T. Itoh et al. / Tetrahedron 60 (2004) 6649–6655
6653
chromatographed on silica gel (CH Cl /AcOEt¼20) to give
3.3. Reaction of various ketones with an amine in the
presence of 1 catalyzed by Sc(OTf)3
2
2
7
d (43 mg, yield 98%).
3
granules; mp 48.6–48.9 8C; H NMR (CDCl ) d: 3.73 (3H,
.2.1. N-Benzyl-p-anisidine (7a). Yield 98%; colorless
1
Typical procedure. To the benzene solution (1 ml) of
acetophenone (27 mg, 0.2 mmol) and p-anisidine (25 mg,
0.2 mmol) were added compound 1 (51 mg, 0.2 mmol),
3
s), 4.26 (2H, s), 6.58 (2H, dt, J¼9.0, 3.0 Hz), 6.76 (2H, dt,
˚
J¼9.0, 2.9 Hz), 7.25 (1H, tt, J¼6.9, 2.1 Hz), 7.30–7.37 (4H,
Sc(OTf) (2 mg, 0.004 mmol) and MS 5 A (400 mg), and
3
1
3
m); C NMR (CDCl ) d: 49.2, 55.8, 114.0, 114.8, 127.0,
3
the mixture was allowed to react for 24 h at room
temperature under Ar. After AcOEt (12 ml) was added,
the mixture was washed with 5% aqueous Na CO solution
1
27.4, 128.4, 139.5, 142.2, 152.0. Anal. Calcd for
C H NO: C, 78.84; H, 7.09; N, 6.57. Found: C, 78.87;
1
4
15
2
3
H, 7.21; N, 6.58.
and brine, and dried over MgSO . The solvent was
4
evaporated off and the residue was chromatographed on
silica gel (EtOAc/hexane¼2) to give 8a (34 mg, yield 75%).
3
yellow granules; mp 97.7–97.9 8C; H NMR (CDCl ) d:
.2.2. N-(p-Nitrobenzyl)-p-anisidine (7b). Yield 93%;
1
3
3
.73 (3H, s), 4.42 (2H, s), 6.55 (2H, dt, J¼9.0, 2.3 Hz), 6.75
3.3.1. N-(1-Phenylethyl)-p-anisidine (8a). Yield 75%;
1
(
2H, dt, J¼9.0, 2.3 Hz), 7.53 (2H, d, J¼8.8 Hz), 8.18 (2H,
white powder; mp 56.3–56.7 8C; H NMR (CDCl ) d:
3
1
3
dt, J¼8.8, 2.0 Hz); C NMR (CDCl ) d: 48.4, 55.6, 114.0,
1.49 (3H, d, J¼6.6 Hz), 3.69 (3H, s), 4.40 (1H, q, J¼
6.8 Hz), 5.40 (1H, brs), 6.47 (2H, d, J¼8.8 Hz), 6.69 (2H, d,
J¼8.8 Hz), 7.21 (1H, tt, J¼7.1, 1.7 Hz), 7.29–7.37 (4H, m);
3
114.7, 123.6, 127.5, 140.9, 146.8, 147.3, 152.3. Anal. Calcd
for C H N O : C, 65.11; H, 5.46; N, 10.85. Found: C,
1
4 14 2 3
1
3
6
4.88; H, 5.48; N, 10.63.
C NMR (CDCl ) d: 25.1, 54.2, 55.7, 114.5, 114.7, 125.9,
3
126.8, 128.6, 141.5, 145.5, 151.9. Anal. Calcd for
3
yellow powder; mp 76.1–76.3 8C; H NMR (CDCl ) d: 3.73
.2.3. N-(p-Cyanobenzyl)-p-anisidine (7c). Yield 89%;
1
C H NO: C, 79.26; H, 7.54; N, 6.16. Found: C, 79.01;
15 17
H, 7.78; N, 6.12.
3
(
3H, s), 4.73 (2H, s), 6.54 (2H, dt, J¼9.0, 2.9 Hz), 6.76 (2H,
dt, J¼9.0, 2.9 Hz), 7.47 (2H, d, J¼8.2 Hz), 7.61 (2H, d,
3.3.2. N-(5-Hexen-2-yl)-p-anisidine (8b). Yield 67%;
1
1
3
J¼8.2 Hz); C NMR (CDCl ) d: 48.6, 55.6, 110.6, 114.0,
yellow viscous oil; H NMR (CDCl ) d: 1.16 (3H, d, J¼
3
3
114.7, 118.6, 127.5, 132.1, 141.1, 145.2, 152.2. Anal. Calcd
for C H N O ·1/4H O: C, 74.28; H, 5.92; N, 11.55.
Found: C, 74.58; H, 5.99; N, 11.21.
6.2 Hz), 1.51 (1H, qui, J¼7.6 Hz), 1.65 (1H, dq, J¼7.2,
6.0 Hz), 2.15 (2H, q, J¼7.4 Hz), 3.40 (1H, sxt, J¼6.3 Hz),
3.74 (3H, s), 4.96 (1H, d, J¼11.0 Hz), 5.03 (1H, dd, J¼17.1,
1
5
14
2
3
2
1
.8 Hz), 5.77–5.87 (1H, m), 6.56 (2H, d, J¼9.0 Hz), 6.77
1
3
3
reddish oil; H NMR (CDCl ) d: 0.92–1.02 (2H, m), 1.12–
.2.4. N-Cyclohexylmethyl-p-anisidine (7d). Yield 98%;
1
(2H, d, J¼9.0 Hz); C NMR (CDCl ) d: 20.8, 30.5, 36.3,
3
49.2, 55.8, 114.6, 114.7, 114.8, 138.2, 141.5, 151.8. Anal.
Calcd for C H NO·1/5H O: C, 74.74; H, 9.36; N, 6.70.
Found: C, 75.01; H, 9.66; N, 6.64.
3
1
.30 (3H, m), 1.56 (1H, m), 1.66–1.82 (5H, m), 2.90 (2H, d,
1
6
17
2
J¼6.6 Hz), 3.40 (1H, brs), 3.74 (3H, s), 6.56 (2H, d, J¼
1
3
9
2
.0 Hz), 6.77 (2H, d, J¼8.8 Hz); C NMR (CDCl ) d: 26.0,
3
6.6, 31.3, 37.6, 51.7, 55.9, 113.9, 114.9, 143.0, 151.8.
3.3.3. N-(1-Methyl-3-phenylpropyl)-p-anisidine (8c).
1
Anal. Calcd for C H NO: C, 76.70; H, 9.65; N, 6.39.
1
Yield 82%; pale yellow oil; H NMR (CDCl ) d: 1.19
3
4
21
Found: C, 76.52; H, 10.22; N, 6.23.
(3H, d, J¼6.4 Hz), 1.73 (1H, m), 1.84 (1H, m), 2.71 (2H, t,
J¼7.9 Hz), 3.39 (1H, sxt, J¼6.3 Hz), 3.73 (3H, s), 6.50 (2H,
13
3.2.5. o-(Benzylamino)phenol (7e). Yield 94%; colorless
1
needles; mp 81–82 8C; H NMR (CDCl ) d: 4.32 (2H, s),
dt, J¼9.0, 2.9 Hz), 6.75 (2H, dt, J¼9.0, 2.9 Hz), 7.18 (3H, t,
J¼7.6 Hz), 7.27 (2H, t, J¼7.7 Hz); C NMR (CDCl ) d:
3
3
4
7
1
1
6
.68 (1H, brs), 6.59–6.68 (3H, m), 6.82 (1H, t, J¼7.4 Hz),
20.8, 32.5, 38.8, 48.9, 55.8, 114.7, 114.9, 125.8, 128.4,
141.7. Anal. Calcd for C H NO·1/8H O: C, 79.32; H,
8.51; N, 5.18. Found: C, 79.26; H, 8.31; N, 5.43.
1
3
.22–7.38 (5H, m); C NMR (CDCl ) d: 48.57, 112.54,
3
17 21
2
14.37, 117.84, 121.71, 127.19, 127.56, 128.59, 136.95,
39.38, 143.45. Anal. Calcd for C H NO: C, 78.36; H,
.58; N, 7.03. Found: C, 78.12; H, 6.60; N, 6.95.
1
3 13
3.3.4. N-(1-Phenylpropyl)-p-anisidine (8d). Yield 62%;
1
yellow viscous oil; H NMR (CDCl ) d: 0.93 (3H, t,
3
3
less needles; mp 172–173 8C; H NMR (CD CN) d: 4.47
.2.6. 2-Benzylaminobenzoic acid (7f). Yield 84%; color-
1
J¼7.5 Hz), 1.74–1.87 (2H, m), 3.67 (3H, s), 4.14 (1H, t,
J¼6.9 Hz), 6.46 (2H, dt, J¼9.0, 2.9 Hz), 6.67 (2H, dt,
J¼9.2, 3.0 Hz), 7.20 (1H, tt, J¼6.6, 2.0 Hz), 7.27–7.34 (4H,
3
(
8
1
2H, s), 6.58 (1H, td, J¼7.0, 0.9 Hz), 6.67 (1H, d, J¼
1
3
.5 Hz), 7.24–7.37 (6H, m), 7.87 (1H, dd, J¼7.8, 1.8 Hz);
m); C NMR (CDCl ) d: 10.9, 31.8, 60.3, 60.9, 114.5
3
3
C NMR (CD CN) d: 47.2, 110.5, 112.8, 115.7, 128.1,
3
(114.7), 126.4, 126.7, 128.3, 141.6, 143.9, 151.6. Anal.
Calcd for C H NO: C, 79.63; H, 7.94; N, 5.80. Found: C,
79.60; H, 8.03; N, 5.83.
128.1, 129.6, 133.0, 135.8, 140.5, 152.3, 170.6. Anal. Calcd
for: C, 73.99; H, 5.77; N, 6.16. Found: C, 73.91; H, 5.72; N,
1
6 17
6
.11.
3
.3.5. N-(1-Naphthalen-2-ylethyl)-p-anisidine (8e). Yield
1
3
Yield 78%; reddish powder; mp 99–101 8C (lit. 98–
.2.7. 2-[(2-Hydroxyphenyl)methyl]aminophenol (7g).
2
68%; yellow oil; H NMR (CDCl ) d: 1.17 (3H, d, J¼
3
9
6.4 Hz), 2.71 (3H, s), 3.51 (1H, qui, J¼6.2 Hz), 6.55 (2H, dt,
J¼9.0, 3.5 Hz), 6.76 (2H, dt, J¼9.0, 3.5 Hz), 7.52–7.61
(2H, m), 7.87 (2H, t, J¼8.6 Hz), 7.94 (1H, d, J¼8.6 Hz),
1
1
00 8C); H NMR (CDCl ) d: 4.42 (2H, s), 6.73–6.79 (2H,
3
m), 6.83–6.90 (4H, m), 7.16 (1H, d, J¼7.2 Hz), 7.22 (1H,
1
3
13
td, J¼8.1, 1.7 Hz); C NMR (CDCl ) d: 48.8, 114.6, 115.2,
8.02 (1H, dd, J¼8.6, 1.8 Hz), 8.45 (1H, s); C NMR
3
1
1
16.5, 119.9, 120.6, 121.5, 123.0, 128.5, 128.9, 135.7,
44.6, 156.6. FAB-MS: 216 (MþH)þ.
(CDCl ) d: 25.1, 26.7, 45.4, 114.7, 123.7, 126.6, 127.6,
3
128.2, 128.3, 129.3, 130.0, 132.3, 134.2, 135.3, 151.7,