Patent GB-949942-A (GB)
Title: Process for preparing phosphine oxides
IPC: C07F9/53
Filed: 1960-08-04
Abstract: A process for modifying or replacing an aryl group of a tertiary phosphine oxide having at least one aryl group bonded to phosphorus and having the general formula An-P(O)-Bm wherein n is an integer from 1 to 3 and m is an integer from 0 to 2, the sum of n and m being 3, A is an aryl group which may be substituted or unsubstituted, the substituent or substituents being inert under the conditions of reaction, and B is alkyl, aralkyl, or alkaryl said alkyl group or alkyl portion of said aralkyl or alkaryl group having from 1 to 20 carbon atoms comprises (a) treating the phosphine oxide with Na, K or Li in the presence of an ethereal solvent under substantially anhydrous and anaerobic conditions, (b) and then treating under substantially anhydrous and anaerobic conditions the reaction product or step (a) with a mono- or dihalo-substituted organic compound of the formula X1-R-X2 wherein X1 is halogen or hydrogen, X2 is halogen, and RX1 is alkyl, aralkyl or alkenyl when X1 is hydrogen or R is alkylene or alkylenearylenealkylene when X1 and X2 are halogen, the double bond of said alkenyl group being in a position at least beta to the halogen atom, said alkyl or alkenyl groups having up to 20 carbon atoms, and when both X1 and X2 are halogen atoms they are on separate carbon atoms whereby (c) when sodium and an organic monohalide are used the product is An-1-P(O)(R1)(Bm) wherein R1 is as defined above for RX1 and A, B, n and m are as defined above except that the sum of n-1 and m is 2, (d) when sodium and an organic dihalide are used the product is: <FORM:0949942/C2/1> wherein A, R, B, n and m are as defined above except that the sum of n-1 and m for each phosphorus is 2, (e) when lithium or potassium and an organic monohalide are used the product is: <FORM:0949942/C2/2> wherein A, R1, B, n and m are as defined above except that the sum of n-1 and m is 2, (f) when lithium or potassium and an organic dihalide are used the product is: <FORM:0949942/C2/3> wherein A, R, B, n and m are as defined above except that the sum of n-1 and m for each phosphorus is 2. Specified ethereal solvents for use in the process are methyl ethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dimethyl or diethyl glycol ethers. Typical substituents for the aryl group or groups in the phosphine oxide reactants are alkyl, alkoxy, and N, N-dialkyl groups.  The reaction may be carried out at atmospheric, sub-atmospheric or super-atmospheric pressure and temperatures from -40 DEG C. to 200 DEG C., preferably 0 DEG C. to 60 DEG C., may be used in step (a) and from -60 DEG C. to 100 DEG C., preferably -10 DEG C. to 60 DEG C. may be used in step (b). The products are useful as additives for gasoline (see Division C5).ALSO:Tertiary phosphine oxides of the formulae <FORM:0949942/C3/1> <FORM:0949942/C3/2> wherein A is an aryl group which may be substituted, e.g. by alkyl, alkoxy or N,N-dialkyl groups, B is alkyl, aralkyl or alkaryl, the alkyl group or alkyl portion of said aralkyl or alkaryl groups having 1 to 20 carbon atoms, R is alkyl, aralkyl, or alkenyl when monovalent (said alkyl or alkenyl groups containing up to 20 carbon atoms) or is alkylene or alkylene-arylenealkylene when divalent; n is an integer from 1 to 3, and m is an integer from 0 to 2, the sum of n-1 and m for each phosphorus atom being 2 and which are prepared in a specified manner (see Division C2) are used as additives for gasoline, e.g. in an amount of up to 10 ml. per gallon of gasoline.