Patent GB-1379813-A (GB)
Title: Benzoylacetanilide yellow forming colour couplers for phtographic silver halide material
IPC: C07C205/59
Filed: 1972-03-10
Abstract: 1379813 Benzoylacetanilides; intermediates therefor AGFA-GEVAERT 10 March 1972 [25 March 1971] 11340/72 Heading C2C [Also in Division G2] The invention comprises compounds of the formula wherein X represents H or a group that exhibits two-equivalent character, R 1  and R 2  represent straight or branched-chain (C 1  to C 20  )alkyl groups, Y represents COOR 3 , where R 3  and R 6  represent straight or branchedchain alkyl groups of which the carbon chain may be interrupted by -O-, and R 4 , R 5 , R, and R 8  represent H or are the same as R 3  and R 6 ; the molecule comprising at least one (C 5  to C 20 ) alkyl group. In examples specified compounds are obtained by reacting an appropriate benzoyl acetic acid ester with an appropriate aniline derivative. They are useful as colour couplers.  3 - n - Hexadecyloxy - 4 - amino - benzoic acid methyl ester is obtained by hydrogenating the corresponding nitro compound which is itself obtained by etherifying the potassium salt of 3-hydroxy-4-nitrobenzoic acid methyl ester with hexadecyl bromide in DMF. 3 - n - Hexadecyloxy - 4 - aminobenzoic acid 2-methoxy-ethyl ester is obtained by hydrogenating the corresponding nitro compound which is itself obtained by transesterifying 3-n-hexadecyloxy-4-nitrobenzoic acid methyl ester with ethylene glycol monomethyl ether in the presence of Na. 3-Methoxy-4-aminobenzoic acid methyl ester is obtained by hydrogenating the corresponding nitro compound which is itself obtained by etherifying the potassium salt of 3-hydroxy-4- nitrobenzoic acid methyl ester with (CH 3 ) 2 SO 4  in DMF. 3-Methoxy-4-aminobenzoic acid n-hexadecyl ester is obtained by transesterifying the corresponding methyl ester with hexadecyl alcohol in the presence of titanium tetrabutoxide as catalyst. 3-Methoxy-4-aminobenzoic acid isooctadecyl ester and 3-methoxy-4-aminobenzoic acid #-methoxyethyl ester are obtained in a similar manner. 2 - Dodecyloxy - 4 - methylsulphonyl - aniline is obtained by oxidizing with urea peroxide 2 - dodecyloxy - 4 - methylthioacetanilide and hydrolysing the resulting acetanilide. 2- Dodecyloxy-4-methylthioacetanilide is obtained by treating the corresponding 4-thiocyanato compound in methanolic CH 3 I with Na in methanol. The 4-thiocyanato compound is itself obtained by acetylating 2 - dodecyloxy - 4 - thiocyanatoaniline which is itself obtained by treating a mixture of 2-dodecyloxyaniline and ammonium thiocyanate in CH 3 CN with Br 2 . 2-Methoxy-4-methylsulphonyl-aniline is obtained in a similar manner via 2 - methoxy - 4 - methylsulphonylacetanilide, 2 - methoxy - 4 - methylthioacetanilide and 2 - methoxy - 4 - thiocyanatoacetanilide from 2-methoxy-4-thiocyanatoaniline. 2 - Amino - 5 - N,N - dimethylaminosulphonylanisole is obtained by etherifying with CH 3 I in methanolic KOH the corresponding 2-acetylamino-phenol compound and deacetylating the product with hydrochloric acid. 2-Acetylamino- 5-N,N-dimethylaminosulphonyl phenol is itself obtained by acetylating the corresponding amine which is itself obtained by treating 6 - N,N - dimethylaminosulphonyl - benzoxazolone-2 with NaOH and neutralizing the product with hydrochloric acid. The latter compound is obtained by treating 6-chlorosulphonyl-benzoxazolone-2 with dimethylamine in dioxan. 2 - n - Hexadecyloxy - 4 - N,N - dimethylaminosulphonyl-aniline is obtained by hydrolysing the corresponding acetanilide which is itself obtained by etherifying 2-acetylamino-5-N,N-dimethylaminosulphonylphenyl with hexadecyl bromide in the presence of ethylene glycol monomethyl ether and sodium.