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was collected by filtration and dried under vacuum. It was
then purified using column chromatography using silica gel
0.69 mmol) were dissolved in dry CH Cl (100 mL) at room tem-
2
2
perature. N, N’-dicyclohexylcarbodiimide (DCC, 1.2 g, 5.8 mmol)
and 4-dimethylaminopyridine (0.5 g, 1.8 mmol) were added to
the solution. The mixture was then stirred at room temperature
2-Hydroxy-3,6,7,10,11-Pentakis(Hexadecyloxy)
Triphenylene
for 10 h. After this the reaction mixture was diluted with CH Cl2
2
In a 1-L round-bottom flask, placed in an ice-water bath, were
dissolved 1,2-di(hexadecyloxy)benzene (20 g, 0.036 mol), 2-
hexadecyloxyphenol (6 g, 0.018 mol), and nitromethane (30 mL)
(200mL). The resulting solution was washed with water
(100 mL) three times. The organic phase was dried over anhy-
drous MgSO , filtered and the solvent was removed. The crude
4
2 2 3
in dried CH Cl (500 mL). Then FeCl (35 g, 0.21 mol) was added
product was purified by column chromatography using silica gel
to the above solution, under vigorous stirring. After 3 h, the solu-
tion was further stirred at room temperature for 1 h. Cold metha-
nol (100 mL) was then slowly added to the reaction mixture. The
organic phase was washed with water three times and dried over
1
with dichloromethane as eluent. H NMR (400 MHz, CDCl , ppm):
3
8
.49–8.11 (b, 1H, Ar-H, c, 1H, Ar-H, f, 1H, Ar-H,), 7.98–7.61 (d, 1H,
Ar-H, l, 1H, Ar-H,), 6.96 (e, 1H, Ar-H,), 6.47 (m, 1H, Ar-H,), 5.00
q, 2H, -HC 5 CH-), 4.30 (g, 10H, -CH2-), 3.41 (n, 2H, -CH-), 2.97
o, 2H, -CH-), 2.25 (p, 2H, -CH2-), 1.97–1.82 (h, 10H, -CH2-),
.51–1.44 (j, 10H. -CH2-), 1.33–1.25 (i, 120H, -CH2-), 1.36–1.26
k, 10H, -CH2-), 0.95–0.92 (l, 15H, -CH3). (MS) (m/z) [M] Calcd
for C113H O N, 1711.39; found, 1710.547.
(
(
1
(
anhydrous MgSO . After removal of the solvent, the crude
4
product was purified by silica-gel column chromatography. (MS)
(
m/z) Calcd. for C H172O6, 1445.32; found, 1445.383.
98
18
7
[3,6,7,10,11-Pentakis(hexadecyloxy)-2-oxytriphenylene]
Methacrylate
4
-[3,6,7,10,11-Pentankis(Hexadecyloxy)-2-
HO-R (0.8 g, 0.00055 mol) and TEA (3 mL) were dissolved in
dry THF (50 mL) to obtain solution A. In another flask, metha-
cryloyl chloride (0.84 g, 0.0081 mol) was dissolved in dry THF
Oxymethylenetriphenylene]Styrene (OTP)
Vinylbenzyl chloride (1.2 g, 7.84 mmol), K CO3 (0.6 g, 4.3
mmol) and very little of tetrabutylammonium bromide
2
(
20 mL) to obtain solution B. The flask containing solution
(
(
TBAB, 80 mg, 0.25 mmol) were dissolved in acetone
100 mL). Then HO-R (0.8 g) and a drop of nitrobenzene
A was cooled in an ice-water bath, and solution B was slowly
added to the solution A, over a period of 0.5 h. The resultant
mixture was further stirred at room temperature for 10 h.
Most of the THF was distilled off under reduced pressure. This
was followed by addition of water to the residue. The crude
solid product was first collected by filtration and dried under
vacuum. The product was purified by column chromatography
on silica gel, using dichloromethane as the eluent.
were added. The reaction mixture was stirred under reflux
and nitrogen atmosphere for 12 h in an oil bath. After this,
the reaction mixture was poured into a large amount of
water. The crude product obtained was dried and then puri-
fied by column chromatograph, using dichloromethane as the
1
eluent. H NMR (400 MH , CDCl , ppm): 7.99–7.74.17 (b, 1H,
Ar-H, c, 1H), 7.68–7.39 (a, 1H, Ar-H, d, 1H, Ar-H, e, 1H, Ar-H,
Z
3
1
f, 1H, Ar-H, m, 1H, Ar-H, n, 1H, Ar-H), 6.73 (o, 1H, Ar-CH5),
H NMR (400 MH , CDCl , ppm): 8.22–8.17 (1H, Ar-H), 7.88–
Z
3
5.71 (p, 1H, 5CH2), 5.41 (l, 2H, -CH2-), 5.28 (q, 1H, 5CH2),
4.24–4.19 (g, 10H, -CH2-), 1.97–1.82 (h, 10H, -CH2-), 1.51–
1.44 (j, 10H. -CH2-), 1.33–1.25 (i, 120H, -CH2-), 1.36–1.26 (k,
10H, -CH2-), 0.95–0.92 (l, 15H, -CH3). MS (m/z) Calcd. for
7
.74 (a, 1H, Ar-H, b, 1H, Ar-H, c and d, 1H, Ar-H, e, 1H, Ar-H,
f, 1H, Ar-H), 6.75 (m, 1H, 5CH2), 6.56 (l, 1H, -CH5), 6.04
n, 1H, 5CH2), 4.24–4.19 (g, 10H, -CH2-), 1.97–1.82 (h, 10H,
CH2-), 1.51–1.44 (j, 10H. -CH2-), 1.33–1.25 (i, 120H, -CH2-),
.36–1.26 (k, 10H, -CH2-), 0.95–0.92 (l, 15H, -CH3). (MS)
m/z) [M] Calcd for C101H174O7, 1500.33; found, 1499.609.
(
-
1
(
C107H108O6, 1562.38; found, 1561.753.
[
3,6,7,10,11-Pentakis(Hexadecyloxy)-2-
Oxytriphenylene]Vinylbenzoate (STP)
N, N’-dicyclohexylcarbodiimide (DCC, 1.7 g, 8.4 mmol),
[
3,6,7,10,11-Pentakis(hexadecyloxy)-2-
oxytriphenylene]methyl Methacrylate
The [3,6,7,10,11-Pentakis(hexadecyloxy)-2-oxytriphenylene]-
methyl methacrylate (MMTP) monomer was synthesized by
a procedure very similar to MTP, mentioned earlier. H NMR
(
4
-dimethylaminopyridine(DMAP, 50 mg, 0.04 mol), HO-
R(1.2 g, 0.84 mmol), and 4-vinylbenzoic acid(1.2 g, 84
1
mmol) were dissolved in CH Cl2 solution and stirred for
2
1
0 h at room temperature. Then the mixture was diluted
400 MH , CDCl , ppm): 8.22–8.17 (b, 1H, Ar-H, c, 1H, Ar-H),
Z 3
with CH Cl (200 mL). The organic phase was washed with
2
2
7
.88–7.74 (a, 1H, Ar-H, d, 1H, Ar-H, e, 1H, Ar-H, f, 1H, Ar-H),
water (100 mL) three times andthe organic phase was
6.45 (o, 1H, 5CH2), 5.81 (n, 1H, 5CH2), 4.24–4.19 (g, 10H, -
CH2-), 2.14 (m, 3H, 5C-CH3), 1.97–1.82 (h, 10H, -CH2-),
dried over anhydrous MgSO , filtered and evaporated. The
4
crude product was purified by column chromatography on
silica gel, with dichloromethane as eluent. H NMR (400
1
1
.51–1.44 (j, 10H. -CH2-), 1.33–1.25 (i, 120H, -CH2-), 1.36–
.26 (k, 10H, -CH2-), 0.95–0.92 (l, 15H, -CH3). MS (m/z)
1
MHz, CDCl , ppm): 8.22–8.17 (b, 1H, Ar-H, c, 1H, Ar-H, f,
3
Calcd. for C102H176O7, 1514.34; found, 1513.775.
1
H, Ar-H, l, 1H, Ar-H,), 7.90–7.74 (a, 1H, Ar-H, e, 1H, Ar-H),
N-{4-[3,6,7,10,11pentakis(Hexadecyloxy)-2-
Oxytriphenylene]Benzoate}-Cis-5-Norbomene-Exo-2,3-
Dicarboximide (NVTP)
7.56 (m, 1H, Ar-H), 6.81 (n, 1H, Ar-CH5), 5.97 (p, 1H,
5CH2), 5.45 (o, 1H, 5CH2), 4.24–4.19 (g, 10H, -CH2-),
1.97–1.82 (h, 10H, -CH2-), 1.51–1.44 (j, 10H. -CH2-),
1.33–1.25 (i, 120H, -CH2-), 1.36–1.26 (k, 10H, -CH2-), 0.95–
N-4-benzoate-cis25-norbomene-exo-2,3-dicarboximide was syn-
41
thesized according to a reported procedure. N-4-benzoate-
0.92 (l, 15H, -CH3). (MS) (m/z) [M] Calcd for C107H O ,
178 7
cis25-norbomene-exo-2,3-dicarboximide (1.0 g) and HO-R (1.0 g,
1574.36; found, 1576.050.
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