Patent GB-872823-A (GB)
Title: New phosphorus esters
IPC: C07F9/6533
Filed: 1959-01-01
Abstract: The Specification comprises phosphorus esters of the general formula <FORM:0872823/IV (b)/1> wherein X1 and X2 are the same or different and are oxygen or sulphur atoms, at least one being a sulphur atom, A is an ethylene or propylene group, B is a methylene or ethylidene group, R and R1 are C1-C4 alkyl groups, and R2 and R3 are the same or different and are either hydrogen atoms, C1-C4 alkyl groups, or phenyl or cyclohexyl groups, or form with the N-atom to which they are attached a mononuclear saturated heterocyclic group such as piperidino, pyrrolidino or morpholino.  They may be obtained either by (a) reacting a halogenophosphate of the general formula (RO)(R1O)P(X1)Hal with an alcohol or thiol or derivative thereof of the formula M.X2ASBCON(R2)(R3) wherein Hal is a halogen atom, M is a hydrogen atom or an alkali metal atom and the other symbols are as defined above, the reaction being carried out in the presence of a basic condensing agent when M is a hydrogen atom, (b) by reacting an alkali metal salt of a compound (RO)(R1O)P(X1)X2H with a reactive ester of the formula Y.A.S.B.CON(R2)(R3) wherein Y is the acid residue of a reactive ester, e.g. a halogen atom, or a sulphuric or sulphonic ester residue, e.g. the toluene p-sulphonic acid residue, or (c) by reacting a compound of the formula (RO)(R1O)P(X1).X2. A.Y with a compound of the formula HS.B. CON(R2)(R3) wherein the various symbols are as defined above in the presence of an acid binding agent. Method (a) is preferably carried out in an organic solvent medium at below 150 DEG C.  Specified solvents are aliphatic alcohols and ketones and chlorinated hydrocarbons and suitable condensing agents are alkali metals and their derivatives, e.g. hydroxide or carbonate.  When X1 is a sulphur atom and X2 is an oxygen atom in the starting material a mixture of the thiono- and thiolo-products is obtained by method (a) and the thiono-form may be transposed into the thiolo form by the action of heat.  In method (b) when X1 is sulphur and X2 is oxygen in the starting material the product is obtained in the thiolo form. Methods (b) and (c) are preferably effected in an organic solvent medium, e.g. an aliphatic alcohol or ketone, at between 15 DEG  and 150 DEG C., e.g. at the boiling temperature of the solvent used.  The products have pesticidal properties (see Group VI).  The following compounds used as starting materials are prepared as follows:-N-methyl-5-hydroxy-3-thiavaleramide by the action of the monochlorhydrin of glycol on N-methyl-thioglycolamide; N-methyl-5-chloro-3-thia-2-methylvaleramide and the corresponding N-ethyl and N-propyl compounds by the action of 1-chloro-2-bromoethane on the corresponding thiolactamides in the presence of a acid binding agent for HCl; N-methyl-5-chloro-5-methyl-3-thiavaleramide by reacting 1-bromo-2-chloropropane on N-methyl-thioglycolamide in the presence of an acid binding agent for HCl; N-methyl-5-bromo-3-thiavaleramide by reacting N-methyl thioglycolamide with 1:2-dibromoethane in the presence of an acid binding agent for HBr; N-ethyl (or isopropyl) -5-chloro-3-thiavaleramide by an analogous reaction between 1-chloro-2-bromoethane and N-ethyl (or isopropyl) thioglycolamide. 5-Chloro-3-thiavaleramide, N-dimethyl-5-chloro-3-thiavaleramide and (5-chloro-3-thiavaleroyl) morpholine are obtained by analogous methods.ALSO:A pesticidal composition comprises one or more phosphorus esters of the formula <FORM:0872823/VI/1> wherein X1 and X2 are the same or different and are oxygen or sulphur atoms, at least one being a sulphur atom, A is an ethylene or propylene group, B is a methylene or ethylidene group, R and R1 are C1-C4 alkyl groups, and R2 and R3 are the same or different and are either hydrogen atoms, C1-C4 alkyl groups, or phenyl or cyclohexyl groups, or form with the N atom to which they are attached a mononuclear saturated heterocyclic group such as piperidino, pyrrolidino or morpholino (see Group IV (b)) in association with one or more diluents compatible with the said esters.  The compositions may be solid or liquid, e.g. in the form of aerosols, suspensions, emulsions or solutions in organic or aqueous organic media, e.g. aromatic hydrocarbons or mineral, animal or vegetable oils or mixtures of such diluents.  Wetting, dispersing, or emulsifying agents of the ionic or non-ionic type may be present.  Other pesticides and substances having a synergistic effect may also be present.