Patent GB-560164-A (GB)
Title: Improvements relating to the manufacture of dyestuffs of the anthraquinone series
IPC: C09B1/32
Filed: 1941-12-08
Abstract: Halogenated amino anthraquinone dyestuffs are obtained by the action of halogenating agents on anthraquinone derivatives of the general formula <FORM:0560164/IV/1> , wherein R1 represents H, alkyl or the residue <FORM:0560164/IV/2> (which may be further substituted in the 31- and 51-positions), R2 represents the residue <FORM:0560164/IV/3> (which may similarly be further substituted), X represents H, halogen, alkyl sulpho or cyano, and Y and Z represent H or halogen, at least one being halogen.  The products may be subjected to sulphonation.  In examples, (1) 1:4-di-(21:41-dimethyl)phenylamino-6-chloro- or bromo-anthraquinone is di-brominated by treatment with bromine in chlorobenzene at 50-120 DEG  C.; the product may be sulphonated with oleum to obtain a wool dyestuff; (2) 1 : 4-di-(21 : 41-dimethyl)phenylamino-6 : 7-dichloroanthraquinone is similarly di-brominated and sulphonated; (3) 1-amino-2-bromo - 4 - (21 : 41 - dimethyl)phenyl - 6 - or 7 - chloro- or 6 : 7 - dichloro-anthraquinone is mono-brominated by treatment with bromine in dichlorobenzene; the product may be treated with aqueous potassium sulphite to replace the bromine in 2-position by the sulphonic acid group and then further sulphonated with oleum; the starting materials may be replaced by the corresponding 2-cyano compounds and the bromination products sulphonated with oleum; (4) 1-amino-2-bromo-4-(21 : 41-dimethyl)phenylamino-6- or 7-bromoanthraquinone is brominated by treatment with bromine in chlorobenzene; the product may be treated as in (3) to introduce sulphonic acid groups; (5) 1 : 4-di-(21 : 41-dimethyl)-phenylamino - 6 - chloroanthraquinone is iodinated by treatment with iodine in chlorobenzene containing sulphuryl chloride and the product is sulphonated; (6) 1 : 4-di-(21 : 41 : 51-trimethyl)phenylamino-6-chloroanthraquinone is brominated by treatment with bromine in chlorobenzene; (7) 1-amino-2-methyl-4-(21 : 41-dimethyl)phenylamino-6- or 7-chloro- or 6 : 7-dichloroanthraquinone is similarly brominated and the product sulphonated with oleum.  Specification 494,802 is referred to.  1 : 4-Di-(21 : 41-dimethyl)phenylamino-6-chloro-anthraquinone is obtained by condensing m-xylidine either with 1 : 4 : 6-trichloroanthraquinone or 6-chloroquinizarin (or its leuco compound), obtainable by condensing 4-chlorophthalic anhydride with p-chlorophenol in conc-sulphuric acid containing boric acid.  1 : 4-Di-(21 : 41-dimethyl)phenylamino-6-bromoanthraquinone is obtained by oxidising the condensation product from leuco - 6 - bromoquinizarin and m-xylidine.  1 : 4-Di-(21 : 41-dimethyl)phenylamino-6 : 7-dichloroanthraquinone is obtained by condensing 6 : 7-dichloroquinizarin (or its leuco compound) with m-xylidine.  1 - Amino - 2 - bromo - 4 - (21 : 41 - dimethyl)-phenylamino-6- or 7-chloro- or 6 : 7-dichloroanthraquinone is obtained by condensing with m-xylidine the product of dibromination of 1-amino-6- or 7-chloro- or 6 : 7-dichloroanthraquinone. 1-Amino-7-chloroanthraquinone is obtained by reducing with sodium sulphide the corresponding 1-nitro compound, obtained by treating 1-nitroanthraquinone-7-sulphonic acid with nascent chlorine.  1 - Amino - 6 : 7 - dichloroanthraquinone is obtained by saponification with sulphuric acid of the condensation product of 1 : 6 : 7-trichloroanthraquinone with toluenesulphamide.  1 : 6 : 7-Trichloroanthraquinone is obtained by treating with nascent chlorine the product of sulphonation of 2 : 3-dichloroanthraquinone in presence of mercury.  1 - Amino - 2 - cyano - 4 - (21 : 41 - dimethyl) phenylamino-6- or 7-chloro- or 6 : 7-dichloroanthraquinone is obtained by treating the corresponding 2-sulphonic acid with potassium cyanide.  1 : 4-Di-(21 : 41 : 51-trimethyl)phenylamino-6-chloroanthraquinone is obtained by oxidising the condensation product from leuco-, 6-chloroquinizarin and 2 : 4 : 5-trimethylaniline.  1 - Amino - 2 - methyl - 4 - (21 : 41 - dimethyl)-phenylamino-6- or 7-chloroanthraquinone is obtained by condensing with m-xylidine the product of bromination of 1-amino-2-methyl-6-or 7-chloroanthraquinone.  1 - Amino - 2 - methyl - 6 - and 7 - chloroanthraquinones are obtained in admixture by reducing the corresponding mixture of 1-nitro compounds, obtainable by nitrating a mixture of 2-methyl-6- and 7-chloroanthraquinones. 2-Methyl-6- and 7-chloroanthraquinone are obtained in admixture by treating with sulphuric acid the condensation product from 4-chlorophthalic anhydride and toluene in presence of aluminium chloride.  1 - Amino - 2 - methyl - 4 - (21 : 41 - dimethyl) phenylamino - 6 : 7 - dichloroanthraquinone is obtained by condensing with m-xylidine the product of bromination of 1-amino-2-methyl-6 : 7-dichloroanthraquinone.  1 - Amino - 2 - methyl - 6 : 7 - dichloroanthraquinone is obtained by reducing the corresponding 1-nitro compound, obtainable by nitrating 2-methyl-6 : 7-dichloroanthraquinone.  2 - Methyl - 6 : 7 - dichloroanthraquinone is obtained by treating with sulphuric acid the condensation product from 4 : 5-dichlorophthalic anhydride and toluene in presence of aluminium chloride.