DE965260C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the preparation of vat dyes. The subject of the patent 836 o66 is a process for the production of vat dyes, which thereby it is indicated that such i-benzoylamino-q.-amino-6, 7-dichloroanthraquinones with such benzoylating agents to products benzoylated in the i- and 4-positions implements,. that one of the benzoyl radicals is substituted by an alkyl sulfone group is.

It has now been found that vat dyes are also valuable if you get i-Benzoylamino-4-amino-6, 7-dichloroanthraquinones with benzoylating Reacts agents to benzoylated products in i- and 4-position and thereby the starting materials is chosen so that one of the benzoyl radicals is substituted by a sulfonic acid dialkylamide group is.

The starting materials used in the present process are in the benzoyl radical optionally substituted i-benzoylamino-4-amino-6, 7-dichloroanthraquinones can from 2,3-dichloroanthraquinone by nitrating, reducing, transferring the obtained i-Amino-6, 7-dichloroanthraquinones into oxamic acid, nitration again, cleavage of the oxalic acid residue, benzoylating and reducing.

The choice of starting materials has to be made in such a way that either Benzoyl radical in the Anthraquinone component is already present, or in that benzoyl radical which is converted into the anthraquinone derivative by the process is introduced, a sulfonic acid dialkylamide group is present as a substituent. The other benzoyl radical can be free of substituents or any substituents have, as they usually occur in vat dyes, z. B. alkyl groups, such as methyl groups, alkoxy groups, such as ethoxy or methoxy groups, and in particular Halogen atoms such as chlorine or bromine. However, a sulfonic acid dialkylamide group is allowed only be present in one of the benzoyl residues, s? that the dyes obtained are asymmetrical are.

The sulfonic acid dialkylamide groups are expediently in the meta or para position to the - CO group of the benzoyl radical and, as alkyl radicals, can preferably have those with about 1 to 5 carbon atoms, so that the sulfonic acid dialkylamide group contains a total of 2 to 10 carbon atoms. Accordingly, the starting materials of the present process advantageously contain z. B. sulfonic acid dimethylamide or sulfonic acid diethylamide groups. However, sulfonic acid dialkylamide groups also include such sulfonic acid amide groups. understand whose alkyl groups together with the nitrogen atom and preferably a further hetero atom, e.g. B. an oxygen atom or a CHZ group, form a ring, as is the case, for example, with the sulfonic acid piperidide group applies, Examples of anthraquinone components that do not contain a benzoylamino-sulfonic acid dialkylamide group and are therefore to be treated with benzoylating agents containing sulfonic acid dialkylamide groups are i-benzoylamino-4-amino-6,7-dichloroanthraquinone, i- (4'-methoxybenzoylamino) and i-benzoylamino-4-amino-6,7-dichloroanthraquinone (4'-Chlorobenzoylamino) -4-amino-6, 7-dichloroanthraquinone called. Appropriate benzoylating agents are reactive derivatives of the benzoic acids in question, e.g. B. the acid chlorides into consideration, so z. B. those of benzoic acid-3- or -4-sulfonic acid dimethylamide, benzoic acid-3- or -4-sulfonic acid diethylamide, benzoic acid-3- or -4-sulfonic acid piperidide and benzoic acid-3- or -4-sulfonic acid morpholide. Conversely, the same dyes can be prepared from the corresponding i- (benzoylamino) -4-amino-6, 7-dichloroanthraquinones, the benzoyl radical of which is already substituted by a sulfonic acid dialkylamide group, and benzoyl chloride, p-methoxy- or p-chlorobenzoyl chloride, while the simultaneous reaction of i, 4-diamino-6, 7-dichloroanthraquinone with the corresponding benzoylating agents generally provides considerable proportions of the less valuable symmetrical dyes.

The treatment with the benzoylating agents in question can, for example in high-boiling solvents such as dichlorobenzene, nitrobenzene or naphthalene, expediently at temperatures above 100 °, if desired with the addition of acid-binding agents and / or catalytically active agents, such as pyridine, diethylaniline and sodium carbonate, be performed.

The vat dyes obtained correspond to the general formula wherein X denotes a sulfonic acid dialkylamide group and the benzene nucleus denoted by I can be substituted, but is different with regard to substitution from the benzene nucleus denoted by II @. They can be used as pigment dyes and for dyeing and printing a wide variety of fibers, especially those of a vegetable nature such as cotton, linen, rayon and rayon made from regenerated cellulose. If desired, they can also be used in the form of their leuco ester salts which can be prepared in the customary manner by the processes known for this class of dyestuffs.

Compared to the known dyes which is obtained according to the USA. Patents 2 5o6 024 and 2 5o6 025 by aminoanthraquinones 4-i-benzoylamino-containing in the 6- or 7-SteHung a halogen atom, to in i and. Reacts 4-position benzoylated products and thereby selects the starting materials so that one of the benzoyl radicals is substituted by a sulfonic acid dialkylamide group, weisell the new dyes obtainable according to the present process have the advantage of better yield when printing cellulosic fabrics.

In the following examples, unless otherwise stated, parts are parts by weight and percentages are percentages by weight. EXAMPLE I 15 parts of 4-sulfonic acid morpholide are suspended in 320 parts of dry nitrobenzene and, after 8 parts of thionyl chloride and 0.1 parts of pyridine have been added, the mixture is stirred at 100 to 100 ° for 1/2 hours. 20.5 parts of i-benzoylamino-4-amino-6, 7-dichloroanthraquinone are then added and the mixture is stirred for a further 2 hours at 125 ° to 130 °. The dye which precipitates out in red crystals on cooling is filtered off with suction, washed with nitrobenzene and hot alcohol and dried. It dissolves in concentrated sulfuric acid with a blue-red color and dyes cotton from an olive-green vat in pure; real, blue-red tones.

The i-benzoylamino-4-amino-6 used in the present example, 7-dichloroanthraquinone can be prepared as follows: To a solution of 50 parts 2, 3-dichloroanthraquinone in 8oo parts of monohydrate are taken within i hour Stirring 115 parts of nitrating acid (50%) were added dropwise. After this mixture still Was stirred for 2 hours at 50 to 55 °, is filtered off with suction and washed neutral. Of the The filter cake is now ground as finely as possible with a little alcohol and after Addition of 3o parts of sodium sulfite and 3ooo parts of water under reflux for 15 hours cooked. Then it is made alkaline with sodium hydroxide solution, filtered hot, washed neutral and dries. Recrystallization from o-dichlorobenzene gives the i-nitro-6, 7-dichloroanthraquinone in almost colorless little nacelles, which at about 29o ° (uncorrected) scribble.

30 parts of the nitro product are ground thoroughly with water and, after the addition of 140o parts of water and 30o parts of sodium sulfhydrate solution (30%), the mixture is stirred at 95 ° for 1 hour. The amino compound of the formula which precipitated out as a red precipitate is sucked off hot, washed neutral and dried. It crystallizes from anisole in red needles, which melt at about 282 to 283 ° (uncorrected).

29.3 parts of the oxamic acid prepared in a known manner from the above i-Amino-6, 7-dichloroanthraquinones are concentrated in 30o parts of sulfuric acid dissolved at 5 to 10 °. This solution is left under at the same temperature Slowly stir 13 parts of nitric acid (65%) in 25 parts of concentrated sulfuric acid to drip. After stirring for a further 3 hours at obis5 °, it becomes cold in 500 parts Water discharged, sucked off and washed neutral. The filter cake is in iooo Parts of water and suspended after adding 3o parts of sodium carbonate for 2 hours Stirred at 9o to 95 °, filtered off with suction while hot, washed neutral and dried. Made of anisole or recrystallized nitrobenzene; i-amino-4-nitro-6,7-dichloroanthraquinone is obtained in red needles. 135 parts of i-amino-4-nitro-6, 7-dichloroanthraquinone and 90 parts Benzoyl chloride in 840 parts of dry nitrobenzene for 3 hours at 135 to 14o ° stirred. The benzoylamino body falls in greenish yellow crystals when it cools the end. I-Benzoylamino-4-amino-6 is obtained by reduction according to the usual methods, 7-dichloroanthraquinone as a purple powder, which is in concentrated sulfuric acid dissolves with red-violet paint. i-Benzoylamino-4-amino-6, 7-dichloroanthraquinone can also prepared by monobenzoylation of i, 4-diamino-6, 7 = dichloroanthraquinone will.

Example 2 28 parts of benzoic acid-4-sulfonic acid dimethylamide are used in Suspended 72o parts of dry nitrobenzene and after adding 20 parts of thionyl chloride and 0.1 parts of pyridine were stirred for 1/2 hours at 90 to 100 °. Then add 4o Part i-benzoylamino-4-amino-6, 7-dichloroanthraquinone and stir more 2 hours at 125 to i30 °. The dye that precipitates in red crystals when it cools is filtered off with suction, washed with nitrobenzene and hot alcohol and dried. He dissolves in concentrated sulfuric acid with a blue-red color and dyes cotton from olive-colored vat in pure, genuine, blue-red tones. Example 3 15 parts of benzoic acid-3-sulfonic acid morpholide are suspended in 32o parts of dry nitrobenzene and after adding 8 parts Thionyl chloride stirred for 1/2 hours at 90 to 100 °. Then add 2o.5 parts i-Benzoylamino-4-amino-6, 7-dichloroanthraquinone is added and the mixture is stirred for a further 2 hours at 125 to i30 °. The dye, which precipitates in red crystals on cooling, becomes suctioned off, washed with nitrobenzene and hot alcohol and dried. He solves in concentrated sulfuric acid with a blue-red color and stains cotton olive-colored vat in blue-tinged real pink tones. Example 4 18 parts of benzoic acid-4-sulfonic acid dimethylamide are suspended in 35o parts of dry nitrobenzene and after adding 12 parts Thionyl chloride and 0.1 part of pyridine were stirred for 1/2 hour at 100 to 100 °. On that 33 parts of i- (4'-chlorobenzoylamino) -4-amino-6,7-dichloroanthraquinone are added and stir for a further 2 hours at 125 to 130 °. The one when it cools in red crystals precipitating dye is filtered off with suction, washed with nitrobenzene and hot alcohol and dried. It dissolves in concentrated sulfuric acid with a blue-red color and dyes cotton. olive green vat in real red tones.

i- (4'-Chloro-benzoylamino) -4-amino-6, 7-dichloroanthraquinone can according to the method given in Example i from 4-chloro-benzoyl chloride and i-Amiho-4-nitro-6, 7-dichloroanthraquinone can be produced. Example 5 14.8 parts of benzoic acid-4-sulfonic acid piperidide are suspended in 32o parts of dry nitrobenzene and after adding 8 parts Thionyl chloride stirred for 1/2 hours at 90 to 100 °. Then add 2o.5 parts i-Benzoylamino-4-amino-6, 7-dichloroanthraquinone is added and the mixture is stirred for a further 2 hours at 125 to i30 °. The dye, which precipitates in red crystals on cooling, becomes suctioned off, washed with nitrobenzene and hot alcohol and dried. He solves in concentrated sulfuric acid with a blue-red color and stains cotton olive-green vat in bluish pink tones.

When using benzoic acid-3-sulfonic acid piperidide one obtains one similar dye, but which stains noticeably weaker.

Claims (1)

PATENT CLAIM: Modification of the process for the production of vat dyes na-eh Patent 836, o66, characterized in that i-benzoylamino-4-amino-6, 7-dichloroanthraquinones are reacted with benzoylating agents to give i- and 4-position benzoylated products and choosing the starting materials so that one of the benzoyl radicals is substituted by a sulfonic acid dialkylamide group which is expediently located in the m- or p-position to the - CO group. References considered: U.S. Patents Nos. 2,5o6,024, 7,5o6,025.