Patent GB-471112-A (GB)
Title: Improvements in the manufacture and production of carbon compounds of high molecularweight
IPC: F23J1/00
Filed: 1936-02-22
Abstract: Organic compounds of high molecular weight of the formula M--(A--X)n, where M is the radicle of a compound having at least four condensed rings, A is a nitrogen bridge, X is a naphthenyl radicle (i.e. a cycloaliphatic radicle attached to the nitrogen bridge A by an aliphatic bridge such as--CH2--) or an abietinyl radicle, and n is a whole number, are manufactured by reacting hydroxy or alkoxy compounds which contain at least four condensed rings with a naphthenylamine or abietinylamine. Suitable starting materials are hydroxy and alkoxy compounds of the pyrene, chrysene, benzanthraquinone, dibenzanthrone, isodibenzanthrone, perylene, dibenzoylperylene, anthanthrone, anthanthrene, pyranthrone, benzanthrone, dibenzanthronyl, pyridinoanthraquinone, azobenzanthrone, anthraquinoneacridone, anthraquinoneazine, coeramidonine, anthrapyrimidine, anthrapyrimidone, anthrapyridine, anthrapyridone and pyrazolanthrone series.  The reaction may be effected by heating the initial materials, if desired in the presence of diluents, e.g. high-boiling hydrocarbons, alcohols, ketones, halogenhydrocarbons or nitrohydrocarbons, agents facilitating the reaction, viz. zinc chloride or alkali bisulphite, or acid-binding agents, in some cases advantageously in a closed vessel.  The products may be used as dyestuffs or intermediates therefor, or for dyeing or rendering fluorescent artificial resins, hydrocarbons, paraffin waxes, oils, waxes, rubber and similar natural and synthetic plastic masses, and cellulose esters and ethers.  In examples: (1) 2-hydroxy-1 : 9-anthrapyrimidine is heated with naphthenylamine (obtainable by reducing with gaseous hydrogen in the presence of a nickel catalyst the naphthenic nitrile obtainable by the action of ammonia in the presence of a dehydrating catalyst or the natural naphthenic acid occurring in crude petroleum); the 2-hydroxyanthrapyrimidine may be replaced by other hydroxy- or alkoxyanthrapyrimidines containing the hydroxy or alkoxy groups in the 2-, 3-, 4-, 5-, 6-, 7-, 8- or PyC- position, or substitution products thereof, e.g. alkyl, hydroxyalkyl, cyano, carbonamide, carboxylic acid or ester derivatives, e.g. 2-hydroxy-PyC-heptadecyl-1 : 9-anthrapyrimidine (obtainable by heating 1-amino-2-hydroxyanthraquinone with stearic amide while leading in dry hydrogen chloride); (2) methoxypyranthrone (prepared by methylation of the hydroxy compound obtained by nitrating pyranthrone, reducing, diazotizing, and replacing the diazo group by a hydroxy group) is heated with naphthenylamine; the methoxypyranthrone may be replaced by hydroxypyranthrone, methoxyanthanthrones, dihydroxyanthanthrones, hydroxy or alkoxy compounds of allo-ms-naphthodianthrones, ms-anthradianthrones, dibenzanthrones, isodibenzanthrones, benzanthraquinones, benzanthrones, dibenzpyrenequinones, isodibenzpyrenequinones, anthraquinoneazines, flavanthrones, anthraquinoneacridones, pyridinoanthraquinones or their reduction products, or hydroxyazapyranthrones, e.g. hydroxypyranthridones (obtainable by heating halogenpyranthridones with dilute caustic soda) or hydroxyflavanthrone; (3) 2 - hydroxy - 4 - amino - 1 : 9-anthrapyrimidine (obtainable by heating the 2-bromo compound with dilute caustic soda) is heated with naphthenylamine in the presence of sodium acetate and amyl alcohol; 2 : 4 dihydroxy-1 : 9-anthrapyrimidine is heated with at least two molecular proportions of naphthenylamine or abietinylamine; similarly hydroxy compounds of benzanthracene, pyrene, chrysene, perylene, fluoranthene, triphenylene, anthraquinoneazines, anthraquinoneacridones, perylenedicarboxylic acid imides and imidazoles, coeramidonines and anthrapyrimidones may be reacted with abietinylamine; (4) Bz2 : Bz2<1>-dihydroxydibenzanthrone is heated with naphthenylamine; the Bz2 : Bz2<1>-dihydroxydibenzanthrone may be replaced by its alkyl ethers or by tri- and tetrahydroxydibenzanthrones; (5) 2-hydroxy-1 : 9 : 4 : 10-anthradipyrimidine (obtainable by heating 2-bromo-4-amino-1 : 9-anthrapyrimidine with formamide and heating the product with dilute caustic soda) is heated with naphthenylamine; instead of anthradipyrimidines there may be used hydroxy compounds of anthracene derivatives containing further rings joined in the 1 : 9 : 4 : 10- or 1 : 9 : 5 : 10-positions, e.g. 1 : 9 : 4 : 10- or 1 : 9 : 5 : 10-anthradipyrimidones; (6), (7) and (8) abietinylamine is used in place of naphthenylamine in the processes of (2), (4) and (5) respectively.  Specifications 461,885 and 462,658 are referred to.ALSO:Rubber and similar plastic masses are dyed or rendered fluorescent by means of compounds of the formlua M-(A-X)n where M is the radicle of a compound having at least four condensed rings, A is a nitrogen bridge, X is a naphthenyl radicle (i.e. a cycloaliphatic radicle attached to the nitrogen bridge A by an aliphatic bridge such as -CH2-) or an abietinyl radicle, and n is a whole number.