Patent GB-983115-A (GB)
Title: Polycyclic diepoxy compounds
IPC: A23L3/349
Filed: 1962-02-07
Abstract: Slime forming organisms in water, e.g. paper mill effluent, are controlled by the addition thereto of polycyclic diepoxy dilutones optionally carrying chlorine or bromine substituents of the general formula.  Specification 962,121 is referred to. <PICT:0983115/C1/1>ALSO:Novel polycyclic diepoxy compounds of the general formula <FORM:0983115/C2/1> wherein X, X1 and X11 each represent a hydrogen, bromine or chlorine atom or an aliphatic or cyclic up to C10 hydrocarbon group, optionally chlorine or bromine substituted, the broken lines indicate that the methano bridge between position 1 and 4 may be absent, in which case carbon atoms 1 and 4 carry hydrogen atoms, and that between carbon atoms 6 and 7 there may be a single or a double bond, the carbon atoms 6 and 7 carrying hydrogen atoms in the case where there is a single bond and in particular the compounds 6,7-dichloro-exo- and endo-2,3: exo-4a, 8a diepoxy - 1,2,3,4,4a,8a - hexahydro - endo-1, 4 - methanonaphthalene - 5,8 are the subject of the invention.  The compounds may be used alone or in suitable admixtures as bactericides, fungicides, molluscicides, slimicides, in food and grain preservation or they may be cured with a polycarboxylic acid to give a polymer (see Divisions A5, C1, C3).  Compounds containing halogen in position 6 and/or 7 are made by the Diels-Alder reaction of an aliphatic or cycloaliphatic diene, e.g. butadiene or cyclopentadiene with a halogenated quinone, reacting the adduct with zinc and acetic acid followed by chromic acid and then epoxidizing in two consecutive steps, in either order, one under alkaline conditions with hydrogen peroxide, the other using peracid and acid conditions. In one of the examples a mixture of isomers of 6,7 - dichloro - 4a,8a - epoxy 1,4,4a,8a - tetrahydro - 1,4 - methanonophthalene - 5,8 - dione is epoxidized with peracetic acid to give a mixture of the four stereo isomers, since the starting material was a mixture of two. Starting with one isomer, the endo-4a,8a-epoxy exo-dione, under identical conditions, a mixture containing largely the exo-2,3- endo-4a, 8a-diepoxy exo-dione is obtained and is separated by crystallization from the endo-2,3-endo - 4a,8a - exo - dione. 6,7-Dichloro-endo-2, 3 - epoxy - 1,2,3,4 - tetrahydro - 1,4 - methano-naphthalene-5, 8-dione, obtained by the reaction of 6,7 - dichloro - 1,4 - dihydro - 1,4 - methanonaphthalene - 5,8 - dione with trifluoroacetic anhydride and hydrogen peroxide, is subjected to the second epoxidation with hydrogen peroxide under alkaline conditions to give the endo-2,3: exo-4a,8a-dipoxy endo-dione. Numerous products according to the invention are named and an explanation of the nomenclature used is given.  Specification 962,121 is referred to.ALSO:Insoluble epoxy resins are made by heating at about 150 DEG C. an equivalent amount of an anhydride of a polycarboxylic acid in the presence of a tertiary amine as curing agent with one or more of novel diepoxides of the general formula <FORM:0983115/C3/1> wherein X, X1 and X11 each represent H, Br, Cl or an up to C10 aliphatic or cyclic hydrocarbon group saturated and unsaturated carrying optionally Cl or Br substituents, the broken lines signifying the optional absence of the 1,4methano bridge, in which case carbon atoms 1 and 4 carry hydrogen atoms, and that there may be a single or a double bond between carbon atoms 6 and 7, the carbon atoms carrying hydrogen atoms in the case where there is a single bond. The two compounds 6,7-dichloroexo- and endo-2,3:exo - 4a,8a - diepoxy -1,2,3,4,4a,8a - hexahydro - endo - methanonaphthalene - 5,8 - dione are the most preferred, a large list of named compounds within the formula is also provided. Specification 962,121 is referred to.ALSO:Novel polycyclic diepoxides of the general formula <FORM:0983115/A5-A6/1> wherein X, X1, X11 each are a hydrogen, bromine or chlorine atom, or an up to C10 aliphatic or cyclic hydrocarbon group optionally chlorine or bromine substituted, the broken lines indicate the optional absence of the 1,4-methane bridge, in which case the valencies of carbon atoms 1, 4 carry hydrogen atoms, and that between carbon atoms 6 and 7.  There may be a single or double bond, the valencies of these atoms carrying hydrogen atoms in the case where there is a single bond and in particular the two isomeric compounds 6,7-dichloro-endo- and exo-2,3: exo-4a, 8a diepoxy-1,2,3,4, 4a, 8a hexahydro-, endo-1,4-methano naphthalene-5,8-dione are suitable as active ingredients for biocidal applications against fungi, bacteria and snails.  The compounds may be employed as dusts, aerosols, solutions and emulsions.  Among the adjuvants there may be mentioned hydrocarbons, surfactants of the non-ionic polyoxyethelene type and the usual alkyl sulphate variety chalk, calcium phosphate, kaolin, diatonsite.  The specific examples describe the use of the two above, particularly preferred compounds as foliage fungicides on growing plants, their effect against human pathogenic bacteria and fungi in vitro, and against snails. Specification 962,121 is referred to.ALSO:A fungicidal, bactericidal, viricidal, insecticidal or acaricidal composition suitable for the treatment of seeds or preserving foods, e.g. cheese, comprises, as active ingredient, a polycyclic di-epoxy compound of the formula <FORM:0983115/A1-A3/1> , wherein X, X1 and X11 each represent a H, Cl, Br atom or an aliphatic or cyclic, saturated or unsaturated hydrocarbon group containing up to 10 carbon atoms and, optionally, Cl or Br substituents, the broken lines indicate the optional absence of the 1, 4 methano bridge, in which case the valencies of the carbon atoms 1 and 4 carry H atoms, and that between carbon atoms 6 and 7 there may be a single or double bond, the valencies of these atoms carrying hydrogen atoms in the case where there is a single bond. The two isomeric compounds 6, 7-dichloro-exo and endo-2, 3, -exo 4a, 8a, diepoxy- 1, 2, 3, 4, 4a, 8a hexa hydro-endo- 1, 4, -methano-naphthalene- 5, 8- dione are specified among many.  The compositions may be in the form of dusts, solutions in organic solvents, aqueous emulsions or aerosols.  Carriers and adjuvants specified for these formulations include chalk, bentonite, kaolin, diatomite, hydrocarbons over the whole range of volatility, non ionic polyoxyethylene emulsifiers, sodium salts of secondary alkyl sulphates and vegetable oils.  In an example sugar-beet or cotton seed is treated.  The effectiveness of the polycyclic di-epoxy compounds as food preservatives is demonstrated in cheddar and cottage cheese, hamburger meats, flours and powdered milk solids. Specification 962,121 is referred to.ALSO:<FORM:0983115/B1-B2/1> Wrapping materials, e.g. paper, parchment, cloth, foils, plastic films, may be coated with novel diepoxy polycyclic diketones of the general formula below, wherein halogen may be present. Specification 962,121 is referred to.