Patent GB-980507-A (GB)
Title: New alpha acylated acetarylides and their use as photographic colour couplers
IPC: C07D271/113
Filed: 1961-04-27
Abstract: The invention comprises compounds of the general formula <FORM:0980507/C2/1> where Q represents a carboxylic acyl group having 5-32 carbon atoms, the carbon atom directly attached to the carbonyl radical of the carboxylic acyl group being trisubstituted, A represents a hydrogen or chlorine atom or a group -S-B (where B represents an aryl or substituted aryl radical or a heterocyclic radical) and R represents an aryl or substituted aryl radical.  The group Q is preferably of the structure (XYZ).C.CO-, where X represents an alkyl, alkoxy, alkoxyalkyl or haloalkyl group and Y and Z represent alkyl groups. Alternatively the tri-substituted carbon atom in the group Q may be the carbon atom in the 1-position of a 1-substituted-1-cycloalkyl group or the carbon atom common to the two rings of a bicycloalkyl group.  Lists of possible values for the groups Q, B and R are given.  Compounds in which A represents a hydrogen atom are prepared by reacting an acyloacetic acid ester QCH2COOR with an amine RNH2.  Compounds in which A represents a chlorine atom are prepared by chlorination, e.g. with sulphuryl chloride, of the compound where A represents hydrogen. Compounds in which A represents the group S-B are prepared by reacting the compound where A represents hydrogen with a sulphenyl chloride B-SCl. Examples describe the preparation of compounds in which Q, A and R have the following values: Q:- pivalyl, a -methoxy-isobutyryl, methoxy-pivalyl, chloropivalyl, a ,a -dimethylvaleryl, a ,a  - dimethyl - stearoyl, a  - methyl - a  - butyl - arachidoyl a  - methyl - a  - n - nonyl - undecanoyl, a ,a  - di - n - amyl - heptanoyl, 7,7 - dimethyl - norbornane - 1 - carbonyl and 1 - methylcyclohexane - 1 - carbonyl; A:- hydrogen, chlorine, 5-phenyl-1,3,4-oxadiazolyl-2-thio, 3 - octadecylcarbamylphenylthio, 3 - dodecylcarbamylphenylthio, and 3 - tetradecylcarbamylphenylthio; and R:- phenyl, 2-chlorophenyl, 2 - dimethylaminophenyl, 2 - chloro - 5 - [2,4 - di - tert. - amylphenoxy - acetamido] - phenyl, 2 - methoxy - 5 - [2,4 - di - tert. - amylphenoxy - acetamido] - phenyl, 4 - [2,4 - di - tert. - amylphenoxy - acetamido] - phenyl, 2 - chloro - 5 - [a - and g  - (2,4 - di - tert. -amylphenoxy) - butyramido] - phenyl, 4 - [N - g  - phenylpropyl - N - p - tolyl - carbamylmethoxy]- phenyl, 4 - [N - g  - phenylpropyl - N - p - tolyl - sulphamyl] - phenyl, 2 - chloro - 5 - (p - toluene sulphonamido) - phenyl, 2 - (2,4 - di - tert. - amylphenoxy) - 5 - (3,5 - dicarbomethoxyphenylcarbamyl) - phenyl, 2 - (2,4 - di - tert. - amylphenoxy) - 5 - (N - morpholinyl carbonyl) - phenyl, 3,5 - dicarbomethoxyphenyl, 3,5 - dicarboxyphenyl, 3,5 - dicarbododecyloxy phenyl, 3,5 - dicarbamyl phenyl, 3,5 - di - (N - ethyl carbamyl) phenyl, 3,5-di-(N-n-octylcarbamyl)-phenyl, 4 - sulphophenyl potassium salt, 4 - chlorosulphonyl phenyl, 2-chloro-5-[a -2,4-di-tert.-amylphenoxy - caproamido] - phenyl and 2-fluoro-5-n-heptanamido-phenyl.  2 - Chloro - 5 - [a  - (2,4 - di - tert. - amylphenoxy)-acetamido]-aniline is prepared by reacting the phenoxy acetyl chloride with 4-chloro-3-nitro-aniline and reducing the nitro group.  The corresponding g  - substituted - butyramido compound is similarly prepared.  5 - Phenyl - 1,3,4 - oxadiazolyl - 2 - sulphenyl chloride and 3 - octadecylcarbamyl - phenyl - sulphenyl chloride are prepared by chlorinating the mercaptan and disulphide respectively.  3,5-Dicarbamyl-aniline is prepared by reacting 5-nitroisophthalic acid with thionyl chloride and then with ammonia and reducing the nitro group.  The N,N1-diethyl and di-octyl compounds are similarly prepared.  Methyl a  - (7,7 - dimethylnorbornane - 1 - carbonyl)-acetate is prepared by converting 7,7-dimethyl norbornane-1-carboxylic acid to its ethyl ester, reacting the ester with acetonitrile to give the 1-cyanoacetyl compound and hydrolysing this in the presence of methanol. Specifications 524,554, 524,555, 541,589, 736,922, 904,364, 932,272, 942,865 and 964,514 are referred to.