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VYDZHAK, PANCHISHIN
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elemental analysis, and structure, by the IR and H
NMR spectroscopy. Heating of hydroxypyrrolones
IVa, IVb in acetic acid leads to their dehydration to
give 1,2-spiro derivatives of dihydrochromeno[2,3-c]-
pyrrole-3,9-diones Va, Vb. The structure of the latter
ppm: 2.39–2.62 m (2Н, СН2), 2.84–3.09 m (6Н,
3СН2), 3.26 s (3H, NСН3), 6.65–7.36 m (17Н, Ph),
7.88 br.s (3Н, NH2, ОН), 8.80 d (1Н, Ph), 13.48 s (1Н,
ОН). Found, %: C 73.24; H 5.70; N 7.57. C27H22N2O5·
C8H11N. Calculated, %: C 73.03; H 5.78; N 7.30.
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was confirmed by the IR and H NMR spectroscopy,
and their composition, by the elemental analysis data.
Compound IVb was prepared similarly without
adding the second portion of amine.
The IR spectra of 1,2-dihydrochromeno[2,3-c]-
pyrrole-3,9-diones recorded from KBr pellets in the
range of 1590–1730 cm–1 contain the following absorp-
tion bands: 1605–1615 (moderate intensity), 1650–1680
(strong band) and 1700–1740 cm–1 (two strong bands).
In the range of 3200–3600 cm–1 no absorption bands
were observed, which confirmed the participation of
3-Hydroxy-4-(2-hydroxybenzoyl)-1-[3-(dimethyl-
amino)propyl]-1,5-dihydro-2H-pyrrole-5-spiro-
[3'(1'-methyl-1',3'-dihydro-2'H-indole)]-2,2'-dione
(IVb). Yield 67%, yellow crystals, mp 241–243ºС
(ethyl acetate). IR spectrum, ν, cm–1: 1612 (C=O,
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ketone), 1697 (С=О), 1727 (С=О), 3432 (OH). Н
NMR spectrum, δ, ppm: 1.51–1.67 m (2Н, СН2), 2.59–
2.76 m [7Н, НВ NCH2, N(CH3)2], 2.81–2.92 m (2Н,
CH2NMe2), 3.15 m (1H, HA NCH2), 3.25 s (3H,
NСН3), 6.56–6.75 m (2Н, Ph), 6.87–7.08 m (3Н, Ph),
7.14–7.32 m (2Н, Ph), 8.75 d (1Н, Ph), 9.68 s (1Н,
ОН), 13.22 s (1Н, ОН). Found, %: C 66.35; H 5.83; N
9.57. C24H25N3O5. Calculated, %: C 66.19; H 5.79; N
9.65.
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OH-groups in the cyclocondensation. In the H NMR
spectra of compounds Va, Vb there are all the signals
of hydrogen atoms. The hydrogen atoms of methylene
groups in position 2 of the heterocycle are diastereo-
topic and appear as two multiplets.
Thus, the spiro derivatives of 1,2-dihydrochromeno-
[2,3-c]pyrrole-3,9-diones, which are interesting as
potential biologically active substances, were first
obtained. The scope of this approach to the synthesis
of condensed derivatives of chromone will be
considered in the future.
2-(2-Phenylethyl)-1,2-dihydrochromeno[2,3-c]-
pyrrole-1-spiro[3'(1'-methyl-1',3'-dihydro-2'H-
indole)]-3,9,2'-trione (Va). A solution of adduct IVa
in 10 ml of glacial acetic acid was refluxed for 1 h,
cooled, and concentrated. The residue was ground with
15 ml of 2-propanol. The precipitate was filtered off,
washed with 2-propanol and crystallized from DMF–
ethanol mixture, 1:3. Yield 67%, colorless crystals, mp
237–238ºС. IR spectrum, ν, cm–1: 1610 (С=C), 1669
The IR spectra of the compounds were recorded on
a VERTEX 70 spectrometer (Bruker) from KBr
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pellets. The H NMR spectra were obtained on a
spectrometer Varian VXR-300 in DMSO-d6 with
internal reference HMDS.
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(С=О), 1715 (С=О), 1726 (С=О). Н NMR spectrum,
3-Hydroxy-4-(2-hydroxybenzoyl)-1-(2-phenylethyl)-
1,5-dihydro-2H-pyrrole-5-spiro[3'(1'-methyl-1',3'-
dihydro-2'H-indole)]-2,2'-dione adduct with 2-phenyl-
ethylamine (IVa). To a suspension of 0.01 mol of N-
methylisatin II in 15 ml of anhydrous methanol was
added 0.01 mol of 2-phenylethylamine IIIa. The mix-
ture was heated to 50ºC and kept for 5 min. Then the
second portion of 0.01 mol of 2-phenylethylamine and
0.01 mol of methyl o-hydroxybenzoylpyruvate I was
added. The reaction mixture was heated to boiling and
then allowed to stand for 30 min at 35–40ºC and
cooled. The precipitate was filtered off, washed with
methanol and ethyl acetate. The formed compound
IVa was used without further purification. Yield 71%,
yellow crystals. For the analysis a sample of the
compound IVa was purified by crystallization from
ethanol and dried at 85ºC for 7 days. mp 153–155ºС.
IR spectrum, ν, cm–1: 1614 (C=O, ketone), 1696
(С=О), 1710 (С=О), 3410 (OH). 1Н NMR spectrum, δ,
δ, ppm: 2.59–2.73 m (2Н, CH2Ph), 3.24–3.31 m (2Н,
NCH2), 3.34 s (3Н, NСН3), 6.96–7.29 m (8Н, Ph),
7.45–7.59 m (2Н, Ph), 7.85–7.92 m (2Н, Ph), 7.99 d
(1Н, Ph). Found, %: C 73.99; H 4.45; N 6.57.
C27H20N2O4. Calculated, %: C 74.30; H 4.62; N 6.42.
2-[3-(Dimethylamino)propyl]-1,2-dihydrochro-
meno[2,3-c]pyrrole-1-spiro[3'(1'-methyl-1',3'-
dihydro-2'H-indol)]-3,9,2'-trione (Vb). A solution of
0.005 mol of dione IVb in 10 ml of glacial acetic acid
was refluxed for 1 h, cooled, and concentrated. The
residue was dissolved in 50 ml of a ice-water mixture,
neutralized with saturated sodium hydrogen carbonate
solution, and alkalinized with 5% NaOH solution to
pH 8.5–9. The precipitate was filtered off, washed with
ice water to the neutral reaction, dried, and crystallized
from ethanol. Yield 67%, colorless crystals, mp 195–
197ºС. IR spectrum, ν, cm–1: 1610 (С=C), 1672
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(С=О), 1718 (С=О), 1731(С=О). Н NMR spectrum,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011