Patent GB-1236767-A (GB)
Title: Benzoylacetamide derivatives and their use in colour photography
Inventor: VERBRUGGHE MARCEL HENDRIK
IPC: G03C7/36
Filed: 1968-07-18
Abstract: 1,236,767. Fluorinated benzoylacetamide derivatives. GEVAERT-AGFA N.V. 20 June, 1969 [18 July, 1968], No. 34341/68. Heading C2C. [Also in Division G2] The invention comprises benzoylacetamide derivatives containing at least one substituent of the formula RCF 2 Q-, in which Q denotes oxygen, sulphur or sulphonyl and R denotes hydrogen, fluorine or polyhaloalkyl, e.g. -CHFCl, -CFCl 2  or -CHFCF 3 . More particularly, the invention comprises compounds of the formula in which R and Q are as defined above, X denotes hydrogen or a substituent, examples of which are given, Z 1  denotes hydrogen or halogen, a group RCF 2 Q- or an alkyl, alkoxy or a dialkylamino group and A denotes an aromatic or heterocyclic nucleus, preferably carrying a substituent -YD, in which D denotes an acyclic hydrocarbon residue of 5-20 carbon atoms and Y denotes a chemical bond, oxygen, sulphur, sulphonyl, -N- (alkyl)-,-CONH-,-NHCO-,-N(R 3 )SO 2 - or -SO 2 N(R 3 )-, R 3  denoting hydrogen or alkyl. The nucleus A may also carry additional substituents, a number of which are specified. The compounds are obtainable by condensing an appropriately substituted benzoylacetic acid ester with appropriate aromatic or heterocyclic amines. Thus, o-(1,1,2-trifluoro-2-chlorethoxy) - benzoyl - (2<SP>1</SP> - hexadecyloxy - 5<SP>1</SP>- carboxy)-acetanilide is obtained from o-(1,1,2- trifluoro - 2 - chloroethoxy) - benzoylacetic acid ethyl ester and 3-amino-4-hexadecyloxybenzoic acid. Other specified products of the invention are p - difluoromethoxybenzoyl - (2<SP>1 </SP>- hexadecyloxy - 5 - carboxy) - acetanilide, o - (1,1,2- trifluoro - 2 - chloroethoxy) - p - methoxybenzoyl - (2<SP>1</SP> - hexadecyloxy - 5<SP>1</SP> - fluorosulphonyl) - acetanilide, o - (1,1,2 - trifluoro- 2 - chloroethoxy) - p - methoxy - benzoyl - (21- hexadecyloxy - 5 - sulpho) - acetanilide potassium salt, o,p - di - (1,1,2 - trifluoro - 2 - chloroethoxy) - benzoyl - (21 - hexadecyloxy - 51 - fluorosulphonyl) - acetanilide, o,p - di - (1,1,2- trifluoro - 2 - chloroethoxy) - benzoyl - (2<SP>1</SP> - hexadecyloxy - 5<SP>1 </SP>- sulpho) - acetanilide potassium salt, p - (1,1,2 - trifluoro - 2 - chloroethoxy) - benzoyl - (2<SP>1</SP>- dodecyloxy) - acetanilide, o - (1,1,2 - trifluoro - 2 - chloroethoxythio) - benzoyl - (2<SP>1 </SP>- hexadecyloxy - 5<SP>1 </SP>- carboxy) - acetanilide, o - (1,1,2 - trifluoro - 2 - chloroethoxy) - p - methoxybenzoyl - [2<SP>1</SP> - chloro - 5<SP>1</SP> - (N - methyl - N - hexadecylsulphamoyl)] - acetanilide and 2 - [o - (1,1,2- trifluoro - 2 - chloroethylthio) - benzoylacetamido] - 4 - p - methoxyphenyl - 5 - tetradecylthiazole. The products are useful in colour photography (see Division G2). The preparation of the following intermediates is described. o- or p-(1,1,2-Trifluoro-2-chloroethoxy)-benzoylacetic acid ethyl ester is prepared from o- (1,1,2 - trifluoro - 2 - chloroethoxy) - benzoyl chloride and the sodium salt of ethyl acetoacetate. Other intermediates are obtained analogously from p-difluoromethoxybenzoylacetic acid ethyl ester, o-(1,1,2-trifluoro-2- chloroethoxy) - p - methoxybenzoyl acetic acid ethyl ester and o,p-di-(1,1,2-trifluoro-2-chloroethoxy)-benzoylacetic acid ethyl ester. o - (1,1,2 - Trifluoro - 2 - chloroethoxy) - p - methoxybenzoic acid methyl ester is obtainable from 2 - hydroxy - 4 - methoxybenzoic acid methyl ester by the method of Lichtenberger. It yields the free acid on hydrolysis. o,p-Di- (1,1,2 - trifluoro - 2 - chloroethoxy) - benzoic acid methyl ester is prepared similarly, and can be similarly hydrolysed. o - (1,1,2 - Trifluoro - 2 - chloroethoxythio). benzoylacetic acid methyl ester is obtainable from o - (1,1,2 - trifluoro - 2 - chloroethylthio)- benzoic acid methyl ester analogously to o- (1,1,2 - trifluoro - 2 - chloroethoxy) - p - methoxybenzoic acid methyl ester above. 3 - Nitro - 4 - hexadecylorybenzoic acid is obtainable from 3-nitro-4-hydroxybenzoic acid methyl ester and hexadecyl bromide, followed by hydrolysis. 3 - Amino - 4 - hexadecyloxybenzoic acid is obtained by catalytic hydrogenation of the corresponding nitro compound. p-Difluoromethoxybenzoic acid is prepared by oxidizing p-tolyl difluoromethyl ether with potassium permanganate. p-Difluoromethoxybenzoyl chloride is prepared from the corresponding acid and thionyl chloride o - (1,1,2 - Trifluoro - 2 - chloroethoxy)- p - methoxybenzoyl chloride and o,p - di - (1,1,2- trifluoro - 2 - chloroethoxy) - benzoyl chloride are prepared similarly.