CH247443A - Process for the preparation of a metallizable monoazo dye of the pyrazolone series. - Google Patents
Process for the preparation of a metallizable monoazo dye of the pyrazolone series.Info
- Publication number
- CH247443A CH247443A CH247443DA CH247443A CH 247443 A CH247443 A CH 247443A CH 247443D A CH247443D A CH 247443DA CH 247443 A CH247443 A CH 247443A
- Authority
- CH
- Switzerland
- Prior art keywords
- pyrazolone
- mol
- monoazo dye
- aminophenyl
- phenyl
- Prior art date
Links
- 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 title claims description 15
- 238000000034 method Methods 0.000 title claims description 8
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000000975 dye Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- JVYBGXSVJFZUTQ-UHFFFAOYSA-N 2-(4-aminophenyl)-5-phenyl-4h-pyrazol-3-one Chemical compound C1=CC(N)=CC=C1N1C(=O)CC(C=2C=CC=CC=2)=N1 JVYBGXSVJFZUTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000008049 diazo compounds Chemical class 0.000 description 3
- FTCOWMWIZNVSPP-UHFFFAOYSA-N 2-phenyl-4h-pyrazol-3-one Chemical class O=C1CC=NN1C1=CC=CC=C1 FTCOWMWIZNVSPP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VNXUPEPDMYVBQY-UHFFFAOYSA-N 2-(4-aminophenyl)-5-methyl-4h-pyrazol-3-one Chemical compound O=C1CC(C)=NN1C1=CC=C(N)C=C1 VNXUPEPDMYVBQY-UHFFFAOYSA-N 0.000 description 1
- XSFKCGABINPZRK-UHFFFAOYSA-N 4-aminopyrazol-3-one Chemical class NC1=CN=NC1=O XSFKCGABINPZRK-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/18—Monoazo compounds containing copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung eines metallisierbaren Monoazofarbstoffes der Pyrazolonreihe. Es wurde gefunden, dass man wertvolle metallisierbare Monoazofarbstoffe der Pyr- azolonreihe herstellen kann, die sich erstaun licherweise durch gute Affinität zur Cellu- losefaser auszeichnen,
wenn man molare Mengen der nitrierten Diazoverbindung von 1-Amino-2-oxynaphthalin-4-sulfonsäure mit molaren Mengen eines Dipyrazolons der all gemeinen Formel
EMI0001.0015
worin X eine CO-, eine CS-Gruppe oder einen Cyanurrest, Y eine Alkyl-, eine Phenyl-, die Carboxyl- gruppe oder eine abgewandelte Carboxyl- gruppe,
Z ein zweiwertiges Radikal der Formel -CjH'. -NH-CO-C,H4-, -CH= CH-CGII" worin der -C"H°-Rest ge gebenenfalls noch substituiert sein kann, und n einen.Index mit dem Werte null oder eins bedeuten, in der für die Herstellung von Pyrazolonazofarbstoffen üblichen Weise in schwach saurem, neutralem oder schwach alkalischem Medium vereinigt.
In den zweiwertigen Radikalen Z befin den sich die Bindungsstellen des Phenylen- restes -C,H, in 1,3- oder vorzugsweise in 1,4-Stellung. Als Bindungsort der Reste Z bezw. der Iminogruppen-NH-am Phenyl- rest in 1-Stellung des Pyrazolonringes kom- men, wie in der Formel angedeutet, die 3'- oder vorzugsweise die V-Stellung in Frage.
Von den verwendbaren Dipyrazolonen seien beispielsweise folgende Typen genannt: der Harnstoff des 1-(4'-Aminophenyl)-3- methyl-5-pyrazolons, der Harnstoff des 1-(4"- oder 3"-Aminobenzoyl-4'- oder -3'-amino- phenyl)-3-methyl-5-pyrazolons, der Harn stoff des 1-Phenyl-(4'-phenyl-4"-amino)-3- methyl - 5 - pyrazolons, der Harnstoff der 1- Phenyl - (4'-styryl - 4"-amino)
-3- methyl-5- pyrazolon-3',2"-disulfonsäure bezw. die Thio- harnstoffe der aufgezählten Aminopyrazolon- abkömmlinge oder deren sekundäre Konden sationsprodukte mit Cyanurhalogenid usw.
Die neuen Farbstoffe sind rotbraune bis dunkle Pulver. Sie lassen sich durch Behand lung mit metallabgebenden Mitteln in Sub stanz oder auf der Faser nach den üblichen Methoden in komplexe Metallverbindungen überführen. Besonders wertvoll durch ihre ausgezeichnete Lichtechtheit sind die kom plexen Kupferverbindungen. Die Kupferung kann, wie bekannt, beispielsweise mit Kupfersulfat in neutralem oder schwach essigsaurem Bad vorgenommen werden oder auch in Anwesenheit von weinsauren Alkali salzen in schwach alkalischem Bad. Man er hält so licht- und alkaliechte, oft auch er staunlich gut nassechte orangerote, rote oder braunrote Färbungen.
Gegenüber den bekannten Disazofarb- stoffen aus denselben Dipyrazolonabkömm- lingen ist die Affinität zur Cellulosefaser erstaunlich gross, weil bekanntlich sonst all gemein der Verlust des konjugierten Systems einer Azogruppe einen Disazofarbstoff zu einem Monoazofarbstoff von wesentlich ge ringerer Affinität zur Cellulosefaser werden lässt.
Zu denselben wertvollen metallisierbaren Monoazofarbstoffen gelangt man auch, wenn man Monoazofarbstoffe aus nitrierter Diazo- verbindung von 1-Amino-2-oxynaphthalin-4- sulfonsäure und einem 1-Phenyl-5-pyrazoIon- derivat, das eine aromatisch gebundene pri märe Aminogruppe in 3'- oder 4'-Stellung des 1-Phenylrestes direkt oder über Brücken glieder gebunden enthält,
mit einem weiteren Molekül eines solchen 1-Phenyl-5-pyrazolon- derivates nach bekannten Methoden mit Phosgen, Thiophosgen oder Cyanurhalogenid bis zum Verschwinden der primären Amino- gruppen kondensiert.
Gegenstand vorliegenden Patentes ist ein Verfahren zur Herstellung eines metallisier- baren Monoazofarbstoffes der Pyrazolon- reihe. Das Verfahren ist dadurch gekenn zeichnet, dass man 1 Mol 1-Diazo-6-nitro-2- oxynaphthalin-4-sulfonsäure, 2 Mol 1-(4'- Aminophenyl)
- 3 - phenyl - 5 - pyrazolon und 1 Mal Phosgen derart aufeinander einwirken lässt, dass ein Monoazofarbstoff der Formel
EMI0002.0055
entsteht. Der neue Monoazofarbstoff stellt ein dunkles Pulver dar, das sich in Wasser mit roter und in konzentrierter Schwefelsäure mit oranger Farbe löst und Cellulosefasern in braunorangen Tönen anfärbt, welche durch Nachkupferung in ein Rot von verbesserter Nass- und Lichtechtheit übergehen.
<I>Beispiel:</I> 29,5 Teile 1-Diazo-6-nitro-2-oxynaphtha- lin-4-sulfonsäure werden mit 52,8 Teilen Harnstoff des 1-(4'-Aminophenyl)-3-phenyl- 5-pyrazolons in Gegenwart von überschüssi ger Soda zum Monoazofarbstoff vereinigt. Nach mehrstündigem Rühren bei Eiskühlung ist die Diazoverbindung verschwunden. Man fällt den Farbstoff mit Kochsalz, filtriert und trocknet.
Zum gleichen Farbstoff gelangt man auch, wenn man 1 Mol des Monoazofarb- stoffes aus 1-Diazo-6-nitro-2-oxynaphthalin- 4-sulfonsKure und 1-(4'-Aminophenyl)-3- phenyl-5-pyrazolon mit 1 Mol 1-(4'-Amino- phenyl)-3-phenyl-5-pyrazolon in sodaalkali- schem Medium mit Phosgen zum asymmetri schen Harnstoff kondensiert,
bis keine freien Aminogruppen mehr nachweisbar sind.
Process for the preparation of a metallizable monoazo dye of the pyrazolone series. It has been found that valuable metallizable monoazo dyes of the pyrazolone series can be produced which, astonishingly, are characterized by good affinity for cellulose fibers,
if you molar amounts of the nitrated diazo compound of 1-amino-2-oxynaphthalene-4-sulfonic acid with molar amounts of a dipyrazolone of the general formula
EMI0001.0015
where X is a CO, a CS group or a cyanuric group, Y is an alkyl, a phenyl, the carboxyl group or a modified carboxyl group,
Z is a divalent radical of the formula -CjH '. -NH-CO-C, H4-, -CH = CH-CGII "in which the -C" H ° radical can optionally be substituted, and n denotes an index with the values zero or one in which for the Production of pyrazolone azo dyes combined in a weakly acidic, neutral or weakly alkaline medium.
In the divalent radicals Z are the binding sites of the phenylene radical -C, H, in 1,3- or preferably in 1,4-position. As a binding site of the residues Z respectively. the imino groups — NH— on the phenyl radical in the 1-position of the pyrazolone ring come, as indicated in the formula, the 3 'or preferably the V-position.
Of the dipyrazolones that can be used, the following types may be mentioned, for example: the urea of 1- (4'-aminophenyl) -3-methyl-5-pyrazolone, the urea of 1- (4 "- or 3" -aminobenzoyl-4'- or - 3'-aminophenyl) -3-methyl-5-pyrazolons, the urea of 1-phenyl- (4'-phenyl-4 "-amino) -3-methyl - 5 - pyrazolons, the urea of 1-phenyl - (4'-styryl - 4 "-amino)
-3-methyl-5-pyrazolone-3 ', 2 "-disulfonic acid or the thioureas of the aminopyrazolone derivatives listed or their secondary condensation products with cyanuric halide, etc.
The new dyes are red-brown to dark powders. They can be converted into complex metal compounds by treatment with metal-releasing agents in substance or on the fiber using conventional methods. The complex copper compounds are particularly valuable due to their excellent lightfastness. The coppering can, as is known, for example, be carried out with copper sulfate in a neutral or weakly acetic acid bath or in the presence of tartaric alkali salts in a weakly alkaline bath. It is kept so light and alkali-proof, and often it is also astonishingly water-fast orange-red, red or brown-red colorations.
Compared to the known disazo dyes from the same dipyrazolone derivatives, the affinity for cellulose fiber is astonishingly high, because it is generally known that otherwise the loss of the conjugated system of an azo group turns a disazo dye into a monoazo dye with significantly lower affinity for cellulose fiber.
The same valuable metallizable monoazo dyes can also be obtained by using monoazo dyes made from a nitrated diazo compound of 1-amino-2-oxynaphthalene-4-sulfonic acid and a 1-phenyl-5-pyrazolone derivative, which has an aromatically bonded primary amino group in 3 contains' - or 4'-position of the 1-phenyl radical bound directly or via bridges,
condensed with a further molecule of such a 1-phenyl-5-pyrazolone derivative by known methods with phosgene, thiophosgene or cyanuric halide until the primary amino groups disappear.
The subject of the present patent is a process for the production of a metallizable monoazo dye of the pyrazolone series. The process is characterized in that 1 mole of 1-diazo-6-nitro-2- oxynaphthalene-4-sulfonic acid, 2 moles of 1- (4'-aminophenyl)
- 3 - phenyl - 5 - pyrazolone and 1 time phosgene can act on one another in such a way that a monoazo dye of the formula
EMI0002.0055
arises. The new monoazo dye is a dark powder that dissolves in water with red and in concentrated sulfuric acid with orange color and dyes cellulose fibers in brown-orange tones, which change to a red with improved wet and lightfastness through subsequent copper plating.
<I> Example: </I> 29.5 parts of 1-diazo-6-nitro-2-oxynaphthalin-4-sulfonic acid are mixed with 52.8 parts of urea of 1- (4'-aminophenyl) -3-phenyl - 5-pyrazolones combined in the presence of excess soda to form the monoazo dye. After stirring for several hours with ice cooling, the diazo compound has disappeared. The dye is precipitated with sodium chloride, filtered and dried.
The same dye can also be obtained if 1 mol of the monoazo dye is obtained from 1-diazo-6-nitro-2-oxynaphthalene-4-sulfonic acid and 1- (4'-aminophenyl) -3-phenyl-5-pyrazolone with 1 Mol of 1- (4'-aminophenyl) -3-phenyl-5-pyrazolone condensed in a soda-alkaline medium with phosgene to form asymmetric urea,
until no more free amino groups can be detected.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH247443T | 1945-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH247443A true CH247443A (en) | 1947-03-15 |
Family
ID=4466224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH247443D CH247443A (en) | 1945-12-27 | 1945-12-27 | Process for the preparation of a metallizable monoazo dye of the pyrazolone series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH247443A (en) |
-
1945
- 1945-12-27 CH CH247443D patent/CH247443A/en unknown
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