Patent GB-873124-A (GB)
Title: Improvements in or relating to a process for the production of photographic colour images
Inventor: JAEKEN JAN
IPC: G03C7/36
Filed: 1956-07-27
Abstract: 5 - (p-Cetyloxybenzoylacetylamino)-2-methylbenzene sodium sulphonate is prepared by acylating p-toluidine to form p-acetyltoluidine, treating with chlorosulphonic acid to give o-sulphochloro-p-acetyltoluidine, transforming this into the corresponding sulphofluoride by boiling in potassium fluoride solution, deacylating the amino group with methanol HCl, condensing the free amine with p-cetyloxybenzoyl acetic acid methyl ester to give 5-p-cetyloxybenzoylacetylamino-2-methyl benzene sulphofluoride, which is then converted to the corresponding sodium sulphonate with caustic soda.  o - (p - Cetyloxybenzoylacetylamino-benzene sodium sulphonate is similarly prepared.  According to the Provisional Specification, similar compounds are produced wherein the benzene sulphonate ring may contain methoxy, dimethoxy or ethoxy substituents, with the benzoylacetylamino group in m- or p-position. Similarly, 3-amino-4-chlorobenzene sulphofluoride is reacted with p-cetyloxybenzoyl acetic acid methyl ester to give 3(p-cetyloxybenzoylacetylamino)-4-chlorobenzene sulphofluoride which is converted to the corresponding sodium sulphonate, and p-(or m-) aminobenzene sulphofluoride is reacted with 3-methoxy-4-cetoxybenzoyl acetic acid methyl ester or with 4-tetradecoxynaphthoyl acetic acid ethyl ester to give p- (or m-) (3-methoxy-4-cetoxy-benzoylacetylamino) benzene sulphofluoride and m-(4-tetradecoxy-naphthoylacetylamino) benzene sulphofluoride respectively, which are then converted to the corresponding sodium sulphonates.  p - p1 - (p11 - Cetyloxybenzoylacetylamino) phenyl-sulphonylamino] benzene sodium sulphonate is prepared by reacting acetylsulphanilic acid with p-aminobenzene sulphofluoride followed by deacylation to give p-(p1-aminophenylsulphonylamino) benzene sulphofluoride which is then reacted with p-cetyloxybenzoyl acetic acid methyl ester and the sulphofluoride transformed into the sodium sulphonate.  N - (p-cetyloxybenzoylacetyl)-5-amino - isophthalic acid is prepared by condensing 5-amino-isophthalic acid dimethyl ester with p-cetyloxybenzoylacetic acid methyl ester and hydrolysing with potassium hydroxide.  The Provisional Specification describes the following preparations.  p-Cetyloxybenzoylacetic acid methyl ester is obtained by adding cetyl bromide to methyl p-hydroxybenzoate, saponifying the ester with caustic potash, forming the acid chloride with thionyl chloride, condensing with sodium acetoacetic acid ethyl ester and converting the product to the methyl ester.  3-Methoxy - 4 - cetyloxybenzoylacetic acid methyl ester is obtained by adding cetyl bromide to vanilline, oxidizing the aldehyde group to the corresponding acid with potassium permanganate forming the acid chloride with thionyl chloride, condensing with sodium acetoacetic acid ethyl ester and converting the product to the methyl ester.  4 - Tetradecoxynaphthoylacetic acid ethyl ester is prepared by rearranging a -naphthyl acetate to 4-acetyl-1-naphthol in the presence of aluminium chloride, refluxing this with tetradecyl bromide, dissolving the product in diethylcarbonate and adding to a heated mixture of sodium and diethylcarbonate. 3-Amino-4-chlorobenzene sulphofluoride is obtained by treating 3-nitro-4-chlorobenzene sodium sulphonate with phosphorus oxychloride and phosphorus pentachloride to obtain the sulphochloride, boiling this with aqueous potassium fluoride to give the sulphofluoride, and then reducing the nitro group with hydrogen and a nickel catalyst. m-(a -Cetoxy - b  - naphthoylacetylamino) benzene sodium sulphonate and m-(3-methoxy- (or 3:5 - dichloro) -4 - cetoxybenzoylacetylamino) benzene sodium sulphonate are similarly prepared.  p - \sTp1 - [p11-(1:1:3:3-tetramethylbutyl) phenoxyethoxy]benzoylacetylamino\sV benzene sulphonamide is prepared by reacting b [p-(1 : 1 : 3:3-tetramethylbutyl)phenoxy] ethanol with p-toluene sulphonylchloride in caustic soda, treating the product with p-hydroxybenzoic acid methyl ester in sodium hydroxide followed by HCl to give p-[p1-(1:1:3:3-tetramethylbutyl)phenoxyethoxy] benzoic acid, forming the acid chloride with thionyl chloride, reacting this with sodium acetoacetic acid ethyl ester followed by ammonia, and reacting the ketoester formed with p-aminobenzene sulphonamide. Corresponding compounds having different substitutents in the benzene ring are similarly obtained by using in place of p-aminobenzene sulphonamide, m-aminobenzene sulphonamide, butyl p-aminobenzene sulphonate (followed by conversion to the potassium sulphonate), 4-aminophthalic acid dimethyl ester (followed by saponification to the free acid), m-aminophenoxyacetic acid methyl ester (followed by saponification), p-aminosalicyclic acid methyl ester (followed by saponification), 5-aminosalicyclic acid methyl ester (followed by saponification), and p-nitroaniline (followed by reduction of the nitro group to the amine and reaction of the product with maleic anhydride).  N-\sTp-[p1-(1:1:3:3-tetramethylbutyl) phenoxyethoxy]-m[b -carboxy-acrylamido]benzylacetyl\sV aniline is prepared by forming p-[p1-(1:1:3:3-tetramethylbutyl)phenoxyethoxy] - m - nitrobenzoic acid as above but from p-hydroxy-m-nitro-benzoic acid methyl ester, forming the acid chloride, and reacting with sodium acetoacetic acid ethyl ester followed by aniline instead of the aminobenzene sulphonamide as above to give N-\sTp-[p1-(1:1:3:3-tetramethylbutyl)phenoxyethoxy]-m-nitro benzoylacetyl\sV aniline, reducing the nitro group to the corresponding amine and reacting this with maleic anhydride. p p-Amino-benzene sulphonic acid n-butyl ester is obtained by adding p-nitrobenzene sulphonyl chloride to cooled n-butanol, and reducing the nitro group to the amine.  Specifications 458,664, 525,765, 531,246, 595,314, 736,922, German Specification 744,265 and U.S.A. Specification 2,184,303 are referred to.