Patent GB-1233222-A (GB)
IPC: A23L27/20
Filed: 1968-05-23
Abstract: 1,233,222. Polyunsaturated compounds. R. FIRMENICH, G. FIRMENICH, R. E. FIRMENICH, and F. H. FIRMENICH, [trading as FIRMENICH & CIE]. 23 May, 1968 [10 May, 1968], No. 54546/70. Divided out of 1,233,221. Heading C2C. Compounds of formula where X is OH or H; R 1 , R 2 , R 3  and R 4  are H or C 1-6  alkyl and each of the symbols R 5 , R 6 , R; and R 8  represents hydrogen, or (a) a linear or branched alkyl radical containing from 1 to 8 carbon atoms; or (b) a linear or branched olefinically unsaturated hydrocarbon radical containing at most two double bonds and from 1 to 8 carbon atoms; or wherein (c) R 5 , R 6  and R 7  or R 8  have the meaning defined sub (a) and (b) whereas either R 7  or R 8  represents a substituted ethyl radical carrying on the terminal carbon atom as a substituent an unsubstituted or mono- or di-methyl-substituted five- or six-membered olefinically unsaturated cycloaliphatic group containing at most two double bonds one of which is in the α-position with respect to the said terminal carbon atom, or a substituted ethyl radical carrying on the terminal carbon atom as a substituent an unsubstituted or mono- or dimethyl - substituted olefinically unsaturated bridged cycloaliphatic group containing a double bond in the α-position with respect to the said terminal carbon atom, or a substituted ethyl radical carrying on the terminal carbon atom as a substituent a 2- or 3-furyl, or 2- or 3- thienyl group; or wherein (d) two of the radicals represented by the symbols R 5 , R 6 , R 7  and R 8  can be linked to each other, except R 5  to R 6 , to form a five- or sixmembered olefinically unsaturated cycloaliphatic ring which contains at most two double bonds and which can carry as substituents alkyl or alkenyl groups containing from 1 to 3 carbon atoms, or a six-membered olefinically unsaturated bridged cycloaliphatic ring which contains one double bond and which can carry one or two methyl groups, or a furan or thiophene ring which can carry a methyl group, are prepared by condensing by heating in the presence of a condensing agent, either (i) a butadienyl ether of formula wherein Y represents a linear or branched alkyl radical containing from 1 to 4 carbon atoms, or a benzyl, p-nitrobenzyl or furfuryl radical; or (ii) a substance capable of generating a butadienyl ether of Formula I under the condensation conditions, with (iii) an allyl alcohol of formula and reducing the aldehyde thereby produced. Reduction to the alcohol may be effected with LiAlH 4  and to the compounds in which X is H by means of a hydrazine and strong alkali or by reducing the tosylate of the alcohols (X = OH) with LiAlH4. The compounds 2,7,11-trimethyl- 2,6,10-dodecatrienol; 2-methyl-2,6-octadienol; 2,6,10 - trimethyl - 2,6,10 - dodecatrienol; 2- methyl - 5 - (2 - furyl) - 2 - pentenol; 2 - methyl- 5 - (3 - furyl) - 2 - pentenol and 2 - methyl - 5- (2 - furyl) - 2 - pentene are claimed per se while examples also prepare 2,6-dimethyl-2,6- octadienol; 9-(3-furyl) -2,6-dimethyl-2,6-nonadienol (neotorreyol); # - (4,8 - dimethyl - 3,7- nonadienyl) - furan (dendrolasin) and 2- methyl - 4 - (8 - α - pineynl) - 2 - butenol.