Patent GB-1061473-A (GB)
Title: Bicyclic sulphur containing olefines
IPC: C07D495/14
Filed: 1964-02-07
Abstract: The invention comprises 9-thiabicyclononenes of the general formula <PICT:1061473/C2/1> wherein the carbon atoms to which the sulphur bridge is attached are separated by at least two carbon atoms, t is 0, 1 or 2, X is one of the following:  (1) a halogen atom;  (2) a radical of formula RZ where R is a hydrogen atom or a "hydrocarbyl" or "acyl" radical or a pyridyl radical and Z is oxygen or sulphur; (3) a radical of the formula NR1R2(R3)n <FORM:1061473/C2/1> wherein R1 and R2 are each a hydrogen atom or an "acyl" or "hydrocarbyl" radical or may be conjoined or may together with N form a heterocyclic ring, R3 is a hydrogen atom or "hydrocarbyl" radical, n is 0 or 1, n being 0 when either R1 or R2 is acyl, Y is an anion of valence v, and n1 is 0 when N is tertiary and 1 when N is quaternary; (4) a carboxyl radical or a salt, nitrile, amide, ester or acid halide thereof; or  (5) a radical of the formula -N=C=Z, wherein Z is oxygen or sulphur, and wherein the X substituent is bonded to the carbon atom 5 when the sulphur bridge extends from carbon atom 1 to carbon atom 6, and the X substituent is bonded to carbon atom 6 when the sulphur bridge extends from carbon atom 1 to carbon atom 5.  The term "hydrocarbyl" is defined as being the radical derived from a hydrocarbon or substituted hydrocarbon by removal of one or more hydrogen atoms from one or more carbon atoms and the term "acyl" is defined as the radical derived from an acid by the removal of an OH group or in the case of a dicarboxylic acid optionally by removal of two OH groups each free valence then being attached to a 9-thiabicyclo[4,2,1] or [3,3,1]-nonenyl group and in the case of thiolo acids by removal of an -SH group.  The compounds of the invention are prepared by various methods from halo-9-thiabicyclononenes which halo compounds are obtained by heating a dihalo-9-thiabicyclononane at 110 DEG  to 220 DEG  C. until substantially 1 molar equivalent of hydrogen halide is evolved. This dehydrohalogenation may be catalysed by addition of Lewis acids or extended-surface solids having catalytic properties.ALSO:Biocidal compositions comprise a compound of the general formula <FORM:1061473/A5-A6/1> wherein the carbon atoms to which the sulphur bridge is attached are separated by at least two carbon atoms, t is 0, 1 or 2, X is one of the following:  (1) a halogen atom;  (2) a radical of formula RZ where R is a hydrogen atom or a "hydrocarbyl" or "acyl" radical or a pyridyl radical and Z is oxygen or sulphur; (3) a radical of the formula NR1R2(R3)n 7(n\sv/v) wherein R1 and R2 are each a hydrogen atom or an "acyl" or "hydrocarbyl" radical or may be conjoined or may together with N form a heterocyclic ring, R3 is a hydrogen atom or a "hyrocarbyl" radical, n is 0 or 1, n being 0 when either R1 or R2 is acyl, 7 is an anion of valence v, and n\sv is 0 when N is tertiary or 1 when N is quaternary;  (4) a carboxyl radical or a salt, nitrile, amide, ester or acid halide thereof; or  (5) a radical of the formula -N=C=Z, wherein Z is oxygen or sulphur, and wherein the X substituent is bonded to the carbon atom 5 when the sulphur bridge extends from carbon atom 1 to carbon atom 6, and the X substituent is bonded to carbon atom 6 when the sulphur bridge extends from carbon atom 1 to carbon atom 5 together with a diluent or carrier therefor.  The term "hydrocarbyl" is defined as being the radical derived from a hydrocarbon or substituted hydrocarbon by removal of one or more hydrogen atoms from one or more carbon atoms and the term "acyl" is defined as the radical derived from an acid by removal of an OH group or in the case of a dicarboxylic acid optionally by removal of two OH groups each free valence then being attached to a 9-thialicyclo [4,2,1] or [3,3,1]-nonenyl group and in the case of thiolo acids by removal of an -SH group.  The biocidal compositions may be organic solutions, aqueous dispersions, aqueous emulsions and wettable powders and may contain other pesticides or insecticides or synergists, e.g. piperaryl butoxide. The solid formulations may also contain surface active agents, sticking agents, stabilizing agents or binders.