DE1159456B - Process for the preparation of anthrapyrimidines - Google Patents

Description

Process for the preparation of anthrapyrimidines Various processes for the preparation of anthrapyrimidines are known from the literature, for example from German patent specification 220 314 a process in which α-aminoanthraquinones are reacted with carboxamides. However, high temperatures are required and the - produced predominantly in molten phenol as a solvent - as little compounds are pure, that they must be purified by recrystallization.

In the German patent 573 556 a process for the preparation of 1,9-anthrapyrimidines is explained in which heteronuclear amidated anthraquinones containing at least one amino group in a-position with amides of monocarboxylic acids or heteronuclear amino-acylaminoanthraquinones with ammonia or its salts treated and cleaves off any remaining acyl groups in the reaction products obtained. The practice of this process requires higher temperatures and the use of special diluents such as phenol and its homologues, and in most cases the use of catalysts such as boric acid, boric anhydride, anhydrous oxalic acid, anhydrous copper sulfate, ammonium vanadate, sodium vanadate, ammonium molybdate, copper chloride, metal oxides , e.g. B. copper oxide, vanadium tri- or pentoxide, or metals, e.g. B. copper, and in the case of the reaction with ammonia, the use of increased pressure.

By the process of German patent 566 474 is obtained anthrapyrimidines substituted in the 2-position by treating being suitable solvent a-aminoanthraquinones or their nuclear substitution products and derivatives with Carbonsäurealkylimidhalogeniden in the presence or waste. Formalkylimide halides and other aliphatic carboxylic acid alkylimide halides required as starting materials for this process are not known, so that anthrapyrimidines which are unsubstituted in the pyrimidine ring or substituted by alkyl radicals cannot be obtained in this way.

Finally, in German patent specification 711775, a process for the preparation of anthrapyrimidines is described in which ammonia and aldehydes or aldehyde-releasing agents are allowed to act on α-aminoanthraquinones, which may contain fused rings and substituents, or on o-aminoalkyl ketone or aryl ketone anthraquinones. The practical implementation of this Ver process requires higher temperatures and, moreover, usually the use of oxidizing agents such. B. of nitro compounds or their sulfonic acids, arsenic acid, copper salts or ammonium vanadate.

All of these processes can lead to the formation of undesirable by-products cannot be prevented at the required high temperatures. It was therefore important a generally applicable process for the production of pure anthrapyrimidines, which may have a low molecular weight alkyl group on the pyridine ring, that the production of these compounds in good yields already with ordinary to moderately elevated temperature in a simple manner without the use of additives enables.

It has now been found that anthrapyrimidines which have a hydrogen atom or a low molecular weight alkyl group in the 2-position of the pyrimidine ring and optionally further substituents on the benzene rings are advantageously obtained when N, N-dialkyl-N'-anthraquinonylcarboxamidinium halides of the general formula allows ammonium salts of weak acids to act in the presence of organic agents capable of dissolving salts of nitrogenous bases.

In this formula, Hale denotes a halogen ion, R and Ri low molecular weight alkyl groups, expediently methyl or ethyl groups, R2 denotes a hydrogen atom or a low molecular weight alkyl group, such as a methyl or ethyl group, R3 denotes a hydrogen atom, a low molecular weight alkyl group or an optionally substituted N- Aryl carboxamide radical, e.g. B. a halogen atom-bearing N-phenylcarboxamide radical, R4 is a hydrogen or halogen atom, z. B. a chlorine or bromine atom, an alkoxy group, e.g. B. a low molecular weight alkoxy group, such as a methoxy or ethoxy group, or an aliphatic or aromatic acylamino group, as carboxylic acid radicals in the acylamino groups are preferably low molecular weight aliphatic acyl radicals, such as the acetyl or propionyl radical, or optionally substituted acyl radicals of benzene carboxylic acids or the benzoyl radical Acyl radicals of halogenated benzoic acids, such as the o- or p-chlorobenzoyl radical, are suitable. In the formula given, R5 stands for a hydrogen atom, for a group of the general formula where R, R, and R2 have the meaning given above, or for an aliphatic or aromatic acylamino group.

If N, N-dialkyl-N'-anthraquinonyl-carboxamidinium halides are used as starting materials, in which R5 denotes a hydrogen atom or an aliphatic or aromatic acylamino group, the process according to the invention proceeds according to the following equation when using ammonium acetate: In the formulas, R, Ri, R2, R3, R4 and Hale have the meanings given above.

The corresponding anthradipyrimidines, for example 1,9,5,10-anthradipyrimidine, are obtained from N, N-dialkyl-N-anthraquinonyl-carboxylic acid amidinium halides, in which R5 denotes an N, N-dialkylamidinium halide radical, e.g. The serving for the method according to the invention as starting materials in N, N-dialkyl-N'-anthraquinonyl-carbonsäureamidiniumhalogenide, for example chlorides or bromides may be prepared from aminoanthraquinones and the N available from N, 9-dialkylcarboxylamides and halogenating agents, N - slightly Dialkylcarbonsäureamidhalogeniden manufacture, e.g. B. the N, N-dimethyl-N '- [anthraquinonyl- (1)] - formamidinium chloride in the manner known from Example 14 of Belgian patent 540 870 by reacting 1-aminoanthraquinone with dimethylformamide and thionyl chloride.

As an organic, capable of dissolving salts of nitrogenous bases Means are, for example, low molecular weight mono- or bifunctional alcohols and their half ethers, such as methanol, ethanol or glycol monomethyl ether or lactams, such as N-methylpyrrolidone or mixtures thereof, called.

As ammonium salts of weak acids come z. B. the ammonium salts simple organic carboxylic acids, such as ammonium formate or ammonium acetate, in Consider and, provided that the new process does not involve a moderately elevated temperature is exceeded, also ammonium carbonate.

In most cases, the reaction takes place at an ordinary temperature between 10 and 30 ° C or at a moderately elevated temperature between 30 and 60 ° C and is generally carried out in a temperature range between 5 and 100 ° C. However, higher temperatures, e.g. B. up to 160'C, generally not harmful.

As a rule, the reaction has already ended after a short time, even at normal temperature in many cases within about 10 to 30 minutes, but in most cases within about 2 hours.

The new process can expediently be carried out with stoichiometric amounts of the starting materials, but to achieve short reaction times it is advantageous to use a large excess of ammonium salt, for example about 3 to 6 mol of monobasic acid ammonium salt or 1.5 to 3 mol of dibasic acid ammonium salt per 1 mol of carboxamidinium chloride.

Anthrapyrimidines are obtained in a particularly advantageous manner by the process according to the invention if one of N, N-dimethyl-N '- [anthraquinonyl- (1)] - formamidinium chloride, N, N-dimethyl-N' - [4-chloroanthraquinonyl- ( 1)] - forinamidinium chloride, N, N-dimethyl-N '- [5-benzoylaminoanthraquinonyl- (1)] - formamidinium chloride, N, N-dimethyl-N' - [4-benzoylaminoanthraquinonyl- (1)] - forrnamidinium chloride or N, N-dimethyl-N '- [4-methoxyanthraquinonyl- (1)] - formamidinium chloride and ammonium formate, ammonium acetate or ammonium carbonate is allowed to act at 10 to 30 ° C.

The process of the invention is expediently carried out in such a way that the N, N-dialkyl-N'-anthraquinonyl-carboxamidinium halides and the ammonium salts enters the solvent, the mixture at the desired temperature up to completed reaction stirs and then the separated reaction material with ordinary Temperature sucks, washes and dries.

One can proceed also necessary so that the ammonium salt of the mixture of N, N - 'N - - anthraquinonyl - carbonsäureamidiniumhalogenids added only with the solvent at the desired temperature dialkyl.

The inventive method has compared to the prior Technique known production methods have the advantage that the anthrapyrimidines at low temperature and within short conversion times in good to very good Can produce yield and purity. Another advantage is that doing so in open vessels and without the addition of catalytically active substances or oxidizing agents can be worked.

The anthrapyrimidines obtainable according to the invention are as intermediates can be used for the production of dyes, some of them already are Dyes with good fastness properties.

The parts given in the examples are parts by weight. EXAMPLE 1 7.8 parts of N, N-dimethyl-N '- [anthraquinonyl- (1)] - formamidinium chloride and 7.8 parts of ammonium acetate are added to 100 parts of glycol monomethyl ether, and the mixture is then stirred at 20 ° C. for 30 minutes. The reaction material is filtered off with suction, washed with methanol and dried. There are 5.2 parts of the compound of formula obtained in the form of pale yellow crystals with a melting point of 232 to 237'C.

The above-mentioned compound can also be prepared by introducing 15.7 parts of N, N-dimethyl-N'- [anthraquinonyl- (1)] -formamidinium chloride and 14.4 parts of ammonium carbonate into 300 parts of methanol and then introducing the reaction mixture for 30 minutes stirs at 20'C for a long time. After the work-up described in the first paragraph, 10.6 parts of 1,9-anthrapyrimidine are obtained in the form of pale yellow crystals with a melting point of 235 to 237.degree. Example 2 15 parts of bis-N, N-dimethylformamidinium chloride from 1,5-diaminoanthraquinone and 15 parts of ammonium acetate are stirred in 100 parts of glycol monomethyl ether at 50 ° C. for 2 hours. The reaction mixture is allowed to cool, the reaction material which has crystallized out is filtered off with suction, washed with methanol and dried. 8 parts of the compound of the formula are obtained in the form of flat greenish yellow prisms that decompose at temperatures above 340 ° C. Example 3 in 100 parts of glycol monomethyl ether wears 7.3 parts of N, N-dimethyl-N '- [2-methylanthrachinonyl- (1)] - formamidine and 5.8 parts of ammonium acetate and the mixture is stirred then for 30 minutes at 100'C . After cooling, the reaction material is filtered off with suction, washed with methanol and dried. 5.7 parts of the compound of the formula are obtained in the form of somewhat brownish crystals with a melting point of 215 to 218 ° C.

One obtains the above identified compound in the same yield and purity when the reaction mixture is stirred for 30 minutes at 50'C instead of 30 minutes at 100'C.

Example 4 12.4 parts of N, N-dimethyl-N '- [4-chloroanthraquinolyl- (1)] - formamidinium chloride and 10.3 parts of ammonium carbonate are stirred in 600 parts of methanol at 20 ° C. for 30 minutes. The reaction mixture is then filtered off with suction, washed with methanol and dried. 8.1 parts of the compound of the formula are obtained in the form of a pale yellow crystal powder with a melting point of 188 to 189 ° C.

EXAMPLE 5 21.7 parts of N, N-dimethyl - N '- [5 - benzoylaminoanthraquinonyl - (I) lformamidinium chloride and 9.5 parts of ammonium formate are added to 520 parts of ethanol, and the mixture is then stirred at 20 ° C. for 1 hour. The reaction material is filtered off with suction, washed with methanol and water and dried. There are 16.9 parts of the compound of the formula obtained in the form of an orange-colored crystal powder with a melting point of 270 to 273'C. This dye dyes cotton from a dark red vat in golden yellow tones with good wet fastness properties.

The above-mentioned dye can also be prepared by 21,7Teile N, N-dimethyl-N '- [5-benzoylaminoanthrachinonyl- (1)] - formamidiniumehlorid and 7.8 parts of ammonium acetate in 21 parts Glykohnonomethyläther 0 for 10 minutes at 85' C stirs. After cooling the mixture to room temperature and working up as described in the first paragraph, 17.1 parts of 5-benzoylamino-1,9-anthrapyrimidine are obtained.

Example 6 A mixture of 10.8 parts of N, N-dimethyl-N '- [4-benzoylaminoanthraquinonyl- (1)] - formamidinium chloride, 7.2 parts of ammonium carbonate and 400 parts of methanol is stirred for 30 minutes at 20 ° C. The reaction material is then suctioned off, washed with methanol and dried. 8.1 parts of the compound of the formula are obtained in the form of a greenish yellow crystal powder with a melting point of 252 to 254'C. This dye dyes cotton from a dark red vat in greenish yellow shades with good wet fastness properties.

If only 4.8 parts of ammonium carbonate are used instead of 7.2 parts of ammonium carbonate, twice the time is required for the reaction. 8.3 parts of the dye indicated by the above formula are obtained in this way.

4-Benzoylamino-1,9-anthrapyrimidine can also be prepared by adding to a mixture of 23 parts of N, N-diethyl-N '- [4-benzoylaminoanthraquinonyl- (1)] - formamidinium chloride and 250 parts of glycol monomethyl ether at 85.degree 7.8 parts of ammonium acetate are introduced and the mixture is then stirred at 85 ° C. for 30 minutes. After cooling, it is worked up as described in the first paragraph and 15.7 parts of the dye are obtained in the form of a yellow crystal powder with a melting point of 256 to 2580.degree.

EXAMPLE 7 20 parts of N, N-dimethyl-N'- [4- (4-chlorobenzoylamino) anthraquinonyl- (1)] formamidinium chloride and 20 parts of ammonium acetate are added to 200 parts of N-methylpyrrolidone, and the mixture is added at 40 ° C. for 2 hours touched. The mixture is then heated to 150 ° C. and allowed to cool. The reaction product which has crystallized out is filtered off with suction, washed with a little N-methylpyrrolidone and then with methanol and dried. 12.5 parts of the compound of the formula are obtained in the form of greenish yellow crystals. This dye dyes cotton from a dark red vat in yellowish green tones with good wet fastness properties.

Example 8 25 parts of N, N-dimethyl-N '- [2- (3-chloroanihnocarboxy) -anthraquinonyl- (1)] - forinamidinium chloride and 20 parts of ammonium acetate are introduced into 500 parts of glycol monomethyl ether; the mixture is stirred at 90 ° C. for 30 minutes. After cooling, the reaction material is filtered off with suction, washed with methanol and dried. 18 parts of the compound of the formula are obtained in the form of a yellowish crystal powder with a melting point of 264'C.

The above-mentioned compound is obtained in the same yield and purity if the reaction mixture is stirred for 1 hour at 60.degree. C. instead of 30 minutes at 90.degree .

Example 9 32 parts of N, N-dimethyl-N '- [anthraquinonyl- (1)] - acetamidinium chlorine and 30 parts of ammonium carbonate are introduced into 500 parts of methanol, and the mixture is stirred at 60 ° C. for 90 minutes. The mixture is allowed to cool, the reaction material is filtered off with suction, washed with methanol and dried. There are 22 parts of the compound of formula obtained in the form of yellowish crystals with a melting point of 201 to 203.degree . Example 10 A mixture of 17.2 parts of N, N-dimethyl-N '- [4-methoxyanthraquinonyl- (1)] - forinamidinium chloride and 14.5 parts of ammonium carbonate in 500 parts of methanol is stirred for 30 minutes at 20 ° C. The reaction material is filtered off with suction, washed with methanol and dried. It will be 11.9 parts of the compound of the formula obtained in the form of a yellow crystal powder with a melting point of 225'C.

Claims (1)

PATENT CLAIM process for manufacturing. of anthrapyrimidines which have a hydrogen atom or a low molecular weight alkyl group in the 2-position of the pyrimidine ring and optionally further substituents on the benzene rings, characterized in that N, N-dialkyl-N'-anthraquinonyl-carboxamidinium halides of the general formula in the Hal'9 a halogen ion, R and R, low molecular weight alkyl radicals, R2 a hydrogen atom or a low molecular weight alkyl radical, R3 a hydrogen atom, a low molecular weight alkyl radical or an optionally substituted N-arylcarboxamide radical, R4 a hydrogen or halogen atom, an alkoxy group or an aliphatic or aromatic acylamino group and R5 a hydrogen atom, a group of the general formula where R, R, and R2 have the meaning given above or are an aliphatic or aromatic acylamino group, in the presence of organic agents capable of dissolving salts of nitrogenous bases allowing ammonium salts of weak acids to act. Considered publications: German Patent Nos. 220 314, 566 474, 573 556, 711775.