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J Am Oil Chem Soc (2009) 86:1101–1114
CH–OH), and 3.66 (s, 3, OCH3); 13C NMR (CDCl3) d,
14.30 (C-18 and branched-chain CH3), 22.87, 23.38, 25.11
(C-3), 26.52, 27.73, 29.00, 29.28, 29.43, 29.53, 29.71,
29.81, 30.10, 30.32, 32.09, 34.17 (C-8), 34.27 (C-2), 43.78
(C-10), 51.62 (OCH3), 73.83 (C-9), 174.50 (C=O).
A total of 417 mg (51.8% yield) of products 3b and 4b
(either pure or as a mixture) was isolated.
isolated from the fractions richest in 4c (324 mg) was
rechromatographed on the column (6% ethyl acetate in
petroleum ether), affording 47.4 mg of pure 4c: mass
spectrum m/z (rel intensity) 241 (0.4), 188 (7), 187 (57),
156 (10), 155 (100), 115 (6), 111 (5), 109 (20), 97 (8), 95
(6), 87 (16), 85 (7), 83 (15), 81 (8), 74 (18), 71 (15), 69
1
(23), 67 (22), 57 (41), 55 (47), 43 (47), 41 (32); H NMR
Continued elution of the column with 8% ethyl acetate
in petroleum ether provided 77.4 mg diols 5a and 6a (Rf
0.28, SiO2, 10% ethyl acetate in petroleum ether): mass
spectrum m/z (rel intensity) 418 (1.2), 379 (4), 361 (1.2),
213 (0.1), 195 (6), 143 (33), 140 (111), 125 (13), 123 (10),
113 (12), 111 (17), 109 (13), 98 (15), 97 (31), 96 (13), 95
(20), 85 (41), 83 (53), 71 (30), 70 (28), 69 (100), 67 (22),
57 (90), 55 (87), 43 (50), 41 (48) 1H NMR (CDCl3) d, 0.88
(t, 3, CH3), 0.90 (t, 3, CH3), 0.91 (t, 6, 2 CH3), 1.27–1.32
[m, 38, –CH2–CH2–CH3 and –(CH2)n–] (1.38 and 1.43)
[m, 6, (–CH2–)3C–OH], 1.65 [m, 1, CHCH(OH)], 3.58 [m,
1,–CH(OH)-]; 13C NMR (CDCl3) d, 14.34 (4C), 23.66,
25.90 (2C), 26.62, 27.75, 29.00, 29.51, 29.84 (2C), 29.97,
30.11, 30.33, 30.41, 30.51, 32.10, 34.17, 39.18 (2C), 39.49,
43.74, 73.86, 74.62. The 13C NMR assignments are pro-
vided pictorially in Fig. 1.
(CDCl3) d 0.88 (t, 6, main-chain and branched-chain CH3),
1.17–1.50 (m, 37, 18 CH2 and CH2CHOHCH-n-Hexyl),
1.62 (pentet, 2, CH2–CH2CO2CH3), 2.31 (t, 2, CH2CO2
CH3), 3.59 (m, 1, CH–OH), and 3.67 (s, 3, OCH3); 13C
NMR (CDCl3) d, 14.33 (C-18 and branched-chain CH3),
22.90, 25.12 (C-3), 26.54, 27.74, 27.82, 29.23, 29.30,
29.46, 29.56, 29.73, 29.83, 29.96, 30.03, 30.34, 30.38,
32.07, 32.11, 34.14 (C-8), 34.29 (C-2), 43.79 (C-10), 51.67
(OCH3), 73.82 (C-9), 174.54 (C=O).
A total of 385 mg (41.3% yield) of products 3c and 4c
(either pure or as a mixture) was isolated.
Synthesis of Methyl
9-Phenyl-10-Hydroxyoctadecanoate 3d and Methyl
9-Hydroxy-10-Phenyloctadecanoate 4d. Isolation
of the Diols 5b and 6b (Fig. 1)
Synthesis of Methyl
Reaction of 2 (2.36 g, 7.55 mmol) with 10.35 mmol lith-
ium diphenylcuprate, afforded 3.68 g crude product as a
colorless liquid (theoretical yield: 2.95 g). A 2.01 g sample
was placed upon a column containing 100 g silica gel and
was eluted (flash chromatography) with 10% ethyl acetate
in petroleum ether (20-ml fractions). Fractions containing
only the least polar isomer (Rf 0.24, SiO2, 10% ethyl
acetate in petroleum ether) gave 169 mg 3d: mass spec-
trum m/z (rel intensity) 249 (3), 248 (17), 217 (9), 216 (46),
143 (2), 125 (11), 117 (23), 112 (20), 105 (27), 104 (36), 98
(24), 92 (55), 91 (100), 87 (25), 74 (56), 69 (26), 57 (20),
9-n-Hexyl-10-Hydroxyoctadecanoate 3c and Methyl
9-Hydroxy-10-n-Hexyloctadecanoate 4c
The reaction of 2 (2.05 g, 6.56 mmol) with 9.08 mmol
lithium di-n-hexylcuprate, afforded 2.80 g crude product as
a colorless liquid (theoretical yield: 2.61 g). A 1.03 g
sample was placed upon a column containing 100 g silica
gel and was eluted (flash chromatography) with 10% ethyl
acetate in petroleum ether (20-ml fractions). Fractions
containing only the least polar isomer (Rf 0.40, SiO2, 10%
ethyl acetate in petroleum ether) yielded 64.5 mg 3c: mass
spectrum m/z (rel intensity) 285 (2), 257 (25), 256 (33), 241
(0.2), 213 (14), 199 (10), 185 (7), 171 (8), 157 (16), 143
(37), 129 (12), 111 (14), 101 (17), 98 (13), 97 (24), 87 (91),
83 (49), 81 (20), 75 (19), 74 (93), 69 (91), 67 (23), 57 (67),
1
55 (51), 43 (31), 41 (37); H NMR (CDCl3) d 0.87 (t, 3,
CH3), 1.10–1.75 (m, 26, 13 CH2), 2.30 (t, 2, CH2CO2CH3),
2.55 (m, 1, (CH2CHOHCHPh), 3.66 (s, 3, OCH3), 3.70 (m,
1, CH–OH), 7.18–7.28 (m, 3, p aromatic H and o aromatic
H) and 7.31 (m, 2, m aromatic H); 13C NMR (CDCl3) d,
14.29 (C-18), 22.84, 25.03 (C-3), 26.02, 27.69, 29.22,
29.45, 29.61, 29.68, 29.77, 29.87, 32.03, 32.21, 34.21 (C-
2), 35.31 (C-11), 51.60 (OCH3), 52.19 (C-9), 75.13 (C-10),
126.72 (p aromatic C) 128.55 (o aromatic C), 129.12 (m
aromatic C), 141.70 (quaternary phenyl C), 174.47 (C=O).
Continued elution with 10% ethyl acetate in petroleum
ether did not provide any fractions containing only 4d (Rf
0.19, SiO2, 10% ethyl acetate in petroleum ether) but
provided 77.4 mg diols 5b and 6b (Rf 0.11): mass spectrum
m/z (rel intensity) 478 (3), 293 (2), 292 (2), 264 (2), 233
(0.7), 220 (3), 219 (2), 206 (9), 205 (26), 204 (12), 193
(15), 180 (12), 178 (8), 167 (16), 165 (7), 143 (2), 129 (7),
117 (13), 115 (34), 105 (20), 104 (8), 92 (58), 91 (100), 78
1
55 (100), 43 (82), 41 (65); H NMR (CDCl3) d 0.88 (t, 6,
main-chain and branched-chain CH3), 1.10–1.50 (m, 37, 18
CH2 and CH2CHOHCH-n-Hexyl), 1.62 (pentet, 2, CH2–
CH2CO2CH3), 2.30 (t, 2, CH2CO2CH3), 3.59 (m, 1, CH–
OH), and 3.67 (s, 3, OCH3); 13C NMR (CDCl3) d, 14.31
(C-18 and branched-chain CH3), 22.88, 25.12 (C-3), 26.60,
27.65, 27.81, 29.28, 29.32, 29.42, 29.50, 29.81, 29.95,
30.01, 30.09, 30.33 (2C), 32.06 (2C), 34.13 (C-11), 34.28
(C-2), 43.73 (C-9), 51.65 (OCH3), 73.79 (C-10), 174.55
(C=O).
Continued elution with 8% ethyl acetate in petroleum
ether did not provide any fractions containing only 4c (Rf
0.35, SiO2, 10% ethyl acetate in petroleum ether). Material
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