Patent GB-965098-A (GB)
Title: Polymeric thiadiazinethiones, their preparation and fungicidal compositions containing them
IPC: C08G73/06
Filed: 1961-05-01
Abstract: Thiadiazinethiones of formula: <FORM:0965098/C1/1> <FORM:0965098/C1/2> <FORM:0965098/C1/3> wherein R is hydrogen, alkyl groups of 1 to 3 carbon atoms, or alkenyl groups of 1 to 3 carbon atoms; R1 and R2 are the same or different and are alkylene groups of 2-6 carbon atoms; R3 is an alkyl or alkenyl group of 1-18 carbon atoms; and n is a positive whole number, are prepared by the addition of an aqueous or aqueous-alcoholic solution of an alkylene diamine or a mixture of alkyl amines and alkylene diamines to an aqueous alcoholic solution of an alkylene-bisdithiocarbamic acid or a mixture of mono and bis dithiocarbamic acids followed by the immediate addition of an aqueous aldehyde solution. The solid reaction mixtures contain the polymeric thiadiazinethiones which are filtered, washed and dried. The structural type of polymer and degree of polymerization are controlled by variation in the ratio of the difunctional reactants (alkylene diamine, alkylenebisdithiocarbamic acids and aldehyde) to mono functional reactants (alkydithiocarbamic acid and/or alkyl amine). Examples describe the preparation of 5,5-[(tetrahydro -2- thiono - 2H - 1,3,5-thiadiazin-3,5-ylene) - diethylene] - bis(tetrahydro -3- methyl-2H-1,3,5-thiadiazine-2-thione); 3,31-ethylene-bis [(tetrahydro -2- thiono -2H- 1,3,5- thiadiazine-3,5-ylene)-diethylene] -bis- (tetrahydro -5- methyl-2H-1,3,5-thiadiazine-2-thione); and 5,51-ethylenbis-[(tetrahydro -2- thione -2H- 1,3,5- thiadiazin-3,5-ylene) diethylene]-bis(tetrahydro -3- methyl-2H-1,3,5-thiadiazine-2-thione), and many other compounds of these three types.  The products, in general, white solids of MP 60-200 DEG C. are insoluble in water and alcohols and are used in fungical compositions with conventional ingredients. Specification 932,152 is referred to.ALSO:The invention comprises polymeric thiadiazinethiones of formula: <FORM:0965098/C3/1> R is either hydrogen or alkyl or alkenyl of 1-3 carbon atoms; R1 and R2 are the same or different and are alkylene of 2-6 carbon atoms; R3 is alkyl or alkenyl, both of 1-18 carbon atoms; and n is a positive whole number which are prepared by the addition of an aqueous or aqueous-alcoholic solution of an alkylene diamine or a mixture of alkylene amines and alkylene diamines to an aqueous alcoholic solution of an alkylene-bis dithiocarbamic acid or a mixture of mono and bis dithiocarbamic acids followed by the immediate addition of an aqueous aldehyde solution.  The solid reaction mixtures contain the polymeric thiadiazinethiones which are filtered, marked and dried. The structural type of polymer and degree of polymerization are controlled by varying the ratio of the difunctional reactants (alkylene diamine, alkylenebisdithiocarbamic acids and aldehyde) to monofunctional reactants (alkyldithiocarbamic acid and/or alkyl amine).  Examples describe the preparation of 5,5-[(tetrahydro-2-thiono -2M- 1,3,5-thiadiazin-3, 5-ylene)-diethylene]-bis (tetrahydro -3- methyl -2M-, 1,3,5-thiadiazine -2- thione); 3,31-ethylene-bis[(tetrahydro -2- thiono -2M- 1,3,5-thiadiazin-3, 5-ylene)-diethylene] -bis- (tetrahydro -5- methyl -2M-1, 3, 5-thiadiazine -2- thione); and 5, 51-ethylene bis-[(tetrahydro -2- thione -2M- 1,3,5-thiadiazin -3,5- ylene) diethylene]- bis (tetrahydro -3- methyl -2M- 1, 3, 5-thia-diazine -2-thione) and many other compounds of these three types.  The products, in general, white solids of MP 60-200 DEG C. are insoluble in water and alcohols and are used in fungicidal compositions with conventional ingredients. ALSO:Fungicidal compositions comprise a thiadiazinethione compound of formula <FORM:0965098/A5-A6/1> <FORM:0965098/A5-A6/2> <FORM:0965098/A5-A6/3> wherein R is hydrogen, alkyl groups of 1 to 3 carbon atoms, or alkenyl groups of 1 to 3 carbon atoms; R1 and R2 are the same or different and are alkylene groups of 2-6 carbon atoms; R3 is an alkyl or alkenyl group of 1-18 carbon atoms; and n is a positive whole number (Division C2) as the active component.  The compounds are stable solids of M.P. 60-200 DEG  C. and are insoluble in water or alcohol, and examples are 5,5 - [(tetrahydro - 2 - thiono-2H-1,3,5 - thiadiazine - 3,5 - ylene) - diethylene] - bis-(tetrahydro - 3 - methyl - 2H - 1,3,5 - thiadiazine - 2 - thione); 3,3-ethylene-bis-[(tetrahydro - 2 -thiono-2H - 1,3,5-thiadiazin - 3,5 - ylene) diethylene] - bis-(tetrahydro - 5 - methyl - 2H - 1,3,5 - thiadiazine - 2 - thione); and 5,51-ethylenebis-[(tetrahydro-2-thione - 2H - 1,3,5 - thiadiazin - 3,5 - ylene) diethylene] - bis - (tetrahydro - 3 - methyl - 2H - 1,3,5 - thiadiazine-2-thione) and many other examples of these three types.  Conventional carriers such as inert solids, liquid diluents and surface-active agents anionic, cationic and non-ionic are listed and auxiliary fungicides, e.g. N-trichloromethylthio - 4 - cyclohexene - 1,2 - dicarboximide, thiuram, ferric dimethyl dithiocarbamate, manganese ethylene bisdithiocarbamate, zinc ethylenebisdithiocarbamate, ziram, tetra, copper calcium oxychloride, tetra - chloro - p - benzoquinone, 2,3 - dichloro - 1,4 - naphthoquinone, 2 - dichloro - 6 - (o - chloroanilino) triazine, ethylene thiuram monosulphide, glyodin, 2-mercapto benzothiazole, manganese dimethyl dithiocarbamate, copper dihydrazinium sulphate, copper-8-quinolinolate, cycloheximide streptomycin and oxytetracycline.  Specified forms are powders, wettable powders, solutions and suspensions.  Specification 932,152 is referred to.