[3+2] Cycloaddition of o-nitrophenyl azide to 3a,6-epoxyisoindoles

Article abstract of DOI:10.1007/s10593-018-2194-1

[3+2] Cycloaddition of o-nitrophenyl azide to the multiple bond of oxabicyclo[2.2.1]heptene moiety in substituted 3a,6-epoxyisoindoles was performed. The 1,3-dipolar addition reaction proceeded stereoselectively, producing a pair of isomeric cis-4,8a-epox

Full text of DOI:10.1007/s10593-018-2194-1

DOI 10.1007/s10593-018-2194-1
Chemistry of Heterocyclic Compounds 2017, 53(11), 1199–1206
[3+2] Cycloaddition of o-nitrophenyl azide
to 3а,6-epoxyisoindoles
Vladimir P. Zaytsev1*, Dmitriy F. Mertsalov1, Maryana A. Nadirova1,
Pavel V. Dorovatovskii2, Victor N. Khrustalev1, Elena A. Sorokina1,
Fedor I. Zubkov1, Aleksey V. Varlamov1
1
RUDN University,
6 Miklukho-Maklaya St., Moscow 117198, Russia; е-mail: vzaitsev@sci.pfu.edu.ru
National Research Center ''Kurchatov Institute'',
1 Akademika Kurchatova Sq., Moscow 123182, Russia; е-mail: paulgemini@mail.ru
2
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2017, 53(11), 1199–1206
Submitted June 22, 2017
Accepted July 20, 2017
R
NO2
R
O
X
R
O
O
N
Alk(Ar)
X
N
N
X
N
N Alk(Ar)
N
N
N
Alk(Ar)
NO2
+
N
N
N
exo-[3+2]
N
12 examples
NO2
48–95%
R = H, CO2Me, CO2Et; X = CO, CH2
[3+2] Cycloaddition of о-nitrophenyl azide to the multiple bond of oxabicyclo[2.2.1]heptene moiety in substituted 3а,6-epoxyisoindoles
was performed. The 1,3-dipolar addition reaction proceeded stereoselectively, producing a pair of isomeric cis-4,8a-epoxy[1,2,3]triazolo-
[4,5-e]isoindoles. This approach demonstrated synthetic access to isomeric epoxy-1,2,3-benzotriazoles fused with a γ-butyrolactam
moiety.
Keywords: 1,2,3-benzotriazoles, 3а,6-epoxyisoindoles, 4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindoles, о-nitrophenyl azide, [3+2] cyclo-
addition, 1,3-dipolar cycloaddition.
[3+2] Cycloaddition reactions are widely used for the
synthesis of five-membered heterocycles containing from
one to three heteroatoms.1 The development of click chemistry
concept since 2001 has led to a particularly frequent use of
organic azides as 1,3-dipoles for rapid assembly of
molecules on the basis of disubstituted 1,2,3-triazole rings.
A suitable dipolarophile for these reactions can be a triple
or double carbon–carbon bond. In the latter case, the
double bond can also be an endocyclic С=С bond, enabling
the preparation of triazoles annulated with other rings.
The cycloaddition of azides to oxabicycloheptene
moiety was first described in 1944 and is still relevant due
to the possible transformations of triazole ring to other
groups, in particular the pharmacophoric aziridine ring
(Scheme 1).2
It is known that substituted hexahydro-1,2,3-benzo-
triazoles inhibit the human enzymes autotaxin3a,b and
SMG1,3c while 4,7-methano-1,2,3-benzotriazoles decrease
the biosynthesis of gibberellins and metabolic degradation
of abscisic acid in plants.3d Despite the lack of data about
the biological activity of epoxy-1,2,3-benzotriazoles
Scheme 1
R
N
N
O
R
N
N
[3+2]
N
R
+
N
O
N
O
Epoxy-1,2,3-
benzotriazoles
8-Oxa-3-aza-
tricyclooctanes
themselves, their easy transformation to 8-oxa-3-azatri-
cyclooctanes, which are analogs of the aforementioned
benzotriazoles, provide motivation to develop methods for
the preparation of such epoxy derivatives.4
Reactions between organic azides and oxabicyclo-
heptenes fused with a γ-butyrolactam ring have not yet
been described, but the ambiguous results obtained with
[3+2] cycloaddition to similar systems require a detailed
study of the stereoselectivity in such processes.
The objects of this study, epoxyisoindoles 2–4 and their
N-arylsulfonyl derivatives 5a,b, are available in two or
three synthetic steps. These compounds were obtained
according to previously described procedures from the
furfurylamines 1a–g and halides or anhydrides of α,β-un-
0009-3122/17/53(11)-1199©2017 Springer Science+Business Media, LLC
1199

Chemistry of Heterocyclic Compounds 2017, 53(11), 1199–1206
Scheme 2
R3
EtO2C
Cl
CO2Et
O
Cl
O
R3 O
H2C
R2
O
O
N R1
O
N R1
Et3N, PhMe, 
Et3N, PhMe, 
R1
4a–c (36–57%)
NH
2a–e (25–81%)
O
R2
From1f
1.
MeO2C
O
O
O
O
1a–g
R4SO2Cl
PhH, 25°C
2. MeOH, H+
N SO2R4
5a,b (53, 64%)
O
N R1
O
Na2CO3, H2O, 
3a,b (57, 82%)
1a,f, 2a,c,d, 4a R1 = Ph; 1b, 2b,e, 3a R1 = Bn; 1c, 4b R1 = Furan-2-ylmethyl; 1d, 4c R1 = 3,4-(MeO) C6H3(CH2)2; 1e, 3b R1 = Me,
2
1
2
2
3
3
4
4
1f
1a f 2a b d e
R = Allyl; – , , , , R = H,
1g 2c
,
2a c
–
2d e
,
5a
5b
R = Me;
R = H;
R = Me;
R = Ph;
R = 4-MeC6H4
saturated carboxylic acids,5 or by a reaction of allyl-
furfurylamine 1f (R1 = allyl, R2 = H) with arylsulfonyl
chlorides6 (Scheme 2). In order to improve the solubility,
the starting carboxylic acids were converted to methyl
esters 3a,b.
Scheme 3
The azide model compound selected by us for the study
of cycloaddition reactions with alkenes 2–4 was the readily
available and sufficiently stable 2-nitrophenyl azide.7
The reaction of о-nitrophenyl azide at the double bond
of oxabicycloheptenes 2–5 in toluene occurred at room
temperature over several days. The target compounds –
4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindoles 6a–l were isolated
in good yields predominantly as single isomers of 3-(2-nitro-
phenyl)triazoloisoindole 6с–e,h–jA or 1-(2-nitrophenyl)-
triazoloisoindole 6bB (Scheme 3). In the case of [3+2]
cycloaddition to isoindoles 2a, 3a,b, 5a,b, mixtures of
triazoloisoindoles А and В were formed, which were
isomers with respect to the position of nitrophenyl
substituent (Table 1). The analysis of data presented in
Table 1 did not provide clear conclusions about the effect
of substituents R1–R5 in isoindoles 2–5 on the yields and
stereochemistry of cycloaddition products.
Even though the literature analogies and spectral data
were not sufficient for determining the position of
nitrophenyl substituent in adducts 6, the cis configuration
of triazole ring relative to the oxygen atom of oxabicyclo-
heptane moiety could be established unequivocally on the
The cycloaddition products 6 theoretically can have four
alternate structures 6A, 6B, 6A*, 6B* (Fig. 1).
Table 1. Substituents, reaction time, and yields of epoxy[1,2,3]triazolo[4,5-e]isoindoles 6
Epoxy-
isoindole
Reaction time,
h
Triazole
R1
R2
R3
R4
R5
X
Yield, % (A:B)
Ph
H
H
H
H
H
H
H
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CH2
CH2
30
0.5
672
432
432
2
78 (1:0.6)
90 (В)
2a
6a
6b
6с
6d
6e
6f
Bn
H
2b
Ph
Me
H
H
H
H
63 (А)
2c
Ph
Me
Me
H
H
H
57 (А)
2d
Bn
H
H
H
48 (А)
2e
Bn
H
CO2Me
H
93 (0.85:1)
80 (0.75:1)
53 (А)
3a
Me
H
H
CO2Me
H
168
312
432
24
3b
6g
6h
6i
Ph
Furan-2-ylmethyl
3,4-(MeO)2C6H3(CH2)2
PhSO2
H
H
H
H
H
H
H
CO2Et
CO2Et
CO2Et
H
4a
H
H
67 (А)
4b
H
H
53 (А)
4c
6j
H
H
24
85 (1:0.5)
91 (0.5:1)
5a
6k
6l
Ts
H
H
H
72
5b
1200

Chemistry of Heterocyclic Compounds 2017, 53(11), 1199–1206
Ar
O
O
method of X-ray structural analysis (the value of Flack
N
4
N
H
exo- N
exo-
N
N
parameter was equal to –0.3(5)). Nevertheless, the relative
configuration of molecules in compounds 6b,с was the
same.
3a
N8b
X
X
X
Ar
H
H
H
N
N
The data obtained by X-ray structural analysis of
compounds 6b,с provided reference parameters for their 1Н
and 13С NMR spectra, which allowed to assign the isomeric
epoxytriazoloisoindoles 6a–l to the series A or B. In
particular, the largest difference of chemical shifts was
observed for the doublet signals of geminal protons in the
8-СН2 methylene group. The signals of these protons in
isomers A were shifted downfield by 0.7–1.4 ppm relative
to the spectra of isomers B. For example, 1Н NMR spectrum
of 4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole 6a showed
signals of 8-СН2 protons at 3.43 and 3.75 ppm (isomer В)
or at 4.21 and 4.62 ppm (isomer А).
R
R
6A
O
6B
O
H
H
H
H
X
N
N
N
N
N
R
Ar
endo-
N
R
N
Ar
endo-
N
6A*
6B*
Figure 1. The possible structures of [3+2] cycloaddition products.
1
basis of Н NMR spectral data. The values of spin-spin
The largest difference of 13С NMR chemical shifts
(Δδ ~ 2 ppm) was observed for the C-8a carbon atoms.
Thus, the signals of these atoms in spectra of 3-(2-nitro-
phenyl)triazoloisoindoles A were found in the range of
83.9–86.9 ppm, while the chemical shifts of the respective
atoms in spectra of 1-(2-nitrophenyl)triazoloisoindoles B
were in the range of 85.5–88.7 ppm.
coupling constants for doublet signals of 3a-СН and 8b-СН
protons (J3a,8b = 8.2–8.9 Hz) and the absence of vicinal spin-
3
spin coupling constants J with the 4-СН proton at the
bridgehead position adjacent to oxygen atom confirmed the
exo orientation of triazine ring in the oxabicycloheptane
system (structures 6А and 6В).
In order to unequivocally establish the positions of 2-nitro-
phenyl substituent in adducts 6, the molecular structures of
triazoloisoindoles 6b,c were studied by X-ray structural
analysis (Figs. 2 and 3).
The structure of the latter was also in good agreement
with the data of IR spectroscopy and mass spectrometry.
Mass spectra featured molecular ion peaks that were in
agreement with the expected molecular formulas. IR
spectra of compounds 6 contained absorption bands due
to asymmetric (1537–1523 cm–1) and symmetric (1362–
1350 cm–1) stretching vibrations of the nitro group.
Thus, in the current work we studied the stereo- and
regioselectivity of 1,3-dipolar cycloaddition reaction of
о-nitrophenyl azide to oxabicycloheptenes that were fused
with γ-butyrolactam ring. The target compounds, 4,8a-epoxy-
[1,2,3]triazolo[4,5-e]isoindoles, were obtained in high
yields as single regioisomers or mixtures of two
regioisomers.
Compounds 6b,с included tetracyclic fused systems
composed of five-membered rings
– 1,2,3-triazole,
pyrrolidin-2-one, and two tetrahydrofuran units, which
were isomeric with respect to each other. The triazole ring
was planar, while the pyrrolidinone and tetrahydrofuran
rings assumed a typical envelope conformation.
The molecules of compounds 6b,с contained five
asymmetric centers at the C-3a, C-4, C-5a, C-8a, and C-8b
carbon atoms, and could potentially form sixteen pairs of
diastereomers. The crystals of compound 6b were racemic
and consisted of enantiomeric pairs of molecules with the
following relative configuration at the stereocenters – rac-
3aS,4R,5aS,8aR,8bR. The crystals of compound 6с were
chiral, but it was not possible in this case to objectively
determine the absolute configuration of its molecules by
Figure 3. The molecular structure compound 6c with atoms
represented by thermal vibration ellipsoids of 50% probability.
Figure 2. The molecular structure of compound 6b with atoms
represented by thermal vibration ellipsoids of 50% probability.
1201

Chemistry of Heterocyclic Compounds 2017, 53(11), 1199–1206
combined organic extracts were dried over anhydrous
Experimental
Na2SO4. The drying agent was separated by filtration, and
the solvent was removed by evaporation. Yield 1.8 g (82%),
light-beige powder, mp 95–96°C (hexane–EtOAc).
IR spectrum, ν, cm–1: 1746 (CO2), 1678 (N–C=O).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.57 (1H, d,
J = 9.2) and 2.64 (1H, d, J = 9.2, 7,7a-СH); 2.73 (3H, s,
NCH3); 3.60 (3H, s, ОCH3); 3.57 (1Н, d, J = 11.4) and 3.86
(1H, d, J = 11.4, 3-СH2); 4.99 (1H, d, J = 1.8, 6-СH); 6.30
(1H, dd, J = 5.9, J = 1.8, 5-СH); 6.40 (1H, d, J = 5.9,
4-СH). 13C NMR spectrum (CDCl3), δ, ppm: 29.9; 44.5;
50.6; 50.8; 52.0; 81.3; 88.4; 135.3; 136.7; 170.5; 172.2.
Mass spectrum, m/z (Irel, %): 223 (2) [M]+, 164 (10), 113
(24), 110 (100), 85 (20), 81 (40), 59 (16), 53 (40), 42 (24).
Found, %: C 59.15; H 5.83; N 6.34. C11H13NO4.
Calculated, %: С 59.19; H 5.87; N 6.27.
Ethyl (3aS*,6R*,7R*,7aR*)-2-[2-(3,4-dimethoxyphenyl)-
ethyl]-1-oxo-1,2,3,6,7,7a-hexahydro-3a,6-epoxyisoindole-
7-carboxylate (4c). A solution of amine 1d (0.06 mol) and
ethyl fumaroyl chloride (0.06 mol) (prepared in situ by
stirring monoethyl fumarate (13.0 g, 0.09 mol) with thionyl
chloride (39.0 ml, 0.54 mol) in anhydrous benzene
(100 ml) for a week, followed by removal of solvent and
the excess of thionyl chloride by distillation at reduced
pressure at 50°С) and triethylamine (16.7 ml, 0.12 mol) in
toluene (100 ml) was refluxed for 10 h while monitoring by
TLC, cooled, and poured into water (100 ml). The organic
layer was separated and the aqueous layer was extracted
with ethyl acetate (3×50 ml). The organic phases were
combined and dried over anhydrous MgSO4, filtered,
evaporated, and the residue was crystallized from hexane–
EtOAc mixture. Yield 8.35 g (36%), light-beige rhombic
crystals, mp 108–109°C. IR spectrum, ν, cm–1: 1723 (CO2),
1687 (N–C=O). 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 1.22 (3H, t, J = 7.6, OCH2CH3); 2.75–2.81 (2H, m,
NCH2CH2); 2.82 (1H, d, J = 3.4, 7a-СH); 3.39 (1H, dd,
J = 3.4, J = 4.4, 7-СH); 3.38–3.42 (1H, m) and 3.64–3.70
(1H, m, NCH2); 3.49 (1H, d, J = 11.7) and 3.79 (1H, d,
J = 11.7, 3-СH2); 3.83 (3Н, s) and 3.84 (3Н, s, 2OCH3);
4.07–4.10 (2H, m, OCH2CH3); 5.18 (1Н, dd, J = 2.1, J = 4.4,
6-СH); 6.26 (1H, dd, J = 6.2, J = 2.1, 5-СH); 6.45 (1H,
J = 6.2, 4-СH); 6.72 (1H, s, H-2 Ar); 6.73 (1H, d, J = 8.9,
H-6 Ar); 6.77 (1H, d, J = 8.9, H-5 Ar). 13C NMR spectrum
(CDCl3), δ, ppm: 14.1; 33.3; 44.4; 46.5; 49.9; 51.3; 55.7;
55.8; 61.0; 80.2; 90.4; 111.2; 111.8; 120.5; 131.0; 134.8;
135.0; 147.6; 148.9; 170.3; 172.3. Mass spectrum, m/z
(Irel, %): 387 [M]+ (4), 165 (12), 164 (100), 151 (20), 149
(8), 99 (8), 81 (58). Found, %: C 65.02; H 6.43; N 3.73.
C21H25NO6. Calculated, %: С 65.10; H 6.50; N 3.62.
IR spectra were recorded on an InfraLUM FT-801
1
FTIR spectrometer for samples in KBr pellets. H NMR
spectra were acquired on a JEOL JNM-ECA600 instrument
(600 MHz), using TMS as internal standard. 13C NMR
spectra were acquired on
a Bruker Avance 600
spectrometer (150 MHz), using the central peak of CDCl3
triplet (77.4 ppm) or DMSO-d6 multiplet (40.0 ppm) as
internal standard. Mass spectra of compounds 3b and 4c
were recorded on a Thermo Trace DSQ mass spectrometer
(EI ionization, 70 eV, source temperature 200°C, direct
introduction of sample) or Thermo DSQ II – Focus GC gas
chromate-mass spectrometer (EI ionization, 70 eV, source
temperature 200°C, carrier gas – helium, RTX-5MS
column). Mass spectra with electrospray ionization for the
rest of the compounds were recorded on a Shimadzu
LCMS-8040 quadrupole mass spectrometer (Chromolith
HighResolution RP-18 reversed-phase chromatography
column, mobile phase – acetonitrile (80%) and water (20%),
flow rate – 0.6 ml/min, temperature 40°C). Elemental
analysis was performed on a EuroVector EA 3000 CHNS-
analyzer. Melting points were determined on Stuart SMP
10 and SMP 30 instruments and were not corrected. TLC
analysis was performed on Sorbfil PTSH-AF-А-UV-254
plates, visualization in iodine vapor or with KMnO4
solution. The product ratios in isomer mixtures were
1
determined by Н NMR spectra as the ratios of integrated
intensities for protons of the same type. The reagents were
purchased from Acros Organics and Alfa Aesar and were
used without additional purification. The solvents were
distilled prior to use.
The synthesis with spectral and physicochemical
characterization, as well as elemental analysis data for
compounds 2a,c,5a 2b,5d 2d,5b 2e,5c 3a,5a 4a,b,5d 5a,6a,6c
5b6b,6c have been described previously.
Methyl (3aS*,6R*,7S*,7aR*)-2-methyl-1-oxo-1,2,3,6,7,7a-
hexahydro-3a,6-epoxyisoindole-7-carboxylate (3b).
A
solution of methylfurfurylamine 1e (2.0 g, 18 mmol) and
maleic anhydride (1.8 g, 18 mmol) in benzene (150 ml)
was stirred at room temperature for 2 days. The obtained
precipitate was filtered off, washed with benzene (2×10 ml),
ether (2×10 ml), and recrystallized from EtOH. Yield 2.4 g
(63%), light-beige prismatic crystals, mp 177–178°C.
IR spectrum, ν, cm–1: 1703 (CO2), 1638 (N–C=O).
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.44 (1H,
d, J = 9.1) and 2.72 (1H, d, J = 9.1, 7,7a-СH); 2.74 (3Н, s,
NCH3); 3.55 (1Н, d, J = 11.3) and 3.99 (1H, d, J = 11.3,
3-СH2); 4.97 (1H, d, J = 1.5, 6-СH); 6.41 (1H, dd, J = 6.0,
J = 1.5, 5-СH); 6.56 (1H, d, J = 6.0, 4-СH); 12.13 (1H, br. s,
CO2H). 13C NMR spectrum (DMSO-d6), δ, ppm: 29.4;
44.4; 49.8; 50.0; 81.1; 88.3; 135.7; 136.7; 170.3; 173.0. Mass
spectrum, m/z: 210 [M+Н]+. Found, %: C 57.37; H 5.27;
N 6.81. C10H11NO4. Calculated, %: С 57.41; H 5.30; N 6.70.
A suspension of the obtained acid (2.0 g, 9.6 mmol) in
methanol (40 ml) was treated by adding 2 drops of concd
H2SO4 and then stirred for 8 days at room temperature
while monitoring by TLC. The reaction mixture was
poured into water (100 ml), neutralized with aqueous 25%
NH3 solution, and extracted with CH2Cl2 (3×50 ml). The
Preparation of 4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindoles
6a–l (General method). A solution of the appropriate 3a,6-
epoxyisoindole 2–5 (0.5 g) in toluene (30 ml) was treated
by adding an equimolar amount of о-nitrophenyl azide.7
The obtained reaction mixture was stirred at room
temperature for 1–28 days, while monitoring by TLC. The
target adducts were isolated by filtration in the form of
fine, yellow precipitates (compounds 6а,b,d–h,j–l) or by
removing toluene by distillation at reduced pressure
(compounds 6c,i).
1202

Chemistry of Heterocyclic Compounds 2017, 53(11), 1199–1206
(3aS*,4R*,5aS*,8aR*,8bR*)-3-(2-Nitrophenyl)-7-phenyl-
3a,8b-СH); 7.15 (1H, t, J = 7.3, H Ar); 7.28 (1H, t, J = 7.8,
H Ar); 7.39 (2H, t, J = 7.8, H Ar); 7.59 (1H, d, J = 8.2,
H Ar); 7.67 (1H, t, J = 8.2, H Ar); 7.74 (2H, d, J = 7.8,
H Ar); 7.82 (1H, d, J = 8.2, H Ar). 13C NMR spectrum
(DMSO-d6), δ, ppm: 16.4; 36.3; 48.6; 50.0; 61.5; 86.9;
87.3; 88.9; 118.1; 119.4; 123.6; 124.1; 125.1; 128.8; 132.1;
133.0; 139.2; 141.0; 173.0. Mass spectrum, m/z: 406 [M+H]+.
Found, %: C 62.15; H 4.67; N 17.36. C21H19N5O4.
Calculated, %: С 62.22; H 4.72; N 17.27.
3,3a,4,5,5a,7,8,8b-octahydro-6H-4,8a-epoxy[1,2,3]triazolo-
[4,5-e]isoindol-6-one (6аA) and (3aS*,4R*,5aS*,8aR*,8bR*)-
1-(2-nitrophenyl)-7-phenyl-1,3a,4,5,5a,7,8,8b-octahydro-
6H-4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindol-6-one (6аB)
(1:0.6 mixture of isomers). Yield 0.62 g (78%), bright-yellow
amorphous material. IR spectrum, ν, cm–1: 1698 (N–C=O),
1
1530 (NO2 ν as), 1349 (NO2 ν s), 1600 (N=N). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.98 (1Н, dd, J = 13.0,
J = 9.4), 2.15 (0.6Н, dd, J = 12.8, J = 9.4), 2.22 (1Н, dt,
J = 13.0, J = 5.0) and 2.32 (0.6H, dt, J = 12.8, J = 5.0,
5-СH2); 2.91 (0.6H, dd, J = 9.4, J = 4.3) and 3.00 (1H, dd,
J = 9.2, J = 4.1, 5a-СН); 3.43 (0.6H, d, J= 11.4), 3.75
(0.6H, d, J= 11.4), 4.21 (1H, d, J= 11.9) and 4.62 (1H, d,
J = 11.9, 8-СH2); 4.35 (1H, d, J = 8.2), 4.51 (0.6H, d,
J = 8.7), 5.20 (0.6H, d, J = 8.7) and 5.26 (1H, d, J = 8.2,
3a,8b-СH); 4.39 (1H, d, J = 5.0) and 4.94 (0.6Н, d, J = 5.0,
4-СH); 7.19 (1H, t, J = 7.3, H Ar); 7.47 (0.6Н, td, J = 8.2,
J = 7.3, H Ar), 7.30–7.33 (3.2H, m, H Ar); 7.37–7.41
(3.2H, m, H Ar); 7.55–7.71 (4.8Н, m, H Ar); 7.93 (1Н, dd,
J = 8.2, J = 1.4, H Ar); 8.00 (0.6H, dd, J = 8.2, J = 1.4, H Ar).
13С NMR spectrum (DMSO-d6), δ, ppm: 30.3; 31.5; 48.2;
48.3; 48.4; 48.7; 58.9; 61.5; 79.6; 80.2; 85.5; 88.6; 88.7;
89.1; 119.4; 119.5; 119.8; 120.5; 124.1; 124.2; 124.3;
124.9; 125.0; 125.4; 128.8(2С); 130.9; 131.7; 133.1; 133.5;
138.9; 139.2; 141.0; 142.0; 172.8; 172.9. Mass spectrum,
m/z: 392 [M]+. Found, %: C 61.31; H 4.32; N 17.98.
C20H17N5O4. Calculated, %: С 61.38; H 4.38; N 17.89.
(3aS*,4R*,5aS*,8aR*,8bR*)-7-Benzyl-1-(2-nitrophenyl)-
1,3a,4,5,5a,7,8,8b-octahydro-6H-4,8a-epoxy[1,2,3]triazolo-
[4,5-e]isoindol-6-one (6b). Yield 0.75 g (90%), lemon-
yellow needles, mp 173–174°С (EtOAc–EtOH). IR spectrum,
ν, cm–1: 1694 (N–C=O), 1526 (NO2 ν as), 1353 (NO2 ν s),
(3aS*,4R*,5aS*,8aR*,8bR*)-5a-Methyl-3-(2-nitro-
phenyl)-7-phenyl-3,3a,4,5,5a,7,8,8b-octahydro-6H-4,8a-
epoxy[1,2,3]triazolo[4,5-e]isoindol-6-one (6d). Yield 0.49 g
(57%), light-yellow amorphous powder, mp 174–175°С.
IR spectrum, ν, cm–1: 1704 (N–C=O), 1523 (NO2 ν as),
1
1350 (NO2 ν s), 1595 (N=N). H NMR spectrum (CDCl3),
δ, ppm (J, Hz): 1.43 (3H, s, CH3); 1.51 (1H, d, J = 13.0)
and 2.49 (1H, dd, J = 13.0, J = 5.8, 5-СH2); 4.26 (1H, d,
J = 5.8, 4-CH); 4.33 (1H, d, J = 8.2) and 5.36 (1H, d,
J = 8.2, 3a,8b-СH); 4.19 (1H, d, J = 11.7) and 4.51 (1H, d,
J = 11.7, 8-СH2); 7.18 (1H, t, J = 7.6, H Ar), 7.38–7.40 (3H,
m, H Ar), 7.56 (1H, d, J = 8.2, H Ar), 7.62–7.65 (3H, m,
H Ar); 7.93 (1Н, d, J = 8.2, H Ar). 13C NMR spectrum
(CDCl3), δ, ppm: 19.1; 38.7; 47.4; 53.8; 62.2; 79.9; 83.9;
90.8; 119.8; 124.9; 125.1; 125.4; 126.3; 128.9; 133.0; 133.7;
139.0; 141.9; 175.6. Mass spectrum, m/z: 406 [M+H]+.
Found, %: C 62.16; H 4.66; N 17.38. C21H19N5O4.
Calculated, %: С 62.22; H 4.72; N 17.27.
(3aS*,4R*,5aS*,8aR*,8bR*)-7-Benzyl-5a-methyl-
3-(2-nitrophenyl)-3,3a,4,5,5a,7,8,8b-octahydro-6H-
4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindol-6-one (6e). Yield
0.40 g (48%), lemon-yellow plates, mp 161–162°С.
IR spectrum, ν, cm–1: 1688 (NC=O), 1535 (NO2 ν as), 1360
(NO2 ν s), 1603 (N=N). 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 1.34 (3Н, s, СН3); 1.45 (1Н, d, J= 13.0) and 2.39
(1Н, dd, J = 13.0, J = 5.8, 5-СH2); 3.57 (1H, d, J = 12.4)
and 3.86 (1H, d, J = 12.4, 8-СH2); 4.21 (1H, d, J = 5.8,
4-CH); 4.25 (1H, d, J = 8.2) and 5.22 (1H, d, J = 8.2,
3a,8b-СH); 4.38 (1H, d, J = 15.1) and 4.61 (1H, d, J = 15.1,
NCH2); 7.22 (2H, d, J = 6.9, H Ar); 7.30 (1H, t, J = 6.9,
H Ar); 7.34–7.38 (3H, m, H Ar); 7.55 (1H, d, J = 8.2, H Ar);
7.62 (1H, t, J = 8.2, H Ar); 7.90 (1H, d, J = 8.2, H Ar).
13C NMR spectrum (CDCl3), δ, ppm: 19.2; 30.9; 38.1; 45.6;
46.7; 62.1; 79.8; 84.2; 89.3; 120.5; 125.1; 125.4; 126.1; 127.8;
128.0; 128.8; 133.2; 133.7; 135.7; 176.2. Mass spectrum, m/z:
420 [M+H]+. Found, %: C 62.95; H 4.99; N 16.82.
C22H21N5O4. Calculated, %: С 63.00; H 5.05; N 16.70.
1
1602 (N=N). H NMR spectrum (CDCl3), δ, ppm (J, Hz):
2.07 (1H, dd, J = 13.0, J = 9.3) and 2.21 (1H, dt, J = 13.0,
J = 5.0, 5-СH2); 2.73 (1H, dd, J = 9.3, J = 5.0, 5a-CH);
2.89 (1H, d, J = 11.5) and 3.14 (1H, d, J = 11.5, 8-СH2);
4.24 (1H, d, J = 15.1) and 4.40 (1H, d, J = 15.1, NCH2);
4.36 (1H, d, J = 8.7) and 5.13 (1H, d, J = 8.7, 3a,8b-СH);
4.88 (1H, d, J = 5.0, 4-CH); 7.05 (2H, d, J = 6.4, H Ar);
7.22–7.28 (3H, m, H Ar); 7.33–7.36 (1H, m, H Ar); 7.44
(1H, dd, J = 8.3, J = 1.4, H Ar); 7.53–7.56 (1Н, m, H Ar);
7.86 (1H, dd, J = 8.3, J = 1.4, H Ar). 13C NMR spectrum
(DMSO-d6), δ, ppm: 30.9; 45.2; 46.7; 46.8; 58.4; 79.3; 88.4;
90.2; 119.5; 124.4; 125.3; 127.2; 127.3; 128.5; 131.5; 133.3;
136.5; 141.6; 173.0. Mass spectrum, m/z: 406 [M+H]+.
Found, %: C 62.15; H 4.64; N 17.35. C21H19N5O4.
Calculated, %: С 62.22; H 4.72; N 17.27.
Methyl
(3aS*,4R*,5R*,5aS*,8aR*,8bR*)-7-benzyl-
3-(2-nitrophenyl)-6-oxo-3a,4,5,5a,6,7,8,8b-octahydro-3H-
4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole-5-carboxylate (6fА)
and methyl (3aS*,4R*,5R*,5aS*,8aR*,8bR*)-7-benzyl-
1-(2-nitrophenyl)-6-oxo-3a,4,5,5a,6,7,8,8b-octahydro-1H-
4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole-5-carboxylate
(6fB) (0.85:1 mixture of isomers). Yield 0.72 g (93%),
bright-yellow amorphous material. IR spectrum, ν, cm–1:
1738 (CO2), 1704 (N–C=O), 1533 (NO2 ν as), 1368 (NO2
(3aS*,4R*,5aS*,8aR*,8bR*)-4-Methyl-3-(2-nitro-
phenyl)-7-phenyl-3,3a,4,5,5a,7,8,8b-octahydro-6H-4,8a-
epoxy[1,2,3]triazolo[4,5-e]isoindol-6-one (6с). Yield 0.54 g
(63%), transparent lemon-yellow rhombic crystals,
mp 185°С (EtOAc–DMF). IR spectrum, ν, cm–1: 1703
(N–C=O), 1530 (NO2 ν as), 1359 (NO2 ν s), 1602 (N=N).
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 1.26 (3Н, s,
СН3); 1.73 (1Н, dd, J = 12.4, J = 4.4) and 2.28 (1Н, dd,
J = 12.4, J = 9.4, 5-СH2); 3.31 (1Н, dd, J = 9.4, J= 4.4,
5a-СH); 4.01 (1H, d, J = 11.5) and 4.65 (1H, d, J = 11.5,
8-СH2); 4.75 (1H, d, J = 8.7) and 5.43 (1H, d, J = 8.7,
1
ν s), 1606 (N=N). H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 2.98 (1H, d, J = 11.7) and 3.11 (1H, d, J = 11.7,
8-СH2); 3.05 (0.85H, d, J = 9.6) and 3.12 (1H, d, J = 9.6,
5-СH); 3.20 (0.85H, d, J = 9.6) and 3.23 (1H, d, J = 9.6,
1203

Chemistry of Heterocyclic Compounds 2017, 53(11), 1199–1206
5a-СH); 3.68 (0.85H, J = 12.4, NCH2); 3.74 (2.55H, s) and
Ethyl (3aS*,4R*,5S*,5aS*,8aR*,8bR*)-7-(2-furan-
2-ylmethyl)-3-(2-nitrophenyl)-6-oxo-3a,4,5,5a,6,7,8,8b-octa-
hydro-3H-4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole-5-carb-
oxylate (6i). Yield 0.52 g (67%), fine yellow prismatic
crystals, mp 142–143°С. IR spectrum, ν, cm–1: 1725 (CO2),
1701 (N–C=O), 1537 (NO2 ν as), 1359 (NO2 ν s), 1603
3.77 (3H, s, СH3); 3.97 (0.85H, d, J =11.7, 8-CH2), 4.23
(1H, d, J = 14.7) and 4.56 (1H, d, J = 14.7, NCH2); 4.33
(1H, d, J = 8.2, 8b-СН); 4.41–4.48 (3.55H, m, 4-CH2,
8-CH2, 8b-CH, NCH2); 5.06 (0.85H, s, 4-СH); 5.17 (0.85Н, d,
J = 8.2) and 5.18 (1Н, d, J = 8.2, 3a-СН); 7.07 (1.85H, d,
J = 6.9, H Ar); 7.24–7.66 (13.1H, m, H Ar); 7.90 (1H, dd,
J = 7.9, J = 1.7, H Ar); 7.95 (0.85Н, dd, J = 7.9, J = 1.7,
H Ar). 13С NMR spectrum (DMSO-d6), δ, ppm: 45.0; 45.3;
46.0; 46.1; 47.0; 50.9; 51.1; 51.3 (2С); 58.4; 61.2; 81.2; 81.9;
85.3; 87.9; 89.2; 89.8; 119.8; 120.3; 124.3; 124.6; 125.0; 125.3;
127.0; 127.1; 127.2; 127.4; 128.4; 128.5; 130.8; 131.4; 133.1;
133.3; 136.3 (2C); 141.0; 141.6; 169.3; 169.8; 170.6; 170.7.
Mass spectrum, m/z: 464 [M+H]+. Found, %: C 59.57;
H 4.53; N 15.20. C23H21N5O6. Calculated, %: С 59.61;
H 4.57; N 15.11.
1
(N=N). H NMR spectrum (СDCl3), δ, ppm (J, Hz): 1.32
(3H, t, J = 7.2, CH2CH3); 3.31 (1H, d, J = 5.1, 5a-СH); 3.32
(1H, dd, J = 5.1, J = 4.1, 5-СH); 3.68 (1H, d, J = 12.4) and
4.09 (1H, d, J = 12.4, 8-СH2); 4.19–4.25 (1H, m) and 4.27–
4.31 (1H, m, CH2CH3); 4.35 (1H, d, J = 8.2) and 5.21 (1H,
d, J = 8.2, 3a,8b-СH); 4.36 (1H, d, J = 15.4) and 4.64 (1H,
d, J = 15.4, NCH2); 4.44 (1H, d, J = 4.1, 4-СH); 6.27 (1H,
d, J = 3.0, H-3 furan); 6.34 (1H, dd, J = 3.0, J = 1.7, H-4
furan); 7.35 (1H, ddd, J = 8.2, J = 7.9, J = 1.4, H Ar); 7.39
(1H, br. s, Н-5 furan); 7.54 (1H, dd, J = 8.2, J = 1.4, H Ar);
7.61 (1H, ddd, J = 8.2, J = 7.9, J = 1.4, H Ar); 7.89 (1H,
dd, J = 8.2, J = 1.4, H Ar). 13C NMR spectrum (CDCl3),
δ, ppm: 14.0; 39.5; 47.2; 48.5; 50.8; 59.3; 62.2; 80.0; 86.4;
90.8; 108.8; 110.4; 124.0; 125.6; 125.8; 132.9; 133.7;
141.0; 142.8; 149.0; 169.4; 170.9. Mass spectrum, m/z: 468
[M+H]+. Found, %: C 56.49; H 4.49; N 15.08. C22H21N5O7.
Calculated, %: С 56.53; H 4.53; N 14.98.
Methyl (3aS*,4R*,5R*,5aS*,8aR*,8bR*)-7-methyl-
3-(2-nitrophenyl)-6-oxo-3a,4,5,5a,6,7,8,8b-octahydro-3H-
4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole-5-carboxylate
(6gA) and methyl (3aS*,4R*,5R*,5aS*,8aR*,8bR*)-
7-methyl-1-(2-nitrophenyl)-6-oxo-3a,4,5,5a,6,7,8,8b-octa-
hydro-1H-4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole-5-carb-
oxylate (6gB) (0.75:1 mixture of isomers). Yield 0.68 g
(80%), bright-yellow amorphous material. IR spectrum,
ν, cm–1: 1732 (CO2), 1692 (N–C=O), 1524 (NO2 ν as),
Ethyl (3aS*,4R*,5S*,5aS*,8aR*,8bR*)-7-[2-(3,4-
dimethoxyphenyl)ethyl]-3-(2-nitrophenyl)-6-oxo-
3a,4,5,5a,6,7,8,8b-octahydro-3H-4,8a-epoxy[1,2,3]tri-
azolo[4,5-e]isoindole-5-carboxylate (6j). Yield 0.38 g (53%),
fine lemon-yellow needles, mp 185–186°С. IR spectrum,
ν, cm-1: 1736 (CO2), 1694 (N–C=O), 1534 (NO2 ν as), 1362
(NO2 ν s), 1604 (N=N). 1H NMR spectrum (СDCl3), δ, ppm
(J, Hz): 1.32 (3H, t, J = 7.3, CH2CH3); 3.22 (1H, d, J = 4.4,
5a-СH); 3.28 (1H, dd, J = 5.5, J= 4.4, 5-СH); 2.78–2.86 (1Н,
m), 3.43–3.49 (1Н, m) and 3.66–3.70 (2Н, m, NСН2CH2);
3.87 (3H, s, OCH3); 3.88 (3H, s, OCH3); 3.62 (1H, d,
J = 12.0) and 4.02 (1H, d, J= 12.0, 8-СH2); 4.20–4.25 (1Н,
m) and 4.28–4.33 (1Н, m, CH2CH3); 4.35 (1H, d, J = 8.2)
and 5.19 (1H, d, J = 8.2, 3a,8b-СH); 4.42 (1H, d, J = 5.5,
4-СH); 6.73 (1H, d, J= 2.1, H Ar); 6.76 (1H, dd, J = 8.2,
J = 2.1, H Ar); 6.82 (1H, d, J = 8.2, H Ar); 7.36 (1H, td,
J = 7.9, J = 1.4, H Ar); 7.54 (1H, dd, J = 8.2, J = 1.4, H Ar);
7.61–7.63 (1H, m, H Ar); 7.90 (1Н, dd, J = 8.2, J = 1.4,
H Ar). 13C NMR spectrum (CDCl3), δ, ppm: 14.0; 33.2;
44.4; 47.8; 48.5; 50.9; 55.8; 55.9; 59.3; 62.2; 79.9; 86.4;
90.9; 111.4; 111.9; 120.5; 124.0; 125.6; 125.8; 130.6; 132.9;
133.6; 141.1; 147.7; 149.0; 169.4; 171.1. Mass spectrum,
m/z: 552 [M+H]+. Found, %: C 58.75; H 5.26; N 12.78.
C27H29N5O8. Calculated, %: С 58.80; H 5.30; N 12.70.
(3aS*,4R*,5aR*,8aR*,8bR*)-3-(2-Nitrophenyl)-
1
1347 (NO2 ν s), 1606 (N=N). H NMR spectrum (CDCl3),
δ, ppm (J, Hz): 2.71 (3H, s) and 2.92 (2.25H, s, NCH3);
3.01–3.07 (2.75H, m) and 3.14–3.23 (2.75H, m, 5,5a-СH,
8-СH2); 3.72 (2.25H, s) and 3.76 (3H, s, СH3); 3.78
(0.75H, d, J = 12.4) and 4.13 (0.75H, d, J = 12.4, 8-СH2);
4.36 (0.75H, d, J = 8.2), 4.51 (1H, d, J = 8.2), 5.17 (1H, d,
J = 8.2) and 5.22 (0.75Н, d, J = 8.2, 3a,8b-СH); 4.46
(0.75H, s) and 5.04 (1H, s, 4-СH); 7.41–7.71 (5.25H, m)
and 7.99 (1.75H, m, H Ar). 13С NMR spectrum (DMSO-d6),
δ, ppm: 29.2; 29.3; 45.8; 46.7; 48.2 (2C); 50.8; 51.0; 51.2;
51.3; 58.4; 61.1; 81.3; 81.9; 85.3; 87.8; 89.2; 89.7; 124.2;
124.8; 125.0; 125.3 (2C); 128.2; 128.9; 130.8; 131.4; 133.1;
133.4; 141.1; 141.7; 169.5; 170.7; 170.8. Mass spectrum, m/z:
388 [M+H]+. Found, %: C 52.65; H 4.37; N 18.19.
C17H17N5O6. Calculated, %: С 52.71; H 4.42; N 18.08.
Ethyl (3aS*,4R*,5S*,5aS*,8aR*,8bR*)-3-(2-nitro-
phenyl)-6-oxo-7-phenyl-3a,4,5,5a,6,7,8,8b-octahydro-3H-
4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole-5-carboxylate (6h).
Yield 0.40 g (53%), light-yellow powder, mp 175–176°С.
IR spectrum, ν, cm–1: 1742 (CO2), 1701 (N–C=O), 1535
(NO2 ν as), 1355 (NO2 ν s), 1601 (N=N). 1H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 1.30 (3Н, t, J=7.3,
CH2CH3); 3.38 (1H, t, J = 5.5, 5-CH); 3.60 (1Н, d, J = 5.5,
5a-CH); 4.19–4.24 (1Н, m) and 4.27–4.32 (1Н, m,
CH2CH3); 4.57 (1Н, d, J = 8.6) and 5.50 (1H, d, J = 8.6,
3a,8b-СH); 4.06 (1H, d, J = 11.7) and 4.71 (1H, d, J = 11.7,
8-СH2); 4.82 (1H, d, J = 5.5, 4-CH); 7.17 (1Н, t, J= 7.6,
H Ar); 7.34–7.41 (4H, m, H Ar); 7.72–7.75 (3Н, m, H Ar);
7.89 (1H, dd, J = 8.2, J= 1.4, H Ar). 13C NMR spectrum
(DMSO-d6), δ, ppm: 14.0; 48.3; 48.7; 51.6; 59.0; 61.5;
80.3; 85.4; 89.8; 119.5; 119.6; 124.5; 125.3; 128.8; 130.8;
133.3; 138.9; 140.8; 169.3; 169.4; 171.2. Mass spectrum, m/z:
464 [M+H]+. Found, %: C 59.56; H 4.51; N 15.20.
C23H21N5O6. Calculated, %: С 59.61; H 4.57; N 15.11.
7-phenylsulfonyl-3a,4,5,5a,6,7,8,8b-octahydro-3H-4,8a-
epoxy[1,2,3]triazolo[4,5-e]isoindole
(6kA)
and
(3aS*,4R*,5aR*,8aR*,8bR*)-1-(2-nitrophenyl)-7-phenyl-
sulfonyl-3a,4,5,5a,6,7,8,8b-octahydro-3H-4,8a-epoxy[1,2,3]-
triazolo[4,5-e]isoindole (6kB) (1:0.5 mixture of isomers).
Yield 0.68 g (85%). Compound 6kA was isolated by
fractional crystallization, fine lemon-yellow needles, mp 174–
175°С (EtOAc). IR spectrum, ν, cm–1: 1532 (NO2 ν as),
1
1336 (SO2 ν as, NO2 ν s), 1165 (SO2 ν s). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.55 (1H, ddd, J = 13.1,
J = 5.5, J = 3.5) and 1.70 (1H, dd, J = 13.1, J = 8.1,
1204

Chemistry of Heterocyclic Compounds 2017, 53(11), 1199–1206
5-СH2); 2.42–2.47 (1H, m, 5a-СH); 2.67 (1H, t, J = 9.3)
11232 reflections were collected, of which 3851 were
independent (Rint 0.0717). The final values of probability
factors R1 0.0790 for 2283 independent reflections with
I ≥ 2σ(I) and wR2 0.2041 for all independent reflections,
S 1.057. The peak values of residual electron density ρmin/max
–0.242/0.285.
Compound 6с (C21H19N5O4, M 405.41): transparent
lemon-yellow rhombic crystals, space group P212121, at
100 K: a 8.8358(18), b 13.074(3), c 16.772(3) Å; V 1937.5
(7) Å3; Z 4; dcalc 1.390 g/cm3; F(000) 848; μ 0.210 mm–1. A
total of 12501 reflections were collected, including 3993
independent reflections (Rint 0.0901). The final values of
probability factors R1 0.0537 for 2960 independent
reflections with I ≥ 2σ(I) and wR2 0.1459 for all
independent reflections, S 1.034. The peak values of
residual electron density ρmin/max –0.271/0.241.
The unit cell parameters and intensities of reflections
were measured at the BELOK beamline of the Kurchatov
synchrotron radiation source, using two-dimensional
Rayonix SX165 CCD array (λ 0.96990 Å, φ-scanning with
a step of 1.0°). The experimental data were processed by
using the iMOSFLM program, which is a part of the CCP4
software suite.8 The X-ray absorption for the obtained data
was accounted for by using the Scala program.9 The
structures were solved by direct method and refined by full-
matrix method of least squares in anisotropic
approximation for non-hydrogen atoms. The hydrogen
atom positions were calculated geometrically and included
in the refinement according to the ''rider'' model with fixed
isotropic displacement parameters (Uiso(H) = 1.5Ueq(C) for
the methyl group and 1.2Ueq(C) for the rest of the groups).
All calculations were performed by using the SHELXTL
software suite.10
and 3.82 (1Н, td, J = 9.3, J = 8.3, 6-СH2); 3.57 (1Н, d,
J = 12.6) and 4.15 (1H, d, J = 12.6, 8-СH2); 4.16 (1Н, d,
J = 8.6) and 5.01 (1H, d, J = 8.6, 3a,8b-СH); 4.23 (1Н, d,
J = 5.5, 4-СH); 7.32–7.34 (1H, m, H Ar); 7.50–7.63 (5H,
m, H Ar); 7.83–7.87 (3H, m, H Ar). 13С NMR spectrum
(CDCl3), δ, ppm: 31.4; 44.0; 48.0; 52.8; 62.0; 80.7; 87.3;
95.2; 124.5; 125.2; 125.3; 125.8; 127.4; 128.1; 129.0;
129.2; 132.9; 133.6. Mass spectrum, m/z: 442 [M+H]+.
Found, %: C 54.38; H 4.32; N 15.93. C20H19N5O5S.
Calculated, %: С 54.41; H 4.34; N 15.86.
1
Compound 6kB. H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 1.67 (1H, ddd, J = 12.6, J= 5.0, J = 3.5) and 1.87
(1H, dd, J = 12.6, J = 8.3, 5-СH2); 2.31–2.36 (1H, m,
5a-CH); 2.66 (1H, t, J = 9.6) and 3.69 (1Н, td, J = 9.6,
J = 8.3, 6-СH2); 3.18 (1Н, d, J = 12.6) and 3.28 (1H, d,
J = 12.6, 8-СH2); 4.27 (1Н, d, J = 8.8) and 5.04 (1Н, d,
J = 8.8, 3a,8b-СH); 4.82 (1Н, d, J = 5.0, 4-СH); 7.44–7.64
(5H, m, H Ar); 7.67–7.70 (1H, m, H Ar); 7.83–7.86 (3H,
m, H Ar); 7.98 (1Н, dd, J= 8.1, J = 1.5, H Ar). 13С NMR
spectrum (CDCl3), δ, ppm: 33.0; 44.0; 48.0; 52.7; 60.9;
80.8; 89.3; 96.0; 124.6; 125.0; 125.4; 125.7; 127.0; 127.2;
127.3; 129.1; 133.0; 133.9.
(3aS*,4R*,5aR*,8aR*,8bR*)-7-[(4-Methylphenyl)sulfonyl]-
3-(2-nitrophenyl)-3a,4,5,5a,6,7,8,8b-octahydro-3H-
4,8a-epoxy[1,2,3]triazolo[4,5-e]isoindole (6lA) and
3aS*,4R*,5aR*,8aR*,8bR*)-7-[(4-methylphenyl)sulfonyl]-
1-(2-nitrophenyl)-3a,4,5,5a,6,7,8,8b-octahydro-1H-4,8a-
epoxy[1,2,3]triazolo[4,5-e]isoindole (6lB) (0.5:1 mixture
of isomers). Yield 0.71 g (91%), lemon-yellow amorphous
material. IR spectrum, ν, cm–1: 1526 (NO2 ν as), 1344
(NO2 ν s), 1605 (N=N), 1278 (SO2 ν as), 1158 (SO2 ν s).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.55 (1Н, ddd,
J = 12.8, J = 5.5, J = 3.5), 1.67 (0.5Н, ddd, J = 12.8,
J = 5.5, J = 3.5), 1.69 (1H, dd, J = 12.8, J = 8.1) and 1.86
(0.5H, dd, J = 12.8, J = 8.1, 5-СH2); 2.30–2.35 (0.5Н, m)
and 2.40–2.45 (1Н, m, 5а-СН); 2.43 (3Н, s) and 2.44
(1.5Н, s, СН3); 2.62–2.66 (1.5H, m), 3.66 (0.5Н, td,
J = 9.6, J = 8.6), 3.79 (1Н, td, J = 9.6, J = 8.1, 6-СH2); 3.16
(0.5Н, d, J = 12.6), 3.26 (0.5Н, d, J = 12.6), 3.55 (1Н, d,
J = 12.6) and 4.15 (1Н, d, J = 12.6, 8-СH2); 4.16 (1H, d,
J = 8.6), 4.26 (0.5Н, d, J = 8.6), 5.00 (1H, d, J = 8.6) and
5.04 (0.5H, d, J = 8.6, 3a,8b-CH); 4.23 (1Н, d, J = 5.5) and
4.82 (0.5Н, d, J = 5.5, 4-СH); 7.31–7.34 (4H, m, H Ar);
7.45–7.60 (4H, m, H Ar); 7.68 (0.5H, td, J = 8.1, J = 1.5,
H Ar); 7.71–7.73 (2H, m, H Ar); 7.85 (1H, dd, J= 8.6,
J = 1.5, H Ar); 7.98 (0.5Н, dd, J = 8.1, J = 1.5, H Ar).
13С NMR spectrum (CDCl3), δ, ppm: 21.4; 21.5; 31.4;
32.9; 44.0 (2С); 47.9; 48.0; 52.7; 52.8; 60.9; 62.0; 80.7;
80.8; 87.4; 89.3; 95.2; 96.0; 124.3; 124.8; 125.2; 125.3;
125.7 (2C); 126.9; 127.3; 127.4; 128.1; 128.9; 129.8;
133.0; 133.3; 133.5; 133.9; 137.8; 141.5; 143.0; 143.8;
143.9. Found, %: C 55.32; H 4.60; N 15.47. C21H21N5O5S.
Calculated, %: С 55.37; H 4.65; N 15.38.
The tables of atomic coordinates, bond lengths, bond
angles, torsion angles, and anisotropic displacement para-
meters for compounds 6b,с were deposited at the Cambridge
Crystallographic Data Center (deposits CCDC 1555312
(compound 6b) and CCDC 1555313 (compound 6с)).
The synthesis of starting isoindoles 2–5 was performed
with financial support from the Russian Foundation for
Basic Research (grant 16-33-00389), the synthesis of
triazoles 6 and X-ray structural analyses received support
from the Ministry of Education and Science of the Russian
Federation (project 4.1154.2017/4.6).
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