T.-C. Lin, et al.
FULL PAPER
(20 mL) under nitrogen, n-butyllithium (1.6 m in hexane, 5.0 mL,
7.98 mmol) was added dropwise at 0 °C. During the addition of n-
butyllithium, the initial orange solid gradually dissolved, and the
color of solution turned to dark brown. The whole system was
stirred at room temperature for 30 min, and then 1-bromohexane
6.96 (m, 24 H, H1, H8), 1.96 (m, 8 H, HfЈ), 1.72–1.70 (m, 32 H,
Hf), 1.10–0.98 (m, 120 H, Hc, Hd, He, HcЈ, HdЈ, HeЈ), 0.81–0.72 (m,
68 H, Ha, HaЈ, HbЈ), 0.62 (m, 32 H, Hb) ppm. 13C NMR (75 MHz,
CDCl3): δ = 154.34 (C17), 153.31 (C7Ј), 152.62 (C18), 152.40 (C5),
150.55 (C16), 148.38 (C10Ј), 147.93 (C4), 147.37 (C11), 145.32 (C19),
(1.12 mL, 7.98 mmol) was added. After the reaction mixture was 142.41 (C10), 141.55 (C22), 141.36 (C9), 139.80 (C8Ј), 138.80 (C9Ј),
stirred for 4 h, the second portion of n-butyllithium (1.6 m in hex- 138.37 (C24), 137.56 (C23), 137.38 (C7), 135.63 (C15), 129.91 (C12),
ane, 5.0 mL, 7.98 mmol) was added dropwise at 0 °C. After another
30 min, the second portion of 1-bromohexane (1.12 mL;
7.98 mmol) was added at room temperature. After the completion
of addition, the resulting mixture was stirred at room temperature
for 12 h, and the reaction was quenched with aqueous ammonium
chloride. The resulting mixture was extracted with ethyl acetate
(30 mLϫ 3). The organic layer was separated, dried with MgSO4
(s), and the solvents were evaporated under vacuum. The crude
product was purified by column chromatography on silica gel,
using hexane as the eluent to give white solid in 58% yield (1.3 g).
1H NMR (300 MHz, CDCl3): δ = 7.75–7.73 (d, J = 7.2 Hz, 2 H,
H2), 7.67 (s, 2 H, H8), 7.63 (s, 2 H, H11), 7.35–7.26 (m, 6 H, H5,
H4, H3), 2.08–2.03 (m, 12 H, Hf, HfЈ), 1.06 (m, 36 H, Hc, Hd, He,
HcЈ, HdЈ, HeЈ), 0.72–0.70 (m, 30 H, Ha, Hb, HaЈ, HbЈ) ppm. 13C
NMR (75 MHz, CDCl3): δ = 151.03 (C1), 150.45 (C10), 150.04 (C7),
141.64 (C6), 141.08 (C12), 140.25 (C9), 126.64 (C4), 126.51 (C2),
122.87 (C8), 119.33 (C3), 113.86 (C5), 113.56 (C11), 54.73 (C13),
54.36 (Cg), 41.03 (Cf), 40.61 (CfЈ), 31.58 (Ce), 31.46 (CeЈ), 29.70 (Cd,
CdЈ), 23.74 (Cc), 23.67 (CcЈ), 22.52 (Cb, CbЈ), 13.97 (Ca, CaЈ) ppm.
129.13 (C2), 128.86 (C3Ј), 127.43 (C2Ј), 125.18 (C1Ј), 124.35 (C13),
123.84 (C3), 123.40 (C14), 122.51 (C1), 120.80 (C6), 120.04 (C4Ј),
119.14 (C8), 118.85 (C21), 118.24 (C5Ј), 113.85 (C20), 55.05 (Cg, C6Ј),
40.08 (Cf, CfЈ), 31.52 (Ce, CeЈ), 29.59 (Cd, CdЈ), 23.84 (Cc, CcЈ), 22.58
(Cb, CbЈ), 14.07 (Ca, CaЈ) ppm. MALDI-TOF: [M + H]+ calcd. for
C372H408N18 5132.3405; found 5132.4873.
Compound 2: Compound 9 (0.42 g, 0.418 mmol), compound 10
(1.9 g, 0.836 mmol), Pd2(dba)3 (15.3 mg, 0.0167 mmol), sodium
tert-butoxide (0.096 g, 1.003 mmol), P(tBu)3 (7 mg, 0.034 mmol),
and dry toluene (15 mL) were charged into a high-pressure tube,
and the whole system was stirred at 110 °C under Ar for 24 h. After
cooling to room temperature, the solution was extracted with ethyl
acetate (30 mLϫ 3) and then dried with MgSO4 (s). After removing
the solvent, the crude product was purified by column chromatog-
raphy on silica gel using THF/hexane (1:6) as the eluent to give a
dark-yellow powder in 53.3% yield (1.2 g). 1H NMR (300 MHz,
CDCl3): δ = 8.11–8.08 (d, J = 9.3 Hz, 4 H, H22), 7.95–7.94 (d, J =
1.8 Hz, 4 H, H19), 7.82–7.80 (d, J = 8.1 Hz, 2 H, H5Ј), 7.71–7.64
(m, 8 H, H21, H8Ј, H11Ј), 7.56–7.48 (m, 32 H, H9, H12, H13, H15),
7.34–7.32 (m, 4 H, H2Ј, H4Ј), 7.23–7.19 (m, 32 H, H2), 7.12–7.07
(m, 40 H, H3, H6), 7.02–6.96 (m, 24 H, H1, H8), 2.08–1.99 (m, 12
H, HfЈ, HfЈЈ), 1.70 (m, 32 H, Hf), 1.10–1.00 (m, 132 H, Hc, Hd, He,
HcЈ, HdЈ, HeЈ, HcЈЈ, HdЈЈ, HeЈЈ), 0.76–0.72 (m, 78 H, Ha, HaЈ, HbЈ,
HaЈЈ, HbЈЈ), 0.62 (m, 32 H, Hb) ppm. 13C NMR (75 MHz, CDCl3):
HRMS-FAB: [M
847.7121.
+
H]+ calcd. for C63H90 847.7043; found
2,10-Dibromo-6,6,12,12,15,15-hexahexyl-12,15-dihydro-6H-cyclo-
penta[1,2-b:5,4-bЈ]difluorene (9): A mixture of compound 8 (1.3 g,
1.53 mmol), zinc chloride (0.48 g, 3.52 mmol), and BTMABr3
(1.26 g, 3.21 mmol) in acetic acid (20 mL) was stirred at 70 °C for δ = 154.32 (C17), 153.22 (C1Ј), 152.61 (C18), 152.36 (C5), 150.77
12 h under nitrogen. After cooling to room temperature, saturated
NaHSO3 (aq, 50 mL) was added to the reaction mixture and stirred
for 1 h. After filtration, the crude solid product was collected and
recrystallized from methanol. The purified product was obtained
as a pale pink solid in 71.2% yield (1.1 g). 1H NMR (300 MHz,
(C10Ј), 150.50 (C16), 148.40 (C7Ј), 147.91 (C4), 147.36 (C11), 145.15
(C19), 142.41 (C10), 141.54 (C22), 141.35 (C9), 140.95 (C9Ј), 139.50
(C12Ј), 139.06 (C6Ј), 138.33 (C24), 137.57 (C23), 137.38 (C7), 135.56
(C15), 129.89 (C12), 129.12 (C2), 128.86 (C4Ј), 127.38 (C3Ј), 125.28
(C2Ј), 124.34 (C13), 123.82 (C3), 123.38 (C14), 122.49 (C1), 121.40
CDCl3): δ = 7.62 (s, 2 H, H8), 7.61–7.59 (d, J = 8.4 Hz, 2 H, H5), (C5Ј), 120.78 (C6), 119.92 (C20), 119.11 (C8), 118.95 (C21), 113.77
7.57 (s, 2 H, H11), 7.48–7.45 (m, 4 H, H2, H4), 2.07–1.99 (m, 12 H, (C11Ј), 113.65 (C8Ј), 55.04 (Cg, CgЈ, C13Ј), 40.07 (Cf, CfЈ, CfЈЈ), 31.52
Hf, HfЈ), 1.05 (m, 36 H, Hc, Hd, He, HcЈ, HdЈ, HeЈ), 0.75–0.67 (m, (Ce, CeЈ, CeЈЈ), 29.54 (Cd, CdЈ, CdЈЈ), 23.81 (Cc, CcЈ, CcЈЈ), 22.57 (Cb,
30 H, Ha, Hb, HaЈ, HbЈ) ppm. 13C NMR (75 MHz, CDCl3): δ = CbЈ, CbЈЈ), 14.05 (Ca, CaЈ, CaЈЈ
) ppm. MALDI-TOF(m/z):
153.29 (C1), 150.70 (C10), 149.77 (C7), 141.26 (C9), 140.58 (C12), [M + H]+ calcd. for C391H436N18, 5388.7661, found 5388.9204.
139.28 (C6), 129.78 (C4), 126.13 (C2), 120.74 (C5), 120.45 (C3),
Supporting Information (see footnote on the first page of this arti-
113.96 (C11), 113.65 (C8), 55.09 (C13), 54.41 (Cg), 40.86 (Cf), 40.43
cle): Numbering of carbons and hydrogens on various structural
(CfЈ), 31.50 (CeЈ), 31.39 (Ce), 29.63 (CdЈ), 29.57 (Cd), 23.59 (Cc, CcЈ),
units and optical experiment details.
22.47 (Cb, CbЈ), 13.93 (Ca, CaЈ) ppm. HRMS-FAB: [M]+ calcd. for
C63H88Br2 1005.1808; found 1005.2076.
Acknowledgments
Compound 1: A mixture of compound 10 (2.21 g, 0.976 mmol),
compound 11 (0.365 g, 0.488 mmol), Pd2(dba)3 (17.9 mg,
0.0195 mmol), sodium tert-butoxide (0.113 g, 1.17 mmol), and
P(tBu)3 (8 mg, 0.039 mmol) in dry toluene (15 mL) was loaded into
a high-pressure tube (from ACE Glass) and stirred at 110 °C under
The authors acknowledge the financial support from National Sci-
ence Council (NSC), Taiwan under grant number 101-2113-M-008-
003-MY2.
Ar for 24 h. After cooling to room temperature, the solution was
extracted with ethyl acetate (30 mLϫ 3), and the organic layer was
collected and dried with MgSO4 (s). After removing the solvent,
the crude product was purified by column chromatography on silica
gel using THF/hexane (1:8) as the eluent to give a dark yellow
[1] For recent reviews, see: a) S. Yao, K. D. Belfield, Eur. J. Org.
Chem. 2012, 3199–3217; b) M. Pawlicki, H. A. Collins, R. G.
Denning, H. L. Anderson, Angew. Chem. 2009, 121, 3292–
3361; Angew. Chem. Int. Ed. 2009, 48, 3244–3266; c) M. Rumi,
S. Barlow, J. Wang, J. W. Perry, S. R. Marder, Adv. Polym. Sci.
2008, 213, 1–95; d) K. D. Belfield, S. Yao, M. V. Bondar, Adv.
Polym. Sci. 2008, 213, 97–156.
[2] For recent reviews, see: a) H. M. Kim, B. R. Cho, Chem. Com-
mun. 2009, 153–164 and the references therein b) F. Terenziani,
C. Katan, E. Badaeva, S. Tretiak, M. Blanchard-Desce, Adv.
Mater. 2008, 20, 4641–4678 , and the references therein.
1
powder in 64.8% yield (1.62 g). H NMR (300 MHz, CDCl3): δ =
8.10–8.07 (d, J = 9.3 Hz, 4 H, H22), 7.95–7.94 (d, J = 2.1 Hz, 4 H,
H19), 7.80–7.78 (d, J = 8.4 Hz, 2 H, H4Ј), 7.70–7.66 (dd, J1 = 9.3,
J2 = 2.1 Hz, 4 H, H21), 7.63 (s, 2 H, H5Ј), 7.55–7.47 (m, 32 H, H9,
H12, H13, H15), 7.34–7.31 (d, J = 8.4 Hz, 2 H, H3Ј), 7.26 (s, 2 H,
H1Ј), 7.24–7.19 (m, 32 H, H2), 7.12–7.08 (m, 40 H, H3, H6), 7.02–
1620
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