CH220107A - Process for the production of a new azo dye. - Google Patents
Process for the production of a new azo dye.Info
- Publication number
- CH220107A CH220107A CH220107DA CH220107A CH 220107 A CH220107 A CH 220107A CH 220107D A CH220107D A CH 220107DA CH 220107 A CH220107 A CH 220107A
- Authority
- CH
- Switzerland
- Prior art keywords
- dye
- pyrazolone
- parts
- phenyl
- amino
- Prior art date
Links
- 239000000987 azo dye Substances 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 9
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 5
- GRGSHONWRKRWGP-UHFFFAOYSA-N 2-amino-4-sulfobenzoic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1C(O)=O GRGSHONWRKRWGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 3
- 150000008049 diazo compounds Chemical class 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-DYCDLGHISA-N Deuterium chloride Chemical compound [2H]Cl VEXZGXHMUGYJMC-DYCDLGHISA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001024304 Mino Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- AOSJNFGVUJMQKB-UHFFFAOYSA-N hydrazine hypochlorous acid Chemical compound NN.ClO AOSJNFGVUJMQKB-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- ACXCKRZOISAYHH-UHFFFAOYSA-N molecular chlorine hydrate Chemical compound O.ClCl ACXCKRZOISAYHH-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- DZQXBXZZSKPMDV-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]acetamide Chemical compound C1=CC(NC(=O)C)=CC=C1C1=CC=C(N)C=C1 DZQXBXZZSKPMDV-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
- C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
- C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Zusatzpatent zum Hauptpatent Nr. 197582. Verfahren zur Herstellung eines neuen Azofarbstoges. Es wurde gefunden, dass man einen neuen Azofarbstoff erhält, wenn man 2 Mol 1-Phenyl- (4'-phenyl-4"-amino)-3-methyl-5-pyrazolon der Formel
EMI0001.0007
1 Mol Cyanurchlorid,
1 Mol Anilin und 2 Mol diazotierte 1-Amino - 3 - sulfobenzol- 6 - carbon- säure derart aufeinander einwirken lässt, dass die 2 Mol des Pyrazolonderivates und das Anilin durch den Cyanurrest verkettet wer den und die Diazoverbindung in die 4-Stel- lung der Pyrazolonkerne eingreift.
Der so erhaltene Farbstoff bildet ein gelb braunes Pulver, das Baumwolle in gelben Tönen färbt. Durch Behandeln in Substanz oder auf der Faser mit kupferabgebenden Mitteln wird der neue Farbstoff in eine sehr lichtecht färbende Kupferverbindung über geführt.
Das 1- Phenyl - (4'- phenyl - 4"- amino) - 3 - methyl-5-pyrazolon kann wie folgt hergestellt werden 22,6 Teile fein gemahlenes Monoacetyl- benzidin werden in 50 'feilen Wasser und etwas Eis angerührt, mit 30 Teilen Salzsäure d =1,15 versetzt. Man tropft bei 0-15 0 langsam eine Lösung von 7 Teilen Natrium nitrit in etwa 20 Teilen Wasser zu und rührt nach beendigter Zugabe des Nitrites noch etwa 1 Stunde und filtriert.
Die filtrierte Diazolösung lässt man unter gutem Rühren in ein von aussen gekühltes Gemisch von 100 Teilen Zinnchlorür etwa 63 o/oig und 50 Teilen Salzsäure d = 1,15 bei 0-5 o einlaufen.
Das gebildete,Hydrazin fällt schwer lös lich aus. Man'rührt noch etwa 12 Stunden, nutscht, wäscht mit verdünnter Salzsäure und dann mit Wasser- nach.
Das so hergestellte Hydrazinchlorhydrat der Formel
EMI0001.0053
wird in 500 Teilen Wasser und 100 Teilen Salzsäure d -= 1,15 etwa 2 - 3 Stunden ge kocht. Das Chlorhydrat des 4-Hy drazino-4'- aminodiphenyls geht in Lösung. Man entzimit, gegebenenfalls mit Schwefelwasserstoff, fil triert und lässt erkalten. Ein grosser Teil des Chlorhydrates fällt aus. Aus der Mutterlauge kann weiteres Chlorhydrat ausgesalzen oder mit Alkalien die =Base irr Freiheit gesetzt werden.
Diese letztere bildet, aus Alkohol um kristallisiert, weisse Kristalle vom F. 179 , die sich an der Luft bräunen.
<B>27,2</B> Teile des Chlorhydrates des Hydra zins werden in heissem Wasser aufgeschlämmt. Man kondensiert mit 14 Teilen Acetessigester bei etwa 60 unter langsamem Abstumpfen der bei der Kondensation frei werdenden Säure. Nach beendigter Kondensation lässt man erkalten, stellt mit Ätzalkali plienol- phthalein-alkalisch, rührt 12 Stunden, erwärmt, bis alles gelöst und fällt das 1-Plienyl-(9'- phenyl-4"-a,mino)-3-methyl-5-py razolori durch Neutralisation aus.
Zur Herstellung des Pyrazolons kann auch von dem nach der Sulfit-Methode hergestellten Hydrazin ausgegangen werden. Das neue Produkt ist ein weisses Pulver vom F. 194', löslich in verdünnter Natron lauge und verdünnten Mineralölen.
<I>Beispiel:</I> Man löst 26,5 Teile 1-Phenyl-(4'-plreriyl- ; 4"-aniirio)-3-iriethyl-5-pyi-azolon der Formel
EMI0002.0029
in etwa 500 Teilen Wasser, enthaltend 10 Teile Natronlauge von<B>36'</B> B@ und 15 Teilen N atriumcarbonat.
Die filtrierte. Lösung versetzt man lang sam mit der Dia zoverbindung aus 21,7 Teilen 1-Arnino-3-sulfobenzol-6-carbonsäure. Nach beendigter Kupplung wird das Alkali der Farbstofflösung mit verdünnter Säure abge stumpft. Man gibt dann dazu eine Lösung von 9,2 Teilen Cyanurchlorid in wenig Aceton. Man rührt zuerst in der Kälte, dann bei etwa 50 " unter Abstumpfen der frei werdenden Säure.
Man isoliert den Farbstoff und behan delt denselben mit Anilin in bekannter Weise zur Absättigung des dritten Chlors des Cyanur- ringes.
Der Farbstoff der mutmasslichen Formel
EMI0002.0044
wird gegebenenfalls nach Überführung in die komplexe Kupferverbindung wie üblich isoliert.
Additional patent to the main patent No. 197582. Process for the production of a new azo dye. It has been found that a new azo dye is obtained if 2 moles of 1-phenyl- (4'-phenyl-4 "-amino) -3-methyl-5-pyrazolone of the formula are used
EMI0001.0007
1 mole of cyanuric chloride,
1 mol of aniline and 2 mol of diazotized 1-amino-3-sulfobenzene-6-carboxylic acid can act on one another in such a way that the 2 mol of the pyrazolone derivative and the aniline are linked by the cyanuric radical and the diazo compound is in the 4-position the pyrazolone nuclei intervene.
The dye thus obtained forms a yellow-brown powder that dyes cotton in yellow tones. By treating in substance or on the fiber with copper-releasing agents, the new dye is converted into a very lightfast, coloring copper compound.
The 1-phenyl- (4'-phenyl-4 "-amino) -3-methyl-5-pyrazolone can be prepared as follows. 22.6 parts of finely ground monoacetylbenzidine are mixed in 50 'of water and a little ice, with 30 parts of hydrochloric acid d = 1.15 are added, a solution of 7 parts of sodium nitrite in about 20 parts of water is slowly added dropwise at 0-15 ° and, when the addition of the nitrite is complete, the mixture is stirred for about 1 hour and filtered.
The filtered diazo solution is allowed to run into an externally cooled mixture of 100 parts of tin chloride about 63% and 50 parts of hydrochloric acid d = 1.15 at 0-5 °, with thorough stirring.
The hydrazine formed is difficult to solve. The mixture is stirred for about 12 hours, suction filtered, washed with dilute hydrochloric acid and then with water.
The hydrazine chlorohydrate of the formula thus prepared
EMI0001.0053
is boiled in 500 parts of water and 100 parts of hydrochloric acid d = 1.15 for about 2-3 hours. The hydrochloride of 4-Hy drazino-4'-aminodiphenyl goes into solution. Decimit, if necessary with hydrogen sulfide, filter and leave to cool. A large part of the hydrochloride precipitates. Further chlorine hydrate can be salted out from the mother liquor or the base can be set free with alkalis.
The latter, recrystallized from alcohol, forms white crystals of F. 179, which brown in the air.
<B> 27.2 </B> parts of the hydrochloride in hydrazine are suspended in hot water. It is condensed with 14 parts of acetoacetic ester at about 60 degrees, slowly blunting the acid released during the condensation. When the condensation is complete, the mixture is allowed to cool, is made alkaline with caustic alkali plienol-phthalein, stirred for 12 hours, heated until everything is dissolved and the 1-plienyl- (9'-phenyl-4 "-a, mino) -3-methyl 5-py razolori by neutralization.
The hydrazine prepared by the sulfite method can also be used as a starting point for the preparation of the pyrazolone. The new product is a white powder from F. 194 ', soluble in dilute caustic soda and diluted mineral oils.
<I> Example: </I> 26.5 parts of 1-phenyl- (4'-plreriyl-; 4 "-aniirio) -3-iriethyl-5-pyi-azolone of the formula are dissolved
EMI0002.0029
in about 500 parts of water, containing 10 parts of sodium hydroxide solution of <B> 36 '</B> B @ and 15 parts of sodium carbonate.
The filtered. The solution is slowly mixed with the diazo compound from 21.7 parts of 1-amino-3-sulfobenzene-6-carboxylic acid. After the coupling is complete, the alkali of the dye solution is blunted with dilute acid. A solution of 9.2 parts of cyanuric chloride in a little acetone is then added. The mixture is stirred first in the cold, then at about 50 "while the acid released is blunted.
The dye is isolated and treated with aniline in a known manner to saturate the third chlorine in the cyanuric ring.
The dye of the putative formula
EMI0002.0044
is optionally isolated as usual after conversion into the complex copper compound.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH197582T | 1935-11-06 | ||
| CH220107T | 1935-11-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH220107A true CH220107A (en) | 1942-03-15 |
Family
ID=25723002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH220107D CH220107A (en) | 1935-11-06 | 1935-11-06 | Process for the production of a new azo dye. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH220107A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2559483A1 (en) * | 1984-02-10 | 1985-08-16 | Sandoz Sa | HETEROCYCLIC COMPOUNDS CONTAINING BASIC AND / OR CATIONIC GROUPS, THEIR PREPARATION AND THEIR USE AS COLORANTS |
-
1935
- 1935-11-06 CH CH220107D patent/CH220107A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2559483A1 (en) * | 1984-02-10 | 1985-08-16 | Sandoz Sa | HETEROCYCLIC COMPOUNDS CONTAINING BASIC AND / OR CATIONIC GROUPS, THEIR PREPARATION AND THEIR USE AS COLORANTS |
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