Patent GB-925991-A (GB)
Title: Addition products of trivalent organic phosphorus compounds with carbonyl compounds
IPC: C07F9/09
Filed: 1959-09-28
Abstract: The invention comprises an addition product of (a) the molecule of a trivalent phosphorus ester having the formula ROP(.Y)X in which R is a hydrocarbon or a halohydrocarbon group having 1 to 12 carbon atoms which is free from olefinic and acetylenic unsaturation, X is R or -OR, or -OR and X taken together represent -OCnH2nO- in which n is 2, 3, 4 or 5, and Y is -R, -OR, -SR or -NR1R2 in which R1 and R2 are alkyl groups having 1 to 5 carbon atoms or together represent CnH2n in which n is 2, 3, 4 or 5 and (b) one molecule of a keto-aldehyde or diketone having the formula ZC(O).C(O).Z1 in which Z is a hydrocarbon group having 1 to 12 carbon atoms which is free from olefinic or acetylenic unsaturation and which may have an alkoxy or a methylenedioxy substituent and Z1 is the same as Z or is a hydrogen atom or Z and Z1 taken together with the two intervening carbon atoms form a cycloaliphatic ring.  They may be obtained by mixing the trivalent phosphorus ester and the a -diketone or a -ketoaldehyde at ordinary, decreased or increased temperature and allowing the mixture to stand until formation of the adduct is complete.  The presence of an inert atmosphere e.g. nitrogen, is advantageous and it is preferred to operate in the substantial absence of moisture.  The reaction may be carried out in the presence of an inert diluent, e.g. benzene, toluene, dioxane, methylene chloride or hexane.  Suitable a -diketones include a -alkane-diones and a -cycloalkanediones having from 4 to 26 carbon atoms including those having an alkoxy substituent, aryl- and cycloalkylsubstituteda -alkanediones and -a -cycloalkanediones including those having an alkoxy substituent, and the diaroyls and hydrocarbon and/or ether substituted diaroyls. The preferred trivalent phosphorus compounds are the phosphite esters P(OR)3 wherein R is as defined above but other specified types of trivalent phosphorus compounds are compounds of the formula (RO)2PSR, cyclic esters of the formula:-  <FORM:0925991/IV(a)/1> wherein n is 2, 3, 4 or 5 and corresponding esters of thiophosphorous acid, diesters of phosphoramidous acid of the formula (RO)2PNR1R2 in which R, R1 and R2 ar as defined above; esters of phosphonous acid of the formula RO-P(R)-X11 in which R is as defined above and X11 is -OR, -SR, or -NR1R2 or X11 and OR taken together represent -OCnH2nO-, R1, R2 and n being as defined above, and esters of phosphinous acid.  The addition products are believed to have the cyclic structure:- <FORM:0925991/IV(a)/2> in which R, X, Y, Z and Z1 are as defined above.  The addition products react readily with a hydrogen donor, e.g. water, mineral acids, e.g. hydrochloric, sulphuric and phosphonic acids, C1-C5 fatty acids, or C7-C12 aryl mono-carboxylic acids to form b -keto phosphates, phosphonates, and phosphinates.  In carrying out this further reaction temperatures up to 100 DEG C. may be used if required and inert solvents or diluents may be present. When water is used the reaction is illustrated by the equation:- <FORM:0925991/IV(a)/3> in which R is as defined above, X1 and Y1 are -R or -OR and Z is a hydrocarbon group having one to twelve carbon atoms.  It is also possible to obtain such further reaction products by reacting a phosphorus ester RO.P.(Y1)(X1) with a diketone Z.CO.CO.Z and a hydrogen donor without isolating the addition product.  The addition products may also be oxidised by treatment with oxygen or an oxygen-containing gas, e.g. air, to yield pentavalent phosphorus esters according to the scheme:- <FORM:0925991/IV(a)/4> Such oxidation products may also be obtained directly by treating a trivalent ester Y-P(OR)-X with oxygen in the presence of an a -diketone-trivalent phosphorus ester addition product without isolating the latter.  Examples are given for the production of 1:1 addition products of 2,3-butanedione with trimethyl, triethyl, triisopropyl, tris(2-chloroethyl), trihexyl triphenyl, and tri(2-ethylhexyl) phosphites-, and with phenyl ethylene phosphite, diethyl butyl phosphonite, diethyl phenyl phosphonite, methyl diphenyl phosphonite, 2-ethyleneimino- 1,3,2-dioxaphospholane (obtained by reacting 2-chloro-1,3,2-dioxaphospholane with ethyleneimine), and with 2-ethylthiol 1,3,2-dioxaphospholane (prepared by reacting 2-chloro-1,3,2-dioxaphospholane with ethyl mercapton respectively; of benzil with trimethyl, triethyl, triphenyl and tris(2-chloroethyl) phosphites; and of triethyl phosphite with 2,3-octanedione, 1 phenyl-1,2-propane-dione, phenylglyoxal, piperil, 4,41-dimethyl benzil, and para-anisil respectively.  The production of the following further reaction products is also exemplified:-diethyl 1 methyl-2-ketopropyl phosphate (by treating the triethyl phosphite-2,3-butanedione addition product with water or anhydrous HCl; di-isopropyl 1-methyl-2-keto-propyl phosphate (by direct treatment of 2,3-butanedione, with triisopropyl phosphite in the presence of water or glacial acetic aid), 1 methyl-2-ketopropyl diphenyl phosphinate (by treating the 1 : 1-methyl diphenylphosphinite- 2,3-butanedione addition product with glacial acetic acid); and triethyl phosphate (by treating a 1 : 1 triethyl phosphite- 2,3-butanedione addition product with oxygen).  The addition products have insecticidal properties.