Reactions of N-and C-alkenylanilines: IX.* synthesis, oxidation, and nitration of some 7-methyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles

Article abstract of DOI:10.1134/S1070428012070123

Heating of 4-acyl-3-iodo-7-methyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b] indoles in piperidine gave 4-acyl-7-methyl-1,3a,4,8b-tetrahydrocyclopenta[b] indoles which were oxidized with KMnO4 to obtain the corresponding 4-acyl-7-methyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole-1,2-diols. Oxidation of 4-acyl-7-methyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles at the olefinic double bond with hydrogen peroxide in acetonitrile in the presence of formic acid afforded stereoisomeric epoxides with cis and trans orientation of the nitrogen-containing and oxirane rings. Nitration with a mixture of ammonium nitrate and trifluoroacetic anhydride produced 5-nitro derivatives. The structure of 1-{(1aR*,1bR*,6bS*,7aS*)-5-methyl-1a,1b,2, 6b,7,7ahexahydrooxireno[4,5]cyclopenta[1,2-b]indol-2-yl}ethanone was determined by X-ray analysis.

Full text of DOI:10.1134/S1070428012070123

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 7, pp. 957–967. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © D.A. Skladchikov, K.Yu. Suponitskii, I.B. Abdrakhmanov, R.R. Gataullin, 2012, published in Zhurnal Organicheskoi Khimii, 2012,
Vol. 48, No. 7, pp. 962–971.
Reactions of N- and C-Alkenylanilines:
IX.* Synthesis, Oxidation, and Nitration of Some
7-Methyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles
D. A. Skladchikova, K. Yu. Suponitskiib, I. B. Abdrakhmanova, and R. R. Gataullina
a Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: gataullin@anrb.ru
b Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Received September 20, 2011
Abstract—Heating of 4-acyl-3-iodo-7-methyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indoles in piperidine gave
4-acyl-7-methyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles which were oxidized with KMnO4 to obtain the
corresponding 4-acyl-7-methyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole-1,2-diols. Oxidation of 4-acyl-7-
methyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles at the olefinic double bond with hydrogen peroxide in aceto-
nitrile in the presence of formic acid afforded stereoisomeric epoxides with cis and trans orientation of the
nitrogen-containing and oxirane rings. Nitration with a mixture of ammonium nitrate and trifluoroacetic
anhydride produced 5-nitro derivatives. The structure of 1-{(1aR*,1bR*,6bS*,7aS*)-5-methyl-1a,1b,2,6b,7,7a-
hexahydrooxireno[4,5]cyclopenta[1,2-b]indol-2-yl}ethanone was determined by X-ray analysis.
DOI: 10.1134/S1070428012070123
Some cyclopenta[b]indoloquinones were reported
[2, 3] to exhibit cancer-specific antitumor activity, in
particular against melanoma. The scheme of their
synthesis included nitration of the aromatic ring and
subsequent reduction of the nitro group to amino. For
example, 3-acetoxy-1-acetyl-7-methylcyclopenta[b]in-
dole was thus converted into aziridinyl-substituted
indoloquinones.
tion product VI with acetic anhydride, ethyl chloro-
formate, or chloroacetyl chloride, respectively. Heating
of compounds IV, V, and VII–IX in boiling piperidine
afforded dehydrohalogenation products X–XIV in
good yields (Scheme 1).
While studying spectral properties of the synthe-
sized compounds we found that signals from some
1
protons in the H NMR spectrum of XII are doubled,
their intensity ratio being 100:28 (in CDCl3; Fig. 1a).
Replacement of the solvent by acetone-d6 changed the
intensity ratio to 100:13 (Fig. 1b). Taking into account
the lack of essential structural reasons, we presumed
that the observed signal doubling results from different
orientations of the N-acyl substituent [5].
The oxidation of XI and XII with potassium
permanganate gave diols XV and XVI, respectively.
N-Acetyl derivative XV was poorly soluble in organic
solvents used to extract it from the reaction mixture.
Therefore, the yield of diol XV was as poor as 10–42%
against 63% for N-tosyl analog XVI. Acetylation of
diols XV and XVI with acetic anhydride in pyridine
afforded diacetates XVII and XVIII. The latter was
also synthesized by reaction of diol XVI with isopro-
With a view to obtain other oxygen-containing
cyclopenta[b]indole derivatives we made an attempt to
synthesize cyclopenta[b]indoles from 2-(cyclopent-2-
en-1-yl)-4-methylaniline (I). The tricyclic skeleton was
built up as a result of formation of C–N bond via
intramolecular amination by the action of iodine. For
this purpose, compound I [4] was treated with meth-
anesulfonyl and p-toluenesulfonyl chlorides, and sul-
fonanilides II and III thus obtained reacted with iodine
to produce 3-iodo-1,2,3,3a,4,8b-hexahydrocyclopenta-
[b]indoles IV and V. Their analogs VII–IX having
an acetyl, ethoxycarbonyl, or chloroacetyl group on the
nitrogen atom were synthesized by reaction of cycliza-
* For communication VIII, see [1].
957

SKLADCHIKOV et al.
958
Scheme 1.
H
MsCl or TsCl
pyridine
I2, NaHCO3
CH2Cl2
Me
Me
Me
I
H
N
NH2
NHTs (Ms)
III (II)
Ts (Ms)
I
V (IV)
I2, NaHCO3
CH2Cl2
Piperidine
reflux
H
H
H
Ac2O or ClC(O)OEt
or ClCH2C(O)Cl
Piperidine
reflux, 5 h
Me
Me
Me
I
I
H
H
H
N
N
N
H
C(O)R
R
VI
VII–IX
X–XIV
VII, R = Me; VIII, R = EtO; IX, R = ClCH2; X, R = MeSO2; XI, R = 4-MeC6H4SO2; XII, R = MeC(O);
XIII, R = EtOC(O); XIV, R = (piperidin-1-yl)acetyl.
penyl acetate in acetonitrile in the presence of TsOH;
in this case the yield of XVIII was comparable with
that in the reaction with acetic anhydride. By nitration
of triacetyl derivative XVII with a mixture of ammo-
nium nitrate and trifluoroacetic anhydride in methylene
chloride at –20°C we obtained 5-nitrocyclopenta[b]in-
dole XIX. N-Tosyl derivative XVIII failed to undergo
nitration under similar conditions. Hydrogenation of
XIX over Raney nickel produced a mixture of approxi-
mately equal amounts of 5-amino and 5-hydroxyamino
(a)
27
98
100
28
6.0
5.5
5.0
4.5
4.0 δ, ppm
(b)
100 13
6.0
5.5
5.0
4.5
4.0 δ, ppm
1
Fig. 1. Fragments of the H NMR spectra of compound XII in (a) CDCl3 and (b) acetone-d6 in the resonance region of the 8b-H,
3a-H, 2-H, and 3-H protons.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

REACTIONS OF N- AND C-ALKENYLANILINES: IX.
959
Scheme 2.
OH
OAc
H
H
H
KMnO4, MeCN
MeOH, H2O, 20°C
Me
Me
Me
Ac2O, pyridine, 20°C
OH
OAc
H
H
H
N
N
N
R
R
R
XI, XII
XV, XVI
XVII, XVIII
OAc
OAc
H
OAc
OAc
H
H
NH4NO3, (F3CCO)2O
CH2Cl2, –30°C, 30 min
H2, Raney Ni
EtOH, 60°C
Me
Me
Me
+
OAc
OAc
H
H
H
N
N
N
Ac
Ac
Ac
NO2
NH2
NHOH
XIX
XX
XXI
XII, XV, XVII, R = Ac; XI, XVI, XVIII, R = Ts.
derivatives XX and XXI. Compounds XX and XXI are
almost insoluble in low-boiling organic solvents, and
we did not succeed in isolating them as pure sub-
stances (Scheme 2).
The structure of epoxide XXIVb was unambigu-
ously determined by X-ray analysis. We failed to ob-
tain single crystals of its analogs XXIIIa, XXIIIb, and
XXIVa, and their structure was confirmed by elemen-
tal analyses and spectral data. According to the X-ray
diffraction data (Fig. 2), both five-membered rings in
molecule XXIVb occur in a flattened envelope con-
formation with the C1b (in the pyrrole ring) and C6b (in
the cyclopentane ring) atoms deviating from the planes
formed by the four other atoms (see table). The oxirane
ring is oriented trans with respect to the hydrogen
atoms on C1b and C6b. The acetyl group on N2 lies in
the dihydropyrrole ring plane, but the intramolecular
contact C3–H3 ···O2 cannot be unambiguously inter-
preted as hydrogen bond only on the basis of geo-
metric parameters (the H3···O2 distance is fairly long,
and the C3H3O2 angle is strongly different from 180°).
A mixture of ammonium nitrate with trifluoroacetic
anhydride used as nitrating agent turned out to be
inactive toward the double bond in the cyclopentene
ring. The nitration of N-ethoxycarbonyl derivative
under analogous conditions gave 90% of 5-nitrocyclo-
penta[b]indole XXII (Scheme 3). The use of sodium
nitrate in sulfuric acid resulted in tarring. Oxidation of
compounds XII and XIII with hydrogen peroxide in
the presence of formic acid led to the formation of
trans- and cis-epoxides XXIIIa/XXIVa and XXIIIb/
XXIVb at ratios of about 1:1, which were similar to
the corresponding isomer ratios obtained previously
[1] from N-mesyl and N-tosyl derivatives (Scheme 4).
Scheme 3.
H
H
NH4NO3, (F3CCO)2O
CH2Cl2, –30°C, 30 min
Me
Me
H
H
N
N
COOEt
COOEt
NO2
XXII
XIII
Scheme 4.
7
H
H
H
7a
O
6
Me
Me
Me
6b
1b
H2O2, MeCN, H2O
1
6a
2a
O
1a
+
2
N
H
H
C(O)R
XXIIIa, XXIIIb
H
N
N
C(O)R
C(O)R
XXIVa, XXIVb
XII, XIII
R = EtO (a), Me (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

SKLADCHIKOV et al.
for structure XXIVb were very consistent with the
960
C10
C5
experimental data (see table). The AIM analysis re-
vealed a set of critical points (3, –1) corresponding to
interatomic bonding interactions. Apart from expected
chemical bonds (Fig. 2), a critical point (3, –1) was
also found between H3 and O2; it was identified as
corresponding to closed shell interaction. From the
correlation between the potential energy density in
critical point and contact energy [12, 13] we estimated
the energy of interaction between the H3 and O2 atoms
at 4.1 kcal/mol. These data allowed us to interpret the
C3–H3···O2 contact as a weak intramolecular H-bond.
C6
C6a
C6b
C1b
N2
C8
C4
C7
O1
C7a
C3 C2a
C1a
O2
1
C9
In the H NMR spectra of XXIIIa/XXIVa and
XXIIIb/XXIVb, the largest difference was observed
between the position of signals from methylene pro-
tons on C7 (AB spin system). anti Isomer XXIIIa dis-
played a difference Δδ of 0.80 ppm between the
chemical shifts of 7-HA and 7-HB which resonated as
Fig. 2. Structure of the molecule of 1-{(1aR*,1bR*,6bS*,7aS*)-
5-methyl-1a,1b,2,6b,7,7a-hexahydrooxireno[4,5]cyclopenta-
[1,2-b]indol-2-yl}ethan-1-one (XXIVb) according to the
X-ray diffraction data; non-hydrogen atoms are shown as
thermal vibration ellipsoids with a probability of 50%.
2
doublets of doublets at δ 1.84 (J7A, 6b = 4.0, J =
2
14.4 Hz) and 2.64 ppm (J7B,6b = 9.0, J = 14.4 Hz),
respectively, which might be expected for interactions
between the corresponding protons and syn- or anti-
oriented epoxide ring. Presumably, the coupling con-
stants of protons in the oxirane ring (7a-H and 1a-H)
with 7-HA, 7-HB, and 1b-H are too small. Therefore,
Geometric parameters of molecule XXIVb were
calculated in terms of the density functional theory
(M052X/6-31G**) using GAUSSIAN software pack-
age [6], followed by analysis in terms of the Atoms in
Molecule (AIM) topological theory [7, 8]. This ap-
proximation was successfully used previously to ana-
lyze the structure of various heterocyclic and π-con-
jugated molecules [9, 10]. The results of calculations
1
their signals in the H NMR spectra of both stereo-
isomers appear as one-proton singlets at δ 3.55 and
3.92 ppm (anti- XXIIIa) and δ 3.63 and 3.88 ppm
(syn-XXIVa). The 1b-H proton shows an appreciable
Principal experimental and calculated (M052X/6-31G**) geometric parameters of the molecule of 1-{(1aR*,1bR*,6bS*,7aS*)-
5-methyl-1a,1b,2,6b,7,7a-hexahydrooxireno[4,5]cyclopenta[1,2-b]indol-2-yl}ethan-1-one (XXIVb)
Parameter
X-Ray diffraction
M052X/6-31G**
Deviation of C1b from the N2C2aC6aC6b plane, Å
000.188(7)
000.263(8)
60.1(2)0
000.243
000.300
63.40
Deviation of C6b from the C7C7aC1aC1b plane, Å
Dihedral angle between the C1bN2C2aC6aC6b and C6bC7C7aC1aC1b rings, deg
Dihedral angles, deg
C3C2aN2C8
–9.6(7)–
0.7(7)
–9.1–
2.5
C2aN2C8O2
Fragmenta C3–H3···O2
C3–H3, Å
1.080
(0)2.857(6)
2.250
01.08
002.873
02.27
C3 ···O2, Å
H3···O2, Å
∠C3H3O2, deg
113.30000
113.500
a
Experimental geometric parameters were calculated for the C3–H3 bond normalized by a standard length of 1.08 Å [11] (neutron diffrac-
tion data), which coincided with the results of quantum-chemical calculations.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

REACTIONS OF N- AND C-ALKENYLANILINES: IX.
EXPERIMENTAL
961
coupling constant (J > 9 Hz) only with 6b-H and gives
a doublet in the spectra of both syn and anti isomers.
The IR spectra were recorded on a UR-20 spec-
trometer. The 1H and 13C NMR spectra were measured
on a Bruker AM-300 spectrometer at 300.13 and
75.47 MHz, respectively. The elemental compositions
were determined on an M-185B CHN analyzer. Silica
gel LS (40–100 μm, Lancaster) was used for column
chromatography. Qualitative TLC analysis was per-
formed on Sorbfil plates (Sorbpolimer, Krasnodar);
spots were detected by treatment with iodine vapor.
Like compound XII (see above), some signals in
the 1H NMR spectrum of syn-XXIVa were doubled. In
CDCl3 the intensity ratio for the 1b-H, 6b-H, OEt, 3-H,
and 4-H protons was 1 :2. The difference in the
chemical shifts of the aromatic 6-H proton (doubled
signal) was 0.4 ppm. The differences for the other
protons were smaller, and their signals were poorly
resolved in CDCl3. Replacement of the solvent by
acetone-d6 changed the signal intensity ratio in the
1H NMR spectrum of syn-XXIVa to the opposite
(~20:1). In this solvent, signals from the geminal 7-HA
and 7-HB protons were well resolved. The 7-HA proton
Colorless whisker single crystals of XXIVb were
obtained by slow crystallization from 95% ethanol.
The X-ray diffraction data were acquired at 100 K
from a 0.12×0.01×0.01-mm single crystal on a Bruker
SMART APEX II diffractometer (λMoKα radiation,
θmax = 52.0°). Rhombic crystals, C14H15NO2
(M 229.27), with the following unit cell parameters
(100 K): a = 5.068(4), b = 14.553(10), c =
14.898(10) Å; V = 1098.8(13) Å3; space group
P212121; Z = 4, dcalc = 1.386 g/cm3. Total of 10389 re-
flection intensities were measured and processed using
SAINT and SADABS programs included into APEX2
software package [14]. The structure was solved by the
direct method and was refined against F2hkl by the full-
matrix least-squares procedure in anisotropic approxi-
mation for non-hydrogen atoms. Hydrogen atoms were
placed into positions calculated on the basis of
geometry considerations and were refined according to
the riding model [Uiso(H) = nUeq(C), where n = 1.5 for
methyl carbon atoms and n = 1.2 for other carbon
atoms]. The structure was refined using 1289 inde-
pendent reflections. The final divergence factors were
wR2 = 0.1420 (all independent reflections) and R1 =
0.0606 [860 reflections with I > 2σ(I)]. All calculations
were performed on an IBM PC with the aid of
SHELXTL software package [15]. The coordinates of
atoms and their temperature factors were deposited to
the Cambridge Crystallographic Data Centre (entry
no. CCDC 820 748) and are available at http://
www.ccdc.cam.ac.uk/products/csd/request/.
2
resonated as a doublet of doublets (J7A,7a = 2.0, J =
14.6 Hz) with no coupling from 6b-H, whereas the
7-HB signal was a double doublet of doublets at
δ 2.41 ppm characterized by a fairly large coupling
2
constant with 6b-H (J7B, 7a = 1.8, J7B,6b = 9.6, J =
14.6 Hz). Well resolved signals from 6b-H (d.d,
J6b,7B = 9.6, J6b,1a = 10.1 Hz) and 1a-H (s, δ 3.82 ppm)
were also observed in the spectrum recorded from
a solution in acetone-d6. The 7a-H proton gave rise to
a doublet of doublets (J7a,7A = 1.8, J7a,7B = 2.0 Hz),
while its coupling with 1a-H was likely to be too small
to be detected. The 1b-H proton (d.d) displayed cou-
pling only with 6b-H (J1b,6b = 10.1 Hz).
Analysis of the proton magnetic resonance spectra
revealed the existence in solution of two forms of
compound XXIVb, which were not identified. In the
1H NMR spectrum of XXIVb in CDCl3 the intensity
ratio of the double signals was 1:1, and it changed to
~1:3 in going to acetone-d6. The solvent nature did not
affect resolution of signals from protons in the epoxide
ring; in both cases, small coupling constants could not
be estimated because of insufficiently high resolution
of the NMR spectrometer, and the 1a-H and 7a-H
signals appeared as singlets. The 6b-H signal of
XXIVb (CDCl3), as in the spectrum of XXIVa, was
doubled, and it appeared as a doublet of triplets at
δ 3.83 ppm and a triplet at δ 3.89 ppm. In the spectrum
of XXIVb in acetone-d6, the 6b-H signal was not
doubled (t, δ 4.03 ppm, J6b,7A = 9.5, J6b,1b = 9.5 Hz),
whereas the 1b-H signal in CDCl3 was doubled with
an appreciable difference in the chemical shifts
(δ 4.75 ppm, d.d, J1b, 1a = 1.75, J1b, 6b = 9.5 Hz;
δ 5.08 ppm, d.d, J1b,1a = 1.7, J1b, 6b = 9.5 Hz; Δδ =
0.33 ppm). The corresponding difference in acetone-d6
is much smaller (Δδ = 0.06 ppm), and the less intense
signal is located in a weaker field (δ 5.04 ppm) relative
to the more intense one (δ 4.98 ppm).
N-[2-(Cyclopent-2-en-1-yl)-4-methylphenyl]-
methanesulfonamide (II). Methanesulfonyl chloride,
1.26 g (11 mmol), was added to a solution of 1.73 g
(10 mmol) of compound I in 20 ml of benzene and
4 ml of triethylamine, and the mixture was left to stand
for 48 h at 20°C. The mixture was treated with 10 ml
of water and stirred for 30 min to decompose excess
methanesulfonyl chloride, 10 ml of benzene was
added, the aqueous phase was separated, and the or-
ganic phase was washed with water (10 ml) and dried
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

SKLADCHIKOV et al.
962
over MgSO4. The solvent was distilled off, and the
residue was crystallized from ethanol. Yield 2.03 g
[b]indole (V) was synthesized from 4.3 g
(13.13 mmol) of II and 3.3 g (13.13 mmol) of I2 in the
presence of 12 g of NaHCO3. Yield 4.93 g (83%).
Colorless crystals, mp 154–155°C (from EtOH).
1H NMR spectrum (CDCl3), δ, ppm: 1.60–2.65 m (4H,
CH2), 2.25 s (3H, CH3), 2.35 s (3H, CH3), 3.65 t (1H,
8b-H, J = 8.5 Hz), 4.75 d (1H, 3a-H, J = 8.5 Hz),
4.90 d (1H, 3-H, J = 4.0 Hz), 6.85 s (1H, 8-H), 7.00 d
(1H, Harom, J = 8.0 Hz), 7.22 d (2H, 2′-H, 4′-H, J =
8.1 Hz), 7.50 d (1H, Harom, J = 8.0 Hz), 7.65 d (2H,
3′-H, 5′-H, J = 8.1 Hz). Found, %: C 50.14; H 4.25;
I 27.78; N 2.90; S 6.87. C19H20INO2S. Calculated, %:
C 50.34; H 4.45; I 27.99; N 3.09; S 7.07.
1
(81%), mp 81–84°C. H NMR spectrum (CDCl3), δ,
ppm: 1.60–2.60 m (4H, CH2), 2.33 s (3H, CH3), 3.00 s
(3H, CH3), 4.02–4.12 m (1H, 1-H), 5.70–5.80 m (1H,
2-H), 6.10 quint (1H, 3′-H, J = 2.3 Hz), 6.50 s (1H,
NH), 7.01 s (1H, 3-H), 7.04 d (1H, 5-H, J = 7.9 Hz),
7.32 d (1H, 6-H, J = 7.9 Hz). Found, %: C 61.95;
H 6.72; N 5.35; S 12.56. C13H17NO2S. Calculated, %:
C 62.12; H 6.82; N 5.57; S 12.76.
N-[2-(Cyclopent-2-en-1-yl)-4-methylphenyl]-4-
methylbenzenesulfonamide (III) was synthesized in
a similar way from 1.73 g (10 mmol) of I and 2.06 g
(10.5 mmol) of p-toluenesulfonyl chloride. Yield
(3R*,3aR*,8bS*)-3-Iodo-7-methyl-1,2,3,3a,4,8b-
hexahydrocyclopenta[b]indole (VI) was synthesized
from 0.478 g (2 mmol) of I and 0.504 g (2 mmol) of I2
in the presence of 2 g of NaHCO3. The product was
isolated by column chromatography on silica gel using
benzene as eluent. Yield 0.352 g (59%), dark viscous
1
2.68 g (82%). H NMR spectrum (CDCl3), δ, ppm:
1.33–2.50 m (4H, CH2), 2.20 s (3H, CH3), 2.25 s (3H,
CH3), 3.78 m (1H, 1-H, J = 2.3 Hz), 5.44 d.q (1H,
3′-H, J = 2.0, 5.5 Hz), 5.95 d.quint (1H, 2-H, J = 2.3,
5.5 Hz), 6.50 s (1H, NH), 6.86 d (1H, 3-H, J = 1.8 Hz),
6.93 d.d (1H, 6-H, J = 1.8, 8.1 Hz), 7.17–7.25 m (3H,
5-H, 3″-H, 5″-H), 7.61 d (2H, 2″-H, 6″-H, J = 8.3 Hz).
Found, %: C 69.59; H 6.25; N 4.09; S 9.59.
C19H21NO2S. Calculated, %: C 69.69; H 6.46; N 4.28;
S 9.79.
1
material. H NMR spectrum (CDCl3), δ, ppm: 1.75–
2.60 m (4H, CH2), 2.20 s (3H, CH3), 3.92 t (1H, 8b-H,
J = 9.0 Hz), 4.25 m (1H, 3-H), 4.73 d (1H, 3a-H, J =
9.0 Hz), 6.47 d and 6.82 d (1H each, 6-H, 7-H, J =
7.9 Hz), 6.90 s (1H, 8-H). Found, %: C 47.98; H 4.52;
I 42.22; N 4.48. C12H14IN. Calculated, %: C 48.18;
H 4.72; I 42.42; N 4.68.
(3R*,3aR*,8bS*)-3-Iodo-4-methylsulfonyl-7-
methyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole
(IV). Compound II, 0.478 g (2 mmol), was dissolved
in 10 ml of methylene chloride, 0.508 g (2 mmol) of
iodine and 2 g of NaHCO3 were added, and the
mixture was stirred for 48 h at room temperature, the
progress of the reaction being monitored by TLC using
benzene as eluent. The mixture was treated with 20 ml
of methylene chloride and 10 ml of 5% aqueous
Na2S2O3 and stirred, the organic phase was separated,
washed with 10 ml of 5% aqueous Na2S2O3 and 10 ml
of water, and dried over MgSO4, the solvent was dis-
tilled off, and the residue was passed through a short
column charged with silica gel for clarification using
benzene as eluent. Yield 0.62 g (82%), mp 173–178°C
1-[(3R*,3aR*,8bS*)-3-Iodo-7-methyl-2,3,3a,8b-
tetrahydrocyclopenta[b]indol-4(1H)-yl]ethanone
(VII). a. Acetic anhydride, 2.08 g, was added to
a solution of 0.478 g (2 mmol) of compound VI in
10 ml of methylene chloride, and the mixture was left
to stand for 24 h at 20°C. The mixture was treated with
10 ml of water and stirred for 30 min to decompose
excess acetic anhydride, the organic phase was separat-
ed and dried over MgSO4, the solvent was distilled off,
and the residue was crystallized from benzene. Yield
1
0.506 g (74%), mp 116°C (from benzene). H NMR
spectrum (CDCl3), δ, ppm: 2.00–2.70 m (4H, CH2),
2.43 s (3H, CH3), 2.47 s (3H, CH3), 4.00 t (1H, 8b-H,
J = 8.2 Hz), 4.43 d (1H, 3-H, J = 5.1 Hz), 4.08 d (1H,
3a-H, J = 8.2 Hz), 6.95 m (2H, Harom), 8.00 d (1H,
Harom, J = 7.9 Hz). Found, %: C 49.08; H 4.52; I 37.00;
N 3.91. C14H16INO. Calculated, %: C 49.28; H 4.73;
I 37.19; N 4.11.
1
(from EtOH). H NMR spectrum (CDCl3), δ, ppm:
2.20 s (3H, CH3), 2.87 s (3H, CH3), 3.92 t (1H, 8b-H,
J = 9.0 Hz), 4.25 m (1H, 3-H), 4.73 d (1H, 3a-H, J =
9.0 Hz), 6.47 d (1H, Harom, J = 7.9 Hz), 6.82 d (1H,
Harom, J = 7.9 Hz), 6.90 s (1H, 8-H). Found, %:
C 41. 29; H 4. 09; I 33. 44; N 3. 51; S 8. 30.
C13H16INO2S. Calculated, %: C 41.39; H 4.28; I 33.64;
N 3.71; S 8.50.
b. N-[2-(1-Cyclopenten-3-yl)-4-methylphenyl]acet-
amide, 2.15 g (10 mmol), was dissolved in 50 ml of
methylene chloride, 2.54 g (10 mmol) of I2 and 10 g of
NaHCO3 were added, and the mixture was stirred for
48 h at room temperature, the progress of the reaction
being monitored by TLC using benzene as eluent.
Compounds V and VI were synthesized in a similar
way.
(3R*,3aR*,8bS*)-3-Iodo-4-methylphenylsul-
fonyl-7-methyl-1,2,3,3a,4,8b-hexahydrocyclopenta-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

REACTIONS OF N- AND C-ALKENYLANILINES: IX.
963
When the reaction was complete, the mixture was
treated with 20 ml of water and stirred, 20 ml of
5% aqueous Na2S2O3 was added, the mixture was
stirred, the organic phase was separated, washed with
10 ml of 5% aqueous Na2S2O3 and 10 ml of water, and
dried over magnesium sulfate, the solvent was distilled
off, and the residue was crystallized from ethanol.
Yield 2 g (59%).
was obtained from 3.5 g (7.8 mmol) of V. Yield 2.1 g
1
(84%), mp 161–165°C (from EtOH). H NMR spec-
trum (CDCl3), δ, ppm: 2.30 s (3H, CH3), 2.38 s (3H,
2
CH3), 2.60 d.quint (1H, 1-HA, J = 2.0, J = 16.8 Hz),
2
2.95 d.d.quint (1H, 1-HB, J = 2.0, 8.4, J = 16.8 Hz),
3.55 t (1H, 8b-H, J = 8.0 Hz), 5.20–5.27 d.quint (1H,
3a-H, J = 2.0, 8.4 Hz), 5.83–5.91 m (2H, 2-H, 3-H),
6.87 s (1H, 8-H), 7.02 d.d (1H, 5-H, J = 0.8, 8.1 Hz),
7.18 d (2H, 3-H, 5′-H, J = 8.0 Hz), 7.51 d (1H, 6-H,
J = 8.1 Hz), 7.59 d.d (2H, 2′-H, 6′-H, J = 8.0 Hz).
Found, %: C 69.92; H 5.68; N 4.10; S 9.65.
C19H19NO2S. Calculated, %: C 70.13; H 5.88; N 4.30;
S 9.85.
2-Chloro-1-[(3R*,3aR*,8bS*)-3-iodo-7-methyl-
2,3,3a,8b-tetrahydrocyclopenta[b]indol-4(1H)-yl]-
ethanone (IX). Compound VI, 5.1 g (17 mmol), was
dissolved in methylene chloride, 5 g of K2CO3 was
added, and 2.3 g (20.35 mmol) of chloroacetyl chloride
was added dropwise under continuous stirring. The
mixture was stirred until the reaction was complete
(TLC), 20 ml of water was added, the mixture was
stirred, the organic phase was separated and dried over
MgSO4, the solvent was removed, and the residue was
crystallized from benzene. Yield 5.3 g (83%), mp 156–
157°C (decomp.). 1H NMR spectrum (CDCl3), δ, ppm:
1.60–1.75 m, 2.00–2.10 m, and 2.55–2.70 m (4H, 1-H,
2-H); 4.05 m (1H, 8b-H), 4.20 d and 4.30 d (1H each,
1-[(3aS*,8bS*)-7-Methyl-3a,8b-dihydrocyclo-
penta[b]indol-4(1H)-yl]ethanone (XII) was obtained
from 0.4 g (1.1 mmol) of VII. Yield 0.208 g (89%),
1
mp 133–135°C (from EtOH). H NMR spectrum
(CDCl3), δ, ppm: 2.31 s (3H, CH3); 2.34 s and 2.42 s
(3:1, CH3); 2.65 d (1H, 1-HA, J = 16.9 Hz), 2.95 d.d.q
(1H, 1-HB, J = 2.0, 8.3, 16.9 Hz), 3.82 t (minor signal,
1H, 8b-H, J = 8.3 Hz), 3.98 t (major signal, 1H, 8b-H,
J = 9.0 Hz), 5.34 d.quint (major signal, 1H, 3a-H, J =
1.6, 8.3 Hz), 5.60 d (minor, 1H, 3a-H, J = 9.0 Hz),
5.68–5.75 m and 5.90–5.93 m (major, 1H each, 2-H,
3-H), 5.79–5.82 m and 5.83–5.88 m (minor, 1H each,
2
CH2Cl, J = 12.6 Hz), 4.45 d (1H, 3-H, J = 5.5 Hz),
5.20 d (1H, 3a-H, J = 8.0 Hz), 6.95 s (1H, 8-H), 7.05 d
(1H, 5-H, J = 7.4 Hz), 8.00 d (1H, 6-H, J = 7.4 Hz).
Found, %: C 44.68; H 3.98; Cl 9.37; I 33.68; N 3.69.
C14H15ClINO. Calculated, %: C 44.77; H 4.02;
Cl 9.44; I 33.78; N 3.73.
2-H, 3-H), 6.90–7.00 m (2H, Harom), 8.00 d (1H, 6-H,
13C
J = 8.0 Hz).
NMR spectrum (DMSO-d6), δC, ppm:
20.6/20.8 and 23.6/24.5 (CH3), 39.5/39.9 (CH2),
40.4/42.3 (C8b), 70.6/71.2 (C3a), 114.0/117.1 (C3);
124.6, 126.1, 128.0, 128.2, 128.3, 129.4, 132.5, 134.3
(C2, C5, C6, C8); 132.9, 133.4, 135.5, 137.8, 138.0,
138.9 (C4a, C7, C8a); 176.67/176.68 (C=O). Found, %:
C 78.64; H 6.90; N 6.37. C14H15NO. Calculated, %:
C 78.84; H 7.09; N 6.57.
(3aS*,8bS*)-7-Methyl-4-methylsulfonyl-
1,3a,4,8b-tetrahydrocyclopenta[b]indole (X). A mix-
ture of 0.4 g (0.8 mmol) of compound IV and 2 ml of
piperidine was heated for 10 h at 110°C. The solvent
was distilled off under reduced pressure, the residue
was dissolved in 50 ml of methylene chloride, the
solution was washed with water and dried over
MgSO4, the solvent was removed, and the residue was
crystallized from ethanol. Yield 0.165 g (83%),
Ethyl (3aS*,8bS*)-7-methyl-3a,8b-dihydrocyclo-
penta[b]indole-4(1H)-carboxylate (XIII). Crude
product VI (27.1 g), obtained by iodocyclization of
17.3 g of cyclopentenylaniline I and appropriate treat-
ment of the reaction mixture, was dissolved 150 ml of
methylene chloride, 46.6 g of potassium carbonate was
added, and a solution of 12.7 ml of ethyl chloroformate
in 50 ml of methylene chloride was added dropwise to
the resulting suspension under stirring at room tem-
perature. When the reaction was complete, the mixture
was treated with 100 ml of water and stirred for
20 min, the organic phase was separated, washed with
water, and dried over MgSO4, the solvent was
removed, the residue (32 g of crude product VIII) was
dissolved in 50 ml of piperidine, and the solution was
heated for 5 h under reflux. Excess piperidine was
removed under reduced pressure, the residue was
1
mp 123–125°C (from EtOH). H NMR spectrum
(CDCl3), δ, ppm: 2.32 s (3H, CH3), 2.60 d.quint (1H,
2
1-HA, J = 2.0, J = 17.0 Hz), 2.85 s (3H, CH3),
2
2.98 d.d.quint (1H, 1-HB, J = 2.0, 8.7, J = 17.0 Hz),
4.08 t (1H, 8b-H, J = 2.0, 8.7 Hz), 5.35 d.quint (1H,
3a-H, J = 2.0, 8.7 Hz), 5.87–5.97 m (2H, 2-H, 3-H),
7.01 d (1H, Harom, J = 8.0 Hz), 7.04 s (1H, 8-H), 7.29 d
(1H, Harom, J = 8.0 Hz). Found, %: C 62.43; H 5.90;
N 5.42; S 12.66. C13H15NO2S. Calculated, %: C 62.63;
H 6.06; N 5.62; S 12.86.
Compounds XI and XII were synthesized in a sim-
ilar way.
(3aS*,8bS*)-7-Methyl-4-(4-methylphenylsul-
fonyl)-1,3a,4,8b-tetrahydrocyclopenta[b]indole (XI)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

SKLADCHIKOV et al.
964
dissolved in 150 ml of methylene chloride, and the
organic phase was washed with water and with a solu-
tion of NaHCO3 and dried over MgSO4. Volatile sub-
stances were removed, and the residue was distilled in
vacuo. Yield 11.5 g (47%), viscous material which
8.15 d (1H, 6-H, J = 8.0 Hz). Found, %: C 76.91;
H 8.12; N 9.42. C19H24N2O. Calculated, %: C 76.99;
H 8.16; N 9.45.
1-[2,3-Dihydroxy-7-methyl-2,3,3a,8b-tetrahydro-
cyclopenta[b]indol-4(1H)-yl]ethanone (XV). A solu-
tion of 1.18 g (7.5 mmol) of KMnO4 in 12 ml of water
was added under stirring to a solution of 0.49 g
(2.2 mmol) of XII in a mixture of 30 ml of acetonitrile
and 17 ml of methanol. The mixture was stirred for 6 h
at room temperature, the precipitate of MnO2 was
filtered off and washed with methylene chloride on
a filter, organic solvents were evaporated from the
filtrate, the residue was diluted with 25 ml of water,
saturated with sodium chloride, and extracted with
methylene chloride (3×50 ml). The extracts were dried
over MgSO4, the solvent was removed, and the residue
was crystallized from benzene. Yield 0.25 g (46%),
1
gradually crystallized, bp 152°C (2 mm). H NMR
spectrum (CDCl3), δ, ppm: 1.40 br.s (3H, CH3), 2.30 s
(3H, CH3), 2.58 d (1H, 1-HA, J = 17.0 Hz), 2.97 d.d
(1H, 1-HB, J = 8.0, 17.0 Hz), 3.95 t (1H, 8b-H, J =
8.0 Hz), 4.25–4.40 m (2H, CH2), 5.33–5.45 m (1H,
3a-H), 5.85–6.03 m (2H, 2-H, 3-H), 6.90–7.05 m (2H,
Harom), 7.73 d (1H, Harom, J = 7.1 Hz). 13C NMR spec-
trum (CDCl3), δC, ppm: 14.6 and 20.8 (CH3), 40.1 (C1),
41,7 (C8b), 60.9 (CH2), 70.3 (C3a), 114.7 (C5); 124.8,
128.3, 129.3, 133.1 (C6, C8, C2, C3); 132.1, 135.1,
138.5 (C4a, C7, C8a). Found, %: C 73.96; H 6.99; N 5.71.
C15H17NO2. Calculated, %: C 74.05; H 7.04; N 5.76.
1
mp 246–248°C (from MeOH). H NMR spectrum, δ,
1-[(3aS*,8bS*)-7-Methyl-3a,8b-dihydrocyclo-
penta[b]indol-4(1H)-yl]-2-(piperidin-1-yl)ethanone
(XIV). Crude product VI, 5.5 g [obtained by iodo-
cyclization of 3.46 g (20 mmol) of cyclopentenyl-
aniline I and appropriate treatment of the reaction
mixture] was dissolved in 50 ml of methylene chloride,
6.5 g of K2CO3 was added, and 2.3 g (20 mmol) of
chloroacetyl chloride in 10 ml of methylene chloride
was added dropwise under stirring at room temperature
to the resulting suspension. The mixture was then
treated with 15 ml of water and stirred for 20 min, and
the organic phase was separated, washed with water,
and dried over MgSO4. Removal of the solvent gave
5.8 g of crude compound XIV which was dissolved in
20 ml of piperidine, the solution was heated for 5 h
under reflux, and excess piperidine was distilled off
under reduced pressure. The residue was dissolved in
150 ml of methylene chloride, the solution was washed
with water, a saturated solution of NaHCO3 until CO2
no longer evolved, and water again, and dried over
MgSO4, the solvent was removed under reduced pres-
sure, and the residue was purified by chromatography
on silica gel. Yield 3.61 g (61%, calculated on the
initial aniline I). Compound XIV was isolated as
a viscous material which gradually transformed into
ppm: in (CDCl3: 1.61 d.d.d (1H, 1-HA, J = 3.6, 8.6,
14.0 Hz), 2.40 m (1H, 1-HB), 2.25 s (3H, CH3), 2.43 s
(3H, CH3), 3.87 d.d (1H, 3-H, J = 3.5, 6.2 Hz), 3.98 q
(1H, 8b-H, J = 10.6 Hz), 4.12 m (1H, 2-H), 4.71 d.d
(1H, 3a-H, J = 6.3, 10.6 Hz), 6.95 s (3H, Harom); in
DMSO-d6: 1.81 d.t (1H, 1-HA, J = 3.6, 12.6 Hz),
2.18 d.t (1H, 1-HB, J = 9.0, 12.6 Hz), 2.25 s (3H, CH3),
2.28 s (3H, CH3), 3.60 m (1H, 2-H), 3.73 q (1H, 3-H,
J = 3.8 Hz), 3.81 t (1H, 8b-H, J = 9.0 Hz), 4.51 d.d
(1H, 3a-H, J = 3.6, 9.0 Hz), 4.78 d (1H, OH, J =
4.9 Hz), 5.07 d (1H, OH, J = 4.7 Hz), 6.90 d (1H,
Harom, J = 8.0 Hz), 7.02 s (1H, 8-H), 7.39 d (1H, Harom
,
J = 8.0 Hz). 13C NMR spectrum (DMSO-d6), δC, ppm:
20.05 and 23.6 (CH3), 36.6 (C1), 40.5 (C8b); 69.3, 71.7,
78.6 (C2, C3, C3a); 115.9, 124.5, 127.5 (C5, C6, C8);
132.6, 135.7, 140.0 (C4a, C7, C8a); 168.8 (C=O).
Found, %: C 67.79; H 6.73; N 5.46. C14H17NO3. Cal-
culated, %: C 68.00; H 6.93; N 5.66.
7-Methyl-4-(4-methylphenylsulfonyl)-
1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole-2,3-diol
(XVI) was synthesized in a similar way from 0.72 g
(2.2 mmol) of compound XI. Yield 0.49 g (63%),
mp 165–166°C (benzene). 1H NMR spectrum (CDCl3),
δ, ppm: 1.65–1.67 m (1H, 1-HA), 2.25 s (3H, CH3),
2.37 s (3H, CH3), 2.35–2.50 m (1H, 1-HB), 2.70 br.s
(1H, OH), 3.60 br.s (1H, OH), 3.80–3.90 m (1H,
8b-H), 4.20–4.35 m (3H, 2-H, 3-H, 3a-H), 6.85 s (1H,
1
colorless powder, Rf = 0.2 (benzene). H NMR spec-
trum (CDCl3), δ, ppm: 1.50–1.75 m, 2.55–2.75 m, and
3.15–3.26 m (10H, CH2); 2.35 s (3H, CH3), 2.70 d
(1H, 1-HA, J = 17.3 Hz), 3.05 d.d (1H, 1-HB, J = 5.5,
17.3 Hz), 3.34 d and 3.49 d (2H, 4-CH2, 2J = 14.0 Hz),
4.08 t (1H, 8b-H, J = 8.0 Hz), 5.71 d (1H, 3a-H, J =
8.0 Hz), 5.89–5.93 m (1H, 2-H), 5.95–6.02 m (1H,
3-H), 7.06 s (1H, 8-H), 7.11 d (1H, 5-H, J = 8.0 Hz),
8-H), 7.01 d (1H, Harom, J = 7.9 Hz), 7.20 d (2H, Harom
,
J = 8.2 Hz), 7.51 d (1H, Harom, J = 7.9 Hz), 7.67 d (2H,
Harom, J = 8.2 Hz). Found, %: C 63.29; H 5.69; N 3.70;
S 8.72. C19H21NO4S. Calculated, %: C 63.49; H 5.89;
N 3.90; S 8.92.
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REACTIONS OF N- AND C-ALKENYLANILINES: IX.
965
with 10 ml of water and extracted with methylene
chloride (30 ml), the extract was washed with water
and dried over Na2SO4, the solvent was removed under
reduced pressure, and the residue was crystallized from
ethanol. Yield 0.341 g (90%), mp 235–237°C (from
4-Acetyl-7-methyl-1,2,3,3a,4,8b-hexahydrocyclo-
penta[b]indole-2,3-diyl diacetate (XVII). Diol XV,
0.53 g (2.14 mmol), was dissolved in 3 ml of pyridine,
2 ml of acetic anhydride and 3 ml of chloroform were
added, and the mixture was left to stand for 24 h at
20°C. The mixture was treated with 10 ml of water and
shaken to decompose excess acetic anhydride, 60 ml of
methylene chloride and 10 ml of water were added,
and the mixture was shaken in a separatory funnel. The
organic phase was washed with 20 ml of 2% hydro-
chloric acid, water, and 10 ml of a saturated aqueous
solution of NaHCO3, dried over MgSO4, and evapo-
rated. Yield 0.637 g (91%), mp 246–248°C (from
1
EtOH). H NMR spectrum (CDCl3), δ, ppm: 2.10 s,
2.15 s, 2.30 s, and 2.39 s (3H each, CH3), 2.13 d.d (1H,
2
1-HA, J = 4.0, J = 14.4 Hz), 2.54 d.d.d (1H, 1-HB, J =
2
4.4, 8.4, J = 14.4 Hz), 4.12 d.t (1H, 8b-H, J = 4.4,
9.2 Hz), 4.89 d.d (1H, 3a-H, J = 6.5, 9.2 Hz), 5.17 d.d
(1H, 3-H, J = 4.0, 6.5 Hz), 5.28 q (1H, 2-H, J =
4.0 Hz), 7.20 s and 7.51 s (1H each, 6-H, 8-H).
13C NMR spectrum (CDCl3), δC, ppm: 20.5, 20.6, 20.7,
22.8 (CH3); 34.7 (C1), 40.5 (C8b), 67.6 (C3a), 72.1 (C3),
78.2 (C2), 123.2 (C6), 128.8 (C8), 130.5 (C4a), 135.8
(C8a), 139.3 (C7), 140.8 (C5); 169.1, 169.6, 169.8
(C=O). Found, %: C 57.31; H 5.28; N 7.36.
C18H20N2O7. Calculated, %: C 57.44; H 5.36; N 7.44.
1
MeOH). H NMR spectrum (CDCl3), δ, ppm: 1.98 s,
2.08 s, 2.19 s, and 2.25 s (3H each, CH3), 2.12–2.35 m
(2H, CH2), 4.05 m (1H, 8b-H), 4.80–4.90 m (2H, 2-H,
3a-H), 5.11 t (1H, 3-H, J = 3.7 Hz), 7.00 d (1H, Harom
,
J = 8.2 Hz), 7.10 s (1H, 8-H), 7.85 d (1H, Harom, J =
8.2 Hz). 13C NMR spectrum (DMSO-d6), δC, ppm:
20.04, 20.05, 20.06, and 23.4 (CH3); 34.1 (C1), 40.2
(C8b); 66.7, 71.9, 77.2 (C2, C3, C3a); 116.3, 124.7,
128.1 (C5, C6, C8); 133.2, 134.2, 139.7 (C4a, C7, C8a);
168.6, 169.3, 169.7 (NCO, CO2). Found, %: C 65.16;
H 6.30; N 4.13. C18H21NO5. Calculated, %: C 65.24;
H 6.39; N 4.23.
Ethyl 7-methyl-5-nitro-3a,8b-dihydrocyclopenta-
[b]indole-4(1H)-carboxylate (XXII) was obtained in
a similar way from 0.245 (1 mmol) of compound XII.
After removal of the solvent, the residue was purified
by column chromatography on silica gel. Yield 0.26 g
(90%), viscous material which gradually solidified;
1
Rf 0.5 (C6H6–EtOAc, 15 : 1). H NMR spectrum
(CDCl3), δ, ppm: 1.29 t (3H, CH3, J = 7.2 Hz), 2.36 s
(3H, CH3), 2.56 d (1H, 1-HA, J = 16.0 Hz), 2.97 d.d
(1H, 1-HB, J = 8.3, 16.0 Hz), 4.03 t (1H, 8b-H, J =
8.3 Hz), 4.23 q (2H, CH2, J = 7.2 Hz), 5.56 d (1H,
3a-H, J = 8.3 Hz), 5.92 s (2H, 2-H, 3-H), 7.19 s and
7.45 s (1H each, 6-H, 8-H). 13C NMR spectrum
(CDCl3), δC, ppm: 14.1, 20.5 (CH3); 39.3 (C1), 42.0
(C8b), 62.5 (CH2), 72.6 (C3a), 123.3 (C3), 129.4 (C2);
129.8, 132.8 (C6, C8); 132.2, 134.1, 139.7, 140.9 (C4a,
C8a, C7, C5); 153.2 (C=O). Found, %: C 62.42; H 5.54;
N 7.67. C15H16N2O4. Calculated, %: C 62.49; H 5.59;
N 9.72.
General procedure for epoxidatin of compounds
XII and XIII. A solution of 3 mmol of compound XII
or XIII in 135 ml of acetonitrile was added to a mix-
ture of 6 ml of formic acid and 5 ml of water, and the
mixture was heated for 10–12 h at 50–60°C. After
cooling to room temperature, NaHCO3 was added until
carbon dioxide no longer evolved, the organic solvent
was evaporated under reduced pressure, and the aque-
ous residue was extracted with methylene chloride.
The extract was dried over MgSO4 and evaporated
under reduced pressure, and stereoisomeric epoxides
XXIIIa/XXIVa and XXIIIb/XXIVb were separated
by chromatography on silica gel using benzene as
eluent.
7-Methyl-4-(4-methylphenylsulfonyl)-
1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole-2,3-diyl
diacetate (XVIII) was synthesized in a similar way
from 0.225 g (0.63 mmol) of diol XVI and 0.6 ml of
acetic anhydride using 0.6 ml of pyridine. The product
was isolated by column chromatography on silica gel
(4 g) using benzene as eluent. Yield 0.233 g (87%),
1
amorphous substance. H NMR spectrum (CDCl3), δ,
ppm: 1.95 s, 2.05 s, 2.21 s, and 2.32 s (3H, CH3), 1.90–
2.40 m (2H, CH2), 3.53 d.t (1H, 8b-H, J = 4.5, 9.7 Hz),
4.43 d.d (1H, 3a-H, J = 4.3, 9.7 Hz), 5.09 q (1H, 2-H,
J = 4.3 Hz), 5.32 t (1H, 3-H, J = 4.3 Hz), 6.72 s (1H,
8-H), 6.95 d (1H, Harom, J = 8.3 Hz), 7.12 d (2H, Harom
,
J = 8.3 Hz), 7.43 d (1H, Harom, J = 8.2 Hz), 7.52 d (2H,
Harom, J = 8.3 Hz). Found, %: C 62.09; H 5.48; N 2.95;
S 7.03. C23H25NO6S. Calculated, %: C 62.29; H 5.68;
N 3.16; S 7.23.
4-Acetyl-7-methyl-5-nitro-1,2,3,3a,4,8b-hexahy-
drocyclopenta[b]indole-2,3-diyl diacetate (XIX).
Trifluoroacetyl nitrate prepared by stirring 1.5 mmol of
ammonium nitrate and 5 mmol of trifluoroacetic
anhydride in 1 ml of methylene chloride was added to
a solution of 0.332 g (1 mmol) of compound XVII in
1 ml of methylene chloride, and the mixture was
stirred for 30 min at –30°C. The mixture was treated
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

SKLADCHIKOV et al.
Ethyl (1aS*,1bR*,6bS*,7aR*)-5-methyl-
966
(5H, 7-H, CH3), 3.60 s (1H), 7a-H), 3.66 t (1H, 7a-H,
J = 1.0 Hz), 3.79 s and 4.00 s (1H, 1a-H), 3.83 d.t (J =
1.5, 9.5 Hz) and 3.89 t (J = 9.5 Hz) (1H, 6b-H),
4.75 d.d (J = 1.5, 9.5 Hz) and 5.09 d.d (J = 1.7, 9.5 Hz)
(1H, 1b-H), 6.84 s and 6.90 s (1H, 6-H), 6.95–6.99 m
(1H, 4-H), 8.04 d (1H, 3-H, J = 8.0 Hz); in acetone-d6:
2.25 s (3H, CH3), 2.35–2.50 m (5H, 7-H, CH3), 3.59 s
and 3.65 s (1H, 7a-H), 3.87 s and 3.90 s (1H, 1a-H),
4.03 t (1H, 6b-H, J = 9.5 Hz), 4.98 d and 5.04 d (1H,
1b-H, J = 9.5 Hz), 6.85–7.05 m (2H, 4-H, 6-H), 7.98 d
(1H, 3-H, J = 8.0 Hz). Found, %: C 73.16; H 6.38;
N 5.97. C14H15NO2. Calculated, %: C 73.34; H 6.59;
N 6.11.
The authors thank Prof. T.V. Timofeeva (New
Mexico Highlands University, USA) for providing
facilities for performing quantum-chemical calcula-
tions. This study was performed under financial
support by the Academy of Sciences of Bashkortostan
Republic.
1a,1b,2,6b,7,7a-hexahydrooxireno[4,5]cyclopenta-
[1,2-b]indole-2-carboxylate (XXIIIa). Yield 0.22 g
(29%), colorless amorphous crystals, Rf 0.26 (C6H6–
1
EtOAc, 40:7). H NMR spectrum (CDCl3), δ, ppm:
1.39 t (3H, CH3, J = 7.1 Hz), 1.84 d.d (1H, 7-HA, J =
4.0, 14.4 Hz), 2.30 s (3H, CH3), 2.64 d.d (1H, 7-HB,
J = 9.0, 14.4 Hz), 3.55 s (1H, 7a-H), 3.67 d.t (1H,
6b-H, J = 4.0, 9.0 Hz), 3.92 s (1H, 1a-H), 4.35 q (2H,
CH2, J = 7.1 Hz), 4.80 d (1H, 1b-H, J = 9.0 Hz), 6.90 s
(1H, 6-H), 7.00 d (1H, Harom, J = 8.6 Hz), 7.75 br.s
(1Harom). Found, %: C 69.37; H 6.54; N 5.32.
C15H17NO3. Calculated, %: C 69.48; H 6.61; N 5.40.
Ethyl (1aR*,1bR*,6bS*,7aS*)-5-methyl-
1a,1b,2,6b,7,7a-hexahydrooxireno[4,5]cyclopenta-
[1,2-b]indole-2-carboxylate (XXIVa). Yield 0.23 g
(30%), amorphous crystals, Rf 0.17 (C6H6–EtOAc,
1
40:7). H NMR spectrum, δ, ppm: in CDCl3: 1.38 t
and 1.44 t (3H, CH3, J = 6.8 Hz), 2.33–2.47 m (2H,
7-H), 2.28 s (3H, CH3), 3.63 s (1H, 7a-H), 3.88 s (1H,
1a-H), 3.91–4.01 m (1H, 6b-H), 4.32 q and 4.39 q (1H
each, CH2, J = 6.8 Hz), 4.79 d and 4.87 d (1H, 1b-H,
J = 9.6 Hz), 6.83 s (1H, 6-H), 6.92–7.00 m (1H, Harom),
7.33 d and 7.73 d (1H, Harom, J = 8.0 Hz); in ace-
tone-d6: 1.31 t and 1.36 t (3H, CH3, J = 7.0 Hz), 2.19 s
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(3H, CH3), 2.28 d.d (1H, 7-HA, J = 2.0, J = 14,6 Hz),
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1 - { ( 1 a S * , 1 b R * , 6 b S * , 7 a R * ) - 5 - M e t h y l -
1a,1b,2,6b,7,7a-hexahydrooxireno[4,5]cyclopenta-
[1,2-b]indol-2-yl}ethan-1-one (XXIIIb). Yield 0.21 g
(31%), Rf 0.3 (benzene); the product was not pure.
1H NMR spectrum (CDCl3), δ, ppm: 2.32 s and 2.41 s
(3H, CH3), 2.00–2.11 m (1H, 7-HA), 2.63 d.d (1H,
7-HB, J = 9.0, 14.6 Hz), 3.55 s (1H, 7a-H), 3.65 d (1H,
1a-H, J = 1.2 Hz), 4.75 d (1H, 1b-H, J = 9.0 Hz), 6.95 s
(1H, 6-H), 7.02 d (1H, 4-H, J = 8.0 Hz), 8.09 d (1H,
3-H, J = 8.0 Hz). Found, %: C 73.07; H 6.54; N 5.89.
C14H15NO2. Calculated, %: C 73.34; H 6.59; N 6.11.
1 - { ( 1 a R * , 1 b R * , 6 b S * , 7 a S * ) - 5 - M e t h y l -
1a,1b,2,6b,7,7a-hexahydrooxireno[4,5]cyclopenta-
[1,2-b]indol-2-yl}ethan-1-one (XXIVb). Yield 0.19 g
(27%), transparent crystals, Rf 0.15 (benzene).
1H NMR spectrum, δ, ppm (some signals are doubled):
in CDCl3: 2.29 s and 2.31 s (3H, CH3), 2.35–2.52 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

REACTIONS OF N- AND C-ALKENYLANILINES: IX.
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