Patent GB-829576-A (GB)
Title: New organic phosphorus compounds, process for their manufacture and preparations containing them
IPC: C07F9/40
Filed: 1956-11-02
Abstract: The invention comprises organic phosphorus compounds of the general formula <FORM:0829576/IV (b)/1> in which R, R1, R3 and R4 represent alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radicals which may contain substituents, or R and R1, on the one hand, and R3 and R4, on the other, may together form part of a ring system, R3 and R4 may also represent hydrogen, R2 represents hydrogen or an alkyl radical or a halogen atom, R5 represents one of the groups <FORM:0829576/IV (b)/2> (in which R6 represents an alkyl, aryl or heterocyclic radical), X and Y represent -O-, -S-, -NH- or >N-R, and Z represents O or S, and n and m each represent 1 or 2.  Where it is theoretically possible, the compounds may exist in the form <FORM:0829576/IV (b)/3> or as a tautomeric mixture of the two forms. The products are prepared by heating a compound <FORM:0829576/IV (b)/4> where R7 represents a C1-4 alkyl radical, with a compound <FORM:0829576/IV (b)/5> where Hal represents a halogen atom, such as bromine or, advantageously, chlorine, a compound of the formula R7-Hal being split off.  Alternatively, a compound <FORM:0829576/IV (b)/6> in which Me represents an alkali metal, advantageously sodium, is heated with a compound <FORM:0829576/IV (b)/7> In order to produce compounds in which R2 represents hydrogen or an alkyl radical, the condensation may be carried out as follows <FORM:0829576/IV (b)/8> The reaction temperature is, for example, 50-200 DEG  C. and advantageously about 90-150 DEG  C., if desired in solution in an inert solvent such as benzene, toluene, xylene, chlorobenzene or benzine, and, again if desired, in an inert atmosphere, e.g. N2, and/or under reduced pressure.  The products have pesticidal activity.  In Examples: (1) to (15) trimethyl phosphite and triethyl phosphite are reacted, separately, with a ,a -dichloroacetoacetic acid amide, monoand di-methylamides, mono- and di-ethylamides, mono- and di-n-propylamides, mono- and di-isopropylamide, mono- and di-n-butylamides, cyclohexylamide, (1-methyl-cyclohexyl)amide, piperidide, morpholide, 4-chloroanilide and 2,3-dichloroanilide; a  - monochloracetoacetic acid dimethylamide and diethylamide; a ,a -dibromoacetoacetic acid diethylamide; a ,a -dichlorobutyrylacetic acid diethylamide; a ,a -dichlorofuroylacetic acid diethylamide; a ,a -dichlorobenzoylacetic acid diethylamide; dichloromalonic acid (N-diethylamide) ethyl ester and dibromocyanacetamide; triethyl phosphite only is reacted with a ,a -dichloroacetoacetic acid anilide; a ,a -dichloro-acetoacetic acid diethylamide is reacted with tri-(iso-propyl) phosphite, diethyl tetrahydrofurfuryl phosphite, allyl diethyl phosphite, benzyl diethyl phosphite, cyclohexyl diethyl phosphite, p-chloro-phenyl diethyl phosphite, ethyl ethylene phosphite, mono-diethyl thioethoxyethyl phosphite, trithioethyl phosphite, o-diethyl N-diethylamido phosphite; a ,a 1-dichloroacetoacetic acid dimethylamide is reacted with phenyl-phosphonous acid diethyl ester; (16) the sodium salt of diethyl phosphite is prepared by reaction with metallic sodium and reacted with a -chloro-a -methyl-acetoacetic acid diethylamide and a -chloroacetoacetic acid diethylamide; similarly the sodium salt of dimethyl thiophosphite is reacted with a -chloro-acetoacetic acid diethylamide; (17) and (18) the sodio derivative of acetoacetic acid diethylamide is prepared and reacted with diethyl thiophosphoric acid ester chloride and with bis-(dimethylamido)-phosphoryl chloride and the sodio derivative of a -methyl-acetoacetic acid diethylamide is prepared and reacted with diethyl phosphoric acid ester chloride.ALSO:Pesticidal compositions comprise organic phosphorus compounds of the formula <FORM:0829576/VI/1> or of the formula or tautomeric mixtures thereof, wherein R, R1, R3 and R4 are alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radicals which may contain substituents or R and R1 on the one hand, and R3 and R4 on the other, may together form part of a heterocyclic system, R3 and R4 may also be hydrogen, R2 is hydrogen, alkyl or halogen, R5 is -CN, -CO-R6, -COOR6 or <FORM:0829576/VI/2> R6 is an alkyl, aryl or heterocyclic radical, X and Y are -O-, -S-, -NH- or >NR, Z is oxygen or sulphur, and m and n are each 1 or 2.  They may be used with gaseous solid or liquid carriers and other pesticides.