4734
Y.J. Chang, T.J. Chow / Tetrahedron 65 (2009) 4726–4734
J¼4.0 Hz), 7.14 (d, 2H, J¼7.6 Hz), 7.08 (d, 1H, J¼3.9 Hz), 7.03 (d, 1H,
6.93–6.98 (m, 2H), 6.88 (d, 1H, J¼3.9 Hz), 6.49 (d, 1H, J¼3.9 Hz). 13C
J¼7.3 Hz), 6.98 (d, 2H, J¼8.7 Hz). 13C NMR (CDCl3):
d
182.3, 148.6,
NMR (CDCl3): d 182.2, 152.8, 148.3, 147.0, 142.8, 141.2, 139.8, 137.3,
147.4, 146.3, 142.9, 141.1, 137.4, 135.3, 133.7, 131.1, 129.3, 128.5, 127.3,
127.2, 126.9, 126.6, 126.5, 126.4, 126.3, 126.1, 124.0, 123.6, 122.9,
122.8, 122.7, 120.9. FAB HRMS (m/z): 487.1068 (Mþ) (calcd for
C31H21NOS2: 487.1065).
135.1, 133.2, 130.6, 129.1, 128.4, 127.8, 127.5, 126.9, 126.8, 126.4,
126.3, 126.2, 123.6, 123.5, 123.3, 123.2, 121.9, 119.5, 117.8. FAB HRMS
(m/z): 493.0620 (Mþ) (calcd for C29H19NOS3: 493.0629).
3.31. 5-(50-(500-(Diphenylamino)thiophen-200-yl)thiophen-20-
yl)thiophene-2-carbaldehyde (10P)
3.27. 5-(50-(p-Diphenylaminophenyl)thiophen-20-yl)-
thiophene-2-carbaldehyde (8P)
Compound 10P was synthesized according to the same pro-
cedure as that of 10N, giving yellow solid of 10P in 60% yield. 1H
Compound 8P was synthesized according to the same procedure
as that of 7N, giving yellow solid of 8P in 68% yield. 1H NMR (CDCl3):
NMR (CDCl3):
d
9.81 (s, 1H), 7.60 (d, 1H, J¼4.0 Hz), 7.26–7.29 (m,
d
9.84 (s, 1H), 7.65 (d, 1H, J¼3.9 Hz), 7.45 (d, 2H, J¼8.3 Hz), 7.22–7.31
4H), 7.15–7.19 (m, 6H), 7.0 (t, 2H, J¼7.3 Hz), 6.97 (d, 1H, J¼3.6 Hz),
(m, 6H), 7.04–7.17 (m, 9H). 13C NMR (CDCl3):
d
182.3, 148.0, 147.3,
6.93 (d, 1H, J¼3.8 Hz), 6.55 (d, 1H, J¼3.8 Hz). 13C NMR (CDCl3):
147.2, 146.2, 141.2, 137.1, 134.0, 129.3, 127.1, 127.0, 126.5, 124.7, 123.6,
123.4, 123.1, 123.0. FAB HRMS (m/z): 437.0912 (Mþ) (calcd for
C27H19NOS2: 437.0809).
d
182.2, 152.0, 147.4, 146.9, 141.3, 139.7, 137.3, 133.5, 129.3, 123.8,
123.7, 123.6, 123.0, 120.1. FAB HRMS (m/z): 443.0472 (Mþ) (calcd for
C25H17NOS3: 443.0472).
3.28. 5-(50-(500-Bromothiophen-200-yl)thiophen-20-yl)-2-
(naphthylphenylamino)thiophene (9N)
Acknowledgements
This work was supported by the National Science Council and
Academia Sinica of the Republic of China.
Compound 9N was synthesized according to the same pro-
cedure as that of 2N, giving yellow solid of 9N in 47% yield. 1H NMR
(CDCl3):
d
8.02 (d,1H, J¼8.3 Hz), 7.86 (d,1H, J¼8.2 Hz), 7.42–7.52 (m,
Supplementary data
4H), 7.21 (t, 2H, J¼7.9 Hz), 7.04 (d, 2H, J¼8.2 Hz), 6.85–6.97 (m, 6H),
6.52 (d, 1H, J¼4.0 Hz). 13C NMR (CDCl3):
d 151.8, 148.5, 142.8, 138.7,
Solvent-dependent absorption spectra of 1P-PSP and 1P-SSS,
TDDFT calculated orbitals, Mulliken charges, and low energy tran-
sitions of selected compounds, 1H and 13C NMR spectra of all
compounds. Supplementary data associated with this article can be
137.2, 135.1, 134.0, 130.7, 130.6, 129.0, 128.4, 127.4, 126.7, 126.4,
126.3, 126.2, 125.7, 124.4, 123.8, 123.6, 123.0, 122.4, 121.6, 119.1,
118.5, 117.8, 110.6. FAB HRMS (m/z): 542.9774 (Mþ) (calcd for
C28H18BrNS3: 542.9785).
3.29. 5-(50-(500-Bromothiophen-200-yl)thiophen-20-yl)-2-
diphenylaminothiophene (9P)
References and notes
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Compound 9P was synthesized according to the same procedure
as that of 2N, giving yellow solid of 9P in 50% yield. 1H NMR (CDCl3):
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d
7.24–7.27 (m, 4H), 7.14–7.16 (m, 4H), 7.03 (t, 2H, J¼7.3 Hz), 6.94 (d,
1H, J¼3.8 Hz), 6.93 (d, 1H, J¼3.8 Hz), 6.91 (d, 1H, J¼3.8 Hz), 6.89 (d,
1H, J¼3.8 Hz), 6.85 (d, 1H, J¼3.8 Hz), 6.55 (d, 1H, J¼3.8 Hz). 13C NMR
(CDCl3):
d 151.0, 147.4, 138.6, 137.1, 134.2, 130.6, 130.3, 129.2, 124.4,
123.4, 123.3, 123.2, 122.7, 122.4, 120.7, 110.7. FAB HRMS (m/z):
492.9628 (Mþ) (calcd for C24H16BrNS3: 492.9628).
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3.30. 5-(50-(500-(Naphthylphenylamino)thiophen-200-yl)-
thiophen-20-yl)thiophene-2-carbaldehyde (10N)
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To a three-necked flask containing a solution of 9N (0.94 g,
1.73 mmol) in dry THF was added dropwise BuLi (1.6 mL, 2.6 mmol,
1.6 M in hexane) at ꢂ78 ꢀC. The solution was allowed to warm up
gradually to 0 ꢀC for about 30 min. The solution was cooled again to
ꢂ78 ꢀC, then to it was added dropwise DMF (0.2 mL, 2.6 mmol). The
reaction mixture was warmed up to room temperature and was
stirred with a magnetic bar for overnight. The reaction was
quenched by the addition of distilled water, and then was extracted
with CH2Cl2. The organic layers were combined and dried over
anhydrous MgSO4. The solvent was evaporated in vacuo to yield
crude product, which was purified by silica gel column chromato-
graph eluted with CH2Cl2/hexane (1/1). Compound 10P was
obtained as yellow solid in 72% yield (0.61 g, 1.24 mmol). Spectro-
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scopic data for 10N. 1H NMR (CDCl3):
d 9.82 (s, 1H), 8.01 (d, 1H,
13. Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508.
14. Knoevenagel, E. Angew. Chem., Int. Ed. Engl. 1922, 35, 29.
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Cheng, Y.-M.; Chou, P. T. Chem. Mater. 2008, 20, 183.
J¼8.2 Hz), 7.91 (d, 1H, J¼8.0 Hz), 7.83 (d, 1H, J¼7.6 Hz), 7.61 (d, 1H,
J¼4.0 Hz), 7.43–7.53 (m, 4H), 7.14–7.25 (m, 4H), 7.06–7.08 (m, 2H),