DE597341C - Process for the preparation of 1íñ9-anthrapyrimidines - Google Patents

Description

Process for the preparation of 1-9-anthrapyrimidines It has been found that i - 9-anthrapyrimidines can be obtained in an extremely simple manner and with good yields can be obtained if a-aminoanthraquinone or its derivatives or: their leuco compounds, which do not contain amino groups in different rings at the same time, in the presence of catalysts with amides of monocarboxylic acids, e.g. B. Formamide, Acetami.d, Propionamide, benzamide, etc., converts.

Suitable catalysts are, for. B. metals such as copper, oxides or Salts of metals such as vanadium tri- and pentoxide, copper oxide, copper sulfate, vanadates, Molybdates and tungstates, as well as borates, boric acid and oxalic acid. -So gives a-aminoanthraquinone with formamide in nitrobenzene in the presence of a few percent vanadium trioxide a reaction temperature of 180 to r85 ° in a short time in an almost quantitative manner Yield of i-9-anthrapyrimidine. i-Aminoq.-p-chlorobenzoylaminoanthraquinone or i-amino-4-benzoylaminoanthraquinone go when heated with formamide in nitrobenzene in the presence of ammonium vanadate smoothly into the corresponding anthrapyrimidine derivatives. z -4-diaminoanthraquinone supplies with formamide when heated in nitrobenzene, trichlorobenzene or anisole Addition of ammonium vanadate quickly and in good yield of 4-amino-i-9-anthrapyrimidine or i - 9 - q. - io-anthrapyrimidine.

The anthrapyrimidines obtained can, if necessary, according to the usual Methods, e.g. B. by crystallization, sublimation, possibly under reduced pressure, Boiling, separating out as salts, e.g. B. as sulfates, purified or from isologues and isomers are separated.

The anthrapyrimidines come partly as dyes, partly as intermediates for the production of such in question.

The present process offers prior to the manufacture of anthrapyrimidines already proposed processes from α-aminoanthraquinones and amides monobasic Carboxylic acids have the great advantage that the anthrapyrimidines are much better Yield arise, with such a-aminoanthraquinones, which according to the known Procedure do not give anthrapyrimidines, can be converted into anthrapyrimidines. So you get z. B. in the known method from i -q.-diaminoanthraquinone and Formamide only then q.-Amino-i - 9-anthrapyrimidine in reasonably useful yields, when using phenol as a diluent. If the phenol is replaced by nitrobenzene, Chlorobenzene or other diluents commonly used in anthraquinone chemistry, see above are the yields are very poor; often occurs practically at all no implementation one. According to the present invention, however, one obtains z. B. off i - 4-Diaminoanthraquinone and formamide in the presence of a catalyst also in nitrobenzene the 4-amino-9-anthrapyrimidine or the 1-9-4-io-anthradipyrimidine in almost quantitative Yield. Also Leuko-i - 4-diaminoanthraquinone, the z. B. with formamide itself in In the presence of phenol, practically no significant amounts of 4-ainino-i-9-anthrapyrimidine supplies, gives in the condensation with formamide in nitrobenzene in the presence of a 4-Amino-i-9-anthrapyrimidine catalyst in very good yield. v.-aminoanthraquinone supplies according to the known process only under very severe reaction conditions i - 9-Anthrapyrimidine in very poor yields - but if you work according to the present invention in the presence of catalysts, one obtains in a short time Time and in theoretical yield i # 9-anthrapyrimidine. Example i 50 parts of α-aminoanthraquinone are in a mixture of 100 parts formamide and 100 parts nitrobenzene Addition of 5 parts of ammonium vanadate heated to i8o to i.9o ° until a Sample dissolved in concentrated sulfuric acid for the addition of formaldehyde does not Color change shows more. After cooling down, you suck. off, washes with alcohol and hot water and dry. The reaction product obtained in almost quantitative yield, the i - 9-anthrapyrimidine, is a brownish crystallized powder that dissolves in concentrated sulfuric acid with a yellow color, due to the addition of formaldehyde not turns over Instead of ammonium vanadate one can also use vanadium trioxide or Use vanadium pentoxide.

Example e zoo parts i -4-diaminoanthraquinone are divided into 400 parts Nitrobenzene after adding 40o parts of formamide and 10 parts of ammonium vanadate Stir until heated to 170 ° until a sample is spread on a pottery shard is, no longer shows a violet run, which is generally already after i1 / 2 bis 2 hours is the case. Then let it cool down and suck it up in the form of coarse needles obtained 4-amino-i - 9-anthrapyrimidine from. The yield is over 90% Theory.

The reaction can also take place at a higher temperature, e.g. B. at 185 °, or at low temperature, e.g. B. at 14o °, with appropriate shortening or lengthening the reaction time can be carried out.

With prolonged heating to temperatures of 17o to 185 ° one obtains 1-9-4-io-anthradipyrimidine.

Instead of nitrobenzene, trichlorobenzene or anisole can be used as Use thinner.

i - 4-Diamino-2-methylantlirachinon delivers in an analogous manner 4-amino-2-methylz-9-anthrapyrimi, din; from i-amino-4-chloro-2-methylanthraquinone can. 2-Methyl-4-chloro-1-9-anthrapyrimidine is obtained in this way.

Example 3 100 parts of i-amino-4-benzoylaminoanthraquinone are used in Zoo parts nitrobenzene after adding Zoo parts acetamide and 10 parts ammonium vanadate cooked until the reaction mixture has turned orange. Then let it cool down and works up in the usual way. The reaction product obtained crystallizes in needles and delivers a purple vat, from the cotton in orange, very real Tones is colored. Example 4 100 parts of leuco-1-4-diaminoanthracllinone in zoo parts nitrobenzene after adding 10 parts ammoniuinvana.dat and zoo parts Formamide is heated to 170 ° with thorough stirring until one is removed and worked up Sample of the reaction product melts towards 27o °. Then you let it cool down and work in the usual way. The 4-amino-i-9-anthrapyrimidine obtained agrees yours obtained according to example e match.

Claims (1)

PATENT CLAIM Process for the preparation of i-9-anthrapyrimidines from u.-Alninoanthraquinone or its derivatives or their leuco compounds, the do not contain amino groups in different rings at the same time, and amides of monobasic Carboxylic acids, characterized in that in the presence of catalysts, e.g. B. metals, their salts or oxides, and the usual high-boiling diluents is working.