2
82 JOURNAL OF CHEMICAL RESEARCH 2010
This compound was quite insoluble in all common organic solvents.
Received 19 January 2010; accepted 21 April 2010
Paper 100053 doi: 10.3184/030823410X12743772163259
Published online 8 June 2010
1
The H NMR spectrum was not obtained in CDCl due to the limited
3
solubility of this compound.
Synthesis of 2-[9,9-bis(3-methyl-butyl)-9H-fluoren-2-yl]-4,4,5,5-
tetramethyl[1,3,2]dioxaborolane (6): Prepared in 70% yield from 2-
bromo-9,9-bis(3-methylbutyl)-9H-fluorene 5 followed by the reported
procedure, the synthetic method completely agreed with the reported
References
1
2
3
4
5
6
Q.-C. Zhou, A.-J. Qin, Q.-G. He, G.-T. Lei, L.-D. Wang, Y.Q. Cheng, F.-T.
Ga and F.-L. Bai, Lumine., 2007, 674, 122.
X.-Y. Jiang, Z.-L. Zhang, X.-Y. Zheng, Y.-Z. Wu and S.-H. Xu, Thin Solid
Films, 2001, 401, 251.
B. Balaganesan, W.-J. Shen and C.H. Chen, Tetrahedron Lett., 2003, 44,
32
literature procedure. 6 was obtained from 5 in 70% yield as a colour-
less powder; m.p. 86–88°C; δ (CDCl ) 0.36–0.54 (4H, m, CH ), 0.65
H
3
2
(
6H, d, J= 4.8 Hz, Me), 0.68 (6H, d, J= 4.8Hz, Me), 1.17–1.30 (2H, m,
5
747.
CH), 1.39 (12H, s, Me), 2.02 (4H, t, CH ), 7.31–7.33 (3H, m, ArH),
2
Y. Shibano, T. Umeyama, Y. Matano and H. Imahori, Org. Lett., 2007, 10,
1
+
7
.68–7.83 (4H, m, ArH); m/z: 432 (M ) (Found C, 80.60; H, 9.43.
971.
C H O B (432.46) requires C, 80.54; H, 9.56%).
Y.-L. Liao, C.-Y. Lin, K.-T. Wong, T.-H. Hou and W.-Y. Hung, Org. Lett.,
2007, 10, 4511.
K.R.J. Thomas, J.T. Lin, Y.-T. Tao and C.-W. Ko, J. Am. Chem. Soc., 2001,
2
9
41
2
Synthesis of 1-(9,9-bis(3-methylbutyl)-9H-fluoren-2-yl)pyrene (7):
1
9
1
-Bromopyrene 2 (200 mg, 0.70 mmol), 2-[9,9-bis(3-methylbutyl)-
H-fluoren-2-yl]-4,4,5,5-tetramethyl[1,3,2]dioxaborolane 6 (461 mg,
.07 mmol) and Pd(PPh ) (23 mg, 0.07mmol) and aqueous 2.0 M
1
23, 9404.
7
8
9
G. Venkataramana and S. Sankararaman, Eur. J. Org. Chem., 2005, 4162.
G. Venkataramana and S. Sankararaman, Org. Lett., 2006, 8, 2739.
V.D. Halleux, J.-P. Calbert, P Brocorens, J. Cornil, J.-P Declercq, J.-L.
Bredas and Y. Greets, Adv. Funct. Mater., 2004, 14, 649.
J.N. Moorthy, P. Natarajin, P. Venkatakrishnan, D.-F. Huang and T.J. Chow,
Org. Lett., 2007, 9, 5215.
3
4
K CO (2 mL) were mixed in a flask containing with argon saturated
2
3
toluene (15 mL). The reaction mixture was stirred at 90 °C for 48 h.
After it was cooled to room temperature, the reaction mixture was
quenched with saturated sodium bicarbonate solution and extracted
with toluene (50 mL × 2). The combined organic extracts were
1
0
1
1
C. Modrakowski, S.C. Flores, M. Beinhoff and A.D. Schlüter, Synthesis,
2001, 2143.
dried with anhydrous MgSO and evaporated. The crude product was
12 J. Hu, M. Era, M.R.J. Elsegood and T. Yamato, Eur. J. Org. Chem., 2010,
2.
4
7
purified by column chromatography using hexane as eluent and
recrystallisation from methanol to afford the desired product 7
1
3
M. Beinhoff, W. Weigel, M. Jurczok, W. Rettig and A.D. Schlüter, Eur. J.
Org. Chem., 2001, 3819.
(
265mg, 75%) as colourless prisms, m.p. 244–246°C; δH (CDCl ):
14 H. Shimizu, K. Fujimoto, M. Furusayo, H. Maeda, Y. Nanai, K. Mizuno
3
0
.64–0.75 (12H, m, Me), 0.30–1.37 (4H, m, CH ), 2.02–2.07 (6H, m,
and M. Inouye, J. Org. Chem., 2007, 72, 1530.
A.C. Benniston, A. Harriman, D.J. Lawrie and S.A. Rostron, Eur. J. Org.
Chem., 2004, 2272.
E. Rivera, M. Belletete, X.X. Zhu, G. Durocher and R. Giasson, Polymer,
2002, 43, 5059.
2
1
5
6
CH and CH), 7.35–7.42 (3H, m, ArH), 7.60–7.62 (4H, m, ArH),
7
C H (506.74) requires C, 92.44; H, 7.56%).
Synthesis of isomer of 1,6-bis[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]
pyrene and 1,8-bis[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]pyrene
2
+
.78–8.27 (9H, m, Py-H); m/z: 506 (M ) (Found C, 92.26; H, 7.34.
1
39
38
17 K.-T. Wong, Y.-Y. Chien, R.-T. Chen, C.-F. Wang, Y.-T. Lin, H.-H. Chiang,
P.-Y. Hsieh, C.-C. Wu, C. H. Chou,Y. O. Su, G.-H. Lee, S.-M. Peng, J. Am.
Chem. Soc., 2002, 124, 11576.
D. Katsis,Y.H. Geng, J.J. Ou, S.W. Culligan, A. Trajkovska, S.H. Chen and
L. Rothberg, J. Chem. Mater., 2002, 14, 1332.
19 Y. Geng, S.W. Culligan, A. Trajkovska, J.U. Wallace and S.H. Chen, Chem.
Mater., 2003, 15, 542.
(
[
8a and 8b): Dibromopyrene (3a and 3b) (200 mg, 0.44 mmol), 2-
9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl[1,3,2]d
18
ioxaborolane 6 (475 mg, 1.10mmol), and Pd(PPh ) (0.044 mmol) and
aqueous 2.0 M K CO (2 mL) were mixed in a flask containing with
3
4
2
3
20
S.W. Culligan,Y. Geng, S.H. Chen, K. Klubek, K.M. Vaeth and C.W. Tang,
Adv. Mater., 2003, 15, 1176.
C.-C. Wu, Y.-T. Lin, K.-T. Wong, R.-T. Chen and Y.-Y. Chien, Adv. Mater.,
argon saturated toluene (15 mL). The reaction mixture was stirred at
0°C for 48 h. After it was cooled to room temperature, the reaction
9
2
1
mixture was quenched with saturated sodium bicarbonate solution
and extracted with toluene (50 mL × 2). The combined organic extracts
were dried with anhydrous MgSO and evaporated. The crude product
2
004, 16, 61.
22 Z.H. Li, M.S. Wong, H. Fukutani and Y. Tao, Chem. Mater., 2005, 17,
5032.
4
2
2
3
4
T. Yasuda, K. Fujita and T. Tsutsui, Chem. Mater., 2005, 17, 264.
W.-Y. Lai, R. Zhu, Q.-L. Fan, L.-T. Hou, Y. Cao and W. Huang,
Macromolecules, 2006, 39, 3707.
was purified by column chromatography using hexane as eluent and
recrystallisation from methanol and hexane to afford the desired pro-
duct 8a/8b (230 mg, 65%) as colourless prisms, m.p. 206–208 °C;
δ (CDCl ): 0.60–0.78 (24H, m, Me), 1.23–1.40 (8H, m, CH ), 1.99–
2
5
G. Klaerner and R.D. Miller, Macromolecules 1998, 31, 2007.
H
3
2
26 U. Lemmer, S. Hein, R.F. Mahrt, U. Scherf, M. Hopmeir, U. Wiegner, R.O.
Göbel, K. Müllen and H. Bassler, Chem. Phys. Lett., 1995, 240, 371.
27 S.A. Jenekhe and J.A. Osaheni, Science, 1994, 265, 765.
2
.09 (12H, m, CH and CH), 7.30–7.43 (6H, m, ArH), 7.57–7.64
2
+
(
8H, m, ArH), 7.76–8.28 (8H, m, Py-H); m/z: 810.48 (M ) (Found C,
2
8
R.H. Mitchell, Y.-H. Lai and R.V. Williams, J. Org. Chem., 1979, 44,
4733.
H. Eguchi, H. Kawaguchi, S. Yoshinaga, A. Nishida, T. Nishiguchi and
S. Fujisaki, Bull. Chem. Soc. Jpn., 1994, 67, 1918.
9
1.74; H, 8.17. C H (811.22) requires C, 91.80; H, 8.20%).
62 66
1
The H NMR spectrum of this compound was not obtained due to
29
its limited solubility in CDCl solution. But a strong blue fluorescence
emission was observed in CH Cl solution condition.
Synthesis of 1,3,6,8-tetrakis-[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]
pyrene (9): 1,3,6,8-Tetrabromopyrene 4 (200 mg, 0.39 mmol), 2-[9,9-
bis(3-methylbutyl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl[1,3,2]dioxa
borolane 6 (1003 mg, 2.32 mmol), and Pd(PPh ) (4 mg, 0.013 mmol)
3
30 H. Volmmann, H. Becker, M. Corell and H. Streeck, Justus Liebigs Ann.
Chem., 1937, 531, 1.
2
2
3
1
J. Grimshaw and J.T. Grimshaw, J. Chem. Soc., Perkin Trans. 1, 1972,
622.
1
3
2
W.-L. Yu, J. Pei, Y. Cao, W. Huang and A.J. Heeger, Chem. Commun.,
1999, 1837.
3
4
and aqueous 2.0 M K CO (2 mL) were mixed in a flask containing
33 N. Miyaura, T. Yanagi and A. Suzuki, Synth. Commun., 1981, 11, 513.
2
3
3
4
N. Miyaura, K. Yamada, H. Suginome and A. Suzuki, J. Am. Chem. Soc.,
985, 107, 972.
with argon saturated toluene (50 mL). The reaction mixture was stirred
at 90 °C for 48 h. After it was cooled to room temperature, the reac-
tion mixture was quenched with saturated sodium bicarbonate solu-
tion and extracted with dichloromethane (100 mL × 2). The combined
organic extracts were dried with anhydrous MgSO and evaporated.
The crude product was purified by column chromatography using
1
3
3
5
6
N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, 2457.
R.M. Adihikari, R. Mondal, B.K. Shah and D.C. Neckers, J. Org. Chem.,
2007, 72, 4727.
H. Maeda, T. Maeda, K. Mizuno, K. Fujimoto, H. Shimizu and M. Inouye,
Chem. Eur. J., 2006, 12, 824.
H.M. Kim, Y.O. Lee, C.S. Lim, J.S. Kim and B.R. Cho, J. Org. Chem.
3
3
7
8
4
hexane/dichloromethane (9:1) as eluent to provide 9 (452mg, 82%)
as a pale green solid and recrystallisation from CHCl /EtOH (3:1 v/v)
2
008, 73, 5127.
3
39 J.C. Sciano, Handbook of Organic Photochemistry; CRC Press: Boca
to afford 9 as pale yellow prisms, m.p. 276–278°C; δ (CDCl ):
Raton, FL, 1989; Vol. 1, p 231.
C. Reichardt, Chem. Rev., 1994, 94, 2319.
T. Soujanya, R.W. Fessenden and A. Samanta, J. Phys. Chem., 1996, 100,
H
3
4
4
0
1
0
.66–0.69 (48H, m, Me), 1.23–1.35 (16H, m, CH ), 2.01–2.06 (24H,
2
m, CH and CH), 7.31–7.41 (12H, m, ArH), 7.66–7.88 (16H, m, ArH),
2
3
507.
+
8
.16 (2H, s, Py-H ), 8.19 (4H, s, Py-H ); m/z: 1418.95 (M ) (Found
a
b
4
2
J. D. Jackson (Ed.), Classical electrodynamics, John Wiley & Sons, 1975.
C, 88.70; H, 8.47. C108H122 ·2H O (1456.21) requires C, 89.08;
43 S. Chew, P. Wang, Z. Hong, H.L. Kwong, J. Tang, S. Sun, C.S. Lee and S.T.
2
H, 8.72%).
Lee, J. Lumin., 2007, 124, 221.