Two directions in spiroheterocyclization of 1H-pyrrole-2,3-diones upon the action of 3-arylamino-1H-inden-1-ones

Article abstract of DOI:10.1007/s11172-012-0009-6

4-Ethoxycarbonyl-5-phenyl-substituted 1H-pyrrole-2,3-diones react with 3-arylamino-1H- inden-1-ones in the ratios 1 : 1 and 1 : 2 to form substituted spiro{indeno[1,2-b]quinoline-10,3-pyrroles} and substituted spiro{diindeno[1,2-b:2,1-e]pyridine-11,3pyrro

Full text of DOI:10.1007/s11172-012-0009-6

Russian Chemical Bulletin, International Edition, Vol. 61, No. 1, pp. 59—63, January, 2012
59
Two directions in spiroheterocyclization of 1Hꢀpyrroleꢀ2,3ꢀdiones
upon the action of 3ꢀarylaminoꢀ1Hꢀindenꢀ1ꢀones*
M. V. Dmitriev,a P. S. Silaichev,a Z. G. Aliev,b S. M. Aldoshin,b and A. N. Maslivetsa
aPerm State University,
15 ul. Bukireva, 614990 Perm, Russian Federation.
Eꢀmail: koh2@psu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation
4ꢀEthoxycarbonylꢀ5ꢀphenylꢀsubstituted 1Hꢀpyrroleꢀ2,3ꢀdiones react with 3ꢀarylaminoꢀ1Hꢀ
indenꢀ1ꢀones in the ratios 1 : 1 and 1 : 2 to form substituted spiro{indeno[1,2ꢀb]quinolineꢀ
10,3´ꢀpyrroles} and substituted spiro{diindeno[1,2ꢀb:2´,1´ꢀe]pyridineꢀ11,3´ꢀpyrroles},
respectively.
Key words: 1Hꢀpyrroleꢀ2,3ꢀdiones, spiroheterocyclization, 3ꢀarylaminoꢀ1Hꢀindenꢀ1ꢀones,
spiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrroles}, spiro{diindeno[1,2ꢀb:2´,1´ꢀe]pyridineꢀ11,3´ꢀ
pyrroles}.
Earlier, we have shown that the reaction of monocyꢀ
clic 1Hꢀpyrroleꢀ2,3ꢀdiones with enamines is directed by
the structure of substituents in the pyrroledione ring.1
1ꢀArylꢀ4ꢀisopropoxalylꢀ5ꢀphenylꢀ1Hꢀpyrroleꢀ2,3ꢀdiones reꢀ
act with enamines to add to the NH and ꢀCH groups of
the enamino fragment to the atoms C(2) and C(3) of pyrꢀ
rolediones, with the cleavage of the pyrroledione ring and
subsequent cyclization. Three ways of the reaction of
1ꢀarylꢀ4ꢀaroylꢀ5ꢀmethoxycarbonylꢀ1Hꢀpyrroleꢀ2,3ꢀdiones
with enamines are described. The most frequent is a seꢀ
quential addition of the ꢀCH and NH groups of the enamꢀ
ino fragment to the atoms C(5) and COOMe group at
position 5 of pyrrolediones.2—5 A sequential addition of
the NH and ꢀCH groups of the enamino fragment to the
atoms C(2) and C(3) of pyrroledione with the cleavage of
the pyrroledione ring and subsequent cyclization is reꢀ
ported as a minor direction.4,5 Enamines unsubstituted at
the N atom tend to sequentially add the ꢀCH and NH
groups of the enamino fragment to the atoms C(5) and
C(3) of pyrrolediones.5 The reaction of 1ꢀalkylꢀ4ꢀethoxyꢀ
carbonylꢀ5ꢀphenylꢀ1Hꢀpyrroleꢀ2,3ꢀdiones with Nꢀarylꢀ
substituted 3ꢀaminoꢀ5,5ꢀdimethylcyclohexꢀ2ꢀenones proꢀ
ceeds as a sequential addition of the oꢀCH group of the
aryl substituent and the ꢀCH group of the enamino fragꢀ
ment of enamines to the pyrroledione atom C(3).6,7 In
order to study the reactivity of 4ꢀethoxycarbonylꢀ5ꢀpheꢀ
nylꢀ1Hꢀpyrroleꢀ2,3ꢀdiones (ethyl 4,5ꢀdioxoꢀ1ꢀphenylꢀ
4,5ꢀdihydroꢀ1Hꢀpyrroleꢀ3ꢀcarboxylates), we studied their
reactions with the other class of Nꢀarylꢀsubstituted cyclic
enamines, viz., 3ꢀarylaminoꢀ1Hꢀindenꢀ1ꢀones.
The reaction of pyrrolediones 1a—c with 3ꢀarylamiꢀ
noꢀ1Hꢀindenꢀ1ꢀones 2a—c in the ratio 1 : 1, carried out
by reflux of a solution of reagents in anhydrous mꢀxylene
at 139—140 C over 5—6 h, leads to the substituted ethyl
carboxylates 3a—g (Scheme 1).** The reaction course was
monitored by chromatography.
Compounds 3a—g are orange crystalline compounds
with high melting points, readily soluble in DMSO and
DMF, poorly soluble in common organic solvents, insolꢀ
uble in alkanes and water.
1
In the H NMR spectra of compounds 3a—g, besides
the signals for the protons of substituents at position 1´,
aromatic rings, and bonded to them groups, a singlet for
the NH group in the region  10.89—11.04, a triplet and
a quartet for the ethyl group of the ethoxycarbonyl substitꢀ
uent in the regions  0.59—0.72 and 3.55—3.87, respecꢀ
tively, are also present. In the 13C NMR spectrum of comꢀ
pound 3c, the signals characteristic of the carbon atoms of
the keto, ester, and lactam carbonyl groups at  187.83,
179.75, and 161.48, respectively, are present, as well as the
signal for the spiro carbon atom at  43.88. The structure
of compound 3a was established by Xꢀray diffraction studꢀ
ies (Fig. 1).
The formation of compounds 3a—g is apparently
effected by initial addition of the ꢀCH group of the enamꢀ
ino fragment of enamines 2a—c to the carbon atom at
position 3 of pyrrolediones 1a—c and formation of the
* Dedicated to Academician of the Russian Academy of Sciences
V. N. Charushin on the occasion of his 60th birthday.
** For preliminary communication, see Ref. 8.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 58—62, January, 2012.
1066ꢀ5285/12/6101ꢀ59 © 2012 Springer Science+Business Media, Inc.

60
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
Dmitriev et al.
Scheme 1
1: R = CH2Ph (a), Ph (b), cycloꢀC6H11 (c);
2: X = H (a), Me (b), OMe (c);
3, 4: R = CH2Ph, X = H (a), Me (b), OMe (c); R = Ph, X = H (d), Me (e), OMe (f); R = cycloꢀC6H11, X = OMe (g)
intermediate compounds 4a—g with subsequent intramoꢀ
lecular cyclization involving an activated oꢀCH group of
the aryl substituent of enamines 2a—c. We observed a simꢀ
ilar scheme of spiroheterocyclization in the reaction of
pyrrolediones 1a,c with Nꢀarylꢀsubstituted 3ꢀaminoꢀ5,5ꢀ
dimethylcyclohexꢀ2ꢀenones.6,7
In the reactions of pyrrolediones 1b,c with indenones
2a—c, besides compounds 3d—g, the substituted ethyl esters
5a—d were isolated as the minor products (Scheme 2).
If similar conditions are applied to the reaction of pyrroleꢀ
dione 1c with enamines 2b, compound 5e is isolated as the
only product.
Compounds 5a—e are bright crimson crystalline subꢀ
stances, readily soluble in common organic solvents and
insoluble in alkanes and water.
In the 1H NMR spectra of compounds 5a—e, in addiꢀ
tion to the signals for the protons of substituents at posiꢀ
tion 1´, aromatic rings, and bonded to them groups,
Scheme 2
2: Ar = Ph (a), C6H4Meꢀ4 (b), С6H4OMeꢀ4 (c);
4: R = Ph, Ar = Ph (d), C6H4Me (e), С6H4OMe (f); R = cycloꢀC6H11, Ar = С6H4OMe (g), C6H4Meꢀ4 (h);
5: R = Ph, Ar = Ph (a), C6H4Meꢀ4 (b), С6H4OMeꢀ4 (c); R = cycloꢀC6H11, Ar = С6H4OMeꢀ4 (d), C6H4Meꢀ4 (e)

Spiro heterocyclization of pyrrolediones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
61
C(14)
C(15)
C(35)
C(13)
C(16)
C(42)
C(41)
O(2)
C(33)
C(34)
O(3)
C(17)
C(12)
C(11)
C(40)
C(18)
C(43)
C(11)
O(4)
C(3)
C(10)
C(19)
C(4)
N(2)
C(16)
C(29)
C(38)
N(2)
C(39)
C(28)
C(10)
C(9)
C(8)
C(17)
C(5)
C(6)
C(7)
C(27)
C(12)
C(7)
C(15)
C(18)
C(9)
C(8)
C(30)
C(31)
C(14)
C(1)
C(2)
N(1)
C(32)
C(13)
C(20)
C(19)
C(21)
C(22)
O(1)
C(20)
C(6)
C(5)
C(1)
O(1)
C(2)
O(4)
O(2)
C(22)
C(21)
C(26)
O(5)
C(23)
C(4)
N(1)
C(23)
C(25)
C(3)
O(3)
C(24)
C(32)
C(24)
Fig. 1. Molecular structure of 3a.
C(36)
C(35)
C(33)
C(37)
C(26)
C(25)
C(34)
C(27)
C(28)
C(31)
a triplet and a quartet for the ethyl group of the ethoxyꢀ
carbonyl substituent in the regions  0.63—0.72 and
3.74—3.87, respectively, are present. In the 13C NMR
spectrum of compound 5b, the signals characteristic of
the carbon atoms of the keto, ester, and lactam carbonyl
groups at  189.88, 177.58, and 162.10, respectively, are
found, as well as the signal for the spiro carbon atom at
 46.90. The structure of compound 5a was established by
Xꢀray diffraction studies (Fig. 2).
The formation of compounds 5a—e is apparently efꢀ
fected by initial addition of the ꢀCH group of the enamino
fragment of enamines 2a—c to the carbon atom at posiꢀ
tion 3 of pyrrolediones 1b,c and the formation of the interꢀ
mediate pyrrolones 4d—h with subsequent assembly of the
diindeno[1,2ꢀb:2´,1´ꢀe]pyridine structural fragment as
a result of a sequential nucleophilic addition of the ꢀCH
group and the NH group of the enamino fragment from
the second molecule of enamines 2a—c to the carbon atom
at position 3 and the imino group of a tautomeric form of
pyrrolones 4d—h, respectively, with elimination of water
and arylamine.
C(30)
C(29)
Fig. 2. Molecular structure of 5a.
ing into the reaction as the CH,NHꢀ1,3ꢀbinucleophiles,
as well as represent a convenient preparative approach to
the synthesis of the earlier unavailable heterocyclic sysꢀ
tems of spiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrrole} and
spiro{diindeno[1,2ꢀb:2´,1´ꢀe]pyridineꢀ11,3´ꢀpyrrole}.
It should be noted that the indenopyridine fragment is
a structural part of the 4ꢀazafluorenone group alkaloids.9
Substituted indenopyridines manifest cytitoxic,10 antiꢀ
inflammatory, and antiallergic activity,11 as well as are
phosphodiesterase inhibitors12 and adenosine A2a recepꢀ
tor antagonists.13
Experimental
The synthesis of compounds 5a—e is a threeꢀcompoꢀ
nent reaction, therefore, its conduction with the ratio of
reagents 1 : 2, in our opinion, should have led to the inꢀ
crease in the yields of these compounds. However, the use
of the ratio 1 : 2 under all the conditions studied gave no
noticeable increase in the yields.
The reactions described illustrate an example of a diꢀ
rect spiroheterocyclization of substituted pyrroledione
upon the action of Nꢀarylꢀsubstituted enamine, involving
into the reaction as the CH,CHꢀ1,5ꢀbinucleophiles, and
a direct threeꢀcomponent spiroheterocyclization of subꢀ
stituted pyrroledione upon the action of enamine, involvꢀ
IR spectra were recorded on a FSMꢀ1201 spectrophotomeꢀ
ter. 1H and 13C NMR spectra were recorded on a Bruker
AMꢀ400 spectrometer (1H 400 MHz; 13C 100 MHz) in DMSOꢀd6,
using Me4Si as an internal standard. Individuality of the syntheꢀ
sized compounds was confirmed by TLC on Silufol plates, using
ethyl acetate and benzene—ethyl acetate (5 : 1) as eluents.
Ethyl 1´ꢀbenzylꢀ2´,11ꢀdioxoꢀ5´ꢀphenylꢀ1´,2´,5,11ꢀtetrahyꢀ
drospiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrrole}ꢀ4´ꢀcarboxylate
(3a). A solution of pyrroledione 1a (1.0 mmol) and enamine 2a
(1.0 mmol) in anhydrous mꢀxylene (15 mL) was refluxed for 5 h,
cooled, an orange precipitate formed was filtered off. The yield
was 54%, m.p. 239—241 C (ethyl acetate). IR, /cm–1: 3252

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
Dmitriev et al.
(NH); 1694, 1688, 1626 (C=O). 1H NMR, : 0.60 (t, 3 H,
CH2CH3, J = 7.1 Hz); 3.58 (q, 2 H, CH2CH3, J = 7.1 Hz); 4.51,
4.67 (both d, 1 H each, CH2Ph, J = 16.3 Hz); 7.08—7.67 (m, 18 H,
Ar); 11.02 (s, 1 H, NH). Found (%): C, 77.98; H, 4.84; N, 5.15.
C35H26N2O4. Calculated (%): C, 78.05; H, 4.87; N, 5.20.
Compounds 3b,c were synthesized similarly.
Found (%): C, 77.96; H, 4.80; N, 5.14. C35H26N2O4. Calculatꢀ
ed (%): C, 78.05; H, 4.87; N, 5.20. The yield of compound 5b
was 17%, m.p. 338—339 C (ethyl acetate). IR, /cm–1: 1740,
1
1688 (C=O). H NMR, : 0.71 (t, 3 H, CH2CH3, J = 7.0 Hz);
2.58 (s, 3 H, Me); 3.86 (q, 2 H, OCH2, J = 7.0 Hz); 5.61 (d, 2 H,
C(4)H, C(6)H, J = 7.5 Hz); 7.16—7.91 (m, 20 H, Ar). 13C NMR,
: 13.47 (OCH2CH3); 21.01 (Me); 46.90 (C(10)); 58.92
(OCH2CH3); 110.11, 110.41, 121.42, 121.66, 127.57—136.08,
141.55 (C(5a), C(4b)); 156.98 (C(5´)); 162.10 (C(2´)); 177.58
(COOEt); 189.88 (C(10), C(12)). Found (%): C, 79.20; H, 4.55;
N, 4.14. C44H30N2O5. Calculated (%): C, 79.26; H, 4.54;
N, 4.20.aa
Ethyl 8ꢀmethoxyꢀ2´,11ꢀdioxoꢀ1´,5´ꢀdiphenylꢀ1´,2´,5,11ꢀ
tetrahydrospiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrrole}ꢀ4´ꢀcarbꢀ
oxylate (3f) and ethyl 5ꢀ(4ꢀmethoxyphenyl)ꢀ2,10,12ꢀtrioxoꢀ1´,5´ꢀ
diphenylꢀ1´,2´,10,12ꢀtetrahydroꢀ5Hꢀspiro{diindeno[1,2ꢀb:
2´,1´ꢀe]pyridineꢀ11,3´ꢀpyrrole}ꢀ4´ꢀcarboxylate (5c). The yield
of compound 3f was 52%, m.p. 287—289 C (ethyl acetate). IR,
/cm–1: 3231 (NH); 1692, 1618 (C=O). 1H NMR, : 0.67 (t, 3 H,
CH2CH3, J = 7.2 Hz); 3.64 (m, 2 H, CH2CH3); 3.78 (s, 3 H,
OMe); 6.74—7.65 (m, 17 H, Ar); 11.04 (s, 1 H, NH). Found (%):
C, 75.73; H, 4.69; N, 5.00. C35H26N2O5. Calculated (%):
C, 75.80; H, 4.73; N, 5.05. The yield of compound 5c was 16%,
Ethyl 1´ꢀbenzylꢀ8ꢀmethylꢀ2´,11ꢀdioxoꢀ5´ꢀphenylꢀ1´,2´,5,11ꢀ
tetrahydrospiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrrole}ꢀ4´ꢀcarbꢀ
oxylate (3b). The yield was 61%, m.p. 290—292 C (ethyl aceꢀ
tate—1,2ꢀdichloroethane (1 : 1)). IR, /cm–1: 3191 (NH); 1678,
1
1626 (C=O). H NMR, : 0.61 (t, 3 H, CH2CH3, J = 7.2 Hz);
2.24 (s, 3 H, Me); 3.58 (m, 2 H, CH2CH3); 4.57, 4.61 (both d,
1 H each, CH2Ph, J = 16.7 Hz); 6.79—7.65 (m, 17 H, Ar); 10.96
(s, 1 H, NH). Found (%): C, 78.15; H, 5.08; N, 5.03. C36H28N2O4.
Calculated (%): C, 78.24; H, 5.11; N, 5.07.
Ethyl 1´ꢀbenzylꢀ8ꢀmethoxyꢀ2´,11ꢀdioxoꢀ5´ꢀphenylꢀ1´,2´,5,11ꢀ
tetrahydrospiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrrole}ꢀ4´ꢀcarbꢀ
oxylate (3c). The yield was 59%, m.p. 293—294 C (ethyl aceꢀ
tate). IR, /cm–1: 3195 (NH); 1686, 1622 (C=O). 1H NMR, :
0.61 (t, 3 H, CH2CH3, J = 7.0 Hz); 3.58 (m, 2 H, CH2CH3);
3.69 (s, 3 H, OMe); 4.57, 4.61 (both d, 1 H each, CH2Ph,
J = 16.1 Hz); 6.50—7.64 (m, 17 H, Ar); 11.02 (s, 1 H, NH).
13C NMR, : 13.12 (OCH2CH3); 43.88 (C(10)); 51.56 (CH2Ph);
55.13 (OMe); 58.48 (OCH2CH3); 99.19 (C(4´)); 111.51 (C(10a));
114.12—136.70, 153.56 (C(5´)); 155.85 (C(8)); 156.19 (C(4b));
161.48 (C(2´)); 179.75 (COOEt); 187.83 (C(11)). Found (%):
C, 75.97; H, 4.91; N, 4.90. C36H28N2O5. Calculated (%): C, 76.04;
H, 4.96; N, 4.93.
Ethyl 2´,11ꢀdioxoꢀ1´,5´ꢀdiphenylꢀ1´,2´,5,11ꢀtetrahydroꢀ
spiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrrole}ꢀ4´ꢀcarboxylate (3d)
and ethyl 2,10,12ꢀtrioxoꢀ1´,5´,5ꢀtriphenylꢀ1´,2´,10,12ꢀtetraꢀ
hydroꢀ5Hꢀspiro{diindeno[1,2ꢀb:2´,1´ꢀe]pyridineꢀ11,3´ꢀpyrrole}ꢀ
4´ꢀcarboxylate (5a). A solution of pyrroledione 1b (1.0 mmol)
and enamine 2a (1.0 mmol) in anhydrous mꢀxylene (15 mL) was
refluxed for 5 h, cooled, an orange precipitate of compound 3d
was filtered off. The yield was 53%, m.p. 279—281 C (ethyl
acetate). IR, /cm–1: 3262 (NH); 1697, 1628 (C=O). 1H NMR,
: 0.66 (t, 3 H, CH2CH3, J = 7.1 Hz); 3.63 (m, 2 H, CH2CH3);
7.11—7.87 (m, 18 H, Ar); 11.07 (s, 1 H, NH). Found (%): C, 77.80;
H, 4.57; N, 5.29. C34H24N2O4. Calculated (%): C, 77.85;
H, 4.61; N, 5.34. The mother liquor was concentrated to dryꢀ
ness, the residue was dissolved in boiling ethyl acetate (10 mL),
cooled, a crimson precipitate of compound 5a was filtered off.
m.p. 305—307 C (benzene—ethyl acetate (1 : 1)). IR, /cm–1
:
1742, 1692 (C=O). 1H NMR, : 0.72 (t, 3 H, CH2CH3, J = 7.0 Hz);
3.86 (q, 2 H, OCH2, J = 7.0 Hz); 3.97 (s, 3 H, OMe); 5.69
(d, 2 H, C(4)H, C(6)H, J = 7.6 Hz); 7.19—7.95 (m, 20 H, Ar).
Found (%): C, 77.36; H, 4.40; N, 4.04. C44H30N2O6. Calculatꢀ
ed (%): C, 77.41; H, 4.43; N, 4.10.
Ethyl 1´ꢀcyclohexylꢀ8ꢀmethoxyꢀ2´,11ꢀdioxoꢀ5´ꢀphenylꢀ
1´,2´,5,11ꢀtetrahydrospiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrꢀ
role}ꢀ4´ꢀcarboxylate (3g) and ethyl 1´ꢀcyclohexylꢀ5ꢀ(4ꢀmethoxyꢀ
phenyl)ꢀ2,10,12ꢀtrioxoꢀ5´ꢀphenylꢀ1´,2´,10,12ꢀtetrahydroꢀ5Hꢀ
spiro{diindeno[1,2ꢀb:2´,1´ꢀe]pyridineꢀ11,3´ꢀpyrrole}ꢀ4´ꢀcarbꢀ
oxylate (5d). The yield of compound 3g was 48%, m.p. 275—276 C
(ethyl acetate). IR, /cm–1: 3195 (NH); 1688, 1620 (C=O).
1H NMR, : 0.59 (t, 3 H, CH2CH3, J = 7.0 Hz); 0.87—2.07
(m, 10 H, cycloꢀC6H11); 3.15 (m, 1 H, cycloꢀC6H11); 3.55 (q, 2 H,
CH2CH3, J = 7.0 Hz); 3.73 (s, 3 H, OMe); 6.46—7.62 (m, 12 H,
Ar); 10.89 (s, 1 H, NH). Found (%): C, 75.11; H, 5.69; N, 5.06.
C35H32N2O5. Calculated (%): C, 74.98; H, 5.75; N, 5.00. The
yield of compound 5d was 18%, m.p. 270—273 C (benzꢀ
ene—ethyl acetate (1 : 1)). IR, /cm–1: 1723, 1690 (C=O).
1H NMR, : 0.65 (t, 3 H, CH2CH3, J = 7.1 Hz); 0.91—2.12
(m, 10 H, cycloꢀC6H11); 3.19 (m, 1 H, cycloꢀC6H11); 3.75 (q, 2 H,
CH2CH3, J = 7.1 Hz); 3.95 (s, 3 H, OMe); 5.65 (d, 2 H, C(4)H,
C(6)H, J = 7.6 Hz); 6.94—7.91 (m, 15 H, Ar). Found (%):
C, 76.79; H, 5.35; N, 4.18. C44H36N2O6. Calculated (%): C, 76.73;
H, 5.27; N, 4.07.
The yield was 14%, m.p. 336—337 C (ethyl acetate). IR, /cm–1
:
1
1734, 1694 (C=O). H NMR, : 0.72 (t, 3 H, Me, J = 7.2 Hz);
3.87 (q, 2 H, OCH2, J = 7.2 Hz); 5.55 (d, 2 H, C(4)H, C(6)H,
J = 7.5 Hz); 7.16—8.07 (m, 21 H, Ar). Found (%): C, 79.07;
H, 4.29; N, 4.25. C43H28N2O5. Calculated (%): C, 79.13;
H, 4.32; N, 4.29.
Compounds 3e—g and 5b—d were synthesized similarly.
The results of Xꢀray diffraction studies will be published sepꢀ
arately.
Ethyl 8ꢀmethylꢀ2´,11ꢀdioxoꢀ1´,5´ꢀdiphenylꢀ1´,2´,5,11ꢀtetraꢀ
hydrospiro{indeno[1,2ꢀb]quinolineꢀ10,3´ꢀpyrrole}ꢀ4´ꢀcarboxylꢀ
ate (3e) and ethyl 2,10,12ꢀtrioxoꢀ1´,5´ꢀdiphenylꢀ5ꢀ(4ꢀtolyl)ꢀ
1´,2´,10,12ꢀtetrahydroꢀ5Hꢀspiro{diindeno[1,2ꢀb:2´,1´ꢀe]pyridꢀ
ineꢀ11,3´ꢀpyrrole}ꢀ4´ꢀcarboxylate (5b). The yield of comꢀ
Ethyl 1´ꢀcyclohexylꢀ2,10,12ꢀtrioxoꢀ5´ꢀphenylꢀ5ꢀ(4ꢀtolyl)ꢀ
1´,2´,10,12ꢀtetrahydroꢀ5Hꢀspiro{diindeno[1,2ꢀb:2´,1´ꢀe]pyridꢀ
ineꢀ11,3´ꢀpyrrole}ꢀ4´ꢀcarboxylate (5e). A solution of pyrroleꢀ
dione 1c (1.0 mmol) and enamine 2b (1.0 mmol) in anhydrous
mꢀxylene (15 mL) was refluxed for 5 h, cooled, the solvent was
evaporated to dryness. The residue was dissolved in boiling ethyl
acetate (20 mL), cooled, a crimson precipitate formed was filꢀ
tered off. The yield was 28%, m.p. 318—319 C (ethyl acetate).
IR, /cm–1: 1734, 1694, 1676 (C=O). 1H NMR, : 0.63 (t, 3 H,
CH2CH3, J = 7.0 Hz); 0.80—2.10 (m, 10 H, cycloꢀC6H11); 2.57
(s, 3 H, Me); 3.18 (m, 1 H, cycloꢀC6H11); 3.74 (q, 2 H, OCH2,
J = 7.0 Hz); 5.58 (d, 2 H, C(4)H, C(6)H, J = 7.6 Hz); 7.15—7.85
pound 3e was 50%, m.p. 307—308 C (ethyl acetate). IR, /cm–1
:
3244 (NH); 1694, 1630 (C=O). 1H NMR, : 0.66 (t, 3 H,
CH2CH3, J = 7.0 Hz); 2.32 (s, 3 H, Me); 3.63 (m, 2 H,
CH2CH3); 7.05—7.66 (m, 17 H, Ar); 11.02 (s, 1 H, NH).

Spiro heterocyclization of pyrrolediones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
63
(m, 15 H, Ar). Found (%): C, 78.45; H, 5.32; N, 4.11. C44H36N2O5.
Calculated (%): C, 78.55; H, 5.39; N, 4.16.
7. P. S. Silaichev, M. V. Dmitriev, Z. G. Aliev, A. N. Maslivꢀ
ets, Zh. Org. Khim., 2010, 46, 1173 [Russ. J. Org. Chem.
(Engl. Transl.), 2010, 46, 1173].
8. M. V. Dmitriev, P. S. Silaichev, Z. G. Aliev, A. N. Masꢀ
livets, Zh. Org. Khim., 2011, 47, 309 [Russ. J. Org. Chem.
(Engl. Transl.), 2011, 47, 304].
References
1. P. S. Silaichev, Z. G. Aliev, A. N. Maslivets, Zh. Org. Khim.,
2009, 45, 130 [Russ. J. Org. Chem. (Engl. Transl.), 2009,
45, 126].
2. Yu. N. Bannikova, E. A. Sedegova, V. V. Khalturina, A. N.
Maslivets, Zh. Org. Khim., 2007, 43, 1343 [Russ. J. Org. Chem.
(Engl. Transl.), 2007, 43, 1338].
3. Yu. N. Bannikova, Yu. S. Rozhkova, Yu. V. Shklyaev, A. N.
Maslivets, Zh. Org. Khim., 2008, 44, 706 [Russ. J. Org. Chem.
(Engl. Transl.), 2008, 44, 697].
9. J. Zhang, A.ꢀR. O. ElꢀShabrawy, M. A. ElꢀShanawany, P. L.
Schiff, D. J. Slatkin, J. Nat. Prod., 1987, 50, 800.
10. R. Miri, K. Javidnia, B. Hemmateenejad, A. Azarpira,
Z. Amirghofran, Bioorg. Med. Chem., 2004, 12, 2529.
11. K. Cooper, M. J. Fray, P. E. Cross, K. Richardson, Eur. Pat.
Appl. EP 0299727 A1; Chem. Abstr., 1989, 110, p231441a.
12. G. R. Heintzelman, K. M. Averill, J. H. Dodd, PCT Int.
Appl. WO 2002085894 A1; Chem. Abstr., 2002, 137,
p337793q.
4. Yu. N. Bannikova, A. N. Maslivets, Z. G. Aliev, Zh. Org.
Khim., 2007, 43, 1339 [Russ. J. Org. Chem. (Engl. Transl.),
2007, 43, 1334].
13. G. R. Heintzelman, K. M. Averill, J. H. Dodd, K. T. Deꢀ
marest, Y. Tang, P. F. Jackson, Pat. Appl. US 20040082578
A1; Chem. Abstr., 2004, 140, p375187q.
5. E. S. Denislamova, A. N. Maslivets, Zh. Org. Khim., 2010,
46, 396 [Russ. J. Org. Chem. (Engl. Transl.), 2010, 46, 389].
6. P. S. Silaichev, Z. G. Aliev, A. N. Maslivets, Zh. Org. Khim.,
2009, 45, 1125 [Russ. J. Org. Chem. (Engl. Transl.), 2009,
45, 1114].
Received February 25, 2011;
in revised form October 3, 2011