Patent GB-868111-A (GB)
Title: Improvements in or relating to thiolcarbamates
Inventor: TILLES HARRY
IPC: C07D307/52
Filed: 1958-10-03
Abstract: The invention comprises compounds of the general formula: <FORM:0868111/IV (b)/1> wherein R1 are methallyl, methyl-mercaptomethyl, crotyl, lower chloroalkyl, 3-chloro-2-butenyl, propargyl or the radical  <FORM:0868111/IV (b)/2> one of the x or y representing a halogen atom whilst the other represents a hydrogen atom and R2, R3 are each an alkyl, alkenyl cycloaliphatic, or chloroalkenyl radical or both R2 and R3 with the nitrogen atom constitute a pyrrolidino-ring or a piperidino or alkylsubstituted piperidino ring, or R2 and R3 are each an alkynyl radical when R1 is a lower chloroalkyl radical or wherein R1, R2 are each a lower alkyl, lower alkenyl, methoxyalkyl or haloalkenyl radical when R3 is a methallyl radical.  The term "lower" is defined to mean a carbon atom content of from 1 to 6 inclusive.  Such compounds, which are employed in phytocidal compositions (see Group VI), are obtained by reacting an appropriate alkali metal mercaptide with the appropriate carbamyl chloride; by reacting an appropriate organic chlorothiolformate with the appropriate amine (using the amine itself as acid binding agent or using caustic alkali as an acid binding agent); by using an appropriate organic chlorothiolformate with an amine hydrochloride with an acid binding agent or by reacting carbonyl sulphide with an appropriate amine and an acid binding agent and treating the product with an appropriate organic sulphate. Representative of the many products specified are methallyl N,N-diethylthiolcarbamate, -N.N-diallylthiolcarbamate, -N-2-chlorallyl-N-n propylthiolcarbamate, -1-piperidinecarbothiolate and 1-(2-methyl)-piperidinecarbothiolate, similar crotyl compounds including crotyl -1(2-methyl)-piperidinecarbothiolate and 1-pyrrolidine-carbothiolate, similar chloalkyl compounds, similar 2-bromo- and 3-bromoallyl compounds, similar 3-chloro-2-butenyl compounds, similar propargyl compounds allyl N-methallyl-N-ethylthiolcarbamate, methoxymethyl N-methallyl-N-ethylthiolcarbamate, ethyl N-methallyl-N-ethylthiolcarbamate, 2-bromoallyl N-methallyl-N-ethylcyclohexylthiolcarbamate, 2-chlorethyl N-thiolcarbamate, 2-chloroethyl N-ethyl-N-propargyl-N-n-propylthiolcarbamate. methylmercaptomethyl N-ethyl-N-cyclohexyl-thiolcarbamate, methylmercaptomethyl-N-2-chlorallyl-N-n-propylthiolcarbamate, methylmercaptomethyl 1-piperidinecarbothiolate and 1-pyrrolidinecarbothiolate.  Specification 862,548 also is referred to.ALSO:A phytocidal composition of matter for combatting undesired plants contains as its essential ingredient a compound of the formula <FORM:0868111/VI/1> wherein R1 may be a methallyl, mercaptomethyl, crotyl, lower chloroalkyl, 3-chloro-2-butenyl, propargyl or the <FORM:0868111/VI/2> radical, one of x or y representing a halogen atom, whilst the other represents a hydrogen atom and R2, R3 are each an alkyl, alkenyl, cycloaliphatic or chloroalkenyl radical or both R2 and R3 together with the nitrogen atom constitute a pyrrolidino ring or a piperidino- or alkyl-substituted piperidino ring, or R2 and R3 are each an alkynyl radical when R1 is a lower chloralkyl radical or wherein R1 and R2 may each be a lower alkenyl, lower alkyl, methoxyalkyl or haloalkenyl radical when R3 is a methallyl radical, the term "lower" being defined to mean a carbon atom content of from 1 to 6 inclusive (see Group IV (b)).  Representative of the large number of active substances specified are methallyl N,N - diallyl thiolcarbamate, methylmercaptomethyl N,N - diethylthiolcarbamate, crotyl N,N-diethylthiolcarbamate, methoxymethyl N-methallyl-N-ethylthiolcarbamate, 2-chloroethyl N-ethyl-N-cyclohexylthiolcarbamate, 3 - bromoally - N,N - di - n - propylthiolcarbamate, 3 - chloro - 2 - butenyl - N,N - di - n - propylthiolcarbamate and propargyl - N,N - diethylthiol - carbamate. Solvents for use in the compositions specified include, benzene, toluene, xylene, petroleum solvents, acetone, isopropanol or methanol.  Emulsifying agents for use in the compositions may be anionic, cationic or non-ionic, e.g. quaternary ammonium salts, sulphonated oils and polyhydric alcohol esters and ethers, mixtures of the first or second with the third type being optionally employed. Dry carriers specified include granular vermiculite, clay granules, finely-ground clay and talc.  Specification 862,548 also is referred to.