T. Shoji et al.
FULL PAPER
give 21 (249 mg, 90%) as red crystals, m.p. 201.0–205.0 °C decomp.
(
(
1
(
(
CH
m), 1698 (m), 1590 (m), 1496 (s), 1441 (m), 1418 (m), 1363 (w),
327 (w), 1291 (m), 1240 (w), 1212 (m), 1181 (s), 1134 (w), 1086
w), 1053 (w), 906 (w), 812 (w), 778 (m), 732 (m), 712 (w), 668
2
Cl
2
/hexane). IR (KBr disk): ν˜ max = 2962 (w), 2879 (w), 2221
[1] a) J. Kido, Y. Okamoto, Chem. Rev. 2002, 102, 2357–2368; b)
A. C. Grimsdale, K. L. Chan, R. E. Martin, P. G. Jokisz, A. B.
Holmes, Chem. Rev. 2009, 109, 897–1091; c) M. Zhu, J. Zou,
X. He, C. Yang, H. Wu, C. Zhong, J. Qin, Y. Cao, Chem. Ma-
ter. 2012, 24, 174–180; d) Y. Zhang, S.-L. Lai, Q.-X. Tong, M.-
F. Lo, T.-W. Ng, M.-Y. Chan, Z.-C. Wen, J. He, K.-S. Jeff, X.-
L. Tang, W.-M. Liu, C.-C. Ko, P.-F. Wang, C.-S. Lee, Chem.
Mater. 2012, 24, 61–70; e) Y. Liu, S. Chen, J. W. Y. Lam, P.
Lu, R. T. K. Kwok, F. Mahtab, H. S. Kwok, B. Z. Tang, Chem.
Mater. 2011, 23, 2536–2544.
–
1
w) cm . UV/Vis (CH
38 sh (4.73), 404 (4.66), 503 (4.86) nm. UV/Vis (20% CH
ane): λmax (logε) = 264 (4.94), 298 (4.91), 338 sh (4.71), 403 (4.64),
2
Cl
2
): λmax (logε) = 264 (4.95), 300 (4.92),
3
2
2
Cl /hex-
1
4
2
88 (4.84) nm. H NMR (500 MHz, CDCl
3 H
): δ = 10.01 (d, J =
.0 Hz, 3 H, 4-H), 8.47 (d, J = 10.0 Hz, 3 H, 8-H), 8.29 (s, 3 H, 2-
H), 8.17 (d, J = 10.0 Hz, 3 H, 6-H), 8.00 (dd, J = 10.0, 10.0 Hz, 3
H, 7-H), 7.87 (d, J = 9.0 Hz, 6 H, 2Ј,6Ј-H), 7.39 (d, J = 9.0 Hz, 6
[2] a) J. Rivnay, S. C. B. Mannsfeld, C. E. Miller, A. Salleo, M. F.
Toney, Chem. Rev. 2012, 112, 5488–5519; b) S. Feser, K. Meer-
holz, Chem. Mater. 2011, 23, 5001–5005.
H, 3Ј,5Ј-H), 3.97 (s, 9 H, CO
.48 (d, J = 7.0 Hz, 18 H, iPr) ppm. 13C NMR (125 MHz, CDCl
= 167.07 [C=C(CN) ], 164.31 (CO Me), 160.38 [C=C(CN)
2
Me), 3.36 (sept, J = 7.0 Hz, 3 H, iPr),
):
],
1
3
[3]
a) S.-C. Lo, P. L. Burn, Chem. Rev. 2007, 107, 1097–1116; b)
Y.-J. Cheng, S.-H. Yang, C.-S. Hsu, Chem. Rev. 2009, 109,
δ
1
2
C
2
2
2
5868–5923; c) X. Ren, S. Jiang, M. Cha, G. Zhou, Z.-S. Wang,
57.31 (C-5), 149.80 (C-1Ј), 146.24 (C-8a), 142.72 (C-6), 142.45 (C-
), 141.98 (C-3a), 140.91 (C-4), 137.63 (C-8), 132.45 (C-7), 132.16
Chem. Mater. 2012, 24, 3493–3499; d) W. Z. Yuan, Y. Gong, S.
Chen, X. Y. Shen, J. W. Y. Lam, P. Lu, Y. Lu, Z. Wang, R. Hu,
N. Xie, H. S. Kwok, Y. Zhang, J. Z. Sun, B. Z. Tang, Chem.
Mater. 2012, 24, 1518–1528; e) Y. Sun, S.-C. Chien, H.-L. Yip,
Y. Zhang, K.-S. Chen, D. F. Zeigler, F.-C. Chen, B. Lin, A. K.-
Y. Je n , Chem. Mater. 2011, 23, 5006–5015.
(
3
[
(
C-2Ј,6Ј), 128.80 (C-4Ј), 125.26 (C-3Ј,5Ј), 119.70 (C-1), 119.50 (C-
), 113.61 (CN), 112.56 (CN), 112.37 (CN), 111.33 (CN), 86.17
C(CN) ], 80.53 [C(CN) ], 51.81 (CO Me), 39.53 (iPr), 24.48
iPr) ppm. HRMS (FAB) calcd. for C87
·3/4H
2
2
2
+
+
57 13 6
H N O [M] 1379.4550,
found 1379.4575. C87
H
57
N
13
O
6
2
O (1380.47): calcd. C 74.96, [4] a) X.-D. Zhuang, Y. Chen, B.-X. Li, D.-G. Ma, B. Zhang, Y.
H 4.23, N 13.06; found C 75.11, H 4.41, N 13.05.
Li, Chem. Mater. 2010, 22, 4455–4461; b) W.-Y. Lee, T. Kuros-
awa, S.-T. Lin, T. Higashihara, M. Ueda, W.-C. Chen, Chem.
Mater. 2011, 23, 4487–4497; c) Q.-D. Ling, D.-J. Liaw, C. Zhu,
D. S.-H. Chan, E.-T. Kang, K.-G. Neoh, Prog. Polym. Sci.
Compound 22: To a solution of 13 (199 mg, 0.20 mmol) in EtOAc
(20 mL) was added TCNQ (204 mg, 1.00 mmol). The resulting mix-
ture was refluxed for 24 h under an Ar atmosphere. The solvent
was removed under reduced pressure. The residue was purified by
2
008, 33, 917–978; d) K.-L. Wang, Y.-L. Liu, I.-H. Shin, K.-
G. Neoh, E.-T. Kang, J. Polym. Sci., Part A: Polym. Chem.
010, 48, 5790–5800; e) K.-L. Wang, Y.-L. Liu, J.-W. Lee, K.-
column chromatography on silica gel with CH
give 22 (280 mg, 87%) as dark green crystals, m.p. 264.0–267.0 °C
decomp. (CH Cl /hexane). IR (KBr disk): ν˜ max = 2959 (w), 2209
m), 1697 (m), 1591 (m), 1503 (s), 1440 (s), 1420 (s), 1383 (m), 1330
2 2
Cl /EtOAc (10:1) to
2
G. Neoh, E.-T. Kang, Macromolecules 2010, 43, 7159–7164.
[5] a) A. Leliege, P. Blanchard, T. Rousseau, J. Roncali, Org. Lett.
2011, 13, 3098–3101; b) J. Wu, J. Liu, T. Zhou, S. Bo, L. Qiu,
Z. Zhen, X. Liu, RSC Adv. 2012, 2, 1416–1423; c) A. R. Mo-
rales, A. Frazer, A. W. Woodward, H.-Y. Ahn-White, A. Fon-
ari, P. Tongwa, T. Timofeeva, K. D. Belfield, J. Org. Chem.
2
2
(
(m), 1279 (m), 1212 (s), 1191 (s), 1128 (w), 1086 (w), 1032 (w), 972
(
6
w), 904 (w), 839 (w), 809 (w), 777 (w), 729 (w), 698 (w), 673 (w),
57 (w) cm . UV/Vis (CH Cl ): λmax (logε) = 243 (5.01), 296
2 2
–1
2013, 78, 1014–1025.
(
5.05), 394 sh (4.83), 422 (4.89), 628 (4.85) nm. UV/Vis (50%
CH Cl /hexane): λmax (logε) = 243 (4.99), 296 (5.02), 394 sh (4.83),
19 (4.89), 617 (4.83) nm. H NMR (500 MHz, CDCl
d, J = 1.5 Hz, 3 H, 4-H), 8.28 (d, J = 10.0 Hz, 3 H, 8-H), 8.15 (s,
H, 2-H), 8.02 (d, J = 10.0 Hz, 3 H, 6-H), 7.72 (d, J = 8.0 Hz, 6
H, 2Ј,6Ј-H), 7.67 (dd, J = 10.0, 10.0 Hz, 1 H, 7-H), 7.19–7.13 (m,
2 H, HDCNQ and 3Ј,5Ј-H), 7.07–7.01 (m, 6 H, HDCNQ), 3.96 (s, 9
H, CO Me), 3.31 (sept, J = 7.0 Hz, 1 H, iPr), 1.47 (d, J = 7.0 Hz,
8 H, iPr) ppm. C NMR (125 MHz, CDCl
DCNQ), 164.64 (CO Me), 155.10 (C-5), 153.62 [C=C(CN)
49.25 (C-1Ј), 145.13 [C=C(CN) ], 144.75 (C-8a), 143.82 (C-3a),
43.05 (C-2), 141.87 (C-6), 140.29 (C-4), 136.37 (C-8), 136.15
[
6] a) S. Kato, F. Diederich, Chem. Commun. 2010, 46, 1994–2006;
2
2
b) M. Kivala, F. Diederich, Acc. Chem. Res. 2009, 42, 235–
1
4
(
3
3 H
): δ = 9.88
248; c) M. Kivala, T. Stanoeva, T. Michinobu, B. Frank, G.
Gescheidt, F. Diederich, Chem. Eur. J. 2008, 14, 7638–7647; d)
B. B. Frank, B. C. Blanco, S. Jakob, F. Ferroni, S. Pieraccini,
A. Ferrarini, C. Boudon, J.-P. Gisselbrecht, P. Seiler, G. P.
Spada, F. Diederich, Chem. Eur. J. 2009, 15, 9005–9016; e) P.
Fesser, C. Iacovita, C. Wäckerlin, S. Vijayaraghavan, N. Ballav,
K. Howes, J.-P. Gisselbrecht, M. Crobu, C. Boudon, M. Stchr,
T. A. Jung, F. Diederich, Chem. Eur. J. 2011, 17, 5246–5250; f)
B. Breiten, Y.-L. Wu, P. D. Jarowski, J.-P. Gisselbrecht, C. Bou-
don, M. Griesser, C. Onitsch, G. Gescheidt, W. B. Schweizer,
N. Langer, C. Lennartz, F. Diederich, Chem. Sci. 2011, 2, 88–
1
2
13
1
3
): δ
C
= 170.23
],
(C
2
2
1
1
2
(CDCNQ), 133.68 (CDCNQ), 133.25 (C-4Ј), 131.78 (C-2Ј,6Ј), 131.19
9
3; g) A. R. Lacy, A. Vogt, C. Boudon, J.-P. Gisselbrecht, W. B.
(C-7), 131.01, 125.78 (CDCNQ), 125.32 (CDCNQ), 124.84 (C-3Ј,5Ј),
Schweizer, F. Diederich, Eur. J. Org. Chem. 2013, 869–879; h)
B. H. Tchitchanov, M. Chiu, M. Jordan, M. Kivala, W. B.
Schweizer, F. Diederich, Eur. J. Org. Chem. 2013, 3729–3740.
124.17 (C-1), 119.13 (C-3), 114.07 (CN), 113.96 (CN), 113.24 (CN),
1
12.27 (CN), 85.93 [C(CN) ], 74.94 [C(CN) ], 51.72 (CO Me),
2
2
2
3
C
C
9.38 (iPr), 24.48 (iPr) ppm. HRMS (FAB) calcd. for
[7] a) T. Michinobu, Chem. Soc. Rev. 2011, 40, 2306–2316; b) Y.
+
[M]+
Yuan, T. Michinobu, J. Polym. Sci., Part A: Polym. Chem.
105
H
H
69
N
N
13
O
O
6
1607.5489,
found
1607.5481.
2
011, 49, 225–233; c) H. Fujita, K. Tsuboi, T. Michinobu,
105
69
13
6
·H
2
O (1608.76): calcd. C 77.52, H 4.40, N 11.19;
Macromol. Chem. Phys. 2011, 212, 1758–1766; d) Y. Washino,
T. Michinobu, Macromol. Rapid Commun. 2011, 32, 644–648;
e) Y. Li, M. Ashizawa, S. Uchida, T. Michinobu, Macromol.
Rapid Commun. 2011, 32, 1804–1808; f) T. Michinobu, C. Seo,
K. Noguchi, T. Mori, Polym. Chem. 2012, 3, 1427–1435; g) Y.
Li, M. Ashizawa, S. Uchida, T. Michinobu, Polym. Chem.
found C 77.65, H 4.52, N 11.12.
Supporting Information (see footnote on the first page of this arti-
1
13
cle): Copies of H and C NMR, UV/Vis spectra and continuous
change in the visible spectra of the reported compounds.
2
012, 3, 1996–2005; h) T. Michinobu, J. Synth. Org. Chem. Jpn.
Acknowledgments
2013, 71, 149–157.
[
8] a) T. Shoji, S. Ito, K. Toyota, M. Yasunami, N. Morita, Chem.
Eur. J. 2008, 14, 8398–8408; b) T. Shoji, S. Ito, K. Toyota, T.
Iwamoto, M. Yasunami, N. Morita, Eur. J. Org. Chem. 2009,
4316–4324; c) T. Shoji, M. Maruyama, S. Ito, N. Morita, Bull.
This work was partially supported by a Grant-in-Aid for Research
from the Ministry of Education, Culture, Sports, Science, and Tech-
nology, Japan 22850007 and 25810019 to T. S.
7798
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 7785–7799