Patent GB-932152-A (GB)
Title: New fungicidal di-tetrahydrothiono thiadiazine compounds and compositions containing them
Inventor: CUMMINS EARL WESLEY
IPC: C07D285/34
Filed: 1959-08-05
Abstract: Fatty material is rendered resistant to attack by fungus by means of a di-tetra hydrothiadiazine having the general formula <FORM:0932152/III/1> wherein R1 and R2 represent eight individually like or different atoms or groups, or one or more of the pairs of R1 and R2 groups on the same carbon atom is a bivalent saturated aliphatic hydrocarbon chain, and the R1 and R2 groups attached to the same carbon atom are such that the compound R1COR2 is an aldehyde or ketone; the R3 radicals represent two individually like or different atoms or groups each being hydrogen, hydroxyl, a sulpho group, a sulpho salt group or an organic radical such that the compound R3NH2 is primary mono-amine; and R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine H2N R4 NH2; with the proviso that (a) at least one of the <FORM:0932152/III/2> groups is different from at least one of the other three <FORM:0932152/III/3> groups, and/or (b) one or more of the pairs R1 plus R2 is a bivalent saturated aliphatic hydrocarbon chain, and/or (c) one or both the R3 radicals is hydroxyl, a sulpho group or a sulpho salt group, or a di-tetrahydrothiadiazine of the above general formula wherein, however, R4 is ethylene and either (i) R1 and R2 are both hydrogen and one R3 is methyl and the other is ethyl, hydroxyethyl or phenyl, or one R3 is hydroxyethyl and the other is b -hydroxy propyl or one R3 is methoxy and the other is chloroethyl; (ii) the R1s are methyl, the R2s are hydrogen, and one R3 is methyl and the other is ethyl; and (iii) the R1s are vinyl, the R2s are hydrogen and one R3 is methyl and the other is hydroxyethyl.  The compounds may be used alone or with a fungicide adjuvant, including inert solid carriers, liquid diluents, surface active agents and with other fungicidally active agents all as described in the parent Specification.  Numerous unsymmetrical thiadiazines of the first above defined type are mentioned.  Specification 918,151 also is referred to.ALSO:The invention comprises di-tetrahydrothiadiazines having the general formula <FORM:0932152/IV(a)/1> wherein R1 and R2 represent 8 individually like or different atoms or groups, or one or more of the pairs R1 and R2 on the same carbon atom is a bivalent saturated aliphatic hydrocarbon chain, and the R1 and R2 groups attached to the same carbon atom are such that the compound R1COR2 is an aldehyde or ketone; the R3 radicals represent two like or different atoms or groups, each being hydrogen, hydroxyl, a sulpho group, a sulpho salt group or an organic radical such that R3NH2 represents a primary mono-amine; and R4 is a covalent bond or the residue of an aliphatic or cyclo aliphatic primary diamine H2NR4NH2; with the proviso that (a) at least one of the <FORM:0932152/IV(a)/2> groups is different from at least one of the other three <FORM:0932152/IV(a)/3> groups, and/or (b) one or more of the pairs R1 and R2 is a divalent saturated hydrocarbon chain and/or (c) one or both the R3 radicals is OH, SO3H or a sulpho salt group. The invention also comprises other specific di-tetrahydrothiadiazines of the above structural formula wherein R4 is ethylene but either (i) R1 and R2 are both hydrogen and one R3 is methyl and the other is ethyl, hydroxyethyl or phenyl, or one R3 is methoxy and the other is b -hydroxypropyl or one R3 is methoxy and the other is chloroethyl; (ii) the R1s are methyl, the R2s are hydrogen and one R3 is methyl and the other is ethyl; and (iii) the R1s are vinyl, the R2s are hydrogen and one R3 is methyl and the other is hydroxyethyl.  The compounds may be prepared by the procedures set forth in the parent Specification e.g. from one molar equivalent of hydrazine or primary diamine, two molar equivalents each of alkali metal hydroxide and CS2, two equivalents of sulphamic acid or salt thereof, a salt of hydroxylamine or primary mono amine and four equivalents of carbonyl reactant.  Compounds wherein the R3s are different are obtained using an equimolar mixture of appropriate amino reactants and compounds asymmetrical in respect of the R1 and R2 radicals are obtained using a mixture of carbonyl reactants; these reactions yield mixtures from which the desired product is separated. Examples describe the preparation of symmetrical ditetrathiadiazines wherein (1) R1 and R2 are hydrogen, R3 is hydroxyl and R4 is ethylene; (2) R1 and R2 are hydrogen, R3 is -SO3H and R4 is ethylene; (3) each pair of R1 and R2 radicals represents a pentamethylene chain, R3 is methyl and R4 is ethylene; (4) and (5) R1 and R2 are hydrogen, R3 is -SO3Na and R4 is cis- or trans-buten-2-ylene; (6) R1 and R2 are hydrogen, R3 is hydroxyl and R4 is -C3H6OC2H4OC3H6. Asymmetrica compounds of the first above defined type are named in Examples (11), (15), (18) and (20)-(27).  The compounds are fungicidal and may be used to protect carbohydrate, protein and fat material (see Groups III, IV(c) and VI).  Specification 918,151 also is referred to.ALSO:Wood, leather, organic fibres and fabrics and other organic material are rendered resistant to attack by fungus by means of a di-tetra hydrothiadiazine having the general formula <FORM:0932152/IV(a)/1> wherein R1 and R2 represent eight individually like or different atoms or groups, or one or more of the pairs of R1 and R2 groups on the same carbon atom is a bivalent saturated aliphatic hydrocarbon chain, and the R1 and R2 groups attached to the same carbon atom are such that the compound R1COR2 is an aldehyde or ketone; the R3 radicals represent two individually like or different atoms or groups each being hydrogen, hydroxyl, a sulpho group, a sulpho salt group or an organic radical such that the compound R3NH2 is primary mono-amine; and R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic primary diamine H2NR4NH2; with the proviso that (a) at least one of the <FORM:0932152/IV(a)/2> groups is different from at least one of the other three <FORM:0932152/IV(a)/3> groups, and/or (b) one or more of the pairs R1 plus R2 is a bivalent saturated aliphatic hydrocarbon chain, and/or (c) one or both the R3 radicals is hydroxyl, a sulpho group or a sulpho salt group, or a di-tetrahydrothiadiazine of the above general formula wherein, however, R4 is ethylene and either (i) R1 and R2 are both hydrogen and one R3 is methyl and the other is ethyl, hydroxyethyl or phenyl, or one R3 is hydroxyethyl and the other is b -hydroxy propyl or one R3 is methoxy and the other is chloroethyl; (ii) the R1s are methyl, the R2s are hydrogen, and one R3 is methyl and the other is ethyl; and (iii) the R1s are vinyl, the R2s are hydrogen and one R3 is methyl and the other is hydroxyethyl.  The compounds may be used alone or with a fungicide adjuvant, including inert solid carriers, liquid diluents, surface active agents and with other fungicidally active agents all as described in the parent Specification.  Typical examples of compositions described are (1) an aqueous dispersion of a thiadiazine as above wherein R1 and R2 are hydrogen, R4 is ethylene and R3 is hydroxyl or -SO3H; (2) a wettable powder comprising the thiadiazine of (1) wherein R3 is -SO3H, sodium lauryl sulphate, sodium lignin sulphonate and kaolin clay; (3) a wettable powder comprising a thiadiazine wherein R1 and R2 are hydrogen, R4 is cis-butenylene and R3 is -SO3Na, alkyl naphthalene sulphonic acid Na salt, low viscosity methyl cellulose and silica; (4) a dust comprising stearated calcium carbonate and a thiadiazine wherein each pair R1 and R2 is a pentamethylene chain, R4 is ethylene and R3 is methyl; (5) a dust comprising a thiadiazine wherein R1 and R2 are hydrogen, R4 is ethylene and one R3 is -OH and the other is -CH2COOH, pyrophyllite and attapulgite; (6) a dust comprising a thiadiazine wherein R1 and R2 are hydrogen, R4 is ethylene and one R3 is hydroxyethyl and the other is methyl, and tobacco dust. Numerous unsymmetrical thiadiazines of the first above defined type are mentioned.ALSO:Fungicidal compositions comprise, with a solid or liquid carrier or other adjuvant, a ditetra hydrothiadiazine having the general formula <FORM:0932152/VI/1> wherein R1 and R2 represent eight individually like or different atoms or groups, or one or more of the pairs of R1 and R2 groups on the same carbon atom is a bivalent saturated aliphatic hydrocarbon chain, and the R1 and R2 groups attached to the same carbon atom are such that the compound R1COR2 is an aldehyde or ketone; the R3 radicals represent two individually like or different atoms or groups each being hydrogen, hydroxyl, a sulpho group, a sulpho salt group or an organic radical such that the compound R3NH2 is primary mono-amine; and R4 is a covalent bond or the residue of an aliphatic or cycloaliphatic p primary diamine H2 N.R.4 NH2; with the proviso that (a) at least one of the <FORM:0932152/VI/2> groups is different from at least one of the other three <FORM:0932152/VI/3> groups, and/or (b) one or more of the pairs R1 plus R2 is a bivalent saturated aliphatic hydrocarbon chain, and/or (c) one or both the R3 radicals is hydroxyl, a sulpho group or a sulpho salt group, or a di-tetrahydrothiadiazine of the above general formula wherein, however, R4 is ethylene and either (i) R1 and R2 are both hydrogen and one R3 is methyl and the other is ethyl, hydroxyethyl or phenyl, or one R3 is hydroxyethyl and the other is b -hydroxy propyl or one R3 is methoxy and the other is chloroethyl; (ii) the R1s are methyl, the R2s are hydrogen, and one R3 is methyl and the other is ethyl; and (iii) the R1s are vinyl, the R2s are hydrogen and one R3 is methyl and the other is hydroxyethyl. The compounds may be used with inert solid carriers, liquid diluents, surface active agents and with other fungicidally active agents all as described in the parent Specification.  Typical examples of compositions described are (1) an aqueous dispersion of a thiadiazine as above