Insertion of carbon disulfide and the nitrile group into the diaziridine ring of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in ionic liquids catalyzed by BF3 ? Et2O

Article abstract of DOI:10.1007/s11172-010-0018-2

The present study revealed two new reactions resulting in the diaziridine ring expansion, viz., the insertion of the CS₂ molecule and the CN group of activated nitriles into the C-N bond of the diaziridine fragment of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes. These reactions can be performed only in ionic liquids in the presence of BF₃ ? Et₂O as the catalyst. Based on these reactions, we developed simple one-pot methods for the synthesis of 3-aryldihydro-5 H-pyrazolo[1,2- c][1,3,4]thiadiazole-1-thiones and 1-aryl-6,7-dihydro-1 H,5H-pyrazolo-[1,2-a][1,2,4]triazoles in high yields. Dipolar intermediates of new reactions, which are direct precursors of the final products, were detected by NMR methods. One of the intermediates was isolated and characterized. The reaction of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with benzoyl cyanide affords (2-benzoyrpyrazolidin-1-yl)(aryl)acetonitriles.

Full text of DOI:10.1007/s11172-010-0018-2

Russian Chemical Bulletin, International Edition, Vol. 58, No. 2, pp. 366—379, February, 2009
366
Insertion of carbon disulfide and the nitrile group
into the diaziridine ring of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes
in ionic liquids catalyzed by BF3•Et2O*
Yu. S. Syroeshkina,a V. V. Kuznetsov,a K. A. Lyssenko,b and N. N. Makhovaa
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: mnn@ioc.ac.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: kostya@xrlab.ineos.ac.ru
The present study revealed two new reactions resulting in the diaziridine ring expansion, viz.,
the insertion of the CS2 molecule and the CN group of activated nitriles into the C—N bond
of the diaziridine fragment of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes. These reactions can be
performed only in ionic liquids in the presence of BF3•Et2O as the catalyst. Based on these
reactions, we developed simple oneꢀpot methods for the synthesis of 3ꢀaryldihydroꢀ
5Hꢀpyrazolo[1,2ꢀc][1,3,4]thiadiazoleꢀ1ꢀthiones and 1ꢀarylꢀ6,7ꢀdihydroꢀ1H,5Hꢀpyrazoloꢀ
[1,2ꢀa][1,2,4]triazoles in high yields. Dipolar intermediates of new reactions, which are direct
precursors of the final products, were detected by NMR methods. One of the intermediates was
isolated and characterized. The reaction of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes with benzoyl
cyanide affords (2ꢀbenzoylpyrazolidinꢀ1ꢀyl)(aryl)acetonitriles.
Key words: 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes, carbon disulfide, activated nitriles, ring
expansion, 3ꢀaryldihydroꢀ5Hꢀpyrazolo[1,2ꢀc][1,3,4]thiadiazoleꢀ1ꢀthiones, 1ꢀarylꢀ6,7ꢀdihydroꢀ
1H,5Hꢀpyrazolo[1,2ꢀa][1,2,4]triazoles, (2ꢀbenzoylpyrazolidinꢀ1ꢀyl)arylacetonitriles, dipolar
intermediates, ionic liquids, BF3•Et2O.
tion of 1,2ꢀdialkyldiaziridines with benzoyl isothiocyanate),
it was found that the use of the ionic liquids ([bmim][BF4]
or [bmim][PF6], where bmim is 1ꢀbutylꢀ3ꢀmethylimidazoꢀ
lium) as the reaction medium results in the unexpected
reaction pathway giving rise to 1,2,4,6ꢀtetrazepaneꢀ
5ꢀthione derivatives.7 In other solvents, these compounds
also reacted with each other, but the reactions were
very unselective and gave mixtures of several inseparable
compounds. Therefore, both the published data and our
results provide evidence that readily available diaziridine
derivatives can serve as the starting compounds for the
development of new rather simple routes to both known
and new heterocyclic systems.
In the present study, we examined the possibility of
inserting less reactive dipolarophiles, such as CS2 and the
CN group of activated nitriles, into the diaziridine ring of
monoꢀ and bicyclic diaziridine derivatives substituted at
the nitrogen atoms. We investigated these reactions for
1,2ꢀdialkyldiaziridines 1 and 6ꢀarylꢀ1,5ꢀdiazabicycloꢀ
[3.1.0]hexanes 2.**
Until recently, the reactions of monocyclic diaziridines
with electrophilic reagents were described primarily for
diaziridines unsubstituted at one or two nitrogen atoms
and were, as a rule, accompanied by the diaziridine ring
opening followed by the intraꢀ or intermolecular cyclizaꢀ
tion of the resulting dipolar intermediate to give expanꢀ
sion products of the starting heterocycle.1—3 However, the
analogous reactions of diaziridine derivatives substituted
at both nitrogen atoms were virtually unknown. Recently,
we have shown4—6 that N,N´ꢀdisubstituted diaziridines
(both monoꢀ and bicyclic) can also react with active elecꢀ
trophilic reagents (heterocumulenes, viz., ketenes, aroyl
isocyanates, aroyl isothiocyanates, and acyl chlorides),
resulting in the diaziridine ring expansion to form derivaꢀ
tives of other heterocyclic systems (imidazolidinꢀ4ꢀones,
4ꢀacylaminoazetidinꢀ2ꢀones, 1,2,4ꢀtriazolidinꢀ3ꢀones,
and Nꢀacylpyrazolidines). Evidently, these reactions also
proceed through dipolar intermediates, which undergo
intramolecular cyclization. For one example (the reacꢀ
* On the occasion of the 75th anniversary of the foundation
of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
** Preliminary data on these reactions have been published preꢀ
viously.8,9
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 362—375, February, 2009.
1066ꢀ5285/09/5802ꢀ0366 © 2009 Springer Science+Business Media, Inc.

Insertion of carbon disulfide and the nitrile group
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
367
In the previous studies, we have found that the
diaziridine ring in 1,2ꢀdialkyldiaziridines 1 can be cleaved
at the C—N and N—N bonds in the reactions with
heterocumulenes, whereas bicyclic diaziridines 2 are
cleaved only at the C—N bond in the reactions with these
reagents. Hence, it could be expected that the reactions of
diaziridines 1 with CS2 and nitriles would afford either
structures 3 and 4 or structures 5 and 6, whereas diaziriꢀ
dines 2 can form only structures 7 and 8 (Scheme 1).
the reaction of 1,2ꢀdisubstituted hydrazines with an
excess of CS2.10 It can be hypothesized that under the
conditions used, diaziridine 1a is hydrolyzed to 1,2ꢀdiꢀ
(2ꢀphenylethyl)hydrazine (10), which reacts with CS2
(Scheme 2). The hydrolysis to hydrazines is the most
characteristic reaction of diaziridines.11
Scheme 2
Scheme 1
It is known that the introduction of alkyl substituents
at position 3 of the diaziridine ring increases the electron
density on the nitrogen atoms.12 Hence, to study the reacꢀ
tions of diaziridines 1 with activated nitriles, we chose
1,2ꢀdialkyldiaziridines 1b—d containing different substituꢀ
ents at the carbon atom of the ring and used trichloroꢀ
acetonitrile as the nitrile. In acetonitrile, the reactions
of these compounds at 20—50 °C either did not proceed
or (in the presence of BF3•Et2O) led to oligomerization
of the starting diaziridine. To increase the reaction rate,
we used the ionic liquids [bmim][BF4] and [emim][HSO4]
(emim is 1ꢀethylꢀ3ꢀmethylimidazolium) as the solvent
for diaziridines 1b,c and diaziridine 1d, respectively. The
reactions in [bmim][BF4] were carried out both in the
presence and in the absence of BF3•Et2O as the catalyst.
The completion of the reaction was judged from the disꢀ
appearance of the starting diaziridine (TLC monitoring).
However, all reactions afforded complex mixtures of comꢀ
pounds, which we failed to separate (Scheme 3).
With the aim of searching for the conditions of the
insertion of CS2 into the diaziridine ring, we consulted
the literature on the introduction of other dipolarophiles
into the diaziridine ring of 1,5ꢀdiazabicyclo[3.1.0]ꢀ
hexanes.13—18 The authors of these studies showed that
the heating of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes 2 at
110—130 °C results in the diaziridine ring opening to
form azomethine imine intermediates 11, and the latter
can react with various dipolarophiles (Nꢀarylmaleimides,
activated acetylene derivatives, isocyanates, or isothioisoꢀ
cyanates) to give other heterocyclic systems. In addition,
The reaction of diaziridines 1 with CS2 was studied in
detail for 1,2ꢀbis(2ꢀphenylethyl)diaziridine 1a. A mixture
of the reagents was kept at 20 °C over a long period of
time (72 h) or refluxed in an excess of CS2, including in
the presence of bases (Et3N and NaOH); however,
diaziridine 1a remained unconsumed. To intensify the
process, we used different conditions, in particular, heatꢀ
ing in acetonitrile in a sealed tube at 100 °C, stirring in the
ionic liquid [bmim][BF4], or stirring in the absence
of the solvent with the addition of a catalytic amount of
BF3•Et2O at 20 °C, in all cases an excess of CS2 (the
molar ratio 1a : CS2=1 : 4) being used. The completion of
the reaction was judged from the disappearance of the
starting diaziridine 1a in the reaction mixture (TLC moniꢀ
toring). The complete conversion of diaziridine 1a in
acetonitrile was achieved within 10 days; in the ionic
liquid, within 4 days; upon heating without a solvent in
the presence of BF3•Et2O, within 25 days. However,
instead of expected compounds 3 or 5, all reactions proꢀ
duced 3,4ꢀdi(2ꢀphenylethyl)ꢀ1,3,4ꢀthiadiazolidineꢀ2,5ꢀ
dithione (9) in similar yields (30—35%). 3,4ꢀDisubstiꢀ
tuted 1,3,4ꢀthiadiazolidineꢀ2,5ꢀdithiones were described
in the literature. These compounds were synthesized by

368
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
Syroeshkina et al.
compounds 2 was the synthesis20 of stable azomethine
imine intermediate 14 (through the introduction of two
phenyl groups) structurally similar to intermediates 11. It
was shown that CS2 can undergo the addition to this
intermediate followed by the cyclization giving rise to
tricyclic system 15. In the cited study, compound 14
was synthesized by passing a solution of diazenium
perchlorate 16 through a column packed with alkaline
aluminum oxide (Scheme 5).
Scheme 3
Scheme 5
1
2
3
Compound
R
R
R
1b
1c
1d
Et
H
H
H
Me
(CH ) Ph,
CH Ph
2 2
2
Et
Me
these authors also found19 that the catalytic cleavage of
the diaziridine fragment in compounds 2 with Lewis acids
(BF3•Et2O or In(OTf)3) also results in the generation of
azomethine imine intermediates 11, which form products
12 as a mixture of cisꢀtrans isomers through the 1,3ꢀdipoꢀ
lar cycloaddition to Nꢀarylmaleimides. In the absence of
dipolarophiles, intermediates 11 form dimers 13.19 These
reactions were carried out in dipolar aprotic solvents
(THF, diethyl ether, or acetonitrile) at 20 °C (Scheme 4).
B is a base
The catalytic cleavage of 1,5ꢀdiazabicyclo[3.1.0]ꢀ
hexanes 2 in the presence of BF3•Et2O with the use of an
excess CS2 was initially carried out for 6ꢀ(4ꢀmethoxyꢀ
phenyl)ꢀ1,5ꢀdiazabicyclo[3.1.0]hexane (2a) in acetoniꢀ
trile at 20 °C. This reaction actually produced the target
3ꢀ(4ꢀmethoxyphenyl)dihydroꢀ5Hꢀpyrazolo[1,2ꢀc][1,3,4]ꢀ
thiadiazoleꢀ1ꢀthione (7a); however, the complete conꢀ
version of compound 2a was achieved only after 20 days.
To increase the reaction rate, the reaction was performed
in the ionic liquids [bmim][BF4] or [bmim][PF6], which,
as we have demonstrated previously,21,22 accelerate the
1,3ꢀdipolar cycloaddition reactions. The reactions of
bicyclic compound 2a with CS2 in the ionic liquids in the
presence of BF3•Et2O were carried out at 20 оC with
the use of the molar ratio 2a : CS2 = 1 : 6. The course
of the reactions was monitored by TLC until the complete
conversion of the starting bicyclic compound 2a was
achieved. The TLC monitoring showed that the first steps
of the reaction afford dimer 13 with Rf = 0.78 as a precipiꢀ
tate, which gradually dissolves to give two new compounds
with Rf = 0.40 and Rf = 0.70 in the 2 : 1 hexane—ethyl
acetate system, with the former compound predominatꢀ
ing. In the course of the reaction, the latter compound
and dimer 13 gradually disappear, and the amount of the
former compound (apparently, the final bicyclic comꢀ
Scheme 4
LA is a Lewis acid
The latter conditions are of interest from the standꢀ
point of the insertion of CS2 into compounds 2, because
the reaction was carried out without heating. An addiꢀ
tional prerequisite for the possible insertion of CS2 into
1
pound 7a) increases. The H NMR spectrum of the mixꢀ
ture of these products isolated after the completion of the
reaction showed signals of both compounds. The signals

Insertion of carbon disulfide and the nitrile group
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
369
Scheme 6
corresponding to the final product 7a are as follows:
2.55 (m, 2H, NCH2CH2), 2.75 and 3.15 (both m, 2 H,
ArCNCH2), 3.78 and 3.93 (both m, 2 H, SCNCH2), 5.75
1
(s, 1 H, SCH). In the H NMR spectrum of the initially
formed compound, the signals of the substituents in
the aromatic ring are shifted downfield by 0.1 ppm,
the singlet at
δ 5.75 is absent, a new singlet appears at
δ
9.85—10.0, and the signals for the protons of the
SCNCH2CH2 groups are shifted downfield. Evidently,
the compound with Rf 0.4 is a reaction intermediate. The
reaction was completed within 4 h and produced comꢀ
pound 7a in a nearly quantitative yield.
Under the aboveꢀdescribed conditions, the reactions
with CS2 were carried out also for other 6ꢀarylꢀ1,5ꢀdiazaꢀ
bicyclo[3.1.0]hexanes 2b—e. The reactions were perꢀ
formed until the complete conversion of the starting comꢀ
pounds 2 was achieved, the intermediate product being
formed in all cases (TLC monitoring). The reaction times
and the yields of bicyclic compounds 7b—e depend on the
nature of the substituent in the aromatic fragment of
the starting compounds 2 (Table 1, Scheme 6). The nearly
quantitative yields of compounds 7 were observed, when
the starting compounds 2 contain electronꢀreleasing subꢀ
stituents in the aromatic fragment (compounds 2c—d).
By contrast, in the case of Ar = 4ꢀClC6H4 (compound
2е), the yield of the corresponding bicyclic compound
7е was low (30%), 4ꢀClC6H4CHO being isolated as the
byꢀproduct.
i. BF3•Et2O
ii. [bmim][BF4] or [PF6]
these signals in the spectrum of the intermediate are shifted
downfield compared to compound 7d. The spectrum of
the latter compound shows a signal at
the carbon atom of the C=S fragment and the signal at
δ 180.7 assigned to
δ
74.6 corresponding to the CH fragment of the thiadiazoꢀ
lidine ring of compound 7d. In the 13C NMR spectrum
of the intermediate, the signal of the CH fragment is
shifted downfield (δ 192.1), whereas the signal for the
carbon atom of the C=S fragment is absent. Based on
the spectroscopic data and taking into account the ease
of the transformation into the final product 7d, it can be
hypothesized that the intermediate has the structure 17d
(Scheme 6). The absence of the signal for the carbon
atom of the C=S fragment in the proposed intermediate,
viz., 1ꢀ(4ꢀmethylbenzylidene)pyrazolidinium 2ꢀcarboꢀ
dithioate (17d), is evidently associated with the delocalizaꢀ
tion of electron density on both sulfur atoms, and the
positive charge is stabilized due to the presence of the aryl
fragment containing the electronꢀreleasing substituent.
The low yield of compound 7е is apparently attributed
to the presence of the electronꢀwithdrawing substituent in
the aryl fragment, which decreases its ability to stabilize the
positive charge in intermediates 17е, resulting in alternaꢀ
tive directions of the transformation.
In the initial step of the reaction, after the addition of
BF3•Et2O, dimer 13 is formed as a precipitate. This fact
suggests that the latter compound exists in equilibrium
with intermediate 11, which is removed from the reaction
zone to form initially the new intermediate, viz., 1ꢀarylꢀ
idenepyrazolidinium 2ꢀcarbothioate (17), and then the
final product 7 (Scheme 6). To confirm this hypothesis,
we synthesized authentic dimer 13a according to a known
procedure19 and performed the reaction of the latter with
CS2 under the aboveꢀdescribed conditions. Actually, this
reaction produced bicyclic compound 7a in quantitative
yield (Scheme 7).
As can be seen from Table 1, in the case of compounds
2a—c, the longest reaction time was observed for comꢀ
pound 2d. Hence, a mixture of the intermediate and the
final product was extracted from the ionic liquid within
2 h after the beginning of the reaction. These compounds
were isolated by silica gel column chromatography. Howꢀ
ever, the intermediate was gradually transformed into
bicyclic compound 7d during the storage both in solution
and in the individual state after evaporation of the solꢀ
vent. Nevertheless, we succeeded in performing elemenꢀ
1
tal analysis and recording H and 13C NMR spectra for
1
each compound. The H NMR spectra were similar to
those measured for a mixture of analogous compounds
produced in the reaction of bicyclic compound 2a. A
comparison of the 13C NMR spectra of compound 7d and
its precursor shows that both spectra have signals for the
carbon atoms of the pyrazolidine and benzene rings, but
Table 1. Reaction times (t) and the yields of compounds 7 in the
ionic liquids [bmim][BF4] and [bmim][PF6]
2
Ar
t/h
Yield 7 (%)
a
b
c
d
e
4ꢀMeOC6H4
4ꢀEtOC6H4
4ꢀPriOC6H4
4ꢀMeC6H4
4ꢀClC6H4
4
2
4
7
7
~99
~99
~99
~99
30
Unfortunately, attempts to insert CS2 under the aboveꢀ
described conditions into other bicyclic diaziridineꢀconꢀ

370
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
Syroeshkina et al.
Scheme 7
under the aboveꢀdescribed conditions with another comꢀ
pound containing the activated C=S group, viz., 1,3ꢀdiꢀ
acetylimidazolidineꢀ2ꢀthione (21). The reaction was carꢀ
ried out both at 20 °C and with heating to 45—50 °C.
However, only dimer 13a was obtained in quantitative
yield as the reaction product, whereas the starting thione
21 remained unconsumed (Scheme 9).
Scheme 9
Ar = 4ꢀMeOC H
6
4
Ar = 4ꢀMeOC H
6
4
taining systems, viz., 7ꢀarylꢀ1,6ꢀdiazabicyclo[4.1.0]ꢀ
heptanes 18, such as 7ꢀphenylꢀsubstituted compound 18a
and 7ꢀ(4ꢀmethylphenyl)ꢀsubstituted compound 18b, were
unsuccessful. In both cases, only dimers 19a,b were isolated
as the reaction products in quantitative yields. Evidently,
the diaziridine ring opening in the ionic liquids [bmim]ꢀ
[BF4] or [bmim][PF6] giving rise to azomethine imine
intermediates 20 was also observed, but 6,13ꢀdiaryloctaꢀ
hydrodipyridazino[1,2ꢀa:1´,2´ꢀd][1,2,4,5]tetrazines 19
were apparently more stable compared to dimers 13, and
the equilibrium 19—20 was not established. The method
for the synthesis of the starting bicyclic compounds 2 and
18 has been developed in our previous study,23 but dimers
having the structure 19 were synthesized for the first time
(Scheme 8, Table 2).
Since we succeeded in inserting CS2 into the diaziriꢀ
dine ring of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes 2a—d,
we decided to investigate the possibility of introducing
the nitrile group of activated nitriles 22a—c under the
conditions found for CS2. Numerous attempts to perform
the reactions of compounds 2 with nitriles 22a—c in usual
organic solvents, including the reactions in the presence
of BF3•Et2O as the catalyst, were unsuccessful. In all
cases, we obtained complex mixtures of compounds (at
least of eight compounds), which we failed to separate.
However, the reaction in the ionic liquid [bmim][BF4]
as the solvent with the use of BF3•Et2O as the catalyst at
20 °C proceeded rather unequivocally to form new comꢀ
pounds. The molar ratio of the starting compounds 2 : 22
was 1 : (1.3—1.5). The completion of the reaction was
judged from the complete conversion of the starting
bicyclic diaziridine 2 (TLC monitoring).
Along with CS2, we made an attempt to perform
the reaction of bicyclic compounds 2 (for compound 2a)
Scheme 8
The reaction time depends on the nature of the subꢀ
stituents in each of the starting bicyclic diaziridines 2 and
nitriles 22 used in the reaction (Table 3). The reactivity
of the starting bicyclic compounds decreases in the order
2b ≥ 2a > 2c> 2d; the reactivity of the nitriles decreases in
the order 22b > 22c > 22a. This reaction was particularly
fast with nitrile 22b. Thus, the reactions of bicyclic comꢀ
pounds 2b,c containing strong electronꢀreleasing substituꢀ
ents in the aromatic moiety with nitrile 22b bearing the
strong electronꢀwithdrawing substituent was completed
already within 30 min, whereas the reaction of diaziridine
2a with nitrile 22a containing the less electronꢀwithdrawꢀ
ing substituent required 18 h to be completed. The reacꢀ
tions of bicyclic diaziridines 2a,d with nitrile 22a at 20 °C
proceeded so slowly that only heating to 70 °C made it
possible to brought the reaction to completion within 20 h
in both cases. 6ꢀ(4ꢀChlorophenyl)ꢀ1,5ꢀdiazabicycloꢀ
[3.1.0]hexane (2е) containing the electronꢀwithdrawing
Ar = Ph (a), 4ꢀMeOC H (b)
6
4
Table 2. Reaction times (t) and the yields of
compounds 19
Compound
t/h
Yield (%)
19a
19b
4
3
~99
~99

Insertion of carbon disulfide and the nitrile group
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
371
Table 3. Reaction times (t) for the reactions of bicyclic diazꢀ
iridines 2a—d with nitriles 22a—c and the yields Y of reaction
products 8 and 24
substituent in the aromatic moiety (4ꢀClC6H4) reacted
with none of nitriles 22a—c.
The study of the structures of the reaction products
showed that the target 1ꢀarylꢀ6,7ꢀdihydroꢀ1H,5Hꢀpyrazoloꢀ
[1,2ꢀa][1,2,4]triazoles 8 were produced only in the reactions
of compounds 2a—d with nitriles 22a,b (Scheme 10). The
yields of bicyclic structures 8a—h also depend on the
nature of the substituents in the starting compounds,
the nature of the substituents in nitriles 22 having a
stronger effect (see Table 3). The lowest yields of comꢀ
pounds 8 were observed in the reactions with nitrile 22a
(no higher than 45%). The latter reactions afforded
polymeric products. Compounds 8f,g were prepared in
the highest yields (~99%) by the reactions of nitrile 22b
with diaziridines 2b,c.
Starting
t/h Product
R
Ar
Y (%)
compounds
22
2
22а
2a
2b
2c
2d
2a
2b
2c
2d
2a
20*
18
11
20*
1
0.5
0.5
5
12
(5**)
8
4
13
8a EtOCO
4ꢀMeOC6H4
4ꢀEtOC6H4
4ꢀPriOC6H4
4ꢀMeC6H4
4ꢀMeOC6H4
4ꢀEtOC6H4
4ꢀPriOC6H4
4ꢀMeC6H4
4ꢀMeOC6H4
45
43
40
37
82
~99
~99
83
52
(54**)
65
8b
8c
8d
22b
22c
8e
8f
Cl3C
8g
8h
24а PhCO
2b
2c
2d
24b
24c
24d
4ꢀEtOC6H4
4ꢀPriOC6H4
4ꢀMeC6H4
Scheme 10
72
47
* The temperature was 70 °C.
** The reaction was carried out in [bmim][PF6].
Scheme 11
R = EtOCO (22a); Cl C (22b)
3
The reaction of benzoyl cyanide (22c) afforded
2ꢀ(1ꢀarylꢀ1ꢀcyanomethyl)ꢀ1ꢀbenzoylpyrazolidines 24a—d
instead of the expected bicyclic compounds 8 (Scheme 11).
Evidently, this reaction, like the reaction giving rise to the
aboveꢀdescribed bicyclic compounds 7 and 8, starts with
the formation of azomethine imine intermediates 11, but
then benzoyl cyanide (22c) acts simply as the benzoylating
agent, whose benzoyl group interacts with the negatively
charged nitrogen atom of intermediate 11, and the CN–
anion that is eliminated is bound to the positively charged
carbon atom of this intermediate.
In some reactions of bicyclic diaziridines 2a—d with
nitriles 22a,b (the reactions of bicyclic compounds 2a—d
with nitrile 22b), the TLC monitoring revealed, along
with the final compounds 8, a compound with a smaller
Rf value, which disappeared in the course of the reaction.
We suggested that this compound is the dipolar interꢀ
mediate, viz., 1ꢀbenzylidenepyrazolidinium 2ꢀtrichloroꢀ
acetamidate (23), as the addition product of the nitrile
fragment of nitriles 22a,b to azomethine imine intermediꢀ
ate 11. The latter is analogous to intermediate 17, which
i
Ar = 4ꢀMeOC H (a); 4ꢀEtOC H (b); 4ꢀPr OC H (c);
6
4
6
4
6 4
4ꢀMeC H (d)
6
4
has been observed previously in the reaction of 6ꢀarylꢀ
1,5ꢀdiazabicyclo[3.1.0]hexanes 2 with CS2 (see Schemes 6
and 10). After the isolation of the reaction products of
diaziridines 2a—d with nitrile 22b, intermediates 23 were
detected by 1H and 13C NMR spectroscopy in an amount
of ~10%. The most characteristic difference of the 1H NMR
spectra of compounds 8 and 23 is the position of the
signal for the hydrogen atom at the carbon atom bound to
the aromatic moiety. This signal in the spectra of comꢀ
pound 8a—h appears as a singlet at
the corresponding signal in the spectra of the interꢀ
mediates 23е—h is observed at 9.80—10.0. A similar
pattern is observed in the 13C NMR spectra, which show
the signal for this carbon atom at 86.00—87.50 and
δ 5.20—6.00, whereas
δ
δ

372
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
Syroeshkina et al.
190.00—192.00 for compounds 8a—h and 23e—h, respecꢀ
tively. These differences in the NMR spectra of the interꢀ
mediates and the final compounds correspond to the difꢀ
ferences described above for dipolar intermediate 17. We
failed to isolate intermediates 23е—h in the individual
state. Thus, the recrystallization of products 8e,f or an
attempt to subject a mixture of compounds 8e—h and
23e—h to chromatography resulted in the quantitative
transformation of these compounds into final bicyclic
compounds 8e—h.
The structures of all the synthesized compounds
were confirmed by elemental analysis and spectroscopic
methods. Compounds 7d and 24d were studied also by
Xꢀray diffraction.* We failed to grow crystals of bicyclic
compounds 8 suitable for Xꢀray diffraction. The structures
of these compounds were confirmed by {1H—1H}NOESY,
{1H—13C}HMBC, and {1H—13C}HSQC experiments for
compound 8a. Selected physicochemical and spectroꢀ
scopic characteristics of the resulting compounds are given
in Tables 4—7.
In addition to nitriles 22a—c, the reaction of bicyclic
diaziridine 2b was performed under the aboveꢀdescribed
conditions also with other nitriles, such as tetracyanoꢀ
ethylene, mꢀnitrobenzoic acid nitrile, and isonicotinic acid
nitrile. In the initial steps of all these reactions, the reacꢀ
tions mixtures were similar to those described above. Thus,
the diaziridine formed azomethine imine intermediate 11,
because the formation of the corresponding dimers 13
(as precipitates) was observed. However, the next steps of
the reactions are different. The reaction with isonicotinic
acid nitrile did not proceed, because this compound is
insoluble in the ionic liquid at room temperature and
is sublimed upon heating. The most active tetracyanoꢀ
ethylene was involved in the reaction, but this reaction
did not proceed unambiguously and produced a complex
mixture of compounds, which we failed to separate. The
reaction products with mꢀnitrobenzoic acid nitrile decomꢀ
posed on a column when attempting to perform the preꢀ
parative separation.
According to the Xꢀray diffraction study (Fig. 1), the
main geometric parameters of 24d are similar to the exꢀ
pected values. In particular, the N(1)—N(2) bond length
(1.423(1) Å) in molecule 24d is virtually equal to the
corresponding bond length (1.418 Å) in 1ꢀbenzoylꢀ2ꢀ
methylpyrazolidine.24 The N(1) atom has a flattened
configuration (the sum of the van der Waals angles is
359.7(1)°) due to its conjugation to the C=O group, which
also leads to an elongation of the C(6)—O(1) bond to
1.237(1) Å and a shortening of the N(1)—C(6) bond
to 1.347(1) Å. The pyrazolidine ring has an envelope
conformation with the N(2) atom deviating from the plane
passing though the other atoms of the ring by 0.51 Å. The
phenyl ring is not conjugated to the carbonyl group (the
O(1)C(6)C(7)C(8) torsion angle is 41.5°) due to the steric
repulsion from the substituent at the N(2) atom. The lone
* The Xꢀray diffraction data for compound 7d were published in
the preliminary communication.8
Table 4. Selected physicochemical characteristics of the compounds prepared by the reactions of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes 2
with carbon disulfide
Comꢀ
pound
M.p./°С
Rf*
Found
Calculated
Molecular
formula
(%)
N
C
H
S
7a
131.5—132.0
118.0—118.5
60.0—60.5
110.0—110.5
Oil
0.71
0.71
0.71
0.72
0.40
0.69
0.72
0.68
54.06
54.11
55.65
55.68
57.06
57.11
57.51
57.56
57.45
57.56
60.27
60.30
75.77
75.82
76.50
76.55
5.35
5.30
5.78
5.75
6.10
6.16
5.55
5.64
5.65
5.64
5.08
5.06
8.19
8.10
8.64
8.57
10.50
10.52
9.96
9.99
9.48
24.05
24.07
22.80
22.87
21.70
21.78
25.54
25.61
25.50
25.61
26.78
26.83
—
С12H14N2S2O
С13H16N2S2O
С14H18N2S2O
С12H14N2S2
С12H14N2S2
С18H18N2S3
C22H28N4
7b
7c
9.51
7d
11.16
11.19
11.14
11.19
7.80
17d
9
159.5—160.5
7.81
19а**
19b**
167.0—168.0
(decomp.)
165.0—166.0
(decomp.)
16.15
16.08
14.85
14.88
—
C24H32N4
* Hexane : ethyl acetate, 2 : 1 (v/v) as the eluent; spots were visualized by spraying with an acetone solution of diphenylamine followed
by heating of the plates and with UV irradiation.
** The reaction was carried out with 7ꢀarylꢀ1,6ꢀdiazabicyclo[4.1.0]heptanes (18).

Insertion of carbon disulfide and the nitrile group
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
373
Table 5. Selected physicochemical characteristics of the compounds prepared by the reactions of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes
2 with activated nitriles 22a—c
Comꢀ
pound
M.p./°C
Rf*
Found
Calculated
Molecular
formulа
(%)
N
C
H
Cl
8a
Oil
0.30
0.43
0.51
0.38
0.58
0.67
0.73
0.77
0.16
0.27
0.31
0.36
62.30
62.27
63.39
63.35
65.25
64.33
65.93
65.91
46.68
46.66
48.27
48.23
49.62
49.67
48.97
49.00
71.04
71.01
72.65
72.70
72.22
72.18
74.66
74.73
6.58
6.62
6.94
6.98
7.26
7.30
6.96
7.01
4.27
4.22
4.60
4.63
5.08
5.00
4.46
4.43
5.88
5.96
6.98
6.93
6.59
6.63
6.32
6.27
14.55
14.52
13.83
13.85
13.20
13.24
15.35
15.37
12.49
12.56
12.07
12.05
11.46
11.59
13.24
13.19
13.05
13.08
11.54
11.56
12.10
12.03
13.73
13.76
—
С15H19N3O3
С16H21N3O3
С17H23N3O3
С15H19N3О2
С13H14N3Cl3O
С14H16N3Cl3O
С15H18N3Cl3O
С13H14N3Cl3
С19H19N3O2
С20H21N3O2
С21H23N3O2
С19H19N3O
8b
Oil
—
—
—
8c
Oil
8d
Oil
Oil
8e
31.70
31.78
30.46
30.51
29.28
29.33
33.29
33.38
—
8f
100.5—101.0
105.0—105.5
Oil
8g
8 h
24a
24b
24c
24d
Oil
Oil
—
—
—
Oil
121.0—121.5
* Hexane : ethyl acetate, 2 : 1 (v/v) as the eluent; spots were visualized by spraying with an acetone solution of diphenylamine followed
by heating of the plates and with UV irradiation.
Table 6. Spectroscopic characteristics of the compounds prepared by the reactions with carbon disulfide
Comꢀ
IR,
MS, m/z,
Irel (%)
NMR, δ, J/Hz (CDCl3)
pound ν/cm–1
1Н
13С
7a
7b
1060, 1132,
266 [M] (6%), 190 [M – CS2] (60%),
120 [M – CS2 – N2C3H6(ring)]
(100%), 76 [CS2, С6Н4] (86%)
2.55 (m, 2 H, NCH2CH2);
2.75, 3.15 (both m, 2 H,
ArCNCH2); 3.78, 3.93 (both m, 55.46 (ArOC);
2 H, SCNCH2); 3.83 (s, 3 H,
OCH3); 5.75 (s, 1 H, SCringH);
6.80, 7.50 (both d, 4 H, CaromH) 132.07 (Ar); 180.30 (CS)
27.66 (NCC);
45.82, 51.35 (both NCC);
1168, 1356,
1440,1508,
1612
74.76 (ArCring);
114.37, 129.28, 126.04,
1052, 1124,
1172, 1336,
1448, 1516,
1612
280 [M] (29%),
1.42 (t, 3 H, CH3);
14.81 (OCC); 27.67 (NCC);
45.82, 51.34 (both NCC);
63.68 (ArOC);
74.82 (ArCring);
114.88, 125.73, 129.28,
160.13 (Ar); 180.34 (CS)
203 [M – CS2 – H] (100%),
175 [M – CS2 – CH3 – H] (12%),
76 [CS2, С6Н4] (62%)
2.55 (m, 2 H, NCH2CH2);
2.75, 3.15 (both m, 2 H,
ArCNCH2); 3.78, 3.93 (both m
2 H, SCNCH2); 4.05 (q,
2 H, OCH2); 5.75 (с, 1 H,
SCringH); 6.80, 7.50 (both d,
4 H, CaromH)
7c
1052, 1124,
1180, 1376,
1448, 1508,
1608
294 [M] (32%),
218 [M – CS2] (63%),
175 [M – CS2 – (Pri)] (100%),
105 [M – CS2 – (Pri) – N2C3 H6(ring)]
(65%), 76 (CS2, С6Н4] (90%),
41 [Pri] (70%)
1.35 (d, 6 H, OC(CH3)2);
2.55 (m, 2 H, NCH2CH2);
2.75, 3.15 (both m, 2 H,
22.01 (OCC);
27.68 (NCC);
45.80, 51.36 (both NCC);
ArCNCH2); 3.78, 3.93 (both m, 70.04 (ArOC);
2 H, SCNCH2); 4.55 (m, 1 H,
OC(CH3)2 H); 5.75 (s, 1 H,
SCringH); 6.80, 7.50 (both d,
4 H, CaromH)
74.83 (ArCring);
115.99, 125.49, 129.28,
159.09 (Ar); 180.07 (CS)
(to be continued)

374
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
Syroeshkina et al.
Таблица 6 (continued)
Comꢀ
IR,
MS, m/z,
Irel (%)
NMR, δ, J/Hz (CDCl3)
pound ν/cm–1
1Н
13С
7d
1060, 1132,
1172, 1352,
1444, 1504
250 [M] (60%), 173 [M – CS2 – H]
(100%), 105 (CH3С6Н4CH] (30%),
91 (CH3С6Н4] (32%),
2.35 (s, 3 H, CH3); 2.55
(m, 2 H, NCH2CH2);
2.75, 3.15 (both m, 2 H,
ArCNCH2); 3.78, 3.93
(both m, 2 H, SCNCH2);
3.83 (s, 3 H, OCH3);
21.25 (CH3Ar);
27.56 (NCH2C);
45.81, 51.29 (both NCH2);
74.67 (ArCring); 127.72,
129,74, 131.34, 139.78 (Ar),
180.05 (CS)
76 [CS2, С6Н4] (12%)
5.75 (s, 1 H, SCringH);
6.80, 7.50 (both d, 4 H, CaromH)
9
1074, 1148,
1164, 1212,
1350, 1444,
1496, 1604
358 [M] (15%),
3.05 (t, 4 H, ArCH2);
4.33 (t, 4 H, NCH2);
7.28 (m, 10 H, Ar)
32.84 (ArC);
254 [M – С6Н5(CH2)2 – H] (40%),
104 (С6Н5CH2CH] (100%),
91 [С6Н5CH2] (60%)
50.88 (NCH2);
127.67 (pꢀCarom);
128.75 (mꢀCarom);
129.19 (oꢀCarom);
135.89 (ipsoꢀCarom);
180.96 (CS)
17а
—
—
0.50, 0.85 (both br.m, 2 H,
S CNCH2); 1.55 (br.m, 2 H,
NCCH2); 3.15, 3.60 (both
br.m, 2 H, N+CH2);
5.75 (s, 1 H, SCringH);
7.02, 7.88 (both d, 4 H, CaromH);
9.91 (s, 1 Н, ArCH—Nring
)
17d
19a
2.45 (s, 3 H, CH3);
0.55, 0.90 (both m, 2 H,
SCNCH2); 1.55 (m, 2 H,
NCCH2); 3.15, 3.60 (both m,
2 H, N+CH2); 6.88,
14.21 (CH3Ar); 31.59
(NCH2C); 48.36, 60.36
(2NCH2); 129.62, 129.85,
134.20, 145.50 (Ar);
192.10 (ArCH=N+
)
ring
7.81 (both d, 4 H, CaromH);
9.95 (s, 1 H, ArCH–=N+
)
ring
672, 696,
740, 816,
844, 920,
160 [pyrazolidine + C6H4CH] (100),
90 [C6H4CH] (80), 77 [C6H5] (27),
70 [pyrazolidine] (10),
1.62 (br.s, 8Н,
24.13 (br.,
NCH2CH2CH2CH2N);
52.27 (br., NCH2);
NCH2CH2CH2CH2N); 2.25,
2.48 (both br.s, 8 Н, NCH2);
4.18 (br.s, ArCH), 7.24
(br.s, 8 Н, оꢀ and mꢀСArН);
7.68 (br.s, 2Н, pꢀСArН)
956, 1028,
1072, 1096,
1208,1272,
1332, 1352,
1444, 1452,
1492, 1620,
2784, 2816,
2912, 2928,
2988, 3060
41 [3 СН2] (55)
90.98 (br., ArCH);
128.40 (оꢀ and mꢀСaromHН);
130.95 (уш, pꢀСaromHН);
139.42 (ipsoꢀCaromHH)
19b
680, 702,
752, 810,
848, 926,
175 [pyrazolidine + МеC6H4CH]] (100), 1.38 (br.s, 8 Н,
21.30 (СН3Ar); 24.14 (br.,
NCH2CH2CH2CH2N);
52.22 (br., NCH2);
105 [МеPHCH] (75), 77 [C6H5] (40),
70 [pyrazolidine] (30), 41 [3СН2] (55)
NCH2CH2CH2CH2N);
2.15, 2.50 (both br.m,
964, 1030,
1076, 1104,
1210,1276,
1330, 1364,
1448, 1458,
1498, 1630,
2778, 2818,
2908, 2914,
3004, 3054
8 Н, NCH2); 2.36 (s, 3 Н,
СН3Ar); 4.12 (br.s,
ArCH); 7.18 (br.s, 8 Н,
оꢀ and mꢀСaromН); 7.55 (br.s,
pꢀСaromН); 2 Н, пꢀСaromН)
90.71 (br., МеArCH);
128.20 (br., оꢀ and
mꢀСArН); 129.78 (br.,
(br., pꢀСaromН);
139.31 (ipsoꢀCaromH)

Insertion of carbon disulfide and the nitrile group
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
375
Table 7. Spectroscopic characteristics of the compounds prepared by the reactions of 1,5ꢀdiazabicyclo[3.1.0]hexanes 2a—d with
activated nitriles 22a—c and of the reaction intermediates 23
Comꢀ
pound
IR,
/cm–1
MS, m/z,
Irel (%)
NMR, δ, J/Hz (CDCl3)
ν
1Н
13С
8a
—
190 [M – EtOCOC
119 [M – EtOCOC
≡
≡
N] (5), 1.23 (t, 3 H, COOCH2CH3, 3J = 7.39);
14.43 (CH3CH2OCO);
24.92 (NCH2CH2);
46.46 (CH2NCAr);
55.27 (CH2NC=N); 60.35
(CH3OAr); 61.99 (CH3CH2OCO);
62.37 (ArCHN); 114.15, 124.29,
129.55, 146.59 (Ar); 157.15
(NC=N); 160.25 (OC=O)
N –
1.98, 2.34 (both m, 2 H, NCH2CH2,
2J = 11.10, Δν = 68.96); 3.03 (m, 2 H,
CH2NC=N, 2J = 13.78); 3.72 (m, 2 H,
CH2NCAr, 2J = 8.96); 3.77 (s, 3 H,
CH3OAr); 4.14 (q, 2 H, COOCH2CH3,
3J = 7.39); 5.28 (s, 1 H, ArCHN);
6.88, 7.47 (both d, 4 H, Ar, 3J = 8.95)
—
pyrazolidine] (20),
99 [EtOCOC≡N] (15),
76 [C6H4] (10), 71
pyrazolidine] (100)
[
8b
618, 784, 950,
1004, 1045,
1118, 1180,
1254, 1370,
1380, 1462,
1582, 1610,
1700, 1740,
1884, 2320,
2942, 2976,
3030
204 [M – EtOCOC
134 [M – EtOCOC
≡
≡
N] (5), 1.24 (t, 3 H, CH3CH2OAr, 3J = 7.12);
N –
15.00 (CH3CH2OAr);
15.11 (CH3CH2OCO);
25.37 (NCH2CH2);
1.34 (t, 3 H, CH3CH2OCO, 3J = 7.02);
–
pyrazolidine] (30),
1.93, 2.30 (both m, 2 H, CH2CH2N,
99 [EtOCOC
≡N] (10),
2J = 10.50, Δν = 181.97); 2.93, 3.05 (both 46.63 (CH2NCAr);
76 [C6H4] (15),
71 [pyrazolidine] (100)
m, 2 H, CH2NC=N, 2J = 13.60, Δν = 60); 49.94 (CH2NC=N); 60.84 (ArCHN);
3.66, 3.71 (both m, 2 H, CH2NCAr,
2J = 12.10, Δν = 25 ); 3.97 (q, 2 H,
CH3CH2OAr, 3J = 7.12); 4.14 (q, 2 H,
CH3CH2OCO, 3J = 7.02); 5.24 (s, 1 H,
ArCHN); 6.84, 7.42 (both d, 4 H, Ar,
3J = 8.70)
62.44 (ArOCH2); 63.96 (COOCH2);
114.76, 118.67, 129.62, 146.57 (Ar);
156.22 (NC=N); 159.72 (OC=O)
8c
620, 632, 788, 848, 218 [M – EtOCOC
≡
N –
N] (7), 1.31 (d, 6 H, (CH3)2CHOAr, 3J = 7.41); 22.03 ((CH3)2CHOAr);
952, 1008, 1048,
1120, 1180, 1260,
1300, 1376, 1384,
1464, 1512, 1584,
1612, 1692, 1740,
1888, 2316, 2932,
2976, 3032
147 [M – EtOCOC
≡
2.57 (m, 1 H, NCH2CH, 2J = 11.11);
3.05 (m, 3 H, NCH2CH, 2J = 11.11,
CH2NC=N, 2J = 14.06, Δν = 88.89);
4.53 (m, 3 H, CH2NCAr, 2J = 8.88,
(CH3)2CHOAr, 3J = 7.41); 5.62 (s, 1 H,
ArCHN); 6.89, 7.48 (both d, 4 H, Ar,
3J = 8.16)
22.12 (CH3CH2OCO);
34.68 (NCH2CH2);
36.17 (CH2NCAr);
49.71 (br., CH2NC=N);
49.78 (COOCH2); 60.18 (ArCHN);
61.87 (ArOCH(CH3)2);
116.02, 124.26, 129.93, 135.50 (Ar);
157.10 (NC=N); 158.73 (OC=O)
–
pyrazolidine] (35),
99 [EtOCOC N] (10),
≡
76 [C6H4] (25),
71 [pyrazolidine] (100)
8d
—
174 [M – EtOCOC
103 [M – EtOCOC
≡
≡
N] (10), 1.23 (t, 3 H, COOCH2CH3, 3J = 7.14);
14.25 (CH3CH2OCO);
20.96 (CH3Ar); 25.04 (NCH2CH2);
46.22 (CH2NCAr);
49.50 (CH2NC=N); 60.74 (ArCHN);
61.93 (CH3CH2OCO); 118.34,
N —
2.02, 2.29 (both m, 2 H, NCH2CH2,
Δν = 73.37); 2.38 (s, 3 H, CH3Ar);
3.02 (m, 2 H, CH2NC=N, 2J = 8.04);
3.73 (m, 2 H, CH2NCAr, 2J = 7.34);
–
pyrazolidine] (15),
99 [EtOCOC≡N] (20),
76 [C6H4] (10),
71 [pyrazolidine] (100)
4.05 (q, 2 H, COOCH2CH3, 3J = 7.14); 128.19, 129.50, 146.18 (Ar);
5.28 (s, 1 H, ArCHN); 7.13, 7.41 (both d, 155.96 (NC=N); 158.50 (OC=O)
4 H, Ar, 3J = 8.69)
8e
8f
—
334 [M] (17),
2.08 (m, 2 H, NCH2CH2, 2J = 12.24);
24.60 (NCH2CH2);
264 [M – pyrazolidine] (12), 2.61, 2.98 (both br.m, 2 H, CH2NC=N, 46.93 (CH2NCAr); 50.40 (br.,
229 [M – MeOC6H4] (95),
144 [Cl3CCN] (100),
92 [OC6H4] (45), 76 [C6H4]
(75), 71 [pyrazolidine] (10)
Δν = 81.60); 3.65, 4.03 (both br.m, 2 H, CH2NC=N); 55.05 (CH3OAr);
CH2NCAr, Δν = 85.70); 3.72 (s, 3 H,
CH3OAr); 5.88 (s, 1 H, ArCHN);
6.85, 7.36 (both d, 4 H, Ar, 3J = 8.16)
87.12 (br., ArCHN); 88.49 (CCl3);
113.69, 127.86, 130.67, 159.37 (Ar);
162.32 (NC=N)
672, 784, 804,
—
1.38 (t, 3 H, CH3CH2OAr, 3J = 7.41);
2.18 (m, 2 H, CH2CH2N, 2J = 9.16);
2.69, 3.05 (both m, 2 H, CH2NC=N,
2J = 9.97, Δν = 74.97); 3.73, 4.09
(both m, 2 H, CH2NCAr, Δν = 79.31);
4.06 (q, 2 H, CH3CH2OAr, 3J = 7.41);
5.99 (s, 1 H, ArCHN); 6.91, 7.40
(both d, 4 H, Ar, 3J = 8.33)
14.86 (CH3CH2OAr);
24.86 (NCH2CH2);
928, 1004, 1044,
1072, 1120, 1172,
1260, 1308, 1392,
1464, 1476, 1520,
1548, 1580, 1608,
1664, 1712, 2852,
2072, 3052, 3420
47.23 (CH2NCAr); 50.08 (br.,
CH2NC=N); 63.52 (CH3CH2OAr);
87.46 (ArCHN); 88.82 (CCl3);
114.58, 121.84, 128.13, 159.04 (Ar);
162.58 (NC=N)
(to be continued)

376
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
Syroeshkina et al.
Таблица 7 (continued)
Comꢀ
pound
IR,
ν
MS, m/z,
Irel (%)
NM,
δ
, J/Hz (CDCl3)
/cm–1
1Н
13С
8g
620, 664, 696, 716,
788, 808, 820, 852,
900, 952, 1080,
1180, 1216, 1300,
1340, 1450, 1480,
1512, 1576, 1620,
2344, 2852, 2980,
3030
362 [M] (44),
292 [M – pyrazolidine] (10),
249 [M – (pyrazolidine + Pri)] 2.69, 3.05 (both br.m, 2 H, CH2NC=N, CH2NCAr); 49.85 (br., CH2NC=N);
(47), 227 [M – PriOC6H4] (50), Δν = 81.63); 3.71, 4.10 (both br.m, 2 H, 69.85 (ArOCH(CH3)2);
135 [PriOC6H4] (85), 76 [C6H4] CH2NCAr, Δν = 87.46); 4.56 (m, 1 H, 87.49 (ArCHN); 88.02 (CCl3);
1.31 (d, 6 H, (CH3)2CHOAr, 3J = 8.33); 22.03 ((CH3)2CHOAr);
2.18 (m, 2 H, CH2CH2N, 2J = 10.00);
24.78 (NCH2CH2); 47.29 (br.,
(30), 71 [pyrazolidine] (10),
43 [Pri] (100)
(CH3)2CHOAr, 3J = 8.33); 5.95 (s,
115.86, 128.13, 157.98 (Ar);
1 H, ArCHN); 6.89, 7.39 (both d, 4 H, 162.96 (NC=N)
Ar, 3J = 8.30)
8h
668, 722, 804,
318 [M] (25),
2.11 (m, 2 H, NCH2CH2, 2J = 14.04);
2.39 (s, 3 H, CH3Ar); 2.68, 3.05 (both
br.m, 2 H, CH2NC=N, Δν = 102.08);
3.69, 4.08 (br.m, 1 H, CH2NCAr,
Δν 127.60); 5.98 (s, 1 H, ArCHN);
7.19, 7.39 (both d, 4 H, Ar, 3J = 6.38)
21.10 (CH3Ar); 24.68 (NCH2CH2);
848, 912, 1076,
1184, 1220, 1310,
1344, 1452, 1484,
1510, 1570, 1624,
2340, 2848, 2976
264 [M – pyrazolidine] (12),
213 [M – MeC6H4] (75),
144 [Cl3CCN] (100),
76 [C6H4] (55),
47.01 (CH2NCAr); 50.72 (br.,
CH2NC=N); 87.46 (br., ArCHN);
88.40 (CCl3); 126.63, 129.08,
137.83 (Ar); 162.43 (NC=N)
71 [pyrazolidine] (10)
23e
—
—
3.84 (s, 3 H, CH3OAr); 6.95, 7.79
(both d, 4 H, Ar, 3J = 8.16);
9.85 (s, 1 H, ArCH=N)
55.36 (CH3OAr); 114.14, 131.74 (Ar),
162.80 (NC=N); 190.49 (ArCHN)
23f
—
—
—
—
7.01, 7.84 (both d, 4 H, Ar, 3J = 8.33);
9.88 (s, 1 H, ArCHN)
7.20, 7.83 (both d, 4 H, Ar, 3J = 8.33);
23g
21.88 ((CH3)2CHOAr);
70.30 (ArOCH(CH3)2); 115.57,
132.04 (Ar); 162.50 (NC=N);
190.87 (ArCHN)
9.88 (s, 1 H, ArCHN)
23h
—
—
2.43 (s, 3 H, CH3Ar); 7.32,
7.78 (both d, 4 H, Ar, 3J = 6.38);
9.95 (s, 1 H, ArCH=N)
20.96 (CH3Ar); 29.59 (NCH2CH2);
36.40 (CH2NCAr); 60.26 (br.,
CH2NC=N); 171.10 (NC=N);
191.85 (ArCHN)
24a 688, 768, 946,
1112, 1154, 1180,
1248, 1300, 1380,
1454, 1510, 1602,
1678, 1710, 1876,
2020, 2524, 2944,
2958, 2978, 3564,
3578
2.05, 2.28 (both m, 2 H, NCH2CH2,
24.51 (br., NCH2CH2); 47.55 (br.,
CH2NCAr); 49.42 (br., CH2NC=N);
2J = 12.00, Δν = 69.60); 3.06, 3.15
(both m, 2 H, CH2NC=N, 2J = 11.50, 55.08 (CH3OAr); 59.03 (br., ArCHN);
Δν 36); 3.71 (s, 3 H, CH3OAr); 3.78,
3.91 (both m, 2 H, CH2NCAr,
2J = 12.50, Δν = 48); 5.35 (br.s,
1 H, ArCHN); 6.83, 7.55 (both d, 2 H,
ArO, 3J = 9.00); 7.31 (m, 5 H, PH)
113.96, 117.99, 123.24, 127.67, 127.89,
129.36, 129.65, 135.15 (Ar, PH);
148.20 (NC=N); 160.06 (OC=O)
24b
—
265 [M – pyrazolidine] (7),
204 [M – PHCOCN] (3),
175 [pyrazolidine + COPH]
(25), 132 [PHCOCN] (40),
105 [PHCO] (100), 76 [C6H4]
(65), 71 [pyrazolidine] (5),
39 [CHCN] (10)
1.44 (t, 3 H, CH3CH2OAr, 3J = 7.14);
2.12, 2.37 (both m, 2 H, CH2CH2N,
2J = 8.57, Δν = 39.27); 3.18 (m, 2 H,
14.80 (CH3CH2OAr);
24.97 (NCH2CH2); 48.10 (br.,
CH2NCAr); 49.61 (CH2NC=N);
CH2NC=N, 2J = 10.71); 3.88 (both m, 59.44 (ArCHN); 63.65 (ArOCH2);
2 H, CH2NCAr, 2J = 12.85); 4.04 (q,
2 H, CH3CH2OAr, 3J = 7.14); 5.52
(br.s, 1 H, ArCHN); 6.86, 7.60
(both d, 4 H, ArО, 3J = 8.16);
7.37 (m, 5 H, PH)
114.81, 123.42, 127.99, 128.26,
129.66, 130.64, 133.50, 135.60 (Ar,
PH); 160.10 (NC=N); 168.80 (br.,
OC=O)
24c 648, 840, 952,1104, 279 [M – pyrazolidine] (10),
1148, 1184, 1252, 175 [pyrazolidine + COPH]
1304, 1384, 1456, (25), 132 [PHCOCN] (30),
1.37 (d, 6 H, (CH3)2CHOAr, 3J = 6.96); 21.80 ((CH3)2CHOAr); 24.71 (br.,
2.12, 2.29 (both m, 2 H, CH2CH2N,
NCH2CH2); 49.54 (br., CH2NCAr);
57.96 (CH2NC=N); 59.16 (br.,
ArOCH(CH3)2); 69.87 (ArCHN);
115.79, 118.15, 122.94, 127.80,
128.10, 129.54, 130.57,
2J = 9.57, Δν = 52.20); 3.18 (m, 2 H,
1508, 1600, 1680, 105 [PHCO] (100), 77 [PH] (50), CH2NC=N, 2J = 10.44); 3.89 (m, 2 H,
1720, 1880, 2040, 71 [pyrazolidine] (5),
2520, 2936, 2952, 39 [CHCN] (10)
2976, 3576, 3584
CH2NCAr, 2J = 9.57); 4.50 (m, 1 H,
(CH3)2CHOAr, 3J = 6.96); 5.37 (br.s,
1 H, ArCHN); 6.81, 7.58 (both d, 4 H,
ArO, 3J = 7.83); 7.23, 7.38 (both m,
5 H, PH)
135.20 (Ar, PH); 158.60 (NC=N);
169.00 (OC=O)
(to be continued)

Insertion of carbon disulfide and the nitrile group
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
377
Таблица 7 (continued)
Comꢀ
pound
IR,
/cm–1
MS, m/z,
Irel. (%)
NM,
δ
, J/Hz (CDCl3)
ν
1Н
13С
24d
—
175 [M – PHCOCN] (15),
131 [PHCOCN] (30),
105 [PHCO] (100),
91 [MeC6H4] (6),
77 [PH] (62),
71 [pyrazolidine] (7),
39 [CHCN] (10)
2.12, 2.29 (both m, 2 H, NCH2CH2,
2J = 8.89, Δν = 48.16); 2.39 (s, 3 H,
CH3Ar); 3.18 (m, 2 H, CH2NC=N,
14.02 (CH3Ar); 22.58 (NCH2CH2);
31.52 (CH2NCAr); 47.85 (br.,
CH2NC=N); 59.63 (br., ArCHN);
127.82, 128.07, 128.47, 129.46,
130.46, 135.461 (Ar, PH); 139.20
2J = 11.12); 3.95 (m, 2 H, CH2NCAr,
2J = 9.63); 5.45 (br.s, 1 H, ArCHN);
7.15, 7.62 (both d, 4 H, ArO, 3J = 6.67); (NC=N); 160.06 (OC=O)
7.40 (m, 5 H, PH)
liquid by the careful evaporation in vacuo of the solvents
after extraction. The yields of the reaction products are
given in Table 8. The results of the present study show
that the repeated synthesis in the same ionic liquid results
in an increase in the yields of the products higher than
100 %. This is apparently associated with the saturation of
the ionic liquid with the final products. However, after
the third synthesis in the same ionic liquid, the yield
of the final products decreases due apparently to the
penetration of moisture into the ionic liquid and incomꢀ
plete drying upon evaporation, resulting in the side
processes.
C(21)
C(18)
C(19)
C(20)
C(17)
C(16)
C(15)
N(3)
H(13A)
C(13)
C(14)
C(3)
Therefore, in the present study we found two new
reactions resulting in the diaziridine ring expansion. Based
N(2)
C(4)
C(10)
C(11)
on these reactions, we developed new simple procedures
for the synthesis of 3ꢀaryldihydroꢀ5Hꢀpyrazolo[1,2ꢀc]ꢀ
[1,3,4]thiadiazoleꢀ1ꢀthiones 7 and 1ꢀarylꢀ6,7ꢀdihydroꢀ
1H,5Hꢀpyrazolo[1,2ꢀa][1,2,4]triazoles 8. Both reactions
were based on the BF3•Et2Oꢀcatalyzed insertion of the
CS2 molecule and the nitrile group of activated nitriles,
respectively, into the C—N bond of the diaziridine ring of
6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes 2a—d. It was found
that for these reactions to proceed, it is necessary to
use ionic liquids as the reaction medium. A new type of
dipolar intermediates 17, which are the addition products
of CS2 to azomethine imine intermediates 11 that are
formed in the first step, was detected by NMR spectroꢀ
scopy. One of the new intermediates, viz., 17d, was isoꢀ
lated, characterized, and then transformed into the final
bicyclic compound 7d, i.e., intermediates 17 are direct
precursors of the final products 7. Structurally similar
intermediates 23 were detected by NMR spectroscopy in
the reactions of bicyclic diaziridines 2a—d with activated
C(12)
N(1)
C(6)
C(5)
C(9)
C(7)
C(8)
O(1)
Fig. 1. Molecular structure of compound 24d shown as thermal
displacement ellipsoids (р = 50%).
electron pair of the N(2) atom is antiperiplanar to the
C(13)—H(13A) bond.
In the crystal structure, the molecules are linked to
form chains through rather strong C—H...O contacts (H...O,
2.08 Å; C—H—O, 168°) with the involvement of the
H(13A) atom. Presumably, in addition to the inductive
effect of the CN group, the stereoelectronic interaction of
the lone electron pair of the N(2)C(13)H(13A) fragment,
which partially compensates the charge on the hydrogen
atom, is one of the factors responsible for the strong interꢀ
actions with the involvement of this hydrogen atom.25
Since ionic liquids were used as the reaction medium,
one of the purposes of the present study was to investigate
the regeneration of ionic liquids with the aim of their
repeated use. For this purpose, we performed several reꢀ
peated syntheses of compounds 7b and 8e,g in the ionic
liquid [bmim][BF4] according to the standard procedure,
but with the use of the triple regeneration of the ionic
Table 8. Yields of selected compounds 7 and 8 in the multiple
synthesis in the ionic liquid [bmim][BF4]
Entry
Yield (%)
7b
8e
8g
1
2
3
∼99
∼100
∼65
∼90
∼110
∼80
∼95
∼105
∼75

378
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
Syroeshkina et al.
chromatography using a 4 : 1 hexane—ethyl acetate mixture as
the eluent followed by crystallization from hexane.
nitrile 22b, but we failed to isolate these intermediates in
the individual state.
B. A solution of compound 1a (0.12 g, 0.5 mmol) and CS2
(0.15 g, 2 mmol) in acetonitrile (2 mL) was sealed in a tube, and
the tube was kept in an oil bath at 100 °C for 10 days. The
solvent was removed on a rotary evaporator. Product 9
was isolated by silica gel column chromatography using a 4 : 1
hexane—ethyl acetate mixture as the eluent followed by the
crystallization from hexane.
C. Boron trifluoride etherate (2 drops, 0.1 mmol) was added
with stirring to a mixture of compound (1a) (0.12 g, 0.5 mmol)
and CS2 (0.15 g, 2 mmol). The reaction mixture was stirred for
25 days. After completion of the reaction, unconsumed carbon
disulfide and boron trifluoride etherate were removed on a
rotary evaporator. Product 9 was isolated by silica gel column
chromatography using a 4 : 1 hexane—ethyl acetate mixture as
the eluent followed by the crystallization from hexane.
Synthesis of 3ꢀaryldihydroꢀ5Hꢀpyrazolo[1,2ꢀc][1,3,4]thiaꢀ
diazoleꢀ1ꢀthiones 7a—e, 1ꢀarylꢀ6,7ꢀdihydroꢀ1H,5Hꢀpyrazoloꢀ
[1,2ꢀa][1,2,4]triazoles 8a—h, and 2ꢀ(1ꢀarylꢀ1ꢀcyanomethyl)ꢀ
1ꢀbenzoylpyrazolidines 24a—d (general procedure). Two drops
of boron trifluoride etherate (0.1 mmol) were added with stirring
to a mixture of 6ꢀarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexane 2a—e
(0.5 mmol; the compounds synthesized according to a known
procedure23) and an electrophilic compound (0.5 mmol; CS2
for the synthesis of compounds 7a—e, activated nitrile 22a,b for
the synthesis of compounds 8a—h, or nitrile 22c for the syntheꢀ
sis of compounds 24a—d) in the ionic liquid [bmim][BF4] or
[bmim][PF6] (0.4 g). The reaction mixture was stirred at ∼20 °C.
To isolate the final product, CH2Cl2 (0.5 mL) was added to the
reaction mixture, the mixture was stirred until a homogeneous
solution was obtained, and the diethyl ether (2.5 mL) was added,
after which the ionic liquid was precipitated. The upper organic
layer was separated by decantation. The operations were
repeated 2—3 times (TLC monitoring until complete extracꢀ
tion). The solvent was removed on a rotary evaporator without
heating. The final product was recrystallized from hexane in the
case of compounds 7a—d, 8e,f or isolated on a silica gel column
using a 2 : 1 hexane—ethyl acetate mixture as the eluent in the
case of the other compounds.
Synthesis of 6,13ꢀdiaryloctahydrodipyridazino[1,2ꢀa:1´,2´ꢀd]ꢀ
[1,2,4,5]tetrazines 19 (general procedure). Two drops of boron
trifluoride etherate (0.1 mmol) were added with stirring to a
mixture of 7ꢀarylꢀ1,6ꢀdiazabicyclo[4.1.0]heptane 18 (0.5 mmol)
and CS2 (2.0 mmol) in the ionic liquid [bmim][BF4] or [bmim]ꢀ
[PF6] (0.4 g). The reaction mixture was stirred at room temperaꢀ
ture (∼20 °C) until the reaction was completed. Compound 19
was isolated from the ionic liquid as described in the above
general procedure for compounds 8a—h. The solvent, which did
not react with CS2, and boron trifluoride etherate were removed
on a rotary evaporator. The precipitate was recrystallized from
hexane.
Compounds containing the pyrazolo[1,2ꢀc][1,3,4]ꢀ
thiadiazole moiety were described in the literature,20 but
the procedure for the synthesis of these compounds
developed in the present study is more simple and allows
the preparation of the reaction products in nearly quantiꢀ
tative yields. 1,3,4ꢀThiadiazolidine derivatives substituted
at the nitrogen atoms were covered by patents as selective
sorbents and extractants for precious metals, special reꢀ
agents for suppression of physiological functions of bacteꢀ
ria in different media, biologically active compounds for
the synthesis of various drugs (antibacterial, antifungal,
and antiviral agents), and lubricating oil additives.26,27
Heterocyclic systems containing the 6,7ꢀdihydroꢀ
1H,5Hꢀpyrazolo[1,2ꢀa][1,2,4]triazole moiety have also
been described previously; however, their synthesis was
based on multistep processes and requires more complex
starting compounds.28—30 Heterocyclic structures containꢀ
ing the 1,2,4ꢀtriazole ring fused with other heterocyclic
compounds are of interest as NO synthase inhibitors and
antidiabetic agents.31,32
Experimental
The IR spectra were recorded on a URꢀ20 spectrometer
in KBr pellets or in a thin layer. The 1H NMR spectra were
measured on Bruker AC 200ꢀ31 (200 MHz) and Bruker AM 300
(300 MHz) spectrometers; the 13C NMR spectra, on a Bruker
AM 300 spectrometer (75.5 MHz) in CDCl3. The 13C NMR
spectra were recorded with proton decoupling. The assignment
of the signals in the 13C NMR spectra of compounds 7 was made
based on selective heteronuclear double resonance experiments.
The assignment of the signals in the 1H NMR spectra was made
based on the NOE.DIFF experiment for compound 7c. The
assignment of the signals in the 13C NMR spectra of compounds
8 was made based on the {1H—1H}NOESY, {1H—13C}HMBC,
and {1H—13C}HSQC experiments performed on a Bruker
DRX 500 spectrometer (500 MHz for 1H and 126 MHz for 13C)
for compound 8a. The melting points were determined on a
Gallenkamp instrument (Sanyo). The mass spectra were
obtained on a Finnigan MAT INCOSꢀ50 spectrometer. The
course of the reactions was monitored by TLC on Silufol
UVꢀ254 plates. The Rf values were determined in a 2 : 1 (v/v)
nꢀhexane—ethyl acetate system. The reaction products and
intermediates were isolated by silica gel column chromatography
(0.060—0.200 mm, 60 Å, Acros).
Synthesis of 3,4ꢀdi(2ꢀphenylethyl)ꢀ1,3,4ꢀthiadiazolidineꢀ
2,5ꢀdithione (9). A. Carbon disulfide (0.15 g, 2 mmol) was added
to a solution of 1,2ꢀbis(2ꢀphenylethyl)diaziridine (1a) (0.12 g,
0.5 mmol), which has been synthesized according to a standard
procedure,33 in the ionic liquid [bmim][BF4] or [bmim][PF6]
(0.5 g). The reaction mixture was stirred at room temperature
(∼20 °C) for 4 days. After completion of the reaction, the reacꢀ
tion mixture was repeatedly extracted with a 4 : 1 hexane—ethyl
acetate mixture ((6—8)×3 mL) until compound 9 disappeared in
the extract (TLC monitoring). The solvent was removed on a
rotary evaporator. Product 9 was isolated by silica gel column
Synthesis of 1ꢀbenzylidenepyrazolidinium 2ꢀcarbodithioates
17a,d (general procedure). Two drops of boron trifluoride etherate
(0.1 mmol) were added with stirring to a mixture of 6ꢀarylꢀ
1,5ꢀdiazabicyclo[3.1.0]hexane 2a,d (0.5 mmol) and CS2
(0.5 mmol) in the ionic liquid [bmim][BF4] or [bmim][PF6]
(0.4 g). The reaction mixture was stirred at room temperature
(∼20 °C) for 2.5 h; the reaction was not brought to completion
(TLC monitoring, spots were visualized with UV irradiation or
by spraying with an acetone solution of diphenylamine followed

Insertion of carbon disulfide and the nitrile group
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 2, February, 2009
379
by heating of the plates). The products were extracted three
times from the ionic liquid with a warm (∼35 °C) hexane—ethyl
acetate mixture (4 : 1) and rapidly concentrated on a rotary
evaporator with slight heating to ∼35—40 °C on a water bath.
Intermediate 17 was separated from compound 7 by passing
through a layer of SiO2 (∼25 mL), the diameter of the column
was 2 cm, nꢀhexane—ethyl acetate, 2 : 1 (v/v), was used as the
eluent. The solvent was rapidly removed on a rotary evaporator
with slight heating (∼40 °C) using a water bath. Intermediate 17
was obtained as an oily viscous brightꢀyellow liquid. The interꢀ
9. Yu. S. Syroeshkina, V. V. Kuznetsov, M. I. Struchkova,
M. A. Epishina, N. N. Makhova, Mendeleev Commun., 2008,
18, 207.
10. R. Grashey, R. Huisgen, K. K. Sun, R. M. Moriarty, J. Org.
Chem., 1965, 30, 74.
11. E. Schmitz, Dreiringe mit zwei Heteroatomen, Springer—
Verlag, Berlin—Heidelberg—New York, 1967, pp. 67—112.
12. G. N. Gorshkova, F. L. Kolodkin, A. A. Dudinskaya, A. E.
Bova, V. A. Ponomarenko, L. I. Khmel´nitskii, S. S. Novikov,
Izv. Akad. Nauk SSSR, Ser. Khim., 1969, 1847 [Bull. Acad.
Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 1969, 18, 1712].
13. V. V. Trofimov, Yu. B. Koptelov, A. P. Molchanov, R. R.
Kostikov, Zh. Org. Khim., 1994, 30, 1389 [Russ. J. Org. Chem.
(Engl. Transl.), 1994, 30, 1342].
14. Yu. B. Koptelov, M. Kh. Kim, A. P. Molchanov, R. R.
Kostikov, Zh. Org. Khim., 1999, 35, 116 [Russ. J. Org. Chem.
(Engl. Transl.), 1999, 35, 110].
15. A. P. Molchanov, D. I. Sipkin, Yu. B. Koptelov, R. R.
Kostikov, Synlett, 2000, 1779.
16. A. P. Molchanov, D. I. Sipkin, Yu. B. Koptelov, R. R.
Kostikov, Zh. Org. Khim., 2001, 37, 888 [Russ. J. Org. Chem.
(Engl. Transl.), 2001, 37, 841].
17. A. P. Molchanov, D. I. Sipkin, Yu. B. Koptelov, R. R.
Kostikov, Eur. J. Org. Chem., 2002, 453.
1
mediate was immediately characterized by H and 13C NMR
spectroscopy and elemental analysis.
Xꢀray diffraction study. Crystals of 24d (C19H19N3O,
M = 305.37) are monoclinic, space group P21/c at 100 K:
a = 10.8081(7) Å, b = 12.6964(9) Å, c = 11.9238(8) Å, β =
= 93.300(2)°, V = 1633.52(19) Å3, Z = 4 (Z´ = 1), dcalc = 1.242 g cm–3
,
μ(MoKα) = 0.79 cm–1, F(000) = 648. The intensities of 11353
reflections were measured on a Bruker SMART APEX II CCD
diffractometer (λ(MoKα) = 0.71072 Å, ωꢀscanning technique,
2θ < 58°), 4350 independent reflections (Rint = 0.0424) were used
in the refinement. The structure was solved by direct methods
and refined by the fullꢀmatrix leastꢀsquares method based on F2
with anisotropic and isotropic displacement parameters. The
hydrogen atoms were positioned geometrically. The final R
factors for 24d were wR2 = 0.1062 and GOOF = 0.979 based on
all independent reflections (R1 = 0.0398 was calculated based
on F for 3167 observed reflections with I > 2σ(I)). All calculaꢀ
tions were carried out with the use of the SHELXTL PLUS 5.0
program package.
18. Yu. B. Koptelov, S. P. Saik, Zh. Org. Khim., 2006, 42, 1515
[Russ. J. Org. Chem. (Engl. Transl.), 2006, 42, 1501].
19. Yu. B. Koptelov, Zh. Org. Khim., 2006, 42, 1524 [Russ. J.
Org. Chem. (Engl. Transl.), 2006, 42, 1510].
20. J. P. Snyder, M. Heyman, M. Gundestrup, J. Org. Chem.,
1978, 43, 2224.
We thank M. I. Struchkova (N. D. Zelinsky Institute
of Organic Chemistry of the Russian Academy of Sciences)
for recording NMR spectra.
This study was in part financially supported by the
Russian Academy of Sciences (Program of the Presidium
of the Russian Academy of Sciences “Directed Synthesis
of Compounds with Desired Properties and Design of
Materials on Their Basis”).
21. I. V. Seregin, L. V. Batog, N. N. Makhova, Mendeleev
Commun., 2002, 83.
22. I. V. Seregin, I. V. Ovchinnikov, N. N. Makhova, D. V.
Lyubeysky, K. A. Lyssenko, Mendeleev Commun., 2003, 230.
23. V. V. Kuznetsov, S. A. Kutepov, N. N. Makhova, K. A.
Lyssenko, D. E. Dmitriev, Izv. Akad. Nauk, Ser. Khim.,
2003, 638 [Russ. Chem. Bull., Int. Ed., 2003, 52, 665].
24. S. Knapp, B. H. Toby, M. Sebastian, K. KroghꢀJespersen,
J. A. Potenza, J. Org. Chem., 1981, 46, 2490.
25. I. S. Bushmarinov, M. Y. Antipin, V. R. Akhmetova, G. R.
Nadyrgulova, K. A. Lyssenko, J. Phys. Chem. A., 2008, 112,
5017.
References
26. WO Pat. 02/099018 A1; Chem. Abstrs, 2003, 138, 2661.
27. RU Pat. 2291149 C1; Chem. Abstrs, 2007, 146, 142693.
28. K. Burger, H. Schickaneder, M. Pinzel, Liebigs Ann. Chem.,
1976, 30.
29. K. Burger, W. Thenn, R. Rauh, H. Schickaneder, A. Gieren,
Chem Ber., 1975, 1460.
30. J. Svetlik, T. Liptaj, J. Chem. Soc., Perkin Trans. 1, 2002,
1260.
31. J. Svetlik, L. Salloi, J. Heterocycl. Chem., 2002, 39, 363.
32. R. Bucala, A. Cerami, H. Vlassara, Diabetes Rev., 1995, 3,
258.
1. E. Schmitz, Adv. Heterocycl. Chem., 1979, 24, 63.
2. E. Schmitz, Comprehensive Heterocyclic Chemistry, Ed.
W. Lwowski, Pergamon Press, 1984, 1, 195.
3. H. W. Heine, in Small Ring Heterocycles, Part 2, Ed.
A. Hassner, WileyꢀInterscience, 1983, Ch. IV, 547—629.
4. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, K. A.
Lyssenko, I. V. Fedyanin, N. N. Makhova, Mendeleev
Commun., 2003, 221.
5. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, K. A.
Lyssenko, N. N. Makhova, V. A. Tartakovskii, Izv. Akad.
Nauk, Ser. Khim., 2005, 997 [Russ. Chem. Bull., Int. Ed.,
2005, 54, 1021].
6. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, N. N.
Makhova, Mendeleev Commun., 2005, 29.
33. N. N. Makhova, A. N. Mikhailyuk, V. V. Kuznetsov, S. A.
Kutepov, P. A. Belyakov, Mendeleev Commun., 2000, 182.
7. A. V. Shevtsov, V. V. Kuznetsov, S. I. Molotov, K. A.
Lyssenko, N. N. Makhova, Izv. Akad. Nauk, Ser. Khim.,
2006, 534 [Russ. Chem. Bull., Int. Ed., 2006, 55, 554].
8. Yu. S. Syroeshkina, V. V. Kuznetsov, K. A. Lyssenko, N. N.
Makhova, Mendeleev Commun., 2008, 18, 42.
Received July 11, 2008;
in revised form October 1, 2008