Synthesis and Properties of 2,3-Dialkynyl-1,4-benzoquinones
FULL PAPER
(m, 4 H), 2.58 (t, 4 H), 6.75 (s, 2 H) ppm. 13C NMR (CDCl3): δ =
14.5, 20.1, 21.8, 30.2, 75.3, 111.4, 132.5, 136.5, 183.0 ppm. MS
(GC-MS): m/z = 268. C18H20O2 (268.36): C 80.56, H 7.51; found:
C 80.76, H 7.73.
pounds 8, 9, 10, 1,4-benzoquinone and 2,3-dioctyl-1,4-benzo-
quionone.
Acknowledgments
2,3-Bis(3,3-dimethylbut-1-ynyl)cyclohexa-2,5-diene-1,4-dione
(9):
Dimethoxy compound 6 (80 mg, 0.27 mmol) was dissolved in ace-
tonitrile (5 mL) and CAN (441 mg, 0.80 mmol, 3 equiv.) dissolved
in water (5 mL) was added during 5 minutes at room temperature.
The homogeneous solution was stirred for 5 minutes and additional
water was added (25 mL). The mixture was extracted with CH2Cl2
(3×15 mL), dried (MgSO4) and filtered through paper. The re-
sulting yellow solution was filtered through a plug of silica and the
solvents evaporated to dryness in vacuo to yield the target com-
pound as a yellow solid. Yield: 68 mg, 95%. M.p. 63–64 °C. 1H
NMR (CDCl3): δ = 1.37 (s, 18 H), 6.72 (s, 2 H) ppm. 13C NMR
(CDCl3): δ = 28.9, 30.5, 73.9, 118.7, 132.2, 136.4, 182.8 ppm. MS
(GC-MS): m/z = 268. C18H20O2 (268.36): C 80.56, H 7.51; found:
C 79.97, H 7.59.
This work would not have been possible without the discussions
with students and staff members at the Department of Chemistry,
University of Copenhagen.
[1] E. Conwell (Ed.), Semiconductors and Semimetals: Highly Con-
ducting Quasi-One-Dimensional Organic Crystals, Academic
Press, Boston, 1988, vol. 27.
[2] T. Murata, Y. Morita, K. Fukui, K. Sato, D. Shiomi, T. Takui,
M. Maesato, H. Yamochi, G. Saito, K. Nakasuji, Angew.
Chem. Int. Ed. 2004, 43, 6343.
[3] R. Bentley, I. M. Campbell, in: The Chemistry of the Quinoid
Compounds, Part 2 (Ed.: S. Patai), John Wiley & Sons, London,
1974, chapter 13.
[4] H. Sies, L. Packer (Eds.), Methods in Enzymology, Elsevier,
Amsterdam, 2004, vol. 378.
[5] H. Sies, L. Packer (Eds.), Methods in Enzymology, Elsevier,
Amsterdam, 2004, vol. 382.
[6] T. Nishinaga, Y. Miyata, N. Nodera, K. Komatsu, Tetrahedron
2004, 60, 3375.
[7] K. C. Nicolaou, A. Liu, Z. Zeng, S. McComb, J. Am. Chem.
Soc. 1992, 114, 9279.
[8] H. W. Moore, K. F. West, U. Wriede, K. Chow, M. Fernandez,
N. V. Nguyen, J. Org. Chem. 1987, 52, 2537.
[9] N. Choy, K. C. Russel, J. C. Alvarez, A. Fider, Tetrahedron
Lett. 2000, 41, 1515–1518.
[10] C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165–195.
[11] R. E. Martin, J. A. Wytko, F. Diederich, C. Boudon, J.-P. Gis-
selbrecht, M. Gross, Helv. Chim. Acta 1999, 82, 1470.
[12] N. N. P. Moonen, C. Boudon, J.-P. Gisselbrecht, P. Seiler, M.
Gross, F. Diederich, Angew. Chem. Int. Ed. 2002, 41, 3044.
[13] A. Auffrant, F. Diederich, C. Boudon, J.-P. Gisselbrecht, M.
Gross, Helv. Chim. Acta 2004, 87, 3085.
[14] G. H. Fisher, H. R. Moreno, J. E. Oatis Jr, H. P. Schultz, J.
Med. Chem. 1975, 18, 746.
[15] C. Flader, J. Liu, R. F. Borch, J. Med. Chem. 2000, 43, 3157.
[16] J. N. H. Reek, A. Rowan, M. J. Crossley, R. J. M. Nolte, J. Org.
Chem. 1999, 64, 6653.
[17] H.-E. Fierz-David, L. Blangey, in Grundlegende Operationen
der Farbenchemie, Springer-Verlag, Wien, 8th ed., 1952, p. 244.
[18] H. H. Hodgson, J. Walker, J. Chem. Soc. 1933, 1620.
[19] H. H. Hodgson, J. Walker, J. Chem. Soc. 1935, 530.
[20] R. Pütter, in: Methoden der Organischen Chemie (Houben-
Weyl), vol. X/3, p. 39, Thieme Verlag, Stuttgart, 1965.
[21] M. Erdélyi, A. Gogoll, J. Org. Chem. 2001, 66, 4165.
[22] J. Eskildsen, T. K. Reenberg, J. B. Christensen, Eur. J. Org.
Chem. 2000, 1637.
[23] P. Jacob, P. S. Callery, A. Shulgin, N. Castagnoli, J. Org. Chem.
1976, 41, 3627.
[24] H. G. Viehe (Ed.), Chemistry of Acetylenes, Dekker, New York,
1962.
[25] F. Diederich, P. J. Stang, R. R. Tykwinski (Eds.), Acetylene
Chemistry, Wiley-VCH, Weinheim, 2005.
[26] M. Pittelkow, T. I. Sølling, J. B. Christensen, Org. Biomol.
Chem. 2005, 3, 2441.
2,3-Bis[(trimethylsilyl)ethynyl]cyclohexa-2,5-diene-1,4-dione
(10):
Dimethoxy compound 7 (0.34 g, 1.0 mmol) was dissolved in aceto-
nitrile (60 mL) and CAN (1.8 g, 3.3 eqv, 3.3 mmol) was added dis-
solved in water (60 mL). The reaction mixture was stirred for
20 minutes at room temperature to give an orange solution. Ad-
ditional water (60 mL) was added and the reaction mixture was
extracted with CH2Cl2 (3×50 mL), dried (MgSO4), filtered
through paper and the solvents evaporated to dryness. The crude
orange oil was purified by dry column vacuum chromatography
(heptane to 20% EtOAc in heptane with 2% increments) to leave
the target compound as a low melting yellow solid material. Yield:
0.28 g, 92%. M.p. 76–77 °C. 1H NMR (CDCl3): δ = 0.29 (s, 18 H),
6.76 (s, 2 H) ppm. 13C NMR (CDCl3): δ = –0.46, 97.3, 117.2, 132.3,
136.5, 182.3 ppm. MS (GC-MS): m/z = 300. C16H20O2Si2 (300.50):
C 63.45, H 6.71; found: C 63.51, H 6.73.
2,3-Diiodo-1,4-benzoquinone (11): Diiodo dimethoxy compound 4
(200 mg, 0.51 mmol) was dissolved in acetonitrile (5 mL), then
CAN (840 mg, 3 equiv., 1.54 mmol) dissolved in water (5 mL), was
added. The reaction mixture was stirred for 20 minutes at room
temperature leaving an orange solution. Additional water (20 mL)
was added and the reaction mixture was extracted with CH2Cl2
(3×30 mL), dried (MgSO4), filtered through paper and the solvents
evaporated to dryness. The crude orange oil was purified by dry
column vacuum chromatography (heptane to 20% EtOAc in hep-
tane with 2% increments) to leave the target compound as a red
solid material. Yield: 179 mg, 97%. M.p. 154–155 °C. 1H NMR
(CDCl3): δ = 7.11 (s, 2 H) ppm. 13C NMR (CDCl3): δ = 133.8,
135.3, 177.6 ppm. MS (GC-MS): m/z = 360. C6H2I2O2 (359.89): C
20.02, H 0.56; found: C 20.30, H 0.62.
2,3-Bis(bromoethynyl)-1,4-dimethoxybenzene (12): Di-TMS com-
pound (7) (200 mg, 6.05 mmol) was dissolved in anhydrous acetone
(10 mL) and NBS (215 mg, 12.1 mmol) was added followed by
AgNO3 (41 mg, 0.2 mmol). The reaction mixture was stirred at
room temperature for 4 hours. The volatiles were removed in vacuo
and the residue was purified by dry column vacuum chromatog-
raphy (heptane to EtOAc with 5% increments) to yield the target
compound as a white solid material. Yield 151 mg, 73%. M.p. 131–
132 °C (decomposes). 1H NMR (CDCl3): δ = 3.82 (s, 6 H), 6.79 (s,
2 H) ppm. 13C NMR (CDCl3): δ = 55.4, 57.8, 74.6, 111.7, 116.4,
154.8 ppm. MS (GC-MS): m/z = 344. C12H8Br2O2 (344.00): C
41.90, H 2.34; found: C 42.25, H 2.17.
[27] A. Kapturkiewicz, J. Electroanal. Chem. 1986, 201, 205.
[28] C. Rüssel, W. Jaenicke, J. Electroanal. Chem. 1984, 180, 205.
[29] C. Rüssel, W. Jaenicke, J. Electroanal. Chem. 1986, 200, 249.
[30] N. Gupta, H. Linschitz, J. Am. Chem. Soc. 1997, 119, 6384.
[31] J. E. Heffner, C. T. Wigal, O. A. Moe, Electroanalysis 1997, 9,
629.
[32] L. H. M. Janssen, A. L. van Til, F. B. van Duijneveldt, Bioelec-
trochem. Bioenerg. 1992, 27, 161.
[33] M. E. Peover, J. Chem. Soc. 1962, 4540.
Supporting Information (see also the footnote on the first page of
this article): Input files used for the TD-DFT calculations on com-
Eur. J. Org. Chem. 2006, 2786–2794
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2793