Five-membered 2,3-dioxoheterocycles: LIX. Reaction of 3-aroyl-1H-pyrrolo[2, 1-c][1,4]benzoxazine-1,2,4-triones with acyclic β-enaminoesters. Crystal and molecular structure of ethyl 3-benzoyl-4-hydroxy-1-o-hydroxyphenyl-5-oxo-2, 3-dihydro-1H-pyrrolo-2-spi

Article abstract of DOI:10.1134/S1070428008050114

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with substituted alkyl 3-amino-2-propenoates to form substituted alkyl 3-aroyl-4-hydroxy-1-o-hydroxyphenyl-5-oxo-2,5-dihydro-1H-pyrrole-2-spiro- 3′-(2-oxo-2,3-dihydro-1H-pyrrole-4-carboxylates)

Full text of DOI:10.1134/S1070428008050114

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 5, pp. 701−705. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © N.L. Racheva, Z.G. Aliev, M.A. Belova, I.V. Mashevskaya, A.N. Maslivets, 2008, published in Zhurnal Organicheskoi Khimii,
2008, Vol. 44, No. 5, pp. 710−714.
Five-Membered 2,3-Dioxoheterocycles: LIX.*
Reaction of 3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-
triones with Acyclic β-Enaminoesters. Crystal and Molecular
Structure of Ethyl 3-Benzoyl-4-hydroxy-1-o-hydroxyphenyl-5-oxo-
2,3-dihydro-1H-pyrrolo-2-spiro-3'-(5-methyl-2-oxo-2,3-dihydro-
1H-pyrrolo-4-carboxylate)
N. L. Rachevaa, Z. G. Alievb, M. A. Belovaa, I. V. Mashevskayaa, and A. N. Maslivetsa
aPerm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
Received June 15, 2006
Abstract—3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with substituted alkyl 3-amino-2-
propenoates to form substituted alkyl 3-aroyl-4-hydroxy-1-o-hydroxyphenyl-5-oxo-2,5-dihydro-1H-pyrrole-2-
spiro-3'-(2-oxo-2,3-dihydro-1H-pyrrole-4-carboxylates). Crystal and molecular structure of ethyl 3-benzoyl-4-
hydroxy-1-o-hydroxyphenyl-5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-(5-methyl-2-oxo-2,3-dihydro-1H-pyrrole-
4-carboxylate) was investigated.
DOI: 10.1134/S1070428008050114
investigated reactions of 3-aroyl-1H-pyrrolo-[2,1-c]-
[1,4]benzoxazine-1,2,4-triones Ia–Ic with potential 1,3-
CH,NH- binucleophiles β-enaminoesters, substituted
alkyl 3-amino2-propenoates IIa–IIf: ethyl (2Z)-3-amino-
2-butenoate (IIa), ethyl (2Z)-3-anilino-2-butenoate (IIb),
ethyl (2Z)-3-(4-toluidino)-2-butenoate (IIc), ethyl (Z)-
3-(4-methoxyanilino)-2-butenoate (IId), ethyl (Z)-3-(4-
chloroanilino)-2-butenoate (IIe), and propyl (2Z)-3-
amino-3-(4-pyridinyl)-2-propenoate (IIf).
The transformations of 4-acyl-1H-pyrrole-2,3-diones,
among them those fused at the [a] side to azaheterocycles
(hetereno[a]pyrrole-2,3-diones), under treatment with
binucleophilic reagents are used for designing versatile
fused heterocyclic systems [2, 3].
We showed formerly that 4-acyl-1H-pyrrole-2,3-
diones fused to 1,4-benzoxazine ring, 3-aroyl-1H-
pyrrolo[2,1-c][1,4]-benzoxazine-1,2,4-triones Ia–Ic,
reacted with acyclic enaminoketones as with 1,3-CH,NH-
binucleophiles by a pathroute involving a consecutive
attacks by the β-CH and NH groups of enaminoketone
on carbon atoms in positions 3a and 4 respectively of
pyrrolobenzoxazinetriones. The reaction includes a cleav-
age of the benzoxazine ring of pyrrolobenzoxazine-
triones at the C4–O5 bond and results in the formation of
substituted 3-aroyl-4-hydroxy-1-o-hydroxy-phenyl-5-
oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-(2-oxo-2,3-
dihydro-1H-pyrroles) [4].
The reaction of equimolar amounts of pyrrolobenz-
oxazinetriones Ia–Ic and substituted alkyl 3-amino2-
propenoates IIa–IIf at boiling in anhydrous benzene for
5–7 min led to the formation in high yields of substituted
alkyl 3-aroyl-4-hydroxy-1-o-hydroxy-phenyl-5-oxo-2,5-
dihydro-1H-pyrrole-2-spiro-3'-(2-oxo-2,3-dihydro-1H-
pyrrole-4-carboxylates) IIIa–IIIn.**
Compounds IIIa–IIIn are colorless or light-yellow
crystalline substances melting at high temperature with
decomposition, readily soluble in DMF and DMSO,
sparingly soluble in common organic solvents, insoluble
In extension of the investigation of reactions between
hetereno[a]pyrrole-2,3-diones and binucleophiles we
** For preliminary communication, see [5].
* For communication LVIII, see [1].
701

RACHEVA et al.
702
H
C
O
O
R1
R2
AlkO
C
O
C
N
COC6H4X-n
N
H
O
O
IIa_IIf
Ia_Ic
R2
R2
N
OH
O
R1
HN
R1
C
O
O
N
C
COOAlk
N
COOAlk
COC6H4X-n
COC6H4X-n
O
OH
IIIa_IIIn
O
OH
I, X = H (a), OMe (b), Br (c); II, Alk = Et, R1 = Me, R2 = H (a), Ph (b), C6H4Me-p (c), C6H4OMe-p (d), C6H4Cl-p (e);
Alk = iso-C3H7, R1 = β-pyridyl, R2 = H (f); III, Alk = Et, R1 = Me: X = H, R2 = H (a), Ph (b), C6H4Me-p (e), C6H4OMe-p
(h), C6H4Cl-n (k); X = OMe, R2 = Ph (c), C6H4Me-n (f),C6H4OMe-p (i), C6H4Cl-p (l); X = Br, R2 = Ph (d), C6H4Me-p (g),
C6H4OMe-p (j), C6H4Cl-p (m); X = R2 = H, Alk = iso-C3H7, R1 = β-pyridyl (n).
1
In the H NMR spectra of solutions of spiro-
compounds IIIa–IIIn in DMSO-d6 alongside the signals
of aromatic rings protons and of the groups attached
thereto appear a triplet and a quartet of the protons from
ethoxycarbonyl group in the region 1.18–1.22 and 4.02–
4.06 ppm respectively (in compounds IIIa–IIIm), a doublet
and multiplet of the protons from isopropoxycarbonyl
group at 1.04 and 4.75 ppm respectively (in compound
IIIn), a singlet of protons of a methyl group in the
position 5 of the 2,3-dihydro-1H-pyrrole ring in the
region 1.99–2.14 ppm (in compounds IIIa–IIIm),
a singlet of phenol hydroxy group in the region 9.62–
in alkanes and water, positive test with iron(III) chloride
on the presence of enol and phenol hydroxy group
(cherry-red coloration).
The IR spectra of spiro-compounds IIIa–IIIn contain
the bands of the stretching vibrations of OH groups as a
broad peak in the region 3156–3231 cm–1, of ethoxy-
carbonyl (in compounds IIIa–IIIm) and isopropoxy-
carbonyl (in compound IIIn) groups in the region 1752–
1765 cm–1, of two lactam carbonyl groups as one or two
peaks in the region 1700–1746 cm–1, of aroyl carbonyl
in the region 1619–1651 cm–1 (in compounds IIIa–IIIm)
and at 1692 cm–1 (in compound IIIn).
13
14
12
11
9
O3
C4
C8
C3
10
O2
O4
C5
C7
C6
2
N2
C1
O1
O7
N1
C18
C15
C24
C16
O6
O5
C17
C19
20
C
C23
22
C21
Fig. 2. Hydrogen bonds in IIIa molecule.
Fig. 1. General view of ester molecule IIIa
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FIVE-MEMBERED 2,3-DIOXOHETEROCYCLES: LIX.
Parameters of hydrogen bonds in the molecule of ethyl 3-benzoyl-4-hydroxy-1-(o-hydroxyphenyl)-5-oxo-2,5-dihydro-1H-pyrrole-
703
°
2-spiro-3'-(5-methyl-2-oxo-2,3-dihydro-1H-pyrrole-4-carboxylate) (IIIa) (bonds, , angles, deg)
Α
10.00 ppm, a singlet from NH gpoup at 10.66–11.00 ppm
(in compounds IIIa and IIIn), and broad singlet of the
enol OH group in the region 12.00–12.82 ppm.
TLC on Silufol plates, eluents ethyl acetate, ethyl acetate–
benzene, 1:5, development in iodine vapor.
Ethyl 3-benzoyl-4-hydroxy-1-(o-hydroxyphenyl)-
5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-(5-methyl-
2-oxo-2,3-dihydro-1H-pyrrole-4-carboxylate) (IIIa).
A solution of 1.0 mmol of compound Ia and 1.0 mmol
of enamine IIa in 10 ml of anhydrous benzene was boiled
for 3 min, cooled, the separated precipitate was filtered
off. Yield 82%, mp 257–259°C (from ethyl acetate). IR
spectrum, ν, cm–1: 3160 br (OH), 1755 (COOEt), 1700,
As showed XRD analysis compound IIIa crystallized
with a molecule of ethyl acetate in an equimolar ratio.
All the bond distances and bond angles in the molecule
(Fig. 1) are in the range common to the corresponding
atoms. In the crystal the molecule forms two hydrogen
bonds with each of three contiguous molecules; these
three molecules are united with the first one through a
center of symmetry (Fig. 2). Parameters of the hydrogen
1
1680 (C2=O, C5=O), 1640 (COPh). H NMR spectrum,
...
δ, ppm: 1.18 t (3H, CH3CH2, J 6.8 Hz), 2.14 s (3H, Me),
4.04 q (2H, CH3CH2, J 7.3 Hz), 6.75–7.74 group of
signals (9H, Ph + C6H4), 9.62 s (1H, OH phenol), 10.66 s
(1H, NH), 12.00 br.s (1H, OH enol). Found, %: C 64.31;
H 4.53; N 6.12. C24H20N2O7. Calculated, %: C 64.27;
H 4.49; N 6.26.
bonds are given in the table. The observed distances D A
indicate that the hydrogen bonds are sufficiently strong,
...
especially the bond O2–H2 O4. The involvement into
the hydrogen bond is adequately reflected in the
interatomic distances C–O in carboxy and carbonyl
groups (see the table).
Compounds IIIb–IIIn were similarly synthesized.
Evidently in the first stage of the reaction the activated
β-CH group of the enamino fragment of β-enaminoesters
IIa–IIf adds to the carbon atom in the position 3a of
pyrrolobenzoxazinetriones Ia–Ic as is described for the
reactions of these compounds with mononucleophiles
[2, 3]; further a pyrrole ring closes by intramolecular
attack of the free amino group of the side chain of
enaminoesters IIa–IIf on the lactone carbonyl group of
the benzoxazine ring of compounds Ia–Ic with the
opening of the ring at the C4–O5 bond. The described
reaction is a rare example of building up a difficultly
accessible spiro-bis-heterocyclic system pyrrole-spiro-
pyrrole with purposefully variable functional substituents
in several positions of both pyrrole rings.
Ethyl 3-benzoyl-4-hydroxy-1-(o-hydroxyphenyl)-
5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-(5-methyl-
2-oxo-1-phenyl-2,3-dihydro-1H-pyrrole-4-carboxy-
late) (IIIb). Yield 80%, mp 212–215°C (from ethyl
acetate). IR spectrum, ν, cm–1: 3164 br (OH), 1753
(COOEt), 1707, 1656 (C2=O, C5=O), 1632 (COAr).
1H NMR spectrum, δ, ppm: 1.22 t (3H, CH3CH2,
J 6.8 Hz), 2.04 s (3H, Me), 4.04 q (2H, CH3CH2,
J 7.3 Hz), 6.81–7.81 group of signals (14H, 2Ph + C6H4),
9.82 s (1H, OH phenol), 12.40 br.s (1H, OH enol). Found,
%: C 68.64; H 4.69; N 5.26. C30H24N2O7. Calculated,
%: C 68.70; H 4.61; N 5.34.
Ethyl 4-hydroxy-1-(o-hydroxyphenyl)-3-(p-
methoxybenzoyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-
spiro-3'-(5-methyl-2-oxo-1-phenyl-2,3-dihydro-1H-
pyrrole-4-carboxylate) (IIIc). Yield 87%, mp 203–
205°C (from ethyl acetate). IR spectrum, ν, cm–1: 3158 br
(OH), 1753 (COOEt), 1705, 1657 (C2=O, C5=O), 1619
EXPERIMENTAL
IR spectra of compounds synthesized were recorded
on a spectrophotometer FSM-1201 from mills in mineral
oil. 1H and 13C NMR spectra were registered on a spec-
trometer BrukerAM-400 (operating frequency 400 MHz)
from solutions in DMSO-d6, internal reference TMS. The
homogeneity of compounds synthesized was checked by
1
(COAr). H NMR spectrum, δ, ppm: 1.21 t (3H, CH3CH2,
J 7.4 Hz), 2.04 s (3H, Me), 3.86 s (1H, OMe), 4.04 q
(2H, CH3CH2, J 7.1 Hz), 6.81–7.83 group of signals
(13H, Ph + 2C6H4), 9.81 s (1H, OH phenol), 12.16 br.s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 5 2008

RACHEVA et al.
704
(1H, OH enol). Found, %: C 67.20; H 4.89; N 5.03.
C31H26N2O8. Calculated, %: C 67.14; H 4.73; N 5.05.
12.60 br.s (1H, OH enol). Found, %: C 60.46; H 4.28;
Br 12.95; N 4.51. C31H25BrN2O7. Calculated, %: C 60.30;
H 4.08; Br 12.94; N 4.54.
Ethyl 3-p-bromobenzoyl-4-hydroxy-1-(o-hydroxy-
phenyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-(5-
methyl-2-oxo-1-phenyl-2,3-dihydro-1H-pyrrole-4-
carboxylate) (IIId). Yield 90%, mp 211–213°C (from
ethyl acetate). IR spectrum, ν, cm–1: 3156 br (OH), 1752
(COOEt), 1707, 1655 (C2=O, C5=O), 1628 (COAr).
1H NMR spectrum, δ, ppm: 1.21 t (3H, CH3CH2,
J 7.0 Hz), 2.04 s (3H, Me), 4.06 q (2H, CH3CH2,
J 7.1 Hz), 6.82–7.79 group of signals (13H, Ph + 2C6H4),
9.84 s (1H, OH phenol), 12.60 br.s (1H, OH enol). Found,
%: C 59.87; H 3.96; Br 13.39; N 4.60. C30H23BrN2O7.
Calculated, %: C 59.71; H 3.84; Br 13.24; N 4.64.
Ethyl 3-benzoyl-4-hydroxy-1-(o-hydroxy-phenyl)-
5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-[5-methyl-
1-(p-methoxyphenyl)-2-oxo-2,3-dihydro-1H-pyrrole-
4-carboxylate] (IIIh). Yield 93%, mp 228–230°C (from
ethyl acetate). IR spectrum, ν, cm-1: 3180 br (OH), 1759
(COOEt), 1737, 1667 (C2=O, C5=O), 1637 (COAr).
1H NMR spectrum, δ, ppm: 1.21 t (3H, CH3CH2, J 7.3 Hz),
2.02 s (3H, Me), 3.81 s (3H, OMe-p), 4.05 q (2H,
CH3CH2, J 7.2 Hz), 6.81–7.81 group of signals (13H, Ph
+ 2C6H4), 9.81 C (1H, OH phenol), 12.30 br.s (1H, OH
enol). Found, %: C 67.44; H 4.54; N 5.14. C31H26N2O8.
Calculated, %: C 67.14; H 4.73; N 5.05.
Ethyl 3-benzoyl-4-hydroxy-1-(o-hydroxyphenyl)-
5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-[5-methyl-
2-oxo-1-(p-tolyl)-2,3-dihydro-1H-pyrrole-4-
carboxylate] (IIIe). Yield 89%, mp 221–223°C (from
ethyl acetate). IR spectrum, ν, cm–1: 3191 br (OH), 1755
(COOEt), 1707, 1655 (C2=O, C5=O), 1628 (COAr).
1H NMR spectrum, δ, ppm: 1.22 t (3H, CH3CH2, J 7.0 Hz),
2.03 s (3H, Me), 2.37 s (3H, C6H4Me-p), 4.05 q (2H,
CH3CH2, J 7.4 Hz), 6.81–7.82 group of signals (13H,
Ph + 2C6H4), 9.82 s (1H, OH phenol), 12.35 br.s (1H,
OH enol). Found, %: C 69.33; H 4.81; N 5.15.
C31H26N2O7. Calculated, %: C 69.14; H 4.87; N 5.20.
Ethyl 4-hydroxy-1-(o-hydroxyphenyl)-3-(p-
methoxybenzoyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-
spiro-3'-[5-methyl-1-(p-methoxyphenyl)-2-oxo-2,3-
dihydro-1H-pyrrole-4-carboxylate] (IIIi). Yield 89%,
mp 210–212°C (from ethyl acetate). IR spectrum, ν, cm–1:
3186 br (OH), 1765 (COOEt), 1735, 1698 (C2=O, C5=O),
1
1630 (COAr). H NMR spectrum, δ, ppm: 1.21 t (3H,
CH3CH2, J 7.2 Hz), 2.01 s (3H, Me), 3.73 s (3H, OMe-
p), 3.81 s (3H, OMe-p), 4.02 q (2H, CH3CH2, J 7.2 Hz),
6.80–7.82 group of signals (12H, 3C6H4), 9.79 C (1H,
OH phenol), 12.20 br.s (1H, OH enol). Found, %: C 65.63;
H 4.90; N 4.69. C32H28N2O9. Calculated, %: C 65.75;
H 4.83; N 4.79.
Ethyl 4-hydroxy-1-(o-hydroxyphenyl)-3-(p-
methoxybenzoyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-
spiro-3'-[5-methyl-2-oxo-1-(p-tolyl)-2,3-dihydro-1H-
pyrrole-4-carboxylate] (IIIf). Yield 96%, mp 198–
199°C (from ethyl acetate). IR spectrum, ν, cm–1: 3180
br (OH), 1753 (COOEt), 1703, 1675 (C2=O, C5=O), 1651
(COAr). 1H NMR spectrum, δ, ppm: 1.20 t (3H,
CH3CH2, J 7.1 Hz), 2.01 s (3H, Me), 2.37 s (3H, C6H4Me-
p), 3.86 s (3H, OMe), 4.04 q (2H, CH3CH2, J 7.4 Hz),
6.80–7.84 group of signals (12H, 3C6H4), 9.78 s (1H, OH
phenol), 12.13 br.s (1H, OH enol). Found, %: C 67.69;
H 5.08; N 5.05. C32H28N2O8. Calculated, %: C 67.60;
H 4.96; N 4.93.
Ethyl 3-(p-bromobenzoyl)-4-hydroxy-1-(o-hy-
droxyphenyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-
3'-[5-methyl-1-(p-methoxyphenyl)-2-oxo-2,3-
dihydro-1H-pyrrole-4-carboxylate] (IIIj). Yield 90%,
mp 206–208°C (from ethyl acetate). IR spectrum, ν, cm–1:
3180 br (OH), 1754 (COOEt), 1701, 1672 (C2=O, C5=O),
1
1639 (COAr). H NMR spectrum, δ, ppm: 1.21 t (3H,
CH3CH2, J 7.1 Hz), 2.03 s (3H, Me), 3.81 s (3H, OMe-
p), 4.05 q (2H, CH3CH2, J 7.1 Hz), 6.80–7.80 group of
signals (12H, 3C6H4), 9.85 C (1H, OH phenol), 12.60
br.s (1H, OH enol). Found, %: C 58.70; H 4.00; Br 12.71;
N 4.33. C31H25BrN2O8. Calculated, %: C 58.78; H 3.98;
Br 12.61; N 4.42.
Ethyl 3-(p-bromobenzoyl)-4-hydroxy-1(o-
hydroxyphenyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-
spiro-3'-[5-methyl-2-oxo-1-(p-toluene)-2,3-dihydro-
1H-pyrrole-4-carboxylate] (IIIg). Yield 90%, mp 199–
202°C (from ethyl acetate). IR spectrum, ν, cm–1: 3189
br (OH), 1754 (COOEt), 1705, 1656 (C2=O, C5=O), 1628
(COAr). 1H NMR spectrum, δ, ppm: 1.20 t (3H,
CH3CH2, J 7.0 Hz), 2.03 s (3H, Me), 2.36 s (3H,
C6H4Me-p), 4.04 q (2H, CH3CH2, J 7.1 Hz), 6.81–7.79
group of signals (12H, 3C6H4), 9.82 C (1H, OH phenol),
Ethyl 3-benzoyl-4-hydroxy-1-(o-hydroxy-phenyl)-
5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-3'-[5-methyl-
2-oxo-1-(p-chlorophenyl)-2,3-dihydro-1H-pyrrole-4-
carboxylate] (IIIk). Yield 91%, mp 179–180°C (from
ethyl acetate). IR spectrum, ν, cm–1: 3187 br (OH), 1754
(COOEt), 1698, 1667 (C2=O, C5=O), 1636 (COAr).
1H NMR spectrum, δ, ppm: 1.21 t (3H, CH3CH2,
J 7.0 Hz), 2.06 s (3H, Me), 4.05 q (2H, CH3CH2,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 5 2008

FIVE-MEMBERED 2,3-DIOXOHETEROCYCLES: LIX.
705
°
J 7.1 Hz), 6.80–7.80 group of signals (13H, Ph + 2C6H4),
9.80 s (1H, OH phenol), 12.40 br.s (1H, OH enol). Found,
%: C 64.29; H 4.21; Cl 6.23; N 5.19. C30H23ClN2O7.
Calculated, %: C 64.46; H 4.15; Cl 6.34; N 5.01.
10.722(2) , α 89.58(3), β 108.50(3), γ 94.08(3)°, V
Α
°
1102.6(4) 3, M 448.42, d 1.351 g/cm3, Z 2, space
Α
calc
group P-1. The set of experimental reflections was
obtained on an automatic four-circle diffractometer QM-
4 with a ÷-geometry, ω/2Θ scanning, monochromated
MOKα-emission (2Θ ≤ 52°). Overall 3209 independent
reflections were measured (Rint 0.1071). No correction
for extinction was done (μ 0.101 mm–1). The structure
was solved by the direct method using SIR92 software
[6] with subsequent calculations of a series of electron
density charts. All hydrogen atoms except those of the
methyl of ethoxycarbonyl group were revealed fron the
difference synthesis of the electron density. Full-matrix
anisotropic (for nonhydrogen atoms) refinement by least-
squares method applying SHELXL-97 program [7] was
finished at R1 0.0817 for 1904 reflections with I ≥ 2σ(I),
GOOF 0.972.
Ethyl 4-hydroxy-1-(o-hydroxyphenyl)-3-(p-
methoxybenzoyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-
spiro-3'-[5-methyl-2-oxo-1-(p-chlorophenyl)-2,3-
dihydro-1H-pyrrole-4-carboxylate] (IIIl). Yield 89%,
mp 203–205°C (from ethyl acetate). IR spectrum, ν, cm–1:
3180 br (OH), 1759 (COOEt), 1699, 1673 (C2=O, C5=O),
1
1632 (COAr). H NMR spectrum, δ, ppm: 1.21 t (3H,
CH3CH2, J 7.1 Hz), 2.06 s (3H, Me), 4.03 q (2H,
CH3CH2, J 7.1 Hz), 6.80–7.81 group of signals (12H,
3C6H4), 9.83 s (1H, OH phenol), 12.20 br.s (1H, OH
enol). Found, %: C 63.42; H 4.44; Cl 5.98; N 4.67.
C31H25ClN2O8. Calculated, %: C 63.22; H 4.28; Cl 6.02;
N 4.76.
The study was carried out under financial support of
the Russian Foundation for Basic Research (grants nos.
07-03-96036, 04-03-33024).
Ethyl 3-(p-bromobenzoyl)-4-hydroxy-1-(o-hy-
droxyphenyl)-5-oxo-2,5-dihydro-1H-pyrrole-2-spiro-
3'-[5-methyl-2-oxo-1-(p-chlorophenyl)-2,3-dihydro-
1H-pyrrole-4-carboxylate] (IIIm). Yield 95%, mp 262–
264°C (from ethyl acetate). IR spectrum, ν, cm–1: 3188 br
(OH), 1754 (COOEt), 1726 (C2=O, C5=O), 1649 (COAr).
1H NMR spectrum, δ, ppm: 1.20 t (3H, CH3CH2,
J 7.1 Hz), 1.99 s (3H, Me), 4.04 q (2H, CH3CH2,
J 7.1 Hz), 6.80–8.00 group of signals (12H, 3C6H4),
9.93 s (1H, OH phenol), 12.82 br.s (1H, OH enol). Found,
%: C 56.57; H 3.38; Br 12.43; Cl 5.38; N 4.33.
C30H22BrClN2O7. Calculated, %: C 56.49; H 3.48; Br 12.53;
Cl 5.56; N 4.39.
REFERENCES
1. Bannikova, Yu.N., Rozhkova, Yu.S., Shklyaev, Yu.V. and
Maslivets, A.N., Zh. Org Khim., 2008, vol. 44, no. 4, p. 555.
2. Maslivets, A.N. and Mashevskaya, I.V., 2,3-Digidro-2,3-
pirrol-diony (2,3-Dihydro-2,3-Pyrrolediones), Perm: Izd.
Perm. Gos. Univ., 2005, p. 126.
3. Mashevskaya, I.V. and Maslivets, A.N., 2,3-Digidro-2,3-
pirrol-diony kondensirovannye s razlichnymi geterotsiklami
storonoi [a] i ikh benzo[b]analogi: sintez khimicheskie
svoistva prakticheskoe primenenie (2,3-Dihydro-2,3-
pyrroldiones Fused with Various Heterocycles by [a] Side,
and Their Benzol [b] Analogs: Synthesis, Chemical
Properties and Practical Analysis), Perm’: Izd. Perm. Gos.
SKhA, 2003, p. 140.
4. Racheva, N.L. and Maslivets, A.N., Zh. Org Khim., 2008,
vol. 44, no. 4, p. 515.
5. Racheva, N.L. and Maslivets, A.N., Zh. Org Khim., 2006,
vol. 42, p. 451.
6. Altomare, A., Cascarano, G., Giacovazzo, C. and Gualardi,
A. J. Appl. Cryst., 1993, vol. 26, p. 343.
Isopropyl 3-benzoyl-4-hydroxy-1-(o-hydroxy-
phenyl)-5-oxo-2,5-dihydro-1H-pyrrolo-2-spiro-3'-[2-
oxo-5-(3-pyridyl)-2,3-dihydro-1H-pyrrole-4-
carboxylate] (IIIn). Yield 89%, mp 214–216°C (from
ethyl acetate). IR spectrum, ν, cm–1: 3231 br (OH), 1765
1
(COOPr-i), 1746, 1717 (C2=O, C5=O), 1692 (COAr). H,
δ, ppm: 1.04 d (6H, 2Me), 4.75 m (1H, CHMe2), 6.80–
8.65 group of signals (13H, Ph + 2C6H4), 9.70 s (1H,
OH phenol), 11.00 s (1H, NH), 12.30 br.s (1H, OH enol).
Found, %: C 66.47; H 4.22; N 8.15. C29H23N3O7.
Calculated, %: C 66.28; H 4.41; N 8.00.
7. Sheldrick, G.M., Shelx 97. Programs for Crystal Structure
Analysis, University of Gottingen, Germany, 1998, p. 2332.
XRD analysis of compound IIIa. Crystals
C24H20N2O7 triclinic: a 10.878(2), b 9.995(2), c
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 5 2008