Patent GB-948581-A (GB)
Title: New nitrogen-containing organo-phosphorus compounds
IPC: C07F9/32
Filed: 1962-01-31
Abstract: The invention comprises phosphorus compounds of the formula: <FORM:0948581/C2/1> wherein n is O or 1, X1, X11, X11, and X111, are hydrogen or halogen atoms, X and X1 are hydrogen or halogen atoms or -Sn-P(:Z)(R1) (R2) groups at least one of X, X1 and X11 and at least one of X1, X11 and X111 being other than hydrogen, R1 and R2 are the same or different, unsubstituted or substituted hydrocarbon residues each of which may be linked directly to the phosphorus atom or via an oxygen or nitrogen atom, the third valency of said nitrogen atom bearing a hydrogen atom or a substituent with the same value as R1 or R2, and Z is an oxygen or sulphur atom.  They may be obtained by reacting a halogenated dimethyl carbamic acid chloride of the formula: <FORM:0948581/C2/2> wherein Y, Y1, Y11, Y1, Y11 and Y111 are halogen atoms and Y1, Y11, Y11 and Y111 may also represent hydrogen atoms, with a phosphorus compound of the formula: <FORM:0948581/C2/3> wherein Me is an alkali metal or ammonium to give compounds in which n is 1 or with a phosphorus compound of the formula: <FORM:0948581/C2/4> wherein R is alkyl, cycloalkyl or haloalkyl, which compound is capable of undergoing an Arbuzor reaction, to give compounds in which n is 0. The phosphorus compound may be used in equimolar proportion or up to twice the equimolar amount may be used. The reactions are preferably carried out in the presence of an inert solvent or diluent, e.g. a hydrocarbon, ether, or ketone. The products have pesticidal properties (see Division A5). Bis-(chloromethyl)-carbamic acid chloride can be obtained by reacting hexamethylene tetramine with phosgene or with a compound splitting off phosgene at an elevated temperature, e.g. oxalyl chloride or chloroformic trichloromethyl ester. The process may be carried out in the presence of an inert organic solvent e.g. an aliphatic or aromatic hydrocarbon or chlorinated hydrocarbon, and specified reaction temperatures are between 120 and 250 DEG C. At least 4 moles, and preferably 8-12 moles of phosgene, are employed per mole of hexamethylene tetramine and if no solvent is used the process should be conducted at an elevated pressure which may be up to 250 atmospheres. The halogenated dimethyl carbamic acid chlorides of the above general formula may also be obtained by the halogenation of dimethyl carbamic acid chloride thus pentachlorodimethyl carbamic acid chloride may be obtained by chlorinating bis (chloromethyl) carbamic acid chloride.ALSO:A pesticidal composition comprises a solid or liquid carrier or diluent and a phosphorus compound of the formula <FORM:0948581/A5-A6/1> wherein n is 0 or 1, X1, X11, X11 and X111 are hydrogen or halogen atoms, X and X1 are hydrogen or halogen atoms or -Sn-P(:Z) (R1)(R2) groups at least one of X,X1 and X11 and at least one of X1, X11 and X111 being other than hydrogen, R1 and R2 are the same or different unsubstituted or substituted hydrocarbon residues each of which may be linked directly to the phosphorus atom or via an oxygen or nitrogen atom, the third valency of said nitrogen atom bearing a hydrogen atom or a substituent with the same value as R1 or R2, and Z is an oxygen or sulphur atom (see Division C2). Specified carriers or diluents are talc, chalk, bentonite, clay, water (if desired with an emulsifier), alcohols, ketones and liquid hydrocarbons. Known insecticides and/or fertilisers may also be present.  A specified form is an emulsion.