Facile One-Pot Transformation of Phenols into o-Cyanophenols
4-tert-Butyl-2-cyanophenol (3d): Yield 110.4 mg (63%); white solid;
(400 MHz, CDCl3): δ = 1.27 (t, J = 7.4 Hz, 3 H), 2.87 (q, J =
7.4 Hz, 2 H), 6.95 (d, J = 8.7 Hz, 1 H), 7.47–7.51 (m, 2 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 14.37, 29.32, 100.20, 115.76,
m.p. 119–121 °C. IR (neat): ν = 2230, 3287 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 1.29 (s, 9 H), 6.92 (d, J = 8.7 Hz, 1 H),
7.47–7.52 (m, 2 H) ppm. 13C NMR (125 Hz, CDCl3): δ = 31.15, 117.30, 128.32, 134.71, 137.74, 157.34 ppm. HRMS (ESI): calcd.
34.21, 98.73, 116.28, 116.79, 129.23, 132.25, 144.14, 156.20 ppm.
HRMS (ESI): calcd. for C11H13NONa [M + Na]+ 198.0889; found
198.0888.
for C13H8NO2 [M – H]– 210.0559; found 210.0561. HRMS (ESI):
calcd. for C9H8NOS [M – H]– 178.0327; found 178.0331.
2-Chloro-6-cyanophenol (3m): Yield 95.2 mg (62%); white solid;
m.p. 103–105 °C. IR (neat): ν = 2245, 3251 cm–1. 1H NMR
4-Butyl-2-cyanophenol (3e): Yield 124.4 mg (71%); white solid; m.p.
˜
59–61 °C. IR (neat): ν = 2231, 3285 cm–1. 1H NMR (400 MHz,
˜
(400 MHz, CDCl3): δ = 6.35 (br., 1 H), 6.97 (t, J = 8.0 Hz, 1 H),
7.48 (dd, J = 8.0, 1.6 Hz, 1 H), 7.57 (dd, J = 8.0, 1.6 Hz, 1 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 101.15, 115.05, 121.13, 121.47,
132.03, 133.77, 153.81 ppm. HRMS (ESI): calcd. for C7H3NOCl
[M – H]– 151.9903; found 151.9903.
CDCl3): δ = 0.92 (t, J = 7.7 Hz, 3 H), 1.33 (sext, J = 7.7 Hz, 2 H),
1.55 (quin, J = 7.7 Hz, 2 H), 2.55 (t, J = 7.7 Hz, 2 H), 6.02 (br., 1
H), 6.90 (d, J = 7.7 Hz, 1 H), 7.26–7.29 (m, 2 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 13.54, 22.07, 33.35, 34.22, 99.05, 116.44,
116.55, 131.96, 135.00, 135.70. 156.43 ppm. HRMS (ESI): calcd.
for C11H12NO [M – H]– 174.0919; found 174.0923.
2-Bromo-6-cyanophenol (3n): Yield 128.7 mg (65%); orange solid;
m.p. 109–112 °C. IR (neat): ν = 2245, 3244 cm–1. 1H NMR
˜
2-Cyano-4-phenylphenol (3f): Yield 109.3 mg (56%); pale yellow so-
(400 MHz, CDCl3): δ = 6.17 (br., 1 H), 6.91 (t, J = 8.0 Hz, 1 H),
7.53 (dd, J = 8.0, 1.6 Hz, 1 H), 7.71 (dd, J = 8.0, 1.6 Hz, 1 H) ppm.
13C NMR (125 MHz, CDCl3): δ = 100.95, 110.96, 115.06, 121.95,
132.86, 136.77, 154.50 ppm. HRMS (ESI): calcd. for C7H3NOBr
[M – H]– 195.9398; found 198.9403.
lid; m.p. 170–171 °C. IR (neat): ν = 2240, 3223 cm–1. 1H NMR
˜
(400 MHz, [D6]DMSO): δ = 7.09 (d, J = 8.4 Hz, 1 H), 7.33 (t, J =
8.4 Hz, 1 H), 7.43 (t, 2 H, J = 8.4 Hz), 7.63 (d, J = 8.4 Hz, 2 H),
7.80 (dd, J = 8.4, 2.5 Hz, 1 H), 7.90 (d, J = 2.5 Hz, 1 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 99.41, 99.46, 116.71, 126.18, 127.27,
128.93, 130.95, 131.59, 133.00, 138.19, 159.68 ppm. HRMS (ESI):
calcd. for C13H8NO [M – H]– 194.0611; found 194.0610.
4-Bromo-2-cyanophenol (3o): Commercially available; yield
122.8 mg (62%); white solid; m.p. 157–158 °C. IR (neat): ν = 2234,
˜
3249 cm–1. 1H NMR (400 MHz, [D6]DMSO): δ = 6.95 (d, J =
8.9 Hz, 1 H), 7.63 (dd, J = 8.9, 2.6 Hz, 1 H), 7.84 (d, J = 2.6 Hz,
1 H) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 100.91, 109.71,
115.59, 118.28, 134.99, 137.48, 159.64 ppm.
2-Cyano-4-methoxyphenol (3g): Yield 89.5 mg (60%); brown solid;
m.p. 124–127 °C. IR (neat): ν = 2231, 3294 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 3.78 (s, 3 H), 6.90–6.96 (m, 2 H), 7.06 (dd,
J = 9.3 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 55.93,
99.39, 115.27, 116.20, 117.86, 122.34, 152.57, 153.33 ppm. HRMS
4-Allyloxy-2-cyanophenol (3p): Yield 113.9 mg (65%); white solid;
+
Na]+ 172.0369; found
m.p. 78–80 °C. IR (neat):
ν =
˜
2242, 3210 cm–1. 1H NMR
(ESI): calcd. for C8H7NO2Na [M
172.0366.
(400 MHz, CDCl3): δ = 4.49 (dt, J = 5.3, 1.5 Hz, 2 H), 5.31 (dq, J
= 11, 1.4 Hz, 1 H), 5.40 (dq, J = 18, 1.4 Hz, 1 H), 5.78 (br., 1 H),
5.96–6.06 (m, 1 H), 6.91 (d, J = 9.2 Hz, 1 H), 6.97 (s, J = 3.0 Hz,
1 H), 7.08 (dd, J = 9.2, 3.0 Hz, 1 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 69.65, 99.39, 116.14, 116.56, 117.81, 118.23, 123.10,
132.52, 152.26, 152.67 ppm. HRMS (ESI): calcd. for C10H8NO2
[M – H]– 174.0555; found 174.0559.
2-Cyano-4-iodo-5-methoxyphenol (3h): Yield 140.28 mg (51%);
white solid; m.p. 191–195 °C. IR (neat): ν = 2238, 3138 cm–1. 1H
˜
NMR (400 MHz, [D6]DMSO): δ = 3.81 (s, 3 H), 6.53 (s, 1 H), 7.91
(s, 1 H) ppm. 13C NMR (125 Hz, [D6]DMSO): δ = 56.87, 73.55,
93.45, 99.48, 116.32, 141.95, 162.40, 162.71 ppm. HRMS (ESI):
calcd. for C8H5INO2 [M – H]– 273.9370; found 273.9378.
2-Cyano-4,6-dimethylphenol (3q): Yield 121.2 mg (64%); yellow so-
4-Buthoxy-2-cyanophenol (3i): Yield 122.4 mg (64%); yellow solid;
lid; m.p. 107–108 °C. IR (neat): ν = 2232, 3330 cm–1; 1H NMR
˜
m.p. 91–93 °C. IR (neat):
ν =
˜
2238, 3220 cm–1. 1H NMR
(400 MHz, CDCl3): δ = 2.24 (s, 3 H), 2.25 (s, 3 H), 5.25 (br., 1 H),
7.11 (s, 1 H), 7.15 (s, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ
= 15.78, 20.11, 98.51, 116.85, 125.68, 129.59, 130.26, 136.97,
154.62 ppm. HRMS (ESI): calcd. for C9H9NONa [M + Na]+
170.0576; found 170.0577.
(400 MHz, CDCl3): δ = 0.97 (t, J = 7.6 Hz, 3 H), 1.48 (sext, J =
7.6 Hz, 2 H), 1.75 (quin, J = 6.9 Hz, 2 H), 3.90 (t, J = 6.9 Hz, 2
H), 6.90 (d, J = 9.2 Hz, 1 H), 6.95 (sd, J = 3.0 Hz, 1 H), 7.04 (dd,
J = 9.2, 3.0 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ =
13.77, 19.14, 31.12, 68.62, 99.32, 116.08, 116.28, 117.80, 122.87,
152.48, 152.86 ppm. HRMS (ESI): calcd. for C11H12NO2 [M –
H]– 190.0874; found 190.0871.
6-tert-Butyl-2-cyano-4-methylphenol (3r): Yield 100.3 mg (53%);
white solid; m.p. 111–113 °C. IR (neat): ν = 2226, 3335 cm–1. 1H
˜
NMR (400 MHz, CDCl3): δ = 1.39 (s, 9 H), 2.27 (s, 3 H), 7.13 (s,
1 H), 7.27 (s, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 20.52,
29.29, 34.86, 99.84, 116.95, 129.24, 130.17, 133.37, 137.49,
154.97 ppm. HRMS (ESI): calcd. for C12H15NONa [M + Na]+
212.1046; found 212.1047.
2-Cyano-4-phenoxyphenol (3j): Yield 135.2 mg (64%); yellow solid;
m.p. 104–107 °C. IR (neat): ν = 2242, 3233 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 6.94–6.99 (m, 3 H), 7.11–7.19 (m, 3 H),
7.35 (t, J = 8.1 Hz, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ =
99.85, 115.70, 118.05, 118.42, 122.04, 123.75, 126.38, 129.98,
150.51, 154.54, 156.9 ppm. HRMS (ESI): calcd. for C13H8NO2
[M – H]– 210.0559; found 210.0561.
4,6-Di-tert-butyl-2-cyanophenol (3s): Yield 127.3 mg (55%); white
1
solid; m.p. 107–111 °C. IR (neat): ν = 2230, 3293 cm–1. H NMR
˜
(400 MHz, CDCl3): δ = 1.29 (s, 9 H), 1.41 (s, 9 H), 5.83 (br., 1 H),
7.30 (d, J = 2.3 Hz, 1 H), 7.52 (d, J = 2.3 Hz, 1 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 29.39, 31.22, 34.42, 35.13, 99.49, 117.24,
125.99, 129.77, 137.01, 143.59, 154.76 ppm. HRMS (ESI): calcd.
for C15H20NO [M – H]– 230.1550; found 230.1557.
2-Cyano-4-methylthiophenol (3k): Yield 97.5 mg (59%); brown so-
lid; m.p. 127–130 °C. IR (neat): ν = 2229, 3299 cm–1. 1H NMR
˜
(400 MHz, [D6]DMSO): δ = 2.43 (s, 3 H), 6.96 (d, J = 8.9 Hz, 1
H), 7.42 (dd, J = 8.9, 2.3 Hz, 1 H), 7.51 (d, J = 2.3 Hz, 1 H), 11.12
(br., 1 H) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 16.28,
99.74, 116.54, 116.97, 127.75, 131.32, 134.34, 158.40 ppm. HRMS
(ESI): calcd. for C8H6NOS [M – H]– 164.0165; found 164.0168.
6-Chloro-4-phenyl-2-cyanophenol (3t): Yield 149.3 mg (65%); white
1
solid; m.p. 120–123 °C. IR (neat): ν = 2240, 3275 cm–1. H NMR
˜
2-Cyano-4-ethylthiophenol (3l): Yield 118.3 mg (66%); pale brown
(400 MHz, CDCl3): δ = 7.37–7.50 (m, 5 H), 7.68 (d, J = 2.0 Hz, 1
solid; m.p. 92–93 °C. IR (neat): ν = 2229, 3299 cm–1. 1H NMR H), 7.78 (d, J = 2.0 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3):
˜
Eur. J. Org. Chem. 2014, 6077–6083
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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