the duplicated triplet signal (1H) at 3.47 and 3.79 ppm). Rf (ethyl
acetate–petroleum ether, 50 : 50) 0.20. 1H NMR (300 MHz,
CDCl3) d (major rotamer) 1.23 (9H, s), 2.86 (2H, distorted t,
J 6.8), 3.09 (3H, s), 3.47 (2H, t, J 6.8), 6.75–7.31 (9H, m), 8.43
(1H, br s). d (distinct peaks for minor rotamer) 2.81 (3H, s), 3.79
(2H, br t, J 7.1), 7.62 (1H, d, J 6.3). 13C NMR (75 MHz, CDCl3)
d (major rotamer) 24.49 (CH2), 31.27 (3CH3), 33.06 (CH3), 34.74
(Cq), 51.99 (CH2), 111.32 (CH), 111.60 (Cq), 118.15 (CH), 119.21
(CH), 121.86 (2CH), 125.22 (3CH), 126.20 (CH), 127.10 (Cq),
133.52 (Cq), 136.34 (Cq), 152.23 (Cq), 172.76 (Cq). d (distinct
peaks for minor rotamer) 22.97 (CH2), 38.29 (CH3), 48.51 (CH2),
112.86 (Cq), 118.70 (CH), 122.28 (2CH), 126.89 (CH), 127.57
(Cq), 133.72 (Cq), 152.55 (Cq), 171.62 (Cq). m/z (ES+) 335 (MH+);
(ES−) 333 (M − H)−; m/z (FAB+) 335 (MH+), 670 (2M + 2H)+
(found: C, 78.92; H, 7.88; N, 8.25; MH+, 335.21232. C22H26N2O
requires C, 79.01; H, 7.84; N, 8.38%; MH, 335.21234).
(found: C, 72.85; H, 5.70; N, 9.35; MH+, 297.14034. C18H17FN2O
requires C, 72.96; H, 5.78; N, 9.45%; MH, 297.14032).
4-Fluoro-N-[2-(1H-indol-3-yl)-e◦thyl]-N-methylbenzamide 9e.
White solid. Yield 58%. Mp 180 C. Rotamers 1 : 1.5 (from the
duplicated singlet signal (19F) observed at room temperature at
−112.22 and −111.49 ppm). Rf (ethyl acetate–petroleum ether
1
50 : 50) 0.14. H NMR (400 MHz, DMSO, 363 K) d 2.98 (2H,
distorted t, J 5.7), 3.05 (3H, s), 3.61 (2H, t, J 5.7), 6.94 (1H, t,
J 6.5), 7.05–7.14 (6H, m), 7.27 (1H, br t, J 7.0), 7.35 (1H, d,
J 8.4), 10.54 (1H, br s). 13C NMR (75 MHz, CDCl3) d (major
rotamer) 24.15 (CH2), 32.85 (CH3), 51.88 (CH2), 110.86 (Cq),
111.85 (CH), 115.41 (2CH, br d, J 20.0), 118.64 (2CH), 121.40
(CH), 123.57 (CH), 127.42 (Cq), 129.13 (2CH, d, J 11.0), 133.63
(Cq), 136.68 (Cq), 162.50 (Cq, d, J 259.6), 170.31 (Cq). d (distinct
peaks for minor rotamer) 23.01 (CH2), 37.91 (CH3), 48.40 (CH2),
115.48 (CH, d, J 29.8), 115.68 (CH, d, J 19.9), 118.24 (CH),
123.29 (CH), 127.74 (Cq), 129.80 (CH, d, J 9.2), 169.43 (Cq). 13
C
2-Fluoro-N-[2-(1H-indol-3-yl)-ethyl]-N-methylbenzamide 9c.
Tan solid. Yield 59%. Mp 125 ◦C. Rotamers 1 : 1.4 (from the
duplicated triplet signal (1H) at 3.40 and 3.79 ppm). Rf (ethyl
acetate–petroleum ether, 50 : 50) 0.27. 1H NMR (300 MHz,
CDCl3) d (major rotamer) 2.84 (2H, t, J 7.4), 3.10 (3H, s), 3.40
(2H, t, J 7.4), 6.73–7.29 (9H, m), 8.39 (1H, br s). d (distinct peaks
for minor rotamer) 2.73 (3H, s), 3.05 (2H, distorted t, J 7.4), 3.79
(2H, t, J 7.4), 7.62 (1H, d, J 7.5). 13C NMR (75 MHz, CDCl3) d
(major rotamer) 24.29 (CH2), 32.92 (CH3), 48.42 (CH2), 111.33
(CH), 111.43 (Cq), 112.62 (Cq), 115.83 (CH, d, J 15.5), 117.96
(CH), 118.66 (CH), 119.25 (CH), 121.90 (CH), 124.43 (CH, d, J
6.3), 127.24 (Cq, d, J 32.5), 128.64 (CH, d, J 4.6), 130.76 (CH,
d, J 7.7), 136.35 (Cq), 158.00 (Cq, d, J 224.8), 166.78 (Cq). d
(distinct peaks for minor rotamer) 23.05 (CH2), 37.01 (CH3),
51.53 (CH2), 115.55 (CH, d, J 15.6), 122.34 (CH), 124.66 (CH,
d, J 7.4), 128.92 (CH, d, J 3.2), 131.13 (CH, d, J 8.0), 136.35
(Cq), 157.78 (Cq, d, J 302.2), 167.21 (Cq). 19F NMR (282 MHz,
CDCl3) d (major rotamer) −115.55. d (minor rotamer) −115.15.
m/z (ES+) 297 (MH+), 593 (2M + H)+; (ES−) 295 (M − H)−, 591
(2M − H)−; m/z (FAB+) 297 (MH+), 594 (2M + 2H)+ (found: C,
72.89; H, 5.70; N, 9.39; MH+, 297.14027. C18H17FN2O requires
C, 72.96; H, 5.78; N, 9.45%; MH, 297.14032).
NMR (100 MHz, 363 K, DMSO) d 23.75 (CH2), 111.69 (Cq),
111.84 (CH), 115.29 (CH), 115.51 (CH), 118.45 (CH), 118.73
(CH), 121.40 (CH), 123.32 (CH), 127.77 (Cq), 129.34 (CH),
129.43 (CH), 133.93 (Cq), 136.96 (Cq), 162.77 (Cq, d, J 245.0),
170.06 (Cq). At this temperature, one CH2 and one CH3 were
not observed. 19F NMR (282 MHz, CDCl3) d (major rotamer)
−112.22. d (minor rotamer) −111.49. m/z (ES+) 297 (MH+), 593
(2M + H)+; (ES−) 295 (M − H)−, 591 (2M − H)−; m/z (FAB+)
297 (MH+), 593 (2M + H)+ (found: C, 72.85; H, 5.93; N, 9.52;
MH+, 297.14035. C18H17FN2O requires C, 72.96; H, 5.78; N,
9.45%; MH, 297.14032).
2-Chloro-N-[2-(1H-indol-3-yl)-ethyl]-N-methylbenzamide 9f.
Tan solid. Yield 55%. Mp 176 ◦C. Rotamers 1 : 1.2 (from the
duplicated singlet signal (1H) at 2.75 and 3.09 ppm). Rf (ethyl
acetate–petroleum ether 50 : 50) 0.26. 1H NMR (300 MHz,
DMSO) d (major rotamer) 2.85–2.93 (2H, m), 3.09 (3H, s),
3.26–3.33 (2H, m), 6.77–7.81 (9H, m), 10.82 (1H, br s). d (distinct
peaks for minor rotamer) 2.75 (3H, s), 3.01–3.07 (2H, m), 3.75
(2H, br s), 10.86 (1H, s). 13C NMR (75 MHz, DMSO) d (major
rotamer) 24.26 (CH2), 32.38 (CH3), 51.25 (CH2), 110.71 (Cq),
111.86 (CH), 118.09 (CH), 118.77 (CH), 121.39 (CH), 123.52
(CH), 127.33 (Cq), 127.69 (CH), 128.44 (CH), 129.43 (Cq),
129.63 (CH), 130.56 (CH), 131.08 (Cq), 136.63 (Cq), 167.48 (Cq).
d (distinct peaks for minor rotamer) 22.99 (CH2), 36.39 (CH3),
47.66 (CH2), 111.64 (Cq), 118.68 (CH), 121.41 (CH), 123.40
(CH), 128.06 (CH), 128.16 (CH), 129.83 (CH), 130.76 (CH),
137.04 (Cq), 172.00 (Cq). m/z (ES+) 313 (MH+), 625 (2M + H)+;
(ES−) 311 (M − H)−, 623 (2M − H)−; m/z (FAB+) 313 (MH+),
(found: C, 68.95; H, 5.57; N, 8.83; MH+, 313.11071. C18H17ClN2O
requires C, 69.12; H, 5.48; N, 8.96%; MH, 313.11077).
3-Fluoro-N-[2-(1H-indol-3-yl)-ethyl]-N-methylbenzamide 9d.
Tan solid. Yield 54%. Mp 144 ◦C. Rotamers 1 : 1.4 (from the
duplicated triplet signal (1H) at 3.44 and 3.76 ppm). Rf (ethyl
acetate–petroleum ether 50 : 50) 0.20. 1H NMR (300 MHz,
CDCl3) d (major rotamer) 2.83 (2H, t, J 7.0), 3.07 (3H, s), 3.44
(2H, t, J 7.0), 6.63–7.22 (9H, m), 8.54 (1H, br s). d (distinct peaks
for minor rotamer) 2.73 (3H, s), 3.76 (2H, t, J 7.1), 7.60 (1H, d,
J 7.2). 13C NMR (75 MHz, CDCl3) d (major rotamer) 24.20
(CH2), 33.03 (CH3), 51.81 (CH2), 111.22 (Cq), 111.42 (CH),
112.52 (Cq), 113.75 (CH, d, J 22.8), 116.06 (CH, d, J 21.0), 117.88
(CH), 118.62 (CH), 119.28 (CH), 121.95 (CH), 122.19 (CH, d,
J 10.6), 127.01 (Cq), 130.02 (CH, d, J 7.6), 136.33 (Cq), 138.26
(Cq, d, J 6.8), 162.28 (Cq, d, J 246.2), 170.96 (Cq). d (distinct
peaks for minor rotamer) 22.92 (CH2), 30.95 (CH3), 48.62 (CH2),
114.16 (CH, d, J 23.7), 116.48 (CH, d, J 20.9), 122.41 (CH),
122.51 (CH, d, J 15.1), 127.51 (Cq), 130.28 (CH, d, J 11.3), 138.75
(Cq, d, J 10.4), 162.50 (Cq, d, J 225.0), 169.99 (Cq). 19F NMR
(282 MHz, CDCl3) d (major rotamer) −111.84. d (minor rotamer)
−111.87. m/z (ES+) 297 (MH+), 593 (2M + H)+; (ES−) 295 (M −
H)−, 591 (2M − H)−; m/z (FAB+) 297 (MH+), 593 (2M + H)+
3-Chloro-N-[2-(1H-indol-3-yl)-ethyl]-N-methylbenzamide 9g.
Beige solid. Yield 52%. Mp 152 ◦C. Rotamers 1 : 1.4 (from the
duplicated triplet signal (1H) at 3.55 and 3.86 ppm). Rf (ethyl
acetate–petroleum ether 50 : 50) 0.23. 1H NMR (300 MHz,
CDCl3) d (major rotamer) 2.96 (2H, t, J 7.1), 3.17 (3H, s), 3.55
(2H, t, J 7.1), 6.89–7.38 (9H, m), 8.11 (1H, br s). d (distinct
peaks for minor rotamer) 2.85 (3H, s), 3.86 (2H, t, J 7.1), 7.71
(1H, d, J 7.5). 13C NMR (75 MHz, CDCl3) d (major rotamer)
24.20 (CH2), 33.04 (CH3), 51.89 (CH2), 111.35 (CH), 111.49 (Cq),
117.97 (CH), 119.44 (CH), 122.14 (2CH), 124.58 (CH), 126.64
This journal is
The Royal Society of Chemistry 2006
Org. Biomol. Chem., 2006, 4, 787–801 | 795
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