4786 Goto et al.
Macromolecules, Vol. 37, No. 13, 2004
114.98, 126.42, 128.36, 129.09, 130.05, 132.62, 145.03, 159.15,
166.17. 19F NMR (470 MHz, CDCl3, δ, ppm): -186.45.
(R)-(-)-1-Meth ylh ep tyl-4′-d ecyloxybip h en yl-4-ca r box-
yla te (m on o-2). This compound was prepared using a method
similar to that described for m on o-1. Quantity used: 5 (1 g,
2.64 mmol) and DEAD (1.15 g, in toluene, 2.64 mmol) in THF
(3 mL); (S)-octanol (0.43 mL) and TPP (0.7 g, 2.64 mmol) in
THF (2 mL). Yield: 75%, 0.97 g (pale orange solid). IR (KBr,
cm-1): 3320 (s, νHC≡), 2130 (w, νC≡C), 1700 (s, νCdO), 640 (m,
1 week at room temperature. Then the insoluble fraction of
the solution was filtered off, and the filtrate was purified by
column chromatography (silica gel, benzene) to afford 1.5 g of
white crystal (yield ) 61%). [R]D27: +3.0°. IR (KBr, cm-1): 3300
(m, νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1252 (s, νCOC), 640 (w,
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t,
3H, J ) 7.1 Hz, CH3), 1.30-1.71 (m, 10H, CH2), 1.82 (t, 1H,
J ) 2.6 Hz, HC≡), 1.85 (m, 2H, CH2), 2.23 (m, 2H, HCtCCH2),
4.13 (m, 4H, OCH2, OCH2C*HF), 4.80 (dm, 1H, J HF ) 49.5
Hz, CH2C*HF), 6.95 (d, J ) 2H, 6.9 Hz, ph), 7.02 (d, 2H, J )
7.5 Hz, ph), 7.58 (d, 2H, J ) 7.3 Hz, ph), 7.67 (d, 2H, J ) 7.4
Hz, ph), 8.22 (d, 2H, 8.5 Hz, J ) 8.5 Hz, ph). 13C NMR (125
MHz, CDCl3, δ from TMS, ppm): 14.06, 15.19, 22.57, 24.88,
28.17, 29.02, 31.50, 31.60, 67.98, 70.22, 70.41, 83.37, 91.93 (d,
J CF ) 171.9 Hz), 115.04, 115.39, 122.59, 126.62, 127.65, 128.44,
130.70, 132.32, 144.91, 145.88, 156.33, 159.34, 171.49. 19F
NMR (470 MHz, CDCl3, δ, ppm): -187.55.
4-((S)-2-F lu or ooctyloxy)-p h en yl-4′-d od ecyn yloxy-4-bi-
p h en yl-ca r boxyla te (m on o-7). This compound was prepared
using a method similar to that described for m on o-6. Quantity
used: 5 (0.52 g, 1.3 mmol), 10 (1.3 g, 1.4 mmol), DCC (0.46 g,
2.2 mmol), and DMAP (0.27 g, 2.2 mmol) in CH2Cl2 (40 mL).
Yield: 63%, 0.5 g (white crystal). IR (KBr, cm-1): 3300 (m,
νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1252 (s, νCOC), 640 (w, γHC≡).
1H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t, 3H,
J ) 7.0 Hz, CH3), 1.25-1.70 (m, 26H, CH2), 1.93 (t, 1H, J )
2.6 Hz, HC≡), 2.16 (m, 2H, HCtCCH2), 4.02 (m, 4H, OCH2,
OCH2C*HF), 4.83 (dm, 1H, J HF ) 49.8 Hz, OCH2C*HF), 6.98
(m, 4H, ph), 7.13 (d, 2H, J ) 7.1 Hz, ph), 7.58 (d, 2h, J ) 7.5
Hz, ph), 7.88 (d, 2H, J ) 8.3 Hz, ph), 8.22 (d, 2H, J ) 8.4 Hz,
ph). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 14.05,
18.42, 18.78, 21.91, 21.57, 24.65, 25.63, 28.78, 29.10, 29.27,
29.38, 29.44, 29.52, 31.51, 31.65, 68.16, 70.23, 70.42, 83.34,
91.93 (d, J CF ) 171.5 Hz), 115.03, 115.39, 122.80, 126.59,
127.59, 128.40, 130.69, 132.04, 144.92, 145.97, 156.33, 159.62,
171.50. 19F NMR (470 MHz, CDCl3, δ, ppm): -187.54.
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.87 (t,
3H, J ) 6.7, CH3), 1.18-1.81 (m, 29 H, CH2, CH3), 1.93 (t, 1H,
J ) 2.5 Hz, HC≡), 2.17 (m, 2H, HCtCCH2), 3.98 (t, 2H, J )
6.52, OCH2), 5.16 (sextet, 1H, J ) 6.6 Hz, COOC*H CH3), 6.98
(d, 2H, J ) 7.4 Hz, ph), 7.04 (d, 2H, J ) 6.8 Hz, ph), 7.01 (d,
2H, J ) 7.0 Hz, ph), 8.06 (d, 2H, J ) 8.3 Hz, ph). 13C NMR
(125 MHz, CDCl3, δ from TMS, ppm): 13.99, 15.16, 18.33,
20.04, 22.53, 25.55, 25.97, 26.15, 28.67, 29.11, 29.25, 29.35,
29.46, 31.69, 32.75, 36.05, 65.98, 70.71, 71.57, 84.67, 114.86,
126.30, 128.23, 128.93, 129.95, 132.22, 145.03, 159.34, 166.11.
4-Octoxy-4′-(12-d od ecyn yloxy)bip h en yl (m on o-3). This
compound was prepared using a method similar to that
described for m on o-1. Quantity used: DEAD (5.66 g, in
toluene 13.0 mmol) and 1-octanol (1.26 g, 9.7 mmol) in THF
(30 mL); 8 (3.00 g, 8.5 mmol) and TPP (3.34 g, 13.7 mmol) in
THF (15 mL). Yield: 46%, 1.82 g (white solid). Mp ) 114-
117 °C. IR (KBr, cm-1): 3287 (m, νHC≡), 2110 (w, νC≡C), 1251
(s, νCOC), 637 (w, γHC≡). 1H NMR (500 MHz, CDCl3, δ from TMS,
ppm): 0.90 (t, 3H, J ) 6.9 Hz, CH3), 1.25-1.89 (m, 28H, CH2),
1.94 (t, 1H, J ) 2.7 Hz, HC≡), 2.19 (m, 2H, HCtCCH2), 3.99
(t, 4H, J ) 6.6 Hz, OCH2), 6.94 (d, 4H, J ) 8.7 Hz, ph), 7.46
(d, 4H, J ) 8.7 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from
TMS, ppm): 14.10, 14.69, 16.41, 22.67, 26.06, 26.08, 28.17,
28.75, 29.09, 29.38, 29.43, 29.45, 29.51, 31.63, 32.64, 33.99,
66.05, 66.12, 84.79, 114.77, 127.65, 133.35, 158.26.
4-[(S)-2-F lu or ooct oxy]-4′-(12-d od ecyn yloxy)b ip h en yl
(m on o-4). This compound was prepared using a method
similar to that described for m on o-1. Quantity used: 8 (2 g,
5.7 mmol) and DEAD (3.70 g, in toluene, 8.5 mmol) in THF
(10 mL); TPP (2.33 g, 8.5 mmol) and 6 (0.84 g, 5.7 mmol) in
THF (20 mL). Yield: 59.5%, 1.62 g (white solid). Mp ) 112-
113 °C. IR (KBr, cm-1): 3286 (m, νHC≡), 2112 (w, νC≡C), 1251
(s, νCOC), 634 (w, γHC≡). 1H NMR (500 MHz, CDCl3, δ from TMS,
ppm): 0.90 (t, 3H, J ) 6.9, CH3), 1.24-1.94 (m, 26H), 1.94 (t,
1H, J ) 2.7 Hz, HC≡), 2.19 (m, 2H, HCtCCH2), 3.98 (t, 2H,
J ) 6.6 Hz, OCH2), 4.10 (m, 2H, OCH2C*HF), 4.83 (dm, 1H,
J HF ) 49.6 Hz, OCH2C*HF), 6.94 (d, 2H, J ) 8.7 Hz, ph), 6.96
(d, 2H, J ) 8.7 Hz, ph), 7.46 (d, 2H, J ) 8.6 Hz, ph), 7.47 (d,
2H, J ) 8.7 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from TMS,
ppm): 14.05, 18.41, 22.56, 24.54, 24.88, 26.07, 28.50, 28.76,
29.09, 29.32, 29.51, 31.64, 31.67, 31.70, 46.51, 66.11, 69.58,
70.05, 84.60, 92.00 (d, J CF ) 171.6 Hz), 114.78, 127.72, 133.17,
134.10, 144.57, 148.48, 157.67, 158.32. 19F NMR (470 MHz,
CDCl3, δ, ppm): -187.74.
4-[4-((S)-2-F lu or ooct yloxy)b en zoyloxy]-4′-(7-oct yn yl-
oxy)bip h en yl (m on o-8). This compound was prepared using
a method similar to that described for m on o-6. Quantity
used: 7 (0.81 g, 2.7 mmol), 12 (0.7 g, 2.6 mmol), DCC (0.82 g,
3.9 mmol), and DMAP (0.48 g, 3.9 mmol) in CH2Cl2 (50 mL).
Yield: 90%, 0.85 g (white crystal). IR (KBr, cm-1): 3285 (m,
νHC≡), 2112 (w, νC≡C), 1737(s, νCdO), 1255 (s, νCOC), 640 (w, γHC≡).
1H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t, 3H,
J ) 7.0, CH3), 1.25-1.91 (m, 18H, CH2), 1.95 (t, 1H, J ) 2.6
Hz, HC≡), 2.22 (dt, 2H, J ) 7.0, HCtCCH2), 4.01 (t, 2H, J )
6.5 Hz, OCH2), 4.10-4.22 (m, 2H, CH2), 4.87 (dm, 1H, J HF
)
49.1 Hz, OCH2C*HF), 6.97 (d, 2H, J ) 8.7 Hz, ph), 7.01 (d,
2H, J ) 8.9 Hz, ph), 7.24 (d, 2H, J ) 8.6 Hz, ph), 7.51 (d, 2H,
J ) 8.7 Hz, ph), 7.58 (d, 2H, J ) 8.7 Hz, ph), 8.18 (d, 2H, J )
8.8 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm):
14.02, 15.56, 16.41, 22.54, 24.52, 26.09, 29.07, 29.46, 29.50,
31.63, 31.64, 67.93, 69.65, 70.01, 94.77, 91.93 (d, J CF ) 171.8
Hz), 114.45, 114.87, 121.94, 122.39, 122.53, 127.74, 128.15,
132.37, 133.43, 138.64, 150.01, 159.01, 163.14.19F NMR (470
MHz, CDCl3, δ, ppm): -187.40.
(S)-2-F lu or ooct yl-4′-p en t yn oxyb ip h en yl-4-ca r b oxyl-
a te (m on o-5). This compound was prepared using a method
similar to that described for m on o-1. Quantity used: 2 (1.4 g
5 mmol) and DEAD (2.17 g, in toluene, 5 mmol) in THF (3
mL); 6 (0.74 g, 5 mmol) and TPP (1.3 g, 5 mmol) in THF (3
mL). Yield: 51%, 1.08 g (white solid). IR (KBr, cm-1): 3300
(m, νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1250 (s, νCOC), 640 (w,
4-[4-((S)-2-F lu or ooctyloxy)ben zoyloxy]-4′-(12-d od ecyn -
yloxy)bip h en yl (m on o-9). This compound was prepared
using a method similar to that described for m on o-6. Quantity
used: 8 (0.65 g, 1.9 mmol), 12 (0.50 g, 1.9 mmol), DCC (0.77
g, 3.7 mmol), and DMAP (0.46 g, 3.7 mmol) in 5 mL of CH2-
Cl2. The residue was purified by column chromatography (silica
gel, benzene/hexane ) 2) followed by recrystallization from
ethanol. Yield: 0.87 g, 76% (white solid). IR (KBr, cm-1): 3300
(m, νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1254 (s, νCOC), 642 (w,
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t,
3H, 7.0 Hz, CH3), 1.35-1.58 (m, 10 H, CH2), 1.86 (t, 1H, J )
2.6 Hz, HC≡), 2.03 (m, 2H, HCtCCH2), 2.44 (m, 2H, CH2),
4.13 (t, 2H, J ) 6.1 Hz, OCH2), 4.44 (m, 2H, OCH2C*HF), 4.82
(dm, 1H, J ) 48.7 Hz, OCH2C*HF), 7.01 (d, 2H, J ) 7.1 Hz,
ph), 7.5 Hz (d, 2H, J ) 6.9 Hz, ph), 7.63 (d, 2H, J ) 7.2 Hz,
ph), 8.12 (d, 2H, J ) 8.4 Hz, ph). 13C NMR (125 MHz, CDCl3,
from TMS, ppm): 14.04, 15.19, 22.55, 24.79, 28.17, 29.05,
31.43, 31.63, 66.16, 66.28, 68.96, 83.37, 91.53 (d, J CF ) 172.0
Hz), 115.00, 126.52, 127.69, 128.40, 130.29, 132.43, 145.52,
159.24, 166.30. 19F NMR (470 MHz, CDCl3, δ, ppm): -187.74.
4-((S)-2-Flu or ooctyloxy)-p h en yl-4′-p en tyloxy-4-biph en -
yl-ca r boxyla te (m on o-6). A solution of 2 (1.4 g, 5 mmol), 10
(0.8 g, 5 mmol), DCC (1.1 g, 5 mmol), and DMAP (0.64 g, 5
mmol) in 80 mL of CH2Cl2 and 30 mL of THF was stirred for
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t,
3H, J ) 6.9, CH3), 1.25-1.91 (m, 26H), 1.94 (t, 1H, J ) 2.6,
HC≡), 2.17-2.22 (m, 2H), 4.00 (t, 2H, J ) 6.5 Hz, OCH2),
4.11-4.22 (m, 2H), 4.86 (dm, 1H, J HF ) 50.5 Hz, OCH2C*HF),
6.96 (d, 2H, J ) 8.7 Hz, ph), 7.01 (d, 2H, J ) 8.9 Hz, ph), 7.24
(d, 2H, J ) 8.7 Hz, ph), 7.51 (d, 2H, J ) 8.7 Hz, ph), 7.58 (d,
2H, J ) 8.5 Hz, ph), 8.17 (d, 2H, J ) 8.9 Hz, ph). 13C NMR
(125 MHz, CDCl3, δ from TMS, ppm): 14.05, 15.58, 16.42,
22.56, 24.56, 26.07, 24.51, 26.76, 29.07, 29.39, 29.44, 29.52,
30.91, 31.60, 31.67, 67.98, 69.66, 70.04, 94.75, 91.91 (d, J CF
)