Macromolecules
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Characterization Data for 1c. White solid; yield 70.5%. IR
(KBr), υ (cm−1): 3063, 2949, 2871, 2219, 1605, 1572, 1508,
1472, 1384, 1303, 1261, 1243, 1176, 1114, 1076, 1044, 1012.
1H NMR (300 MHz, DMSO-d6), δ (ppm): 7.75 (d, J = 7.6 Hz,
2H), 7.55 (d, J = 9.6 Hz, 4H), 7.38−7.32 (m, 4H), 7.28−7.24
(m, 2H), 7.10 (d, J = 6.8 Hz, 4H), 6.90 (d, J = 9.2 Hz, 4H),
6.73 (d, J = 6.8 Hz, 4H), 4.05 (t, J = 6.0 Hz, 4H), 3.96 (m, J =
6.0 Hz, 4H), 1.98−1.91 (m, 8H). 13C NMR (75 MHz, DMSO-
d6), δ (ppm): 162.9, 158.3, 152.4, 140.6, 138.9, 134.7, 129.9,
128.4, 128.0, 126.6, 120.9, 120.0, 115.8, 114.7, 104.5, 68.6, 67.8,
64.8, 26.5, 26.5. HRMS (MALDI-TOF): m/z 696.3051 (M+,
calcd 696.2988). Anal. Calcd for C47H40N2O4: C, 81.01; H,
5.79; N, 4.02; O, 9.18. Found: C, 81.02; H, 5.73; N, 4.13; O,
9.12.
using the standard Schlenk technique in a vacuum line system
or an inert atmosphere glovebox (Vacuum Atmosphere).
Purification of the polymers, on the other hand, was done in
an open atmosphere. The polycyclotrimerization reactions were
catalyzed by trifluoromethanesulfonic acid (CF3SO3H) in o-
dichlorobenzene (o-DCB). A typical experimental procedure
for the polymerization of 1a is given in the following as an
example.
In a 20 mL test tube equipped with a magnetic stirrer were
placed 1a (0.25 mmol) and CF3SO3H (1 mmol) in 2 mL o-
DCB. The mixture solution was stirred at room temperature for
1 h. Afterward, the polymerization was terminated by pouring
the reaction mixture into 300 mL of methanol/hexane solvent
mixture (1:5 v/v) via cotton filter. The precipitates were filtered
by a Gooch crucible, washed with methanol and hexane for
three times, and finally dried in vacuum overnight at room
temperature.
Characterization Data for hb-P1a. Pale yellow solid;
yield 74.7% (Table 4, no. 2). Mw 15 660; Mw/Mn 2.17 (GPC,
polystyrene calibration). IR (KBr), υ (cm−1): 2940, 2867, 1607,
1584, 1505, 1419, 1367, 1249, 1173, 1146, 1109. 1H NMR (300
MHz, DMSO-d6), δ (ppm): 8.67, 7.90, 7.85, 7.19, 7.07, 6.91,
6.88, 4.18, 3.61, 3.38, 3.27, 1.79. 13C NMR (75 MHz, DMSO-
d6), δ (ppm): 170.8, 170.6, 170.0, 165.9, 165.7, 162.4, 161.8,
160.8, 160.0, 134.1, 130.7, 130.4, 129.0, 128.9, 127.9, 126.7,
126.5, 125.4, 115.6, 114.7, 113.8, 71.5, 69.7, 67.4, 26.0, 25.6,
25.3.
Synthesis of 4-(4-Bromobutoxy)benzophenone (8). Com-
pound 8 was prepared from 7 (20.18 mmol), 4 (13.45 mmol),
and K2CO3 (33.63 mmol). The procedures were similar to
1
those of 1a. White solid; yield 35.0%. H NMR (300 MHz,
CDCl3), δ (ppm): 7.82 (d, J = 8.7 Hz, 2H), 7.74 (d, J = 8.3 Hz,
2H), 7.58−7.49 (m, 1H), 7.46−7.43 (m, 2H), 6.94 (d, J = 8.8
Hz, 2H), 4.11−4.05 (m, 2H), 3.51−3.47 (m, 2H), 2.10−1.95
(m, 4H). 13C NMR (75 MHz, CDCl3), δ (ppm): 196.1, 163.1,
138.8, 133.2, 132.5, 130.7, 130.3, 128.8, 114.6, 67.7, 33.9, 29.9,
28.3. HRMS (MALDI-TOF): m/z 333.0110 [(M+1)+, calcd
333.0412].
Synthesis of 1,2-Bis[4-(4-bromobutoxy)phenyl]-1,2-diphe-
nylethene (9). In a two-necked flask equipped with a magnetic
stirrer were added 8 (1.5g, 4.5 mmol), zinc powder (0.59 g, 9.0
mmol), and 40 mL of THF. After the mixture was cooled to
−78 °C, TiCl4 (0.5 mL, 4.5 mmol) was slowly added by a
syringe. The mixture was warmed to room temperature, stirred
for 0.5 h, and then heated to reflux for overnight. After being
cooled to room temperature, the reaction mixture was
quenched with aqueous hydrochloric acid solution and
extracted with dichloromethane. The organic layer was
collected and concentrated. The crude product was purified
by silica-gel column chromatography using hexane as eluent to
hb-P1b: Yellow solid; yield 41.9% (Table 4, no. 5). Mw 8
490; Mw/Mn 1.54 (GPC, polystyrene calibration). IR (KBr), υ
(cm−1): 2950, 2868, 1606, 1584, 1507, 1419, 1368, 1246, 1172,
1
1145, 1029. H NMR (300 MHz, DMSO-d6), δ (ppm): 8.69,
8.63, 8.60, 8.34, 7.86, 7.74, 7.69, 7.30, 7.10, 7.04, 6.94, 6.90,
6.77, 4.19, 4.06, 3.88, 1.96. 13C NMR (75 MHz, DMSO-d6), δ
(ppm): 171.1, 170.8, 170.0, 166.9, 162.3, 158.5, 156.2, 150.0,
144.0, 137.5, 133.8, 131.1, 130.3, 129.2, 128.9, 128.5, 128.1,
128.0, 127.2, 126.7, 126.3, 125.1, 120.2, 115.2, 114.2, 113.8,
113.6, 69.8, 67.3, 66.9, 26.0, 25.4.
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hb-P1c: Pale yellow solid; yield 60.4% (Table 4, no. 8). Mw 8
770; Mw/Mn 1.80 (GPC, polystyrene calibration). IR (KBr), υ
(cm−1): 3037, 2942, 2871, 1606, 1584, 1507, 1473, 1447, 1419,
give a yellow liquid in 82.6% yield (1.18 g). H NMR (300
MHz, CDCl3), δ (ppm): 7.10−7.03 (m, 10H), 6.96−6.89 (m,
4H), 6.62 (t, J = 8.8 Hz, 4H), 3.95−3.89 (m, 4H), 3.51−3.45
(m, 4H), 2.10−2.02 (m, 4H), 1.99−1.87 (m, 4H). 13C NMR
(75 MHz, CDCl3), δ (ppm): 157.9, 144.9, 144.9, 140.3, 137.2,
137.1, 133.2, 132.1, 128.3, 128.2, 126.9, 114.3, 114.2, 67.3, 67.2,
34.2, 30.2, 28.6. HRMS (MALDI-TOF): m/z 634.0459 (M+,
calcd 634.0905).
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1369, 1247, 1174, 1147, 1112, 1030. H NMR (300 MHz,
DMSO-d6), δ (ppm): 8.66, 7.73, 7.65, 7.60, 7.55, 7.52, 7.36,
7.09, 7.02, 6.99, 6.93, 6.91, 6.87, 6.83, 6.81, 6.74, 6.71, 3.97,
3.95, 3.47, 3.41, 3.37, 3.33, 1.93. 13C NMR (75 MHz, DMSO-
d6), δ (ppm): 171.5, 162.7, 161.4, 153.9, 141.2, 139.8, 133.7,
131.4, 130.2, 130.1, 130.0, 129.9, 128.4, 128.0, 127.9, 127.4,
126.7, 126.2, 120.8, 120.5, 115.8, 115.5, 115.3, 115.2, 115.0,
114.8, 71.3, 68.3, 68.0, 66.5, 27.2, 26.7.
Synthesis of 4,4′-[1,2-Diphenylethenylenebis(1,4-
phenylene)dioxybis(1,4-butylene)dioxy] Dibenzonitrile (1d).
Monomer 1d was prepared from 9 (1.39 mmol), 3 (4.16
mmol), and K2CO3 (6.94 mmol) using procedures similar to
those for 1a. Yellow liquid; yield 94.8%. IR (KBr), υ (cm−1):
3050, 2943, 2873, 2223, 1605, 1573, 1508, 1471, 1390, 1302,
hb-P1d: Pale yellow solid; yield 65.6% (Table 4, no. 11). Mw
16 640; Mw/Mn 2.23 (GPC, polystyrene calibration). IR (KBr),
υ (cm−1): 3051, 2944, 2872, 2224, 1584, 1507, 1472, 1419,
1
1
1369, 1301, 1243, 1172, 1146, 1111, 1015. H NMR (300
1242, 1171, 1111, 1044, 1013. H NMR (300 MHz, DMSO-
MHz, DMSO-d6), δ (ppm): 8.70, 8.68, 7.57, 7.54, 7.08, 7.04,
7.01, 6.95, 6.92, 6.89, 6.66, 6.63, 6.60, 4.13, 4.04, 4.02, 3.98,
3.96, 3.94, 1.98, 1.94. 13C NMR (75 MHz, DMSO-d6), δ
(ppm): 171.4, 163.2, 162.9, 158.2, 158.0, 145.0, 144.9, 140.7,
140.1, 139.9, 137.1, 137.0, 135.0, 134.6, 134.0, 133.3, 132.0,
131.4, 129.7, 128.3, 126.8, 126.7, 119.9, 118.1, 115.8, 115.0,
114.2, 114.2, 106.0, 104.5, 68.6, 68.4, 67.9, 67.7, 26.7, 26.5,
26.5.
d6), δ (ppm): 7.57 (d, J = 8.8 Hz, 4H), 7.10−7.02 (m, 10H),
6.96−6.89 (m, 8H), 6.62 (t, J = 9.1 Hz, 4H), 4.09−4.04 (m,
4H), 3.98−3.93 (m, 4H), 2.00−1.92 (m, 8H). 13C NMR (75
MHz, DMSO-d6), δ (ppm): 162.9, 157.9, 145.0, 144.8, 140.3,
137.2, 137.1, 134.7, 133.2, 132.1, 128.3, 128.2, 126.9, 120.0,
115.8, 114.2, 114.2, 104.5, 68.6, 67.8, 26.5. HRMS (MALDI-
TOF): m/z 710.2960 (M+, calcd 710.3145). Anal. Calcd for
C48H42N2O4: C, 81.10; H, 5.96; N, 3.94; O, 9.00. Found: C,
81.10; H, 6.03; N, 4.03; O, 8.84.
Model Reaction. 4-Ethoxybenzonitrile (10) was prepared
from etherization of 3 (40.19 mmol) with 1-bromoethane (26.8
mmol) in the presence of K2CO3 (67.0 mmol). The procedures
Polymer Synthesis. All the polymerization reactions and
manipulations were performed under nitrogen atmosphere
D
dx.doi.org/10.1021/ma402066k | Macromolecules XXXX, XXX, XXX−XXX