Nitropyrazoles 17.* Synthesis of 1-(3,5-dinitrophenyl)-4-methyl-3,5- dinitropyrazole and the study of its chemical transformations

Article abstract of DOI:10.1007/s11172-009-0290-1

A new one-step method for the synthesis of 4-methyl-3(5)-nitropyrazole by nitration of 4-methylpyrazole is developed. Arylation of 4-methyl-3(5)- nitropyrazole with 1,3,5-trinitrobenzene gives 1-(3,5-dinitrophenyl)-4-methyl-3- nitropyrazole, nitration of

Full text of DOI:10.1007/s11172-009-0290-1

Russian Chemical Bulletin, International Edition, Vol. 58, No. 10, pp. 2122—2128, October, 2009
2122
Nitropyrazoles
17.* Synthesis of 1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole and the study
of its chemical transformations
A. A. Zaitsev,a D. V. Zaiko,b I. L. Dalinger,a V. V. Kachala,а T. K. Shkineva,a and S. A. Sheveleva
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: shevelev@ioc.ac.ru
bD. I. Mendeleev University of Chemical Technology of Russia,
9 Miusskaya pl., 125047 Moscow, Russian Federation
A new oneꢀstep method for the synthesis of 4ꢀmethylꢀ3(5)ꢀnitropyrazole by nitration of
4ꢀmethylpyrazole is developed. Arylation of 4ꢀmethylꢀ3(5)ꢀnitropyrazole with 1,3,5ꢀtrinitrobenꢀ
zene gives 1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀmethylꢀ3ꢀnitropyrazole, nitration of which leads to 1ꢀ(3,5ꢀ
dinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole. The action of 1 equiv. of an Oꢀ or Sꢀnucleophile
(phenolate, pꢀchlorobenzenethiolate and ethoxide ions; anions of glycolanilide and thioglycolꢀ
anilide) on 1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole led to the substitution of the
5ꢀNO2 group of the pyrazole ring; under the action of one more equivalent of a nucleophile the
NO2 group of the benzene ring was substituted. The substitution product of the anion of
thioglycolanilide for the 5ꢀNO2 group undergoes the intramolecular cyclization — oxidative
nucleophilic hydrogen substitution in the benzene ring under the action of K2CO3.
Key words: nitropyrazoles, dinitropyrazoles, 1,3,5ꢀtrinitrobenzene, nitration, nucleophilic
substitution, nucleophiles, enamines, protecting groups, the Smiles rearrangement.
In our previous work,2 we have demonstrated that the
of the position 5 in reactions with nucleophilic reagents.
We assumed that 3,5ꢀdinitrophenyl group can be such
a substituent, as, from one hand, the presence of two nitro
groups would provide electronꢀwithdrawing effect similar
to that of the isomeric 2,4ꢀdinitrophenyl substituent, and,
from the other hand, the nitro groups are located in such
a way that the position 1 of the benzene ring is not actiꢀ
vated with respect to nucleophilic substitution.
We considered three possible approaches to the synꢀ
thesis of 1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyraꢀ
zole (3) (Scheme 1): (a) arylation of 4ꢀmethylpyrazole (4)
with trinitrobenzene (TNB) followed by nitration of prodꢀ
uct 5; (b) nitration of methylpyrazole 4 to dinitro derivaꢀ
tive1 2 and arylation of the latter with TNB; (c) nitration
of methylpyrazole 4 to mononitro derivative 6, its arylaꢀ
tion with TNB followed by nitration of product 7.
Methylpyrazole 4 does not react with TNB in the presꢀ
ence of K2CO3 in refluxing acetonitrile (80 °C), or in
DMF at 100 °С for 20—30 h. This is in accord with the data
from publication3 in which it was noted that NHꢀpyrazoles
having high pKa values either do not undergo arylation
with TNB (3,5ꢀdimethylpyrazole), or are arylated over
long period in low yields (pyrazole).
The attempts of arylation of nitropyrazole 2, which
was obtained by nitration of methylpyrazole 4 using the
method that we have developed earlier,1 were also unsucꢀ
introduction of the 2,4ꢀdinitrophenyl substituent in the
position 1 of the pyrazole ring increases the mobility of
hydrogen atoms of the 4ꢀMe group in comparison with
the corresponding 1ꢀMe analog. So, 1ꢀ(2,4ꢀdinitropheꢀ
nyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole (1) undergoes condenꢀ
sation reaction with dimethylformamide dimethylacetal
(DMF DMA) and aromatic aldehydes under much milder
conditions than 1,4ꢀdimethylꢀ3,5ꢀdinitropyrazole. This
fact can be used for the functionalization of the pyrazole
ring at the position 4. At the same time, the sensitivity of
the position 1 of the benzene ring in compound 1 is very
high, it considerably exceeds the sensitivity of the position
5 of the pyrazole ring. The substitution at C(1) atom of the
2,4ꢀdinitrophenyl fragment occurs under the action of anꢀ
ionic nucleophilic reagents Nu– so that 1ꢀRꢀ2,4ꢀdiꢀ
nitrobenzenes and 4ꢀmethylꢀ3,5ꢀdinitropyrazole (2) are
formed. The introduction of an electronꢀwithdrawing subꢀ
stituent that is resistant to the action of a nucleophile in
the position 1 of the pyrazole ring would enable carrying
out nucleophilic substitution in the position 5 of the pyraꢀ
zole ring, and hence, functionalization of the position 5 of
the pyrazole ring. Moreover, the electronꢀwithdrawing
substituent in the position 1 should enhance the reactivity
* For Part 16, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2058—2064, October, 2009.
1066ꢀ5285/09/5810ꢀ2122 © 2009 Springer Science+Business Media, Inc.

1ꢀ(3,5ꢀDinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2123
Scheme 1
Table 1. Conditions of nitration of 4ꢀmethylpyrazole (4)
and yields of the reaction products
Run
[H2SO4]
(%)
HNO3 : 4
(mol.)
Yield (%)*
6
2
1
2
3
4
5
6
7
8
9
10
92.5
94.5
95.0
95.5
96.5
96.5
97.5
97.5
97.5
97.5
2.0
1.5
1.5
1.5
1.5
1.25
1.5
1.25
1.05
3.0
6
20
25
36
52
57
46
50
39
0
0
3
5
10
14
6
29
22
12
75
* Yields of reaction products in mixtures of compounds
6 + 2 are given; the yields were determined using masses of
1
the obtained mixtures and the ratio 6 : 2 in the H NMR
spectra.
Scheme 2
i. Arylation; ii. Nitration.
i. HNO3 (d = 1.5 g cm–3), H2SO4, 100 °C, 2 h.
cessful. Trinitrobenzene does not react with nitropyrazole
2 in refluxing acetonitrile in the presence of K2CO3, resinꢀ
ification of the reaction mixture occurs when the reaction
is carried out at 100 °C in DMF. This result, apparently, is
caused by low nucleophilicity of 4ꢀmethylꢀ3,5ꢀdinitroꢀ
pyrazolate anion.
We developed direct oneꢀstep method for the synthesis
of 4ꢀmethylꢀ3(5)ꢀnitropyrazole (6) from methylpyrazole
4 in order to realize the approach (c) for the synthesis of
nitropyrazole 3.*
In order to find the optimum conditions for the oneꢀ
step synthesis of compound 6, we carried out a series of
experiments on nitration of methylpyrazole 4 with nitric
acid ⎯ sulfuric acid mixture at 100 °C for 2 h, where the
concentration of sulfuric acid and the nitric acid : methꢀ
ylpyrazole 4 ratio were varied (Scheme 2, Table 1).
The results of the experiments show that the yields of
nitropyrazoles 6 and 2 increase with the increase in the
sulfuric acid concentration, and the maximum yield of
mononitro derivative 6 is observed at [H2SO4] = 96.5%;
the conditions of run 6 (see Table 1) are optimal for the
synthesis of nitropyrazole 6, the yield of pure nitropyrꢀ
azole 6 was 47% (after removal of admixture 2).
It is worth noting that the formation of dinitro derivaꢀ
tive 2 occurs at any concentration of H2SO4 starting from
94.5%, and at any HNO3 : 4 ratio (the most representative
are the results of the run 9 where the use of 5% excess of
nitric acid as regards mononitration led to compound 2 in
12% yield). This implies that the rate of nitration of nitroꢀ
pyrazole 6 is higher than that of methylpyrazole 4. The
possible explanation of this fact is as follows: according to
the literature data,5 pyrazoles that are substituted in the
position 4 undergo nitration in the form of free bases and
the observed difference in nitration rates is due to differꢀ
ences in concentration of the free bases of 4 and 6 in the
* The known method for synthesis of compound 6 from 4 comꢀ
prises two steps: Nꢀnitration of 4ꢀmethylpyrazole 4 with acetyl
nitrate and subsequent thermal rearrangement of 4ꢀmethylꢀ1ꢀ
nitropyrazole that formed.4 Total yield of nitropyrazole 6 in this
method is 36%, but it should be taken into account that the
claimed yield of 62% for the rearrangement step is accessible
only when preliminarily purified Nꢀnitropyrazole is used. At the
same time, the yield of unpurified 4ꢀmethylꢀ1ꢀnitropyrazole is
61%,4 i.e., the real yield of 4ꢀmethylꢀ3(5)ꢀnitropyrazole 6 is
smaller than 36%.
reaction medium — methylpyrazole 4 (pKBH = 3.04)6 is
+
totally in the form of the conjugated acid in concentrated
sulfuric acid, while nitropyrazole 6, whose pKBH+ value is
seven orders of magnitude lower than that of 4 (for
3(5)ꢀnitropyrazole pKBH+ = –4.66)6, is predominately in

2124
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
Zaitsev et al.
the form of a free base. Thus, on the basis of the aforesaid,
the existence of the maximum of yield of compound 6 at
the concentration of H2SO4 of 96.5% becomes underꢀ
standable. Simultaneous formation of monoꢀ and dinitro
products as the incomplete conversion of the starting pyrꢀ
azole has earlier been described.7
Nitropyrazole 3 is formed upon nitration of arylation
product 7 with a sulfuric—nitric acid mixture (see Scheme 3).
The optimum conditions for the nitration of compound 7
are those of run 2 (see Table 2).
We investigated the behavior of nitropyrazole 3 in the
condensation reaction with DMF DMA. It turned out
that enamine 8 is formed in refluxing toluene for 10 h
(Scheme 4). The mobility of hydrogen atoms of 4ꢀMe
group of compound 3 in this reaction is very close to that
of nitropyrazole 1, which reacts with DMF DMA under
similar conditions,2 and is much higher than the mobility
of hydrogen atoms of the 4ꢀMe group in 1,4ꢀdimethylꢀ
3,5ꢀdinitropyrazole, which reacts with DMF DMA only
in refluxing DMF.9 Thus, the electronꢀwithdrawing effect
of the isomeric 2,4ꢀdinitroꢀ and 3,5ꢀdinitrophenyl groups
is approximately the same.
The reaction of nitropyrazole 6 with TNB in the presꢀ
ence of K2CO3 led to the single arylation product 7
(Scheme 3). The position of the nitro group in the pyraꢀ
zole ring in compound 7 was determined in the following
way. The signals for the C atoms of the CHꢀ and CNO2
groups in the 13C NMR of compound 7 are at δ 132.24 and
155.17, respectively (the assignment was made using
2D correlation spectroscopy on the basis of longꢀrange
(HMBC) and direct (HSQC) spinꢀcoupling constants
1H—13C), the difference magnitude |δ(C(3)) – δ(C(5))|
was 22.93 ppm. Analysis of data8 of the 13C NMR specꢀ
tra of 3ꢀNO2ꢀ5ꢀHꢀ and 5ꢀNO2ꢀ3ꢀHꢀpyrazoles, which
contain hydrogen or an aliphatic carbon atom in the posiꢀ
tion 4, demonstrates that chemical shifts for the C(3) and
C(5) atoms of 3ꢀnitropyrazoles are at δ 148.9—160.1 and
δ 124.4—137.1, respectively, and the difference magꢀ
nitude |δ(C(3)) – δ(C(5))| is 20.0—27.9 ppm; the chemiꢀ
cal shifts for C(3) and C(5) atoms of 5ꢀnitropyrazoles
are at δ 133.6—139.6 and δ 142.3—146.6, and the difꢀ
ference magnitude |δ(C(3)) – δ(C(5))| is in the range
6.4—8.7 ppm. Thus, the comparison of values of chemical
shifts for C(3) and C(5) atoms in the 13C NMR spectrum
of compound 7 with the literature data shows unambiguꢀ
ously that the NO2 group is in the position 3 of the pyrꢀ
azole ring.
Scheme 4
i. Me2NCH(OMe)2, PhCH3, reflux, 10 h.
We investigated the substitution reactions of nitropyꢀ
razole 3 with different Sꢀ and Oꢀnucleophiles. Theoretiꢀ
cally, one can expect that under the action of nucleophilic
reagents compound 3 would react along one of the followꢀ
ing routes: (a) substitution of one or several NO2 group in
the position 5 of the pyrazole ring; (b) substitution of the
NO2 group in the position 3 of the pyrazole ring; (c) subꢀ
stitution of the NO2 group in the position 3 of the benzene
ring; (d) substitution of the 4ꢀmethylꢀ3,5ꢀdinitropyrazolate
anion in the position 1 of the benzene ring; (e) the formaꢀ
tion of anionic σꢀcomplexes under nucleophile attack on
the positions 2 or 4 of the benzene ring and their further
transformations.
The reaction of nitropyrazole 3 with equimolar
amounts of phenolate or pꢀchlorobenzenethiolate anions
results in single products 9a and 9b, respectively (Scheme 5).
The fact that it is the NO2 group of the pyrazole ring of
compound 3 that is substituted followed from the 1H NMR
spectra of compounds 9a and 9b where only two signals
for the protons of the benzene ring (a) are observed in the
ratio 2 : 1. The use of the 2D correlation spectroscopy
ROESY for compound 9a and NOESY for 9b shows the
existence of the interaction between H(2´) and H(2″) proꢀ
tons, which is possible only in the case where the phenoxyl
Scheme 3
i. K2CO3/MeCN, 80 °C, 4 h; ii. HNO3 (d = 1.5 g cm–3), H2SO4,
100 °C, 2 h.
Table 2. Conditions of nitration of 1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀmeꢀ
thylꢀ3ꢀnitropyrazole (7) and yields of 1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀ
methylꢀ3,5ꢀdinitropyrazole (3)
Run
[H2SO4] (%)
HNO3 : 7 (mol.)
Yield of 3 (%)
1
2
3
96.5
96.5
98.5
5
2
5
46
79
74

1ꢀ(3,5ꢀDinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2125
(pꢀchlorophenylsulfanyl) substituent is in the position 5 of
NO2 group of the benzene ring to give compounds 10a and
the pyrazole ring.
10b, respectively (see Scheme 5).
Similarly, the action of the thioglycolanilide or glycolꢀ
anilide anions on nitropyrazole 3 leads to the substitution
products of the 5ꢀNO2 group of the pyrazole ring, whereby
not the corresponding amide but 5ꢀanilinoꢀ1ꢀ(3,5ꢀdiꢀ
nitrophenyl)ꢀ4ꢀmethylꢀ3ꢀnitropyrazole (11), the product
of the Smiles rearrangement of the intermediate oxygenꢀ
containing anilide, analogous to sulfurꢀcontaining comꢀ
pound 12, is formed (Scheme 6). We have demonstrated
the occurrence of the Smiles rearrangement in the nitroꢀ
pyrazole series in our previous work.10 It is worth noting
that nucleophilic substitution the ethoxide anion for the
5ꢀNO2 group in compound 3 occurs on simple reflux in
ethanol in the presence of K2CO3 (compound 13 is formed,
see Scheme 6).
Scheme 5
The action of K2CO3 on compound 12 in MeCN leads
to intramolecular oxidative substitution of hydrogen atom
in the position 2 of the dinitrophenyl fragment, which
gives compound 14, a representative of the earlier unꢀ
known tricyclic system 5Hꢀpyrazolo[1,5ꢀa][3,1]benzoꢀ
thiazine (see Scheme 6). The question of the oxidation
reagent in this reaction needs special investigation. For
example, both the starting compound 12 and atmospheric
oxygen can serve as the oxidating reagent.
X
O
S
O
S
R
H
Cl
H
Yield (%)
9a
9b
10a
10b
83
70
62
48
Cl
i. pꢀRC6H4XH (1 equiv.), K2CO3, MeCN, 80 °C; ii. pꢀRC6H4XH
(2 equiv.), K2CO3, MeCN, 80 °C.
The position of the nitro group at the C(3) atom of
the pyrazole ring in compound 11 was determined
in the following way. In the 2D correlation spectrum
HMBC 1H—15N, the only interaction of the hydrogen
The action of 2 equiv. of phenolate or pꢀchlorobenꢀ
zenethiolate ions on compound 3 leads to the substitution
of both of the NO2 group of the pyrazole ring, and the
Scheme 6
i. HOCH2CONHPh, K2CO3, MeCN, 80 °C, 4 h; ii. HSCH2CONHPh, K2CO3, MeCN, 25 °C, 20 h; iii. K2CO3/EtOH, ~80 °C,
6 h; iv. K2CO3/MeCN, 25 °C, 48 h.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
Zaitsev et al.
pH 2—3; the precipitate that formed was filtered off, washed
with water, and dried in air. Orangeꢀbrown solid compound 7
was obtained (0.765 g, 77%). M.p. 172—174 °С. Found (%):
C, 40.91; H, 2.49; N, 23.54. C10H7N5O6. Calculated (%): C, 40.97;
H, 2.41; N, 23.89. 1Н NMR ((CD3)2SO), δ: 9.07 (s, 1 H, H(5));
9.04 (d, 2 H, H(2´), J = 2.1 Hz); 8.84 (t, 1 H, H(4´), J = 2.1 Hz);
2.37 (s, 3 H, Me). 1Н NMR (CDCl3), δ: 9.05 (s, 1 H, H(5)); 8.95
(s, 2 H, H(2´)); 8.06 (s, 1 H, H(4´)); 2.49 (s, 3 H, Me). 13С NMR
((CD3)2SO), δ: 155.17 (C(3)); 148.87 (C(3´)); 139.49 (C(1´));
132.24 (C(5)); 118.98 (C(2´)); 117.10 (C(4´)); 116.53 (C(4));
9.45 (Me). IR, ν/cm–1: 1548, 1520, 1344 (NO2). MS, m/z:
293 [M]+.
1ꢀ(3,5ꢀDinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole (3). Oleꢀ
um (41%, d = 1.963 g cm–3, 2.2 mL) was added to sulfuric acid
(92.5%, d = 1.826 g cm–3, 7.5 mL) keeping the temperature at
30—40 °C, then nitropyrazole 7 (1.00 g, 3.4 mmol) was added
portionwise to the solution at 30—40 °C, and then fuming nitric
acid (d = 1.5 g cm–3, 0.3 mL, 7.1 mmol) was added dropwise.
The reaction mixture was heated at 100—105 °C for 2 h, cooled
to ~20 °C, poured onto crushed ice (~70 g); air was bubbled for
2 h through the suspension obtained until total removal of nitroꢀ
gen oxides. The precipitate that formed was filtered off, washed
with water to neutral pH, dried in air and recrystallized from
MeCNꢀEtOH mixture (1 : 1). Lightꢀbeige compound 3 was obꢀ
tained (0.916 g, 79%). M.p. 220—222 °С. Found (%): C, 35.40;
H, 1.88; N, 24.59. C10H6N6O8. Calculated (%): C, 35.51;
H, 1.79; N, 24.85. 1Н NMR ((CD3)2SO), δ: 9.11 (d, 2 H, H(2´),
J = 1.8 Hz); 9.03 (t, 1 H, H(4´), J = 1.8 Hz); 2.70 (s, 3 H, Me).
13С NMR ((CD3)2SO), δ: 153.06 (C(3)); 148.10 (C(3´)); 144.39
(C(5)); 139.69 (C(1´)); 127.67 (C(2´)); 120.42 (C(4´)); 115.21
(C(4)); 9.78 (Me). IR, ν/cmꢀ1: 1560, 1544, 1540, 1532, 1348,
1332 (NO2). MS, m/z: 338 [M]+.
atom of the NH group with the nitrogen atom N(1) of the
pyrazole ring is observed (δ –175.3), which is possible
only in the case where the NHPh substituent is linked
to the C(5) atom of the pyrazole ring. The formation of
compound 14 from 12 is the chemical proof of the locaꢀ
tion of the SCH2CONHPh group in the position 5 of the
pyrazole ring.
Thus, the introduction of the 3,5ꢀdinitrophenyl subꢀ
stituent in the position 1 of the pyrazole ring, first, inꢀ
creases the reactivity of the 4ꢀMe group with respect to
DMF DMA in comparison with the 1ꢀmethyl analog and,
second, increases the reactivity of the position 5 of the
pyrazole ring with respect to nucleophilic reagents. Thus,
dinitropyrazole 3, unlike 1,4ꢀdimethylꢀ3,5ꢀdinitropyrꢀ
azole, reacts with Sꢀ, as well as with Oꢀnucleophiles, which
extends the potential of functionalization of the pyrazole
ring at the position 5.
Experimental
1
H and 13C NMR spectra were recorded on Bruker ACꢀ300
(300.13 MHz) and Bruker DRXꢀ500 (125 MHz) spectrometers
at 295 K (unless other temperature is indicated). Chemical shifts
for 1H and 13C are given relative to Me4Si. IR spectra were
recorded on a Specord Mꢀ80 instrument in KBr pellets. Mass
spectra were obtained on a Kratos MSꢀ30 spectrometer (direct
inlet, electron impact, ionization energy 70 eV). The course of
the reactions and the control of purity of the compounds were
carried out by TLC on Silufol UVꢀ254 plates in CHCl3—Me2CO
(10 : 1). Elemental analysis was carried out on a Perkin—Elmer
Series II 2400 apparatus.
(E)ꢀN,NꢀDimethylꢀ2ꢀ[1ꢀ(3,5ꢀdinitrophenyl)ꢀ3,5ꢀdinitropyrꢀ
azolꢀ4ꢀyl]vinylamine (8). Dimethylformamide dimethylacetal
(1.0 mL, 7.5 mmol) was added to a mixture of toluene (20 mL)
and dinitropyrazole 3 (1.00 g, 3.5 mmol), the reaction mixture
was refluxed for 10 h (TLC). The reaction mixture was cooled to
~20 °C, toluene was removed under reduced pressure. The resiꢀ
due was recrystallized from ethanol, darkꢀpurple solid compound
8 was obtained (0.87 g, 75%). M.p. 186—187 °С (decomp.).
Found (%): C, 39.43; H, 2.53; N, 24.75. C13H11N7O8. Calculatꢀ
4ꢀMethylpyrazole,11 thioglycolanilide,12 and glycolanilide13
were synthesized by the previously described methods.
4ꢀMethylꢀ3(5)ꢀnitropyrazole (6). Oleum (41%, d = 1.963 g
cm–3, 230 mL) was added to sulfuric acid (d = 1.826 g cm–3
,
780 mL) keeping the temperature at 30—40 °C, then methylpyraꢀ
zole 4 (52.0 mL, 0.629 mol) was added portionwise to the soluꢀ
tion at 30—40 °C, and then fuming nitric acid (d = 1.5 g cm–3
,
1
33.0 mL, 0.786 mol) was added dropwise. The reaction mixture
was heated at 100—105 °C for 2 h, cooled to ~20 °C, poured onto
crushed ice (~3 kg); air was bubbled for 3—4 h through the
suspension obtained until total removal of nitrogen oxides. The
solution was extracted with ethyl acetate (3×500 mL), the comꢀ
bined extracts were washed with brine to neutral pH and with 5%
solution of NaOAc until all nitropyrazole 2 was removed (TLC)
and dried over Na2SO4. The solvent was removed under reduced
pressure, the residue was recrystallized from water. Colorless
crystals of compound 6 were obtained (37.6 g, 47%). M.p.
187—188 °С (lit. data4: m.p. 187 °С). 1H NMR ((CD3)2SO), δ:
13.62 (s, 1 H, NH); 7.82 (s, 1 H, CH); 2.26 (s, 3 H, Me).
13С NMR ((CD3)2SO), δ: 153.97 (C(3)); 131.44 (C(5)); 112.85
(C(4)); 9.43 (Me). IR, ν/cm–1: 3152, 3132, 2940 (NH); 1528,
1376, 1344 (NO2). MS, m/z: 127 [M]+.
ed (%): C, 39.70; H, 2.82; N, 24.93. Н NMR ((CD3)2SO), δ:
9.03 (s, 2 H, H(2´)); 8.97 (s, 1 H, H(4´)); 8.14 (d, 1 H,
CH=CHNMe2, J = 12.4 Hz); 5.77 (d, 1 H, CH=CHNMe2,
J = 12.4 Hz); 3.08 (br.s, 6 H, 2 Me). 13С NMR ((CD3)2SO), δ:
153.47 (CH=CHNMe2); 150.40 (C(3)); 147.89 (C(3´)); 140.67
(C(1´)); 139.31 (C(5)); 126.49 (C(2´)); 121.87 (C(4)); 119.26
(C(4´)); 79.99 (CH=CHNMe2); the broad peak of the C atoms
of the Me groups is hidden under the solvent peak in the region δ
40.5—38.5. IR, ν/cm–1: 1540, 1380, 1364, 1352, 1336 (NO2).
MS, m/z: 393 [M]+.
1ꢀ(3,5ꢀDinitrophenyl)ꢀ4ꢀmethylꢀ3ꢀnitroꢀ5ꢀphenoxypyrazole
(9a). K2CO3 (0.220 g, 1.6 mmol) was added to a solution of
dinitropyrazole 3 (0.502 g, 1.5 mmol) and phenol (0.150 g,
1.6 mmol) in acetonitrile (30 mL), the reaction mixture was
refluxed for 1—1.5 h (TLC). The reaction mixture was cooled to
~20 °C, poured into water (120 mL), acidified with HCl to
pH 2—3, extracted with ethyl acetate (2×40 mL); the organic
layers were combined, washed with water to neutral pH, dried
over Na2SO4, the solvent was removed under reduced pressure.
The residue was chromatographed on silica gel (CHCl3). Lightꢀ
1ꢀ(3,5ꢀDinitrophenyl)ꢀ4ꢀmethylꢀ3ꢀnitropyrazole (7). K2CO3
(0.397 g, 2.9 mmol) was added to a solution of nitropyrazole 6
(0.429 g, 3.4 mmol) and TNB (0.720 g, 3.4 mmol) in acetonitrile
(45 mL). The reaction mixture was refluxed for 4 h (TLC), then
cooled and poured into water (250 mL), acidified with HCl to

1ꢀ(3,5ꢀDinitrophenyl)ꢀ4ꢀmethylꢀ3,5ꢀdinitropyrazole Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2127
yellow solid compound 9a was obtained (0.477 g, 83%). M.p.
108—110 °С. Found (%): C, 49.81; H, 2.66; N, 18.41.
C16H11N5O7. Calculated (%): C, 49.88; H, 2.88; N, 18.18.
1Н NMR ((CD3)2SO), δ: 8.87 (s, 2 H, H(2´)); 8.84 (s, 1 H,
H(4´)); 7.41 (t, 2 H, oꢀH, Ph, J = 7.7 Hz); 7.21 (m, 3 H, mꢀH,
Ph + pꢀH, Ph); 2.08 (s, 3 H, Me). 13С NMR ((CD3)2SO), δ:
155.06 (ipsoꢀC, Ph); 153.62 (C(3)); 148.48 (C(3´)); 147.27 (C(5));
137.44 (C(1´)); 130.48 (mꢀC, Ph); 124.85 (pꢀC, Ph);
122.60 (С(2´)); 118.15 (C(4´)); 115.75 (oꢀC, Ph); 103.28 (C(4));
7.77 (Me). IR, ν/cm–1: 1548, 1344 (NO2). MS, m/z: 385 [M]+.
5ꢀ(4ꢀChlorophenylsulfanyl)ꢀ1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀmethylꢀ
3ꢀnitropyrazole (9b). K2CO3 (0.225 g, 1.6 mmol) was added to
a solution of dinitropyrazole 3 (0.500 g, 1.5 mmol) and pꢀchloꢀ
robenzenethiol (0.214 g, 1.5 mmol) in acetonitrile (30 mL), the
reaction mixture was refluxed in a flow of argon for 30 min
(TLC). The reaction mixture was cooled to ~20 °C, poured into
water (120 mL), acidified with HCl to pH 2—3; the precipitate
that formed was filtered off, washed with water, and chromatoꢀ
graphed on silica gel (CHCl3). Lightꢀyellow solid compound 9b
was obtained (0.450 g, 70%). M.p. 176—179 °С. Found (%):
C, 43.86; H, 2.23; N, 15.83; S, 7.62. C16H10ClN5O6S. Calcuꢀ
lated (%): C, 44.10; H, 2.31; N, 16.07; S, 7.36. 1Н NMR
((CD3)2SO), δ: 8.94 (s, 1 H, H(4´)); 8.89 (s, 2 H, H(2´)); 7.33
(d, 2 H, mꢀH, C6H4Clꢀp, J = 8.8 Hz); 7.15 (d, 2 H, oꢀH, C6H4Clꢀp,
J = 8.8 Hz); 2.41 (s, 3 H, Me). 13С NMR ((CD3)2SO), δ: 154.72
(C(3)); 148.06 (C(3´)); 138.59 (C(1´)); 134.53 (C(5)); 132.18
(pꢀC, C6H4Clꢀp); 131.58 (ipsoꢀC, C6H4Clꢀp); 129.63 (mꢀC,
C6H4Clꢀp); 129.25 (oꢀC, C6H4Clꢀp); 126.36 (C(2´)); 121.86
(C(4)); 119.43 (C(4´)); 10.09 (Me). IR, ν/cm–1: 1548, 1344
(NO2). MS, m/z: 437, 435 (1 : 3) [M]+.
4ꢀMethylꢀ3ꢀnitroꢀ1ꢀ(3ꢀnitroꢀ5ꢀphenoxyphenyl)ꢀ5ꢀphenoxyꢀ
pyrazole (10a). K2CO3 (0.460 g, 3.3 mmol) was added to a soluꢀ
tion of dinitropyrazole 3 (0.505 g, 1.5 mmol) and phenol (0.303 g,
3.2 mmol) in acetonitrile (30 mL), the reaction mixture was
refluxed for 8—10 h (TLC). The reaction mixture was cooled to
~20 °C, poured into water (120 mL), acidified with HCl to
pH 2—3, extracted with ethyl acetate (2×40 mL); the organic
layers were combined, washed with water to neutral pH, dried
over Na2SO4, the solvent was removed under reduced pressure.
The residue was chromatographed on silica gel (CHCl3). Lightꢀ
yellow solid compound 10a was obtained (0.401 g, 62%).
M.p. 114—115 °С. Found (%): C, 60.82; H, 3.61; N, 13.01.
C22H16N4O6. Calculated (%): C, 61.11; H, 3.73; N, 12.96.
1Н NMR ((CD3)2SO), δ: 8.21 (t, 1 H, H(2´), J = 1.9 Hz); 7.77
(t, 1 H, H(4´), J = 2.1 Hz); 7.65 (t, 1 H, H(6´), J = 2.1 Hz); 7.46
(t, 2 H, mꢀH, Ph(y), J = 8.1 Hz); 7.37 (t, 2 H, mꢀH, Ph(x),
J = 8.1 Hz); 7.29 (t, 1 H, pꢀH, Ph(y), J = 7.5 Hz); 7.17 (t, 1 H, pꢀH,
Ph(x), J = 7.3 Hz); 7.12 (d, 2 H, oꢀH, Ph(y), J = 8.5 Hz); 7.04
(d, 2 H, oꢀH, Ph(x), J = 8.5 Hz); 2.04 (s, 3 H, Me). 13С NMR
((CD3)2SO), δ: 158.55 (C(5´)); 155.03 (ipsoꢀC, Ph(x)); 154.26
(ipsoꢀC, Ph(y)); 153.16 (C(3)); 149.17 (C(3´)); 146.70 (C(5));
137.87 (C(1´)); 130.54 (mꢀC, Ph(y)); 130.40 (mꢀC, Ph(x)); 125.54
(pꢀC, Ph(y)); 124.56 (pꢀC, Ph(x)); 119.99 (oꢀC, Ph(y)); 116.85
(C(6´)); 115.33 (oꢀC, Ph(x)); 112.16 (C(4´)); 111.51 (C(2´));
103.27 (C(4)); 7.71 (Me). IR, ν/cm–1: 1536, 1344 (NO2). MS,
m/z: 432 [M]+.
of argon for 3 h (TLC). The reaction mixture was cooled to
~20 °C, poured into water (75 mL), acidified with HCl to pH 2—3;
the precipitate that formed was filtered off, washed with water,
and chromatographed on silica gel (CHCl3). Lightꢀyellow solid
compound 10b was obtained (0.076 g, 48%). M.p. 120—122 °С.
Found (%): C, 49.09; H, 2.69; N, 10.11; S, 12.25.
C22H14Cl2N4O4S2. Calculated (%): C, 49.54; H, 2.65; N, 10.50;
S, 12.02. 1Н NMR ((CD3)2SO), δ: 8.26 (s, 1 H, H(6´)); 8.11 (s, 1 H,
H(4´)); 7.76 (s, 1 H, H(2´)); 7.52 (s, 4 H, oꢀH, C6H4Clꢀp(y) +
+ mꢀH, C6H4Clꢀp(y)); 7.32 (d, 2 H, mꢀH, C6H4Clꢀp(x), J = 8.1 Hz);
7.05 (d, 2 H, oꢀH, C6H4Clꢀp(x), J = 8.1 Hz); 2.34 (s, 3 H, Me).
13С NMR ((CD3)2SO), δ: 154.37 (C(3)); 148.25 (C(5´)); 140.20
(C(3´)); 138.63 (C(1´)); 134.90 (oꢀC, C6H4Clꢀp(y)); 134.40 (ipsoꢀC,
C6H4Clꢀp(y)); 133.93 (C(5)); 131.97 (pꢀC, C6H4Clꢀp(x)); 131.56
(ipsoꢀC, C6H4Clꢀp(x)); 130.67 (C(2´)); 130.05 (mꢀC, C6H4Clꢀp(y));
129.49 (mꢀC, C6H4Clꢀp(x)); 129.43 (pꢀC, C6H4Clꢀp(y)); 128.93
(oꢀC, C6H4Clꢀp(x)); 123.31 (C(4´)); 121.47 (C(4)); 118.87
(C(6´)); 9.93 (Me). IR, ν/cm–1: 1540, 1348 (NO2). MS, m/z:
536, 534, 532 (1 : 6 : 9) [M]+.
5ꢀAnilinoꢀ1ꢀ(3,5ꢀdinitrophenyl)ꢀ4ꢀmethylꢀ3ꢀnitropyrazole
(11). K2CO3 (0.225 g, 1.6 mmol) was added to a solution of
dinitropyrazole 3 (0.500 g, 1.5 mmol) and glycolanilide (0.223 g,
1.5 mmol) in acetonitrile (30 mL), the reaction mixture was
refluxed for 4 h (TLC). The reaction mixture was cooled to
~20 °C, poured into water (120 mL), acidified with HCl to
pH 2—3; the precipitate that formed was filtered off, washed
with water, and chromatographed on silica gel (CHCl3—Me2CO
(10 : 1)). Lightꢀyellow compound 11 was obtained (0.325 g,
57%). M.p. 74—76 °С. Found (%): C, 50.04; H, 3.00; N, 22.19.
C16H12N6O6. Calculated (%): C, 50.01; H, 3.15; N, 21.87.
1Н NMR ((CD3)2SO), δ: 8.87 (s, 2 H, H(2´)); 8.83 (s, 1 H,
H(4´)); 8.58 (s, 1 H, NH); 7.15 (t, 2 H, mꢀH, Ph, J = 7.5 Hz);
6.78 (t, 1 H, pꢀH, Ph, J = 6.9 Hz); 6.70 (d, 2 H, oꢀH, Ph, J = 7.5 Hz);
2.15 (s, 3 H, Me). 13С NMR ((CD3)2SO), δ: 154.30 (C(3));
148.30 (C(3´)); 143.70 (ipsoꢀC, Ph); 141.38 (C(5)); 138.65
(C(1´)); 129.45 (mꢀC, Ph); 123.54 (C(2´)); 119.98 (pꢀC, Ph);
117.94 (C(4´)); 114.23 (oꢀC, Ph); 110.19 (C(4)); 8.75 (Me).
15N NMR ((CD3)2SO, δ: –16.8 (C(3´)NO2); –175.3 (N(1));
–315.2 (NH). MS, m/z: 384 [M]+.
([1ꢀ(3,5ꢀDinitrophenyl)ꢀ4ꢀmethylꢀ3ꢀnitropyrazolꢀ5ꢀyl]sulꢀ
fanyl)acetanilide (12). K2CO3 (0.455 g, 3.3 mmol) was added to
a solution of dinitropyrazole 3 (1.002 g, 2.9 mmol) and thioglyꢀ
colanilide (0.496 g, 3.0 mmol) in acetonitrile (50 mL), the reacꢀ
tion mixture was stirred for 20 h (TLC), poured into water
(150 mL), acidified with HCl to pH 2—3; the precipitate that
formed was filtered off, washed with water, and chromotographed
on silica gel (CHCl3). Lightꢀyellow solid compound 12 was obꢀ
tained (0.936 g, 69%). M.p. 192—194 °С. Found (%): C, 47.27;
H, 3.05; N, 18.41; S, 7.08. C18H14N6O7S. Calculated (%):
1
C, 47.16; H, 3.08; N, 18.33; S, 7.00. Н NMR ((CD3)2SO): δ,
9.89 (s, 1 H, NH); 8.94 (d, 2 H, H(2´), J = 2.2 Hz); 8.61 (t, 1 H,
H(4´), J = 2.2 Hz); 7.22—7.13 (m, 4 H, oꢀH, Ph + mꢀH, Ph);
6.99 (t, 1 H, pꢀH, Ph, J = 6.6 Hz); 3.36 (s, 2 H, CH2); 2.46 (s, 3 H,
Me). 1Н NMR ((CD3)2CO), δ: 9.29 (s, 1 H, NH); 9.01 (d, 2 H,
H(2´), J = 2.2 Hz); 8.70 (t, 1 H, H(4´), J = 2.2 Hz); 7.25 (d, 2 H,
oꢀH, Ph, J = 8.1 Hz); 7.16 (t, 2 H, mꢀH, Ph, J = 7.9 Hz); 7.01
(t, 1 H, pꢀH, Ph, J = 6.6 Hz); 3.46 (s, 2 H, CH2); 2.54 (s, 3 H, Me).
13С NMR ((CD3)2SO), δ: 165.56 (CO); 154.50 (C(3)); 147.49
(C(3´)); 138.83 (C(1´)); 138.29 (ipsoꢀC, Ph); 136.85 (C(5));
128.52 (mꢀC, Ph); 126.16 (C(2´)); 123.66 (pꢀC, Ph); 121.63
(C(4)); 118.34 (C(4´) + oꢀC, Ph); 39.33 (CH2); 10.16 (Me).
5ꢀ(4ꢀChlorophenylsulfanyl)ꢀ4ꢀmethylꢀ3ꢀnitroꢀ1ꢀ[5ꢀnitroꢀ3ꢀ
(4ꢀchlorophenylsulfanyl)phenyl]pyrazole (10b). K2CO3 (0.090 g,
0.65 mmol) was added to a solution of dinitropyrazole 3 (0.100 g,
0.30 mmol) and pꢀchlorobenzenethiol (0.087 g, 0.60 mmol) in
acetonitrile (20 mL), the reaction mixture was refluxed in a flow

2128
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
Zaitsev et al.
13С NMR ((CD3)2SO), δ: 343 K): 165.42 (CO); 154.43 (C(3));
147.74 (C(3´)); 139.05 (C(1´)); 138.27 (ipsoꢀC, Ph); 136.84
(C(5)); 128.44 (mꢀC, Ph); 126.07 (C(2´)); 123.65 (pꢀC, Ph);
121.56 (C(4)); 118.66 (oꢀC, Ph); 118.37 (C(4´)); 39.34 (CH2);
9.93 (Me). IR, ν/cm–1: 1664 (CO); 1556, 1516, 1344 (NO2).
MS, m/z: 458 [M]+.
5. A. R. Katritzky, H. O. Tarhan, B. Terem, J. Chem. Soc.,
Perkin Trans. 2, 1975, 1632.
6. J. Catalan, J. L. M. Abboud, J. Elguero, Adv. Heterocycl.
Chem., 1987, 41, 187.
7. (a) M. D. Coburn, J. Heterocycl. Chem., 1970, 7, 707; (b) V. P.
Perevalov, Yu. A. Manaev, L. I. Baryshnenkova, E. E.
Kanep, M. A. Andreeva, B. I. Stepanov, Khim. Geteroꢀ
tsikl. Soed., 1987, 23, 1350 [Chem. Heterocycl. Compd.
(Engl. Transl.), 1987, 23, 1081].
1ꢀ(3,5ꢀDinitrophenyl)ꢀ5ꢀethoxyꢀ4ꢀmethylꢀ3ꢀnitropyrꢀ
azole (13). A mixture of K2CO3 (0.230 g, 1.7 mmol) and diꢀ
nitropyrazole 3 (0.512 g, 1.5 mmol) in ethanol (30 mL) was
refluxed for 6 h (TLC). The reaction mixture was cooled to
~20 °C, poured into water (100 mL), acidified with HCl to
pH 2—3; the precipitate that formed was filtered off, washed
with water, and chromatographed on silica gel (nꢀC6H14—EtOAc
(3 : 1)). Lightꢀyellow compound 13 was obtained (0.137 g, 27%).
M.p. 129—132 °C. Found (%): C, 43.36; H, 3.34; N, 20.40.
C12H11N5O7. Calculated (%): C, 42.74; H, 3.29; N, 20.77.
1Н NMR ((CD3)2SO), δ: 8.91 (d, 2 H, H(2´), J = 2.2 Hz); 8.88
(t, 1 H, H(4´), J = 2.2 Hz); 4.35 (q, 2 H, CH2, J = 6.8 Hz); 2.31
(s, 3 H, 4ꢀMe); 1.34 (t, 3 H, CH2CH3, J = 6.8 Hz). 13С NMR
((CD3)2SO), δ: 153.50 (C(3)); 152.20 (C(5)); 148.52 (C(3´));
138.08 (C(1´)); 122.33 (C(2´)); 117.58 (C(4´)); 101.02 (C(4));
72.48 (CH2); 15.02 (CH2CH3); 7.87 (4ꢀMe). IR, ν/cm–1: 1552,
1544, 1536, 1344 (NO2). MS, m/z: 337 [M]+.
3ꢀMethylꢀ2,6,8ꢀtrinitropyrazolo[1,5ꢀa][3,1]benzothiazineꢀ
5ꢀcarboxanilide (14). K2CO3 (0.334 g, 2.4 mmol) was added to
a solution of compound 12 (0.303 g, 0.67 mmol) in acetonitrile
(20 mL), the reaction mixture was stirred for 48 h at ~20 °C
(TLC), poured into water (100 mL), acidified with HCl to
pH 2—3, and extracted with ethyl acetate (2×20 mL); the organꢀ
ic layers were combined, washed with water to neutral pH, dried
over Na2SO4, the solvent was removed under reduced pressure.
The residue was chromatographed on silica gel (CHCl3—Me2CO
(10 : 1)). Orange compound 14 was obtained (0.198 g, 65%).
M.p. 162—165 °C. Found (%): C, 47.30; H, 2.89; N, 18.75;
S, 7.50. C18H12N6O7S. Calculated (%): C, 47.37; H, 2.65; N, 18.41;
S, 7.03. 1Н NMR ((CD3)2SO), δ: 10.74 (s, 1 H, NH); 8.89, 8.82
(both s, 1 H + 1 H, H(7) + H(9), J = 2.2 Hz); 7.49 (d, 2 H, oꢀH,
Ph, J = 8.1 Hz); 7.30 (t, 2 H, mꢀH, Ph, J = 8.1 Hz); 7.08 (t, 1 H,
pꢀH, Ph, J = 7.7 Hz); 5.82 (s, 1 H, H(5)); 2.24 (s, 3 H, Me).
13С NMR ((CD3)2SO), δ: 164.87 (CO); 155.13 (C(2)); 148.54
(C(6)); 147.49 (C(8)); 138.25 (ipsoꢀC, Ph); 136.72 (C(9a));
131.77 (C(3a)); 128.88 (mꢀC, Ph); 125.67 (C(5a)); 123.94 (pꢀC,
Ph); 119.24 (oꢀC, Ph); 118.37, 117.52 (C(7) + C(9)); 113.60
(C(3)); 39.95 (C(5)); 9.08 (Me). IR, ν/cm–1: 1696 (CO); 1548,
1340 (NO2). MS, m/z: 456 [M]+.
8. (a) M. Begtrup, G. Boyer, P. Cabildo, C. Cativiela, R. M.
Claramunt, J. Elguero, J. I. García, C. Toiron, P. Vedsø,
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S. A. Shevelev, Izv. Akad. Nauk, Ser. Khim., 1995, 2181 [Russ.
Chem. Bull. (Engl. Transl.), 1995, 44, 2087]; (d) V. V. Seꢀ
menov, B. I. Ugrak, S. A. Shevelev, M. I. Kanishchev, A. T.
Baryshnikov, A. A. Fainzil´berg, Izv. Akad. Nauk, Ser. Khim.,
1990, 1827 [Bull. Acad. Sci. USSR, Div. Chem. Sci.
(Engl. Transl.), 1990, 39, 1658]; (e) J. Torres, J. L. Lavanꢀ
dera, P. Cabildo, R. M. Claramunt, J. Elguero, J. Heterocycl.
Chem., 1988, 25, 771; (f) A. S. Gavrilov, E. L. Golod, V. V.
Kachala, B. I. Ugrak, Zh. Orh. Khim., 2001, 37, 1822 [Russ.
J. Org. Chem. (Engl. Transl.), 2001, 37, 1741]; (g) A. V. Samet,
A. L. Laikhter, D. N. Reznikov, A. N. Yamskov, B. I. Ugrak,
N. B. Chernysheva, V. V. Yelkin, V. V. Semenov, Izv.
Akad. Nauk, Ser. Khim., 1994, 1135 [Russ. Chem. Bull.
(Engl. Transl.), 1994, 43, 1073]; (h) A. V. Samet, M. E.
Niyazymbetov, V. V. Semenov, A. L. Laikhter, D. H. Evans,
J. Org. Chem., 1996, 61, 8786; (i) R. M. Claramunt, J. Elgueꢀ
ro, C. Marzin, J. Seita, An. Quim., 1979, 75, 701; (j) S. A.
Shevelev, V. M. Vinorgadov, I. L. Dalinger, B. I. Ugrak,
A. A. Fainzil´berg, V. I. Filippov, Izv. Akad. Nauk, Ser.
Khim., 1992, 2419 [Bull. Russ. Acad. Sci., Div. Chem. Sci.
(Engl. Transl.), 1992, 41, 1901]; (k) B. I. Ugrak, V. S.
Bogdanov, S. A. Shevelev, I. L. Dalinger, Izv. Akad. Nauk,
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1993, 42, 1555]; (l) M. Begtrup, P. Larsen, P. Vedsø, Acta
Chem. Scand., 1992, 46, 972.
9. A. A. Zaitsev, I. L. Dalinger, A. M. Starosotnikov, V. V.
Kachala, Yu. A. Strelenko, T. K. Shkineva, S. A. Shevelev,
Zh. Org. Khim., 2005, 41, 1538 [Russ. J. Org. Chem.
(Engl. Transl.), 2005, 41, 1507].
10. A. A. Zaitsev, T. I. Cherkasova, I. L. Dalinger, V. V. Kachaꢀ
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Shkineva, G. P. Popova, S. A. Shevelev, Izv. Akad. Nauk,
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Received March 11, 2009;
in revised form September 9, 2009