Journal of Agricultural and Food Chemistry
ARTICLE
diethyl ether. After drying over Na2SO4 and evaporation of the solvent,
the lactones so obtained were purified by distillation under vacuum or by
flash chromatography.
(96), 67 (100), 55 (53), 54 (32), 41 (75), 39 (24); HR-ToF MS,
196.1467 (C12H20O2, þ2.0 ppm).
(Z)-10-Dodecen-4-olide, 6. From 1.55 g (11 mmol) of (Z)-7-none-
nal, purified by distillation over a Vigreux column: bp 74 °C/0.014
mmHg; yield, 25%; 91% by GC-FID; <4% (E); 1H NMR (CDCl3) δ
5.48ꢀ5.33 (m, 2H), 4.52ꢀ4.45 (m, 1H), 2.55ꢀ2.51 (m, 2H), 2.36ꢀ
2.28 (m, 1H), 2.07ꢀ2.01 (m, 2H), 1.90ꢀ1.80 (m, 1H), 1.78ꢀ1.70 (m,
1H), 1.65ꢀ1.62 (m, 1H), 1.62ꢀ1.59 (m, 3H), 1.52ꢀ1.42 (m, 1H),
1.41ꢀ1.32 (m, 7H); 13C NMR (100 MHz, CDCl3) δ 177.2 (s, C(1)),
130.5 (d, C(10)), 123.9 (d, C(11)), 81.0 (d, C(4)), 35.6 (t, C(5)), 29.4
(t, C(8)), 28.9 (t, C(2)), 28.9 (t, C(7)), 28.0 (t, C(3)), 26.7 (t, C(9)),
25.2 (t, C(6)), 12.8 (q, C(12)); EI-MS, m/z (rel intensity) 196 (3), 178
(2), 167 (2), 154 (5), 153 (5), 136 (36), 123 (13), 109 (16), 95 (34), 85
(62), 81 (64), 68 (100), 67 (72), 55 (73), 54 (46), 41 (48), 39 (24); HR-
ToF MS, 196.1462 (C12H20O2, ꢀ0.5 ppm).
All of the following lactones consisted of racemic mixtures.
(E)-5-Dodecen-4-olide, 1. From 5.0 g (35.7 mmol) of (E)-2-nonenal,
purified by distillation over a Vigreux column: bp 65 °C/0.027 mmHg;
yield, 37%; 99% by GC-FID, <3% of (Z) isomer; 1H NMR (CDCl3) δ
5.85ꢀ5.77 (m, 1HꢀC(6)), 5.52ꢀ5.46 (ddt, J = 14.8, 7.1, 1.7 Hz,
1HꢀC(5)), 4.89 (dd, J = 7.3, 7.1 Hz, 1HꢀC(4)), 2.56ꢀ2.51 (m, 2H),
2.41ꢀ2.33 (m, 1H), 2.09ꢀ2.03 (m, 2H), 2.02ꢀ1.93 (m, 1H),
1.42ꢀ1.35 (m, 2H), 1.33ꢀ1.25 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 177.1 (s, C(1)), 135.8 (d, C(6)), 127.4 (d,
C(5)), 81.2 (d, C(4)), 32.1 (t, C(7)), 31.6 (t, C(10)), 28.9 (t, C(3)),
28.8 (t, C(2), C(8), C(9)), 22.6 (t, C(11)), 14.1 (q, C(12)); EI-MS, m/z
(rel intensity) 196 (1), 153 (6), 136 (10), 125 (14), 111 (100), 98 (19),
85 (19), 81 (24), 67 (19), 55 (28), 41 (28); HR-ToF MS, 196.1466
(C12H20O2, þ1.5 ppm).
(E)-10-Dodecen-4-olide, 7. From 1.55 g (11 mmol) of (E)-7-nonenal,
purified by distillation over a Vigreux column: bp 78 °C/0.019 mmHg;
yield, 41%; 91% by GC-FID; <2% (Z); 1H NMR (CDCl3) δ 5.45ꢀ5.38
(m, 2H), 4.52ꢀ4.45 (m, 1H), 2.56ꢀ2.51 (m, 2H), 2.36ꢀ2.28 (m, 1H),
2.00ꢀ1.94 (m, 2H), 1.90ꢀ1.80 (m, 1H), 1.77ꢀ1.68 (m, 1H), 1.65ꢀ
1.63 (m, 3H), 1.62ꢀ1.55 (m, 1H), 1.51ꢀ1.41 (m, 1H), 1.38ꢀ1.31 (m,
5H); 13C NMR (100 MHz, CDCl3) δ 177.3 (s, C(1)), 131.3 (d, C(10)),
124.9 (d, C(11)), 81.0 (d, C(4)), 35.6 (t, C(5)), 32.4 (t, C(9)), 29.4 (t,
C(7)), 28.9 (t, C(2)), 28.8 (t, C(8)), 28.0 (t, C(3)), 25.1 (t, C(6)), 17.9
(q, C(12)); EI-MS, m/z (rel intensity) 196 (5), 178 (2), 167 (2), 154
(6), 136 (42), 123 (15), 109 (17), 95 (37), 85 (66), 81 (67), 68 (100),
67 (72), 55 (79), 54 (44), 41 (44), 39 (23); HR-ToF MS, 196.1464
(C12H20O2, þ0.5 ppm).
(E)-6-Dodecen-4-olide, 2. From 1.0 g (7.1 mmol) of (E)-3-nonenal,
purified by bulb-to-bulb distillation: yield, 42%; 94% by GC-FID, <1% of
(Z) isomer; 1H NMR (CDCl3) δ 5.61ꢀ5.53 (m, 1HꢀC(7)), 5.41ꢀ5.33
(m, 1HꢀC(6)), 4.56ꢀ4.49 (m, 1HꢀC(4)), 2.55ꢀ2.51 (m, 2H),
2.48ꢀ2.24 (m, 3H), 2.04ꢀ1.98 (m, 2H), 1.97ꢀ1.87 (m, 1H),
1.39ꢀ1.21 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 177.4 (s, C(1)), 135.5 (d, C(7)), 123.0 (d, C(6)), 80.4 (d,
C(4)), 38.3 (t, C(5)), 32.6 (t, C(8)), 31.4 (t, C(10)), 29.0 (t, C(9)),
28.7 (t, C(2)), 26.9 (t, C(3)), 22.5 (t, C(11)), 14.0 (q, C(12)); EI-MS,
m/z (rel intensity) 196 (1), 136 (1), 96 (3), 85 (100), 57 (7), 55 (8), 41
(15), 39 (8); HR-ToF MS, 196.1463 (C12H20O2, þ0.0 ppm).
(E)-7-Dodecen-4-olide, 3. From 0.6 g (4.3 mmol) of (E)-4-nonenal,
purified by distillation over a Vigreux column: bp 78 °C/0.019 mmHg;
11-Dodecen-4-olide, 8. From 5.6 g of 8-nonenal (40 mmol), purified
by distillation over a Vigreux column: bp 93 °C/0.026 mmHg; yield,
1
1
yield, 41%; 91% by GC-FID, around 1% (Z); H NMR (CDCl3) δ
77%; 95% by GC-FID; H NMR (CDCl3) δ 5.85ꢀ5.75 (m, 1Hꢀ
5.50ꢀ5.34 (m, 2H), 4.53ꢀ4.46 (m, 1H), 2.55ꢀ2.51 (m, 2H),
2.36ꢀ2.28 (m, 1H), 2.21ꢀ2.06 (m, 2H), 2.01ꢀ1.96 (m, 2H),
1.91ꢀ1.77 (m, 2H), 1.69ꢀ1.60 (m, 1H), 1.37ꢀ1.25 (m, 4H), 0.89 (t,
J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 177.2 (s, C(1)), 132.0
(d, C(8)), 128.2 (d, C(7)), 80.3 (d, C(4)), 35.5 (t, C(5)), 32.2 (t, C(9)),
31.7 (t, C(10)), 28.8 (t, C(2)), 28.3 (t, C(6)), 28.0 (t, C(3)), 22.2 (t,
C(11)), 13.9 (q, C(12)); EI-MS, m/z (rel intensity) 196 (2), 136 (5),
121 (4), 111 (9), 96 (100), 85 (43), 81 (61), 67 (40), 55 (37), 54 (48),
41 (31), 39 (13); HR-ToF MS, 196.1467 (C12H20O2, þ2.0 ppm).
(Z)-9-Dodecen-4-olide, 4. From 5.6 g (40 mmol) of (Z)-6-nonenal,
purified by distillation over a Vigreux column: bp 77 °C/0.018 mmHg;
C(11)), 4.99 (dd, J = 17.1, 1.7 Hz, 1HꢀC(12)), 4.93 (dd, J = 10.2, 1.3
Hz, 1HꢀC(12)), 4.52ꢀ4.45 (m, 1HꢀC(4)), 2.55ꢀ2.51 (m, 2H),
2.36ꢀ2.28 (m, 1H), 2.07ꢀ2.01 (m, 2HꢀC(9)), 1.90ꢀ1.80 (m, 1H),
1.77ꢀ1.69 (m, 1H), 1.65ꢀ1.55 (m, 1H), 1.50ꢀ1.43 (m, 1H), 1.41ꢀ
1.30 (m, 7H); 13C NMR (100 MHz, CDCl3) δ 177.2 (s, C(1)), 139.0 (d,
C(11)), 114.3 (t, C(12)), 81.0 (d, C(4)), 35.6 (t, C(5)), 33.7 (t, C(10)),
29.2 (t, C(7)), 28.9 (t, C(8)), 28.9 (t, C(2)), 28.8 (t, C(9)), 28.0 (t,
C(3)), 25.2 (t, C(6)); EI-MS, m/z (rel intensity) 196 (0.1), 136 (22), 95
(28), 85 (100), 81 (40), 68 (52), 67 (51), 55 (72), 54 (61), 41 (88), 39
(47); HR-ToF MS, 196.1467 (C12H20O2, þ2.0 ppm).
(Z)-11-Tetradecen-4-olide, 9. From 6.05 g (36 mmol) of (Z)-8-
undecenal, purified by distillation over a Vigreux column: bp 95 °C/
0.019 mmHg; yield, 52%; 99% by GC-FID; 94% (Z)- and 6% (E); 1H
NMR (CDCl3) δ 5.40ꢀ5.28 (m, 2H), 4.52ꢀ4.45 (m, 1H), 2.55ꢀ2.50
(m, 2H), 2.36ꢀ2.28 (m, 1H), 2.07ꢀ1.99/m, 4H), 1.90ꢀ1.80 (m, 1H),
1.77ꢀ1.69 (m, 1H), 1.64ꢀ1.55 (m, 1H), 1.50ꢀ1.32 (br m, 8H), 0.95 (t,
J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 177.3 (s, C(1)), 131.7
(d, C(12)), 129.1 (d, C(11)), 81.0 (d, C(4)), 35.6 (t, C(5)), 29.6 (t,
C(9)), 29.2 (t, C(7)), 29.1 (t, C(8)), 28.9 (t, C(2)), 28.0 (t, C(3)), 27.0
(t, C(10)), 25.2 (t, C(6)), 20.5 (t, C(13)), 14.4 (q, C14)); EI-MS, m/z
(rel intensity) 224 (5), 164 (9), 150 (8), 136 (13), 122 (11), 109 (22),
95 (53), 85 (63), 82 (68), 81 (77), 68 (100), 67 (94), 55 (74), 41 (84);
HR-ToF MS, 224.1779 (C14H24O2, þ1.3 ppm).
1
yield, 38%; purity, 99% by GC-FID; 94% (Z)- and 6% (E); H NMR
(CDCl3) δ 5.41ꢀ5.27 (m, 2H), 4.52ꢀ4.45 (m, 1H), 2.55ꢀ2.51 (m,
2H), 2.36ꢀ2.28 (m, 1H), 2.07ꢀ1.99 (m, 4H), 1.90ꢀ1.80 (m, 1H),
1.78ꢀ1.70 (m, 1H), 1.64ꢀ1.56 (m, 1H), 1.52ꢀ1.45 (m, 1H),
1.44ꢀ1.35 (m, 3H), 0.96 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 177.2 (s, C(1)), 132.1 (d, C(10)), 128.6 (d, C(9)), 81.0 (d,
C(4)), 35.5 (t, C(5)), 29.4 (t, C(7)), 28.8 (t, C(2)), 28.0 (t, C(3)), 26.9
(t, C(8)), 24.9 (t, C(6)), 20.5 (t, C(11)), 14.4 (q, C(12)); EI-MS, m/z
(rel intensity) 196 (7), 136 (53), 123 (21), 121 (22), 109 (18), 107 (16),
95 (38), 85 (58), 81 (78), 68 (92), 67 (100), 55 (47), 41 (56); HR-ToF
MS, 196.1465 (C12H20O2, þ1.0 ppm).
(E)-9-Dodecen-4-olide, 5. From 1.13 g (7.3 mmol) of (E)-6-nonenal,
purified by microdistillation (no Vigreux column): bp 72 °C/0.024
mmHg; yield, 26%; 91% by GC-FID; <1% (Z); 1H NMR (CDCl3) δ
5.49ꢀ5.33 (m, 2H), 4.52ꢀ4.45 (m, 1H), 2.55ꢀ2.51 (m, 2H), 2.37ꢀ
2.28 (m, 1H), 2.03ꢀ1.96 (m, 4H), 1.90ꢀ1.80 (m, 1H), 1.78ꢀ1.70 (m,
1H), 1.68ꢀ1.55 (m, 1H), 1.50ꢀ1.43 (m, 1H), 1.43ꢀ1.36 (m, 3H), 0.96
(t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 177.3 (s, C(1)),
132.5 (d, C(10)), 128.7 (d, C(9)), 81.0 (d, C(4)), 35.5 (t, C(5)), 32.3 (t,
C(8)), 29.3 (t, C(7)), 28.9 (t, C(2)), 28.0 (t, C(3)), 25.6 (t, C(11)),
24.7 (t, C(6)), 14.0 (q, C(12)); EI-MS, m/z (rel intensity) 196 (5), 178
(2), 167 (2), 154 (5), 109 (14), 107 (14), 95 (33), 85 (51), 81 (70), 68
(Z,Z)-6,9-Dodecadien-4-olide, 10. From 2.7 g (20 mmol) of (Z,Z)-
3,6-nonadienal, purified by distillation over a Vigreux column, bp 87 °C/
0.017 mmHg, and then by flash chromatography (cyclohexane/THF
86:14): yield, 8%; purity, 60% by GC-FID and NMR. It contained 20%
of (E,Z)-5,9-dodecadien-4-olide and impurities from the solvent. Spec-
tral data were consistent with those described by Maurer and Hauser.3
HR-ToF MS: 194.1305 (C12H18O2, ꢀ1.0 ppm).
(E,Z)-5,9-Dodecadien-4-olide, 11. From 4.98 g (36 mmol) of (E,Z)-
2,6-nonadienal, purified by distillation over a Vigreux column: bp 94 °C/
0.027 mmHg; yield, 36%; 98% by GC-FID; 1H NMR (CDCl3) δ
4059
dx.doi.org/10.1021/jf104711x |J. Agric. Food Chem. 2011, 59, 4057–4061