Patent GB-516130-A (GB)
Title: Manufacture of derivatives of chrysene
IPC: C09B1/32
Filed: 1938-06-21
Abstract: 516,130. Chrysene derivatives. SOC. OF CHEMICAL INDUSTRY IN BASLE. June 21, 1938, Nos. 18394, 18395, 18396, 18397, 18398 and 18399. Convention dates, .Tune 21, 1937, Sept. 14, 1937, Dec. 1, 1937, Dec. 20, 1937, March 2, 1938, and May 18, 1938. [Class 2 (iii)] Chrysene derivatives are obtained by reacting a halogen-chrysene with a compound which contains at least one hydrogen atom attached to nitrogen and contains the radical of a compound capable of being vatted. Halogenchrysenes, for example, 2-bromo,- 2.8-dibromo- and 2.8-dichloro-chrysene, may contain substituents other than halogen, and when they contain more than one halogen atom may be reacted with more than one mol. of the same or different vattable compounds simultaneously or successively. Vattable compounds specified are 1-aminoanthraquinone, 1-amino-arylaminoanthraquinones, 1-amino-4 or 5-benzoylaminoanthraquinone, 1-amino-5-benzoylamino-8- methoxyanthraquinone, 1-amino-5.8-dibenzoylaminoanthraquinone, 1-aminoanthraquinonoylamino-anthraquinone (obtainable by condensing 1-nitro-5-aminoanthraquinone with anthraquinone-2-cirboxylic acid chloride and reducing the product with sodium sulphide), aminopyranthrones, aminodibenzanthrones, amino- 1.9-anthrapyrimidines, amino-1.9-anthrapyridones, amino-1.9-isothiazoleanthrones, amino- 1.9-pyrazole-anthrones, amino-1.2-anthraquinone-aeridones. The reaction components may be heated in a diluent such as nitrobenzene, chlornaphthalene, or amyl alcohol, in presence of copper or a copper compound and an alkali carbonate or acetate. In examples, (1) 2.8-dibromochrysene is reacted with two mols. 1-aminoanthraquinone ; (2) 2-bromochrysene is reacted with 1-aminoanthraquinone ; (3) 2-bromochrysene or 2-brom-8-nitrochrysene is reacted with 1-amino-4 (or 5)- benzoylaminoanthraquinone ; (4) 2.8-dibromochrysene or 2.8-dichlorochrysene is reacted with two mols. 1-amino-4-benzoylaminoanthraquinone ; 2.8-dibromochrysene is reacted with two mols. (5) 1-amino-5-benzoylamino-anthraquinone; (6) 1-amino-5-benzoylamino-8- methoxyanthraquinone; (7) 1-amino-4-methoxyanthraquinone, 1-amino-8-benzoylaminoanthraquinone, 4.4<1>-diamino-1.1<1>-dianthrimide, 1-amino-4-anilinoanthraquinone, 1-amino-3- (N).4-benz-anthraquinone-acridone, or 1.4-diaminoanthraquinone. In further examples,. (8) 2.8-dibromochrysene is reacted with 1 mol. 1-amino-4-benzoylamino-anthraquinone, the product from which is reacted in (9) with 1-amino-5-benzoylaminoanthraquinone; (10) a tetrabromchrysene obtained by brominating chrysene in nitrobenzene in presence of iodine, a brominated chrysene obtained by brominating dibromo-chrysene in sulphuric acid in presence of iodine, or a highly brominated chrysene obtained by reacting a considerable excess of bromine with 2.8-dibromochrysene in nitrobenzene in presence of iodine is reacted with excess 1-amino-4 or 5-benzoylaminoanthraquinone (grey-green tints on cotton). In examples (11) and (12), 2.8-dibromochrysene is reacted in succession with two mols. of 1-amino-5-benzoylamino-anthraquinone and in further examples, 2.8-dibromochrysene is reacted with two mols. of (13) 1-amino-5-(pmethoxybenzoylamino)anthraquinone, ; (14)1- amino-5- (p-, o-, or m-chlorobenzoylamino)- anthraquinone ; (15) 1-amino-5-acetylaminoanthraquinone ; (16) 5-amin6-1.9-anthrapyrimidine (grey-green tints on cotton) ; (17) 4- amino-N-methyl-1.9-anthrapyridone; (18) 1- amino-5-cinnamoylamino-anthraquinone or 1- amino-5-#-pyridoylamino-anthraquinone or 1- amino - 5 -(2' - anthraquinonoyl) -aminoanthraquinone (olive-brown tints on cotton); (19) aminodibenzanthrone (greenish-grey tints). In examples (20) and (21), (4<1>-benzoylaminoanthraquinonyl) -1<1>.2 - amino - 8 -bromochrysene (product of 8 above) is reacted with 1-amino-4- anilinoanthraquinone and 4-amino-2.(N)1-benzanthraquinone-acridone (green tints). Dyeing examples describe the use of the dyestuffs of examples 18, 19 and 16 in the dyeing of cotton. 2-Bromochrysene is obtained by brominating chrysene in nitrobenzene. 2.8-Dibromochrysene is obtained by dibrominating chrysene in nitrobenzene or glacial acetic acid. A tetrabromchrysene and other highly brominated chrysenes are obtained as described under (10) above. -