The Journal of Organic Chemistry
Article
CDCl3) δ 158.9, 158.6, 148.2, 137.4, 131.1, 128.7, 114.0, 113.1, 106.8,
55.3, 45.8; IR (diamond-ATR, neat) 3219, 2931, 1575, 1507, 1437,
1226, 1031, 817, 769, 521 cm−1; HRMS (ESI+) calcd for C13H15N2O
[M + H]+ 215.1184, found 215.1179; Rf 0.21 (petroleum ether/EtOAc,
5/1).
(dichloromethane/petroleum ether); 1H NMR (400 MHz, CDCl3) δ
8.10 (d, J = 5.0 Hz, 1 H), 7.44−7.37 (m, 1 H), 7.29 (dd, J = 5.0, 3.0 Hz, 1
H), 7.17 (d, J = 2.9 Hz, 1 H), 7.06 (d, J = 5.0 Hz, 1 H), 6.59 (dd, J = 7.0,
5.1 Hz, 1 H), 6.39 (d, J = 8.4 Hz, 1 H), 4.81 (s, 1 H), 4.50 (d, J = 5.7 Hz,
2 H); 13C{1H} NMR (101 MHz, CDCl3) δ 158.5, 148.2, 140.2, 137.4,
127.1, 126.2, 121.6, 113.2, 106.9, 41.8; IR (diamond-ATR, neat) 3198,
2925, 1575, 1507, 1436, 1148, 766, 687 cm−1; HRMS (ESI+) calcd for
C10H11N2S [M + H]+ 191.0643, found 191.0639; Rf 0.55 (petroleum
ether/EtOAc, 2/1).
N-Benzyl-2,5-dimethoxyaniline (3c). According to TP2, MnBr-
(CO)5-catalyzed N-alkylation of 2,5-dimethoxyaniline (153 mg, 1
mmol) with benzyl alcohol (130 mg, 1.2 mmol) afforded the desired
product 3c as a colorless oil (224 mg, 92%).
N-(4-Methylbenzyl)pyridin-2-amine (3r). According to TP1, the
reaction of pyridin-2-amine (94 mg, 1 mmol) with p-tolyl-methanol
(147 mg, 1.2 mmol) afforded the desired product 3r as a white solid
(129 mg, 65%): mp 193−195 °C (dichloromethane/petroleum ether);
1H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 4.5 Hz, 1 H), 7.35 (ddd, J =
8.6, 7.2, 1.9 Hz, 1 H), 7.21 (d, J = 7.6 Hz, 2 H), 7.10 (d, J = 7.6 Hz, 2 H),
6.54 (dd, J = 7.2, 5.1 Hz, 1 H), 6.32 (d, J = 8.3 Hz, 1 H), 4.84 (s, 1 H),
4.41 (d, J = 5.5 Hz, 2 H), 2.30 (s, 3 H); 13C{1H} NMR (101 MHz,
CDCl3) δ 158.7, 148.2, 137.4, 136.8, 136.1, 129.3, 127.4, 113.1, 106.7,
46.1, 21.1; IR (diamond-ATR, neat) 3217, 2919, 1575, 1521, 1437,
1332, 1155, 805, 764, 517 cm−1; HRMS (ESI+) calcd for C13H15N2 [M
+ H]+ 199.1235, found 199.1230; Rf 0.27 (petroleum ether/EtOAc, 5/
1).
N-(4-Bromobenzyl)pyridin-2-amine (3s). According to TP1, the
reaction of pyridin-2-amine (94 mg, 1 mmol) with (4-bromophenyl)-
methanol (224 mg, 1.2 mmol) afforded the desired product 3s as a
white solid (184 mg, 70%): mp 99−100 °C (dichloromethane/
petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 4.3 Hz, 1
H), 7.48−7.33 (m, 3 H), 7.22 (d, J = 8.1 Hz, 2 H), 6.59 (t, J = 6.1 Hz, 1
H), 6.34 (d, J = 8.4 Hz, 1 H), 4.87 (s, 1 H), 4.46 (d, J = 6.0 Hz, 2 H);
13C{1H} NMR (101 MHz, CDCl3) δ 158.4, 148.2, 138.4, 137.5, 131.7,
129.0, 120.9, 113.4, 106.9, 45.6; IR (diamond-ATR, neat) 3217, 2976,
1575, 1523, 1439, 1329, 1155, 1011, 769, 515 cm−1; HRMS (ESI+)
calcd for C12H12BrN2 [M + H]+ 263.0184, found 263.0179; Rf 0.23
(petroleum ether/EtOAc, 5/1).
N-(4-Chlorobenzyl)pyridin-2-amine (3t). According to TP1, the
reaction of pyridin-2-amine (94 mg, 1 mmol) with (4-chlorophenyl)-
methanol (171 mg, 1.2 mmol) afforded the desired product 3t as a
white solid (151 mg, 69%): mp 102−103 °C (dichloromethane/
petroleum ether); 1H NMR (400 MHz, CDCl3) δ 8.09 (dd, J = 5.1, 2.0
Hz, 1 H), 7.39 (ddd, J = 8.8, 7.1, 1.9 Hz, 1 H), 7.30−7.26 (m, 4 H), 6.59
(dd, J = 7.2, 5.1 Hz, 1 H), 6.34 (d, J = 8.4 Hz, 1 H), 4.93 (s, 1 H), 4.48
(d, J = 5.9 Hz, 2 H); 13C{1H} NMR (101 MHz, CDCl3) δ 158.4, 148.2,
137.8, 137.5, 132.9, 128.7, 128.6, 113.4, 106.9, 45.5; IR (diamond-ATR,
neat) 3215, 2927, 1574, 1439, 1328, 1157, 1081, 769, 688, 515 cm−1;
HRMS (ESI+) calcd for C12H12ClN2 [M + H]+ 219.0689, found
219.0685; Rf 0.24 (petroleum ether/EtOAc, 5/1).
N-(Thiophen-2-yl-methyl)pyridin-2-amine (3v). According to
TP2, MnBr(CO)5-catalyzed N-alkylation of pyridin-2-amine (94 mg,
1 mmol) with thiophen-2-yl-methanol (137 mg, 1.2 mmol) afforded the
desired product 3v as a yellow solid (118 mg, 62%).
4-((4-Methylbenzyl)amino)benzonitrile (3x). According to TP2,
MnBr(CO)5-catalyzed N-alkylation of 4-aminobenzonitrile (118 mg, 1
mmol) with p-tolyl-methanol (147 mg, 1.2 mmol) afforded the desired
product 3x as a pale yellow solid (73 mg, 33%): mp 234−236 °C
(dichloromethane/petroleum ether); 1H NMR (400 MHz, CDCl3) δ
7.40 (d, J = 8.5 Hz, 2 H), 7.21 (d, J = 7.9 Hz, 2 H), 7.16 (d, J = 7.9 Hz, 2
H), 6.57 (d, J = 8.5 Hz, 2 H), 4.54 (s, 1 H), 4.32 (d, J = 5.4 Hz, 2 H),
2.34 (s, 3 H); 13C{1H} NMR (101 MHz, CDCl3) δ 151.1, 137.4, 134.7,
133.7, 129.5, 127.3, 120.4, 112.4, 99.0, 47.3, 21.1; IR (diamond-ATR,
neat) 3400, 2919, 2209, 1601, 1511, 1338, 1175, 836, 807, 543 cm−1;
HRMS (ESI+) calcd for C15H15N2 [M + H]+ 223.1235, found
223.1225; Rf 0.36 (petroleum ether/EtOAc, 5/1).
N-Ethyl-9H-fluoren-2-amine (4a). According to TP2, MnBr(CO)5-
catalyzed N-alkylation of 9H-fluoren-2-amine (181 mg, 1 mmol) with
ethanol (185 mg, 4 mmol) afforded the desired product 4a as a pale
yellow oil (97 mg, 46%): 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 7.5
Hz, 1 H), 7.53 (d, J = 8.0 Hz, 1 H), 7.44 (d, J = 7.4 Hz, 1 H), 7.30 (t, J =
7.4 Hz, 1 H), 7.20 (td, J = 7.4, 1.2 Hz, 1 H), 6.84 (s, 1 H), 6.69 (dd, J =
8.1, 2.1 Hz, 1 H), 3.87 (t, J = 5.6 Hz, 1 H), 3.74 (s, 2 H), 2.05 (td, J = 7.5,
5.7 Hz, 2 H), 0.72 (t, J = 7.4 Hz, 3 H); 13C{1H} NMR (101 MHz,
CDCl3) δ 149.1, 146.2, 145.8, 141.8, 132.6, 126.7, 125.1, 124.0, 120.5,
118.4, 114.0, 111.2, 48.3, 25.8, 9.6; IR (diamond-ATR, neat) 3363,
2923, 1614, 1453, 1276, 1126, 819, 766, 735 cm−1; HRMS (ESI+) calcd
for C15H16N [M + H]+ 210.1283, found 210.1276; Rf 0.51 (petroleum
ether/EtOAc, 5/1).
N-Butyl-9H-fluoren-2-amine (4b). According to TP2, MnBr(CO)5-
catalyzed N-alkylation of 9H-fluoren-2-amine (181 mg, 1 mmol) with
butan-1-ol (89 mg, 1.2 mmol) afforded the desired product 4b as a pale
yellow oil (141 mg, 59%): 1H NMR (400 MHz, CDCl3) δ 7.59 (d, J =
7.5 Hz, 1 H), 7.52 (d, J = 8.0 Hz, 1 H), 7.43 (d, J = 7.5 Hz, 1 H), 7.29 (t,
J = 7.5 Hz, 1 H), 7.19 (t, J = 7.4 Hz, 1 H), 6.84 (s, 1 H), 6.68 (dd, J = 8.1,
2.1 Hz, 1 H), 3.87 (t, J = 5.9 Hz, 1 H), 3.73 (s, 2 H), 2.01−1.90 (m, 2
H), 1.34−1.22 (m, 2 H), 1.21−1.10 (m, 2 H), 0.83 (t, J = 7.2 Hz, 3 H);
13C{1H} NMR (101 MHz, CDCl3) δ 149.5, 146.7, 145.8, 141.6, 132.4,
126.7, 125.1, 124.0, 120.5, 118.4, 114.0, 111.2, 47.3, 32.9, 27.7, 23.0,
13.9; IR (diamond-ATR, neat) 3370, 2926, 1615, 1454, 1269, 818, 765,
737 cm−1; HRMS (ESI+) calcd for C17H20N [M + H]+ 238.1596, found
238.1590; Rf 0.52 (petroleum ether/EtOAc, 5/1).
N-Pentyl-9H-fluoren-2-amine (4c). According to TP2, MnBr-
(CO)5-catalyzed N-alkylation of 9H-fluoren-2-amine (181 mg, 1
mmol) with pentan-1-ol (106 mg, 1.2 mmol) afforded the desired
product 4c as a pale yellow oil (178 mg, 71%): 1H NMR (400 MHz,
CDCl3) δ 7.60 (d, J = 7.5 Hz, 1 H), 7.53 (d, J = 8.0 Hz, 1 H), 7.44 (d, J =
7.5 Hz, 1 H), 7.30 (t, J = 7.5 Hz, 1 H), 7.19 (t, J = 7.4 Hz, 1 H), 6.84 (s, 1
H), 6.69 (dd, J = 8.1, 2.1 Hz, 1 H), 3.87 (t, J = 6.0 Hz, 1 H), 3.74 (s, 2
H), 2.02−1.89 (m, 2 H), 1.31−1.13 (m, 6 H), 0.84 (t, J = 6.6 Hz, 3 H);
13C{1H} NMR (101 MHz, CDCl3) δ 149.5, 146.7, 145.7, 141.5, 132.4,
126.7, 125.1, 124.0, 120.5, 118.4, 113.9, 111.2, 47.3, 33.2, 32.2, 25.2,
22.5, 14.1; IR (diamond-ATR, neat) 3372, 2925, 1614, 1455, 1274,
1128, 817, 727 cm−1; HRMS (ESI+) calcd for C18H22N [M + H]+
252.1752, found 252.1753; Rf 0.52 (petroleum ether/EtOAc, 5/1).
N-Hexyl-9H-fluoren-2-amine (4d). According to TP2, MnBr-
(CO)5-catalyzed N-alkylation of 9H-fluoren-2-amine (181 mg, 1
N-(Pyridin-3-yl-methyl)pyridin-2-amine (3u). According to TP1,
the reaction of pyridin-2-amine (94 mg, 1 mmol) with pyridin-3-yl-
methanol (131 mg, 1.2 mmol) afforded the desired product 3u as a
colorless oil (89 mg, 48%): 1H NMR (400 MHz, CDCl3) δ 8.60 (s, 1
H), 8.49 (d, J = 4.6 Hz, 1 H), 8.08 (d, J = 5.1 Hz, 1 H), 7.67 (d, J = 7.7
Hz, 1 H), 7.39 (dt, J = 10.8, 5.0 Hz, 1 H), 7.22 (dd, J = 8.1, 4.3 Hz, 1 H),
6.59 (dd, J = 8.1, 5.1 Hz, 1 H), 6.37 (d, J = 8.1 Hz, 1 H), 4.96 (d, J = 32.3
Hz, 1 H), 4.54 (s, 2 H); 13C{1H} NMR (101 MHz, CDCl3) δ 158.2,
149.1, 148.6, 148.1, 137.5, 135.1, 134.9, 123.5, 113.5, 107.2, 43.6; IR
(diamond-ATR, neat) 3266, 3024, 2921, 1603, 1487, 1420, 1293, 769,
712 cm−1; HRMS (ESI+) calcd for C11H12N3 [M + H]+ 186.1031,
found 186.1030; Rf 0.33 (petroleum ether/EtOAc, 2/1).
N-(Thiophen-2-yl-methyl)pyridin-2-amine (3v). According to
TP1, the reaction of pyridin-2-amine (94 mg, 1 mmol) with
thiophen-2-yl-methanol (137 mg, 1.2 mmol) afforded the desired
product 3v as a yellow solid (68 mg, 36%): mp 156−158 °C
(dichloromethane/petroleum ether); 1H NMR (400 MHz, CDCl3) δ
8.12 (d, J = 0.8 Hz, 1 H), 7.41 (t, J = 7.7 Hz, 1 H), 7.19 (d, J = 5.0 Hz, 1
H), 7.04−6.90 (m, 2 H), 6.64−6.56 (m, 1 H), 6.42 (d, J = 8.4 Hz, 1 H),
4.90 (s, 1 H), 4.69 (d, J = 5.7 Hz, 2 H); 13C{1H} NMR (101 MHz,
CDCl3) δ 158.1, 148.1, 142.6, 137.4, 126.8, 125.1, 124.6, 113.5, 107.3,
41.2; IR (diamond-ATR, neat) 3207, 2850, 1575, 1524, 1454, 1293,
1511, 770, 697, 524 cm−1; HRMS (ESI+) calcd for C10H11N2S [M +
H]+ 191.0643, found 191.0641; Rf 0.56 (petroleum ether/EtOAc, 2/1).
N-(Thiophen-3-yl-methyl)pyridin-2-amine (3w). According to
TP1, the reaction of pyridin-2-amine (94 mg, 1 mmol) with
thiophen-3-yl-methanol (137 mg, 1.2 mmol) afforded the desired
product 3w as a yellow solid (114 mg, 60%): mp 91−93 °C
2260
J. Org. Chem. 2021, 86, 2254−2263