Patent GB-385295-A (GB)
Title: Process for the manufacture and production of products of the anthrapyrimidine series
IPC: C09B5/16
Filed: 1931-05-18
Abstract: Acylaminoanthrapyrimidines are prepared by the following methods:--(1) by acylation of aminoanthrapyrimidines: (2) by treating a -amino-acylaminoanthraquinones with amides of monobasic organic acids: (3) by condensing halogenanthrapyrimidines with acid amides: (4) by stabilizing acylaminoanthrapyrimidones in their enolic form by esterification: (5) by treating acylaminoanthraquinone-2 : 1 (N)-oxazoles with ammonia.  Reaction according to (1) and (3) is best carried out in an inert organic solvent or diluent, for example nitrobenzene, halogenbenzenes, nitro- and halogen derivatives of benzene and naphthalene, and at temperatures above 100 DEG  C.; catalysts such as copper, iron, their oxides, acetates or carbonates, and acid-binding agents such as pyridine, quinoline, tertiary organic bases (dimethylaniline), sodium and potassium carbonates, acetates or phosphates, may advantageously be added.  Reaction according to (2) may be carried out in the absence or presence of indifferent diluents such as phenol, nitrobenzene, trichlorbenzene, and agents accelerating the reaction such as anhydrous boric oxide, oxalic acid, potash, zinc chloride, copper and its salts, may be present. Reaction according to (4) is effected by treatment with agents capable of replacing an oxygen atom or a hydroxyl group by halogen, for example phosphorus tri- and pentachloride, tribromide, thionyl chloride, antimony and arsenic pentachloride, benzotrichloride or benzoyl chloride.  The products may be purified by usual methods and their dyeing shades may be varied by halogenation.  Halogenation may be carried out in organic or inorganic media such as nitrobenzene, chlorbenzene, sulphuric acid, chlorsulphonic acid, alkylsulphonic acids, or water, or in the absence of a diluent.  Halogen transferrers such as iodine, sulphur, iodinechloride, selenium, dimethylaniline, antimony, iron, iron chloride and aluminium chloride may be present.  These halogenated products are in part superior to the non-halogenated products in fastness to washing and chlorine. Starting materials for use in the above methods include halogen- and aminoanthrapyrimidines, a -amino-acylaminoanthraquinones (also a -amino-halogenanthraquinones, which are converted by the action of monobasic organic acid amides into acylaminoanthrapyrimidines directly), acylaminoanthraquinone-2 : 1 (N)-oxazoles and acylaminoanthrapyrimidones.  These may be further substituted by alkyl, aryl, acyl substituents, by fluorine, chlorine, bromine, iodine, nitro, hydroxy, alkoxy, aryloxy, amino, substituted amino, cyano, thiocyano, mercapto, substituted mercapto, or carboxylic acid (esterified or amidated) radicles, and such substituents, in particular the halogen, alkyl, aryl, aralkyl, amino, substituted amino, hydroxy, alkoxy, nitro and cyano radicles, may be attached to the Py-C-atom of the anthrapyrimidines.  The treatment of the appropriate 2.2<1>-dianthrapyrimidyls is also included.  In examples the following derivatives of 1.9-anthrapyrimidines are prepared by one or more of the above methods which are numerically indicated in brackets together with dyeing shades:--(A) 4-benzoylamino- (1, 2, 3, 4; green-yellow on wool and cotton), 4-p<1>-chlorbenzoylamino (1, 2; green-yellow), 4-amino acylated according to (1) by o- and p-chlorbenzoic, o- and m-toluic, p-brom-, p-iodo-, p-cyano- and p-fluorbenzoic, 2 : 4-, 2 : 5-, 2 : 3-, and 3 : 4-dichlorbenzoic, 2 : 4 : 5- and 3 : 4 : 5-trichlorbenzoic, m- and p-methoxybenzoic, p-ethoxybenzoic, m- and p-nitrobenzoic, m-nitro-p-toluic, b -naphthoic, bromo-a -naphthoic, cinnamic, acetic, acetic with p-chlorbenzoic, oxalic (\ba1/2\be mol.), isophthalic (\ba1/2\be mol.), terephthalic (\ba1/2\be mol.), salicylic, cresotinic, diphenylcarboxylic, diphenylmethane carboxylic, hexahydrobenzoic, diphenyl-4-carboxylic, 4<1>-bromo-, 4<1>-chloro-, 4<1>-ethyl-, 4<1>-nitro-, and 4<1>-benzoyl-diphenyl-4-carboxylic, dichlordiphenyl-4-carboxylic, diphenyl-p : p<1>-dicarboxylic (\ba1/2\be mol.), naphthalene-1 : 4- and -1 : 5-dicarboxylic (\ba1/2\be mols.), sebacic, adipic, stearic, pyroracemic, benzophenone-p.p<1>-dicarboxylic (\ba1/2\be mol.), diphenylether carboxylic, diphenylsulphide dicarboxylic (\ba1/2\be mol.), quinoline-6-carboxylic, anthraquinone 1- and 2-carboxylic, 1-aminoanthraquinone-2-carboxylic, 2-aminoanthraquinone-3-carboxylic, phosgene with 1-aminoanthraquinone (1 mol. each), 1<1>-anthraquinonylaminophenyl-4-carboxylic, anthrimido-carboxylic, benzanthrone-2-carboxylic, anthanthrone carboxylic, allo-ms-naphthodianthrone carboxylic, pyrazolanthrone-2-carboxylic and anthrapyrimidine carboxylic acids (mainly yellow, orange and brown shades); 4 - (dichloranthraquinone - 2 : 1 - benzacridone-3<1>-carboxyamino-) (2), 4-urethane (1), 4 : 4<1>-urea (1); the 4-p<1>-nitrobenzoylamino reduced and acylated with benzoic, p-chlorbenzoic, 2.5-dichlorbenzoic, oxalic, m-methoxybenzoic, anthraquinone-2-carboxylic, thiazolanthrone carboxylic, benzanthrone carboxylic, anthraquinone-acridone carboxylic, anthraquinonethioxanthone carboxylic and anthrapyrimidine-2-carboxylic acids (yellow shades): (B) 5-amino acylated according to (1) with o-, m-, and p-chlorbenzoic, 2.4- and 3 : 4-dichlorbenzoic, p-brom-, p-iodo-, p-methyl, and p-cyanobenzoic, b -naphthoic, diphenyl-4-carboxylic, acetic, phenacetic, anthraquinone-2-carboxylic, 1-chloranthraquinone-2-carboxylic, 1-aminoanthraquinone-2-carboxylic, isophthalic (\ba1/2\be mol.), terephthalic (\ba1/2\be mol.), a mixture of iso- and terephthalic, succinic (\ba1/2\be mol.), adipic (\ba1/2\be mol.), sebacic (\ba1/2\be mol.), diphenyl-p.p<1>-di carboxylic (\ba1/2\be mol.), and benzophenone-p.p<1>-dicarboxylic acids (\ba1/2\be mol.) (mainly yellow to orange shades); 5-benzoylamino (2; yellow), 5-(2<1> : 5<1>-dichlorbenzoylamino-) (1,2; greenish-yellow), 5-(6<1>benzanthraquinonoylamino-) (2), 5-(4<1>-bromdiphenyl-4<11>-carboxyamino-) (1, 2, orange; (C) 2-amino acylated according to (1) with benzoic, m-chlorbenzoic, 2.3-, 2 : 5-, and 3.4-dichlorbenzoic, trichlorbenzoic, halogentoluic, halogenterephthalic and anthraquinone-2-carboxylic acids (yellow shades): 3-p<1>-chlorbenzoylamino-(1; yellow); 6-p<1>-chlorbenzoylamino- (1; yellow); 7-benzoylamino (1; green-yellow), 7-benzene-, o<1>- or p<1>-toluene sulphonamido (1, 3; yellow); 8-benzoylamino (2; yellow): (D) 5-p<1>-chlorbenzoyl-N-methylamino (1; currant), 5-p<1>-chlorbenzoyl-N-ethylamino-(1), 5-p<1>-chlorbenzoyl-N-propylamino-(1); Py-C-p<1>-chlorbenzoylamino (1; yellow), Py-C-benzoylamino (3); benzoylamino - 4-amino- (3; yellow), benzoylamino-4-p<1>-chlorbenzoylamino (3 and 1; yellow), a b -methoxy-4-p<1>-chlorbenzoylamino (1; yellow), a b -bromo-4-p<1>-chlorbenzoylamino (1; yellow), 5.8-di-benzoylamino (2; rose-red), 5-(or 8-) nitro-4-benzoylamino (1; reddish-yellow), 4-p<1>-toluenesulphonamido-2-methyl (3; greenish-yellow), a bromo-5-(2<1> : 5<1>-dichlorbenzoylamino (1; yellow), a b -naphthoylamino-5-benzoylamino (1), a polychlor- 5 -p<1>-chlorbenzoylamino (1; orange), 4-benzoylamino-Py-C-(2<1> : 5<1>-dichlorbenzoylamino) (1; yellow), 4-(2<1> : 5<1>-dichlorbenzoylamino)-Py-C-benzoylamino (1 and 3), Py-C-amino-4-benzoylamino- (2, i.e. by using cyanamide or 1-amino-4-benzoylaminoanthraquinone), 2-benzoylamino-Py-C-phenyl (1), 2-b  - anthraquinonoylamino-Py-C - phenyl (1; green-yellow), 2- (a - and b -anthraquinonesulphonamido)-Py-C-phenyl (1; yellow), 2-b -anthraquinonoylamino-Py-C-methyl (1; yellow), 2-benzoylamino-Py-C-methyl (1; yellow), 2-benzoylamino-Py-C-ethyl (1; yellow), 2-benzoylamino-Py-C-propyl (1; yellow), 4-p<1>-chlorbenzoylamino-Py-C-phenyl (1; red-yellow), 4-p<1>-chlorbenzoylamino-Py-C-naphthyl (1; red-yellow), 4-p<1>-chlorbenzoylamino-Py-C-p<1>-chlorphenyl (1; red-yellow), 4-benzoylamino-2-amino-Py-C-phenyl (5), 4-p<1>-toluenesulphonamido-2-methyl-Py-C-phenyl (3; yellow): (E) 4-p<1>-chlorbenzoylamino-Py-C-chloro-(1; green-yellow); by treatment according to (4) with phosphorous pentachloride Py-C-chlor-4-benzoylamino-(greenish - yellow), Py - C - chlor-5-benzoylamino (yellow), Py-C-chlor-8-(2<1> : 5<1>-dichlorbenzoylamino)-(yellow), Py-C-chlor-5-benzoylamino-8-methoxy, Py-C-chlor-1.4-dibenzoylamino-, Py-C-chlor-3-methyl-4-benzoylamino-derivatives are obtained, and in like manner Py-C-chlor-acylamino derivatives wherein the acyl residue is a chlorbenzoyl, nitrobenzoyl, alkylbenzoyl, alkoxybenzoyl, phenylbenzoyl, naphthoyl, benzophenone-carboxy, diarylether-carboxy, diarylsulphide-carboxy, anthraquinone-carboxy, benzanthrone-carboxy, benzanthraquinone-carboxy, acridone-carboxy, anthraquinoneacridone - carboxy, anthraquinonethioxanthone-carboxy, anthanthrone-carboxy, allo-ms-naphthodianthrone-carboxy, acetic, oxalic, succinic or hexahydrobenzoic residue are obtained; by treatment according to (4) with 2 : 5-dichlorbenzoyl chloride, 4-(2<1> : 5<1>-dichlorbenzoylamino)-PyC-(2<1> : 5<1>-dichlorbenzoyl ester (yellow) is obtained.  In further examples (F) 2.2<1>-dianthrapyrimidyl is nitrated, reduced, and benzoylated (yellow); (G) amino- and polyamino-1 : 9 : 5 : 10-anthradipyrimidine are acylated with anthraquinone-2-carboxylic acid and 1-aminoanthraquinone-2-carboxylic acid respectively (the latter dyes brown shades); (H) 4- and 5-benzoylamino-1-9-anthrapyrimidine, 2-(b -anthraquinonoylamino)-Py-C-phenyl-1 : 9-anthrapyrimidine and 5-(2<1> : 5<1>-dichlorbenzoylamino)-1 : 9-anthrapyrimidine are chlorinated in trichlorbenzene and in presence of iodine as catalyst (orange to yellow dyes); (I) aqueous pastes of 4- and 5-(diphenyl-4<1>-carboxyamino)-1 : 9-anthrapyrimidine are brominated (dyes greenish-yellow); (J) 4-diphenyl-4<1>-carboxyamino)-1 : 9-anthrapyrimidine is treated with sulphuryl chloride in nitrobenzene and in presence of iodine (yellow); (K) 5-benzoylamino-1 : 9-anthrapyrimidine is brominated in chlorsulphonic acid in presence of iodine (orange). In addition to the acids employed in preparing the foregoing products re