Five-membered 2,3-dioxo heterocycles: LXXXV. Synthesis of methyl 1-Aryl-4,5-dioxo-3-(1-oxo-3-phenylprop-2-en-1-yl)-4,5-dihydro-1H-pyrrole-2- carboxylates and their reaction with 3-Amino-5,5-dimethylcyclohex-2-en-1-ones.

Article abstract of DOI:10.1134/S1070428012040173

Treatment of methyl 2-arylamino-4-oxo-6-phenylhexa-2,5-dienoates with oxalyl chloride gave methyl 1-aryl-4,5-dioxo-3-(1-oxo-3-phenylprop-2-en-1-yl)-4, 5-dihydro-1H-pyrrole-2-carboxylates which reacted with 3-benzylamino- and 3-arylamino-5,5-dimethylcyclohex-2-en-1-ones to produce 1'-aryl-1-benzyl- and 1,1'-diaryl-4'-hydroxy-6,6-dimethyl-3'-(1-oxo-3-phenylprop-2-en-1-yl)-6, 7-dihydrospiro[indole-3,2;-pyrrole]- 2,4,5';(1H,1'H,5H)-triones. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012040173

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 4, pp. 561–565. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © P.S. Silaichev, V.O. Filimonov, P.A. Slepukhin, A.N. Maslivets, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 4, pp. 563–567.
Five-Membered 2,3-Dioxo Heterocycles: LXXXV.* Synthesis
of Methyl 1-Aryl-4,5-dioxo-3-(1-oxo-3-phenylprop-2-en-1-yl)-
4,5-dihydro-1H-pyrrole-2-carboxylates and Their Reaction
with 3-Amino-5,5-dimethylcyclohex-2-en-1-ones. Molecular
and Crystalline Structure of 4′-Hydroxy-1′-(4-methoxyphenyl)-
6,6-dimethyl-3′-(1-oxo-3-phenylprop-2-en-1-yl)-1-phenyl-
6,7-dihydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-trione
P. S. Silaicheva, b, V. O. Filimonovb, P. A. Slepukhinc, and A. N. Maslivetsa, b
a Institute of Natural Sciences, Perm State University, ul. Genkelya 4, Perm, 614990 Russia
e-mail: koh2@psu.ru
b Perm State University, ul. Bukireva 15, Perm, 614990 Russia
c Postovskii Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences,
ul. S. Kovalevskoi/Akademicheskaya 22/20, Yekaterinburg, 620041 Russia
Received June 29, 2011
Abstract—Treatment of methyl 2-arylamino-4-oxo-6-phenylhexa-2,5-dienoates with oxalyl chloride gave
methyl 1-aryl-4,5-dioxo-3-(1-oxo-3-phenylprop-2-en-1-yl)-4,5-dihydro-1H-pyrrole-2-carboxylates which react-
ed with 3-benzylamino- and 3-arylamino-5,5-dimethylcyclohex-2-en-1-ones to produce 1′-aryl-1-benzyl- and
1,1′-diaryl-4′-hydroxy-6,6-dimethyl-3′-(1-oxo-3-phenylprop-2-en-1-yl)-6,7-dihydrospiro[indole-3,2′-pyrrole]-
2,4,5′(1H,1′H,5H)-triones.
DOI: 10.1134/S1070428012040173
It is known that the direction of reactions of
1H-pyrrole-2,3-diones with carbocyclic enamines is
determined by the nature of substituents in the pyrrole
ring. Reactions of ethyl 1-alkyl-4,5-dioxo-2-phenyl-
4,5-dihydro-1H-pyrrole-3-carboxylates with N-aryl-
substituted enamines involve successive addition of the
ortho-carbon atom in the aryl substituent and β-carbon
atom in the enamino fragment to the C4=O carbonyl
carbon atom in dioxopyrrole [2, 3]. Isopropyl (1-aryl-
4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrol-3-yl)oxo-
acetates react via addition of the NH and β-CH groups
in the enamine to C5 and C4 in the pyrrole ring, open-
ing of the latter, and subsequent cyclization [4]. Di-
methyl 1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2,3-
dicarboxylates react with enamines via successive
addition of the β-CH and NH groups in the enamine to
C2 and ester carbonyl carbon atom at C2 in the initial
pyrrole [5]. Reactions of methyl 3-aroyl-1-aryl-4,5-di-
oxo-4,5-dihydro-1H-pyrrole-2-carboxylates with
enamines take three reaction paths: successive addition
of the β-CH and NH groups in the enamine to C2 and
C4 or C2 and 2-C=O and (minor path) addition of the
NH and β-CH groups in the enamine to C5 and C4,
followed by pyrrole ring opening and cyclization [6].
In the present work we examined the reaction of
methyl 1-aryl-4,5-dioxo-3-(1-oxo-3-phenylprop-2-en-
1-yl)-4,5-dihydro-1H-pyrrole-2-carboxylates Іa and Ib
with carbocyclic enamines, 3-benzylamino- and 3-aryl-
amino-5,5-dimethylcyclohex-2-en-1-ones IІa–IIe,
with a view to elucidate how introduction of a cin-
namoyl fragment into position 3 of dioxopyrroles I
affects their reactivity. Compounds Іa and Ib were
synthesized from methyl (2Z,5E)-2-arylamino-4-oxo-
6-phenylhexa-2,5-dienoates IIIa and IIIb which were
prepared in turn by reaction of methyl (2Z,5E)-2-hy-
droxy-4-oxo-6-phenylhexa-2,5-dienoate with aromatic
* For communication LXXXIV, see [1].
561

FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LXXXV.
562
Scheme 1.
O
Ph
O
O
OH
O
NHAr
O
ArNH2
–H2O
ClC(O)COCl
–HCl
OMe
OMe
MeO
Ph
Ph
O
N
O
O
Ar
IIIa, IIIb
Ia, Ib
O
Ph
O
O
Ph
O
Me
Me
R
OH
O
MeO
NH
NHR
R
N
OH
O
IIa–IIe
O
N
–MeOH
N
Me
Me
Ar
Ar
O
Me
Me
O
IVa–IVh
I, III, Ar = 4-MeC6H4 (a), 4-MeOC6H4 (b); ІІ, R = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c), 4-BrC6H4 (d), PhCH2 (e); IV, Ar =
4-MeC6H4, R = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c); Ar = 4-MeOC6H4, R = Ph (d), 4-MeC6H4 (e), 4-MeOC6H4 (f), 4-BrC6H4 (g),
PhCH2 (h).
amines. Compounds IIIa and IIIb were isolated as red
oily liquids, which are readily soluble in common
organic solvents, poorly soluble in alkanes, and insol-
uble in water. They were brought into reaction with
oxalyl chloride without additional purification. By
heating enamines IIIa and IIIb with an equimolar
amount of oxalyl chloride in boiling anhydrous ben-
zene over a period of 70–80 min (until hydrogen
chloride no longer evolved) we obtained desired di-
oxopyrroles Ia and Ib as orange crystalline substances
which melted with decomposition at a high tempera-
ture. Compounds Ia and Ib were readily soluble in
common organic solvent and insoluble in alkanes; they
lost their color on storage due to reaction with atmos-
pheric moisture. The IR spectra of Іa and Ib contained
absorption bands due to stretching vibrations of the
lactam (1773–1775 cm–1) and ketone carbonyl groups
(1725–1727 cm–1) in the pyrrole ring, ester carbonyl
group (1744–1745 cm–1), and carbonyl group in the
cinnamoyl fragment (1659–1663 cm–1).
Compounds Іa and Ib reacted with enamines IІa–
IIe at a ratio of 1:1 in boiling anhydrous toluene
(reaction time 15–20 min; until the color intrinsic to
initial compounds I disappeared) to give 1-substituted
1′-aryl-4′-hydroxy-6,6-dimethyl-3′-(1-oxo-3-phenyl-
prop-2-en-1-yl)-6,7-dihydrospiro[indole-3,2′-pyrrole]-
2,4,5′(1H,1′H,5H)-triones IVa–IVh (Scheme 1). Com-
pounds IVa–IVh were isolated as colorless or light
yellow high-melting crystalline substances, which
were readily soluble in DMF and DMSO, poorly sol-
uble in other common organic solvents, and insoluble
in alkanes and water. The products showed a positive
color test for enolic hydroxy group upon treatment
with an alcoholic solution of iron(III) chloride.
O2
O1
C4
C23
C27
C8
C1
C13
C18
O5
C10
N1
C19
C14
O4
C15
C3
C2
C7
C28
C20
C9
C29
C6
C12
C11
O3
C22
C5
C26
C35
O6
C16
N2
C17
C25
C24
C21
C30
The IR spectra of IVa–IVh contained absorption
bands belonging to stretching vibrations of the enolic
O–H group (3167–3306 cm–1), lactam carbonyl groups
C2=O (1755–1761 cm–1) and C5′=O (1719–1730 cm–1),
and ketone carbonyl groups C4=O (1659–1669 cm–1)
and 3′-C=O (1640–1645 cm–1). Compounds IVa–IVh
C31
C34
C32
C33
Structure of the molecule of 4′-hydroxy-1′-(4-methoxyphen-
yl)-6,6-dimethyl-3′-(1-oxo-3-phenylprop-2-en-1-yl)-1-phen-
yl-6,7-dihydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1H′,5H)-
trione (IVd) according to the X-ray diffraction data.
1
displayed in the H NMR spectra signals from protons
in the aromatic rings and substituents attached thereto,
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SILAICHEV et al.
two singlets from nonequivalent methyl groups at
563
EXPERIMENTAL
δ 0.53–0.96 ppm, four doublets from methylene pro-
tons at δ 1.97–2.54 ppm (2JHH = 16–18 Hz), doublets
from protons at the double bond in the cinnamoyl sub-
stituent at δ 7.59–7.72 ppm with a coupling constant
typical of trans-configured double bond (3Jtrans = 15.7–
16.2 Hz) [7], and a broadened signal at δ 13.08–
13.48 ppm from the enolic hydroxy proton.
The IR spectra were recorded on an FSM-1201
spectrometer from samples dispersed in mineral oil.
The NMR spectra were measured on a Bruker AM-400
instrument at 400 (1H) and 100 MHz (13C) from solu-
tions in DMSO-d6 using tetramethylsilane as internal
reference.
13
Methyl 1-(4-methylphenyl)-4,5-dioxo-3-(1-oxo-
3-phenylprop-2-en-2-yl)-4,5-dihydro-1H-pyrrole-2-
carboxylate (Ia). Methyl (2Z,5E)-2-hydroxy-4-oxo-6-
phenylhexa-2,5-dienoate, 0.1 mol, was dissolved in
200 ml of toluene, 0.1 mol of p-toluidine was added,
and the mixture was heated for 5 h under reflux in
a flask equipped with a Dean–Stark trap until water no
longer separated. The solvent was removed under
reduced pressure, and the residue was passed through
a column charged with silica gel (L 100–400 μm)
using toluene–isooctane (1:1) as eluent. The first
bright red fraction was collected, the solvent was
removed under reduced pressure, and the residue, oily
methyl 4-oxo-2-(4-methylphenylamino)-6-phenylhexa-
2,5-dienoate (IIIa), was used without additional purifi-
cation. Com-pound IIIa, 0.05 mol, was dissolved in
30 ml of anhydrous benzene, 0.05 mol of oxalyl chlo-
ride was added dropwise, and the mixture was heated
for 70 min under reflux, diluted with 30 ml of anhy-
drous hexane, and cooled. The precipitate was filtered
off and recrystallized from benzene–hexane (1:1).
Yield 76%, mp 201–202°C. IR spectrum, ν, cm–1: 1773
(C5=O), 1744 (C=O, ester), 1725 (C4=O), 1659
(3-C=O). 1H NMR spectrum, δ, ppm: 2.36 s (3H, Me),
3.78 s (3H, OMe), 7.23–7.78 m (11H, Harom, CH=CH).
Found, %: C 70.32; H 4.52; N 3.70. C22H17NO5. Cal-
culated, %: C 70.39; H 4.56; N 3.73.
In the C NMR spectrum of compound IVd, apart
from signals typical of carbon atoms in the aromatic
rings, substituents therein, methyl and methylene
groups, and vinylene fragment, we observed signals
from carbonyl carbon atoms at δC 190.58 (C4), 182.39
(3′-C=O), 164.87 (C2), and 165.73 ppm (C5′); signals
from C3′ and C4′ were located at δC 118.20 and
174.60 ppm, respectively; the spiro carbon atom reso-
nated at δC 68.63 ppm; and signals at δC 109.80 and
137.24 ppm were assigned to C3a and C7a, respectively.
The chemical shifts of carbon nuclei in the 6,7-dihy-
drospiro[indole-3,2′-pyrrole] heterocyclic system were
consistent with those observed for methyl 4′-hydroxy-
6,6-dimethyl-1′-(4-methylphenyl)-2,4,5′-trioxo-1-
phenyl-1,1′,2,4,5,5′,6,7-octahydrospiro[indole-3,2′-
pyrrole]-3′-carboxylate, δC, ppm: 190.56 (C4), 161.99
(C2), 165.04 (C5′), 107.94 (C3′), 174.45 (C4′), 68.31
(Cspiro), 109.52 (C3a), 138.03 (C7a) [5]. An appreciable
shift of the C3′ signal of IVd (by 10.26 ppm) may be
rationalized in terms of stronger electron-acceptor
power of the cinnamoyl group compared to methoxy-
carbonyl.
According to the X-ray diffraction data, compound
IVd (see figure) crystallized in centrosymmetric point
symmetry group as a 1:1 solvate with toluene. The
bond lengths and bond angles in molecule IVd are
similar to the corresponding standard values. Mole-
cules IVd in crystal a linked to dimers through inter-
molecular hydrogen bonds O1–H1···O4 [–x, –y, –z]
[O1–H1 0.92(2), O1···O4 2.593(2) Å, ∠O1H1O4 148(1)°].
Methyl 1-(4-methoxyphenyl)- 4,5-dioxo-3-(1-oxo-
3-phenylprop-2-en-2-yl)-4,5-dihydro-1H-pyrrole-2-
carboxylate (Ib) was synthesized in a similar way.
Yield 84%, mp 193–194°C (from benzene–hexane,
1:1). IR spectrum, ν, cm–1: 1775 (C5=O), 1745 (C=O,
Presumably, compounds IVa–IVh are formed via
initial addition of the activated β-CH group in the
enamine fragment of IІ to the C2=O carbon atom in І,
followed by closure of new pyrrole ring as a result of
nucleophilic addition of the secondary amino group at
the ester carbonyl group and elimination of methanol
according to a scheme analogous to that described
previously [5, 6]. In this case, intramolecular cycliza-
tion due to reaction of the enolic hydroxy group at the
activated double bond in the cinnamoyl substituent
does not occur.
1
ester), 1727 (C4=O), 1663 (3-C=O). H NMR spec-
trum, δ, ppm: 3.78 s (3H, COOMe), 3.80 s (3H, OMe),
7.00–7.78 m (11H, Harom, CH=CH). Found, %:
C 67.48; H 4.36; N 3.52. C22H17NO6. Calculated, %:
C 67.52; H 4.38; N 3.58.
4′-Hydroxy-6,6-dimethyl-1′-(4-methylphenyl)-
3′-(1-oxo-3-phenylprop-2-en-2-yl)-1-phenyl-6,7-di-
hydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-
trione (IVa). Enamine IІa, 1.0 mmol, was added to
a solution of 1.0 mmol of compound Іa in 15 ml of
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FIVE-MEMBERED 2,3-DIOXO HETEROCYCLES: LXXXV.
564
anhydrous toluene, the mixture was heated for 20 min
under reflux and cooled, and the precipitate was
filtered off and recrystallized from toluene. Yield 79%,
mp 252–253°C. IR spectrum, ν, cm–1: 3167 (OH),
1755 (C2=O), 1721 (C5′=O), 1669 (C4=O), 1642
(3′-C=O). 1H NMR spectrum, δ, ppm: 0.53 s and 0.92 s
(3H each, 6-Me), 1.98 d (1H, 7-H, J = 16.1 Hz), 2.10 d
(1H, 5-H, J = 18.1 Hz), 2.16 d (1H, 7-H, J = 16.1 Hz),
2.31 s (3H, Me), 2.37 d (1H, 5-H, J = 18.1 Hz), 6.98–
7.74 m (14H, Harom), 7.64 d (1H, 2″-H, J = 15.8 Hz),
7.72 d (1H, 3″-H, J = 15.8 Hz), 13.40 br.s (1H, OH).
Found, %: C 75.22; H 5.37; N 5.06. C35H30N2O5. Cal-
culated, %: C 75.25; H 5.41; N 5.01.
spectrum, δ, ppm: 0.57 s and 0.93 s (3H each, 6-Me),
1.99 d (1H, 7-H, J = 16.1 Hz), 2.10 d (1H, 5-H, J =
18.4 Hz), 2.13 d (1H, 7-H, J = 16.1 Hz), 2.39 d (1H,
5-H, J = 18.4 Hz), 3.76 s (3H, OMe), 6.99–7.71 m
(14H, Harom), 7.62 d (1H, 2″-H, J = 15.7 Hz), 7.71 d
(1H, 3′-H, J = 15.7 Hz), 13.34 br.s (1H, OH). 13C NMR
spectrum, δC, ppm: 26.44 and 27.98 (6-Me), 33.78
(C6), 35.85 (C7), 50.43 (C5), 55.34 (OMe), 68.63 (C3),
109.80 (C3a), 114.59 (Co in C6H4OMe-4), 118.20 (C3′),
123.86 (C2″), 125.25–134.39, 137.24 (C7a), 142.23 (C3″),
159.05 (COMe), 164.87 (C2), 165.73 (C5′) 174.60
(C4′), 182.39 (3′-CO), 190.58 (C4). Found, %: C 73.18;
H 5.21; N 4.85. C35H30N2O6. Calculated, %: C 73.16;
H 5.26; N 4.88.
Compounds IVb–IVh were synthesized in a similar
X-Ray analysis of compound IVd was performed
on an Xcalibur-3 automatic four-circle diffractometer
with a CCD detector [λ(MoKα) 0.71073 Å, temperature
295(2) K, graphite monochromator, ω-scanning
through a step of 1°]. A fragment of a 0.25×0.20×
0.15-mm colorless prism was used. No correction for
absorption was introduced taking into account its low
value (μ = 0.082 mm–1). Total of 19826 reflection in-
tensities were measured in the range 2.94 < θ < 33.34°;
11424 reflections were independent (Rint = 0.0435),
and 3560 reflections were characterized by I > 2σ(I).
The completeness was 81.8% for θ < 33.34° and
96.6% for θ < 26.00°. Triclinic crystal system, space
group P-1; unit cell parameters: a = 10.1696(8), b =
13.3383(9), c = 13.5975(13) Å; α = 83.622(7), β =
80.102(7), γ = 85.880(6)°. The structure was solved
and refined using SHELXTL 5.1 software package [8].
The positions and temperature parameters of non-hy-
drogen atoms were refined against F2 first in isotropic
and then in anisotropic approximation by the full-
matrix least-squares procedure. Hydrogen atoms
(except for the OH hydrogen atom) were localized by
the electron density maxima and were included in the
refinement in isotropic approximation according to the
riding model. The OH hydrogen atom was refined
independently in isotropic approximation. The final
divergence factors were R1 = 0.0627, wR2 = 0.1218
[for reflections with I > 2σ(I)] and R1 = 0.1751, wR2 =
0.1320 (for all reflections); goodness of fit S = 0.991.
The crystallographic data for compound IVd were
deposited to the Cambridge Crystallographic Data
Centre (entry no. CCDC 872845) and are available at
www.ccdc.cam.ac.uk/data_request/cif upon request.
way.
4′-Hydroxy-6,6-dimethyl-1,1′-bis(4-methylphen-
yl)-3′-(1-oxo-3-phenylprop-2-en-2-yl)-6,7-dihydro-
spiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-trione
(IVb). Yield 84%, mp 256–257°C (from toluene). IR
spectrum, ν, cm–1: 3181 (OH), 1759 (C2=O), 1725
(C5′=O), 1667 (C4=O), 1644 (3′-C=O). H NMR spec-
1
trum, δ, ppm: 0.53 s and 0.91 s (3H each, 6-Me),
1.97 d (1H, 7-H, J = 16.0 Hz), 2.08 d (1H, 5-H, J =
18.4 Hz), 2.14 d (1H, 7-H, J = 16.0 Hz), 2.31 s (3H,
Me), 2.37 d (1H, 5-H, J = 18.4 Hz), 2.39 s (3H, Me),
6.96–7.70 m (13H, Harom), 7.63 d (1H, 2″-H, J =
15.8 Hz), 7.71 d (1H, 3″-H, J = 15.8 Hz), 13.37 br.s
(1H, OH). Found, %: C 75.47; H 5.67; N 4.85.
C36H32N2O5. Calculated, %: C 75.51; H 5.63; N 4.89.
4′-Hydroxy-1-(4-methoxyphenyl)-6,6-dimethyl-
1′-(4-methylphenyl)-3′-(1-oxo-3-phenylprop-2-en-
2-yl)-6,7-dihydrospiro[indole-3,2′-pyrrole]-
2,4,5′(1H,1′H,5H)-trione (IVc). Yield 78%, mp 244–
246°C (from toluene). IR spectrum, ν, cm-1: 3306
(OH), 1757 (C2=O), 1719 (C5′=O), 1669 (C4=O), 1640
(3′-C=O). 1H NMR spectrum, δ, ppm: 0.53 s and 0.92 s
(3H each, 6-Me), 1.97 d (1H, 7-H, J = 16.4 Hz), 2.07 d
(1H, 5-H, J = 18.4 Hz), 2.14 d (1H, 7-H, J = 16.4 Hz),
2.30 s (3H, Me), 2.33 d (1H, 5-H, J = 18.4 Hz), 3.83 s
(3H, OMe), 6.97–7.70 m (13H, Harom), 7.62 d (1H,
2″-H, J = 15.8 Hz), 7.71 d (1H, 3″-H, J = 15.8 Hz),
13.48 br.s (1H, OH). Found, %: C 73.47; H 5.44;
N 4.73. C36H32N2O6. Calculated, %: C 73.45; H 5.48;
N 4.76.
4′-Hydroxy-1′-(4-methoxyphenyl)-6,6-dimethyl-
3′-(1-oxo-3-phenylprop-2-en-2-yl)-1-phenyl-6,7-di-
hydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-
trione (IVd). Yield 75%, mp 242–243°C (from tolu-
ene). IR spectrum, ν, cm–1: 3181 (OH), 1761 (C2=O),
4′-Hydroxy-1′-(4-methoxyphenyl)-6,6-dimethyl-
1-(4-methylphenyl)-3′-(1-oxo-3-phenylprop-2-en-
2-yl)-6,7-dihydrospiro[indole-3,2′-pyrrole]-
2,4,5′(1H,1′H,5H)-trione (IVe). Yield 81%, mp 258–
1723 (C5′=O), 1669 (C4=O), 1644 (3′-C=O). H NMR
1
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SILAICHEV et al.
565
259°C (from toluene). IR spectrum, ν, cm–1: 3174
(OH), 1757 (C2=O), 1727 (C5′=O), 1661 (C4=O), 1645
(3′-C=O). 1H NMR spectrum, δ, ppm: 0.57 s and 0.92 s
(3H each, 6-Me), 1.98 d (1H, 7-H, J = 16.3 Hz), 2.09 d
(1H, 5-H, J = 18.4 Hz), 2.15 d (1H, 7-H, J = 16.3 Hz),
2.33 d (1H, 5-H, J = 18.4 Hz), 2.39 s (3H, Me), 3.76 s
(3H, OMe), 6.97–7.70 m (13H, Harom), 7.62 d (1H,
2″-H, J = 16.2 Hz), 7.70 d (1H, 3″-H, J = 16.2 Hz),
13.08 br.s (1H, OH). Found, %: C 73.46; H 5.50;
N 4.82. C36H32N2O6. Calculated, %: C 73.45; H 5.48;
N 4.76.
1-Benzyl-4′-hydroxy-1′-(4-methoxyphenyl)-6,6-
dimethyl-3′-(1-oxo-3-phenylprop-2-en-2-yl)-6,7-di-
hydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-
trione (IVh). Yield 75%, mp 233–234°C (from tolu-
ene). IR spectrum, ν, cm–1: 3179 (OH), 1757 (C2=O),
1
1723 (C5′=O), 1669 (C4=O), 1645 (3′-C=O). H NMR
spectrum, δ, ppm: 0.70 s and 0.96 s (3H each, 6-Me),
2.07 d (1H, 7-H, J = 16.0 Hz), 2.11 d (1H, 7-H, J =
16.0 Hz), 2.16 d (1H, 5-H, J = 18.0 Hz), 2.54 d (1H,
5-H, J = 18.0 Hz), 3.77 s (3H, OMe), 4.75 d and 4.91 d
(1H each, CH2Ph, J = 16.1 Hz), 6.84–7.68 m (14H,
H
arom), 7.59 d (1H, 2″-H, J = 15.8 Hz), 7.70 d (1H,
4′-Hydroxy-1,1′-bis(4-methoxyphenyl)-6,6-di-
methyl-3′-(1-oxo-3-phenylprop-2-en-2-yl)-6,7-dihy-
drospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-
trione (IVf). Yield 78%, mp 237–238°C (from tolu-
ene). IR spectrum, ν, cm–1: 3243 (OH), 1755 (C2=O),
3″-H, J = 15.8 Hz), 13.31 br.s (1H, OH). Found, %:
C 73.48; H 5.43; N 4.77. C36H32N2O6. Calculated, %:
C 73.45; H 5.48; N 4.76.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 2.19.10).
1
1721 (C5′=O), 1667 (C4=O), 1642 (3′-C=O). H NMR
spectrum, δ, ppm: 0.57 s and 0.92 s (3H each, 6-Me),
1.98 d (1H, 7-H, J = 16.1 Hz), 2.08 d (1H, 5-H, J =
18.2 Hz), 2.15 d (1H, 7-H, J = 16.1 Hz), 2.32 d (1H,
5-H, J = 18.2 Hz), 3.76 s and 3.83 s (3H each, OMe),
6.98–7.71 m (13H, Harom), 7.64 d (1H, 2″-H, J =
15.7 Hz), 7.71 d (1H, 3″-H, J = 15.7 Hz), 13.26 br.s
(1H, OH). Found, %: C 71.54; H 5.28; N 4.64.
C36H32N2O7. Calculated, %: C 71.51; H 5.33; N 4.63.
REFERENCES
1. Silaichev, P.S., Kudrevatykh, N.V., Aliev, Z.G., and Mas-
livets, A.N., Russ. J. Org. Chem., 2012, vol. 48, p. 253.
2. Silaichev, P.S., Aliev, Z.G., and Maslivets, A.N., Russ. J.
Org. Chem., 2009, vol. 45, p. 1114.
3. Silaichev, P.S., Dmitriev, M.V., Aliev, Z.G., and Masli-
1-(4-Bromophenyl)-4′-hydroxy-1′-(4-methoxy-
phenyl)-6,6-dimethyl-3′-(1-oxo-3-phenylprop-2-
en-2-yl)-6,7-dihydrospiro[indole-3,2′-pyrrole]-
2,4,5′(1H,1′H,5H)-trione (IVg). Yield 87%, mp 265–
266°C (from toluene). IR spectrum, ν, cm–1: 3170
(OH), 1757 (C2=O), 1730 (C5′=O), 1659 (C4=O), 1644
(3′-C=O). 1H NMR spectrum, δ, ppm: 0.58 s and 0.93 s
(3H each, 6-Me), 2.00 d (1H, 7-H, J = 16.1 Hz), 2.16 d
(1H, 5-H, J = 18.5 Hz), 2.17 d (1H, 7-H, J = 16.1 Hz),
2.39 d (1H, 5-H, J = 18.5 Hz), 3.76 s (3H, OMe),
6.98–7.81 m (13H, Harom), 7.63 d (1H, 2″-H, J =
15.8 Hz), 7.71 d (1H, 3″-H, J = 15.8 Hz), 13.38 br.s
(1H, OH). Found, %: C 64.28; H 4.51; N 4.31.
C35H29BrN2O6. Calculated, %: C 64.32; H 4.47; N 4.29.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012