Verfahren zur Herstellung von 2, 4, 6-Triphenyl-5-benzyl-1, 3-dioxa-5-phosphacyclohexan-5-oxyd

摘要

The invention comprises substituted and unsubstituted 1,3 - dioxa - 5 - phosphacyclohexanes of the general formula wherein R1 to R3 are one of the following: a hydrogen atom, substituted or unsubstituted C1-C8 n-alkyl radicals, substituted or unsubstituted aryl radicals, alicyclic, aralkyl or alkaryl radicals, and Y is one of the radicals > PH, > PRa, > P(O)OH, > P(O)ORb and > P(O)Ra in which Ra is a substituted or unsubstituted C1-C6 alkyl radical, a substituted or unsubstituted aryl radical, or an alicyclic radical, and Rb is a substituted or unsubstituted C1-C6 alkyl radical. They may be obtained by condensing in the presence of an acid catalyst and under substantially anhydrous conditions an aldehyde of the formula R3CHO with a compound of the formula R1.CH(OH).Y.CH(OH)R2. Suitable acid catalysts are the mineral acids, e.g. HCl, HBr, HI and H2SO4 and salts thereof which are acidic under the reaction conditions, e.g. CaCl2 or FeCl3, and organic sulphonic acids, e.g. p-toluene-, benzene-, and methane sulphonic acids. Suitable reaction temperatures are generally from 10 DEG C. to 150 DEG C. and the process may be carried out continuously, semi-continuously or batchwise and at atmospheric or higher or lower pressure. An inert solvent may be present, e.g. benzene, dioxane, or ether. Examples are given for the production of compounds of the given formula in which (1) Y is /s7 P(O) benzyl and R1, R2 and R3 are each phenyl; (2) Y is /s7 PH, R1 and R2 are - CCl3, and R3 is n-hexyl; (3) Y is /s7 P(O)OH, R1 and R2 are hydrogen, and R3 is cyclohexyl; (4) Y is /s7 P.(CH2)3CH3, R1 and R2 are CH3 and R3 is p-tolyl; and also of the compounds ethyl 2-m-nitrophenyl-4-phenyl - 1,3 - dioxa - 5 - phosphacyclohexan - 5 - oate; 2,5 - dicyclohexyl - 4,6 - dimethyl - 1,3 - dioxa - 5 - phosphacyclohexane and 2 - benzyl - 4,6 - dihexyl - 5 - phenyl - 1,3 - dioxa - 5 - phosphacyclohexane. The products are useful in extracting metal values, e.g. uranium values, from ores containing such values. Bis (1-hydroxyethyl) butyl (or cyclohexyl) phosphine is obtained by reacting n-butyl (or cyclohexyl) phosphine with acetaldehyde in ether while passing dry HCl gas through the solution; ethyl (1-hydroxy-benzyl) hydroxymethyl phosphinate is obtained by treating an aqueous solution of 1-hydroxy-benzyl hydroxymethyl phosphinic acid with an aqueous solution of silver nitrate, separating the silver salt formed and then treating it with ethyl iodide in acetonitrile; bis (1-hydroxy-heptyl) phenyl phosphine is obtained by reacting phenyl phosphine and heptaldehyde in dry ether while passing dry HCl into the solution.