Patent GB-896373-A (GB)
Title: Ethenyl alkyl sulphones and pesticidal compositions containing them
IPC: C07C317/08
Filed: 1958-05-23
Abstract: Cloth, leather, wood and painted surfaces of articles are rendered resistant to attack by fungal organisms by being coated with an ethylenically unsaturated sulphone of the general formula RSO2-C(X) = C(Y)Z, RSO2-C(A) = C(B)-SO2R or (RSO2)2C = C(D)SO2R wherein the Rs represent alkyl radicals, at least two members of X, Y and Z are halogen, and the other is hydrogen or halogen, at least one of the members A and B is halogen and the other is hydrogen or halogen, and D is hydrogen or halogen, the term  "halogen" denoting chlorine, bromine and fluorine only.  The sulphones may be applied in aqueous or non-aqueous liquid media and in conjunction with surface-active agents, e.g. by brushing, spraying or dipping. Typical of many specified sulphones are 1,2-dichloro-ethenyl n-butyl sulphone, 1,2-difluoro ethenyl ethyl sulphone, tribromo-ethenyl n-hexyl sulphone, 2,2-dibromo ethenyl ethyl sulphone, 1,2-bis(n-propyl sulphonyl)-1-chloro-ethylene and tris(methyl sulphonyl)ethylene.  The preparation of the sulphones is described (see Group IV(b)).ALSO:The invention comprises ethylenically unsaturated sulphones of the general formulae RSO2-C(X)=C(Y)Z, RSO2-C(A)=C(B)-SO2R and (RSO2)2C=C(D)-SO2R, wherein the Rs represent alkyl groups, two of the members X, Y and Z are halogen and the other is hydrogen, at least one of the members A and B is halogen and the other is hydrogen or halogen and D is hydrogen or halogen; in all cases herein "halogen" denotes chlorine, bromine and fluorine only.  The invention also comprises a method for the preparation of mono-sulphones having the first above general formula wherein, however, X is halogen, at least one of Y and Z is halogen and the other is hydrogen or halogen, and of the above defined di- and tri-sulphones, which comprises reacting in the presence of an acid acceptor, a polyhalo-ethylene T(U)C=C(V)W wherein three members of T, U, V and W are halogen and the other is hydrogen or halogen, with an alkyl mercaptan RSH in proportions yielding an ethenyl mono-, di- or tri (alkyl sulphide) and oxidising the sulphide to the corresponding sulphone.  The mono-sulphones of the first above general formula wherein X is hydrogen and Y and Z are halogen are prepared by reacting an alkyl vinyl sulphide with a halogen to form a monohaloethenyl alkyl sulphide, oxidising the latter to form the corresponding sulphone, reacting the sulphone with a halogen to form the trihaloethyl alkyl sulphone and dehydrohalogenating the latter to form the desired dihaloethenyl alkyl sulphone.  The oxidation may be effected with hydrogen peroxide, suitably in acetic acid, or with permanganate, chromic acid, nitric acid or a hypo chlorite.  The reactions may be effected in an organic solvent.  Typical examples describe the preparation of (1) 1,2-dichloro ethenyl n-butyl sulphone, (5) 1,2-difluoroethenyl ethyl sulphone, (7) tri-bromo ethenyl n - hexyl sulphone, (8) 2,2 - dibromo ethenyl ethyl sulphone, (12) bis (n-propyl sulphonyl) - 1 - chloroethylene, (15) 1,2 - bis (ethyl sulphonyl) - 1,2 - dichloro ethylene, (18) tris (n-propyl sulphonyl)-chloro-ethylene and (24) tris (methyl sulphonyl) ethylene.  Numerous other examples of sulphones are also given including compounds containing different halogen atoms in the molecule.  The compounds are used in pesticidal and fungicidal compositions (see Groups III and VI).ALSO:Seeds are protected against fungal attack by being coated with an unsaturated sulphone of the general formula R SO2-C(X)=C(Y) Z, R SO2 -C(A)=C(B)-SO2 R or (R SO2)2C= C(D) SO2 R, wherein the Rs represent alkyl radicals, at least two of the members X, Y and Z are halogen and the other is hydrogen or halogen, at least one of the members A and B is halogen and the other is hydrogen or hologen and D is hydrogen or halogen, the term "halogen" denoting chlorine, bromine and fluorine only.  Typical of many specified sulphones are 1, 2-dichloro ethenyl butyl sulphone, 1, 2-difluoro ethenyl ethyl sulphone, tribromo-ethenyl n-hexyl sulphone, 2, 2-dibromo-ethenyl ethyl sulphone, 1, 2-bis (n-propyl sulphonyl)-1-chloroethylene and tris (methyl sulphonyl) ethylene. The sulphones may be applied in the form of a dust, wettable powder, slurry, emulsion or solution and numerous solvents, solid carriers and surface-active agents are specified for use therewith; other fungicides may also be present.ALSO:Pesticidal and fungicidal compositions comprise as active ingredients an ethylenically unsaturated sulphone of the general formula RSO2-C(X) = C(Y)Z, RSO2-C(A) = C(B)-SO2R or (RSO2)2C = C(D)SO2R wherein the R's represent alkyl groups, at least two of the members X, Y and Z are halogen and the other is hydrogen or halogen, at least one of the members A and B is halogen and the other is hydrogen or halogen and D is hydrogen or halogen, the term "halogen" denoting chlorine, bromine and fluorine only.  The compositions may be in solid or liquid form and comprise surface-active agents which can be anionic, cationic or non-ionic and numerous agents of all classes are named.  There may also be present solvents, various hydrocarbons, chlorinated hydrocarbons, ethers, esters, alcohols and ketones being specified or a solid carrier including inter alia, talc, kieselguhr, wheat flour, wood flour and lignin. Other pesticides such as phenothiazine, pyrethrum, rotenone and D.D.T. may be included.  Specific compositions described are (1) a solid powder comprising 1,2-dichloroethenyl methyl sulphone, diatomaceous earth, kaolin clay and a wetting agent; (2) an emulsifiable spray concentrate comprising 1,2-dichloroethenyl - n - butyl sulphone, polyoxyethylene sorbitan monolaurate and xylene. Tables are provided illustrating the use of numerous mono-, di- and tri-sulphones of the above formul  in control of various fungi, the treatment of soil and the protection of seeds and seedlings against fungi attack.  The compositions can also be used as weedicides.  The preparation of the sulphones is described (see Group IV (b)).