Patent GB-320324-A (GB)
Title: The manufacture of water soluble secondary diazoamino compounds and of azo dyestuffstherefrom
Filed: 1928-07-04
Abstract: 320,324. Carpmael, A., (I. G. Farbenindustrie Akt.-Ges.). July 4, 1928. Diazoamino compounds soluble in water and useful as dye intermediates and insecticides are obtained by coupling an aromatic diazo, diazoazo or tetrazo compound in the presence of an acid fixing substance with a derivative of a secondary base of the general formula : NH#<R1>R2 in which R1 and R2 = alkyl, aryl, aralkyl or hydroaromatic residues and R2 may be either the same as or different from R1, provided that R1 or R2 or both residues is or are substituted by a group inducing solubility in water such as the sulphonic or carboxylic group with the exception of those described in Specification 309,610. In examples the following pairs of amines are specified in each case the first-mentioned amine being diazotized (or tetrazotized) and coupled with the secondary amino compound in presence of either potassium or sodium carbonate or bicarbonate, magnesia or caustic alkalis :-(1) 4-chlor- 2-toluidine and monoethyl-2-toluidine-4-sulphonic acid, (2) 5-nitro-2-anisidine and monoethyl-msulphanilic acid, (3) m-nitraniline and monomethylaniline-4-sulphonic acid, (4) 1-aminocarbazole and sarcosin, (5) 4-chloro-2-anisidine and monoethyl-p-toluidine sulphonic acid, (6) dianisidine and monoethyl-p-toluidine-3-sulphonic acid, (2 mols.), (7) 4-chloroaniline and monoglycinated 4-sulphanilic acid, (8) 5-nitro-2-anisidine and monoethyl-4-toluidine-3-sulphonic acid, (9) mnitraniline-azo-aminohydroquinone dimethylether and sarcosin, (10) 4-chloro-2-toluidine and sarcosin,( 11) 4-chloro-2-toluidine and diglycolamino acid, (12) 5-chloro-2-toluidine and dibenzylamine disulphonic acid, (13) 5-nitro-2-toluidine and the condensation product from hexahydroaniline and chloracetic acid, (14) o-anisidine and N-methylbenzylaminosulphonic acid. The Provisional Specification describes also the preparation of diazoamino compounds from the following :-5-chloro-2-toluidine and diphenylamine-4- sulphonic acid, 4-aminoazotoluene and monoethyl-2-toluidine disulphonic acid (prepared by heating monoethyl-2-toluidine-4-sulphonic acid with oleum), 4-nitro-2-anisidine and monobenzylated-p-sulphanilic acid, o-anisidine and monoglycinated 4-chloro-2-aminobenzoic acid. Monoethyl - 2 - toluidine - 4 - sulphonic acid is obtained by ethylation of 2-toluidine-4-Sulphonic acid or by sulphonation of monoethyl-o-toluidine. N-methylbenzylaminosulphonic acid is made by treating N-methylbenzylamine with oleum. Azo dyes.-Azo dyes are made in substance by treating the above diazoamino compounds with dyestuff components in the presence of acid. The following examples are specified. (15) The diazoamino compound from 3-nitro-4-toluidine and monoethyl-2-toluidine-4-sulphonic acid is dissolved in an alkaline solution of acetoacetic acid anilide. The dyestuff forms on addition of acetic acid. (18) A solution of the diazoamino compound from 4-chloro-2-toluidine and sarcosin is mixed with an alkaline solution of 2 : 3-oxynaphthoic acid-2<1>-toluidide and evaporated to dryness and a printing paste made by mixing with Turkey red oil and starch tragacanth. (19) Potassium 2-methyl-4-nitrobenzeneazo-N-ethylaminobenzene- 3<1>-sulphonate are mixed with 2 : 3-oxynaphthoio acid-2<1>-toluidide and a neutral thickener. The coupling component may be substituted by #- naphthol, a-naphthol derivatives, pyrazolones, diacyl acetic acid arylides and 1 : 3-dioxyquinolines. (20) A printing paste is made from the diazoamino compound from 1-amino-2 : 5-diethoxy-4-benzoylaminobenzene and sarcosin, 2 : 3. oxynaphthoic acid-o-toluidide, caustic soda, sulphonated castor oil and tragacanth. (21) The compound from 1- amino - 4 - benzoylamino -2- methoxy-5-methylbenzene and sarcosin and 2 : 3- oxynaphthoic acid anilide are used as in (20). (22) The diazoamino compound from p-nitrobenzene - azo - aminohydroquinonedimethylether and sarcosin and 2-oxy-3-naphthoylaminohydroquinone dimethylether are used as in (18). (23) The product from dianisidine and ethyl-p-toluidine sulphonic acid (example 6) and 2 :3-hydroxynaphthoyl-a-naphthylamine and that from 4-chlor-2- toluidine and sarcosin and diacetoacetic acid-otoluidine are used as in (20). 1-Amino-2 : 5-diethoxy-4-benzoylaminobenzene is made by benzoylating aminohydroquinone-diethylether, nitrating and reducing. 1- Amino -4- benzoylamino-2-methoxy-5-methylbenzene is made by acetylating and reducing 3- amino-6-nitro-4-cresolmethylether, benzoylating and splitting off the acetyl group.