The Journal of Organic Chemistry
Article
n-Propyl Dihydrocinnamate. EI-MS: m/z (%), 192 [M+•, 36], 133
(20), 107 (37), 105 (44), 104 (100), 103 (16), 91 (63), 79 (16), 78 (16),
77 (24), 65 (11), 51 (13).
and water (500 μL) and diethyl ether (300 μL) were added. The upper
layer was separated, and the solvent was evaporated to obtain the
product as an oil.
Isopropyl Dihydrocinnamate. EI-MS: m/z (%), 192 [M+•, 20], 150
(43), 133 (26), 105 (58), 104 (100), 103 (17), 91 (74), 79 (16), 78 (18),
77 (28), 65 (11), 51 (15), 43 (30).
Methyl [Carbonyl-18O]dihydrocinnamate. EI-MS: m/z (%), 166
[M+•, 34], 135 (8), 105 (32), 104 (100), 103 (14), 91 (48), 79 (10), 78
(13), 77 (20), 65 (9), 51 (10).
n-Butyl dihydrocinnamate. EI-MS: m/z (%), 206 [M+•, 27], 150
(18), 133 (11), 107 (25), 105 (37), 104 (100), 103 (13), 91 (60), 79
(12), 78 (13), 77 (19), 41 (16); 1H NMR (400 MHz, CDCl3) δH 1.07
(8H, t, J = 7.38, CH3), 1.50 (5H, m, CH2), 1.74 (6H, m, CH2), 2.78 (6H,
m, CH2), 3.11 (6H, t, J = 7.91, CH2), 4.23 (5H, t, J = 6.66, CH2), 7.35
(8H, m, H-2,4,6), 7.44 (6H, m, H-3,5).
Ethyl [Carbonyl-18O]dihydrocinnamate. EI-MS: m/z (%), 180
[M+•, 37], 135 (10), 107 (40), 105 (42), 104 (100), 91 (50), 79 (20), 77
(25), 65 (10), 51(14).
n-Butyl [Carbonyl-18O]dihydrocinnamate. EI-MS: m/z (%), 208
[M+•, 24], 152 (19), 133 (11), 105 (37), 104 (100), 91 (60), 79 (15), 78
(14), 77 (23), 41 (19).
sec-Butyl Dihydrocinnamate. EI-MS: m/z (%), 206 [M+•, 9], 150
(59), 133 (39), 107 (14), 105 (62), 104 (100), 103 (16), 91 (78), 79
(14), 78 (16), 77 (24), 51 (14), 41 (18); 1H NMR (400 MHz, CDCl3)
δH 1.01 (7H, t, J = 7.45, CH3), 1.32 (7H, d, J = 6.25, CH3), 1.69 (4H,
m,CH2), 2.76 (5H, m, CH2), 3.11 (6H, t, J = 7.75, CH2), 4.99 (1H, s,
CH), 5.00 (1H, d, J = 6.25), 7.36 (9H, m, H-2,4,6), 7.43 (7H, m, H-3,5).
Isobutyl Dihydrocinnamate. EI-MS: m/z (%), 206 [M+•, 22], 150
(41), 133 (25), 107 (18), 105 (54), 104 (100), 103 (17), 91 (77), 79
(16), 78 (17), 77 (25), 57 (25), 41 (26); 1H NMR (400 MHz, CDCl3)
δH 1.07 (4H, m, CH3), 1.07 (12H, d, J = 6.78, CH3), 2.06 (2H, m, CH),
2.83 (6H, m, CH2), 3.12 (6H, m, CH2), 4.02 (5H, d, J = 6.70, CH2), 7.37
(9H, m, H-2,4,6), 7.45 (6H, m, H-3,5).
[2,2-2H2]Heptanenitrile. Heptanenitrile (500 μL) was added to a
mixture of D2O/dioxane (7:2) (2 mL) and diazabicyclo[5.4.0]undec-7-
ene (DBU, 1 mL). The mixture was heated at 100 °C for 2 h, and the
solvent was removed under reduced pressure. After four repetitions of
the D/H procedure, the residue was washed with aqueous HCl and the
product was extracted into diethyl ether. EI-MS: m/z (%), 113 [M+•, 5],
112 (3), 99 (11), 98 (27), 97 (19), 85 (25), 84 (66), 83 (39), 82 (12), 71
(17), 70 (14), 57 (14), 56 (18), 54 (20), 53 (13), 43 (66), 42 (46), 41
(100), 40 (22).
[2,2-2H2]Octanoic Acid. Hydrochloric acid (1.0 mL) was added to
[2,2-2H2]heptanenitrile (300 μL), and the mixture was kept at 100 °C.
After 6 h, the product was isolated under reduced pressure as a white
solid. EI-MS: m/z (%), 87 (28), 74 (100), 59 (24), 57 (21), 55 (33), 43
(62), 42 (21), 41 (53), 39 (24).
tert-Butyl dihydrocinnamate. EI-MS: m/z (%),105 (21), 104 (30),
103 (21), 91 (29), 79 (14), 78 (23), 77 (35), 58 (11), 57 (80), 51 (26),
1
[2,2-2H2]Octanol. LiAlH4 in THF (200 μL) was slowly added to
[2,2-2H2]octanoic acid at room temperature. After 15 min, water (350
μL) was added to the mixture. The upper layer was separated, and the
product was evaporated as an oil.
43 (100), 42 (23), 41 (64), 39 (54), 59 (36); H NMR (400 MHz,
CDCl3) δH 1.57 (16H, m,CH3), 2.69 (6H, m, CH2), 3.06 (6H, m, CH2),
7.36 (6H, m, H-2,4,6), 7.41 (10H, m, H-3,5).
n-Pentyl Dihydrocinnamate. EI-MS: m/z (%), 220 [M+•, 5], 150
(14), 133 (5), 107 (18), 105 (38), 104 (100), 103 (19), 91 (85), 79 (18),
78 (24), 77 (33), 65 (18), 51 (23), 43 (76).
[2,2-2H2]Octyl Dihydrocinnamate. Dihydrocinnamic acid (300 mg,
2.00 mmol) and p-toluenesulfonic acid (25 mg, 0.15 mmol) were added
to [2,2-2H2]octanol at room temperature. After 30 min, water (500 μL)
and diethyl ether (300 μL) were added. The upper layer was separated,
and the product was evaporated as an oil. EI-MS: m/z (%), 264 [M+•,
10], 150 (21), 133 (12), 107 (37), 104 (100), 91 (63), 79 (5), 78 (9), 77
(13), 59 (20), 58 (17), 57 (14), 45 (21), 44 (35), 43 (12), 42 (20).
[2,2,3,3-2H4]Dihydrocinnamic Acid. Phenylpropiolic acid (0.1 g,
0.68 mmol) was added to 10% Pd/C (10.0 mg) in ethyl acetate (2.0
mL). Deuterium gas was infused into the solution at room temperature.
After 12 h, the mixture was filtered and the filtrate was concentrated to
obtain the desired compound as a white solid (85 mg, 81%). EI-MS: m/z
(%), 154 [M+•, 22], 107 (44), 106 (48), 105 (34), 93 (72), 92 (100), 91
(40).
n-Hexyl Dihydrocinnamate. EI-MS: m/z (%), 234 [M+•, 18], 150
(36), 133 (8), 105 (34), 104 (100), 103 (10), 91 (55), 79 (10), 78 (10),
77 (15), 43 (23), 41 (19).
n-Octyl Dihydrocinnamate. EI-MS: m/z (%), 262 [M+•, 13], 150
(53), 133 (8), 105 (34), 104 (100), 103 (9), 91 (53), 79 (9), 78 (9), 77
(12), 57 (16), 43 (21), 41 (26).
n-Decyl Dihydrocinnamate. EI-MS: m/z (%), 290 [M+•, 12], 150
(70), 133 (10), 107 (13), 105 (36), 104 (100), 91 (49), 77 (11), 57 (17),
55 (17), 43 (30), 41 (30).
n-[1,1-2H2]Decyl Dihydrocinnamate. EI-MS: m/z (%), 292 [M+•,
1], 150 (12), 133(3), 105 (24), 104 (69), 91 (51), 79 (11), 78 (11), 77
(13), 71 (13), 59 (22), 58 (13), 57 (46), 56 (16), 55 (26), 45 (20), 44
(23), 43 (100), 42 (31), 41 (67), 39 (15).
Methyl [2,2,3,3-2H4]Dihydrocinnamate. [2,2,3,3-2H4]Dihydro-
cinnamic acid (15.0 mg, 0.09 mmol) and p-toluenesulfonic acid (1.0
mg) were added to methanol (0.5 mL) at room temperature. The
mixture was stirred for 12 h, and the solvent was removed under reduced
pressure. The residue was washed with ethyl acetate (5.0 mL), NaHCO3
solution (5.0 mL), and water (5.0 mL). The upper layer was separated
and dried with Na2SO4, and the solvent was removed to obtain the
product as a colorless oil (8.0 mg, 50%). EI-MS: m/z (%), 168 [M+•, 32],
137 (8), 107 (100), 93 (88), 79 (33), 66 (12), 51 (25).
Computational Methods. Full geometry optimizations were
performed by the density functional theory method B3LYP with a 6-
311++G(2d,2p) basis set for all atoms using the Gaussian 09 program,28
which was also used to calculate the zero-point-energy-corrected
electronic energies, enthalpies, and Gibbs free energies. The latter two
calculations were performed at 298.15 K and 1 atm, as standard output
from the Gaussian 09 program. Frequency analysis was undertaken at
the same level to confirm that the optimized structures are the
corresponding stationary states on the respective potential energy
surfaces.
n-[3,3-2H2]Decyl Dihydrocinnamate. EI-MS: m/z (%), 292 [M+•,
1], 150 (12), 133(3), 105 (33), 104 (75), 91 (59), 79 (13), 78 (11), 77
(15), 72 (12), 71 (12), 59 (15), 58 (34), 57 (42), 56 (24), 55 (22), 45
(17), 44 (44), 43 (100), 42 (38), 41 (64), 39 (16).
n-[4,4-2H2]Decyl Dihydrocinnamate. EI-MS: m/z (%), 292 [M+•,
1], 150 (16), 133(5), 107 (14), 105 (42), 104 (100), 92 (10), 91 (73),
86 (10), 79 (15), 78 (14), 77 (18), 72 (15), 71 (14), 65 (11), 59 (15), 58
(37), 57 (44), 56 (25), 55 (19), 51 (10), 45 (14), 43 (90), 42 (37), 41
(56), 39 (14).
n-[5,5-2H2]Decyl Dihydrocinnamate. EI-MS: m/z (%), 292 [M+•,
1], 150 (19), 133(5), 107 (14), 105 (40), 104 (100), 103 (11), 91 (69),
79 (12), 78 (12), 77 (15), 72 (13), 71 (11), 59 (11), 58 (29), 57 (31), 56
(18), 55 (16), 45 (12), 44 (35), 43 (60), 42 (27), 41 (40), 39 (10).
[Carbonyl-18O]Dihydrocinnamic acid. To a solution of dihydrocin-
namic acid (300 mg, 2.00 mmol) in THF (0.5 mL), H218O (about 100
μL) and concentrated sulfuric acid (5 μL) were added and the mixture
was kept at room temperature (20 °C). After 30 min, THF was removed
and the residue was dried with a stream of dry nitrogen to give
[carbonyl-18O]dihydrocinnamic acid. EI-MS: m/z (%), 104 (60), 91
(100), 79 (9), 77 (16), 65 (10), 51 (14).
Methyl, Ethyl, and n-Butyl [Carbonyl-18O]dihydrocinnamates.
Absolute methanol (64 mg, 2.00 mmol), ethanol (92 mg, 2.00 mmol),
or n-butanol (148 mg, 2.00 mmol) and p-toluenesulfonic acid (25 mg,
0.15 mmol) were added to [carbonyl-18O]dihydrocinnamic acid (300
mg, 2.00 mmol). The mixture was kept at room temperature for 30 min,
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J. Org. Chem. XXXX, XXX, XXX−XXX