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CHEMISTRY & BIODIVERSITY – Vol. 6 (2009)
HꢁC(5), HꢁC(8), HꢁC(9)); 3.65 (t, J¼6.5, 2 HꢁC(1)); 2.06–2.16 (m, 2 HꢁC(3), 2 HꢁC(6),
2 HꢁC(7)); 1.99–2.05 (m, 2 HꢁC(10)); 1.63 (dt, J¼13.9, 6.5, 2 HꢁC(2)); 1.44 (br. s, OH); 1.23–1.37 (m,
2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3):
.
130.5; 130.1; 129.3; 128.9; 62.6; 32.6; 31.5; 29.4; 27.4; 27.3; 27.2; 23.6; 22.6; 14.1. MS (70 eV): 210 (2, Mþ ),
192 (0.4), 167 (1), 151 (2), 149 (1), 138 (6), 135 (4), 121 (10), 110 (9), 107 (5), 99 (7), 96 (8), 95 (12), 93
(7), 91 (2), 82 (20), 81 (100), 79 (22), 77 (3), 69 (48), 67 (21), 61 (0), 57 (10), 55 (50), 53 (10), 43 (19), 41
(51), 39 (11), 31 (7).
(4Z,8Z)-Tetradeca-4,8-dien-1-yl Acetate (1). Compound 7 (4.4 g, 21 mmol) was acetylated with Ac2O
(4.59 g, 45 mmol) in dry pyridine (25 ml) by keeping the reaction mixture in refrigerator (2–48)
overnight. Usual workup gave 1 (4.80g, 91%). 1H-NMR (500 Mz, CDCl3): 5.32–5.45 (m, HꢁC(4),
HꢁC(5), HꢁC(8), HꢁC(9)); 4.05 (t, J¼6.6, 2 HꢁC(1)); 2.10–2.13 (m, 2 HꢁC(3)); 2.05–2.08 (m,
2 HꢁC(6), 2 HꢁC(7)); 2.04 (s, MeCO); 1.97–2.02 (m, 2 HꢁC(10)); 1.68 (dt, J¼14.6, 7.6, 2 HꢁC(2));
1.22–1.37 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz,
CDCl3): 171.1; 130.5; 130.4; 128.9; 128.5; 64.0; 31.5; 29.4; 28.5; 27.3; 27.23; 27.20; 23.6; 22.5; 21.0; 14.0. MS
.
(70 eV): 252 (0.5, Mþ ), 192 (10), 167 (0), 151 (2), 149 (4), 138 (3), 135 (14), 121 (20), 110 (10), 107 (7),
99 (1), 96 (5), 95 (9), 93 (9), 91 (2), 82 (23), 81 (100), 79 (22), 77 (2), 69 (32), 67 (22), 61 (1), 57 (4), 55
(30), 53 (6), 43 (51), 41 (33), 39 (8), 31 (0).
(4Z,8E)-1-[(Tetrahydropyran-2-yl)oxy]tetradeca-4,8-diene (8). Compound 8 was prepared analo-
gously to 6. A soln. of 5 (19.6 g, 36 mmol) in dry THF (200 ml) was treated with NaHMDS (2m soln. in
THF, 20 ml, 40 mmol) at 08. The mixture was stirred for 1.5 h at r.t. before it was cooled to ꢁ788, and
treated with (E)-dec-4-enal (4.86 g, 31.6 mmol) in THF (5 ml). The mixture was allowed slowly to warm
to r.t. and stirred overnight before pouring into sat. aq. NH4Cl soln. After workup similar to that for 6, the
crude product was chromatographed on SiO2 to give 8 (7.48 g, 80.6%). 13C-NMR (125.8 MHz, CDCl3):
130.8; 129.8; 129.6; 129.3; 98.8; 67.0; 62.3; 32.7; 32.5; 31.4; 30.8; 29.7; 29.3; 27.3; 25.5; 23.9; 22.5; 19.6; 14.1.
(4Z,8E)-Tetradeca-4,8-dien-1-ol (9). Compound 8 (7.25 g, 24.6 mmol) was stirred in MeOH (30 ml)
at 508 in the presence of Amberlyst-15 for 5 h. The catalyst was filtered off, and the residue yielded 9
1
(4.92 g, 95.2%) after MPLC. H-NMR (500 Mz, CDCl3): 5.35–5.45 (m, HꢁC(4), HꢁC(5), HꢁC(8),
HꢁC(9)); 3.65 (t, J¼6.5, 2 HꢁC(1)); 2.08–2.15 (m, 2 HꢁC(6), 2 HꢁC(7)); 2.01–2.06 (m, 2 HꢁC(3));
1.94–1.99 (m, 2 HꢁC(10)); 1.63 (dt, J¼14.0, 6.6, 2 HꢁC(2)); 1.45 (br. s, OH); 1.22–1.37 (m, 2 HꢁC(11),
2 HꢁC(12), 2 HꢁC(13)); 0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 131.0; 130.1;
.
129.5; 129.1; 62.6; 32.62; 32.56; 32.54; 31.4; 29.3; 27.4; 23.6; 22.5; 14.1. MS (70 eV): 210 (1, Mþ ), 192
(0.5), 167 (1), 151 (2), 149 (1), 138 (8), 135 (7), 121 (10), 110 (12), 107 (4), 99 (9), 96 (8), 95 (12), 93 (6),
91 (2), 82 (20), 81 (100), 79 (22), 77 (3), 69 (80), 67 (20), 61 (0), 57 (11), 55 (64), 53 (10), 43 (20), 41 (55),
39 (12), 31 (7).
(4Z,8E)-Tetradeca-4,8-dien-1-yl Acetate (2). Alcohol 9 (4.86 g, 23 mmol) in pyridine (30 ml) was
mixed with Ac2O (5.1 g, 50 mmol) at 08 and kept in refrigerator overnight. Usual workup and MPLC
yielded 2 (4.88 g, 83.7%). 1H-NMR (500 Mz, CDCl3): 5.31–5.45 (m, HꢁC(4), HꢁC(5), HꢁC(8),
HꢁC(9)); 4.05 (t, J¼6.7, 2 HꢁC(1)); 1.94–2.12 (m, 2 HꢁC(3), 2 HꢁC(6), 2 HꢁC(7), 2 HꢁC(10));
2.04 (s, MeCO); 1.67 (dt, J¼11.6, 6.5, 2 HꢁC(2)); 1.22–1.36 (m, 2 HꢁC(11), 2 HꢁC(12), 2 HꢁC(13));
0.88 (t, J¼7.0, 3 HꢁC(14)). 13C-NMR (125.8 MHz, CDCl3): 171.1; 131.0; 130.4; 129.4; 128.3; 64.0; 32.6;
.
32.5; 31.4; 29.2; 28.5; 27.3; 23.6; 22.5; 21.0; 14.0. MS (70 eV): 252 (0.7, Mþ ), 192 (11), 167 (0), 151 (2),
149 (4), 138 (3), 135 (12), 121 (20), 110 (13), 107 (6), 99 (1), 96 (5), 95 (9), 93 (9), 91 (2), 82 (32), 81
(100), 79 (20), 77 (2), 69 (51), 67 (24), 61 (1), 57 (5), 55 (37), 53 (5), 43 (52), 41 (35), 39 (8), 31 (0).
1-[(Tetrahydropyran-2-yl)oxy]but-3-yne (12) [58]. Compound 12 was prepared from but-3-yn-1-ol in
93% yield similarly to procedure described for 3.
1-[(Tetrahydropyran-2-yl)oxy]non-3-yne (14) [50]. Method 1. Compound 12 (7.70 g, 50 mmol) in
THF (80 ml) was lithiated with BuLi at ꢁ308. The bath temp. was allowed to rise to r.t., and the mixture
was stirred for 30 min before returning to ꢁ308. Pentyl bromide (9.06 g, 60 mmol) in THF (40 ml) along
with NaI (0.9 g, 6 mmol) was added. The mixture was gently refluxed and stirred for 16 h before it was
cooled and poured into ice-water. Usual workup and MPLC yielded 14 (8.90 g, 79%).
Method 2. Hept-1-yne (6.72 g, 70 mmol) in THF (180 ml) was lithiated by BuLi (28 ml of 2.5m soln.
in hexanes, 70 mmol) at ꢁ408. After stirring for 30 min at r.t., the mixture was cooled to ꢁ408 again.
Bromide 13 (12.5 g, 60 mmol) in THF (10 ml) was added along with NaI (1.5 g, 10 mmol), and the