Patent GB-516131-A (GB)
Title: Manufacture of nitrogenous condensation products
IPC: C09B5/00
Filed: 1938-06-21
Abstract: 516,131. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. June 21, 1938, Nos. 18400, 18401, 18402, 18403, 18404, and 18405. Convention dates, June 21, 1937, Sept. 14, 1937, Dec. 1, 1937, Dec. 20, 1937, March 2, 1938, and May 18, 1938. [Classes 2 (iii) and 15 (ii)] Nitrogenous condensation products are obtained by reacting with a condensing agent on a compound of the formula wherein R1 is the radical of a compound capable of being vatted, R is a chrysene radical, and n indicates 1 or a greater number, and wherein in at least one radical R1 and also in the chrysene radical R2 the carbon atom in at least one of the positions capable of being substituted which are adjacent to the imino group - connecting the radicals R1 and R 2 is attached to hydrogen. A product of the above process which contains halogen may oe reacted with - an amine containing the radical of a compound capable of being vatted, and the reaction product is treated, if desired, with a condensing agent. The products of either process may be treated with halogenating agents or converted to leuco-derivatives, e.g., leuco-sulphuric acid - esters. The starting materials of the above formula may be obtained according to Specification 516,130, but di- and tri-chlorbenzene are specified as additional diluents for the preparation. They may also be prepared by reaction of an aminochrysene with a halogenated vattable. compound, e.g., by reaction of an amino- -chrysenesulphonic acid with a 1-amino-4- halogenanthraquinone-2-sulphonic acid in aqueous or aqueous-alcoholic media. The - condensing agent may be aluminium chloride, 'if desired in presence of an organic acid chloride - and a diluent or solvent, or sulphuric acid, which may contain a little nitrosyl-sulphuric acid. The products may be purified by re- - crystallization from organic solvents, conversion into their salts with strong acids, or by treatment with oxidizing agents, for example alkali nitrite in acid solution, alkali hypochlorite or perborate. The products are in part dyestuffs, -and may be used for dyeing and printing cotton, -artificial silk, wool and natural silk. In examples, the following substances are reacted with con- - centrated sulphuric acid at moderate temperatures ; (1) -di-(1<1>-anthraquinonyl)-2.8-diaminochrysene (red tints on cotton), (2) (1'- anthraquinonyl)-2-aminochrysene (orange tints on wool), (3) (4<1>-benzoylamino-anthraquinonyl- 1<1>)-2-aminochrysene (brown-red tints on wool), (4) di-(4<1>-benzoylamino-1<1>-anthraquinonyl)-2.8- diaminochrysene (red-brown tints on cottonmore brown if chlorsulphonic acid is used instead of sulphuric acid), (5) di-(5<1>-benzoylamino-1<1>-anthraquinonyl)-2.8-diaminochrysene (yellow-brown tints on cotton), (6) di-(5'- benzoylamino-8<1>-methoxy-1<1>-anthraquinonyl)- 2.8-diaminochrysene, (red-brown tints on cotton), (7) (4<1>-benzoylamino-anthraquinonyl-1<1>)- 2-amino-8-bromochrysene (red-brown-violet tints), (8) the product of the reaction of 2.8- dibromochrysene with 1-amino-4-benzoylaminoanthraquinone and 1-amino-5-benzoylaminoanthraquinone either simultaneously or successively (brown tints on cotton), (9) the product from 1-amino-4-benzoylamino-anthraquinone and tetrabromchrysene or brominated chrysene of m.p. 345‹C. (see example 10 of Specification 516,130) (brown-violet-black tints on cotton), (10) the product from tetrabromchrysene and 1-amino-5-benzoylamino-anthraquinone (brown tints on cotton), (11) (5<1>-benzoylamino-anthraquinonyl-1<1>)-2-amino-8-bromochrysene (yellowbrown tints on cotton), the product then being further condensed with 1-amino-5-benzoylamino-anthraquinone (brown tints) and again treated with sulphuric acid (yellow-brown tints on cotton), (12) di-(5<1>-p-methoxybenzoylaminoanthraquinonyl - 1<1>) - 2.8 - diaminochrysene (brown tints on cotton), (13) di-(5<1>-p, o-, or m - chlorbenzoylamino - anthraquinonyl-1<1>) - 2.8 - diaminochrysene (brown tints on cotton), (14) di - (5<1> - acetylamino - anthraquinonyl - 11) - 2.8 - diaminochrysene (brown tints on cotton), (15) the condensation product from 1-amino-4- bromanthraquinone-2-sulphonic acid and 2- aminochrysene-monosulphonic acid (orangeyellow tints on wool), (16) the product from 1 mol. 2.8-dibromochrysene and 2 mols. 5- amino-1.9-anthrapyrimidine (brown tints), (17) di-(5-cinnamoylamino - anthraquinonyl - 1<1>) - 2.8-diaminochrysene (yellow-brown tints on cotton), (18) di-(5<1>-#-pyridoylamino-anthraquinonyl-1<1>)-2.8-diaminochrysene (brown tints on cotton), (19) di-[5<1>-(2<11>-anthraquinonoylamino)- anthraquinonyl-1<1>]-2.8-diaminochrysene (brown tints), (20) (5<1>-benzoylamino-anthraquinonyl- 1<1>)-2-aminochrysene (red-brown tints on cotton), (21) (5<1>-benzoylamino-anthraquinonyl-1<1>)-2-amino-8-nitrochrysene (yellow-brown tints on cotton), (22) the product from 1 mol. 2.8- dibromochrysene, 1 mol. 1-amino-4-benzoylamino-anthraquinone and 1 mol. 4-amino-2, (N) 1-benzanthraquinone-acridona (violet-greyblack tints on cotton). In further examples, (23) (4<1>-benzoylamino-anthraquinonyl-1<1>)-2-amino-8-bromochrysene is treated with concentrated sulphuric acid, and the carbazolized product is condensed with 5-amino-1.9-anthrapyrimidine to give a product which dyes cotton brown-violet tints and which is further carbazolised with sulphuric acid. to give a product which dyes cotton red-brown tints ; if (5<1>-benzoylamino-anthraquinonyl-1<1>)-2-amino-8-bromochrysene is used, a product dyeing cotton yellow-brown tints is obtained. Also in examples, (24) (5<1>-benzoylamino-1<1>-anthraquinonyl)-2-amino-8-bromochrysene is reacted with 4-amino-N-methyl-1.9-anthrapyrid one,. followed by treatment of the product with concentrated sulphuric acid (brown 'tints), or alternatively it may be treated with sulphuric acid and then condensed with 4-amino-N-methyl-19-anthrapyridone; also (4<1>-benzoylamino-anthraquinonyl-1<1>)-2-amino-8-bromochrysene may be condensed with 4-amino-N-methyl-1.9-anthrapyridone, followed by' treatment with sulphuric acid (violet-brown) (25) (4<1>-benzoylamino-1<1>- anthraquinonyl)-2-amino-8-bromochrysene is condensed with 5-amino-isothiozoloeanthrone, followed by treatment with sulphuric acid (red-brown tints), or alternatively (51-benzoylamino-anthraquinonyl-1<1>)-2-amino-8-bromochrysene may be treated with sulphuric acid and then condensed with 5-amino-isothiozoleanthrone (yellow-brown tints) ; (26) di-(4<1>-benzoylamino -anthraquinonyl - 1<1>) - 2.8 - diaminochrysene is condensed with a mixture of aluminium chloride and acetyl or benzoyl chloride or with a mixture of aluininium chloride and nitrobenzene (brown tints); (27) the product of (4) above is brominated in sulphuric acid or in nitrobenzene (brown tints). Further examples describe the use of the products of (4) and (5) above in the vat dyeing of cotton, and of the product of (15) above in the direct dyeing of wool. 2-Aminochrysenesulphonic acid is made by sulphonating 2-aminochrysene.