FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LXXXIX.
1331
Presumably, compounds IIIa–IIIg are formed via
initial addition of the β-CH group in the enamine frag-
ment of IІa–IId at the C2 carbon atom in the pyrrole
ring of Іa–Ic and subsequent closure of a new pyrrole
ring as a result of nucleophilic attack by the secondary
amino group on the ester carbonyl carbon atom and
elimination of methanol, i.e., according to a scheme
analogous to that proposed in [3].
(4-C=O). 1H NMR spectrum, δ, ppm: 2.12 s (3H, Me),
2.13 s (3H, COMe), 2.34 s (3H, C6H4Me), 7.00–
7.71 m (14H, Harom), 7.66 d (1H, COCH=CHPh, J =
16.2 Hz), 7.74 d (1H, COCH=CHPh, J = 16.2 Hz),
12.88 br.s (1H, OH). Found, %: C 74.16; H 5.01;
N 5.44. C32H26N2O5. Calculated, %: C 74.12; H 5.05;
N 5.40.
9-Acetyl-7-(4-bromophenyl)-4-cinnamoyl-3-hy-
droxy-8-methyl-1-(4-methylphenyl)-1,7-diazaspiro-
[4.4]nona-3,8-diene-2,6-dione (ІІІd). Yield 81%,
mp 222–223°C (from ethyl acetate). IR spectrum, ν,
cm–1: 3310 (OH), 1753 (C6=O), 1713 (C2=O), 1672
EXPERIMENTAL
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
1
1
(9-C=O), 1642 (4-C=O). H NMR spectrum, δ, ppm:
The H NMR spectra were run on a Bruker AM-400
2.12 s (3H, Me), 2.15 s (3H, COMe), 2.33 s (3H,
C6H4Me), 6.98–7.81 m (13H, Harom), 7.64 d (1H,
C O C H = C H P h , J = 1 5 . 7 H z ) , 7 . 7 2 d ( 1 H,
COCH=CHPh, J = 15.7 Hz), 12.88 br.s (1H, OH).
Found, %: C 64.25; H 4.20; N 4.65. C32H25BrN2O5.
Calculated, %: C 64.33; H 4.22; N 4.69.
spectrometer at 400 MHz using DMSO-d6 as solvent
and tetramethylsilane as internal reference.
9-Acetyl-7-benzyl-4-cinnamoyl-3-hydroxy-8-
methyl-1-phenyl-1,7-diazaspiro[4.4]nona-3,8-diene-
2,6-dione (ІІІa). Compound Іa, 1.0 mmol, was dis-
solved in 15 ml of anhydrous toluene, 1.0 mmol of
enamino ketone IIa in 5 ml of anhydrous toluene was
added, and the mixture was heated for 3 h under reflux.
The mixture was cooled, and the precipitate was
filtered off, and recrystallized from ethyl acetate. Yield
81%, mp 215–217°C. IR spectrum, ν, cm–1: 3179
(OH), 1754 (C6=O), 1721 (C2=O), 1678 (9-C=O),
1645 (4-C=O). 1H NMR spectrum, δ, ppm: 2.13 s (3H,
COMe), 2.28 s (3H, Me), 4.77 d and 4.92 d (1H each,
J = 16.7 Hz), 6.88–7.69 m (15H, Harom), 7.60 d
(1H, COCH=CHPh, J = 16.0 Hz), 7.73 d (1H,
COCH=CHPh, J = 16.0 Hz), 13.08 br.s (1H, OH).
Found, %: C 74.08; H 5.02; N 5.35. C32H26N2O5. Cal-
culated, %: C 74.12; H 5.05; N 5.40.
9-Acetyl-7-benzyl-4-cinnamoyl-3-hydroxy-1-
(4-methoxyphenyl)-8-methyl-1,7-diazaspiro[4.4]-
nona-3,8-diene-2,6-dione (ІІІe). Yield 74%, mp 216–
217°C (from ethyl acetate). IR spectrum, ν, cm–1: 3304
(OH), 1748 (C6=O), 1707 (C2=O), 1669 (9-C=O),
1647 (4-C=O). 1H NMR spectrum, δ, ppm: 2.15 s (3H,
COMe), 2.28 s (3H, Me), 4.74 d and 4.93 d (1H each,
CH2Ph, J = 16.7 Hz), 6.84–7.69 m (14H, Harom) 7.60 d
(1H, COCH=CHPh, J = 15.8 Hz), 7.72 d (1H,
COCH=CHPh, J = 15.8 Hz), 13.13 br.s (1H, OH).
Found, %: C 72.19; H 5.10; N 5.13. C33H28N2O6. Cal-
culated, %: C 72.25; H 5.14; N 5.11.
9-Acetyl-4-cinnamoyl-3-hydroxy-1-(4-methoxy-
phenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-
3,8-diene-2,6-dione (ІІІf). Yield 84%, mp 222–223°C
(from ethyl acetate). IR spectrum, ν, cm–1: 3313 (OH),
1746 (C6=O), 1713 (C2=O), 1671 (9-C=O), 1642
(4-C=O). 1H NMR spectrum, δ, ppm: 2.13 s (3H, Me),
2.14 s (3H, COMe), 3.79 s (3H, OMe), 7.01–7.71 m
(14H, Harom), 7.65 d (1H, COCH=CHPh, J = 15.8 Hz),
7.73 d (1H, COCH=CHPh, J = 15.8 Hz), 12.81 br.s
(1H, OH). Found, %: C 71.81; H 4.93; N 5.22.
C32H26N2O6. Calculated, %: C 71.90; H 4.90; N 5.24.
Compounds IIIb–IIIg were synthesized in a sim-
ilar way.
9-Acetyl-4-cinnamoyl-3-hydroxy-8-methyl-7-
(4-methylphenyl)-1-phenyl-1,7-diazaspiro[4.4]nona-
3,8-diene-2,6-dione (ІІІb). Yield 77%, mp 209–210°C
(from ethyl acetate). IR spectrum, ν, cm–1: 3170 (OH),
1748 (C6=O), 1725 (C2=O), 1665 (9-C=O), 1645
1
(4-C=O). H NMR spectrum, δ, ppm: 2.12 s (6H, Me,
COMe), 2.38 s (3H, C6H4Me), 7.09–7.72 m (14H,
Harom), 7.66 d (1H, COCH=CHPh, J = 16.2 Hz), 7.74 d
(1H, COCH=CHPh, J = 16.2 Hz), 12.97 br.s (1H, OH).
Found, %: C 74.05; H 5.01; N 5.36. C32H26N2O5. Cal-
culated, %: C 74.12; H 5.05; N 5.40.
The X-ray diffraction data for compound IIIf were
acquired on an Xcalibur-3 automatic four-circle dif-
fractometer with a CCD detector [λ(MoKα) 0.71073 Å,
295(2) K, graphite monochromator, ω-scanning
through a step of 1°] from a 0.25 × 0.20×0.15-mm
fragment of a light-yellow prismatic crystal. No cor-
rection for absorption was introduced because of its
smallness (μ = 0.092 mm–1). Total of 16326 reflection
9-Acetyl-4-cinnamoyl-3-hydroxy-8-methyl-1-
(4-methylphenyl)-7-phenyl-1,7-diazaspiro[4.4]nona-
3,8-diene-2,6-dione (ІІІc). Yield 76%, mp 229–230°C
(from ethyl acetate). IR spectrum, ν, cm–1: 3153 (OH),
1748 (C6=O), 1717 (C2=O), 1673 (9-C=O), 1644
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 10 2012