Three-component reaction of imidazoles, cyanophenylacetylene, and chalcogens: Stereoselective synthesis of 3-alkenyl-2-imidazolethiones and -selones

Article abstract of DOI:10.1016/j.tet.2013.10.094

The three-component reaction of 1-substituted imidazoles, cyanophenylacetylene, and elemental sulfur or selenium proceeds readily (for sulfur at room temperature without solvent, and for selenium in boiling MeCN) to stereoselectively afford 3-(Z)-cyanophe

Full text of DOI:10.1016/j.tet.2013.10.094

Tetrahedron 70 (2014) 1091e1098
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Three-component reaction of imidazoles, cyanophenylacetylene,
and chalcogens: stereoselective synthesis of 3-alkenyl-2-
imidazolethiones and -selones
Kseniya V. Belyaeva a, Ludmila V. Andriyankova a, Lina P. Nikitina a,
Anastasiya G. Mal’kina a, Andrei V. Afonin a, Igor’ A. Ushakova, Irina Yu. Bagryanskaya b,
,
Boris A. Trofimova
*
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
b N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Lavrentjev Ave. 9, 630090 Novosibirsk,
Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 21 August 2013
Received in revised form 17 October 2013
Accepted 28 October 2013
Available online 1 November 2013
The three-component reaction of 1-substituted imidazoles, cyanophenylacetylene, and elemental sulfur
or selenium proceeds readily (for sulfur at room temperature without solvent, and for selenium in boiling
MeCN) to stereoselectively afford 3-(Z)-cyanophenylethenyl-2-imidazolethiones or -selones in yields
ranging 39e97% (for thiones) and 39e84% (for selones). In this reaction, tellurium is inactive both under
the above conditions and upon heating (50e55 ꢀC) in DMSO, instead, only the C(2)-vinylation of the
imidazole ring in up to 98% yield takes place. The Z-stereoselectivity of the reaction is close to 100% (for
sulfur) and reaches 91e99% (for selenium). The reaction involves the zwitterionic adduct of imidazoles
with cyanophenylacetylene, which converts to the carbene via proton transfer (from the imidazole 2
position to the carbanionic site of the zwitterion) further reacting with chalcogens.
Keywords:
Heterocycles
Alkynes
Chalcogenes
Zwitterions
Ó 2013 Elsevier Ltd. All rights reserved.
Multicomponent reactions
1. Introduction
elemental chalcogens (boiling methanol, dry K2CO3).5,13a,b Imidaz-
ole-2-thiones have also been prepared in two steps by the reaction
Imidazole-2-thiones are important organic compounds that
have gained increased attention because of their pharmacological
activities.1e6 Their derivatives, e.g., 1-methylimidazole-2-thione
(Methimazole), are being used for the treatment of several dis-
eases (hyperthyroidism, rheumatoid arthritis etc.).1e3 Imidazole-2-
thione C-nucleosides are intermediates in the synthesis of azido-
nucleosides and fluoronucleosides having anti-AIDS activity.4 The
corresponding selone analogs exhibit anti-hyperthyroid activity.5,6
Imidazole-2-thiones are known as rubber antioxidants7 and vul-
canization agents.8 1,3-Disubstituted imidazole-2-thiones possess
versatile catalytic activity.9,10 These compounds are also readily
converted to halide-free ionic liquids.11
of imidazolium salts with potassium thioacetate or thiocyanate
under microwave irradiation.13c
To the best of our knowledge, 1,3-disubstituted imidazole-2-
thiones or -selones with unsaturated functional substituents at the
N(3) atom remain almost unknown.14 Probably, the addition of 1-
anilino-4,5-dimethylimidazole-2-thione to dimethyl acetylenedi-
carboxylate to give 2-(3-anilino-4,5-dimethyl-2-thioxoimidazolyl)-
2-butenedioate is the only synthesis of such compound.
2. Results and discussion
Here we report the three-component reaction between 1-
substituted imidazoles 1aef, cyanophenylacetylene (2), and ele-
mental sulfur or selenium affording thiones 3aee or selones 4aed
(Table 1).
The synthesis was carried out as a one-pot procedure avoiding
the initial preparation of imidazolium salts and hence the addi-
tional basic reagent for their conversion to the carbene. In the case
of sulfur, the reaction proceeded at room temperature under
solvent-free conditions for 24 h, to give the corresponding thiones
Imidazoline-2-selone is a precursor of good-quality cubic phase
copper selenide nanodiscs.12
Imidazole-2-thiones or selones have been synthesized in two
steps: preparation of imidazolium salts and their treatment with
* Corresponding author. Tel.: þ7 3952 421411; fax: þ7 3952 41 9346; e-mail
address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.10.094

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K.V. Belyaeva et al. / Tetrahedron 70 (2014) 1091e1098
Table 1
Three-component reaction of 1-substituted imidazoles 1aef, cyanophenylacetylene (2), and chalcogens (S, Se) (molar ratio 1:2:S/Se¼1:1:1)
Ph
N
N
CN
+
Ph
CN + E
E
N
R
1a-f
N
R
2
3a-f or 4a-d
E = S (20-24 oC, 24 h);
E = Se (MeCN, 82 oC, 5-15 h)
E
S
Imidazole 1
Products 3, 4
Conversion of 1 (%)
Isolated yieldsa (%)
Content of (E)-isomerb (%)
82
67
39
60
Not observed
1a
3a
3b
3c
S
S
57
97
Not observed
1b
1c
Not observed
S
53
18
79
83
62
97
96
87
39
84
Not observed
1d
1e
3d
3e
S
Not observed
S
Not observed
1f
1a
1b
3f
4a
4b
Se
Se
5
9

K.V. Belyaeva et al. / Tetrahedron 70 (2014) 1091e1098
1093
Table 1 (continued )
E
Imidazole 1
Products 3, 4
Conversion of 1 (%)
Isolated yieldsa (%)
Content of (E)-isomerb (%)
Se
100
39
1
1e
4c
Se
84
58
5
1f
4d
a
Based on reacted imidazole.
b
According to the 1H NMR spectrum.
3aef in yields ranging from 39 to 97%. The conversion of imidazoles
is 18e97% depending on their structure. The alkenyl moiety is of
the Z-configuration (Z-selectivity is close to 100%). The reaction
with selenium requires solvent and a higher temperature (refluxing
in MeCN), but for a shorter time (5e15 h). The yields of selones
4aed span 39e84%, the conversion of imidazoles being 62e100%.
The products are mainly of the Z-configuration (the selectivity is
91e99%). The above reaction conditions come from a number of
experiments carried out both in MeCN and solvent-free at room
temperature up to 82 ꢀC (boiling in MeCN).
In all cases (both with sulfur and selenium), along with the
major products 3aef or 4aed of the three-component reaction, the
formation of C(2)-vinylated imidazoles, (Z)-2-(2-cyano-1-
phenylethenyl)imidazoles 5, have been observed from traces to
37% (for sulfur) and from 24 to 58% yields (for selenium)
(Scheme 1), the imidazoles 5 being separated from compounds 3
and 4 by column chromatography. These are resulted from the
previously found two-component reaction between imidazoles 1
and cyanophenylacetylene (2).15
The structure of products 3aef and 4aed was established by X-
ray diffraction analysis and confirmed using NMR (1H, 13C, 2D, 15N,
77Se) and IR spectroscopy.
The key structural issue here is whether the C(2)]S and C(2)]
Se bonds are indeed double or single ones or, in other words,
whether the products represent real thiones 3 and selones 4 or
isomeric zwitterions with anionic center on the sulfur or selenium
(Scheme 2).
Ph
Ph
+
N
N
N
R
CN
_
CN
E
E
N
R
3
4
E = S ( ), Se ( )
Scheme 2.
For the simpler 1,3-dialkyl- or 1,3-alkylbenzylsubstituted ana-
logs of compounds 3 and 4, it has been shown that in the crystalline
state they have C(2)]S and C(2)]Se bonds, while in solution
(CDCl3) the selones are actually the zwitterions with C(2)eSe single
bond according to 77Se NMR spectroscopy.5,6
N
N
N
R
1a-c,e,f
Ph
E
+ Ph
CN
N
2
NC
5a-c,e,f
R
Our X-ray diffraction analysis (Fig. 1) showed that both sulfur
(3d, 3e) and selenium (4a) products possess C(2)]S and C(2)]Se
double bonds, i.e., in the crystalline state they are real thiones and
selones. This follows from the comparison of the bond lengths. The
E = S (trace to 37%), Se (24-58%), Te (91-98%);
a
b
c
e
f
R = Me ( ), n-Bu ( ), i-Bu ( ), Bn ( ), Allyl ( )
Scheme 1. Synthesis of the (Z)-2-(2-cyano-1-phenylethenyl)imidazoles 5.
ꢀ
observed length of the C(2)]S bond is 1.675 A whereas the liter-
ature data for the lengths of C(2)]S bond in imidazole-derived
16
ꢀ
ꢀ
structures are 1.681 A and 1.718 A. This means that the C(2)]S
ꢀ
Noteworthy, tellurium is inactive in the above three-component
reaction. Since the reaction with selenium without solvent does not
occur and for its realization the reactants (1, 2, and selenium) have
to be boiled in MeCN (82 ꢀC, 12 h), the experiments with tellurium
have been carried out also upon boiling in MeCN and heating in
DMSO (50e55 ꢀC, 14 h). However, under these conditions, no ex-
pected tellurium-containing imidazole has been detected in the
reaction mixture. The only product, obtained in DMSO at room
temperature or upon heating at 50e55 ꢀC, is C(2)-vinylated imid-
azole 5a isolated in up to 98% yield (based on the imidazole con-
sumed, conversion of the imidazoles being 72e88%). When
imidazole 1a and acetylene 2 react in DMSO at room temperature
without tellurium for 24 h, the C(2)-vinylation takes place almost
with the same result to afford product 5a in 82% yield, conversion of
imidazole 1a being 93%. One may even imply that metal tellurium
exhibits a weak catalytic effect on the C-vinylation reaction.
bond length in compound 3d just negligibly differ (0.006e0.043 A)
from the literature precedent. Correspondingly, the observed
ꢀ
length of the C(2)]Se bond is 1.837 A, whereas the literature values
for similar compounds are 1.819e1.858 A.17,18 Again, the difference
ꢀ
ꢀ
is within experimental error (0.003e0.021 A). At the same time, the
16
ꢀ
lengths of the C(2)eS and C(2)eSe bonds are 1.817 A and
16b,17,18
ꢀ
1.884e1.912 A.
Therefore, the experimental bonds between
ꢀ
C(2) and sulfur and selenium are much shorter (0.142 A for sulfur
and 0.075 A for selenium) than the ordinary C(2)eS and C(2)eSe
ꢀ
bonds and correspond to C(2)]S and C(2)]Se bonds.
The evidence that compounds 3 exist in solution in the thione
form is the absence of any response of their UV spectra to the ad-
dition of acid (MeCN solution, 0.1 M HCl). For example, the solution
of compound 3a in MeCN absorbs at 209, 225, 270 and 329 nm and
the spectrum remains absolutely the same in the presence of HCl.
Meanwhile, the zwitterionic form upon acidification should give

1094
K.V. Belyaeva et al. / Tetrahedron 70 (2014) 1091e1098
Imidazole-2-selone (Z)-4a is characterized by the following
ꢀ
ꢀ
bond lengths: Se(1)eC(1) 1.837 A, N(1)eC(1) 1.358 A, N(1)eC(2)
ꢀ
ꢀ
ꢀ
ꢀ
1.378 A, N(1)eC(13) 1.455 A, N(2)eC(1) 1.363 A, N(2)eC(3) 1.389 A,
ꢀ
ꢀ
N(2)eC(10) 1.434 A, N(3)eC(12) 1.138 A. Other geometry parame-
ters of selone 4a correspond to average statistical values.18
In the 1H NMR spectra of products (Z)-3aef and (Z)-4aed, there
is an olefin proton signal at 6.05e6.15 ppm, while olefinic proton H-
7
of the corresponding (E)-isomers
4
are observed at
6.91e6.96 ppm. The Z-configuration of the isomers followed from
the fact that in the 2D NOESY spectrum of compounds 3 and 4, the
cross-peak between signals of the olefin proton 7-H and ortho-
protons of phenyl are observed (Fig. 2).
Tetrahedron
Fig. 2. Cross-peaks in the 2D NOESY spectrum of products (Z and E)-3, 4.
In the 13C NMR spectra of products 3aef and 4aed, the signals of
C-4 and C-5 have the similar values as in the starting imidazoles,
while the C-2 signal is downfield shifted (from 136 to 165 ppm for
3aef, and to 160 ppm for 4aed) by the negative inductive effect of
the substituent (S, Se) and becomes quaternary. In the 13C NMR
spectra, carbons of the cyano group in the adducts resonate in the
region 114.3e114.9 ppm. In the 15N NMR spectra, nitrogen atoms of
the imidazole ring have the following values: ꢁ217.9 (N-1), ꢁ207.8
(N-3) [for C(2)]S] and ꢁ197.8 (N-1), ꢁ200.8 (N-3) [for C(2)]
Se] ppm.
The IR spectra show absorption bands in the region of
2220e2222 cmꢁ1, assignable to the cyano group at the double
bond, as well as bands in the region of 1383e1399 cmꢁ1, which are
typical for the C]S and C]Se bonds.
The path of the three-component reaction (Table 1) can be ra-
tionalized as follows (Scheme 4). The primary zwitterion A, resul-
ted from the nucleophilic attack of imidazole to the carbonecarbon
triple bond, abstracts the proton from position 2 (most probably
intermolecularly) by its carbanionic site to generate thereby the
intermediate carbene B. Then the cleavage of the EeE bonds, by the
insertion of the carbene B in between these bonds, occurs to deliver
the final products 3 or 4.
Fig. 1. Molecular structures of thiones 3d, 3e, and selone 4a.
the corresponding salt with its own UV spectrum (Scheme 3). In
other words, the thione structure should be less prone to pro-
tonation than the alternative zwitterionic structure.
Ph
Ph
+
N
N
_
CN
C_N
+
+
HCl
Cl
N
SH
N
S
R
R
Scheme 3. Unobserved acidification of zwitterion by HCl.
Ph
Ph
_
+
2
H+-transfer
N
N
E
CN
CN
:
1
3 or 4
N
R
N
R
Unlike the 1,3-dialkylimidazole-2-selones, products 4 retain the
selone structure in solution as exemplified by the 77Se NMR (CDCl3)
spectrum of compound 4c: its selenium atom resonates at
77.7 ppm, while the chemical shift of zwitterionic selenium in
analogous compounds is reported to be ꢁ3 to ꢁ6 ppm.5,6
Fig. 1 shows spatial structure of thiones (Z)-3d, (E)-3e, and
selone (Z)-4a.
A
B
E = S, Se
Scheme 4. Tentative mechanism of products 3 and 4 formation.
In the case of elemental sulfur, the reaction should proceed as
usual via the subsequent cleavage of the SeS bond in cyclic octamer
S8 under the action of the nucleophilic carbene intermediate
(Scheme 5). The intermediate zwitterion C, formed after the first
cleavage of the SeS bond in elemental sulfur octamer, gives the
complex zwitterion, which then releases the S7 species, which is
further subjected to the same cleavage with the next carbene B
molecule until complete sulfur consumption.
For thiones (Z)-3d, (E)-3e, and selone (Z)-4a, selected bond
lengths are given according to X-ray analysis. Bond lengths for
ꢀ
ꢀ
imidazole-2-thione (Z)-3d: S(2)eC(6) 1.675 A, N(1)eC(6) 1.371 A,
ꢀ
ꢀ
ꢀ
N(1)eC(13) 1.393 A, N(2)eC(6) 1.355 A, N(2)eC(15) 1.381 A. Bond
ꢀ
lengths for imidazole-2-thione (E)-3e: S(1)eC(6) 1.675 A, N(1)e
ꢀ
ꢀ
ꢀ
C(6) 1.389 A, N(1)eC(14) 1.404 A, N(2)eC(6) 1.358 A, N(2)eC(15)
ꢀ
1.339 A.

K.V. Belyaeva et al. / Tetrahedron 70 (2014) 1091e1098
1095
1112 Series. 1-Substituted imidazoles 1c,d were prepared according
to literature procedures.25 Column and thin-layer chromatography
were carried out on neutral Al2O3 with chloroform/benzene/etha-
nol (20:4:1) mixture as eluent. The reaction was monitored by the
disappearance of absorption bands of initial acetylene 2 in the re-
action mixture (IR spectroscopy). For labeling of NMR assignments,
see Fig. 3.
Ph
Ph
Ph
+
+
S8
N
N
N
CN
CN
_
CN
_
:
etc
S
S S7
N
R
N
R
N
R
-[S7]
B
C
Scheme 5. The process of sulfurization of carbene B.
This mechanism is in agreement with the Z-configuration of the
alkenyl substituents that is typical for the nucleophilic addition to
acetylenes.19,20 Indeed, nucleophilic attack at the triple bond
commonly proceeds as a concerted trans-addition (with simulta-
neous proton transfer) to deliver adducts of the Z-configura-
tion.19,20 The kinetic nature of this stereochemistry is supported by
the conversion of thione (Z)-3e to its thermodynamic (E)-isomer
during the slow monocrystal growth (about 4 months). In keeping
with this mechanism is also the fact that when the carbene B is
sterically screened by such bulky N(1)-substituents as benzyl or
(CH2)2SBu-n, the three-component reaction is replaced by the two-
component one (Scheme 1) leading to C(2)-vinylated imidazoles. As
expected, this is particularly pronounced in the cases of chalcogens
with larger atomic radii.
Ph
6
7
H
3
3
4
4
HB
HA
N
N2 Ph
N2
1
CN
1
6
5
5
H2C
E
N
R
N
H
NC 7
HX
Allyl for 3f, 4c
R
3a-f 4a-d
5b c
,
,
Fig. 3. Labeling of hydrogen and carbon atoms used for NMR assignments for com-
pounds 3e5.
4.2. X-ray diffraction
Notably, the only example of the reaction of 1-methylimidazole
with dimethyl acetylenedicarboxylate and sulfur was reported to
give a quite different product, the zwitterion with the sulfur atom
attached to the ethylenic moiety.21
X-ray crystallography studies of compounds 3d, 3e and 4a were
carried out with a Bruker KAPPA APEX II CCD diffractometer with
Mo-Ka radiation and a graphite monochromator. Absorption cor-
rections were applied using the empirical multiscan method with
the SADABS program.22 The structure was solved by direct
methods and refined by full-matrix least-squares methods in an
anisotropic approximation using the SHELX-97 programs set.23
The positions of the hydrogen atoms were calculated geo-
metrically and refined with the riding model (parameters of hy-
drogen atoms were calculated in every cycle of refinement
according to coordinates of the corresponding carbon atoms). Final
refinement of the structure was performed according to all F2 up
3. Conclusion
In conclusion, we have found a facile stereoselective three-
component reaction between 1-substituted imidazoles, cyano-
phenylacetylene, and sulfur or selenium, which leads to 3-(Z)-
cyanophenylethenyl-2-imidazolethiones or -selones in moderate to
good yields. The reaction is assumed to involve the carbene in-
termediate, which is inserted into the SeS or SeeSe bonds of the
elemental chalcogens. Until this work, imidazole-2-thiones or
-selones with unsaturated functionalized substituents at the N(3)
atom remained almost unknown. Additionally, unlike the literature
precedents, the imidazole derivatives thus synthesized retain their
thione or selone structures not only in the crystalline state but also
in solution. Since imidazole-2-thiones and -selones are the subject
of sustainable pharmacological interest, the reaction discussed may
extend the toolkit for drug-oriented heterocyclic synthesis. The
synthesized compounds also represent a new family of cinnamo-
nitrile derivatives. The latter is known as one of the most important
pharmaceutical intermediates, itself exhibiting antiviral, antican-
cer, and antihypertensive activities. It is also applied in food, spices,
chemical, pesticide, and other industries. In addition, the synthesis
developed appears to be a short-cut to a range of unknown func-
tionalized N-vinylimidazoles containing thione and selone moieties
that additionally extend the scope of the reaction found.
to wR2¼0.0763, S¼1.04, 155 parameters (R¼0.0269 for 3091 F>4
s)
were refined. CIF files contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.ca-
m.ac.uk/data_request/cif. The obtained crystal structures were
analyzed for short contacts between nonbonded atoms using
PLATON program.24 Crystalline packing of compound 4a was
characterized by dimer pairs due to shortened non-valence con-
ꢀ
ꢀ
tact Se/Se (3.584 A), van-der-Waals radius being 3.80 A. Any
request to the CCDC for data should quote the full literature ci-
tation and CCDC reference number CCDC 936583 (for 3d), CCDC
936584 (for 3e), CCDC 936585 (for 4a).
4.3. Preparation of 3-(2-thioxo-imidazolyl)-3-phenyl-2-
propenenitriles 3
4.3.1. (Z)-3-(3-Methyl-2-thioxo-2,3-dihydro-1H-imidazol-1-yl)-3-
phenyl-2-propenenitrile (3a). To a mixture of acetylene 2 (127 mg,
1 mmol) and S (32 mg, 1 mmol) was added 1-methylimidazole (1a;
82 mg, 1 mmol). The mixture was stirred at 20e25 ꢀC for 24 h.
Column chromatography afforded thione 3a (132 mg, 67%), yellow
microcrystalline powder, mp 159e161 ꢀC (washed with ether).
Initial imidazole 1a was recovered (15 mg, conversion was 82%). 1H
4. Experimental section
4.1. General
1H, 13C, 15N, 77Se NMR, and 2D NOESY spectra were recorded
with an AV-400 Bruker BioSpin spectrometer with HMDS (1H, 13C),
nitromethane (15N) or Me2Se (77Se) as an internal standards. IR
spectra were recorded on a Bruker Vertex 70 instrument. UV
spectra were recorded on a Lambda 35 UV/vis spectrometer in the
spectrometer cuvette. 1-Substituted imidazoles 1a,b,e,f, cyano-
phenylacetylene (2), sulfur, and selenium are commercial reagents
(‘Alfa Aesar’). Elemental analyses were performed on a FLASH EA
NMR (400.13 MHz, CDCl3):
Ph], 6.89 (s, 1H, 4-H), 6.80 (s, 1H, 5-H), 6.05 (s, 1H, 7-H), 3.63 (s, 3H
from NeCH3) ppm. 13C NMR (100.62 MHz, CDCl3):
d¼7.45e7.25 [m, 5H, Ho,m,p from C(6)e
d¼164.4 (C-2),
154.2 (C-6), 132.5 [Ci from C(6)ePh], 131.8 [Cp from C(6)ePh], 129.1
[Cm from C(6)ePh], 126.8 [Co from C(6)ePh], 119.8 (C-4), 116.9 (C-5),
114.6 (CN), 97.0 (C-7), 35.3 (NeCH3) ppm. 15N NMR (40.55 MHz,
CDCl3):
d
¼ꢁ110.6 (CN), ꢁ207.8 (N-3), ꢁ217.9 (N-1) ppm. IR (KBr):

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K.V. Belyaeva et al. / Tetrahedron 70 (2014) 1091e1098
2220 (CN), 1621 (C]C), 1383 (C]S) cmꢁ1. Anal. Calcd for C13H11N3S
(241.31): C, 64.70; H, 4.59; N, 17.41; S, 13.29. Found: C, 64.44; H,
4.32; N, 17.72; S, 13.34.
Ph], 131.1 [Cp from C(6)ePh], 129.6 (C-4), 129.1 [Cm from C(6)ePh],
127.4 [Co from C(6)ePh], 122.3 (C-5), 116.7 (CN), 99.6 (C-7), 54.6
[CH2CH(CH3)2 from N-i-Bu], 30.1 [CH2CH(CH3)2 from N-i-Bu], 19.7
[CH2CH(CH3)2 from N-i-Bu] ppm. IR (microlayer): 2217 (CN), 1670
(C]C) cmꢁ1. Anal. Calcd for C16H17N3 (251.33): C, 76.46; H, 6.82; N,
16.72. Found: C, 76.76; H, 6.68; N, 16.57.
4.3.2. (Z)-3-(3-n-Butyl-2-thioxo-2,3-dihydro-1H-imidazol-1-yl)-3-
phenyl-2-propenenitrile (3b). Analogously, from acetylene
2
(64.0 mg, 0.5 mmol), S (16.0 mg, 0.5 mmol), and 1-n-butylimidazole
(1b; 62.0 mg, 0.5 mmol) (20e25 ꢀC, 24 h), thione 3b (31 mg, 39%)
was obtained as a light-brown oil. Initial imidazole 1b was re-
covered (27 mg, conversion was 57%). 1H NMR (400.13 MHz, CDCl3):
4.3.6. (Z)-3-{3-[2-(Butylsulfanyl)ethyl]-2-thioxo-2,3-dihydro-1H-
imidazol-1-yl}-3-phenyl-2-propenenitrile (3d). Analogously, from
acetylene 2 (127 mg, 1 mmol), S (32 mg, 1 mmol), and 1-n-butylth-
ioethylimidazole (1d; 184 mg, 1 mmol) (20e25 ꢀC, 24 h) thione 3d
(178 mg, 97%) was obtained as a yellow microcrystalline powder, mp
110e112 ꢀC (hexane). Initial imidazole 1d was recovered (86 mg,
d
¼7.50e7.30 [m, 5H, Ho,m,p from C(6)ePh], 6.90 (s, 1H, 4-H), 6.79 (s,
3
1H, 5-H), 6.06 (s, 1H, 7-H), 4.08 [t, JH,H¼7.7 Hz, 2H, CH2(CH2)2CH3
from N-n-Bu], 1.83e1.80 (m, 2H, CH2CH2CH2CH3 from N-n-Bu),
1.45e1.40 [m, 2H, (CH2)2CH2CH3 from N-n-Bu], 0.98 [t, 3JH,H¼7.3 Hz,
3H, (CH2)3CH3, from N-n-Bu] ppm. 13C NMR (100.62 MHz, CDCl3):
conversion was 53%). 1H NMR (400.13 MHz, CDCl3):
d
¼7.45e7.30 [m,
5H, Ho,m,p fromC(6)ePh], 6.98(s,1H, 4-H), 6.78(s,1H, 5-H), 6.05(s,1H,
3
d¼164.0 (C-2), 154.4 (C-6), 132.6 [Ci from C(6)ePh], 131.9 [Cp from
7-H), 4.26 [t, JH,H¼6.8 Hz, 2H, CH2CH2S(CH2)3CH3 from N-n-
C(6)ePh], 129.2 [Cm from C(6)ePh], 126.8 [Co from C(6)ePh], 118.5
(C-4), 117.0 (C-5), 114.7 (CN), 97.2 (C-7), 47.9 [CH2(CH2)2CH3 from N-
n-Bu], 30.7 (CH2CH2CH2CH3 from N-n-Bu), 19.8 [(CH2)2CH2CH3
from N-n-Bu], 13.7 [(CH2)3CH3 from N-n-Bu] ppm. IR (film): 2222
(CN), 1622 (C]C), 1402 (C]S) cmꢁ1. Anal. Calcd for C16H17N3S
(283.39): C, 67.81; H, 6.05; N, 14.83; S, 11.32. Found: C, 68.04; H,
5.96; N, 14.92; S, 11.03.
butylthioethyl], 2.97 [t, 2H, CH2CH2S(CH2)3CH3 from N-n-butylth-
3
ioethyl], 2.56 [t, JH,H¼7.2 Hz, 2H, (CH2)2SCH2,(CH2)2CH3 from N-n-
butylthioethyl], 1.60e1.54 [m, 2H, (CH2)2SCH2CH2CH2CH3 from N-n-
butylthioethyl], 1.45e1.35 [m, 2H, (CH2)2S(CH2)2CH2CH3 from N-n-
butylthioethyl], 0.90 [t, 3JH,H¼7.2 Hz, 3H, (CH2)2S(CH2)3CH3 from N-n-
butylthioethyl] ppm. 13C NMR (100.62 MHz, CDCl3):
d¼163.9 (C-2),
153.9 (C-6), 132.3 [Ci from C(6)ePh], 131.6 [Cp from C(6)ePh], 128.9
[Cm from C(6)ePh], 126.5 [Co from C(6)ePh], 119.2 (C-4), 116.5 (C-5),
114.3 (CN), 96.9 (C-7), 48.0 [CH2CH2S(CH2)3CH3 from N-n-butylth-
ioethyl], 31.9 [CH2CH2S(CH2)3CH3 from N-n-butylthioethyl], 31.5
[(CH2)2SCH2(CH2)2CH3 from N-n-butylthioethyl], 29.9 [(CH2)2SCH2
CH2CH2CH3 from N-n-butylthioethyl], 21.6 [(CH2)2S(CH2)2CH2CH3
from N-n-butylthioethyl], 13.3 [(CH2)2S(CH2)3CH3 from N-n-
butylthioethyl] ppm. IR (KBr): 2222 (CN), 1621 (C]C), 1399 (C]
S) cmꢁ1. Anal. Calcd for C18H21N3S2 (343.51): C, 62.94; H, 6.16; N,
12.23; S, 18.67. Found C, 62.65; H, 5.92; N, 12.02; S, 18.39.
4.3.3. (Z)-3-(1-n-Butyl-1H-imidazol-2-yl)-3-phenyl-2-propenenitrile
(5b). Brown oil (26 mg, 37%). 1H NMR (400.13 MHz, CDCl3):
d
¼7.50e7.26 [m, 5H, Ho,m,p from C(6)ePh], 7.25 (s, 1H, 4-H), 7.06 (s,
3
1H, 5-H), 5.94 (s, 1H, 7-H), 3.61 [t, JH,H¼7.2 Hz, 2H, CH2(CH2)2CH3
from N-n-Bu], 1.60e1.50 (m, 2H, CH2CH2CH2CH3 from N-n-Bu),
1.15e1.10 [m, 2H, (CH2)2CH2CH3 from N-n-Bu], 0.77 [t, 3JH,H¼7.6 Hz,
3H, (CH2)3CH3 from N-nBu] ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼151.6 (C-6), 142.3 (C-2), 136.2 [Ci from C(6)ePh], 130.9 [Cp from
C(6)ePh], 129.7 (C-4), 129.0 [Cm from C(6)ePh], 127.3 [Co from
C(6)ePh], 121.6 (C-5), 116.6 (CN), 99.5 (C-7), 46.7 [CH2(CH2)2CH3
from N-n-Bu], 32.6 (CH2CH2CH2CH3 from N-n-Bu), 19.4
[(CH2)2CH2CH3 from N-n-Bu], 13.2 [(CH2)3CH3 from N-n-Bu] ppm.
IR (microlayer): 2216 (CN), 1650 (C]C) cmꢁ1. Anal. Calcd for
4.3.7. (Z)-3-(3-Benzyl-2-thioxo-2,3-dihydro-1H-imidazol-1-yl)-3-
phenyl-2-propenenitrile (3e). Analogously, from acetylene
2
(64.0 mg, 0.5 mmol), S (16.0 mg, 0.5 mmol), and 1-benzylimidazole
(1e; 79.0 mg, 0.5 mmol) in MeCN (1 mL) (20e25 ꢀC, 24 h) thione 3e
(27 mg, 96%) was obtained as a light-yellow microcrystalline
powder, mp 129e131 ꢀC (washed with ether). Initial imidazole 1e
was recovered (65 mg, conversion was 18%). 1H NMR (400.13 MHz,
C
16H17N3 (251.33): C, 76.46; H, 6.82; N, 16.72. Found: C, 76.15; H,
6.56; N, 16.39.
4.3.4. (Z)-3-(3-Isobutyl-2-thioxo-2,3-dihydro-1H-imidazol-1-yl)-3-
CDCl3):
NeBn], 6.74 (s, 2H, 4-H, 5-H), 6.06 (s, 1H, 7-H), 5.27 (s, 2H, CH2 from
NeBn) ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼7.50e7.30 [m, 10H, Ho,m,p from C(6)ePh and Ph from
phenyl-2-propenenitrile (3c). Analogously, from acetylene
2
(64.0 mg, 0.5 mmol), S (16.0 mg, 0.5 mmol), and 1-isobutylimidazole
(1c; 62.0 mg, 0.5 mmol) (20e25 ꢀC, 24 h), thione 3c (82 mg, 60%) was
obtained as a light-yellow microcrystalline powder, mp 109e110 ꢀC
(washed with ether). Initial imidazole 1c was recovered (2 mg,
d
¼164.7 (C-2), 154.1 (C-
6), 135.2 (Ci, Ph from NeBn), 132.4 [Ci from C(6)ePh], 131.8 [Cp from
C(6)ePh], 129.1 [Cm from C(6)ePh], 128.9 (Cm, Ph from NeBn), 128.2
(Cp, Ph from NeBn), 128.1 (Co, Ph from NeBn), 126.7 [Co from C(6)e
Ph], 118.3 (C-4), 117.1 (C-5), 114.5 (CN), 97.2 (C-7), 51.3 (CH2 from
conversionwas 97%).1H NMR (400.13 MHz, CDCl3):
d
¼7.50e7.25 [m,
5H, Ho,m,p from C(6)ePh], 6.86 (s, 1H, 4-H), 6.77 (s, 1H, 5-H), 6.07 (s,
NeBn) ppm. IR (KBr): 2221 (CN), 1621 (C]C), 1398 (C]S) cmꢁ1
.
3
1H, 7-H), 3.90 [d, JH,H¼7.2 Hz, 2H, CH2CH(CH3)2 from N-i-Bu],
Anal. Calcd for C19H15N3S (317.41): C, 71.90; H, 4.76; N, 13.24; S,
10.10. Found: C, 71.67; H, 4.85; N, 12.92; S, 9.84.
2.34e2.27 [m, 1H, CH2CH(CH3)2 from N-i-Bu], 0.98 [d, 3JH,H¼7.2 Hz,
6H, 2CH3, CH2CH(CH3)2 from N-i-Bu] ppm. 13C NMR (100.62 MHz,
CDCl3):
d
¼164.5 (C-2), 154.4 (C-6), 132.6 [Ci,p from C(6)ePh], 129.2
4.3.8. (Z)-3-(3-Allyl-2-thioxo-2,3-dihydro-1H-imidazol-1-yl)-3-
[Cm from C(6)ePh], 126.8 [Co from C(6)ePh], 119.3 (C-4), 116.7 (C-5),
114.6 (CN), 97.3 (C-7), 55.2 [CH2CH(CH3)2 from N-i-Bu], 28.1
[CH2CH(CH3)2 from N-i-Bu], 19.8 [2CH3, CH2CH(CH3)2 from N-i-
Bu] ppm. IR (KBr): 2222 (CN), 1621 (C]C), 1390 (C]S) cmꢁ1. Anal.
Calcd for C16H17N3S (283.39): C, 67.81; H, 6.05; N, 14.83; S, 11.32.
Found: C, 68.04; H, 5.86; N, 14.92; S, 11.03.
phenyl-2-propenenitrile (3f). Analogously, from acetylene
2
(127 mg, 1 mmol), S (32 mg, 1 mmol), and 1-allylimidazole (1f;
108 mg, 1 mmol) (20e25 ꢀC, 24 h) thione 3f (186 mg, 87%) was
obtained as a yellow microcrystalline powder, mp 140e142 ꢀC
(washed with ether). Initial imidazole 1f was recovered (23 mg,
conversion was 79%). 1H NMR (400.13 MHz, CDCl3):
d¼7.49e7.29
[m, 5H, Ho,m,p from C(6)ePh], 6.90 (s,1H, 4-H), 6.80 (s,1H, 5-H), 6.07
(s, 1H, 7-H), 6.02e5.92 (m, 1H, Hx from N-Allyl), 5.34 (d,
4.3.5. (Z)-3-(1-Isobutyl-1H-imidazol-2-yl)-3-phenyl-2-propenenitrile
(5c). Brown oil (33 mg, 27%). 1H NMR (400.13 MHz, CDCl3):
3JHA,Hx¼10.3 Hz, 1H, HA from N-Allyl), 5.28 (d, JHB,Hx¼17.0 Hz, 1H,
3
3
d
¼7.50e7.25 [m, 5H, Ho,m,p from C(6)ePh], 7.25 (s, 1H, 4-H), 7.03 (s,
HB from N-Allyl), 4.70 (d, JCH ;HX¼5.9 Hz, 2H, NeCH2 from N-
2
3
1H, 5-H), 5.93 (s, 1H, 7-H), 3.40 [d, JH,H¼7.6 Hz, 2H, CH2CH(CH3)2
from N-i-Bu], 1.89e1.83 [m, 1H, CH2CH(CH3)2 from N-i-Bu], 0.75 [d,
3JH,H¼6.6 Hz, 6H, CH2CH(CH3)2 from N-i-Bu] ppm. 13C NMR
Allyl) ppm. 13C NMR (100.62 MHz, CDCl3):
6),132.6 [Ci from C(6)ePh],132.0 [Cp from C(6)ePh],131.3 (CHx from
N-Allyl), 129.3 [Cm from C(6)ePh], 126.9 [Co from C(6)ePh], 119.7
(C-4), 118.4 (CHA,HB from N-Allyl), 117.2 (C-5), 114.7 (CN), 97.3 (C-7),
d
¼164.3 (C-2), 154.3 (C-
(100.62 MHz, CDCl3):
d¼151.8 (C-6),142.6 (C-2),136.3 [Ci from C(6)e

K.V. Belyaeva et al. / Tetrahedron 70 (2014) 1091e1098
1097
50.3 (CH2 from N-Allyl) ppm. IR (KBr): 2222 (CN), 1621 (C]C), 1398
(C]S) cmꢁ1. Anal. Calcd for C15H13N3S (267.35): C, 67.39; H, 4.90; N,
15.72; S, 11.99. Found: C, 67.26; H, 4.81; N, 15.80; S, 11.69.
(127 mg, 1 mmol), Se (79 mg, 1 mmol) in MeCN (2 mL), and 1-
benzylimidazole (1e; 158 mg, 1 mmol) in MeCN (1 mL) (82 ꢀC,
15 h) selone (Z)-4c (143 mg, 39%) was obtained as a yellow mi-
crocrystalline powder, mp 172e173 ꢀC (ethanol). Initial Se was re-
covered (37 mg, conversion was 53%). Z:E-isomers ratio was 40:1
[(E)-isomer, 1%, data 1H NMR]. (Z)-Isomer: 1H NMR (400.13 MHz,
4.4. Preparation of 3-(2-selenoxo-imidazolyl)-3-phenyl-2-
propenenitriles 4
CDCl3):
d
¼7.50e7.30 [m, 10H, Ho,m,p from C(6)ePh and Ho,m,p, Ph
4.4.1. (ZþE)-3-(3-Methyl-2-selenoxo-2,3-dihydro-1H-imidazol-1-
yl)-3-phenyl-2-propenenitrile (4a). To a mixture of acetylene 2
(64.0 mg, 0.5 mmol) and Se (40.0 mg, 0.5 mmol) in MeCN (1 mL) was
added 1-methylimidazole (1a; 41.0 mg, 0.5 mmol) in MeCN (1 mL).
The mixture was stirred at 82 ꢀC for 5 h. After cooling to 20e25 ꢀC,
the solvent was removed and column chromatography afforded
selone (Z)-4a (46 mg, 39%) as a yellow microcrystalline powder, mp
208e209 ꢀC (ethanol). Initial imidazole 1a was recovered (7 mg,
conversion was 83%). Initial Se was recovered (20 mg, conversion
was 50%). Z:E-isomers ratio was 5:1 [(E)-isomer, 5%, data 1H NMR].
from NeBn], 6.94 (s, 1H, 4-H), 6.89 (s, 1H, 5-H), 6.15 (s, 1H, 7-H),
5.39 (s, 2H, CH2 from NeBn) ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼159.5 (C-2), 154.7 (C-6), 134.9 (Ci, Ph from NeBn), 132.2 [Ci from
C(6)ePh], 132.0 [Cp from C(6)ePh], 129.3 [Cm from C(6)ePh], 129.0
(Cm, Ph from NeBn), 128.5 (Cp, Ph from NeBn), 128.3 (Co, Ph from
NeBn), 126.9 [Co from C(6)ePh], 120.3 (C-4), 119.5 (C-5), 114.5 (CN),
98.0 (C-7), 53.3 (CH2 from NeBn) ppm. 15N NMR (40.55 MHz,
CDCl3):
CDCl3):
d
¼ꢁ197.8 (N-1), ꢁ200.8 (N-3) ppm. 77Se NMR (76.31 MHz,
d
¼77.7. (E)-Isomer: 1H NMR (400.13 MHz, CDCl3):
d
¼7.45e7.30 [m, 10H, Ho,m,p from C(6)ePh and Ho,m,p, Ph from
(Z)-Isomer: 1H NMR (400.13 MHz, CDCl3):
o,m,p from C(6)ePh], 7.07 (s,1H, 4-H), 6.98 (s,1H, 5-H), 6.12 (s,1H, 7-
H), 3.76 (s, 3H, NeCH3) ppm. 13C NMR (100.62 MHz, CDCl3):
d
¼7.50e7.27 [m, 5H,
NeBn], 6.96 (s, 1H, 7-H), 6.71 (s, 1H, 4-H), 6.62 (s, 1H, 5-H), 5.38 (s,
2H, CH2 from NeBn) ppm. IR (KBr): 2222 (CN), 1621 (C]C), 1391
(C]Se) cmꢁ1. Anal. Calcd for C19H15N3Se (364.30): C, 62.64; H, 4.16;
N, 11.53; Se, 21.67. Found: C, 62.63: H, 4.31; N, 11.22; Se, 21.28.
H
d
¼159.2
(C-2), 154.9 (C-6), 132.4 [Ci from C(6)ePh], 132.0 [Cp from C(6)ePh],
129.3 [Cm from C(6)ePh], 127.0 [Co from C(6)ePh], 121.7 (C-4), 119.3
(C-5), 114.5 (CN), 97.7 (C-7), 37.5 (NeCH3) ppm. (E)-Isomer: 1H NMR
4.4.4. (ZþE)-3-(3-Allyl-2-selenoxo-2,3-dihydro-1H-imidazol-1-yl)-
(400.13 MHz, CDCl3):
6.94 (s, 1H, 7-H), 6.90 (s, 1H, 4-H), 6.65 (s, 1H, 5-H), 3.73 (s, 3H,
NeCH3) ppm. IR (KBr): 2222 (CN), 1622 (C]C), 1368 (C]Se) cmꢁ1
d¼7.50e7.45 [m, 5H, Ho,m,p from C(6)ePh],
3-phenyl-2-propenenitrile (4d). Analogously, from acetylene 2
(127 mg, 1 mmol), Se (79 mg, 1 mmol) in MeCN (2 mL), and 1-
allylimidazole (1f; 108 mg, 1 mmol) in MeCN (1 mL) (82 ꢀC, 14 h)
was obtained selone (Z)-4d (154 mg, 58%) as a yellow microcrys-
talline powder, mp 160e161 ꢀC (ethanol). Initial imidazole 1f was
recovered (17 mg, conversion was 84%). Initial Se was recovered
(35 mg, conversion was 56%). Z:E-isomers ratio was 8:1 [(E)-isomer,
5%, data 1H NMR]. (Z)-Isomer: 1H NMR (400.13 MHz, CDCl3):
.
Anal. Calcd for C13H11N3Se (288.21): C, 54.18; H, 3.85; N, 14.58; Se,
27.40. Found: C, 54.50; H, 3.99; N, 14.52; Se, 27.07.
4.4.2. (ZþE)-3-(3-n-Butyl-2-selenoxo-2,3-dihydro-1H-imidazol-1-
yl)-3-phenyl-2-propenenitrile (4b). Analogously, from acetylene 2
(127 mg, 1 mmol), Se (79 mg, 1 mmol) in MeCN (2 mL), and 1-n-
butylimidazole (1b; 124 mg, 1 mmol) in MeCN (1 mL) (82 ꢀC, 7 h)
selone (ZþE)-4b (173 mg, 84%) was obtained as a yellow micro-
crystalline powder, mp 53e65 ꢀC (ethanol). Initial Se was recovered
(31 mg, conversion was 62%). Initial imidazole 1b was recovered
(47 mg, conversion was 62%). Z:E-isomers ratio was 5:1 [(E)-isomer,
9%, data 1H NMR]. (Z)-Isomer: 1H NMR (400.13 MHz, CDCl3):
d
¼7.50e7.29 [m, 5H, Ho,m,p from C(6)ePh], 7.08 (s, 1H, 4-H), 7.00 (s,
1H, 5-H), 6.15 (s, 1H, 7-H), 6.03e5.97 (m, 1H, Hx from N-Allyl), 5.37
3
3
(d, JHA,Hx¼10.2 Hz, 1H, HA from N-Allyl), 5.30 (d, JHB,Hx¼17.2 Hz,
1H, HB from N-Allyl), 4.82e4.80 (m, 2H, CH2 from N-Allyl) ppm. 13
NMR (100.62 MHz, CDCl3):
C(6)ePh], 131.9 [Cp from C(6)ePh], 130.9 (CHx from N-Allyl), 129.2
[Cm from C(6)ePh], 126.8 [Co from C(6)ePh], 120.3 (C-4), 120.0
(CHA,HB from N-Allyl), 119.4 (C-5), 114.4 (CN), 97.8 (C-7), 52.2 (CH2
from N-Allyl) ppm. (E)-Isomer: 1H NMR (400.13 MHz, CDCl3):
C
d¼158.6 (C-2), 154.6 (C-6),132.1 [Ci from
d
¼7.46e7.25 [m, 5H, Ho,m,p from C(6)ePh], 7.09 (s, 1H, 4-H), 6.92
3
(s, 1H, 5-H), 6.15 (s, 1H, 7-H), 4.15 [t, JH,H¼7.6 Hz, 2H,
CH2e(CH2)2eCH3 from N-n-Bu], 1.84e1.80 (m, 2H, CH2eCH2
eCH2eCH3 from N-n-Bu), 1.42e1.37 [m, 2H, (CH2)2eCH2eCH3 from
d
¼7.55e7.45 [m, 5H, Ho,m,p from C(6)ePh], 6.91 (s, 1H, 7-H), 6.89 (s,
1H, 4-H), 6.67 (s, 1H, 5-H), 5.97e5.93 (m, 1H, Hx from N-Allyl), 5.37
3
3
3
N-n-Bu], 0.96 [t, JH,H¼7.6 Hz, 3H, (CH2)3eCH3 from N-n-Bu] ppm.
(d, JHA,Hx¼10.2 Hz, 1H, HA from N-Allyl), 5.32 (d, JHB,Hx¼17.6 Hz,
13C NMR (100.62 MHz, CDCl3):
d¼157.8 (C-2), 154.7 (C-6), 132.2 [Ci
1H, HB from N-Allyl), 4.82 (d, JCH ;HX¼6.2 Hz, 2H, NeCH2 from N-
3
2
from C(6)ePh], 132.0 [Cp from C(6)ePh], 129.3 [Cm from C(6)ePh],
126.9 [Co from C(6)ePh],120.7 (C-4), 119.4 (C-5),114.6 (CN), 98.0 (C-
7), 49.7 [CH2e(CH2)2eCH3 from N-n-Bu], 30.9 (CH2eCH2eCH2eCH3
from N-n-Bu), 19.7 [(CH2)2eCH2eCH3 from N-n-Bu], 13.7
[(CH2)3eCH3 from N-n-Bu] ppm. (E)-Isomer: 1H NMR (400.13 MHz,
Allyl) ppm. IR (KBr): 2222 (CN), 1613 (C]C), 1393 (C]Se) cmꢁ1
.
Anal. Calcd for C15H13N3Se (314.24): C, 57.33; H, 4.17; N, 13.37; Se,
25.13. Found: C, 57.17; H, 4.12; N, 13.28; Se, 25.26.
4.5. Improved methodology for synthesis (Z)-3-(1-methyl-1H-
CDCl3):
d
¼7.50e7.45 [m, 5H, Ho,m,p from C(6)ePh], 6.93 (s, 1H, 7-H),
imidazol-2-yl)-3-phenyl-2-propenenitrile
3
6.89 (s, 1H, 4-H), 6.66 (s, 1H, 5-H), 4.18 [t, JH,H¼7.2 Hz, 2H,
CH2e(CH2)2eCH3
from
from
N-n-Bu],
N-n-Bu), 1.44e1.39
1.84e1.80
(m,
[m,
2H,
2H,
4.5.1. (Z)-3-(1-Methyl-1H-imidazol-2-yl)-3-phenyl-2-propenenitrile
(5a). A mixture of 1-methylimidazole (1a) (41.0 mg, 0.5 mmol) and
acetylene 2 (64.0 mg, 0.5 mmol) was stirred in dry DMSO (1.5 mL)
at 20e25 ꢀC for 24 h. The reaction mixture was diluted with water,
extracted with chloroform (10ꢂ2 mL), washed with water
(3ꢂ5 mL). Chloroform extracts was dried under the MgSO4 over the
night. Then solvent was removed and residue passed through
a chromatography column, and the reaction product 5a (80 mg,
82%, brown oil) and initial imidazole 1a (3 mg, conversion is 93%)
were separated. Full spectroscopic characterization was given in
the previous work.15
CH2eCH2eCH2eCH3
3
(CH2)2eCH2eCH3 from N-n-Bu], 0.98 [t, JH,H¼7.6 Hz, 3H,
(CH2)3eCH3 from N-n-Bu] ppm. 13C NMR (100.62 MHz, CDCl3):
d¼158.8 (C-2), 153.7 (C-6), 132.5 [Ci from C(6)ePh], 131.7 [Cp from
C(6)ePh], 129.2 [Cm from C(6)ePh], 129.0 [Co from C(6)ePh], 119.8
(C-4), 119.6 (C-5), 114.9 (CN), 97.0 (C-7), 50.0 [CH2e(CH2)2eCH3
from N-n-Bu], 30.8 (CH2eCH2eCH2eCH3 from N-n-Bu), 20.0
[(CH2)2eCH2eCH3 from N-n-Bu], 13.8 [(CH2)3eCH3 from N-n-
Bu] ppm. IR (KBr): 2222 (CN), 1622 (C]C), 1394 (C]Se) cmꢁ1. Anal.
Calcd for C16H17N3Se (330.29): C, 58.18; H, 5.19; N, 12.72; Se, 23.91.
Found: C, 58.33; H, 5.14; N, 12.97; Se, 23.58.
To a mixture of acetylene 2 (127 mg, 1 mmol) and Te (128 mg,
1 mmol) in dry DMSO (3 mL) was added 1-methylimidazole (1a;
82 mg, 1 mmol). The mixture was stirred at 20e25 ꢀC for 24 h. The
reaction mixture was filtrated, diluted with water, extracted with
4.4.3. (ZþE)-3-(3-Benzyl-2-selenoxo-2,3-dihydro-1H-imidazol-1-
yl)-3-phenyl-2-propenenitrile (4c). Analogously, from acetylene 2

1098
K.V. Belyaeva et al. / Tetrahedron 70 (2014) 1091e1098
8. Fujita, T.; Kaide, T. J. Patent 62265334, 1987; Chem. Abstr. 1988, 108, 113624.
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chloroform (10ꢂ4 mL), washed with water (3ꢂ10 mL). Chloroform
extracts was dried under the MgSO4 over the night. Then solvent
was removed and residue passed through a chromatography col-
umn, and the reaction product 5a (179 mg, 98%, brown oil) and
initial imidazole 1a (10 mg, conversion is 88%) were separated. Full
spectroscopic characterization of C(2)-vinylated imidazoles 5 was
given in previously works.15,26
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Acknowledgements
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L. P. Russ. Chem. Bull. 2008, 57, 2233; (b) Trofimov, B. A.; Andriyankova, L. V.;
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This work was supported by leading scientific schools by the
President of the Russian Federation (Grant NSh-1550.2012.3),
Russian Fund for Basic Research (Grant No. 11-03-00203) and
Presidium of Department of Chemical Sciences and Materials RAS
(Grant No. 5.1.3.). The main results were obtained using the
equipment of Baikal analytical center of collective using SB RAS.
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