Geminally activated nitroethenes in reactions with sodium azide. Synthesis of functionalized 1,2,3-triazoles

Article abstract of DOI:10.1134/S1070363216060086

Reactions of geminally activated alkoxycarbonyl(acetyl, benzoyl, cyano)nitroethenes with sodium azide provided a series of functionally substituted 1,2,3-triazoles. Their structure was characterized by IR, ¹H, and ¹³C–{¹H}

Full text of DOI:10.1134/S1070363216060086

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 6, pp. 1266–1273. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.M. Berestovitskaya, R.I. Baichurin, N.I. Aboskalova, L.V. Baichurina, E.V. Trukhin, A.V. Fel’gendler, M.A. Gensirovskaya, 2016,
published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 6, pp. 936–943.
Geminally Activated Nitroethenes in Reactions
with Sodium Azide. Synthesis of Functionalized 1,2,3-Triazoles
V. M. Berestovitskayaa, R. I. Baichurina, N. I. Aboskalovaa, L. V. Baichurinab,
E. V. Trukhina, A. V. Fel’gendlerb, and M. A. Gensirovskayaa
a Herzen State Pedagogical University of Russia, nab. reki Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
b Kirov Military Medical Academy, St. Petersburg, Russia
Received January 28, 2016
Abstract—Reactions of geminally activated alkoxycarbonyl(acetyl, benzoyl, cyano)nitroethenes with sodium
1
azide provided a series of functionally substituted 1,2,3-triazoles. Their structure was characterized by IR, H,
and 13C–{1H} NMR spectroscopy.
Keywords: geminally activated nitroalkenes, 2-nitroacrylates, gem-acylnitroethenes, 2-nitroacrylonitriles, sodium
azide, 1,2,3-triazoles
DOI: 10.1134/S1070363216060086
Conjugated nitroethenes are highly reactive com-
pounds and convenient synthons for different classes
of organic substances [1]. The introduction of ester,
nitrile or acyl groups into the gem-position to the nitro
function broadens significantly the range of synthetic
possibilities of these unsaturated nitro compounds as a
result of increasing electrophilicity of the double bond
and the possibility of participation of substituents in
additional transformations [2].
preparation of cyano-containing 1,2,3-triazoles by the
reaction of gem-cyanonitroethenes with sodium azide;
some of them could be synthesized only by using
sodium trimethylsilyl azide instead of sodium azide
[13, 14]. This reagent has been also successfully
applied to the synthesis of 4-alkoxycarbonyl-5-aryl-
1,2,3-triazoles [13, 15].
Increased interest in the 1,2,3-triazoles is due to a
wide range of their practically useful properties. Many
of them show antifungal, antimicrobial, and antiviral
activity [3, 16–21]. For example, 5-(4-bromophenyl)-
4-nitro-1,2,3-triazole and its p-nitrophenyl analog
exhibit tuberculostatic and antifungal activity [3].
Structures of Tazobactam and Cefatrizine antibiotics
contain a triazole ring [17]. 1,2,3-Triazole derivatives
are used as herbicides, light stabilizers and optical
brighteners. Therefore, the search for a simple and
convenient preparative method of the synthesis of
substituted 1,2,3-triazoles containing ester, nitrile, or
acyl groups is very important.
Reactions of [4π + 2π] cycloaddition are of
particular interest where the geminally activated
nitroethenes serve as dieno- or dipolarophiles and
which may result in functionalized carbocyclic and
heterocyclic structures. It is known that electron
deficient nitroethenes like gem-bromonitrostyrenes [3,
4] and gem-dinitrostyrenes [5] react readily with
inorganic 1,3-dipole sodium azide. The originally
formed 1,2,3-triazolines underwent aromatization by
dehydrobromination or denitration to form nitro-
containing 1,2,3-triazoles. Similar reactions of gem-
acylnitroethenes of furan, thiophene and indole series,
as well as two spicemens of gem-acetylnitrostyrenes
Here we report on the synthesis of functionally
substituted 1,2,3-triazoles by reacting gem-activated
nitroethenes 1–14 containing ethoxycarbonyl, acetyl,
benzoyl, or nitrile function with sodium azide.
afforded
4-acyl-1,2,3-triazoles
[6–10].
Some
alkoxycarbonyl-substituted 1,2,3-triazoles were ob-
tained reacting α-nitrocinnamic esters as well as their
indole and furan analogs with sodium azide [10–12]. It
should be noted that no information exists on the
Starting β-aryl-α-nitroacrylates 1, 2 [22], 4 [23],
gem-acetylnitrostyrenes 5 [24], 6, 7 [25, 26], gem-
1266

GEMINALLY ACTIVATED NITROETHENES IN REACTIONS WITH SODIUM AZIDE
1267
Scheme 1.
O
H
NO2
X
R
NO2
X
C6H6, AcOH, β-Ala, Δ
+
R
3, 11, 12
X = COOEt, R = 4-BrC6H4 (3); X = C(O)Ph, R = 4-ClC6H4 (11), 4-BrC6H4 (12).
Scheme 2.
R
X
R
NO2
X
5
4
DMSO (DMF)
NaN3
+
N1
N
3
2
N
H
1_14
15_28
X = COOEt, R = 4-Me2NC6H4 (1, 15), 4-ClC6H4 (2, 16), 4-BrC6H4 (3, 17), 4-O2NC6H4 (4, 18); X = C(O)Me,
R = 4-Me2NC6H4 (5, 19), 4-ClC6H4 (6, 20), 4-O2NC6H4 (7, 21); X = C(O)Ph, R = Ph (8, 22), 4-MeOC6H4 (9, 23),
4-Me2NC6H4 (10, 24), 4-ClC6H4 (11, 25), 4-BrC6H4 (12, 26); X = CN, R = 4-MeOC6H4 (13, 27), 1-Me-3-indolyl (14, 28).
benzoylnitrostyrenes 10, 8 [24, 27], and gem-
cyanonitroethenes 13 [28], 14 [29] were prepared by
the known procedures.
brought into the reaction of 1,3-dipolar cycloaddition
with sodium azide (2–4 mol) in DMSO or DMF; yields
of the desired 1,2,3-triazoles 15–28 reached 86%. In
most cases (with the initial nitroalkenes 2–4, 6–9, 11–
14), the reaction proceeded at room temperature.
α-Nitroacrylate 1 and gem-acylnitroethenes 5, 10
bearing para-dimethylamino-substituted benzene ring
reacted at heating (Scheme 2).
Substituted gem-nitroethenes 3, 11, 12 were
synthesized by boiling mixtures of the corresponding
aldehydes and nitro-containing CH acids (ethyl
nitroacetate or nitroacetophenone) in benzene in the
presence of acetic acid and β-alanine similar to the
procedures reported in [22, 27, 30]. 1-Benzoyl-2-(4-
bromophenyl)-1-nitroethene 12 was obtained for the
first time (Scheme 1).
Melting points of 1,2,3-triazoles 16, 18, 22, 23, 27
corresponded to those for samples obtained by the
other methods [13, 16, 36–38]. Compounds 15, 19–21,
24–26, 28 were synthesized for the first time.
Compound 3 was synthesized previously from an
appropriate aldehyde and ethyl nitroacetate in the
presence of TiCl4 (Δ, 48 h) [12] or from a Schiff base
and nitroacetic acid [31], but the specific method of its
preparation and the melting point were absent.
According to Ciller et al. [32], nitroethene 11 was
obtained from α-nitroacetophenone and a Schiff base
by the method [33], but its melting point and spectral
characteristics also were not given.
Triazoles 16 and 17 containing an ethoxycarbonyl
group were obtained recently [12] from the
corresponding α-nitrocinnamic ester and sodium azide
in DMSO at heating (50°C) for 1.5 hours, but with
somewhat lower yields (e. g., the yield of 17 equaled
62% [12] instead of 86%).
The structure of 1,2,3-triazoles 15–28 was
confirmed by spectroscopy methods. For example, in
the IR spectra there were absorption bands of
stretching vibrations of NH (3152–3443 cm–1) and
carbonyl groups (1655–1728 cm–1). In addition, the
spectra of compounds 27 and 28 contained absorption
due to the stretching vibrations of the nitrile function
(2237–2238 cm–1).
In the 1H and 13C–{1H} NMR spectra of derivatives
15–28 there were the signals of all the structural
fragments of the molecules. In particular, the 1H NMR
Previously, the structure of compounds 1, 2, 4, 5, 8–
10, 13 has been studied [6, 22, 34, 35]. Analysis of the
structure of geminally substituted nitroethenes 3, 6, 7,
1
11, 12 and 14 by means of H, 13C–{1H} NMR, UV,
and IR spectroscopy showed that compounds 3, 6 and
7 are possessed the Z-configuration, and compounds
11, 12, 14 had the E-configuration.
α-Nitroacrylates 1–4, gem-acetyl(benzoyl)nitro-
styrenes 5–12, and α-nitroacrylonitriles 13, 14 were
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 6 2016

1268
BERESTOVITSKAYA et al.
spectra of alkoxycarbonyl-containing 1,2,3-triazoles
15–18 contained a quartet and a triplet signals of
COOCH2CH3 fragment at 4.25–4.33 and 1.21–
benzoyl, and cyano functionalized triazoles are of
interest as potential biologically active substances.
EXPERIMENTAL
1
1.28 ppm, respectively. In the H NMR spectra of
Physicochemical studies were carried out using the
equipment of the Center for Collective Use of the
faculty of chemistry of the Herzen State Pedagogical
University of Russia.
acetyl-containing 1,2,3-triazoles 19, 20, and 21 the
singlet signals of acetyl groups appeared at 2.59, 2.72,
and 2.74 ppm, respectively. The signals in the region
14.25–14.46, 61.37–61.67, and 160.92–161.63 ppm in
the 13C–{1H} NMR spectra of 1,2,3-triazoles 15, 17,
and 18 corresponded to ethoxy groups.
1
1
1H, 13C–{1H}, H–13C HMQC, and H–13C HMBC
NMR spectra were recorded on a Jeol JNM-ECX400A
spectrometer operating at 399.78 (1H) and 100.53 MHz
(13C) and using chloroform-d or DMSO-d6 as the
solvent and internal standart. IR spectra were
registered on a Shimadzu IR-Prestige-21 Fourier
spectrometer from chloroform solutions (40 mg mL–1)
or KBr pellets. Electron absorption spectra of ethanol
or acetonitrile solutions were recorded on a Shimadzu
UV 2401PC spectrometer using quartz cells (l =
1.01 mm). Elemental analysis was performed on a
EuroVector EA 3000 analyzer (CHN Dual).
The signals of acetyl group in the spectrum of
compound 19 appeared at 29.03 and 193.10 ppm,
whereas the nitrile group in compounds 27 and 28
resonated at 114.29 and 114.38 ppm, respectively. The
validity of the signals assignement in the NMR spectra
of 1,2,3-triazoles 15–28 was confirmed by two-
dimensional 1H–13C HMQC and 1H–13C HMBC
spectroscopy. For example, in compounds 19, the
signal in the weaker field (142.14 ppm) was
unambiguously assigned to the carbon atom C5 of the
triazole ring owing to the presence of cross peaks with
ortho-protons (7.73 ppm) of aromatic substituent in the
1H–13C HMBC spectrum. The signal of acetyl group at
2.59 ppm correlated with the signal of the carbon atom
of C4 of the triazole ring (140.83 ppm). Moreover, it
should be noted that for all compounds 15–28 obtained
the signal of the carbon atom C5 of triazole ring
appeared in a weaker field than that of the C4 atom.
Moreover, in most cases, the signals of the carbon
atoms C4 and C5 of the triazole ring and the ipso-
carbon atom of the aromatic substituent are broadened,
indicating a possible prototropic transformations caused
by NH- proton migration.
gem-Activated nitroalkenes 1, 2, 4–10, 13, 14 were
prepared according to the known methods [22–29].
Z-Ethyl 3-(4-bromophenyl)-2-nitropropenoate
(3). A mixture of 3.3 g (25 mmol) of ethyl nitroacetate,
5.55 g (30 mmol) of p-bromobenzaldehyde, a catalytic
amount (0.19 g) of β-alanine, and 4 mL of glacial
acetic acid in 40 mL of anhydrous benzene was
refluxed for 5 h in a flask equipped with a Dean–Stark
trap. After cooling, the reaction mixture was washed
with brine and dried with calcined MgSO4. Benzene
was evaporated on a rotary evaporator, and the residue
was placed into the refrigerator. After treatment with
ethanol the resulting crystalline solid was filtered off
and dried. Yield 2.92 g (39%), colorless crystals, mp
69–71°C (ethanol). IR spectrum (CHCl3), ν, cm–1:
1730 (C=O), 1646 (C=C), 1540, 1370 (NO2). 1Н NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.34 t (3Н, CH3,
3J = 7.2), 4.35 q (2Н, OCH2, 3J = 7.2), 7.25 d and 7.53
CH3
N
H
H3C
m
i
p
H
о
O
H
3
d (4H, Нo,m, BrС6Н4, J = 8.5), 7.45 (1Н, =СН).
13С–{1H} NMR spectrum (СDCl3), δC, ppm: 14.11
(СH3), 63.35 (ОСН2), 127.08 (Сipso, BrС6Н4), 127.88
(Сp, BrС6Н4), 131.08 (Сo, BrС6Н4), 132.82 (Сm,
BrС6Н4), 131.67 (=СН), 140.60 (=СNO2), 159.06
(С=О). UV spectrum (ethanol), λmax, nm (ε, mol L–1 cm–1):
292 (19550).1 Found, %: C 44.32, 44.18; H 3.45, 3.33;
CH3
H
5 4
1
3
N
N
2
N
H
19
In summary, a simple method for the synthesis of
functionalized 1,2,3-triazoles by reacting geminally
activated nitroalkenes with sodium azide was
developed. The obtained alkoxycarbonyl, acetyl,
1
The UV spectra of nitroethenes of 3, 6, 7, 11, 12, 14 contain
absorption bands in a longwave region above 270 nm.
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GEMINALLY ACTIVATED NITROETHENES IN REACTIONS WITH SODIUM AZIDE
1269
N 4.75, 4.73. C11H10BrNO4. Calculated, %: С 44.02; Н
3.36; N 4.67.
(CDCl3), δ, ppm (J, Hz): 7.26 d and 7.46 d (4H, Нo,m,
BrС6Н4, 3J = 8.6), 7.49 t [2Н, Нm, C(O)C6H5, J = 7.6],
7.64 t [1Н, Нp, C(O)C6H5, J = 7.5], 7.93 d [2Н, Нo,
C(O)C6H5, J = 8.3], 8.25 s (1Н, =СН). 13С–{1H} NMR
spectrum (СDCl3), δC, ppm: 127.23 (Сipso, BrС6Н4),
127.78 (Сp, BrС6Н4), 132.23 (Сo, BrС6Н4), 132.68 (Сm,
BrС6Н4), 129.17 (Сo, СOС6Н5), 129.37 (Сm, СOС6Н5),
134.76 (Сipso, СOС6Н5), 135.20 (Сp, СOС6Н5), 136.00
(=СН), 145.12 (=СNO2), 187.96 (С=О). UV spectrum
(ethanol), λmax, nm (ε, mol L–1 cm–1): 323 (30000).
Found, %: C 54.38, 54.41; H 3.10, 3.14; N 4.28, 4.34.
C15H10BrNO3. Calculated, %: С 54.24; Н 3.03; N 4.22.
Z-4-(4-Chlorophenyl)-3-nitro-3-buten-2-one (6).
IR spectrum (CHCl3), ν, cm–1: 1695 (C=O), 1634
(C=C), 1540, 1364 (NO2). 1Н NMR spectrum (СDCl3),
δ, ppm (J, Hz): 2.45 s (3Н, СН3), 7.35 d and 7.40 d
3
(4H, ClС6Н4, J = 8.9), 7.34 s (1Н, =СН). 13С–{1H}
NMR spectrum (СDCl3), δC, ppm: 25.30 (СН3), 127.34
(Сipso, ClС6Н4), 129.98, 131.19 (Сo,m, ClС6Н4), 138.92
(Сp, ClС6Н4), 130.92 (=СН), 148.10 (=СNO2), 187.72
(С=О). UV spectrum (CH3CN), λmax, nm (ε, mol L–1 cm–1):
294 (19100).
E-3-(1-Methyl-3-indolyl)-2-nitropropenenitrile
(14). IR spectrum (CHCl3), ν, cm–1: 2225 (C≡N), 1580,
Z-3-Nitro-4-(4-nitrophenyl)-3-butene-2-one (7).
IR spectrum (CHCl3), ν, cm–1: 1701 (C=O), 1630
1
1590 (C=C, C=N+), 1285, 1300 (NOO−). Н NMR
1
(C=C), 1544, 1530, 1349 (NO2, Ar-NO2). Н NMR
spectrum [(СD3)2SO], δ, ppm (J, Hz): 3.98 s (3Н,
NСН3), 7.32–7.44 m (2Н, Н5,6), 7.64 d (1Н, H7, 3J7,6
=
spectrum (СDCl3), δ, ppm (J, Hz): 2.49 s (3Н, СН3),
7.59 d and 8.28 d (Нo,m, 4H, O2NС6Н4, 3J = 8.9), 7.47 s
(1Н, =СН). 13С–{1H} NMR spectrum (СDCl3), δС,
ppm: 25.44 (СН3), 124.58 (Сm, O2NС6Н4), 130.45 (Сo,
O2NС6Н4), 135.06 (Сipso, O2NС6Н4), 149.40 (Сp,
O2NС6Н4), 129.28 (=СН), 149.67 (=СNO2), 187.24
(С=О). UV spectrum (CH3CN), λmax, nm (ε, mol L–1 cm–1):
291 (19000).
3
8.9), 8.08 d (1Н, H4, J4,5 7.2), 8.59 s (1Н, Н2),
8.99 s (1Н, =СН). 13С–{1H} NMR spectrum [(СD3)2SO],
δС, ppm: 34.90 (NСН3), 114.43 (CN), 107.15 (С3),
112.59 (С7), 120.25 (С4), 124.29 (С5), 125.23 (С6),
127.97 (С3a), 138.62 (С7a), 140.66 (С2), 115.26
(=СNO2), 141.59 (=СН). UV spectrum (ethanol), λmax
,
nm (ε, mol L–1 cm–1): 445 (46000).
E-3-(4-chlorophenyl)-2-nitro-1-phenylpropene-
1-one (11) was prepared analogously to compound 5
from nitroacetophenone and p-chlorobenzaldehyde; re-
action time 6 h (after benzene was removed the residue
was treated with methanol). Yield 39%, pale yellow
crystals, mp 58–60°C (petroleum ether). IR spectrum
(CHCl3), ν, cm–1: 1679 (C=O), 1641 (C=C), 1532,
Ethyl 5-(4-N,N-dimethylaminophenyl)-1,2,3-tri-
azole-4-carboxylate (15). A mixture of 0.422 g
(1.6 mmol) of ethyl 3-(4-N,N-dimethylaminophenyl)-
2-nitropropenoate 1 and 0.416 g (6.4 mmol) of sodium
azide in 7 mL of DMSO was stirred at 60°C for 3 h.
The reaction mixture was poured into finely crushed
ice. The separated oily product was extracted with
diethyl ether. The extract was dried with calcinated
magnesium sulfate, and then the solvent was
evaporated. After treatment of the residue with ethanol
the precipitate was filtered off and dried. Yield 0.205 g
(49%), beige crystals, mp 109–110°C (petroleum
ether : benzene = 1 : 1). IR spectrum (CHCl3), ν, cm–1:
1
1326 (NO2). Н NMR spectrum (CDCl3), δ, ppm (J,
3
Hz): 7.29 d and 7.34 d (Нm,о, 4H, ClС6Н4, J = 8.7),
7.48 t [2Н, Нm, C(O)C6H5, J = 7.6], 7.64 t [1Н, Нp,
C(O)C6H5, J = 7.5], 7.93 d [2Н, Нo, C(O)C6H5, J =
8.4], 8.27 s (1Н, =СН). 13С–{1H} NMR spectrum
(СDCl3), δC, ppm: 127.49 (Сipso, ClС6Н4), 129.83 (Сm,
ClС6Н4), 132.26 (Сo, ClС6Н4), 138.77 (Сp, ClС6Н4),
129.31 (Сo, СOС6Н5), 129.48 (Сm, СOС6Н5), 134.92
(Сipso, СOС6Н5), 135.29 (Сp, СOС6Н5), 136.00 (=СН),
145.19 (=СNO2), 188.10 (С=О). UV spectrum
(ethanol), λmax, nm (ε, mol L–1 cm–1): 322 (20000).
Found, %: C 62.78, 62.73; H 3.54, 3.61; N 5.03, 4.99.
C15H10ClNO3. Calculated, %: С 62.62; Н 3.50; N 4.87.
1
1722 (C=O), 3175 br, 3421 (NH). Н NMR spectrum
3
(CDCl3), δ, ppm (J, Hz): 1.28 t (3Н, CH3, J = 7.2),
3
2.97 s [6Н, N(CH3)2], 4.33 q (2Н, OCH2, J = 7.2),
3
6.68 d and 7.72 d (4H, Нm,o, NС6Н4, J = 9.0), 12.24
br.s (NH). 13С–{1H} NMR spectrum (CDCl3), δС, ppm:
14.25 (СH3), 40.27 (NCH3), 61.37 (ОСН2), 111.69
(Сm, NС6Н4), 113.77 (Сipso, NС6Н4), 130.22 (Сo,
NС6Н4), 151.37 (Сp, NС6Н4), 132.88 (С4), 144.86 br
(С5), 161.63 (С=О). Found, %: C 60.12, 60.15; H 6.39,
6.27; N 21.73, 21.75. C13H16N4O2. Calculated, %: С
59.99; Н 6.20; N 21.52.
E-3-(4-Bromophenyl)-2-nitro-1-phenylpropene-
1-one (12) was prepared analogously to compound 5
from nitroacetophenone and p-bromobenzaldehyde.
Yield 53%, pale yellow crystals, mp 90–92°C
(ethanol). IR spectrum (CHCl3), ν, cm–1: 1678 (C=O),
Ethyl 5-(4-chlorophenyl)-1,2,3-triazole-4-carbo-
xylate (16). A mixture of 0.256 g (1 mmol) of ethyl
1
1641 (C=C), 1529, 1325 (NO2). Н NMR spectrum
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 6 2016

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BERESTOVITSKAYA et al.
1
3-(4-chlorophenyl)-2-nitropropenoate 2 and 0.130 g
(2 mmol) of sodium azide in 7 mL of DMSO was
stirred at room temperature for 3 h, then poured into
finely crushed ice. The precipitate was filtered off,
washed with distilled water, and dried. Yield 0.181 g
(72%), colorless crystals, mp 171–172°C (ethanol)
{mp 172–172.5°C (water) [36]. IR spectrum (KBr), ν,
(NH). Н NMR spectrum [(СD3)2SO], δ, ppm (J, Hz):
2.59 s [3Н, C(O)CH3], 2.94 s [6Н, N(CH3)2], 6.74 d
and 7.73 d (4H, Нm,о, NС6Н4, J = 8.5), 15.56 br.s
3
(NH). 13С–{1H} NMR spectrum [(СD3)2SO], δC, ppm:
29.03 (СH3), 40.27 (NCH3), 111.81 (Сm, NС6Н4),
114.12 br (Сipso, NС6Н4), 130.35 (Сo, NС6Н4), 151.57
(Сp, NС6Н4), 140.83 (С4), 142.14 br (С5), 193.10
(С=О). Found, %: С 62.73, 62.78; Н 6.22, 6.29; N
24.50, 24.45. C12H14N4O. Calculated, %: С 62.59; Н
6.13; N 24.33.
1
cm–1: 1709 (C=O), 3219 br (NH). Н NMR spectrum
[(СD3)2SO], δ, ppm (J, Hz): 1.22 t (3Н, CH3, 3J = 7.1),
3
4.25 q (2Н, OCH2, J = 7.1), 7.52 d and 7.78 d (4H,
3
ClС6Н4, J = 9.0). Found, %: C 52.37, 52.43; H 4.11,
4-Acetyl-5-(4-chlorophenyl)-1,2,3-triazole (20) was
prepared analogously to compounds 16 from 4-(4-
chlorophenyl)-3-nitro-3-buten-2-one 6 and sodium
azide in DMF; reaction time 2.5 h. Yield 73%, pale
yellow crystals, mp 154–156°C (CCl4). IR spectrum
4.14; N 16.61, 16.56. C11H10ClN3O2. Calculated, %: С
52.50; Н 4.01; N 16.70.
Ethyl 5-(4-bromophenyl)-1,2,3-triazole-4-carbo-
xylate (17) was prepared analogously to compound 16
from ethyl 3-(4-bromophenyl)-2-nitropropenoate 3 and
sodium azide. Yield 86%, colorless crystals, mp 173–
175°C (ethanol : water = 2 : 1) (mp 173–174°C [12]).
IR spectrum (CHCl3), ν, cm–1: 1728 (C=O), 3200 br,
(KBr), ν, cm–1: 1696 (C=O), 3436 br (NH). Н NMR
1
spectrum (CDCl3), δ, ppm (J, Hz): 2.72 s (3Н, CH3),
7.42 d and 7.84 br. d (4H, ClС6Н4, 3J = 8.5), 12.22 br.s
(NH). Found N, %: 18.88, 18.90. C10H8ClN3O.
Calculated N, %: 18.96.
1
3418 (NH). Н NMR spectrum [(СD3)2SO], δ, ppm (J,
Hz): 1.21 t (3Н, CH3, 3J = 7.1), 4.25 q (2Н, OCH2, 3J =
4-Acetyl-5-(4-nitrophenyl)-1,2,3-triazole (21) was
prepared analogously to compounds 16 from 3-nitro-4-
(4-nitrophenyl)-3-buten-2-one 7 and sodium azide in
DMF; reaction time 2.5 h. Yield 38%, pale yellow
crystals, mp 146–148°C (benzene). IR spectrum (KBr),
ν, cm–1: 1685 (C=O), 1521, 1345 (NO2), 3236 br (NH).
1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.74 s
(3Н, CH3), 8.15 d and 8.29 d (4H, OС6Н4, J = 8.9),
12.48 br.s (NH). Found N, %: 24.04, 24.25. C10H8N4O3.
Calculated N, %: 24.14.
3
7.1), 7.65 d and 7.70 br. d (4H, BrС6Н4, J = 8.4 Hz),
15.86 br.s (NH). 13С–{1H} NMR spectrum [(СD3)2SO],
δС, ppm: 14.46 (СH3), 61.40 (ОСН2), 123.29, 128.32
br, 131.62, 131.71 (BrС6Н4), 135.03 br (С4), 145.75 br
(С5), 161.29 (С=О).
Ethyl 5-(4-nitrophenyl)-1,2,3-triazole-4-carbo-
xylate (18) was prepared analogously to compound 16
from ethyl 2-nitro-3-(4-nitrophenyl)propenoate 4 and
sodium azide in DMF; reaction time 2 h. Yield 69%,
pale yellow crystals, mp 169–170°C (ethanol) {mp 170–
171°C (water) [36, 37]}. IR spectrum (KBr), ν, cm–1:
1718 (C=O), 1523, 1347 (NO2), 3219 br (NH).
1Н NMR spectrum [(СD3)2SO], δ, ppm (J, Hz): 1.23 t
3
4-Benzoyl-5-phenyl-1,2,3-triazole (22) was pre-
pared analogously to compounds 16 from 1,3-di-
phenyl-2-nitropropen-1-one 8 and sodium azide in
DMF; reaction time 4 h. Yield 75%, colorless crystals,
mp 121–122°C (benzene) (mp 120.5–122°C [16]). IR
spectrum (CHCl3), ν, cm–1: 1662 (C=O), 3198 br, 3421
3
(3Н, CH3, J = 7.1), 4.27 q (2Н, OCH2, 3J = 7.1), 8.05
3
d and 8.28 d (4H, Нo,m, O2NС6Н4, J = 8.7), 15.96 br.s
(NH). 13С–{1H} NMR spectrum [(СD3)2SO], δС, ppm:
14.41 (СH3), 61.67 (ОСН2), 123.82 (Сm, O2NС6Н4),
136.04 (Сipso, O2NС6Н4), 130.80 (Сo, O2NС6Н4),
148.10 (Сp, O2NС6Н4), 134.34 (С4), 144.93 br (С5),
160.92 (С=О). Found, %: C 50.46, 50.42; H 3.76,
3.69; N 21.26, 21.32. C11H10N4O4. Calculated, %: С
50.38; Н 3.84; N 21.37.
1
(NH). Н NMR spectrum (СDCl3), δ, ppm (J, Hz):
7.34–7.44 m (3Н, Нm,p), 7.60–7.70 m (2Н, Нo), 7.39 t
[2Н, Нm, C(O)C6H5, J = 7.5], 7.53 t [1Н, Нp,
C(O)C6H5, J = 7.3], 8.01 d [2Н, Нo, C(O)C6H5, J =
7.5], 13.53 br.s (NH). 13С–{1H} NMR spectrum
(СDCl3), δC, ppm: 127.52 (Сipso, С6Н5), 128.68 (Сm,
С6Н5), 128.90 (Сo, С6Н5), 129.83 (Сp, С6Н5), 128.47
(Сm, СOС6Н5), 130.61 (Сo, СOС6Н5), 133.66 (Сp,
СOС6Н5), 137.02 (Сipso, СOС6Н5), 140.97 (С4), 145.84
br (С5), 188.44 (С=О). Found N, %: 16.80, 16.81.
C15H11N3O. Calculated N, %: 16.87.
4-Acetyl-5-(4-N,N-dimethylaminophenyl)-1,2,3-
triazole (19) was prepared analogously to compound
15 from 4-(4-N,N-dimethylaminophenyl)-3-nitro-3-
buten-2-one 5 and sodium azide in DMF. Yield 42%,
beige crystals, mp 176–178°C (ethanol : water = 2 : 1).
IR spectrum (KBr), ν, cm–1: 1657 (C=O), 3152 br
4-Benzoyl-5-(4-methoxyphenyl)-1,2,3-triazole (23)
was prepared analogously to compound 16 from 3-(4-
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GEMINALLY ACTIVATED NITROETHENES IN REACTIONS WITH SODIUM AZIDE
1271
methoxyphenyl)-2-nitro-1-phenylpropen-1-one 9 and
sodium azide in DMF; reaction time 2.5 h. Yield 58%,
colorless crystals, mp 119–120°C (benzene) (mp 126–
128°C [38]). IR spectrum (CHCl3), ν, cm–1: 1658
(C=O), 3158 br, 3421 (NH). 1Н NMR spectrum
(СDCl3), δ, ppm (J, Hz): 3.77 s (3Н, OCH3), 6.84 d
and 7.65 d (4H, Нm,о, OС6Н4, 3J = 8.2), 7.41 t [2Н, Нm,
C(O)C6H5, J = 7.3], 7.54 t [1Н, Нp, C(O)C6H5, J =
7.0], 8.05 d [2Н, Нo, C(O)C6H5, J = 7.0], 13.75 br.s
(NH). 13С–{1H} NMR spectrum (СDCl3), δC, ppm:
14.95, 15.02. C15H10ClN3O. Calculated, %: С 63.50; Н
3.55; N 14.81.
4-Benzoyl-5-(4-bromophenyl)-1,2,3-triazole (26)
was prepared analogously to compound 16 from 3-(4-
bromophenyl)-2-nitro-1-phenylpropene-1-one 12 and
sodium azide. Yield 41%, colorless crystals, mp 164–
166°C (ethanol : water = 2 : 1). IR spectrum (CHCl3),
1
ν, cm–1: 1663 (C=O), 3200 br, 3420 (NH). Н NMR
spectrum (СDCl3), δ, ppm (J, Hz): 7.51 d and 7.65 d
(4H, Нm,о, BrС6Н4, 3J = 8.4), 7.47 t [2Н, Нm,
C(O)C6H5, J = 7.7], 7.60 t [1Н, Нp, C(O)C6H5, J =
7.4], 8.05 d [2Н, Нo, C(O)C6H5, J = 7.6], 12.31 br.s
(NH). 13С–{1H} NMR spectrum (СDCl3), δC, ppm:
124.08 (Сipso, BrС6Н4), 127.26 (Сp, BrС6Н4), 130.36
(Сo, BrС6Н4), 131.77 (Сm, BrС6Н4), 128.47 (Сm,
СOС6Н5), 130.46 (Сo, СOС6Н5), 133.76 (Сp, СOС6Н5),
136.78 (Сipso, СOС6Н5), 141.29 br (С4), 146.58 br (С5),
187.91 (С=О). Found N, %: 12.86, 12.93. C15H10BrN3O.
Calculated N, %: 12.80.
55.41 (OСH3), 114.14 (Сm, OС6Н4), 119.60 br (Сipso
,
OС6Н4), 130.38 (Сo, OС6Н4), 160.86 (Сp, OС6Н4),
128.42 (Сm, СOС6Н5), 130.61 (Сo, СOС6Н5), 133.47
(Сp, СOС6Н5), 137.27 (Сipso, СOС6Н5), 140.71 br (С4),
145.35 br (С5), 188.31 (С=О). Found N, %: 14.98,
15.00. C16H13N3O2. Calculated N, %: 15.05.
4-Benzoyl-5-(4-N,N-dimethylaminophenyl)-1,2,3-
triazole (24) was prepared analogously to compound
15 from 3-(4-N,N-dimethylaminophenyl)-2-nitro-1-
phenylpropen-1-one 10 and sodium azide. Yield 60%,
beige crystals, mp 126–127°C (ethanol). IR spectrum
(CHCl3), ν, cm–1: 1655 (C=O), 3174 br, 3423 (NH). 1Н
NMR spectrum (СDCl3), δ, ppm (J, Hz): 2.92 s [6Н, N
(CH3)2], 6.60 d and 7.65 d (4H, Нm,о, NС6Н4, 3J = 8.8),
7.41 t [2Н, Нm, C(O)C6H5, J = 7.6], 7.52 t [1Н, Нp,
C(O)C6H5, J = 7.4], 8.09 d [2Н, Нo, C(O)C6H5, J =
7.4], 13.94 br.s (NH). 13С–{1H} NMR spectrum (СDCl3),
δC, ppm: 40.28 (NСH3), 111.91 (Сm, NС6Н4), 113.75
br (Сipso, NС6Н4), 129.95 (Сo, NС6Н4), 151.37 (Сp,
NС6Н4), 128.30 (Сm, СOС6Н5), 130.68 (Сo, СOС6Н5),
133.06 (Сp, СOС6Н5), 137.83 (Сipso, СOС6Н5), 140.20
(С4), 144.71 br (С5), 188.43 (С=О). Found N, %:
19.29, 19.34. C17H16N4O. Calculated N, %: 19.17.
5-(4-Methoxyphenyl)-1,2,3-triazole-4-carbonitrile
(27) was prepared analogously to compound 16 from
2-nitro-3-phenylpropenenitrile 13 and sodium azide in
DMF. Yield 31%, colorless crystals, mp 198–200°C
{mp 197–198°C (ethyl acetate) [13]}. IR spectrum
1
(KBr), ν, cm–1: 2238 (C≡N), 3187 (NH). Н NMR
spectrum [(СD3)2SO], δ, ppm (J, Hz): 3.79 s (3Н,
3
OCH3), 7.11 d and 7.77 d (4H, Нm,о, OС6Н4, J = 8.5),
9.05 br.s (NH). 13С–{1H} NMR spectrum [(СD3)2SO],
δС, ppm: 55.94 (ОСН3), 114.29 (CN), 115.44 (Сm,
OС6Н4), 118.26 (Сipso, OС6Н4), 128.75 (Сo, OС6Н4),
161.43 (Сp, OС6Н4), 115.64 (С4), 146.14 (С5). Found,
%: С 59.88, 60.13; Н 4.15, 4.09; N 27.86, 27.83.
C10H8N4O. Calculated, %: С 59.99; Н 4.03; N 27.99.
4-Benzoyl-5-(4-chlorophenyl)-1,2,3-triazole (25)
was prepared analogously to compound 16 from 3-(4-
chlorophenyl)-2-nitro-1-phenylpropen-1-one 11 and
sodium azide. Yield 46%, colorless crystals, mp 154–
156°C (ethanol : water = 2 : 1). IR spectrum (CHCl3),
5-(1-Methyl-3-indolyl)-1,2,3-triazole-4-carbonitrile
(28) was prepared analogously to compound 16 from
3-(1-methyl-3-indolyl)-2-nitro-propenenitrile 14 and
sodium azide; reaction time 1 day. Yield 30%, beige
crystals, mp 138–140°C. IR spectrum (KBr), ν, cm–1:
1
1
ν, cm–1: 1662 (C=O), 3207 br, 3420 (NH). Н NMR
2237 (C≡N), 3192, 3443 (NH). Н NMR spectrum
spectrum (СDCl3), δ, ppm (J, Hz): 7.34 d and 7.70 d
(4H, Нm,о, ClС6Н4, 3J = 8.5), 7.46 t [2Н, Нm,
C(O)C6H5, J = 7.7], 7.59 t [1Н, Нp, C(O)C6H5, J =
7.4], 8.04 d [2Н, Нo, C(O)C6H5, J = 8.2], 9.03 br.s
(NH). 13С–{1H} NMR spectrum (СDCl3), δC, ppm:
126.90 (Сipso, ClС6Н4), 128.90 (Сm, ClС6Н4), 130.24
(Сo, ClС6Н4), 135.83 (Сp, ClС6Н4), 128.55 (Сm, СOС6Н5),
130.56 (Сo, СOС6Н5), 133.82 (Сp, СOС6Н5), 136.92
(Сipso, СOС6Н5), 141.36 (С4), 146.51 (С5), 188.01
(С=О). Found, %: С 63.68, 63.73; Н 3.71, 3.68; N
[(СD3)2SO], δ, ppm (J, Hz): 3.87 s (3Н, NCH3), 7.20
m (1Н, 3-indolyl), 7.28 m (1Н, 3-indolyl), 7.53 d (1Н,
3-indolyl, J = 8.0), 7.95 s (1Н, Н2, 3-indolyl), 7.99 d
(1Н, 3-indolyl, J = 7.9), 16.12 br.s (NH). 13С–{1H}
NMR spectrum [(СD3)2SO], δС, ppm: 33.49 (NСН3),
114.38 (CN), 100.51, 111.17, 120.62, 121.35, 123.22,
125.10, 130.34, 137.34 (3-indolyl), 115.41 (C4),
143.37 br (С5). Found, %: С 64.75, 64.79; Н 4.15,
4.19; N 31.55, 31.58. C12H9N5. Calculated, %: С
64.56; Н 4.06; N 31.37.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 6 2016

1272
BERESTOVITSKAYA et al.
14. Fringuelli, F., Lanari, D., Pizzo, F., and Vaccaro, L.,
ACKNOWLEDGMENTS
Eur. J. Org. Chem., 2008, no. 23, p. 3928. DOI:
10.1002/ejoc.200800142.
This work was financially supported by the
Ministry of Education and Science of the Russian
Federation in the framework of the basic part of
governmental contract.
15. Badiger, S., Behnke, D., Betschart, C., Chaudhari, V.,
Cotesta, S., Hintermann, S., Lerchner, A, Limam, F.,
Ofner, S., Pandit, C., and Wagner, J., US Patent
2012/165331 A1 (2012).
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