Patent GB-737105-A (GB)
Title: Improvements in and relating to pyrazolone derivatives and their use as colour couplers in colour photographic development
IPC: G03C7/384
Filed: 1952-12-04
Abstract: A pyrazolone derivative of the general formula <FORM:0737105/IV (b)/1> wherein D represents a p-arylene group of the benzene series, X represents an aryl group of the benzene series and Z represents an alkyl group or an aralkyl or aryl group of the benzene series, are prepared by acylating a 1-nitroaryl-3-amino-5-pyrazolone, reducing the nitro group, and acylating the resulting amino group. Alternatively, the nitro group may first be reduced and both amino groups acylated simultaneously.  1 - {41 - [311 - (4111 - Tert. - amylphenoxybenzamido] - phenyl} - 3 - [311 - (4111 - tert. amylphenoxy) - benzamido] - 5 - pyrazolone is prepared by adding 3-(4-tert.-amylphenoxy)-benzoyl chloride to a pyridine solution of 1-p-aminophenyl - 3 - amino - 5 - pyrazolone at a controlled rate.  1 - {4 - [3 - (4 - tert. - amylphenoxy) - x - chlorosulphonyl - benzamido] - phenyl} - 3 - [3 - (4 - tert. - amylphenoxy) - x - chlorosulphonyl] - benzamido - 5 - pyrazolone is similarly prepared. 1 - {41 - [311 - (4111 - Tert. - amylphenoxy) - x - chlorosulphonyl - benzamido] - phenyl} - 3 - (2 : 4 - di - tert. - amylphenoxy) - acetamido - 5 - pyrazolone is prepared by treating a dioxane solution of 1 - (4 - aminophenyl) - 3 - (2 : 4 - di - tert. - amylphenoxy) - acetamido - 5 - pyrazolone with a dioxane solution of 3-(4-tert.-amylphenoxy)-x-chlorosulphonyl-benzoyl chloride and then adding quinoline.  1 - [4 - (3 - Chlorosulphonylbenzamido) - phenyl] - 3 - lauramido - 5 - pyrazolone, 1 - [41 - (211 - sulphobenzamido) - phenyl] - 3 - stearamido - 5 - pyrazolone, 1 - [4 - (3 - chlorosulphonylbenzamido) - phenyl] - 3 - stearamido - 5 - pyrazolone, 1 - [4 - (3 - sulphobenzamido) - phenyl] - 3 - [g  - (2 : 4 - di - tert. - amylphenoxy) - butyramido] - 5 - pyrazolone, and 1 - [4 - (3 - sulphobenzamido) - phenyl] - 3 - (2 : 4 - di - tert. - amylphenoxy) - acetamido - 5 - pyrazolone are similarly prepared.  1 - p - Aminophenyl - 3 - amino - 5 - pyrazolone is prepared by reducing 1-p-nitrophenyl-3-amino-5-pyrazolone suspended in water with hydrogen in the presence of Raney nickel.  1 - p - Nitrophenyl - 3 - amino - 5 - pyrazolone is prepared by heating together ethyl (b -ethoxy : b -imino)-propionate and p-nitrophenylhydrazine in pyridine.  1 - (4 - Nitrophenyl) - 3 - (2 : 4 - di - tert. - amylphenoxy) - acetamido - 5 - pyrazolone is prepared by acylating 1 - (p - nitrophenyl) - 3 - amino - 5-pyrazolone with 2 : 4-di-tert.-amylphenoxyacetyl chloride in dry dioxane.  1 - (4 - Aminophenyl) - 3 - (2 : 4 - di - tert. - amylphenoxy) - acetamido - 5 - pyrazolone is prepared by reducing 1-(4-nitrophenyl)-3-(2 : 4-di-tert. - amylphenoxy) - acetamido - 5 - pyrazolone with hydrogen in benzene in the presence of Raney nickel.  1 - (4 - Nitrophenyl) - 3 - lauramido - 5 - pyrazolone is prepared by reacting 1-(4-nitrophenyl) - 3 - amino - 5 - pyrazolone with lauroyl chloride in pyridine, and 1-(4-aminophenyl)-3-lauramido-5-pyrazolone by reduction as above 1 - (4 - Nitrophenyl) - 3 - stearamido - 5 - pyrazolone and 1 - (4 - aminophenyl) - 3 - stearamido - 5-pyrazolone are similarly prepared.  3 - (4 - Tert. - amylphenoxy) - x - chlorosulphonyl benzoyl chloride is prepared by refluxing together x-chlorosulphonyl-4-tert.-amylphenoxy-3-benzoic acid and phosphorus pentachloride.  X - Chlorosulphonyl - 4 - tert. - amylphenoxy - 3 - benzoic acid is prepared by adding 41-tert.-amylphenoxy-3-benzoic acid in small portions to cooled chlorosulphonic acid.  41 - Tert. - amylphenoxy - 3 - benzoic acid is prepared by heating together m-bromobenzoic acid, p-tert.-amylphenol, sodium hydroxide, and copper bronze powder.  Specifications 541,589, [Group XX], and 737,103 are referred to.