LETTER
Synthesis of Anthracene-1,8-ditriflate
1795
product 729 in 79% isolated yield and 6 (11%). Note that
analytically pure 7 was obtained here as well. The actual
yield of 7 was larger than that estimated from its statistical
formation (50%), suggesting that the first substitution oc-
curs easier than the second one. The remaining triflate of
7 was then used for the subsequent Sonogashira coupling
with triisopropylsilylacetylene, which furnished the un-
symmetrically diethynylated product 8,30 where the two
ethynyl groups are orthogonally protected. This com-
pound is useful for further unsymmetric functionaliza-
tions.
(8) Pauvert, M.; Laine, P.; Jonas, M.; Wiest, O. J. Org. Chem.
2004, 69, 543.
(9) (a) Liebermann, C.; Boeck, K. Ber. Dtsch. Chem. Ges. 1878,
11, 1613. (b) Lampe, B. Ber. Dtsch. Chem. Ges. 1909, 42,
1413.
(10) See, for example: (a) Lu, L.; Chen, Q.; Zhu, X.; Chen, C.
Synthesis 2003, 2464. (b) Hui, C. W.; Mak, T. C. W.; Wong,
H. N. C. Tetrahedron 2004, 60, 3523.
(11) Chen, Q.-Y.; Chen, C.-F. Tetrahedron Lett. 2004, 45, 6493.
(12) Andreani, A.; Rambaldi, M.; Bonazzi, D.; Lelli, G.; Greci,
L.; Bossa, R.; Galatulas, I. Arch. Pharm. 1985, 318, 400.
(13) Instead of pyridine, dichloromethane is also usable for the
acetylation as solvent in combination with acetyl chloride
and triethylamine for acid scavenging, affording a
comparable yield of 2.
In conclusion, an easy and robust synthetic access to an-
thracene-1,8-ditriflate was demonstrated as well as its
symmetric and unsymmetric 1,8-diethynylations accord-
ing to the Sonogashira protocol. Particularly, the key re-
(14) 1,8-Diacetoxyanthraquinone (2)12
1H NMR (200 MHz, CDCl3): d = 8.21 (dd, 3J = 7.6 Hz,
4J = 1.1 Hz, 2 H), 7.75 (dd, 3J = 8.0, 7.6 Hz, 2 H), 7.39 (dd,
3J = 8.0 Hz, 4J = 1.1 Hz, 2 H), 2.44 (s, 6 H). 13C NMR (75.5
MHz, CDCl3): d = 181.9, 180.8, 169.4, 150.0, 134.6, 134.4,
130.2, 125.6, 125.4, 21.1. ESI-HRMS: m/z calcd for
C18H12O6 [M + Na]+: 347.0526; found: 347.0527.
(15) The products were separated by preparative recycling gel
permeation chromatography (Japan Analytical Industry Co.
Ltd., LC 9101) equipped with a pump (Hitachi L-7110, flow
rate 3.5 mL/min), a degasser (GASTORR-702), a RI
detector (Jai RI-7), a UV detector (Jai UV-3702, l = 254
nm), and two columns (Jaigel 2H and 2.5H, 20 × 600 mm for
each) using CHCl3 as eluent at r.t.
duction step from the anthraquinone
2
to the
corresponding anthracene 3 was successfully conducted
by minimizing the amount of zinc used. Besides being
facile and reproducible, the present synthesis does not re-
quire toxic reagents, and readily affords 1,8-disubstituted
anthracenes on a multigram scale.
Acknowledgment
Financial support by the ETH grant (TH-05 07-1) is gratefully ack-
nowledged.
(16) 1-Acetoxy-8-hydroxy-10(9H)-anthrone
1H NMR (200 MHz, CDCl3): d = 8.27 (d, 3J = 7.8 Hz, 1 H),
7.96 (d, 3J = 8.4 Hz, 1 H), 7.50 (t, 3J = 7.8 Hz, 1 H), 7.41–
7.28 (m, 2 H), 7.03 (d, 3J = 7.8 Hz, 1 H), 5.27 (br, 1 H), 4.02
(s, 2 H), 2.44 (s, 3 H). HRMS (EI): m/z calcd for C6H12O4
[M]+: 268.0730; found: 268.0730.
References and Notes
(1) See, for example: (a) Bouas-Laurent, H.; Castellan, A.;
Desvergne, J.-P.; Lapouyadé, R. Chem. Soc. Rev. 2001, 30,
248. (b) Bouas-Laurent, H.; Castellan, A.; Desvergne, J.-P.;
Lapouyadé, R. Chem. Soc. Rev. 2000, 29, 43. (c) Becker,
H.-D. Chem. Rev. 1993, 93, 145.
1-Acetoxy-8-hydroxyanthracene
1H NMR (200 MHz, CDCl3): d = 8.76 (s, 1 H), 8.39 (s, 1 H),
7.86 (d, 3J = 8.4 Hz, 1 H), 7.57 (d, 3J = 8.7 Hz, 1 H), 7.48–
7.18 (m, 3 H), 6.75 (d, 3J = 7.2 Hz, 1 H), 5.53 (br, 1 H), 2.54
(s, 3 H). HRMS (EI): m/z calcd for C6H12O3 [M]+: 252.0781;
found: 252.0778.
(2) See, for example: (a) Balan, B.; Gopidas, K. R. Chem. Eur.
J. 2007, 13, 5173. (b) Zhang, G.; Zhang, D.; Ziao, X.; Ai,
X.; Zhang, J.; Zhu, D. Chem. Eur. J. 2006, 12, 1067.
(c) Fudickar, W.; Linker, T. Chem. Eur. J. 2006, 12, 9276.
(d) Okada, M.; Harada, A. Macromolecules 2003, 36, 9701.
(e) Niwa, M.; Morikawa, M.; Nabeta, T.; Higashi, N.
Macromolecules 2002, 35, 2769. (f) Toyota, S.; Kuga, M.;
Takatsu, A.; Goichi, M.; Iwanaga, T. Chem. Commun. 2008,
1323. (g) Ishikawa, T.; Shimasaki, T.; Akashi, H.; Toyota, S.
Org. Lett. 2008, 10, 417. (h) Toyota, S.; Kurokawa, M.;
Araki, M.; Nakamura, K.; Iwanaga, T. Org. Lett. 2007, 9,
3655. (i) Toyota, S.; Suzuki, S.; Goichi, M. Chem. Eur. J.
2006, 12, 2482. (j) Toyota, S.; Goichi, M.; Kotani, M.;
Takezaki, M. Bull. Chem. Soc. Jpn. 2005, 78, 2214.
(k) Sasayama, M.; Naruta, Y. Chem. Lett. 1995, 63.
(3) (a) House, H. O.; Koepsell, D.; Jaeger, W. J. Org. Chem.
1973, 38, 1167. (b) House, H. O.; Ghali, N. I.; Haack, J. L.;
VanDerveer, D. J. Org. Chem. 1980, 45, 1807. (c) House,
H. O.; Hrabie, J. A.; VanDerveer, D. J. Org. Chem. 1986, 51,
921.
1-Acetoxy-8-hydroxy-9,10-dihydroanthracene31
1H NMR (200 MHz, CDCl3): d = 7.33–7.18 (m, 2 H), 7.09
(t, 3J = 7.7 Hz, 1 H), 6.99 (dd, 3J = 7.2 Hz, 4J = 1.5 Hz, 1 H),
6.90 (d, 3J = 7.7 Hz, 1 H), 6.67 (d, 3J = 7.7 Hz, 1 H), 5.75 (br,
1 H), 4.04 (s, 2 H), 3.85 (s, 2 H), 2.46 (s, 3 H). HRMS (EI):
m/z calcd for C6H14O3 [M]+: 254.0938; found: 254.0938.
1,8-Dihydroxyanthracene8,9
1H NMR (200 MHz, DMSO-d6): d = 10.34 (s, 2 H), 9.08 (s,
1 H), 8.37 (s, 1 H), 7.51 (d, 3J = 8.4 Hz, 2 H), 7.32 (dd,
3J = 8.4, 7.0 Hz, 2 H), 6.82 (d, 3J = 7.0 Hz, 2 H). 13C NMR
(50.3 MHz, DMSO-d6): d = 154.4, 133.6, 127.1, 125.5,
124.4, 119.2, 116.7, 106.2. HRMS (EI): m/z calcd for
C14H10O2 [M]+: 210.0676; found: 210.0675.
(17) Hadler, H. I.; Raha, C. R. J. Org. Chem. 1957, 22, 433.
(18) 1,8,10-Triacetoxyanthracene20
1H NMR (200 MHz, CDCl3): d = 8.42 (s, 1 H), 7.82 (d,
3J = 8.8 Hz, 2 H), 7.50 (dd, 3J = 8.8, 7.3 Hz, 2 H), 7.31 (d,
3J = 7.3 Hz, 2 H), 2.62 (s, 3 H), 2.51 (s, 6 H). 13C NMR (75.5
MHz, CDCl3): d = 169.2, 168.9, 146.8, 142.9, 126.0, 125.9,
125.3, 119.5, 117.7, 112.2 21.0, 20.7. HRMS (EI): m/z calcd
for C20H16O6 [M]+: 352.0941; found: 352.0942.
(19) 1,8-Diacetoxy-9,10-dihydroanthracene (3¢)31
1H NMR (300 MHz, CDCl3): d = 7.22–7.13 (m, 4 H), 6.96
(dd, 3J = 7.8 Hz, 4J = 1.1 Hz, 2 H), 4.02 (s, 2 H), 3.66 (s, 2
H), 2.36 (s, 6 H).
(4) (a) Haenel, M. W.; Jakubik, D.; Krueger, C.; Betz, P. Chem.
Ber. 1991, 124, 333. (b) Perez-Trujillo, M.; Maestre, I.;
Jaime, C.; Alvarez-Larena, A.; Piniella, J. F.; Virgili, A.
Tetrahedron: Asymmetry 2005, 16, 3084.
(5) Lovell, J. M.; Joule, J. A. Synth. Commun. 1997, 27, 1209.
(6) Goichi, M.; Segawa, K.; Suzuki, S.; Toyota, S. Synthesis
2005, 2116.
(7) Marquardt, D. J.; McCormick, F. A. Tetrahedron Lett. 1994,
35, 1131.
(20) Brockmann, H.; Budde, G. Chem. Ber. 1953, 86, 432.
Synlett 2008, No. 12, 1793–1796 © Thieme Stuttgart · New York