CH496773A - Water insoluble azo dyes for synthetic fibres - Google Patents
Water insoluble azo dyes for synthetic fibresInfo
- Publication number
- CH496773A CH496773A CH1763366A CH1763366A CH496773A CH 496773 A CH496773 A CH 496773A CH 1763366 A CH1763366 A CH 1763366A CH 1763366 A CH1763366 A CH 1763366A CH 496773 A CH496773 A CH 496773A
- Authority
- CH
- Switzerland
- Prior art keywords
- amino
- group
- water
- insoluble azo
- formula
- Prior art date
Links
- 239000000987 azo dye Substances 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 5
- 229920002994 synthetic fiber Polymers 0.000 title description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims abstract description 7
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229920002301 cellulose acetate Polymers 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 229920002239 polyacrylonitrile Polymers 0.000 abstract description 2
- 238000000859 sublimation Methods 0.000 abstract description 2
- 230000008022 sublimation Effects 0.000 abstract description 2
- 125000001624 naphthyl group Chemical group 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 carbalkoxy Chemical group 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical class NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 2
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical class C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- CXNVOWPRHWWCQR-UHFFFAOYSA-N p-chloro-o-methylaniline Natural products CC1=CC(Cl)=CC=C1N CXNVOWPRHWWCQR-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VJHTZTZXOKVQRN-UHFFFAOYSA-N 1,2,4-thiadiazol-5-amine Chemical compound NC1=NC=NS1 VJHTZTZXOKVQRN-UHFFFAOYSA-N 0.000 description 1
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical compound NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 description 1
- DYSRXWYRUJCNFI-UHFFFAOYSA-N 2,4-dibromoaniline Chemical compound NC1=CC=C(Br)C=C1Br DYSRXWYRUJCNFI-UHFFFAOYSA-N 0.000 description 1
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 description 1
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 description 1
- MIHADVKEHAFNPG-UHFFFAOYSA-N 2-Amino-5-nitrothiazole Chemical compound NC1=NC=C([N+]([O-])=O)S1 MIHADVKEHAFNPG-UHFFFAOYSA-N 0.000 description 1
- YJTBHWXNEMGNDC-UHFFFAOYSA-N 2-amino-1,3-thiazole-5-carbonitrile Chemical compound NC1=NC=C(C#N)S1 YJTBHWXNEMGNDC-UHFFFAOYSA-N 0.000 description 1
- QYRDWARBHMCOAG-UHFFFAOYSA-N 2-amino-5-chlorobenzonitrile Chemical compound NC1=CC=C(Cl)C=C1C#N QYRDWARBHMCOAG-UHFFFAOYSA-N 0.000 description 1
- MGCGMYPNXAFGFA-UHFFFAOYSA-N 2-amino-5-nitrobenzonitrile Chemical compound NC1=CC=C([N+]([O-])=O)C=C1C#N MGCGMYPNXAFGFA-UHFFFAOYSA-N 0.000 description 1
- 229940018167 2-amino-5-nitrothiazole Drugs 0.000 description 1
- IXNKCWJILKDDBZ-UHFFFAOYSA-N 2-aminobenzene-1,4-dicarbonitrile Chemical compound NC1=CC(C#N)=CC=C1C#N IXNKCWJILKDDBZ-UHFFFAOYSA-N 0.000 description 1
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 1
- OYAHSBDYBOBAAQ-UHFFFAOYSA-N 3-phenyl-1,2,4-thiadiazol-5-amine Chemical compound S1C(N)=NC(C=2C=CC=CC=2)=N1 OYAHSBDYBOBAAQ-UHFFFAOYSA-N 0.000 description 1
- CVINWVPRKDIGLL-UHFFFAOYSA-N 4-chloro-2-(trifluoromethyl)aniline Chemical compound NC1=CC=C(Cl)C=C1C(F)(F)F CVINWVPRKDIGLL-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- OUQMXTJYCAJLGO-UHFFFAOYSA-N 4-methyl-1,3-thiazol-2-amine Chemical compound CC1=CSC(N)=N1 OUQMXTJYCAJLGO-UHFFFAOYSA-N 0.000 description 1
- NDWBXTNRCBNGAK-UHFFFAOYSA-N 4-methyl-5-nitro-1,3-thiazol-2-amine Chemical compound CC=1N=C(N)SC=1[N+]([O-])=O NDWBXTNRCBNGAK-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- PYSJLPAOBIGQPK-UHFFFAOYSA-N 4-phenyl-1,3-thiazol-2-amine Chemical compound S1C(N)=NC(C=2C=CC=CC=2)=C1 PYSJLPAOBIGQPK-UHFFFAOYSA-N 0.000 description 1
- VMNXKIDUTPOHPO-UHFFFAOYSA-N 6-chloro-1,3-benzothiazol-2-amine Chemical compound C1=C(Cl)C=C2SC(N)=NC2=C1 VMNXKIDUTPOHPO-UHFFFAOYSA-N 0.000 description 1
- KZHGPDSVHSDCMX-UHFFFAOYSA-N 6-methoxy-1,3-benzothiazol-2-amine Chemical compound COC1=CC=C2N=C(N)SC2=C1 KZHGPDSVHSDCMX-UHFFFAOYSA-N 0.000 description 1
- DZWTXWPRWRLHIL-UHFFFAOYSA-N 6-methyl-1,3-benzothiazol-2-amine Chemical compound CC1=CC=C2N=C(N)SC2=C1 DZWTXWPRWRLHIL-UHFFFAOYSA-N 0.000 description 1
- GPNAVOJCQIEKQF-UHFFFAOYSA-N 6-nitro-1,3-benzothiazol-2-amine Chemical compound C1=C([N+]([O-])=O)C=C2SC(N)=NC2=C1 GPNAVOJCQIEKQF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- BIXZHMJUSMUDOQ-UHFFFAOYSA-N dichloran Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl BIXZHMJUSMUDOQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- IGHVUURTQGBABT-UHFFFAOYSA-N methyl 2-amino-5-chlorobenzoate Chemical compound COC(=O)C1=CC(Cl)=CC=C1N IGHVUURTQGBABT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
Water-insoluble azo dyes have the formula:- A-N=N-B-NR1,R2, where A = the residue of a diazo component; B = a benzene or naphthalene group, in which the amino and azo groups are in the p-posn. relative to each other; R1 = an alkyl group which is substd. by a group which is not hydroxyl or alkoxy; and R2 = an alkylene group which is bonded to a pyridine residue. The dyes (I) are used in depserse form for dyeing/printing cellulose acetate, and particularly aromatic polyesters in orange red to red tints with excellent light and sublimation fastness. Good dyeings of excellent light fastness are also obtd. with polyacrylonitrile fibres.
Description
Verfahren zur Herstellung wasserunlöslicher Azofarbstoffe
Es wurde gefunden, dass man zu wertvollen wasserunlöslichen, von sauren wasserlöslichmachenden Gruppen, insbesondere von Sulfonsäure- und Carbonsäuregruppen freien Azofarbstoffen der Formel
EMI1.1
gelangt, worin A den Rest einer Diazokomponente, B einen Benzol- oder Naphthalinrest, in welchem die Amino- und die Azogruppe in p-Stellung zueinander stehen, R1 einen Acyloxyalkylrest und R2 eine Alkylengruppe, die an einen Pyridinrest gebunden ist, bedeuten, wenn man einen wasserunlöslichen Azofarbstoff der Formel
EMI1.2
worin A, B und R2 die angegebene Bedeutung haben und R'1 eine Hydroxyalkylgruppe bedeutet, mit acylierenden Mitteln behandelt.
Zu besonders wertvollen Farbstoffen gelangt man erfindungsgemäss, wenn man einen Farbstoff der Formel
EMI1.3
worin X1, Y, Z, V, W und R3 die angegebene Bedeutung haben, mit acylierenden Mitteln behandelt. Als acylierende Mittel seien insbesondere die Halogenide oder Anhydride niederer aliphatischer Carbonsäuren, beispielsweise der Essigsäure, Propionsäure oder Buttersäure genannt. Die Acylierung findet zweckmässig in der Wärme mit einem organischen Lösungsmittel statt.
Als Diazokomponenten, deren Reste in den erfindungsgemäss als Ausgangsstoffe verwendeten Azoverbindungen in Frage kommen, seien vorzugsweise Aminobenzole, insbesondere solche der Formel
EMI1.4
genannt, worin X1 ein Wasserstoff- oder Halogenatom, eine Cyan-, Carbalkoxy-, Alkylsulfonyl-, Phenylazooder Nitrogruppe, Y ein Wasserstoff- oder Halogenatom, eine Nitro-, Alkyl-, Alkoxy-, Trifluormethyl-, Carbalkoxy- oder Cyanogruppe und Z ein Wasserstoffoder Halogenatom bedeutet, wobei mindestens einer der Reste Xt und Y eine Nitro-, Carbalkoxy-, Cyan-, Alkylsulfonyl- oder Phenylazogruppe bedeutet.
Als Beispiele seien die folgenden Amine genannt: 1-Amino-4-chlorbenzol, 1-Amino-5-brombenzol, 1-Amino-4-methylbenzol, 1 -Amino-4-nitrobenzol, 1-Amino-cyanbenzol, 1 -Amino-2,5-dicyanbenzol, 1 -Amino-4-carbalkoxybenzol, 1 -Amino-2,4 -dichlorbenzol, 1 -Amino-2,4-dibrombenzol, 1-Amino-2-methyl-4-chlorbenzol, 1-Amino-2-trifluormethyl-4-chlorbenzol, 1 -Amino-2-cyan-4-chlorbenzol, 1 -Amino-2-cyan-4-nitrobenzol, 1 -Amino-2-carbomethoxy-4-chlorbenzol, 1-Amino-2-carbomethoxyffinitrobenzol, l-Amino-2-chlor-4-cyanbenzol, l-Amino-2-chlor-4-nitrobenzol, l-Amino-2-chlor-4-carbäthoxybenzol, 1 -Amino-2,4-dinitrobenzol, l-Amino-2,4-dicyanbenzol,
l-Amino-2,6-dichlor-4-cyanbenzol, 1 -Amino-2,6-dichlor-4-nitrobenzol, l-Amino-2,4-dicyan-6-chlorbenzol, l-Amino-2,4-dinitro-6-chlorbenzol,
Aus der Reihe der heterocyclischen Diazokomponenten seien beispielsweise die 2-Aminothiazole oder insbesondere die 2-Aminobenzthiazole genannt, beispielsweise 2-Aminothiazol, 2-Amino-5-nitrothiazol, 2-Amino-5-cyanthiazol, 2-Amino-4-methyl-5-nitrothiazol, 2-Amino-4-methylthiazol, 2-Amino-4-phenylthiazol, 2-Amino-4-(4'-chlor)-phenylthiazol, 2-Amino-4-(4'-nitro)-phenylthiazol, 2-Aminobenzthiazol, 2-Amino-6-methylbenzthiazol, 2-Amino-6-methoxybenzthiazol, 2-Amino-6-chlorbenzthiazol, 2-Amino-6-nitrobenzthiazol, ferner, 2-Amino-1 ,3,4-thiadiazol, 2-Amino-1,3,5-thiadiazol, 2,Amino-4-phenyl-1,3,5-thiadiazol.
Die für die Herstellung der als Ausgangsstoffe verwendeten Azoverbindungen in Frage kommenden Azokomponenten entsprechen vorzugsweise der Formel
EMI2.1
worin V ein Wasserstoff- oder Halogenatom, eine Alkyl-, Alkoxy- oder Acylaminogruppe, W ein Wasserstoffatom, eine Alkyl- oder Alkoxygruppe und R2 ein Wasserstoffatom oder eine Alkylgruppe bedeutet, X eine Hydroxygruppe bedeuten und worin der Pyridinring vorzugsweise in 3-Stellung an die Alkylengruppe gebunden ist und m und n Zahlen im Werte von 1 bis bedeuten.
Ebenfalls von besonderem Interesse sind Azokomponenten der Formel
EMI2.2
worin X, V, W und R5 die angegebene Bedeutung haben.
Die erfindungsgemäss hergestellten neuen Monoazofarbstoffe eignen sich, nach Überführung in eine feindisperse Form, ausgezeichnet zum Färben und Drukken synthetischer Fasern, beispielsweise aus Celluloseacetat und insbesondere aromatischer Polyester in orangen bis roten Tönen von ausgezeichneter Lichtund Sublimierechtheit. Überraschenderweise werden auch auf Polyacrylnitrilfasern kräftige und sehr lichtechte Färbungen erhalten.
Im nachfolgenden Beispiel bedeuten die Teile, sofern nichts anderes angegeben wird, Gewichtsteile, die Prozente Gewichtsprozente, und die Temperaturen sind in Celsiusgraden angegeben.
Beispiel
7 Teile Natriumnitrit werden in 136 Teilen konzentrierter Schwefelsäure gelöst. 20,5 Teile 4-Amino3-chlorphenylmethylsulfor werden eingetragen und gut verrührt. Nach einiger Zeit wird die Lösung in 600 teile Eis und Wasser ausgetragen. Die so erhaltene Diazolösung wird zu einer Lösung von 25,6 Teilen N-Hydroxyäthyl-N-2,2'-pyridyläthyl-m-toluidin in 20 Teilen Eisessig zugegeben. Nach einiger Zeit wird das Kupplungsgemisch mit Natriumhydroxydlösung neutralisiert. Nach beendeter Kupplung wird der ausgefallene Farbstoff abfiltriert, mit Wasser nachgewaschen und getrocknet.
23,6 Teile des getrockneten Produktes, 25 Teile Essigsäureanhydrid und 25 Teile Eisessig werden während 7 Stunden bei ca. 120"C gerührt. Das Reaktionsgemisch wird abgekühlt, auf Eis und Wasser ausgetragen und mit Natriumhydroxydlösung zentralisiert. Der ausgefallene Farbstoff wird abfiltriert, mit Wasser nachgewaschen und getrocknet. Er färbt Polyacylnitril, Polyester, Acetatseidefasern aus wässriger Dispersion in rotstichig orangen Tönen von sehr guten Echtheiten.
Process for the preparation of water-insoluble azo dyes
It has been found that valuable water-insoluble azo dyes of the formula which are free of acidic water-solubilizing groups, in particular sulfonic acid and carboxylic acid groups, can be obtained
EMI1.1
where A is the radical of a diazo component, B is a benzene or naphthalene radical in which the amino and azo groups are in the p-position to one another, R1 is an acyloxyalkyl radical and R2 is an alkylene group bonded to a pyridine radical, if one a water-insoluble azo dye of the formula
EMI1.2
in which A, B and R2 have the meaning given and R'1 is a hydroxyalkyl group, treated with acylating agents.
According to the invention, particularly valuable dyes are obtained if a dye of the formula
EMI1.3
wherein X1, Y, Z, V, W and R3 have the meaning given, treated with acylating agents. The halides or anhydrides of lower aliphatic carboxylic acids, for example acetic acid, propionic acid or butyric acid, may be mentioned as acylating agents. The acylation conveniently takes place in the heat with an organic solvent.
As diazo components whose radicals are suitable in the azo compounds used as starting materials according to the invention are preferably aminobenzenes, in particular those of the formula
EMI1.4
called, where X1 is a hydrogen or halogen atom, a cyano, carbalkoxy, alkylsulfonyl, phenylazo or nitro group, Y is a hydrogen or halogen atom, a nitro, alkyl, alkoxy, trifluoromethyl, carbalkoxy or cyano group and Z is a Is hydrogen or halogen, at least one of the radicals Xt and Y being a nitro, carbalkoxy, cyano, alkylsulfonyl or phenylazo group.
The following amines may be mentioned as examples: 1-amino-4-chlorobenzene, 1-amino-5-bromobenzene, 1-amino-4-methylbenzene, 1-amino-4-nitrobenzene, 1-amino-cyanobenzene, 1-amino- 2,5-dicyanobenzene, 1-amino-4-carbalkoxybenzene, 1-amino-2,4-dichlorobenzene, 1-amino-2,4-dibromobenzene, 1-amino-2-methyl-4-chlorobenzene, 1-amino 2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino-2-cyano-4-nitrobenzene, 1-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2- carbomethoxyffinitrobenzene, l-amino-2-chloro-4-cyanobenzene, l-amino-2-chloro-4-nitrobenzene, l-amino-2-chloro-4-carbethoxybenzene, 1-amino-2,4-dinitrobenzene, l- Amino-2,4-dicyanobenzene,
l-amino-2,6-dichloro-4-cyanobenzene, 1-amino-2,6-dichloro-4-nitrobenzene, l-amino-2,4-dicyano-6-chlorobenzene, l-amino-2,4- dinitro-6-chlorobenzene,
From the series of heterocyclic diazo components, there may be mentioned, for example, the 2-aminothiazoles or, in particular, the 2-aminobenzothiazoles, for example 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-cyanthiazole, 2-amino-4-methyl-5 - nitrothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4- (4'-chloro) -phenylthiazole, 2-amino-4- (4'-nitro) -phenylthiazole, 2 -Aminobenzthiazole, 2-Amino-6-methylbenzthiazole, 2-Amino-6-methoxybenzthiazole, 2-Amino-6-chlorobenzthiazole, 2-Amino-6-nitrobenzthiazole, also, 2-Amino-1, 3,4-thiadiazole, 2 -Amino-1,3,5-thiadiazole, 2, amino-4-phenyl-1,3,5-thiadiazole.
The azo components suitable for the preparation of the azo compounds used as starting materials preferably correspond to the formula
EMI2.1
where V is a hydrogen or halogen atom, an alkyl, alkoxy or acylamino group, W is a hydrogen atom, an alkyl or alkoxy group and R2 is a hydrogen atom or an alkyl group, X is a hydroxy group and the pyridine ring is preferably in the 3-position to Alkylene group is bonded and m and n are numbers ranging from 1 to.
Azo components of the formula are also of particular interest
EMI2.2
wherein X, V, W and R5 have the meaning given.
The new monoazo dyes prepared according to the invention, after conversion into a finely dispersed form, are excellently suited for dyeing and printing synthetic fibers, for example made of cellulose acetate and in particular aromatic polyesters in orange to red shades of excellent light fastness and sublimation fastness. Surprisingly, strong and very lightfast dyeings are also obtained on polyacrylonitrile fibers.
In the following example, unless otherwise specified, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius.
example
7 parts of sodium nitrite are dissolved in 136 parts of concentrated sulfuric acid. 20.5 parts of 4-amino-3-chlorophenylmethylsulfur are added and stirred well. After some time, the solution is poured into 600 parts of ice and water. The diazo solution thus obtained is added to a solution of 25.6 parts of N-hydroxyethyl-N-2,2'-pyridylethyl-m-toluidine in 20 parts of glacial acetic acid. After some time, the coupling mixture is neutralized with sodium hydroxide solution. After the coupling has ended, the dyestuff which has precipitated out is filtered off, washed with water and dried.
23.6 parts of the dried product, 25 parts of acetic anhydride and 25 parts of glacial acetic acid are stirred for 7 hours at about 120 ° C. The reaction mixture is cooled, poured onto ice and water and centralized with sodium hydroxide solution. The precipitated dye is filtered off with water Washed and dried, it dyes polyacyl nitrile, polyester, and acetate silk fibers from an aqueous dispersion in reddish orange shades with very good fastness properties.
Claims (1)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES336374A ES336374A1 (en) | 1966-02-03 | 1966-02-02 | Water-insoluble azo dyestuffs and processes for their manufacture and use |
| CH152866A CH480407A (en) | 1966-02-03 | 1966-02-03 | Process for the preparation of water-insoluble azo dyes |
| CH1763366A CH496773A (en) | 1966-02-03 | 1966-12-09 | Water insoluble azo dyes for synthetic fibres |
| DE19671644094 DE1644094C3 (en) | 1966-02-03 | 1967-01-25 | Water-insoluble azo dyes |
| FR92634A FR1510499A (en) | 1966-02-03 | 1967-01-26 | Water insoluble azo dyes and process for their preparation |
| GB424867A GB1122317A (en) | 1966-02-03 | 1967-01-27 | Water-insoluble azo dyestuffs and processes for their manufacture and use |
| BE693400D BE693400A (en) | 1966-02-03 | 1967-01-31 | |
| NL6701627A NL6701627A (en) | 1966-02-03 | 1967-02-02 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH152866A CH480407A (en) | 1966-02-03 | 1966-02-03 | Process for the preparation of water-insoluble azo dyes |
| CH1763366A CH496773A (en) | 1966-02-03 | 1966-12-09 | Water insoluble azo dyes for synthetic fibres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH496773A true CH496773A (en) | 1970-09-30 |
Family
ID=25687907
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH152866A CH480407A (en) | 1966-02-03 | 1966-02-03 | Process for the preparation of water-insoluble azo dyes |
| CH1763366A CH496773A (en) | 1966-02-03 | 1966-12-09 | Water insoluble azo dyes for synthetic fibres |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH152866A CH480407A (en) | 1966-02-03 | 1966-02-03 | Process for the preparation of water-insoluble azo dyes |
Country Status (6)
| Country | Link |
|---|---|
| BE (1) | BE693400A (en) |
| CH (2) | CH480407A (en) |
| ES (1) | ES336374A1 (en) |
| FR (1) | FR1510499A (en) |
| GB (1) | GB1122317A (en) |
| NL (1) | NL6701627A (en) |
-
1966
- 1966-02-02 ES ES336374A patent/ES336374A1/en not_active Expired
- 1966-02-03 CH CH152866A patent/CH480407A/en not_active IP Right Cessation
- 1966-12-09 CH CH1763366A patent/CH496773A/en not_active IP Right Cessation
-
1967
- 1967-01-26 FR FR92634A patent/FR1510499A/en not_active Expired
- 1967-01-27 GB GB424867A patent/GB1122317A/en not_active Expired
- 1967-01-31 BE BE693400D patent/BE693400A/xx unknown
- 1967-02-02 NL NL6701627A patent/NL6701627A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1122317A (en) | 1968-08-07 |
| DE1644094B2 (en) | 1976-03-11 |
| NL6701627A (en) | 1967-08-04 |
| BE693400A (en) | 1967-07-03 |
| DE1644094A1 (en) | 1971-07-01 |
| ES336374A1 (en) | 1968-04-01 |
| FR1510499A (en) | 1968-01-19 |
| CH480407A (en) | 1969-10-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |