6438 J . Org. Chem., Vol. 66, No. 19, 2001
Gu et al.
points were measured on an Electrothermal Digital Melting
Point apparatus and are uncorrected. UV/Vis spectra (λmax in
nm (ꢀ))were measured on a Hitachi U-3000 spectrophotometer.
IR spectra (cm-1) were measured on an ATI Mattson Genesis
Series FTIR instrument. NMR spectra were recorded on a
Bruker AC 200 (200 MHz) or a Bruker AM 400 (400 MHz) with
solvent peaks as reference. FAB-mass spectra (m/z) were taken
on a ZA HF instrument with 4-nitrobenzyl alcohol as matrix.
MALDI-TOF mass spectra were taken on a on a Brucker
BIFLEX matrix-assisted laser desorption time-of-flight mass
spectrometer (MALD-TOF) equipped with the SCOUT High-
Resolution Optics with a X-Y multi-sample probe and a
gridless reflector, a saturated solution of 1,8,9-trihydroxyan-
thracene (dithranol Aldrich EC: 214-538-0) in CH2Cl2 was
used as a matrix. Elemental analysis were performed by the
analytical service at the Institut Charles Sadron (Strasbourg,
France).
Com p ou n d 6. I2 (313 mg, 1.23 mmol) was added in portions
to a mixture of CF3CO2Ag (272 mg, 1.23 mmol) and 5 (200
mg, 0.31 mmol) in refluxing CHCl3 (10 mL). The resulting
mixture was refluxed for 15 min, then cooled to room temper-
ature, filtered over Celite and evaporated to dryness. The
residue was taken up with AcOEt. The organic layer was
washed with an aqueous solution of Na2S2O5 and water (3x),
dried (MgSO4), filtered and evaporated. Recrystallization from
CHCl3/MeOH afforded 6 (320 mg, 91%) as colorless crystals
(mp 217 °C). 1H NMR (200 MHz, CDCl3): 7.00 (s, 8H), 4.28
(d, J ) 13.5 Hz, 4H), 3.85 (t, J ) 7.5 Hz, 8H), 3.05 (d, J ) 13.5
Hz, 4H), 1.84 (m, 8H), 1.40 (m, 8H), 0.98 (t, J ) 7 Hz, 12H).
13C NMR (50 MHz, CDCl3): 156.28, 137.00, 136.76, 86.06,
75.14, 31.98, 30.28, 19.19, 13.97.
Com p ou n d 7. A mixture of 6 (305 mg, 0.26 mmol),
4-methylstyrene (140 mg, 1.18 mmol), Pd(OAc)2 (3 mg), and
POT (7 mg) in xylene/Et3N 2:1 (15 mL) was stirred under Ar
at 130 °C for 48 h. After cooling, the resulting mixture was
filtered and evaporated. The brown residue was taken up in
CH2Cl2. The organic layer was washed with water, dried
(MgSO4), filtered and evaporated to dryness. Column chroma-
tography (SiO2, hexane/CH2Cl2 7:3) followed by recrystalliza-
tion from CHCl3/MeOH gave 7 (230 mg, 78%) as colorless
crystals (mp 97 °C). 1H NMR (200 MHz, CD2Cl2): 7.17 (d, J )
7 Hz, 8H), 6.95 (d, J ) 7 Hz, 8H), 6.85 (s, 8H), 6.74 (AB, J )
17 Hz, 8H), 4.48 (d, J ) 13 Hz, 4H), 3.94 (t, J ) 7.5 Hz, 8H),
3.21 (d, J ) 13 Hz, 4H), 2.32 (m, 12H), 1.94 (m, 8H), 1.48 (m,
8H), 1.01 (t, J ) 7 Hz, 12H). 13C NMR (50 MHz, CDCl3):
156.49, 136.32, 134.98, 134.87, 131.76, 129.07, 127.96, 126.68,
126.36, 126.07, 74.94, 32.26, 31.14, 21.16, 19.36, 14.06. FAB-
MS: 1112.8 (M+, calcd for C80H88O4: 1112.67).
Hz, 4H), 3.99 (t, J ) 6.5 Hz, 2H), 1.82 (m, 6H), 1.57-1.27 (m,
54H), 0.89 (t, J ) 6.5 Hz, 9H). 13C NMR (50 MHz, CDCl3):
191.43, 153.35, 143.51, 139.01, 135.12, 132.44, 131.70, 130.19,
126.69, 126.21, 105.55, 73.53, 69.17, 31.94, 30.36, 29.68, 29.43,
26.14, 22.70, 14.12. Anal. Calcd for C51H84O4 (761.23): C 80.47,
H 11.12. Found: C 80.68 H 11.29.
Com p ou n d 12. A mixture of 10 (1.50 g, 1.97 mmol), t-BuOK
(243 mg, 2.16 mmol) and methyltriphenylphosphonium bro-
mide (774 mg, 2.16 mmol) in dry THF (10 mL) was stirred at
room temperature for 1 h. A saturated aqueous NH4Cl solution
was then added and the resulting mixture was concentrated.
The aqueous layer was extracted twice with CH2Cl2. The
combined organic layers were washed with water, dried
(MgSO4), filtered and evaporated to dryness. Column chroma-
tography (SiO2, hexane/CH2Cl2 7:3) gave 12 (1.24 g, 83%) as a
pale yellow solid (mp 43 °C). 1H NMR (200 MHz, CDCl3): 7.44
(AB, J ) 7 Hz, 4H), 7.03 (AB, J ) 16 Hz, 2H), 6.73 (dd, J ) 17
and 11 Hz, 1H), 6.72 (s, 2H), 5.76 (dd, J ) 17 and 2 Hz, 1H),
5.25 (dd, J ) 11 and 2 Hz, 1H), 4.03 (t, J ) 6.5 Hz, 4H), 3.98
(t, J ) 6.5 Hz, 2H), 1.79 (m, 6H), 1.56-1.43 (m, 54H), 0.89 (t,
J ) 6.5 Hz, 9H).
Com p ou n d 14. A mixture of 13 (3.50 g, 3.69 mmol) and
CF3CO2H (35 mL) in CH2Cl2/H2O 2:1 (105 mL) was stirred at
room temperature for 5 h. The organic layer was then washed
with water (3x), dried (MgSO4), filtered and evaporated to
dryness. Recrystallization from CHCl3/MeOH gave 14 (3.10 g,
97%) as yellow crystals (mp 83 °C). 1H NMR (200 MHz,
CDCl3): 8.59 (s, 1H), 7.89 (d, J ) 7 Hz, 2H), 7.67 (d, J ) 7 Hz,
2H), 7.53 (s, 4H), 7.21 (AB, J ) 16 Hz, 2H), 7.01 (AB, J ) 16
Hz, 2H), 6.73 (s, 2H), 4.03 (t, J ) 6.5 Hz, 4H), 3.97 (t, J ) 6.5
Hz, 2H), 1.80 (m, 6H), 1.56-1.27 (m, 54H), 0.89 (t, J ) 6.5
Hz, 9H). 13C NMR (50 MHz, CDCl3): 191.51, 153.32, 143.42,
138.49, 137.68, 135.60, 135.25, 132.36, 131.73, 130.23, 129.41,
127.27, 126.99, 126.81, 105.24, 73.54, 69.16, 31.96, 30.37,
29.70, 29.46, 29.41, 26.15, 22.71, 14.14.
Com p ou n d 15. A mixture of 14 (3.07 g, 3.556 mmol),
t-BuOK (439 mg, 3.91 mmol) and methyltriphenylphospho-
nium bromide (1.397 g, 3.91 mmol) in dry THF (20 mL) was
stirred at room temperature for 1 h. A saturated aqueous NH4-
Cl solution was then added and the resulting mixture was con-
centrated. The aqueous layer was extracted twice with CH2Cl2.
The combined organic layers were washed with water, dried
(MgSO4), filtered and evaporated to dryness. Column chroma-
tography (SiO2, hexane/CH2Cl2 7:3) gave 15 (1.96 g, 64%) as a
1
yellow solid (mp 90 °C). H NMR (200 MHz, CDCl3): 7.50 (s,
4H), 7.45 (AB, J ) 7 Hz, 4H), 7.11 (s, 2H), 7.01 (AB, J ) 16
Hz, 2H), 6.75 (dd, J ) 17 and 11 Hz, 1H), 6.73 (s, 2H), 5.77
(dd, J ) 17 and 2 Hz, 1H), 5.26 (dd, J ) 11 and 2 Hz, 1H),
4.04 (t, J ) 6.5 Hz, 4H), 3.98 (t, J ) 6.5 Hz, 2H), 1.80 (m, 6H),
1.56-1.27 (m, 54H), 0.89 (t, J ) 6.5 Hz, 9H).
Com p ou n d 10. t-BuOK (2.28 g, 19.70 mmol) was added to
a solution of 8 (4.00 g, 5.45 mmol) and 9 (1.12 g, 5.45 mmol)
in dry DMF (30 mL) under argon at 80 °C. The mixture was
stirred for 1 h at 85 °C and, after cooling, it was poured into
an aqueous 0.5 M HCl solution (200 mL). The mixture was
extracted with CH2Cl2. The organic layer was washed with
water, dried (MgSO4) and evaporated to dryness. Column
chromatography (SiO2, CH2Cl2/hexane 1:1) gave 10 (2.56 g,
Com p ou n d 16. A mixture of 4-bromo-2,6-dimethylphenol
(1.00 g, 5 mmol), NaH (2.00 g, 50 mmol) and 1-bromobutane
(5.5 mL) in dry DMF (25 mL) was heated at 70 °C for 48 h.
After cooling, the resulting mixture was filtered and evapo-
rated to dryness. The brown residue was taken up in CH2Cl2.
The organic layer was washed with a saturated aqueous NaCl
solution, then with water, dried (MgSO4), filtered and evapo-
rated to dryness. Column chromatography (SiO2, hexane/CH2-
1
55%) as pale yellow crystals (mp 62 °C). H NMR (200 MHz,
CDCl3): 7.49 (s, 4H), 7.00 (s, 2H), 6.71 (s, 2H), 5.40 (s, 1H),
4.03 (t, J ) 6.5 Hz, 4H), 3.92 (t, J ) 6.5 Hz, 2H), 3.79 (d, J )
11 Hz, 2H), 3.67 (d, J ) 11 Hz, 2H), 1.81 (m, 6H), 1.56-1.27
(m, 57H), 0.88 (t, J ) 6.5 Hz, 9H), 0.81 (s, 3H). 13C NMR (50
MHz, CDCl3): 153.25, 138.27, 137.96; 137.54, 132.40, 129.18,
127.32, 126.44, 126.28, 105.12, 101.55, 73.50, 69.12, 31.93,
30.32, 30.24, 29.67, 29.40, 26.11, 23.05, 22.68, 21.88, 14.12.
Anal. Calcd for C56H94O5 (847.36): C 79.38, H 11.18. Found:
C 79.32 H 11.31.
Com p ou n d 11. A mixture of 10 (2.0 g, 2.36 mmol) and CF3-
CO2H (28 mL) in CH2Cl2/H2O 2:1 (75 mL) was stirred at room
temperature for 5 h. The organic layer was then washed with
water (3 x), dried (MgSO4), filtered and evaporated to dryness.
Column chromatography (SiO2, CH2Cl2/hexane 3:2) gave 8
(1.70 g, 94%) as a pale yellow solid (mp 49 °C). IR (CH2Cl2):
1700 (CdO). 1H NMR (200 MHz, CDCl3): 8.60 (s, 1H), 7.87
(d, J ) 7 Hz, 2H), 7.64 (d, J ) 7 Hz, 2H), 7.18 (d, J ) 16.0 Hz,
1H), 7.00 (d, J ) 16.0 Hz, 1H), 6.75 (s, 2H), 4.04 (t, J ) 6.5
1
Cl2 4:1) gave 16 (1.12 g, 87%) as a colorless oil. H NMR (200
MHz, CDCl3): 7.14 (s, 2H), 3.73 (t, J ) 6.5 Hz, 2H), 2.24 (s,
6H), 1.76 (m, 2H), 1.54 (m, 2H), 0.99 (t, J ) 7 Hz, 3H).
Com p ou n d 17. A mixture of 2,6-dimethylphenol (4.00 g,
32.6 mmol), NaH (3.00 g, 75 mmol) and 1-bromobutane (9 mL,
83 mmol) in dry DMF (60 mL) was heated at 70 °C for 48 h.
After cooling, the resulting mixture was filtered and evapo-
rated to dryness. The brown residue was taken up in CH2Cl2.
The organic layer was washed with a saturated aqueous NaCl
solution, then with water, dried (MgSO4), filtered and evapo-
rated to dryness. Column chromatography (SiO2, hexane/CH2-
1
Cl2 3:2) gave 17 (2.59 g, 44%) as a colorless oil. H NMR (200
MHz, CDCl3): 7.01 (B from AB2, J ) 7 Hz, 2H), 6.92 (A from
AB2, J ) 7 Hz, 1H), 3.77 (t, J ) 6.5 Hz, 2H), 2.29 (s, 6H), 1.80
(m, 2H), 1.55 (m, 2H), 1.00 (t, J ) 7 Hz, 3H).
Com p ou n d 18. I2 (1.84 g, 7.27 mmol) was added in portions
to a mixture of CF3CO2Ag (1.60 g, 7.27 mmol) and 17 (1.30 g,