DE620345C - Process for the preparation of substitution products of anthrones - Google Patents

Description

Process for the preparation of substitution products of anthrones It has been found that valuable substitution products of anthrones are obtained, if one looks at leuco compounds of anthrones with attached heterocyclic Ring in z - 9 position in an alkaline medium aldehydes or aldehyde-releasing substances can act. As starting materials come z. B. in question: the leuco compounds of r # 9-anthrapyrimidine and its derivatives, such as halogen, nitro, amino, oxy, Acylaminoanthrapyrimidines, etc., also the leuco compounds of r - 9-anthrapyrimidone and its derivatives, e.g. B. ¢ - or 5-amino-N-methylanthrapyrimidone, the t # 9-pyridinoanthrones, etc. The aldehydes can be aliphatic, aromatic or heterocyclic Belong series, suitable aldehydes are z. B. formaldehyde, paraformaldehyde, benzaldehyde, Furfural etc. As aldehyde-releasing substances come z. B. bisulfite or hydrosulfite compounds of aldehydes in question.

The reaction can be carried out in such a way that one on the mentioned leuco compounds in aqueous solution or suspension aldehydes or aldehydes Allowing releasing substances to act at normal or moderately elevated temperatures. There is a particularly advantageous embodiment of the present method in that you put the aldehyde, etc. in an alkaline vat of the anthrone derivative in question enters with stirring. The implementation starts immediately, which is often due to the failure a precipitate can be seen from the previously clear vat. After finished The reaction is filtered off with suction from the reaction product which has precipitated out. Unless it is should precipitate without further ado, air or air is passed through the reaction mixture an oxidizing agent is added to the reaction mixture. Sometimes it can also be necessary be, for the purpose of complete separation of the reaction product, the filtrate still to heat.

The reaction products are usually obtained in very good yields and are in part homologues of the starting materials, e.g. B. in the case of use of formaldehyde methyl derivatives and of benzaldehyde benzyl derivatives. With some anthrone derivatives, z. B. in the case of the amino-z-9-anthrapyrimidines, condensation may occur under certain circumstances higher molecular weight compounds take place.

The reaction products are e.g. T. dyes, some are intermediates for the production of dyes. They can be cleaned by the usual methods be e.g. B. by crystallization, sublimation or via their salts with strong Acids such as sulfuric acid. Example i Add to a vat (manufactured from 10 parts of finely divided i # 9-althrapyrimidine, 100 parts of water, 44 parts 48% sodium hydroxide solution and 24 parts of sodium hydrosulfite) with stirring and passing over of nitrogen g parts of a 3oo% aqueous formaldehyde solution, leaves about 2 hours stand at 400-, then sucks off the precipitated small precipitate and passes air through the filtrate. After suctioning off and washing the precipitate about 10 parts of a brownish reaction product are obtained, which after recrystallization is obtained from chlorobenzene or glacial acetic acid in the form of brownish needles, which at Melting 217 °: The reaction product is in concentrated sulfuric acid with yellow Color, soluble in organic solvents with a yellow-red color. According to the analysis it is a methyl derivative of i # 9-anthrapyrimidine. By fusing with Alcoholic Käli is used to produce a vat dye, the cotton from red The vat is colored in yellow tones.

In the above example, 6 parts are used instead of formaldehyde Benzaldehyde and held for about 2 hours at 50 to 60, one obtains after filtering and bubbling air through the filtrate, suction and washing with water a light brown reaction product, which after recrystallization, for. B. from trichlorobenzene, in the form of orange diamond-shaped leaflets with a melting point 1 & 5 ° is obtained. It is in concentrated sulfuric acid with a yellow color soluble and the analysis according to a benzyl-i # 9-anthrapyrdmidine. Examples io parts Distributed S-amino-i # 9-anthrapyrimidine are suspended in 100 parts of water; Then, with stirring and passing over nitrogen, -4o parts of 48% sodium hydroxide solution are added and 23 parts of sodium hydrosulfite. As soon as full mating has occurred, - 9 parts of a 300% aqueous formaldehyde solution are introduced and hold about For 2 hours at 3o to 4o °. The precipitate which has separated out is then suctioned off off, washes neutral and dries. From 'the filtrate can be by introducing Air gain further amounts of the reaction product.

The reaction product is a red powder that melts above 360 ° and is soluble in concentrated sulfuric acid with yellow color, which on addition changes from formaldehyde to green. When diluted with water, the sulfuric acid gives Solution a red-violet sulfate. The vegetable fiber turns from red vat into red Tones stained.

If 5-amino-Py-C-methylz is used instead of 5-amino-i # 9-anthrapyrimidine - 9-anthrapyrimidine, a red colored reaction product is also obtained. Example 3 For one of 10 parts of 5-benzoylaminoi-9-anthrapyrimidine, 100 parts Water, 3o parts of 48% sodium hydroxide solution and 16 parts of sodium hydrosulfite 6.4 parts of a 3oo / oigen vat are added while stirring and passing nitrogen over them aqueous formaldehyde solution. After two to three hours of stirring at 3o to 4o ° it is suctioned off and a brownish yellow powder is obtained, which is crystallized by recrystallization obtained from trichlorobenzene in golden yellow needles with a melting point of 26o to 262 ° can be. Passing air into the filtrate gives further amounts of the Reaction product. It dyes cotton from a red vat in good yellow tones Authenticity. When saponified with concentrated sulfuric acid, sparkling ones are obtained red needles - melting point 253 to 25q. °. 'If you use - instead of 5-Benzoylamino-i - 9-anthrapyrimidine the equivalent amount of 4- (p-chlorobenzoylamino) -i - 9-anthrapyrimidine, a yellow dye is obtained, which at 28o to 2.82 ° melts and cotton in less greenish yellow tones than the starting material colors.

Example l4.

5 parts of 5-amino-N-methylanthrapyrimidone are with. 500 parts of water, 18 parts of 48% sodium hydroxide solution and 10 parts of sodium hydrosulphite with the exclusion of air condensed. 12 parts are added to the vat while stirring and passing nitrogen over it a 10% formaldehyde solution at a temperature of 3o to -40.degree. After short Time begins the deposition of a precipitate, which after two hours of stirring is suctioned off and washed at 3o to 40 °. The reaction product obtained is a dark red powder that melts above 360 ° in concentrated sulfuric acid dissolves with a golden yellow color, which turns blue when formaldehyde is added; at the Dilution of the sulfuric acid solution with water produces a purple-red precipitate. Cotton is dyed in burgundy tones from a red vat. Treated one in the same way the q.-amino-N-methylauthrapyrimidone with formaldehyde, this gives matleine a dark red compound that dyes acetate silk in pink tones. example 100 parts of finely divided Bz3-azabenzanthrone are suspended in 100 parts of water. 45o parts of 50% sodium hydroxide solution and 24o parts of sodium hydrosulfite are added to this suspension and heated to 65 to 70 ° while passing in nitrogen. At this temperature zoo parts of an aqueous 20% formaldehyde solution are allowed to flow in and heated 3 hours after addition. After cooling, you vacuum off. The main part of the reaction product remains there, the remainder can be removed from the filtrate by introducing air be precipitated. The methyl Bz 3-azabenzanthrone obtained in this way melts at 2o8 up to 2o9 °, represents pale yellow needles, which are in concentrated sulfuric acid solve with yellow paint; the yield is almost quantitative. Example 6 50 parts C-methyl-i - 9-pyridinoanthrone are mixed with 40oo parts of water, 220 parts of 48% Sodium hydroxide solution and i2o parts of sodium hydrosulfite vat at 50 °. Then be under Stir and pass over 100 parts of 10% formaldehyde solution with nitrogen in the course of the process added half an hour. Nice. during the lifetime of the formaldehyde solution the precipitation of a crystalline precipitate begins. After about 6 hours the resulting precipitate is filtered off, washed neutral and recrystallized, z. B. from glacial acetic acid, in the form of yellowish needles with a melting point of 245 to 2q. 6 ° received. Another part of the reaction product is obtained from the filtrate by introducing air and sucking off the precipitated precipitate. When acidifying of the last filtrate with hydrochloric acid, a precipitate separates out again however differs from the first two reaction products. Beigpie17 5o parts 8-Amino-i # 9-anthrapyrimidine are dissolved in a solution of 10 parts of sodium hydrosulfite vat in 4,000 parts of a 2.5% sodium hydroxide solution, whereupon the vat obtained at 45 to 50 ° 300 parts of 8.5% strength aqueous formaldehyde solution are added. Man then stirs while passing in nitrogen for about 2 hours and sucks the cooling off. A red-violet powder is obtained, which, if necessary, is carried out Recrystallization can be purified. By introducing air into the filtrate further amounts of the resulting compound can be obtained. The connection obtained dissolves in concentrated sulfuric acid with a yellow color, which, however, is much more intense than that of the 8-aminoi is # 9-anthrapyrimidine; with formaldehyde there is sulfuric acid Solution of the compound obtained a blue-green color, while 8-amino-i - 9-anthrapyrimidine gives a blue color under these conditions. The yellow-red vat becomes cotton strong red-violet colored, while the 8-aminoi - 9-anthrapyrimidine on cotton gives only faint reddish tints.

A connection with similar properties is obtained by doing this - by nitrating i -9-anthrapyrimidine with a nitric acid-sulfuric acid mixture available nitro-i - 9-anthrapyrimidine treated in the same way.

When treating a mixture of 6- and 7-amino-i - 9-enthrapyrimidine, as it is from the technical mixture of i - 6- and 1-7-diaminoanthraquinone through Exposure to formamide can be obtained in the manner indicated in paragraph i you get a purple-brown compound, the cotton from the red vat in strong colors in violet-brown tones, while the raw material on cotton is only weak provides brown-red colorations. Obtained from 5-chloro-i-9-anthrapyrimidine and formaldehyde one in their behavior of the starting material in the manner indicated in paragraph i different yellowish compound. Example 8 Add to a vat, prepared from 10 parts of 5-amino-oxy-1-9-anthrapyrimidine (obtained from 5-amino-1-9-anthrapyrimidine by treatment with sulfuric acid in the presence of boric acid at 180 to 200 °), 10000 Parts of 2% sodium hydroxide solution and 24 parts of sodium hydroxide, while passing in Nitrogen at 45 to 50 ° 100 parts of a 5% aqueous solution of formaldehyde and- holds at this temperature for 2 hours in the absence of air. Then oxidized by bubbling in air, the violet-red solution is acidified weakly and suctioned the separated compound. She is a purple powder that is sulphate about its or purified by recrystallization. Purple-brown crystals are obtained, which melt above 36o ° and dissolve in concentrated sulfuric acid with red-violet Color dissolve while the starting material is in concentrated sulfuric acid with-yellow-red colour solves. Cotton is dyed in brownish tones from a yellow-red vat.

Claims (1)

PATENT CLAIM: A process for the production of substitution products of anthrones, characterized in that leuco compounds of anthrones with a heterocyclic ring attached in the z # 9 position are allowed to act in an alkaline medium with aldehydes or aldehyde-releasing agents.