Patent GB-1101864-A (GB)
Title: Manufacture of quaternary phosphonium salts and derivatives thereof
IPC: C07F9/54
Filed: 1965-02-11
Abstract: Carotenoids are obtained by reacting retinal with a compound of the formula <FORM:1101864/C4-C5/1> wherein R is hydrogen or methyl, P1 is selected from (1) unsaturated aliphatic radicals containing at least one olefinic bond which may be substituted by a carbocyclic substituent and carbocyclic radicals containing a double or benzenoid bond, said olefinic or benzenoid bonds being at the a -position in the radicals and (2) carbalkoxy radicals wherein the alkoxy moieties have 1-8 carbons, each P11 is a substituted or unsubstituted, saturated or unsaturated aliphatic, carbocyclic or carbocyclic-aliphatic radical and X is an anion of a strong acid. In examples, by reacting the b -ionylidene-ethyl, b -ionyl and cinnamyl triphenyl phosphonium salts with a base, e.g. KoH, and retinal in a liquid solvent, e.g. MeoH, the carotenoids 1,14-bis(2,6,6-trimethylcyclohex-1-enyl) - 3,7,12 - trimethyltertradec - 1,3,5,7,9,11, 13 - heptaene, 1,12 - bis(2,6,6-trimethyl-cyclohex - 1 - enyl) - 3,7,10 - trimethyldodec - 1,3,5,7,9,11 - hexaene and 1 - (2,6,6-trimethyl-cyclohex - 1 - enyl) - 12 - phenyl -3,7 - dimethyldodec - 1,3,5,7,9,11 - hexaene respectively are obtained.ALSO:Quaternary phosphonium salts of the formula <FORM:1101864/C2/1> wherein R is hydrogen or methyl, R1 is selected from (1) unsaturated aliphatic radicals containing at least one olefinic bond which may be substituted by a carbocyclic substituent and carbocyclic radicals containing a double or benzenoid bond said olefinic or benzenoid bonds being at the a -position in the radicals and (ii) carbalkoxy radicals wherein the alkoxy moieties have 1-8 carbons, each R11 is a substituted or unsubstituted, saturated or unsaturated aliphatic, carbocyclic or carbocylic-aliphatic radical and X is an anion of a strong acid, are made by reacting an ether of the formula <FORM:1101864/C2/2> where R111 is an aliphatic hydrocarbon or the tetrahydropyranyl radical, with a tertiary phosphine salt of the formula <FORM:1101864/C2/3> The reaction may be effected by adding the tertiary phosphine salt to the ether but is preferably effected by dissolving the ether and a tertiary phosphine in an inert monohydric C1- 8 alcohol, dissolving a strong acid, e.g. HCl, H2SO4, H3PO4, HBr or p-toluene sulphonic acid, in a second portion of the alcohol and adding the second mixture to the first to form the above tertiary phosphine salt in situ.  The reactants are preferably used in chemically equivalent amounts and suitable reaction temperatures are generally from 20 DEG  to 150 DEG C.  The reaction is suitably effected under an inert gas such as nitrogen. Specified products of the process are the retinyl, b -ionylideneethyl, b -ionyl, cinnammyl, allyl, benzyl and ethyl propionyl, triphenyl phosphonium salts.  By reacting the retinyl, b -ionylideneethyl, b -ionyl and cinnammyl triphenylphosphonium salts with a base, e.g. KOH and retinal in a suitable liquid solvent, e.g. MeOH, the carotenoids b -carotene, 1,14-bis-(2,6,6-trimethylcyclohex - 1 - enyl) - 3,7,12 - trimethyltetradec-1,3,5,7,9,11,13 - heptaene, 1,12-bis - (2,6,6 - trimethylcyclohex - 1 - enyl) - 3,7,10 - trimethyl dodec - 1,3,5,7,9,11 - hexaene and 1 - (2,6,6-trimethylcyclohex - 1 - enyl) - 12 - phenyl - 3,7-dimethyldodec - 1,3,5,7,9,11 - hexaene respectively are obtained.