5
0
N.M. Carballeira et al. / Chemistry and Physics of Lipids 136 (2005) 47–54
(
(
(
(
5
1
6), 89 (1), 87 (2), 86 (3), 85 (50), 84 (5), 83 (21), 82
5), 81 (2), 77 (1), 75 (8), 74 (10), 73 (2), 72 (3), 71
53), 70 (9), 69 (16), 68 (4), 67 (3), 62 (1), 61 (17), 60
3), 59 (1), 58 (8), 57 (100), 56 (14), 55 (34), 54 (3),
3 (3); analysis calculated for C13H28O3: C, 67.20; H,
2.14; found: C, 67.01; H, 12.45.
dimethylsilanyloxy)-3-decyloxypropan-2-ol (0.16 g,
0.46 mmol), the reaction was stirred for 5 min, then
methyl iodide (0.04 ml, 0.65 mmol) was added drop-
wise. The reaction was stirred at room temperature
for 2 h. The reaction mixture was extracted with ether
(2 × 25 ml) and dried over Na2SO4, which after evap-
oration in vacuo afforded 0.12 g (70% yield) of tert-
butyl-(3-decyloxy-2-methoxypropoxy)dimethylsilane
2
.4. 1-(tert-Butyldimethylsilanyloxy)-3-
decyloxypropan-2-ol (5a)
(6a) as a colorless oil after purification using silica gel
column chromatography and eluting with hexane/ether
To a solution of 3-decyloxypropane-1,2-diol
0.41 g, 1.7 mmol), dibutyltin oxide (0.44 g,
.7 mmol) and triethylamine (0.3 ml, 2.1 mmol)
in dichloromethane (20 ml) was added dropwise
tert-butyldimethylsilyl chloride (0.26 g, 1.7 mmol) in
dichloromethane. The reaction mixture was stirred
at room temperature for 90 min, extracted with ether
1
(9:1); H NMR (CDCl3, 500 MHz) δ: 3.68 (2H, m),
(
1
3
.53 (1H, dd, J = 10.2 Hz, J = 4.0 Hz), 3.46 (3H, s,
OCH3), 3.45 (2H, m), 3.37 (2H, m, OCH2 ),
.55 (2H, m), 1.25 (14H, brs, CH2 ), 0.85 (9H, s,
1
C(CH3)3), 0.83 (3H, t, J = 6.9 Hz, CH3), 0.07 (6H,
s CH3–Si); 13C NMR (CDCl3, 125 MHz) δ: 81.0 (d,
C-2), 71.7 (t), 70.1 (t), 62.4 (t, C-1), 58.1 (q, OCH3),
(
2 × 25 ml), dried over Na2SO4 and the solvent
31.9 (t), 29.62 (t), 29.60 (t), 29.56 (t), 29.3 (t), 26.1
was evaporated in vacuo. The crude product was
purified using silica gel column chromatography
and eluting with hexane/ether (9:1), affording 0.46 g
(
(
(
(
(
(
(
t), 25.9 (t), 25.9 (q), 22.7 (t), 18.3 (s), 14.1 (q), −5.4
q, CH3–Si), −5.5 (q, CH3–Si); GC–MS (70 eV) m/z
+
relative intensity) 360 (M ,1), 305 (1), 304 (3), 303
(
75% yield) of 1-(tert-butyldimethylsilanyloxy)-3-
13), 273 (1), 272 (3), 271 (12), 243 (1), 215 (1), 197
1), 189 (1), 173 (1), 171 (1), 165 (1), 164 (2), 163
13), 149 (1), 148 (3), 147 (26), 145 (5), 141 (1), 134
1), 133 (7), 132 (11), 131 (100), 129 (4), 121 (1),
1
decyloxypropan-2-ol (5a) as a colorless oil. H NMR
CDCl3, 300 MHz) δ: 3.80 (1H, m, H-2), 3.63 (2H, m),
(
3
.48–3.43 (4H, m, OCH2 ), 2.47 (1H, d, J = 5.0 Hz,
OH), 1.60 (2H, m), 1.25 (14H, brs, CH2 ), 0.85
9H, s, C(CH3)3), 0.83 (3H, t, J = 6.9 Hz, CH3), 0.07
6H, s CH3–Si); 13C NMR (CDCl3, 75 MHz) δ: 71.6
d, C-2), 71.4 (t), 70.6 (t), 64.0 (t, C-1), 31.9 (t), 29.63
t), 29.56 (t), 29.5 (t), 29.3 (t), 26.4 (t), 26.1 (t), 25.9
1
1
1
8
7
20 (3), 119 (32), 118 (2), 117 (15), 116 (2), 115 (5),
09 (1), 107 (1), 105 (5), 103 (1), 102 (1), 101 (9),
00 (1), 99 (7), 97 (3), 95 (2), 91 (7), 90 (5), 89 (65),
7 (1), 86 (2), 85 (35), 83 (7), 81 (2), 77 (2), 76 (1),
5 (19), 74 (4), 73 (31), 72 (3), 71 (38), 70 (2), 69
(
(
(
(
(
q), 22.6 (t), 18.3 (s), 14.1 (q, CH3), −5.4 (q, CH3–Si);
(
(
9), 68 (1), 67 (2), 61 (2), 60 (1), 59 (12), 58 (10), 57
77), 56 (6), 55 (19), 54 (1); analysis calculated for
+
GC–MS (70 eV) m/z (relative intensity) 346 (M , 1),
2
(
(
90 (1), 271 (1), 289 (5), 231 (1), 207 (1), 175 (3), 173
1), 159 (1), 151 (1), 150 (2), 149 (14), 135 (1), 134
2), 133 (21), 132 (11), 131 (100), 129 (1), 119 (3),
C20H44SiO3–C H14Si: C, 68.25; H, 12.27; found: C,
6
68.47; H, 12.60.
1
1
9
8
7
6
5
6
18 (1), 117 (10), 116 (1), 115 (4), 107 (1), 106 (1),
05 (15), 104 (1), 103 (6), 102 (1), 101 (12), 99 (3),
7 (2), 91 (1), 90 (1), 89 (8), 88 (1), 86 (1), 85 (18),
4 (1), 83 (4), 81 (1), 77 (4), 76 (2), 75 (30), 74 (2),
3 (19), 72 (1), 71 (19), 70 (2), 69 (6), 68 (1), 67 (1),
1 (1), 60 (1), 59 (6), 58 (4), 57 (41), 56 (5), 55 (13),
4 (1), 53 (1); analysis calculated for C19H42SiO3: C,
5.84; H, 12.21; found: C, 65.75; H, 12.46.
2
.6. 3-Decyloxy-2-methoxypropan-1-ol (7a)
To
a
solution of tert-butyl-(3-decyloxy-2-
methoxypropoxy)dimethylsilane (0.11 g, 0.31 mmol)
in THF (10 ml) at 0 C under argon was added
◦
tetrabutylammonium fluoride (0.09 ml, 0.31 mmol).
The reaction was stirred for 24 h and extracted with
ether (2 × 25 ml), dried over Na2SO4 and the solvent
evaporated in vacuo. The crude product was purified
using silica gel column chromatography and eluting
with hexane/ether (9:1) followed by ether to obtain
the 3-decyloxy-2-methoxypropan-1-ol (7a) (0.06 g,
74% yield) as a colorless oil. IR (neat) νmax 3430,
2
.5. tert-Butyl-(3-decyloxy-2-
methoxypropoxy)dimethylsilane (6a)
To a solution of NaH (0.02 g, 0.83 mmol) in
◦
THF at 0 C under argon was added 1-(tert-butyl-