1232
M. C. Murguía, R. J. Grau
LETTER
putification was performed by column chromatography on
silica gel with acetone hexane (30:70) as eluent. It afforded
1.138 g of 3 (81% yield). Syrup. IR (cm-1) 1100, 1460.0,
2980.0; 1H NMR (200 MHz), CDCl3 1.44-1.51 (m, 10H),
2.45-2.60 (m, 4H), 2.96 (m, 2H), 3.46-3.64 (m, 4H), 3.80 (s,
4H), 4.13 (m, 2H), 4.23 (m, 2H); 13C NMR CDCl3 22.00,
24.26, 33.22, 41.58, 44.73, 63.19, 86.08, 99.28; MS, m/e (rel.
intensity) 328 (M+,3), 299 (4), 285 (12), 113 (10), 83 (42), 55
(95), 31 (100).
removed by Kugelrohr distillation. Column chromatography
on silica gel with acetone hexane (10:30) afforded 837.3 mg
of 8 (74% yield). Syrup. IR (cm-1) 1091.0, 1460.0, 2875.0,
3500.0; 1H NMR (200 MHz), CDCl3 0.80-0.87 (m, 12H),
1.16-1.37 (m, 56H), 1.55-1.69 (m, 8H), 2.78 (m, 8H), 3.28-
3.53 (m, 24H), 3.71-3.79 (m, 8H); 13C NMR CDCl3 14.01,
22.80, 25.95, 28.93, 29.23, 29.55, 29.60, 29.90, 32.20, 40.97,
63.76, 70.11, 71.14, 72.71, 73.77.
(14) Chlorosulfonic acid (6 mmol) in CH2Cl2 (2.5 mL) was
dropped into a stirred solution of 4, 5 or 8 (0.6 mmol) in
CH2Cl2 (4 mL) below 0 °C. The reaction was kept for 4 hours
at 0 °C. Alcoholic sodium hydroxide solution was then added
until pH 10 was achieved. After evaporation and extraction
with n-BuOH (3 45 mL) water (100 mL) solvent system,
the combined organic extracts were evaporated. The residue
was dissolved in CH2Cl2. and dried over MgSO4. Evaporation
of the filtrate followed by column chromatography on silica
gel with CH2Cl2 EtOH (10:1) solvent system afforded 9, 10
and 11 in 72%, 71% and 70% yields, respectively, as white
waxy products.
(9) Kida, T.; Yokota, M.; Masuyama, A.; Nakatsuji, Y.; Okahara,
M. Synthesis 1993, 5, 487.
(10) Zhu, Y.-P.; Masuyama, A.; Kirito, Y.; Okahara, M.; Rosen,
M. J. JAOCS 1992, 69, 7, 626.
(11) A stirred alkoxide solution of metallic potassium (6 mmol)
and n-decanol (48 mmol) was heated at 60 °C, and compound
3 (2.45 mmol) was dropped slowly. The reaction was kept for
16 hours at 80 °C. After cooling, the reaction mixture was
neutralized with 10% ClH, and extracted with CH2Cl2 (3 50
mL):water (50 mL). The organic layer was dried over MgSO4,
and the n-decanol removed by Kugelrohr distillation. Column
chromatography on silica gel with acetone hexane (30:10) as
eluent afforded 4 in good yield (72%). Syrup; IR (cm-1)
1100.0, 2980.0, 3500.0; 1H NMR (200 MHz), CDCl3 0.86 (t,
6H), 1.25-1.76 (m, 40H), 3.40-3.71 (m, 20H), 3.90 (s, 4H),
3.93 (m, 2H); 13C NMR CDCl3 14.07, 22.50, 22.64, 25.60,
26.06, 29.29, 29.46, 29.59, 31.85, 32.53, 39.29, 61.96, 69.37,
71.04, 71.69, 71.77, 72.82, 98.29.
9: IR (cm-1) 1045.0, 1225.0, 2920.0, 3382.9; 1H NMR (200
MHz), D2O 0.80-0.87 (m, 6H), 1.13-1.35 (m, 20H), 1.37-
1.61 (m, 16H), 3.32-3.39 (m, 4H), 3.53-3.73 (m, 8H), 3.78-
3.89 (m, 12H), 4.13 (m, 2H), 4.23 (m, 2H); 13C NMR D2O
14.05, 22.00, 22.80, 24.26, 25.95, 28.93, 29.23, 29.60, 29.90,
32.20, 34.22, 41.11, 63.07, 63.16, 69.56, 71.14, 71.44, 72.50,
98.28.
(12) A stirred solution of 4 (0.78 mmol) in a solution of acetic acid
(4 mL) and water (1.0 mL) was stirred at 60 °C for 4 hours.
The mixture was quenched with cold aqueous sodium
bicarbonate (75 mL). After dissolution of the mixture with
saturated brine (50 mL), the product was isolated by extraction
with dichloromethane (3 50 mL). The organic layer was
dried over MgSO4, and the residue was distilled. Column
chromatography on silica gel with petroleum ether EtAc
(50:50) gave 5 as a syrup, quantitatively. Syrup. IR (cm-1)
1090.0, 1460.0, 2876.0, 3500.0; 1H NMR (200 MHz), CDCl3
0.80-0.87 (m, 6H), 1.19-1.37 (m, 26H), 1.55-1.69 (m, 8H),
2.86 (m, 4H), 3.29-3-53 (m, 8H), 3.71-3.79 (m, 4H), 4.18 (s,
4H), 4.42 (s, 4H); 13C NMR CDCl3 14.00, 22.80, 25.95,
28.93, 29.23, 29.55, 29.60, 29.90, 32.20, 42.24, 62.74, 64.09,
70.11, 71.14, 72.71, 73.77.
(13) A stirred alkoxide solution of metallic potassium (2 mmol)
and n-decanol (96 mmol) was heated at 60 °C, and compound
6 (1.14 mmol) was dropped slowly. The reaction was kept for
24 hours at 80 °C. After completion and cooling the reaction
mixture was neutralized with 10% HCl and extracted with
CH2Cl2 (3 150 mL) water (150 mL) solvent system. The
organic layer was dried over MgSO4 and the n-decanol
10: IR (cm-1) 1046.0, 1230.0, 2920.0, 3380.0; 1H NMR (200
MHz), D2O 0.80-0.87 (m, 6H), 1.16-1.35 (m, 20H), 1.43-
1.57 (m, 6H), 3.32-3.39 (m, 12H), 3.53-3.73 (m, 8H), 3.81-
3.89 (m, 4H), 4.18 (s, 4H); 13C NMR D2O 14.00, 22.80,
25.95, 28.93, 29.23, 29.55, 29.60, 29.90, 32.20, 41.60, 62.76,
63.61, 69.56, 71.14, 71.44, 72.50.
11: IR (cm-1) 1041.0, 1222.0, 2919.0, 3383.0; 1H NMR (200
MHz), D2O 0.80-0.87 (m, 12H), 1.09-1.57 (m, 50H), 3.32-
3.38 (m, 8H), 3.57-3.99 (m, 34H), 4.18 (s, 8H); 13C NMR D2O
14.05, 22.80, 25.95, 28.93, 29.23, 29.55, 29.60, 29.90,
32.20, 40.97, 63.76, 69.44, 69.56, 71.14, 71.44, 72.50.
(15) (a) Zhu, Y.-P.; Masuyama, A.;Kobata, Y.; Nakatsuji, Y.;
Okahara, M.; Rosen, M. J. J. Colloid Interface Sci. 1993, 158,
40. (b) Zhu, Y.-P.; Masuyama, A.; Hirito, Y.; Okahara, M.;
Rosen, M. J. JAOCS 1992, 69, 7, 626. (c) Zhu, Y.-P.;
Masuyama, A.; Hirito, Y.; Okahara, M. JAOCS 1991, 68, 7,
539.
Article Identifier:
1437-2096,E;2001,0,08,1229,1232,ftx,en;S02001ST.pdf
Synlett 2001, No. 8, 1229–1232 ISSN 0936-5214 © Thieme Stuttgart · New York