2480
T. Zhang et al. / Tetrahedron 70 (2014) 2478e2486
d
ppm): 179.6, 140.2, 125.6, 122.8, 120.3, 118.8, 108.5, 42.5, 33.6,
8.3, 22.3.
100 MHz, d ppm): 139.2, 128.9, 123.4, 123.2, 111.9, 110.3, 43.3, 31.8,
29.7, 29.1, 28.8, 27.2, 22.6, 14.0.
2
2
.2.9. 5-(9H-Carbazol-9-yl)pentanoyl chloride (i). Compound i was
2.2.14. 2-(3,6-Dibromo-9H-carbazol-9-yl)-N-(3-(3,5,7,9,11,13,15-
heptaisobutyl-2,4,6,8,10,12,14,16,17,18,19,20-dodecaoxa-
1,3,5,7,9,11,13,15-octasilapentacyclo[9.5.1.1 .1 .1 ]icosan-1-yl)
propyl)acetamide (M4). A solution of g (10 g, 0.009 mol), NBS
(3.56 g, 0.02 mol) in THF (150 mL) was refluxing for 12 h under
nitrogen atmosphere. After completion of the reaction, the mixture
similarly prepared following the procedure for f by using h. 5.0 g.
Yield: 80%. 1H NMR (CDCl
, 400 MHz, ppm): 8.14 (d, 2H,
d
3,9
5,15 7,13
3
J¼7.7 Hz), 7.53e7.28 (m, 6H), 4.35 (t, 2H, J¼5.9 Hz), 2.86 (m, 2H),
13
2
d
3
.38e1.94 (m, 2H), 1.80e1.72 (m, 2H). C NMR (CDCl , 100 MHz,
ppm): 173.4, 140.2, 125.7, 122.9, 120.4, 119.0, 108.4, 46.5, 42.3,
7.8, 22.8.
2
was concentrated, then purified by column chromatography (SiO
PE/CH Cl , 2/1, v/v). 9.6 g of product was obtained as white powder.
Yield: 86%. H NMR (CDCl
2
,
2
2
1
2
2
.2.10. 5-(9H-Carbazol-9-yl)-N-(3-(3,5,7,9,11,13,15-heptaisobutyl-
,4,6,8,10,12,14,16,17,18,19,20-dodecaoxa-1,3,5,7,9,11,13,15-
3
, 400 MHz,
d
ppm): 8.19 (d, 2H, J¼1.8 Hz),
7.60 (dd, 2H, J¼1.8, 8.6 Hz), 7.23 (d, 2H, J¼8.6 Hz), 5.45 (t, 1H,
J¼5.9 Hz), 4.86 (s, 2H), 3.15 (q, 2H, J¼6.7 Hz), 1.81 (m, 7H), 1.41 (m,
3
,9 5,15 7,13
octasilapentacyclo[9.5.1.1 .1 .1 ]icosan-1-yl)propyl)pentana-
mide (j). Compound j was similarly prepared from i following the
procedure for g. 13.0 g. Yield: 82%. H NMR (CDCl
13
3
2H), 0.95e0.89 (m, 42H), 0.58e0.55 (m, 16H). C NMR (CDCl ,
1
3
, 400 MHz,
100 MHz, d ppm): 166.8, 139.2, 129.9, 124.0, 123.6, 113.6, 110.2, 47.2,
d
ppm): 8.11 (d, 2H, J¼7.8 Hz), 7.52e7.42 (m, 4H), 7.24 (m, 2H), 5.27
s,1H), 4.36 (t, 2H, J¼6.9 Hz), 3.2 (m, 2H), 2.10 (m, 2H),1.98e1.82 (m,
0H), 1.78 (m, 2H), 1.72 (m, 2H), 0.98 (m, 42H), 0.68e0.50 (m, 16H).
41.0, 25.6, 25.6, 23.9, 23.8, 23.0, 22.8, 22.4, 22.3, 21.9, 9.1. HRMS (ESI)
þ
(
calcd m/z for
C
45
H
79Br
2
N
2
O13Si
8
(MþH ) 1239.2083, found
1
1239.2076.
1
3
3
C NMR (CDCl , 100 MHz, d ppm): 172.0, 140.3, 125.6, 122.8, 120.3,
1
2
18.8, 108.6, 42.8, 41.7, 36.3, 28.5, 25.7, 25.6, 23.8, 23.8, 23.1, 22.9,
2.2.15. 5-(3,6-Dibromo-9H-carbazol-9-yl)-N-(3-(3,5,7,9,11,13,15-
heptaisobutyl-2,4,6,8,10,12,14,16,17,18,19,20-dodecaoxa-
1,3,5,7,9,11,13,15-octasilapentacyclo[9.5.1.1 .1 .1 ]icosan-1-yl)
þ
2.5, 22.4, 9.4. HRMS (ESI) calcd m/z for C47
H
85
N
2
O
13Si
8
(MþH )
3
,9 5,15 7,13
1109.4206, found 1109.4238.
propyl)pentanamide (M5). M5 was prepared in a manner similar to
1
2.2.11. 3,6-Divinyl-9-octylcarbazole (M1). To a solution of 3.36 g
M4 by using j instead of g. 8.4 g. Yield: 82%. H NMR (CDCl
3
,
(
(
0.03 mol) potassium tert-butoxide in 100 mL of dried THF, 10.71 g
0.03 mol) methyltriphenylphosphonium bromide was added. After
400 MHz,
d
ppm): 8.16 (d, 2H, J¼1.7 Hz), 7.55 (dd, 2H, J¼1.8, 8.6 Hz),
7.24 (d, 2H, J¼8.6 Hz), 5.27 (m, 1H), 4.36 (t, 2H, J¼7.0 Hz), 3.2 (q, 2H,
stirring for 30 min, 5 g (0.015 mol) of b was slowly added to the
mixture, stirred at room temperature for 30 min, then followed by
J¼6.5 Hz), 2.10 (t, 2H, J¼7.2 Hz), 1.93e1.80 (m, 10H), 1.71 (m, 2H),
13
3
1.58 (m, 2H), 0.98 (m, 42H), 0.68e0.50 (m, 16H). C NMR (CDCl ,
refluxing for 6 h under N
reaction, the mixture was poured into ice water (100 mL), extracted
with methylene chloride, dried over MgSO , filtered, and concen-
trated. The residue was purified by column chromatography (SiO
hexane/methylene chloride 100/1, v/v). As a result, pure product
2
atmosphere. After completion of the
100 MHz, d ppm): 171.9, 139.2, 129.1, 123.4, 123.3, 112.0, 110.4, 43.1,
41.7, 36.3, 28.5, 25.7, 25.6, 23.8, 23.8, 23.1, 22.9, 22.5, 22.4, 9.4. HRMS
þ
4
(ESI) calcd m/z for C47
1267.2357.
2
H83Br N
2
O13Si
8
(MþH ) 1267.2396, found
2
,
P1 The preparation of P1 is given as a typical example for the
preparation of the polymers. A flask was charged with 3,6-divinyl-
9-octylcarbazole (M1) (0.4 g, 1.21 mmol), 3,6-dibromo-9-octyl-
1
was obtained as the colorless oil. 3.67 g. Yield: 74%. H NMR (CDCl
00 MHz,
ppm): 8.10 (d, 2H, J¼0.7 Hz), 7.55 (dd, 2H, J¼1.4, 8.5 Hz),
.31 (d, 2H, J¼1.4 Hz), 6.90 (dd, 1H, J¼10.8, 17.5 Hz), 5.77 (d, 1H,
3
,
4
d
7
2
carbazole (M3) (0.53 g, 1.21 mmol), Pd(OAc) (0.054 g, 0.24 mmol),
J¼17.5 Hz), 5.19 (d, 1H, J¼10.8 Hz), 4.24 (t, 2H, J¼7.2 Hz), 1.84 (m,
and P(o-tolyl) (0.54 g, 2.42 mmol). The flask was evacuated and
3
1
3
2
d
H), 1.28 (m, 10H), 0.85 (t, 3H, J¼6.9 Hz). C NMR (CDCl
3
, 100 MHz,
purged with argon for three times. Then, DMF (10 mL) and trie-
ꢀ
ppm): 140.6, 137.5, 128.9, 124.1, 123.1, 118.4, 111.0, 108.8, 43.2, 31.8,
9.3, 29.1, 28.9, 27.2, 22.6, 14.0.
thylamine (2 mL) were added and the mixture was heated at 90 C
2
for 36 h. Subsequently, it was poured into methanol and the pre-
cipitate was filtered, washed with methanol, and dried. Polymer P1
2.2.12. Bis[6-vinyl-9-octylcarbazol-3-yl] (M2). M2 was prepared in
2 2
was purified by dissolving in CH Cl and was purified by column
a manner similar to M1 by using b. After purified by column
chromatography (neutral alumina oxide, hexane/methylene chlo-
chromatography (neutral alumina oxide, methylene chloride),
concentrated, and dropped into methanol. The precipitate was fil-
tered and dried, then subjected to Soxhlet extraction with ethanol,
hexane. Light yellow powder, 0.37 g. Yield: 41%.
ride 2/1, v/v), 3.9 g of product was obtained as a pale yellow oil.
1
Yield: 70%. H NMR (CDCl
3
, 400 MHz,
d
ppm): 8.46 (s, 2H), 8.27 (s,
2
H), 7.82 (d, 2H, J¼8.4 Hz), 7.65 (d, 2H, J¼8.5 Hz), 7.52 (d, 2H,
J¼8.4 Hz), 7.40 (d, 2H, J¼8.4 Hz), 6.90 (dd, 2H, J¼10.8, 17.5 Hz), 5.78
d, 2H, J¼17.5 Hz), 5.20 (d, 2H, J¼10.8 Hz), 4.40 (t, 6H, J¼7.1 Hz),
P2, P3, P4, P5 were similarly prepared following the P1 pro-
cedures and the reactions depicted in synthetic routes.
(
13
1
1
1
1
.95 (m, 4H), 1.42 (m, 20H), 0.87 (t, 6H, J¼6.8 Hz). C NMR (CDCl
00 MHz, ppm): 140.0, 136.8, 132.7, 128.1, 124.8, 123.3, 122.5,
18.2, 117.8, 110.1, 108.3, 108.0, 42.5, 31.1, 28.6, 28.4, 28.1, 26.5, 21.8,
3.3.
3
,
2.3. Characterization
d
1H NMR and 13C NMR measurements were carried out on
a Bruker arx-500 spectrometer at room temperature with deute-
rium solvents and TMS as an internal reference. FTIR measurements
were performed on a Bruker Tensor-27 Fourier transform infrared
spectrometer using the KBr disk method. Relative molecular weight
and molecular weight distribution of polymer were determined
with a Waters 515-2410 gel permeation chromatography (GPC)
instrument equipped with a Styragel HT6E-H T5-HT3 chromato-
graphic column following a guard column and a differential re-
fractive index detector. The sample solution was filtered with
2.2.13. 3,6-Dibromo-9-octylcarbazole (M3). A solution of 9-
octylcarbazole (5 g, 0.03 mol), NBS (12.46 g, 0.07 mol) in CHCl
3
ꢀ
(
150 mL) was stirred at 40 C for 8 h under nitrogen atmosphere.
Water was added; the organic layer was separated; the aqueous
layer was extracted with CH Cl
for three times (50 mLꢁ3). The
extracts were combined and dried over MgSO , filtered, and con-
2
2
4
centrated. Pure product was obtained after column chromatogra-
phy (SiO2, PE/EA, 80/1, v/v) as light yellow crystals, 11.8 g. Yield:
a 0.45
m
m syringe filter prior to injection. The measurements were
1
ꢀ
9
0%. H NMR (CDCl
3
, 400 MHz,
d
ppm): 8.12 (d, 2H, J¼1.9 Hz), 7.53
carried out at 35 C, and THF was used as the eluent at a flow rate of
1.0 mL/min. The system was calibrated with polystyrene standards.
TGA was recorded with a simultaneous thermal analyzer (STA)
(
dd, 2H, J¼1.9, 8.7 Hz), 7.25 (d, 2H, J¼8.7 Hz), 4.21 (t, 2H, J¼7.2 Hz),
13
1
.81 (m, 2H), 1.25 (m, 10H), 0.85 (t, 3H, J¼6.9 Hz). C NMR (CDCl
3
,