Patent GB-407363-A (GB)
Title: Improvements in the manufacture and production of products of the anthrapyrimidine series
IPC: C09B5/16
Filed: 1932-08-03
Abstract: Anthrapyrimidine derivatives.--Amino, hydroxy- or mercaptoanthrapyrimidines are condensed with organic compounds to which a negative substituent is attached and which are not saponifiable to form acids, or anthrapyrimidines containing a negative substituent attached to the nucleus are condensed with amines or organic compounds containing a hydroxy or mercapto group. The resulting anthrapyrimidines contain a group X--R, wherein X denotes the group --NH-- in which the hydrogen atom may be replaced by a low alkyl radicle, or --O--or --S--, and wherein R denotes an alkyl, aralkyl, aryl, or heterocyclic radicle.  Both condensations are preferably carried out in inert organic diluents and in presence of acid-binding agents; catalysts such as iron, copper and their compounds such as their oxides, acetates and carbonates, may also be present.  The anthrapyrimidine compound may be condensed with several molecular proportions of the same or different organic compound, the following starting materials being specified: methyl- and ethyl chlorides, propyl-, butyl-and cetyliodides, ethylene chloride, monobromo-and dibromocyclohexane, halogen or nitro derivatives of benzene, naphthalene, anthracene, phenanthrene, anthraquinone, benzanthrone, dibenzanthrones, ms-naphthodianthrone, allo-ms-naphthodianthrone, anthanthrone, pyranthrone, dibenzpyrenequinone, acridine, acridone, anthraquinone benzacridone, anthraquinone-thioxanthone, benzanthronepyrazolanthrone, anthrapyrimidine, anthrapyridone, anthrapyrimidone, and alkyl, aryl, acylamino, cyano, thiocyano, substituted amino, mercapto, carboxy or sulphosubstituted derivatives thereof.  The corresponding amino, hydroxy or mercapto derivatives of the above organic compounds may be used for condensation with the negatively substituted anthrapyrimidines. The following condensations are described or referred to in examples:--5-aminoanthrapyrimidine (prepared by saponifying the 5-benzoylamino derivative) with a - or b -chlor-anthraquinones (red dyes), 4-chlor-1-benzoyl aminoanthraquinone (blue-violet), 5-chlor-1-benzoylaminoanthraquinone (brown), 1-nitro-2-methylanthraquinone (brown-violet), 2.6-, 2.7, 1.5-, or 1.8-dichloranthraquinones (\ba1/2\be mol. violet to red shades), 1-amino-4-bromanthraquinone-2-sulphonic acid (red-violet), 6-chlor-benzanthrone, dibromodibenzanthrone (grey-blue), dibromoisodibenzanthrone (navy-blue), dibromo-3.4.8.9-dibenzpyrenequinone (grey to violet-black), dibromanthanthrone (blue), dibromo- and tetrabromopyranthrone (olive green; grey-black), dibromobenzanthrone-pyrazolanthrone (blue-grey), 5-chloranthrapyrimidine (blue-violet), 2.6- (or 2.7- or 1.5-or 1.8-)-dichloranthraquinone and aminodibenzanthrone (1 : 1 : 1 ; grey shades), dibromanthanthrone and a - or b -aminoanthraquinone (1 : 1 : 1 ; blue shades), dibromanthanthrone and aminodibenzanthrone (1 : 1 : 1 ; green-blue), dibromopyranthrone and aminodibenzanthrone (1 : 1 : 1 ; olive-green), tetrabromopyranthrone and p aminobenzanthronepyrazolanthrone (grey), tetrabromopyranthrone and aminodibenzanthrone (3 : 1 : 1, 2 : 1 : 2, 1 : 1 : 3 ; black shades), dibromdibenzanthrone and aminodibenzanthrone (1 : 1 : 1 ; green-blue), dibromisodibenzanthrone and aminodibenzanthrone (1 : 1 : 1 ; blue), dibromoisodibenzanthrone and a -aminoanthraquinone (1 : 1 : 1 ; blue), dibromo-3.4.8.9-dibenzpyrenequinone and aminodibenzanthrone (1 : 1 : 1 ; grey-black), dibromo-3.4.8.9-dibenzpyrenequinone and a - or b -aminoanthraquinone (1 : 1 : 1 ; violet to grey shades), dibromo-3.4.8.9-dibenzpyrenequinone and aminobenzanthronepyrazolanthrone (grey), dibrombenzanthronepyrazolanthrone and aminodibenzanthrone (1 : 1 : 1 ; green-blue), Bz1-pyrazolanthronyl-6-brombenzanthrone, Bz1.6-dibromobenzanthrone and 1-aminoanthraquinone (1 : 1 : 1 ; brown), Bzl.6-dibromobenzanthrone and pyrazolanthrone (1 : 1 : 1 ; grey), dichloranthrapyrimidine and aminodibenzanthrone (1 : 1 : 1 ; grey-blue), dichloranthrapyrimidine and a - or b -aminoanthraquinone (1 : 1 : 1 ; currant shades) : 5-chloro- or bromo-1.9-anthrapyrimidine with 3-hydroxypropylamine (dyes acetate silk red shades), hydroxyethylamine, 3-hydroxybutylamine, methylamine (dyes acetate silk rose-red), dimethylamine (dyes acetate silk bluish-pink), phenol, p-cresol, salicylaldehyde, p-toluidine (dyes acetate silk blue-violet) with sulphonation, naphtylamines, anthranilic acid (red-violet), a - or b -aminoanthraquinone, 1-mercapto-2-aminoanthraquinone (grey-blue), 1-amino-4-bromanthraquinone-2-sulphonic acid (red-violet); (5-bromo-1.9-anthrapyrimidine is prepared from the 5-amino body by a Sandmeyer reaction); 5-methylamino-1.9-anthrapyrimidine with 1-chloranthraquinone (violet on acetate silk) : 4-amino-1.9-anthrapyrimidine with dibromo-3.4.8.9-dibenzpyrenequinone (brown), dibromanthanthrone, dibromo-allo-ms-naphthodianthrone, 4-Bz3.5-trichloranthraquinone-2.1-benzacridone : 2 - amino - 1.9 - anthrapyrimidine with b -chloro- or other halogenanthraquinones (red-brown) : 8-aminoanthrapyrimidine with dibromanthanthrone (grey), tetrabromopyranthrone (violet-grey), dibromo-3.4.8.9-dibenzpyrenequinone (violet-grey), 4-bromo-N-methyl-1.9-anthrapyridone (violet), tetrabrompyranthrone and aminodibenzanthrone (1 : 1 : 3 ; black), Bz1.6-dibrombenzanthrone and a -aminoanthraquinone (grey) : PyC-chloro-1.9-anthrapyrimidine (from anthrapyrimidone with phosphorus pentachloride) with hydrazine, 1 - amino - 5 - benzoylaminoanthraquinone (orange), b -aminoanthraquinone (yellow), thiophenol, 1-mercaptoanthraquinone : dichloranthrapyrimidine (prepared by chlorinating the 5-chloro body with chlorine in trichlorbenzene) with methylamine (rose-red on acetate silk) : 5-oxy-1.9-anthrapyrimidine (from the 5-chloro body by treatment with sodium methylate) with a -chloranthraquinone (pink) : 5-mercapto-1.9-anthrapyrimidine (5-chloro body and sodium sulphide) with a -chloranthraquinone (brown) : bromo-5-aminoanthrapyrimidine (brominate 5-amino body in chlorsulphonic acid) with methylamine (brown-violet on acetate silk) : 5-chloro-nitroanthrapyrimidine (prepared by nitrating 5-chloro body) with methylamine (violet on acetate silk) : 2-amino-C-phenylanthrapyrimidine (prepared by heating C-phenylanthraquinone-2.1-oxazole with ammonia) with a - or b -chloranthraquinone (red shades), 1-chloro-4- or 5-benzoylaminoanthraquinone (violet and violet-grey), 2.6- or 2.7- dichloranthraquinone (\ba1/2\be mol.) : PyC-chloro-4-benzoylaminoanthrapyrimidine (from the corresponding anthrapyrimidone and phosphorus pentachloride) with phenol, and the resulting aminophenoxy-derivative with halogenanthraquinone, a - or b -aminoanthraquinone (orange-red), aniline (bluish-red), hydrazine, methylamine (pink), dimethylamine : the following PyC-chlor-aroylaminoanthrapyrimidines (prepared from the corresponding aroylaminoanthrapyrimidones by treatment with phosphorus pentachloride) may also be used for condensation with amines:--PyC-chlor-5-benzoylamino-, PyC-chlor-5-benzoylamino-8-methoxy-, PyC-chlor - 1.4 - dibenzoylamino-, PyC-chlor - 4 - benzoylamino - 3 - methyl - anthrapyrimidines and those derivatives containing amino groups acylated with chlorbenzoic, nitrobenzoic, alkylbenzoic, alkoxybenzoic, phenylbenzoic, naphthoic, benzophenone carboxylic, diphenylether carboxylic, diphenylsulphide carboxylic, anthraquinone carboxylic, benzanthrone carboxylic, benzanthraquinone carboxylic, acridone carboxylic, anthraquinone-acridone carboxylic, anthraquinone - thioxanthone carboxylic, anthanthrone carboxylic, allo-ms-naphthodianthrone carboxylic, acetic, oxalic, succinic, hexahydrobenzoic acids: PyC-chloro-4-, -6-, and -7-amino-1.9-anthrapyrimidines (prepared by saponifying the corresponding aroylamino groups with concentrated sulphuric acid), 2-, 3-, 6-, and 7-amino-1.9-anthrapyrimidines, and an aminoanthrapyrimidine prepared by nitration and reduction are also specified as suitable reactants for some of the foregoing condensations. Specifications 307,947, 318,180, 325,550, [all in Class 2 (iii)], 385,295, and 401,731 are referred to. Anthrapyrimidones involved in the preparation of starting-materials employed in the foregoing condensations are prepared from the corresponding a -amino-aroylaminoanthraquinones by treatment with urea in phenol or nitrobenzene.  Nitro derivatives are obtained by nitration in aqueous solution or in nitrobenzene, if desired. 4-Bromo-N-methyl-1.9-anthrapyridone is prepared by treating 4-bromo-1-acetylmethyl-aminoanthraquinone with alcoholic potash. Benzanthronepyrazolanthrones.  Nitro derivatives are prepared by nitration, if desired, in water or nitrobenzene; reduction gives the amino derivative.  A dibromo derivative is obtained by bromination in chlorsulphonic acid in presence of iodine. Anthraquinone-thioxanthone.  Nitro derivatives are obtained by nitration, if desired in presence of water or nitrobenzene. Dibenzanthrones.  The amino derivative used above is prepared by nitration and reduction by means of sodium sulphide.  The dibromo derivative is prepared by bromination in nitrobenzene. Dibromoisodibenzanthrone referred to above is prepared by bromination in chlorsulphonic acid in presence of antimony.  Pyranthrones.  The dibromo and tetrabromo derivatives employed are prepared by brominating with approximately theoretical proportions of bromine in presence of sulphur.  Anthanthrones.  The dibromo derivative used is prepared by treating anthanthrone in nitrobenzene with bromine in presence of iodine.  Allo-ms-naphthodianthrones.  The dibromo derivative used is obtained by bromination in chlorsulphonic acid. 3.4.8.9--Dibenzpyrenequinones.  The dibromo derivative is prepared by brominating in chlorsulphonic acid in presence of iodine.  Reference has been directed by the Comptroller to Specifications 307,947, 318,180, and 325,550.