WanWong et al.
9
|
(0.08 g, 0.28 mmol), followed by addition of Et3N (1 mL).
The reaction mixture was refluxed under N2 for 36 hours. The
mixture was filtered and the solid was washed with DCM.
The reaction mixture was then concentrated under reduced
pressure and extracted with DCM and water. The organic
layers were dried over Na2SO4 and concentrated using a ro-
tary evaporator. The crude mixture was then purified by col-
umn chromatography over silica with DCM/hexane to yield
mixture was extracted with DCM and water. The organic
layer was dried over Na2SO4 and concentrated using a ro-
tary evaporator. The crude mixture was then purified by col-
umn chromatography over silica with EtOAc/hexane to yield
4-ethynyltriphenylamine 7 (0.17 g, 85%) as a brown solid. 1H
NMR (125 MHz, CDCl3): δ (ppm) 7.29 (m, 2H, CHAR), 7.22
(d, 6H, CHAR), 6.91–7.12 (m, 6H, CHAR), 3.03 (s, 1H, ≡C–
H); 13C-NMR (500 MHz, CDCl3): δ (ppm) 148.36, 147.25,
133.06, 129.42, 125.05, 123.64, 122.05, 114.74, 83.93; EIS
MS (m/z) calculated for C20H15N, 269.12 founded; 270.12
(M + H).
1
5 (0.015 g, 22%) as a dark blue solid. H NMR (500 MHz,
CDCl3): δ (ppm), 7.65 (d, 2H, CHAR), 7.30–7.24 (m, 14H,
CHAR), 7.10 (d, 8H, CHAR), 7.03 (d, 4H, CHAR), 6.99 (d,
4H, CHAR), 2.69 (s, 6H, CH3), 1.52 (s, 6H, CH3), 0.29 (s,
9H, Si(CH3)3); 13C NMR (125 MHz, CDCl3)): δ (ppm)
158.61, 147.86, 147.17, 143.21, 132.86, 132.29, 129.51,
128.03, 124.91, 123.52, 122.40, 116.18, 96.84, 80.59, 29.68,
13.70, −0.13; 11B NMR (160 MHz, CDCl3): δ (ppm), 0.79
(1B, JB–F = 32 Hz); 19F NMR (470 MHz, CDCl3): δ (ppm),
−147.59 (2F, JB–F = 33 Hz); HRMS (ESI) (m/z) calculated
for C64H53BF2N4Si, 954.41; found 954.41.
ACKNOWLEDGEMENTS
ThisworkhasbeensupportedbytheNationalNanotechnology
Center (NANOTEC), NSTDA, Ministry of Science and
Technology, through its program of Center of Excellence
Network and the Thailand Research Fund (Grant no.
TRG5880211 and RSA5980028) and the Center of Excellence
for Innovation in Chemistry (PERCH-CIC).
4.3.6
Synthesis of compound 6
|
REFERENCES
4-Bromotriphenylamine (1.0 g, 3.0 mmol) was dissolved
in toluene (30 mL). The reaction mixture was degassed
for 10 minutes. PdCl2(PPh3)2 (0.1 g, 0.1 mmol) and CuI
(0.03 g, 0.1 mmol) were added, followed by addition of
trimethylsilylacetylene (0.45 g, 4.6 mmol). The reaction
mixture was stirred at room temperature for 30 minutes, fol-
lowed by addition of 1,8-diazabicycloundec-7-ene (DBU;
0.9 g, 6.2 mmol). The reaction mixture was refluxed under
N2 and the completion of the reaction was followed by thin
layer chromatography (TLC). The mixture was filtered and
the solid was washed with DCM. The reaction mixture was
then concentrated under reduced pressure and extracted with
DCM and water. The organic layers were dried over Na2SO4
and concentrated using a rotary evaporator. The crude mix-
ture was then purified by column chromatography over silica
with EtOAc/hexane to afford 4-(trimethylsilyl)ethynyl triar-
ylamine 6 (0.25 g, 26%) as a viscous brown liquid. 1H NMR
(500 MHz, CDCl3): δ (ppm) 7.29 (m, 2H, CHAR), 7.24 (m,
4H, CHAR), 7.03–7.08 (m, 6H, CHAR), 6.94 (d, 2H, CHAR),
0.23 (s, 9H, Si(CH3)3); 13C NMR (125 MHz, CDCl3): δ
(ppm), 148.06, 147.17, 132.92, 129.34, 124.91, 123.49,
122.17, 115.97, 105.39, 98.05, 0.06; MALDI-TOF MS (m/z)
calculated for C23H23NSi, 341.15; found 342.16 (M + H).
[1] J. H. Jou, S. Kumar, A. Agrawal, T. H. Lia, S. Sahooa, J. Mater. Chem. C
2015, 3, 2974.
[2] C. Wang, H. Dong, W. Hu, Y. Liu, D. Zhu, Chem. Rev. 2012, 112, 2208.
[3] S. Wanwong, A. Poe, G. Balaji, S. Thayumanavan, Org. Biomol. Chem.
2014, 12, 2474.
[4] Y. Lin, Y. Lia, X. Zhan, Chem. Soc. Rev. 2012, 41, 4245.
[5] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Petterson, Chem. Rev. 2010,
110, 6595.
[6] B. E. Hardin, H. J. Snaith, M. D. McGehee, Nat. Photonics 2012, 6, 162.
[7] C. Winder, N. Z. Sariciftci, J. Mat. Chem. 2004, 14, 1077.
[8] M. Kivala, F. Diederich, Acc. Chem. Res. 2009, 42, 235.
[9] S. N. Keller, N. L. Veltri, T. C. Sutherland, J. Org. Chem. 2013, 15, 4798.
[10] A. Slama-Schwok, M. Blanchard-Desce, J. M. Lehn, J. Phys. Chem. 1990,
94, 3894.
[11] A. Loudet, K. Burgess, Chem. Rev. 2007, 107, 4891.
[12] N. Boen, V. Leen, W. Dehaen, Chem. Soc. Rev. 2012, 41, 1130.
[13] P. C. Bhooshan, A. M. D. Pelle, S. Thayumanvan, Macromolecules 2011,
44, 4767.
[14] H. Lu, J. Mack, Y. Yanga, Z. Shen, Chem. Soc. Rev. 2014, 43, 4778.
[15] A. M. Poe, A. M. D. Pella, A. V. Subrahmayam, W. White, G. Wantz, S.
Thayumanavan, Chem. Commun. 2014, 50, 2913.
[16] D. Zhang, Y. Wang, Y. Xiao, S. Qian, X. Qian, Tetrahedron 2009, 65, 8099.
[17] J. Wenzel, A. Dreuw, I. Burghardt, Phys. Chem. Chem. Phys. 2013, 15,
11704.
[18] S. K. Gupta, V. A. Raghunathan, S. Kumar, New J. Chem. 2009, 33, 112.
[19] P. Gautam, B. Dhokale, S. M. Mobin, R. Misra, RSC Adv. 2012, 2, 12105.
[20] Z. Ning, H. Tian, Chem. Commun. 2009, 37, 5483.
[21] A. Mishra, P. Bäuerle, Angew. Chem. Int. Ed. 2012, 51, 2020.
[22] Y. Chen, J. Zhao, H. Guo, L. Xie, J. Org. Chem. 2012, 77, 2192.
[23] C. M. Cardona, W. Li, A. E. Kaifer, D. Stockdale, G. C. Bazan, Adv. Mater.
2011, 23, 2367.
4.3.7
Synthesis of compound 7
|
[24] A. B. Nepomhyashchii, A. J. Bard, Acc. Chem. Res. 2012, 45, 1844.
[25] T. Rousseau, A. Gravino, T. Bura, G. Ulrich, R. Ziesselb, J. Roncali, J. Mat.
Chem. 2009, 19, 2298.
[26] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J.
R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H.
Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino,
4-(Trimethylsilyl)ethynyl triarylamine (0.25 g, 0.7 mmol)
was mixed with KOH (0.20 g, 3 mmol) in 20 mL MeOH. The
mixture was refluxed under N2 atmosphere for 48 hours. The
reaction mixture was concentrated under reduced pressure.
A quantity of 1N HCl (10 mL) was added and the reaction