(30 mL), chilled to 0–5°C, and treated in portions with NaBH (0.025 mol) with ice cooling. The MeOH was distilled off.
4
The solid was dissolved in H O and extracted with CHCl . The solvent was distilled off. The mixture consisted mainly of
2
3
three compounds with R 0.9, 0.5, and 0.2 (8:1 system). The CHCl -soluble compounds (1.6 g) were separated over a column
f
3
of silica gel (30 g) to afford three compounds with R 0.9, 0.5, and 0.2, i.e., 7 (0.3 g, R 0.9, mp 129–131°C); 11 (0.075 g, R 0.2,
f
f
f
mp 133–135°C), and 12 (0.5 g, oil, R 0.5).
f
–1
N,Nꢃ-bis(3,4-Dimethoxyphenylethyl)-4-aminobutanamide (11), mp 133–135°C. IR spectrum (KBr, , cm ): 3434,
3258, 2940, 1651, 1590, 1519. Í NMR spectrum (400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 2.12 (2H, br.s, H-3ꢃꢃ), 2.49 (2H, t, J = 6.5,
1
3
H-2ꢃꢃ), 2.78 (2H, t, J = 7.1, H-ꢁ), 3.00 (2H, br.s, H-4ꢃꢃ), 3.15 (4H, br, H-ꢁꢃ, ꢀ), 3.46 (2H, t, J = 7, H-ꢀꢃ), 3.83 (3H, s, OCH ),
3
3.84 (3H, s, OCH ), 3.86 (3H, s, OCH ), 3.87 (3H, s, OCH ), 6.73–6.85 (6H, m, Ar–H).
3
3
3
1-(3,4-Dimethoxyphenylethyl)-5-(3,4-dimethoxyphenylethylamino)pyrrolidin-2-one (12), oil. IR spectrum
–1
1
( , cm ): 3359, 2935, 1672, 1591, 1516, 1461. Í NMR spectrum (400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 2.13 (1H, m, H-ꢁ), 2.29
3
(1H, m, H-ꢁꢃ), 2.42 (1H, m, H-ꢁ), 2.69 (2H, m, H-4ꢃꢃ), 2.76 (2H, m, H-ꢁꢃ, ꢀ), 2.79 (2H, m, H-3ꢃꢃ), 3.08 (1H, m, H-ꢀ), 3.76
(1H, m, H-ꢀꢃ), 3.79 (1H, m, H-ꢀꢃ), 3.85 (12H, s, 4-OCH ), 4.23 (1H, m, H-5ꢃꢃ), 6.65 (1H, dd, J = 2, 8, H-6), 6.70 (2H, br.s,
3
H-2, 2ꢃ), 6.72 (1H, dd, J = 2, 8, H-6ꢃ), 6.77 (1H, d, J = 8, H-5), 6.79 (1H, d, J = 8, H-5ꢃ).
Reaction of 8 with NaBH . A solution of 8 (0.8 g) in MeOH (20 mL) at room temperature was treated in portions
4
with NaBH (4 g), held at room temperature for 1 h, treated with conc. HCl until acidic, and refluxed on a water bath for 2 h.
4
The course of the reaction was monitored by TLC. The solvent was distilled off. The solid was dissolved in H O and extracted
2
with CHCl to afford two crystalline compounds, i.e., imide 7 and amine 1.
3
Compound 7. Yield 50% (0.4 g), mp 129–131°C.
–1
1
Compound 1. Yield 30% (0.15 g). IR spectrum (KBr, , cm ): 3325, 2935, 2838, 1590, 1519. Í NMR spectrum
(400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 1.43 (2H, br.s, NH ), 2.70 (2H, t, J = 8, H-ꢁ), 2.95 (2H, t, J = 8, H-ꢀ), 3.86 (3H, s, OCH ),
3
2
3
3.87 (3H, s, OCH ), 6.73 (2H, d, J = 8, H-5), 6.81 (2H, dd, J = 8, 2, H-6), 6.80 (2H, d, J = 2, H-2).
3
8,9-Dimethoxy-1,2,5,6-tetrahydropyrrolo[2,1-a]isoquinoline-3(10bH)-one (13). A solution of 7 (0.3 g) in MeOH
(20 mL) at room temperature was treated in portions with NaBH (1.2 g), held at room temperature for 1 h, treated with conc.
4
HCl until acidic, and refluxed for 2 h. The course of the reaction was monitored by TLC. The solvent was distilled off.
The solid was dissolved in H O and extracted with CHCl . The CHCl was removed to afford 13. Yield 64% (0.18 g), oil,
2
3
3
1
R 0.68 (10:1 system). Í NMR spectrum (400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 1.84 (1H, m, H-2), 2.48 (1H, m, H-2), 2.55–2.70
f
3
(2H, m, H-1), 2.90 (2H, m, H-6), 3.00 (1H, m, H-5), 3.84 (3H, s, OCH ), 3.85 (3H, s, OCH ), 4.31 (1H, m, H-5), 4.73 (1H, t,
3
3
J = 5.2, H-10b), 6.57 (1Í, s, Í-10), 6.62 (1H, s, H-7).
XSA. Crystals of 7 were triclinic, space group P1, a = 7.305(2), b = 7.527(2), c = 13.070(3) A ; ꢁ = 78.57(3),
°
° 3
3
–1
ꢀ = 74.36(3), ꢈ = 70.00(3)°; V = 645.8(2) A ; C H NO ; MW = 263.29; Z = 2; d = 1.354 g/cm ; ꢉ = 0.075 mm ; crystal
14 17
4
calcd
size 0.55 ꢊ 0.45 ꢊ 0.30 mm; 2ꢆ < 120°. Absorption corrections were applied empirically using ꢋ-curves (transmission 0.89–0.99).
The structure was solved using the SHELXS-97 program and refined to wR2 = 0.1448, S = 1.125 for all 1755
independent reflections [R = 0.0554 for 1512 F0 > 4ꢌ(F)].
The XSA was performed on a STOE STADI-IV diffractometer (Cu Kꢁ-radiation, 300 K, graphite monochromator,
ꢆ/2ꢆ-scanning). The structure was refined by anisotropic least-squares methods using the SHELXL-97 program [10]. Parameters
of H atoms were calculated geometrically in each refinement cycle.
Data from the XSA were deposited in the Cambridge Crystallographic Data Centre (CCDC 1040323).
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