Patent GB-1019215-A (GB)
Title: Substituted phenyl esters of phosphorus and thiophosphorus acids
IPC: C07F9/12
Filed: 1964-01-22
Abstract: The invention comprises compounds of the general formula <FORM:1019215/C2/1> wherein R1 and R11, which may be the same or different, denote C1-C8 alkyl, C1-C8 alkenyl, C1-C4 halogen substituted alkyl, phenyl, halogen substituted phenyl, C1-C4 alkyl substituted phenyl, C1-C4 alkoxy-substituted phenyl, C1-C4 alkylmercapto - substituted phenyl, cyclohexyl, benzyl, C1-C4 alkoxy, C1-C4 halogen-substituted alkoxy, C1-C4 alkylamino, C1-C8 dialkylamino and cyclohexylamino, X is oxygen or sulphur, and R1 and R2 represent hydrogen, alkyl or alkenyl radicals containing up to 4 carbon atoms or, together with the nitrogen atom, form a morpholine, thiomorpholine, pyrrolidine or piperidine residue and wherein the nitro group is ortho or para to the amino or substituted amino group. They may be obtained by reacting (thiono) phosphoric (phosphonic, phosphinic) acid halides of the general formula <FORM:1019215/C2/2> with nitro substituted amino phenols of the formula <FORM:1019215/C2/3> wherein R1, R11, R1, R2 and X have the same meaning as indicated above, Hal denotes a halogen atom and the NO2 group being ortho or para to the amino or substituted amino group. The reaction may be carried out in the presence of inert organic solvents, e.g. aliphatic alcohols, ketones and nitriles; aliphatic or aromatic hydrocarbons which may be chlorinated and dimethyl formamide.  The reaction is preferably carried out in the presence of acid binding agents such as alkali metal carbonates and alcoholates, and tertiary aliphatic or aromatic amines.  Alternatively the reaction may be carried out using alkali metal or ammonium salts of the above nitro-substituted aminophenols as starting materials.  It is also possible to start from the hydrohalides of the said phenols, provided that twice the quantity of acid-binding agent is used. The process is preferably carried out at slightly elevated temperatures (40 DEG  to 100 DEG  C.).  Examples are given for the production of compounds where R1 and R11 include methyl, ethyl, methoxy, ethoxy, chloroethoxy, isopropoxy, or dimethyl amino; R1 and R2 are methyl or R1 and R2 together with the nitrogen atom are morpholyl, piperidyl and pyrrolidyl; and X is sulphur or oxygen.  The nitro-substituted aminophenols used as starting materials e.g. 3-N,N-dimethylamino-4-nitro-, 3 - pyrrolidino - 4 - nitro- and 3 - N,N - dimethylamino - 2 - nitrophenol, can be obtained by reacting 3-chloro-4-nitro- or 3-chloro-2-nitro-phenol with an aqueous, aqueous-alcoholic or alcoholic solution of a nitrogen containing base of the formula <FORM:1019215/C2/4> where R1 and R2 have the same meanings as before, at temperatures between 50 DEG  and 150 DEG C.ALSO:Pesticidal compositions comprise a solid or liquid carrier or diluent and a phosphorus compound of the general formula: <FORM:1019215/A5-A6/1> wherein R1 and R11 which may be the same or different represent C1-C8 alkyl, C1-C8 alkenyl, C1-C4 halogen substituted alkyl phenyl, halogen substituted phenyl, C1-C4 alkyl substituted phenyl, C1-C4 alkoxy substituted phenyl, C1-C4 alkylmercapto substituted phenyl, cyclohexyl benzyl, C1-C4 alkoxy, C1-C4 halogen substituted alkoxy, C1-C4 alkylamino, C1-C8 dialkylamino and cyclohexylamino, X is oxygen or sulphur, and R1 and R2 represent hydrogen, alkyl or alkenyl radicals or, together with the nitrogen atom form a morpholine, thiomorpholine, pyrrolidine or piperidine residue and wherein the NO2 group is ortho or para to the amino or substituted amino group (see Division C2).  The usual solid carriers are suitable and aliphatic solvents are suitable liquid diluents.  In addition the compounds of the above formula may be used in combination with each other and other known insecticides and fertilizers.  Examples are given where the active ingredient is mixed with dimethyl formamide and benzyl hydroxy diphenyl polyglycol ether as an emulsifier and applied to aphids, spider mites and caterpillars infesting bean plants and white cabbages.