Patent GB-663005-A (GB)
Title: Photographic silver halide emulsions containing non-diffusing azo dyes
IPC: G03C7/29
Filed: 1949-06-08
Abstract: 2-Tetradecoxyacetanilide is prepared by treating a solution of 2-hydroxyacetanilide and tetradecyl bromide in boiling absolute alcohol with a solution of sodium metal in absolute ethyl alcohol and refluxing.  2-Tetradecoxyaniline is prepared by treating an absolute ethyl alcohol solution of 2-tetradecoxyacetanilide with aqueous potassium hydroxide and refluxing, forming the hydrochloride, and treating with aqueous sodium hydroxide to reform the amine.  2 - Octadecoxyacetanilide, 2 - octadecoxyaniline, 2 - dodecoxyacetanilide, 2 - dodecoxyaniline, 2 - decoxyacetanilide, 2 - decoxyaniline, 4 - decoxyacetanilide, 4 - decoxyaniline, 4 - octoxyacetanilide, 4 - octoxyaniline, 4 - dodecoxyacetanilide, 4 - dodecoxyaniline, 4 - tetradecoxyacetanilide, 4 - tetradecoxyaniline, 4 - octadecoxyacetanilide, 4 - octadecoxyaniline, 3 - decoxyacetanilide, 3 - decoxyaniline, 3 - tetradecoxyacetanilide, and 3-tetradecoxyaniline are similarly prepared.  2 - Dodecoyxaniline - 5 - sulphonic acid is prepared by adding 25 per cent oleum to a solution of 2-dodecoxyaniline in concentrated sulphuric acid, and heating.  2-Decoxyaniline-5-sulphonic acid, 2-tetradecoxyaniline-5-sulphonic acid, 2 - octadecoxyaniline - 5 - sulphonic acid, 4 - decoxyaniline - 3 - sulphonic acid, 4 - tetradecoxyaniline - 3 - sulphonic acid, and 4 - octadecoxyaniline - 3 - sulphonic acid are similarly prepared. 3 - Tetradecoxyaniline - 6 - sulphonic acid is prepared by heating a suspension of 3-tetradecoxyaniline in concentrated sulphuric acid on the steam bath.  4-Nitrolauranilide is prepared by heating 4-nitroaniline with lauric acid chloride in pyridine.  4-Aminolauranilide is prepared by reducing 4-nitrolauranilide with iron and acetic acid in ethyl alcohol.  6-Nitrometanilic acid is prepared by nitrating 3-acetamidobenzenesulphonic acid.  5-Stearamido-orthanilic acid is prepared by heating 6-nitrometanilic acid with stearoyl chloride in pyridine and reducing with iron filings in acetic acid. 4-Methyl-5-stearamidometanilic acid is prepared by nitrating p-toluenesulphonyl chloride, selectively reducing one of the nitro groups of the 3 : 5 - dinitro - p - toluenesulphonic acid obtained with ammonium sulphide to yield 4-methyl-5-nitrometanilic acid, reacting with stearoyl chloride in pyridine to yield 3-stearamido-5-nitro-p-toluenesulphonic acid, and reducing with iron and acetic acid.  3-Amino-N-dodecylbenzamide is prepared by treating 3-nitrobenzoyl chloride with dodecylamine and sodium bicarbonate in ether solution, and reducing the resulting 3-nitro-N-dodecylbenzamide with iron and acetic acid in ethyl alcohol.  p - Aminobenzene - N - dodecylsulphonamide is prepared by reacting p-acetamidobenzenesulphonyl chloride with dodecylamine and removing the acetyl group by alkaline hydrolysis.ALSO:Azo dyes are prepared by coupling a diazotized primary aromatic amine bearing as a substituent a long aliphatic chain radical linked to a nuclear carbon atom of the amine by an ether, carbonamide, carbamyl, sulphonamide, or sulphamyl linkage.  The dyes may be obtained by coupling the diazotized amine with a naphthol, an acylaminonaphthol polysulphonic acid, or a 1-phenyl-5-pyrazolone, e.g. b -naphthol, H-acid, R-acid, G-acid, acetyl-H-acid, benzoyl-H-acid, benzenesulphonyl-H-acid, 1 - phenyl - 3 - methyl - 5 - pyrazolone, 1-phenyl - 3 - carboxy - 5 - pyrazolone, 1 - (41-sulphophenyl) - 3 - carboxy - 5 - pyrazolone, or 1 - (31 - sulphophenyl) - 3 - carbethoxy - 5-pyrazolone.  Amines specified are 2-, 3-, and 4-decoxyaniline; 2- and 4-dodecoxyaniline; 2-, 3-, and 4-tetradecoxyaniline; 2- and 4-octadecoxyaniline; 4-octoxyaniline; 2-decoxy-, 2-dodecoxy-, 2-tetradecoxy-, and 2-octadecoxyaniline-5-sulphonic acid; 4-decoxy-, 4-tetradecoxy-, and 4-octadecoxy-aniline-3-sulphonic acid; 3-tetradecoxyaniline-6-sulphonic acid; 4-aminocaprylanilide; 4-aminocapranilide; 4-aminolauranilide; 4-aminomyristanilide; 4-aminostearanilide; 4-amino-N1-methylmyristanilide; 5-stearamido-orthanilic acid; 5-octadecanesulphonamido-orthanilic acid; 5-lauramido-anthranilic acid; 3-amino-6-methoxycapranilide; 3-amino-4-methoxydodecanesulphonanilide; 3-amino-6-methylcaprylanilide; 4 - amino - 2 - methyltetradecanesulphonanilide; 4 - methyl - 5 - stearamido - metanilic acid; 4-amino-N1-decylbenzamide; 3- and 4-amino-N1-dodecylbenzamide; 3-amino-N1 : N1 - dioctylbenzamide; 3 - amino - N1 - methyl : N1-dodecylbenzamide; N1-dodecyl-, N1 : N1-dioctyl-, N1-caprylyl-, N1-lauryl-, N1-myristyl-, and N1-methyl : N1 - lauryl - sulphanilamide; N1 - tetradecyl -, 4 - methoxy - N1 - decyl-, 4 - methoxy - N1 - methyl - N1 - decyl -, and 4-methyl - N1 - octyl - metanilamide; 6 : 61 - bis-(N1 - octylmetanilamide); 4 - lauramido - 31-aminobenzenesulphonanilide; 4 - dodecoxy-31 - aminobenzenesulphon - p - anisidide; and 3 : 31 - dioctoxybenzidine. The diazotized amine may be coupled with a naphthylamine (e.g. 1-aminonaphthalene-6-sulphonic acid or 1-amino - 2 - methoxynaphthalene - 6 - sulphonic acid), and the product diazotized and coupled with a naphthol; or dyes may be produced by tetrazoting one of the benzidine derivatives and coupling with a naphtholsulphonic acid.  In specific examples, dyes are prepared by coupling diazotized 2-dodecoxyaniline or 2-tetradecoxyaniline hydrochloride with benzoyl-H-acid, acetyl-H-acid, benzenesulphonyl-H-acid, or 1 - (41 - sulphophenyl) - 3 - carboxy - 5-pyrazolone; by coupling diazotized 2-decoxy-aniline with benzenesulphonyl-H-acid, or 1-(41 - sulphophenyl) - 3 - carboxy - 5 - pyrazolone; by coupling diazotized 2-octadecoxyaniline-5-sulphonic acid, 2 - decoxyaniline - 5 - sulphonic acid, 2 - dodecoxyaniline - 5 - sulphonic acid, or 2 - tetradecoxyaniline - 5 - sulphonic acid with benzoyl-H-acid; by coupling diazotized 2 - octadecoxyaniline - 5 - sulphonic acid with 1 - (31 - sulphophenyl) - 3 - carbethoxy - 5-pyrazolone; by coupling diazotized 4-lauramidoaniline with benzoyl-H-acid or 1-(31-sulphophenyl) - 3 - carbethoxy - 5 - pyrazolone; by coupling diazotized 5-stearamido-orthanilic acid (prepared by adding aqueous sodium nitrite to an aqueous-ethanol solution of 5-stearamido-orthanilic acid and sodium carbonate and adding the mixture slowly to an agitated mixture of aqueous hydrochloric acid and ice) with benzenesulphonyl-H-acid or 1-(31 - sulphophenyl) - 3 - carbethoxy - 5 - pyrazolone; by coupling diazotized 4-methyl-5-stearamido-metanilic acid with benzoyl-H-acid or 1 - (31 - sulphophenyl) - 3 - carbethoxy - 5-pyrazolone; by coupling diazotized 3-amino-N-dodecylbenzamide with benzenesulphonyl-H-acid or 1-(31-sulphophenyl)-3-carbethoxy-5-pyrazolone; by coupling diazotized p-amino-benzene - N - dodecylsulphonamide with benzoyl-H-acid or 1-(31-sulphophenyl)-3-carbethoxy-5-pyrazolone; by coupling diazotized 2-dodecoxyaniline-5-sulphonic acid with 1-amino-2 - ethoxynaphthalene - 6 - sulphonic acid, diazotizing the product, and coupling with benzoyl-H-acid in ammonium hydroxide solution. Specification 602,881, [Group XX], is referred to.