Patent GB-896936-A (GB)
Title: Tetrahydrothiamidine-thione derivatives
Filed: 1958-08-07
Abstract: The invention comprises tetrahydrothiamidine thiones of general formula <FORM:0896936/IV (b)/1> wherein R1 and R2 are different and R1 is an alkyl, alkoxy alkyl, carboxyalkyl or alkoxy carbonyl radical or the group <FORM:0896936/IV (b)/2> R2 is an alkyl, alkoxyalkyl, hydroxyalkyl, cycloalkyl, carboxyalkyl or a salt thereof, esterified carboxyalkyl, sulphonic acid substituted alkyl or a salt thereof, halo-substituted alkyl, benzyl, halo-substituted phenyl, sulphonic acid-substituted or carboxylic acid-substituted phenyl or a salt thereof or carboxyalkyl or esterified carboxyalkyl each containing a keto group in the alkyl group, or when R1 is alkyl, alkoxyalkyl, carboxyalkyl or alkoxy carbonyl, R2 can be <FORM:0896936/IV (b)/3> and n is 2 or 3.  Those compounds wherein neither R1 nor R2 represents a heterocyclic radical defined above are prepared by reacting formaldehyde with a dithiocarbamate R1NHCSSH.R2NH2 or, preferably, by reacting an equivalent of a dithiocarbamate R1NHCSSH.Me where Me is an alkali metal, ammonium or alkaline earth metal, with one equivalent of a primary amine R2NH2 or a mineral salt thereof, and two equivalents of formaldehyde.  The compounds wherein R2 is the specified heterocyclic radical are analogously prepared using ethylene or propylene diamine as the amine R2NH2, while those in which R1 is the specified heterocyclic radical are similarly prepared from the appropriate alkylene bis thiocarbamate.  The reactions are effected at or slightly above room temperature. Typical examples describe the preparation of those products in which (1) R1=CH3, R2=CH2CH2OH, (3) R1=CH3, R2=CH2COOH, (6) R1=isobutyl, R2=n-butyl, (7) R1=CH3, R2=CH2CH2SO3Na, (8) R1=the above-mentioned heterocyclic radical, n=2 and R2=CH3, (9) R1=CH3, R2=the above-mentioned heterocyclic radical and n=2, (10) R2=CH2,COOH, R2=CH3, or R1=CH2,CR2= cyclohexyl or benzyl, (11) R1=CH3, R2=sulphophenyl (Na salt), (12) R1=CH3, R2=carboxyphenyl (Na salt), (14) R1=propoxymethyl, R1=CH3, (15) R1=COO Et, R2=CH3, (16) R1=CH3, R2=CH2CH2Cl, (18) R1=CH3, R2= (CH2)5COOH and (20) R1=CH3, R2=CH2 SO3Na, from the appropriate dithiocarbamate and primary amine. Additional suitable starting materials are mentioned including amino keto alkanoic acids and esters thereof to provide radical R2.  Some examples describe the preparation of the dithiocarbamate from the appropriate amine R1NH2, CS2 and aqueous caustic soda.  Methoxy methyl-dithio carbamic acid potassium salt is prepared by reacting methoxymethyl mustard oil with alcoholic KHS; the propoxy methyl compound is obtained similarly; potassium carbonyloxyethyl dithio carbamate is likewise obtained using carbonyloxyethyl thio carbiamide.ALSO:Nematicidal, fungicidal and herbicidal compositions comprise as active ingredient a tetrahydro thiamidine thione of the general formula <FORM:0896936/VI/1> wherein R1 and R2 are different and R1 is an alkyl, alkoxyalkyl, carboxyalkyl or alkoxy carbonyl radical or the group <FORM:0896936/VI/2> R2 is an alkyl, alkoxyalkyl, hydroxyalkyl, cycloalkyl, carboxyalkyl or a salt thereof, esterified carboxyalkyl, sulphonic acid substituted alkyl or a salt thereof, halo-substituted alkyl, benzyl, halo-substituted phenyl, sulphonic or carboxylic acid substituted phenyl or a salt thereof, or carboxyalkyl or esterified carboxyalkyl each containing a keto-group in the alkyl group or when R1 is alkyl, alkoxyalkyl, carboxyalkyl or alkoxycarbonyl, R2 can be <FORM:0896936/VI/3> and n is 2 or 3, and a solid or liquid diluent or carrier. Numerous examples of such thiones are given and their preparation is described (see Group IV (b)).