Patent GB-744441-A (GB)
Title: New dyestuffs of the anthraquinone series
IPC: C09B43/145
Filed: 1953-11-09
Abstract: The invention comprises green substantive dyestuffs of the anthraquinone series of the general formula <FORM:0744441/IV(c)/1> wherein R denotes a phenylene or diphenylene radical which may be substituted by alkyl, alkoxy or halogen, wherein the nucleus A may bear a sulphonic acid group in one of the positions 5, 6, 7 or 8 or one halogen atom in one of the positions 6 or 7, or two halogen atoms in the positions 6 and 7, X1 denotes the same or a different grouping defined by X or the residue of a yellow azo dyestuff, Me denotes a heavy metal atom, u is zero or one of the numerals 1 or 2, and wherein the hydrogen atoms of the -CH=CH-CH= CH- bridge may be substituted by methyl or chlorine.  The dyestuffs may be made by condensing 2 mols of an anthraquinone compound of the formula <FORM:0744441/IV(c)/2> the definitions of R and of the nuclear substituents which A may bear being the same as those given above; with 1 mol of a 1, 3 - butadiene - 1.4 - dicarboxylic halogenide or of a substitution derivative thereof having as substituent or substituents a methyl group or chlorine atoms.  Alternatively there may be used 2 mols of any desired mixture of two or more anthraquinone compounds having the above general formula or 2 mols of a mixture of one or more of the anthraquinone compounds and one or more yellow aminoazo compounds.  In a variation of the above process 1 mol of the 1, 3- butadiene- 1, 4-dicarboxylic halogenide is condensed with 2 mols of a mixture of one or more of the anthraquinone compounds of the above general formula and one or more amino compounds having a carbon atom capable of coupling, and which amino compounds may contain an azo group, and the condsation product is coupled with a diazo compound.  Metallized dyestuffs of the above general formula are obtained by treating the products of the above processes with metal-yielding agents.  Anthraquinone compounds employed as starting materials mentioned include condensation products from 1 - amino - 4 - bromanthraquinone - 2 - sulphonic acid, 1 - amino - 4 - bromanthraquinone - 2.5 or 2.6 - or 2.7 or 2.8 disulphonic acid, 1 - amino - 4 brom - 6 or 7 - fluor - or - chlor - or bromanthraquinone - 2 sulphonic acid and 1 - amino - 4 - brom-6.7 - dichlor - or dibromanthraquinone - 2 - sulphonic acid with 1.4 - diaminobenzene, 1, 4 - diamino - 2 chlorobenzene, 1.4 - diamino - 2 - methyl or ethyl benzene, 1.4 - diamino - 2 - methoxy - or ethoxybenzene, 4, 41 diamino - 1.11 - diphenyl and 4.41 - diamino - 3.31 - dimethyl - or dimethoxy - 1.11 - diphenyl.  Yellow aminoazo compounds which may be condensed in admixture with the anthraquinones with the 1.3-butadiene - 1.4 - dicarboxylic halogenide mentioned include those of the benzene series, e.g. 4 - amino - 1.11 - azobenzene - 41 - sulphonic acid or 4 - amino - 21.3 - dimethyl - 1.11 - azobenzene - 41 - sulphonic acid and yellow amino azo dyestuffs of the stilbene, naphthalene, pyrazolone and acetoacetylaminoaryl series. Where metal complex forming groups are introduced with the aminoazo compounds the end-products can be converted into metallic complex compounds by treatment with metal yielding agents in substance or on the fibre.  Also metallized aminoazo compounds may be condensed with the 1, 3 - butadiene - 1, 4 - dicarboxylic halogenide and the anthraquinone compounds.  Starting materials, e.g. in the form of alkali metal salts are dissolved in water and the 1, 3 - butadiene - 1.4 - dicarboxylic halogenide is added to the solution, optionally dissolved in a solvent such as carbon tetrachloride, chloroform, methyl benzene, chlorobenzene or 1.2 - dichlorobenzene.  Advantageously a pH of between 6 and 8 is maintained during the reaction and solutions, e.g. of sodium acetate, carbonate, borate or hydroxide or lithium carbonate or a buffer, e.g. sodium bicarbonate may be employed to neutralize liberated acid.  The dyestuffs are precipitated from the solution by salting out or by acidifying.  The products may be converted to alkali metal salts. Aqueous solutions of the dyes dye objects of natural cellulose, e.g. cotton, or regenerated cellulose.  Where dyes contain groups favourable to metal complex formation metallizing may be carried out with copper- or nickel-yielding agents.  Coppering can take place by heating the dye with copper salts in weakly acid to weakly alkaline aqueous solution, optionally under pressure and/or in the presence of ammonia or organic bases such as diethanolamine, pyridine or quinoline or in the melt of an alkali metal salt of a lower molecular aliphatic monocarboxylic acid.  If the dye contains an alkoxy group favouring metallization the latter is preferably carried out with removal of this alkoxy group.  Starting materials of the anthraquinone series employed in the examples are of the general formula <FORM:0744441/IV(c)/3> in which, in the absence of x and ysubstituents, R is p - aminophenyl-, o- or m-methoxy - p - aminophenyl-, o- or m-chloro - p - aminophenyl; or in which R is p - aminophenyl and the substituent x is 5, 6, 7 or 8 sulphonic acid, or 6- or 7- bromo, or 6 - fluoro there being no y substituent or both the x and y substituents are bromo; or in which R is o - or m - methoxy - p - amino - phenyl and the substituent x is 6 - sulphonic acid, or in which R is o - or m - methyl - p - amino - phenyl and x is 6 - sulphonic acid; or in which R is o- or m-methyl - p - amino - phenyl and x is 6-sulphonic acid; or in which R is p-( p1-aminophenyl) phenyl- or o - methyl - p-(p1 - amino - o1 - methyl phenyl) phenyl - and x is 7-sulphonic acid. 1, 3 - butadiene - 1, 4 - dicarboxylic halogenides specified are 1, 3 - butadiene 1, 4 - dicarboxylic chloride, 1, 4 - dichloro - 1, 3 - butadiene - 1, 4 - dicarboxylic chloride and 2 - methyl - 1, 3 - butadiene - 1, 4 - dicarboxylic chloride.  Specific aminoazo compounds employed are 4 - amino - 1, 11 - azobenzene - 4 - sulphonic acid, the trisodium salt of 1 - carboxy - 2 - aminobenzene - 5 - sulphonic acid --> 1 - [411 - amino - 1.111 - stilbenyl (41)] - 3 - methyl - 5 - pyrazolone - 21.211 - disulphonic acid and trisodium salt of the copper complex thereof, the monosodium salt of 1 - carboxy - 2 - aminobenzene - 5 - sulphonic acid --> 1 - (41 - amino - phenyl - 3 - methyl - 5 - pyrazolone, the monosodium salt of 1 - carboxy - 2 - aminobenzene - 4 - sulphonic acid --> 1 - (31 - amino) - phenyl - 3 - methyl - 5 - pyrazolone, monosodium salt of 1 - carboxy - 2 - amino - benzene - 5 - sulphonic acid --> 1 - acetoacetylamino - 4 - aminobenzene, the monosodium salt of the reduction product of 1-methoxy - 2 - amino - 5 - nitrobenzene --> 1 - acetoacetylaminobenzene - 4 - sulphonic acid, the disodium salt of 2-aminonaphthalene - 6.8 - disulphonic acid --> 1 - amino - 3 - methylbenzene, the disodium salt of 2-aminonaphthalene - 4.8 - disulphonic acid 1 - amino - 3 - acetylaminobenzene, the trisodium salt of 1 - hydroxy - 2 - amino - 6 - chlorobenzene - 4 - sulphonic acid --> 1-[411 - amino - 11.111 - stilbenyl - (41)] - 3 - methyl - 5 - pyrazolone - 2.21 - disulphonic acid, the monosodium salt of 4 - amino 41 - hydroxy - 1.11 - azobenzene - 31 - carboxylic acid, 41 - amino - 1.11 - azobenzene - 3.41 - disulphonic acid --> 1 - (41 - amino) - benzoylamino - 3 - methyl - benzene, 4 - amino -1.11 - azobenzene - 3.41 - disulphonic acid --> 1 - amino - 3 - acetylaminobenzene, and the trisodium salt of 1 - methoxy - 2 - aminobenzene - 4 - sulphonic acid --> 1 - [411 - amino - 11.111 - stilbenyl - (41)] - 3 - methyl - 5 pyrazolone - 21.211 - disulphonic acid.  Examples are furnished in which from one to three anthraquinone starting materials are reacted with a 1, 3 - butadiene - 1, 4 - dicarboxylic halogenide or in which one or two aminoazo compounds and an anthraquinone compound are reacted with a 1, 3 - butadiene - 1, 4 - dicarboxylic halogenide.  In a further example sodium 1 - [411-amino-11.111 - stilbenyl (41)] - 3 - methyl - 5 - pyrazolone - 21.211 - disulphonate and an anthraquinone starting material are reacted with a 1, 3 - butadiene - 1.4 - dicarboxylic acid and the product is coupled with diazotized 1- carboxy - 2 - aminobenzene - 5 - sulphonic acid.  Dyes containing pyrazolone residues are converted to copper- or nickel-complexes.  The dyeing of cotton, the coppering of dyeings and after-treatment of dyeings with an aqueous solution of a copper-containing polyamine -dicyandiamide condensation product are illustrated.  The use of the products obtained by the process of Specification 657,753 in treating the dyeings with metallizable and metal containing dyestuffs is mentioned.  Specification 554,463 also is referred to