Reaction Steps
To a solution of (Z,Z,Z)-3,6,9-nonadecatrien-11-yne (516 mg, 2 mmol) in 10 ml of dry pentane (0° C.) was added 4.2 ml of 0.5 M dicyclohexylborane in pentane. After 2 h at 0° C., the reaction mixture was diluted with 15 ml of THF and treated with 0.6 ml of glacial acetic acid for 3 h at 50° C. The mixture was then made basic with 4 ml of 5.0 N aqueous sodium hydroxide and treated with 0.86 ml of 30% hydrogen peroxide for 0.5 h. The hexane extract (3×30 ml) was washed with water (3×30 ml), dried over MgSO4 and evaporated to leave an oily residue. Elution of the residue through silica gel (hexane) gave 292 mg (56.2%) of the desired (Z,Z,Z,Z)3,6,9,11-19:H (89% isomeric purity). This material contained (Z,Z,Z,E)3,6,9,11-19:H (1.1%) and 3 major unknown impurities (8.3%). Purification by HPLC on the silver ion-loaded Partisil M9™ 10/50 SCX column (eluted with 0.1% dimethoxyethane in hexane) yielded material which was greater than 99.0% pure; PMR (360 MHz, C6D6) δ ##STR2## 0.88 (3H, t, J=7.0 Hz, CH3CH2CH2 --). IR 3020 cm-1 (m, C--H stretch of alkenes), 2980 cm-hu -1, 2950 cm-1, 2880 cm-1 (s, C--H stretch of alkanes). CMR (90 MHz, CDCl3) δ132.8, 132.1, 129.4, 128.8, 127.7, 127.1, 123.9, 123.3, 31.8, 29.65, 29.26, 29.17, 27.6, 25.90, 25.60, 22.6, 20.6, 14.21, 14.03. EIMS (% relative abundance) 260 (0.3), 231 (0.2), 217 (0.2), 206 (0.2), 191 (0.1), 180 (1.5), 178 (0.8), 161 (1.2), 147 (1.1), 133 (1.8), 119 (5.0), 108 (67.5), 93 (26.3), 91 (24.1), 79 (100), 67 (25.6), 55 (18.2). Analysis: Calc. for C 19 H32 : 260.46. C, 87.62; H, 12.38. Found: C, 87.66, H, 12.32.
