Reactions of bicyclo[2.2.1]hept-5-ene-2,3-dicarboximides with aromatic azides

Article abstract of DOI:10.1023/B:RUJO.0000045191.12939.47

Reactions of N-substituted bicyclo[2.2.1]hept-5-ene-endo-2,endo-3- dicarboximides with o- and p-nitrophenyl azides, as well as with p-nitrophenylsulfonyl azide and p-toluenesulfonyl azide, afforded the corresponding substituted dihydrotriazole (from aryl azides) and arylsulfonylaziridine derivatives (from sulfonyl azides). The exo orientation of the nitrogen-containing cyclic fragments (in keeping with the Alder rule) and endo orientation of the imide ring were confirmed by analysis of the IR and ¹H and ¹³C NMR spectra. The molecular structure of one of the products was examined by X-ray analysis.

Full text of DOI:10.1023/B:RUJO.0000045191.12939.47

Russian Journal of Organic Chemistry, Vol. 40, No. 7, 2004, pp. 992–998. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 7, 2004,
pp. 1033–1039.
Original Russian Text Copyright © 2004 by Tarabara, A. Kas’yan, Yarovoi, Shishkina, Shishkin, L. Kas’yan.
Reactions of Bicyclo[2.2.1]hept-5-ene-2,3-dicarboximides
with Aromatic Azides
I. N. Tarabara1, A. O. Kas’yan2, M. Yu. Yarovoi1, S. V. Shishkina3,
O. V. Shishkin3, and L. I. Kas’yan1
1 Dnepropetrovsk National University, per. Nauchnyi 13, Dnepropetrovsk, 49050 Ukraine
2 Rheinisch-Westfälische technische Höchschule, Aachen, Germany
3 Institute of Single Crystals, National Academy of Sciences of Ukraine, Kharkiv, Ukraine
Received May 10, 2003
Abstract—Reactions of N-substituted bicyclo[2.2.1]hept-5-ene-endo-2,endo-3-dicarboximides with o- and
p-nitrophenyl azides, as well as with p-nitrophenylsulfonyl azide and p-toluenesulfonyl azide, afforded the
corresponding substituted dihydrotriazole (from aryl azides) and arylsulfonylaziridine derivatives (from
sulfonyl azides). The exo orientation of the nitrogen-containing cyclic fragments (in keeping with the Alder
rule) and endo orientation of the imide ring were confirmed by analysis of the IR and 1H and 13C NMR spectra.
The molecular structure of one of the products was examined by X-ray analysis.
Norbornene and its derivatives occupy a specific
place in organic chemistry. The presence of a rigid
bicyclic skeleton gives rise to stereoisomers with fixed
spatial orientation of substituents [1]. The double bond
in substituted norbornenes exhibits specific properties
arising from steric strain therein; it can readily be
involved in reactions implying formation of cyclic
transition states, in particular in 1,3-dipolar addition
with azides [2, 3]. The mechanism of these reactions
was established on the basis of kinetic data [4]. Using
reactions of aryl azides with stereoisomeric bicyclo-
[2.2.1]hept-5-ene-2,3-dicarboximides as examples [4],
it was found that both electron-donor and electron-
acceptor substituents in the azide molecules accelerate
the reaction. This affect was interpreted in terms of
variation in orbital donor–acceptor interactions be-
tween the dipolarophiles and 1,3-dipoles [4]. The
reaction of phenyl azide with bicyclo[2.2.1]hept-5-ene-
endo-2,endo-3-dicarbonitrile was also examined, and
the products thus obtained were tested for anticarcino-
genic activity [5].
Reactions of norbornene, endic anhydride, and the
exo stereoisomer of the latter with phenylsulfonyl
azide were reported to give phenylsulfonylaziridines;
however, the stereochemical aspects of these reactions
were doubtful [6], so that they require further con-
firmation. According to the data of [6, 7], the forma-
tion of aziridines from the corresponding dihydrotri-
azole intermediates is accompanied by change of the
initial exo orientation of the nitrogen-containing
fragment with respect to the bicyclic skeleton, which is
known as the Alder exo-attack rule and is also typical
of reactions of substituted norbornenes with peroxy
acids, leading to oxirane ring fusion [8].
The goal of the present work was to study reactions
of N-substituted bicyclo[2.2.1]hept-5-ene-endo-2,endo-
3-dicarboxylic (endic) acid imides with aryl- and
Scheme 1.
RNH2, PhH, 20°C
AcOH, reflux
O
O
O
OH
NHR
O
NR
O
O
O
I
IIa–IIi
II, R = H (a), i-Pr (b), t-Bu (c), PhCH2 (d), p-MeC6H4 (e), o,p-Me2C6H3 (f), m,p-Cl2C6H3 (g), p-O2NC6H4 (h), 2-pyridyl (i).
1070-4280/04/4007-0992 © 2004 MAIK “Nauka/Interperiodica”

REACTIONS OF BICYCLO[2.2.1]HEPT-5-ENE-2,3-DICARBOXIMIDES
993
sulfonyl azides. The initial imides were synthesized by
the known procedure including aminolysis of endic
anhydride under mild conditions and subsequent de-
hydration of amido acids thus formed by heating in
boiling glacial acetic acid (Scheme 1). Imides IIa and
IId–IIh were described in [9]. The IR spectra of
compounds II contained absorption bands belonging to
asymmetric and symmetric stretching vibrations of the
carbonyl groups at 1780–1730 and 1710–1680 cm–1
and bands from vibrations of the aromatic ring (in
the spectra of N-aryl and N-benzyl derivatives); com-
pound IIa showed in the spectrum a distinct band
at 3157 cm–1 due to stretching vibrations of the
NH group, and in the spectrum of imide IIh bands at
1520 and 1355 cm–1 were present due to stretching
vibrations of the nitro group [10].
belong to stretching vibrations of the N=N bond in the
triazole fragment [10, 11].
1
The H NMR spectra of triazolonorbornenes III
and IV reflect asymmetric structure of their molecules.
Unlike initial imides, “twin” protons (2-H/6-H and
1-H/7-H) and in some cases 8-H and 12-H in III and
IV are nonequivalent. The strongest differences in the
chemical shifts were observed for protons in the
triazole fragment (2-H and 6-H), whose signals are
located at δ 3.8–4.2 and 4.5–5.0 ppm, respectively.
3
These protons are coupled through a constant J of
9.0–9.3 Hz. One proton at the methylene bridge (anti-
13-H) resonates in a stronger field (δ 1.12–1.45 ppm),
while the position of signal from the other proton is
retained. The upfield shift of the signal from anti-13-H
which is located above the triazole ring plane indicates
that the reaction of imides II with aryl azides follows
the Alder rule [1].
An analogous pattern was observed in the 13C NMR
spectra of compounds IIIa, IVc, IVd, and IVf. The
signals therein were assigned using the Rubenstein–
Nakashima technique. The chemical shifts of C2 and
C6 are δC 56–57 and 83–84 ppm, respectively. The
carbonyl carbon nuclei of the imide fragment give
signals in the δC region 175–177 ppm. Comparison
with the spectra of unsaturated imides [9] shows
an upfield shift of signals from carbon nuclei belong-
ing to the triazole fragment (C2, C6) and from protons
of the methylene bridge (C13).
The reactions of imides IIa–IIi with p- and o-nitro-
phenyl azides were carried out in boiling chloroform
with equimolar amounts of the reactants. The progress
of reactions was monitored by TLC. The reactions took
7 to 15 h, the slowest reaction was that with imide IIh
containing an electron-acceptor nitro group. From
o-nitrophenyl azide and imides IIa–IIe and IIi we
obtained dihydrotriazole derivatives IIIa–IIIf, while
p-nitrophenyl azide gave rise to compounds IVa–IVf.
The IR spectra of products IIIa–IIIf and IVa–IVf
retained carbonyl absorption of the imide fragment
(1765–1750 and 1720–1690 cm–1) and absorption
bands due to stretching vibrations of the nitro group
(1530–1510 and 1360–1325 cm–1). A medium-intensity
band in the region 1610–1595 cm–1 (which was absent
in the IR spectra of the initial imides) is likely to
The structure of compound IIIa was proved by
the X-ray diffraction data (see table and figure).
Compound IIIa crystallizes as a 1:1 solvate with
a 1H-isoindol-1-one molecule. The pyrrole and triazole
rings are planar within 0.03 and 0.02 Å, respectively.
13
N3
4N
5 N
12
2
N4
6
O
7
11
8
6
N3
O1
C9
9
O3
10
C8
O2
NR
O
NO2
C10
N1
C1
C13
C14
IIIa–IIIf
N2
N
C7
N
C6
C2
N5
C12
O
C11
N
C15
NR
C5
O
C3
O2N
O4
IVa–IVf
C4
IIIa, IVa, R = H; IIIb, IVb, R = i-Pr; IIIc, R = t-Bu;
IIId, R = PhCH2; IIIe, IVc, R = p-MeC6H4; IVd, R =
m,p-Cl2C6H3; IVe, R = p-O2NC6H4; IIIf, IVf, R = 2-pyridyl.
Molecular structure of 5-o-nitrophenyl-3,4,5,10-tetraaza-
tricyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione (IIIa)
according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

TARABARA et al.
994
Coordinates (×104) of non-hydrogen atoms and their
equivalent isotropic thermal parameters (E2 ×103) in the
structure of 5-o-nitrophenyl-3,4,5,10-tetraazatricyclo-
[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione (IIIa) as a sol-
vate with 1H-isoindol-1-one molecule (S)
The O3 atom slightly deviates from the pyrrole ring
plane: the torsion angle O3C14C10C11 is –174.9(4)°.
The nitro group is turned with respect to the benzene
ring plane: the torsion angle O1N1C1N2 is –54.4(5)°,
but the C1–N1 bond is not elongated: 1.452(6) Å
against the standard value 1.468 Å [12]. The benzene
and triazole ring planes form an angle of –28.9(5)°
(C1C6N3N3) due to repulsion between the N1 and N3
atoms (the N1···N3 distance is 2.75 Å which is shorter
than the sum of the corresponding van der Waals radii,
3.00 Å [13]). The N2–C6 bond [1.409(5) Å] is longer
than the standard C–N bond [1.371(16) Å], presum-
ably due to electron-acceptor character of the nitro-
phenyl and triazole rings.
The torsion angles H8C8C7H7 and H10C10C11H11 are
equal to –5°, indicating cis-junction of the bicyclo-
heptane fragment with the triazole and pyrrole rings.
Orientation of the five-membered rings with respect
to the bicycloheptane fragment is determined by the
transoid orientation of the H10/H11 and H7/H8. Thus the
triazole ring lies approximately in the plane formed by
the C7, C8, C10, and C11 atoms, while the pyrrole ring is
almost orthogonal to that plane. This arrangement of
the rings gives rise to shortened intramolecular con-
tacts H8···C14 2.50, H7···C15 2.56, H10···C13 2.68,
H11 ···C13 2.87, and H2···H13-anti 2.56 Å (2.66 Å). The
molecule of 1H-isoindol-1-one is planar within 0.01 Å.
Molecules IIIa in crystal are linked to dimers through
intramolecular hydrogen bonds N5H···O4 [N5H···O4
2.06 Å, ∠N5HO4 168°).
Atom
O1
O2
O3
O4
N1
N2
N3
N4
N5
C1
C2
C3
C4
C5
C6
C7
C8
C9
y
z
Ueq
106(2)0
92(1)
71(1)
75(1)
70(1)
54(1)
61(1)
64(1)
57(1)
50(1)
61(1)
59(1)
64(1)
53(1)
44(1)
45(1)
x
1386(6)
1815(5)
3835(5)
1930(4)
4060(3)
4216(3)
0180(5) –1280(3)– 9712(2)
6091(5) 0–202(3)– 8627(2)
2230(6)
2876(5)
1079(6)
0000(6)
2960(6)
2034(3)
2359(3)
1778(4)
4329(3)
6374(3)
6393(3)
7041(3)
3133(5) 0–607(3)– 9359(3)
3917(6)
5232(7)
6918(7)
7281(7)
5959(6)
4249(6)
3131(6)
1121(6)
3153(4)
3800(4)
3905(4)
3380(4)
2758(4)
2629(3)
1112(4)
0892(4)
4750(3)
4144(3)
4438(3)
5353(4)
5984(3)
5702(3)
7163(3)
7581(3)
53(1)
57(1)
55(1)
58(1)
51(1)
0879(7) 0–388(4)– 7250(3)
1890(6) –1252(4)– 7914(3)
3905(7) 0–969(4)– 7579(3)
3886(6) 00–70(4)– 6658(3)
C10
C11
C12
Apart from aryl azides, we examined arylsulfonyl
azides as reagents for addition at the strained double
bond of norbornenedicarboximides. p-Nitrophenylsul-
fonyl and p-tolylsulfonyl azides were synthesized by
the procedure described in [14]. Their reactions with
imides IIa and IIe–IIi were performed in boiling
chloroform using equimolar amounts of the reactants
(Scheme 2). The reaction time was 23–30 h (TLC),
and the products were isolated in 50–70% yield. From
p-tolylsulfonyl azide, we obtained compounds Vg
(R = p-MeC6H4) and Vh (R = o,p-Me2C6H3). The IR
spectra of the products lacked absorption in the region
1600 cm–1, typical of dihydrotriazole derivatives.
Therefore, they were assigned the structure of sul-
fonylaziridines as products of transformation of the
initially formed triazoles. The formation of aziridine
derivatives in reactions with azides containing elec-
tron-acceptor groups was also reported for other sub-
stituted norbornenes [6]. In the IR spectra of com-
pounds V we observed absorption bands corresponding
C13
C14
C15
C1S
C2S
2190(6) 0–450(4)– 6199(3)
1567(8) –1080(4)– 9092(4)
4583(7) 0–561(4)– 8552(4)
63(1)
60(1)
55(1)
84(2)
2549(7)
1935(9)
4535(6)
9869(4)
3690(6) 10622(5)0 112(2)0
C3S
C4S
C5S
C6S
C7S
N1S
C8S
O1S
1396(9)
1422(9)
2048(9)
2617(9)
3311(9)
3602(7)
3193(9)
3364(9)
4134(6) 11606(4)0
5327(6) 11796(4)0
99(2)
99(2)
6173(6) 11065(5)0 105(2)0
5723(6) 10078(5)0
97(2)
6395(6)
5606(7)
4489(7)
3591(6)
9169(6)
8463(4)
8807(6)
8295(5)
105(2)0
108(2)0
107(2)0
187(2)0
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

REACTIONS OF BICYCLO[2.2.1]HEPT-5-ENE-2,3-DICARBOXIMIDES
995
Scheme 2.
11
SO2 N3
2
1
O2N
4-O2NC6H4SO2N3
CHCl3, reflux
10
O
O
5
9
6
4
7
NR
IIa, IIe–IIi
N8R
O
O
Va–Vf
Me
SO2
N
O
NR
O
Vg, Vh
V, R = H (a), p-MeC6H4 (b), o,p-Me2C6H3 (c), m,p-Cl2C6H3 (d), p-O2NC6H4 (e), 2-pyridyl (f).
X-Ray diffraction data for compound IIIa. Tri-
clinic crystals, C15H13N5O4·C8H5NO, with the fol-
lowing unit cell parameters (20°C) a = 7.337(2), b =
11.294(3), c = 12.879(4) Å; α = 89.05(2), β = 81.09(2),
γ = 87.53(2)°; V = 1053.3(5) Å3; M 458.43; Z = 2;
space group PI; dcalc = 1.445 g/cm3; µ(MoKα) =
0.106 mm–1; F(000) = 476. The unit cell parameters
and the intensities of 3714 reflections (3440 independ-
ent reflections with Rint = 0.043) were measured on
a Siemens P3/PC automatic four-circle diffractometer
(MoKα irradiation, graphite monochromator, 2θ/θ-
scanning to 2θmax ≤ 50°). The structure was solved by
the direct method using SHELX97 software package
[16]. The positions of hydrogen atoms were deter-
mined from the difference synthesis of electron density
to stretching vibrations of the imide carbonyl groups,
as well as of the sulfonyl and nitro groups in one or
both benzene rings. The aziridine ring is likely to give
rise to absorption bands in the regions 1160–1190 and
860–900 cm–1 [6].
1
The H NMR spectral data also confirm the
presence of a fused aziridine ring in molecules Va, Vd,
and Vf–Vh. Their spectra considerably differ from
those of the triazole derivatives, primarily in the
chemical shifts of 2-H and 4-H. In addition, the
chemical shifts of the “twin” protons, 2-H/4-H and
1-H/5-H are fairly similar. The upfield shift of the anti-
11-H signal (∆δ = 1.12–1.28 ppm) is also illustrative.
The 13C NMR spectra of V also showed a tendency
for the chemical shifts of C2 and C4 to become closer
(δC 47–50 ppm) and some similarity with the spectra of
structurally related epoxy derivatives (δC 49–51 ppm).
The signal from the bridging C11 atom is displaced to
δC 31–32 ppm due to effect of the exo-oriented three-
membered ring (aziridine or oxirane) [15].
and were refined using the rider model with Uiso
=
1.2Ueq. During the refinement, the bond lengths in the
1H-isoindol-1-one molecule were limited as follows:
C1S–C2S 1.380(3), C2S–C3S 1.38(1), C3S–C4S 1.38(1),
C4S–C5S 1.380(3), C5S–C6S 1.38(1), C1S–C6S 1.38(1),
N1S–C8S 1.38(1), C8S–O1S 1.220(3), C6S–C13S 1.47(1),
C
13S–N1S 1.28(1) Å. The structure was refined with
EXPERIMENTAL
respect to F2 by the full-matrix least-squares procedure
in anisotropic approximation for non-hydrogen atoms
to wR2 = 0.185 from 3440 reflections [R1 = 0.062
from 1354 reflections with F > 4σ(F), S = 0.931]. The
coordinates of atoms are given in table.
The IR spectra were recorded on a Specord 75IR
spectrometer from samples prepared as KBr pellets.
The 1H NMR spectra were obtained on a Varian VXR-
400 instrument operating at 400 MHz from solutions
in DMSO-d6 or chloroform-d using TMS as internal
reference. The 13C NMR spectra were measured on
a Varian Gemini-BB spectrometer (100.57 MHz). The
progress of reactions and the purity of products were
monitored by TLC on Silufol UV-254 plates using
diethyl ether as eluent and iodine vapor as developer.
The elemental compositions were determined on
a Carlo Erba analyzer.
N-Substituted bicyclo[2.2.1]hept-5-ene-endo-2,-
endo-3-dicarboximides IIb, IIc, IIf, and IIi (general
procedure). Appropriate amine, 0.01 mol, was added
under stirring to a solution of 0.01 mol of endic
anhydride in 10 ml of benzene, and the mixture was
stirred until the reaction was complete (TLC). The
precipitate was filtered off, dried, and dissolved in
10 ml of glacial acetic acid, and the solution was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

TARABARA et al.
996
heated under reflux until the reaction was complete
(TLC). The solvent was removed under reduced pres-
sure, water was added to the residue, and the precip-
itate was filtered off, dried, and recrystallized from
benzene.
(IIIb). Yield 72%, mp 158–159°C. 1H NMR spectrum,
δ, ppm: 7.75–7.27 (4H, Harom), 4.51 d (1H, 6-H),
4.49 m (1H, i-Pr), 3.87 d (1H, 2-H), 3.23 m (1H, 8-H),
3.18 m (1H, 12-H), 3.14 m (1H, 7-H), 2.86 m (1H,
1-H), 1.63 d (1H, syn-13-H), 1.42 d (1H, anti-13-H),
1.38 d (6H, i-Pr). Found, %: N 19.12. C18H19N5O4.
Calculated, %: N 18.97.
10-tert-Butyl-5-o-nitrophenyl-3,4,5,10-tetraaza-
tricyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IIIc). Yield 95%, mp 188–190°C. 1H NMR spectrum,
δ, ppm: 7.75–7.23 (4H, Harom), 4.56 d (1H, 6-H),
3.93 d (1H, 2-H), 3.14 m (2H, 8-H, 12-H), 3.12 m (1H,
7-H), 2.85 m (1H, 1-H), 1.60 d (1H, syn-13-H), 1.58 s
(9H, t-Bu), 1.38 d (1H, anti-13-H). Found, %: N 18.36.
C19H21N5O4. Calculated, %: N 18.28.
10-Benzyl-5-o-nitrophenyl-3,4,5,10-tetraazatri-
cyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IIId). Yield 54%, mp 190–191°C. IR spectrum, ν,
cm–1: 1760, 1700, 1690, 1605, 1530, 1360, 1170, 850.
1H NMR spectrum, δ, ppm: 8.17–7.06 (9H, Harom),
4.58 s (2H, PhCH2), 4.28 d (1H, 6-H), 3.63 d (1H,
2-H), 3.28 m (1H, 8-H), 3.23 m (1H, 12-H), 3.12 m (1H,
7-H), 2.85 m (1H, 1-H), 1.63 d (1H, syn-13-H), 1.40 d
(1H, anti-13-H). Found, %: N 16.90. C22H19N5O4. Cal-
culated, %: N 16.79.
5-o-Nitrophenyl-10-(p-tolyl)-3,4,5,10-tetraazatri-
cyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IIIe). Yield 65%, mp 139–140°C. IR spectrum, ν,
cm–1: 1705, 1690, 1605, 1530, 1360, 1185, 855.
1H NMR spectrum, δ, ppm: 7.74–7.19 (8H, Harom),
4.73 d (1H, 6-H), 4.14 d (1H, 2-H), 3.47 m (1H, 8-H),
3.43 m (1H, 12-H), 3.22 m (1H, 7-H), 2.90 m (1H,
1-H), 2.42 (3H, Me), 1.72 d (1H, syn-13-H), 1.49 d
(1H, anti-13-H). Found, %: N 16.65. C22H19N5O4. Cal-
culated, %: N 16.79.
N-Isopropylbicyclo[2.2.1]hept-5-ene-endo-2,-
endo-3-dicarboximide (IIb). Yield 71%, mp 92–
93°C. Found, %: N 6.74. C12H15NO2. Calculated, %:
N 6.83.
N-tert-Butylbicyclo[2.2.1]hept-5-ene-endo-2,-
endo-3-dicarboximide (IIc). Yield 66%, mp 97–98°C.
IR spectrum, ν, cm–1: 3030, 1710, 1680, 1565, 715.
Found, %: N 6.43. C13H17NO2. Calculated, %: N 6.39.
N-(o,p-Dimethylphenyl)bicyclo[2.2.1]hept-5-ene-
endo-2,endo-3-dicarboximide (IIf). Yield 84%,
mp 162–164°C. IR spectrum, ν, cm–1: 3052, 1684,
1370, 846, 712. Found, %: N 5.05. C17H17NO2. Calcu-
lated, %: N 5.24.
N-(α-Pyridyl)bicyclo[2.2.1]hept-5-ene-endo-2,-
endo-3-dicarboximide (IIi). Yield 74%, mp 167–
169°C. IR spectrum, ν, cm–1: 3020, 1780, 1715, 1508,
1340. Found, %: N 11.64. C14H122-HO2. Calculated,
%: N 11.67.
The properties of bicyclo[2.2.1]hept-5-ene-endo-2,-
endo-3-dicarboximides reported previously [9] were
consistent with published data.
Reaction of N-substituted bicyclo[2.2.1]hept-5-
ene-endo-2,endo-3-dicarboximides IIa–IIi with o-
and p-nitrophenyl azides. Equimolar amounts of the
corresponding imide and azide were dissolved in
chloroform, and the solution was heated under reflux
until the reaction was complete (TLC). The solvent
was removed, and the residue was recrystallized from
50% aqueous acetone. We thus obtained compounds
IIIa–IIIf and IVa–IVf.
5-o-Nitrophenyl-10-(2-pyridyl)-3,4,5,10-tetraaza-
tricyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IIIf). Yield 71%, mp 143–144°C. IR spectrum, ν,
cm–1: 1715, 1705, 1600, 1590, 1530, 1360, 1185, 855.
Found, %: N 20.59. C20H16N6O4. Calculated, %:
N 20.79.
5-o-Nitrophenyl-3,4,5,10-tetraazatricyclo-
[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione (IIIa).
Yield 50%, mp 128–130°C. IR spectrum, ν, cm–1:
3180, 1750, 1685, 1600, 1524, 1350, 1190, 845.
1H NMR spectrum, δ, ppm: 10.20 s (1H, NH), 7.79–
7.25 (4H, Harom), 4.72 d (1H, 6-H), 4.19 d (1H, 2-H),
3.40 m (1H, 8-H), 3.36 m (1H, 12-H), 3.11 m (1H,
7-H), 2.91 m (1H, 1-H), 1.68 d (1H, syn-13-H), 1.45 d
(1H, anti-13-H). 13C NMR spectrum, δC, ppm: 177.1
(C=O); 142.2, 133.4, 131.7, 125.7, 124.2, 119.0
(Carom); 82.9 (C6); 56.8 (C2); 47.6 (C8); 47.4 (C12);
43.9 (C7); 43.2 (C1); 35.7 (C13). Found, %: N 21.27.
C15H13N5O4. Calculated, %: N 21.41.
5-p-Nitrophenyl-3,4,5,10-tetraazatricyclo-
[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione (IVa).
Yield 55%, mp 237–238°C. IR spectrum, ν, cm–1:
1
3260, 1755, 1710, 1530, 1355, 1185, 860. H NMR
spectrum, δ, ppm: 11.19 s (1H, NH), 8.25 d (2H,
Harom), 7.32 d (2H, Harom), 4.77 d (1H, 6-H), 3.94 d
(1H, 2-H), 3.30 m (2H, 8-H, 12-H), 3.13 m (1H, 7-H),
3.00 m (1H, 1-H), 1.63 d (1H, syn-13-H), 1.20 d (1H,
anti-13-H). Found, %: N 21.29. C15H13N5O4. Calcu-
lated, %: N 21.41.
10-Isopropyl-5-o-nitrophenyl-3,4,5,10-tetraaza-
tricyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

REACTIONS OF BICYCLO[2.2.1]HEPT-5-ENE-2,3-DICARBOXIMIDES
997
ppm: 176.1 (C=O); 150.2, 126.7, 124.0, 114.1 (Carom);
84.0 (C6); 56.4 (C2); 46.5 (C8); 46.4 (C12); 43.9 (C7);
43.0 (C1); 36.0 (C13). Found, %: N 20.65. C20H16N6O4.
Calculated, %: N 20.79.
10-Isopropyl-5-p-nitrophenyl-3,4,5,10-tetraaza-
tricyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IVb). Yield 78%, mp 229–230°C. IR spectrum, ν,
cm–1: 1770, 1690, 1595, 1505, 1335, 1090, 845.
1H NMR spectrum, δ, ppm: 8.25 d (2H, Harom), 7.83 d
(2H, Harom), 4.61 d (1H, 6-H), 4.31 m (1H, i-Pr), 3.76 d
(1H, 2-H), 3.29 m (2H, 8-H, 12-H), 3.15 m (1H, 7-H),
3.04 m (1H, 1-H), 1.65 d (1H, syn-13-H), 1.38 d (6H,
i-Pr), 1.19 d (1H, anti-13-H). Found, %: N 19.15.
C18H19N5O4. Calculated, %: N 18.97.
Reactions of N-substituted bicyclo[2.2.1]hept-5-
ene-endo-2,endo-3-dicarboximides IIa and IIe–IIi
with arylsulfonyl azides. Equimolar amounts of imide
IIa or IIe–IIi and p-nitrophenyl- or p-tolylsulfonyl
azide were dissolved in chloroform, and the mixture
was heated under reflux until the reaction was com-
plete (TLC). The solvent was removed, and the residue
was recrystallized from isopropyl alcohol.
5-p-Nitrophenyl-10-p-tolyl-3,4,5,10-tetraazatri-
cyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IVc). Yield 86%, mp 197–199°C. IR spectrum, ν,
cm–1: 1720, 1607, 1524, 1510, 1344, 1180, 850.
1H NMR spectrum, δ, ppm: 8.17 d (2H, Harom), 7.28 d
(2H, Harom), 7.22 d (2H, Harom), 7.06 d (2H, Harom),
4.83 d (1H, 6-H), 3.88 d (1H, 2-H), 3.39 m (2H, 8-H,
12-H), 3.38 m (1H, 7-H), 3.16 m (1H, 1-H), 2.32 s
(3H, Me), 1.63 d (1H, syn-13-H), 1.36 d (1H, anti-
13-H). 13C NMR spectrum, δC, ppm: 175.6 (C=O);
144.4, 142.7, 139.7, 130.3, 128.6, 126.4 (Carom); 83.3
(C6); 55.9 (C2); 46.1 (C8); 45.9 (C12); 44.2 (C7); 43.2
(C1); 36.1 (C13); 21.6 (Me). Found, %: N 16.95.
C22H19N5O4. Calculated, %: N 16.79.
3-p-Nitrophenylsulfonyl-3,8-diazatricyclo-
[5.3.1.02,4-exo.06,10-endo]undecane-7,9-dione (Va). Yield
84%, mp 243–245°C. IR spectrum, ν, cm–1: 3260,
3045, 1755, 1710, 1530, 1355, 1327, 1185, 1170,
1095, 860. 1H NMR spectrum, δ, ppm: 10.1 (1H, NH),
8.47 d (2H, Harom), 8.26 d (2H, Harom), 3.34 m (1H,
6-H), 3.32 m (1H, 10-H), 3.10 m (2H, 2-H, 4-H),
2.93 m (2H, 1-H, 5-H), 1.63 d (1H, syn-11-H), 1.25 d
(1H, anti-11-H). 13C NMR spectrum, δC, ppm: 176.8
(C=O); 144.0, 129.5, 124.8 (Carom); 48.7 (C2, C4); 39.1
(C6, C10); 38.2 (C1, C5); 31.1 (C11). Found, %: N 11.45.
C15H13N3O6S. Calculated, %: N 11.57.
10-(m,p-Dichlorophenyl)-5-p-nitrophenyl-
3,4,5,10-tetraazatricyclo[5.5.1.02,6-exo.08,12-endo]tridec-
3-ene-9,11-dione (IVd). Yield 62%, mp 185–187°C.
IR spectrum, ν, cm–1: 1765, 1705, 1595, 1510, 1325,
3-p-Nitrophenylsulfonyl-8-(p-tolyl)-3,8-diazatri-
cyclo[5.3.1.02,4-exo.06,10-endo]undecane-7,9-dione (Vb).
Yield 73%, mp 158–160°C. IR spectrum, ν, cm–1:
3080, 3054, 1718, 1688, 1540, 1387, 1360, 1190,
1172, 1096, 862. Found, %: N 9.20. C22H19N3O6S. Cal-
culated, %: N 9.27.
1
1170, 1080, 850. H NMR spectrum, δ, ppm: 8.29 d
(2H, Harom), 7.70 d (2H, Harom), 7.41–7.33 (3H, Harom),
5.00 d (1H, 6-H), 4.23 d (1H, 2-H), 3.65 m (1H, 8-H),
3.63 m (1H, 12-H), 3.29 m (1H, 7-H), 3.23 m (1H,
1-H), 1.81 d (1H, syn-13-H), 1.31 d (1H, anti-13-H).
13C NMR spectrum, δC, ppm: 175.2 (C=O); 145.5,
130.9, 129.5, 127.6, 126.0 (Carom); 84.1 (C6); 56.1 (C2);
46.2 (C8); 46.1 (C12); 43.7 (C7); 42.8 (C1); 35.5 (C13).
Found, %: N 14.71. C21H15Cl2N5O4. Calculated, %:
N 14.83.
8-(o,p-Dimethylphenyl)-3-p-nitrophenylsulfonyl-
3,8-diazatricyclo[5.3.1.02,4-exo.06,10-endo]undecane-7,9-
dione (Vc). Yield 72%, mp 126–127°C. Found, %:
N 8.76. C23H21N3O6S. Calculated, %: N 8.99.
8-(m,p-Dichlorophenyl)-3-p-nitrophenylsulfonyl-
3,8-diazatricyclo[5.3.1.02,4-exo.06,10-endo]undecane-7,9-
dione (Vd). Yield 69%, mp 186–188°C. IR spectrum,
ν, cm–1: 3078, 1768, 1710, 1700, 1526, 1366, 1347,
5,10-Bis(p-nitrophenyl)-3,4,5,10-tetraazatri-
cyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IVe). Yield 57%, mp 242–244°C. Found, %: N 18.63.
C21H16N6O6. Calculated, %: N 18.75.
1
1162, 1092, 860. H NMR spectrum, δ, ppm: 8.43 d
(2H, Harom), 8.24 d (2H, Harom), 7.80–7.25 (3H, Harom),
3.43 m (2H, 6-H, 10-H), 3.18 m (2H, 2-H, 4-H),
3.04 m (2H, 1-H, 5-H), 1.54 d (1H, syn-11-H), 1.28 d
(1H, anti-11-H). Found, %: N 8.12. C21H15Cl2N3O6S.
Calculated, %: N 8.27.
5-p-Nitrophenyl-10-(2-pyridyl)-3,4,5,10-tetraaza-
tricyclo[5.5.1.02,6-exo.08,12-endo]tridec-3-ene-9,11-dione
(IVf). Yield 86%, mp 211–213°C. IR spectrum, ν, cm–1:
1
8-p-Nitrophenyl-3-p-nitrophenylsulfonyl-3,8-di-
azatricyclo[5.3.1.02,4-exo.06,10-endo]undecane-7,9-dione
(Ve). Yield 80%, mp 177–179°C. IR spectrum, ν, cm–1:
1735, 1710, 1548, 1540, 1368, 1345, 1167. Found, %:
N 11.41. C21H16N4O8S. Calculated, %: N 11.57.
1779, 1597, 1506, 1366, 1205, 1149, 843. H NMR
spectrum, δ, ppm: 7.79–7.25 (8H, Harom), 4.84 d (1H,
6-H), 4.05 d (1H, 2-H), 3.56 m (2H, 8-H, 12-H),
3.20 m (1H, 7-H), 3.10 m (1H, 1-H), 1.65 d (1H, syn-
13-H), 1.12 d (1H, anti-13-H). 13C NMR spectrum, δC,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004

TARABARA et al.
3. Shea, K.J. and Kim, J., J. Am. Chem. Soc., 1992,
998
3-p-Nitrophenylsulfonyl-8-(2-pyridyl)-3,8-diaza-
tricyclo[5.3.1.02,4-exo.06,10-endo]undecane-7,9-dione
(Vf). Yield 55%, mp 215–217°C. IR spectrum, ν, cm–1:
3071, 1765, 1712, 1700, 1527, 1367, 1345, 1170,
1090, 860. 1H NMR spectrum, δ, ppm: 8.45–7.35 (8H,
Harom), 3.42 m (1H, 6-H), 3.40 m (1H, 10-H), 3.07 m
(2H, 2-H, 4-H), 2.97 m (2H, 1-H, 5-H), 1.61 d (1H,
syn-11-H), 1.25 d (1H, anti-11-H). 13C NMR spectrum,
δC, ppm: 174.9 (C=O); 149.9, 146.9, 143.6, 138.6,
124.8, 124.5, 122.9 (Carom); 47.6 (C2, C4); 38.9 (C6,
C10); 38.8 (C1, C5); 31.1 (C11). Found, %: N 12.64.
C20H16N4O6S. Calculated, %: N 12.73.
vol. 114, p. 4846.
4. Scheiner, P., Schomaker, J.H., and Deming, S., J. Am.
Chem. Soc., 1965, vol. 87, p. 306; Samuilov, Ya.D.,
Movchan, A.I., and Konoshenko, L.V., Zh. Org. Khim.,
1981, vol. 17, p. 1626; Roof, A.A.M., Winter, W.J., and
Bartlett, P.D., J. Org. Chem., 1985, vol. 50, p. 4093.
5. Scheiner, P. and Vaughan, W.R., J. Org. Chem., 1961,
vol. 26, p. 1923.
6. Zalkow, L.H. and Oehlschlager, A.C., J. Org. Chem.,
1963, vol. 28, p. 3303; Zalkow, L.H. and Ken-
nedy, C.D., J. Org. Chem., 1963, vol. 28, p. 3309;
Oehlschlager, A.C. and Zalkow, L.H., Can. J. Chem.,
1969, vol. 47, p. 461.
7. Gassmann, P.G., Schaffhausen, J.G., Starkey, F.D., and
Raynolds, P.W., J. Am. Chem. Soc., 1982, vol. 104,
p. 6411.
8. Kas’yan, L.I., Usp. Khim., 1998, vol. 67, p. 299;
Kas’yan, L.I., Seferova, M.F., and Okovityi, S.I.,
Alitsiklicheskie epoksidnye soedineniya. Metody sinteza
(Alicyclic Epoxy Compounds. Methods of Synthesis),
Dnepropetrovsk: Dnepropetr. Gos. Univ., 1996.
9. Kas’yan, L.I., Krishchik, O.V., Umrikhina, L.K., and
Kas’yan, A.O., Visn. Dnipropetr. Univ., Khim., 1998,
vol. 3, p. 87; Moench, S.I., Pagani, G., Gaecialanza, G.,
Viearini, L., and Baruffini, A., Farmaco, Ed. Sci., 1970,
vol. 25, p. 203.
10. Nakanishi, K., Infrared Absorption Spectroscopy.
Practical, San Francisco: Holden-Day, 1962.
11. Bellamy, L.J., The Infra-red Spectra of Complex
Molecules, London: Methuen, 1958.
12. Burgi, H.-B. and Dunitz, G.D., Structure Correlation,
Weinheim: VCH, 1994, vol. 2, p. 741.
13. Zefirov, Yu.V. and Zorkii, P.M., Usp. Khim., 1989,
vol. 58, p. 713.
14. Organic Syntheses, Noland, W.E., Ed., New York:
Wiley, 1963, collect. vol. 4; Organic Syntheses, Baum-
garten, H.E., Ed., New York: Wiley, 1973, collect. vol. 5.
8-p-Tolyl-3-p-tolylsulfonyl-3,8-diazatricyclo-
[5.3.1.02,4-exo.06,10-endo]undecane-7,9-dione (Vg). Yield
78%, mp 216–217°C. IR spectrum, ν, cm–1: 3046,
1
1705, 1515, 1378, 1322, 1160, 1091, 881. H NMR
spectrum, δ, ppm: 7.70 d (2H, Harom), 7.35 d (2H,
Harom), 7.15 d (2H, Harom), 6.84 d (2H, Harom), 3.32 m
(1H, 6-H), 3.31 m (1H, 10-H), 3.23 m (2H, 2-H, 4-H),
2.76 m (2H, 1-H, 5-H), 2.34 s (3H, Me), 2.24 s (3H,
Me), 1.60 d (1H, syn-11-H), 1.20 d (1H, anti-11-H).
13C NMR spectrum, δ, ppm: 175.5 (C=O); 145.2,
138.6, 130.2, 129.7, 128.4, 127.0, 121.5 (Carom); 49.9
(C2, C4); 40.1 (C6, C10); 37.7 (C1, C5); 31.1 (C11); 20.9
(Me); 20.5 (Me). Found, %: N 6.58. C23H22N2O4S.
Calculated, %: N 6.64.
8-(o,p-Dimethylphenyl)-3-p-tolylsulfonyl-3,8-di-
azatricyclo[5.3.1.02,4-exo.06,10-endo]undecane-7,9-dione
(Vh). Yield 51%, mp 176–178°C. IR spectrum, ν, cm–1:
1
1708, 1507, 1380, 1324, 1163, 1069, 880. H NMR
spectrum, δ, ppm: 7.71 d (2H, Harom), 7.28 d (2H,
Harom), 7.07–6.80 (3H, Harom), 3.25 m (2H, 6-H, 10-H),
3.10 m (2H, 2-H, 4-H), 3.02 m (2H, 1-H, 5-H), 2.39 s
(3H, Me), 2.28 s (3H, Me), 2.00 s (3H, Me), 1.79 d
(1H, syn-11-H), 1.12 d (1H, anti-11-H). Found, %:
N 6.33. C24H24N2O4S. Calculated, %: N 6.42.
15. Tori, K., Aono, K., Kitahonoki, K., Muneyuki, R.,
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panova, E.G., Kas’yan, L.I., Gnedenkov, L.Yu., and
Bombushkar’, M.F., Izv. Akad. Nauk SSSR, Ser. Khim.,
1980, p. 564.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 7 2004