Fullerene-OligophenyleneVinylene Hybrids
J. Am. Chem. Soc., Vol. 122, No. 31, 2000 7477
degassed solution of 4 (13.3 g, 49 mmol) in dry THF (130 mL) at -78
°C under Ar. After 30 min at -78 °C, the solution was allowed to
warm to 0 °C (over 1 h) and cooled again to -78 °C. Dry DMF (7.6
mL, 98 mmol) was then added and the resulting mixture allowed to
warm to 0 °C (over 1 h). An aqueous 1 M HCl solution (60 mL) was
added and the mixture was concentrated. The aqueous layer was
extracted twice with CH2Cl2. The combined organic layers were washed
with water, dried (MgSO4), and evaporated to dryness. Column
chromatography (SiO2, hexane/CH2Cl2 7:3) gave 5 (10.5 g, 98%) as
(30 mL) under argon at 80 °C. The mixture was stirred for 1 h at 80
°C and, after cooling, it was poured into an aqueous 0.5 M HCl solution
(500 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 3PV (14.55
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g, 91%) as yellow crystals (mp 82 °C). H NMR (200 MHz, CDCl3):
7.51 (m, 8 H), 7.12 (s, 2 H), 7.06 (s, 2 H), 6.66 (d, J ) 2 Hz, 2 H),
6.39 (t, J ) 2 Hz, 1 H), 5.41 (s, 1 H), 3.98 (t, J ) 6.5 Hz, 4 H), 3.70
(AB, J ) 10.5 Hz, 4 H), 1.79-1.76 (m, 4 H), 1.43-1.27 (m, 39 H),
0.90 (t, J ) 6.5 Hz, 6 H), 0.82 (s, 3 H). 13C NMR (50 MHz, CDCl3):
160.43, 139.08, 137.75, 136.54, 129.31, 128.64, 128.48, 128.13, 127.23,
126.79, 126.43, 126.21, 105.01, 101.44, 100.88, 77.57, 67.96, 31.88,
30.14, 29.58, 29.37, 29.31, 29.26, 26.02, 22.99, 22.64, 21.81, 14.09.
UV-vis (CH2Cl2): see Table 2. Anal. Calcd for C52H76O4 (765.2): C
81.62, H 10.01. Found: C 81.51, H 10.01.
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colorless crystals (mp 65 °C). H NMR (200 MHz, CDCl3): 9.59 (s,
1H), 7.90 (d, J ) 9 Hz, 2 H), 7.67 (d, J ) 9 Hz, 2 H), 5.45 (s, 1 H),
3.74 (AB, J ) 10.5 Hz, 4 H), 1.29 (s, 3 H), 0.82 (s, 3 H). 13C NMR
(50 MHz, CDCl3): δ 192.06, 144.54, 136.62, 129.74, 126.91, 100.71,
77.66, 53.41, 30.27, 22.99, 21.84.
(Z)-1-[4-(4,4-Dimethyl-2,6-dioxan-1-yl)phenyl]-2-(4-methylphen-
yl)ethene (Z-6) and (E)-1-[4-(4,4-Dimethyl-2,6-dioxan-1-yl)phenyl]-
2-(4-methylphenyl)ethene (E-6). A mixture of 5 (5.0 g, 22.6 mmol),
(4-methylbenzyl)triphenylphosphonium chloride (9.14 g, 22.6 mmol),
and t-BuOK (2.94 g, 24.9 mmol) in EtOH (30 mL) was stirred at room
temperature for 1 h under Ar. A saturated aqueous NH4Cl solution was
then added and the mixture concentrated. The aqueous layer was
extracted twice with CH2Cl2. The combined organic layers were washed
with water and dried (MgSO4) and evaporated to dryness. Column
chromatography (SiO2, hexane/CH2Cl2 6:4) gave 6 as an E:Z isomer
mixture in a 55:45 ratio. Both isomers could be isolated in a pure form
by column chromatography on SiO2 and characterized. In a preparative
procedure, the E:Z mixture obtained after the first chromatographic
purification was directly isomerized as follows: a solution of the E:Z
mixture and I2 (100 mg) in toluene was refluxed for 12 h and then
cooled to room temperature. The resulting toluene solution was washed
with an aqueous 0.3 M Na2S2O6 solution and water, dried (MgSO4),
filtered, and evaporated to dryness. Column chromatography (SiO2,
hexane/CH2Cl2 6:4) gave E-6 (4.9 g, 70% from 5).
Z-6. 1H NMR (200 MHz, CDCl3): 7.37 (d, J ) 9 Hz, 2 H), 7.28 (d,
J ) 9 Hz, 2 H), 7.15 (d, J ) 9 Hz, 2 H), 6.01 (d, J ) 9 Hz, 2 H), 6.54
(AB, J ) 12 Hz, 2 H), 5.36 (s, 1 H), 3.70 (AB, J ) 10.5 Hz, 4 H),
2.31 (s, 3 H), 1.30 (s, 3 H), 0.80 (s, 3 H). 13C NMR (50 MHz, CDCl3):
138.02, 137.00, 136.81, 134.02, 130.39, 129.08, 128.86, 128.73, 125.99,
101.64, 77.60, 30.14, 22.99, 21.81, 21.17. Anal. Calcd for C21H24O2
(308.4): C 81.78, H 7.84; Found: C 81.86, H 7.79.
E-6. 1H NMR (200 MHz, CDCl3): 7.50 (s, 4 H), 7.42 (d, J ) 8 Hz,
2 H), 7.17 (d, J ) 8 Hz, 2 H), 7.08 (s, 2 H), 5.40 (s, 1 H), 3.70 (AB,
J ) 10.5 Hz, 4 H), 2.36 (s, 3 H), 1.31 (s, 3 H), 0.81 (s, 3 H). 13C NMR
(50 MHz, CDCl3): 138.04, 137.51, 134.42, 130.20, 129.53, 129.37,
128.89, 127.30, 126.82, 126.41, 126.27, 101.54, 77.63, 30.22, 23.03,
21.87, 21.24. Anal. Calcd for C21H24O2 (308.4): C 81.78, H 7.84.
Found: C 81.84, H 7.79.
Compound 8. A mixture of 3PV (8.0 g, 10.4 mmol) and CF3CO2H
(80 mL) in CH2Cl2/H2O 1:1 (150 mL) was stirred at room temperature
for 5 h. The organic layer was then washed with water (4×), dried
(MgSO4), and evaporated to dryness. Column chromatography (SiO2,
CH2Cl2/hexane 1:1) gave 8 (6.98 g, 96%). 1H NMR (200 MHz,
CDCl3): 9.60 (s, 1 H), 7.88 (d, J ) 9.5 Hz, 2 H), 7.67 (d, J ) 9.5 Hz,
2 H), 7.55 (m, 4 H), 7.22 (q, J ) 16.5 Hz, 2 H), 7.08 (s, 2 H), 6.66 (d,
J ) 2 Hz, 2 H), 6.39 (t, J ) 2 Hz, 1 H) 3.98 (t, J ) 6.5 Hz, 4 H),
1.79-1.76 (m, 4 H), 1.43-1.27 (m, 36 H), 0.90 (t, J ) 6.5 Hz, 6 H).
13C NMR (50 MHz, CDCl3): 191.59, 160.48, 143.38, 138.95, 137.45,
135.80, 135.24, 131.70, 130.20, 129.28, 128.26, 127.23, 127.05, 126.94,
126.83, 105.12, 101.01, 68.06, 31.90, 29.62, 29.35, 29.28, 26.06, 22.67,
14.12. UV-vis (CH2Cl2): 232 (24708), 375 (58143). Anal. Calcd for
C47H66O3 (679.0): C 83.13, H 9.80. Found: C 83.08, H 9.83.
Compound 9. A mixture of 8 (800 mg, 1.17 mmol), t-BuOK (153
mg, 1.29 mmol), and methyltriphenylphosphonium bromide (472 mg,
1.29 mmol) in dry THF (5 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), and evaporated to dryness. Column chromatography (SiO2,
CH2Cl2/hexane 1:3) gave 9 (650 mg, 82%). 1H NMR (200 MHz,
CDCl3): 7.50-7.39 (m, 8 H), 7.12 (s, 2 H), 7.06 (s, 2 H), 6.75 (m, 1
H), 6.66 (d, J ) 2 Hz, 2 H), 6.39 (t, J ) 2 Hz, 1 H), 5.78 (d, J ) 17.5
Hz, 1 H), 5.26 (d, J ) 11.5 Hz, 1 H), 3.98 (t, J ) 6.5 Hz, 4 H), 1.79-
1.76 (m, 4 H), 1.43-1.27 (m, 36 H), 0.90 (t, J ) 6.5 Hz, 6 H). 13C
NMR (50 MHz, CDCl3): 160.46, 139.11, 136.85, 136.65, 136.57,
136.40, 128.70, 128.48, 128.12, 126.84, 126.65, 126.53, 113.70, 105.05,
100.90, 68.03, 31.91, 30.27, 29.61, 29.40, 29.34, 29.28, 26.06, 22.68,
14.12.
Compound 10. A mixture of 9 (650 mg, 0.96 mmol), 4-bromoben-
zaldehyde (177 mg, 0.96 mmol), Pd(OAc2) (9 mg, 0.04 mmol), and
POT (58 mg, 0.19 mmol) in Et3N/xylene 1:1 (8 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 chromatography (SiO2, hexane/CH2Cl2 6:4) gave
10 (450 mg, 60%) as yellow crystals (mp 160 °C). 1H NMR (200 MHz,
CDCl3): 9.59 (s,1 H), 7.89 (d, J ) 8.5 Hz, 2 H), 7.67 (d, J ) 8.5 Hz,
2 H), 7.55 (m, 8 H), 7.22 (q, J ) 16.5 Hz, 2 H), 7.15 (s, 2 H), 7.07 (s,
2 H), 6.66 (d, J ) 2 Hz, 2 H), 6.39 (t, J ) 2 Hz, 1 H) 3.98 (t, J ) 6.5
Hz, 4 H), 1.79-1.76 (m, 4 H), 1.43-1.27 (m, 36 H), 0.90 (t, J ) 6.5
Hz, 6 H). 13C NMR (50 MHz, CDCl3): 191.60, 160.46, 143.39, 139.08,
137.55, 136.75, 136.49, 135.79, 135.21, 131.70, 130.59, 130.24, 128.82,
128.69, 128.43, 127.85, 127.27, 127.05, 126.89, 118.59, 105.07, 100.92,
68.05, 34.26, 31.90, 29.61, 29.35, 29.28, 26.05, 22.67, 19.65, 14.12.
IR (CH2Cl2): 1641 (CdO). UV-vis (CH2Cl2:): 227 (27295), 284
(12927), 396 (82866). Anal. Calcd for C55H72O3 (781.2): C 84.57, H
9.29. Found: C 84.22 H 9.43.
(E)-1-(4-Formylphenyl)-2-(4-methylphenyl)ethene (E-7). A mix-
ture of p-bromobenzaldehyde (8.0 g, 43.2 mmol), p-methylstyrene (5.62
g, 47.5 mmol), Pd(OAc)2 (291 mg, 1.3 mmol), and POT (789 mg, 2.6
mmol) in Et3N/xylene 1:1 (100 mL) was heated to 130 °C under Ar
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 chromatography (SiO2, hexane/CH2Cl2 6:4) gave
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E-7 (6.76 g, 70%). H NMR (200 MHz, CDCl3): 9.61 (s, 1H), 7.87
(AB, J ) 8.5 Hz, 2 H), 7.65 (AB, J ) 8.5 Hz, 2 H), 7.46 (AB, J ) 8.5
Hz, 2 H), 7.22 (AB, J ) 8.5 Hz, 2 H), 7.18 (AB, J ) 16 Hz, 2 H),
2.38 (s, 3 H). 13C NMR (50 MHz, CDCl3): 191.58, 143.60, 138.56,
135.08, 133.71, 132.12, 130.20, 129.53, 126.81, 126.72, 126.25, 21.30.
Anal. Calcd for C16H14O (222.3): C 86.45, H 6.35. Found: C 86.43,
H 6.36.
(E)-1-[4-(4,4-Dimethyl-2,6-dioxan-1-yl)phenyl]-2-(4-methylphen-
yl)ethene (E-6) from E-7. A solution of E-7 (2.5 g, 11.3 mmol), 2,2-
dimethylpropane-1,3-diol (2.36 g, 22.7 mmol), and p-TsOH (50 mg)
in benzene (100 mL) was refluxed for 24 h using a Dean-Stark trap.
After cooling, the solution was evaporated to dryness and column
chromatography (SiO2, hexane/CH2Cl2 7:3) gave E-6 (3.31 g, 95%) as
colorless crystals (mp 166 °C).
Compound 4PV. A solution of 8 (800 mg, 1.17 mmol), t-BuOK
(153 mg, 1.32 mmol), and (4-methylbenzyl)triphenylphosphonium
chloride (472 mg, 1.32 mmol) in dry THF (20 mL) was stirred under
Ar at room temperature for 2 h. A saturated aqueous NH4Cl solution
was then added and the mixture concentrated. The aqueous layer was
extracted twice with CH2Cl2. The combined organic layers were washed
with water, dried (MgSO4), and evaporated to dryness to give a mixture
Compound 3PV. t-BuOK (8.94 g, 75 mmol) was added to a solution
of 3 (11.46 g, 20.9 mmol) and E-6 (6.45 g, 20.9 mmol) in dry DMF