Patent GB-569646-A (GB)
Title: Improvements in or relating to colour photography
IPC: G03C7/32
Filed: 1943-10-29
Abstract: Dye intermediates which are basic and are naphthylamines connected through the amino nitrogen atom by means of a divalent hydrocarbon radical, or a divalent hydrocarbon radical interrupted by ether oxygen, of at least two carbon atoms, to the nitrogen atom of an acid amide, e.g. of formula <FORM:0569646/IV/1> wherein X is a divalent hydrocarbon radical, which may be interrupted by ether-oxygen of at least 2 carbon atoms, Y is the acid-hydroxylfree portion of an organic carboxylic or sulphonic acid, or a unit of a polymeric acid containing a carboxylic or sulphuric acid group linked through the CO- or SO2 groups to the N atom may be prepared by condensing either (a) an N-substituted naphthylamine containing an amino group on the N-substituent with an amidating agent such as acids or derivatives thereof including acid esters, acid halides (e.g. chlorides), and anhydrides, or (b) by the reaction of a naphthylamine with a substituted alkyl halide containing an acylamide group or groups easily converted to an acylamide group.  The substituent group may be in an a -position.  The intermediates may have a molecular weight of at least 300, and either the hydrocarbon radical may be of high molecular weight or the naphthalene nucleus may be substituted with hydrocarbon groups.  A naphthylamine may be condensed in an anhydrous solvent with a substituted alkyl halide containing an amide group (e.g. b -acetylaminoethyl bromide or p-acetaminophenoxyethyl bromide) and the resulting compound may be hydrolysed to remove the acetyl group and the amino group re-acylated with acid or derivative (e.g. the ethyl or methyl ester, acyl halide, acid anhydride, or sulphonyl chloride or bromide); acylating agents include straight chain saturated acids of formula CH3(CH2)XCOOH, where X is O to 30, e.g. stearic acid, hydroxystearic, oleic, ricinoleic, stearolic, campholic phenylacetic, cholic, piconilic, furic, glycocholic, benzoic, opianic, naphthoic, abietic, naphthenic, acids, a residue of a polymeric acid, e.g. a polypeptide or polyamide, polyacrylic, polymethacrylic and poly-olefinemaleic acids dicarboxylic acids of formula HOOC-(CH2)X-COOH, where X is 2 to 20, maleic, camphoric, phthalic, naphphthalic, melophanic, terebinic, tricarballylic, cyclobutanedicarboxylic acids, sulphonyl chlorides, e.g. benzenesulphonyl chloride dodecanesulphonyl chloride, p-dodecylbenzenesulphonyl chloride, and polymeric sulphonyl chlorides.  A similar reaction may be p  effected, using a nitroalkyl halide (e.g. p-nitrobenzyl chloride or p-nitrophenoxyethyl bromide), and the product reduced and acylated.  A nitroaldehyde (e.g. m-nitrobenzaldehyde) may be condensed with a naphthylamine to form a Schiff's base, both the nitro group and double bond reduced, and the product acylated.  A naphthylamine or naphthol may be condensed with an aliphatic diamine to form an N-aminoalkylaminonaphthalene (e.g. ethylenediamine in aqueous sodium bisulphite condenses with b -naphthol) which is acylated.  A naphthylamine may be condensed with excess alkylene dihalide, e.g. ethylene dibromide, and the resulting N - (bromoalkyl) - naphthylamine treated with liquid ammonia to give the amino compound which is then acylated.  1-(b -(p-Acetaminophenoxy)-ethylamino)-naphthalene is prepared by boiling together a -naphthylamine and p-(b -bromoethoxy)-acetanilide adding diethylaniline and p-(b -bromoethoxy)-acetanilide and continuing boiling, repeating the second addition and continuing boiling, pouring into ice water containing NaOH, and purifying.  This may be used as a dye intermediate itself, or may be hydrolysed by boiling with HCl to 1-(b -p-aminophenoxy)-ethylamino)-naphthalene, which may be reacted with an ethylene-maleic anhydride heteropolymer to yield a high molecular dye intermediate, which may be dissolved in sodium carbonate solution and mixed with a gelatin silver chlorobromide emulsion and coated on a subbed support.  Exposed material may be developed in a 4-aminodiethylaniline developer and bleached and fixed to yield a magenta image, or may be treated with diazonium solutions derived from aniline, 2 : 4-dichloroaniline, dianisidene, 2-chloro-4-nitroaniline, 4-nitroaniline-2-sulphonic acid, or 2 : 4-dinitroaniline. 1-(N-p-Nitrophenoxyethylamino)-naphthalene-6-sulphonic acid is prepared by boiling together the sodium salt of 1-aminonaphthalene-6-sulphonic acid, water, sodium acetate, dioxane, and p-nitrophenoxyethylbromide, adding small quantities of NaOH solution to keep the solution neutral to litmus and further quantities of p-nitrophenoxyethyl bromide, and purifying. 1-(N-p-Aminophenoxyethylamino)-naphthalene-6-sulphonic acid is prepared by boiling 1-(N-p-nitrophenoxyethylamino) - naphthalene - 6 - sulphonic acid with acetic acid and iron filings.  A dye intermediate is prepared by boiling the amino compound with dimethylformamide, NaOH, and a styrene-maleic anhydride heteropolymer.  2-(m-Aminobenzylamino)-naphthalene is prepared by reacting 2-naphthylamine with m-nitrobenzaldehyde and reducing in the presence of nickel catalyst with hydrogen.  A high molecular dye intermediate is prepared by condensing with an ethylene-maleic anhydride heteropolymer.  N - (b  - Aminoethyl - 1 - naphthylamine is prepared by heating together in an autoclave a -naphthol, ethylenediamine water, and sulphur dioxide.  High molecular dye intermediates may be produced therefrom.  N - (b  - Aminoethyl) - 2 - naphthylamine - 7 - sulphonic acid is prepared by reacting together 2-naphthylamine-7-sulphonic acid, ethylenediamine, and aqueous sodium bisulphite.  N - (b  - Laurylaminoethyl) - 2 - naphthylamine-7-sulphonic acid is prepared by reacting together N-(b -aminoethyl)-2-naphthylamine-7-sulphonic acid and lauric acid chloride.  1-(N-p-Octadecanesulphonamidophenoxyethylamino) -naphthalene-6-sulphonic acid is prepared by reacting together 1-(N-p-amino-phenoxyethylamino) - naphthalene - 6 - sulphonic acid, NaOH and octadecanesulphonyl chloride.  n-Octadecanesulphonyl chloride is prepared by reacting n-octadecyl sulphonate with a mixture of phosphorus oxychloride and phosphorus pentachloride. Specifications 2562/13, [Class 98 (ii)], 436,587; 458,400, 478,345, 487,769, 520,528, [all in Group XX], 539,494, 541,649; 545,443, [Group XX], 554,302, 556,768; 556,858, [Group XX], and 562,092 are referred to.