728 JOURNAL OF CHEMICAL RESEARCH 2017
3
Experimental
CDCl3): δ 190.6, 161.7, 158.4, 132.3, 132.1, 127.5 (q, JC–F = 3.7 Hz),
126.7 (q, 2JC–F = 32.7 Hz), 123.9 (q, 1JC–F = 270.1 Hz), 119.8, 118.7.
4,4’-Oxydibenzaldehyde (3i): Pale yellow oil;22 1H NMR (400 MHz,
CDCl3): δ 9.98 (s, 1H), 7.93 (d, J = 8.4 Hz, 4H), 7.19 (d, J = 8.4 Hz, 4H);
13C NMR (100 MHz, CDCl3): δ 190.6, 161.0, 132.6, 132.1, 119.4.
4-(2-Bromophenoxy)benzaldehyde (3j): Colourless oil;22 1H NMR
(400 MHz, CDCl3): δ 9.92 (s, 1H), 7.85 (d, J = 8.8 Hz, 2H), 7.67 (d,
J = 8.0 Hz, 1H), 7.37 (t, J = 7.8 Hz, 1H), 7.19–7.02 (m, 2H), 7.00 (d,
J = 8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 190.8, 162.4, 151.7,
134.2, 132.0, 129.1, 126.8, 122.7, 116.9, 116.2, 116.1.
4-(2-Methylphenoxy)benzaldehyde (3k): Colourless oil;22 1H NMR
(400 MHz, CDCl3): δ 9.89 (s, 1H), 7.82 (d, J = 8.4 Hz, 2H), 7.31–7.15
(m, 3H), 7.00 (d, J = 8.0 Hz, 1H), 6.96 (d, J = 8.4 Hz, 2H), 2.18 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 190.8, 163.4, 152.8, 132.1, 131.9, 131.0,
130.9, 127.6, 125.5, 121.1, 116.5, 16.0.
All reagents were used as received without further purification. The
MCM-41-2N-CuCl [A], MCM-41-2N-CuI [B], MCM-41-2N-CuCl2 [C],
MCM-41-2N-CuBr2 [D], MCM-41-2N-Cu(OAc)2 [E] and MCM-41-
2N-Cu(OTf)2 [F] were prepared according to our previous procedure.31
The copper contents were determined to be 0.48 mmol g–1, 0.46 mmol
g–1, 0.51 mmol g–1, 0.53 mmol g–1, 0.55 mmol g–1 and 0.57 mmol g–1
respectively. All reactions were carried out under Ar in oven-dried
1
glassware with magnetic stirring. H NMR spectra were recorded on a
Bruker Avance 400 (400 MHz) spectrometer with TMS as an internal
standard using CDCl3 as the solvent. 13C NMR spectra were recorded
on a Bruker Avance 400 (100 MHz) spectrometer using CDCl3 as the
solvent. HRMS spectra were recorded on a quadrupole-time of flight
Bruker MicroTOF-Q II mass spectrometer equipped with an ESI and
APCI source. Copper content was determined with inductively coupled
plasma atom emission spectroscopy using an Atomscan16 instrument
(TJA Corporation).
4-(Biphenyl-2-yloxy)benzaldehyde (3l): Colourless oil; 1H NMR
(400 MHz, CDCl3): δ 9.83 (s, 1H), 7.73 (d, J = 8.4 Hz, 2H), 7.52–7.24
(m, 8H), 7.12 (d, J = 8.0 Hz, 1H), 6.92 (d, J = 8.4 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 190.8, 163.3, 151.6, 137.1, 134.8, 131.9, 131.6,
130.9, 129.1, 129.0, 128.3, 127.5, 125.8, 121.8, 117.0; HRMS calcd for
Heterogeneous copper-catalysed O-arylation of phenols by nitroarenes;
general procedure
C19H14O2 : [M+]: 274.0994; found: 274.0989.
+
Under an argon atmosphere, a Schlenk tube was charged with MCM-
41-2N-Cu(OAc)2 (46 mg, 0.025 mmol), nitroarene 1 (0.5 mmol),
phenol 2 (1.0 mmol), Cs2CO3 (1.0 mmol) and DMF (3 mL). The
reaction mixture was stirred at 100 °C for 5 h under Ar. After being
cooled to room temperature, the mixture was diluted with ethyl acetate
(20 mL) and filtered. The MCM-41-2N-Cu(OAc)2 catalyst was washed
with distilled water (2 × 5 mL), DMF (2 × 5 mL) and EtOH (2 × 5 mL)
and could be reused in the next run. The filtrate was washed with water
(2 × 10 mL) and dried over anhydrous MgSO4. After removal of the
solvent under reduced pressure, the residue was purified by column
chromatography (EtOAc/hexane) on silica gel to afford the desired
product 3.
4-Phenoxybenzaldehyde (3a): Colourless oil;22 1H NMR (400 MHz,
CDCl3): δ 9.91 (s, 1H), 7.86–7.82 (m, 2H), 7.43–7.38 (m, 2H), 7.26–7.19
(m, 1H), 7.10–7.03 (m, 4H); 13C NMR (100 MHz, CDCl3): δ 190.8,
163.2, 155.1, 131.9, 131.3, 130.2, 124.9, 120.4, 117.6.
4-(4-Methylphenoxy)benzaldehyde (3b): Colourless oil;22 1H NMR
(400 MHz, CDCl3): δ 9.90 (s, 1H), 7.82 (d, J = 8.8 Hz, 2H), 7.20 (d,
J = 8.4 Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H), 6.97 (d, J = 8.4 Hz, 2H),
2.37 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 190.8, 163.7, 152.7, 134.7,
131.9, 131.0, 130.7, 120.4, 117.2, 20.8.
4-(2,6-Dimethylphenoxy)benzaldehyde (3m): Colourless oil;
1H NMR (400 MHz, CDCl3): δ 9.89 (s, 1H), 7.83–7.79 (m, 2H),
7.15–7.07 (m, 3H), 6.90–6.85 (m, 2H), 2.11 (s, 6H); 13C NMR
(100 MHz, CDCl3): δ 190.8, 162.9, 150.4, 132.3, 131.1, 130.7, 129.2,
125.8, 115.1, 16.2; HRMS calcd for C15H14O2 : [M+]: 226.0994; found:
+
226.0995.
4-(Pyridin-4-yloxy)benzaldehyde (3n): Pale yellow oil; 1H NMR
(400 MHz, CDCl3): δ 10.01 (s, 1H), 8.56 (d, J = 5.6 Hz, 2H), 7.96 (d,
J = 8.4 Hz, 2H), 7.23 (d, J = 8.4 Hz, 2H), 6.94 (d, J = 6.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 190.6, 163.2, 159.6, 151.8, 133.2, 132.1, 120.3, 113.4;
HRMS calcd for C12H9NO2+: [M+]: 199.0633; found: 199.0625.
Methyl 3-(4-formylphenoxy)thiophene-2-carboxylate (3o): Colourless
oil; 1H NMR (400 MHz, CDCl3): δ 9.94 (s, 1H), 7.89–7.84 (m, 2H), 7.54
(t, J = 2.8 Hz, 1H), 7.12–7.08 (m, 2H), 6.84 (d, J = 5.6 Hz, 1H), 3.79 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 190.7, 162.7, 161.0, 155.0, 131.7,
131.6, 130.8, 122.5, 117.0, 99.6, 52.1; HRMS calcd for C13H10O4S+: [M+]:
262.0300; found: 262.0295.
2-Phenoxybenzaldehyde (3p): Colourless oil;22 1H NMR (400 MHz,
CDCl3): δ 10.45 (s, 1H), 7.87 (dd, J = 7.8, 1.4 Hz, 1H), 7.47–7.44 (m,
1H), 7.33 (t, J = 7.8 Hz, 2H), 7.15–7.08 (m, 2H), 7.00 (d, J = 8.0 Hz,
2H), 6.83 (d, J = 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 189.4,
160.0, 156.4, 135.8, 130.1, 128.5, 126.9, 124.3, 123.3, 119.4, 118.5.
2-(2-Bromophenoxy)benzaldehyde (3q): Colourless oil;38 1H NMR
(400 MHz, CDCl3): δ 10.52 (s, 1H), 7.89–7.86 (m, 1H), 7.61–7.58 (m,
1H), 7.44–7.38 (m, 1H), 7.29–6.97 (m, 4H), 6.66 (d, J = 8.4 Hz, 1H);
13C NMR (100 MHz, CDCl3): δ 189.3, 159.5, 152.5, 135.8, 134.2, 129.0,
128.6, 126.3, 123.4, 121.7, 117.0, 116.4, 115.5.
4-Phenoxybenzonitrile (3r): Colourless oil;22 1H NMR (400 MHz,
CDCl3): δ 7.59 (d, J = 8.8 Hz, 2H), 7.41 (t, J = 8.0 Hz, 2H), 7.23 (t,
J = 7.4 Hz, 1H), 7.06 (d, J = 8.4 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H);
13C NMR (100 MHz, CDCl3): δ 161.7, 154.8, 134.2, 130.3, 125.2, 120.4,
118.9, 117.9, 105.8.
4-(Biphenyl-2-yloxy)benzonitrile (3s): Colourless oil;39 1H NMR
(400 MHz, CDCl3): δ 7.54–7.24 (m, 10H), 7.11 (dd, J = 8.0, 1.2 Hz,
1H), 6.87–6.83 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 161.7, 151.3,
137.0, 134.8, 134.0, 131.7, 129.2, 129.0, 128.3, 127.6, 126.0, 121.8,
118.9, 117.3, 105.3.
4-(4-Aminophenoxy)benzonitrile (3t): Yellow oil;40 1H NMR
(400 MHz, CDCl3): δ 7.57–7.53 (m, 2H), 6.96–6.92 (m, 2H), 6.89–6.85
(m, 2H), 6.73–6.69 (m, 2H), 3.71 (s, 2H); 13C NMR (100 MHz, CDCl3):
δ 162.9, 146.3, 144.1, 134.0, 121.9, 119.1, 117.0, 116.3, 104.9.
Methyl 3-(4-cyanophenoxy)thiophene-2-carboxylate (3u): Colourless
oil; 1H NMR (400 MHz, CDCl3): δ 7.64–7.60 (m, 2H), 7.55 (d, J = 5.6 Hz,
1H), 7.06–7.02 (m, 2H), 6.83 (d, J = 5.6 Hz, 1H), 3.79 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 161.2, 160.9, 159.2, 134.2, 130.9, 122.5, 118.7, 118.1,
106.5, 97.8, 52.1; HRMS calcd for C13H9NO3S+: [M+]: 259.0303; found:
259.0307.
4-(4-Methoxyphenoxy)benzaldehyde (3c): Colourless oil;22 1H NMR
(400 MHz, CDCl3): δ 9.90 (s, 1H), 7.82 (d, J = 8.8 Hz, 2H), 7.06–6.99
(m, 4H), 6.96–6.91 (m, 2H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 190.8, 164.1, 156.9, 148.2, 131.9, 130.9, 121.8, 116.8, 115.2, 55.7.
4-(3,5-Dimethylphenoxy)benzaldehyde (3d): Colourless oil;
1H NMR (400 MHz, CDCl3): δ 9.91 (s, 1H), 7.83 (d, J = 8.0 Hz,
2H), 7.04 (d, J = 8.0 Hz, 2H), 6.86 (s, 1H), 6.70 (s, 2H), 2.31 (s, 6H);
13C NMR (100 MHz, CDCl3): δ 190.8, 163.5, 155.0, 140.1, 131.9, 131.1,
126.7, 118.1, 117.5, 21.3; HRMS calcd for C15H14O2 : [M+]: 226.0994;
+
found: 226.0986.
4-(4-Chlorophenoxy)benzaldehyde (3e): Colourless oil;22 1H NMR
(400 MHz, CDCl3): δ 9.93 (s, 1H), 7.86 (d, J = 8.8 Hz, 2H), 7.37 (d,
J = 8.8 Hz, 2H), 7.07–7.01 (m, 4H); 13C NMR (100 MHz, CDCl3): δ
190.7, 162.7, 153.8, 132.0, 131.6, 130.2, 130.1, 121.7, 117.7.
4-(4-Bromophenoxy)benzaldehyde (3f): Colourless oil;22 1H NMR
(400 MHz, CDCl3): δ 9.93 (s, 1H), 7.86 (d, J = 8.4 Hz, 2H), 7.52 (d,
J = 8.8 Hz, 2H), 7.06 (d, J = 8.8 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H);
13C NMR (100 MHz, CDCl3): δ 190.7, 162.6, 154.4, 133.2, 132.0, 131.7,
122.1, 117.8, 117.6.
4-(4-Fluorophenoxy)benzaldehyde (3g): Colourless oil;22 1H NMR
(400 MHz, CDCl3): δ 9.92 (s, 1H), 7.85 (d, J = 8.8 Hz, 2H), 7.14–7.01
(m, 6H); 13C NMR (100 MHz, CDCl3): δ 190.7, 163.4, 159.7 (d,
4
1JC–F = 242.4 Hz), 150.8 (d, JC–F = 2.7 Hz), 132.0, 131.3, 122.5 (d,
3JC–F = 8.4 Hz), 117.2, 116.8 (d, 2JC–F = 23.3 Hz).
4-(4-Trifluoromethylphenoxy)benzaldehyde (3h): Colourless oil;22
1H NMR (400 MHz, CDCl3): δ 9.96 (s, 1H), 7.91 (d, J = 8.4 Hz, 2H),
7.67 (d, J = 8.4 Hz, 2H), 7.18–7.12 (m, 4H); 13C NMR (100 MHz,