Patent GB-587467-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B43/20
Filed: 1944-09-04
Abstract: Azo dyestuffs of the general formula <FORM:0587467/IV/1> in which y is the residue of a polybasic acid bound in the form of an acid ester (e.g. the residue of sulphuric, oxalic, malonic, succinic, adipic, pimelic, suberic, maleic, phthalic, m-sulphobenzoic, sulphophthalic, sulphoacetic or chlorosulphoacetic acid).  A is the residue of a yellow component, and R is an alkylene group which contains at least 2 but not more than 6 carbon atoms directly connected with one another, and may contain halogen atoms as substituents, and in which the benzene nucleus may contain further substituents, e.g. halogen atoms, alkyl, alkoxy or nitro groups, are manufactured by treating a dyestuff of the general formula <FORM:0587467/IV/2> (obtainable from, for example, aniline-o-, m- or p-(b -hydroxyethyl)-sulphone) with at least an equimolecular proportion of a polybasic acid or the anhydride or a halide or reactive ester thereof, or by diazotizing an aromatic amine of the general formula <FORM:0587467/IV/3> and coupling with a yellow component, e.g. a phenol such as phenol itself and especially a phenol coupling in o-position to the hydroxy group, such as p-cresol, resorcinol or a monoalkyl ether of hydroquinone, a dihydroxyquinoline, a -methylketol, an ester or amide of acetoacetic acid, or especially a pyrazolone such as 1 - phenyl - 3 - methyl - 5 - pyrazolone, a 1 - tolyl- or 1 - chlorophenyl - 3 - methyl - 5 - pyrazolone, a pyrazolone carboxylic or sulphonic acid, or 3-methyl-5-pyrazolone.  The products, which are soluble in water, especially in the form of their salts, dye cellulose esters and ethers from aqueous solution in yellow shades, and are also suitable for dyeing artificial masses, e.g. nitrocellulose lacquers and artificial fibres composed of superpolyamides or superpolyurethanes, and in some cases for dyeing animal fibres, e.g. wool or silk.  In examples: (1) aniline - p - (b  - hydroxyethyl)- sulphone is diazotized and coupled with 1-(21-chloro)-phenyl - 3 - methyl - 5 - pyrazolone, and the product is treated with sulphuric acid and then neutralized with sodium carbonate; alternatively the diazo component is treated with sulphuric acid before diazotization; (2) the coupling component in (1) is replaced by p-cresol; (3) the initial dyestuff of (1) is heated with succinic anhydride in glacial acetic acid (or other solvent, e.g. toluene, benzene or xylene), and the product is neutralized with sodium carbonate; (4) cellulose acetate artificial silk yarn is dyed with the product of (1) from a bath containing sodium sulphate.  Formul  are given further dyestuffs, including one derived from aniline-p-(g -hydroxy-b -chloropropyl)-sulphone. Aminoaryl - b  - hydroxyethyl - sulphones are obtainable by converting the corresponding acylaminoarylsulphohalide, e.g. an acetanilidesulphohalide, into the sulphinic acid, treating this with an ethylene halohydrin and then saponifying the acylamino group, or by treating the appropriate mercaptan of nitrobenzene with an ethylene halohydrin, oxidizing the thioether to the sulphone, and reducing the nitro group.  Specification 516,929 is referred to.  The Specification as open to inspection under Sect. 91 comprises also the manufacture of dyestuffs containing, instead of the -SO2-group in the general formula above, the grouping <FORM:0587467/IV/4> wherein Z is hydrogen or an alkyl or substituted alkyl group containing not more than 6 carbon atoms directly connected to one another.  Additional diazo components specified are aniline-o-, -m- and -p-sulpho-N-(b -hydroxyethyl)-amides (obtainable by the action of ethanolamine on the corresponding sulphonic acid halide of nitrobenzene or acetanilide, followed by reduction or saponification), or their esters with polybasic acids, and formul  are given of dyestuffs derived from these components, and also one from sulphanilic acid N - (b  - sulphatoethyl)-N-phenylamide (sic).  This subject-matter does not appear in the Specification as accepted.