NOVIKOV et al.
1504
Compound XVb. mp 190–192°C (from EtOAc–
(1RS,10bSR)-3-Fluoro-8,9-dimethoxy-1,5,6,10b-
tetrahydropyrrolo[2,1-a]isoquinoline-1,2-dicarbo-
nitrile (XIVd) and (1RS,10bRS)-3-fluoro-8,9-di-
methoxy-1,5,6,10b-tetrahydropyrrolo[2,1-a]iso-
quinoline-1,2-dicarbonitrile (XVd) were obtained
from 0.53 g (2.8 mmol) of 6,7-dimethoxy-3,4-dihydro-
isoquinoline (XIIId) and 0.44 g (5.6 mmol) of fumaro-
nitrile according to the general procedure (reaction
time 47 h). By column chromatography using hexane–
ethyl acetate as eluent we isolated 0.22 g (26%)
of compound XIVd. Compound XVd was detected by
1H NMR spectroscopy as a mixture with XIVd. Re-
peated chromatographic treatment resulted in hydrol-
ysis of XVd to (1RS,10bSR)-8,9-dimethoxy-3-oxo-
1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinoline-
1,2-dicarbonitrile (XVI) (0.075 g, 9%).
CH2Cl2). IR spectrum (CHCl3), Ȟ, cm–1: 2217 (CŁN).
1H NMR spectrum (CDCl3), į, ppm: 2.84–2.89 (1H,
CH2), 3.11–3.22 (1H, CH2), 3.25–3.35 (1H, CH2),
3.81–3.86 m (1H, CH2), 4.73 d (1H, 1-H, ȳ = 4.4 Hz),
13
7.15–7.45 m (9H, Harom). C NMR spectrum (CDCl3),
įC, ppm: 28.3 (C6); 37.8 (C5); 44.3 d (C1; ȳ = 2.8 Hz);
53.4 d (C2, ȳ = 14.4 Hz); 68.7 (C10b); 113.1 d (CH,
ȳ = 4.4 Hz); 115.8 d (CH, ȳ = 1.7 Hz); 125.7, 126.7,
128.5, 128.6, 128.7, 129.0, 129.1, 132.9, 133.6, 141.7
(Carom); 163.2 d (C3, ȳ = 286 Hz). Found, %: C 76.31;
H 4.48; N 13.23. C20H14FN3. Calculated, %: C 76.18;
H 4.47; N 13.32.
Following the general procedure, from 0.505 g
(2 mmol) of 1-(1,3-benzodioxol-5-yl)-3,4-dihydroiso-
quinoline (XIIIc) and 0.31 g (4 mmol) of fumaronitrile
(reaction time 64 h) we obtained 0.29 g (40%) of
(1RS,10bSR)-10b-(1,3-benzodioxol-5-yl)-3-fluoro-
1,5,6,10b-tetrahydropyrrolo-[2,1-a]isoquinoline-1,2-
dicarbonitrile (XVc) and 0.21 g (29%) of a mixture of
XVc and (1RS,10bRS)-10b-(1,3-benzodioxol-5-yl)-3-
fluoro-1,5,6,10b-tetrahydropyrrolo[2,1-a]isoquinoline-
1,2-dicarbonitrile (XIVc) at a ratio of 1.3:1. The prod-
ucts were isolated by column chromatography using
hexane–ethyl acetate as eluent, followed by recrystal-
lization from diethyl ether–methylene chloride.
5-Amino-1-methyl-2,2-diphenyl-2,3-dihydro-1H-
pyrrole-3,4-dicarbonitrile (XX). A mixture of 0.3 g
(0.99 mmol) of dihydropyrrole IIa and 5 ml of 25%
aqueous ammonia was stirred for 7 days at room tem-
perature. The mixture was poured into 25 ml of water,
and the precipitate was filtered off, washed with water,
dried in air, and recrystallized from ethanol. Yield
0.224 g (53%), colorless crystals with mp 189°C
(decomp.). IR spectrum (CHCl3), Ȟ, cm–1: 3500, 3410
1
(N–H); 2250, 2190 (CŁN). H NMR spectrum
1
(DMSO-d6), į, ppm: 2.46 s (3H, CH3), 4.97 s (1H,
3-H), 7.02 s (2H, NH2), 7.21–7.45 m (10H, Harom).
13C NMR spectrum (DMSO-d6), įC, ppm: 30.9 (CH3);
45.9 (C4); 46.9 (C3); 77.3 (C2); 119.8 (CN); 121.2
(CN); 128.3, 128.9, 129.1, 129.2, 129.3, 140.2, 140.6
(Carom); 163.6 (C5). Found, %: C 75.64; H 5.54; N 17.91.
C19H16N4. Calculated, %: C 75.98; H 5.37; N 18.68.
Compound XIVc. H NMR spectrum (CDCl3), į,
ppm: 2.62–2.71 m (1H, CH2), 2.95–3.06 m (1H, CH2),
3.34–3.44 m (1H, CH2), 3.66–3.77 m (1H, CH2),
4.77 d (1H, 1-H, ȳ = 3.1 Hz), 6.01 (OCH2O), 6.72–
6.83 m (3H, Harom), 7.15–7.27 m (4H, Harom). 13C NMR
spectrum (CDCl3), įC, ppm: 26.5 (C6); 38.1 (C5);
43.8 d (C1, ȳ = 5.7 Hz); 52.3 d (C2, ȳ = 13.8 Hz); 70.2
(C10b); 101.4 (OCH2O); 107.6, 107.8 (Carom); 113.0 d
(CH, ȳ = 4.6 Hz); 115.6 d (CH, ȳ = 3.5 Hz); 118.1,
121.5, 125.7, 126.8, 129.5, 131.1, 133.2, 136.0, 147.9,
148.0 (Carom); 165.2 d (C3, ȳ = 286 Hz).
1-Methyl-5-methylamino-2,2-diphenyl-2,3-dihy-
dro-1H-pyrrole-3,4-dicarbonitrile (XXI). A mixture
of 0.2 g (0.66 mmol) of compound IIa, 0.045 g
(0.67 mmol) of methylamine hydrochloride, 0.2 g
(1.45 mmol) of calcined potassium carbonate, and 3 ml
of anhydrous 1,2-dimethoxyethane was stirred for 1 h
at room temperature. The mixture was poured into
25 ml of water, and the precipitate was filtered off,
dried in air, and recrystallized from methanol. Yield
0.157 g (75%), colorless crystals with mp 212–215°C
(decomp.). IR spectrum (CHCl3), Ȟ, cm–1: 3460 (N–H);
Compound XVc. mp 192–194°C (from Et2O–
CH2Cl2). IR spectrum (CHCl3), Ȟ, cm–1: 2217 (CŁN).
1H NMR spectrum (CDCl3), į, ppm: 2.81–2.89 m (1H,
CH2), 3.09–3.20 m (1H, CH2), 3.24–3.33 m (1H, CH2),
3.79–3.86 m (1H, CH2), 4.66 d (1H, 1-H, ȳ = 4.63 Hz),
6.01 (OCH2O), 6.72–6.77 m (3H, Harom), 7.15–7.40 m
(4H, Harom). 13C NMR spectrum (CDCl3), įC, ppm:
28.3 (C6); 37.6 (C5); 44.5 d (C1, ȳ = 2.8 Hz); 53.2 d
(C2, ȳ = 14.4 Hz); 68.7 (C10b); 101.4 (OCH2O); 106.4,
107.8 (Carom); 113.1 d (CH, ȳ = 5.0 Hz); 115.7 (CH);
119.8, 126.8, 128.6, 128.7, 129.2, 133.1, 133.6, 135.8,
148.0, 148.1 (Carom); 163.1 d (C3, ȳ = 285 Hz). Found,
%: C 70.26; H 4.00; N 11.67. C21H14FN3O2. Calcu-
lated, %: C 70.19; H 3.93; N 11.69.
1
2250, 2185 (CŁN). H NMR spectrum (CDCl3), į,
ppm: 2.44 s (3H, 1-CH3), 3.14 d (3H, 5-NHCH3, J =
5.1 Hz), 4.57 s (1H, 3-H), 5.09 q (1H, NH, J = 5.1 Hz),
7.29–7.40 m (10H, Harom). 13C NMR spectrum
(CDCl3), įC, ppm: 29.8 (CH3); 30.3 (CH3); 46.6 (C4);
46.9 (C3); 76.5 (C2); 117.7 (CN); 121.0 (CN); 127.0,
128.0, 128.2, 128.3, 128.4, 128.5, 138.4, 139.7 (Carom);
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005