1500
SHMIDT et al.
IFS-25. The analysis of reaction mixtures composition
was done by GLC on a chromatograph Agilent Techno-
logies 6890N. Initial 1-vinyl-2-phenylazopyrroles I–III
were synthesized by procedure [13].
6.1 Hz), 1.13 t [3H, CH –Me, J(CH –Me) 6.8 Hz].
2 2
13
2
C NMR spectrum, δ, ppm: 153.6 (C ), 146.6 (C ), 129.6
i
5
4
(C ), 129.1 (C ), 122.1 (C ), 121.8 (C ), 111.3 (C ), 99.6
(C ), 80.8 (N–CH), 63.9 (CH –Me), 23.1 (Me), 15.0
CH –Me). N NMR spectrum, δ, ppm: –194.9 (N ),
2
1.7 (N ), 89.7 (N ). Found, %: C 69.60; H 7.44; N 17.61.
p
3
m
o
2
15
1
(
9
General synthetic procedure. In 100 mmol of
alcohol was dissolved 1 mmol of 1-vinyl-2-phenyl-azo-
2
3
C H N O. Calculated, %: C 69.11; H 7.04; N 17.27.
pyrrole I–III, CF COOH was added (~1% to the weight
14 17
3
3
of compound I–III), the mixture was heated at reflux,
the acid was added dropwise each hour during the total
reaction time. The reaction progress was monitored by
GLC. Then the reaction mixture was neutralized with
K CO , the alcohol was distilled off, the residue was
treated with ethyl ether (10×2 ml), the extract was
evaporated. The crude product obtained from pyrrole I
and methanol containing solely adduct IV was purified
by flash-chromatography (eluent hexane). In all other
cases the crude product contained a mixture of initial
azopyrrole I–III, adduct V–VII, and 2-methylquinoline
1-(1-Isopropoxyethyl)-2-phenylazopyrrole (VI).
2
0
Yield 0.05 g (20%). Light-yellow viscous fluid, n
D
–
1
1.5100. IR spectrum, cm : 3127, 3063, 3031, 2973,
2931, 1510, 1483, 1456, 1421, 1362, 1329, 1300, 1281,
1229, 1199, 1186, 1139, 1121, 1096, 1058, 1036, 1020,
977, 917, 891, 874, 813, 765, 734, 690, 659, 619, 597,
2
3
1
569, 529, 515. H NMR spectrum, δ, ppm: 7.76 m (2H,
H ), 7.48 m (2H, H ), 7.33 m (1H, H ), 7.20 d.d (1H,
o
5
m
p
3
H , J 2.7, J3-5 1.7 Hz), 6.70 d.d (1H, H , J3-4 4.2,
4
-5
J3-5 1.7 Hz), 6.46 q [1H, N–CH, J(CH-Me) 6.1 Hz]
4
6.35 d.d (1H, H , J 2.7, J3-4 4.2 Hz), 3.56 m (1H, CH–
4
-5
(
VIII), which were separated by column chromatograpy
Me ), 1.67 d [3H, Me, J(CH–Me) 6.1 Hz], 1.18 d, 1.00 d
2
13
on basic alumina (pH 8.25), gradient elution with
hexane–ethyl ether from 1:0 till 0:1.
[6H, Me , J(CH–Me) 6.1 Hz]. C NMR spectrum, δ,
2
2
ppm: 153.7 (C ), 146.5 (C ), 129.6 (C ), 129.1 (C ), 122.2
C , C ), 111.6 (C ), 99.8 (C ), 78.4 (N-CH), 69.1 (CH-
o
i
p
m
5
4
3
(
1
-(1-Methoxyethyl)-2-phenylazopyrrole (IV). Yield
15
20
Me ), 23.8 (Me), 23.2, 21.5 (Me ). N NMR spectrum,
0
.11 g (49%). Light-yellow viscous fluid, n 1.5125. IR
2
2
D
1
2
3
–1
δ, ppm: –201.5 (N ), 83.9 (N ), 79.8 (N ). Found, %:
C 70.41; H 7.74; N 15.91. C H N O. Calculated, %:
spectrum, cm : 3128, 3062, 2990, 2936, 2829, 1643,
511, 1483, 1455, 1419, 1363, 1327, 1282, 1231, 1209,
198, 1131, 1097, 1053, 1021, 918, 861, 808, 765, 733,
1
1
6
15 19
3
C 70.01; H 7.44; N 16.33.
1-(1-tert-Butoxyethyl)-2-phenylazopyrrole (VII).
1
90, 618, 594, 566, 529, 512, 462. H NMR spectrum, δ,
2
0
ppm: 7.77 m (2H, H ), 7.43 m (2H, H ), 7.32 m (1H,
H ), 7.14 d.d (1H, H , J 2.7, J3-5 1.5 Hz), 6.71 d.d (1H,
H , J 4.1, J3-5 1.5 Hz), 6.36 d.d (1H, H , J 2.7, J3-4
4
Yield 0.03 g (12%). Light-yellow viscous fluid, n
o
m
D
5
–1
1.5050. IR spectrum, cm : 3103, 3062, 2923, 2853,
1731, 1599, 1482, 1459, 1365, 1328, 1299, 1283, 1229,
1196, 1156, 1107, 1059, 1037, 1020, 966, 916, 875, 807,
p
3
4-5
4
3
-4
4-5
.1 Hz), 6.24 q [1H, N–CH, J(CH–Me) 6.1 Hz], 3.22 s
3H, OMe), 1.68 d [3H, Me, J(CH–Me) 6.1 Hz].
1
(
1
764, 733, 690, 620, 597, 567, 515. H NMR spectrum, δ,
3
2
C NMR spectrum, δ, ppm: 153.5 (C ), 146.7 (C ), 129.5
ppm: 7.79 m (2H, H ), 7.45 m (2H, H ), 7.35 m (1H,
i
o
m
5
4
5
(
(
C ), 129.0 (C ), 122.1 (C ), 121.6 (C ), 111.3 (C ), 99.5
C ), 82.4 (N–CH), 56.0 (OMe), 22.8 (Me). N NMR
H ), 7.25 m (1H, H , J 2.7, J3-5 1.3 Hz), 6.69 d.d (1H,
H , J 4.0, J3-5 1.3 Hz), 6.60 q [1H, N–CH, J(CH–Me)
6.0 Hz], 6.32 d.d (1H, H , J 2.7, J3-4 4.0 Hz), 1.59 d
4-5
[3H, Me, J(CH–Me) 6.0 Hz], 1.14 C (9H, Me ). C NMR
spectrum, δ, ppm: 153.7 (C ), 144.8 (C ), 129.4 (C ),
29.1 (C ), 122.1 (C ), 122.8 (C ), 110.9 (C ), 100.6 (C ),
p
3
m
o
p
3
4-5
15
3
-4
1
2
3
4
spectrum, δ, ppm: –203.6 (N ), 85.3 (N ), 83.4 (N ).
Found, %: C 68.59; H 6.48; N 18.37. C H N O.
Calculated, %: C 68.10; H 6.59; N 18.33.
13
1
3
15
3
3
2
i
p
3
5
4
1
2
-Phenylazo-1-(1-ethoxyethyl)pyrrole (V). Yield
m
o
20
75.8 (N–CH), 75.7 (C–Me ), 28.1 (Me ), 25.7 (Me).
0
.08 g (33%). Light-yellow viscous fluid, n 1.5115. IR
3
3
D
1
5
1
2
–1
N NMR spectrum, δ, ppm: –196.0 (N ), 84.0 (N ), 79.5
N ). Found, %: C 71.21; H 8.00; N 15.89. C H N O.
spectrum, cm : 3127, 2976, 2925, 2852, 1545, 1483,
457, 1421, 1363, 1327, 1299, 1281, 1230, 1199, 1152,
119, 1093, 1068, 1054, 1019, 948, 917, 849, 806, 764,
3
(
1
1
7
16 21
3
Calculated, %: C 70.82; H 7.80; N 15.48.
1
31, 690, 618, 595, 567, 525, 512, 494. H NMR
2-Methyl-6-ethoxyquinoline (XI). In 6.00 g
(100 mmol) of 2-propanol was dissolved 0.25 g (1 mmol)
of 1-vinyl-5-methyl-2-(4-ethoxyphenylazo)pyrrole (X),
spectrum, δ, ppm: 7.77 m (2H, H ), 7.44 m (2H, H ),
7
6
o
m
5
.34 m (1H, H ), 7.19 d.d (1H, H , J 2.7, J3-5 1.6 Hz),
p 4-5
.72 d.d (1H, H , J 4.1, J3-5 1.6 Hz), 6.38 d.d (1H, H ,
3
4
0.12 g (1 mmol) of CF COOH was added, the mixture
3
-4
3
J4-5 2.7, J3-4 4.1 Hz), 6.36 q [1H, N–CH, J(CH–Me)
.1 Hz], 3.40 m (2H, OCH ), 1.69 d (3H, Me, J
was heated at reflux. After 6 h the reaction mixture was
neutralized with K CO , the alcohol was distilled off,
6
2
CH-Me
2
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007