May 2009
479
Octadecyl Ferulate (3) According to the general procedure for Mitsu-
nobu reaction described above, the title compound was prepared from ferulic
acid and octadecanol. mp 65—66 °C. IR (Nujol) cmꢂ1: 3550, 1682, 1622,
1597. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.6 Hz), 1.2—1.5 (30H, m), 1.70
(2H, quintet, Jꢀ6.9 Hz), 3.92 (3H, s), 4.19 (2H, t, Jꢀ6.9 Hz), 5.92 (1H, s),
6.29 (1H, d, Jꢀ15.9 Hz), 6.91 (1H, d, Jꢀ7.8 Hz), 7.03 (1H, d, Jꢀ1.8 Hz),
7.07 (1H, dd, Jꢀ1.8, 7.8 Hz), 7.61 (1H, d, Jꢀ15.9 Hz). 13C-NMR (CDCl3) d:
14.1, 22.7, 26.0, 28.8, 29.3—29.7 (29.28, 29.34, 29.52, 29.57, 29.63, 29.67),
31.9, 55.9, 64.6, 109.3, 114.7, 115.6, 123.0, 127.1, 144.6, 146.7, 147.9,
167.4. MS (EI) m/z: 446 (Mꢃ), 194. HR-MS (EI) m/z: 446.3412 (Calcd for
C28H46O4: 446.3396).
1.5 (22H, m), 1.65 (2H, quintet, Jꢀ6.9 Hz), 4.13 (2H, t, Jꢀ6.9 Hz), 5.83
(1H, d, Jꢀ12.6 Hz), 6.10 (1H, br), 6.77 (2H, d, Jꢀ6.9 Hz), 6.86 (1H, d,
Jꢀ12.6 Hz), 7.59 (2H, d, Jꢀ6.9 Hz). 13C-NMR (CDCl3) d: 14.1, 22.7, 26.0,
28.5, 29.3—29.6 (29.25, 29.34, 29.50, 29.57, 29.64), 31.9, 64.7, 115.1,
116.9, 127.1, 132.2, 144.0, 157.0, 167.2. MS (EI) m/z: 360 (Mꢃ), 164. HR-
MS (EI) m/z: 360.2682 (Calcd for C23H36O3: 360.2664).
Icosyl cis-p-Coumarate: cis-1 (nꢀ20) mp 74—75 °C. IR (Nujol) cmꢂ1
:
3383, 1712, 1686, 1601. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—
1.5 (34H, m), 1.65 (2H, quintet, Jꢀ6.9 Hz), 4.13 (2H, t, Jꢀ6.9 Hz), 5.83
(1H, d, Jꢀ12.6 Hz), 6.10 (1H, br), 6.77 (2H, d, Jꢀ6.9 Hz), 6.86 (1H, d,
Jꢀ12.6 Hz), 7.59 (2H, d, Jꢀ6.9 Hz). 13C-NMR (CDCl3) d: 14.1, 22.7, 25.9,
28.5, 29.3—29.7 (29.25, 29.34, 29.50, 29.57, 29.64, 29.69), 31.9, 64.7,
115.1, 116.9, 127.1, 132.2, 144.0, 157.1, 167.2. MS (EI) m/z: 444 (Mꢃ),
164. HR-MS (EI) m/z: 444.3623 (Calcd for C29H48O3: 444.3603).
Octadecyl Isoferulate (4) mp 68—69 °C. IR (Nujol) cmꢂ1: 3566, 1697,
1631, 1614, 1583. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—1.5
(30H, m), 1.69 (2H, quintet, Jꢀ6.9 Hz), 3.92 (3H, s), 4.18 (2H, t, Jꢀ6.9 Hz),
5.70 (1H, s), 6.29 (1H, d, Jꢀ15.9 Hz), 6.83 (1H, d, Jꢀ8.4 Hz), 7.03 (1H, dd,
Jꢀ2.1, 8.4 Hz), 7.14 (1H, d, Jꢀ2.1 Hz), 7.58 (1H, d, Jꢀ15.9 Hz). 13C-NMR
(CDCl3) d: 14.1, 22.7, 26.0, 28.7, 29.3—29.7 (29.28, 29.34, 29.52, 29.57,
29.64, 29.68), 31.9, 56.0, 64.6, 110.5, 113.0, 116.3, 121.7, 128.1, 144.3,
145.8, 148.4, 167.4. MS (EI) m/z: 446 (Mꢃ), 194. HR-MS (EI) m/z:
446.3413 (Calcd for C28H46O4: 446.3396).
Docosyl cis-p-Coumarate: cis-1 (nꢀ22) mp 76—77 °C. IR (Nujol)
cmꢂ1: 3383, 1713, 1686, 1603. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz),
1.2—1.5 (38H, m), 1.65 (2H, quintet, Jꢀ6.9 Hz), 4.13 (2H, t, Jꢀ6.9 Hz),
5.83 (1H, d, Jꢀ12.6 Hz), 6.07 (1H, br s), 6.78 (2H, d, Jꢀ6.9 Hz), 6.86 (1H,
d, Jꢀ12.6 Hz), 7.59 (2H, d, Jꢀ6.9 Hz). 13C-NMR (CDCl3) d: 14.1, 22.7,
26.0, 28.6, 29.3—29.7 (29.26, 29.35, 29.52, 29.57, 29.65, 29.69), 31.9, 64.7,
115.1, 116.9, 127.2, 132.2, 143.9, 157.0, 167.2. MS (EI) m/z: 472 (Mꢃ),
164. HR-MS (EI) m/z: 472.3940 (Calcd for C31H52O3: 472.3916).
Tetracosyl cis-p-Coumarate: cis-1 (nꢀ24) mp 81—83 °C. IR (Nujol)
cmꢂ1: 3385, 1713, 1686, 1601. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz),
1.2—1.5 (42H, m), 1.65 (2H, quintet, Jꢀ6.9 Hz), 4.13 (2H, t, Jꢀ6.9 Hz),
5.83 (1H, d, Jꢀ12.6 Hz), 6.09 (1H, br s), 6.78 (2H, d, Jꢀ6.9 Hz), 6.86 (1H,
d, Jꢀ12.6 Hz), 7.59 (2H, d, Jꢀ6.9 Hz). 13C-NMR (CDCl3) d: 14.1, 22.7,
26.0, 28.6, 29.3—29.7 (29.26, 29.35, 29.52, 29.57, 29.65, 29.69), 31.9, 64.7,
115.1, 116.9, 127.2, 132.2, 143.9, 157.0, 167.1. MS (EI) m/z: 500 (Mꢃ),
164. HR-MS (EI) m/z: 500.4238 (Calcd for C33H56O3: 500.4229).
Octadecyl Sinapate (5) mp 72—73 °C. IR (Nujol) cmꢂ1: 3521, 1707,
1636, 1609. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—1.5 (30H,
m), 1.70 (2H, quintet, Jꢀ6.9 Hz), 3.92 (6H, s), 4.19 (2H, t, Jꢀ6.9 Hz), 5.78
(1H, s), 6.31 (1H, d, Jꢀ15.9 Hz), 6.77 (2H, s), 7.59 (1H, d, Jꢀ15.9 Hz). 13C-
NMR (CDCl3) d: 14.1, 22.7, 26.0, 28.8, 29.3—29.7 (29.28, 29.33, 29.53,
29.58, 29.63, 29.67), 31.9, 56.3, 64.6, 105.0, 116.0, 125.9, 137.0, 144.8,
147.2, 167.2. MS (EI) m/z: 476 (Mꢃ), 180. HR-MS (EI) m/z: 476.3520
(Calcd for C29H48O5: 476.3502).
Octadecyl Caffeate (6) mp 107—108 °C. IR (Nujol) cmꢂ1: 3479, 3308,
1682, 1607. 1H-NMR (CDCl3 : DMSO-d6ꢀ10 : 1) d: 0.88 (3H, t, Jꢀ6.9 Hz),
1.2—1.5 (30H, m), 1.69 (2H, quintet, Jꢀ6.9 Hz), 4.16 (2H, t, Jꢀ6.9 Hz),
6.21 (1H, d, Jꢀ15.9 Hz), 6.84 (1H, d, Jꢀ8.1 Hz), 6.91 (1H, dd, Jꢀ2.1, 8.1
Hz), 7.07 (1H, d, Jꢀ2.1 Hz), 7.53 (1H, d, Jꢀ15.9 Hz), 8.37 (2H, br). 13C-
NMR (CDCl3 : DMSO-d6ꢀ10 : 1) d: 13.6, 22.1, 25.4, 28.2, 28.8—29.1
(28.75, 28.79, 28.99, 29.03, 29.09, 29.12), 31.4, 63.9, 113.9, 114.3, 115.2,
121.1, 126.1, 144.5, 144.7, 147.2, 167.0. MS (EI) m/z: 432 (Mꢃ), 180. HR-
MS (EI) m/z: 432.3254 (Calcd for C27H44O4: 432.3240).
Octadecyl p-Hydroxyphenylpropiolate: 2 (nꢀ18) By the same proce-
dure (Mitsunobu reaction) for preparation of p-coumarate ester, the title
compound was prepared from p-hydroxyphenylpropiolic acid and octade-
canol in 91% yield after purification by silica gel column chromatography
eluting with hexane/ethyl acetateꢀ9/1. mp 87—88 °C. IR (Nujol) cmꢂ1
:
3219, 2206, 1659, 1602. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—
1.5 (30H, m), 1.71 (2H, quintet, Jꢀ6.9 Hz), 4.23 (2H, t, Jꢀ6.9 Hz), 5,95
(1H, s), 6.85 (2H, d, Jꢀ6.9 Hz), 7.45 (2H, d, Jꢀ6.9 Hz). 13C-NMR (CDCl3)
d: 14.1, 22.7, 25.8, 28.5, 29.2—29.7 (29.20, 29.34, 29.47, 29.56, 29.68),
31.9, 66.4, 80.0, 87.4, 111.3, 115.9, 135.2, 154.9, 158.1. MS (EI) m/z: 414
(Mꢃ), 165. HR-MS (EI) m/z: 414.3130 (Calcd for C27H42O3: 414.3134).
Tetradecyl p-Hydroxyphenylpropiolate: 2 (nꢀ14) mp 72—74 °C. IR
(Nujol) cmꢂ1: 3219, 2206, 1660, 1605. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ
6.9 Hz), 1.2—1.5 (22H, m), 1.71 (2H, quintet, Jꢀ6.9 Hz), 4.23 (2H, t, Jꢀ
6.9 Hz), 6.10 (1H, br), 6.84 (2H, d, Jꢀ6.9 Hz), 7.46 (2H, d, Jꢀ6.9 Hz). 13C-
NMR (CDCl3) d: 14.1, 22.7, 25.8, 28.4, 29.2—29.7 (29.19, 29.33, 29.46,
29.54, 29.63, 29.66), 31.9, 66.4, 79.9, 87.5, 111.2, 115.9, 135.2, 155.0,
158.2. MS (EI) m/z: 358 (Mꢃ), 164. HR-MS (EI) m/z: 358.2516 (Calcd for
C23H34O3: 358.2508).
Octadecyl o-Coumarate (7) mp 83—85 °C. IR (Nujol) cmꢂ1: 3196,
1670, 1601. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—1.5 (30H,
m), 1.71 (2H, quintet, Jꢀ6.9 Hz), 4.23 (2H, t, Jꢀ6.9 Hz), 6.66 (1H, d, Jꢀ
16.2 Hz), 6.88 (1H, ddd, Jꢀ1.2, 7.5, 7.5 Hz), 6.92 (1H, dd, Jꢀ1.2, 7.5 Hz),
7.01 (1H, s), 7.23 (1H, ddd, Jꢀ1.2, 7.5, 7.5 Hz), 7.47 (1H, dd, Jꢀ1.2, 7.5
Hz), 8.06 (1H, d, Jꢀ16.2 Hz). 13C-NMR (CDCl3) d: 14.1, 22.7, 26.0, 28.7,
29.3—29.7 (29.28, 29.34, 29.53, 29.58, 29.65, 29.69), 31.9, 65.0, 116.4,
118.3, 120.6, 121.7, 129.2, 131.4, 140.7, 155.5, 168.7. MS (EI) m/z: 416
(Mꢃ), 146. HR-MS (EI) m/z: 416.3303 (Calcd for C27H44O3: 416.3290).
Octadecyl m-Coumarate (8) mp 78—79 °C. IR (Nujol) cmꢂ1: 3379,
1688, 1641, 1595. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—1.5
(30H, m), 1.70 (2H, quintet, Jꢀ6.9 Hz), 4.21 (2H, t, Jꢀ6.9 Hz), 6.00 (1H,
br), 6.41 (1H, d, Jꢀ15.9 Hz), 6.89 (1H, m), 7.04 (1H, m), 7.09 (1H, m), 7.25
(1H, t, Jꢀ7.8 Hz), 7.63 (1H, d, Jꢀ15.9 Hz). 13C-NMR (CDCl3) d: 14.1,
22.7, 26.0, 28.7, 29.3—29.7 (29.28, 29.35, 29.53, 29.58, 29.65, 29.69), 31.9,
65.0, 114.6, 117.5, 118.4, 120.6, 130.1, 135.9, 144.7, 156.3, 167.6. MS (EI)
m/z: 416 (Mꢃ), 164. HR-MS (EI) m/z: 416.3287 (Calcd for C27H44O3:
416.3290.).
Icosyl p-Hydroxyphenylpropiolate:
2 (nꢀ20) mp 92—93 °C. IR
(Nujol) cmꢂ1: 3223, 2206, 1661, 1605. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ
6.9 Hz), 1.2—1.5 (34H, m), 1.73 (2H, quintet, Jꢀ6.9 Hz), 4.23 (2H, t, Jꢀ
6.9 Hz), 6.02 (1H, s), 6.84 (2H, d, Jꢀ6.9 Hz), 7.46 (2H, d, Jꢀ6.9 Hz). 13C-
NMR (CDCl3) d: 14.1, 22.7, 25.8, 28.5, 29.2—29.7 (29.21, 29.35, 29.48,
29.57, 29.69), 31.9, 66.4, 80.0, 87.5, 111.3, 115.9, 135.2, 155.0, 158.1. MS
(EI) m/z: 442 (Mꢃ), 164. HR-MS (EI) m/z: 442.3452 (Calcd for C29H46O3:
442.3447).
Octadecyl Cinnamate (9) mp 45—46 °C. IR (Nujol) cmꢂ1: 1713, 1639,
1580. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—1.5 (30H, m), 1.70
(2H, quintet, Jꢀ6.9 Hz), 4.20 (2H, t, Jꢀ6.9 Hz), 6.44 (1H, d, Jꢀ16.2 Hz),
7.36—7.39 (3H, m), 7.53 (2H, m), 7.68 (1H, d, Jꢀ16.2 Hz). 13C-NMR
(CDCl3) d: 14.1, 22.7, 26.0, 28.7, 29.3—29.7 (29.28, 29.35, 29.53, 29.58,
29.65, 29.69), 31.9, 64.7, 118.3, 128.0, 128.8, 130.2, 134.5, 144.5, 167.1.
MS (EI) m/z: 400 (Mꢃ), 148. HR-MS (EI) m/z: 400.3351 (Calcd for
C27H44O2: 400.3341).
Docosyl p-Hydroxyphenylpropiolate: 2 (nꢀ22) mp 95—96 °C. IR
(Nujol) cmꢂ1: 3223, 2206, 1661, 1605. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ
6.9 Hz), 1.2—1.5 (38H, m), 1.71 (2H, quintet, Jꢀ6.9 Hz), 4.22 (2H, t, Jꢀ
6.9 Hz), 6.03 (1H, s), 6.84 (2H, d, Jꢀ6.6 Hz), 7.46 (2H, d, Jꢀ6.6 Hz). 13C-
NMR (CDCl3 : DMSO-d6ꢀ10 : 1) d: 13.8, 22.4, 25.5, 28.2, 28.9, 29.0—29.4
(29.03, 29.18, 29.25, 29.37), 31.6, 65.7, 79.5, 87.5, 109.3, 115.8, 134.7,
154.3, 159.8. MS (EI) m/z: 470 (Mꢃ), 164. HR-MS (EI) m/z: 470.3761
(Calcd for C31H50O3: 470.3760).
Tetracosyl p-Hydroxyphenylpropiolate: 2 (nꢀ24) mp 98—99 °C. IR
(Nujol) cmꢂ1: 3223, 2208, 1661, 1605. 1H-NMR (CDCl3 : DMSO-d6ꢀ10 : 1)
d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—1.5 (42H, m), 1.70 (2H, quintet, Jꢀ6.9 Hz),
4.20 (2H, t, Jꢀ6.9 Hz), 6.83 (2H, d, Jꢀ6.9 Hz), 7.44 (2H, d, Jꢀ6.9 Hz), 9.38
(1H, s). 13C-NMR (CDCl3 : DMSO-d6ꢀ10 : 1) d: 14.0, 22.5, 25.7, 28.3,
29.1—29.5 (29.06, 29.18, 29.32, 29.40, 29.51), 31.7, 65.8, 79.6, 87.7, 109.6,
115.9, 134.9, 154.5, 159.8. MS (EI) m/z: 498 (Mꢃ), 164. HR-MS (EI) m/z:
498.4069 (Calcd for C33H54O3: 498.4073).
Icosyl p-Hydroxybenzoate (10) mp 70—72 °C. IR (Nujol) cmꢂ1: 3396,
1688, 1605, 1587. 1H-NMR (CDCl3) d: 0.88 (3H, t, Jꢀ6.9 Hz), 1.2—1.5
(34H, m), 1.75 (2H, quintet. Jꢀ6.9 Hz), 4.29 (2H, t, Jꢀ6.9 Hz), 6.48 (1H, s),
6.88 (2H, d, Jꢀ6.9 Hz), 7.95 (2H, d, Jꢀ6.9 Hz). 13C-NMR (CDCl3) d: 14.1,
22.7, 26.1, 28.7, 29.3—29.7 (29.29, 29.35, 29.53, 29.59, 29.65, 29.69), 31.9,
65.1, 115.2, 122.7, 131.9, 160.2, 167.0. MS (EI) m/z: 418 (Mꢃ), 138. HR-
MS (EI) m/z: 418.3448 (Calcd for C27H46O3: 418.3447).
N-Octadecyl-p-coumaramide (11) To a solution of p-coumaric acid
(394 mg, 2.4 mmol) in dichloromethane (10 ml) were added triethylamine
(0.67 ml, 4.8 mmol) and ethyl chloroformate (0.46 ml, 4.8 mmol) at 0 °C,