N. Takeda, O. Miyata, T. Naito
13C NMR (CDCl3, 50 MHz): δ = 154.3, 153.1, 134.3, 131.0, 129.8, rable (14De/14ЈDe = 1:1); colorless solid. 1H NMR (CDCl3,
FULL PAPER
129.4, 128.8, 127.5, 124.8, 123.0, 121.4, 120.7, 111.1, 107.0 ppm.
HRMS (EI, m/z) calcd. for C14H979BrO (M+) 271.9837, found
271.9835.
300 MHz): δ = 7.88 and 7.84 ppm (br. d, J = 8.5 Hz, each 2/2 H),
7.69 (br. s, 1/2 H), 7.49–7.34 (m, 10/2 H), 7.15 (br. t, J = 8 Hz, 1/
2 H), 7.06 and 6.98 (d, J = 1 Hz, each 1/2 H) ppm. 13C NMR
(CDCl3, 50 MHz): δ = 156.5, 156.4, 155.0, 154.4, 130.7, 129.9,
129.8, 129.2, 129.0, 128.8, 128.5, 128.2, 126.3, 125.9, 125.0, 124.9,
121.7, 117.3, 114.6, 113.8, 111.1, 110.2, 101.3, 101.0 ppm. HRMS
(EI, m/z) calcd. for C14H979BrO (M+) 271.9837, found 271.9862.
2,2,2-Trifluoro-N-[2-(2-hydroxyphenyl)-1-(2-nitrophenyl)-1-ethenyl]-
acetamide (19As): The rearranged products (E)-19As and (Z)-19As
were inseparable. Stereostructures of E and Z isomers (1:1) have
1
not been established; yellow oil. H NMR (CDCl3, 300 MHz): δ =
4-Nitro-2-phenylbenzofuran (14Je) and 6-Nitro-2-phenylbenzofuran
9.60 (br. s, 1/2 H), 8.04 (br. d, J = 8 Hz, 2/2 H), 7.98 (br. s, 1/2 H),
7,70–7.67 (m, 2/2 H), 7,52–7.49 (m, 2/2 H), 7,38–7.35 (m, 2/2 H),
7.25 (br. t, J = 8 Hz, 1/2 H), 7.24 (br. d, J = 8 Hz, 1/2 H), 7.20 (br.
s, 1/2 H), 7.03 (br. t, J = 8 Hz, 1/2 H), 7.01 (br. t, J = 8 Hz, 1/2
H), 6.92 (br. d, J = 8 Hz, 1/2 H), 6.70–6,61 (m, 3/2 H), 6.30 (br. s,
1/2 H) ppm. 13C NMR (CDCl3, 125 MHz): δ = 155.5 (q, COCF3),
154.6 (q, COCF3), 153.4, 151.6, 148.1, 147.6, 134.0, 133.6, 133.5,
132.6, 132.3, 131.3, 131.0, 130.4, 130.2, 130.0, 129.63, 129.58,
125.0, 124.6, 121.7, 121.2, 120.6, 120.5, 120.4, 116.8, 115.9, 115.6
(14ЈJe):[46] The benzofurans 14Je and 14ЈJe were inseparable (14Je/
1
14ЈJe = 2:1); yellow solid. H NMR (CDCl3, 300 MHz): δ = 8.40
(br. s, 1/3 H), 8.18 (br. d, J = 8 Hz, 1/3 H), 8.16 (br. dd, J = 8 Hz,
2/3 H), 7.93 (br. d, J = 8.5 Hz, 4/3 H), 7.89 (br. d, J = 8.5 Hz, 2/3
H), 7.81 (br. d, J = 8 Hz, 2/3 H), 7.74 (d, J = 1 Hz, 2/3 H), 7.63
(d, J = 8 Hz, 1/3 H), 7.52–7.41 (m, 9/3 H), 7.37 (t, J = 8 Hz, 2/3
H), 7.09 (d, J = 1 Hz, 1/3 H) ppm. 13C NMR (CDCl3, 50 MHz): δ
= 161.3, 159.9, 155.9, 153.4, 144.7, 140.4, 135.2, 130.0, 129.1, 129.0,
125.6, 125.5, 125.3, 123.2, 120.5, 119.7, 118.9, 117.2, 107.6, 101.4,
(q, COCF ) ppm. IR (CHCl ): ν = 3589 (OH), 3406 (NH), 1730
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3
101.3 ppm. IR (CHCl ): ν = 1519 and 1337 cm–1 (NO2). HRMS
(NCOCF3), 1531 and 1353 cm–1 (NO2). HRMS (EI, m/z) calcd. for
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(EI, m/z) calcd. for C14H9NO3 (M+) 239.0582, found 239.0610.
C16H11F3N2O4 (M+) 352.0670, found 352.0682.
2-(2-Benzofuranyl)phenol (14At):[39] Colorless crystals. M.p. 94–
4-Methyl-2-phenylbenzofuran (14Ee) and 6-Methyl-2-phenylbenzo-
furan (14ЈEe):[47,48] The benzofurans 14Ee and 14ЈEe were insepa-
rable (14Ee/14ЈEe = 1:1.5); colorless solid. 1H NMR (CDCl3,
300 MHz): δ = 7.87 (br. d, J = 8.5 Hz, 4/5 H), 7.83 (br. d, J =
8.5 Hz, 6/5 H), 7.47–7.23 (m, 23/5 H), 7.18 (br. t, J = 8 Hz, 2/5 H),
7.06 (br. s, 3/5 H), 7.03 (d, J = 1 Hz, 2/5 H), 7.02 (br. d, J = 8 Hz,
2/5 H), 6.96 (d, J = 1 Hz, 3/5 H), 2.54 (s, 6/5 H), 2.48 (s, 9/5 H)
ppm. 13C NMR (CDCl3, 75 MHz): δ = 155.3, 154.7, 134.5, 130.8,
130.7, 130.6, 129.0, 128.7, 128.4, 128.2, 126.7, 124.8, 124.7, 124.3,
124.2, 123.2, 120.3, 111.4, 108.6, 101.1, 100.0, 21.7, 18.6 ppm.
HRMS (EI, m/z) calcd. for C15H12O (M+) 208.0888, found
208.0897.
1
95 °C (n-hexane) (ref.[39] 93–94 °C). H NMR (CDCl3, 300 MHz):
δ = 7.71 (dd, J = 8, 1.5 Hz, 1 H), 7.60 (br. d, J = 8 Hz, 1 H), 7.53
(br. d, J = 8 Hz, 1 H), 7.34–7.24 (m, 3 H), 7.14 (br. s, 1 H), 7.09
(d, J = 1 Hz, 1 H), 7.03–6.97 (m, 2 H) ppm. 13C NMR (CDCl3,
50 MHz): δ = 154.3, 154.0, 153.3, 130.3, 128.5, 127.2, 124.4, 123.4,
121.0, 120.8, 117.4, 116.1, 111.0, 103.3 ppm. IR (CHCl ): ν =
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3527 cm–1 (OH). HRMS (EI, m/z) calcd. for C14H10O2 (M+)
210.0681, found 210.0689.
2-(2-Methoxyphenyl)benzofuran (14Au):[40] Colorless crystals. M.p.
78–79 °C (n-hexane) (ref.[40] 78.5–80 °C). 1H NMR (CDCl3,
300 MHz): δ = 8.07 (br. dd, J = 8, 1.5 Hz, 1 H), 7.60–7.57 (dm, J
= 8 Hz, 1 H), 7.52–7.549 (dm, J = 8 Hz, 1 H), 7.35 (br. s, 1 H),
7.35–7.18 (m, 3 H), 7.08 (br. t, J = 8 Hz, 1 H), 7.00 (br. d, J =
8 Hz, 1 H), 4.00 (s, 3 H) ppm. 13C NMR (CDCl3, 50 MHz): δ =
155.9, 153.2, 151.5, 129.1, 128.6, 126.4, 123.4, 122.0, 120.4, 120.1,
118.7, 110.4, 110.4, 110.2, 105.7, 54.8 ppm. HRMS (EI, m/z) calcd.
for C15H12O2 (M+) 224.0837, found 224.0851.
5-Bromo-2-phenylbenzofuran (14Be):[41] Colorless crystals. M.p.
158–159 °C (MeOH) (ref.[41] 158–159 °C). 1H NMR (CDCl3,
300 MHz): δ = 7.85 (br. d, J = 8.5 Hz, 2 H), 7.71–7.70 (m, 1 H),
7.49–7.34 (m, 5 H), 6.96 (br. s, 1 H) ppm. 13C NMR (CDCl3,
50 MHz): δ = 157.3, 153.6, 131.2, 129.9, 129.0, 128.9, 127.1, 125.1,
123.5, 116.0, 112.6, 100.6 ppm. HRMS (EI, m/z) calcd. for
C14H979BrO (M+) 271.9837, found 271.9837.
2-Phenyl-4-benzofuranol (14Le) and 2-Phenyl-6-benzofuranol
(14ЈLe):[49] The benzofurans 14Le and 14ЈLe were inseparable
(14Le/14ЈLe = 1:1.5); colorless solid. 1H NMR (CDCl3, 300 MHz):
δ = 7.85 (br. d, J = 8.5 Hz, 4/5 H), 7.81 (br. d, J = 8.5 Hz, 6/5 H),
7.47–7.29 (m, 20/5 H), 7.14 (br. d, J = 8 Hz, 2/5 H), 7.10 (br. d, J
= 1 Hz, 2/5 H), 7.01 (br. d, J = 2 Hz, 3/5 H), 6.94 (br. d, J = 1 Hz,
3/5 H), 6.77 (br. dd, J = 8, 2 Hz, 3/5 H), 6.63 (br. dd, J = 8, 2 Hz,
2/5 H), 5.01 (br. s, 5/5 H) ppm. 13C NMR (CDCl3, 75 MHz): δ =
156.5, 155.8, 155.3, 154.9, 153.6, 149.1, 130.6, 130.4, 128.8, 128.7,
128.5, 128.1, 124.9, 124.8, 124.5, 122.9, 121.1, 118.5, 112.0, 108.0,
104.4, 101.1, 98.3, 98.0 ppm. IR (CHCl ): ν = 3597 cm–1 (OH).
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HRMS (EI, m/z) calcd. for C14H10O2 (M+) 210.0681, found
210.0681.
4-Methoxy-2-phenylbenzofuran (14Fe) and 6-Methoxy-2-phenylben-
zofuran (14ЈFe):[50,51] The benzofurans 14Fe and 14ЈFe were insepa-
rable (14Fe/14ЈFe = 1:4); colorless solid. 1H NMR (CDCl3,
300 MHz): δ = 7.84 (br. d, J = 8.5 Hz, 2/5 H), 7.80 (br. d, J =
8.5 Hz, 8/5 H), 7.45–7.39 (m, 14/5 H), 7.33 (br. t, J = 8.5 Hz, 1/5
H), 7.31 (br. t, J = 8.5 Hz, 4/5 H), 7.21 (t, J = 8 Hz, 1/5 H), 7.15
(br. d, J = 8 Hz, 1/5 H), 7.12 (d, J = 1 Hz, 1/5 H), 7.07 (br. d, J =
2 Hz, 4/5 H), 6.94 (d, J = 1 Hz, 4/5 H), 6.87 (br. dd, J = 8, 2 Hz,
4/5 H), 6.66 (br. d, J = 8 Hz, 1/5 H), 3.96 (s, 3/5 H), 3.87 (s, 12/5
H) ppm. 13C NMR (CDCl3, 50 MHz): δ = 158.1, 156.1, 155.9,
155.1, 154.6, 153.4, 130.7, 130.5, 128.7, 128.2, 128.0, 124.9, 124.7,
124.4, 122.5, 121.0, 119.5, 111.9, 104.4, 103.3, 101.1, 98.8, 95.9,
55.7, 55.5 ppm. HRMS (EI, m/z) calcd. for C15H12O2 (M+)
224.0837, found 224.0852.
5-Nitro-2-phenylbenzofuran (14Ie):[42] Yellow crystals. M.p. 159–
161 °C (MeOH) (ref.[42] 158–161 °C). 1H NMR (CDCl3, 300 MHz):
δ = 8.48 (d, J = 2 Hz, 1 H), 8.20 (br. dd, J = 8, 2 Hz, 1 H), 7.86
(br. d, J = 8.5 Hz, 2 H), 7.57 (br. d, J = 8 Hz, 1 H), 7.51–7.39 (m,
3 H), 7.10 (d, J = 1 Hz, 1 H) ppm. 13C NMR (CDCl3, 50 MHz): δ
= 159.2, 157.6, 144.3, 129.7, 129.6, 129.1, 129.0, 125.2, 120.1, 117.2,
111.4, 101.6 ppm. IR (CHCl ): ν = 1525 and 1350 cm–1 (NO2).
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HRMS (EI, m/z) calcd. for C14H9NO3 (M+) 239.0582, found
239.0581.
5-Methyl-2-phenylbenzofuran (14Ce):[43] Colorless crystals.
M.p.128–130 °C (EtOH) (ref.[43] 125–126 °C). 13C NMR (CDCl3,
50 MHz): δ = 156.0, 153.3, 132.3, 130.6, 129.3, 128.7, 128.4, 125.5,
124.8, 120.7, 110.6, 101.1, 21.3 ppm. HRMS (EI, m/z) calcd. for
C15H12O (M+) 208.0888, found 208.0888.
7-Bromo-2-phenylbenzofuran (14Ge): A colorless oil. 1H NMR
(CDCl3, 300 MHz): δ = 7.89 (br. d, J = 8.5 Hz, 2 H), 7.52–7.35 (m,
5 H), 7.10 (br. t, J = 8 Hz, 1 H), 7.07 (s, 1 H) ppm. 13C NMR
4-Bromo-2-phenylbenzofuran (14De) and 6-Bromo-2-phenylbenzo-
furan (14ЈDe):[44,45] The benzofurans 14De and 14ЈDe were insepa-
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Eur. J. Org. Chem. 2007, 1491–1509