DEI0008263MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration day: February 11, 1954 Announced on November 22, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 22b GROUP 309 INTERNAT / CLASS C 09b

18263 IVb / 22b

Harold Thompson Howard, Francis Irving and Alistair Livingston, Blackley, Manchester, Lancashire (Great Britain)

have been named as inventors

Imperial Chemical Industries Limited, London

Representative: Dipl.-Ing. A. Bohr, Dr.-Ing. H. Fincke and Dipl.-Ing. H. Bohr, patent attorneys, Berlin-Lichterfelde West, Freiwaldauer Weg 28

Process for the production of vat dyes

.-, A \ The priority of registrations in Great Britain from 1.1. February 1963 and January 27, 1964

is used, ·> '"Vv ^ ■ / ■ *"

The invention relates to a process for the production of new vat dyes.

British Patent 339,396 states that that 9-, 11- or 14-aminobenzanthrone anthraquinone acridines by acylation with, for example, acetyl or benzoyl chlorides or the corresponding Anhydrides can be converted into olive-colored vat dyes. It was now found that if ii-aminobenzanthrone anthraquinone acridine and 3,11 -diaminobenzanthronic ic anthraquinone acridine with an acylating derivative of i-aminoanthraquinone-2-carboxylic acid (or with one of the corresponding 1-chloro- or i-nitroanthraquinone-2-carboxylic acids) is treated and the ι-chlorine or nitro group then by a 1; Amino group is replaced, valuable dark brown vat dyes are obtained with those in strong tones and the in-

609 708/323

18263 IVb / 22b

follow their stability at high vat temperatures for the modern continuous ones. Dyeing process are particularly useful.

The new vat dye © according to deirErfoidurig have the following formula:

O NH,

- CO - NH

wherein X is hydrogen or a 2'-aminoa, n-thraquinone-2-carboxylamino radical ,designated.

That used in the present specification for the benzanthronanithraquinone acridine ring The numbering system corresponds to that of P.atter-: 3o son and Capell in the book "The Ring Index", Verlag Reinhold Publishing Corporation, 1940, p. 571, no. 388.8.

According to another feature of the invention

a process for the preparation of new vat dyes is proposed, which is characterized in that ii-amino or 3, 11-diaminobenzanthr.onanihraehinonacridin, with a halide of i-aminoanthraquinone-2-carboxylic acid or with a halide of i-nitro or i-Chloranthrachino ⁱ n-2-carboxylic acid treated and then the nitro or chloro group is replaced by an amino group.

This acylation is preferably 'carried out such that the reactants are combined iti a suitable diluent, such as o-dichlorobenzene or nitrobenzene, heated.

If for acylation i-nitroanthraehinone-2-carboxylic acid halide is used, the reduction to the amino group can be done during the vat process, but is done preferably the reduction before the vatting process, for example by adding the nitrate compound treated with ammonia or a commonly used reducing agent will.

That used in the method according to the invention .1 i-Amino- or 3., .i: i-Di.aminobenzanthronanthraquinonacridine can be obtained by condensing equimolecular amounts of 3-B.rDmbenzanthr © n or 9-nitro'-3-bromobenzanthrone.mi.t 1,5-diaminoantbrachinone or a 5-acylamino-i-aminoanthraquinone 'produced, with the possibility of

densationsprodukt is melted with potassium hydroxide in order to bring about Rkigsehluß ', -and then, if necessary, the acyl radical is hydrolyzed to remove ies -zn ,, and if necessary, the nitro group is reduced .to ¹ amino group.

The new manufactured according to the invention! Dyes dye - cellulose threads in brown tones, which build up very well, and the good fastness properties to the action of Own detergents and light. These dyes are the previously known brown vat dyes They are superior to the fact that they are compared to the conditions of vetting carried out in high teroperatureii are stable, making them particularly useful in modern continuous dyeing processes to be used for vat dyes,: hei. those with teHipersa-tures from about 85 to ioo ° is being worked.

It is known that vat dyes can be produced by acylating the starting compounds containing benzanthrone anthraquinone acridine radical and containing an NH ₂ group in the 11-position with ι-nitroanthraquinone-2-carboxylic acid chloride. Such dyes are described in German patents 650 229 and 650 230. The dyes produced according to the invention are superior to these known dyes in that respect that dyeings which are produced with the dyes according to the invention on white textile material do not rub off to the same extent as in the known ones. Dyes. the case is. It should also be stated that the dye according to Example 4 of German patent specification 65.0 230 cannot be regarded as a dark brown dye in the sense of the present invention.

In the following examples, some embodiments of the invention are given. The parts are parts by weight.

708/323

18263 IVb / 22b

Example ι

29 parts of 11 - aminobenzanthrone anthraquinone acridine in a very fine state of distribution and 24 parts of i-nitroanthraquinone-2-carboxylic acid chloride are introduced into 500 parts of o-dichlorobenzene. The mixture is stirred and slowly heated to 175 ° and then for so long at 175 to 180 ° stirred until no further evolution of hydrogen chloride occurs. The solid product will filtered off and entered into 500 parts of fresh o> -dichlorobenzene. The mixture is turned to 180 ° heated, and ammonia is passed through to replace the nitro group with an amino group substitute. The o-dichlorobenzene is removed by steam distillation and the dye is filtered off and dried.

The dye is a brownish black compound, which dissolves in concentrated sulfuric acid to a green solution and cellulose threads from a dull corinth colored alkaline hydrosulfite vat colors in tones which, depending on the amount of the dye used, of chocolate brown to brownish black.

Instead of the o-dichlorobenzene, which is used as a diluent for the reaction of the nitro compound with ammonia, an equal amount of nitrobenzene can also be used. Optionally, the nitro compound can be reduced to the amino compound in such a way that this in one. Is heated autoclave long with a 25 ° / o solution of ammonia in water at 125 ⁰ for 15 hours. .

The nitro compound can, if desired, be used as a vat dye, the ' Reduction to the amino compound takes place in the entanglement process itself.

Example 2

15 parts of 3, ii-diaminobenzanthronanthraehinonacridine in a very fine state of distribution and 24 parts of i-nitro- ^i- anthraquinone-2-carboxylic acid chloride are mixed with 500 parts of nitrobenzene and stirred at 150 to 160 ° until no more hydrogen chloride development takes place. The solid reaction product is isolated and the nitro group is replaced by an amino group in the manner described in Example 1. The resulting dye dyes cellulose fibers from chocolate brown to brownish black, depending on the amount of dye used. Tones.

The 3, 11-diaminobenzanthronanthraquinoniacridine used in the above example can be obtained by nitrating 3-bromobenzanthrone, the 3-bromo-9-nitrobenzanthrone thus obtained condensed with i-aminO'-s-benzoylaminoanthraquinone, the resulting condensation product melted with alcoholic potassium hydroxide, the melt product reduced with an alkaline solution of sodium hydrosulfite, the so 'obtained The solution is filtered, the filtrate is oxidized and the precipitated solid compound is filtered off.

Claims (1)

PATENT CLAIM: Process for the preparation of vat dyes of the formula O NH, CO - NH wherein X is hydrogen or a 2'-aminoanthraquinone-2-carboxylamino radical referred to, characterized in that 11-amino or 3, 11 - Diaminobenzanthrone anthraquinone acridine with a halide of an i-aminoanthraquinone-2-carboxylic acid or with a halide of 'ι-nitro or i-chloroanthraquinone-2-carboxylic acid treated and then replaced the nitro or chlorine group with an amino group will. Considered publications:
German patent specifications No. 650 229, 650 230. 708/323 11:56