PAPER
Palladium Catalyst for the N-Alkylation of Nitrogenated Compounds
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1H NMR (300 MHz, CDCl3): d = 0.95–1.05, 1.10–1.30, 1.35–1.41
and 1.65–1.75 (4 m, 2 H, 3 H, 1 H, and 5 H, HCy), 2.94 (d, J = 6.7
Hz, 2 H, NHCH2), 3.62 (s, 1 H, NH), 6.58 (dd, J = 8.5, 0.9 Hz, 2 H,
o-HPh), 6.66. (td, J = 7.3, 0.9 Hz, 1 H, p-HPh), 7.15–7.20 (m, 2 H, m-
HPh).
13C NMR (75 MHz, CDCl3): d = 25.95 (2 C), 26.55, 31.25 (2 C),
37.50, 50.55, 112.55 (2 C), 116.80, 129.15 (2 C), 148.60.
MS (EI, 70 eV): m/z (%) = 51 (18), 52 (14), 65 (16), 77 (11), 78
(35), 79 (82), 91 (46), 106 (86), 107 (20), 154 (10), 181 (45), 182
(19), 183 (54), 184 (100) [M]+, 185 (13) [M + H]+.
N-(4-Methylbenzyl)pyridin-2-amine (3l)11f
Colorless solid; mp 77–79 °C (EtOAc); tR = 16.9 min (A); Rf = 0.52
(hexanes–EtOAc, 1:1).
IR (KBr): 3390, 3040, 1603, 1574, 766 cm–1.
MS (EI, 70 eV): m/z (%) = 106 (100), 107 (10), 189 (21) [M]+.
1H NMR (300 MHz, CDCl3): d = 2.34 (s, 3 H, CH3), 4.45 (d, J = 5.8
Hz, 2 H, CH2), 4.88 (s, 1 H, NH), 6.37 (d, J = 8.5 Hz, 1 H, H3Py),
6.50–6.60 (m, 1 H, H4Py), 7.15 (d, J = 7.9 Hz, 2 H, o-H4-MeBn), 7.23
(d, J = 7.9 Hz, 2 H, m-H4-MeBn), 7.35–7.45 (m, 1 H, H5Py), 8.10 (d,
J = 4.1 Hz, 1 H, H6Py).
13C NMR (75 MHz, CDCl3): d = 20.85, 45.85, 106.45, 112.65,
127.15 (2 C), 128.90, 129.10 (2 C), 135.80, 137.50, 147.60, 158.50.
N-Benzyl-4-methoxyaniline (3h)11f
Yellow oil; tR = 18.0 min (A); Rf = 0.76 (hexanes–EtOAc, 1:1).
IR (film): 3377, 3050, 2831, 1610, 1512, 1237, 740 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.72 (s, 3 H, CH3), 4.27 (s, 2 H,
CH2), 6.59 (d, J = 8.85 Hz, 2 H, o-H4-MeOPh), 6.77 (d, J = 8.85 Hz, 2
H, m-H4-MeOPh), 7.25–7.40 (m, 5 H, HBn).
MS (EI, 70 eV): m/z (%) = 51 (12), 52 (11), 77 (20), 78 (34), 79
(76), 91 (14), 103 (11), 105 (60), 120 (83), 183 (16), 195 (33), 196
(16), 197 (45), 198 (100), 199 (14) [M]+.
13C NMR (75 MHz, CDCl3): d = 49.20, 55.80, 114.05 (2 C), 114.85
(2 C), 127.10 (2 C), 127.50, 128.55 (2 C), 139.65, 139.85, 152.15.
MS (EI, 70 eV): m/z (%) = 167 (24), 196 (100), 197 (15), 210 (15),
211 (90), 212 (15), 213 (12) [M]+.
N-(4-Methoxybenzyl)pyridin-2-amine (3m)11f
Colorless solid; mp 125–126 °C (EtOAc); tR = 18.3 min (A);
Rf = 0.52 (hexanes–EtOAc, 1:1).
N-Benzyl-2-methoxyaniline (3i)11f
Yellow oil; tR = 17.4 min (A); Rf = 0.85 (hexanes–EtOAc 1:1).
IR (film): 3411, 3060, 2838, 1601, 1513, 1222, 735 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.84 (s, 3 H, CH3), 4.35 (s, 2 H,
CH2), 4.63 (s, 1 H, NH), 6.55–6.60 (m, 1 H, H62-MeOPh), 6.65–6.70
(m, 1 H, H52-MeOPh), 6.75–6.85 (m, 2 H, H32-MeOPh, H42-MeOPh), 7.25–
7.40 (m, 5 H, HBn).
IR (KBr): 3323, 3036, 1601, 1573, 1242, 770 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.79 (s, 3 H, CH3), 4.41 (d, J = 5.7
Hz, 2 H, CH2), 4.90 (s, 1 H, NH), 6.35 (d, J = 8.6 Hz, 1 H, H3Py),
6.55–6.60 (m, 1 H, H4Py), 6.86 (d, J = 8.4 Hz, 2 H, m-H4-MeOBn), 7.27
(d, J = 8.4 Hz, 2 H, o-H4-MeOBn), 7.35–7.40 (m, 1 H, H5Py), 8.08 (d,
J = 5.1 Hz, 1 H, H6Py).
13C NMR (75 MHz, CDCl3): d = 48.00, 57.35, 109.30, 110.05,
116.60, 121.20, 127.10, 127.50 (2 C), 128.50 (2 C), 138.05, 139.50,
146.50.
13C NMR (75 MHz, CDCl3): d = 45.75, 55.20, 106.70, 113.00,
113.95 (2 C), 128.65 (2 C), 131.10, 137.40, 148.10, 158.60, 158.80.
MS (EI, 70 eV): m/z (%) = 78 (23), 79 (30), 121 (100), 136 (22), 213
(34), 214 (57) [M]+.
MS (EI, 70 eV): m/z (%) = 51 (12), 63 (12), 65 (18), 77 (25), 89
(10), 91 (37), 92 (14), 104 (33), 105 (15), 106 (16), 120 (41), 134
(15), 167 (26), 180 (30), 182 (13), 1995 (10), 196 (20), 210 (20),
211 (100), 212 (21), 213 (32) [M]+.
N-(2-Methoxybenzyl)pyridin-2-amine (3n)11f
Colorless solid; mp 75–76 °C (EtOAc); tR = 17.8 min (A); Rf = 0.66
(hexanes–EtOAc, 1:1).
N-Benzyl-3-chloroaniline (3j)11f
Yellow oil; tR = 17.8 min (A); Rf = 0.83 (hexanes–EtOAc 1:1).
IR (film): 3428, 3051, 1597, 1324, 1067, 782 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.11 (s, 1 H, NH), 4.30 (s, 2 H,
CH2), 6.45–6.50 (m, 1 H, H63-ClPh), 6.60–6.65 (m, 1 H, H23-ClPh),
6.65–6.68 (m, 1 H, H43-ClPh), 7.05–7.10 (m, 1 H, H53-ClPh), 7.25–
7.40 (m, 5 H, HBn).
13C NMR (75 MHz, CDCl3): d = 48.05, 111.10, 112.45, 117.40,
127.40, 127.45 (2 C), 128.70 (2 C), 130.20, 135.00, 138.70, 149.20.
IR (KBr): 3328, 3019, 1603, 1556, 1236, 753 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.87 (s, 3 H, CH3), 4.49 (d, J = 6.0
Hz, 2 H, CH2), 5.0 (s, 1 H, NH), 6.40 (d, J = 8.4 Hz, 1 H, H3Py),
6.55–6.60 (m, 1 H, H4Py), 6.85–6.95 (m, 2 H, H32-MeOBn, H52-MeOBn),
7.20–7.30 (m, 2 H, H42-MeOBn, H62-MeOBn), 7.30–7.40 (m, 1 H, H5Py),
8.09 (d, J = 4.1 Hz, 1 H, H6Py).
13C NMR (75 MHz, CDCl3): d = 41.50, 51.10, 99.00, 112.10,
123.00, 123.20, 124.00, 125.80, 141.35, 143.35, 147.95, 158.05,
159.05.
MS (EI, 70 eV): m/z (%) = 51 (10), 65 (13), 75 (21), 76 (11), 77
(14), 89 (13), 91 (100), 111 (34), 113 (11), 138 (12), 140 (20), 152
(10), 180 (13), 215 (73), 216 (62), 217 (75) [M]+, 218 (16) [M + 1]+,
219 (21) [M + 2]+.
MS (EI, 70 eV): m/z (%) = 51 (19), 52 (15), 65 (20), 77 (15), 80
(47), 91 (91), 105 (16), 107 (18), 121 (34), 136 (44), 180 (12), 181
(64), 182 (14), 183 (100), 184 (15), 199 (26), 213 (18), 214 (76)
[M]+, 215 (11) [M + H]+.
N-Benzylpyridin-2-amine (3k)11f
Colorless solid; mp 99–101 °C (EtOAc); tR = 17.8 min (A);
Rf = 0.64 (hexanes–EtOAc, 1:1).
N-(4-Chlorobenzyl)pyridin-2-amine (3o)11f
Colorless solid; mp 104–105 °C (EtOAc); tR = 17.8 min (A);
Rf = 0.50 (hexanes–EtOAc, 1:1).
IR (KBr): 3313, 3056, 1597, 1532, 1294, 748 cm–1.
IR (KBr): 3349, 3016, 1602, 1509, 1276, 770 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.49 (d, J = 5.8 Hz, 2 H, CH2),
4.98 (s, 1 H, NH), 6.35 (d, J = 8.4 Hz, 1 H, H3Py), 6.55–6.60 (m, 1
H, H4Py), 7.25–7.30 (m, 1 H, H5Py), 7.30–7.40 (m, 5 H, HBn), 8.08
(d, J = 5.1 Hz, 1 H, H6Py).
13C NMR (75 MHz, CDCl3): d = 46.25, 106.70, 113.10 (2 C),
127.20, 127.35 (2 C), 128.60, 137.40, 139.10, 148.15, 158.60.
1H NMR (300 MHz, CDCl3): d = 4.49 (d, J = 5.9 Hz, 2 H, CH2),
4.92 (s, 1 H, NH), 6.36 (d, J = 8.4 Hz, 1 H, H3Py), 6.60–6.65 (m, 1
H, H4Py), 7.25–7.30 (m, 4 H, o,m-H4-ClBn), 7.30–7.45 (m, 1 H, H5Py),
8.10 (d, J = 4.0 Hz, 1 H, H6Py).
13C NMR (75 MHz, CDCl3): d = 45.55, 106.65, 113.05, 128.65 (2
C), 128.75 (2 C), 132.80, 137.45, 147.95, 148.00, 159.10.
Synthesis 2011, No. 22, 3730–3740 © Thieme Stuttgart · New York