caa a22 4500 465766021 CHVBK 20180323111914.0 cr unu---uuuuu 170327e19900301xx s 000 0 eng 10.1007/BF02544326 doi (NATIONALLICENCE)springer-10.1007/BF02544326 Rakoff Henry Northern Regional Research Center, Agricultural Research Service, U.S. Department of Agriculture, 1815 North University Street, 61604, Peoria, IL aut Preparation of deuterated methyl 6,9,12-octadecatrienoates and methyl 6,9,12,15-octadecatetraenoates [Elektronische Daten] [Henry Rakoff] Methyl 6,9,12-octadecatrienoate-15,15,16,16-d 4 was obtained by Wittig coupling between 6,6,7,7-tetradeutero-3-nonenyltriphenylphosphonium iodide, 8, and the aldehyde ester, methyl 9-oxo-6-nonenoate. Methyl 6-oxohexanoate, obtained by ozonolysis of cyclohexene, was coupled in a Wittig reaction with [2-(1,3-dioxan-2-yl)ethyl]triphenylphosphonium bromide to give methyl 8-dioxanyl-6-octenoate. This compound was transacetalized to methyl 9,9-dimethoxy-6-nonenoate, which was then hydrolyzed to the aldehyde ester. For the preparation of compound 8, the tetrahydropyranyl ether of 2-pentynol was deuterated with deuterium gas and tris-(triphenylphosphine)chlororhodium. The tetradeuterated tetrahydropyranyl ether was converted to the bromide with triphenylphosphine dibromide, and the bromide was coupled with 3-butynol by means of lithium amide in liquid ammonia to give 3-nonynol-6,6,7,7-d 4. Hydrogenation over Lindlar's catalyst converted the deuterated alkynol to 3-nonenol-6,6,7,7-d 4. This deuterated alkenol was converted to the bromide with triphenylphosphine dibromide, then to the iodide with sodium iodide in acetone, and finally to 8 with triphenylphosphine in acetonitrile. Methyl 6,9,12,15-octadecatetraenoate-12,13,15,16-d 4 was obtained by Wittig coupling between methyl 9-oxo-6-nonenoate and 3,4,6,7-tetradeutero-3,6-nonadienyltriphenylphosphonium iodide, 15. For the preparation of compound 15, the bromide obtained from the reaction of 2-pentynol with triphenylphosphine dibromide was coupled with 3-butynol with lithium amide in liquid ammonia. The resulting 3,6-nonadiynol was deuterated with deuterium gas in the presence of P-2 nickel, and the resultant deuterated nonadienol was converted to 15 through the bromide and iodide. The final products were separated from isomers formed during the synthetic sequences by silver resin chromatography. American Oil Chemists' Society (AOCS), 1985 Lipids Springer-Verlag 25/3(1990-03-01), 130-134 0024-4201 25:3<130 1990 25 11745 https://doi.org/10.1007/BF02544326 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02544326 text/html Onlinezugriff via DOI NATIONALLICENCE 100 1- Rakoff Henry Northern Regional Research Center, Agricultural Research Service, U.S. Department of Agriculture, 1815 North University Street, 61604, Peoria, IL aut NATIONALLICENCE 773 0- Lipids Springer-Verlag 25/3(1990-03-01), 130-134 0024-4201 25:3<130 1990 25 11745 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer