Patent GB-1087066-A (GB)
Title: Azido substituted organophosphorus compounds, processes for preparing them, and pesticidal compositions containing the same
IPC: C07F9/40
Filed: 1964-12-09
Abstract: The invention comprises organo-phosphorus compounds of the formula <FORM:1087066/C2/1> wherein A is <FORM:1087066/C2/2> <FORM:1087066/C2/3> <FORM:1087066/C2/4> the azido group being in the para or ortho position of the benzene ring, and G and M which may be the same or different are hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl and wherein X and Z which may be the same or different are O, S or N-R, R being hydrogen or a hydrocarbon as defined hereinafter and wherein L, E and R which may be the same or different represent alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl, aralkenyl, cycloalkyl or cyclo-alkenyl and wherein any one of the radicals L, E, G, M and R, whenever it stands for hydrocarbon may be substituted by halogen, cyano, hydroxy, amine, alkylamino, dialkyl-amino, alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl, aryloxycarbonyl, nitro, or azido, provided that no carbon carries more than one azido group and that the total number of azido groups in the molecule is not more than two and wherein E and L may be linked to form a heterocyclic ring with the phosphorus atom and wherein whenever both X and Z stand for Y where Y is either O or S, L may also be hydrogen or a cation and wherein either one or both groups -XE and -ZL may represent a chlorine atom.  Compounds of the formula <FORM:1087066/C2/5> wherein E1 equals E and D1 equal a radical D which represents alkyl, alkenyl, alkynyl, aralkyl, aralkenyl, cycloalkyl or cycloalkenyl except that D1 and E1 cannot be an allylic or acetylenic radical are prepared by reacting a compound of the general formula <FORM:1087066/C2/6> with a water-soluble azide in a polar solvent, wherein Q is chlorine, bromine or iodine.  The reaction preferably takes place at a temperature between 50 DEG  and 170 DEG  C. with a dipolar aprotic solvent such as dimethyl sulphoxide, N,N-di-methylformamide, N,N - diethylformamide, sulpholane, N-methylpyrrolidone and N,N-di-methylacetamide. Suitable water-soluble azides are the alkali and alkaline earth metal azides and zinc azide.  The reaction leads predominantly to the half ester salt of the general formula <FORM:1087066/C2/7> wherein Cat is the cation of the azide used. Alternatively, whenever dealkylation occurs to a substantial degree an alkalizing agent may be used to remove the labile ester group prior to reaction with the azide.  Suitable alkalizing agents are the alkali metal hydroxides, carbonates and when a dipolar aprotic solvent is used alkali metal halides.  The half ester salts may be converted into diesters by reaction with an alkylating agent such as alkyl iodides, alkyl bromides, aryl halides, benzyl halides, alkyl sulphonates and dialkyl sulphates and into a half ester acid by reacting with an ion exchange resin in the acid form or with a strong mineral acid.  The half ester acid may be converted into a diester by reaction with an alcohol or phenol in the presence of dicyclohexylcarbodimide, into an alkyl ester by reaction with a diazoalkane or into other suitable diesters by reaction with an ester of orthoformic acid HC(OD)3.  Dichlorides of the formula <FORM:1087066/C2/8> may be prepared by reaction of the half ester salts with thionyl chloride and these dichlorides may be converted into esters, thiolesters, amides and ester-chloridates by reaction with compounds of the formula EZH or E1XH or both.  If only one mole of thionyl chloride is reacted then the monochloride is produced which may similarly be reacted with a compound of the formula E1ZH. A further process comprises reacting a half ester salt with an ester of chlorocarbonic acid and a compound of formula DOH.  An epoxy compound of the formula <FORM:1087066/C2/9> may also be reacted with a water-soluble azide to produce a mixture of a 1-azido and a 2-azido compounds.  Transesterification reactions may also be used to produce difficulty formed di-esters. An integrated 3-step process comprises reacting one mole of a dichloride of the formula <FORM:1087066/C2/100> with one mole of a compound EYH in the absence of water to produce the corresponding monochloride which is reacted with at least one mole of water and one mole of an alkalizing agent to form the half ester salt which is then reacted with a water-soluble azide. Compounds of the general formula <FORM:1087066/C2/111> wherein N3 is in the ortho or para position and the phenylene ring may be further substituted are prepared by diazotizing an aminobenzyl-phosphonate and reacting the formed diazonium salt intermediate at low temperatures with a water soluble azide.  The compounds of the formula <FORM:1087066/C2/122> may be used as the active ingredient in pesticidal compositions (see Division A5).ALSO:Pesticidal compositions contain in conjunction with a carrier an active ingredient of the formula: <FORM:1087066/A5-A6/1> wherein A is <FORM:1087066/A5-A6/2> ; <FORM:1087066/A5-A6/3> or <FORM:1087066/A5-A6/4> the azido group being in the para or ortho position of the benzene ring and G and M, which may be the same or different are hydrogen, alkyl, aryl, alkaryl, aralkyl or cycloalkyl and wherein Y is O or S and Z is O or S or NR and Y and Z may be the same or different, R being either hydrogen or a hydrocarbon as defined hereinafter and wherein D is alkyl, alkenyl, alkynyl, aralkyl, aralkenyl, cycloalkyl or cycloalkenyl and wherein E and R which may be the same or different are alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl, aralkenyl, cycloalkyl or cycloalkenyl and any one of the radicals D, E, G, M and A whenever it stands for hydrocarbon may be substituted by halogen cyano, hydroxy, amine, alkylamino, dialkylamino, alkoxy, aryloxy, alkylthio, arylthio alkoxycarbonyl, aryloxycarbonyl, nitro or azido provided that no carbon carries more than one azido group and that the total number of azido groups in the molecule is not more than two and wherein E and D may be linked to form a heterocyclic ring with the phosphorus atom (see Division C2).  The compounds are preferably used in the form of solutions, suspensions or dispersions in aqueous media containing suspending or dispersing agents such as sodium dinephthylmethanedisulphonate and sodium lauryl sulphate. Carriers or diluents other than water, e.g. organic solvents, mixtures of organic solvents or mixtures of water and organic solvents, auxiliary agents and/or plant nutrients may also be used.  Solid carriers are talc, kieselguhr, bentonite, and other colloidal clays and powdered chalk and the composition may be in the form of a shaped tablet or a non-hygroscopic free-flowing granular preparation.  Suitable auxiliary agents are spindle oil, glycerol, woolfat, sodium lauryl sulphate, glues and resins and U.V. screening agents.  Plant nutrients are, e.g. urea and magnesium sulphate.