Patent GB-840211-A (GB)
Title: Fungicides
Inventor: FLIEG OSKAR
IPC: C07D295/21
Filed: 1958-08-15
Abstract: Mixtures having anti-fungal activity of dithiocarbamates and thiuram mono and disulphides of general formulae <FORM:0840211/IV(b)/1> wherein X(+) is a metal cation especially of a metal of Groups Ia, Ib, IIb, VIIa or VIII of the Periodic Table and R1 and R2 are organic radicals are prepared by reacting together one or more amines R1-NH-R2 with carbon disulphide in the presence of further bases e.g. NaOH, KOH, or ammonia solution, precipitating a part of the dithiocarbamic acid thus formed by the addition of a soluble salt of a metal which forms an invioluble dithiocarbamate of ZnSO4 and oxidizing the remainder e.g. with H2O2 and an acid.  Depending on the reaction conditions the product may contain the thiuram disulphides and also thiuram monosulphides and substances of higher sulphur content.  The oxidation and precipitation steps may be carried out simultaneously.  The substituents R1 and R2 which may be the same or different may be hydrogen, straight or branched chain, saturated or unsaturated alkyl groups, cycloalkyl, alkyl aryl or heterocyclic residues which may contain additional substituents, e.g. nitro groups and additional amino groups.  The substituents together with the common nitrogen atom may form a ring which may contain additional hetero-atoms e.g. nitrogen, oxygen or sulphur.  Examples of amines given are monoand di-alkylamines, pyrrolidine, piperidine, hexamethylene imine, morpholine, thiomorpholine, thiomorpholine dioxide, aminopyrimidine; pyrimidine, ethylene diamine, 1,2- or 1,3-propylene diamine, cyclohexylene diamine and diethylene triamine. Specific examples relate to the partial oxidation of a mixture of pyrrolidyl dithiocarbamic acid and ethylenebis-dithiocarbamic acid and the reacting together of methylamine, dimethylamine and carbon disulphide in the presence of caustic soda and the partial oxidation by the same method as above of the resulting mixture of methyl and dimethylcarbamic acids.ALSO:Anti-fungal agents comprise at least one dithiocarbamate having the general formula <FORM:0840211/VI/1> and at least one thiuram mono or disulphide having the general formula <FORM:0840211/VI/2> wherein the cation X(+) may be one or more metals of Group IA, IB, IIB, VIIA or VIII of the Periodic Table or a non-metallic cation, e.g. ammonium; and R1 is hydrogen or an organic radical and R2 is an organic radical e.g. saturated or unsaturated alkyl, cycloalkyl, alkaryl or heterocyclic radicals which may be optionally substituted e.g. by nitro or amino groups.  Aliphatic radicals preferably contain from 1 to 6 carbon atoms.  The substituting radicals may form a heterocyclic ring with the common nitrogen atom when -R1-R2- represents a chain of 4 to 7 atoms which may be exclusively carbon atoms or may include a nitrogen, sulphur or oxygen atom.  Examples of heterocyclic groups which may be present are the pyrrole, pyrollidine, pyridine, piperidine, pyrimidine, morpholine and thiomorpholine radicals. When R1 and R2 separately or in a ring bear an additional amino group this may be substituted by a further dithiocarboxylic acid group giving a bis-dithiocarbamate and the corresponding bis-compounds of Formula II.  Specific di-thiocarbamates mentioned are dimethyl, pyrrolidyl, methyl and ethylene-bis-dithiocarbamates (Zn, Fe or Mn salts) and specified thiuram disulphides are dimethyl, tetramethyl, dipyrrolidyl and polyethylene thiuram disulphides.  For use, the mixtures may be prepared mechanically or chemically (see Group IV (b)) and may be worked up with the addition of diluents, dispersing, wetting and adhesive agents to give compositions suitable for dusting, spraying or atomization.  The substances of Formulae I and II may be present in the ratio of from 9 : 1 to 1 : 9 (preferably 1 : 4 to 4 : 1).