Regioselective one-pot synthesis of functionalised 6,7-dihydro-1H-indol-4(5H )-ones

Article abstract of DOI:10.3184/174751915X14242775299602

A one-pot two-step synthesis of functionalised 6,7-dihydro-1H-indol-4(5H )-ones from 1,3-cyclohexanediones, benzylamines, and 2-(2-oxo-2-phenylethylidene)-1H-indene-1,3(2H )-dione has been achieved. The advantages of this approach are operational simplicity, good yields of the products and avoidance of the use of any ligands, metal catalysts, acidic media, or column chromatography.

Full text of DOI:10.3184/174751915X14242775299602

166 RESEARCH PAPER
VOL. 39 MARCH, 166–169
JOURNAL OF CHEMICAL RESEARCH 2015
Regioselective one-pot synthesis of functionalised 6,7-dihydro-1H-indol-
4(5H)-ones
Abdolali Alizadeh* and Fahimeh Bayat
Chemistry Department, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran
A one-pot two-step synthesis of functionalised 6,7-dihydro-1H-indol-4(5H)-ones from 1,3-cyclohexanediones, benzylamines,
and 2-(2-oxo-2-phenylethylidene)-1H-indene-1,3(2H)-dione has been achieved. The advantages of this approach are
operational simplicity, good yields of the products and avoidance of the use of any ligands, metal catalysts, acidic media, or
column chromatography.
Keywords: 6,7-dihydro-1H-indol-4(5H)-one, 2-(2-oxo-2-phenylethylidene)-1H-indene-1,3(2H)-dione, benzylamine, 1,3-cyclo-
hexanedione, one-pot reaction
Heterocycles containing the indole and pyrrole rings are
significant targets for synthetic and medicinal chemists as
these fragments are key structures in various biologically
active compounds such as atorvastatin and mitomycin.1–3 They
also exhibit a range of biological properties including anti-
tubulin,4 antifouling, antibacterial,5 and antifungal activity.6
They can also act as potent inhibitors of AKT7 and fructose-
1,6-bisphosphatase8 and are apoptosis protein antagonists.9
Moreover, appropriately functionalised 6,7-dihydro-1H-
indol-4(5H)-ones have been identified as anti-psychotic
agents,10 inhibitors of heat-shock protein 90 (scaffolds A and
B in Fig. 1),11,12 and inhibitors of aurora kinase (scaffold C in
Fig. 1).13 These structures are commonly employed as building
blocks for the synthesis of indole-based scaffolds.14,15
phenylethylidene)-1H-indene-1,3(2H)-dione for construction
of 6,7-dihydro-1H-indol-4(5H)-ones.
Results and discussion
We started our study with the optimisation of the condensation
of 1,3-cyclohexanedione 1a (R1 =H) and benzylamine 2a
(R2 =H). Although this condensation occurred well under
solvent-free conditions at 100 °C in 30 min, the reaction did
not proceed well in various solvents at reflux temperature
(Table 1, entries 1–6). Then we investigated the one-pot
sequential reaction of the enamine 3a (R1, R2 =H), the product
of the solvent-free condensation of 1,3-cyclohexanedione
1a (R1 =H) and benzylamine 2a (R2 =H), with 2-(2-oxo-2-
Most of the syntheses of 6,7-dihydro-1H-indol-4(5H)-ones
involve multistep synthetic transformations and consequently
they suffer from tedious isolation steps.16,17 Despite the
importance of the 6,7-dihydro-1H-indol-4(5H)-ones, known
approaches for obtaining them based on multicomponent
reactions are scarce. In this area, Shi recently reported the three-
component reaction of 1,3-dicarbonyl compounds, arylglyoxal
monohydrate, and enaminones leading to functionalised
6,7-dihydro-1H-indol-4(5H)-ones.18 These structures were also
synthesised by reaction of alkenoyl bis(ketene dithioacetals)
and tosylmethyl isocyanide.19 Batra synthesised 2-(substituted)
phenyl-6,7-dihydro-1H-indol-4(5H)-ones from adducts of the
Morita–Baylis–Hillman reaction between 2-oxo-(substituted)
phenylacetaldehydes and cyclohex-2-enone.20
Enaminones as active intermediates have shown good
reactivity in MCRs for they readily attack electrophiles to give
interesting bioactive N-heterocyclic compounds.21–23 Based on
these findings and as part of our program aimed at construction
of new heterocyclic compounds,24–30 here we report the reaction
of 1,3-cyclohexanediones, benzylamines, and 2-(2-oxo-2-
Table 1 Optimisation of the reaction conditions for converting
cyclohexanedione 1a (R1 =H) and benzylamine 2a (R2 =H) to 2-(1-benzyl-4-
oxo-2-phenyl-4,5,6,7-tetrahydro-1H-indol-3-yl)-1H-indene-1,3(2H)-dione
4a (R1, R2 =H)
Entry
Solvent 1a/ Temp/°C
Solvent 2a/ Temp/°C Yield of 4a/%
1
2
3
4
5
CH3CN/rf
MeOH/rf
EtOH/rf
DMF/rf
DCM/rf
CH3CN/rf
MeOH/rf
EtOH/rf
DMF/rf
DCM/rf
THF/rf
10
20
17
14
0
6
THF/rf
0
7
8
9
10
11
12
13
SF/100 °C
SF/100 °C
SF/100 °C
SF/100 °C
SF/100 °C
SF/100 °C
SF/100 °C
SF/100 °C
MeOH/rf
EtOH/rf
CH3CN/rf
DCM/rf
DMF/rf
0
67
64
45
20
30
10
H2O/rf
aSF, solvent-free conditions.
O
NH
CO
2
R¢
H
X
O
R
N
X
Y
N
n
N
NH
R
N
O
H
m
O
F
N
N
H
H
H2N
O
O
A
B
C
Fig. 1 Examples of biologically active 6,7-dihydro-1H-indol-4(5H)-one scaffolds.
* Correspondent. E-mail: aAlizadeh@modares.ac.ir

JOURNAL OF CHEMICAL RESEARCH 2015 167
phenylethylidene)-1H-indene-1,3(2H)-dione. The results are
also shown in Table 1. Following trials with other solvents
at reflux (entries 9–13) we found that the highest yield of
the desired functionalised 6,7-dihydro-1H-indol-4(5H)-one
4a (R1, R2 =H) could be achieved using MeOH at the reflux
temperature (entry 8).
form 6. Then the NH group of 6 attacks the carbonyl group,
through an intramolecular 5-exo-trig cyclisation to form 7.
This is followed by loss of one molecule of H2O from 7 which
effects aromatisation to form product 4.
Experimental
With optimal conditions established (Scheme 1), we then
explored the scope of this reaction by varying the structures
of 1,3-cyclohexanedione 1 and benzylamine 2. The results
are shown in Table 2. As can be seen, yields were in the range
63–82%.
Elemental analyses for C, H and N were performed using a Heraeus
CHN–O–Rapid analyser. Mass spectra were recorded on a Finnigan-
Mat 8430 mass spectrometer operating at an ionisation potential of
70 eV. NMR spectra were obtained on a Bruker DRX-400 Avance
spectrometer (1H NMR at 400 Hz, 13C NMR at 100 Hz) in DMSO-d6
using tetramethylsilane as internal standard. Chemical shifts (δ)
are given in ppm and coupling constants (J) in Hz. IR spectra were
recorded as KBr pellets on a NICOLET FTIR 100 spectrometer;
absorbencies are reported in cm–1. Melting points were measured on an
Electrothermal 9100.
The newly synthesised products 4a−j were fully characterised
1
by their IR, H NMR, 13C NMR and mass spectra and their
elemental analysis. Some selected spectral data are discussed
below.
The mass spectrum of 4f displayed the molecular ion peak at
m/z=473, which is in agreement with the proposed structure.
In the IR spectrum of 4f absorption bands at 3054 (aromatic
C–H), 2931 and 2865 (alkyl C–H), 1714 (C=O), and 1649 (C=C)
Synthesis of 2-(1-R2-benzyl-4-oxo-2-phenyl-6,7-dihydro-1H-indol-
4(5H)-one derivatives 4a–j (R1 =H, Me; R2 =various); general
procedure
1
cm–1 are most significant stretching frequencies. In the H
A mixture of 1,3-cyclohexanedione 1 (1 mmol) and a benzylamine 2
(1 mmol) was heated at 100 °C for 30 min and cooled. Then a solution
of 2-(2-oxo-2-phenylethylidene)-1H-indene-1,3(2H)-dione (1 mmol)
in MeOH (3 mL) was added. The mixture was stirred at reflux
temperature for another 4 h, during which time precipitation of the
product occurred. Progress of reaction was monitored by TLC, and
upon completion (4 h) the mixture was filtered and the precipitate was
washed with MeOH (4 mL) to afford the pure product 4a–j (R1 =H,
Me; R2 =various). NMR and IR spectra were recorded and a sample
was recrystallised for elemental analysis.
2-(1-Benzyl-4-oxo-2-phenyl-4,5,6,7-tetrahydro-1H-indol-3-yl)-1H-
indene-1,3(2H)-dione (4a): White powder, yield 0.30 g (67%); m.p.
226–228 °C; IR (KBr): 3059 (aromatic C–H), 2926 and 2861 (alkyl
C–H), 1711 (C=O), 1645 (C=C), 1600 and 1475 (Ar), 1252 (C–N) cm–1;
1H NMR: δ 1.92–2.01 (m, 2 H, CH2), 2.14 (t, 3JHH =5.6 Hz, 2 H, CH2),
2.70 (t, 3JHH =6.0 Hz, 2 H, CH2), 4.29 (s, 1 H, CH), 5.18 (s, 2 H, CH2Bn),
6.91 (d, 3JHH =7.2 Hz, 2 H, 2×CHortho of Ph), 7.27 (t, 3JHH =6.8 Hz, 1 H,
CHpara of Ph), 7.32 (t, 3JHH =7.2 Hz, 2 H, 2×CHmeta of Ph), 7.35–7.45 (m,
5 H, 5×CH of Ph), 7.85–7.95 (m, 4 H, 4×CH of Ar); 13C NMR: δ 21.5
(CH2CH2CH2), 23.0 (CH2), 36.7 (CH2–CO), 47.3 (CH2Ar), 53.4 (CH),
110.2 (C3 of pyrrole), 116.9 (C3a of pyrrole), 122.4 (2×CH of Ar), 125.9
(2×CH of Ph), 127.3 (CH of Ph), 128.5 (CH of Ph), 128.7 (4×CH of
Ph), 129.4 (Cipso of Ph), 130.4 (2×CH of Ph), 134.9 (2×CH of Ar), 137.1
(C7a of pyrrole), 137.3 (Cipso of Ph), 141.8 (2×Cipso–CO), 144.3 (C2 of
pyrrole). 192.7 (2×C=O), 198.4 (C=O); MS (EI, 70 eV): m/z (%)=445
[M+], 401, 354, 298, 270, 139, 91. Anal. calcd for C30H23NO3 (445.51):
C, 80.88; H, 5.20; N, 3.14; found: C, 80.81; H, 5.26; N, 3.05%.
NMR spectrum of 4f, two methyl groups appeared as a singlet
at δ 0.94 ppm as expected. Three singlets at δ 2.05, 2.59 and
5.18 ppm are attributed to three CH2 groups. The singlet at
δ 4.35 ppm is ascribed to the CH group, and the 14 aromatic
hydrogen atoms gave rise to characteristic resonances in the
aromatic region of the spectrum. Observation of 23 distinct
1
signals in the H-decoupled 13C NMR spectrum of 4f is in
agreement with the proposed structure.
Based on these results, a plausible mechanism for the
construction of 6,7-dihydro-1H-indol-4(5H)-ones is proposed
(Scheme 2). The formation of enaminone 3 occurs through
condensation of 1,3-cyclohexanedione 1 and benzylamine 2.
Then, the enaminone 3 attacks 2-(2-oxo-2-phenylethylidene)-
1H-indene-1,3(2H)-dione in a Michael-type addition to
generate intermediate 5 which tautomerises to the enamine
Table 2 Yields for the conversion of cyclohexanediones 1 and various
benzylamines 2 to the enamines 3 (R1 =H, Me; R2 =various), and thence
to 2-(1-R2-benzyl-4-oxo-2-phenyl-4,5,6,7-tetrahydro-1H-indol-3-yl)-1H-
indene-1,3(2H)-diones 4 (R1 =H, Me; R2 =various) (Scheme 1)
Entry
R1
R2
Product
Yield/%
1
2
3
4
5
6
7
8
9
H
H
H
H
H
2-Cl
4-Cl
4-OCH3
4-CH3
H
2-Cl
4-Cl
4a
4b
4c
4d
4e
4f
4g
4h
4i
67
63
72
65
82
66
70
69
80
78
2-(1-(2-Chlorobenzyl)-4-oxo-2-phenyl-4,5,6,7-tetrahydro-1H-
indol-3-yl)-1H-indene-1,3(2H)-dione (4b): White powder, yield 0.30 g
(63%); m.p. 201–203 °C; IR (KBr): 3060 (aromatic C–H), 2926 and
2862 (alkyl C–H), 1713 (C=O), 1644 (C=C), 1602 and 1466 (Ar), 1255
(C–N) cm–1; 1H NMR: δ 1.90–2.05 (m, 2 H, CH2), 2.10–2.25 (m, 2 H,
CH2), 2.59–2.75 (m, 2 H, CH2), 4.34 (s, 1 H, CH), 5.21 (s, 2 H, CH2Bn),
6.46–6.62 (m, 1 H, CH of Ar), 7.20–7.52 (m, 8 H, 8×CH of Ar),
H
CH3
CH3
CH3
CH3
CH3
4-OCH3
4-CH3
10
4j
O
R1
R1
O
NH2
O
O
O
Ph
R1
R1
R1
R1
Solvent free
O
O
+
O
NH
100 °C, 30 min
N
MeOH, 64
4 h
°
C
R2
R2
O
Ph
R1 = H, Me
R2
1
2
3
4
Scheme 1

168 JOURNAL OF CHEMICAL RESEARCH 2015
O
O
NH2
R1
R1
R1
R1
enaminone formation
+
-
H
2O
NH
O
R2
1
2
3
R2
O
R1
R1
O
O
O
R1
R2
O
Michael addition
HN
R1
N
+
Ph
O
O
O
Ph
5
3
R2
R1
R1
R1
R1
O
O
O
O
R2
R2
imine-enamine
tautomerization
N
HN
O
O
O
O
Ph
5
Ph
6
R1
R1
R1
R1
O
O
O
O
O
5-exo-trig
aromatization
-
cyclization
N
N
H2O
H
O
R2
R2
Ph
Ph
O
7
4
Scheme 2 Mechanistic rationale for the synthesis of 4.
7.82–8.02 (m, 4 H, 4×CH of Ar);. 13C NMR: δ 21.2 (CH2CH2CH2), 23.0
(CH2), 36.7 (CH2–CO), 45.5 (CH2Ar), 53.3 (CH), 110.5 (C3 of pyrrole),
117.0 (C3a of pyrrole), 122.4 (2×CH of Ar), 126.5 (CH of Ar), 127.8 (CH
of Ar), 128.6 (CH of Ph), 128.7 (2×CH of Ph), 129.1 (Cipso of Ph), 129.2
(CH of Ar), 129.4 (CH of Ar), 130.1 (2×CH of Ph), 130.7 (Cipso of Ar),
134.5 (Cipso of Ar), 135.0 (2×CH of Ar), 137.1 (C7a of pyrrole), 141.8
(2×Cipso–CO), 144.5 (C2 of pyrrole). 192.8 (2×C=O), 198.3 (C=O); MS
(EI, 70 eV): m/z (%)=479 [M+], 354, 326, 298, 165, 139, 125, 89. Anal.
calcd for C30H22ClNO3 (479.96): C, 75.07; H, 4.62; N, 2.92; found: C,
75.14; H, 4.68; N, 2.88%.
CH), 5.10 (s, 2 H, CH2Bn), 6.70–6.98 (m, 4 H, 4×CH of Ar), 7.34–7.54
(m, 5 H, 5×CH of Ph), 7.80–8.00 (m, 4 H, 4×CH of Ar); 13C NMR:
δ 21.5 (CH2CH2CH2), 23.0 (CH2), 36.7 (CH2–CO), 46.7 (CH2Ar), 53.4
(CH), 55.0 (OCH3), 110.1 (C3 of pyrrole), 114.1 (2×CH of Ar), 116.8
(C3a of pyrrole), 122.4 (2×CH of Ar), 127.4 (2×CH of Ph), 128.5
(CH of Ph), 128.7 (2×CH of Ph), 129.0 (Cipso of Ar), 129.5 (Cipso of
Ph), 130.4 (2×CH of Ar), 134.9 (2×CH of Ar), 137.0 (C7a of pyrrole),
141.8 (2×Cipso–CO), 144.2 (C2 of pyrrole). 158.4 (Cipso–OMe), 192.7
(2×C=O), 198.5 (C=O); MS (EI, 70 eV): m/z (%)=475 [M+], 354, 298,
139, 121, 91, 77. Anal. calcd for C31H25NO4 (475.54): C, 78.30; H, 5.30;
N, 2.95; found: C, 78.36; H, 5.39; N, 2.89%.
2-(1-(4-Chlorobenzyl)-4-oxo-2-phenyl-4,5,6,7-tetrahydro-1H-indol-
3-yl)-1H-indene-1,3(2H)-dione (4c): White powder, yield 0.35 g (72%);
m.p. 205–207 °C; IR (KBr): 3051 (aromatic C–H), 2939 and 2855
(alkyl C–H), 1712 (C=O), 1641 (C=C), 1590 and 1481 (Ar), 1254 (C–N)
2-(1-(4-Methylbenzyl)-4-oxo-2-phenyl-4,5,6,7-tetrahydro-1H-
indol-3-yl)-1H-indene-1,3(2H)-dione (4e): White powder, yield
0.38 (82%); m.p. 237–239 °C; IR (KBr): 3023 (aromatic C–H), 2939
and 2854 (alkyl C–H), 1713 (C=O), 1639 (C=C), 1600 and 1476 (Ar),
1253 (C–N) cm–1; 1H NMR: δ 1.87–2.01 (m, 2 H, CH2), 2.07–2.18 (m,
2 H, CH2), 2.26 (s, 3 H, CH3), 2.60–2.75 (m, 2 H, CH2), 4.32 (s, 1 H,
1
cm–1; H NMR: δ 1.90–2.03 (m, 2 H, CH2), 2.10–2.20 (m, 2 H, CH2),
2.65–2.76 (m, 2 H, CH2), 4.31 (s, 1 H, CH), 5.18 (s, 2 H, CH2Bn), 6.92
(d, 3JHH =7.2 Hz, 2 H, 2×CH of Ar), 7.38–7.50 (m, 7 H, 7×CH of Ar),
7.85–7.95 (m, 4 H, 4×CH of Ar); 13C NMR: δ 21.4 (CH2CH2CH2), 23.0
(CH2), 36.7 (CH2–CO), 46.7 (CH2Ar), 53.3 (CH), 110.3 (C3 of pyrrole),
116.9 (C3a of pyrrole), 122.4 (2×CH of Ar), 127.8 (2×CH of Ph), 128.6
(CH of Ph), 128.7 (2×CH of Ar), 128.8 (2×CH of Ph), 129.3 (Cipso of
Ph), 130.4 (2×CH of Ar), 131.9 (Cipso–Cl), 135.0 (2×CH of Ar), 136.3
(Cipso of Ar), 137.0 (C7a of pyrrole), 141.8 (2×Cipso–CO), 144.3 (C2 of
pyrrole). 192.7 (2×C=O), 198.4 (C=O); MS (EI, 70 eV): m/z (%)=479
[M+], 354, 298, 165, 139, 125, 89. Anal. calcd for C30H22ClNO3 (479.96):
C, 75.07; H, 4.62; N, 2.92; found: C, 75.13; H, 4.56; N, 2.99%.
2-(1-(4-Methoxybenzyl)-4-oxo-2-phenyl-4,5,6,7-tetrahydro-1H-
indol-3-yl)-1H-indene-1,3(2H)-dione (4d): White powder, yield 0.31 g
(65%); m.p. 223–224 °C; IR (KBr): 3059 (aromatic C–H), 2926 and
2850 (alkyl C–H), 1713 (C=O), 1642 (C=C), 1600, 1509 and 1473 (Ar),
1252 (C–N) cm–1; 1H NMR: δ 1.82–2.02 (m, 2 H, CH2), 2.06–2.22 (m,
2 H, CH2), 2.64–2.85 (m, 2 H, CH2), 3.71 (s, 3 H, OCH3), 4.30 (s, 1 H,
3
CH), 5.13 (s, 2 H, CH2Bn), 6.80 (d, JHH =6.8 Hz, 2 H, 2×CH of Ar),
7.13 (d, 3JHH =6.8 Hz, 2 H, 2×CH of Ar), 7.35–7.46 (m, 5 H, 5×CH of
Ph), 7.84–8.00 (m, 4 H, 4×CH of Ar); 13C NMR: δ 20.6 (CH3), 21.5
(CH2CH2CH2), 23.0 (CH2), 36.7 (CH2–CO), 47.1 (CH2Ar), 53.3 (CH),
110.0 (C3 of pyrrole), 116.8 (C3a of pyrrole), 122.4 (2×CH of Ar), 125.9
(2×CH of Ar), 128.5 (CH of Ph), 128.7 (2×CH of Ph), 129.3 (2×CH
of Ar), 129.4 (Cipso of Ph), 130.4 (2×CH of Ph), 134.2 (Cipso–Me),
135.0 (2×CH of Ar), 136.5 (Cipso of Ar), 137.1 (C7a of pyrrole), 141.8
(2×Cipso–CO), 144.2 (C2 of pyrrole). 192.7 (2×C=O), 198.5 (C=O); MS
(EI, 70 eV): m/z (%)=459 [M+], 354, 298, 165, 139, 105, 77. Anal. calcd
for C31H25NO3 (459.54): C, 81.02; H, 5.48; N, 3.05; found: C, 80.97; H,
5.41; N, 3.12%.
2-(1-Benzyl-6,6-dimethyl-4-oxo-2-phenyl-4,5,6,7-tetrahydro-
1H-indol-3-yl)-1H-indene-1,3(2H)-dione (4f): White powder, yield
0.31 (66%); m.p. 217–219 °C; IR (KBr): 3054 (aromatic C–H), 2931

JOURNAL OF CHEMICAL RESEARCH 2015 169
and 2865 (alkyl C–H), 1714 (C=O), 1649 (C=C), 1603 and 1467 (Ar),
1252 (C–N) cm–1; 1H NMR: δ 0.94 (s, 6 H, 2×CH3), 2.05 (s, 2H, CH2),
2.59 (s, 2 H, CH2), 4.35 (s, 1H, s, CH), 5.18 (s, 2H, CH2Bn), 6.89 (d,
3JHH =6.8 Hz, 2 H, 2×CHortho of Ph), 7.27 (t, 3JHH =6.0 Hz, 1 H, CHpara
2-(6,6-Dimethyl-1-(4-methylbenzyl)-4-oxo-2-phenyl-4,5,6,7-
tetrahydro-1H-indol-3-yl)-1H-indene-1,3(2H)-dione (4j): White
powder, yield 0.38 (78%); m.p. 272–274 °C; IR (KBr): 3024 (aromatic
C–H), 2927 and 2861 (alkyl C–H), 1714 (C=O), 1644 (C=C), 1606
and 1470 (Ar), 1251 (C–N) cm–1; H NMR: δ 0.94 (s, 6 H, 2×CH3),
3
1
of Ph), 7.33 (, t, JHH =6.4 Hz, 2 H, 2×CHmeta of Ph), 7.37–7.45 (m, 5
H, 5×CH of Ph), 7.85–7.95 (m, 4 H, 4×CH of Ar); 13C NMR: δ 28.0
(2×CH3), 35.0 (CH2), 35.2 (CMe2), 47.2 (CH2Ph), 50.7 (CH2–CO), 53.4
(CH), 110.1 (C3 of pyrrole), 115.8 (C3a of pyrrole), 122.4 (2×CH of Ar),
125.7 (2×CH of Ph), 127.3 (CH of Ph), 128.5 (CH of Ph), 128.6 (2×CH
of Ph), 128.7 (2×CH of Ph), 129.4 (Cipso of Ph), 130.3 (2×CH of Ph),
135.0 (2×CH of Ar), 137.3 (C7a of pyrrole), 137.4 (Cipso of Ph), 141.8
(2×Cipso–CO), 143.1 (C2 of pyrrole). 192.1 (2×C=O), 198.5 (C=O); MS
(EI, 70 eV): m/z (%)=473 [M+], 382, 326, 298, 167, 139, 91, 65. Anal.
calcd for C32H27NO3 (473.57): C, 81.16; H, 5.75; N, 2.96; found: C,
81.23; H, 6.00; N, 2.92%.
2-(1-(2-Chlorobenzyl)-6,6-dimethyl-4-oxo-2-phenyl-4,5,6,7-
tetrahydro-1H-indol-3-yl)-1H-indene-1,3(2H)-dione (4g): White
powder, yield 0.36 (70%); m.p. 217–219 °C; IR (KBr): 3049 (aromatic
C–H), 2952 and 2924 (alkyl C–H), 1714 (C=O), 1645 (C=C), 1602 and
1467 (Ar), 1254 (C–N) cm–1; 1H NMR: δ 0.95 (s, 6 H, 2×CH3), 2.07 (s,
2 H, CH2), 2.57 (s, 2 H, CH2), 4.37 (s, 1 H, CH), 5.19 (s, 2 H, CH2Bn),
6.50 (d, 3JHH =6.8 Hz, 2 H, 2×CH of Ar), 7.30–7.42 (m, 7 H, 7×CH of
Ar), 7.46 (d, 3JHH =7.2 Hz, 1 H, CH of Ar), 7.85–7.95 (m, 4 H, 4×CH of
Ar); 13C NMR: δ 28.0 (2×CH3), 34.9 (CMe2), 35.1 (CH2), 45.5 (CH2Ar),
50.8 (CH2–CO), 53.3 (CH), 110.5 (C3 of pyrrole), 116.0 (C3a of pyrrole),
122.4 (2×CH of Ar), 126.4 (CH of Ar), 127.7 (CH of Ar), 128.6 (CH of
Ph), 128.7 (2×CH of Ph), 129.1 (Cipso of Ph), 129.2 (CH of Ar), 129.4
(CH of Ar), 130.0 (2×CH of Ph), 130.6 (Cipso–Cl), 134.7 (Cipso of Ar),
135.0 (2×CH of Ar), 137.3 (C7a of pyrrole), 141.8 (2×Cipso–CO), 143.3
(C2 of pyrrole).192.2 (2×C=O), 198.54 (C=O); MS (EI, 70 eV): m/z
(%)=508 [M+], 507, 416, 382, 326, 298, 167, 139, 125, 89. Anal. calcd
for C32H26ClNO3 (508.01): C, 75.66; H, 5.16; N, 2.76; found: C, 75.58;
H, 5.11; N, 2.83%.
2.04 (s, 2 H, CH2), 2.26 (s, 3 H, CH3), 2.58 (s, 2 H, CH2), 4.33 (s, 1 H,
3
CH), 5.12 (s, 2 H, CH2Bn), 6.78 (d, JHH =6.8 Hz, 2 H, 2×CH of Ar),
3
7.13 (d, JHH =7.2 Hz, 2 H, 2×CH of Ar), 7.36–7.46 (m, 5 H, 5×CH
of Ph), 7.86–7.96 (m, 4H, 4×CH of Ar); 13C NMR: δ 20.6 (CH3), 28.1
(2×CH3), 35.0 (CH2), 35.2 (CMe2), 47.0 (CH2Ar), 50.8 (CH2–CO),
53.4 (CH), 110.1 (C3 of pyrrole), 115.8 (C3a of pyrrole), 122.4 (2×CH of
Ar), 125.6 (2×CH of Ar), 128.4 (CH of Ph), 128.7 (2×CH of Ph), 129.2
(2×CH of Ar), 129.4 (Cipso of Ph), 130.3 (2×CH of Ph), 134.4 (Cipso of
Ar) 135.0 (2×CH of Ar), 136.4 (Cipso of Ar), 137.2 (C7a of pyrrole), 141.8
(2×Cipso–CO), 143.0 (C2 of pyrrole). 192.1 (2×C=O), 198.5 (C=O); MS
(EI, 70 eV): m/z (%)=487 [M+], 382, 326, 298, 133, 105, 83. Anal. calcd
for C33H29NO3 (487.59): C, 81.29; H, 5.99; N, 2.87; found: C, 81.21; H,
6.59; N, 2.78%.
Financial support of this research from Tarbiat Modares
University, Iran is gratefully acknowledged.
Received 23 December 2014; accepted 9 February 2015
Paper 1403098 doi: 10.3184/174751915X14242775299602
Published online: 18 March 2015
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(s, 2 H, CH2Bn), 6.90 (d, JHH =7.6 Hz, 2 H, 2×CH of Ar), 7.35–7.46
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1
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