Molecules 2013, 18
2105
N-[2-(1-adamantyloxy)ethyl]-7-chloroquinolin-4-amine (7a). Obtained from 4,7-dichloroquinoline (50 mg),
amine 1a (49 mg) in the presence of Pd(dba)2 (6 mg), BINAP (7 mg) and t-BuONa (36 mg). Eluent
1
CH2Cl2/MeOH 50:1–35:1. Yield 46 mg (52%), beige crystalline powder, m.p. 173–175 °C. H-NMR
(CDCl3) 1.55–1.67 (m, 6H), 1.74–1.77 (m, 6H), 2.15 (br.s, 3H), 3.39 (q, J = 5.1 Hz, 2H), 3.72 (t,
J = 5.2 Hz, 2H), 5.54 (br.s, 1H), 6.38 (d, J = 5.3 Hz, 1H), 7.35 (dd, J = 9.0, 2.2 Hz, 1H), 7.64 (d,
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J = 9.0 Hz, 1H), 7.93 (d, J = 2.2 Hz, 1H), 8.50 (d, J = 5.3 Hz, 1H). C-NMR (CDCl3) 30.4 (3C),
36.3 (3C), 41.6 (3C), 43.3 (1C), 57.6 (1C), 72.8 (1C), 99.2 (1C), 117.3 (1C), 121.0 (1C), 125.3 (1C),
128.6 (1C), 134.8 (1C), 149.0 (1C), 149.9 (1C), 151.9 (1C). HRMS (MALDI-TOF): C21H26ClN2O
(M+H)+ calcd.; 357.1734 observed; 357.1715.
N,N'-bis[2-(1-Adamantyloxy)ethyl]quinoline-4,7-diamine (8a). Obtained from 4,7-dichloroquinoline
(50 mg), amine 1a (195 mg) in the presence of Pd(dba)2 (12 mg), DavePhos (9 mg) and t-BuONa (60 mg).
Eluent CH2Cl2/MeOH 20:1–3:1. Yield 92 mg (71%), beige crystalline powder, m.p. 160–162 °C.
1H-NMR (CDCl3) 1.53–1.66 (m, 12H), 1.72 (br.s, 12H), 2.12 (br.s, 6H), 3.31 (q, J = 4.5 Hz, 2H), 3.42
(q, J = 5.1 Hz, 2H), 3.63 (t, J = 5.0 Hz, 2H), 3.70 (t, J = 5.4 Hz, 2H), 4.59 (br.s, 1H), 6.16 (br.s, 1H),
6.22 (d, J = 5.9 Hz, 1H), 6.79 (dd, J = 9.0, 1.9 Hz, 1H), 6.94 (d, J = 1.9 Hz, 1H), 7.62 (d, J = 9.0 Hz,
13
1H), 8.21 (d, J = 5.9 Hz, 1H). C-NMR (CDCl3) 30.4 (6C), 36.3 (6C), 41.5 (6C), 43.4 (1C), 43.9
(1C), 57.9 (2C), 72.4 (1C), 72.7 (1C), 99.7 (1C), 104.0 (1C), 110.6 (1C), 116.4 (1C), 121.0 (1C), 148.0
(1C), 148.1 (1C), 149.6 (1C), 151.2 (1C). HRMS (MALDI-TOF): C33H46N3O2 (M+H)+ calcd.;
516.3590 observed; 516.3634.
N-(1-Adamantylmethyl)-7-chloroquinolin-4-amine (7b). Obtained from 4,7-dichloroquinoline (50 mg),
amine 1b (41 mg) in the presence of Pd(dba)2 (6 mg), BINAP (7 mg) and t-BuONa (36 mg). Eluent
CH2Cl2/MeOH 100:1–50:1. Yield 50 mg (61%), beige crystalline powder, m.p. 225–227 °C. 1H-NMR
(CD3OD) 1.65 (br.s, 6H), 1.65–1.78 (m, 6H), 1.97 (br.s, 3H), 3.09 (s, 2H), 6.60 (d, J = 5.8 Hz, 1H),
7.39 (dd, J = 9.0, 2.1 Hz, 1H), 7.76 (d, J = 2.1 Hz, 1H), 8.13 (d, J = 9.0 Hz, 1H), 8.30 (d,
J = 5.8 Hz, 1H), NH proton was not observed. 13C-NMR (CD3OD) 29.8 (3C), 36.7 (1C), 38.0 (3C),
41.7 (3C), 55.5 (1C), 100.0 (1C), 118.6 (1C), 124.2 (1C), 125.9 (1C), 127.5 (1C), 136.3 (1C), 149.7 (1C),
152.2 (1C), 153.8 (1C). HRMS (MALDI-TOF): C20H24ClN2 (M+H)+ calcd.; 327.1628 observed; 327.1649.
N-[2-(1-Adamantyl)-1-methylethyl]-7-chloroquinolin-4-amine (7c). Obtained from 4,7-dichloroquinoline
(50 mg), amine 1c (49 mg) in the presence of Pd(dba)2 (6 mg), BINAP (7 mg) and t-BuONa (36 mg).
Eluent CH2Cl2/MeOH 50:1. Yield 73 mg (79%), beige crystalline powder, m.p. 207–209 °C. 1H-NMR
(CDCl3) 1.26 (d, J = 6.2 Hz, 3H), 1.39 (dd, J = 14.8, 3.9 Hz, 1H), 1.46 (dd, J = 14.8, 7.6 Hz, 1H), 1.54
(br.s, 6H), 1.54–1.69 (m, 6H), 1.91 (br.s, 3H), 3.78–3.87 (m, 1H), 4.78 (d, J = 7.2 Hz, 1H), 6.42 (d,
J = 5.5 Hz, 1H), 7.33 (dd, J = 9.1, 2.2 Hz, 1H), 7.60 (d, J = 9.1 Hz, 1H), 7.93 (d, J = 2.2 Hz, 1H), 8.51
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(d, J = 5.5 Hz, 1H). C-NMR (CDCl3) 22.4 (1C), 28.5 (3C), 32.5 (1C), 36.8 (3C), 43.0 (3C), 44.1
(1C), 52.6 (1C), 98.8 (1C), 117.2 (1C), 120.7 (1C), 125.1 (1C), 128.8 (1C), 134.8 (1C), 148.2 (1C), 149.3
(1C), 152.0 (1C). HRMS (MALDI-TOF): C22H28ClN2 (M+H)+ calcd.; 355.1941 observed; 355.1904.
N-[1-Adamantyl(phenyl)methyl]-7-chloroquinolin-4-amine (7d). Obtained from 4,7-dichloroquinoline
(50 mg), amine 1d (60 mg) in the presence of Pd(dba)2 (6 mg), BINAP (7 mg) and t-BuONa (36 mg).
Eluent CH2Cl2/MeOH 100:1. Yield 77 mg (77%), yellowish viscous oil. 1H-NMR (CDCl3) 1.54–1.66