Patent GB-475158-A (GB)
Title: Improvements in the manufacture and production of compounds of the 1.9-anthrapyridone series
IPC: C09B5/00
Filed: 1936-05-11
Abstract: Dyes of the 1.9-anthrapyridone series containing in the Py.3-position an esterified carboxylic or a cyano group and at least one acylamino group in the anthrone part of the molecule are made by reacting 1-amino-acylaminoanthraquinones or 1 - alkylamino - acylaminoanthraquinones with malonic acid dialkyl esters or cyanoacetic esters or by treating with acylating agents amino - 1.9 - anthrapyridones containing in the Py.3-position a free or esterified carboxylic group or a cyano group and in which the imino group in the pyridone ring may be alkylated, or by treating halogen - 1.9 - anthrapyridones or halogen - N - alkyl-1.9-anthrapyridones containing in the Py.3-position a group of the said kind with amides.  Any free carboxylic groups may be esterified during or after the reaction, or the products may be alkylated.  Diluents specified are phenols and aromatic halogen or nitro hydrocarbons or an excess of the malonic acid dialkyl ester, cyanoacetic ester, or acylating agent, and condensing agents such as sodium acetate may be added.  (The second Provisional Specification refers also to sodium or potassium carbonate and potassium acetate.)  The products dye vegetable fibres yellow or orange shades from the vat.  In examples: (1) 1-amino-5-benzoylaminoanthraquinone is condensed with diethyl malonate in nitrobenzene in presence of sodium acetate to give 5 - benzoylamino - Py. 3 - carbethoxy-1.9-anthrapyridone; the radicle of benzoic acid may be replaced by that of acetic, propionic, butyric, stearic, phenylacetic, cinnamic, succinic, sebacic, oxalic, or adipic acids, a mono- or poly-chlor-, bromo-, iodo-, fluoro- or -alkylbenzene carboxylic acid, a nitro-, cyano-, hexahydro-, hydroxy-, or methoxybenzene carboxylic acid, a benzene dicarboxylic acid, a naphthalene mono- or di-carboxylic acid, diphenyl-4-mono- or -4.4<1>-dicarboxylic acid, diphenylene oxide-, diphenyl sulphide-, diphenyl methane-, benzophenone-, diphenyl benzene-, phenanthrene-, azaphenanthrene-, carbazole-, 9.10-diazaphenanthrene- or perylene mono- or dicarboxylic acids, pyridine and quinoline mono- or di-carboxylic acids, quinolylbenzoic acid, carboxyquinolyl-benzoic acid, phenylquinoline or phenylisoquinoline carboxylic acid, benzoxazole or benzthiazole carboxylic acid, anthraquinone-1- and -2-carboxylic acid, 1- or 6-aminoanthraquinone - 2 - carboxylic acid, 1-or 6 - nitroanthraquinone - 2 - carboxylic acid, 1 - chloranthraquinone - 2 - carboxylic acid, 5.8-dichloranthraquinone-2-carboxylic acid or a carboxylic acid of the benzanthrone, anthrapyridone, anthrapyrimidone, anthrapyrimidine, pyrazolanthrone, thiazolanthrone, thiophenoanthrone, selenazolanthrone, benzanthraquinone, benzacridone, pyridinoanthraquinone, anthraquinone-1.2-pyrazole, anthraquinone-1.2-pyrazolylbenzene, anthraquinonebenzthiazole, aminoanthraquinonebenzthiazole, 1(N).2-pyridinoanthraquinone, anthraquinonethioxanthone, anthraquinonebenzoxazole, peryleneperi-tetracarboxylic acid arylimide, naphthaleneperi-tetracarboxylic acid arylimide, anthraquinonyl-benzene, anthraquinonyl-phenyl-sulphide or thioindigo carboxylic acid series; the 1 - amino - 5 - benzoylaminoanthraquinone may be replaced by 1-amino-4 or 8-acylamino anthraquinones or 1 - amino - 5 - acylamino-8-methoxy- or 1-amino-4-acylamino-5-aminoanthraquinones; the diethyl malonate may be replaced by dimethyl malonate; (2) 5-amino-Py.3-carbethoxy-1.9-anthrapyridone is heated with p-chlorbenzoyl chloride in nitrobenzene to give 5-p-chlorbenzoylamino-Py.3-carbethoxy-1.9-anthrapyridone or with anthraquinone-1(N).2 - benzacridone - 5<1> - carboxylic acid chloride to give anthraquinone-1(N) .2-benzacridone-5<1>-carbonyl-5-amino-Py.3-carbethoxy-1.9 -anthrapyridone or with a halide of one of the carboxylic acids set out under (1) above; the 5 - amino - Py.3 - carbethoxy - 1.9 - anthrapyridone may be replaced by the 3-, 6-, or 7-aminobody; (3) 5-amino-Py.3-carbethoxy-1.9-anthrapyridone is heated with benzamide in nitrobenzene while leading in hydrogen chloride to give 5 - benzoylamino - Py.3 - carbethoxy-1.9-anthrapyridone; the benzamide may be replaced by acetamide, propionamide, stearic acid amide, naphthenic acid amide, abietic acid amide, hexahydrobenzamide, or substituted benzamides such as p-fluorbenzamide, o-, m-, and p-chlorbenzamides, 2.5-dichlorbenzamide, 2.4 - dichlorbenzamide, p-brombenzamide, o-, m-, and p-cyanbenzamides, o-, m-, or p-methylbenzamides, p-nitrobenzamides, p-aminobenzamides or also quinoline carboxylic acid amides or arylacetic acid amides; the 5 - amino - Py.3 - carbethoxy-1.9-anthrapyridone may be replaced by 2-, 3-, 4-, 6-, 7- or 8-amino-Py.3-carbalkoxy-1.9-anthrapyridones; e.g. 2-amino-Py.3-carbethoxy-1.9-anthrapyridone and urea give 2.2<1>-Py.3-carbethoxy-1.9-anthrapyridone urea or 6-amino-Py.3 - carbethoxy - 1.9 - anthrapyridone and diphenyl-4-carboxylic amide give the (diphenyl-4<1>-carbonyl)-6-amino compound; the hydrogen chloride may be replaced by other acid condensing agents such as sulphuric acid, boric acid, ammonium bisulphate, alkali bisulphates or sulphur dioxide; the nitrobenzene may be replaced by other diluents such as trichlorbenzene or excess of the amide; (4) 5-benzoylamino - Py.3 - carbethoxy - 1.9 - anthrapyridone is treated with p-toluene sulphonic acid methyl ester in trichlorbenzene to give 5 - benzoylamino - N - methyl - Py.3 - carbethoxy-1.9-anthrapyridone; the 5-benzoylamino-Py.3-carbethoxy-1.9-anthrapyridone may be replaced by other acylamino - Py.3 - carbalkoxy - 1.9-anthrapyridone; (5) 4 - amino - Py.3 - carbethoxy - 1.9 - anthrapyridone or 4-amino-N-methyl-Py.3-carbethoxy-1.9-anthrapyridone is heated with benzoyl chloride in nitrobenzene to give the 4-benzoylamino body; (6) 1-amino-5-benzoylaminoanthraquinone is heated with the ethyl ester of cyanoacetic acid to give 5-benzoylamino - Py.3 - cyan - 1.9 - anthrapyridone; the 1-amino-5-benzoylaminoanthraquinone may be replaced by 1-amino-4 or 8-benzoylaminoanthraquinone, and the radicle of benzoic acid may be replaced by that of a 2-, 3-, or 4-chlor-, 4-brom-, 2-, 3-, or 4-methyl-, 4-phenyl-, 2- or 4-oxy-, 2- or 4-methoxy-, 4-ethoxy or 4-aminobenzene carboxylic acid or by the radicle of a naphthalene carboxylic acid or a vattable carboxylic acid such as anthraquinone-2-carboxylic acid, an anthraquinone benzacridone-, a thiazolanthrone-, an anthrapyridone- or an anthrapyrimidone-carboxylic acid; the products may be N-alkylated, e.g. by treating 4-benzoylamino-Py.C-cyan-1.9-anthrapyridone with p-toluene sulphonic acid methyl ester; (7) 5 - amino - Py.3 - carbethoxy - 1.9 - anthrapyridone is heated with cyanuric chloride and phenol in the proportion of three or two molecules of the anthrapyridone to one of cyanuric chloride; (8) 5 - chloro - Py.3 - carbethoxy-1.9-anthrapyridone is reacted with benzamide in nitrobenzene in presence of sodium acetate and copper acetate to give 5-benzoylamino - Py.3 - carbethoxy - 1.9 - anthrapyridone; the benzamide may be replaced by substituted benzamides. Specification 393,632 is referred to.  Samples have been furnished under Sect. 2 (5) of (A) 5-(Py.C-phenyl-1(N).2-pyrazoloanthraquinone - 4<1> - carbonyl)amino - Py.3 - carbethoxy-1.9-anthrapyridone which is obtained by reacting 1-amino-5-(Py.C-phenyl-1(N).2-pyrazoloanthraquinone - 4<1> - carbonyl) - aminoanthraquinone with diethyl malonate in nitrobenzene in presence of sodium acetate and of (B) 5-(4<1>-azaphenanthrene - 8<1> - carbonyl) - amino - Py.3-carbethoxy-1.9-anthrapyridone which is prepared from 1-amino-5-(4<1>-azaphenanthrene-8<1>-carbonyl) aminoanthraquinone and diethyl malonate.  1-Amino - 5 - (Py.C - phenyl - 1(N).2-pyrazoloanthraquinone-4<1>-carbonyl) -aminoanthraquinone is obtained by reacting the chloride of Py.C-phenyl - 1(N).2 - pyrazoloanthraquinone - 4<1>-carboxylic acid with 1-p-toluenesulphamino-5-aminoanthraquinone and saponification of the compound obtained with sulphuric acid.  1 - Amino - 5 - (4<1> - azaphenanthrene - 8<1> - carbonyl)aminoanthraquinone is prepared similarly from 1 - p - toluenesulphamino - 5 - amino - anthraquinone and 4-azaphenanthrene-8-carboxylic acid chloride.