6
of 9
SADOVOY et Al.
|
with water. The crystalline substances obtained were dried
in a desiccator over P O and recrystallized from MeOH-
ether, 5:1.
(
E)-1-Benzyl-5-(1-methyl-(2-p-tolyl)indol-3-yl)-2-
2
5
nitromethylenepyrrolidine (5e)
Yield: 62%, mp 191-193°C. Yellow crystals. IR spectrum:
−
1
1
1
2
580, 1350 cm (NO ). H NMR spectrum, δ, ppm (J, Hz):
2
(
E)-1-Benzyl-5-(1H-indol-3-yl)-2-
.41-2.44 (2H, m, H-4); 2.43 (3H, s, Ar-CH ,); 3.41-3.43 (1H,
3
nitromethylenepyrrolidine (5a)
m, H3); 3.60 (3H, s, N-CH ); 3.96-3.98 (1H, m, H3); 4.16
3
Yellow crystals. Yield: 52%, mp 183-184°C. IR spectrum:
−
1
1
(1H, d, J = 16, CH2Ph); 4.31 (1H, d, J = 17, CH2Ph); 5.01-
3
280 (NH), 1580, 1370 cm (NO ). H NMR spectrum,
2
5
.03 (1H, m, H2); 6.98 (1H, s, CH-NO ); 6.90-7.44 (13H,
2
δ, ppm (J, Hz): 2.37-2.39, 2.55-2.57 (2H, two m, H-4);
m, Ar). Found, %: C 76.94, H 6.39, N 9.48. C H N O .
2
8
27
3
2
3
.60-3.62, 3.92-3.94 (2H, two m, H3); 4.17 (1H, d, J = 16,
2
J = 9, H2); 6.97 (1H, s, CHNO ); 7.06-7.49 (10H, m, Ar);
.42 (1H, wide s, NH). C NMR spectrum, δ, ppm: 28.7;
3,6; 48.2; 62.5; 110.1; 112.0; 118.6; 120.5; 123.0; 123.7;
27.0(2C); 128.1; 129.0; 131.4; 134.3; 137.0; 146.6; 153.3;
81.2. Found, %: C 71.79, H 5.73, N 12.43. C H N O .
1
Calculated, %: C 76.86, H 6.22, N 9.60.
CH Ph); 4.39 (1H, d, J = 16, CH Ph); 5.17 (1H, dd, J = 8,
2
2
2
1
3
(E)-1-Benzyl-5-(1,2-dimethylindol-3-yl)-2-
8
nitromethylenepyrrolidine (5f)
3
Yield: 77%, mp 198-200°C. Yellow crystals. IR spectrum:
1
−
1
1
1
2
3
570, 1360 cm (NO ). H NMR spectrum, δ, ppm (J, Hz):
2
1
2
0
19
3
2
,17 (3H, s, Ind-CH ); 2.37-2.39, 2.47-2.49 (2H, m, H-4);
3
Calculated, %: C 72.05, H 5.74, N 12.60.
.52-3.54 (1H, m, H3); 3.70 (3H, s, N-CH ); 4.00-4.03 (1H,
3
m, H3); 4.02 (1H, d, J = 16, CH Ph); 4.37 (1H, d, J = 16,
2
(
E)-1-Benzyl-5-(2-(p-tolyl)-1H-indol-3-yl)-2-
nitromethylenepyrrolidine (5b)
Yield: 62%, mp 211-213°C. Orange crystals. IR spectrum:
CH Ph); 5.09 (1H, m, H2); 6.93-6.94 (1H, m, Ar); 7.03 (1H,
2
1
3
s, CH-NO ); 7.12-7.43 (9H, m, Ar). C NMR spectrum, δ,
2
−
1
−1
1
ppm: 8.8; 29.7; 33.8; 46.1; 47.9; 61.9; 107.2; 109.4; 110.0;
3
300 (NH), 1570 cm , 1370 cm (NO ). H NMR spec-
2
1
20.1; 121.6; 127.3(2C); 127.8; 128.3; 128.9(2C); 134.3;
trum, δ, ppm (J, Hz): 2.43 (3H, s, Ar-CH ); 2.42-2.44 (1H, m,
3
1
36.9; 140.5; 154.8; 164.3. Mass spectrum, m/z (I , %);
rel
H-4); 2.54-2.56 (1H, m, H-4); 3.55-3.57, 4.03-4.05 (2H, two
+
3
61[M] (80), 331(13), 315(67), 255(20), 236(34), 224(33),
m, H-3); 4.12 (1H, d, J = 16, CH -Ph); 4.37 (1H, d, J = 16,
2
2
23(27), 211(13), 209(13), 184(45), 171(89), 170(65),
60(50), 158(78), 145(29), 144(38), 128(12), 115(15),
1(100). Found, %: C 72.96, H 6.59, N 11.33. C H N O .
CH -Ph); 5.24-5.26 (1H, m, H-5); 6.95 (1H, s, CHNO );
2
2
1
7
7
.00-7.48 (13H, m, Ar); 8.22 (1H, wide s, NH). Found, %: C
6.35, H 6.11 N 9.52. C H N O . Calculated, %: C 76.59,
9
2
2
23
3
2
2
7
25
3
2
Calculated, %: C 73.13, H 6.41, N 11.63.
H 5.91, N 9.92.
1
-Benzyl-5-(1,2-dimethylindol-3-yl)-2-ethoxycarbonyl-
(
E)-1-Benzyl-5-(2-methyl-1H-indol-3-yl)-2-
nitromethylenepyrrolidine (5c)
Yield: 48%, mp 197-199°C. Yellow crystals. IR spectrum:
nitromethylenepyrrolidine (7f)
Two equivalents (0.2 mL) of trimethylamine were added
to a solution of 350 mg (0.7 mmol) of 1-benzyl-2-(1,2-di
methylindol-3-yl)-5-(methylthio)-3,4-dihydro-2H-pyrrolid
inium iodide 3f and an equimolar amount (98 mg) of ni-
troacetic ester in 15 mL of anhydrous methylene chloride
and were stirred for ~6 hour. After the reaction complete
−
1
1
3
290 (NH), 1580, 1370 cm (NO ). H NMR spectrum,
2
δ, ppm (J, Hz): 2,20 (3H, s, Ind-CH ); 2.36-2.38, 2.60-
3
2
.62 (2H, two m, H-4); 3.61-3.63, 3.92-3.94 (2H, two m,
H-3); 4.01 (1H, d, J = 16, CH -Ph); 4.41 (1H, d, J = 16,
2
CH -Ph); 5.06-5.08 (1H, m, H-5); 7.01 (1H, s, CHNO );
2
2
(
TLC control, benzene-ethylacetate, 3:1), the reaction mix-
7
.05-7.46 (9H, m, Ar); 8.25 (1H, wide s, NH). Found, %:
ture was washed with water several times and dried over
sodium sulfate. The solvent was removed by evaporation,
and the further purification from indolylpyrrolidone was
carried out by dry-column flash chromatography (eluent
C 72.50, H 6.28, N 11.78. C H N O . Calculated, %: C
2
1
21
3
2
7
2.62, H 6.05, N 12.10.
(
E)-1-Benzyl-5-(1-methylindol-3-yl)-2-
benzene).
1-Benzyl-5-(1,2-dimethylindol-3-yl)-2-ethox
nitromethylenepyrrolidine (5d)
ycarbonyl-nitromethylenepyrrolidine 7f was obtained in
Yield: 69%, mp 124-125°C. Light yellow crystals. IR spec-
trum: 1580, 1360 cm (NO ). H NMR spectrum, δ, ppm
−1
1
small amounts.
2
−1
IR spectrum: 1767(COOEt), 1579, 1360 (NO ) cm .
2
(
(
J, Hz): 2.38-2.40, 2.56-2.58 (2H, two m, H-4); 3.60-3.62
1
H NMR spectrum, δ, ppm (J, Hz): 1.35 (3H, t, J = 7, O-
1H, m, H3); 3.81 (3H, s, N-CH ); 3.90-3.92 (1H, m, H3);
3
CH CH ); 2,35 (3H, s, Ind-CH ); 2.40-2.42, 3.18-3.20 (2H,
2
3
3
4
5
.19 (1H, d, J = 16, CH Ph); 4.37 (1H, d, J = 16, CH Ph);
2
2
m, H-3); 3.43-3.45 (H, m, H-4); 3.70 (3H, s, N-CH ); 4.24
3
.14-5.16 (1H, m, H2); 6.93-6.95 (1H, m, Ar); 6.98 (1H,
(
2H, q, J = 7, O-CH CH ), 4.34-4.35 (1H, m, H-4), 4.36 (1H,
2 3
s, CHNO ); 6.99-7.43 (10H, m, Ar). Found, %: C 72.39, H
2
d, J = 16, CH -Ph); 5.97 (1H, d, J = 16, CH -Ph); 5.00-5.02
2
2
6
.17, N 11.83. C H N O . Calculated, %: C 72.62, H 6.05,
21 21 3 2
(1H, m, H-5); 7.15-7.54 (9H, m, Ar).
N 12.10.