B. A. Trofimov et al. / Tetrahedron Letters 50 (2009) 97–100
99
i, ii
iii
iv
H
H
Ph
Ph
Ph
CN
Ph
N
N
N
N
O
N
OH
9
10
1c
2c
58%
Scheme 5. Reagents and conditions: (i). DMF/(COCl)2/CH2Cl2, 10–20 °C, 40 min; (ii) NaOAc/H2O, rt, 30 min; (iii) H2NOHÁHCl, 40–50 °C, 10 min; (iv) Ac2O, 90–100 °C, 5 h.
in the KOH/DMSO–acetylene system, the yield of nitrile 2f being
only 53% (vs 89% according to Scheme 4).21,25
Acknowledgments
Of interest is the one-pot, multi-component synthesis of 1-
vinylpyrrole-2-carbonitriles which involves treatment of pyrroles
with the complex DMF/(COCl)2 and hydroxylamine hydrochloride
in pyridine.27 However, when applied to vinylpyrroles, this method
(according to our experiments) proved to be inefficient
(resinification).
Nevertheless, we found that the direct one-pot synthesis of 1-
vinylpyrrole-2-carbonitriles 2a–f from 1-vinylpyrroles occurred
when pyridine was replaced by sodium acetate and when acetic
anhydride was added. Under these modified conditions, 2-phe-
nyl-1-vinylpyrrole 9 gave nitrile 2c in 58% yield,28 which is 8%
higher than that obtained with isolation of the intermediate 1-
vinylpyrrole-2-carbaldehyde 10 (Scheme 5).17
The structures of nitriles 2a–f were consistent with their IR,
NMR (1H, 13C, 15N), and UV/Vis spectra and elemental analysis
(see the Supplementary data). In the IR spectra of nitriles 2a–f,
intensive C„N and C@C stretching vibrations (2200–2215 cmÀ1
and 1637–1646 cmÀ1, respectively) were observed. The C„N
groups appeared in the region of 112–114 ppm in the 13C NMR
spectra and at À113 to À110 ppm in the 15N NMR spectra. In the
UV/Vis spectra of nitriles 2a–f, absorption bands at 256–315 nm
This work has been carried out under financial support of lead-
ing scientific schools by the President of the Russian Federation
(Grant NSH-263.2008.3) and Presidium of RAS (Project No. 8.20
and Program No. 18).
Supplementary data
Supplementary data associated with this article can be found, in
References and notes
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ˇ
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uged system. The same trends were observed for other nitriles
when compared with the corresponding unsubstituted 1-vinylpyr-
roles22,29 (Table 1).
In conclusion, two expedient methods for the synthesis of 1-
vinylpyrrole-2-carbonitriles, a new series of bifunctionalized pyr-
roles, have been developed. The key reaction of the methods is
dehydration of 1-vinylpyrrole-2-carbaldehyde oximes under the
action of KOH/DMSO–acetylene (method 1) or acetic anhydride
(method 2). Also, the one-pot synthesis of 1-vinylpyrrole-2-carbo-
nitriles directly from 1-vinylpyrroles has been realized.
The synthesized 1-vinylpyrrole-2-carbonitriles are promising
building blocks for the preparation of new pyrrole-based com-
pounds and the design of materials for optoelectronic devices.
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Table 1
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UV/vis and fluorescence spectra of nitriles 2a–f (in hexane)
Nitrile
Absorption
kmax (nm)
Emission kmax
(nm)
Stokes shift
(nm)
log
e
2a
2b
260
256
280
280
284
310
315
3.97
4.01
3.95
4.03
4.05
4.02
4.07
None
337
337
352
355
370
378
—
81
57
72
71
60
63
´
19. (a) Mikhaleva, A. I.; Zaitsev, A. B.; Ivanov, A. V.; Schmidt, E. Yu.; Vasiltsov, A. M.;
Trofimov, B. A. Tetrahedron Lett. 2006, 47, 3693–3696; (b) Vasil’tsov, A. M.;
Ivanov, A. V.; Ushakov, I. A.; Mikhaleva, A. I.; Trofimov, B. A. Synthesis 2007,
452–456.
2c
2d
2e
2f
20. Schmidt, E. Yu.; Mikhaleva, A. I.; Senotrusova, E. Yu.; Vasil’tsov, A. M.; Ivanov, A.
V.; Trofimov, B. A. Russ. J. Org. Chem. 2008, 44, 1395–1396.