3-Azabicyclo[3.3.1]nonane derivatives: VIII. Synthesis and properties of 6(7)-R-3,3-dimethyl-1,5- dinitro-3-azoniabicyclo[3.3.1]non-6-ene iodides

Article abstract of DOI:10.1023/B:RUJO.0000034949.33987.6b

N-Alkylation of 6(7)-R-1,5-dinitro-3-methyl-3-azabicyclo[3.3.1]non-6-enes with methyl iodide afforded a series of quaternary ammonium salts whose yield depended on the solvent polarity and character of substituents located in positions 6 or 7 of substrate. The presence of electron-withdrawing groups reduced the yield of the target products compared to unsubstituted compound, whereas the electron-donor substituents increased the yield. As shown by the X-ray diffractionstudy the congormation of the substances was not changed in the course of quaternization. The DTA-TG analysis revealed that in the first stage of thermolysis the 6(7)-R-3,3-dimethyl-1,5-dinitro-3-azoniabicyclo[3.3.1]non-6- ene iodides suffer dealkylation. Two fragmentation paths of compounds synthesized under electron impact were observed: elimination either of methyl iodide or aziridinium cation.

Full text of DOI:10.1023/B:RUJO.0000034949.33987.6b

Russian Journal of Organic Chemistry, Vol. 40, No. 2, 2004, pp. 247-254. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 2, 2004,
pp. 275-282.
Original Russian Text Copyright Ó 2004 by Shakhkeldyan, Melekhina, Atroshenko, Kopyshev, Borbulevich, Suponitskii, Antipin, Efremov,
Alifanova, Nikisina, Subbotin.
3-Azabicyclo[3.3.1]nonane Derivatives:
VIII.* Synthesis and Properties of 6(7)-R-3,3-Dimethyl-1,5-
dinitro-3-azoniabicyclo[3.3.1]non-6-ene Iodides
I. V. Shakhkeldyan1, N. K. Melekhina1, Yu. M. Atroshenko1, M.V. Kopyshev2,
O. Ya. Borbulevich3, K. Yu. Suponitskii3, M. Yu.Antipin3,Yu.A. Efremov1,
E. N. Alifanova1, M. B. Nikisina1, and V.A. Subbotin1
1Tolstoy Tula State Pedagogical University, Tula, 300600 Russia
e-mail: reaktiv@tspu.tula.ru
2Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow, Russia
3Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Received April 10, 2002
Abstract—N-Alkylation of 6(7)-R-1,5-dinitro-3-methyl-3-azabicyclo[3.3.1]non-6-enes with methyl iodide afforded
a series of quaternary ammonium salts whose yield depended on the solvent polarity and character of substituents
located in positions 6 or 7 of substrate. The presence of electron-withdrawing groups reduced the yield of the
target products compared to unsubstituted compound, whereas the electron-donor substituents increased the
yield. As shown by the X-ray diffraction study the congormation of the substances was not changed in the course
of quaternization. The DTA-TG analysis revealed that in the first stage of thermolysis the 6(7)-R-3,3-dimethyl-1,5-
dinitro-3-azoniabicyclo[3.3.1]non-6-ene iodides suffer dealkylation. Two fragmentation paths of compounds
synthesized under electron impact were observed: elimination either of methyl iodide or aziridinium cation.
In extension of research [1–5] on the synthesis of
polyfunctional 3-azabicyclo[3.3.1]nonanes, a valuable
class of biologically active substances [6], in the present
study we investigated alkylation of 1,5-dinitro-3-methyl-
3-azabicyclo[3.3.1]non-6-ene derivatives with alkyl
iodides. The interest of this reaction lies in the change in
the hydrophilic/lipophilic characteristics of compounds on
going from neutral nitrogen-containing heterocycles to
their quaternary salts. These properties are important for
bonding with enzymes and receptors, for transport
through membranes, penetration into cells, and distribution
in tissues
replacement the solvent by less polar tetrahydrofuran
resulted in decreased a yield of alkylation products. These
reactions furnished compounds IIa–i whose composition
and structure are confirmed by elemental analyses and
spectral data. The yield of quaternary salts is significantly
affected with the nature of substituents located in positions
6 or 7 of substrate I. . The presence of electron-
withdrawing groups reduced the yield of the target
products compared to unsubstituted compound, whereas
the electron-donor substituents increased the yield. We
failed to obtain alkylation products from 3-azabicyclo-
[3.3.1]-nonane derivatives containing other substituents
at the nitrogen atom, like Et, EtBr, CH2Ph, CH2CO2H,
EtOH, CH(C2H5)OH. These data indicate that more
bulky groups provide steric hindrances to the attack of
the nitrogen by methyl iodide. This conclusion is indirectly
supported by the fact that the attempt to carry out the
alkylation with ethyl iodide failed even with N-methyl
derivatives of 3-azabicyclononane.
As substrates in the study of 3-azabicyclononanes
alkylation were selected 6(7)-R-3-methyl-1,5-dinitro-3-
azabicyclo[3.3.1]non-6-enes I prepared from derivatives
of 1,3-dinitrobenzene along Scheme 1 [2–4, 7, 8], and
methyl iodide was used as alkylation agent. The reaction
in acetonitrile at 60°C completed within 48 h. The
* For Communication VII see [1].
1070-4280/04/4002-0247Ó2004 MAIK “Nauka/Interperiodica”

248
SHAKHKELDYAN et al.
Scheme 1.
&+ 2ꢂ
5
5
5
5
1D%+
1+ 0Hꢂꢁ+
0H,
2 1
12
2 1
12
2 1
12
2 1
12
ꢀꢁ1D
1
1
,
0H
0H
0H
,D ,L
,,D ,,L
R = H (a), 6-Me (b), 6-OMe (c), 6-O(CH2)2Cl (d), 6-OPh (e), 6-Cl (f), 6-Br (g), 7-OMe (h), 7-CONH2 (i).
1
In the IR spectra of compounds synthesized the most
characteristic absorption bands are those of stretching
vibrations of C=C bonds and NO2 groups in the region
The assignment of signals in the H NMR spectra
can be illustrated by an example of iodide IIe (Fig. 1).
The most downfield signals at d 7.10–7.50 ppm are a
doublet and two triplets (3J 7.93 Hz) with integral intensity
ratio 2:2:1 corresponding to aromatic protons from the
OPh group. The signal of olefin proton H7 gives an ABX
system with protons H8 and is observed as a doublet of
doublets (3J 4.89 and 2.80 Hz) at d 5.50 ppm. Therewith
the signals of the AB part contains a broadened doublet
–1
1630–1675, 1540–1570, and 1340–1375 cm . The
absorption bands in the IR spectra of quaternary salts II
are shifted to higher frequencies as compared to those
of the initial 3-azabicyclo[3.3.1]-non-6-enes I due to the
presence in the former of a positive charge on the nitrogen
atom.
+
+
+
10H
+
+
2
ꢃ+
+
2 1
+
ꢃ+
+
+
12
+
1
+
+
+ &
&+
,
+ +
+
+
+
+
+
+
+
+
ꢀꢁꢂ
ꢀꢁꢃ
ꢂꢁꢄ
ꢂꢁꢅ
ꢂꢁꢆ
ꢇꢁꢂ
ꢇꢁꢃ
ꢅꢁꢄ
ꢅꢁꢅ
ꢅꢁꢆ
ꢈꢁꢂ
ꢈꢁꢃ
ꢃꢁꢄ
Fig. 1. 1H NMR spectrum of 6-phenoxy-3,3-dimethyl-1,5-dinitro-3-azoniabicyclo-[3.3.1]non-6-ene iodide IIe.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

249
3-AZABICYCLO[3.3.1]NONANE DERIVATIVES: VIII.
(2J 18.31 Hz) of H8e proton and a well resolved doublet
of doublets (2J 18.31, 3J 4.89 Hz) of H8a proton at d 3.21
and 2.30 ppm respectively. The signals of bridging protons
H9 appear as two doublets (2J 11.60 Hz) at d 3.34 and
3.25 ppm The positive charge on the nitrogen of the
piperidine ring causes a strong downfield shift
(Dd ~1.0 ppm) of methylene protons H2,4 signals (d 4.11–
4.66 ppm) and those of nonequivalent N-methyl groups
(d 3.52, 3.53 ppm) as compared to the signals of the
corresponding protons in the initial compound Ie (d 2.47–
3.53 and 2.53 ppm respectively) (see EXPERI-
MENTAL).
The bonds C–N+ in cation IIa are somewhat longer
that usual bonds of this type (1.499 A [12]) indicating
that in cation IIa exist steric hindrances. This is confirmed
°
by the presence in this fragment of cation of quite a
7
11
...
number of shortened interatomic contacts: C C 3.30
°
(3.42 A, here and hereinafter in parentheses is given the
sum of vander Waals radii [13] of the corresponding
8
11
7
11C
8
11C
...
...
...
atoms), C
C
3.24, C
H
2.68 (2.87), C
H
11B
10B
°
2.77, H2B
H
2.21 (2.32), H4B
H
2.02 A. Eight
...
...
hydrogen atoms are present in the nearest coordination
...
sphere of the iodide ion forming shortened contacts I H
that are closer than the sum of van der Waals radii of C
°
1
2B
1
and H atoms ( 3.30 A [13]): I
H
2.92, I
H
11B 3.12,
...
H
...
Similar values of the geminal coupling constants of
the protons in the piperidine ring in the 1H NMR spectra
of quaternary salts II and the initial 3-azabicyclo[3.3.1]-
non-6-enes I evidence that the spatial structure of the
bicyclononenes does not considerably change during
quaternization. It was formerly established with the use
of X-ray diffraction analysis [2–4, 9] that in the series of
1,5-dinitro-3-azabicyclo[3.3.1]non-6-ene derivatives the
piperidine ring exists in the chair form, and the
cyclohexane ring has sofa conformation. Yet the X-ray
data on 7,7-dimethyl-3-thia-7-azoniabicyclo[3.3.1]-nonan-
9-one iodide [10] revealed that the ring containing the
1
6B2
1
4A2
1
4B2
...
...
...
H
I
H
(1 + x, 1 + y, z) 3.24, I
(1 – x, 0.5 + y, 1 – z) 3.09, I
(1 + x, y, 1 + z) 2.91 A. It is interesting
that all these contacts save I
shorter than the so-called statistical mean value (3.13 A)
established recently for I H contact [14].
3.00, I
2.94, I
2
2
1
9B2 2
1
10B2
...
...
H
H
1
9A2 2 2
°
...
3.13, I
H
1
6B2
°
...
H
3.24 A are also
°
...
Sterical “overloading” of the molecules of compounds
synthesized is reflected in the pattern of their
2 ꢀ
+
NMe2 group was in a boat form. It was therefore
expectable that on alkylation of 1,5-dinitro-3-azabi-
cyclo[3.3.1]non-6-enes I the nitrogen-containing fragment
would acquire a boat form. To clear up this problem we
subjected one of the compounds synthesized, 3,3-dimethyl-
1,5-dinitro-3-azoniabicyclo[3.3.1]non-6-ene iodide IIa, to
X-ray diffraction analysis.
2 ꢀ
1 ꢀ
& ꢀ
& ꢀ
& ꢀ
As show the data obtained (Tables 1, 2, Fig. 2) the
cation of quaternary salt IIa retained the conformation
of the initial compound. The piperidine ring in the
compound under study has the chair form. Deviations
of atoms N3 and C9 from the plane going through the rest
& ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
1 ꢀ
°
ring atoms amount to 0.512 and –0.799 Arespectively.
The conformation of cyclohexene ring C1C8C7C6C5C9 is
sofa with a deviation of C9 atom from the plane of the
°
& ꢀ
other ring atoms of -0.776 A. The conformation of the
& ꢀ
eight-membered ring is close to boat-boat one and its
Zefirov-Palyulin folding parameters [11] are as follows:
S2 1.186, S3 0.382, S4 0.683, j2 182.93, j3 180.66. The
nitro groups attached to atoms C1 and C5 take an
equatorial positions [torsion angles N1C1C9C5 and
N2C5C9C1 are equal to 179.6(3) and –179.1(3) deg
respectively]. They are also considerably turned with
respect to relatively planar fragment of the cyclohexene
ring [torsion angles O2N1C1C8 and O3N2C5C6 are equal
to 44.9(5) and 93.4(4) deg respectively].
1 ꢀ
, ꢀ
2 ꢀ
2 ꢀ
Fig. 2. Molecular structure of 3,3-dimethyl-1,5-dinitro-3-
azoniabicyclo[3.3.1]non-6-ene iodide IIa.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

250
SHAKHKELDYAN et al.
Table 1. Coordinates (´104) and equivalent isotropic thermal
In contrast to initial compounds I for salts IIf, g a primary
dissociation of the C–N bonds in the heterocyclic
fragment is characteristic in keeping with the X-ray
analysis data and in agreement with the properties of
amines quaternary salts [16]. Along one of the
fragmentation paths of molecular ions an elimination of
dimethylaminocation Me2N+ (m/z 44) occurs (path A).
The cation further loses a hydrogen molecule converting
into an aziridinylium cation of m/z 42 with a very high
relative peak intensity (maximum in the case of compound
IIf). Further fragmentation of the F2 ion results in
bicyclodiene (m/z 91) (Scheme 2).
parameters (Å2 ´ 103) of nonhydrogen atoms in the structure of
3,3-dimethyl-1,5-dinitro-3-azoniabicyclo[3.3.1]non-6-ene iodide IIa
$WRPꢀ
, ꢀ
[ꢀ
\ꢀ
]ꢀ
8 ꢀ
ꢁꢂꢂꢃꢄꢅꢆꢀ
±ꢋꢋꢋꢁꢄꢇꢆꢀ
ꢂꢅꢊꢌꢄꢇꢆꢀ
ꢋꢃꢇꢈꢄꢇꢆꢀ
±ꢋꢊꢊꢂꢄꢇꢆꢀ
±ꢋꢃꢁꢇꢄꢇꢆꢀ
ꢋꢃꢈꢇꢄꢈꢆꢀ
ꢇꢇꢂꢈꢄꢇꢆꢀ
±ꢇꢈꢇꢄꢈꢆꢀ
ꢃꢉꢃꢄꢇꢆꢀ
ꢇꢈꢃꢉꢄꢅꢆꢀ
ꢋꢈꢌꢉꢄꢂꢆꢀ
ꢂꢉꢈꢅꢄꢂꢆꢀ
ꢂꢋꢊꢊꢄꢂꢆꢀ
ꢋꢅꢊꢅꢄꢂꢆꢀ
ꢋꢋꢃꢁꢄꢂꢆꢀ
ꢋꢃꢃꢌꢄꢇꢆꢀ
ꢇꢇꢌꢅꢄꢇꢆꢀ
ꢂꢋꢊꢁꢄꢂꢆꢀ
ꢋꢁꢂꢁꢄꢂꢆꢀ
ꢂꢂꢌꢁꢄꢇꢆꢀ
ꢂꢁꢂꢂꢄꢇꢆꢀ
ꢈꢋꢂꢌꢄꢈꢆꢀ
ꢈꢈꢇꢋꢄꢇꢆꢀ
ꢇꢉꢈꢉꢄꢃꢆꢀ
ꢂꢌꢇꢌꢄꢂꢆꢀ
ꢇꢈꢇꢃꢄꢉꢆꢀ
ꢋꢂꢁꢋꢄꢂꢆꢀ
ꢉꢊꢋꢉꢄꢅꢆꢀ
ꢋꢌꢅꢂꢄꢇꢆꢀ
ꢊꢃꢂꢄꢇꢆꢀ
ꢅꢃꢄꢅꢆꢀ
ꢅꢁꢄꢅꢆꢀ
ꢋꢅꢄꢅꢆꢀ
ꢅꢇꢄꢅꢆꢀ
ꢋꢊꢄꢅꢆꢀ
ꢋꢉꢄꢅꢆꢀ
ꢂꢈꢄꢅꢆꢀ
ꢂꢋꢄꢅꢆꢀ
ꢅꢂꢄꢅꢆꢀ
ꢅꢃꢄꢅꢆꢀ
ꢅꢉꢄꢅꢆꢀ
ꢅꢃꢄꢅꢆꢀ
ꢋꢅꢄꢅꢆꢀ
ꢋꢈꢄꢅꢆꢀ
ꢅꢊꢄꢅꢆꢀ
ꢅꢈꢄꢅꢆꢀ
ꢅꢊꢄꢅꢆꢀ
ꢅꢊꢄꢅꢆꢀ
1 ꢀ
1 ꢀ
1 ꢀ
2 ꢀ
2 ꢀ
2 ꢀ
2 ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
& ꢀ
ꢈꢅꢉꢃꢄꢇꢆꢀ
ꢈꢅꢇꢄꢇꢆꢀ
ꢂꢌꢊꢉꢄꢇꢆꢀ
±ꢋꢊꢄꢈꢆꢀ
Another fragmentation path (path B) consists in
elimination of methyl iodide and formation of ion F1.
Interestingly, the positive charge can be localized either
on the eliminated species or on the remaining fragment.
The prevailing direction is formation of a cation-radical
MeI+· (m/z 142) whose peak in the mass spectrum of
compound IIg is the strongest. In the course of cation
F1 fragmentation it loses in succession radical species
ꢅꢅꢁꢋꢄꢇꢆꢀ
ꢋꢉꢌꢂꢄꢇꢆꢀ
ꢇꢇꢂꢊꢄꢇꢆꢀ
ꢂꢁꢇꢇꢄꢈꢆꢀ
ꢋꢌꢁꢇꢄꢈꢆꢀ
ꢋꢌꢉꢅꢄꢉꢆꢀ
ꢋꢋꢌꢊꢄꢈꢆꢀ
ꢋꢇꢇꢁꢄꢇꢆꢀ
ꢅꢂꢊꢌꢄꢇꢆꢀ
ꢉꢌꢃꢅꢄꢇꢆꢀ
ꢉꢈꢈꢋꢄꢇꢆꢀ
ꢂꢈꢂꢉꢄꢈꢆꢀ
ꢋꢅꢈꢌꢄꢉꢆꢀ
ꢅꢃꢋꢋꢄꢉꢆꢀ
ꢅꢇꢂꢄꢉꢆꢀ
·
NO·, OH·, and NO2 . Another path of cation F1
fragmentation starts with halogen atoms elimination
(Scheme 2).
±ꢅꢌꢊꢉꢄꢇꢆꢀ
ꢇꢋꢊꢄꢈꢆꢀ
The study of the thermal stability of 1,5-dinitro-3-
azabicyclo[3.3.1]non-6-ene derivatives [1] showed that
they were prone to decomposition with elimination of one
or two nitro groups in agreement with the properties of
aliphatic nitro compounds [17]. Therefore we studied the
behavior of compounds IIa–i at heating by means of
derivatography. The thermogravimetric data (DTG and
TG) reveled that for all compounds under study two
pronounced stages of mass loss are observed: the first
one with an endo effect, the second one with exo effect
(Table 3). From analysis of signals on DTAthermograms
ehthalpy (Q), apparent activation energy (Ea), and orders
(n) of the thermal degradation of compounds IIa–i were
calculated. The comparison of calculated and
experimental values of mass loss (Dm) suggests that in
the first stage of thermolysis (115–220°C) dealkylation
occurs with methyl iodide elimination and formation of
the corresponding derivatives of 1,5-dinitro-3-aza-
bicyclo[3.3.1]non-6-ene I. The process occurs with heat
consumption and with relatively high activation energy
(101–163 kJ mol-1) evidencing the high stability of the
quaternary salts. The second stage (218–310°C) for the
most compounds proceeds with notable heat liberation
(163–361 kJ mol-1) and with low activation energy (40–
ꢋꢊꢁꢉꢄꢇꢆꢀ
ꢂꢊꢅꢇꢄꢈꢆꢀ
ꢀ
°
Table 2. Some bond lengths (d, A) in the structure of 3,3-
dimethyl-1,5-dinitro-3-azoniabicyclo[3.3.1]non-6-ene iodide IIa.
%RQGꢀ
2 ±1 ꢀ
2 ±1 ꢀ
2 ±1 ꢀ
2 ±1 ꢀ
1 ±& ꢀ
1 ±& ꢀ
1 ±& ꢀ
1 ±& ꢀ
1 ±& ꢀ
Gꢁꢀ ꢀ
%RQGꢀ
1 ±& ꢀ
& ±& ꢀ
& ±& ꢀ
& ±& ꢀ
& ±& ꢀ
& ±& ꢀ
& ±& ꢀ
& ±& ꢀ
& ±& ꢀ
Gꢁꢀ ꢀ
ꢂꢃꢄꢄꢄꢅꢆꢇꢀ
ꢂꢃꢄꢊꢈꢅꢆꢇꢀ
ꢂꢃꢄꢂꢆꢅꢈꢇꢀ
ꢂꢃꢄꢄꢆꢅꢈꢇꢀ
ꢂꢃꢆꢊꢆꢅꢆꢇꢀ
ꢂꢃꢆꢈꢈꢅꢈꢇꢀ
ꢂꢃꢆꢊꢂꢅꢈꢇꢀ
ꢂꢃꢆꢂꢋꢅꢈꢇꢀ
ꢂꢃꢆꢂꢉꢅꢈꢇꢀ
ꢂꢃꢆꢂꢈꢅꢉꢇꢀ
ꢂꢃꢆꢈꢋꢅꢉꢇꢀ
ꢂꢃꢆꢌꢋꢅꢆꢇꢀ
ꢂꢃꢆꢄꢍꢅꢆꢇꢀ
ꢂꢃꢊꢎꢊꢅꢉꢇꢀ
ꢂꢃꢈꢆꢄꢅꢎꢇꢀ
ꢂꢃꢆꢄꢉꢅꢋꢇꢀ
ꢂꢃꢆꢄꢆꢅꢆꢇꢀ
ꢂꢃꢆꢊꢍꢅꢆꢇꢀ
ꢀ
decomposition under electron impact as revealed in
analysis of the mass spectra of compounds IIf, g (Scheme
2; relative intensities of ion peaks with respect to the
total ion current are given in parentheses). It was shown
formerly [1, 4] that the main fragmentation path for
molecular ion of 1,5-dinitro-3-azabicyclo[3.3.1]non-6-
enes I was the rapture of C–N bond with radicals NO2
elimination which in some cases involved nitro-nitrite
rearrangement often observed in nitro compounds [15].
110 kJ mol-1)
. Compounds with alkoxy groups in positions
6 or 7 IIc, d, h form an exception with an enthalpy in
the limits 71–94 kJ mol-1.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

251
3-AZABICYCLO[3.3.1]NONANE DERIVATIVES: VIII.
Scheme 2.
5
5
5
$
%
0H,
5
2 1
12
2 1
12
2 1
12
2 1
12 ꢅ 12
1ꢀ0Hꢆ
,
1
1
1
&+
)
ꢀꢁꢂꢇꢄ ꢁꢂꢈꢆ
12
1
+ &
&+
&+
Pꢉ]ꢀꢃꢇꢈ
ꢀꢅꢂꢇꢄ ꢇꢂꢈꢆ
&+
Pꢉ]ꢀꢅꢅꢊ
ꢀꢁꢂꢃꢄ ꢁꢂꢃꢆ
)
ꢀꢁꢂꢃꢄ ꢁꢂꢅꢆ
12
+2
&+
+2
5
5
5
1+
2 1
2 1
2 1
&+
1+
1
+
)
1
&+
)
)
Pꢉ]ꢀꢃꢁꢈ
ꢀꢁꢂꢈꢄ ꢁꢂꢋꢆ
Pꢉ]ꢀꢃꢃꢌ
ꢀꢁꢂꢊꢄ ꢁꢂꢋꢆ
ꢀꢁꢂꢅꢄ ꢁꢂꢃꢆ
ꢀꢁꢂꢃꢄ ꢁꢂꢋꢆ
ꢀꢃꢂꢈꢄ ꢃꢂꢃꢆ
12
12
& +
5
5
+5
&
1
&+
Pꢉ]ꢀꢊꢎ
ꢀꢅꢂꢋꢄ ꢇꢂꢈꢆ
Pꢉ]ꢀꢃꢁꢇ
ꢀꢁꢂꢊꢄ ꢁꢂꢋꢆ
)
Pꢉ]ꢀꢋꢋ
ꢀꢃꢂꢍꢄ ꢅꢂꢅꢆ
)
ꢀꢊꢂꢌꢄ ꢈꢂꢌꢆ
ꢀꢃꢂꢊꢄ ꢁꢂꢋꢆ
&
&+
5
+5
1+
1+
)
Pꢉ]ꢀꢃꢃꢍ
ꢀꢁꢂꢊꢄ ꢃꢂꢁꢆ
Pꢉ]ꢀꢌꢃ
ꢀꢇꢂꢌꢄ ꢌꢂꢊꢆ
ꢀꢁꢂꢈꢄ ꢁꢂꢇꢆ
Alumina calcined at 1200°C was used as inert carrier.
Weight of the samples studied was 100 mg. The sensitivity
to mass loss in TG was 0.2 mg, the sensitivity in recording
DTG and DTA was 50 and 500 mV respectively. The
temperature of the start and the end of decomposition
was determined at the points were DTG and DTAcurves
crossed the basis lines. The maximum temperature of
decomposition process corresponded to the extremum
on the DTA curve. The enthalpy was estimated from the
DTA curves by procedure [19].
EXPERIMENTAL
IR spectra were recorded on spectrophotometer
Specord 75-IR from films prepared from acetone solution
1
or from mulls in mineral oil. H NMR spectra were
registered on spectrometer Bruker DRX-500 (500 MHz)
in DMSO-d6, internal references HMDS. Mass spectra
of compounds were taken on Varian MAT-311 instrument
at ionizing electrons energy 70 eV. Combined
measurements of DTA, DTG, and TG were carried out
on derivatogrph Q-1500 (MOM, Hungary) in a labyrinth
crucible in air under dynamic conditions [18], heating rate
Initial compounds Ia–c, f, h, i were prepared by
procedures from [2, 7, 8]. Compounds Id, e, g were
synthesized in a similar way.
–1
1.25 deg min in the temperature range 20–500°C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

252
SHAKHKELDYAN et al.
Table 3. Evaluation of thermal stability of 6(7)-R-3,3-dimethyl-1,5-dinitro-3-azoniabicyclo[3.3.1]non-6-ene iodides IIa–i
6WDJHꢀ,ꢀꢀ
6WDJHꢀ,,ꢀ
VWDUWꢎꢀ PD[Lꢏ HQGꢀ 'Pꢎꢀ
q ꢀ PXPꢎꢀq ꢀ q ꢀ FDOFꢍꢎꢀ(ꢀ H[Sꢎꢀ(ꢀ N-ꢐPROꢀ N-ꢐPROꢀ RUGHUꢎꢀQꢀ q ꢀ PXPꢎꢀq ꢀ
'Pꢎꢀ
4ꢎꢀ
( ꢎꢀ UHDFWLRQꢀ VWDUWꢎꢀ PD[Lꢏ
'Pꢀ
4ꢎꢀ
( ꢎꢀ
HQGꢎꢀqꢀ ꢀ
FDOFꢍꢎꢀ(ꢀN-ꢐPROꢀ N-ꢐPROꢀ
,, ꢀ ꢅꢈꢁꢀ
ꢅꢁꢈꢀ ꢋꢌꢇꢀ ꢂꢊꢀ
ꢅꢊꢌꢀ ꢋꢌꢂꢀ ꢂꢃꢀ
ꢅꢃꢇꢀ ꢅꢊꢁꢀ ꢂꢉꢀ
ꢅꢉꢃꢀ ꢅꢊꢂꢀ ꢂꢅꢀ
ꢅꢉꢊꢀ ꢋꢌꢌꢀ ꢂꢅꢀ
ꢅꢃꢂꢀ ꢋꢌꢌꢀ ꢂꢈꢀ
ꢅꢁꢅꢀ ꢋꢌꢌꢀ ꢂꢋꢀ
ꢅꢊꢂꢀ ꢋꢋꢌꢀ ꢂꢉꢀ
ꢋꢌꢂꢀ ꢋꢋꢌꢀ ꢂꢈꢀ
ꢇꢅꢀ
ꢇꢉꢀ
ꢂꢇꢀ
ꢋꢊꢀ
ꢋꢊꢀ
ꢂꢃꢀ
ꢋꢊꢀ
ꢂꢋꢀ
ꢂꢇꢀ
±ꢊꢁꢀ
±ꢅꢋꢃꢀ
±ꢅꢂꢋꢀ
±ꢋꢉꢇꢀ
±ꢅꢋꢇꢀ
±ꢅꢌꢉꢀ
±ꢅꢌꢃꢀ
±ꢊꢉꢀ
ꢅꢅꢇꢀ
ꢅꢋꢅꢀ
ꢅꢌꢅꢀ
ꢅꢂꢁꢀ
ꢅꢈꢉꢀ
ꢅꢌꢂꢀ
ꢅꢌꢋꢀ
ꢅꢇꢉꢀ
ꢅꢉꢂꢀ
ꢋꢍꢈꢀ
ꢋꢍꢁꢀ
ꢅꢍꢂꢀ
ꢋꢍꢋꢀ
ꢋꢍꢊꢀ
ꢋꢍꢋꢀ
ꢋꢍꢋꢀ
ꢋꢍꢈꢀ
ꢅꢍꢂꢀ
ꢋꢅꢊꢀ
ꢋꢅꢊꢀ
ꢋꢂꢋꢀ
ꢋꢇꢌꢀ
ꢋꢈꢇꢀ
ꢋꢅꢁꢀ
ꢋꢂꢌꢀ
ꢋꢂꢁꢀ
ꢋꢋꢌꢀ
ꢋꢈꢃꢀ
ꢋꢉꢂꢀ
ꢋꢁꢈꢀ
ꢋꢈꢌꢀ
ꢋꢊꢂꢀ
ꢋꢉꢋꢀ
ꢋꢈꢂꢀ
ꢋꢁꢁꢀ
ꢋꢇꢌꢀ
ꢋꢉꢁꢀ
ꢋꢁꢈꢀ
ꢂꢌꢋꢀ
ꢋꢃꢃꢀ
ꢂꢅꢌꢀ
ꢋꢁꢉꢀ
ꢋꢃꢂꢀ
ꢂꢅꢉꢀ
ꢋꢉꢋꢀ
ꢃꢈꢀ ꢂꢌꢋꢀ
ꢊꢌꢀ ꢅꢉꢂꢀ
ꢉꢉꢀ
ꢅꢌꢈꢀ
ꢇꢈꢀ
ꢅꢃꢈꢀ
ꢅꢈꢈꢀ
ꢅꢈꢃꢀ
ꢅꢉꢂꢀ
ꢅꢉꢈꢀ
ꢅꢃꢈꢀ
ꢅꢃꢂꢀ
ꢅꢊꢂꢀ
,,Eꢀ
,,F ꢀ
,,Gꢀ
,,H ꢀ
,,Iꢀ
ꢁꢉꢀ
ꢉꢅꢀ
ꢁꢂꢀ
ꢃꢅꢀ
ꢅꢅꢌꢀ
ꢈꢌꢀ
ꢃꢅꢀ ꢂꢉꢋꢀ
ꢁꢉꢀ ꢋꢉꢂꢀ
ꢉꢌꢀ ꢋꢉꢇꢀ
ꢇꢊꢀ
ꢇꢌꢀ
,,Jꢀ
,,Kꢀ
,,Lꢀ
ꢁꢋꢀ
ꢊꢇꢀ
ꢃꢌꢀ
±ꢅꢊꢉꢀ
ꢈꢂꢀ ꢋꢌꢌꢀ
ꢇꢈꢀ
ꢀ
a Sublimation of compound is observed.
d, ppm: 6.34 d.d (1H, H7, J 4.89, 3.05 Hz), 3.25 d (1H,
H4e, J 10.38 Hz), 3.15 d (1H, H2e, J 10.98 Hz), 3.14 d (1H,
H9e, J 11.59 Hz), 2.97 br.d (1H, H8e, J 18.32 Hz), 2.77 d.d
(1H, H8a, J 18.32, 4.89 Hz), 2.76 d (1H, H9a, J 11.59 Hz),
2.55 d (1H, H2a, J 10.98 Hz), 2.53 d (1H, H4a, J 10.38 Hz),
2.45 s (3H, N–CH3). Found, %: C 35.96, 36.02; H 3.97,
4.11; N 13.48, 13.59; Br 26.01, 25.79. C9H12BrN3O4.
Calculated, %: C 35.31; H 3.95; N 13.73; Br 26.14.
6-(2-Chloroethoxy)-3-methyl-1,5-dinitro-3-
azabicyclo[3.3.1]non-6-ene (Id). Yield 27%. Colorless
–1
crystals, mp 83–84°C. IR spectrum, cm : 1669 (C=C),
1
1527, 1333 (NO2), 1226 (C–O). H NMR spectrum
(DMSO-d6), d, ppm: 5.01 d.d (1H, H7, J 4.89, 3.05 Hz),
3.99 m (2H, OCH2), 3.73 m (2H, CH2Cl), 3.25 d (1H,
H4 , J 10.68 Hz), 3.25 d (1H, H2 , J 10.68 Hz), 3.10 d
e
e
(1H, H9 , J 10.99 Hz), 2.88 br.d (1H, H8 , J 17.09 Hz),
e
e
2.72 d.d (1H, H8a, J 17.09, 4.88 Hz), 2.58 d (1H, H9a,
J 10.99 Hz), 2.50 d (1H, H2a, J 10.68 Hz), 2.45 d (1H,
H4a, J 10.68 Hz), 2.41 s (3H, N–CH3). Found, %: C 43.30,
43.16; H 5.26, 5.11; N 13.52, 13.48; Cl 11.84, 11.71.
C11H16ClN3O5. Calculated, %: C 43.22; H 5.28; N 13.74;
Cl 11.62.
6(7)-R-3,3-Dimethyl-1,5-dinitro-3-azoniabicyclo-
[3.3.1]non-6-ene iodides (IIa–i). To a solution of 0.4
mmol of an appropriate 1,5-dinitro-3-azabicyclo[3.3.1]-
non-6-ene derivative I in a minimal amount of anhydrous
acetonitrile was added 0.75 ml (12 mmol) of methyl
iodide. The flask equipped with a reflux condenser was
tightly stoppered and placed in the dark at 60°C for 48 h.
The precipitated quaternary salt was filtered off and
washed with a little acetonitrile.
3-Methyl-1,5-dinitro-6-phenoxy-3-azabicyclo-
[3.3.1]non-6-ene (Ie). Yield 35%. Colorless crystals,
–1
mp 123–124°C. IR spectrum, cm : 1692 (C=C), 1547,
1
1345 (NO2), 1128 (C–O). H NMR spectrum (CDCl3),
3,3-Dimethyl-1,5-dinitro-3-azoniabicyclo-
d, ppm: 7.34 t (2H, Hb, J 8.10 Hz), 7.14 t (1H, Hg, J 8.10
Hz), 7.04 t (2H, Ha, J 8.10 Hz), 5.25 d.d (1H, H7, J 6.25,
1.97 Hz), 3.53 d (1H, H4e, J 11.16 Hz), 3.37 d (1H, H2e,
J 10.5 Hz), 3.35 d (1H, H9e, J 11.6 Hz), 2.85 d.d (1H, H8e,
J 17.72, 1.97 Hz), 2.74 d.d (1H, H8a, J 17.72, 6.25 Hz),
2.57 d (1H, H9a, J 11.6 Hz), 2.53 s (3H, N–CH3), 2.49 d
(1H, H2a, J 10.5 Hz), 2.47 d (1H, H4a, J 11.16 Hz). Found,
%: C 56.72, 56.73; H 5.30, 5.41;N13.10, 13.25.
C15H17N3O5. Calculated, %: C 56.42; H 5.37; N 13.16.
[3.3.1]non-6-ene iodide (IIa). Yield 73%, mp 184–
186°C (decomp.). IR spectrum, cm : 1542, 1342 (NO2),
–1
1671 (C=C). 1H NMR spectrum (DMSO-d6), d, ppm:
6.28 br.s (1H, H7), 4.29 d (1H, H4e, J 13.43 Hz), 2.54 d
(1H, H4a, J 10.38 Hz), 3.115 d (1H, H2e, J 10.38 Hz), 4.16 d
(1H, H2a, J 13.43 Hz), 3.11 d (1H, H9e, J 10.99 Hz), 2.99 d
(1H, H9a, J 10.99 Hz), 3.20 d (1H, H8e, J 18.61 Hz), 3.08 d
(1H, H8a, J 18.61 Hz), 3.44 s, 3.36 s (6H, N+Me2). Found,
%: C 33.01, 32.79; H 4.37, 4.26; N 11.44, 11.50; I 33.94,
34.14. C10H16IN3O4. Calculated, %: C 32.52; H 4.34;
N 11.38; I 34.42.
6-Bromo-3-methyl-1,5-dinitro-3-azabicyclo-
[3.3.1]non-6-ene (Ig). Yield 43%. Colorless crystals
,
–1
3,3,6-Trimethyl-1,5-dinitro-3-azoniabicyclo-
[3.3.1]non-6-ene iodide (IIb). Yield 87%, mp 189–
mp 134–135°C. IR spectrum, cm : 1646 (C=C), 1532,
1
1346 (NO2). H NMR spectrum (DMSO-d6–CCl4, 1:3),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

253
3-AZABICYCLO[3.3.1]NONANE DERIVATIVES: VIII.
Ha, J 7.93 Hz), 7.47 t (2H, Hb, J 7.93 Hz), 7.29 t (1H, Hg,
J 7.93 Hz). Found, %: C 41.86, 41.70; H 4.48, 4.52;
N 9.10, 9.22; I 27.28, 27.68. C16H20IN3O5. Calculated,
%: C 41.65; H 4.34; N 9.1; I 27.55.
–1
191°C (decomp.). IR spectrum, cm : 1571, 1343 (NO2),
1642 (C=C). 1H NMR spectrum (DMSO-d6), d, ppm:
6.01 br.s (1H, H7), 4.47 d (1H, H4e, J 13.43 Hz), 4.02 d
(1H, H4a, J 10.38 Hz), 4.27 d (1H, H2e, J 13.43 Hz), 4.11 d
(1H, H2a, J 13.42 Hz), 3.13 d (1H, H9e, J 10.99 Hz), 3.07 d
(1H, H9a, J 10.99 Hz), 3.21 d (1H, H8e, J 18.61 Hz), 3.04 d
(1H, H8a, J 18.61 Hz), 3.41 s, 3.34 s (6H, N+Me2), 1.69 s
(3H, CH3). Found, %: C 34.37, 34.94; H 4.56, 4.82; N
11.60, 11.24; I 33.82, 33.89. C11H18IN3O4. Calculated,
%: C 34.46; H 4.70; N 10.97; I 33.16.
3,3-Dimethyl-1,5-dinitro-6-chloro-3-azoniabi-
cyclo[3.3.1]non-6-ene iodide (IIf). Yield 45%, mp 172–
–1
174°C (decomp.). IR spectrum, cm : 1569, 1367 (NO2),
1630 (C=C). 1H NMR spectrum (DMSO-d6), d, ppm:
6.74 d.d (1H, H7, J 4.88, 3.05 Hz), 4.39 d (1H, H4e,
J 13.43 Hz), 4.09 d (1H, H4a, J 13.43 Hz), 4.37 d (1H, He2,
J 13.43 Hz), 4.24 d (1H, H2a, J 13.43 Hz), 3.34 d (1H, He9,
J 11.59 Hz), 3.30 d (1H, H9a, J 11.6 Hz), 3.40 d (1H, He8,
J 18.92 Hz), 3.19 d.d (1H, H8a, J 18.92, 4.88 Hz), 3.51 s,
3.40 s (6H, N+Me2). Mass spectrum, m/z: 261 M+, 250,
231, 214, 201, 200, 179, 168, 154, 150, 142, 134, 127, 118,
103, 100, 91, 77, 65, 51, 50, 42. Found, %: C 29.75, 29.94;
H 3.82, 3.77; Cl 8.64, 8.67; I 30.92, 31.02; N 10.12, 10.18.
C10H15ClIN3O4. Calculated, %: C 29.74; H 3.72; Cl 8.80;
I 31.47; N 10.41.
3,3-Dimethyl-6-methoxy-1,5-dinitro-3-
azoniabicyclo[3.3.1]non-6-ene iodide (IIc). Yield
95%, mp 173–175°C (decomp.). IR spectrum, cm :
1570, 1358 (NO2), 1685 (C=C), 1257 (C–O). H NMR
–1
1
spectrum (DMSO-d6), d, ppm: 5.25 d.d (1H, H7, J 4.88,
2.80 Hz), 4.35 d (1H, H4e, J 13.43 Hz), 4.05 d (1H, H4a,
J 13.43 Hz), 4.31 d (1H, H2e, J 13.43 Hz), 4.17 d (1H, Ha2,
J 13.43 Hz), 3.22 d (1H, H9e, J 10.99 Hz), 3.11 d (1H, Ha9,
J 10.99 Hz), 3.24 d (1H, H8e, J 18.31 Hz), 3.04 d.d (1H,
H8a, J 18.31, 4.88 Hz), 3.46 s, 3.40 s (6H, N+Me2), 3.65 s
(3H, CH3). Found, %: C 33.02, 33.09; H 4.60, 4.49; N
10.32, 10.30; I 31.46, 31.35. C11H18IN3O5. Calculated,
%: C 33.08; H 4.51; N 10.53; I 31.83.
6-Bromo-3,3-dimethyl-1,5-dinitro-3-azoniabi-
cyclo[3.3.1]non-6-ene iodide (IIg). Yield 42%, mp
–1
180–182°C (decomp.). IR spectrum, cm : 1567, 1365
1
(NO2), 1635 (C=C). H NMR spectrum (DMSO-d6), d,
ppm: 6.57 d.d (1H, H7, J 5.49, 3.05 Hz), 4.43 d (1H, H4e,
J 13.42 Hz), 4.11 d (1H, H4a, J 13.42 Hz), 4.35 d (1H, He2,
J 13.42 Hz), 4.29 d (1H, H2a, J 13.42 Hz), 3.34 d (1H, He9,
J 11.6 Hz), 3.31 d (1H, H9a, J 11.6 Hz), 3.44 d (1H, He8,
J 18.92 Hz), 3.23 d.d (1H, H8a, J 18.92, 4.88 Hz), 3.50 s,
3.39 s (6H, N+Me2). Mass spectrum, m/z: 305 M+, 280,
258, 245, 226, 212, 200, 172, 150, 142, 134, 127, 118, 103,
100, 91, 77, 65, 51, 50, 42. Found, %: C 26.98, 26.70;
H 3.36, 3.43; Br 17.54, 17.61; I 27.85, 27.95; N 9.24,
9.08. C10H15BrIN3O4. Calculated, %: C 26.79; H 3.35;
Br 17.86; I 28.35; N 9.38.
3,3-Dèmethyl-1,5-dinitro-6-(2-chloroetoxi)-3-
azoniabicyclo[3.3.1]non-6-ene iodide (IId). Yield
–1
83%, mp 166–168°C (decomp.). IR spectrum, cm :
1
1554, 1338 (NO2), 1675 (C=C), 1229 (C–O). H NMR
spectrum (DMSO-d6), d, ppm: 5.32 d.d (1H, H7 J 4.88,
3.05 Hz), 4.29 d (1H, H4e, J 13.43 Hz), 4.06 d (1H, H4a,
J 13.43 Hz), 4.29 d (1H, H2 , J 13.43 Hz), 4.21 d (1H,
e
H2a, J 13.43 Hz), 3.25 d (1H, H9e, J 10.99 Hz), 3.14 d (1H,
H9a, J 10.99 Hz), 3.28 d (1H, H8e, J 18.61 Hz), 3.01 d.d
(1H, H8a, J 18.61, 4.88 Hz), 3.47 s, 3.38 s (6H, N+Me2),
3.82 t (2H, CH2CH2Cl, J 4.88 Hz), 4.12 m (2H,
CH2CH2Cl). Found, %: C 32.07, 32.33; H 4.62, 4.58;
N 10.96, 10.01; I 27.50, 27.47; Cl 7.41, 7.41.
C12H19ClIN3O5. Calculated, %: C 32.18; H 4.25; N 9.39;
I 28.38; Cl 7.93.
3,3-Dimethyl-7-methoxy-1,5-dinitro-3-azoniabi-
cyclo[3.3.1]non-6-ene iodide (IIh). Yield 87%, mp
–1
192–194°C (decomp.). IR spectrum, cm : 1557, 1357
(NO2), 1658 (C=C), 1242 (C–O). 1H NMR spectrum
(DMSO-d6), d, ppm: 5.32 br.s (1H, H7), 4.30 d (1H, He4,
J 13.43 Hz), 4.06 d (1H, H4a, J 13.43 Hz), 4.19 d (1H, He2,
J 13.43 Hz), 4.16 d (1H, H2a, J 13.43 Hz), 3.10 d (1H, He9,
J 10.98 Hz), 3.01 d (1H, H9a, J 10.98 Hz), 3.30 d (1H, He8,
J 17.71 Hz), 3.04 d (1H, H8a, J 17.71 Hz), 3.66 s, 3.44 s
(6H, N+Me2), 3.29 s (3H, CH3). Found, %: C 33.40,
33.20; H 4.87, 4.96; I 31.61, 31.93; N 10.54, 10.58.
C11H18IN3O5. Calculated, %: C 33.08; H 4.51; I 31.83;
N 10.53.
3,3-Dimethyl-1,5-dinitro-6-phenoxi-3-azoniabi-
cyclo[3.3.1]non-6-ene iodide (IIe). Yield 54%, mp
–1
168–170°C (decomp.). IR spectrum, cm : 1562, 1365
(NO2), 1676 (C=C), 1222 (C–O). 1H NMR spectrum
NMR spectrum (DMSO-d6), d, ppm: 5.00 d.d (1H, H7,
J 4.88, 2.80 Hz), 4.66 d (1H, H4e, J 3.93 Hz), 4.11 d (1H,
H4a, J 3.43 Hz), 4.35 d (1H, H2e, J 0.38 Hz), 4.33 d (1H,
H2a, J 0.38 Hz), 3.34 d (1H, He9, J 1.6 Hz), 3.25 d (1H, H9a,
J 1.6 Hz), 3.21 d (1H, H8e, J 8.31 Hz), 2.3 d.d (1H, H8a,
J 8.31, 4.89 Hz), 3.53 s, 3.52 s (6H N+Me2), 7.13 d (2H,
7-Carbamoyl-3,3-dimethyl-1,5-dinitro-3-
azoniabicyclo[3.3.1]non-6-ene iodide (IIi). Yield 46%,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

254
SHAKHKELDYAN et al.
–1
2. Atroshchenko, Yu.M., Nikiforova, E.G., Gitis, S.S., Grud-
tsyn, Yu.D., Shishkin, O.V., Andrianov, V.F., and
Shakhkel’dyan, I.V., Zh. Org. Khim., 1999, vol. 35, p. 1339.
3.Atroshchenko, Yu.M., Nikiforova, E.G., Shakhkel’dyan, I.V.,
Grudtsyn, Yu.D., Akhmedov, N.G., Alifanova, E.N.,
Borbulevich, O.Ya., Shishkin, O.V., Gitis, S.S., and
Kaminskii,A.Ya., Zh. Org. Khim., 2000, vol. 36, p. 771.
4. Shakhkel’dyan, I.V., Nikiforova, E.G., Grudtsyn, Yu.D.,
Atroshchenko, Yu.M., Borbulevich, O.Ya., Efremov, Yu.A.,
Gitis, S.S., Moiseev, D.N.,Alifanova, E.N., Chudakov, P.V.,
and Kovalevskii,A.Yu., Zh. Org. Khim., 2001, 37, p. 617.
5. Nikiforova, E.G., Korolev, M.A., Shakhkel’dyan, I.V., Du-
tov, PPM, Grudtsyn, Yu.D., Atroshchenko, Yu.M., Sheve-
lev, S.A., and Subbotin, V.A., Zh. Org. Khim., 2001, vol. 37,
p. 771.
6. Jeyaraman, R. andAvila, S., Chem. Rev., 1981, vol. 81, p. 149.
7. Severin, T., Schmitz, M., andAdam, M., Chem. Ber., 1963,
vol. 96, p. 3076.
8. Wall, R.T., Tetrahedron, 1970, vol. 26, p. 2107.
9. Shishkin, O.V., Atroschenko, Yu.M., Gitis, S.S., Alifano-
va, E.N., and Shahkheldyan, I.V., Acta Cryst., 1998, vol. 54,
p. 271.
10. Levina, O.I., Potekhin, K.A., Goncharov, A.V., Kurkuto-
va, E.N., Struchkov,Yu.T., Palyulin, V.A., and Zefirov, N.S.,
Dokl. Akad. Nauk SSSR., 1987, vol. 296, p. 1121.
11. Zefirov, N.S., Palyulin, V.A., and Dashevskaya, E.E., J. Phys.
Org. Chem., 1990, vol. 3, p. 147.
12. Allen, F.H., Kennard, O., Watson, D.G., Brammer, L.,
Orpen,A.G., and Taylor, R., J. Chem. Soc., Perkin Trans. II,
1987, vol. 1, p. 1.
13. Zefirov, Yu.V. and Zorkii, P.M., Usp. Khim., 1989, vol. 58,
p. 713.
14. Rowland, R.S. and Taylor, R., J. Phys. Chem., 1996, vol. 100,
p. 7384.
mp 202–204°C (decomp.). IR spectrum, cm : 1572, 1358
(NO2), 1657 (C=C), 1685 (C=O). 1H NMR spectrum
(DMSO-d6), d, ppm: 6.90 br.s (1H, H7), 4.31 d (1H, He4,
J 13.43 Hz), 4.15 d (1H, H4a, J 13.43 Hz), 4.30 d (1H, He2,
J 12.81 Hz), 4.22 d (1H, H2a, J 12.81 Hz), 3.17 d (1H, He9,
J 11.59 Hz), 3.03 d (1H, H9a, J 11.59 Hz), 3.32 d (1H, He8,
J 18.32 Hz), 3.28 d (1H, H8a, J 18.32 Hz), 3.46 s, 3.29 s
(6H, N+Me2), 7.75 br.s, 7.43 br.s (2H, CONH2). Found,
%: C 32.51, 32.80; H 4.30, 4.28; I 30.66, 30.27; N 12.64,
12.58. C11H17IN4O5. Calculated, %: C 32.04; H 4.13;
I 30.83; N 13.59.
X-ray diffraction study of compound (IIa). The
crystals were obtained by slow isothermal evaporation
of compound IIa solution in ethanol. Crystals of
C10H16O4N3+ I at 110(2) K monoclinic, a 8.051(3),
–
°
° 3
b 10.679(3), c 8.635(3) A, b 115.738(5)°, V 668.7(4) A ,
crystal habit 0.3´0.3´0.2 mm, space group P21, Z 2, dcalc
1.833 g/cm3, F(000) 364, m 2.406 mm .
–1
Intensities of 7351 reflections (3517 independent, Rint
0.021) were measured on an automatic diffractometer
Bruker 1K SMART CCD (graphite monochromator,
MoKa-radiation, j and w scanning, 2qmax 58°). The
processing of diffraction data was performed with
software SAINT [20]. The absorption was taken into
account with the use of software SADABS [21]. The
structure was solved by the direct method applying the
software package SHELXTL-97 [22]. Hydrogen atoms
positions were revealed from the difference synthesis of
the electron density and were refined in isotropic
approximation except for atoms H attached to C2 and
C4 atoms; these positions were calculated geometrically
and refined in the ritter model with fixed Uiso 1.2 Ueq of
the corresponding carbon atom. The refinement along
F2 in anisotropic approximation for nonhydrogen atoms
by full-matrix least-squares procedure (219 parameters)
involving 3517 reflections was carried out till R1 0.031
[for 3470 reflections with F > 4ó(F)], wR2 0.083, S 1.078.
The coordinates of nonhydrogen atoms are listed in
Table 1, and the bond lengths in Table 2.
15. Khmel’nitskii, R.A. and Terent’ev, P.B., Usp. Khim., 1979,
vol. 48, p. 854.
16. Zaikin, V.G., Varlamov, A.V., Mikaya, A.I., and Prosta-
kov, N.S., Osnovy mass spectrumometrii organicheskikh
soedinenii (Bases of Mass Spectrometry in Organic
Chemistry), Moscow: MAIK, 2001, p. 131.
17. Nazin, G.M. and Manelis, G.B., Usp. Khim., 1994, vol. 63,
p. 327.
18. Paulik, F. and Paulik, J., J. Term. Anal., 1973, vol. 5, p. 253.
19. Wendlandt, W. Wm., Thermal Methods of Analysis, New
York: Interscience, 1964.
20. SMART V5.051 and SAINT V5.00. Area detector control
and integration software, 1998, BrukerAXS Inc. Madison,
WI-53719, USA.
Zefirov–Palyulin folding parameters were calculated
by RICON routine [23].
The study was carried out under financial support of
the Russian Foundation for Basic Research (grant 01-
03-96002).
REFERENCES
21. Sheldrick, G.M., SADABS, 1997, BrukerAXS Inc. Madison,
WI-53719, USA.
22. Sheldrick, G.M., SHELXTL-97, 1997, Bruker AXS Inc.
Madison, WI-53719, USA.
23. Zotov,A.Yu., Palyulin, V.A., and Zefirov, N.S., J. Chem. Inf.
Comput. Sci., 1997, vol. 37, p. 766.
1. Shakhkel’dyan, I.V., Melekhina, E.K.,Atroshchenko, Yu.M.,
Efremov, Yu.A.,Alifanova, E.N., Kopyshev, M.V., Troitskii,
N.A., Subbotin, V.A., and Nikishina, M.B., Zh. Org. Khim.,
2003, vol. 39, p. 625.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004