GB715241A - - Google Patents

Abstract

715,241. Dyes. SANDOZ, Ltd. July 7, 1952 [July 12, 1951; Dec. 14, 1951; Dec. 20, 1951], No. 17038/52. Class 2(4) The invention comprises compounds of the anthrapyridine series of the formula: wherein, if X is chlorine, bromine, NO2, or OCH3, Y is hydrogen, chlorine, bromine, alkyl, or sulpho, and n is 1 but if X is arylamino, Y may also be alkoxy or aryloxy and n is 1, 2, or 3. They are made by condensing anthraquinones of the formula: under acid conditions with an ester of acetoacetic acid with an alcohol of 1-5 carbon atoms. When X is arylamino the products may be treated with sulphonating agents, or if Y is halogen, it may be replaced by sulpho by reaction with aqueous sodium or potassium sulphite. The products which contain sulpho groups are yellow to red acid dyes for wool, silk, and nylon. To create the acid conditions, sulphuric, phosphoric, alkaline or aryl sulphonic acid may be added, or hydrogen chloride or bromide may be passed through the reaction mixture. In examples, acetoacetic acid ethyl ester is heated with the following, in presence of acid as indicated above in those cases where a free sulpho group is not present in the reactant listed below, and in presence of excess ester as solvent or another solvent such as chlorbenzene or nitrobenzene;-(1) 1-amino-4-bromoanthraquinone, (2) 1-amino-4.2'-naphthylaminoanthraquinone inylamino-anthraquinone, (4) 1- amino-2.4-dibromo- (3) 1-amino-4-(4'-methyl)-phe anthraquinone, (5) 1-amino-2.4-dichloroanthraquinone, (6) 1-amino-2-bromo-4-(4'-methyl)-phenylaminoanthraquinone, (7) 1-amino-2-methyl-4- chloro or bromo-anthraquinone, (8) a 1-amino-2-methylanthraquinone having in 4-position one of the following groups; chloro-, bromo-, phenylamino-, 2'-3'- or 4'-methylphenylamino, 3'.4'-dimethylphenylamino, 2'6'-dimethylphenylamino-2.4'.6'- trimethylphenylamino-, 2',.3'-, or 4'- chlorophenylamino, 2'- or 4'- methoxyphenylamino, 2'- methoxy-5'-methyphenyl-amino 1'- or 2'- naphthylamino or ar-tetrahydronaphthylamino, 4'- pheny-phenylamino, 4'-(4" chlorophenoxy)-phenylamino 4'-phenoxyphenyl-amino, (4'benzyl-2'-methyl) phenylamino, nitro, or methoxy, the last two variants being combined with the methyl ester of acetoacetic acid; (9) 1-amino-2-sulpho-anthraquinones having substantially the same substituents and also 2'-, 3', or 4'- carboxy-phenylaminoin 4-position; (10) 1-amino-2-phenoxy-4-(4'-methyl) -phenylaminoanthraquinone . or 1-amino-2-(4'-tert-amyl)- phenoxy-4-phenyl-amino-anth,raquinone. Those products having arylamino groups in 4-position are sulphonated, or where halogen is also present in 2-position, the product is reacted with potassium sulphite solution. Specification 412,270 is referred to.