DE575832C

DE575832C - Process for the preparation of diazo preparations

Info

Publication number: DE575832C
Application number: DE1930575832D
Authority: DE
Original assignee: Chemische Ind Ges; GESELLSCHAFT fur CHEMISCHE INDUSTRIE; Gesellschaft fuer Chemische Industrie in Basel CIBA
Current assignee: Chemische Ind Ges; GESELLSCHAFT fur CHEMISCHE INDUSTRIE; BASF Schweiz AG
Priority date: 1930-12-04
Filing date: 1930-12-07
Publication date: 1933-05-03
Also published as: FR727293A; CH152611A

Description

Es wurde gefunden, daß man ganz allgemein Diazopräparate von beliebigen primären aromatischen Aminen, welche keine Sulfonsäure- oder Carboxylgruppe besitzen, in hydroxylfreien organischen Flüssigkeiten, welche für die Salze der primären aromatischen Amine ein beträchtliches Lösungsvermögen haben, wie z. B. Aceton oder Essigester, herstellen kann, indem man geeignete Salze der Amine in die Flüssigkeiten einträgt und mit salpetriger Säure (bzw. deren Ester oder Anhydrid) behandelt. Die Diazopräparate scheiden sich aus den genannten Flüssigkeiten in großer Reinheit und mit sehr guter Ausbeute aus. Um sie in handelsübliche Form überzuführen, versetzt man sie vor oder nach dem Abfütrieren mit den üblichen färberischen Hilfsstoffen, wie Aluminiumsulfat, Salzen aromatischer Sulfonsäuren, wasserfreiem Natriumsulfat, Natriumacetat, Borax, Natriumchlorid usw. Vorliegende Arbeitsweise zeichnet sich von der Arbeitsweise, die darin besteht, daß die Diazoverbindungen in Alkohol oder Essigsäure hergestellt und dann gegebenenfalls mit Äther ausgefällt werden (vgl. Berichte 23 [1890] S. 2994; 28 [1895] S. 2048; 34 [1901] S. 3337), durch ihre Einfachheit aus, ferner durch die Arbeitsweise in Lösungsmitteln, wie Tetrachlorkohlenstoff, Tetrachloräthan, Benzol, Xylol, Äther usw., dadurch, daß die Diazoverbindungen sofort leicht in kristalliner Form ausfallen und kaum Neigung zur Bildimg von schmierigen Ausscheidungen zeigen. Die neuen Präparate kuppeln mit den verschiedensten Kupplungskomponenten leicht. Sie sind insbesondere sehr gut zur Herstellung echter Töne auf der Faser geeignet, indem sie mit /S-Naphthol, Aryliden der 2, 3-Oxynaphthoesäure, Aryliden bzw. Diaryliden der Acetessigsäure, Pyrazolonderivaten, Dioxychinolinen, i-Oxynaphthalin-4-aryl- bzw. -alkylketonen, Aryliden der i-Oxynapnthalin-4-carbonsäure usw. schöne lebhafte Töne liefern.It has been found that you can generally diazo preparations of any primary aromatic amines, which no sulfonic acid or Carboxyl group, in hydroxyl-free organic liquids, which are responsible for the salts of the primary aromatic amines have considerable solvent power, e.g. B. acetone or ethyl acetate, can be prepared by adding suitable salts of the amines to the liquids enters and treated with nitrous acid (or its ester or anhydride). The diazo preparations separate from the liquids mentioned in great purity and with a high degree of purity good yield. In order to convert them into a commercially available form, they are placed in front of or after filtering with the usual dyeing auxiliaries, such as aluminum sulfate, salts aromatic sulfonic acids, anhydrous sodium sulfate, sodium acetate, borax, sodium chloride etc. The present way of working is characterized by the way of working, which consists in that the diazo compounds are prepared in alcohol or acetic acid and then optionally be precipitated with ether (see reports 23 [1890] p. 2994; 28 [1895] p. 2048; 34 [1901] P. 3337), by their simplicity, also by the way they work in solvents, such as Carbon tetrachloride, tetrachloroethane, benzene, xylene, ether, etc., in that the diazo compounds instantly easily precipitate in crystalline form and show hardly any tendency to form greasy precipitates. The new Preparations couple easily with a wide variety of coupling components. You are particular very suitable for producing real tones on the fiber by using / S-naphthol, Arylides of 2, 3-oxynaphthoic acid, arylides or diarylides of acetoacetic acid, pyrazolone derivatives, Dioxyquinolines, i-oxynaphthalene-4-aryl- or alkyl ketones, arylids of i-oxynapnthalin-4-carboxylic acid etc. deliver beautiful lively tones.

example 1

38 Teile m-Nitro-p-toluidin (i-Methyl-3-nitro--4-aminobenzol) werden in 400 Raumteilen Aceton gelöst und unter guter Kühlung mit Eis 25 Gewichtsteile wasserfreie Schwefelsäure zugetropft. Das saure Sulfat der Base bleibt in · Lösung. Nun werden ebenfalls unter guter Kühlung 19,6 Gewichtsteile Äthylnitrit in die Lösung eingeleitet, welche z. B. in bekannter Weise durch Versetzen einer Lösung von 18 Gewichtsteilen Natriumnitrit in 40 Teilen Wasser und 17 Raumteilen Alkohol mit etwa 35 Teilen 5o°/₀iger Schwefelsäure entwickelt werden. Das entstehende Diazoniumsalz fällt dabei aus. Nach einer Viertelstunde wird der38 parts of m-nitro-p-toluidine (i-methyl-3-nitro-4-aminobenzene) are dissolved in 400 parts by volume of acetone and 25 parts by weight of anhydrous sulfuric acid are added dropwise with good cooling with ice. The acidic sulphate of the base remains in solution. Now 19.6 parts by weight of ethyl nitrite are also introduced into the solution with good cooling, which z. B. be developed in a known manner by treating a solution of 18 parts by weight of sodium nitrite in 40 parts of water and 17 parts by volume of alcohol with about 35 parts of 5o ° / ₀ sulfuric acid. The resulting diazonium salt precipitates out. After a quarter of an hour the

Claims

crystalline precipitate mixed with 20 Teüen anhydrous sodium sulfate and after a another quarter of an hour filtered. By briefly drying in vacuo and mixing with suitable It is brought to the usual commercial form.

Instead of introducing the ethyl nitrite into the suspension or solution of the acid sulphate, You can often use the suspension beforehand

run into a solution of ethyl nitrite. If one proceeds in this way according to Example with other bases, e.g. B. with 43 parts of 4-chloro-2-nitranüin or with 55 parts of 4-chloro-2-aminodiphenyl ether or with 57 parts by weight of aminoazotoluene (it is advisable to use more Solvent used) or with 30.5 parts by weight of o-dianisidine, etc., so you get to the diazonium salts of the corresponding bases.

Of course, instead of converting the base into the acidic sulphate first, you can immediately start from the acid sulphate and this in finely powdered form in the organic Suspend the liquid.

Example 2

² 3> 5 parts by weight of aniline are dissolved in 400 parts by volume of acetone and 37 parts by weight of anhydrous sulfuric acid are added dropwise with stirring and while cooling with ice. The acid sulphate of the aniline which precipitates out at the beginning goes back into solution. Ethyl nitrite, which is developed from 18 parts by weight of sodium nitrite, as indicated in Example 1, is now introduced into the solution. The acid benzene diazonium sulfate which precipitates out is filtered off after half an hour and washed well with acetone. It can be brought into a commercially available form by adding dyeing auxiliaries. The various toluidines, xylidines and anisidines can be converted into diazo salts in an analogous manner.

Example 3

35 parts by weight of o-Nitranüin are dissolved in 400 parts by volume of acetone and while cooling with ice and stirring 25 parts by weight of anhydrous sulfuric acid added dropwise, the sulfate of the amine partially precipitates. Nitrogen trioxide (or a mixture of nitrogen oxide and nitrogen dioxide), which consists of 50 parts by weight of glassy arsenic and 100 volume parts of nitric acid of specific gravity 1.35 by gentle heating is being developed. As soon as a filtered sample dissolves clearly in water, nitration is carried out and the acidic Diazonium sulphate of o-nitroaniline by mixing with dye-based additives on commercially available Brought shape. The procedure is analogous with other bases and other suitable solvents, such as. B. ethyl acetate. Instead of sulfates, of course, other salts such as chlorides, bromides, phosphates, salts can be used organic sulfonic acids, etc. can be used.

Example 4

35 parts of m-Nitranüin are dissolved in 300 Raumteüen ethyl acetate and with cooling in an ice-cold solution of 25 parts of anhydrous sulfuric acid in 200 parts of ethyl acetate allowed to flow in, the sulfate of the amine precipitating in part. The resulting suspension is then in, an ice-cold solution of 19.6 parts of ethyl nitrite in 100 Raumteüen Allow ethyl acetate to flow in slowly so that the temperature does not exceed 7 to 10 °. Afterwards, stirring is continued for half an hour, then with 20 parts of anhydrous sodium salt added and nitrated after a further quarter of an hour. The well washed product is dried in vacuo at low temperature and mixed with the appropriate Auxiliary materials brought to standard commercial form.

PATIiNTANSl ¹ UU CH:

Process for the production of diazo preparations, characterized in that go suitable salts of primary aromatic amines which do not have a sulfonic acid or carboxyl group in the presence of hydroxyl-free organic liquids, which are responsible for the salts of the primary aromatic amines have considerable dissolving power with nitrous acid or their ester or anhydride treated.