Patent GB-930522-A (GB)
Title: Manufacture of olefinic compounds
IPC: C07C1/34
Filed: 1961-07-12
Abstract: Polyolefinic compounds are prepared by condensing, in the presence of an alkali metal alkoxide or alkali metal amide, an aldehyde or ketone of the formula R1 CO R2, in which R1 is alkyl, alkenyl, aralkyl, aralkenyl or aryl and R2 may be one of the same groups or hydrogen or R1 and R2 together with the carbonyl group may form a 5- or 6-membered ring, with a compound of the formula <FORM:0930522/III/1> in which each R is alkyl, aryl, alkoxy or aryloxy and X is a saturated or unsaturated aliphatic group which may be interrupted by an arylene group and which carries at least one hydrogen atom on each carbon adjacent to the phosphorus groups, with the exception that when R represents alkyl groups attached to phosphorus by an oxygen atom, X does not represent -CH2- (CR1 = CHn-CH = CH-(CH = CR1)n-CH\2 in which R1 is hydrogen alkyl, cycloalkyl, aralkyl or aryl and n is 0, 1 or 2.  A phosphate or phosphinic acid is also formed.  The compounds are reacted in equivalent amounts, i.e. 2 mols. of aldehyde or ketone to each mol. of bis-phosphine oxide or bis-phosphonic acid ester at 50 DEG -200 DEG C. in a hydrocarbon or ether solvent.  The examples illustrate the preparations of (1) 1,4-bis-(diphenylethenyl)-benzene from p-xylylene-bis-phosphonic acid tetraethyl ester and benzophenone; (2) 1,4-bis-(4-phenylbutadienyl)-benzene from p-xylene-bis-phosphonic acid tetraethyl ester and cinnamaldehyde; (3) 2,21-bis-(pentamethylene)-p-divinylbenzene from p-xylene-bis-phosphonic acid tetraethyl ester and cyclohexanone; (4) 1,4-bis-(9-phenanthryl-ethenyl)-benzene from p-xylylene-bis-phosphonic acid tetraethyl ester and phenanthrene-9- aldehyde; (5) 1,4-bis-(9-anthranyl-ethenyl)-benzene from p-xylylene-bis-phosphonic acid tetraethyl ester and anthracene-9-aldehyde; (6) 1,4-bis-(4-biphenyl-1-ethenyl)-benzene from p-xylylenebis-phosphonic acid tetraethyl ester and diphenyl-4-aldehyde; (7) 1,4-bis-(styryl)-benzene from p-xylylene-bis-phosphonic acid tetraethyl ester and benzaldehyde; (8) 1, 1, 6, 6,-tetraphenyl-hexatriene-1,3,5 from 1,4-butene-2-bis-phosphonic acid tetraethyl ester and benzophenone; (9) 1,10-diphenyl-deca-pentaene-1,3,5,7,9 from 1,4-butene-2-bis-phosphonic acid tetraethyl ester and cinnamaldehyde; (10) 1,4-bis-(4-phenylbutadienyl)-benzen from p-xylylene-bis-diphenyl-phosphine oxide and cinnamaldehyde; (11) 1,1,4,4-tetraphenyl-butadiene-1,3 from ethylene-1,2-bis-diphenyl-phosphine oxide and benzophenone; (12) 1,1,8,8-tetraphenyl-octadiene-1,7 from hexamethylene-1,6-bis-diphenylphosphine oxide and benzophenone and (13) 1,1,6,6-tetraphenyl-hexadiene-1,5 from tetramethylene-1,4-bis-diphenylphosphine oxide and benzophenone.ALSO:Polyolefinic compounds are prepared by condensing, in the presence of an alkali metal alkoxide or alkali metal amide, an aldehyde or ketone of the formula R1COR2, in which R1 is alkyl, alkenyl, aralkyl, aralkenyl, aryl or heterocyclic and R2 may be one of the same groups or hydrogen or acyl or R1 and R2 together with the carbonyl group may form a 5- or 6-membered ring, with a compound of the formula  <FORM:0930522/IV(a)/1> in which each R is alkyl, aryl, alkoxy or aryloxy and X is a saturated or unsaturated aliphatic group which may be interrupted by an arylene group and which carries at least one hydrogen atom on each carbon adjacent to the phosphorus groups, with the exception that when R represents alkyl groups attached to phosphorus by an oxygen atom, X does not represent -CH2-(CR1 = CH)n-CH = CH-(CH = CR1)n-CH2- in which R1 is hydrogen, alkyl, cycloalkyl, aralkyl or aryl and n is 0, 1 or 2.  A phosphate or phosphinic acid is also formed.  The compounds are reacted in equivalent amounts, i.e. 2 mols of aldehyde or ketone to each mol of bisphosphine oxide or bis phosphonic acid ester at 50-200 DEG C. in a hydrocarbon or ether solvent.  The corresponding mono-phosphine oxide or mono phosphonic acid ester is obtained as by-product or when equimolar amounts of the starting materials are reacted. Examples describe (12) the recovery of diphenylphosphinic acid and of 1-(7,7-diphenylheptenyl-6)-diphenyl-phosphine oxide from the product of reacting hexamethylene-1,6-bis-diphenylphosphine oxide with benzophenone, and (13) the recovery of diphenyl phosphinic acid and 1-(5,5-diphenylpentenyl-4)-diphenyl phosphine oxide from the product of reacting tetramethylene-1,4-bis-diphenylphosphine oxide with benzophenone.