Heteroaryl Substituted Propenones
647
extracted with 3ꢃ10 cm3 of CH2Cl2. The combined organic layers were washed with 50cm3 of satd.
NaCl solution, and dried (MgSO4). After a few days at room temperature, the crystals were collected.
Yield 0.65 g (92%); colorless crystals; mp 138ꢂC (CH2Cl2); IR: ꢂꢀ¼ 3300 (NH), 3010 (CH), 2200
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(CN), 1640 (CO), 1590, 760, 700 (ar) cmꢁ1; H NMR (DMSO-d6, 200 MHz): Isomer I: ꢁ ¼ 1.81 (dt,
J ¼ 13.4, 11.3Hz, 5-Hax), 2.3–2.4 (m, 5-Heq), 3.85 (dd, J ¼ 11.4, 6.2Hz, 4-H), 5.49 (dd, J ¼ 11.3,
1.2 Hz, 6-H), 6.45, 6.55 (2s, 3-H, N–H), 6.80–7.65 (m, 8 ar H) ppm; Isomer II: ꢁ ¼ 1.96–2.17 (m,
5-Hax), 2.3–2.4 (m, 5-Heq), 3.74 (dd, J ¼ 6.0, 3.5 Hz, 4-H), 5.21 (dd, J ¼ 10.0, 1.9 Hz, 6-H), 6.45, 6.55
(2s, 3-H, N–H), 6.80–7.65 (m, 8 ar H) ppm.
6-(3-Bromo-2-thienyl)-4-(4-chlorophenyl)-3-cyanopiperidin-2-one (15b, C16H12BrClN2OS)
From 7b (3.94 g, 10 mmol), and 0.19 g of NaH (5mmol) as described for 15a. The reaction mixture
was concentrated in vacuo, 20 cm3 H2O were added to the residue, then it was extracted with Et2O.
Yield 3.5 g (90%); colorless crystals; mp 122ꢂC (EtOH); IR: ꢂꢀ¼ 3310 (NH), 2940 (CH), 2190 (CN),
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1630 (CO), 1590, 830 (ar) cmꢁ1; H NMR: ꢁ ¼ 1.90–2.65 (m, CH2), 3.75–4.15 (m, 3-H), 4.75 (bs,
N-H, 2-H), 5.15–5.70 (m, 5-H), 6.90–8.00 (m, 6 ar H) ppm.
1-(2-Furyl)-4-nitro-3-phenylbutan-1-one (16a, C14H13NO4)
From nitromethane (3.0g, 50 mmol) and 1.98g of 1a (10 mmol) as described for 9a. Yield 1.7 g (66%);
colorless crystals; mp 60ꢂC (MeOH); IR: ꢂꢀ¼ 1670 (CO), 1565 (ar), 1540, 1360 (NO2), 700, 760 (ar)
cmꢁ1; 1H NMR: ꢁ ¼ 3.25 (d, J ¼ 6 Hz, 2H, 2-H), 4.10 (m, 3-H), 4.70 (dd, J ¼ 3, 6 Hz, 2H, 4-H), 6.50
(m, 1H, 4-Hfuryl), 7.15–7.60 (m, 7 ar H) ppm.
3-(4-Chlorophenyl)-4-nitro-1-(2-thienyl)butan-1-one (16b, C14H12ClNO3S)
a. From nitromethane (3.0g, 50 mmol) and 2.49g of 2b (10 mmol) as described for 9a, 1 h reflux. b.
From 18 (1.3g, 10 mmol) and 1.84g of 17 (10 mmol) with MeONa (5mmol) in MeOH, 3 h reflux. The
product was purified by Kugelrohr distillation. Yield a. 1.7 g (55%), b. 2.1 g (68%); light yellow liquid;
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bp 190ꢂC=133 Pa; IR (film): ꢂꢀ¼ 1660 (CO), 1550, 1375 (NO2), 830 (ar) cmꢁ1; H NMR: ꢁ ¼ 3.35
(d, J ¼ 7 Hz, 2H, 2-H), 4.15 (m, 3-H), 4.75 (dd, J ¼ 4, 4 Hz, 2H, 4-H), 7.00–7.75 (m, 7 ar H) ppm.
3-(3,4-Dimethoxyphenyl)-4-nitro-1-(2-thienyl)butan-1-one (16c, C16H15NO5S)
From nitromethane (3.0g, 50 mmol) and 2.49g of 2d (10 mmol) as described for 9a, 1 h reflux. Yield
2.0 g (60%); colorless crystals; mp 91ꢂC (MeOH); IR: ꢂꢀ¼ 1650 (CO), 1530, 1350 (NO2), 810 (ar)
cmꢁ1; 1H NMR: ꢁ ¼ 3.35 (d, J ¼ 7 Hz, 2H, 2-H), 3.90 (s, 2 OMe), 4.10 (m, 3-H), 4.80 (dd, J ¼ 3, 3 Hz,
2H, 4-H), 6.80–7.75 (m, 6 ar H) ppm.
1-(3-Bromo-2-thienyl)-4-nitro-3-phenylbutan-1-one (16d, C14H12BrNO3S)
From nitromethane (3.0g, 50 mmol) and 2.94g of 6a (10 mmol) as described for 9a, 1 h reflux. Yield
2.5 g (71%); brownish liquid; IR (film): ꢂꢀ¼ 3020 (CH), 1655 (CO), 1550, 1380 (NO2) cmꢁ1; 1H NMR:
ꢁ ¼ 3.40 (dd, J ¼ 7, 16Hz, 2H, 2-H), 4.15 (m, 3-H), 4.70, (dd, J ¼ 4, 7 Hz, 2H, 4-H), 6.90–7.50 (m, 7
ar H) ppm.
1-(3-Bromo-2-thienyl)-3-(4-chlorophenyl)-4-nitrobutan-1-one (16e, C14H11BrClNO3S)
From 6b (3.27 g, 10 mmol) as described 16d. Yield 3.25 g (84%); brownish liquid; IR (film): ꢂꢀ¼ 3020
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(CH), 1655 (CO), 1550, 1380 (NO2) cmꢁ1; H NMR: ꢁ ¼ 3.45 (dd, J ¼ 7, 16 Hz, 2H, 2-H), 4.15 (m,
3-H), 4.70 (dd, J ¼ 4, 7 Hz, 2H, 4-H), 7.00–7.55 (m, 6 ar H) ppm.