H. Fu et al.
4-Methoxy-N-(2-nitrophenyl)aniline (3l):[29] Yellowsolid, yield 80%
(391 mg), m.p. 87–888C (lit.[29a] 87–888C). 1H NMR (CDCl3, 300 MHz):
d=9.41 (brs, 1H), 8.19 (d, J=8.60 Hz, 1H), 7.32 (t, J=7.91 Hz, 1H),
7.20 (d, J=8.60 Hz, 2H), 7.00 (d, J=8.94 Hz, 1H), 6.96 (dd, J=8.60,
1.72 Hz, 2H), 6.71 (t, J=7.74 Hz, 1H), 3.84 ppm (s, 3H); 13C NMR
(CDCl3, 75 MHz): d=157.9, 144.5, 135.7, 132.4, 131.2, 127.1, 126.6, 116.8,
115.7, 114.9, 55.5 ppm; HR-EI-MS: [M]+ m/z calcd for C13H12N2O3:
244.0848; found: 244.0842.
N-(2,6-dimethylphenyl)-3-nitroaniline (3m):[25] Yellowsolid, yield 75%
(363 mg), m.p. 79–838C. 1H NMR (CDCl3, 300 MHz): d=7.71 (d, J=
8.58 Hz, 1H), 7.21 (s, 1H), 6.99–7.08 (m, 5H), 6.40 (s, 1H), 1.98 ppm (s,
6H); 13C NMR (CDCl3, 75 MHz): d=158.9, 141.3, 137.6, 129.3, 128.6,
128.0, 125.6, 124.5, 124.3, 113.6, 18.3 ppm; HR-EI-MS: [M]+ m/z calcd
for C14H14N2O2: 242.1055; found: 242.1051.
Scheme 3. Copper-catalyzed reaction of aryl bromides with KI.
7.54 Hz, 2H), 6.70 (t, J=7.20 Hz, 1H), 6.62 (d, J=7.89 Hz, 2H), 3.11 (t,
J=7.03 Hz, 2H), 1.67–1.65 (m, 2H), 1.29 (m, 18H), 0.91 ppm (t, J=
6.00 Hz, 3H); 13C NMR (CDCl3, 75 MHz): d=148.7, 129.3, 117.2, 112.8,
44.1, 32.1, 29.7, 29.6, 29.5, 27.3, 22.8, 14.2 ppm; HR-EI-MS: [M]+ m/z
calcd for C18H31N: 261.2457; found: 261.2461.
4-phenylmorpholine (3c):[24] White solid, yield 91% (297 mg), m.p. 51–
548C(lit.[24c] 548C). 1H NMR (CDCl3, 300 MHz): d=7.29 (t, J=7.89 Hz,
2H), 6.88–6.96 (m, 3H), 3.88 (t, J=4.83 Hz, 4H), 3.17 ppm (t, J=
4.83 Hz, 4H); 13C NMR (CDCl3, 75 MHz): d=151.2, 129.3, 120.7, 116.0,
67.0, 49.6 ppm; HR-EI-MS: [M]+ m/z calcd for C10H13NO: 163.0997;
found: 163.0990.
4-(4-methoxyphenyl)morpholine (3d):[25] White solid, yield 87%
(337 mg), m.p. 72–748C (lit.[25b] 758C). 1H NMR (CDCl3, 300 MHz): d=
6.90 (d, J=9.29 Hz, 2H), 6.85 (d, J=9.29 Hz, 2H), 3.86 (t, J=4.82 Hz,
4H), 3.77 (s, 3H), 3.06 ppm (t, J=4.82 Hz, 4H); 13C NMR (CDCl3,
75 MHz): d=154.1, 145.7, 117.9, 114.6, 67.1, 55.7, 50.9 ppm; HR-EI-MS:
[M]+ m/z calcd for C11H15NO2: 193.1103; found: 193.1110.
Diphenylamine (3e):[26] White solid, yield 77% (261 mg), m.p. 52–538C
(lit.[26b] 548C). 1H NMR (CDCl3, 300 MHz): d=7.24–7.29 (m, 4H), 7.08
(d, J=7.57 Hz, 4H), 6.93 ppm (t, J=7.22 Hz, 2H); 13C NMR (CDCl3,
75 MHz): d=143.1, 129.4, 121.2, 118.0 ppm; HR-EI-MS: [M]+ m/z calcd
for C12H11N: 169.0891; found: 169.0886.
N-(2,6-dimethylphenyl)aniline (3n):[25] Slightly yellowoil, yield 82%
1
(324 mg). H NMR (CDCl3, 300 MHz): d=7.27 (t, J=8.08 Hz, 2H), 7.01–
7.17 (m, 3H), 6.90 (d, J=7.91 Hz, 2H), 6.74 (t, J=7.22 Hz, 1H),
2.21 ppm (s, 6H); 13C NMR (CDCl3, 75 MHz): d=146.4, 135.9, 129.6,
129.3, 128.6, 118.3, 117.7, 113.6, 18.5 ppm; HR-EI-MS: [M]+ m/z calcd
for C14H15N: 197.1204; found: 197.1210.
4-(4-bromophenylamino)phenyl methyl ketone (3o):[30] White solid, yield
91% (529 mg), m.p. 114–1168C (lit.[30] 114–1168C). 1H NMR (CDCl3,
300 MHz): d=7.82 (d, J=8.60 Hz, 2H), 7.60 (d, J=8.60 Hz, 2H), 7.42 (d,
J=8.94 Hz, 2H), 7.02 (d, J=8.94 Hz, 2H); 13C NMR (CDCl3, 75 MHz):
d=196.6, 145.4, 138.8, 132.9, 131.0, 130.1, 127.1, 121.0, 117.6, 26.4 ppm;
HR-EI-MS: [M]+ m/z calcd for C14H12BrNO: 289.0102; found: 289.0108.
4-Bromo-N-(2-nitrophenyl)aniline (3p):[29] Yellowpowder, yield 98%
(575 mg), m.p. 166–1688C (lit.[29b] 1678C). 1H NMR (CDCl3, 300 MHz):
d=9.39 (brs, 1H), 8.20 (dd, J=8.23, 1.35 Hz, 1H), 7.52 (d, J=8.61 Hz,
2H), 7.39 (t, J=7.22 Hz, 1H), 7.15–7.21 (m, 3H), 6.81 ppm (t, J=
8.23 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d=142.5, 138.9, 135.9, 132.9,
126.9, 125.8, 118.5, 118.2, 116.1. 116.1 ppm; HR-EI-MS: [M]+ m/z calcd
for C12H9BrN2O2: 291.9847; found: 291.9852.
4-Bromo-N-methyl-N-phenylaniline (3q):[31] Yellowoil, yield 71%
(372 mg). 1H NMR (CDCl3, 300 MHz): d=7.41 (d, J=8.94, 2H), 7.33
(dd, J=7.89, 7.56 Hz, 2H), 7.11 (t, J=7.56 Hz, 1H), 6.99 (d, J=7.89 Hz,
2H), 6.87 (d, J=8.94 Hz, 2H), 2.85 ppm (s, 3H); 13C NMR (CDCl3,
75 MHz): d=156.7, 138.8, 132.8, 130.0, 120.9, 120.6, 119.2, 115.7,
41.8 ppm; HR-EI-MS: [M]+ m/z calcd for C13H12BrN: 261.0153; found:
261.0151.
N-phenylacetamide (3r):[32] White powder, yield 89% (241 mg), m.p.
161–1648C (lit.[32] 1638C). 1H NMR (CDCl3, 300 MHz): d=7.50 (d, J=
7.89 Hz, 2H), 7.26–7.33 (dd, J=7.89, 7.56 Hz, 2H), 7.07–7.12 (dd, J=
7.57, 7.22 Hz, 1H), 2.16 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz): d=
168.5, 138.0, 129.0, 124.4, 120.0, 24.6. 24.6 ppm; HR-EI-MS: [M]+ m/z
calcd for C8H9NO: 135.0684; found: 135.0681.
N-(4-bromophenyl)acetamide (3s):[33] White powder, yield 94%
(403 mg), m.p. 166–1698C (lit.[33] 1688C). 1H NMR (CDCl3, 300 MHz):
d=8.15 (brs, 1H), 7.22–7.57 (m, 4H), 2.13 ppm (s, 3H); 13C NMR
(CDCl3, 75 MHz): d=168.4, 138.0, 132.0, 121.7, 121.5, 24.7; HR-EI-MS:
[M]+ m/z calcd for C8H8BrNO: 212.9789; found: 212.9785.
N-Phenyl-e-caprolactam (3t):[34] White powder, yield 84% (318 mg), m.p.
75–788C (lit.[34] 72–738C). 1H NMR (CDCl3, 300 MHz): d=7.37 (dd, J=
8.58, 1.38 Hz, 2H), 7.19–7.24 (m, 3H), 3.74–3.76 (m, 2H), 2.69–2.71 (m,
2H), 1.81–1.83 ppm (m, 6H); 13C NMR (CDCl3, 75 MHz): d=175.6,
144.7, 129.2, 126.5, 126.3, 53.1, 37.8, 30.0, 29.0, 23.6 ppm; HR-EI-MS:
[M]+ m/z calcd for C12H15NO: 189.1154; found: 189.1161.
N-phenylindole (3u):[35] Oil, yield 96% (371 mg). 1H NMR (CDCl3,
300 MHz): d=7.68 (dd, 1.72 Hz, J=8.60), 7.55 (d, J=8.26 Hz, 1H), 7.47–
7.49 (m, 4H), 7.31–7.35 (m, 2H), 7.15–7.18 (m, 2H), 6.67 ppm (d, J=
8.26 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d=140.0, 136.0, 129.7, 129.5,
128.1, 126.6, 124.5, 122.5, 121.3, 120.5, 110.6, 103.7 ppm; HR-EI-MS:
[M]+ m/z calcd for C14H11N: 193.0891; found: 193.0887.
N-(2-nitrophenyl)aniline (3 f):[24] Yellowpowder, yield 90% (386 mg),
1
m.p. 72–748C (lit.[24b] 75.58C). H NMR (CDCl3, 300 MHz): d=9.50 (brs,
1H), 8.21 (dd, J=7.22, 1.38 Hz, 1H), 7.35–7.45 (m, 3H), 7.21–7.29 (m,
4H), 6.78 ppm (t, J=6.88 Hz, 1H); 13C NMR (CDCl3, 75 MHz): d=
143.1, 138.7, 135.7, 132.3, 129.7, 126.7, 125.7, 124.4, 117.5, 116.0 ppm; HR-
EI-MS: [M]+ m/z calcd for C12H10N2O2: 214.0742; found: 214.0748.
N-(3-nitrophenyl)aniline (3g):[27] White solid, yield 83% (356 mg), m.p.
1
85–878C (lit.[27] 898C). H NMR (CDCl3, 300 MHz): d=7.84 (s, 1H), 7.69
(d, J=7.84 Hz, 1H), 7.29–7.38 (m, 4H), 7.14 (d, J=8.25 Hz, 2H), 7.08 (t,
J=7.57 Hz, 1H), 5.90 ppm (brs, 1H); 13C NMR (CDCl3, 75 MHz): d=
145.2, 141.0, 140.2, 130.1, 129.8, 123.3, 121.9, 120.0, 114.8, 110.4 ppm; HR-
EI-MS: [M]+ m/z calcd for C12H10N2O2: 214.0742; found: 214.0750.
N-(4-nitrophenyl)aniline (3h):[27] Yellowpowder, yield 86% (369 mg),
m.p. 132–1358C (lit.[27] 1318C). 1H NMR (CDCl3, 300 MHz): d=8.12 (d,
J=9.27 Hz, 2H), 7.39 (t, J=7.56 Hz, 2H), 7.16–7.22 (m, 3H), 6.94 (d, J=
9.27 Hz, 2H), 6.37 ppm (brs, 1H); 13C NMR (CDCl3, 75 MHz): d=150.3,
139.8, 139.6, 129.8, 126.3, 124.8, 122.0, 113.8 ppm; HR-EI-MS: [M]+ m/z
calcd for C12H10N2O2: 214.0742; found: 214.0747.
Methyl 2-(phenylamino)benzoate (3i):[24] White solid, yield 84%
(382 mg), m.p. 54–568C (lit.[24a] 52–548C). 1H NMR (CDCl3, 600 MHz):
d=9.46 (br, 1H), 7.95 (dd, J=8.25, 1.37 Hz, 1H), 7.33 (t, J=7.91 Hz,
2H), 7.29 (td, J=6.87, 1.37 Hz, 1H), 7.23–7.25 (m, 3H), 7.08 (t, J=
7.56 Hz, 1H), 6.71 (t, J=7.56 Hz, 1H), 3.88 ppm (s, 3H); 13C NMR
(CDCl3, 150 MHz): d=169.0, 148.0, 140.9, 134.2, 131.7, 129.5, 123.7,
122.6, 117.2, 114.1, 112.0, 51.9. 51.9 ppm; HR-EI-MS: [M]+ m/z calcd for
C14H13NO2: 227.0946; found: 227.0951.
1-(4-phenylamino)phenyl methyl ketone (3j):[28] White solid, yield 85%
(359 mg), m.p. 105–1068C (lit.[28] 1068C). 1H NMR (CDCl3, 300 MHz):
d=7.79 (dd, J=8.94, 1.72 Hz, 1H), 7.32 (m, 3H), 7.14 (d, 4H), 6.98 (dd,
J=8.60, 1.72 Hz, 1H), 2.52 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz): d=
196.5, 152.1, 146.4, 129.9, 129.6, 125.9, 124.6, 119.6, 26.2 ppm; HR-EI-MS:
[M]+ m/z calcd for C14H13NO: 211.0997; found: 211.0995.
N-(2-methoxyphenyl)aniline (3k):[26] Yellowoil, yield 82% (327 mg).
1H NMR (CDCl3, 300 MHz): d=7.23–7.28 (m, 3H), 7.13 (d, J=7.91 Hz,
2H), 6.92 (t, J=7.40 Hz, 1H), 6.84–6.53 (m, 3H), 6.14 (brs, 1H),
3.85 ppm (s, 3H); 13C NMR (CDCl3, 75 MHz): d=148.4, 142.9, 133.1,
129.4, 121.3, 120.9, 120.0, 118.7, 114.8, 110.7, 55.7 ppm; HR-EI-MS: [M]+
m/z calcd for C13H13NO: 199.0997; found: 199.0993.
N-(4-bromophenyl)indole (3v):[35] Yellowsolid, yield 95% (518 mg), m.p.
64–658C (lit.[35] 64–658C). 1H NMR (CDCl3, 300 MHz): d=7.63 (d, J=
7.2 Hz, 1H), 7.47–7.49 (m, 3H), 7.43 (d, J=8.58 Hz, 1H), 7.16–7.22 (m,
2H), 7.13–7.15 (m, 2H), 6.61 ppm (d, J=3.09 Hz, 1H); 13C NMR
3642
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 3636 – 3646