SYNTHESIS
November 1998
1621
Chloride (6):
3.50 (t, 2 H, J = 7 Hz, CH2OH), 2.40 (t, 2 H, J = 7.5 Hz, ArCH2), 1.16–
1.60 (m, 13 H), 1.00 [s, 18 H, SiC(CH3)3], 0.16 [s, 12 H, Si(CH3)2].
IR (film): ν = 3350 (br), 2950, 2930, 2860, 1590, 1470, 1250, 1160,
1020, 830, 770 cm–1.
A mixture of 5 (90 mg, 0.23 mmol) and PPh3 (65 mg, 0.25 mmol) was
heated to melting state and then to 100°C for 5 h. The mixture was
cooled to r.t. and washed with Et2O (5 mL) to give salt 6 (130 mg,
86%); mp 229–233°C.
MS: m/z = 409, 352, 311, 239.
1H NMR (100 MHz, TFA): δ = 7.51 [m, 15 H, P(C6H5)3], 6.48 (s, 1
H, ArH), 6.18 (s, 2 H, ArH), 4.36 (s, 1 H, ArCHPPh3Cl), 4.22 (s, 1 H,
ArCHPPh3Cl), 0.8 [s, 18 H, 2 SiC(CH3)3], 0.0 [s, 12 H, 2 Si(CH3)2].
IR (film): ν = 3400 (br), 3100, 2950, 2930, 2860, 2760, 1590, 1470,
1460, 1450, 1440, 1335, 1250, 1160, 1025, 830, 770 cm–1.
MS: m/z = 613, 612, 555.
Anal. Calcd. for C26H50O3Si2: C, 66.89; H, 10.80. Found: C, 66.73;
H, 10.58
8-(3,5-Bis(tert-butyldimethylsilyloxy)phenyl)octan-1-al (12):
To a mixture of PCC (57 mg, 0.28 mmol) in CH2Cl2 (1 mL) was add-
ed 11 (80 mg, 0.17 mmol) in CH2Cl2 (1 mL) at r.t. The mixture was
stirred for 2 h, then diluted with a solution of hexane/Et2O (2:1) and
filtered through a silica gel column, and concentrated. The residue
was chromatographed (hexane/Et2O, 4:1) to give the aldehyde 12 as
an oil (70 mg, 80%).
Anal. Calcd. for C37H50ClO2PSi2: C, 68.43; H, 7.76. Found: C, 68.50
H, 7.81
7-(1-Ethoxyethoxy)heptanal (9):
To a solution of 7 (100 mg, 0.55 mmol) and TsOH (10 mg) in CH2Cl2
(2 mL) was added ethyl vinyl ether (42 mg, 0.58 mmol) at 0°C. The
mixture was stirred for 10 min, diluted with Et2O (20 mL) and then
washed with 5% aq NaHCO3 solution to pH 8. The organic layer was
dried (Na2SO4) and concentrated. The residue was chromatographed
(hexane/Et2O, 20:1) to give 1-bromo-7-(ethoxyethyl)heptane (8) as
an oil (140 mg, 95%).
1H NMR (100 MHz, CCl4): δ = 9.60 (s, 1 H, CHO), 6.06 (s, 2 H,
ArH), 5.92 (s, 1 H, ArH), 2.34 (m, 4 H), 1.20–1.60 (m, 10 H), 0.92 [s,
18 H, SiC(CH3)3], 0.12 [s, 12 H, Si(CH3)2].
IR (film): ν = 2950, 2930, 2860, 1730, 1590, 1470, 1250, 1165, 830,
770 cm–1.
MS: m/z = 464 (M+), 449, 435, 407, 379, 365, 351.
Anal. Calcd. for C26H48O3Si2: C, 67.18; H, 10.41. Found: C, 67.03;
H, 10.40
1H NMR (100 MHz, CCl4): δ = 4.48 (q, 1 H, J = 6 Hz, OCH), 3.25
(m, 6 H, BrCH2, OCH2, OCH2), 1.72 (m, 2 H), 1.38 (m, 6 H), 1.02–
1.20 (m, 8 H).
(Z)-5-(8'-Tridecenyl)resorcinol Disilyl Ether (13):
To a solution of C5H11P+Ph3Br– (80 mg, 0.19 mmol) in THF (1 mL)
was added BuLi (0.14 mL, 1.39 M, 0.19 mmol) at –20°C. The mix-
ture was stirred for 2 h and then cooled to –70°C. To this solution was
added aldehyde 12 (70 mg, 0.15 mmol) in THF (1 mL) at –70°C. The
mixture was stirred at –70°C for 2 h and diluted with Et2O. The Et2O
layer was washed with H2O and brine. The organic layer was dried
(Na2SO4) and concentrated. The residue was chromatographed on
AgNO3/SiO2 (hexane/Et2O, 20:1) to give Z-13 (47 mg, 60%) and E-
13 (8 mg, 10%).
A solution of 8 (267 mg, 1 mmol) and NaHCO3 (100 mg, 1 mmol) in
DMSO (5 mL) was heated at 120°C for 3 h. To this mixture was add-
ed NaI (15 mg) and ether (10 mL) at r.t. The mixture was washed with
a solution of hexane/Et2O (1:1, 30mL). The organic layer was dried
(Na2SO4) and concentrated. The residue was chromatographed (hex-
ane/Et2O, 2:1) to give aldehyde 9 as an oil (100 mg, 50%).
1H NMR (100 MHz, CCl4): δ = 9.64 (s, 1 H, CHO), 4.50 (q, 1 H, J =
6 Hz, OCH), 3.10–3.54 (m, 4 H, 2 OCH2), 2.30 (t, 2 H, J = 7 Hz,
CH2CHO), 1.36 (m, 6 H), 1.02–1.18 (m, 8 H).
IR (film): ν = 2950, 1720, 1250, 1025 cm–1.
1H NMR (100 MHz, CCl4): δ = 6.00 (2 H, s, ArH), 5.84 (1 H, s, ArH),
5.21 (2 H, t, J = 5 Hz, CH=CH), 2.26 (2 H, t, J = 7.5 Hz, ArCH2), 1.80
(4 H, m, CH2C=CCH2), 1.10–1.17 [17 H, m, (CH2)7, CH3] 0.80 [18
H, s, SiC(CH3)3], 0.00 [12 H, s, Si(CH3)2].
MS: m/z = 202 (M+), 173, 156, 109.
Anal. Calcd. for C11H22O3: C, 65.31; H, 10.96. Found: C, 65.12 H,
10.79
IR (film): ν = 2960, 2930, 2860, 1590, 1475, 1465,1450, 1260, 1250,
1-[3,5-Bis(tert-butyldimethylsilyloxy)phenyl]-8-(1-ethoxy-
ethoxy)oct-1-ene (10):
1165, 835, 770 cm–1.
MS: m/z = 518 (M+), 461, 447, 433,419, 405, 391, 377.
Anal. Calcd. for C31H58O2Si2: C, 71.75; H, 11.26. Found: C, 71.89;
H, 11.40
To a suspension of 6 (2.5 g, 4.47 mmol) in THF (8 mL) was added
BuLi (3.4 mL, 1.39 M, 4.73 mmol) at r.t. The mixture was stirred for
75 min and then cooled to –70°C. To this solution was added alde-
hyde 9 (880 mg, 4.36 mmol) in THF (3 mL) at that temperature and
then the mixture was stirred overnight at r.t. The solution was diluted
with Et2O (200 mL), washed with H2O, brine, dried (Na2SO4) and
evaporated. The residue was chromatographed (hexane/Et2O, 12.5:1)
to give the olefin triether 10 as an oil (1 g, 43%).
(Z)-5-(8'-Tridecenyl)resorcinol (1):
To a solution of 13 (130 mg, 0.25 mmol) in THF (1 mL) was added
Bu4NF (250 mg, 0.79 mmol) in THF (1 mL) at r.t. The mixture was
stirred for 0.5 h and concentrated. The residue was chromatographed
(benzene/EtOAc, 15:1) to give 1 as an oil (73 mg, ≈100%).
1H NMR (100 MHz, CCl4): δ = 6.08 (br, 1 H, OH), 6.08 (s, 2 H, ArH),
6.00 (s, 1 H, ArH), 5.21 (t, 2 H, J = 5 Hz, CH=CH) 2.06 (t, 2 H,
ArCH2), 1.90 (m, 4 H, CH2C=CCH2), 1.20 [m, 14 H, (CH2)7] 0.82 (t,
3 H, J = 7 Hz, CH3).
1H NMR (100 MHz, CCl4): δ = 6.00–6.20 (m, 5 H, ArH, CH=CH),
4.48 (q, 1 H, J = 6 Hz, OCH), 3.20–3.40 (m, 4 H, 2 OCH2), 2.10 (m,
2 H), 1.00–1.40 (m, 14 H) 0.94 [s, 18 H, 2 SiC(CH3)3], 0.12 [s, 12 H,
Si(CH3)2].
IR (film): ν = 2950, 2930, 2860, 1590, 1470, 1250, 1060, 1030, 830,
770 cm–1.
1H NMR (400 MHz, CDCl3): δ = 6.23 (d, 2 H, J = 2 Hz, ArH), 6.16
(s, 1 H, ArH), 5.68 (br, 1 H, OH), 5.35 (m, 2 H, J = 5, 10Hz, CH=CH),
2.44 (t, 2 H, J = 7.5 Hz, ArCH2), 1.98(m, 4 H, CH2C=CCH2), 1.30 (m,
14 H, (CH2)7], 0.88 (t, 3 H, J = 7 Hz, CH3).
MS: m/z = 537 (M++1), 536 (M+), 522, 507, 490, 464, 448, 443, 407,
389, 377, 366, 352.
Anal. Calcd. for C30H56O4Si2: C, 67.11; H, 10.51. Found: C, 67.12;
H, 10.60
IR (film): ν = 3350 (br), 2950, 2930, 2860, 1630, 1600, 1470, 1340,
1305, 1260, 1155, 1000, 840, 790, 700 cm–1.
UV (MeOH): λmax = 208, 275, 280 nm.
8-(3,5-Bis(tert-butyldimethylsilyloxy)phenyl)octan-1-ol (11)
A solution of 10 (60 mg, 0.11 mmol) and Pd/C (70 mg, 5%) in EtOH
(2 mL) was hydrogenated for 16 h under 1 atm at r.t. The mixture was
filtered and the filtrate concentrated. The residue was chromato-
graphed (hexane/Et2O, 2:1) to give the disilyl ether alcohol 11 as an
oil (40 mg, 77%).
MS: m/z = 290 (M+), 247, 233, 208, 205, 194, 191, 177, 163, 149, 137,
124 (100), 111.
Anal. Calcd. for C19H30O2: C, 78.57; H, 10.41. Found: C, 78.50; H,
10.41
Dodec-7-yn-1-ol (18):
1H NMR (100 MHz, CCl4): δ = 6.12 (s, 2 H, ArH), 6.00 (s, 1 H, ArH),
To a solution of Fe(NO3)3 (200 mg, 0.83 mmol) in liquid NH3