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G. Cahiez et al.
Paper
Synthesis
Phenol10
13C NMR (100 MHz, CDCl3): δ = 157.44 (d, J = 238.4 Hz, C4), 151.47 (d,
J = 2 Hz, C1), 116.37 (d, J = 8.1 Hz, C2+C6), 116.15 (d, J = 23.2 Hz,
C3+C5).
Yield: 386 mg (82%); white solid, mp = 45 ºC.
1H NMR (400 MHz, CDCl3): δ = 7.24 (dd, J = 8.6, 7.6 Hz, 2 H, H3+H5),
6.93 (tt, J = 7.6, 1.0 Hz, 1 H, H4), 6.83 (dd, J = 8.6, 1.0 Hz, 2 H, H2+H6),
5.13 (s, 1 H, H7).
MS (EI, 70 eV): m/z [M]+ = 112.
4-Aminophenol17
13C NMR (100 MHz, CDCl3): δ = 155.47 (C1), 129.83 (C3+C5), 120.98
Yield: 431 mg (79%); white solid, mp = 190 ºC.
(C4), 115.43 (C2+C6).
1H NMR (400 MHz, DMSO-d6): δ = 6.48 (d, J = 8.9 Hz, 2 H, H2+H6),
6.42 (d, J = 8.9 Hz, 2 H, H3+H5), 4.40 (s, 1 H, H7).
MS (EI, 70 eV): m/z [M]+ = 94.
3-Methoxyphenol11
13C NMR (100 MHz, DMSO-d6): δ = 148.28 (C1), 140.64 (C4), 115.58
(C2+C6), 115.31 (C3+C5).
MS (EI, 70 eV): m/z [M]+ = 109.
Yield: 490 mg (79%); yellow oil.
1H NMR (400 MHz, CDCl3): δ = 7.11 (t, J = 8.0 Hz, 1 H, H5), 6.53–6.38
(m, 3 H, H2+H4+H6), 3.74 (s, 3 H, H8).
13C NMR (100 MHz, CDCl3): δ = 160.82 (C3), 156.74 (C1), 130.36 (C5),
2-Naphthol18
Yield: 505 mg (70%); white solid, mp = 120 ºC.
108.14 (C6), 106.61 (C4), 101.71 (C2), 55.42 (C8).
1H NMR (400 MHz, DMSO-d6): δ = 9.73 (s, 1 H, H11), 7.78–7.73 (m, 2
H, H4+H6), 7.70–7.65 (m, 1 H, H9), 7.38 (ddd, J = 8.2, 6.8, 1.2 Hz, 1 H,
H7), 7.25 (ddd, J = 8.2, 6.8, 1.2 Hz, 1 H, H8), 7.15 (d, J = 2.4 Hz, 1 H, H1),
7.11 (dd, J = 8.8, 2.4 Hz, 1 H, H3).
13C NMR (100 MHz, DMSO-d6): δ = 155.35 (C2), 134.65 (C10), 129.34
(C4), 127.77 (C5), 127.58 (C6), 126.14 (C8), 126.03 (C9), 122.67 (C7),
118.66 (C3), 108.70 (C1).
MS (EI, 70 eV): m/z [M]+ = 124.
4-Methoxyphenol12
Yield: 441 mg (71%); white solid, mp = 56 ºC.
1H NMR (400 MHz, CDCl3): δ = 6.78 - 677 (m, 4 H, H2+H3+H5+H6),
4.84 (s, 1 H, H7), 3.76 (s, 3 H, H8).
13C NMR (100 MHz, CDCl3): δ = 153.81 (C4), 149.59 (C1), 116.19
MS (EI, 70 eV): m/z [M]+ = 144.
(C2+C6), 115.01 (C3+C5), 55.96 (C8).
MS (EI, 70 eV): m/z [M]+ = 124.
Funding Information
2-Methoxyphenol13
We thank the CNRS for its financial support, the Ministère de l’Educa-
tion Nationale et de la Recherche for a grant to M.P. and M2i company
for a grant to E.Z.
Yield: 472 mg (76%); colorless oil.
1H NMR (400 MHz, CDCl3): δ = 6.95–6.84 (m, 4 H, H3+H4+H5+H6),
5.61 (s, 1 H, H7), 3.89 (s, 3 H, H8).
)(
13C NMR (100 MHz, CDCl3): δ = 146.68 (C2), 145.78 (C1), 121.58 (C5),
120.27 (C4), 114.64 (C6), 110.81 (C3), 56.00 (C8).
MS (EI, 70 eV): m/z [M]+ = 124.
Supporting Information
Supporting information for this article is available online at
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4-Methylphenol14
Yield: 379 mg (70%); white solid, mp = 34 ºC.
1H NMR (400 MHz, CDCl3): δ = 7.03 (d, J = 8.3 Hz, 2 H, H3+H5), 6.73 (d,
J = 8.3 Hz, 2 H, H2+H6), 4.84 (s, 1 H, H7), 2.27 (s, 3 H, H8).
References
(1) For selected references on Cu-mediated decarboxylation of aro-
matic carboxylic acids, see: (a) Fager, E. W. J. Am. Chem. Soc.
1945, 67, 2217. (b) Turnbull, S. G. Jr. US Patent 2453103, 1948.
(c) Cairncross, A.; Roland, J. R.; Henderson, R. M.; Sheppard, W.
A. J. Am. Chem. Soc. 1970, 92, 3187. (d) Cohen, T.; Schambach, R.
A. J. Am. Chem. Soc. 1970, 92, 3189. (e) Cohen, T.; Berninger, R.
W.; Wood, J. T. J. Org. Chem. 1978, 43, 837. (f) Nilsson, M. Acta
Chem. Scand. 1966, 20, 423. (g) Björklung, C.; Nilsson, M. Acta
Chem. Scand. 1968, 22, 2585. (h) Chodowska-Palicka, J.; Nilsson,
M. Acta Chem. Scand. 1970, 24, 3353. (i) Nilsson, M.; Ullenius, C.
Acta Chem. Scand. 1971, 25, 2428. (j) Chodowska-Palicka, J.;
Nilsson, M. Acta Chem. Scand. 1971, 25, 3451. (k) Shepard, A. F.;
Winslow, N. R.; Johnson, J. R. J. Am. Chem. Soc. 1930, 52, 2083.
(l) Shang, R.; Liu, L. Sci. China: Chem. 2011, 54, 1670.
(m) Goossen, L. J.; Rodriguez, N.; Goossen, K. Angew. Chem. Int.
Ed. 2008, 47, 3100. (n) Goossen, L. J.; Goossen, K.; Rodriguez, N.;
Blanchot, M.; Linder, C.; Zimmermann, B. Pure Appl. Chem.
2008, 80, 1725. (o) Goossen, L. J.; Deng, G.; Levy, L. M. Science
2006, 313, 662. (p) Goossen, L. J.; Thiel, W. R.; Rodriguez, N.;
Linder, C.; Melzer, B. Adv. Synth. Catal. 2007, 349, 2241.
13C NMR (100 MHz, CDCl3): δ = 153.27 (C1), 130.21 (C3+C5), 130.14
(C4), 115.20 (C2+C6), 20.59 (C8).
MS (EI, 70 eV): m/z [M]+ = 108.
4-Chlorophenol15
Yield: 411 mg (64%); white solid, mp = 43 ºC.
1H NMR (400 MHz, CDCl3): δ = 7.19 (d, J = 8.8 Hz, 2 H, H3+H5), 6.77 (d,
J = 8.8 Hz, 2 H, H2+H6), 4.86 (s, 1 H, H7).
13C NMR (100 MHz, CDCl3): δ = 154.19 (C1), 129.67 (C3+C5), 125.82
(C4), 116.78 (C2+C6).
MS (EI, 70 eV): m/z [M]+ = 128.
4-Fluorophenol16
Yield: 336 mg (60%); white solid, mp = 46 ºC.
1H NMR (400 MHz, CDCl3): δ = 6.96–6.89 (m, 2 H, H3+H5), 6.80–6.74
(m, 2 H, H2+H6), 5.02 (s, 1 H, H7).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, 2119–2123