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G. Hornyanszky, J. Rohaly, and L. Novak
1538
dropwise. The reaction mixture was stirred at 260 8C for 1 h and then at rt
overnight. The solvent was evaporated in vacuo, the residue was trituated
with ether (150 mL each) three times and filtered, and the solvent was evap-
orated in vacuo. The residue was purified by column chromatography
(hexane–EtOAc 9:1) to afford pheromone component 1a (2.8 g, 54%) as a
colorless oil. Isomeric purity was more than 96%. GC: Rt ¼ 7.65 min
[(E,E)-diastereomer Rt ¼ 7.97 min] (150–180 8C, 2 8C/min, 10 psi). 1H
NMR (CDCl3): 1.30 (10H, m, 5CH2), 1.62 (2H, t, J ¼ 7.0 Hz, CH2), 1.66
(3H, d, J ¼ 5.0 Hz, CH3), 2.02 (2H, m, CH2), 2.05 (3H, s, CH3), 2.72 (2H,
m, CH2), 4.06 (2H, t, J ¼ 6.7 Hz, OCH2), 5.39 (4H, m, 4CH55). 13C NMR
(CDCl3): 17.84 (CH3), 20.95 (CH3), 25.84 (CH2), 27.00 (CH2), 28.53
(CH2), 29.11 (CH2), 29.14 (CH2), 29.30 (CH2), 29.53 (CH2), 30.35 (CH2),
64.46 (OCH2), 124.73 (CH55), 127.33 (CH55), 129.25 (CH55), 129.99
(CH55), 170.73 (CO).
Method B
n-BuLi (2.5 M in hexane, 14.6 mL, 36.5 mmol) was added dropwise to a
stirred suspension of phosphonium salt 5 (15 g, 36.5 mmol) in dry THF
(150 mL) at 270 8C. After stirring at 270 8C for 0.5 h, a solution of
aldehyde 8 (8.2 g, 36.5 mmol) in dry THF (50 mL) was added dropwise,
and the mixture was stirred at 270 8C for 1 h and then at rt for overnight.
The reaction mixture was diluted with ether and filtered, and the solvent
was evaporated in vacuo. The residue was purified by column chromatography
(hexane–EtOAc 20:1 as eluent) to give sex pheromone component 1a (5.6 g,
61%) consisting of 85% (Z,E)- and 15% (E,E)-stereoisomers.
(Z,E)-Tetraeca-9,12-dien-1-ol (1b)
Aq NaOH (2N, 30 mL), was added to a stirred solution of compound 1a (3.5 g,
13.8 mmol) in methanol (30 mL) and the resulting mixture was stirred at rt for
3 h. The methanol was evaporated in vacuo, the residue was extracted three
times with ether (50 mL each), and the combined ethereal solutions were
dried over MgSO4. The solvent was evaporated, and the residue was
purified by column chromatography (hexane–EtOAc 7:3) to afford
pheromone component 1b (2.5 g, 87%) as a colorless oil. The isomeric
purity was more than 96%. GC: Rt ¼ 9.48 min [(E,E)-diastereomer
1
Rt ¼ 9.85 min] (150–180 8C, 2 8C/min, 10 psi). H NMR (CDCl3): 1.30
(10H, m, 5CH2), 1.49 (1H, b, OH), 1.55 (2H, t, J ¼ 6.5 Hz, CH2), 1.65 (3H,
d, J ¼ 5.0 Hz, CH3), 2.02 (2H, q, J ¼ 7.0 Hz, CH2), 2.71 (2H, m, CH2),
3.63 (2H, t, J ¼ 6.6 Hz, OCH2), 5.39 (4H, m, 4CH55). 13C NMR (CDCl3):
18.27 (CH3), 26.09 (CH2), 27.44 (CH2), 29.55 (CH2), 29.74 (CH2), 29.82
(CH2), 29.98 (CH2), 30.78 (CH2), 33.14 (CH2), 63.32 (OCH2), 125.15
(CH55), 127.73 (CH55), 129.68 (CH55), 130.45 (CH55).