Patent GB-929727-A (GB)
Title: New fungicidal bis-tetrahydrothiadiazinethione compounds and compositions containingthem
Inventor: CUMMINS EARL WESLEY
IPC: C07D285/34
Filed: 1959-07-14
Abstract: Organic material susceptible to fungal attack including fats and lubricating oils is protected by applying thereto as a fungicide a bis tetrahydrothiadiazine thione having the general formula <FORM:0929727/III/1> wherein R1 and R2 which may be the same or different are such that the compound R1COR2 is an aldehyde or ketone, R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine H2N-R4-NH2 and R3 is a cyano, alkoxy (1-18 carbons), alkenoxy (2-18 carbons), dialkylamino (2-10 carbons), carboxyalkyl (2-18 carbons), carboalkoxyalkyl (3-18 carbons), sulphatealkyl (1-18 carbons), sulphoalkyl (1-18 carbons), sulphinethyl, cyanoalkyl (2-18 carbons), cyclohexyl, cyclopentenyl, nitrophenyl, chloronitrophenyl, dichlorophenyl, dialkylphenyl, chlorobenzyl, b -methoxymethyl, g -methoxypropyl, tris (hydroxymethyl) methyl, b , g -dihydroxypropyl, b -hydroxy-a , a -dimethylethyl or g -diethylamino-b -hydroxypropyl group or alternatively R3 is an organic group such that the compound R3NH2 is ammonia or an organic mono-primary amine with the proviso that either (1) R1 is a chloroalkyl (1-18 carbons), or dichlorophenyl group or (2) R1 is a styryl, methoxymethyl, a , b -dihydroxyethyl, dodecyl, or a b -carboxy-a , b -dichlorovinyl group and R2 is hydrogen or (3) R4 is an alkynylene (2-18 carbons), alkylene bis (oxyalkyl) or (oxyalkylalkyline) (2-18 carbons) or carboxyalkylene (3-18 carbons) radical, including the salts with bases of the compounds which contain an acidic group, and also certain other analogous compounds specified in the examples which do not fall within the general classes given above.  The thiadiazines may be used with solid or liquid carriers, numerous examples being given, or with other fungicide adjuvants including surface active agents.  The thiadiazines may be used with other fungicides, examples being given. The compounds are used in accordance with Example XXII of the parent Specification.  Specification 918,152 also is referred to.  Reference has been directed by the Comptroller to Specification 896,936.ALSO:The invention comprises new compounds of the general formula <FORM:0929727/IV(a)/1> where R1 and R2, which may be the same or different, are such that the compound R1COR2 is an aldehyde or ketone, R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine H2N-R4-NH2 (in particular those compounds wherein R1 is an aliphatic radical of 1-5 carbon atoms, a substituted or unsubstituted phenyl group, or an alpha-furyl group, R2 is a hydrogen atom or an aliphatic radical of 1-4 carbon atoms, and R4 is a substituted or unsubstituted alkylene, alkenylene or cycloalkylene radical especially an alkylene radical of 2 to 6 carbon atoms or a cyclohexylene radical) and R3 is a cyano, alkoxy (1-18 carbons), alkenoxy (2-18 carbon atoms), dialkylamino (2-10 carbons), alkyl mercapto alkyl (2-18 carbons), chloroalkyl (2-18 carbons), carboxyalkyl (2-18 carbons), carboalkoxy alkyl (3-18 carbons), sulphate alkyl (1-18 carbons), sulphoalkyl (1-18 carbons), sulphinethyl, cyanoalkyl (2-18 carbons), cyclohexyl, cyclopentenyl, nitrophenyl, chloronitrophenyl, dichlorophenyl, dialkylphenyl, chlorobenzyl, b -methoxyethyl, g -methoxypropyl, tris(hydroxymethyl)methyl, b ,g -dihydroxypropyl, b -hydroxy-a ,a -dimethylethyl, or g -diethylamino-b -hydroxypropyl group, or alternatively R3 is an organic group such that the compound R3NH2 is ammonia or an organic mono-primary amine with the proviso that either (1) R1 is a chloro alkyl (1-18 carbons), or dichlorophenyl group or (2) R1 is a styryl, methoxymethyl, a ,b -dihydroxyethyl, dodecyl, or a b -carboxy-a ,b -dichlorovinyl group and R2 is a hydrogen, or (3) R4 is an alkynylene (2-18 carbons), alkylenebis(oxyethyl) or (oxyalkylalkylene) (2-18 carbons) or carboxyalkylene (3-18 carbons) radical, including the salts with bases of the compounds which contain an acidic group, and also certain other analogous compounds not covered by the above general formula, which are specified in the examples, including compounds wherein R3 is a -hydroxymethyl acetic acid (VI); 2-thiomethyl-ethyl acetic acid (VII); succinic acid residue (HOOC.CH.CH2COOH) (X); a -glutamic acid residue (X); 2-vinyloxyethyl (XIV); 2-hydroxypropyl (XXIII); 2-methyl-1,3-propane diol (XXIV); b -hydroxy ter. butyl (XLVII); allyl (XLVIII); propyl (L); octadecyl (LV); octadecenyl (LVI); methoxy phenyl (LX); 2,4-xylyl (LXI); benzyl (LXII) and R1 = vinyl (XXXIX); methallyl (XL); propyl (LI); hydroxyphenyl (LXVI) and R4 = 2-hydroxypropyl (LIII). The compounds may be prepared by the methods described in Exs I and XXII of the parent Specification using the appropriate reactants.  Specification 918,152 also is referred to. Reference has been directed by the Comptroller to Specification 896,936.ALSO:Organic material susceptable to fungal attack, including organic fibres, fabrics, leather, wood, is protected by applying thereto as a fungicide a bis tetrahydro thia diazine thione having the general formula <FORM:0929727/IV(a)/1> wherein R1 and R2 which may be the same or different are such that the compound R1COR2 is an aldehyde or ketone, R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine H2N-R4-NH2, and R3 is a cyano, alkoxy (1-18 carbons), alkinoxy (2-18 carbons), dialkylamino (2-10 carbons) alkylmercapto alkyl (2-18 carbons), chloroalkyl (2-18 carbons), carboxy alkyl (2-18 carbons), carbo alkoxy alkyl (3-18 carbons), sulphatealkyl (1-18 carbons) sulpho alkyl (1-18 carbons) sulphinethyl, cyano alkyl (2-18 carbons) cyclo hexyl, cyclo pentenyl, nitro phenyl, chloronitrophenyl, dichloro phenyl, dialkyl phenyl, chlorobenzyl, b -methoxyethyl, g -methoxypropyl, tris (hydroxy methyl) methyl, b ,g -dihydroxy propyl, b -hydroxy-a ,a -di methyl ethyl or g -diethylamino-b -hydroxy propyl group, or alternatively R3 is an organic group such that the compound R3 NH2 is ammonia or an organic mono-primary amine with the proviso that either (1) R1 is a chloro alkyl (1-18 carbons), or dichloro phenyl group or (2) R1 is a styryl, methoxy methyl, a ,b -dihydroxy ethyl, dodecyl, or a b -carboxy-a ,b -dichloro vinyl group and R2 is hydrogen, or (3) R4 is an alkyryline (2-18 carbons) alkyline bis (oxyalkyl) or (oxyalkyl alkyline) (2-18 carbons) or carboxy alkyline (3-18 carbons) radical, including the salts with bases of the compounds which contain an acidic group, and also certain other analogous compounds specified in the examples, which do not fall within the general classes above. Organic material which may be treated also includes carbohydrates, fats, and proteins; reference is made to living plants for example ornamental plants, fruit bearing trees, and various cellulosic material, paints and lubricating oils.  The thia diazines may be used with solid or liquid carriers, numerous examples being given, or with other fungicide adjuvants including surface active agents the specific additives and auxiliary fungicides are those described in the parent Specifications.  The thia diazines may be used with other fungicides, examples being given.  Specification 918,152 also is referred to.  Reference has been directed by the Comptroller to Specification 896,936.ALSO:Organic material susceptible to fungal attack is protected by applying a bistetrahydrothiadiazine thione of the general formula <FORM:0929727/VI/1> wherein R1, R2, which may be the same or different, are such that the compound R1COR2 is an aldehyde or ketone, R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine H2N-R4-NH2 and R3 is a cyano, alkoxy (1-18 carbons), alkenoxy (2-18 carbons), dialkylamino (2-10 carbons), alkyl mercapto alkyl (2-18 carbons), chloroalkyl (2-18 carbons), carboxyalkyl (2-18 carbons), carboalkoxy alkyl (3-18 carbons), sulphate alkyl (1-18 carbons), sulpho alkyl (1-18 carbons), sulphinethyl, cyanoalkyl (2-18 carbons), cyclohexyl, cyclopentenyl, nitrophenyl, chloronitrophenyl, dichlorophenyl, dialkylphenyl, chlorobenzyl, b  - methoxyethyl, g  - methoxypropyl, tris(hydroxymethyl) methyl, b ,g -dihydroxypropyl, b -hydroxy-a ,a -dimethyl ethyl or g -diethyl amino-b -hydroxypropyl group, or alternatively R3 is an organic group such that the compound R3NH2 is ammonia or an organic mono-primary amine with the proviso that either (1) R1 is a chloro-alkyl (1-18 carbons), or dichlorophenyl group or (2) R1 is a styryl methoxymethyl, a ,b -dihydroxyethyl, dodecyl, or a a -carboxy-a ,b -dichlorovinyl group and R2 is hydrogen or (3) R4 is an alkynylene (2-18 carbons) alkylene bis (oxyalkyl) or (oxyalkyl alkylene) (2-18 carbons) or carboxy alkylene (3-18 carbons) radical including the salts with bases of the compounds which contain an acidic group, and also certain other analogous compounds, specified in the examples, not within the general classes above. Organic material which may be treated may be a carbohydrate, a fat, or a protein; reference is made to living plants, for example, vegetables, ornamental plants and fruit-bearing trees, organic fibres and fabrics, leather and various cellulosic materials such as wood.  The thiadiazines may be used with solid or liquid carriers, e.g. attapulgite, kaolin diatomaceous earth, walnut shell flour, tobacco dust, redwood flour, fine silica, calcium silicate talc, pyrophyllite, tobacco dust, volcanic ash, kerosene, Stoddard solvent, xylene, alcohols, alkylated naphthalenes and glycols, or with other fungicide adjuvants and surface-active agents.  Typical auxiliary fungicides that can be employed in association with the compounds are: N-trichloro-methylthio-4-cyclo-hexene-1,2-dicarboximide, tetramethylthiuram disulphide, manganese ethylene-bis-dithiocarbamate, ferric dimethyl dithiocarbamate, zinc ethylene-bis-dithiocarbamate, zinc dimethyl dithiocarbamate (ziram), tetra copper calcium oxychloride, tetra chloro-p-benzoquinone (chloranil), 2,3-dichlor