Patent GB-891178-A (GB)
Title: Manufacture of olefinically unsaturated compounds
IPC: C07C1/32
Filed: 1959-06-03
Abstract: Olefinically unsaturated compounds are prepared by condensation of a carbonyl compound and a phosphine oxide or phosphonate in the presence of a metal alcoholate according to the equation <FORM:0891178/IV (b)/1> wherein: R1 is alkyl, alkenyl, aralkyl, aralkenyl, aryl or heterocyclic;  R2 is hydrogen, alkyl, alkenyl, aralkyl, aralkenyl, aryl or heterocyclic or is acyl, in which case condensation also occurs at the second carbonyl group, or  R1 and R2 together with the carbonyl group form a five- or six-membered ring system;  R3 is alkyl, alkyloxy, aryl or aryloxy;  R4 is alkyl, alkyloxy, aralkyl, aralkyloxy, aryl or aryloxy;  R5 is hydrogen, alkyl, alkenyl, aralkyl or aryl;  R6 is hydrogen, alkyl or aryl provided that R3, R4, R5 and R6 do not all represent ary groups. Usually equivalent proportions of the reactants are reacted in an inert solvent such as benzene, toluene, xylene, cyclohexane, anisol or benzonitrile, at 50 DEG C.-150 DEG C.  The sodium or potassium alcoholates especially of secondary and tertiary alcohols are preferred, e.g., sodium ethylate, propylate isobutylate or benzylate or potassium tert.-butylate or tert.-amylate.  The examples refer to condensations between (1) diphenyl benzyl phosphine oxide and benzophenone to form triphenylethylene; (2) diphenyl methyl phosphine oxide and benzophenone to form 1 : 1-diphenylethylene; (3) diphenyl ethyl phosphine oxide and benzophenone to form diphenylpropene; (4) diphenyl butyl phosphine oxide and benzophenone to form diphenylpentene; (5) diphenyl benzyl phosphine oxide and acetophenone to form a -methyl stilbene; (6) diphenyl benzyl phosphine oxide and benzaldehyde to form stilbene; (7) diphenyl benzyl phosphine oxide and cyclohexanone to form benzylidene cyclohexane; (8) diphenyl benzyl phosphine oxide and cinnamic aldehyde to form 1 : 4-diphenyl butadiene; (9) diphenyl benzyl phosphine oxide and fluorenone to form benzalfluorene; (10) diphenyl benzyl phosphine oxide and methyl ethyl ketone to form 1-methyl-1-ethyl styrene; (11) diphenyl benzyl phosphine oxide and benzil to form 1,2,3,4-tetraphenyl butadiene; (12) diphenyl benzyl phosphine oxide and terephthalaldehyde to form distyryl benzene; (13) diphenyl benzyl phosphine oxide and pyridine-3-aldehyde to form b -stilbazole; (14) diphenyl benzyl phosphine oxide and pyridine-4-aldehyde to form g -stilbazole; (15) diphenyl allyl phosphine oxide and benzophenone to form 1 : 1-diphenylbutadiene; (16) diphenyl-1-phenylethyl phosphine oxide and benzaldehyde to form a -methylstilbene; (17) diphenyl benzyl phosphine oxide and methyl isopropyl ketone to form 1-methyl-1-isopropyl styrene; (18) diphenyl butyl phosphine oxide and benzophenone to form 1 : 1-diphenyl-2-propyl ethylene and diphenyl benzyl phosphine oxide and benzaldehyde to form 1 : 2-diphenyl ethylene; (19) diethyl benzylphosphonate and benzophenone to form triphenylethylene; (20) dibutyl benzylphosphonate and benzaldehyde to form stilbene; (21) diethyl butylphosphonate and benzophenone to form diphenylpentane; (22) diethyl butylphosphonate and benzaldehyde to form phenylpentene; (23) diethyl 1-phenylethylphosphonate and benzaldehyde to form a -methyl stilbene; (24) diethyl o -carbomethoxy allyl-phosphonate and benzaldehyde to form, after hydrolysis, cinnamyl acetic acid.  The phosphinic acid or phosphonic acid ester also formed may be recovered and the phosphinic acid reconverted to the phosphine oxide by a Grignard reagent by way of the chloride.