potassium carbonate (8.4 g, 61 mmol) followed by 18-crown-6
(20 mg, 0.07 mmol) were added. The reaction mixture was stirred
at room temperature for 1 h. 3-Chloro-4-undec-10-enyloxy-
benzaldehyde (5.56 g, 18 mmol) was added to the yellow reaction
mixture which was heated under reflux for 20 h. After filtration
of inorganic salts, the reaction mixture was evaporated to
dryness and ethanol was added to the oily residue, which led to
the crystallization of product 3. According to the spectral data,
only (E)-stilbene was crystallized from the reaction mixture.
Yield 45%.
gel eluted with 0.5% of methanol in toluene. The disubstituted
product was crystallized from ethyl acetate. Yield of mono-
substituted derivative ¼ 40%, disubstituted ¼ 30%. To the
mixture monosubstituted derivative 6 (0.40 g, 0.75 mmol),
triethylamine (1 ml, 7.13 mmol), tetrahydrofuran (100 ml),
DMAP (20 mg, 0.16 mmol), {(E)-2-[4-nitro-3-(dodecyloxy)-
phenyl]ethenyl}benzoic acid 4 (0.42 g, 0.90 mmol) were added
and the mixture was kept under reflux for 8 h. The asymmetric
final product 12-NCl-11d was purified by column chromatog-
raphy and double recrystallization from ethyl acetate. Yield of
12-NCl-11d ¼ 20% The range of yields of this step varied from
20–40%.
3: NMR: d1H (300 MHz, CDCl3) 8.01 (d, J ¼ 8.4 Hz, 2H, Ar),
7.56 (d, J ¼ 2.4 Hz, 1H, Ar), 7.52 (d, J ¼ 8.1 Hz, 2H, Ar), 7.33
(dd, J1 ¼ 8.7 Hz, J2 ¼ 2.4 Hz, 1H, Ar), 7.03 (q, J ¼ 16.5 Hz, 2H,
CH]CH), 6.89 (d, J ¼ 8.7 Hz, 1H, Ar), 5.86–5.77 (m, 1H,
CH]CH2), 5.02–4.90 (m, 2H, CH]CH2), 4.04 (t, J ¼ 6.6 Hz,
2H, OCH2CH2), 3.92 (s, 3H, OCH3), 2.05–2.00 (m, 2H, CH2),
1.86–1.79 (m, 2H, CH2), 1.51–1.24 (m, 12H, CH2). d13C (75 MHz,
CDCl3) 166.83, 154.55, 141.71, 139.20, 130.18, 130.02, 129.52,
128.76, 128.10, 126.50, 126.41, 126.12, 123.34, 114.11, 113.18,
69.23, 52.04, 33.78, 29.45, 29.38, 29.28, 29.09, 29.03, 28.90, 25.90.
IR (KBr): nmax/cmꢂ1, 2924, 2852, 1713, 1593, 1501, 1469, 1284,
1192, 1108, 970. Elemental analysis calc. (%) for C27H33ClO3
(440,21): C, 73.53, H, 7.54, Cl, 8.04; found C, 73.15, H, 7.60, Cl,
7.95
All asymmetrical products were synthesized using the same
procedure.
6: NMR: d1H (300 MHz, DMSO) 9.60 (s, 1H, Ar–OH), 8.10 (d,
J ¼ 8.4 Hz, 2H, Ar), 7.77–7.74 (m, 3H, Ar), 7.55 (dd, J1 ¼ 8.7 Hz,
J2 ¼ 1.8 Hz, 1H, Ar), 7.34 (q, J ¼ 16.2 Hz, 2H, CH]CH), 7.14 (d,
J ¼ 8.4 Hz, 1H, Ar), 7.05 (t, J ¼ 8.1 Hz, 1H, Ar), 6.75 (d, J ¼ 8.1
Hz, 1H, Ar), 6.38 (d, J ¼ 7.8 Hz, 1H, Ar), 5.83–5.70 (m, 1H,
CH]CH2), 4.99–4.88 (m, 2H, CH]CH2), 4.05 (t, J ¼ 6.3 Hz,
2H, OCH2CH2), 2.07–1.87 (m, 5H, Ar–CH3, CH2), 1.76 (m, 2H,
CH2), 1.42–1.13 (m, 12H, CH2); d (75 MHz, DMSO) 164.01,
13C
156.49, 153.93, 150.13, 142.66, 138.84, 130.24, 130.15, 130.08,
127.88, 127.24, 127.17, 126.62, 126.33, 126.22, 121.87, 116.78,
114.63, 113.83, 112.67, 68.66, 40.33, 40.05, 39.77, 39.50, 39.22,
38.94, 38.66, 33.20, 28.95, 28.79, 28.66, 28.51, 28.30, 25.39, 9.13.
IR (KBr): nmax/cmꢂ1, 3348, 2927, 2851, 1692, 1593, 1497, 1274,
1261, 1098. Elemental analysis calc. (%) for C33H37ClO4 (532.24):
C, 74.35, H, 7.00, Cl, 6.65; found C, 74.61, H, 6.89, Cl, 6.71.
7 (11d-ClCl-11d): NMR: d1H (300 MHz, CDCl3) 8.20 (d, J ¼
8.4 Hz, 4H, Ar), 7.63–7.60 (m, 6H, Ar), 7.39–7.35 (dd, J1 ¼ 2.1
Hz, J2 ¼ 8.7 Hz, 2H, Ar), 7.33–6.91 (m, 9H, Ar, CH]CH), 5.89–
5.75 (m, 2H, CH]CH2), 5.03–4.91(m, 4H, CH]CH2), 4.06 (t, J
¼ 6.6 Hz, 4H, OCH2CH2), 2.12 (s, 3H, Ar–CH3), 2.08–2.01 (m,
All stilbene derivatives were synthesized using a similar
procedure.
Synthesis of 4-{(E)-2-[3-chloro-4-(undec-10-
enyloxy)phenyl]ethenyl}benzoic acid chloride 4
To the solution of 4-{(E)-2-[3-chloro-4-(undec-10-enyloxy)-
phenyl]ethenyl}benzoic acid methyl ester (3 g, 6.81 mmol) in
ethanol (200 ml), a solution of potassium hydroxide (1.15 g, 20.4
mmol) in ethanol (15 ml) was added and the mixture was heated
under reflux for 10–12 h. After cooling the solution, crude
product precipitated as a potassium salt. After drying under
vacuum over sodium hydroxide, the obtained salt was suspended
in toluene (200 ml) and treated with an excess of oxalyl chloride
(5 ml). The reaction mixture was heated under reflux for 8 h.
After filtration of the precipitated potassium chloride, the
remaining solution was evaporated to dryness. The product
slowly solidified at room temperature with a yield of 98%.
All benzoic acid chlorides were synthesized using a similar
procedure.
4H, CH2), 1.90–1.81 (m, 4H, CH2), 1.50–1.32 (m, 24H, CH2); d
13C
(75 MHz, CDCl3) 164.35, 154.65, 150.29, 142.56, 139.18, 130.68,
130.05, 130.00, 128.15, 127.64, 126.54, 126.33, 126.27, 123.94,
123.33, 119.89, 114.11, 113.12, 69.19, 33.78, 29.45, 29.37, 29.28,
29.08, 29.01, 28.88, 25.89, 10.09 IR (KBr): nmax/cmꢂ1, 2924, 2853,
1723, 1593, 1507, 1260, 1103. Elemental analysis calc. (%) for
C59H66Cl2O6 (942.06): C, 75.22, H 7.06, Cl, 7.53; found C, 74.96,
H, 7.05, Cl, 7.78.
12-NCl-11d: NMR: d1H (300 MHz, CDCl3) 8.23–8.19 (m, 4H,
Ar), 8.02 (d, J ¼ 2.4 Hz, 1H, Ar), 7.69–7.59 (m, 6H, Ar), 7.36 (dd,
J1 ¼ 8.7 Hz, J2 ¼ 2.1 Hz, 1H, Ar), 7.33–6.91 (m, 9H, Ar,
CH]CH), 5.86–7.75 (m, 1H, CH]CH2), 5.03–4.92 (m, 2H,
CH]CH2), 4.13 (t, J ¼ 6.3 Hz, 2H, OCH2CH2), 4.06 (t, J ¼ 6.6
Hz, 2H, OCH2CH2), 2.13 (s, 3H, Ar–CH3), 2.06–2.02 (m, 2H,
CH2), 1.88–1.83 (m, 4H, CH2), 1.50–1.27 (m, 30H, CH2), 0.88 (t,
J ¼ 6.6 Hz, 3H, CH2CH3); d13C (75 MHz, CDCl3) 164.28, 152.25,
150.33, 150.28, 142.61, 141.97, 139.22, 132.07, 130.77, 130.71,
130.11, 130.03, 129.19, 128.86, 128.17, 127.92, 127.66, 126.37,
126.30, 123.96, 123.45, 123.38, 114.67, 114.11, 113.17, 69.88,
69.27, 33.80, 31.90, 29.62, 29.56, 29.49, 29.46, 29.38, 29.34, 29.29,
29.26, 29.09, 29.02, 28.90, 25.91, 25.80, 22.68, 14.12, 10.11. IR
(KBr): nmax/cmꢂ1, 2923, 2853, 1732, 1723, 1603, 1592, 1535, 1262,
1231, 1104, 1081. Elemental analysis calc. (%) for C60H70ClNO8
(954.63): C, 74.40, H 7.28, N, 1.45, Cl, 3.66; found C, 74.30, H,
7.06, N, 1.46, Cl, 3.57.
Synthesis of 2-methyl-1,3-{[4-{(E)-2-[4-(dodecyloxy)-3-
nitrophenyl]-1-ethenyl}benzoyloxy]methyl}benzyl-4-{(E)-2-[3-
chloro-4-(undec-10-enyloxy)phenyl]-1-ethenyl}benzoate 12-NCl-
11d
To a solution of 2-methylresorcinol (1.2 g, 9.67 mmol), trie-
thylamine (1 ml, 7.13 mmol) and DMAP (20 mg, 0.16 mmol) in
tetrahydrofuran (100 ml), 4-{(E)-2-[3-chloro-4-(undec-10-eny-
loxy)phenyl]ethenyl}benzoic acid chloride 4 (0.86 g, 1.93 mmol)
in dichloromethane (30 ml) was added dropwise. The reaction
mixture was stirred at room temperature for 4–5 h, then the
solvent was evaporated to dryness under reduced pressure. The
obtained mixture of monosubstituted 6 and disubstituted 7
products was separated by column chromatography using silica
4246 | J. Mater. Chem., 2009, 19, 4240–4247
This journal is ª The Royal Society of Chemistry 2009