DE293608C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

The main patent 291894 describes the representation of yellow to yellow-brown dyes, which are made from acetylated arainocarbazoles or (N) -alkyl- and (N) -aralkylcarbazoles Melting with sulfur at higher temperatures results. If one subjects the halogen derivatives These acetylated bases undergo the same reaction, so new dyes are formed of similar hues, which the Products of the main patent for resistance to strong laundry and chlorine bleach and especially for tummy fastness and possess the valuable property, both with alkaline sulfur and in to color the hydrosulfite vat. Since in the formed dyes halogen completely or is for the most part replaced by sulfur or sulfhydryl groups, this is likely to be the unusual Authenticity of the new dyes on a very high level of sulfurization of the carbaz oil molecule are based.

For the representation of the starting materials "the halogen derivatives of the acetylated aminocarbazoles" you can take different paths.

One can first of all add halogen to the molecule of carbazole or its (N) -alkyl or Introduce (N) -aralkyl derivatives and nitrate the halogen bodies formed on them, reduce them and acetylate.

One goes z. B. of the known mono-, di- and trichlorocarbazoles, dissolves or suspends this in glacial acetic acid and nitrates it with ι or 2 molecules of nitric acid to mono- or dinitrochlorocarbazoles. The reduction of the nitro derivatives to the corresponding aminochlorocarbazoles and their acetylation takes place according to the usual methods and offers no difficulty whatsoever. The previously unknown mono- and polyhalogen- (N) -alkylcarbazoles emerge easily and quite analogously, as Mazzara and Lamberti (Gaz. Chim. ital. 26, II. [1896], pp. 238 to 240) for mono- and dichlorocarbazole and Graebe (Annalen 202 [1880], p. 27 ff.) For tri- and polychlorocarbazoles have described. They deliver during nitration (preferably in glacial acetic acid) and afterwards Reduction of halogen-containing amino- (N) -alkylcarbazoles, which are easily acetylated and then form excellent starting materials for the new dyes.

One arrives at isomeric bodies by using the carbazole or its (N) -substituted Derivatives are first nitrated and the nitro bodies formed are then halogenated, then reduced and acetylated. P. Ziersch (reports of D. Chem. Ges. 42 [1909], p. 3799) has already taken the last route mentioned Dichlorodiaminocarbazole shown. This procedure, applied to (N) -alkylcarbazoles, leads

completely analogous to dichlorodiamino- (N) -alkylcarbazoles. If one goes from mononitro derivatives of carbazole or (N) -alkylcarbazole and chlorinated them in glacial acetic suspension Introducing chlorine exhaustively, one can have three or more chlorine atoms in the molecule introduce. Reduction and acetylation of this body leads to polyhalogen derivatives Monoacetylmonoaminocarbazoles or (N) -alkylcarbazoles.

The bodies of this group show the following properties: the diacetyldiaminodichlorocarbazole (Obtained by nitrating and acetylating the from Mazzara and Lamberti, Gaz.

Chim. Ital. 26. II. [1896], p. 240 Dichlorocarbazole) crystallizes from glacial acetic acid in small, shiny needles, which at 300 ° C not melt yet; they are sparingly soluble in alcohol, benzene and chloroform, easily soluble

ao Hch in pyridine, aniline and nitrobenzene. At the Heating with dilute acids or alkalis will easily restore the compound saponified free diaminodichlorocarbazole.

The completely analogous route from dichloro (N) ethyl carbazole Diacetdiaminodichloro- (N) -äthylcarbazole obtained is a gray, crystalline one Powder, which is easily soluble in glacial acetic acid, nitrobenzene and pyridine, hardly soluble in alcohol, chloroform and benzene and is insoluble in water. This connection too is easily saponified by diluted alkalis or acids when boiled.

The isomeric Diacetdiaminodichlorcarbazol (obtained by acetylating the Dichlordiaminocarbazols of P. Ziersch, Ber. 42 [1909], p 3799) is crystallized from glacial acetic acid in small, colorless columns, whose melting point is above 300 ⁰ C. The compound is easily soluble in glacial acetic acid and nitrobenzene, less soluble in benzene and chloroform and insoluble in water.

The diacetyldiaminodichloro (N) - ethylcarbazole obtained in an analogous way crystallizes from glacial acetic acid in colorless, wart-shaped crystals with a melting point above 270 ". The compound is easily soluble in glacial acetic acid and nitrobenzene, sparingly soluble in benzene and Chloroform and insoluble in water.

The acetylaminotrichlor - (N) - äthylcarbazol (obtained by exhaustive chlorination of mononitro- (N) -äthylcarbazol) is a light gray, crystalline powder, which is sparingly soluble in chloroform and naphtha, more easily soluble in glacial acetic acid and benzene and very easily soluble in nitrobenzene and Is aniline. The compound crystallizes from glacial acetic acid in colorless needles with a melting point of 211 to 214 ^° C.

In general, those prepared by the first-mentioned process call for halogenated ones Acetylamino bases in the sulfur melt somewhat higher reaction temperature and also provide slightly greener hues than the isomeric compounds which are produced by halogenation the nitrocarbazole can be obtained.

The dye is represented in a completely analogous manner, as described in the main patent.

Example 1.

100 kg dichlorodiacetyldiaminocarbazole (obtained from the dichlorocarbazole from Mazzara and Lamberti), 100 kg of benzidine and 250 kg Sulfur is first finely ground and then placed in the oven for a long time (8 to 12 hours) heated to 200 to 250 ° C. The cooled melt is ground and by digesting with a concentrated sodium sulphide or caustic soda solution 90 to 120 ° C converted into a form which is easily soluble in dilute alkaline sulfur. Of the When dried, the dye forms a yellow-green powder and dyes cotton in a sodium sulphide bath or greenish yellow olive in the hydrosulfite vat. The colorations are excellent washing, light and chlorine law.

Replacing the dichlorodiacetyldiaminocarbazole with the same in this example Amount of dichlorodiacetyldiamino (N) -ethylcarbgo presented in a completely analogous way azoles, a similar dye of a slightly more yellow hue is obtained.

Example 2.

50 kg dichlorodiacetyldiaminocarbazole (obtained from the dichlorodiaminocarbazole from P. Ziersch), 60 kg benzidine and 200 kg sulfur are heated in the oven to 180 to 230 ° C for a long time. The work-up happens as described in Example 1. The dye has great color strength and colors Cotton yellow. The dyeings are very fast to washing and chlorine.

The replacement of the dichlorodiacetyldiaminocarbazole by the corresponding compound of (N) -Methylcarbazole leads to a purely yellow coloring product with the same fastness properties.

110 Example 3.

50 kg of the mononitro (N) ethyl carbazole by exhaustive chlorination and subsequent Reduction and acetylation are obtained with 40 kg of benzidine and base 180 kg of sulfur flowers, as indicated in Example 2, melted and worked up. Of the Dyestuff dyes cotton with a pure greenish yellow.

Claims (1)

Patent-An s PRU c h: Process for the preparation of yellow to yellow-brown sulfur-containing cotton dyes, consisting in that in place of that in the main patent 291894 used Acetyl compounds of the amino, nitroamino and diaminocarbazoles or (N) -alkyl and (N) -Aralkylcarbazole here the halogen derivatives of these bodies with sulfur, expediently in the presence of benzidine, tolidine or similarly acting compounds, be heated to higher temperatures.