Patent GB-1007816-A (GB)
Title: Organic phosphine oxides and methods of preparing same
IPC: C07F9/53
Filed: 1962-05-04
Abstract: Gasoline contains as additive an alkylene diphosphine dioxide of the general formula <FORM:1007816/C4-C5/1> wherein R and R1 may be the same or different and represent substituted straight or branched chain alkyl or alkenyl radicals containing up to 20 carbon atoms, substituted saturated or unsaturated cycloaliphatic hydrocarbon radicals, substituted mononuclear and dinuclear aryl, or R and R1 taken together with the P atom may be the residue of a 2,4,6-trisecondary alkyl-1,3 - dioxa - 5 - phosphacyclohexane, R2 is hydrogen or branched or straight chain substituted or unsubstituted C1-C16 alkyl radical and R3 is hydrogen or a branched or straight chain substituted or unsubstituted C1-C16 alkyl radical or a cycloalkyl radical or R2 and R3 together with the carbon atoms to which they are attached may be the residue of cyclohexane (see Division C2). The substituents when R2 and R3 are substituted alkyl may be OH, CN and C1-C6 alkoxy and substituents on R and R1 include alkoxy, OH, halogen, aryloxy, amino, carbamyl, carbalkoxy and aryl (where appropriate).ALSO:The invention comprises phosphine oxides of the general formula <FORM:1007816/C2/1> wherein R and R1 may be the same or different and represent substituted branched or straight chain alkyl or alkenyl radicals having up to 20 carbon atoms, substituted saturated or unsaturated cyclo-aliphatic hydrocarbon radicals or substituted mononuclear and dinuclear aryl, or R and R1 taken together with the P atom may be the residue of a 2,4,6-trisecondary alkyl - 1,3 - dioxa - 5 - phosphacyclohexane, R2 is hydrogen or branched or straight chain substituted or unsubstituted C1-C16 alkyl and R3 is H or branched or straight chain substituted or unsubstituted C1-C16 alkyl or a cycloalkyl radical or R2 and R3 together with the carbon atoms to which they are attached may be the residue of cyclohexane.  Specified substituents on the alkyl radicals R2 and R3 are OH, CN and C1-C6 alkoxy.  Typical RR1P radicals are bis- (4 - chlorophenyl), bis - (2 - phenylethyl), bis- (3 - chloropropyl), bis - (3 - methoxycyclohexyl), and bis - (3 - ethoxycyclopentyl) phosphine radicals 2,4,6 - tris - (3 - heptyl) - 1,3 - dioxa - 5 - phosphacyclohexane, 2 - (3 - hexyl)- 4,6 diisopropyl - 1,3 - dioxa - 5 - phosphacyclohexane and bis - (2 - phenoxyethyl), bis - (2- aminoethyl), bis - (3 - hydroxypropyl), bis - (2- butoxyethyl), bis - (carbamylethyl), -bis - (2- chloroethyl), bis - (hydroxymethyl), bis - (1- hydroxyhexyl), bis - (3 - ethylthiopropyl), bis- (3 - carbethoxypropyl), bis - (4 - aminophenyl) and bis - [2 - (4 - aminophenyl) ethyl] phosphine radical.  The products may be obtained by reacting a cyclic carbonic acid ester of the formula <FORM:1007816/C2/2> or <FORM:1007816/C2/3> with a secondary phosphine or phosphine oxide of the formula <FORM:1007816/C2/4> The reaction is generally carried out at 50-250 DEG  C. when R2 and R3 are other than hydrogen and at 80-100 DEG  C. when R2 and R3 are both hydrogen and atmospheric or subatmospheric pressure may be used.  A catalyst, e.g. copper powder or an organic or inorganic base may also be present. Several examples are given and the products are useful as additives for gasoline (see Division C5).