MIKHED’KINA et al.
570
aldehyde I in 5 ml of ethanol was added to a solution
of 0.20 g (1 mmol) of 2,4-dinitrophenylhydrazine in
a mixture of 5 ml of ethanol, 1.5 ml of water, and 1 ml
of sulfuric acid. The mixture was heated for 15 min
under reflux, and the precipitate was filtered off and
washed on a filter with water and ethanol. Yield 0.42 g
(96%), mp 229–230°C. IR spectrum, ν, cm–1: 3288
(NH), 1680 (C=O), 1623, 1608, 1560, 1512, 1424,
1336, 1320, 1280, 1136, 1096, 1024, 832, 744.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.29 t (3H,
CH2CH3, J = 7.1 Hz), 2.28 s (3H, 3-CH3), 2.30 s (3H,
5-CH3), 4.23 q (2H, OCH2, J = 7.1 Hz), 6.47 d (1H,
=CH, J = 9.1 Hz), 7.88 d (1H, 6′-H, J = 9.7 Hz),
8.36 d.d (1H, 5′-H, J = 9.7, 2.7 Hz), 8.84 d (1H, 3′-H,
J = 2.7 Hz), 8.85 d (1H, =CH, J = 9.1 Hz), 11.73 s and
11.79 s (1H each, NH). Mass spectrum: m/z 437/435
[M]+. Found, %: C 49.55; H 4.25; N 15.98.
C18H18ClN5O6. Calculated, %: C 49.61; H 4.16;
N 16.07. M 435.82.
Ethyl 4-[1-chloro-3-(2,2-dimethylhydrazono)-
prop-1-en-1-yl]-3,5-dimethyl-1H-pyrrole-2-carbox-
ylate (X). A solution of 1.51 g (6 mmol) of aldehyde I
and 0.9 ml (12 mmol) of N,N-dimethylhydrazine in
30 ml of diethyl ether was stirred for 48 h at room tem-
perature. The mixture was evaporated, and the residue
was washed with water and recrystallized from etha-
nol. Yield 1.13 g (64%), mp 134–135°C. IR spectrum,
ν, cm–1: 3272 (NH), 1672 (C=O), 1536, 1504, 1440,
1384, 1352, 1288, 1200, 1104, 1048, 1024, 872, 776.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.28 t (3H,
CH2CH3, J = 7.1 Hz), 2.20 s (3H, 3-CH3), 2.24 s (3H,
5-CH3), 2.91 s (6H, NCH3), 4.22 q (2H, OCH2, J =
7.1 Hz), 6.24 d (1H, =CH, J = 8.6 Hz), 7.13 d (1H,
=CH, J = 8.6 Hz), 11.55 s (1H, 1-H). Mass spectrum:
m/z 299/297 [M]+. Found, %: C 56.42; H 6.86;
N 14.02. C14H20ClN3O2. Calculated, %: C 56.47;
H 6.77; N 14.11. M 297.78.
Ethyl 3,5-dimethyl-4-[1H-pyrazol-3(5)-yl]-1H-
pyrrole-2-carboxylate (XI). A mixture of 0.52 g
(2 mmol) of aldehyde I, 0.33 g (4 mmol) of sodium
acetate, and 0.6 ml (12 mmol) of hydrazine hydrate in
10 ml of ethanol was heated for 10 h under reflux. The
mixture was evaporated under reduced pressure, and
the residue was washed with water and recrystallized
from ethanol. Yield 0.44 g (95%), mp 158°C. IR spec-
trum, ν, cm–1: 3288 (NH), 1656 (C=O), 1600, 1512,
Ethyl 4-{3-[2-(4-bromophenyl)hydrazono]-1-
chloroprop-1-en-1-yl}-3,5-dimethyl-1H-pyrrole-2-
carboxylate (IXc). A solution of 0.26 g (1 mmol) of
aldehyde I and 0.19 g (1 mmol) of 4-bromophenyl-
hydrazine (IIc) in 10 ml of acetonitrile was heated for
2 h under reflux. The mixture was cooled, and the
precipitate was filtered off and washed on a filter with
ethanol. Yield 0.34 g (81%), mp 144°C (from EtOH).
IR spectrum, ν, cm–1: 3304 (NH), 1672 (C=O), 1616,
1592, 1568, 1512, 1480, 1440, 1288, 1256, 1192,
1
1440, 1280, 1208, 1096, 928, 776. H NMR spectrum
(DMSO-d6), δ, ppm: 1.29 t (3H, CH2CH3, J = 7.1 Hz),
2.25 s (3H, 3-CH3), 2.30 s (3H, 5-CH3), 4.22 q (2H,
OCH2, J = 7.1 Hz), 6.22 s and 7.62 s (1H each, 4′-H,
5′-H), 11.43 s (1H, 1-H), 12.64 s (1H, 1′-H). Mass
spectrum: m/z 233 [M]+. Found, %: C 61.90; H 6.56;
N 18.05. C12H15N3O2. Calculated, %: C 61.79; H 6.48;
N 18.01. M 233.27.
1
1168, 1136, 1096, 1024, 856, 808. H NMR spectrum
(DMSO-d6), δ, ppm: 1.29 t (3H, CH2CH3, J = 7.1 Hz),
2.24 s (3H, 3-CH3), 2.27 s (3H, 5-CH3), 4.23 q (2H,
OCH2, J = 7.1 Hz), 6.34 d (1H, =CH, J = 9.1 Hz),
6.88–7.40 m (4H, C6H4), 7.96 d (1H, =CH, J = 9.1 Hz),
10.68 s and 11.61 s (1H each, NH). Mass spectrum:
m/z 425/423 [M]+. Found, %: C 50.81; H 4.60; N 9.81.
C18H19BrClN3O2. Calculated, %: C 50.90; H 4.51;
N 9.89. M 424.72.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 4 2009