Patent GB-824587-A (GB)
Title: Neutral spiro heterocyclic esters of phosphoric acid and their preparation
IPC: C07F9/6574
Filed: 1957-10-17
Abstract: The invention comprises as new compounds spiro heterocyclic phosphorus-containing esters of the formula <FORM:0824587/IV (b)/1> wherein R1 to R8 respectively designate a hydrogen or halogen atom or a phenyl or alkyl radical, each X is a hydrogen atom or the two X's collectively designate a second bond between the adjacent carbon atoms, Y is an oxygen or sulphur atom, and R9 is an alkyl, alkenyl, alkoxyalkyl, aralkyl, haloalkyl, monocyclic aryl, alkaryl, haloaryl, nitroaryl or alkyl mercaptoalkyl radical.  They may be obtained by reacting the corresponding spiro heterocyclic halide (i.e. a compound of the above formula in which OR9 is replaced by Hal) with an aliphatic monohydric alcohol or phenol having the formula R9OH in the presence of a tertiary amine or an alkali metal hydroxide or carbonate, or with an alkali metal alcoholate or phenolate of the formula MOR10 wherein M is the alkali metal and R10 is an alkyl, aryl, haloaryl, nitroaryl or alkaryl radical or with an epoxide compound having the formula <FORM:0824587/IV (b)/2> wherein R11 is a hydrogen atom or an alkyl or haloalkyl radical having 6 or fewer carbon atoms and separating the resulting reaction products.  The halides used are the chlorides, bromides, or fluorides-and each type of reaction may be carried out in the presence of an inert solvent. When an alkali metal alcoholate or phenolate is used as reactant the reaction may be carried out in the presence of a tertiary amine, e.g. triethylamine, or copper powder as catalyst and the reaction using the epoxide may be carried out in the presence of titanium tetrachloride as catalyst.  Examples are given for the production of: (1) spiro-[(2-ethoxy - 2 - thiono - 1,3,2 - dioxaphosphorinane) - 5,11 - cyclohexane]; (2) spiro - [(2 - ethoxy - 2 - thiono - 1,3,2 - dioxaphosphorinane) - 5,41 - cyclohexene]; (3) spiro - [(2 - ethoxy - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,41 - cyclohexene]; (4) spiro - {[2 - (2 - ethylmercapto-ethoxy) - 2 - oxo - 1,3,2 - dioxaphosphorinane] - 5,41 - cyclohexene}; (5) spiro - {[2 - oxo - 2 - (2 - propoxy) - 1,3,2 - dioxaphosphorinane] - 5,41 - cyclohexene}; (6) spiro - {[2 - (2 - chloroethoxy) - 2 - oxo - 1,3,2 - dioxaphosphorinane] - 5,41 - cyclohexene}; (7) spiro - [(2 - oxo - 2 - phenoxy - 1,3,2 - dioxaphosphorinane) - 5,41 - cyclohexene]; (8) spiro - [(2 - oxo - 2 - propenoxy - 1,3,2 - dioxaphosphorinane) - 5,31 (and/or 5,41) - (11 - (4 - methyl pentyl) - cyclohexane)]; and (9) spiro - [(2 - p - nitrophenoxy - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,41 - cyclohexene].  The products are useful as insecticides and as plasticizers for vinyl chloride-containing resins whilst the compounds containing olefinic unsaturation, e.g. compound (8), may be polymerized either alone or in conjunction with other polymerizable monomers (see Group IV (a)).  Specification 807,896 is referred to.ALSO:Spiro heterocyclic phosphorus-containing esters of the formula <FORM:0824587/IV (a)/1> wherein R1 to R8 respectively designate a hydrogen or halogen atom or a phenyl or alkyl radical, each X is a hydrogen atom or the two X's collectively designate a second bond between the adjacent carbon atoms, Y is an oxygen or sulphur atom and R9 is an alkyl, alkenyl, alkoxyalkoxyalkyl, aralkyl, haloalkyl, monocyclic aryl, alkaryl, haloaryl, nitroaryl or alkylmercaptoalkyl radical (see Group IV (b)) may be used as plasticizers for vinyl chloride-containing resins. Thus, the compounds (1) spiro ((2 - ethoxy - 2 - thions - 1,3,2 - dioxaphosphorinone) - 5,41 - cyclohexene); and (2) spiro ((2 - oxo - 2 - propenoxy - 1,3,2 - dioxaphosphorinane - 5,31 (and/or 5,41) - (11 - (4-methyl pentyl) cyclohexane) readily plasticize resinous copolymers of vinyl chloride and vinyl acetate containing 96% of the chloride.  Also, those compounds containing olefinic unsaturation, e.g. compound or compounds (2) above may be polymerized either alone or in conjunction with other polymerizable monomers, e.g. vinyl chloride, the vinyl esters of fatty acids having up to 10 carbon atoms and acrylic compounds such as acrylonitrile and alkyl acrylates in which the alkyl group contains up to 6 carbon atoms.