7.48 (d, J = 8 Hz, 2H), 7.15 (AB, J = 17 Hz, 2H), 6.91 (d, J =
8 Hz, 2H), 3.99 (t, J = 7 Hz, 2H), 1.78 (m, 2H), 1.55–1.30 (m,
18H), 0.89 (t, J = 6.5 Hz, 3H). 13C NMR (50 MHz, CDCl3):
191.5, 159.6, 143.9, 134.9, 131.8, 130.2, 129.0, 128.2, 126.5,
124.9, 114.8, 68.1, 31.9, 29.5, 29.4, 29.3, 29.2, 26.0, 22.6, 14.1.
Anal. calcd. for C27H36O2: C 82.61, H 9.24. Found: C 82.79,
H 9.36.
134.7, 131.8, 131.5, 128.0, 127.5, 123.6, 117.1, 89.8, 88.1, 75.1,
32.2, 30.8, 19.3, 14.0. Anal. calcd. for C76H72O4: C 86.99, H
6.92. Found: C 86.86, H 6.99.
Compound 13. PdCl2(PPh3)2 (3 mol %) and CuI (5 mol %)
were added to a stirred degassed solution of 12 (4.30 g, 15
mmol) and 4-bromobenzaldehyde (4.16 g, 22.5 mmol) in dry
triethylamine (40 ml) at rt. The resulting mixture was stirred at
rt for 48 h, then concentrated. The residue was taken up in
CH2Cl2. The organic layer was washed with water, dried
(MgSO4), filtered and evaporated. Column chromatography
(SiO2, hexane–CH2Cl2 7 : 3) gave 13 (4.10 g, 70%) as a colour-
less solid glassy product. 1H NMR (200 MHz, CDCl3): 8.58 (s,
1H), 7.86 (d, J = 8 Hz, 2H), 7.65 (d, J = 8 Hz, 2H), 7.49 d,
J = 8 Hz, 2H), 6.89 (d, J = 8 Hz, 2H), 3.98 (t, J = 6.5 Hz,
2H), 1.77 (m, 2H), 1.60–1.30 (m, 18H), 0.89 (t, J = 6.5 Hz,
3H). 13C NMR (50 MHz, CDCl3): 191.3, 159.7, 135.0, 133.3,
131.8, 130.0, 129.5, 114.6, 114.2, 93.9, 87.4, 68.1, 31.9, 29.6,
29.5, 29.3, 29.1, 25.9, 22.6, 14.1. Anal. calcd. for C27H34O2: C
83.03, H 8.77. Found: C 83.29, H 8.99.
Compound 9. A mixture of 8 (1.90 g, 4.84 mmol), t-BuOK
(0.56 g, 5.32 mmol) and methyltriphenylphosphonium bromide
(1.90 g, 5.32 mmol) in dry THF (30 ml) was stirred at rt for 1 h.
A saturated aqueous NH4Cl solution was then added and the
resulting mixture concentrated. The aqueous layer was ex-
tracted 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 9
1
(1.51 g, 80 %) as a pale yellow solid (mp 160 1C). H NMR
(200 MHz, CDCl3) 7.48 (d, J 8 Hz, 2H), 7.41 (AB, J = 8 Hz,
4H), 7.01 (AB, J = 17 Hz, 2H), 6.89 (d, J = 8 Hz, 2H), 6.70
(dd, J = 17 and 11 Hz, 1H), 5.75 (dd, J = 17 and 2 Hz, 1H),
5.23 (d, J = 11 and 2 Hz, 1H), 3.98 (t, J = 6.5 Hz, 2H), 1.76
(m, 2H), 1.56–1.28 (m, 18H), 0.83 (t, J = 6 Hz, 3H). Anal.
calcd. for C28H38O2: C 82.71, H 9.42. Found: C 82.50, H 9.55.
Compound 14. A mixture of CBr4 (17.18 g, 51.8 mmol), PPh3
(13.64 g, 51.8 mmol) and Zn dust (3.39 g, 51.8 mmol) in dry
CH2Cl2 (200 ml) was stirred at rt for 24 h. The suspension was
then cooled to 0 1C and a solution of 13 (4.05 g, 10.37 mmol) in
CH2Cl2 (30 ml) was added at once. The resulting mixture was
slowly warmed up to rt (1 h) and stirred at this temperature
overnight. The resulting thick suspension was filtered over SiO2
(CH2Cl2) to remove the zinc salts and some of the P-containing
by-products. The solution was concentrated and column chro-
matography (SiO2, CH2Cl2–hexane 1 : 1) gave 14 (5.4 g, 95%)
as colourless glassy product. 1H NMR (200 MHz, CDCl3):
7.50 (AB, J = 8 Hz, 4H), 7.47 (s, 1H), 7.45 (d, J = 8 Hz, 2H),
6.85 (d, J = 8 Hz, 2H), 3.97 (t, J = 6.5 Hz, 2H), 1.77 (m, 2H),
1.60–1.30 (m, 18H), 0.89 (t, J = 6.5 Hz, 3H). 13C NMR (50
MHz, CDCl3): 159.4, 136.2, 134.5, 133.0, 131.3, 128.3, 123.9,
114.5, 92.3, 91.0, 90.0, 87.7, 68.1, 31.9, 29.6, 29.5, 29.4, 29.2,
26.0, 22.7, 14.1. Anal. calcd. for C28H34OBr2: C 61.55, H 6.27.
Found: C 61.52, H 6.36.
Compound 1a. A mixture of 3 (300 mg, 0.26 mmol), 9 (458
mg, 1.17 mmol), TOP (6 mg) and Pd(OAc)2 (3 mg) in NEt3–
xylene 1 : 4 (25 ml) was stirred at 120 1C under argon for 48 h.
After cooling to rt, the mixture was filtered through celite
(CH2Cl2) and evaporated. The residue was dissolved in
CH2Cl2. The solution was washed with water (3ꢁ), dried
(MgSO4) and evaporated. Column chromatography (SiO2,
hexane–CH2Cl2 1 : 1), followed by recrystallization (CH2Cl2–
MeOH) afforded 1a (390 mg, 68%) as a yellow solid (140 1C
smectic liquid crystalline phase; 180 1C isotropic liquid). 1H
NMR (200 MHz, CD2Cl2): 7.44–6.50 (m, 56H), 4.50 (br d, J =
13 Hz, 4H), 3.90 (m, 16H), 3.24 (br d, J = 13 Hz, 4H), 1.94 (m,
8H), 1.78 (m, 8H), 1.55–1.30 (m, 80H), 1.03 (t, J = 7 Hz, 12H),
0.88 (t, J = 6.5 Hz, 12H). FAB-MS: 2203.5 (M+ calcd. for
C156H200O8: 2203.3). Anal. calcd. for C156H200O8: C 85.04,
H 9.15. Found: C 85.39, H 8.99.
Compound 15. A 2.0 M solution of LDA in THF (30 ml, 60
mmol) was added dropwise to a solution of 14 (5.35 g, 9.79
mmol) in dry THF (120 ml) at ꢀ78 1C under argon. The
resulting was stirred for 2 h at ꢀ78 1C, then allowed to warm
up to 0 1C (1 h) and a saturated aqueous NH4Cl solution (60
ml) was added. The mixture was then diluted with hexane. The
organic layer was washed with H2O (2ꢁ), dried (MgSO4),
filtered and evaporated. Column chromatography (SiO2, hex-
ane–CH2Cl2 7 : 3) gave 15 (3.25 g, 86%) as pale yellow glassy
product. 1H NMR (200 MHz, CDCl3): 7.46 (d, J = 8 Hz, 2H),
7.45 (s, 4H), 6.87 d, J = 8 Hz, 2H), 3.97 (t, J = 6.5 Hz, 2H),
3.16 (s, 1H), 1.78 (m, 2H), 1.55–1.30 (m, 18H), 0.88 (t, J = 6.5
Hz, 3H). 13C NMR (50 MHz, CDCl3): 159.4, 136.2, 133.1,
132.0, 131.2, 128.3, 124.2, 121.4, 114.7, 114.5, 91.6, 87.5, 83.3,
78.7, 68.0, 31.9, 29.7, 29.6, 29.4, 29.2, 26.0, 22.7, 14.1. Anal.
calcd. for C28H34O: C 87.00, H 8.86. Found: C 86.88, H 9.01.
Compound 10. PdCl2(PPh3)2 (3 mol %) and CuI (5 mol %)
were added to a degassed solution of 3 (200 mg, 0.174 mmol)
and trimethylsilylacetylene (0.25 ml, 1.73 mmol) in dry triethyl-
amine (40 ml) at rt. The resulting mixture was stirred under
argon at rt for 72 h, then concentrated. The residue was taken
up in CH2Cl2. The organic layer was washed with water, dried
(MgSO4), filtered and evaporated. Column chromatography
(SiO2, hexane–CH2Cl2 9 : 1) gave 10 (160 mg, 89%) as a
colourless solid. 1H NMR (200 MHz, CDCl3): 6.94 (s, 8H),
4.35 (d, J = 13 Hz, 4H), 3.88 (t, J = 7 Hz), 3.10 (d, J = 13 Hz,
4H), 1.89 (m, 8H), 1.42 (m, 8H), 0.98 (t, J = 6.5 Hz, 12H), 0.25
(s, 36H). 13C NMR (50 MHz, CDCl3): 156.8, 134.3, 132.4,
116.9, 105.5, 92.7, 75.2, 32.1, 30.7, 19.3, 14.0, 0.15. Anal. calcd.
for C64H88O4Si4: C 74.36, H 8.58. Found: C 74.50, H 8.45.
Compound 11. PdCl2(PPh3)2 (3 mol %) and CuI (5 mol %)
were added to a degassed solution of 3 (200 mg, 0.174 mmol)
and phenylacetylene (0.2 ml, 1.74 mmol) in dry triethylamine
(40 ml) at rt. The resulting mixture was stirred under argon at
rt for 48 h, then concentrated. The residue was taken up in
CH2Cl2. The organic layer was washed with water, dried
(MgSO4), filtered and evaporated. Column chromatography
(SiO2, hexane–CH2Cl2 4 : 1) gave 11 (149 mg, 81%) as a
Compound 2. PdCl2(PPh3)2 (3 mol %) and CuI (5 mol %)
were added to a degassed solution of 3 (100 mg, 0.087 mmol)
and 15 (325 mg, 0.87 mmol) in dry triethylamine (40 ml) at rt.
The resulting mixture was stirred under argon at rt for 48 h,
then concentrated. The residue was taken up in CH2Cl2. The
organic layer was washed with water, dried (MgSO4), filtered
and evaporated. Column chromatography (SiO2, hexane–
CH2Cl2 4 : 1) gave 2 (135 mg, 71%) as a pale yellow solid
(mp 126 1C). 1H NMR (400 MHz, CD2Cl2): 7.41 (d, J = 8 Hz,
8H), 7.36 (AB, J = 8 Hz, 16H), 6.97 (s, 8H), 6.77 (d, J = 8 Hz,
8H), 4.52 (d, J = 13 Hz, 4H), 3.99 (t, J = 6.5 Hz, 8H), 3.97
1
colourless solid. H NMR (200 MHz, CDCl3): 7.43 (m, 8H),
7.17 (m, 12H), 6.97 (s, 8H), 4.44 (d, J = 13 Hz, 4H), 3.95 (t,
J = 7 Hz), 3.19 (d, J = 13 Hz, 4H), 1.92 (m, 8H), 1.45 (m, 8H),
1.02 (t, J = 6.5 Hz, 12H). 13C NMR (50 MHz, CDCl3): 156.8,
N e w J . C h e m . , 2 0 0 4 , 2 8 , 1 6 2 7 – 1 6 3 7
1635