Patent GB-461883-A (GB)
Title: Improvements in the manufacture and production of carboxylic acid amides and nitrogenous condensation products
Filed: 1935-07-20
Abstract: Nitrogenous condensation products are prepared by heating a polynuclear cyclic amine with a carboxylic acid amide in the presence of hydrogen halide, sulphur dioxide, sulphuric acid or an alkali metal or ammonium bisulphite or bisulphate.  Acylation of the amino group of the polynuclear amine occurs, in some cases with further condensation.  The initial materials may comprise primary or secondary amines and/or amides wherein at least one hydrogen atom in the acid amide group is replaced by a radicle of low molecular weight.  Reaction generally proceeds with gentle heating, in some cases in the presence of diluents, in other cases working under increased pressure.  In examples, the following condensations are described or referred to, the condensing agent being hydrochloric acid except where otherwise stated: (A) 1-aminoanthraquinone with benzamide, b -naphthoic acid amide, quinoline 4- or 6-carboxylic acid amides, nicotinic acid amide, anthraquinone-2-carboxylic acid amide, anthraquinone-benzacridone-4<1>-carboxylic acid amide, anthraquinone - thioxanthone carboxylic acid amide, 1.9-pyrazolanthrone-2-carboxylic acid amide, 1.9-selenazolanthrone-2-carboxylic acid amide, 1.9-thiazolanthrone-2-carboxylic acid amide, pyridinoanthraquinone carboxylic acid amides, benzanthrone-carboxylic acid amides, anthrapyridine-carboxylic acid amides, anthrapyrimidine-carboxylic acid amides, anthrapyridone - carboxylic acid amides, anthraquinoneazole carboxylic acid amides, 1-azaanthraquinone carboxylic acid amides, fluorene carboxylic acid amides, phenanthrene carboxylic acid amides, pyrene carboxylic acid amides, diphenyleneoxide carboxylic acid amides, carbazole carboxylic acid amides, formamide, acetamide, lauric acid amide, phenylacetic acid amide, urethane (to give 1.9-anthrapyrimidone; ammonium bisulphate, alkali metal bisulphite, sulphuric acid or sulphur dioxide may also be employed as condensing agent) and urea; 1.8 - diaminoanthraquinone with benzamide; 1.5 - diaminoanthraquinone with benzamide; 1.4 - diaminoanthraquinone or 1.4 - di - (monomethylamino)-anthraquinone with benzamide; 1.2-diaminoanthraquinone with formamide (2-amino - 1.9 - anthrapyrimidine obtained); 1 - amino - 5 - benzoylaminoanthraquinone with oxamide or acetamide; 1-methylaminoanthraquinone with benzamide, N-methyl- or N-dimethylbenzamide; 1-amino-5-p-chlorbenzoylaminoanthraquinone with benzamide; 1-amino5 - chloranthraquinone with benzamide; 1-amino - 4 - chloranthraquinone with cinnamic acid amide; 1-amino (or 1-methylamino-)-2-bromanthraquinone with p - chlorbenzamide, anthraquinone-2-carboxylic acid amide (oxazole ring formed in each case); 1-2.4-triaminoanthraquinone with benzamide (an imidazole ring formed); 1-amino-2-methylaminoanthraquinone with formamide (an anthrapyrimidine); 1 - amino - 2 - methyl - 4 - p - toluidoanthraquinone with formamide; 1-amino-4-anilido- or -4-pseudocumidino- or -4-(2<1>.6<1>-dimethylanilido)-or 2<1>.6<1>-dihalogenanilidoanthraquinones with formamide; 1-amino-2-oxyanthraquinone with acetamide, propionamide, butyric acid amide, capric acid amide, lauric acid amide, oleic acid amide, stearic acid amide, cyanacetamide, chloracetamide, phenylacetamide, pyridylacetamide, hexahydrobenzamide, naphthenic acid amide, abietic acid amide, dihydroabietic acid amide or formamide (anthrapyrimidines formed in all cases; ammonium and sodium bisulphate, sulphuric acid, hydrobromic acid, hydriodic acid, sulphur dioxide, may also be used as condensing agents); 1 - amino - 4 - oxyanthraquinone, 1 - amino - 2.4 - dioxyanthraquinone, 1.2 - dioxy - 4 - aminoanthraquinone, 1 - oxy - 2.4-diaminoanthraquinone, 1 - amino - 2 - oxy - bromanthraquinone, 1-amino-3-, 6- or 7-oxyanthraquinones, 1 - amino - 2 - acetoxyanthraquinone, 1-amino-2-methoxyanthraquinone, 1-amino-2-mercaptoanthraquinone or 1-amino-2-selenoanthraquinone with formamide to give the corresponding pyrimidines; 1-amino-3-, -4-, -5-or -8-acylaminoanthraquinones, 1-amino-oxy-, -methoxy-, -halogen-, -nitro-, or -carboxyanthraquinones, 1 - aminoanthraquinone - aldehydes, -carboxylic acids or -sulphonic acids with formamide to give the corresponding anthrapyrimidones; (B) 2-aminoanthraquinone with benzamide or urea; 1-mercapto-2-aminoanthraquinone with benzamide or formamide (a thiazole ring formed); 2-amino-3-oxyanthraquinone with 1-amino-2-carboxyanthraquinone or benzamide (an oxazole ring formed); 2-amino-3-bromanthraquinone with benzamide (an oxazole ring formed); 1-chlor-2-aminoanthraquinone with urea; 1-seleno-2-aminoanthraquinone with formamide (a selenazole ring formed); (C) aminoanthraquinones with chlorbenzamide, methoxybenzamide, diphenylcarboxylic acid amide, toluyl acid amide, bromobenzoic acid amide, nitrobenzoic acid amide, hydroxybenzoic acid amide, benzoylaminobenzoic acid amide, oxalic acid diamides or succinic acid diamides, aminonaphthalenes with urea; (D) aminobenzanthrones with p-chlorbenzamide; aminobenzanthraquinones, aminopyranthrone, aminodibenzanthrone, mono- and poly - amino - allo - ms - naphthodianthrones with benzamide; aminodibenzpyrenequinone, aminoisodibenzpyrenequinone, aminoanthranthrone, aminopyranthrone, aminodibenzanthrone or aminoisodibenzanthrone with urea; (E) aminoanthrapyrimidones, aminoanthrapyridones, aminoanthrapyrimidines (including 4-amino-1.9-anthrapyrimidine), aminoazabenzanthrones with p-chlorbenzamide or urea; aminopyrazolanthrones, aminoindoloanthrones or amino-1.9-selenazolanthrones with p-chlorbenzamide; (F) 4-amino-3<1>.4<1>.6<1>-trichloranthraquinone-2.1 -benzacridone, 4-amino-o - chlorphenyl - 1.2 - anthraquinoneimidazole, aminopyridinoanthraquinones, aminoanthraquinone - thiazoles, aminoanthraquinoneoxazoles, aminoanthraquinone - selenazoles, aminoanthraquinoneazines with benzamide; aminopyridinoanthraquinones, aminoanthraquinone - benzacridone, aminoanthraquinoneazoles with urea.  The products may be dyes, dye-intermediates, dyeing assistants or medicaments. Specifications 27098/08, [Class 2], 5998/09, 1970/12, [both in Class 2 (iii)], and 385,295 are referred to.  Carboxylic acid amides of 1-azanthraquinone, fluorene, phenanthrene, pyrene or diphenyleneoxide are prepared by diazotizing the corresponding amino compounds, treating these with cuprous cyanide, saponifying, converting the resulting acids to acid chlorides by means of phosphorus pentachloride, and reacting these with ammonia. Anthraquinone-thioxanthone carboxylic acid amide is prepared by condensing 1 - mercaptoanthraquinone - 2 - carboxylic acid with o-halogenbenzoic acid, ring-closing by means of sulphuric acid, treating with thionyl chloride and then with ammonia.  Amino compounds of anthraquinone-thiazoles, -oxazoles, and -selenazoles are prepared from polyaminoanthraquinones containing in o-position to one amino group a group capable of forming by the usual methods an azole ring and converting these derivatives to azoles by the known methods. Aminoindoloanthrones are prepared by nitrating and reducing indoloanthrones. Amino-1.9-selenazolanthrones are prepared by treating amino derivatives of 1 - chloranthraquinone - 2 - carboxylic acid with sodium selenide and ammonia under pressure.