Patent GB-577679-A (GB)
Title: Improvements in or relating to colour photography
Filed: 1944-03-09
Abstract: An azo dye intermediate for reaction with the oxidation products of an aromatic hydrazine photographic developing agent or with a diazo compound is a polymeric quaternary ammonium salt having in the recurring polymeric units a quaternary nitrogen atom which has attached thereto by acyclic carbon a nucleus capable of reacting to form the azo dye.  The dye intermediate may have intralinear quaternary nitrogen atoms connected through bivalent hydrocarbon radicals or through bivalent radicals comprising hydrocarbon residues interrupted by non-terminal oxy, carbonamido, or carbonoxy groups, the remaining three valencies of the quaternary nitrogen atoms being connected to a salt-forming anion, an acyclic carbon atom (e.g. a methylene group) connected to a nucleus capable of forming an azo dye, and an aliphatic hydrocarbon radical.  Alternatively, the quaternary nitrogen atoms may be extra-linear, being connected through a bivalent connecting radical to the linear polymeric chain, the remaining four valencies of the quaternary nitrogen atoms being connected to a salt-forming anion, an acyclic carbon atom connected to a dye-forming nucleus, and aliphatic hydrocarbon radicals.  The linear polymeric chains may be polymeric hydrocarbon, polyamide, or carbohydrate, or the polymeric reaction products derived essentially from phenol and formaldehyde.  The polymeric quaternary ammonium salts may be prepared by heating in solution a polymeric compound containing a tertiary amino group with a dye-forming nucleus containing a mono-halogenomethyl group, e.g. a polyamide prepared from hexamethylene diamine and piperazine diacetic acid may be boiled in dilute alcohol solution with m-bromacetaminophenol, sodium p-chloromethylbenzenesulphonate added, and boiling continued, the dye-intermediate being precipitated with hydrochloric acid.  A dye-intermediate may also be formed by mixing together a dioxane solution of polymerized dimethylaminoethyl methacrylate and an aqueous solution of sodium 1-N-(31-chloro-21-hydroxypropyl) -aminonaphthalene-6-sulphonate, and heating and acidifying. Dye-intermediates are similarly obtained from an ethanolaminepolymeric methylvinyl ketone and sodium 1-N-(31-chloro-21-hydroxypropyl) -aminonaphthalene-5-sulphonate; from phenol-formaldehyde methylamine resin and 1-N-(31-chloro-21-hydroxypropyl) -aminonaphthalene-5-sulphonic acid; from a dimethylamine-formaldehyde-resin and 1 - N - (31-chloro-21-hydroxypropyl) -amino-5-naphthol-7-sulphonic acid; and from diethylaminoethylcellulose, 1 - m - chloroacet - aminophenyl - 3 - methyl - 5 - pyrazolone, and sodium p-chloromethylbenzenesulphonate.  The dye-forming nucleus may be a phenol having either hydrogen or a readily replaceable group in the 2- or 4-position; an aromatic primary, secondary, or tertiary amine having either hydrogen or a readily replaceable group in the 2- or 4-position; or a compound having a reactive acyclic or intracyclic methylene group.  The dye-intermediates may have acidic salt-forming groups as substituents either on the dye-forming nucleus or on the linear polymeric chain, and may be used as the Na, K, Li, or Mg salts.  The carboxylic or sulphonic groups may be introduced by reaction with halogenomethyl carboxylic or sulphonic acids.  The halogenomethyl group may be introduced by the reaction of a halo-acid halide or aliphatic polyhalide with an amino or phenolic dye intermediate, by the reaction of a primary aromatic amino sulphonic acid with an epihalohydrin, by addition of hydrogen halide to terminally unsaturated side chains, or by condensation of an aromatic amine with an aliphatic halo-aldehyde followed by reduction of the Schiff's base.  Dye-intermediates described are the reaction products of poly-N-methyliminodi-n-propylsebacamide with sodium 1-N-(31-chloro-21-hydroxypropyl) -aminonaphthalene-6-sulphonate, of polyhexamethylene-N-methylimonodiacetamide and 1-N-(31-chloro-21-hydropropyl) -amino-5-naphthol-7-sulphonic acid, of poly-N-methylimino-di-n-propyladipamide and 1 - (31 - bromacetylaminophenyl) - 3 - methyl - 5 - pyrazolone, of poly - b  - dimethylaminoethyl methacrylate with N-benzoylacet-4-b -bromethoxyanilide and chloracetic acid, and of phenol-formaldehyde-methylamine resin with resorcinol mono-b -bromethyl ether and bromacetic acid. 1-m-Chloracetaminophenyl-3-methyl-5-pyrazolone is prepared by reacting 1-m-aminophenyl-3-methyl-5-pyrazolone with chloracetyl chloride in aqueous solution. 1-m-Bromacetaminophenyl-3-methyl-5-pyrazolone is similarly prepared using bromacetyl bromide.  N-(Benzoylacet-4-b -bromethoxyanilide) is prepared by refluxing a mixture of N-benzoylacet-4-hydroxyanilide with ethylene dibromide, alcohol and potassium carbonate. Resorcinol-mono-b -bromethyl ether is prepared by refluxing m-acetaminophenolate with excess ethylene dibromide, followed by acid hydrolysis, diazotization and hydrolysis in boiling water.