Patent GB-918152-A (GB)
Title: New fungicidal bis-tetrahydrothiadiazinethione compounds and compositions containing them
IPC: A01N43/88
Filed: 1959-01-30
Abstract: Fats are protected against fungal attack by means of a thione having the general formula <FORM:0918152/III/1> wherein R3 is hydrogen or an organic group such that 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, with the proviso that when R3 is methyl, R4 is not CH2CH2.  Numerous examples of such thiones are given. The thiones 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-tetrahydrothiadiazine thiones of the general formula <FORM:0918152/IV (b)/1> wherein 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 H2N-R4-NH2, with the proviso that when R3\h is methyl, R4 is not CH2CH2.  The compounds may be prepared by reacting one mole of hydrazine or a primary diamine H2N-R4-NH2 with two moles of an alkali metal hydroxide and two moles of carbon disulphide in an aqueous or lower alcoholic medium to give a solution of the alkali metal salt of a bis-dithiocarbamic acid which is reacted with two moles of a strong acid salt of ammonia or amine R3NH2 and four moles of formaldehyde.  Examples describe the preparation of 3 : 31-ethylene bis-(tetrahydro-5-ethyl-2H-1 : 3 : 5-thiadiazine-2-thione from ethylene diamine, CS2, NaOH, ethylamine hydrochloride and formaldehyde as above described and 3 : 31-ethylene bis(tetrahydro-5-dodecyl-2H - 1 : 3 : 5-thiadiazine-2-thione using dodecylamine hydrochloride in place of the ethylamine salt.  Numerous starting materials are specified for the preparation of other thiadiazine thiones including hexamethylene diamine, diamino cyclohexanes, 1 : 4 - diamino - butene - 2, 2-hydroxy-1 : 3-diamin propane, hydrazine and isobutylene diamine; ammonia, ethanolamine, tert-butylamine, ethoxy-propylamine, cyclohexylamine, aniline, chloraniline, toluidine, allylamine, 2-amino-2-methyl-1 : 3-propanediol, anisidines and naphthylamines.  The compounds may be used alone or with adjuvants to protect organic material such as protein from fungal attack (see also Groups VI and VIII).ALSO:Fungicidal compositions comprise a thione having the general formula <FORM:0918152/VI/1> wherein R3 is hydrogen or an organic group such that R3NH2 is ammonia or an organic mono-primary amine and R4 is a covalent bond or the residue of an aliphatic or cyclo aliphatic diamine NH2-R4-NH2, with the proviso that when R3 is methyl, R4 is not CH2CH2, and a solid or liquid carrier or other adjuvant.  Numerous thiones are specified wherein typically R3 represents hydrogen, ethyl, hydroxypropyl, ethoxypropyl, dodecyl, cyclo hexyl, allyl, chlor phenyl or naphthyl and R4 represents ethylene, hexamethylene, cyclohexylene, butenylene or a covalent bond.  Numerous solid and liquid carriers, surface active agents and also other fungicides for use with the thiones are specified as described in the parent Specification.  Examples of the compositions are given.  The thiones and the above compositions may be used to protect carbohydrates, proteins, fats and living plants from attack by fungi.