Patent GB-798703-A (GB)
Title: Iminyl phosphates, their preparation and application
IPC: C07F9/32
Filed: 1955-11-24
Abstract: The invention comprises an O-organo iminyl phosphate containing the fundamental grouping: <FORM:0798703/IV (b)/1> and an O-organo iminyl thionophosphate containing the fundamental grouping: <FORM:0798703/IV (b)/2> Specified compounds of this type are those having the general formula (R1)(R2)P(X).O.N = A, wherein R1 and R2 are alkoxy, alkylthio, or alkylamino radicals, A is a carbocyclic or a =C(R3)(R4) radical in which R3 is hydrogen or an organic radical and R4 is an organic or inorganic radical, and X is oxygen or sulphur.  The organic radicals R3 and/or R4 may be heterocyclic, aromatic, acyclic or alicylic.  Also, where R1 and R2 are alkoxy radicals they should preferably contain from 1 to 5 carbon atoms. The compounds may be obtained by condensing an oxime or metal salt of an oxime with a halophosphate or halothionophosphate in accordance with the equation: <FORM:0798703/IV (b)/3> wherein Y is hydrogen or a metal, e.g. an alkali metal.  When a metal salt of the oxime is used the reaction is preferably conducted in a non-aqueous system and preferably in the presence of an inert solvent such as petroleum ether, benzene, toluene or cyclohexane, and at a reaction temperature between about 0 DEG  C. and 120 DEG  C.  The free oxime may be reacted with the halophosphate in the presence of a hydrogen halide sequestering agent such as pyridine or an acid binding agent such as sodium carbonate. The latter process also may be carried out in the presence of an inert solvent and in a nonaqueous system and a catalyst such as metallic copper and/or potassium bromide may be present.  Examples are given for the production of (1) O,O-diethyl-O-propyliden-2-iminyl phosphate from diethylchlorophosphate and the sodium salt of acetoxime; (2) O,O-diethyl-O-propyliden-2-iminyl thionophosphate from diethylchlorothionophosphate and the sodium salt of acetoxime; (3) the same product as in (1) by refluxing acetoxime with diethylchlorophosphate in the presence of pyridine and benzene; (4) the same product as in (2) by heating a solution of acetoxime in dry toluene with diethylchlorothionophosphate in the presence of sodium carbonate and a small amount of metallic copper; (5) O,O - dimethyl - O - propyliden - 2-iminyl phosphate from the sodium salt of acetoxime and dimethylchlorophosphate; (6) N,N,N1,N1 - tetramethyldiamido - O - propyliden - 2 - iminyl phosphate from tetramethyldiamidochlorophosphate and the sodium salt of acetoxime; (7) O,O-diethyl-O-(4 - methyl - 3 - pentenyliden - 2 - iminyl)-phosphate from the sodium salt of mesityl oxime and diethylchlorophosphate; (8) O,O-diethyl - O - (4 - methyl - 3 - pentenyliden - 2-iminyl) thionophosphate from the sodium salt of mesityl oxime and diethylchlorothionophosphate; (9) to (12) O,O-diethyl-O-[1-(4-chlorophenyl) ethyliden - 1 - iminyl] phosphate, O,O-diethyl - O - (3,5,5 - trimethyl - 2 - cyclohexen-1 - iminyl) phosphate, O,O - diethyl - O - cyclohexaniminyl phosphate and O,O-diethyl-O-(3,3-dimethylbutyliden - 2 - iminyl) phosphate respectively from diethylchlorophosphate and the sodium salt of p-chloroacetophenone oxime, isophorone oxime, cyclohexanone oxime and pinacolone oxime respectively; (13) O,O-diethyl-O-ethylideneiminyl phosphate from acetaldoxime and diethylchlorophosphate in the presence of dry pyridine and ether; (14) O,O-diethyl - O - (3 - oximinobutyliden - 2 - iminyl)-thionophosphate from the mono sodium salt of dimethylglyoxime and diethylchlorothionophosphate; (15) O,O - diethyl - O - (1 - nitroethyliden - 1 - iminyl) phosphate from the sodium salt of ethylnitrolic acid and diethylchlorophosphate; (16) bis-(O,O-diethyl)-O,O-(butyliden-2,3 diiminyl) dithionodiphosphate from the disodium salt of dimethylglyoxime and diethylchlorophosphate; (17) O,O-diethyl-O - (1 - carbethoxypropyliden - 2 - iminyl) phosphate from the sodium salt of ethyloximinoacetoacetate and diethyl chlorophosphate.  It is stated that the sodium salts of the following oximes may also be reacted with diethylchlorothionophosphate to form the corresponding iminyl thionophosphates: methyl n-propyl ketoxime, methyl isopropyl ketoxime, methyl cyclopropyl ketoxime, methyl isobutyl ketoxime, monochloroacetoxime, and cyclopentanone oxime.  Other compounds specified are O,O - diethyl - O - (3,3 - dimethylbutyliden - 2-iminyl) thionophosphate and O,O-diethyl O-(1-carbethoxypropyliden - 2 - iminyl) thionophosphate, these being prepared from methyl tert. isobutyl ketoxime and ethyloximinoacetoacetate respectively.  The use of dl-camphor oxime as starting material is also mentioned.  The products are stated to be valuable insecticides (see Group VI).ALSO:An insecticidal composition comprises an inert carrier and an O-organo iminyl phosphate or thionophosphate containing the fundamental grouping: <FORM:0798703/VI/1> wherein X is an oxygen or sulphur atom (see Group IV (b)). Specified O-organo iminyl phosphates and thionophosphates are those having the general formula (R1)(R2)P(X).  O.N = A, wherein R1 and R2 are alkoxy, alkylthio or alkylamino radicals, A is a carbocyclic or = C(R3)(R4) radical in which R3 is hydrogen or an organic radical and in which R4 is an inorganic or organic radical and X is oxygen or sulphur.  The insecticidal compositions may include dispersing or emulsifying agents and other active toxicants may also be present.  An example is given to show the insecticidal effect of compositions comprising aqueous emulsions made by diluting with water a concentrate containing 30 per cent of the active ingredient, 60 per cent of a mixed xylene solvent and 10 per cent of a nonionic emulsifier of the alkylphenol polyethylene glycol ether type.  Specified active ingredients are those of the above formula in which X is oxygen, R1 and R2 are both ethoxy groups and the grouping N = A is propyliden-2-iminyl, ethylideneiminyl, 4 - methyl - 3 - pentenyliden - 2 - iminyl, 1-carbethoxypropyliden - 2 - iminyl, 1 - (4-chlorophenyl) ethyliden - 1 - iminyl, cyclohexaniminyl, 3,5,5 - trimethyl - 2 - cyclohexen - 1 - iminyl and 1 - nitroethyliden - 1-iminyl respectively and those in which X is sulphur R1 and R2 are both ethoxy and the grouping N = A is propyliden-2-iminyl, pentyliden - 2 - iminyl, 3 - methylbutyliden - 2-iminyl, 1 - cyclopropylethyliden - 1 - iminyl, 4-methyl - 3 - pentenyliden - 2 - iminyl, 3,3 - dimethylbutyliden - 2 - iminyl, 1 - carbethoxypropyliden - 2 - iminyl and 3 - oximino butyliden - 2 - iminyl respectively, also O,O - dimethyl - O - propyliden - 2 - iminyl phosphate and bis - (O,O - diethyl) - O,O - (butyliden - 2,3-diiminyl) dithionodiphosphate.  The compound N,N,N1,N1 - tetramethyldiamido - O - propyliden-2-iminyl phosphate is also referred to.