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Table 4 Application for the synthesis of tetracenediones bearing an
anthraquinone moietya
Science, and Technology (2012M3A7B4049675). This work was
also supported by the National Research Foundation of Korea
(NRF) grant funded by the Korea government (MSIP) (NRF-
2014R1A2A1A11052391).
Notes and references
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a
The ratio of regioisomers was determined by 1H NMR.
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Scheme 3
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Scheme 4
9a was confirmed by comparison with spectral data of the
reported compound.18
Considering the general applicability of the benzannulation
reaction employing 1,4-naphthoquinones, 1,4-anthracenedione,
and 1,2-naphthoquinone, the possibility of the synthesis of
anthraquinones using 1,4-benzoquinone (10) was tested. The
reaction of 1,4-benzoquinoe (10) with 2a at 90 1C for 8 h afforded
two inseparable regioisomers 3t and 3t0 as a 50: 50 mixture in
62% yield. The 1H NMR spectra of 3t and 3t0 were so similar that
the two compounds could not be distinguished by their 1H NMR
spectra. On the other hand, two isomers could be differentiated by
the two carbonyl peaks (3t: 183.1 ppm, 3t0: 183.5 and 182.7 ppm)
in their 13C NMR spectra. With 2b, the desired product 3b was
produced in 41% yield (Scheme 4).
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C. F. Barbas III, Angew. Chem., Int. Ed., 2005, 44, 3706–3710; (c) G. Sabitha,
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1353–1355; (d) S. N. Rao, D. C. Mohan and S. Adimurthy, Org. Lett., 2013,
15, 1496–1499.
In summary, this study developed an efficient and convenient
one-pot synthesis of anthraquinones and tetracenediones from
the benzannulation reaction of various 1,4-naphthoquinones or
1,4-anthracenediones with a,b-unsaturated aldehydes using an
inexpensive, non-toxic and readily available catalyst, L-proline.
This benzannulation process allows the synthesis of various 13 M. Endale, A. Ekberg, J. P. Alao, H. M. Akala, A. Ndakala, P. Sunnerhagen,
M. Erdelyi and A. Yenesew, Molecules, 2013, 18, 311–321.
14 H. Shi, X. Huang, G. Liu, K. Yu, C. Xu, W. Li, B. Zeng and Y. Tang,
functionalized 9,10-anthraquinones and tetracenediones, which
should find a wide range of applications in the synthesis of
Int. J. Quantum Chem., 2013, 113, 1339–1348.
natural products, dyes and pharmaceuticals. Using this method- 15 T. Furumoto, M. Iwata, A. F. M. Feroj Hasan and H. Fukui,
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16 (a) T. R. Kelly, N. D. Parekh and E. N. Trachtenberg, J. Org. Chem.,
ology, phenanthrenequinone derivatives were also synthesized.
As an application of this methodology, 9,10-anthraquinones were
1982, 47, 5009–5013; (b) L. Boisvert and P. Brassard, J. Org. Chem.,
also obtained using 1,4-benzoquinoe as the starting material.
This research was supported by the Nano Material Technology
Development Program through the Korean National Research
Foundation (NRF) funded by the Korean Ministry of Education,
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18 J. E. Gready, K. Hata, S. Sternhell and C. W. Tansey, Aust. J. Chem.,
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Chem. Commun.
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