January 2001
21
C18H26O4: 306.1830).
subjected to silica gel chromatography (hexane : AcOEtϭ4 : 1) to yield
KBr
1
311.2 mg (91.1%) of 20 as a colorless oil. IR n cmϪ1: 3362, 2230. H-
Hepthyltriphenylphosphonium Iodide (16) PPh3 (1.73 g) was added to
a solution of 1-iodoheptane (995 mg) in acetonitrile (30 ml), and the whole
was stirred at 90 °C for 24 h under nitrogen. The mixture was allowed to
stand at room temperature for 18 h with stirring. After filtration, the solid
obtained was washed with THF to yield 1.92 g (97.1%) of 16 as a colorless
solid. This compound was employed for next reaction without purification.
1H-NMR (CDCl3) d: 0.82 (3H, t, Jϭ5.6 Hz), 1.10—1.80 (10H, m), 3.45—
3.85 (2H, m), 7.66—7.96 (15H, m).
Ethyl 2-Methoxy-6-[8(Z)-pentadecenyl]benzoate (17) BuLi (1.58 M,
159 ml) was successively added to a stirred solution of 16 (115 mg) in THF
(2 ml) at room temperature under a nitrogen. After 1 h, a solution of 15
(14.4 mg) in THF was added to the reaction mixture and the whole was
stirred at 0 °C for 30 min under a nitrogen. And then the reaction mixture
was quenched with saturated NH4Cl, extracted with AcOEt. The organic
layer was washed with saturated NaCl solution, dried (MgSO4) and concen-
trated. The residue was subjected to silica gel chromatography (hexane :
max
NMR (CDCl3) d: 0.97 (3H, t, Jϭ7.3 Hz), 1.45—1.59 (2H, m), 1.87 (1H, br s),
2.15 (2H, dd, Jϭ7.0, 2.4 Hz), 2.44 (2H, dd, Jϭ6.3, 2.4 Hz), 3.68 (2H, br s).
3(Z)-Heptenol (21) A mixture of Lindlar’s catalyst (Pd CaCO3, 40 mg),
quinoline (10 ml) and 20 (193.5 mg) in hexane (4.0 ml) was stirred at room
temperature for 16 h under H2. After the mixture was filtered, 10% HCl was
added to the filter liquid and extracted with ether. The organic layer was
washed with saturated NaCl solution, dried and concentrated. The residue
was subjected to silica gel chromatography (hexane : AcOEtϭ2 : 1) to yield
KBr
1
128.3 mg (65.1%) of 21 as a colorless oil. IR n cmϪ1: 3350, 1660. H-
max
NMR (CDCl3) d: 0.90 (3H, t, Jϭ7.1 Hz), 1.19—1.52 (2H, m), 1.56 (1H,
br s), 2.05 (2H, q, Jϭ6.5 Hz), 2.33 (2H, q, Jϭ6.5 Hz), 3.64 (2H, t,
Jϭ7.2 Hz), 5.34—5.64 (2H, m).
1-Iodo-3(Z)-heptene (22) A solution of PPh3 (378 mg) and imidazole
(98 mg) in mixture of diethyl ether and acetonitrile (3 : 1, 35 ml) was stirred
at 0 °C for 10 min and then iodine (366 mg) was added to this solution. The
whole was stirred at 0 °C for 15 min. A solution of 21 (54.4 mg) in mixture
of diethyl ether and acetonitrile (3 : 1, 1 ml) was added to this solution with
stirring at 0 °C. The mixture was then allowed to stand at room temperature
for 1 h. The reaction mixture was treated with saturated NaHCO3 solution
and extracted with ether. The organic layer was washed with saturated NaCl
solution, dried and concentrated. The residue was subjected to silica gel
AcOEtϭ9 : 1) to yield 13.9 mg (76.4%) of 17 as a colorless oil. IR
KBr
max
n
cmϪ1: 1730, 1590. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jϭ6.7 Hz), 1.20—
1.40 (18H, m), 1.37 (3H, t, Jϭ7.2 Hz), 1.99 (4H, t, Jϭ6.0 Hz), 2.55 (2H, t,
Jϭ7.9 Hz), 3.81 (3H, s), 4.39(2H, q, Jϭ7.2 Hz), 5.35 (2H,t, Jϭ5.5 Hz), 6.75
(1H, d, Jϭ7.8 Hz), 6.81 (1H, t, Jϭ7.8 Hz), 7.25 (1H, t, Jϭ7.8 Hz). High-MS
m/z: 388.1865 (Calcd for C25H40O3: 388.1830).
Ethyl 6-[8(Z)-Pentadecenyl]salycylate (18) A solution of 17 (13.2 mg)
in absolute CH2Cl2 was added to a solution of BBr3 (6.4 ml) in anhydrous
CH2Cl2 at 0 °C under a nitrogen, and the whole was stirred at room tempera-
ture for 15 min under a nitrogen. And then the reaction mixture was
quenched with cold water and extracted with CH2Cl2. The organic layer was
washed with saturated NaCl solution, dried (MgSO4) and concentrated. The
chromatography (hexane : AcOEtϭ9 : 1) to yield 70.4 mg (65.5%) of 22 as a
KBr
colorless oil. IR n cmϪ1: 1660. 1H-NMR (CDCl3) d: 0.90 (3H, t,
max
Jϭ7.1 Hz), 1.20—1.53 (2H, m), 2.01 (2H, q, Jϭ6.7 Hz), 2.63 (2H, q,
Jϭ6.7 Hz), 3.13 (2H, t, Jϭ7.2 Hz), 5.29 (1H, m), 5.38 (1H, m).
3(Z)-Heptenyltriphenylphosphonyl Iodide (23) PPh3 (123.5 mg) was
added to a solution of 22 (70.4 mg) in acetonitrile (5 ml) and the whole was
stirred at 90 °C for 24 h. After the mixture was then allowed to stand at room
temperature for 24 h, the reaction mixture was concentrated under vacuum.
The residue was washed with diethyl ether. A colorless solid was obtained
almost quantitatively, and this compound was employed in the next reaction
residue was subjected to silica gel chromatography (hexane : AcOEtϭ9 : 1)
KBr
to yield 8.5 mg (66.9%) of 18 as a colorless oil. IR n cmϪ1: 3100, 1660,
max
1
1608. H-NMR (CDCl3) d: 0.87 (3H, t, Jϭ5.7 Hz), 1.25—1.60 (21H, m),
1.98 (4H, m), 2.91 (2H, t, Jϭ7.4 Hz), 4.43 (2H, q, Jϭ7.1 Hz), 5.34 (2H, m),
6.71 (1H, dd, Jϭ8.3, 1.3 Hz), 6.81 (1H, dd, Jϭ7.4, 1.3 Hz), 7.28 (1H, dd,
Jϭ8.3, 7.4 Hz), 11.20 (1H, s). Low MS m/z: 374 (Mϩ), High MS m/z Calcd
for C24H38O3 (Mϩ): 374.2821. Found: 374.2827.
1
without purification. H-NMR (CDCl3) d: 0.82 (3H, m), 1.15—1.40 (2H,
m), 1.50—1.90 (2H, m), 2.30—2.60 (2H, m), 3.52—3.83 (2H, m), 5.46 (1H,
m), 5.54 (1H, m), 7.75—7.97 (15H, m).
6-(8-Pentadecenyl)salicylic Acid (2) A solution of 18 (10.2 mg) in
EtOH and 10% NaOH (1 ml) were refluxd for 2 h. A solution of the reaction
mixture was acidified with 10% HCl and then extracted with hexane. The or-
ganic layer was washed with saturated NaCl solution., dried and concen-
trated. The residue was subjected to silica gel chromatography
(hexane : AcOEtϭ1 : 2). The eluate fraction was recrystalized from hexane
6-Hepten-3-ynol (24) A solution of 19 (490.6 mg) in THF (3 ml) was
successively added dropwise to a solution of EtMgBr in THF (0.9 M,
23.3 ml) with stirring, and the mixture was stirred at 40 °C for 1 h under a
nitrogen atmosphere. After a solution of allyl iodide (3.5 g) in THF (5 ml)
was added to this solution, the whole was stirred for 20 min. And then CuCl
(21 mg) was added to the reaction mixture, the whole was refluxed for 1 h.
The reaction mixture was quenched with cold water and upper solution was
removed by decantation. The precipitate was dissolved in THF, dried and
concentrated. The residue was subjected to silica gel chromatography
(hexane : AcOEtϭ4 : 1) to yield 695.7 mg (90.4%) of 24 as a colorless oil. IR
to yield 9.2 mg (92.9%) of 2 as colorless crystals, mp 45—48 °C. IR
KBr
max
n
cmϪ1: 2930, 2850, 1650, 1600. 1H-NMR (CDCl3) d: 0.88 (3H, t,
Jϭ5.7 Hz), 1.25—1.60 (18H, m), 1.97 (4H, m), 2.93 (2H, t, Jϭ7.4 Hz), 5.35
(2H, m), 6.71 (1H, dd, Jϭ8.3, 1.3 Hz), 6.81 (1H, dd, Jϭ7.4, 1.3 Hz), 7.28
(1H, dd, Jϭ8.3, 7.4 Hz). Low MS m/z: 346 (Mϩ). Anal. Calcd for C22H34O3:
C, 76.25; H, 9.90. Found: C, 76.08; H, 10.06.
KBr
max
1
n
cmϪ1: 3352, 1650. H-NMR (CDCl3) d: 1.83 (1H, br s), 2.48 (2H, m),
2.97 (2H, m), 3.71 (2H, q, Jϭ5.4 Hz), 5.11 (1H, dt, Jϭ10.0, 1.7 Hz), 5.31
(1H, dt, Jϭ16.9, 1.7 Hz), 5.84 (1H, m).
3-Heptynol (20) Dihydropyrane (DHP) (4.88 ml) and p-toluenesulfonic
acid (TsOH) (120 mg) were added to a solution of 19 (3.6 g) in CH2Cl2 and
the mixture was stirred at room temperature for 3 h. The reaction mixture
was quenched with cold water and saturated NaHCO3 solution, and ex-
tructed with CH2Cl2. The organic layer was washed with saturated NaCl so-
lution, dried and concentrated. The residue was subjected to silica gel chro-
matography (hexane : AcOEtϭ4 : 1) to yield 9.63 g (95.2%) of 1-[2-(tetrahy-
3(Z),6-Heptadienol (25) A mixture of Lindlar’s catalyst (Pd CaCO3,
100 mg), quinoline (50 ml) and 24 (550 mg) in hexane (20 ml) was stirred at
room temperature for 16 h under H2. After the mixture was filtered, 10%
HCl was added to the filter liquid and extracted with diethyl ether. The or-
ganic layer was washed with saturated NaCl solution, dried and concen-
trated. The residue was subjected to silica gel chromatography
(hexane : AcOEtϭ2 : 1) to yield 421.6 mg (75.3%) of 25 as a colorless oil. IR
KBr
1
dropyranyl)oxy]-3-butyne as a colorless oil. [IR n cmϪ1: 3270. H-NMR
max
KBr
max
1
n
cmϪ1: 3350, 1640. H-NMR (CDCl3) d: 2.34 (2H, q, Jϭ6.3 Hz), 2.84
(CDCl3) d: 1.40—1.81 (6H, m), 1.97 (1H, t, Jϭ2.6 Hz), 2.49 (2H, dd,
Jϭ7.0, 2.6 Hz), 3.44—4.00 (4H, m), 4.64 (1H, br s). CI-MS m/z: 155
(Mϩϩ1).] BuLi (1.58 M, 9.45 ml) and HMPA (2.7 ml) were successively
added to a solution of 1-[2-(tetrahydropyranyl)oxy]-3-butyne (2.0 g) in THF
(10 ml) at 0 °C with stirring. After a solution of propyl iodide (3.79 g) in
THF was added to this solution, the whole was stirred at 0 °C for 1 h. The
mixture was then allowed to stand at room temperature for 1 h. The reaction
mixture was treated with saturated NH4Cl solution and extracted with
AcOEt. The organic layer was washed with saturated NaCl solution, dried
and concentrated. The residue was subjected to silica gel chromatography
(2H, q, Jϭ6.4 Hz), 3.66 (2H, q, Jϭ6.0 Hz), 4.95 (1H, m), 5.15 (1H, m), 5.41
(1H, m), 5.53 (1H, m), 5.68 (1H, m).
1-Iodo-3(Z),6-heptadiene (26) A solution of PPh3 (952 mg) and imida-
zole (247 mg) in a mixture of diethyl ether and acetonitrile (3 : 1, 60 ml) was
stirred at 0 °C for 10 min and then iodine (922 mg) was added to this solu-
tion, the whole was stirred at 0 °C for 15 min. A solution of 25 (135.3 mg) in
mixture of diethyl ether and acetonitrile (3 : 1, 1 ml) was added to this solu-
tion with stirring at 0 °C. The mixture was then allowed to stand at room
temperature for 1 h. The reaction mixture was treated with saturated
NaHCO3 solution and extracted with diethyl ether. The organic layer was
washed with saturated NaCl solution, dried and concentrated. The residue
(hexane : AcOEtϭ9 : 1) to yield 2.07 g (81.4%) of 1-[2-(tetrahydropyranyl)-
KBr
oxy]-3-heptyne as a colorless oil. [IR n cmϪ1: 2250. 1H-NMR (CDCl3) d:
max
0.97 (3H, t, Jϭ7.5 Hz), 1.43—1.86 (6H, m), 2.12 (2H, dd, Jϭ7.0, 2.4 Hz),
2.46 (2H, dd, Jϭ7.0, 2.4 Hz), 3.47—3.57 (2H, m), 3.75—3.93 (2H, m), 4.65
(1H, t, Jϭ3.6 Hz). CI-MS m/z: 197 (Mϩϩ1). A solution of 1-[2-(tetrahy-
dropyranyl)oxy]-3-heptyne (597 mg) in anhydrous EeOH (20 ml) and pyri-
dinium paratoluenesulfonic acid (PPTS) (153.3 mg) was stirred at 55 °C for
3 h. The reaction mixture was concentrated under vacuum. The residue was
was subjected to silica gel chromatography (hexane : AcOEtϭ9 : 1) to yield
KBr
70.4 mg (65.5%) of 26 as a colorless oil. IR n cmϪ1: 1640. 1H-NMR
max
(CDCl3) d: 2.55—2.95 (4H, m), 3.15 (2H, t, Jϭ7.3 Hz), 4.95—5.30 (2H,
m), 5.35—6.05 (3H, m).
3(Z),6-Heptadienyltriphenylphosphonium Iodide (27) PPh3 (105.0 mg)
was added to a solution of 26 (68.3 mg) in acetonitrile (5 ml), the whole was