Patent GB-737104-A (GB)
Title: Coloured couplers containing isophthalic ester groups
IPC: G03C7/32
Filed: 1952-12-04
Abstract: The invention comprises colour couplers of formul  <FORM:0737104/IV (c)/1> and <FORM:0737104/IV (c)/2> where R is a mononuclear aryl radicle, Z is an alkali metal atom or a methyl group and Y is a hydroxyl or arylamido group (i.e. -NR-R1 where R1 is an aryl radicle) or, when Z is an alkali metal, the group OZ.  The compounds are made by reaction of the uncoloured coupler with the appropriate diazonium compound. Thus phenyl 1-hydroxy-2-naphthoate is condensed with p-nitrophenethylamine to yield 1 - hydroxy - N - (p - nitrophenethyl) - 2-naphthamide which is reduced to the amine which is condensed with 2-(2,4-di-tert.-amylphenoxy)-5-nitrobenzoyl chloride and the product reduced to 1-hydroxy-N-{4 - [2 - (2,4 - di-tert. - amyl - phenoxy) - 5 - aminobenzamido]-phenethyl}-2-naphthamide which is condensed with 3-chlorosulphonyl-benzoyl chloride in pyridine and the product treated with isophthalic dimethyl ester diazonium chloride to yield <FORM:0737104/IV (c)/3> Using 3,5-dichlorosulphonyl benzoyl chloride in place of 3-chloro-sulphonyl-benzoyl chloride in the above preparation yields <FORM:0737104/IV (c)/4> 1 - Hydroxy - N - {4 - [2 - (2,4 - di - tert. - amylphenoxy) - 5 - aminobenzamido} - phenethyl}-2-naphthamide (see above) is acylated with m-chlorosulphonylbenzoyl chloride and the resultant sulphochloride used to acylate dimethyl - 5 - aminoisophthalate to give a product which on treatment with 3,5-dicarbomethoxybenzene diazonium chloride yields <FORM:0737104/IV (c)/5> 1 - Phenyl - 3 - amino - 5 - pyrazolone is condensed with m-nitrobenzoyl chloride and the nitro group reduced to yield <FORM:0737104/IV (c)/6> which is condensed with 2-(2,4-di-tert.-amyl phenoxy)-5-nitrobenzoyl chloride in acetic acid and sodium acetate, the nitro group of the product reduced to yield 1-phenyl-3-{3-[2-(2,4 - di - tert. - amylphenoxy) - 5 - amino benzamido] - benzamido} - 5 - pyrazolone which is coupled with 3,5-dicarbomethoxybenzene diazonium chloride to yield 1-phenyl-3-{3-[2-(2,4 - di - tert. - amylphenoxy) - 5 - aminobenzamido] - benzamido} - 4 - (3,5 - dicarbomethoxyphenylazo) - 5 - pyrazolone which is acylated with o-sulphobenzoic anhydride to yield <FORM:0737104/IV (c)/7> Using m-chlorosulphonylbenzoyl chloride in place of o-sulphobenzoic anhydride in the above preparation and acylating dimethyl 5-amino-isophthalate with the product <FORM:0737104/IV (c)/8> is obtained.  Specifications 524,154, 524,554, 524,555, 541,589, [all in Group XX], 586,211, 598,174, 598,657; 599,377, [Group XX], 627,814 and 737,103, [Group IV (b)], are referred to.ALSO:The following amides and pyrazolones are made as intermediates in the preparation of colour couplers, cf. Group IV (c):-Phenyl 1-hydroxy-2-naphthoate is condensed with p-nitrophenethylamine to yield 1-hydroxy-N-(p-nitrophenethyl)-2-naphthamide which is reduced to the amine which is condensed with 2-(2,4-di-tert.-amylphenoxy)-5-nitrobenzoyl chloride and the product reduced to 1-hydroxy-N-{4-[2-(2,4-di - tert. - amyl - phenoxy) - 5 - aminobenzamido] - phenethyl} - 2 - naphthamide which is condensed with 3-chlorosulphonyl-benzoyl chloride in pyridine to yield the pyridine salt of 1-hydroxy-N - {4 - [2 - (2,4 - di - tert. - amylphenoxy) - 5 - (3 - sulphobenzamido) - benzamido] - phenethyl} - 2 - naphthamide.  Using 3,5 - dichlorosulphonylbenzoyl chloride in place of 3-chlorosulphonylbenzoyl chloride in the above preparation the corresponding di-sulpho-chloride is obtained.  The above naphthamide may be acylated with m-chlorosulphonyl-benzoyl chloride and the resultant sulphochloride used to acylate dimethyl-5-amino-isophthalate to yield 1-hydroxy-2-{4-[2 - (2,4 - di - tert.-amylphenoxy) - 5 - (3 - chlorosulphonylbenzamido) - benzamido] - phenethyl} - naphthamide.  1 - Phenyl - 3 - amino - 5 - pyrazolone is condensed with m-nitrobenzoyl chloride and the nitro group reduced to yield the amine which is condensed with 2-(2,4-di-tert.-amyl-phenoxyl)-5-nitrobenzoyl chloride in acetic acid and sodium acetate, the nitro group of the product being reduced to yield 1-phenyl-3-{3-[2-(2,4-di-tert. - amylphenoxy) - 5 - aminobenzamido] - benzamido} - 5 - pyrazolone.  Specification 737,103 is referred to.