO2010000780A1 (fr) 2008-07-02 2010-01-07 Clariant International Ltd Colorants acides
US20120050382A1 (en) * 2010-08-26 2012-03-01 Yasuhiro Tanaka Ink jet ink composition, ink jet recording method, ink cartridge, recording unit, and ink jet recording apparatus
EP2457956A1 (fr) * 2010-11-30 2012-05-30 Kemira Oyj Colorants azoïques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11945785B2 (en) 2021-12-30 2024-04-02 Biomea Fusion, Inc. Pyrazine compounds as inhibitors of FLT3

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