was stirred at 80 ꢀC for 48 h and then solvent was removed under
reduced pressure. Dichloromethane was added into the solid
residue. The suspension was stirred at room temperature for 15
min and then was filtered off. The dichloromethane was removed
and the residue was recrystallized in dichloromethane to afford
white solid 3. Yield: 0.76 g, 42%.
1H NMR d [ppm]: 7.43(t, overlapped dd, 4H, Ar–H), 6.94
(d, 2H, J ¼ 8.4 Hz, Ar–H), 6.88 (d, 2H, J ¼ 8.4 Hz, Ar–H), 5.82
(m, 1H, HC]CH2), 5.02 (m, 2H, HC]CH2), 4.79(s, 1H, OH),
3.98(t, 2H, J ¼ 6.4 Hz, OCH2), 2.05(m, 2H, CH2HC]CH2), 1.79
(m, 2H, OCH2CH2), 1.51–1.25 (br, 12H, (CH2)6). 13C NMR
d [ppm]: 158.60, 154.86, 139.47, 134.11, 133.52, 128.19, 127.93,
115.85, 115.09, 114.37. Anal. Calc for C23H30O2: C 81.62%, H
8.93%, found: C 81.35%, H 8.69%.
40-(Undec-10-enyloxy)biphenyl-4-yl 4-(octyloxy)benzoate (5c).
1
Yield: 66%. H NMR d [ppm]: 8.08 (d, 2H, J ¼ 8.4 Hz, Ar–H),
7.51 (d, 2H, J ¼ 8.4 Hz, Ar–H), 7.43 (d, 2H, J ¼ 8.4 Hz, Ar–H),
6.90 (overlapped, dd, 4H, J ¼ 8.8 Hz, Ar–H), 5.74 (m, 1H, HC ¼
CH2), 4.89 (m, 2H, HC]CH2), 3.98 (t, 2H, J ¼ 6.4 Hz, OCH2),
3.93 (t, 2H, J ¼ 6.4 Hz, OCH2), 1.98 (m, 2H, CH2HC ¼ CH2),
1.74 (m, 4H, OCH2CH2), 1.46–1.35 (m, 4H, OCH2CH2CH2),
1.34–1.16 (m, 18H, (CH2)9), 0.83 (t, 3H, J ¼ 6.8 Hz, CH3). 13C
NMR d [ppm]: 165.36, 163.93, 159.16, 150.43, 139.54, 138.91,
133.22, 132.63, 128.44, 128.01, 122.32, 122.03, 115.23, 114.69,
114.46, 68.72, 68.51, 34.13, 32.15, 29.86, 29.77, 29.73, 29.67,
29.55, 29.47, 29.46, 29.29, 26.41, 26.345, 22.99, 14.40. EI-MS
(m/z): Found: 570.5. Calc: 570.8. Anal. Calc for C38H50O4: C
79.96%, H 8.83%, found: C 79.63%, H 8.59%
40-(Undec-10-enyloxy)biphenyl-4-yl 4-(dodecyloxy)benzoate (5d).
Yield: 56%. 1H NMR d [ppm]: 8.15 (d, 2H, J ¼ 8.8 Hz, Ar–H), 7.57
(d, 2H, J ¼ 8.4 Hz, Ar–H), 7.50 (d, 2H, J ¼ 8.4 Hz, Ar–H), 7.23 (d,
2H, J ¼ 8.8 Hz, Ar–H), 6.97 (overlapped, dd, 4H, J ¼ 8.8 Hz, Ar–
H), 5.81 (m, 1H, HC]CH2), 4.98 (m, 2H, HC]CH2), 4.04 (t, 2H, J
¼ 6.4 Hz, OCH2), 3.99 (t, 2H, J ¼ 6.4 Hz, OCH2), 2.06 (m, 2H,
CH2HC]CH2), 1.81 (m, 4H, OCH2CH2), 1.44 (m, 4H,
OCH2CH2CH2), 1.38–1.27 (m, 26H, (CH2)13), 0.89 (t, 3H, J ¼ 6.4
Hz, CH3). 13C NMR d [ppm]: 165.37, 163.94, 159.16, 150.43, 139.55,
138.92, 133.23, 132.64, 128.45, 128.02, 122.03, 121.55, 115.23,
114.70, 114.47, 68.73, 68.52, 34.14, 32.27, 30.01, 29.98, 29.94, 29.91,
29.87, 29.78, 29.74, 29.72, 29.69, 29.67, 29.47, 29.30, 26.42, 26.35,
23.03, 14.44. EI-MS (m/z): Found: 626.5. Calc.:626.9. Anal. Calc for
C42H58O4: 80.47%, H 9.33%, found: C 80.30%, H 9.04%
General synthetic procedures of 5a–h
4-n-Alkoxybenzoic acid (0.71 mmol), 40-hydroxybiphenyl unde-
cene-1-yl ether (0.20 g, 0.59 mmol) and dimethylaminopyridine
(DMAP) (0.030 g, 0.24 mmol) were dissolved in 13.0 mL of dry
dichloromethene. The reaction mixture was purged with argon gas
for 10 min before the addition of dicyclohexylcarbodiimide (DCC)
(0.19 g, 0.89 mmol) in 4.0 mL dry dichloromethene. The mixture
was then refluxed for 16 h under argon gas protection. After the
reaction is complete, the resulting suspension was removed by
filtration. The filtrate was washed with water and dried, and the
organic solvent was removed. The residue was column chroma-
tographed on silica gel using a mixture of dichloromethane and
hexane (V : V ¼ 65 : 35) as eluent to afford 5 as a white solid.
40-(Undec-10-enyloxy)biphenyl-4-yl 4-(pentyloxy)benzoate (5a).
Yield: 73%. 1H NMR d [ppm]: 8.09 (d, 2H, J ¼ 8.8 Hz, Ar–H), 7.50
(d, 2H, J ¼ 8.8 Hz, Ar–H), 7.44 (d, 2H, J ¼ 8.4 Hz, Ar–H), 7.17 (d,
2H, J ¼ 8.4, Ar–H), 6.90 (dd, 4H, J ¼ 8.8 Hz, Ar–H), 5.76 (m, 1H,
HC]CH2), 4.90 (m, 2H, HC]CH2), 3.98 (t, 2H, J ¼ 6.6 Hz
OCH2), 3.93 (t, 2H, J ¼ 6.6 OCH2) 1.98 (m, 2H, CH2HC ¼ CH2),
1.74 (m, 4H, OCH2CH2), 1.40 (m, 4H, OCH2CH2CH2), 1.38–1.19
(m, 12H, (CH2)6), 0.88(t, 3H, J ¼ 6.8, CH3). 13C NMR d [ppm]:
165.45, 163.94, 159.17, 150.43, 139.56, 138.93, 133.24, 132.65,
128.45, 128.02, 122.33, 122.04, 115.24, 114.70, 114.47, 68.72, 68.53,
34.15, 29.87, 29.78, 29.74, 29.68, 29.48, 29.30, 29.17, 28.51, 26.42,
22.78, 14.32. EI-MS (m/z): Found: 528.4. Calc.: 528.7. Anal. Calc
for C35H44O4: C 79.51%, H 8.39%, found: C 79.05%, H 8.16%.
40-(Undec-10-enyloxy)biphenyl-4-yl 3,5-di(hexyloxy)benzoate
(5e). Yield: 78%. 1H NMR d [ppm]: 7.60 (d, 2H, J ¼ 8.5 Hz, Ar–H),
7.53 (d, 2H, J ¼ 10.1 Hz, Ar–H), 7.37 (s, 2H, Ar–H), 7.27 (d, 2H, J ¼
8.6 Hz, Ar–H), 6.99 (d, 2H, J ¼ 8.7 Hz, Ar–H), 6.75 (s, 1H, Ar–H),
5.84 (m, 1H, HC]CH2), 4.98 (m, 2H, HC]CH2), 4.02 (m, 6H,
OCH2), 2.08 (m, 2H, CH2HC]CH2), 1.82 (m, 6H, OCH2CH2),
1.49–1.20 (m, 24H, (CH2)12), 0.97 (t, 6H, J ¼ 6.8 Hz, CH3). 13C
NMR (CDCl3) d [ppm]: 165.59, 160.71, 159.20, 150.29, 139.64,
139.13, 133.14, 131.62, 128.51, 128.12, 122.27, 115.23, 114.53, 108.62,
107.55, 38.83, 68.52, 34.21, 31.96, 31.92, 29.79, 29.70, 29.55, 29.34,
26.46, 26.10, 23.00, 14.43. EI-MS (m/z): Found, 642.6; Calc. 642.4
40-(Undec-10-enyloxy)biphenyl-4-yl 3,5-di(dodecyloxy)benzoate
(5f). Yield: 60%. 1H NMR d [ppm]: 7.58 (d, 2H, J ¼ 8.6 Hz, Ar–
H), 7.51 (d, 2H, J ¼ 8.6 Hz, Ar–H), 7.33 (s, 2H, Ar–H), 7.24
(d, 2H, J ¼ 8.8 Hz, Ar–H), 6.97 (d, 2H, J ¼ 8.7 Hz, Ar–H), 6.71
(s, 1H, Ar–H), 5.84 (m, 1H, HC]CH2), 4.98 (m, 2H, HC]
CH2), 4.00 (m, 6H, OCH2), 2.05 (m, 2H, CH2HC]CH2), 1.80
(m, 6H, OCH2CH2), 1.49–1.20 (m, 54H, (CH2)), 0.88 (t, 6H, J ¼
6.5 Hz, CH3). 13C NMR (CDCl3) d [ppm]: 165.51, 160.75, 159.24,
150.36, 139.57, 139.12, 133.19, 131.69, 128.47, 128.07, 122.22,
115.29, 114.47, 108.70, 107.64, 68.87, 68.56, 34.15, 32.28, 30.00,
29.95, 29.88, 29.74, 29.70, 29.58, 29.48, 29.32, 26.40, 23.03, 14.43.
EI-MS (m/z): Found, 810.9; Calc. 810.6
40-(Undec-10-enyloxy)biphenyl-4-yl 4-(heptyloxy)benzoate (5b).
Yield: 71%. 1H NMR d [ppm]: 8.10 (d, 2H, J ¼ 8.8 Hz, Ar–H),
7.51 (d, 2H, J ¼ 8.8 Hz, Ar–H), 7.44 (d, 2H, J ¼ 8.8 Hz, Ar–H),
7.17 (d, 2H, J ¼ 8.4 Hz, Ar–H), 6.90 (overlapped, dd, 4H, J ¼
8.8 Hz, Ar–H), 5.81 (m, 1H, HC]CH2), 4.95 (m, 2H, HC ¼
CH2), 3.98 (t, 2H, J ¼ 6.4, 6.8 Hz, OCH2), 4.02 (t, 2H, J ¼ 6.4,
6.8 Hz, OCH2), 2.03 (m, 2H, CH2HC ¼ CH2), 1.81 (m, 4H,
OCH2CH2), 1.50 (m, 4H, OCH2CH2CH2), 1.31–1.19 (m, 16H,
(CH2)8), 0.90 (t, 3H, J ¼ 6.6 Hz, CH3). 13C NMR d [ppm]:
165.36, 163.93, 159.16, 150.43, 139.54, 138.91, 133.23, 132.63,
128.44, 128.00, 122.31, 122.03, 115.23, 114.70, 114.46, 68.72,
68.51, 34.14, 32.11, 29.86, 29.77, 29.73, 29.67, 29.48, 29.46,
29.37, 29.29, 26.41, 26.31, 22.94, 14.39. EI-MS (m/z): Found:
556.4. Calc. 556.7. Anal. Calc for C37H48O4: C 79.82%, H
8.69%, found: C 79.58%, H 8.48%
40-(Undec-10-enyloxy)biphenyl-4-yl
3,4,5-tris(butyloxy)
benzoate (5g). Yield: 76%. 1H NMR d [ppm]: 7.59 (d, 2H, J ¼ 8.4
Hz, Ar–H), 7.51 (d, 2H, J ¼ 8.8 Hz, Ar–H), 7.43 (s, 2H, Ar–H),
7.23 (d, 2H, J ¼ 8.4 Hz, Ar–H), 6.97 (d, 2H, J ¼ 8.8 Hz, Ar–H),
This journal is ª The Royal Society of Chemistry 2011
J. Mater. Chem., 2011, 21, 5248–5257 | 5255