Patent GB-1055093-A (GB)
Title: Heterocyclic esters of phosphorus acids,their preparation and use, and pesticidal compositions containing them
Inventor: HACKMANN JOHANNES THOMAS
IPC: C07F9/553
Filed: 1963-12-10
Abstract: The invention comprises compounds of the formula <FORM:1055093/C2/1> wherein A represents a C = O group; B represents a C = O or SO2 group; R1 and R2 each represent an alkyl or alkoxy group; R3 and R4 each represent a hydrogen or halogen atom or a nitro or alkyl group; R5 represents a hydrogen atom or a substituted or unsubstituted hydrocarbyl group; X and Y each represent O or S. Compounds in which Y is O may be prepared either by reacting a compound of the formula <FORM:1055093/C2/2> wherein hal represents a halogen atom, preferably chlorine, with a compound of the formula <FORM:1055093/C2/3> in the presence of a hydrogen halide acceptor, such as an alkali or alkaline earth metal carbonate or a nitrogenous base; or by reacting a compound of the formula <FORM:1055093/C2/4> with a compound of the formula <FORM:1055093/C2/5> wherein M represents an alkali or alkaline earth metal or an ammonium radical.  Compounds in which Y is S may be prepared by phosphorylating a compound of Formula II in which the HO- group is replaced by HS-, or a compound of Formula III in which the MO-group is replaced by MS- n the manner described for the phenolic compounds II and III.  Alternatively, compounds in which both X and Y are S may be prepared by reacting the diazonium fluorborate of a compound of the formula <FORM:1055093/C2/6> with a compound of the formula <FORM:1055093/C2/7> wherein Me represents an alkali metal, preferably in a suitable solvent at elevated temperature. The phosphorylation of compounds of Formulae II and III is preferably carried out in an inert liquid medium such as an aliphatic ketone, C6H6, (C2H5)2O, diisopropyl ether, tetrahydrofuran, CHCl3 or CCl4.  Preferred unsubstituted hydrocarbyl groups represented by R5 are branched or unbranched C1-C8 alkyl or alkenyl groups, cyclo-alkyl, aryl, aralkyl and alkaryl groups containing up to 10 carbon atoms. The substituents present in substituted hydrocarbyl groups may be halogen, or alkoxy, cycloalkoxy, aryloxy, alkaryloxy, aralkyloxy, alkylthio, cycloalkylthio, arylthio, alkarylthio, aralkylthio; alkyl-, cycloalkyl-, aryl-, alkaryl- or aralkylcarbonyl or -oxycarbonyl; alkyl-, aryl-, alkaryl- or aralkyl-sulphonyl; acyl, cyano, imino or nitro groups or groups represented by the formulae <FORM:1055093/C2/8> wherein each R represents H or an alkyl, cycloalkyl, aryl, alkaryl or aralkyl group. The products may be used in pesticidal compositions (see Division A5).  The hydroxy-1,3-isoindolediones of the formula <FORM:1055093/C2/9> used as starting materials may be obtained by mixing ethanolic solutions of 4-hydroxy-phthalic acid and the amine R5NH2, evaporating the ethanol, heating the residue, cooling and purifying. A compound in which R5 is methoxy-carbonylmethyl may be obtained by heating 4-hydroxyphthalic acid and glycine at 175-180 DEG C. for 20 minutes, cooling, dissolving in boiling ethanol, and precipitating with ether to give 5-hydroxy - 2 - carboxy - methyl - 1,3 - isoindoledione, and treating a methanolic solution of the latter with hydrogen chloride.  4-Hydroxy-2-alkyl -1,3-isoindolediones may be obtained by reacting 3-nitrophthalic acid with an alkylamine, reducing the 4-nitro-2-alkyl-1,3-isoindoledione to the amino-derivative, diazotizing and treating with hot dilute H2SO4. 5 - Hydroxy - 6 - nitro - 2 - methyl - 1,3 - isoindoledione and 5 - hydroxy - 4 - chloro - 2 - methyl - 1,3 - isoindoledione may be obtained by reacting 4 - hydroxy - 5 - nitrophthalic acid and 4-hydroxy-3-chlorophthalic acid with methylamine at 180 DEG C.ALSO:Pesticidal compositions comprise as active ingredient a compound of formula:  <FORM:1055093/A5-A6/1> wherein A represents a C=O group; B represents a C=O, or SO2 group; R1 and R2 each represent an alkyl or alkoxy group; R3 and R4 each represent H, halogen, nitro or an alkyl group; R5 represents H, or a substituted or unsubstituted hydrocarbyl group, and X and Y each represent O or S (see Division C2) together with a carrier and/or surface active agent.  The carrier may be a conventional solid or liquid carrier including resins such as polyvinyl chloride and polymers and copolymers of styrene; waxes; solid fertilizers and horticultural petroleum spray oils; or a compressed gas, conventional surface active agents may be used such as alkylaryl sulphonates alkyl sulphates containing at least 10C atoms in the alkyl chain, alkylaryl polyoxethylene glycol ethers, sorbitan esters of fatty acids, alkylamide sulphonates, and condensation products of ethylene oxide with fatty acid esters.  The compositions may contain other ingredients such as stickers, wetting agents, synergists, stabilizers or biologically active substances such as other insecticides, fungicides or herbicides. Specified insecticides are 1,1,1-trichloro-2,2-bis (p-chlorophenyl)-ethane; endrin; dieldrin; aldrin; O,O-dimethyl-0-(2,2-dichlorovinyl) phosphate; O,O-dimethyl- O-(1,2-dibromo-2, 2-dichloroethyl)-phosphate; O,O-dimethyl - O - [1-methyl-2-(1-phenyl-carbethoxy) vinyl] phosphate; O,O-dimethyl-O-[2-N,N-dimethylcarbamoyl-1-methyl-vinyl] phosphate; rotenone and pyrethrum.  The compositions may be formulated as dusts, as wettable powders, or as emulsifiable concentrates.  Aqueous emulsions or dispersions containing an organo-phosphorus compound as specified above may also be used. The products may be used for combating insects by bringing them into contact with one or more of the said compounds or compositions, and for improving crop yields by applying one or more of the said compounds or compositions to a crop area before or after crop planting, or before or after crop emergence.