Job/Unit: O30167
/KAP1
Date: 11-04-13 12:38:28
Pages: 10
D. Thomae, M. Jeanty, J. Coste, G. Guillaumet, F. Suzenet
FULL PAPER
2956, 2927, 2868, 1646 cm–1. 1H NMR (400 MHz, DMSO): δ =
(CIV), 112.84 (CH), 110.20 (CIV), 23.29 (CH2), 22.97 (CH2), 22.82
11.61 (s, 1 H, NH), 10.80 (s, 1 H, NH), 7.05 (s, 1 H, 2-H), 6.83 (m, (CH2), 20.91 (CH2) ppm. MS (IS+): m/z = 207/209 [M + H]+.
3
1 H, 5-H), 6.41 (d, JH,H = 6.9 Hz, 1 H, 4-H), 2.54–2.51 (m, 2 H,
HRMS (ESI+): calcd. for C11H12ClN2O [M + H]+ 207.0689; found
3
CH2-CH2), 1.68–1.48 (sext, JH,H = 8.0 Hz, 2 H, CH2-CH3) 0.88 207.0680.
(t, 3JH,H = 8.0 Hz, 2 H, CH3) ppm. 13C NMR (100 MHz, DMSO):
Supporting Information (see footnote on the first page of this arti-
δ = 155.54 (C=O), 129.86 (CIV), 124.44 (CH), 124.25 (CIV), 124.19
(CH), 117.15 (CIV), 99.78 (CH), 27.05 (CH2), 23.94 (CH2), 14.28
(CH3) ppm. MS (IS+): 177 [M + H]+. HRMS (ESI): calcd. for
C10H12NaN2O [M + Na]+ 199.0847; found 199.0845.
1
cle): Copies of the H and 13C NMR spectra.
Acknowledgments
3-Phenyl-1,6-dihydro-7H-pyrrolo[2,3-c]pyridin-7-one (32): Com-
pound 32 was obtained from the Fischer reaction of 3-hydrazino-
2-methoxypyridine (27) and (2,2-dimethoxyethyl)benzene, and was
purified by recrystallization (CH2Cl2/pentane), yield 80% (0.168 g)
The authors acknowledge Les Laboratoires Servier for financial
support (to D. T., M. J., J. C.), and Mathieu Perrier for technical
assistance.
after MW 160 °C, 5 min. Yellow solid, m.p. 264 °C (dec). IR: ν =
˜
3133, 1637, 1575 cm–1. 1H NMR (400 MHz, DMSO): δ = 12.18
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(br. s, 1 H, NH), 11.02 (br. s, 1 H, NH), 7.65–7.53 (m, 3 H, 2-H,
3
3
2Ј-H), 7.40 (t, JH,H = 7.7 Hz, 2 H, 3Ј-H), 7.23 (t, JH,H = 7.7 Hz,
3
1 H, 4Ј-H), 6.95 (m, 1 H, 5-H), 6.70 (d, JH,H = 7.0 Hz, 1 H, 4-H)
ppm. 13C NMR (100 MHz, DMSO): δ = 155.55 (C=O), 135.45
(CIV), 129.27 (CHPh), 127.89 (CIV), 126.98 (CHPh), 126.14 (CH),
125.63 (CH), 125.29 (CIV), 124.89 (CH), 118.25 (CIV), 99.95 (CH)
ppm. MS (IS+): m/z = 211 [M + H]+. HRMS (ESI+): calcd. for
C13H10NaN2O [M + Na]+ 233.0691; found 233.0691.
2,5,6,7,8,9-Hexahydro-1H-β-carbolin-1-one (33): Compound 33 was
obtained from the Fischer reaction of 3-hydrazino-2-methoxypyr-
idine (27) and cyclohexanone, and was purified by recrystallization
(CH2Cl2/pentane), yield 98% (0.184 g) after MW 160 °C, 20 min.
Pale brown solid, m.p. 174 °C (dec). IR: ν = 2112, 2948, 2920, 2833,
˜
1651 cm–1. 1H NMR (400 MHz, DMSO): δ = 11.40 (br. s, 1 H,
3
NH), 10.70 (br. s, 1 H, NH), 6.80 (m, 1 H, 3-H), 7.00 (d, JH,H
=
8.0 Hz, 1 H, 4-H), 2.61–2.51 (m, 4 H, 5-H, 8-H), 1.74 (m, 4 H, 6-
H, 7-H) ppm. 13C NMR (100 MHz, DMSO): δ = 151.13 (C=O),
136.64 (CIV), 129.51 (CIV), 124.32 (CH), 122.78 (CIV), 110.80 (CIV),
99.32 (CH), 23.34 (CH2), 23.22 (CH2), 23.11 (CH2), 21.12 (CH2)
ppm. MS (IS+): m/z = 189 [M + H]+. HRMS (ESI+): calcd. for
C11H12NaN2O [M + Na]+ 211.0847; found 211.0857.
7-Chloro-3-propyl-1H-pyrrolo[2,3-c]pyridine (36): Compound 36
was obtained from the Fischer reaction of 2-chloro-3-hydrazino-
pyridine (35) and valeraldehyde, and was purified by column
chromatography (petroleum ether/EtOAc, 8:2), yield 36% (0.070 g)
after reflux, 24 h; 96% (0.187 g) after MW 160 °C, 20 min. Pale
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1120–1132.
brown solid, m.p. 186 °C (dec). IR: ν = 3133, 2961, 1615,
˜
1096 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.46 (s, 1 H, NH),
3
3
8.02 (d, JH,H = 5.5 Hz, 1 H, 5-H), 7.45 (d, JH,H = 5.5 Hz, 1 H,
3
4-H), 7.19 (s, 1 H, 2-H), 2.71 (t, JH,H = 7.5 Hz, 2 H, CH2-CH2),
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1.72 (sext, 3JH,H = 7.5 Hz, 2 H, CH2-CH3), 0.98 (t, 3JH,H = 7.5 Hz,
3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.59 (CH),
134.23 (CIV), 134.18 (CIV), 130.09 (CIV), 125.38 (CH), 118.19 (CIV),
113.61 (CH), 27.07 (CH2), 23.29 (CH2), 13.95 (CH3) ppm. MS
[4] a) N. R. Curtis, J. J. Kulagowski, P. D. Leeson, M. P. Ridgill,
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(IS+): m/z
= 195/197 [M +
H]+. HRMS (ESI): calcd. for
C10H12ClN2 [M + H]+ 195.0689; found 195.0688.
1-Chloro-6,7,8,9-tetrahydro-5H-β-carboline (37): Compound 37 was
obtained from the Fischer reaction of 2-chloro-3-hydrazinopyridine
(35) and cyclohexanone, and was purified by recrystallization
(CH2Cl2/pentane), yield 51% (0.105 g) after reflux, 48 h; 65%
(0.134 g) after MW 160 °C, 1 min. Pale brown solid, m.p. 146 °C
(dec). IR: ν = 3171, 2929, 2847, 1620, 1562 cm–1. 1H NMR
˜
3
(400 MHz, CDCl3): δ = 11.51 (br. s, 1 H, NH), 7.82 (d, JH,H
=
3
5.4 Hz, 1 H, 3-H), 7.36 (d, JH,H = 5.4 Hz, 1 H, 4-H), 2.76 (m,
3JH,H = 5.4 Hz, 2 H, 8-H), 2.62 (m, JH,H = 5.4 Hz, 2 H, 5-H),
3
1.88–1.76 (m, 4 H, 6-H, 7-H) ppm. 13C NMR (100 MHz, DMSO):
δ = 141.07 (CIV), 137.09 (CH), 134.14 (CIV), 132.93 (CIV), 129.20
8
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