Patent GB-783697-A (GB)
Title: Organic phosphorus compounds
IPC: C07F9/40
Filed: 1953-10-28
Abstract: The invention comprises halogen-alkenyl esters of phosphorus of the general formula <FORM:0783697/IV (a)/1> in which Q is oxygen or sulphur, X is a halogen, R1 or R2 are unsubstituted or substituted alkyl, aryl, alkoxy or aryloxy groups, or jointly form an unsubstituted or substituted divalent alkylene dioxy or arylenedioxy radical, R3 and R4 are hydrogen, halogen, or carbalkoxy, or unsubstituted or substituted alkyl, aryl, alkoxy, aryloxy, alkylamino or alkylphosphoryl group or jointly an unsubstituted or substituted divalent alkylene or cycloalkylene radical, especially organic phosphates as above having at least one beta-halogen on the alkenyl radical, monothiophosphates as above having at least one beta-halogen on the alkenyl radical, phosphonates as above having at least one beta-halogen on the alkenyl radical, and phosphinates as above having at least one beta-halogen atom on the alkenyl radical.  The above halogenalkenyl esters may be prepared by the reaction between an esterified phosphorus acid of the general formula <FORM:0783697/IV (a)/2> where R is a substituted or unsubstituted alkyl group and R1 and R2 have the above significance, with an alpha-polyhalogenated carbonyl or thiocarbonyl compound of the general formula <FORM:0783697/IV (a)/3> wherein Q, X, R3 and R4 have the above significance. Suitable substituents that R1, R2, R3 and R4 may bear are halogen, cyano, nitro, ether, carbethoxy, and diethylamino substituents.  In examples: triethyl phosphite reacts with chloral to give diethyl 2 : 2-dichlorovinyl phosphate, with N : N-diethyl-trichloroacetamide to give diethyl-alpha-diethylamino-beta-beta-dichlorovinyl phosphate, with ethyl trichloroacetate to give diethyl a -ethoxy-beta-beta-dichlorovinyl phosphate, with 2 : 2 : 6-trichlorocyclohexanone, to give diethyl-2,2-dichlorocyclohexenyl - (1) phosphate, and with a polymer of thiochloral to give di-ethyl-S-2 : 2-dichlorovinyl monothiophosphate; chloral reacts with dimethylbenzene-phosphonite to give 2 : 2 - dichlorovinyl - methyl - benzene phosphonate, with ethylene methyl phosphite to give 2 : 2-dichlorovinyl ethylene phosphate and another product 2,2-dichlorovinyl 2-chloroethyl methyl phosphate, and with tris-2-chloroethylphosphite to give bis-2-chloroethyl 2 : 2-dichlorovinyl phosphate; bromal reacts with triethylphosphite to give 2 : 2-dibromovinyl diethyl phosphate; and triethyl phosphite reacts with trichloroacetyl chloride in two steps to form a phosphonate of the formula (C2H5O)2P(O)-C(O)CCl3 which then reacts with triethyl phosphite to form 1 - (diethylphosphoryl) - 2,2 - dichlorovinyl phosphate.  In a table a large number of reactants and products obtainable therefrom are listed.  Carbonyl reactants referred to in the table are chloral, bromal, dichloro- and dibromo - acetaldehyde, trichloroacetophenone, <FORM:0783697/IV (a)/4> <FORM:0783697/IV (a)/5> <FORM:0783697/IV (a)/6> and <FORM:0783697/IV (a)/7> Esterified phosphorus acids referred to in the table are trialkyl phosphites including those in which the alkyl groups contain alkoxy, nitro, dialkylamino, chloro, heterocyclic, carbalkoxy, acyloxy and nitrile substituents, tricyclohexyl phosphite, diaryl alkyl phosphites including those in which the aryl groups contain hydroxy, chloro and alkyl substituents, aryl dialkyl phosphites including those in which the aryl group contains a nitro substituent, alkylene alkyl phosphites including those in which the alkylene groups contain alkoxy, aryloxy, acyloxy, chloro, carbalkoxy, and alkyl substituents, ethyl o-phenylene phosphite, diethyl phenylphosphinate, diethyl propylphosphinate, and di-(methoxyethoxyethyl) phenylphosphinate.ALSO:Insecticidal, acaricidal, herbicidal and medicinal preparations contain a carrier and as the active ingredient a halogen-alkenyl ester of a pentavelent phosphorus acid having the general formula <FORM:0783697/VI/1> wherein Q represents oxygen or sulphur, X represents a halogen atom, R1 and R2 represent unsubstituted or substituted alkyl, aryl, alkoxy or aryloxy groups or R1 and R2 together form an unsubstituted or substituted divalent alkylenedioxy or arylenedioxy group, and R3 and R4 represent hydrogen or halogen atoms, or carbalkoxy, unsubstituted or substituted alkyl, aryl, alkoxy, aryloxy, alkylamino or alkylphosphoryl groups or R3 and R4 together form an unsubstituted or substituted divalent alkylene or cycloalkylene group.  A typical compound of the above general formula is diethyl 2-chlorovinyl phosphate.