Patent GB-587930-A (GB)
Title: Compositions containing diazotizable amines or diazonium salts thereof
IPC: D06P1/12
Filed: 1943-03-10
Abstract: Azo dyes, forming on the material; printing.-A diazotizable amine free from water-solubilizing groups or a water-soluble diazonium salt derived therefrom is incorporated with at least one organic nitrogenous base free from sulphonic acid groups, soluble in aqueous mineral acids, containing not more than 15 carbon atoms and containing at least one olefinic double bond or acetylenic triple bond or with a water-soluble salt thereof with an acid incapable of azoic coupling or of decomposing diazonium salts at room temperature, the base or its salt being in sufficient amount to inhibit thinning of a printing paste containing a carbohydrate thickener.  The base must be free from groups capable of azoic coupling and when incorporated before the diazotization must be free from groups capable of reaction with nitrous acid.  A large number of diazotizable amines is specified.  In examples: (1) a paste for printing blue patterns on cellulosic material impregnated with arylides of 2 : 3-hydroxynaphthoic acid contains the zinc chloride double salt of the tetrazonium chloride from o-dianisidine, magnesium sulphate, N-allyl-N : N : N-triethylammonium chloride and Carob bean gum; (2) a paste for producing red prints on cotton cloth impregnated with 2 : 3-hydroxynaphthoic anilide contains diazotized 5-nitro-2-aminoanisole, Carob bean gum and N-allyl-N : N : N-triethylammonium chloride or other water-soluble salt of this base, e.g. its sulphate, phosphate, nitrate, ethanesulphonate, benzenesulphonate or succinate; (3) a paste for producing scarlet or orange prints on cotton cloth impregnated with 2 : 3 - hydroxynaphthoic anilide or o-phenetidide respectively, contains the zinc chloride double salt of the diazonium chloride from 2 : 5-dichloraniline, N-b -methylallyl-N : N : N-triethylammonium chloride and Carob bean gum; (4) printing pastes contain the zinc chloride double salt of the diazonium chloride from 3-nitro-4-aminoanisole, N-b -methylallyl - N : N : N - triethylammonium chloride and one of the following thickeners: Carob bean gum, methylcellulose, sweet potato starch or gum tragacanth; (5) printing pastes contain the zinc chloride double salt of the diazonium chloride from 3-nitro-4-aminoanisole or 2 : 5-dichloraniline, N - vinyl - N : N : N - trimethylammonium bromide, Carob bean gum, and (in the case of the former diazo compound) magnesium sulphate; (6) pastes for producing blue prints on cellulosic fibre impregnated with 2 : 3-hydroxynaphthoic anilide contain the zinc chloride double salt of the tetrazonium chloride from o-dianisidine, magnesium sulphate, N-allylpyridinium sulphate or chloride and Carob bean gum; (7) a paste for producing scarlet, reddish orange or yellow prints respectively on cloth impregnated with 2 : 3-hydroxynaphthoic anilide or o-phenetidide or bis-acetoacetic o-tolidide, contain the zinc chloride double salt of the diazonium chloride from 2 : 5-dichloraniline, S-allyl-isothiourea hydrochloride and Carob bean gum; (8) printing pastes contain the zinc chloride double salt of the diazonium chloride from 3-nitro-4-aminoanilole, S-allyl-isothiourea hydrochloride and one of the thickeners of (4), or R.P.G. gum (mixed starches); (9) a mixture of 3-nitro-4-aminoanisole, S-allyl-isothiourea hydrochloride and common salt is added to dilute hydrochloric acid, sodium nitrite solution is added, the solution is mixed with Carob bean gum and the resulting paste is printed on cloth impregnated with 2 : 3-hydroxynaphthoic anilide, yielding Bordeaux prints; (10) the inhibitor in (7) is replaced by S-b -methylallyl-isothiourea hydrochloride; (11) and (12) the inhibitor in (8) and (9) is similarly replaced; (13) a paste for producing Bordeaux prints on cloth impregnate with 2 : 3-hydroxynaphthoic anilide contains the zinc chloride double salt of the diazonium chloride from 3-nitro-4-aminoanisole, aluminium sulphate, allylamine hydrochloride and Carob bean gum; (14) the aluminium sulphate in (13) is omitted; (15) the allylamine hydrochloride in (14) is replaced by tetra-allylammonium bromide, and (16) by N-allyl-N : N-dimethyl-N-phenylammonium chloride; (17) the allylamine hydrochloride in (13) is replaced by N-allylurea; (18) pastes for printing on cloth impregnated with 2 : 3-hydroxynaphthoic arylides contain allylguanidine sulphate, Carob bean gum and the zinc chloride double salts of the diazonium (or tetrazonium) chlorides from 2 : 5-dichloraniline, 4-nitro-2-aminoanisole, 3-nitro-4-aminoanisole or o-dianisidine. In each case comparative results omitting the inhibitor are described.  Other inhibitors specified are: N-methyl-N-allylamine, diallylamine, N : N - dimethyl - N - allylamine, triallylamine, N : N : N-trimethyl-N-allylammonium hydroxide, N-propyl- and N-isobutyl-N-allylamine, N-methyl-N-propyl-N-allylamine, N-b -methylallyltrimethylammonium hydroxide, N-g -methylallylamine, 4-aminopentene-1, 5-aminohexene-1, 4-allyl-5-aminopentene-1, 2 : 6-dimethyl-8-amino-octadiene-2 : 6, 2-propinylamine, N-ethyl-N1-allylurea, N : N1-diallylurea, O - allylisourea, o  - allyl - biguanide 4 - aminocyclohexene - 1, 3 - N : N - dimethylaminocyclohexene-1, the corresponding quaternary ammonium base containing an additional N-methyl group, 5-dimethylaminocyclo - octene - 1, 6 - amino - p - menthene - 1, 2 - amino -p - menthene - 3, N : N - diallyl - p - chlor - aniline, N : N : N - triallyl - N - p - tolylammonium hydroxide, N - propargyl - N : N - dimethyl - N - phenylammonium hydroxide, N - allyl - N : N - dimethyl-N-a -naphthylammonium hydroxide, N : N - diallylfurfurylamine, N : N - diallyl - 6 - amino-1 : 4-benzodioxane and tropidine.  N : b  : Methylallyl - triethyl- and trimethyl - ammonium chlorides are obtainable by heating the corresponding amines with b -methylallyl chloride in a closed vessel.  N-Allyl-N : N-dimethyl-N-phenylammonium chloride is obtainable by warming dimethylaniline with allyl chloride.  N : N-Diallyl-p-chloraniline is obtainable in the form of its hydrobromide by the action of allyl bromide on p-chloraniline.  N : N : N-Triallyl-N-p-tolylammonium bromide is obtainable by the action of allyl bromide on N : N-diallyl-p-toluidine.  N - Propargyl - N : N - dimethyl - N - phenyl - ammonium bromide is obtainable by the action of propargyl bromide on dimethylaniline.  N - Allyl - N : N - dimethyl - N - a  - naphthyl - ammonium bromide is obtainable by the action of allyl bromide on N : N-dimethyl-a -naphthylamine.  N : N-diallylfurfurylamine is obtainable in the form of its hydrobromide by the action of allyl bromide on furfurylamine.  N : N - Diallyl - 6 - amino - 1 : 4 - benzodioxane is obtainable in the form of its hydrobromide by the action of allyl bromide on the base prepared by reduction of the product of condensation of 4-nitrocatechol with ethylene bromide in the presence of alkali.  N-Allylpyridinium chloride is obtainable by the action of allyl chloride on pyridine.  S-b -Methylallyl-isothiourea hydrochloride is obtainable from thiourea and b -methylallyl chloride.  The Specification as open to inspection under Sect. 91 comprises also the use of b -aminoethyl allyl ether and thioether and N : N : N1 : N1-tetrallylethylenediamine.  This subject-matter does not appear in the Specification as accepted.