PAPER
Mild Oxidation of Diarylacetylenes to 1,2-Diketones
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1-Phenyl-2-p-tolylethane-1,2-dione (2n)8l
Pale-yellow viscous liquid; Rf = 0.41 (n-hexane–EtOAc, 30:1).
13C NMR (100 MHz, CDCl3): d = 111.7 (Cq), 115.8 (CH), 125.6
(CH), 126.1 (CH), 128.4 (2 × CH), 129.7 (2 × CH), 131.1 (Cq),
133.0 (CH), 136.5 (CH), 145.8 (Cq), 163.8 (Cq), 164.1 (Cq).
MS (ESI): m/z = 262 [M + Na]+.
HRMS (ESI): m/z [M + Na]+ calcd for C14H9NO3Na: 262.0482;
1H NMR (400 MHz, CDCl3): d = 2.44 (s, 3 H), 7.31 (d, J = 8.0 Hz,
2 H), 7.48–7.53 (m, 2 H), 7.65 (tt, J = 7.2, 1.2 Hz, 1 H), 7.87 (d,
J = 8.0 Hz, 2 H), 7.95–7.98 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 21.9 (CH3), 129.0 (2 × CH),
129.7 (2 × CH), 129.9 (2 × CH), 130.0 (2 × CH), 130.5 (Cq), 133.1
(Cq), 134.8 (CH), 146.2 (Cq), 194.3 (Cq), 194.8 (Cq).
found: 262.0481.
Benzo[c]isoxazol-3-yl(4-nitrophenyl)methanone (5)17
White solid; mp 175–177 °C; Rf = 0.61 (n-hexane–EtOAc, 5:1).
MS (EI, 70 eV): m/z (%) = 224 (5) [M+], 119 (100), 105 (15), 91
(41).
1H NMR (400 MHz, CDCl3): d = 7.38 (ddd, J = 8.8, 6.0, 0.8 Hz,
1 H), 7.47 (ddd, J = 9.6, 6.4, 0.8 Hz, 1 H), 7.82 (d, J = 9.2 Hz, 1 H),
8.18 (dt, J = 8.8, 1.2 Hz, 1 H), 8.44 (d, J = 8.8 Hz, 2 H), 8.48 (d,
J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 116.2 (CH), 121.4 (CH), 122.2
(Cq), 123.9 (2 × CH), 129.6 (CH), 131.1 (2 × CH), 131.7 (CH),
140.6 (Cq), 150.5 (Cq), 157.5 (Cq), 159.4 (Cq), 179.6 (Cq).
1,2-Di-p-tolylethane-1,2-dione (2o)15
Pale-yellow solid; mp 93–95 °C (Lit.15 103–105 °C); Rf = 0.41
(n-hexane–EtOAc, 30:1).
1H NMR (400 MHz, CDCl3): d = 2.43 (s, 6 H), 7.30 (d, J = 8.4 Hz,
4 H), 7.86 (d, J = 8.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3): d = 21.9 (2 × CH3), 129.7 (4 × CH),
130.0 (4 × CH), 130.6 (2 × Cq), 146.1 (2 × Cq), 194.5 (2 × Cq).
MS (EI, 70 eV): m/z (%) = 268 (100) [M+], 224 (48), 178 (22).
1-(4-Nitrobenzoyl)benzo[c]isoxazol-3(1H)-one (6)
White solid; mp 157–159 °C; Rf = 0.39 (n-hexane–EtOAc, 5:1).
MS (EI, 70 eV): m/z (%) = 238 (8) [M+], 119 (100), 91 (50).
1-(4-Methoxyphenyl)-2-phenylethane-1,2-dione (2p)8l
Pale-yellow solid; mp 62–64 °C (Lit.8l 65 °C); Rf = 0.46 (n-hexane–
EtOAc, 5:1).
1H NMR (400 MHz, CDCl3): d = 7.52 (td, J = 7.6, 0.8 Hz, 1 H), 7.90
(td, J = 8.0, 0.8 Hz, 1 H), 7.99 (dt, J = 7.6, 0.8 Hz, 1 H), 8.16 (d,
J = 8.8 Hz, 2 H), 8.28 (d, J = 8.4 Hz, 1 H), 8.38–8.40 (m, 2 H).
1H NMR (400 MHz, CDCl3): d = 3.89 (s, 3 H), 6.98 (d, J = 8.8 Hz,
2 H), 7.51 (td, J = 7.2, 1.2 Hz, 2 H), 7.65 (tt, J = 7.6, 1.2 Hz, 1 H),
7.95 (d, J = 8.8 Hz, 2 H), 7.99 (dd, J = 7.6, 1.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 111.8 (Cq), 115.8 (CH), 123.6
(2 × CH), 125.9 (CH), 126.8 (CH), 130.8 (2 × CH), 131.8 (Cq),
136.9 (CH), 145.3 (Cq), 150.0 (Cq), 161.7 (Cq), 163.1 (Cq).
13C NMR (100 MHz, CDCl3): d = 55.6 (CH), 114.4 (2 × CH), 126.1
(Cq), 128.9 (2 × CH), 129.9 (2 × CH), 132.4 (2 × CH), 133.2 (Cq),
134.7 (CH), 165.0 (Cq), 193.2 (Cq), 194.9 (Cq).
MS (ESI): m/z = 307 [M + Na]+.
HRMS (ESI): m/z [M + Na]+ calcd for C14H8N2O5Na: 307.0331;
found: 307.0334.
MS (EI, 70 eV): m/z (%) = 135 (100) [M+ – 105], 77 (27).
1-(4-Hydroxyphenyl)-2-phenylethane-1,2-dione (2q)8l
Pale-yellow solid; mp 115–117 °C; Rf = 0.61 (n-hexane–EtOAc,
2:1).
1H NMR (400 MHz, CDCl3): d = 6.18 (br s, 1 H), 6.92 (d, J = 9.0
Hz, 2 H), 7.49–7.53 (m, 2 H), 7.65 (tt, J = 7.2, 1.2 Hz, 1 H), 7.90 (d,
J = 9.0 Hz, 2 H), 7.96–7.99 (m, 2 H).
Acknowledgment
We thank the National Science Council of the Republic of China,
Taiwan for financial support.
References
13C NMR (100 MHz, CDCl3): d = 116.0 (2 × CH), 126.1 (Cq), 129.0
(2 × CH), 129.9 (2 × CH), 132.7 (2 × CH), 133.1 (Cq), 134.8 (CH),
161.7 (Cq), 193.1 (Cq), 194.9 (Cq).
(1) (a) Prasad, K. R. K.; Joshi, N. N. J. Org. Chem. 1996, 61,
3888. (b) Li, X.; Zhao, G.; Cao, W.-G. Chin. J. Chem. 2006,
24, 1402.
MS (EI, 70 eV): m/z (%) = 226 (3) [M+], 121 (100), 105 (13).
(2) (a) Wolkenberg, S. E.; Wisnoski, D. D.; Leister, W. H.;
Wang, Y.; Zhao, Z.; Lindsley, C. L. Org. Lett. 2004, 6,
1453. (b) Deng, X.; Mani, N. Org. Lett. 2006, 8, 269.
(3) (a) Bhosale, R. S.; Sarda, S. E.; Ardhapure, S. S.; Jadhav,
W. N.; Bhusare, S. R.; Pawar, R. P. Tetrahedron Lett. 2005,
46, 7183. (b) Hui, X.; Desrivot, J.; Bories, C.; Loiseau, P.
M.; Franck, X.; Hocquemiller, R.; Figadère, B. Bioorg. Med.
Chem. 2006, 16, 815.
(4) Boyer, J.; Bernardes-Genisson, V.; Nepveu, F. J. Chem.
Res., Synop. 2003, 507.
(5) Mousset, C.; Giraud, A.; Provot, O.; Hamze, A.; Bignon, J.;
Liu, J.-M.; Thoret, S.; Dubois, J.; Brion, J.-D.; Alami, M.
Bioorg. Med. Chem. Lett. 2008, 18, 3266.
1-(2-Nitrophenyl)-2-phenylethane-1,2-dione (2r)16
Pale-yellow solid; mp 124–126 °C; Rf = 0.57 (n-hexane–EtOAc,
1:5).
1H NMR (400 MHz, CDCl3): d = 7.55 (tt, J = 7.6, 1.2 Hz, 2 H), 7.68
(tt, J = 7.2, 1.2 Hz, 1 H), 7.73–7.79 (m, 2 H), 7.86 (td, J = 7.6, 1.2
Hz, 1 H), 8.20–8.23 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 124.1 (CH), 128.6 (2 × CH),
130.8 (2 × CH), 131.1 (CH), 132.4 (CH and Cq), 133.6 (Cq), 134.5
(CH), 134.9 (CH), 150.0 (Cq), 188.0 (Cq), 189.8 (Cq).
MS (EI, 70 eV): m/z (%) = 105 (100) [M+ – 150], 77 (60).
(6) Sessler, J.; Cho, D.-G. Org. Lett. 2008, 10, 73.
(7) (a) Kósa, C.; Lukáč, I.; Weiss, R. G. Macromolecules 2000,
33, 4015. (b) Mosnáček, J.; Weiss, R. G.; Lukáč, I.
Macromolecules 2002, 35, 3870. (c) Mosnáček, J.; Lukáč,
I.; Chromik, Š.; Kostič, I.; Hrdlovič, P. J. Polym. Sci., Part
A: Polym. Chem. 2004, 42, 765. (d) Mosnáček, J.; Weiss,
R. G.; Lukáč, I. Macromolecules 2004, 37, 1304. (e) Kósa,
C.; Mosnáček, J.; Lukáč, I.; Hrdlovič, P.; Chmela, Š.;
Habicher, W. D. J. Appl. Polym. Sci. 2006, 100, 4420.
(f) Husár, H.; Commereuc, S.; Lukáč, I.; Chmela, Š.;
1-Benzoylbenzo[c]isoxazol-3(1H)-one (4)
White solid; mp 134–136 °C; Rf = 0.42 (n-hexane–EtOAc, 10:1).
1H NMR (400 MHz, CDCl3): d = 7.46 (td, J = 7.4, 0.8 Hz, 1 H), 7.53
(tt, J = 8.0, 1.2 Hz, 2 H), 7.63 (tt, J = 7.2, 1.2 Hz, 1 H), 7.85 (td,
J = 7.6, 1.2 Hz, 1 H), 7.95 (dt, J = 7.2, 0.8 Hz, 1 H), 7.99 (dd,
J = 8.0, 1.2 Hz, 2 H), 8.25 (dd, J = 8.0, 0.6 Hz, 1 H).
Synthesis 2009, No. 13, 2155–2162 © Thieme Stuttgart · New York