Synthesis of 1H-[1,2,3]triazolo[4,5-e][1,2,3,4]tetrazine 4,6-dioxide and its methyl derivatives

Article abstract of DOI:10.1007/s11172-015-0922-6

1H-[1,2,3]Triazolo[4,5-e][1,2,3,4]tetrazine 4,6-dioxide (3) was synthesized by reduction of 1-hydroxy-1H-[1,2,3]triazolo[4,5-e][1,2,3,4]tetrazine 5,7-dioxide (1) with PCl3, reduction of 1-methoxy-1H-[1,2,3]triazolo[4,5-e][1,2,3,4]tetrazine 5,7-dioxide (4)

Full text of DOI:10.1007/s11172-015-0922-6

Russian Chemical Bulletin, International Edition, Vol. 64, No. 3, pp. 699—703, March, 2015
699
Synthesis of 1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine 4,6ꢀdioxide
and its methyl derivatives*
A. A. Voronin, V. P. Zelenov, A. M. Churakov, Yu. A. Strelenko, and V. A. Tartakovsky
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Eꢀmail: churakov@ioc.ac.ru
1Hꢀ[1,2,3]Triazolo[4,5ꢀe][1,2,3,4]tetrazine 4,6ꢀdioxide (3) was synthesized by reduction
of 1ꢀhydroxyꢀ1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine 5,7ꢀdioxide (1) with PCl3, reduction
of 1ꢀmethoxyꢀ1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine 5,7ꢀdioxide (4) with Na2S2O4, and
by the reaction of compound 4 with Et3N. Both methylation of compound 3 with diazomethane
and reaction of Agꢀsalt of compound 3 with MeI occur at the triazole cycle to give all three
possible isomers. The structures of the synthesized compounds were confirmed by 1H, 13C, 14N,
and 15N NMR spectroscopy.
Key words: 1,2,3ꢀtriazole 1ꢀoxides, 1,2,3ꢀtriazoles, 1,2,3,4ꢀtetrazine 1,3ꢀdioxides, methylꢀ
ation, deoxigenation, 14N and 15N NMR spectroscopy.
Fused 1,2,3,4ꢀtetrazine 1,3ꢀdioxides first synthesized
in our research group1 are potential energetic compounds
and attract great attention as the objects for quantum
chemistry calculations and properties predicting.2—6 Thereꢀ
fore, synthesis of these type of compounds and study of
their properties are important.
We have recently developed procedure towards triꢀ
azolotetrazine (TT) 1 (see Ref. 7) via reaction of triazole
oxide 2 (see Ref. 8) with the HNO3/H2SO4/Ac2O mixꢀ
Scheme 2
ture. Upon the reaction, tertꢀbutyl group of the starting
compound 2 is cleaved to give target compound 1 (Scheme 1).
Scheme 1
Reagents: i. PCl3, MeCN; ii. Na2S2O4, MeOH.
The first approach is the reduction of hydroxyꢀsubstiꢀ
tuted TT 1 with PCl3 in anhydrous MeCN at room temꢀ
perature. The reaction is completed within 18 h to give
target TT 3 in 94% yield (see Scheme 2).
The second approach involves the reduction of methꢀ
oxyꢀsubstituted TT 4** with Na2S2O4 in MeOH at room
temperature. The reaction is very fast and affords TT 3 in
the yield of 89% (see Scheme 2).
Reagents: HNO3, H2SO4, Ac2O.
Triazolotetrazine 3 and its derivatives are also of interꢀ
est as high energy density compounds. In the present work,
we describe synthesis of TT 3 and study of its methylation.
Synthesis of TT 3. We developed two synthetic apꢀ
proaches to access TT 3 (Scheme 2).
To our surprise, treatment of methoxyꢀsubstituted TT 4
with strong base also results in TT 3. We were interested in
this unexpected result and studied this reaction in more
* Dedicated to Academician of the Russian Academy of Sciences
V. I. Minkin on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0699—0703, March, 2015.
1066ꢀ5285/15/6403ꢀ0699 © 2015 Springer Science+Business Media, Inc.

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Voronin et al.
detail including in consideration compounds 5 and 69,*
bearing more acidic protons then the methyl group proꢀ
tons (Scheme 3).
Prototropic tautomerism of TT 3. Acidic proton of
TT 3 can formally be attached to any nitrogen or oxyꢀ
gen of the triazolotetrazine framework. Preliminary quanꢀ
tum chemical calculations (Gaussian 0912, B3LYP
6ꢀ311+G(d,2p) level of theory, gas phase) reveal that
tautomers 3´, 3, and 3´´´ (Scheme 5) are most thermoꢀ
dynamically favorable. It was found that TT 3´ is more
Scheme 3
stable than tautomers 3 and 3´´´ by 1.1 and 4.9 kcal mol–1
,
respectively. Accounting for the solvation effect (H2O,
selfꢀconsistent reaction field (SCRF) PCM) does not virꢀ
tually impact on the relative stability of tautomers. Triꢀ
azolotetrazine 3´ is more thermodynamically favorable
then tautomers 3 and 3´´´ by 1.2 and 4.1 kcal mol–1, resꢀ
pectively.
R = Me (4), CH2C(O)Me (5), CH2C(O)Ph (6)
Reagents: 1) Et3N, MeOH; 2) silica gel.
Scheme 5
Triethylamine was found to be very convenient as
a base. For transformation to occur, 1 equiv. Et3N is
enough for TTs 5 and 6, and 2 equiv. Et3N for TT 4.
Triazolotetrazine 3 was obtained in the yields of 77—80%.
Thus, this reaction can be regarded as another approach
to TT 3.
The reaction mechanism involves, apparently, the proꢀ
ton abstraction and the O—N bond breaking to give the
triazolotetrazine anion and aldehyde (Scheme 4). The reꢀ
action proceeds more easily in the case of compounds 5
and 6 bearing acidic methylene protons. At the same time,
the triazolotetrazine anion is a very good leaving group
and the reaction readily proceeds even in the case of TT 4
bearing the Oꢀmethyl group.
Similar calculations were performed for methylated
derivatives 7a—c (Scheme 6). The results of calculations
are close to those obtained for Hꢀform of TT 3. Triazoloꢀ
tetrazine 7b is more thermodynamically stable then 7a
and 7c by 0.3 and 5.3 kcal mol–1, respectively.
Thus, thermodynamic stabilities of tautomers 3´ and 3
are close. The same conclusion can be drawn for isomers
7a and 7b. At the same time, TTs 3´´´ and 7c are relatively
less stable.
Scheme 4
Methylation of TT 3. Diazomethane methylation of
TT 3 leads to a mixture of all three isomers with a ratio of
7a : 7b : 7c = 41 : 33 : 26 (1H NMR data) in 34% total
yield (see Scheme 6).
Methylation of Agꢀsalt 8 with iodomethane in anhyꢀ
drous MeCN also affords a mixture of three isomers (83%
total yield); however, in this case the reaction proceeds
more selectively and produces isomers in the ratio of
7a : 7b : 7c = 30 : 56 : 14 (1H NMR data).
The formation of 2ꢀoxoꢀ2ꢀphenylacetaldehyde (phenylꢀ
glyoxal) in the reaction of TT 6 with Et3N (see Scheme 4)
was confirmed by its transformation into the correspondꢀ
ing bisꢀhydrazone upon the reaction with 2,4ꢀdinitroꢀ
phenylhydrazine. The structure of bisꢀhydrazone was conꢀ
firmed by a comparison with a product of counter synthesis.
Earlier,10,11 similar reactions were described for a seꢀ
ries of tetrazole derivatives. Thus, treatment of 1ꢀ(2ꢀoxoꢀ
propoxy)ꢀ1Hꢀtetrazole derivatives with a K2CO3 excess in
refluxing EtOH resulted in tetrazole and methylglyoxal.
In both cases, the lowest content was found for less
thermodynamically stable isomer 7c.
NMR spectroscopy. We succeeded to assign all 1H and
13C NMR signals and observed 14N and 15N NMR signals
of TTs 3, 7a—c, and 8 (Table 1, Fig. 1). In 13C NMR
spectra, the signal of the C(7a) carbon atom bonded to
Nꢀoxide fragment of tetrazineꢀdioxide (TDO) cycle is
broadened due to spinꢀspin coupling to 14N. We failed to
observe the acidic proton signal for compound 3 by
1H NMR spectroscopy (acetoneꢀd6 and DMSOꢀd6) owing
to fast proton exchange. Special NMR techniques (INEPT,
* Compounds 4—6 were synthesized by alkylation of TT 1
(see Ref. 9).

Fused 1,2,3,4ꢀtetrazine 1,3ꢀdioxides
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
701
Table 1. 1H, 13C, 14N, and 15N NMR spectra of compounds 3, 7a—c, and 8a
Comꢀ
pound
NMR
b
13C, 
C(7a)c
1H, 
14N,  (1/2/Hz) [15N, ]b
(J/Hz)b
C(3a)
R
N(1)
N(2)
N(3)
N(5)
N(7)
d
d
d
d
d
3
8
7a
156.8
156.9
147.9
137.0
137.6
137.1
—
—
—
—
4.39
—
—
—
—
—
—
—
—
–43 (60)
–43 (280) –57 (200)
–57 (30)
d
d
d
35.1 (CH3)
[–161]e
–39 (40)
–42 (50)
–42(55)
–53 (25)
–50 (20)
–60(20)
(s, 3 H, CH3)
4.64
(s, 3 H, CH3)
4.51
7bf
7с
153.3
155.5
136.4
125.9
46.0 (CH3)
37.4 (CH3)
[–65]e
[–112]e [–65]e
[–158.8]g
—
—
d
d
(s, 3 H, CH3)
a Numbering scheme for atoms in compounds 3, 7a—c, and 8 is given in Fig. 1.
b 1H, 13C, 14N, and 15N NMR spectra of TTs 3 and 7a,c were recorded in acetoneꢀd6, and spectra of TT 8 were run in
DMSOꢀd6.
c Signal of the C(7a) atom bonded to the NO group of TDO cycle is broadened.
d No signals were observed.
e 1H—15N HSQC data.
f See Ref. 7
g INEPT data:  –158.8, 2JN(1),Me = 3.65 Hz.
Scheme 6
8
1H—15N HSQC, 1H—13C HMBC, 1H—13C HSQC) were
applied to evaluate the positions of the substituent at the
N atom of 1,2,3ꢀtriazole moiety. 14N NMR spectra of
compounds 3, 7a—c, and 8 contain signals of the N(5)
being comparable to the stability of Agꢀsalt of hydroxytriꢀ
azolotetrazine 1 (m.p. >197 C (decomp.)7).
Triazolotetrazines 7a—c melt with decomposition over
a temperature range of 200—220 C (Table 2). These
compounds are noticeably more stable then structurally
related furazanoꢀ1,2,3,4ꢀtetrazine 1,3ꢀdioxide melting
with decomposition at 112—114 C.13,14
and N(7) atoms of TDO cycle at  –(40—60) (1/2
=
= 25—60 Hz). In 15N NMR (1H—15N HSQC) spectra of
TTs 7a,c, the signals of the N(1) (compound 7a) and N(3)
(compound 7c) of 1,2,3ꢀtriazole cycle, which are directly
bonded to the methyl group, were found about  –160. In
the case of TT 7b, the N(2) atom directly bonded to the
methyl groups resonates at  –112. This large difference in
the chemical shifts can be used to distinguish isomers.
Thermal stability of TTs were examined by monitoring
the behavior of compounds upon heating with a Kofler
apparatus. Although this method is not accurate, it serves
for drawing a number of preliminary conclusions.
In summary, we developed versatile procedures to
access TT 3 by reduction of TT 1 and by treatment of
HꢀForm of TT 3 melts with decomposition at
150—152 C and has inferior stability then hydroxytriazoꢀ
lotetrazine 1 (m.p. 180—185 C (decomp.)7). Stability of
Agꢀsalt 8 is higher as compared to Hꢀform of compound 3
Fig. 1. Numbering scheme for compounds 3, 7a—c, and 8 used
for the description of the NMR spectra.

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Voronin et al.
Table 2. Melting points for TT 3, 7a—c, and 8
gen is often underestimated upon microanalysis of polynitrogen
compounds (see, for instance, Refs 17 and 18).
Synthesis of 1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine
4,6ꢀdioxide (3) by the reaction of 1ꢀmethoxyꢀ1Hꢀ[1,2,3]triazoloꢀ
[4,5ꢀe][1,2,3,4]tetrazine 5,7ꢀdioxide (4) with Na2S2O4. To a vigꢀ
orously stirred solution of TT 4 (198 mg, 1.07 mmol) in 95%
MeOH (15 mL), Na2S2O4 (186 mg, 1.07 mmol) was added at
25 C. The reaction mixture was stirred at this temperature for
15 min and precipitate was filtered off. Small amount of silica gel
(Merk 40—63) was added to the filtrate, and the volatiles were
removed in vacuo. Triazolotetrazine 3 was isolated by silica gel
column chromatography (elution with AcOEt—MeOH, 4 : 1) in
the yield of 140 mg (85%), yellow crystals.
Synthesis of TT 3 by the reaction of 1ꢀRꢀ1Hꢀ[1,2,3]triazoꢀ
lo[4,5ꢀe][1,2,3,4]tetrazine 4,6ꢀdioxides 4—6 with Et3N (general
procedure). To a stirred solution of Oꢀalkyl derivative 4, 5 or 6
(1 mmol) in MeOH, Et3N (2 mmol for TT 4 or 1 mmol for TTs 5
and 6) was added dropwise at 25 C. The reaction mixture was
stirred at this temperature until complete consumption of the
starting TTs 4—6 (TLC monitoring), the solvent was removed
in vacuo. Triazolotetrazine 3 was purified by silica gel column
chromatography (elution with EtOAc—MeOH, 5 : 1). The yields
of TT 3 were as follows: 77% from TT 4 (R = Me), 80% from
TT 5 (R = CH2C(O)Me), and 80% from TT 6 (R = CH2C(O)Ph).
Synthesis of phenylglyoxal bis(dinitrophenyl)hydrazone. To
a vigorously stirred solution of TT 6 (30 mg, 0.104 mmol) in MeCN
(2 mL), a solution of triethylamine (14.5 L, 10.5 mg,
0.104 mmol) in MeCN (0.2 mL) was added at 25 C. The reacꢀ
tion mixture was stirred at this temperature until complete conꢀ
sumption of the starting TT 6 (TLC monitoring). Then freshly
prepared Bradly reagent (1 mL) was added and the mixture was
kept for 20 min. Precipitated bishydrazone was collected by filꢀ
tration, washed with chilled MeCN (2×0.5 mL), and dried. 2ꢀ[2ꢀ
(2,4ꢀDinitrophenyl)hydrazonoꢀ1ꢀphenylpropanꢀ1ꢀone was obꢀ
tained in the yield of 34 mg (58%), red brown crystals. From
mother liquor, TT 3 was isolated by silica gel column chromatoꢀ
graphy (elution with petroleum ether—EtOAc, 3 : 1 (removal of
nonꢀpolar impurities), then EtOAc—MeOH, 4 : 1) in the yield
of 8 mg (50%), yellow crystals.
1Hꢀ[1,2,3]Triazolo[4,5ꢀe][1,2,3,4]tetrazine 4,6ꢀdioxide
Agꢀsalt (8). Caution! AgꢀSalt is very sensitive to impact and friction
and has to be handled as a primary explosive. To a vigorously
stirred solution of TT 3 (166 mg, 1.07 mmol) in H2O (3 mL),
AgNO3 (272 mg, 1.6 mmol) was added at 25 C. The reaction
mixture was stirred at 25 C for 5 min and the precipitate was
collected using porous metal funnel, washed with H2O (3×5 mL)
and dried in vacuo over P4O10. AgꢀSalt 8 was obtained in the
yield of 206 mg (72%); oliveꢀcolored crystals.
Diazomethane methylation of TT 3. To a suspension of TT 3
(130 mg, 0.84 mmol) in EtOAc (5 mL), a solution of CH2N2 in
Et2O was added portionwise until complete consumption of the
starting compound (TLC monitoring). Purification by silica gel
column chromatography (elution with petroleum ether—AcOEt,
1 : 1) afforded a mixture of three isomers 7a, 7b, and 7c in the
ratio of 41: 33 : 26 (1H NMR data), yield of 48 mg (34%), yellow
crystals. The mixture of isomers were resolved as follows: first,
chromatography using CHCl3 as an eluent afforded TT 7c (5 mg,
lemonꢀcolored crystals) and a mixture of TTs 7a and 7b (27 mg,
light yellow crystals), subsequent resolution of the mixture of
TTs 7a and 7b with benzene as a solvent afforded TT 7b (6 mg,
yellow crystals) and TT 7a (7 mg, light yellow crystals).
Compound
M.p. (decomp.)/C
3
8
7a
7b
7c
150—152
182—192
213—214
198—199*
200—201
* See Ref. 7.
Oꢀsubstituted TTs 4—6 with bases. It is found that both
TT 3 and Agꢀsalt 8 react nonꢀselectively with diazoꢀ
methane to afford a mixture of three isomers.
Experimental
1
H, 13C, 14N, and 15N NMR spectra were run with a Bruker
DRXꢀ500 spectrometer (working frequencies of 500.1, 125.8,
36.1, and 50.7 MHz, respectively). The chemical shifts are given
in the  scale relative to Me4Si (1H, 13C) and MeNO2 (14N, 15N,
internal standard), strong field shifts are negative. Electron imꢀ
pact mass spectra (70 eV) were recorded with a Kratos MSꢀ300
instrument. High resolution mass spectra were obtained on
a Bruker micrOTOF II instrument. The course of the reactions
was monitored by TLC on precoated Merck 60 F254 plates. Silica
gel Merck 40—63 was used for column chromatography. Meltꢀ
ing points are given uncorrected. A solution of diazomethane in
Et2O,15 the Brady reagent (a solution of 2,4ꢀdinitrophenyl hydrꢀ
azine in H2SO4),16 and 1ꢀhydroxyꢀ1Hꢀ[1,2,3]triazolo[4,5ꢀe]ꢀ
[1,2,3,4]tetrazine 5,7ꢀdioxide 1)7,*** were obtained by the known
procedures.
Caution! All compounds synthesized in the present work are
sensitive to impact and friction and have to be handled as exꢀ
plosives.
Synthesis of 1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine 4,6ꢀdiꢀ
oxide (3) by the reaction of 1ꢀhydroxyꢀ1Hꢀ[1,2,3]triazolo[4,5ꢀe]ꢀ
[1,2,3,4]tetrazine 5,7ꢀdioxide (1) with PCl3. To a stirred solution
of hydroxytriazolotetrazine monohydrate 1 (61 mg, 0.32 mmol)
in anhydrous MeCN (2.5 mL), PCl3 (132 mg, 0.96 mmol) was
added dropwise at 25 C under argon. The reaction mixture was
stirred at this temperature for 18 h until complete consumption
of the starting TT 1 (TLC monitoring) and the solvent was reꢀ
moved in vacuo. Purification of the residue by column chromatoꢀ
graphy (elution with EtOAc) afforded triazolotetrazine 3 in the
yield of 47 mg (94%); yellow crystals well soluble in polar solvents
(MeCN, H2O, MeOH). MS (ESI), m/z: 154.0114 [M – H]–.
C2N7O2. Calculated: 154.0108 [M – H]–. IR (KBr), /cm–1
1636 s, 1612 s, 1601 s, 1484 w, 1436 s, 1388 s, 1340 s, 1312 s.
Found (%): C, 15.79; H, 0.91; N, 58.51. C2HN7O2. Calculatꢀ
ed (%): C, 15.49; H, 0.65; N, 63.23. Note that content of nitroꢀ
:
* Compound 1 synthesized by the described procedure is a monoꢀ
hydrate, which dehydrates at prolonged drying over P4O10
in vacuo. Microanalysis data for 1ꢀhydroxyꢀ1Hꢀ[1,2,3]triazoloꢀ
[4,5ꢀe][1,2,3,4]tetrazine 5,7ꢀdioxide monohydrate: found (%):
C, 13.03; H, 1.68; N, 45.54. C2H3N7O4. Calculated (%):
C, 12.70; H, 1.60; N, 51.85.

Fused 1,2,3,4ꢀtetrazine 1,3ꢀdioxides
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
703
Physicochemical and spectral data for triazolotetrazine 7b
are in agreement with those published previously.7
9. A. A. Voronin, V. P. Zelenov, A. M. Churakov, Yu. A. Streꢀ
lenko, V. A. Tartakovsky, Russ. Chem. Bull. (Int. Ed.), 2014,
63, 475 [Izv. Akad. Nauk, Ser. Khim., 2014, 475].
10. J. Plenkiewicz, E. StefanskaꢀHalladin, Bull. Ac. Pol. Sci.,
Ser. Sci. Chim., 1978, 26, 189.
11. O. A. Luk´yanov, N. I. Shlykova, Bull. Acad. Sci. USSR, Div.
Chem. Sci. (Engl. Transl.), 1987, 36, 2358 [Izv. Akad. Nauk,
Ser. Khim., 1987, 2540].
1ꢀMethylꢀ1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine 4,6ꢀdiꢀ
oxide (7a). MS (EI), m/z: 169 [M]+. MS (ESI), m/z: 192.0247
[M + Na]+. C3H3N7O2. Calculated: 192.0240 [M + Na]+.
1ꢀMethylꢀ1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine 5,7ꢀdiꢀ
oxide (7c). MS (EI), m/z: 169 [M]+, 125 [M – N2O]+, 81
[M – 2 N2O]+. MS (ESI), m/z: 192.0243 [M + Na]+. C3H3N7O2.
Calculated: 192.0240 [M + Na]+.
12. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,
J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuꢀ
da, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E.
Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers,
K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Norꢀ
mand, K. Raghavachari, A. Rendell, J. C. Burant, S. S.
Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam,
M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J.
Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Marꢀ
tin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvaꢀ
dor, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farꢀ
kas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox,
Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford
(CT), 2013.
Methylation of 1Hꢀ[1,2,3]triazolo[4,5ꢀe][1,2,3,4]tetrazine
4,6ꢀdioxide Agꢀsalt (8) with iodomethane. To a vigorously stirred
suspension of Agꢀsalt 8 (45 mg, 0.172 mmol) in MeCN (1 mL),
MeI (122 mg, 0.860 mmol) was added at 25 C. The reaction
mixture was stirred at this temperature for 12 h, the precipitate
was collected by filtration, and washed with MeCN (3×2 ml).
Removal of the solvent in vacuo afforded a mixture of three
isomers 7a, 7b, and 7c in the ratio of 30 : 56 : 14 (1H NMR data),
yield of 24 mg (83%), yellow crystals. The isomers were resolved
as above described.
This work was financially supported by the Russian
Science Foundation (Project No. 14ꢀ50ꢀ00126).
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Received January 15, 2015