DE1258995B - Process for the preparation of anthraquinone dyes - Google Patents
Process for the preparation of anthraquinone dyesInfo
- Publication number
- DE1258995B DE1258995B DEJ23981A DEJ0023981A DE1258995B DE 1258995 B DE1258995 B DE 1258995B DE J23981 A DEJ23981 A DE J23981A DE J0023981 A DEJ0023981 A DE J0023981A DE 1258995 B DE1258995 B DE 1258995B
- Authority
- DE
- Germany
- Prior art keywords
- anthraquinone
- hydroxy
- triamino
- dye
- alkylated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0038—Mixtures of anthraquinones
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/22—Dyes with unsubstituted amino groups
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone
- C09B1/5035—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone only amino and hydroxy groups
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/515—N-alkyl, N-aralkyl or N-cycloalkyl derivatives
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/515—N-alkyl, N-aralkyl or N-cycloalkyl derivatives
- C09B1/5155—N-alkyl, N-aralkyl or N-cycloalkyl derivatives only amino and hydroxy groups
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/54—Amino-hydroxy-anthraquinones; Ethers and esters thereof etherified
- C09B1/545—Anthraquinones with aliphatic, cycloaliphatic or araliphatic ether groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Cl.:Int. Cl .:
C09bC09b
Deutsche KL: 22 b-3/01 German KL: 22 b -3/01
Nummer: 1258 995Number: 1258 995
Aktenzeichen: J23981IVc/22bFile number: J23981IVc / 22b
Anmeldetag: 29. Juni 1963 Filing date: June 29, 1963
Auslegetag: 18. Januar 1968Opening day: January 18, 1968
Die Erfindung betrifft ein Verfahren zur Herstellung von Anthrachinonfarbstoffen, insbesondere Triaminodi-hydroxy-anthrachinonfarbstoffen, die eine große Affinität zu Celluloseacetat und Polyesterfasern haben.The invention relates to a method of manufacture of anthraquinone dyes, in particular triaminodi-hydroxy-anthraquinone dyes, which have a great affinity for cellulose acetate and polyester fibers.
Die nach dem erfindungsgemäßen Verfahren hergestellten Farbstoffe bestehen aus einer Mischung von l,4,5-Triamino-2,8-di-hydroxy-anthrachinon mit 1,4,5-Triamino-3,8-di-hydroxy-anthrachinon als solche oder den alkylierten Derivaten dieser Mischung. Das erfindungsgemäße Verfahren zur Herstellung des nicht alkylierten Farbstoffes besteht darin, daß cyclisches 5 - Nitro - anthrachinon -1,4 - disulfonimid mit Schwefel in Gegenwart von Oleum als Reaktionsmittel zu Triamino-di-hydroxy-anthrachinon reduziert wird.The dyes produced by the process of the invention consist of a mixture of 1,4,5-triamino-2,8-di-hydroxy-anthraquinone with 1,4,5-triamino-3,8-di-hydroxy-anthraquinone as such or the alkylated derivatives of this mixture. The inventive method for producing the non-alkylated dye consists in the fact that cyclic 5 - nitro - anthraquinone -1,4 - disulfonimide with Sulfur is reduced to triamino-di-hydroxy-anthraquinone in the presence of oleum as a reactant.
Es ist allgemein bekannt, Nitro-anthrachinon mit Schwefel in Gegenwart von Oleum zu Amino-hydroxy-anthrachinon zu reduzieren. Es ist aber bisher nicht bekannt gewesen, dieses Verfahren bei cyclischem 5-Nitro-anthrachinon-l,4-disulfonimid anzuwenden, und der nach dem erfindungsgemäßen Verfahren erhaltene Farbstoff, nämlich das Triamino-di-hydroxyanthrachinon, wurde bisher in der Literatur nicht beschrieben. Durch das erfindungsgemäße Verfahren wird somit ein neuer Farbstoff erhalten.It is generally known to convert nitro-anthraquinone with sulfur in the presence of oleum to amino-hydroxy-anthraquinone to reduce. However, it has not previously been known to use this method for cyclic 5-nitro-anthraquinone-l, 4-disulfonimide to be used, and that obtained by the process according to the invention Dye, namely triamino-di-hydroxyanthraquinone, has not yet been described in the literature. A new dye is thus obtained by the process according to the invention.
Es war zu erwarten, daß bei der vorstehend angegebenen Reaktion lAo-Triamino-S-hydroxy-anthrachinon erhalten würde.It was to be expected that lAo-triamino-S-hydroxy-anthraquinone in the above reaction would receive.
Überraschenderweise und für den Fachmann nicht zu erwarten, haben aber chromatographische und analytische Versuche gezeigt, daß der nach diesem Verfahren erhaltene Farbstoff zwei Hydroxylgruppen enthält statt nur einer. Man hat dann herausgefunden, daß die eine Hydroxylgruppe eine Alphastellung und die andere Hydroxylgruppe eine Betastellung einnimmt. Surprisingly and not to be expected by the person skilled in the art, but have chromatographic and Analytical tests have shown that the dye obtained by this process has two hydroxyl groups contains instead of just one. It was then found that the one hydroxyl group is alpha and the other hydroxyl group is beta.
Die in dem folgenden Beispiel angegebenen Prozente sind Gewichtsprozente.The percentages given in the following example are percentages by weight.
111 g 40%igen Oleums werden in einer Flasche von 500 cm3 Inhalt auf 20°C abgekühlt. Anschließend
werden 11,1 g Schwefel unter Beibehaltung der Temperatur unterhalb 20° C beigegeben. Nach halbstündigem
Umrühren werden 167 g 100%ige Schwefelsäure hinzugefügt, wobei die Temperatur weiter unterhalb
20° C gehalten wird. Im Anschluß daran werden 31,2 g S-Nitro-l^-diamino-anthrachinon hinzugegeben
und 2 Stunden lang bei einer Temperatur von 25 bis 280C umgerührt. Danach wird auf 6O0C erhitzt, und
zwar stufenweise während einer Zeit von 2 Stunden und anschließend ebenfalls stufenweise innerhalb einer
Verfahren zur Herstellung von
Anthrachinonfarbstoffen111 g of 40% oleum are cooled to 20 ° C. in a 500 cm 3 bottle. 11.1 g of sulfur are then added while maintaining the temperature below 20 ° C. After stirring for half an hour, 167 g of 100% sulfuric acid are added, the temperature being kept below 20 ° C. Following this, 31.2 g of S-nitro-l ^ stirred diamino-anthraquinone was added and 2 hours at a temperature of 25 to 28 0 C. Thereafter, it is heated to 6O 0 C, namely gradually over a period of 2 hours and then likewise stepwise within a process for the preparation of
Anthraquinone dyes
Anmelder:Applicant:
Interchemical Corporation,Interchemical Corporation,
New York, N. Y. (V. St. A.)New York, N.Y. (V. St. A.)
Vertreter:Representative:
Dr. H. Feder, Patentanwalt,Dr. H. Feder, patent attorney,
4000 Düsseldorf 1, Am Wehrhahn 774000 Düsseldorf 1, Am Wehrhahn 77
Als Erfinder benannt:Named as inventor:
John E. Ferrari, New York, N. Y. (V. St. A.)John E. Ferrari, New York, N.Y. (V. St. A.)
Stunde auf 90° C. Dis Lösung hat eine tiefe violette Farbe. 67 g 85%iger Schwefelsäure werden hinzugefügt, worauf die Temperatur auf 98 bis 108 0C ansteigt und die Lösung eine braune Farbe annimmt. Das Umsetzungsgemisch wird auf 1150C erhitzt, bevor es auf 25 bis 28° C abgekühlt wird. Der übrigbleibende Schwefel wird ausgefiltert und das Filtrat in eine Mischung von 100 g Natriumsulfat in 300 g Wasser und 1500 g Eis geschüttet. Der Brei wird mit 25°/oigeni Ätznatron bis zum Umschlagpunkt von Kongorot und anschließend mit einer 5°/oigen Natriumcarbonatlösung bis zum Umschlagpunkt von Lackmus neutralisiert. Nachdem der Brei eine Nacht lang stehengelassen worden ist, wird er abgefiltert und gewaschen. Die feuchte Paste, bei einer Temperatur zwischen 60 und 65° C getrocknet, ergibt 21,6 g Farbstoff.Hour at 90 ° C. The solution has a deep purple color. 67 g of 85% strength sulfuric acid are added, whereupon the temperature rises to 98 to 108 ° C. and the solution takes on a brown color. The reaction mixture is heated to 115 0 C, before it is cooled to 25 to 28 ° C. The remaining sulfur is filtered out and the filtrate poured into a mixture of 100 g of sodium sulfate in 300 g of water and 1500 g of ice. The slurry is neutralized with 25 ° / oigeni caustic soda up to the transition point of Congo red and then a 5 ° / o solution of sodium carbonate until the transition point of litmus. After the pulp has been left to stand for a night, it is filtered off and washed. The moist paste, dried at a temperature between 60 and 65 ° C., gives 21.6 g of dye.
Der auf diese Weise erhaltene violettblaue Farbstoff hat eine ausgezeichnete Affinität zu Celluloseacetat und Polyesterfasern. Die Bindung an diese Fasern ist bei weitem besser als die aller anderen bekannten und im Handel erhältlichen Farbstoffe, die meistens aus Tetramino-anthrachinon bestehen. Der nach dem erfindungsgemäßen Verfahren erhaltene Farbstoff hat eine ausgezeichnete Lichtechtheit und ist außerordentlich abgasecht.The violet-blue dye obtained in this way has an excellent affinity for cellulose acetate and polyester fibers. The binding to these fibers is far better than that of any other known and commercially available dyes, which mostly consist of tetramino-anthraquinone. According to the invention The dye obtained by the process has excellent lightfastness and is extraordinary emission-proof.
Durch Alkylierung werden die Eigenschaften des Triamino-di-hydroxy-anthrachinonfarbstoffes noch weiter verbessert. Die Farbtönung wird dadurch etwas grüner als bei dem nicht alkylierten Farbstoff.The properties of the triamino-di-hydroxy-anthraquinone dye are enhanced by alkylation further improved. This makes the color shade a little greener than that of the non-alkylated dye.
709 719/387709 719/387
Die Alkylierung wird wie folgt durchgeführt: Eine Mischung von 22,8 g Triamino-di-hydroxy-anthrachinon, 100 cm3 96°/oiger Schwefelsäure und 97,2 g Dimethylsulfat werden innerhalb einer Stunde auf 135 bis 1400C erhitzt. Die Temperatur wird 4 Stunden lang auf dieser Höhe gehalten. Nach Abkühlung auf 25 bis 300C wird die Mischung in 3,5 bis 41 Wasser und Eis geschüttet, mit etwa 300 g 50°/0igem Ätznatron bis zum Umschlagpunkt von Kongopapier und anschließend mit 29%igeni Ammoniak so lange neutralisiert, bis Brillantgelbpapier darauf reagiert. Das Ganze bleibt über Nacht stehen und wird gefiltert und mit ungefähr 21 Wasser ausgewaschen. Die Ausbeute beträgt 20,3 g Farbstoff. Die färberischen Eigenschaften sind die gleichen wie die des nicht alkylierten Faibstoffes, außer daß der alkylierte Farbstoff weniger rötlich ist.The alkylation is carried out as follows: A mixture of 22.8 g triamino-di-hydroxy-anthraquinone, 100 cm 3 96 ° / o sulfuric acid and 97.2 g of dimethyl sulfate are heated within an hour at 135 to 140 0 C. The temperature is held at this level for 4 hours. After cooling to 25 to 30 0 C, the mixture in from 3.5 to 41 water and ice is poured, with about 300 g of 50 ° / 0 caustic soda up to the transition point of Congo red paper, and then neutralized with 29% igeni ammonia until Brilliant Yellow paper responds to it. The whole thing stays overnight and is filtered and washed out with about 21% of water. The yield is 20.3 g of dye. The coloring properties are the same as those of the non-alkylated fiber except that the alkylated dye is less reddish in color.
Claims (2)
Deutsche Patentschrift Nr. 490 812.Considered publications:
German patent specification No. 490 812.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEJ23981A DE1258995B (en) | 1963-01-22 | 1963-06-29 | Process for the preparation of anthraquinone dyes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US253041A US3188163A (en) | 1963-01-22 | 1963-01-22 | Blue dyed polypropylene fibers and process of dyeing them |
| DEJ23981A DE1258995B (en) | 1963-01-22 | 1963-06-29 | Process for the preparation of anthraquinone dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1258995B true DE1258995B (en) | 1968-01-18 |
Family
ID=25982453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEJ23981A Pending DE1258995B (en) | 1963-01-22 | 1963-06-29 | Process for the preparation of anthraquinone dyes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1258995B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE490812C (en) * | 1926-01-11 | 1930-02-07 | British Dyestuffs Corp Ltd | Process for the production of 1íñ4-diaminoanthraquinone, its offshoots and substitution products |
-
1963
- 1963-06-29 DE DEJ23981A patent/DE1258995B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE490812C (en) * | 1926-01-11 | 1930-02-07 | British Dyestuffs Corp Ltd | Process for the production of 1íñ4-diaminoanthraquinone, its offshoots and substitution products |
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