Patent GB-774421-A (GB)
Title: Improvements in or relating to substituted colour couplers and to the production of coloured photographic images
IPC: G03C7/32
Filed: 1954-09-30
Abstract: 1 - (41 - Phenoxy - 31 - sulphophenyl) - 3 - {41 - [411 - (1111 : 1111 : 3111 : 3111 - tetramethyl-n-butyl)]-phenoxyethoxy}-phenyl-5-pyrazolone is prepared by heating together in aqueous iso-propanol in presence of sodium acetate 3-sulpho-4-phenoxyphenylhydrazine and methyl 4-[41-(111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - benzoylacetate.  Methyl 4 - [41 - (111 : 111 : 311 : 311 - tetramethyl-n - butyl) - phenoxyethoxy] - benzoylacetate (compound B) is prepared by heating together the sodium derivative of ethyl acetoacetate and 4 - [41 - (111 : 111 : 311 : 311 - tetramethyl - n - butyl)-phenoxyethoxy] - benzoyl chloride (itself prepared by reacting the corresponding acid, obtained by hydrolysis of the corresponding ethyl ester with aqueous NaOH, with SOCl2 in benzene), adding sodium methoxide, and then acetic acid.  Ethyl 4 - [41 - (111 : 111 : 311 : 311 - tetramethyl-n-butyl) - phenoxyethoxy] - benzoate is prepared by reacting 4 - (111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethyl p - toluenesulphonate (compound A) (itself prepared by reacting 4-(111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethanol with p-toluenesulphonyl chloride in acetone) with ethyl p-hydroxybenzoate in methyl ethyl ketone.  4 - [41 - (111 : 111 : 311 : 311 - Tetramethyl - n - butyl) - phenoxyethoxy] - benzoylacetyl - 3 : 5 - dicarbomethoxyanilide is prepared by heating compound B above with methyl 5-amino-isophthalate in xylene.  2 - Nitro - 1 - [41 - (111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - benzene is prepared by reacting together in ethylene glycol monomethyl ether compound A above and o-nitrophenol, and the corresponding amino compound, which is prepared by reduction of the nitro compound with hydrogen in presence of Raney nickel, may be boiled with ethyl m-nitrobenzoylacetate in xylene containing pyridine to yield 2-(31-nitrobenzoylacetamido)-1-[41-(111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxybenzene, which may be reduced with iron and acetic acid to yield the corresponding amine, which may then be reacted with maleic anhydride in benzene to yield 3-{21-[411-(1111 : 1111 : 3111 : 3111 - tetramethyl - n - butyl) - phenoxyethoxy] - phenylcarbamylacetyl} - N - phenylmaleamic acid. Ethyl 3 - nitro - 4 - [41 - (111 : (111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - benzoate (compound C) is prepared by reacting together in ethylene glycol monomethyl ether compound A above and ethyl 3-nitro-4-hydroxybenzoate.  The corresponding acid is prepared by hydrolysis of this ester with NaOH in aqueous ethanol, and is converted to the corresponding acid chloride (compound D) by heating with SOCl2.  Reaction of the acid chloride in dioxane with 1-hydroxy-2-naphthoyl-b -aminoethanol (from phenyl 1-hydroxy-2-naphtoate and monoethanolamine) yields 1 - hydroxy - 2 - naphthoyl - b  - aminoethyl 3 - nitro - 4 - [41 - (111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - benzoate, which may be reduced with hydrogen in presence of Raney nickel to yield the corresponding amino compound, which may be heated in benzene with maleic anhydride to yield 2 - [41 - (111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - 5 - [b  - (11 - hydroxy - 21 - naphthamido)-carbethoxy]-phenylmaleamic acid.  Compound C above may be reduced with hydrogen in presence of Raney nickel to yield the corresponding 3-amino compound, which may be heated with phenyl 1-hydroxy-2-naphthoate in vacuo to yield ethyl 3-(11-hydroxy-21-naphthamido) - 4 - [41 - (111 : 111 : 311 311 - tetramethyl - n - butyl) - phenoxyethoxy] - benzoate, which may be hydrolysed to the corresponding acid by heating with dioxane and an aqueous solution of NaOH.  Methyl 3 - nitro - 4 - [41 - (111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - benzoylacetate is prepared by reacting compound D above with the sodium derivative of ethyl acetoacetate in benzene, and by heating with aniline in xylene the corresponding anilide is formed.  This anilide may be reduced with iron and acetic acid to yield the corresponding 3-amino compound, which may be reacted with maleic anhydride to yield 2-[41-(111 : 111 : 311 : 311-tetramethyl - n - butyl) - phenoxyethoxy] - 5 - phenylcarbamylacetyl-phenylmaleamic acid.  1 - (11 : 11 : 31 : 31 - Tetramethyl - n - butyl) - 4 - (21 : 41 - dinitrophenoxyethoxy) - benzene is prepared by reacting compound A above with 2 : 4-dinitrophenol (sodium salt) in ethylene glycol monomethyl ether, and may be reduced to the corresponding 21-amino-41-nitro compound with sodium polysulphide solution in the presence of magnesium sulphate.  Reaction of this compound with phenyl 1-hydroxy-2-naphthoate yields the corresponding 21 - (111 - hydroxy - 211 - naphthamido-41-nitro compound, subsequent reduction with hydrogen in presence of Raney nickel the corresponding 21-(111-hydroxy-211-naphthamido)-41-amino compound, and reaction of this with maleic anhydride in benzene 4-[41-(111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - 3 - (11 - hydroxy - 21 - naphthamido) - phenylmaleamic acid.  1 - Hydroxy - 2 - naphthoyl - b - aminoethylamine is prepared by boiling together phenyl 1-hydroxy-2-naphthoate and ethylenediamine in ether, and may be sulphonated with concentrated sulphuric acid to yield the 4-sulphonic acid, which may be reacted with 4-[41-(111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy]-phenylacetyl chloride (compound E) to yield 1 - {41 - [411 - (1111 : 1111 : 3111 : 3111 - tetramethyl - n - butyl) - phenoxyethoxy] - phenylacetyl} - 4 - (11 - hydroxy - 41 - sulpho - 21 - naphthoyl) - ethylenediamine.  Compound E above is prepared by reacting with thionyl chloride the corresponding acid, itself prepared by heating with ethanol 4-[41-(111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxy] - phenylthioacetylmorpholine, prepared by boiling together with sulphur and morpholine 4-[41-(111 : 111 : 311 : 311 - tetramethyl-n-butyl) - phenoxyethoxy] - acetophenone.  The last-mentioned compound is prepared by reacting compound A above with p-hydroxyacetophenone in ethylene glycol monomethyl ether in the presence of sodium hydroxide.  4 - (11 : 11 : 31 : 31 - Tetramethyl - n - butyl) - phenoxyethoxyacetic acid is prepared by reacting b  - [41 : 11 : 31 : 31 - tetramethyl - n - butyl) - phenoxy]-ethanol with monochloracetic acid in the presence of finely divided sodium in xylene.  The corresponding acid chloride (compound F) is obtained by reaction with SOCl2, and this may be reacted with 3-aminobenzoylacet - 31 : 51 - dicarboxyanilide to yield 3-[41-(111 : 111 : 311 : 311-tetramethyl - n - butyl) - phenoxyethoxyacetamido]-benzoylacet-5-amino-isophthalic acid.  1 - [41 - (111 : 111 : 311 : 311 - Tetramethyl - n - butyl) - phenoxyethoxyacetyl] - 4 - (11 - hydroxy - 41 - sulpho - 21 - naphthoyl) - ethylenediamine is prepared by reacting together compound F above with 1-hydroxy-2-naphthoyl-b -aminoethylamide-4-sulphonic acid.  b  - [4 - (11 : 11 : 31 : 31 - Tetramethyl - n - butyl)-phenoxy] - ethoxyethyl - p - toluenesulphonate is prepared by reacting the corresponding alcohol with p-toluenesulphonyl chloride in pyridine, and may be reacted with sodium p-nitrophenolate in ethylene glycol monomethylether to yield 4 - [41 - (111 : 111 : 311 : 311 - tetramethyl - n - butyl) - phenoxyethoxyethoxy] - nitrobenzene, which may be reduced with zinc and acetic acid to yield the corresponding amino compound, which may be heated with phenyl 1-hydroxy-2-naphthoate to yield 1-hydroxy-2-{41-[411-(1111 : 1111 : 3111 : 3111 - tetramethyl - n - butyl)-phenoxyethoxyethoxy]}naphthanilide.