Patent GB-737112-A (GB)
Title: Improvements in photographic colour couplers and photographic emulsions and developers containing them
IPC: G03C7/32
Filed: 1953-01-14
Abstract: a  - (o - Methoxybenzoyl) - 4 - [5 - (2 - carboxy - x - chlorosulphonylbenzamido) - 2 - (2 : 4 - di - tert.-amylphenoxy) - benzamido] - 2 - methoxyacetanilide is prepared by reacting a -(o-methoxybenzoyl) - 4 - [5 - amino - 2 - (2 : 4 - di - tert. - amylphenoxy) - benzamido] - 2 - methoxyacetanilide with 4-chlorosulphonylphthalic anhydride in benzene. 1-Phenyl-3-{3-[5-(2-carboxy - x - chlorosulphonylbenzamido) - 2 - (2 : 4 - di - tert.-amylphenoxy)] - benzamido} - benzamido - 5 - pyrazolone, 1 - hydroxy - N - {4 - [5 - (2 - carboxy-x - chlorosulphonylbenzamido) - 2 - (2 : 4 - di - tert.-amylphenoxy) - benzamido] - phenylethyl} - 4 - chloro - 2 - naphthamide, 1 - [4 - (8 - carboxy - x - chlorosulphonylnaphthamido) - phenyl] - 3 - (8 - carboxy - x - chlorosulphonylnaphthamido) - 5 - pyrazolone, and 1 - hydroxy - N - {4 - [5 - (8 - carboxy - x - chlorosulphonylnaphthamido) - 2 - (2 : 4 - di - tert. - amylphenoxy) - benzamido] - phenylethyl} - 4 - chloro - 2 - naphthamide are similarly prepared.  a  - (o - Methoxybenzoyl) - 4 - [5 - amino - 2 - (2 : 4 - di - tert. - amylphenoxy) - benzamido] - 2 - methoxyacetanilide is prepared by reducing with hydrogen in the presence of Raney nickel a  - (o - methoxybenzoyl) - 4 - [5 - nitro - 2 - (2 : 4 - di - tert. - amylphenoxy) - benzamido] - 2 - methoxyacetanilide in ethyl acetate.  1 - Hydroxy - N - {4 - [5 - amino - 2 - (2 : 4 - di - tert. - amylphenoxy) - benzamido] - phenylethyl} - 4 - chloro-2-naphthamide is similarly prepared.  a - (o - Methoxybenzoyl) - 4 - [5 - nitro - 2 - (2 : 4-di - tert. - amylphenoxy) - benzamido] - 2 - methoxyacetanilide is prepared by reacting a -(o-methoxybenzoyl) - 4 - amino - 2 - methoxyacetanilide with 2-(2 : 4-di-tert.-amylphenoxy)-5-nitrobenzoyl chloride in glacial acetic acid and in presence of anydrous sodium acetate.  a  - (o - Methoxybenzoyl) - 4 - amino - 2 - methoxyacetanilide is prepared by reducing a -(o-methoxybenzoyl) - 4 - nitro - 2 - methoxyacetanilide in water, acetic acid, and denatured alcohol with iron, adding concentrated hydrochloric acid to precipitate the hydrochloride, and isolating the free base by adding an intimate mixture of the dry hydrochloride and anhydrous sodium acetate to denatured alcohol, and adding water.  a  - (o - Methoxybenzoyl) - 4 - nitro - 2 - methoxyanilide is prepared by refluxing together ethyl o-methoxybenzoylacetate and 2-amino-5-nitroanisole in xylene containing anhydrous sodium acetate.  Ethyl o-methoxybenzoylacetate is prepared by adding sodium gradually to a heated mixture of methyl o-methoxybenzoate and anhydrous ethyl acetate, decomposing excess sodium with absolute methanol, and, after steps involving the separation of the ester layer and ether extraction of the aqueous layer, fractionally distilling under low pressure.  2 - (2 : 4 - Di - tert. - amylphenoxy) - 5 - nitrobenzoyl chloride is prepared by refluxing together thionyl chloride and 2-(2 : 4-di-tert.-amylphenoxy) - 5 - nitrobenzoic acid, itself prepared by heating together di-tert.-amylphenol, potassium hydroxide, and 2-chloro-5-nitrobenzoic acid and acidifying a benzene solution of the melt.  1 - Phenyl - 3 - [3 - {5 - amino - 2 - (2 : 4 - di - tert. - amylphenoxy)] - benzamido} - benzamido - 5-pyrazolone is prepared by refluxing together 1 - phenyl - 3 - {3 - [5 - nitro - 2 - (2 : 4 - di - tert. - amylphenoxy)] - benzamido} - benzamido - 5 - pyrazolone in acetic acid and denatured alcohol with iron powder.  1 - Phenyl - 3 - {3 - [5 - nitro - 2 - (2 : 4 - di - tert. - amylphenoxy)] - benzamido} - benzamido - 5-pyrazolone is prepared by reacting together 1 - phenyl - 3 - m - aminobenzamido - 5 - pyrazolone and 2-(2 : 4-di-tert.-amylphenoxy-5-nitrobenzoyl chloride in acetic acid containing anhydrous sodium acetate.  1 - Phenyl - 3 - m - aminobenzamido - 5 - pyrazolone is prepared by reducing with iron powder and acetic acid in aqueous ethanol 1 - phenyl - 3 - m - nitrobenzamido - 5 - pyrazolone, itself prepared by reacting 1-phenyl-3-amino-5-pyrazolone with m-nitrobenzoyl chloride in ethyl oxalate.  1-Phenyl-3-amino-5-pyrazolone is prepared by heating together phenylhydrazine, ethyl cyanacetate, and sodium ethoxide.  1 - p - Nitrophenyl - 3 - amino - 5 - pyrazolone is prepared by heating together ethyl b -imino: b  - (p - nitrophenylhydrazino) - propionate and sodium carbonate in aqueous alcohol and then acidifying with acetic acid.  4 - Chloro - 1 - hydroxy - 2 - {b  - [4 - (2 : 4 - di - tert. - amylphenoxy) - 5 - aminobenzamido)] - phenylethyl} - naphthamide is prepared by reducing 4 - chloro - 1 - hydroxy - 2 - [b - {4 - [2 - (2 : 4 - di - tert. - amylphenoxy) - 5 - nitrobenzamido]} - phenylethyl] - naphthamide with hydrogen under pressure in anhydrous ethyl acetate in the presence of anhydrous sodium carbonate and Raney nickel.  4 - Chloro - 1 - hydroxy - 2 - [b  - {4 - [2 - (2 : 4 - di - tert. - amylphenoxy) - 5 - nitrobenzamido]} - phenylethyl]-naphthamide is prepared by reacting 4 - chloro - 1 - hydroxy - 2 - [b  - (4 - amino) - phenylethyl] - naphthamide with 2 - (2 : 4 - di - tert. - amylphenoxy) - nitrobenzoyl chloride in glacial acetic acid containing anhydrous sodium acetate.  4 - Chloro - 1 - hydroxy - 2 - [b  - (4 - amino) - ethyl] - naphthamide is prepared by reducing 4 - chloro - 1 - hydroxy - 2 - [b  - (4 - nitro) - phenylethyl] - naphthamide with hydrogen in anhydrous ethyl acetate in the presence of anhydrous carbonate and Raney nickel.  4 - Chloro - 1 - hydroxy - 2 - [b  - (4 - nitro) - phenylethyl] - naphthamide is prepared by heating together 4-nitro-b -phenylethylamine (obtained by hydrolysing acetyl-4-nitro-b -phenylethylamine, itself obtained by nitrating acetyl-b -phenylethylamine, acetyl - 2 - nitro - b  - phenylethylamine being obtained as a by-product) and phenyl - 4 - chloro - 1 - hydroxy - 2 - naphthoate and pouring into glacial acetic acid.  Specifications 737,103 and 737,105 are referred to.