Vinyltetrazoles: II. Synthesis of 5-substituted 1(2)-vinyltetrazoles

Article abstract of DOI:10.1134/S1070428011120177

5-R-Substituted 1(2)-vinyltetrazoles (R = Ar, Alk, CH₂=CH, NH₂, H) were synthesized by alkylation of 5-R-tetrazoles with 1,2-dibromoethane in the presence of triethylamine in acetonitrile, followed by elimination of triethylamine hydrobromide. Vinylation of dinuclear substrates, such as bis(1H-tetrazol-5-yl)-methane and 1,3-bis(1H-tetrazol-5-yl)benzene, under analogous conditions gave the corresponding N¹,N ^2′- and N²,N^2′-divinyl derivatives.

Full text of DOI:10.1134/S1070428011120177

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 12, pp. 1882–1888. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © P.A. Aleshunin, U.N. Dmitrieva, V.A. Ostrovskii, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 12,
pp. 1846–1852.
Vinyltetrazoles:
II.* Synthesis of 5-Substituted 1(2)-Vinyltetrazoles
P. A. Aleshunin, U. N. Dmitrieva, and V. A. Ostrovskii
St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: apa-ti@mail.ru
Received April 23, 2011
Abstract—5-R-Substituted 1(2)-vinyltetrazoles (R = Ar, Alk, CH2=CH, NH2, H) were synthesized by alkyla-
tion of 5-R-tetrazoles with 1,2-dibromoethane in the presence of triethylamine in acetonitrile, followed by
elimination of triethylamine hydrobromide. Vinylation of dinuclear substrates, such as bis(1H-tetrazol-5-yl)-
methane and 1,3-bis(1H-tetrazol-5-yl)benzene, under analogous conditions gave the corresponding N1,N2′- and
N2,N2′-divinyl derivatives.
DOI: 10.1134/S1070428011120177
C,N-Vinyl-substituted tetrazole derivatives are
promising as monomers; products of their polymeriza-
tion are base components of binding energetic mate-
rials, super desiccants, and components of filter mate-
rials and polymeric membranes [2–6].
or p-toluenesulfonate group [9]. Another method is
based on direct introduction of a vinyl group into 5-R-
tetrazole molecule by metal-catalyzed alkylation with
electrophilic reagents containing a CH=CH2 group.
Vinyl acetate and butyl vinyl ether [10–12] are com-
monly used as such reagents, and the alkylation proc-
ess is generally catalyzed by mercury(II) acetate with
addition of acetic, trifluoroacetic, or sulfuric acid, as
well as of boron trifluoride–diethyl ether complex [6].
The main disadvantages of the above procedures are
large number of steps, low yields of intermediate and
target products, necessity of using toxic reagents, and
unsatisfactory reproducibility.
In addition, C,N-vinyltetrazoles attract interest as
reagents for the synthesis of new tetrazole derivatives.
Functionalization of vinyltetrazoles generally implies
addition of electrophilic or nucleophilic reagents at the
CH=CH2 bond [7]. In recent years, extensive studies
have been performed on the development of alternative
methods for functionalization of vinyltetrazoles with
conservation of the double bond. We previously report-
ed on the first examples of metal-catalyzed arylation of
C-vinyl- and C-ethynyltetrazoles according to Heck
and Sonogashira, respectively; as a result, the corre-
sponding C-styryl- and C-arylethynyltetrazoles were
obtained [8]. The application of analogous function-
alization methodology to N-vinyltetrazoles is compli-
cated because of their limited accessibility. Obviously,
development of an afficient procedure for the synthesis
of regioisomeric N-vinyl-5-R-tetrazoles is an important
problem.
One of the most promising methods for the synthe-
sis of vinylazoles is their metal-catalyzed vinylation
according to Ullmann. Vinylation of various imidaz-
oles, pyrazoles, and triazoles with vinyl halides in
the presence of copper(I) iodide was performed in
[13, 14], and the corresponding N-vinyl derivatives
were obtained. However, according to [13], tetrazoles
failed to react under analogous conditions.
The synthesis of N-vinyl-5-R-tetrazoles by alkyla-
tion of 5-R-tetrazoles with 1,2-dibromoethane in the
presence of triethylamine in different solvents,
followed by elimination (in situ) of triethylammonium
bromide, was recently described in [15–17]. It should
be noted that the yields of vinyltetrazoles in [15, 16]
were fairly poor (8–16%), whereas Roh et al. [17]
succeeded in obtaining 2-vinyl-5-R-tetrazoles in up to
88% yield. The procedure proposed in [17] may now
Let us consider known synthetic approaches to
N-vinyltetrazoles. One of these implies formation of
double bond via elimination of exocyclic substituents
from the side chain attached to the nitrogen atom of
5-substituted tetrazoles, in particular halide ion [2, 7]
* For communication I, see [1].
1882

VINYLTETRAZOLES: II. SYNTHESIS OF 5-SUBSTITUTED 1(2)-VINYLTETRAZOLES
1883
Scheme 1.
CH2
H
R
R
R
CH2
N
Et3N, MeCN
N
N
N
N
Br
+
+
N
N
N
Br
–2Et3NH· HBr
N
N
N
N
Ia–Ii
Va–Vi
VIIa–VIIi
R = Ph (a), p-MeC6H4 (b), p-F3CC6H4 (c), o-NCC6H4 (d), Me (e), Et (f), CH2=CH (g), H2N (h), H (i).
be regarded as the most efficient for the synthesis of
N-vinyltetrazoles; it ensures high yields of target
compounds and does not require the use of difficultly
accessible and toxic reagents. According to [17],
vinylation of 5-aryl and 5-alkyltetrazoles gives only
one regioisomer, 2-vinyl-5-R-tetrazole. However, the
results of studying the kinetics, selectivity, and mech-
anism of alkylation of salts derived from NH-5-R-
tetrazoles with various electrophiles indicated the
possibility for formation of isomeric N-substituted
5-R-tetrazoles even if R = Ar [18, 19]. Obviously, the
procedure described in [17] requires further study.
The regioselectivity in the vinylation of 5-R-tetra-
zoles is determined at the stage of alkylation of salts
IIa–IIi with 2-bromoethyl(triethyl)ammonium
bromide (III), which leads to the formation of isomeric
tetrazoles IVa–IVi and VIa–VIi. Elimination of tri-
ethylammonium bromide from compounds IVa–IVi
and VIa–VIi yields vinyltetrazoles Va–Vi and VIIa–
VIIi (Scheme 2).
In the vinylation of 5-aryltetrazoles, the ratio of
1- and 2-vinyl derivatives was 5:95 (according to the
1H NMR data); if R is a relatively small group (R =
Alk, CH-=CH, NH2, H), the fraction of 1-vinyl-substi-
tuted isomer increases, and the ratio V:VII attains
40:60. Our results are consistent with the data ob-
tained previously [18] by studying the kinetics, selec-
tivity, and mechanism of alkylation of 5-aryltetrazole
salts with ethyl bromoacetate in acetonitrile.
For this purpose, we reproduced the conditions
reported in [17] for the vinylation of 5-substituted
tetrazoles with 1,2-dibromoethane. As model sub-
strates we selected tetrazoles Ia–Ii. The conversion of
initial compounds Ia–Ii and accumulation of final
products Va–Vi and VIIa–VIIi were monitored by
Roh et al. [17] detected dimeric products in the
reaction mixtures obtained by vinylation of 5-R-tetra-
zoles. Such by-products can be formed due to the pres-
ence of two electrophilic centers in the alkylating
agent. In the present work no by-products were
detected in the reaction mixtures.
1
TLC and H NMR spectroscopy (Scheme 1). The
results showed that the alkylation of all 5-R-tetrazoles
Ia–Ii with 1,2-dibromoethane (2 equiv) in the presence
of Et3N (4 equiv) in acetonitrile gives regioisomeric
1(2)-vinyl-5-R-tetrazoles Va–Vi and VIIa–VIIi.
Scheme 2.
H
N
R
R
N
N
MeCN
+
+
Et3N
Et3N
Et3NH
NEt3
N
N
N
N
N
Ia–Ii
IIa–IIi
MeCN
Br–
Br
Br
Br
III
NEt3 Br–
R
R
NEt3 Br–
N
N
N
N
MeCN
IIa–IIi
+
III
+
N
N
–Et3NH·HBr
N
N
IVa–IVi
–Et3NH·HBr
VIa–VIi
–Et3NH·HBr
Va–Vi
VIIa–VIIi
R = Ph (a), p-MeC6H4 (b), p-F3CC6H4 (c), o-NCC6H4 (d), Me (e), Et (f), CH2=CH (g), H2N (h), H (i).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

ALESHUNIN et al.
1884
Scheme 3.
H2C
H
H
CH2
N
N
N
N
N
N
Et3N, MeCN
Br
+
+
N
N
N
N
N
N
Br
–4Et3NH·HBr
N
N
N
N
N
N
H2C
H2C
N
N
N
N
N
N
VIII
IX
X
Scheme 4.
Et3N, MeCN
N
N
N
N
Br
+
N
N
N
N
Br
–4Et3NH·HBr
NH
HN
N
N
H2C
CH2
N
N
N
N
XI
XII
CH2
N
N
+
N
N
N
N
H2C
N
N
XIII
We then tried to extend the above procedure for the
vinylation of mononuclear 5-R-tetrazoles to dinuclear
substrates, bis(1H-tetrazol-5-yl)methane (VIII) and
1,3-bis(1H-tetrazol-5-yl)benzene (XI). Taking into
account the presence of two tetrazole rings in mole-
cules VIII and XI, the reactions were carried out using
4 equiv of 1,2-dibromoethane and 8 equiv of triethyl-
amine, other conditions being equal. In both cases,
mixtures of regioisomeric vinyltetrazoles IX/X and
XII/XIII were formed, and the reactions involved
positions 2,2′ and 1,2′ of the dinuclear substrate. No
1,1′-divinyl isomers were detected (Schemes 3, 4).
According to the 1H NMR data, the ratio of 2,2′ and
1,2′ isomers was 63:37 (IX:X) or 70:30 (XII:XIII).
The complete conversion of dinuclear tetrazoles VIII
and XI required a longer time (up to 25 h) as compared
to mononuclear derivatives Ia–Ii. Compounds IX, X,
XII, and XIII were isolated and purified by column
chromatography on silica gel. Their yields were not
high, presumably due to their poor solubility in
solvents used as eluents for column chromatography.
In the vinylation of bis-tetrazole XI we isolated and
identified dimeric product XIV (yield 2%).
Thus the described procedure is applicable to the
synthesis of N-vinyl derivatives of dinuclear tetrazoles;
it ensures preparation of regioisomeric 1,2′- and
2,2′-substituted compounds.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
a Bruker DPX-300 spectrometer at 300.1 and
75.5 MHz, respectively, using the residual proton and
carbon signals of deuterated solvents as reference
(DMSO-d6, δ 2.50, δC 39.52 ppm; CDCl3, δ 7.26,
δC 77.16 ppm). The mass spectrum was obtained on
a Waters LCT Premier (ESI, TOF) LC–MS system.
The elemental compositions were determined on
a Hewlett–Packard 185 automatic analyzer. The melt-
ing points were measured on a PTP melting point ap-
paratus; samples were heated at a rate of 1 deg/min in
the vicinity of melting point. The purity of the products
was checked by TLC on Kieselgel 60F245 plates
(Merck). Column chromatography was performed on
Silicagel 60 (0.063–0.200 mm, Merck). The ratio of
regioisomeric 1- and 2-vinyltetrazoles in the reaction
mixtures were determined by 1H NMR spectroscopy.
H2C
N
The properties of compounds Ia–Ii, VIII, and XI
were consistent with published data [20].
H2C
N
N
N
N
N
N
N
Vinylation of 5-R-tetrazoles (general procedure).
A solution of 46.4 mmol of 1,2-dibromoethane in
15 ml of acetonitrile was heated to the boiling point,
and a solution of 23.2 mmol of tetrazole Ia–Ii, VIII, or
XI and 50 mmol of triethylamine in 50 ml of aceto-
N
N
N
N
N
N
N
N
XIV
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

VINYLTETRAZOLES: II. SYNTHESIS OF 5-SUBSTITUTED 1(2)-VINYLTETRAZOLES
1885
nitrile was added under stirring over a period of 3 h.
The mixture was heated for 8 h under reflux, and the
resulting suspension was cooled and filtered from tri-
ethylamine hydrobromide. The filtrate was evaporated
to dryness under reduced pressure, the residue was
dispersed in appropriate solvent system which was
then used as eluent for column chromatography (in-
dicated below for each compound), and the precipitate
was filtered off. The filtrate was evaporated to dryness
under reduced pressure, and the residue (a mixture
of regioisomeric vinyltetrazoles) was separated by
column chromatography on silica gel.
C 64.20; H 5.63; N 30.17. C10H10N4. Calculated, %:
C 64.50; H 5.41; N 30.09.
5-(4-Methylphenyl)-1-vinyl-1H-tetrazole (VIIb).
Yield 0.04 g (1%), colorless crystals. Rf 0.2 (hexane–
1
ethyl acetate, 7:3). H NMR spectrum (CDCl3), δ,
ppm: 2.42 s (1H, CH3), 5.40 d (1H, CH2=, J =
8.83 Hz), 6.15 d (1H, CH2=, J = 15.44 Hz), 7.05 d.d
(1H, =CH, J = 8.83, 15.44 Hz), 7.34 d and 7.56 d (2H
each, C6H4).
5-[4-(Trifluoromethyl)phenyl]-2-vinyl-2H-tetra-
zole (Vc). Yield 4.6 g (83%), colorless crystals,
1
mp 44°C, Rf 0.9 (hexane–ethyl acetate, 6:4). H NMR
In the vinylation of tetrazoles VIII and XI, the
residue obtained after first evaporation of the reaction
mixture was extracted with chloroform under TLC
monitoring. The combined extracts were dried over
anhydrous sodium sulfate and evaporated to dryness
under reduced pressure. The residue was separated by
column chromatography on silica gel.
spectrum (CDCl3), δ, ppm: 5.41–5.44 m (1H, CH2=,
J = 7.36 Hz), 6.26 d (1H, CH2=, J = 14.71 Hz),
7.54 d.d (1H, =CH, J = 7.36, 14.71 Hz), 7.56 d and
13
8.29 d (2H each, C6H4). C NMR spectrum, δC, ppm:
109.16 (CH2=); 125.44 q (CF3, J = 5.19 Hz); 125.97,
126.02, 127.46, 132.42 (C6H4); 129.84 (=CH), 163.78
(C5). Found, %: C 50.21; H 3.10; N 23.00. C10H7N4F3.
Calculated, %: C 50.01; H 2.94; N 23.33.
In the vinylation of 5-vinyltetrazole (Ig) 0.2 g of
hydroquinone was added to the reaction mixture.
5-[4-(Trifluoromethyl)phenyl]-1-vinyl-1H-tetra-
zole (VIIc). Yield 0.1 g (2%), colorless crystals,
mp 79–80°C, Rf 0.1 (hexane–ethyl acetate, 6:4).
1H NMR spectrum (CDCl3), δ, ppm: 5.50 d (1H, CH2=,
J = 8.09 Hz), 6.19 d.d (1H, CH2=, J = 1.47, 13.97 Hz),
7.05 d.d (1H, =CH, J = 8.09, 13.97 Hz), 7.84 m (4H,
C6H4). 13C NMR spectrum, δC, ppm: 112.45 (CH2=);
124.40 q (CF3, J = 5.18 Hz); 125.32, 125.94, 126.44,
133.42 (C6H4); 129.87 (=CH), 151.96 (C5).
5-Phenyl-2-vinyl-2H-tetrazole (Va). Yield 3.4 g
(85%), colorless crystals, mp 41°C, Rf 0.8 (hexane–
ethyl acetate, 7:3). H NMR spectrum (CDCl3), δ,
ppm: 5.35 d (1H, CH2=, J = 8.82 Hz), 6.22 d (1H,
CH2=, J = 16.18 Hz), 7.45 m (3H, C6H5), 7.51 d.d (1H,
=CH, J = 8.82, 16.18 Hz), 8.14 t (2H, C6H5). 13C NMR
spectrum, δC, ppm: 108.52 (CH2=); 127.02, 127.16,
129.02, 130.73 (C6H5); 129.87 (=CH); 164.97 (C5).
Found, %: C 62.09; H 5.90; N 32.01. C9H8N4. Calcu-
lated, %: C 62.78; H 4.68; N 32.54.
1
2-(2-Vinyl-2H-tetrazol-5-yl)benzonitrile (Vd).
Yield 3.4 g (75%), colorless crystals, mp 95–96°C,
Rf 0.8 (methylene chloride–methanol, 9:1). 1H NMR
spectrum (CDCl3), δ, ppm: 5.48 d (1H, CH2=, J =
8.83 Hz), 6.38 d (1H, CH2=, J = 15.45 Hz), 7.57–
7.63 m (2H, =CH, Harom), 7.67 d (1H, Harom), 7.75 m
(1H, Harom), 8.32 d (1H, Harom). 13C NMR spectrum, δC,
ppm: 110.41 (CH2=), 117.37 (CN); 128.25, 130.27,
131.43, 133.87, 135.11 (C6H4); 129.43 (=CH), 161.71
(C5). Found, %: C 60.50; H 4.60; N 34.90. C10H7N5.
Calculated, %: C 60.91; H 3.58; N 35.51.
5-Phenyl-1-vinyl-1H-tetrazole (VIIa). Yield
0.23 g (6%), colorless crystals, mp 105°C, Rf 0.1
1
(hexane–ethyl acetate, 7 : 3). H NMR spectrum
(CDCl3), δ, ppm: 5.43 d (1H, CH2=, J = 8.71 Hz),
6.18 d (1H, CH2=, J = 15.26 Hz), 7.07 d.d (1H, =CH,
J = 8.71, 15.25 Hz), 7.55 m (3H, C6H5), 7.68 m (2H,
C6H5). 13C NMR spectrum, δC, ppm: 111.29 (CH2=);
123.44, 129.33, 129.42, 131.71 (C6H5); 126.26 (=CH),
153.10 (C5). Found, %: C 62.15; H 4.20; N 33.65.
C9H8N4. Calculated, %: C 62.78; H 4.68; N 32.54.
2-(1-Vinyl-1H-tetrazol-5-yl)benzonitrile (VIId).
Yield 0.05 g (1%), colorless crystals, Rf 0.1 (methylene
chloride–methanol, 9:1). H NMR spectrum (CDCl3),
δ, ppm: 5.44 d.d (1H, CH2=, J = 1.47, 7.36 Hz), 6.10 d
(1H, CH2=CH, J = 16.91 Hz), 6.93 d.d (1H, =CH, J =
7.36, 16.91 Hz), 7.67 d (1H, Harom), 7.77 m (1H,
Harom), 7.82 m (1H, Harom), 7.85 d (1H, Harom).
5-(4-Methylphenyl)-2-vinyl-2H-tetrazole (Vb).
Yield 3.2 g (75%), colorless crystals, mp 40–41°C,
1
1
Rf 0.7 (hexane–ethyl acetate, 7:3). H NMR spectrum
(CDCl3), δ, ppm: 2.38 s (3H, CH3), 5.33 d (1H, CH2=,
J = 8.82 Hz), 6.23 d (1H, CH2=, J = 16.92 Hz), 7.27 d
(2H, C6H4), 7.51 d.d (1H, =CH, J = 8.82, 16.92 Hz),
8.04 d (2H, C6H4). 13C NMR spectrum, δC, ppm: 21.59
(CH3), 108.26 (CH2=); 124.20, 129.70, 129.86, 140.93
(C6H4); 127.07 (=CH), 165.04 (C5). Found, %:
5-Methyl-2-vinyl-2H-tetrazole (Ve). Yield 0.6 g
(25%), light yellow oily liquid, Rf 0.8 (hexane–ethyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

ALESHUNIN et al.
1886
1
acetate, 4:6). H NMR spectrum (CDCl3), δ, ppm:
2.55 s (3H, CH3), 5.29 d (1H, CH2=, J = 8.83 Hz),
6.10 d (1H, CH2=, J = 16.18 Hz), 7.44 d.d (1H, =CH,
J = 8.83, 16.18 Hz). 13C NMR spectrum, δC, ppm:
10.79 (CH3), 107.83 (CH2=), 129.66 (=CH), 162.87
(C5). Found, %: C 43.50; H 6.10; N 50.40. C4H6N4.
Calculated, %: C 43.6; H 5.49; N 50.88.
1,5-Divinyl-1H-tetrazole (VIIg). Yield 0.7 g
(25%), light yellow oily liquid, Rf 0.6 (hexane–
methylene chloride–ethyl acetate, 4:4:2). H NMR
1
spectrum (DMSO-d6), δ, ppm: 5.47 d (1H, CH2=CHN,
J = 8.82 Hz), 5.99 m (2H, CH2=CHC, CH2=CHN),
6.47 d (1H, CH2=CHC, J = 11.03 Hz), 7.00 d.d (1H,
5-CH, J = 11.03, 15.45 Hz), 7.55 d.d (1H, 1-CH, J =
13
8.82, 15.44 Hz). C NMR spectrum, δC, ppm: 111.00
5-Methyl-1-vinyl-1H-tetrazole (VIIe). Yield 0.8 g
(30%), light yellow oily liquid, Rf 0.2 (hexane–ethyl
(CH2=CHN), 122.60 (CH2=CHC), 123.80 (5-CH),
126.30 (1-CH), 151.09 (C5). Found, %: C 49.30;
H 5.07; N 45.63. C5H6N4. Calculated, %: C 49.17;
H 4.95; N 45.88.
1
acetate, 4:6). H NMR spectrum (CDCl3), δ, ppm:
2.53 s (3H, CH3), 5.34 d (1H, CH2=, J = 8.83 Hz),
5.95 d (1H, CH2=, J = 15.44 Hz), 6.97 d.d (1H, =CH,
J = 8.83, 15.44 Hz). 13C NMR spectrum, δC, ppm:
9.26 (CH3), 110.36 (CH2=), 125.43 (=CH), 150.47
(C5). Found, %: C 43.80; H 5.16; N 51.04. C4H6N4.
Calculated, %: C 43.63; H 5.49; N 50.88.
2-Vinyl-2H-tetrazol--5-amine (Vh). Yield 1.3 g
(53%), colorless crystals, mp 47–49°C, Rf 0.8 (hex-
ane–ethyl acetate, 1:1). 1H NMR spectrum (CDCl3), δ,
ppm: 4.69 br.s (2H, NH2), 5.18 d (1H, CH2=, J =
8.83 Hz), 5.92 d (1H, CH2=, J = 15.44 Hz), 7.32 d.d
(1H, =CH, J = 8.83, 15.44 Hz). 13C NMR spectrum δC,
ppm: 106.35 (CH2=), 129.63 (=CH), 166.09 (C5).
Found, %: C 32.22; H 4.21; N 63.57. C3H5N5. Calcu-
lated, %: C 32.43; H 4.54; N 63.03.
5-Ethyl-2-vinyl-2H-tetrazole (Vf). Yield 1.2 g
(40%), light yellow oily liquid, Rf 0.8 (hexane–ethyl
1
acetate, 8:2). H NMR spectrum (CDCl3), δ, ppm:
1.39 t (3H, CH2CH3), 2.29 m (2H, CH2CH3), 5.30 d
(1H, CH2=, J = 8.82 Hz), 6.14 d (1H, CH2=, J =
15.44 Hz), 7.47 d.d (1H, =CH, J = 8.82, 15.44 Hz).
13C NMR spectrum, δC, ppm: 12.36 (CH2CH3), 19.15
(CH2CH3), 108.01 (CH2=), 129.88 (=CH), 168.00 (C5).
Found, %: C 48.20; H 6.22; N 45.58. C5H8N4. Cal-
culated, %: C 48.37; H 6.50; N 45.13.
1-Vinyl-1H-tetrazol-5-amine (VIIh). Yield 0.5 g
(18%), light yellow crystals, mp 158°C, Rf 0.3 (hex-
ane–ethyl acetate, 1:1). 1H NMR spectrum (CDCl3), δ,
ppm: 4.96 br.s (2H, NH2), 5.34 d (1H, CH2=, J =
8.09 Hz), 5.83 d (1H, CH2=, J = 15.45 Hz), 6.92 d.d
(1H, =CH, J = 8.09, 15.45 Hz). 13C NMR spectrum,
δC, ppm: 104.22 (CH2=), 124.53 (=CH), 153.27 (C5).
Found, %: C 32.40; H 4.65; N 62.95. C3H5N5. Cal-
culated, %: C 32.43; H 4.54; N 63.03.
5-Ethyl-1-vinyl-1H-tetrazole (VIIf). Yield 1.2 g
(40%), light yellow oily liquid, Rf 0.1 (hexane–ethyl
1
acetate, 8:2). H NMR spectrum (CDCl3), δ, ppm:
1.41 t (3H, CH2CH3), 2.90 m (2H, CH2CH3), 5.37 d
(1H, CH2=, J = 8.83 Hz), 6.03 d (1H, CH2=, J =
15.45 Hz), 6.99 d.d (1H, =CH, J = 8.83, 15.45 Hz).
13C NMR spectrum, δC, ppm: 11.32 (CH2CH3), 17.16
(CH2CH3), 110.32 (CH2=), 125.26 (=CH), 154.79 (C5).
Found, %: C 48.70; H 6.20; N 45.10. C5H8N4. Calcu-
lated, %: C 48.37; H 6.50; N 45.13.
2-Vinyl-2H-tetrazole (Vi). Yield 0.6 g (30%), light
yellow oily liquid, Rf 0.6 (hexane–ethyl acetate, 1:1).
1H NMR spectrum (CDCl3), δ, ppm: 5.39 d (1H,
CH2=, J = 8.82 Hz), 6.23 d (1H, CH2=, J = 15.44 Hz),
7.54 d.d (1H, =CH, J = 8.82, 15.44 Hz). 13C NMR
spectrum, δC, ppm: 109.15 (CH2=), 129.06 (=CH),
153.41 (C5). Found, %: C 35.70; H 4.47; N 59.83.
C3H4N4. Calculated, %: C 35.50; H 4.20; N 58.31.
2,5-Divinyl-2H-tetrazole (Vg). Yield 1.7 g (60%),
colorless crystals, mp 35–37°C, Rf 0.9 (hexane–meth-
1-Vinyl-1H-tetrazole (VIIi). Yield 1.0 g (45%),
light yellow oily liquid, Rf 0.2 (hexane–ethyl acetate,
1
ylene chloride–ethyl acetate, 4:4:2). H NMR spec-
1
1:1). H NMR spectrum (CDCl3), δ, ppm: 5.40 d (1H,
trum (DMSO-d6), δ, ppm: 5.47 d (1H, CH2=CHN, J =
8.86 Hz), 5.77 d (1H, CH2=CHC, J = 8.86 Hz), 6.10 d
(1H, CH2=CHN, J = 15.75 Hz), 6.37 d (1H,
CH2=CHC, J = 15.75 Hz), 6.84 d.d (1H, 5-CH, J =
8.86, 15.75 Hz), 7.75 d.d (1H, 2-CH, J = 8.86,
15.75 Hz). 13C NMR spectrum, δC, ppm: 109.23
(CH2=CHN), 122.67 (CH2=CHC), 123.62 (5-CH),
130.22 (2-CH), 163.10 (C5). Found, %: C 49.50;
H 5.00; N 45.50. C5H6N4. Calculated, %: C 49.17;
H 4.95; N 45.88.
CH2=, J = 8.71 Hz), 5.98 d (1H, CH2=, J = 15.25 Hz),
7.30 d.d (1H, =CH, J = 8.71, 15.25 Hz). 13C NMR
spectrum, δC, ppm: 109.66 (CH2=), 127.20 (=CH),
141.98 (C5). Found, %: C 35.55; H 4.35; N 60.1.
C3H4N4. Calculated, %: C 35.50; H 4.20; N 58.31.
5,5′-Methylenebis(2-vinyl-2H-tetrazole) (IX).
Yield 1.4 g (30%), light yellow crystals, mp 53–54°C,
Rf 0.6 (methylene chloride–hexane–ethyl acetate,
8:1:1). 1H NMR spectrum (DMSO-d6), δ, ppm: 4.72 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

VINYLTETRAZOLES: II. SYNTHESIS OF 5-SUBSTITUTED 1(2)-VINYLTETRAZOLES
1887
(2H, CH2), 5.51 d (2H, CH2=, J = 8.72 Hz), 6.10 d
(2H, CH2=, J = 15.99 Hz), 7.83 d.d (2H, =CH, J =
8.72, 15.99 Hz). 13C NMR spectrum, δC, ppm: 22.04
(CH2), 109.58 (CH2=), 130.14 (=CH), 162.08 (C5).
Found, %: C 41.10; H 4.19; N 54.71. C7H8N8. Cal-
culated, %: C 41.17; H 3.95; N 54.88.
15.26 Hz), 7.70 m (2H, Harom), 7.87 d.d (2H, =CH, J =
8.72, 15.26 Hz), 8.12–8.19 m (4H, Harom), 8.61 s (2H,
arom). 13C NMR spectrum, δC, ppm: 51.94 (CH2),
H
109.75 (CH2=), 128.44 (=CH); 124.13, 127.22, 127.51,
128.51, 130.18, 130.43 (Carom); 163.25 (C5), 163.64
(C5′). Mass spectrum: m/z 507.48 [M + H]+. M 506.49.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 10-03-00700-a, 11-08-00757-a).
1-Vinyl-5-(2-vinyl-2H-tetrazol-5-ylmethyl)-1H-
tetrazole (X). Yield 0.9 g (20%), light yellow crystals,
mp 46–47°C, Rf 0.2 (methylene chloride–hexane–ethyl
1
acetate, 8:1:1). H NMR spectrum (DMSO-d6), δ,
REFERENCES
ppm: 4.91 s (2H, CH2), 5.48–5.54 m and 6.01–6.12 m
(2H each, 1-CH=CH2, 2′-CH=CH2), 7.48 d.d (1H,
1-CH, J = 8.02, 14.21 Hz), 7.84 d.d (1H, 2′-CH, J =
1. Ostrovskii, V.A., Aleshunin, P.A., Zubarev, V.Yu.,
Popova, E.A., Pavlyukova, Yu.N., Shumilova, E.A.,
Trifonov, R.E., and Artamonova, T.V., Russ. J. Org.
Chem., 2010, vol. 46, p. 1678.
13
8.72, 15.99 Hz). C NMR spectrum, δC, ppm: 20.01
(CH2), 109.77 (2′-CH=CH2), 110.31 (1-CH=CH2),
126.52 (1-CH), 130.12 (2′-CH), 153.41 (C5), 160.81
(C5′). Found, %: C 41.60; H 3.90; N 54.50. C7H8N8.
Calculated, %: C 41.17; H 3.95; N 54.88.
2. Kizhnyaev, V.N. and Vereshchagin, L.I., Usp. Khim.,
2003, vol. 72, p. 159.
3. Ostrovskii, V.A., Koldobskii, G.I., and Trifonov, R.E.,
Comprehensive Heterocyclic Chemistry III, Katritz-
ky, A.R., Ramsden, C.A., Scriven, E.F.V., and
Taylor, R.J.K., Eds., Amsterdam: Elsevier, 2008, vol. 6,
p. 257.
5,5′-(Benzene-1,3-diyl)bis(2-vinyl-2H-tetrazole)
(XII). Yield 3.6 g (59%), colorless crystals, mp 130–
131°C, Rf 0.7 (methylene chloride–hexane–ethyl
1
acetate, 8.5:1:0.5). H NMR spectrum (DMSO-d6), δ,
4. Ostrovskii, V.A., Zubarev, V.Yu., Putis, S.M., Trifo-
nov, R.E., Popova, E.A., Pinchuk, L.S., and Makare-
vich, A.V., Khim. Promst., 2005, vol. 82, p. 605.
5. Uspenskaya, M.V., Tetrazolsoderzhashchie akrilovye
polimery (Tetrazole-Containing Acrylic Monomers),
St. Petersburg: ITMO, 2008, p. 110.
6. Ostrovskii, V.A., Pevzner, M.S., Kofman, T.P., Shcher-
binin, M.B., and Tselinskii, I.V., Targets in Heterocyclic
Systems: Chemistry and Properties: Reviews and
Accounts on Heterocyclic Chemistry, Attanasi, O.A. and
Spinelli, D., Rome: Ital. Soc. Chem., 1999, vol. 3,
p. 4677.
7. Kizhnyaev, V.N. and Vereshchagin, L.I., Viniltetrazoly
(Vinyltetrazoles), Irkutsk: Irkutsk. Gos. Univ., 2003,
p. 41.
ppm: 5.58 d (2H, CH2=, J = 8.72 Hz), 6.23 d (2H,
CH2=, J = 15.26 Hz), 7.75 m (1H, C6H4), 7.90 d.d (2H,
=CH, J = 8.72, 15.26 Hz), 8.21 d (2H, C6H4), 8.71 s
(1H, C6H4). 13C NMR spectrum, δC, ppm: 109.82
(CH2=); 124.33, 127.24, 130.24, 130.47 (C6H4);
128.76 (=CH); 163.28 (C5). Found, %: C 54.27;
H 3.45; N 42.28. C12H10N8. Calculated, %: C 54.13;
H 3.79; N 42.08.
1-Vinyl-5-[3-(2-vinyl-2H-tetrazol-5-yl)phenyl]-
1H-tetrazole (XIII). Yield 0.9 g (15%), colorless
crystals, mp 146–147°C, Rf 0.5 (methylene chloride–
1
hexane–ethyl acetate, 8.5:1:0.5). H NMR spectrum
(DMSO-d6), δ, ppm: 5.60 d (2H, 2′-CH=CH2,
1-CH=CH2, J = 8.72 Hz), 6.08 d (1H, 1-CH=CH2, J =
15.26 Hz), 6.27 d (1H, 2′-CH=CH2, J = 16.71 Hz),
7.41 d.d (1H, 1-CH, J = 8.72, 15.26 Hz), 7.83–7.89 m
(3H, 2′-CH, Harom), 8.37 d (2H, Harom), 8.48 s (1H,
8. Aleshunin, P.A., Esikov, K.A., and Ostrovskii, V.A.,
Khim. Geterotsikl. Soedin., 2010, p. 1733.
9. Klapötke, T.M. and Sproll, S.M., Eur. J. Org. Chem.,
H
arom). 13C NMR spectrum, δC, ppm: 110.03
2010, p. 1170.
10. Buzilova, S.R., Shul’gina, V.M., Sakovich, G.V., and
Vereshchagin, L.I., Khim. Geterotsikl. Soedin., 1980,
p. 842.
11. Gaponik, P.N., Ivashkevich, O.A., and Degtyarik, M.M.,
Izv. Vyssh. Uchebn. Zaved., Ser. Khim. Khim. Tekhnol.,
1985, vol. 28, p. 43.
12. Vereshchagin, L.I., Buzilova, S.R., Mityukova, T.K.,
Proidakov, A.G., Kizhnyaev, V.N., Sukhanov, G.T.,
Gareev, G.A., and Bogens, A.K., Zh. Org. Khim., 1986,
vol. 22, p. 1979.
(2′-CH=CH2), 112.52 (1-CH=CH2), 124.42 (1-CH),
129.40 (2′-CH); 127.28, 130.30, 130.47, 131.57
(C6H4); 152.21 (C5), 163.16 (C5′). Found, %: C 54.23;
H 3.75; N 42.02. C12H10N8. Calculated, %: C 54.13;
H 3.79; N 42.08.
1,2-Bis{5-[3-(2-vinyl-2H-tetrazol-5-yl)phenyl]-
2H-tetrazol-2-yl}ethane (XIV). Yield 0.1 g (2%),
colorless crystals, mp 204–205°C, Rf 0.3 (methylene
1
chloride–hexane–ethyl acetate, 8.5:1:0.5). H NMR
spectrum (DMSO-d6), δ, ppm: 5.48 s (4H, CH2), 5.55 d
(2H, CH2=, J = 8.72 Hz), 6.18 d (2H, CH2=, J =
13. Taillefer, M., Ouali, A., Renard, B., and Spindler, J.-F.,
Chem. Eur. J., 2006, vol. 12, p. 5301.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011

ALESHUNIN et al.
1888
18. Ostrovskii, V.A. and Koren, A.O., Heterocycles, 2000,
vol. 53, p. 1421.
14. Zhu, L., Guo, P., Li, G., Lan, J., Xie, R., and You, J.,
J. Org. Chem., 2007, vol. 72, p. 8535.
19. Pavlyukova, Yu.N., Trifonov, R.E., Yugai, E.V., Aleshu-
nin, P.A., Tselinskii, I.V., and Ostrovskii, V.A., Russ. J.
Org. Chem., 2008, vol. 44, p. 1711.
20. Vereshchagin, L.I., Kizhnyaev, V.N., and Pokati-
lov, F.A., Nekondensirovannye tetrazoly: spravochnoe
izdanie (Non-Fused Tetrazoles: Reference Book),
Irkutsk: Irkut. Gos. Univ., 2007, p. 8.
15. Fleming, A., Kellehera, F., Mahonb, M.F., McGinley, J.,
and Prajapati, V., Tetrahedron, 2005, vol. 61, p. 7002.
16. Bond, A.D., Fleming, A., Kelleher, F., McGinley, J., and
Prajapati, V., Tetrahedron, 2006, vol. 62, p. 9577.
17. Roh, J., Vávrová, K., and Hrabálek, A., Tetrahedron
Lett., 2010, vol. 51, p. 1411.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 12 2011