One-step method for the synthesis of nitroisoindoles via 1,3-dipolar cycloaddition of azomethine ylides to polynitrobenzenes

Article abstract of DOI:10.1055/S-0032-1317115

A new one-step method for the synthesis of nitroisoindoles was developed on the basis of 1,3-dipolar cycloadditions of unstabilized A'-alkyl azomethine ylides with di- and trinitrobenzenes. Georg Thieme Verlag Stuttgart ? New York.

Full text of DOI:10.1055/S-0032-1317115

2400▌
LETTER
letter
One-Step Method for the Synthesis of Nitroisoindoles via 1,3-Dipolar Cyclo-
addition of Azomethine Ylides to Polynitrobenzenes
Synthesis of Nitroisoindoles
Alexey M. Starosotnikov,*a Maxim A. Bastrakov,a Vadim V. Kachala,a Pavel A. Belyakov,a Ivan V. Fedyanin,b
Svyatoslav A. Sheveleva
a
N. D. Zelinsky Institute of Organic Chemistry, Leninsky pr. 47, Moscow 119991, Russia
Fax +7(499)135 5328; E-mail: alexey41@list.ru
b
A. N. Nesmeyanov Institute of Organoelement Compounds, Vavilova Str. 28, Moscow, 119991, Russia
Received: 28.06.2012; Accepted after revision: 24.07.2012
with the reactions of nonstabilized N-methyl azomethine
Abstract: A new one-step method for the synthesis of nitroiso-
ylide with mono- and dinitrobenzene fused with azoles
indoles was developed on the basis of 1,3-dipolar cycloadditions of
and azines (Scheme 1).
unstabilized N-alkyl azomethine ylides with di- and trinitroben-
zenes.
In all cases the cycloaddition of one or two double C–C-
Key words: isoindoles, 1,3-dipolar cycloaddition, nitroarenes, azo- bond(s) activated by the nitro group was observed giving
methine ylides, heterocycles
rise to the loss of aromaticity of the nitrobenzene ring and
annulation of the pyrrolidine or pyrroline rings, for exam-
ple, formation of tetrahydroisoindole or isoindoline sys-
tems.8 Later Lee et al. described9 a facile dearomatization
Benzo[c]pyrroles (isoindoles) and their hydrogenated de-
of nitrobenzene derivatives under the action of N-benzyl
azomethine ylide giving rise to tetrahydroisoindoles.
rivatives are of considerable interest to the researchers
since they were found to be useful precursors for a wide
range of heterocyclic systems. Many representatives of
these heterocycles possess varied biological activity: anti-
hypertonic,1a sedative, or CNS stimulating;1b,1c some of
them were synthesized as potential agents for the symp-
tomatic treatment of benign prostatic hyperplasia
(BPH).1d Among the known methods for the preparation
of compounds of these classes the following are to be
mentioned: Wittig’s method,2 synthesis via hydrazine
salts,3 from phthalimidines,4 and ortho-diacylbenzenes.5
Also of interest are methods for the synthesis of isoindoles
by means of annulation of the pyrrole or benzene ring with
formation of two C–C bonds, such as interaction of
1,4-diketones with pyrroles6 or modified Barton–Zard
synthesis.7
In continuation of our recent research we studied the reac-
tions of 1,3,5-trinitrobenzene (TNB, 1) and its derivatives
with symmetrical N-methyl azomethine ylide (2) that was
generated in situ from N-methyl glycine and paraform-
aldehyde on refluxing in toluene (Scheme 2). It was found
that instead of the expected annulation of the pyrrolidine
ring in contrast to mono- and dinitrobenzazoles8 (Scheme 1)
as well as substituted nitrobenzenes,9 the reaction of TNB
with 1,3-dipole 2 afforded 2-methyl-4,6-dinitroisoindole
(3a), for example, annulation of a pyrrole ring at only one
C–C bond activated by the nitro group. This reaction was
accompanied by considerable resinification, therefore the
yield of the product was not very high. To the best of our
knowledge this is the first example of the one-step isoin-
dole synthesis via 1,3-dipolar cycloaddition of azome-
thine ylides to nitroarenes. Recently,8b,10 we found two
examples of azomethine ylide utilization for the annula-
tion of pyrrole rings to the benzene cycle of nitroarenes.
However, it proceeded in two steps (cycloaddition and ox-
idation with an external oxidant). In addition, 1,3-dipolar
cycloaddition of 1,3-oxazolium-5-olates (münchnones)
with benzazoles nitrated at the benzene ring affords the
In course of our research on aromatic nitro compounds in
cycloaddition reactions we herein report a new simple
method for the synthesis of novel functionalized
nitroisoindoles on the basis of 1,3-dipolar cycloaddition
reactions of N-alkyl azomethine ylides with di- and tri-
nitrobenzenes. The first examples of the [3+2] cyclo-
addition to nitroarenes (aromatic nitro carbocycles) were
published recently by our group.8 These publications dealt
Me
Me
Me
N
Me
N
Me
N
NO2
N
N
NO2
(O2N)n
H2C
CH2
H2C
CH2
N
O2N
Me
or
N
N
N
n = 1
n = 2
R
R
R
N
Scheme 1 1,3-Dipolar cycloaddition of N-methyl azomethine ylide with mono- and dinitrobenzazoles
SYNLETT 2012, 23, 2400–2404
Advanced online publication: 14.09.2012
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
DOI: 10.1055/s-0032-1317115; Art ID: ST-2012-D0551-L
© Georg Thieme Verlag Stuttgart · New York

LETTER
Synthesis of Nitroisoindoles
2401
NO2
R
NO2
Me
N
COOH
Me
N
O2N
NO2
H
N
Me
toluene
reflux
O2N
+
– HNO2
H2C
CH2
R
1 R = H
4 R = Me
(HCHO)n
2
3a R = H
3b R = Me
Scheme 2 Reaction of TNB and TNT with N-methyl azomethine ylide 2
pyrrole ring giving rise to the corresponding azoloisoin- alkenic double bonds. The only products in these cases
dole derivatives.11
were isoindoles 6a,b. The 1H NMR spectra of compounds
3 and 6 showed a singlet for the NCH3 protons at
δ = 4.13–4.16 ppm. The protons Ha and Hb of the pyrrole
ring usually appeared as two singlets (or sometimes as
two doublets with J = 2.0 Hz) in the region of δ = 7.90–
8.27 ppm and 8.27–8.60 ppm, respectively. This assign-
ment was made on the basis of 2D NOESY spectra where
cross-peaks were observed for Hb and the protons of the
double bond. At the same time dinitrobenzoxepin (7) un-
der similar conditions afforded tetracyclic adduct 8
(Scheme 3), for example, the cycloaddition to aromatic di-
nitrobenzene cycle was not favored. It should be noted
that in this case only formation of the pyrrolidine deriva-
tive occurs as a quite unstable yellow oil whose structure
was assigned by 1H NMR spectroscopy.
Methyl-substituted TNB [2,4,6-trinitrotoluene (TNT, 4)]
under the action of dipole 2 gave the corresponding di-
methyl derivative 3b (Scheme 2). The structures of com-
pounds 3 were assigned using polynuclear 2D NMR
experiments. For example, NOE was observed between
the protons of the 7-Me group at δ = 2.85 ppm and one of
the pyrrole protons in compound 3b (H-1 at δ = 8.30
ppm). This allowed us to prove unambiguously the direc-
tion of the cycloaddition. Moreover, the structure of 3b
was confirmed by single-crystal X-ray crystallographic
analysis12 (Figure 1).
According to quantum-chemical calculations (performed
by D.V. Khakimov, IOC RAS, using HF/STO-3G and
B3LYP/6-31G* methods) the plane of the ethylene frag-
ment of 5a is turned by 42.5° with respect to the plane of
the trinitrobenzene ring. Therefore, the conjugation of this
double bond with the picryl cycle is quite weak. At the
same time in compound 7 the double bond is fixed in the
frame of the heterocycle which probably provides the ac-
tivation of this bond by conjugation with the dinitro-
benzene cycle.
Figure 1 Crystal structure of compounds 3b (left) and 13b (right)
Surprisingly, compound 5a as well as its sulfonyl ana-
logue 5b (Scheme 3) containing 2-phenylvinyl substitu-
ents did not give the corresponding cycloadducts by
Another azomethine ylide 9 can be generated from L-pro-
line and paraformaldehyde (Scheme 4). This cyclic dipole
was found to be reactive as well towards polynitro deriv-
atives 5a,b and TNT (4), and as a result tricyclic deriva-
tives 10 were isolated.
R2
R1
R2
R1
Although in these cases the formation of two regioisomers
10a–c and 10′a–c is possible, NMR spectroscopic data
showed that the structures of the cycloadducts corre-
sponded to 10a–c (Scheme 4). The full assignment of the
signals in the NMR spectra was made for compounds
10a–c, and the cross-peaks in the 2D NOESY spectra
were observed between the protons of the alkenic double
bond (or methyl group for 10c) and the protons of the cy-
clic CH2 groups (Figure 2).
2
Hb
O2N
O2N
NO2
toluene, reflux
N
Ha
Me
5a R1 = NO2, R2 = H
5b R1 = SO2-i-Bu, R2 = Cl
6a R1 = NO2, R2 = H
6b R1 = SO2-i-Bu, R2 = Cl
NO2
Me
N
NO2
2
We have found similar regioselectivity in reactions of 4
and 5a with unsymmetrical dipole 11 which was generat-
ed by a standard procedure from L-thiazolidine-4-carbox-
ylic acid and paraformaldehyde (Scheme 5). This reaction
afforded isoindolines 12. In the case of compound 5a the
formation of isoindole 13b was also observed. Iso-
indolines 12 were rather stable towards further oxidation
O2N
O
toluene, reflux
O2N
O
7
8
Scheme 3 Synthesis of compounds 6a,b and 8 via cycloaddition of N-
methyl azomethine ylide
© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2400–2404

2402
A. M. Starosotnikov et al.
LETTER
O
(HCHO)n
O
N
N
toluene, reflux
– CO2
N
H
OH
O
CH2
9
R1
R1
R1
R2
R2
R2
9
or
toluene, reflux
O2N
O2N
O2N
NO2
N
N
5a R1 = NO2, R2 = CH=CHPh
5b R1 = SO2-i-Bu,
10a R1 = NO2, R2 = CH=CHPh
10b R1 = SO2-i-Bu,
R2 = CH=CH-(4-Cl-C6H4)
10c R1 = NO2, R2 = Me
10'a–c
R2 = CH=CH-(4-Cl-C6H4)
4
R
1 = NO2, R2 = Me
Scheme 4 Reactions of compounds 4 and 5a,b with cyclic azomethine ylide 9
of about 71%. These compounds were separated by flash
chromatography and identified separately.
H
H
H(Cl)
H
H
R
H
NO2
H
In 2D NOESY spectra of compounds 12 and 13 several in-
teractions were observed proving the structures indicated
in Scheme 5 (Figure 2). In addition, the structure of com-
pound 13b was confirmed by X-ray crystal structure
analysis12 (Figure 1).
H
H
H
H
H
O2N
H
H
O2N
H
N
N
S
H
H
H
H
H
H
In all cases the cycloaddition proceeded regioselectively
at the aromatic C–C bond activated by the nitro group in
the ortho position relative to the R group. The yields of
isoindoles were moderate (32–58%) except of those com-
pounds obtained on the basis of TNT (4) – the yields of 3b
and 10c did not exceed 11%. In the case of TNT the side
processes are possible due to the deprotonation of the
methyl group under the action of bases giving rise to reac-
tive 2,4,6-trinitrobenzyl anions (see, for example, ref.13).
NO2
Me
H
H
H
O2N
H
N
S
H
H
H
In most cases mentioned above the cycloaddition of azo-
methine ylide resulted in formation of a pyrrole ring. The
only exceptions we found were compounds 12 which
could not be completely converted into isoindoles 13 upon
prolonged heating. The most probable reaction scheme
consists of the cycloaddition itself to give adduct A, re-
aromatization of the benzene ring with loss of nitrous acid
and further oxidative dehydrogenation of pyrroline B
Figure 2 Selected connectivities found in 2D NOESY spectra of the
products 10a,b and 12a,b
under the reaction conditions unlike the cycloadducts with
other azomethine ylides (see above) where the corre-
sponding intermediate isoindolines could not be isolated
due to a rapid oxidation to isoindoles. It should be noted
that the ratio of 12b and 13b was 1:1 with an overall yield
S
O
S
(HCHO)n
S
O
N
N
toluene, reflux
– CO2
N
OH
O
CH2
H
11
NO2
NO2
NO2
R
R
R
11
+
toluene, reflux
O2N
O2N
O2N
NO2
N
S
N
S
4 R = Me
5a R = CH=CHPh
12a R = Me
12b R = CH=CHPh
13b R = CH=CHC6H5
Scheme 5 Reaction of compounds 4 and 5a with dipole 11
Synlett 2012, 23, 2400–2404
© Georg Thieme Verlag Stuttgart · New York

LETTER
Synthesis of Nitroisoindoles
2403
C9H7N3O4: C, 48.87; H, 3.19; N, 19.00. Found: C, 48.64; H, 3.27;
N, 18.82.
X
X
N
R
R
2,7-Dimethyl-4,6-dinitro-2H-isoindole (3b)
CH2
Red crystals; mp 223–225 °C; yield 11%. IR (KBr): 3167, 3135,
1625, 1567, 1529, 1494, 1347, 1302, 1161, 1014, 787, 620 cm–1. 1H
NMR (600.13 MHz, DMSO-d6): δ = 2.85 (s, 3 H, 7-CH3), 4.13 (s, 3
H, 2-CH3), 7.90 (s, 1 H, H-1), 8.30 (s, 1 H, H-3), 8.54 (s, 1 H, H-5).
13C NMR (150.90 MHz, DMSO-d6): δ = 17.25, 38.17, 113.50,
115.55, 116.71, 122.13, 126.83, 136.39, 138.61, 139.73. MS:
m/z = 235 [M+], 189 [M+ – NO2], 143 [M+ – 2NO2]. Anal. Calcd for
C10H9N3O4: C, 51.07; H, 3.86; N, 17.87. Found: C, 50.76; H, 3.67;
N, 17.52.
NO2
toluene, reflux
– HNO2
O2N
O2N
NO2
H
N
A
X
X
R
R
[O]
O2N
O2N
N
N
2-Methyl-5,7-dinitro-4-[(E)-2-phenylvinyl]-2H-isoindole (6a)
1
Dark red crystals; mp 209–211 °C; yield 49%. H NMR (600.13
MHz, DMSO-d6): δ = 4.14 (s, 3 H, CH3), 7.39 (d, J = 16.2 Hz, 1 H,
CH=), 7.41 (t, J = 7.2 Hz, 1 H, 4-Ph), 7.47 (t, J = 7.4 Hz, 2 H, 3-Ph)
7.73 (d, J = 8.4 Hz, 2 H, 2-Ph), 7.80 (d, J = 16.3 Hz, 1 H, CH=),
7.98 (d, J = 2.0 Hz, 1 H), 8.28 (d, J = 1.9 Hz, 1 H), 8.60 (s, 1 H, H-
6). 13C NMR (150.90 MHz, DMSO-d6): δ = 38.71, 114.83, 116.04,
117.36, 123.53, 123.56, 124.48, 127.96, 129.36, 129.69, 136.64,
137.16, 137.88, 137.96, 138.36. MS: m/z = 323 [M+]. Anal. Calcd
for C17H13N3O4: C, 63.16; H, 4.05; N, 13.00. Found: C, 63.21; H,
3.76; N, 12.60.
B
C
Scheme 6 Proposed scheme for the formation of the cycloadducts
either with air oxygen or with starting polynitro com-
pounds present in the reaction mixture (Scheme 6). The
latter could explain the moderate yields of the products
and the observed resinification of the probable reduction
products of polynitro compounds. In addition, when the
reactions were carried out under inert atmosphere the
product yields were approximately the same.
4-[(E)-2-(4-Chlorophenyl)vinyl]-5-(isobutylsulfonyl)-2-methyl-
7-nitro-2H-isoindole (6b)
Red crystals; mp 156–158 °C; yield 44%. 1H NMR (600.13 MHz,
DMSO-d6): δ = 0.92 (d, J = 6.7 Hz, 6 H, 2 CH3), 2.07 (sept, J = 6.6
In conclusion, we developed a new simple one-step meth- Hz, 1 H, CH), 3.26 (d, J = 6.2 Hz, 2 H, CH2), 4.16 (s, 3 H, NCH3),
7.49–7.57 (m, 3 H), 7.74 (d, J = 8.4 Hz, 2 H), 7.99 (s, 1 H), 8.05 (d,
od for the annulation of a pyrrole ring to polynitroben-
zenes providing a pathway to the previously unknown
functionalized nitroisoindoles based on 1,3-dipolar cyclo-
addition of azomethine ylides to polynitroarenes. The
products are not readily available by other methods. All
reactions proceed with excellent site selectivity.
J = 16.4 Hz, 1 H), 8.27 (s, 1 H), 8.47 (s, 1 H). 13C NMR (150.90
MHz, DMSO-d6): δ = 22.23, 23.85, 38.25, 62.86, 114.88, 115.39,
120.31, 121.17, 123.22, 124.76, 126.83, 129.03, 129.12, 133.85,
135.12, 136.91, 137.14, 140.96. Anal. Calcd for C21H21ClN2O4S: C,
58.26; H, 4.89; N, 6.47. Found: C, 58.44; H, 4.71; N, 6.59.
2-Methyl-4,6-dinitro-2,3,3a,12b-tetrahydro-1H-diben-
zo[2,3:6,7]oxepino[4,5-c]pyrrole (8)
Yellow oil; yield 47%. 1H NMR (600.13 MHz, DMSO-d6): δ = 2.27
(s, 3 H, CH3), 2.32–2.46 (m, 2 H), 3.26 (t, J = 8.2 Hz, 1 H), 3.36 (t,
J = 8.2 Hz, 1 H), 3.73 (dd, J = 17.9, 10.1 Hz, 1 H), 3.93 (dd,
J = 18.0, 10.0 Hz, 1 H), 7.14 (t, J = 7.3 Hz, 1 H), 7.24–7.29 (m, 2
H), 7.57 (d, J = 7.8 Hz, 1 H), 8.51 (d, J = 2.1 Hz, 1 H), 8.56 (d,
J = 2.1 Hz, 1 H).
Melting points were measured on a Boetius apparatus and are un-
corrected. NMR spectra were recorded on a Bruker Avance II 600
spectrometer in DMSO-d6 or CDCl3 as a solvent. Chemical shifts
are reported in ppm downfield from TMS. IR spectra of samples
prepared as KBr pellets were recorded on a Bruker Alpha spectrom-
eter. Mass spectra (EI, 70eV) were obtained using a MS-30 Kratos
spectrometer. All reactions were monitored by TLC using Silufol
plates which were visualized with UV light. Compounds 5a,b14 and
715 were prepared according to the procedures described in the liter-
ature.
6,8-Dinitro-9-[(E)-2-phenylvinyl]-2,3-dihydro-1H-pyrrolo[2,1-
a]isoindole (10a)
Dark red crystals; mp 242–243 °C; yield 38%. IR (KBr): 3157,
1
1557, 1512, 1323, 1287, 1113, 969, 901, 778, 694 cm–1. H NMR
(600.13 MHz, CDCl3): δ = 2.68 (t, J = 6.9 Hz, 2 H), 3.21 (t, J = 6.9
Hz, 2 H), 4.44 (t, J = 7.0 Hz, 2 H, NCH2), 6.82 (d, J = 16.3 Hz, 1 H,
CH=), 7.42–7.60 (m, 5 H), 7.78–7.86 (m, 2 H), 8.88 (s, 1 H). 13C
NMR (150.90 MHz, CDCl3): δ = 27.11, 28.16, 48.72, 107.69,
117.63, 118.98, 119.45, 122.70, 127.14, 129.04, 129.16, 135.95,
137.36, 137.67, 139.86, 153.87. MS: m/z = 349 [M+], 257 [M+ –
2NO2]. Anal. Calcd for C19H15N3O4: C, 65.32; H, 4.33; N, 12.03.
Found: C, 65.17; H, 4.56; N, 12.24.
Synthesis of the Polycyclic Isoindole Derivatives – General
Procedure
A mixture of nitro compound (1 mmol), corresponding amino acid
(5 mmol), paraformaldehyde (0.18 g, 6 mmol), and toluene (15 mL)
was heated under reflux for 4–6 h (5 min in the case of the synthesis
of 6a and 10a). After the starting material disappeared (TLC) the
mixture was cooled to r.t. and filtered. The solvent was evaporated
under reduced pressure, and the residue was purified by column
chromatography on MN Kieselgel 60 (0.04–0.063 mm/230–400
mesh) using CHCl3 to afford the target compounds basically as a red
or brown solid.
9-[(E)-2-(4-Chlorophenyl)vinyl]-8-(isobutylsulfonyl)-6-nitro-
2,3-dihydro-1H-pyrrolo[2,1-a]isoindole (10b)
Dark red solid; mp 190–192 °C; yield 58%. 1H NMR (600.13 MHz,
CDCl3): δ = 0.93 (d, J = 6.8 Hz, 1 H, 2 CH3), 2.13 (m, 1 H, CH),
2.70 (m, 2 H, CH2), 3.13 (t, J = 7.3 Hz, 2 H, CH2), 4.43 (t, J = 7.3
Hz, 2 H, CH2), 6.78 (d, J = 16.5 Hz, 1 H), 7.41 (d, J = 8.5 Hz, 2 H),
7.55 (d, J = 8.3 Hz, 2 H), 7.65 (s, 1 H), 7.96 (d, J = 16.5 Hz, 1 H),
8.38 (s, 1 H). 13C NMR (150.90 MHz, CDCl3): δ = 22.67, 24.01,
27.05, 27.79, 48.63, 63.67, 107.03, 119.28, 119.76, 120.36, 123.31,
126.26, 128.29, 129.28, 134.27, 135.03, 135.11, 137.13, 137.22,
2-Methyl-4,6-dinitro-2H-isoindole (3a)
Red crystals; mp 236–237 °C; yield 32%. IR (KBr): 3114, 1626,
1566, 1521, 1477, 1331, 1289, 1160, 1063, 799, 725, 623 cm–1. 1H
NMR (600.13 MHz, DMSO-d6): δ = 4.16 (s, 3 H, CH3), 7.95 (s, 1
H, H-1), 8.17 (s, 1 H, H-3), 8.60 (s, 1 H, H-7), 9.16 (s, 1 H, H-5).
13C NMR (150.90 MHz, DMSO-d6): δ = 38.39, 114.22, 114.34,
115.20, 122.97, 124.24, 127.30, 138.10, 138.89. MS: m/z = 221
[M+], 175 [M+ – NO2], 129 [M+ – 2NO2]. Anal. Calcd for
© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2400–2404

2404
A. M. Starosotnikov et al.
LETTER
Basha, F. Z.; Carroll, W. A.; Condon, S.; Elmore, S. W.;
Kerwin, J. F.; Sippy, K. B.; Tietje, K.; Wendt, M. D.;
Hancock, A. A.; Brune, M. E.; Buckner, S. A.; Drizin, I.
J. Med. Chem. 2000, 43, 1586.
142.61. Anal. Calcd for C23H23ClN2O4S: C, 60.19; H, 5.05; N, 6.10.
Found: C, 60.34; H, 5.21; N, 5.98.
9-Methyl-6,8-dinitro-2,3-dihydro-1H-pyrrolo[2,1-a]isoindole
(10c)
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Heterocycl. Chem. 2010, 47, 893. (b) Starosotnikov, A. M.;
Bastrakov, M. A.; Pechenkin, S. Y.; Leontieva, M. A.;
Kachala, V. V.; Shevelev, S. A. J. Heterocycl. Chem. 2011,
48, 824. (c) Konstantinova, L. S.; Bastrakov, M. A.;
Starosotnikov, A. M.; Glukhov, I. V.; Lysov, K. A.; Rakitin,
O. A.; Shevelev, S. A. Mendeleev Commun. 2010, 20, 353.
(d) For a recent review, see: Terrier, F.; Dust, J. M.; Buncel,
E. Tetrahedron 2012, 68, 1829.
Red solid; mp 255–257 °C; yield 11%. IR (KBr): 3158, 1621, 1561,
1525, 1495, 1316, 1286, 1159, 1111, 997, 889, 762, 698 cm–1. H
1
NMR (600.13 MHz, DMSO-d6): δ = 2.68 (pent, J = 7.3 Hz, 2 H),
2.92 (s, 3 H), 3.47 (t, J = 7.3 Hz, 2 H), 4.44 (t, J = 7.4 Hz, 2 H), 7.87
(s, 1 H), 8.58 (s, 1 H). HRMS: m/z calcd for C12H11N3O4: 262.0822;
found: 262.0828. Anal. Calcd for C12H11N3O4: C, 55.17; H, 4.24; N,
16.09. Found: C, 55.48; H, 4.39; N, 15.78.
9-Methyl-6,8-dinitro-5,9b-dihydro-1H-[1,3]thiazolo[4,3-
a]isoindole (12a)
Orange solid; mp 133–135 °C; yield 34%. MS: m/z = 281 [M+], 235
[M+ – NO2], 189 [M+ – 2NO2]. IR (KBr): 3453, 3117, 1603, 1532,
1352, 1125, 900, 873, 750, 702, 687 cm–1. 1H NMR (600.13 MHz,
CDCl3): δ = 2.65 (s, 3 H, CH3), 2.83 (dd, J = 11.0, 4.7 Hz, 1 H), 3.44
(dd, J = 11.0, 8.2 Hz, 1 H), 4.35 (s, 2 H), 4.56 (dd, J = 17.8, 1.7 Hz,
1 H), 4.93–4.96 (m, 2 H), 8.73 (s, 1 H). 13C NMR (150.90 MHz,
CDCl3): δ = 17.12, 39.25, 59.87, 60.86, 72.61, 120.45, 134.07,
140.34, 141.11, 148.20, 149.24. Anal. Calcd for C11H11N3O4S: C,
46.97; H, 3.94; N, 14.94. Found: C, 47.11; H, 3.99; N, 14.58.
6,8-Dinitro-9-[(E)-2-phenylvinyl]-5,9b-dihydro-1H-[1,3]thiazo-
lo[4,3-a]isoindole (12b)
Brown solid; mp 160–162 °C; yield 36%. 1H NMR (600.13 MHz,
CDCl3): δ = 2.92 (dd, J = 11.1, 5.1 Hz, 1 H), 3.37 (dd, J = 11.1, 8.1
Hz, 1 H), 4.35 (s, 2 H), 4.57 (d, J = 17.9 Hz, 1 H), 4.96 (d, J = 17.9
Hz, 1 H), 5.12 (t, J = 5.8 Hz, 1 H), 6.94 (d, J = 16.6 Hz, 1 H), 7.27
(d, J = 16.6 Hz, 1 H), 7.39–7.44 (m, 3 H), 7.52 (d, J = 7.2 Hz, 2 H),
8.71 (s, 1 H). 13C NMR (150.90 MHz, CDCl3): δ = 39.59, 59.40,
60.77, 72.94, 119.99, 120.41, 127.16, 129.05, 129.70, 133.83,
135.28, 138.03, 140.73, 146.89, 148.38. Anal. Calcd for
C18H15N3O4: C, 58.53; H, 4.09; N, 11.38. Found: C, 58.66; H, 3.91;
N, 11.20.
6,8-Dinitro-9-[(E)-2-phenylvinyl]-1H-[1,3]thiazolo[4,3-a]isoin-
(9) Lee, S.; Chataigner, I.; Piettre, S. R. Angew. Chem. Int. Ed.
2011, 59, 472.
dole (13b)
1
Dark red crystals; mp 237–239 °C; yield 35%. H NMR (600.13
(10) Pechenkin, S. Y.; Starosotnikov, A. M.; Bastrakov, M. A.;
Glukhov, I. V.; Shevelev, S. A. Russ. Chem. Bull. Int. Ed.
2012, in press; Izv. Akad. Nauk. Ser. Khim. 2012, 1, 73.
(11) Pechenkin, S. Y.; Starosotnikov, A. M.; Bastrakov, M. A.;
Kachala, V. V.; Shevelev, S. A. Mendeleev Commun. 2012,
22, 35.
(12) Crystallographic data of 3b and 13b crystals have been
deposited at the Cambridge Crystallographic Data Centre
(CCDC) with the reference numbers 874401 and 874402,
respectively. These data can be obtained free of charge via
http://www.ccdc.cam.uk/conts/retrieving.html.
(13) (a) Buncel, E.; Crampron, M. R.; Strauss, M. J.; Terrier, F.
Electron-Deficient Aromatic- and Heteroaromatic-Base
Interactions; Elsevier: Amsterdam, 1984. (b) Sugimoto, N.;
Sasaki, M.; Osugi, J. J. Chem. Soc., Perkin Trans. 1 1984,
655. (c) Shipp, K. C.; Kaplan, L. A.; Sitzmann, M. E. J. Org.
Chem. 1972, 37, 1966.
(14) Rozhkov, V. V.; Kuvshinov, A. M.; Gulevskaya, V. I.;
Chervin, I. I.; Shevelev, S. A. Synthesis 1999, 2065.
(15) Hoyer, H.; Vogel, M. Monatsh. Chem. 1962, 93, 766.
MHz, CDCl3): δ = 4.35 (s, 2 H), 5.49 (s, 2 H), 6.77 (d, J = 16.3 Hz,
1 H), 7.43–7.62 (m, 5 H), 7.82 (d, J = 16.3 Hz, 1 H), 7.97 (s, 1 H),
8.92 (s, 1 H). 13C NMR (150.90 MHz, DMSO): δ = 30.67, 50.33,
109.22, 117.34, 117.80, 118.07, 122.31, 127.22, 128.92, 129.05,
134.87, 135.74, 136.82, 137.12, 137.50, 139.72. Anal. Calcd for
C18H13N3O4S: C, 58.85; H, 3.57; N, 11.44. Found: C, 58.74; H,
3.72; N, 11.63.
Acknowledgment
This work was supported by the Russian Foundation for Basic Re-
search (RFBR, Project No.10-03-00185a) and the President of the
Russian Federation [the program of state supporting for young sci-
entists (Grant MK-220.2011.3)].
References
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1953, 75, 4911. (b) Jaunin, R. CH 612670, 1979. (c) Jaunin,
R. CH 610304, 1979. (d) Meyer, M. D.; Altenbach, R. J.;
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