Patent GB-899701-A (GB)
Title: New phosphorus-containing organic compounds
Inventor: CALDERBANK ALAN
IPC: C07F9/6539
Filed: 1957-10-25
Abstract: The invention comprises s-triazine derivatives of the formula <FORM:0899701/IV (b)/1> wherein R1 and R2 are methyl or ethyl radicals, R3, R4, R5 and R6 which can be the same or different are hydrogen, or methyl, ethyl, propyl or butyl radicals or R3 and R4 or R5 and R6\t together with the adjacent N atom constitute a piperidino ring and X is an oxygen or sulphur atom, and acid addition salts thereof.  The acid addition salts may be salts of inorganic or organic acids, e.g. hydrochlorides, oxalates, p-toluene sulphonates, methane sulphonates or isethionates.  The s-triazine derivatives may be obtained by reacting a compound of the formula (R1O)(R2O)P(X)SM wherein R1, R2, and X hav the meanings stated above and M is an alkali metal, e.g. sodium, or an ammonium radical, with a compound of the formula <FORM:0899701/IV (b)/2> wherein R3, R4, R5 and R6 are as defined above and Y is a halogen atom, e.g. Cl, Br, or I.  Suitable reaction temperatures are between 20 DEG C. and 150 DEG C. and an inert solvent or diluent, e.g. methanol or ethanol, may be present. Products in which at least one of the radicals R3, R4, R5 and R6 is hydrogen may also be obtained by reacting a compound of the formula <FORM:0899701/IV (b)/3> wherein R1, R2 and X are as defined above and R7 is a lower alkyl radical with a biguanide of the formula <FORM:0899701/IV (b)/4> wherein R3, R4, R5, and R6 are as defined above, at least one of them being hydrogen.  This reaction may also be carried out in a solvent or inert diluent, e.g. methanol. Several examples are given.  The products have insecticidal properties (see Group VI) the particularly preferred compounds being 2-dimethoxyphosphinothioylthiomethyl-4 : 6-diamino-s-triazine and 2-dimethoxyphosphinothioylthiomethyl - 4 - amino - 6-methylamino-s-triazine and their acid addition salts.  The halomethyl-s-triazines used as starting materials may be obtained by reacting a compound of the formula Y.CH2-COOR7 wherein Y and R7 are as defined above with a biguanide of the above formula in which at least one of R3, R4, R5, and R6 is hydrogen, or by reaction of the corresponding diazo-methyl-s-triazine derivative with gaseous hydrogen halide, e.g. gaseous HCl.  Examples are given for the production of 2-chloromethyl-4 : 6-bis(methylamino)-s-triazine and the corresponding 4-amino-6-methylamino, 4-amino-6-dimethylamino, and -4-amino-6-piperidino compounds, and of 2-bromomethyl-4- : 6-diamino-s-triazine and the corresponding 2-iodomethyl compound. The O,O1-dialkyl S-alkoxycarbonylmethyl phosthorothiolates and thiolothionates also used as starting materials may be obtained by reacting a compound of the formula (R1O)(R2O)P(X)SM wherein R1, R2, X and M are as defined above with a compound of the formula Y.CH2.COOR7 wherein R7 and Y are as defined above and examples are given for the production of O,O1-diethyl S - ethoxycarbonylmethyl phosphoro - thiolothionate and O,O1 - diethyl S - ethoxycarbonylmethyl phosphorothiolate.  According to the Provisional Specification the radicals R3 and R4 or R5 and R6 in the triazine products may be joined together with the adjacent nitrogen atom to form a morpholino ring.ALSO:An insecticidal composition contains in admixture with a suitable carrier or diluent a compound of the formula <FORM:0899701/VI/1> wherein R1 and R2 are methyl or ethyl radicals, R3, R4, R5 and R6 which can be the same or different are hydrogen, or methyl, ethyl, propyl or butyl radicals, or R3 and R4, or R5 and R6, together with the adjacent nitrogen atom constitute a piperidino ring, or an acid addition salt of such compound.  The acid addition salt may be a salt of an inorganic or organic acid, e.g. a hydrochloride, oxalate, p-toluene sulphonate, methane sulphonate, or isethionate.  The composition may be in the form of an aqueous formulation which may contain an organic solvent, e.g. methanol, tetrahydrofurfuryl alcohol or b -ethoxyethanol, or in the form of a powder in which the carrier is an inert pulverulent solid.  The composition may also contain a wetting or dispersing agent or other auxiliary agent.  Particularly preferred compounds on account of their high aphicidal activity and low mammalian toxicity are 2-dimethoxyphosphinothioylthiomethyl - 4 : 6 - diamino - s - triazine and 2 - dimethoxyphosphinothioylthiomethyl - 4 - amino - 6 - methyl - amino-s-triazine and their acid addition salts.  According to the Provisional Specifications the radical NR3R4 or NR5R6 may be morpholino.