CH373496A - Process for the preparation of water-insoluble azo dyes - Google Patents
Process for the preparation of water-insoluble azo dyesInfo
- Publication number
- CH373496A CH373496A CH7546259A CH7546259A CH373496A CH 373496 A CH373496 A CH 373496A CH 7546259 A CH7546259 A CH 7546259A CH 7546259 A CH7546259 A CH 7546259A CH 373496 A CH373496 A CH 373496A
- Authority
- CH
- Switzerland
- Prior art keywords
- water
- parts
- amino
- benzene
- pyrazolone
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- 239000000987 azo dye Substances 0.000 title claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 7
- -1 monocyclic amine Chemical class 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001555 benzenes Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical group O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical group 0.000 claims 1
- 239000000975 dye Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 5
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- DLURHXYXQYMPLT-UHFFFAOYSA-N 2-nitro-p-toluidine Chemical compound CC1=CC=C(N)C([N+]([O-])=O)=C1 DLURHXYXQYMPLT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWLLPUMZVVGILS-UHFFFAOYSA-N Ethyl 2-aminobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1N TWLLPUMZVVGILS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IGHVUURTQGBABT-UHFFFAOYSA-N methyl 2-amino-5-chlorobenzoate Chemical compound COC(=O)C1=CC(Cl)=CC=C1N IGHVUURTQGBABT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture 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
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- ZMESHQOXZMOOQQ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZMESHQOXZMOOQQ-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
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- XJEVFFNOMKXBLU-UHFFFAOYSA-N 4-methylsulfonylaniline Chemical compound CS(=O)(=O)C1=CC=C(N)C=C1 XJEVFFNOMKXBLU-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
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- MDHYFUPTSWXVIA-UHFFFAOYSA-N methyl 2-amino-5-methylbenzoate Chemical compound COC(=O)C1=CC(C)=CC=C1N MDHYFUPTSWXVIA-UHFFFAOYSA-N 0.000 description 1
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 description 1
- 229940102398 methyl anthranilate Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
- C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
- C09B29/366—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles containing hydroxy-1,2-diazoles, e.g. pyrazolone
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung wasserunlöslicher Azofarbstof% Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer, von sauren wasserlöslich- machenden Gruppen freier Azofarbstoffe der Formel A-N=N-B,
worin A den Rest einer monocyclischen Diazokom- ponente der Benzolreihe und B einen in 4-Stellung an die Azogruppe gebundenen 1-Arylsulfonyl-pyrazolon- 5-rest bedeutet.
Das erfindungsgemässe Verfahren ist dadurch ge kennzeichnet, dass man ein diazotiertes monocyc- lisches Amin der Benzolreihe mit einem 1-Aryl- sulfonyl-pyrazolon-5 kuppelt, wobei die Komponen ten von sauren wasserlöslichmachenden Gruppen frei sind.
Für das vorliegende Verfahren geeignete Diazo- komponenten sind z. B. das Anilin und seine im Benzolkern beispielsweise durch Halogenatome, Alkyl- oder Alkoxy-, Nitro- oder Alkylsulfonylgruppen substituierten Derivate.
Von besonderem Interesse sind Aminobenzole, die in o-Stellung zur Aminogruppe eine funktionell abgewandelte Carbonsäuregruppe aufweisen, bei spielsweise eine Carbonsäureamidgruppe oder eine Carbonsäurenitrilgruppe, insbesondere aber eine Car- bonsäureestergruppe und vorzugsweise eine niedere Carbalkoxygruppe, beispielsweise eine Carbomethoxy- oder Carbäthoxygruppe oder Carbisopropoxygruppe.
Als Beispiele geeigneter Diazokomponenten seien genannt: 1-Amino-benzol, 1-Amino-4-chlor- oder -brom-benzol, I -Amino-4-methyl-benzol, 1-Amino-4-nitro-benzol, 1-Amino-4-cyan-benzol, 1-Amino-4-carbomethoxy-benzol, 1-Amino-4-methylsulfonyl-benzol, 1-Amino-2,4-dichlor-benzol, 1-Amino-2-nitro-4-methyl-benzol, 1-Amino-2-methyl-4-chlor-benzol, 1-Amino-2-carbomethoxy-benzol,
1-Amino-2-carbäthoxy-benzol, 1-Amino-2-cyano-benzol, 1-Amino-2-carbomethoxy-4-chlor-benzol, 1-Amino-2-carbomethoxy-4-methyl-benzol. Als Azokomponenten seien vorzugsweise Pyrazo- lone der Formel
EMI0001.0065
genannt, worin Ar einen Benzolrest bedeutet, der gegebenenfalls durch nicht wasserlöslichmachende Reste, beispielsweise Halogenatome, Alkylgruppen oder Acylaminogruppen substituiert sein kann.
Als Beispiele seien genannt: 1-Phenylsulfonyl-3-methyl-pyrazolon-5, 1-(4'-Methyl-phenyl-sulfonyl)-3-methyl- pyrazolon-5, 1-(4'-Chlor-phenyl-sulfonyl)-3-methyl- pyrazolon-5. Die genannten Azokomponenten stellen grössten teils bekannte Verbindungen dar und werden zweck mässig erhalten durch Kondensation eines Mono- phenylsulfonylhydrazins mit Acetessigsäureamid oder Acetessigester zum entsprechenden Hydrazon,
welch letzteres sich durch Erhitzen in wässriger Suspension leicht zum Pyrazolon cyclisiert oder durch direkte Kondensation und Cyclisierung von Monophenyl- sulfonylhydrazin mit Diketen. Die Diazotierung der erwähnten Diazokomponen- ten kann nach an sich bekannten Methoden, z. B. mit Hilfe von Mineralsäure, insbesondere Salzsäure und Natriumnitrit oder z.
B. mit einer Lösung von Nitro- sylschwefelsäure in konzentrierter Schwefelsäure, er folgen.
Die Kupplung kann ebenfalls in an sich bekannter Weise, z. B. in neutralem bis saurem Mittel, gege benenfalls in Gegenwart von Natriumacetat oder ähn lichen die Kupplungsgeschwindigkeit beeinflussenden Puffersubstanzen oder Katalysatoren wie z. B. Pyridin respektive dessen Salzen, vorgenommen werden.
Nach erfolgter Kupplungsreaktion können die ge bildeten Farbstoffe aus dem Kupplungsgemisch leicht, z. B. durch Filtration, abgetrennt werden, da sie in Wasser praktisch unlöslich sind.
Die neuen Monoazofarbstoffe eignen sich vor züglich zum Färben und Bedrucken von Gebilden, beispielsweise von Fasern aus Acetatkunstseide, Tri- acetat und insbesondere Polyäthylenterephthalat.
Die auf den genannten Gebilden mit den neuen Farbstoffen erzeugten Färbungen zeichnen sich durch eine hohe Sublimier- und Lichtechtheit aus.
Die mit Farbstoffen, welche in o-Stellung zur Azogruppe eine funktionell abgewandelte Carbon- säure aufweisen, erhaltenen Färbungen zeichnen sich durch einen rein grünstichig gelben Farbton aus.
In den nachfolgenden Beispielen bedeuten die Teile, sofern nichts anderes angegeben wird, Gewichts teile, die Prozente Gewichtsprozente, und die Tem peraturen sind in Celsiusgraden angegeben.
<I>Beispiel 1</I> 15,1 Teile Anthranilsäuremethylester werden mit 120 Teilen Wasser und 31 Teilen 30'o/oiger Salzsäure gelöst und bei 0 mit 50 Teilen 2n-Nitritlösung dia- zotiert. Die klare Diazolösung lässt man in eine Lösung von 23,8 Teilen 1-(Phenylsulfonyl)-3-methyl- pyrazolon-5 in 200 Teilen Wasser und 15 Teilen Soda einfliessen. Durch Zugabe von gesättigter Natrium acetatlösung wird die Kupplung zu Ende geführt.
Der ausgefallene Farbstoff der Formel
EMI0002.0033
wird mit Wasser gewaschen und im Vakuum ge trocknet. Es stellt ein gelbes Pulver dar, welches in fein dispergierte Form gebracht Polyesterfasem in grünstichig gelben Tönen von guter Licht- und Sub- limierechtheit färbt.
Das im Absatz 1 verwendete 1-Phenylsulfonyl-3- methyl-pyrazolon-5 wird wie folgt erhalten: 17,2 Teile Benzolsulfonsäurehydrazid in 70 Teilen 50 % igem Alkohol werden bei 80 C tropfenweise mit einer Lösung von 11,5 Teilen Acetessigamid in 100 Teilen Wasser versetzt.
Der Ansatz wird zwei Stunden lang bei 80 bis 90 gerührt. Nach dem Er kalten wird das abgeschiedene 1-Phenylsulfonyl-3- methyl-pyrazolon-5 abgenutscht und aus Alkohol um kristallisiert. Man erhält Nadeln, die bei 164 bis 165 schmelzen. Verwendet man anstelle des Anthranilsäure- methylesters den Anthranilsäureäthylester oder das 1-Amino-2-carbomethoxy-4-chlorbenzol, so erhält man Farbstoffe mit ähnlichen Eigenschaften.
<I>Beispiel 2</I> <B>15,2</B> Teile 1-Amino-2-nitro-4-methylbenzol ver rührt man in 220 Teilen 5o/oiger Salzsäure drei Stunden bei Zimmertemperatur und setzt dann der Mischung 100 Teile Eis und eine Lösung von 7,5 Teilen Natriumnitrit in 35 Teilen Wasser zu. Nach 3 stündigem Rühren lässt man in die Diazolösung eine Lösung von 24 Teilen 1-(Phenylsulfon)-3-methyl-5- pyrazolon in 200 Teile einer l0o/oigen wässrigen Natriumcarbonatlösung einfliessen.
Der ausgefallene Farbstoff färbt Polyesterfasern in gelben Tönen von guter Licht- und Sublimierecht- heit.
<I>Färbevorschrift</I> 1 g des mit 1,5 g Sulfitablauge oder Dinaphthyl- methan-disulfonsäure oder einem Fettalkohol-äthylen- oxydkondensationsprodukt verpasteten, gemäss Bei spiel 1, Absatz 1 erhältlichen Farbstoffes wird mit Wasser auf 4000 cm3 verdünnt, wobei noch 1 em3/1 Essigsäure (40o/oig) und 1 g l eines Fettalkohol- äthylenoxydkondensationsproduktes zugegeben wer den.
In diesem Färbebad färbt man 100 g Polyester fasergarn während 1/2 bis 1 Stunde bei 115 bis 132 , wobei eine grünstichige Gelbfärbung von sehr guter Licht- und Sublimierechtheit erhalten wird.
Process for the production of water-insoluble azo dye% The present invention relates to a process for the production of new azo dyes of the formula A-N = N-B, free of acidic water-solubilizing groups,
in which A is the radical of a monocyclic diazo component of the benzene series and B is a 1-arylsulfonylpyrazolone-5 radical bonded to the azo group in the 4-position.
The process according to the invention is characterized in that a diazotized monocyclic amine of the benzene series is coupled with a 1-arylsulfonyl-pyrazolone-5, the components being free from acidic water-solubilizing groups.
Diazo components suitable for the present process are e.g. B. the aniline and its derivatives substituted in the benzene nucleus, for example by halogen atoms, alkyl or alkoxy, nitro or alkylsulfonyl groups.
Of particular interest are aminobenzenes which have a functionally modified carboxylic acid group in the o-position to the amino group, for example a carboxamide group or a carboxonitrile group, but in particular a carboxy ester group and preferably a lower carbalkoxy group, for example a carbomethoxy or carbethoxy group or carbisopropoxy group.
Examples of suitable diazo components are: 1-amino-benzene, 1-amino-4-chloro- or -bromobenzene, I-amino-4-methyl-benzene, 1-amino-4-nitro-benzene, 1-amino -4-cyano-benzene, 1-amino-4-carbomethoxy-benzene, 1-amino-4-methylsulfonyl-benzene, 1-amino-2,4-dichlorobenzene, 1-amino-2-nitro-4-methyl -benzene, 1-amino-2-methyl-4-chlorobenzene, 1-amino-2-carbomethoxy-benzene,
1-amino-2-carbethoxy-benzene, 1-amino-2-cyano-benzene, 1-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2-carbomethoxy-4-methyl-benzene. Azo components are preferably pyrazolones of the formula
EMI0001.0065
called, in which Ar is a benzene radical which can optionally be substituted by radicals which do not render water soluble, for example halogen atoms, alkyl groups or acylamino groups.
Examples include: 1-phenylsulfonyl-3-methyl-pyrazolone-5, 1- (4'-methyl-phenyl-sulfonyl) -3-methyl-pyrazolone-5, 1- (4'-chloro-phenyl-sulfonyl) -3-methyl-pyrazolone-5. The azo components mentioned are mostly known compounds and are expediently obtained by condensation of a monophenylsulfonylhydrazine with acetoacetic acid amide or acetoacetic acid ester to give the corresponding hydrazone,
which the latter easily cyclizes to the pyrazolone by heating in aqueous suspension or by direct condensation and cyclization of monophenylsulfonylhydrazine with diketene. The diazotization of the diazo components mentioned can be carried out by methods known per se, eg. B. with the help of mineral acid, especially hydrochloric acid and sodium nitrite or z.
B. with a solution of nitro- sylsulfuric acid in concentrated sulfuric acid, he follow.
The coupling can also be carried out in a manner known per se, e.g. B. in a neutral to acidic agent, if necessary in the presence of sodium acetate or similar union, the coupling speed influencing buffer substances or catalysts such. B. pyridine or its salts are made.
After the coupling reaction, the dyes formed can easily from the coupling mixture, for. B. by filtration, because they are practically insoluble in water.
The new monoazo dyes are particularly suitable for dyeing and printing structures, for example fibers made of acetate rayon, triacetate and, in particular, polyethylene terephthalate.
The dyeings produced on the structures mentioned with the new dyes are distinguished by a high degree of fastness to sublimation and light.
The colorations obtained with dyes which have a functionally modified carboxylic acid in the o-position to the azo group are distinguished by a purely greenish yellow hue.
In the following examples, unless otherwise specified, parts are parts by weight, percentages are percentages by weight, and the temperatures are given in degrees Celsius.
<I> Example 1 </I> 15.1 parts of anthranilic acid methyl ester are dissolved with 120 parts of water and 31 parts of 30% hydrochloric acid and diazotized at 0 with 50 parts of 2N nitrite solution. The clear diazo solution is allowed to flow into a solution of 23.8 parts of 1- (phenylsulfonyl) -3-methylpyrazolone-5 in 200 parts of water and 15 parts of soda. The coupling is brought to an end by adding saturated sodium acetate solution.
The unusual dye of the formula
EMI0002.0033
is washed with water and dried in vacuo. It is a yellow powder which, when finely dispersed, dyes polyester fibers in greenish yellow tones of good lightfastness and sublimation fastness.
The 1-phenylsulfonyl-3-methyl-pyrazolone-5 used in paragraph 1 is obtained as follows: 17.2 parts of benzenesulfonic acid hydrazide in 70 parts of 50% alcohol are added dropwise at 80 ° C. to a solution of 11.5 parts of acetoacetic amide in 100 parts Water added.
The batch is stirred at 80 to 90 for two hours. After he cold, the separated 1-phenylsulfonyl-3-methyl-pyrazolone-5 is suction filtered and crystallized from alcohol. Needles are obtained which melt at 164 to 165. If, instead of the methyl anthranilate, the ethyl anthranilate or 1-amino-2-carbomethoxy-4-chlorobenzene is used, dyes with similar properties are obtained.
<I> Example 2 </I> <B> 15.2 </B> parts of 1-amino-2-nitro-4-methylbenzene are stirred in 220 parts of 50% hydrochloric acid for three hours at room temperature and then added to the mixture 100 parts of ice and a solution of 7.5 parts of sodium nitrite in 35 parts of water. After stirring for 3 hours, a solution of 24 parts of 1- (phenylsulfone) -3-methyl-5-pyrazolone in 200 parts of a 10% aqueous sodium carbonate solution is allowed to flow into the diazo solution.
The unusual dye dyes polyester fibers in yellow shades with good lightfastness and sublimation fastness.
<I> Dyeing instructions </I> 1 g of the dyestuff available in a paste with 1.5 g of sulphite waste liquor or dinaphthyl methane disulphonic acid or a fatty alcohol / ethylene oxide condensation product according to Example 1, paragraph 1 is diluted with water to 4000 cm3, whereby 1 em3 / 1 acetic acid (40%) and 1 g of a fatty alcohol äthylenoxydkondensationsproduktes added to who.
In this dyebath, 100 g of polyester fiber yarn are dyed for 1/2 to 1 hour at 115 to 132, a greenish yellow coloration of very good fastness to light and sublimation being obtained.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH7546259A CH373496A (en) | 1959-07-08 | 1959-07-08 | Process for the preparation of water-insoluble azo dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH7546259A CH373496A (en) | 1959-07-08 | 1959-07-08 | Process for the preparation of water-insoluble azo dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH373496A true CH373496A (en) | 1963-11-30 |
Family
ID=4534160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH7546259A CH373496A (en) | 1959-07-08 | 1959-07-08 | Process for the preparation of water-insoluble azo dyes |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH373496A (en) |
-
1959
- 1959-07-08 CH CH7546259A patent/CH373496A/en unknown
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