Patent GB-680474-A (GB)
Title: Improvements in and relating to colour forming developers and processes of colour development
IPC: G03C7/384
Filed: 1950-03-27
Abstract: 1 - (p - Cyanophenyl) - 3 - amino - 5 - pyrazolone is prepared by refluxing together ethyl p-cyanophenylhydrazine - b  - iminopropionate, diluting with water, and acidifying. 1-(m-Cyanophenyl)-3-amino-5-pyrazolone is similarly prepared. 1-(p-Cyanophenyl)-3-benzamido-5-pyrazolone is prepared by adding benzoyl chloride to a pyridine solution of 1-(p-cyanophenyl)-3-amino-5-pyrazolone and heating, separating the dibenzoyl derivative obtained, and saponifying in alcoholic potassium hydroxide.  1-(p-Cyanophenyl) - 3 - acetamido - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (21 : 41 - di - tert. - amylphenoxyacetamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - {[4 - (211 : 411 - di - tert. - amylphenoxy) - phenyl] - carbamyl - n - valeramido} - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - [21 - (211 : 411 - di - tert. - amylphenoxy) - 51 - nitrobenzamido] - 5 - pyrazolone, 1 - (p - cyanophenyl)-3 - (41 - (211 : 411 - di - tert. - amylphenoxy) - 31 - nitrobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (41 - nitrobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (m - nitrophenylacetamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (31 - nitrobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (21-chlorobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (41 - sec. - amylbenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl)-3 - (41 - n - amoxybenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (p - toluamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (o - toluamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (p - methoxybenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (o - methoxybenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (21 : 41 - dichlorobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl)-3 - (p - chlorobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (31 : 41 - dichlorobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (m - methoxybenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (m - chlorobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (o - nitrobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - phenylacetamido - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - (p - cyanobenzamido) - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - nicotinamido - 5 - pyrazolone, 1 - (p - cyanophenyl) - 3 - [b  - (21 : 41-di - tert. - amylphenoxy) - n - propionamido] - 5 - pyrazolone, 1-(p-cyanophenyl)-3-[31-(211 : 411-di-tert. - amylphenoxyacetamido) - benzamido] - 5 - pyrazolone, 1 - (m - cyanophenyl) - 3 - benzamido - 5 - pyrazolone, 1 - (21 : 61 - dichloro - 41 - cyanophenyl)-3-benzamido-5-pyrazolone, 1-(21 : 61-dichloro - 41 - cyanophenyl) - 3 - [31 - (211 : 411 - di - tert. - amylphenoxyacetamido) - benzamido] - 5 - pyrazolone, 1 - (21 : 61 - dichloro - 41 - cyanophenyl) - 3 - [b  - (21 : 41 - di - tert. - amylphenoxy)-propionamido] - 5 - pyrazolone, and 1 - (p - cyanophenyl) - 3 - furoamido - 5 - pyrazolone are similarly prepared. 1 - (p - Cyanophenyl) - 3 - [41 - (211 : 411 - diamylphenoxy) - 31 - (p - sec. - amylbenzamido) - benzamido] - 5 - pyrazolone is prepared by reducing 1 - (p - cyanophenyl) - 3 - [41 - (211 : 411-di - tert. - amylphenoxy) - 31 - nitrobenzamido] - 5-pyrazolone to obtain 1-(p-cyanophenyl)-3-[41 - (211 : 411 - di - tert. - amylphenoxy) - 31 - aminobenzamido] - 5 - pyrazolone, and reacting this with p-sec.-amylbenzoyl chloride. 1-(p-Cyanophenyl) - 3 - [21 - (211 : 411 - di - tert. - amylphenoxy) - 51 - aminobenzamido] - 5 - pyrazolone and 1 - (p - cyanophenyl) - 3 - [21 - (211 : 411 - di - tert. - amylphenoxy) - 51 - (p11 - sec. - amylbenzamido) - benzamido] - 5 - pyrazolone are similarly prepared.  1 - (p - Cyanophenyl) - 3 - (31 - nitrobenzamido-) 5-pyrazolone is prepared by refluxing together 1 - p - cyanophenyl - 3 - amino - 5 - pyrazolone, glacial acetic acid, and m-nitrobenzoyl chloride, separating the diacyl derivative obtained, hydrolysing by stirring aqueous caustic soda into an ethyl alcohol suspension of the diacyl derivative and acidifying.  1 - (p - Cyanophenyl) - 3 - (31 - aminobenzamido) - 5 - pyrazolone is prepared by reducing 1 - (p - cyanophenyl) - 3 - (31 - nitrobenzamido) - 5-pyrazolone in acetic acid with iron powder, the mixture being refluxed.  1 - (p - Cyanophenyl) - 3 - {31 - [a  - (211 : 411 - di - tert. amylphenoxy) - butyramido] - benzamido}-5-pyrazolone is prepared by reacting 1 - (p - cyanophenyl) - 3 - (31 - aminobenzamido)-5-pyrazolone with a -diamyl-n-butyryl chloride.  1 - (p - Cyanophenyl) - 3 - [41 - (211 : 411 - di - tert. - amylphenoxyacetamido) - phenylacetamido]-5-pyrazolone is prepared by reacting 1-(p-cyanophenyl) - 3 - amino - 5 - pyrazolone with p - nitrophenylacetyl chloride, reducing the 1-(p-cyanophenyl) - 3 - (41 - nitro) - phenylacetamido - 5-pyrazolone obtained to 1-(p-cyanophenyl)-3-(41 - amino) - phenylacetamido - 5 - pyrazolone, and reacting with 2 : 4-diamylphenoxyacetyl chloride. 1-(p-Cyanophenyl)-3-[31-(211 : 411-di tert.-amylphenoxyacetamido) - phenylacetamido] - 5 - pyrazolone and 1 - (p - cyanophenyl) - 3 - [41 - (211\h : 411 - di - tert. - amylphenoxy) - acetamidobenzamido] - 5 - pyrazolone, 1 - (p - cyanophenyl)-3 - (31 - nitro) - phenylacetamido - 5 - pyrazolone and 1 - (p - cyanophenyl) - 3 - (41 - nitro) - benzamido - 5 - pyrazolone, and 1 - (p - cyanophenyl) - 3 - (31 - amino) - phenylacetamido - 5 - pyrazolone and 1 - (p - cyanophenyl) - 3 - (41 - amino) - benzamido-5-pyrazolone are similarly prepared.  1 - (p - Cyanophenyl) - 3 - [41 - (211 : 411 - di - tert. - amylphenoxy) - 31 - (411 - methylbenzamido)-benzamido]-5-pyrazolone is prepared by condensing 1 - (p - cyanophenyl) - 3 - amino - 5 - pyrazolone in dioxane, with or without quinoline, with 3-(2 : 4-di-tert.-amylphenoxy)-3-nitrobenzoyl chloride to form a diacylated derivative, hydrolysing to form 1-(p-cyanophenyl)-3-[41-(211 : 411 - di - tert. - amylphenoxy) - 51 - nitrobenzamido]-5-pyrazolone, reducing with iron and acetic acid to form 1-(p-cyanophenyl)-3-[41 - (211 : 411 - di - tert. - amylphenoxy) - 51 - aminobenzamido]-5-pyrazolone, and condensing this in acetic acid containing sodium acetate with p-methylbenzoyl chloride. 1-(p-Cyanophenyl) - 3 - [41 - (211 : 411 - di - tert. - amylphenoxy) - 31 - (411 - chlorobenzamido) - benzamido]-5-pyrazolone is similarly prepared.  1 - (p - Cyanophenyl) - 3 - {31 - [211 - (211 : 411 - di - tert. - amylphenoxy) - 511 - (3111 : 5111 - di chlorosulphonylbenzamido) - benzamido] - benzamido}-5-pyrazolone is prepared by condensing 1 - (p - cyanophenyl) - 3 - amino - 5 - pyrazolone with 3 - [21 - (211 : 411 - di - tert. - amylphenoxy)-51 - nitrobenzamido] - benzoyl chloride in presence of sodium acetate to yield 1-(p-cyanophenyl) - 3 - {31 - [211 - (211 : 411 - di - tert. - amylphenoxy) - 511 - nitrobenzamido] - benzamido} - 5 - pyrazolone, reducing with iron and acetic acid to 1 - (p - cyanophenyl) - 3 - {31 - [211 - (211 : 411 - di - tert. - amylphenoxy) - 511 - aminobenzamido] - benzamido} - 5 - pyrazolone, and condensing in dioxane in presence of quinoline with 3 : 5-di-(chlorosulphonyl) - benzoyl chloride.  1 - (p - Cyanophenyl) - 3 - {31 - [211 - (2111 : 4111 - di - tert. - amylphenoxy) - 511 - (3111 - carboxy - 4111 - hydroxybenzenesulphonamido) - benzamido] - benzamido} - 5 - pyrazolone and 1 - (p - cyanophenyl)-3 - {31 - [211 - (2111 : 4111 - di - tert. - amylphenoxy) - 511 - (3111 : 4111 - - dicarboxybenzenesulphonamido) - benzamido] - benzamido} - 5 - pyrazolone are similarly prepared.  p-Cyanoaniline is prepared by reducing p-nitrobenzonitrile with stannous chloride in concentrated hydrochloric acid below 40 DEG  C., filtering, and treating with crushed ice and sodium hydroxide. m-Cyanoaniline is similarly prepared.  p-Cyanophenylhydrazine is prepared by diazotizing p-cyanoaniline, adding the cold solution of the diazonium salt to a cold sodium sulphite solution, and warming.  m-Cyanophenylhydrazine is similarly prepared.  Ethyl (b  - (p - cyanophenyl) - hydrazino) - b  - iminopropionate is prepared by adding p-cyanophenylhydrazine to boiling chlorobenzene, adding ethyl b -ethoxy-b -iminopropionate and then acetic acid, and refluxing.  Ethyl [b -(m-cyanophenyl) - hydrazino] - b  - iminopropionate is similarly prepared.  2 : 4 - Di - tert. - amylphenoxyacetyl chloride is prepared by refluxing di-tert.-amylphenol with water, ethyl alcohol, and sodium hydroxide, cooling, adding chloracetic acid and refluxing, and acidifying to obtain di-tert.-amylphenoxyacetic acid, and heating this acid with thionyl chloride.  2 - (21 : 41 - Di - tert. - amylphenoxy) - 5 - nitrobenzoyl chloride and 2-(21 : 41-di-tert.-amylphenoxy)-5-nitrobenzoic acid, 4-(21 : 41-di-tert.-amylphenoxy) - 3 - nitrobenzoyl chloride and 4 - (21 : 41 - di - tert. - amylphenoxy) - 3 - nitrobenzoic acid, a  - di - tert. - amylphenoxy - n - butyryl chloride and a -di-tert.-amylphenoxy-n-butyric acid, and 41-tert.-amyl-3-phenoxybenzoyl chloride and 41-tert.-amyl-3-phenoxybenzoic acid are similarly prepared.  b  - 2 : 4 - Di - tert. - amylphenoxypropionyl chloride is prepared by adding trimethylbenzyl ammonium hydroxide solution and dioxane to a mixture of di-tert.-amylphenol and acrylonitrile to obtain b -2 : 4-di-tert.-amylphenoxypropionitrile, hydrolysing this to b -2 : 4-di-tert.-amylphenoxypropionic acid by heating an acetic acid solution thereof with hydrochloric acid, and reacting with thionyl chloride.  3 - [21 - (211 : 411 - Di - tert. - amylphenoxy) - 51-nitrobenzamido] - benzoyl chloride is prepared by adding a dioxane solution of 2-(21 : 41-di-tert.-amylphenoxy)-5-nitrobenzoyl chloride to a heated mixture of m-aminobenzoic acid, quinoline, and dioxane and continuing heating to obtain 3 - [21 - (211 : 411 - di - tert. - amylphenoxy) - 51 - nitrobenzamino] - benzoic acid, and reacting with thionyl chloride.  2 : 6 - Dichloro - 4 - cyanophenylhydrazine is prepared by diazotizing 2 : 6-dichloro-4-cyanoaniline, and reducing wi