Patent GB-1070967-A (GB)
Title: Phosphorimidic triamide salts
IPC: C07F9/06
Filed: 1964-06-18
Abstract: The invention comprises phosphorimidic triamide salts of the general formula:-[(RNH)4P]nX where R represents the same or different organic groups which are C1-C18 alkyl, C3-C12 alkenyl, or C5 or C6 cycloalkyl groups; X is a salt forming anion such as Br-, Cl-,I-, SO4=, NO3-, PO43-, CH3COO-, (COO-)2, borat or phthalate and n represents the valency of the anion X.  They may be prepared by reacting aliphatic primary amines or their hydrohalides with PCl5 or PBr5 under anhydrous conditions, usually in the presence of an inert solvent. Unsymmetrical (RNH)3(R1NH)PCl compounds wherein R1 has the same meaning as R may be obtained by the following reaction:  (RNH)3PCl2 + 2R1NH2--> (RNH)3(R1NH)PCl + R1NH2HCl. The salts other than the hydrochlorides may be prepared (a) by neutralization of the phosphorimidic triamide base with an acid, usually in the presence of an inert solvent; (b) by metathesis of phosphorimidic triamide hydrochlorides or hydrobromides with metallic salts, suitable salts being those of alkali metals, alkaline earth metals, silver and lead and suitable solvents being water, alcohols and ketones; (c) by reacting a phosphorimidic triamide base with water and a salt, such as KI; and (d) by reacting the phosphorimidic triamide hydrochlorides or hydrobromides with an acid as in the equation:-  (RNH)4PCl + HxX1-->[(RNH)4P]xX1\h + HCl where X1 is a salt forming anion other than Cl and x represents the valency of X1.  An inert solvent is usually employed.  Suitable alkylamines for use in the above reactions are methylamine, ethylamine, isopropylamine, sec.-butylamine, t.-butylamine; 1,1,3,3-tetramethyl-butylamine (t.-octylamine), dodecylamine and octadecylamine.  Suitable alkenylamines include allylamine, methallylamine and 5,5,7,7-tetramethyl - 2 - octenylamine.  An acid acceptor may be employed which may be an excess of the amine reactant or another basic acid acceptor such as triethylamine or pyridine. Suitable solvents are ethers, hydrocarbons and chlorinated hydrocarbons or an excess of the amine reactant.  Examples are given for the preparation of these compounds.  The products are useful as pesticides and fungicides (see Division A5).  The (RNH)3PCl2 starting materials may be prepared by reacting phosphoric triamides with acid chlorides, e.g. as in the equation:-  (RNH)3PO + PCl5-->(RNH)3PCl2 + POCl3  The (RNH)3PO used above may be prepared by reacting an amine RNH2 with POCl3 as in the equation 6RNH2 + POCl3-->(RNH)3PO + 3RNH2.HCl.  The phosphorimidic triamide base may be obtained by treating a phosphorimidic triamide hydrochloride with a basic material such as an alkali metal oxide or hydride.  Examples are given for the preparation of some of the above bases.ALSO:A pesticidal composition comprises, as active ingredient, one or more phosphorimidic triamide salts each of the formula [(RNH)4P]nX where R represents the same or different organic groups which are C1-C18 alkyl, C3-C12 alkenyl or C5 or C6 cycloalkyl groups; X is a salt-forming anion, and n represents the valency of the anion X (see Division C2); and a diluent which is a solid or a liquid usually containing a surface active agent.  The compositions may be formulated as wettable powders, emulsion concentrates, dusts, granular formulations and aerosols.  They may be used in combination with other known biologically active materials such as insecticides, miticides and other fungicides. Adjuvants are preferably incorporated in foliage sprays; they are suitably wetting agents, spreading agents, dispersing agents, stickers and adhesives. The conventional dispersing and wetting agents may be used, particularly cationic and non-ionic types. Such surfactants include polyoxyethylated alkylphenols, fatty alcohols, fatty acids, mercaptans, alkylamines, polyoxyethylene sorbitan monolaurate, alkyl quaternary ammonium salts, lignin sulphonates, fatty acid alkyd resins and salts of maleicanhydride-diisobutylene copolymers. Water-soluble phosphorimidic triamide salts may be dissolved in water or a p  water-miscible liquid.  For the preparation of emulsion concentrates, the compound may be dissolved in organic solvents together with an emulsifying agent.  Wettable powders may be prepared by admixing the compound with a finely divided solid and incorporating wetting agents, sticking agents and/or dispersing agents in such mixtures.  Dusts may incorporate finely divided inert solids which may be organic or inorganic in nature such as botanical flours, silicas, silicates, carbonates and clays.  The compositions may be used as fungicidal sprays.