Patent GB-918151-A (GB)
Title: New fungicidal bis-tetrahydrothiadiazine thione compounds and compositions containing them
IPC: C07D417/04
Filed: 1959-01-30
Abstract: Fats are protected against attack by fungus by means of a thione having the general formula <FORM:0918151/III/1> wherein R1 and R2 are hydrogen atoms or organic groups such that the compound R1 COR2 represents a ketone or an aldehyde other than formaldehyde, R3 is hydrogen or an organic group such that the compound R3NH2 represents ammonia or an organic primary amine and R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine NH2-R4-NH2. Numerous examples of such compounds are given.  They may be used in conjunction with solid or liquid carriers or other adjuvants, e.g. surface-active agents and if desired with other fungicides.ALSO:The invention comprises bis-tetrahydro thiadiazine thiones having the general formula <FORM:0918151/IV (b)/1> wherein R1 and R2, which may be the same or different, are hydrogen atoms or organic groups such that the compound R1COR2 is an aldehyde or ketone but not formaldehyde, R3 is hydrogen or an organic group such that the compound R3NH2 is ammonia or an organic mono-primary amine and R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary di-amine NH2-R4-NH2. R1\h is preferably a C1-5 aliphatic radical, a phenyl group which may be substituted or an a -furyl group, R2 is preferably hydrogen or a C1-4 aliphatic radical, R3 is preferably an alkyl, alkenyl or phenyl radical which may be substituted or a naphthyl radical and R4 is preferably a C2-6 alkylene radical or a cyclohexylene radical.  The thiones may be prepared by reacting one mole of hydrazine or primary diamine with two moles each of an alkali metal hydroxide and CS2 in an aqueous or alcoholic medium at 0 DEG -45 DEG C., to form a solution of an alkali metal bis-dithiocarbamate which solution is then reacted with 4 moles of the aldehyde or ketone R1COR2 and two moles of a strong acid salt of ammonia or mono primary amine R4NH2 at 0 DEG -50 DEG C.  Examples describe the preparation as above of (1) 3,31-ethylene bis-tetrahydro-4,5,6-trimethyl-2H-1,3,5-thiadiazine-2-thione from CS2, NaOH, ethylene diamine, methylamine hydrochloride and acetaldehyde and (2) in similar manner, 3,31-ethylene bis tetrahydro-4,6-dimethyl-5-dodecyl-2H-1,3,5-thiadiazine - thione-2 using dodecylamine in place of methylamine.  Tables are given listing other thiones derived variously from ethylene diamine, hexamethylene diamine, 1 : 4-diamino butene-2, 2-hydroxy-1 : 3-diamino propane, diamino cyclohexane or 2 : 4-diamino-1-methyl cyclohexane, acetaldehyde, isobutyraldehyde, acetone, benzaldehyde or chloro benzaldehyde; and NH3, ethanol amine, methyl amine, aniline or dodecyl amine.  Numerous other reactants are also specified including diamino butane, allyl amine, chlor aniline, anisidines, naphthyl amines, acrolein, 2 : 21-dimethyl-3-hydroxypropionaldehyde, methoxy isobutyraldehyde, cyclopentaldehyde, chlorbenzaldehyde, trifluoromethyl benzaldehyde, methoxy benzaldehyde, salicylaldehyde, naphthaldehydes, aceto acetic ester and chloraceto-phenone.  The thiones may be used to protect organic material such as protein from fungal attack (see also Groups VI and VIII).ALSO:Fungicidal compositions comprise, with a solid or liquid carrier or other adjuvant, a thione having the general formula <FORM:0918151/VI/1> wherein R1 and R2 which may be the same or different are hydrogen atoms or organic groups such that the compound R1COR2 is a ketone or an aldehyde other than formaldehyde, R3 is hydrogen or an organic group such that the compound R3NH2 is ammonia or an organic mono-primary amine and R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine NH2-R4-NH2.  Numerous thiones are specified including typically those derived from acetaldehyde, acetone, isobutyraldehyde, cyclopentylaldehyde, trifluoromethyl benzaldehyde, acrolein, naphthaldehyde, chloraceto phenone or aceto acetic ester; ethylene diamine, diamino hydroxy propane or diamino cyclohexane; and methylamine, allyl amine, chloro aniline, anisidine or naphthylamine.  Numerous solid and liquid carriers are mentioned as well as surface active agents.  The thiones may be used with other fungicides including N-trichloro-methyl thio-4-cyclohexene-1,2-dicarbox imide, tetramethyl thiuram disulphide, various metal organic dithiocarbamates with or without 2-mercaptobenzothiazole and quinones, tetra-copper calcium oxychloride, dichloro - (o - chlor anilino) - triazine, ethylene thiuram mono sulphide 2-heptadecyl glyoxalidine acetate, copper dihydrazinium sulphate, copper quinolinolate, cycloheximide, Terramycin and Streptomycin.  Specified carriers are clays, diatomaceous earth, walnut shell flour, tobacco dust, red wood flour, silica, calcium silicate and volcanic ash, kerosene, Studdart solvent, xylene alcohols, alkylated naphthalenes and glycols.  Many surface active agents are specified.  A fungicidal dust comprises 3,31 - ethylene bis (tetrahydro-4,5,6-trimethyl - 2H - 1,3,5 - thiadiazine - 2 - thione, pyrophyllite and attapulgite.  The thiones and the above compositions may be used to protect carbohydrate, protein and fat material and living plants from attack by fungus.