DE264942C

DE264942C -

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Publication number: DE264942C
Application number: DENDAT264942D
Authority: DE

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KAISERLICHESIMPERIAL

PATENTAMT.PATENT OFFICE.

PATENTSCHRIFTPATENT LETTERING

- JYl 264942 '-KLASSE 22b. GRUPPE- JYl 264942 '- CLASS 22b. GROUP

Heumann und Heidlberg (B. B. 19, 1989 [18S6J) erhielten Dkhlorpararosanilin, indem sie o-Chloranilin, p-Toluidin und Arsensäure auf 190⁰ erhitzten. Das Verfahren, das der technischen Fuchsindarstellung nachgebildet ist, liefert im Gegensatz zu dieser nur.ganz minimale Ausbeuten an Rosanilinfarbstoff; hauptsachlich bilden sich dabei unlösliche violette und lösliche gelbe. (Akridin-) Färbstoffe, so daß das Verfahren technisch unbrauchbar ist. ...Heumann and Heidlberg (BB 19 1989 [18S6J) received Dkhlorpararosanilin by o-chloroaniline, p-toluidine and arsenic acid to 190 ⁰ heated. In contrast to this, the process, which is modeled on the technical production of fuchsin, provides only minimal yields of rosaniline dye; mainly insoluble violet and soluble yellow are formed. (Acridine) dyes, so that the process is technically useless. ...

Es wurde nun gefunden, daß man Dichlorpararosanilin wie auch andere halogenierte Rosäniline in verhältnismäßig sehr guter Ausbeute und Reinheit erhält, wenn man p-Aminobenzaldehyd mit orthohalogenierten primären Arylmonoaminen oder ihren in der Aminogruppe monoalkylierten Derivaten und Arsensäure mit oder ohne Zusatz von Chlorzink erhitzt Die Farbstoffbildung geht schon bei· etwa 140° C. vor sich, die Bildung unlöslicher Nebenprodukte wird auf ein Minimum reduziert, und der erhaltene rohe Farbstoff kann auf einfachste Weise in den gebrauchsfertigen Zustand übergeführt werden.It has now been found that dichloroparosaniline, like others, can be halogenated Rosaniline is obtained in relatively very good yield and purity if p-aminobenzaldehyde is used with orthohalogenated primary aryl monoamines or their derivatives monoalkylated in the amino group and arsenic acid heated with or without the addition of zinc chloride. about 140 ° C. in front of you, the formation of insoluble by-products is reduced to a minimum, and the raw dye obtained can be put into the ready-to-use in the simplest possible manner State to be transferred.

Otto Fischer (Patentschrift 16710 und B. B. 13, 669 [1880]) hat p-Leukanilin aus p-Aminobenzaldehyd, salzsaurem Anilin und Clilörzink dargestellt.Otto Fischer (patent specification 16710 and B. B. 13, 669 [1880]) has p-leukaniline from p-aminobenzaldehyde, hydrochloric aniline and Clilörzink.

Diese Leukoverbindung kann jedoch nur mit Chloranil oder Quecksilberchlorid, also technisch überhaupt nicht, zum Farbstoff oxydiert werden. Dassel be gilt für die Leukoverbindung aus p-Aminobenzaldehyd + Chloranilin sowie allgemein für Leukoverbindungen, die primäre oder sekundäre Aminogruppen enthalten. This leuco compound can only work with chloranil or mercury chloride, so technically not at all, to be oxidized to the dye. The same applies to the leuco connection from p-aminobenzaldehyde + chloroaniline and generally for leuco compounds, which contain primary or secondary amino groups.

Durch das vorliegende, neue Verfahren wird die. Isolierung und nachherige Oxydation der Leukovcrbindungen vermieden und hierdurch das Dichlorpararosanilin und seine Analogen überhaupt erst technisch zugänglich.The present, new method is the. Isolation and subsequent oxidation of the Leukov bonds avoided, and thereby dichloroparosaniline and its analogues technically accessible in the first place.

Diese Farbstoffe haben große praktische Bedeutung durch ihre Säureechtheit sowie durch die von Ehrjlich festgestellte Einwirkung auf Trypanosomen, die Erreger der Schlafkfankeit und einer Reihe von Tierkrankheiten, wie Nagana, Dourine (Beschälseuche der Pferde), Mal Congolense usw.These dyes are of great practical importance due to their acid fastness as well through the action on trypanosomes, the causative agents of Chances of sleep and a number of animal diseases, like Nagana, Dourine (horse stalls), Mal Congolense etc.

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Example 1.

Darstellung von Dichlorpararosanilin.Presentation of dichloroparosaniline.

12 kg p-Aminobenzaldehyd werden mit 25,5 kg ο Chloranilin und 44 kg Arsensäure gut gemischt und hierauf in einem mit Rührwerk versehenen, im Ölbad befindlichen Kessel erhitzt. Sobald die Innentemperatur etwa 105⁰ beträgt, setzt man den Rührer in Gang und heizt dann langsam bis auf 140 bis 145 °, bei welcher Temperatur man die Schmelze während 5 bis 6 Stunden hält. Von Zeit zu Zeit wird die Farbstoffbildung durch Lösen einer Probe in Alkohol oder Essigsäure kontrolliert.12 kg of p-aminobenzaldehyde are mixed well with 25.5 kg of chloroaniline and 44 kg of arsenic acid and then heated in a kettle equipped with a stirrer and located in an oil bath. As soon as the internal temperature is about 105 ⁰ , the stirrer is started and then slowly heated to 140 to 145 °, at which temperature the melt is kept for 5 to 6 hours. From time to time the dye formation is checked by dissolving a sample in alcohol or acetic acid.

Nimmt die Intensität der so erhaltenen Probelösungen nicht mehr zu, so läßt man die Schmelze erkalten. Sie wird dann fein gemahlen und mehrere Male mit heißem Wasser ausgezogen. Man filtriert und salzt den Farbstoff mit Salzwasser aus. Das so erhaltene Produkt wird durch Digerieren mitIf the intensity of the sample solutions obtained in this way no longer increases, it is left cool the melt. It is then finely ground and hot several times Stripped of water. It is filtered and the dye is salted out with salt water. That so obtained product is digested with

Claims

excess, double no: painter soda solution transferred into the color base. The latter is washed out well and then converted into the chlorhydrate by known methods.
If the melt is carried out in the presence of zinc chloride, then the work-up is expediently modified in such a way that the color base obtained by digestion with soda is also treated with excess ammonia

ίο treated before turning them into the chlorohydrate convicted.

The dichloroparafuchsin is a microcrystalline powder with a metallic green sheen. It dissolves in water with a blue-red color; by adding normal hydrochloric acid the Color a little bluer, while ρ-fuchsin turns yellow under the same conditions. The alcoholic solution is colored fiery bluish red. Tanned cotton is used in clear tones, which are much more bluish than those produced with ρ fuchsin. the The amounts and temperature conditions given in the above example can be used in certain Limits can be varied.

Example 2.

Representation of dibromoparosaniline.

12 parts of p-aminobenzaldehyde are with

38 parts of ο-bromoaniline and 44 parts of arsenic acid are mixed in the apparatus described above and slowly ^{heated to 148 0} , at which temperature vigorous dye formation occurs. After four hours of heating, the melt is allowed to cool, it is ground as finely as possible and extracted with warm, dilute hydrochloric acid. The dye can be separated from the filtrate by adding sodium chloride. The purification of the crude product can be accomplished according to the procedure given in Example 1.

The chlorohydrate of dibromoparosaniline forms an olive-green, crystalline powder. In hot water it dissolves with a bluish red color, which is diluted on addition of diluted Hydrochloric acid shifted even further to blue.

Tanned cotton has a slightly more bluish tinge than dichloroparosaniline;

Example 3.

Preparation of dichlorodimethylpararosaniline.

If in example 1 the o-chloroaniline is replaced by 28 kg of o-chloromonomethylaniline

C_RH_a C _R H _a

-NH-CH₃(I)-NH-CH ₃ (I)

a purple dye is obtained.

The raw melt is expediently extracted with dilute hydrochloric acid (instead of water)

The chlorine hydrate of the new dye forms a greenish, metallic shiny powder, which dissolves in water with a purple color; on the addition of dilute hydrochloric acid the solution turns blue.

Tanned cotton is dyed in purple tones.

Patent τ claim:

Process for the preparation of halogenated dyes of the rosaniline series, consisting in that one orthohalogenated primary or secondary aromatic monoamines with p-aminobenzaldehyde and Arsenic acid heated with or without the addition of zinc chloride.