Patent GB-882110-A (GB)
Title: Esters of thiocarbamic acid
IPC: C23F11/16
Filed: 1958-02-28
Abstract: A detergent composition suitable for removing or preventing the tarnish of silver plate comprises (a) a detergent such as soap, an alkali metal, ammonium, or amine alkylaryl sulphonate, e.g. ammonium dodecylbenzene sulphonate, an alkali metal alkyl sulphate, or an ethylene oxide condensate with an alkylphenol or with tall oil, and (b) thiocarbamic ester of the formula:- <FORM:0882110/III/1> in which R is an organic amino substituent, the nitrogen atom of which is directly linked to the carbonyl carbon atom and to two other carbon atoms, provided that R does not comprise more than one carbocyclic group, and R1 is an unsaturated aliphatic group which does not contain a thiocarbamyl group, but excluding compounds having the formula:- <FORM:0882110/III/2> where R1 is a 2, 3-dichloroallyl group and R2 an R3 are each C1-4 alkyl groups (see Specification 882,111), and also compounds of the formula:- <FORM:0882110/III/3> where R1 is a C2-5 alkenyl group and R2 an R3 are alkyl groups having at least 3 carbon atoms (see Specification 808,753).ALSO:The invention comprises thiocarbamic esters of the formula <FORM:0882110/IV (b)/1> in which R is an organic amino substituent the nitrogen atom of which is directly linked to the carbonyl carbon atom and to two other carbon atoms, provided that R does not comprise more then one carbocyclic group, and R1 is an unsaturated aliphatic group which does not contain a thiocarbamyl group, but excluding compounds having the formula <FORM:0882110/IV (b)/2> where R1 is a 2,3-dichloroalkyl group and R2 and R3 are each C1-4 alkyl groups (see Specification 882,111), and also compounds of the formula <FORM:0882110/IV (b)/3> where R1 is a C2-5 alkenyl group and R2 an R3 are alkyl groups having at least 3 carbon atoms (see Specification 808,753).  The substituent R is preferably represented by -NR2R3, where R2 and R3 are each alkyl, cycloalkyl, alkoxy alkyl, aryl, aryloxyalkyl, aralkyl, aralkoxyalkyl, cyanoalkyl, alkenyl, cycloalkenyl or halogenated alkenyl groups, provided not more than one of R2 and R3 represents a cycloalkyl, aryl, aryloxyalkyl, aralkyl or aralkoxyalkyl group, or together represent a polymethylene group which is optionally interrupted by an oxygen or nitrogen atom.  The above compounds are prepared by heating an aqueous solution of an alkali metal salt of a thiocarbamic acid of the formula R-CO-S-M (where M represents an alkali metal ion) with a halide of the formula R1-X (where X represents halogen), or by heating an alkyl thionocarbamate of the formula R-CS-O-Alkyl with a halide of the formula R1-X (rearrangement to the corresponding thiocarbamate occurring during the ester interchange.  Thiocarbamates of the formula R-CO-S-M are prepared by reacting an amine of the formula R-H with carbon oxysulphide in the presence of aqueous caustic alkali.ALSO:A phytotoxicidal composition having additionally some defoliant and nematoidal activity comprises a thiocarbamic ester of the formula <FORM:0882110/VI/1> in which R is an organic amino substituent the nitrogen atom of which is directly linked to the carbonyl carbon atom and to two other carbon atoms, provided that R does not comprise more than one carbocyclic group, and R1 is an unsaturated aliphatic group which does not contain a thiocarbamyl group, but excluding compounds having the formula <FORM:0882110/VI/2> where R1 is a 2,3-dichloroallyl group and R2 and R3 are each C1-4 alkyl groups (see Specification 882,111), and also compounds of the formula <FORM:0882110/VI/3> where R1 is a C2-5 alkenyl group and R2 and R3 are alkyl groups having at least 3 carbon atoms (see Specification 808,753), together with an inert liquid or finely divided solid diluent and, if desired, a dispersing agent.