S. Blanchard et al. / Tetrahedron Letters 42 (2001) 7037–7039
7039
9. General procedure: To the complex base prepared accord-
ing to Ref. 1b was added, at 40°C, the amine (2 equiv.) or
the thiolate (2 equiv.) (generated in situ with 2 equiv. of
NaNH2). The mixture was stirred for 2 h at 40°C. After
cooling at 0°C, a solution of 3-bromoquinoline in THF
was added. The mixture was stirred at rt. The reaction was
monitored by TLC and stopped when the 3-bromoquino-
line had disappeared. The mixture was then hydrolyzed at
0°C and extracted with CH2Cl2. The combined extracts
were dried with MgSO4 and the solvent was removed
under reduced pressure. The product was purified by flash
chromatography on silica gel using as eluent ethyl acetate–
hexane (5–30%).
J=4.8 Hz), 2.73 (4H, t, J=4.8 Hz); 13C NMR (CDCl3,
62.9 MHz): l ppm 156.5 (C), 150.3 (CH), 149.0 (C), 137.4,
129.4, 128.8 (CH), 128.6 (C), 127.9, 126.8, 124.7, 123.3
(CH), 123.0 (C), 108.2 (CH), 62.6 (CH2), 52.6 (2×CH2),
51.7 (2×CH2); MS (IS)=304.5 (M+H)+. Anal. calcd for
C20H21N3: C, 79.17; H, 6.98; N, 13.85. Found: C, 78.94;
1
H, 7.04; N, 13.61. 6b: mp: 171–172°C; H NMR (CDCl3,
250 MHz): l ppm 8.51 (1H, d, J=2.1 Hz), 8.36 (1H, d,
J=8.5 Hz), 7.84 (1H, J=8.2 Hz), 7.69–7.76 (1H, m),
7.51–7.57 (2H, m), 7.40–7.52 (2H, m), 6.99 (1H, d, J=7.9
Hz), 4.19 (3H, s) 13C NMR (CDCl3, 62.9 MHz): l ppm
158.5, 146.5, 143.1, 130.9 (C), 130.6, 130.1 (CH), 128.4
(3×CH), 126.7, 126.1 (3×CH), 125.4 (C), 115.4, 106.9
(CH), 56.2 (CH3); MS (IS)=268 (M+H)+. Anal. calcd for
C16H13NOS: C, 71.88; H, 4.90; N, 5.24. Found: C, 71.63;
Data for selected compounds 3e–4e and 6b–7b; 3e: mp:
104–105°C; 1H NMR (CDCl3, 250 MHz): l ppm 8.79 (1H,
d, J=2.7 Hz), 7.98 (1H, dd, J=7.3 Hz, J=1.8 Hz),
7.63–7.67 (1H, m), 7.40–7.49 (2H, m), 7.33–7.36 (4H, m),
3.30–3.31 (2H, m), 3.59 (2H, s, 2H), 3.30 (4H, t, J=5.0
Hz), 2.66 (4H, t, J=5.0 Hz); 13C NMR (CDCl3, 62.9
MHz): l ppm 145.6 (CH), 141.8, 139.9 (C), 129.0 (C),
128.8, 126.7, 126.0, 124.9 (CH), 113.8 (CH), 51.5 (CH2),
29.3 (4×CH2); MS (IS)=304.5 (M+H)+. Anal. calcd for
C20H21N3: C, 79.17; H, 6.98; N, 13.85. Found: C, 78.87;
1
H, 4.62; N, 5.15 7b: mp: 78–79°C; H NMR (CDCl3, 250
MHz): l ppm 8.58 (1H, d, J=4.8 Hz), 8.20 (1H, d, J=8.2
Hz ), 8.09 (1H, J=8.2 Hz), 7.69–7.76 (1H, m), 7.53–7.60
(1H, m), 7.37 (1H, t, J=7.9 Hz), 7.10–7.18 (2H, m),
6.97–7.02 (1H, m), 6.83 (1H, d, J=4.8 Hz), 3.22 (3H, s),
13C NMR (CDCl3, 62.9 MHz): l ppm 160.5, 149.4 (CH),
148.3, 147.5 (C), 130.7 (CH), 130.6 (C), 129.9, 129.8, 127.2,
126.5 (CH), 125.9 (C), 123.4, 119.9, 118.0, 115.6 (CH),
55.4 (CH3); MS (IS)=268 (M+H)+. Anal. calcd for
C16H13NOS: C, 71.88; H, 4.90; N, 5.24. Found: C, 71.97;
H, 4.75; N, 5.37.
1
H, 7.13; N, 13.55. 4e: oil; H NMR (CDCl3, 250 MHz): l
ppm 8.70 (1H, d, J=4.8 Hz), 8.00–8.06 (2H, m), 7.60–7.66
(1H, m), 7.41–7.48 (1H, m), 7.35–7.37 (3H, m), 7.35 (1H,
d, J=4.8 Hz), 7.25–7.31 (1H, m), 3.63 (2H, s), 3.24 (4H, t,