Polyfunctional imidazoles: XIII.1 Addition and cyclization reactions of 1-aryl-4-chloro-5-(2-nitroethenyl)-1H-imidazoles with sulfur and nitrogen nucleophiles

Article abstract of DOI:10.1134/S1070428017030150

1-Aryl-4-chloro-5-(2-nitroethenyl)-1H-imidazoles reacted with thiols and aromatic amines via Michael addition to give 5-[(1-arylsulfanyl)-2-nitroethyl)]-4-chloro-1H-imidazoles and N-[1-(1-aryl-4-chloro-1H-imidazol-5-yl)-2-nitroethyl]anilines, respectively

Full text of DOI:10.1134/S1070428017030150

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 3, pp. 407–412. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © V.A. Chornous, O.Ya. Mel’nik, A.N. Grozav, S.Yu. Suikov, M.V. Vovk, 2017, published in Zhurnal Organicheskoi Khimii, 2017,
Vol. 53, No. 3, pp. 408–412.
1
Polyfunctional Imidazoles: XІІІ. Addition and Cyclization
Reactions of 1-Aryl-4-chloro-5-(2-nitroethenyl)-1H-imidazoles
with Sulfur and Nitrogen Nucleophiles
a
b
a
c
c
V. A. Chornous , O. Ya. Mel’nik , A. N. Grozav , S. Yu. Suikov , and M. V. Vovk *
a
Bukovinian State Medical University, Theatralna pl. 2, Chernivtsi, 58002 Ukraine
b
Ivano-Frankivsk National Medical University, Galitska ul. 2, Ivano-Frankivsk, 76018 Ukraine
c
Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 5, Kiev, 02660 Ukraine
*
e-mail: mvovk@ioch.kiev.ua
Received September 14, 2016
Abstract—1-Aryl-4-chloro-5-(2-nitroethenyl)-1H-imidazoles reacted with thiols and aromatic amines via
Michael addition to give 5-[(1-arylsulfanyl)-2-nitroethyl)]-4-chloro-1H-imidazoles and N-[1-(1-aryl-4-chloro-
1
H-imidazol-5-yl)-2-nitroethyl]anilines, respectively. [2+3]-Cycloaddition of the title compounds to sodium
azide afforded 4-(4-chloro-1H-imidazol-5-yl)-1H-1,2,3-triazoles.
DOI: 10.1134/S1070428017030150
Highly electron-deficient nitro group in nitroal-
kenes is often regarded as a “synthetic chameleon” [2]
since it can readily be converted to other function-
alities [3, 4]. A particular role of nitroalkenes as
acceptors is reflected in conjugate Michael addition
reactions with sulfur and nitrogen nucleophiles; the
corresponding products, sulfides and nitroamines, are
convenient building blocks for the synthesis of analogs
of natural compounds and pharmacologically impor-
tant substances [5, 6]. Derivatives of 1-aryl-2-nitro-
ethyl sulfides were reported as intermediate products
in the synthesis of such biologically active compounds
as thromboxane A and leukotriene D dual antagonist
nucleophiles to 1-aryl-4-chloro-5-(2-nitroethenyl)-1H-
imidazoles [20].
1-Aryl-5-(2-nitroethenyl)imidazoles 1a–1d reacted
with phenylmethanethiol (2a), sulfanylacetic acid (2b),
and 4-chlorobenzenethiol (2c) in methanol at room
temperature to give mixtures of Michael adducts 3a–3e
and compounds 4a–4e resulting from substitution of
the nitro group (Scheme 1). According to the GC/MS
data, the ratio 3:4 ranged from 88:12 to 93:7. Major
products 3a–3e were isolated as analytically pure
substances in 67–73% yield by crystallization of the
product mixtures from methanol. Taking into account
published data [18], we presumed that compounds
3a–3e are formed according to the Michael addition
scheme through intermediate A and aci-nitro form B.
Sulfides 4a–4e are likely to result from radical addition
through intermediate C.
2
4
[7], analogs of the natural alkaloid amathamide A [8],
and sulconazole (fungicide) [9]. 1,2-Nitroamines were
used as precursors to many organic compounds
[
[
10, 11] that can be readily converted to 1,2-diamines
12] or α-amino acids [13].
The structure of 5-[1-(arylsulfanyl)-2-nitroethyl]-
imidazoles 3a–3e was confirmed by spectral data.
Michael additions of SH and NH nucleophiles to
the activated double bond of β-nitrostyrenes [14–17]
and their heterocyclic analogs, 2-(2-nitroethenyl)furan
18] and 2-(2-nitroethenyl)thiophene [19], have been
studied most thoroughly. It seemed reasonable to
examine addition reactions of sulfur and nitrogen
1
Their H NMR spectra (DMSO-d ) characteristically
6
showed a triplet of the CHS proton at δ 4.27–4.71 ppm
and a multiplet signal of the CH NO protons at
[
2
2
δ 5.13–5.39 ppm. Restricted rotation of the 2-chloro-
1
phenyl substituent on the N nitrogen atom of the imid-
azole ring in 3c gives rise to atropisomerism, so that all
1
*
For communication XII, see [1].
signals in the H NMR spectrum of 3c are doubled.
4
07

4
08
CHORNOUS et al.
Scheme 1.
Cl
Cl
Cl
N
O–
N
O–
N
N
N
NO2
N
N
N
O–
H
OH
S
SR
SR
3a–3e
Cl
Ar
Ar
Ar
R
RSH
2a–2c)
N
(
A
B
NO2
N
Cl
Cl
Ar
H
N
N
1
a–1d
NO2
SR
SR
N
–HNO2
N
H
Ar
Ar
C
4a–4e
1
, Ar = Ph (a), 2-ClC
6
H
4
(b), 3-MeC
6
H
4
(c), 4-ClC
6
H
4
(d); 2, R = PhCH
2
(a), HOC(O)CH
2
(b), 4-ClC
6
H
2
4
(c); 3, 4, Ar = Ph,
(d); Ar = 4-ClC
R = HOC(O)CH (a), 4-ClC
2
6
H
4
(b); Ar = 2-ClC
6
H
4
, R = 4-ClC
6
H
4
(c); Ar = 3-MeC
(e).
6
H
4
, R = HOC(O)CH
6 4
H ,
R = PhCH
2
Scheme 2.
Cl
Cl
N
N
MeOH
DMSO-d6
NO2
NO2
+
Ar'NH2
5a–5d
N
N
NHAr'
Ar
Ar
1
a, 1c
6a–6d
5
, Ar′ = 3-MeOC
6
H
4
(a), 4-BrC H
6 4
(b), 4-MeC H
6 4
(c), 4-MeOC H
6 4
6 4 6 4
(d); 6, Ar = Ph, Ar′ = 3-MeOC H (a), 4-BrC H (b),
4
-MeC (c); Ar = 3-MeC
6
H
4
6
H
4
, Ar′ = 4-MeOC (d).
6 4
H
The reaction of 1-aryl-5-(2-nitroethenyl)imidazoles
with amines was largely determined by the amine
structure. Compounds 1a and 1c failed to react with
primary or secondary aliphatic amines. However, they
reacted with anilines 5a–5d in methanol to give 58–
ortho-Protons of the tolyl substituent on the NH
nitrogen atom give a doublet at δ 6.51 ppm, and the
singlet at δ 8.36 ppm is likely to belong to the CH
proton of the pyrazole ring occurring in a different
solvation environment (see figure, curve 1). The
intensity of these signals grows with time, whereas the
overall intensity of the doublets at δ 6.25 and 6.51 ppm
1
6
7% of Michael addition products 6a–6d (Scheme 2).
1
Detailed analysis of the H NMR spectra of 6a–6d
(
(
(
2H), as well as of the singlets at δ 8.36 and 7.84 ppm
1H) remains constant up to a fairly high conversion
~12–14 days). The signal intensity of the NHCHCH2
showed that these compounds in weakly polar CDCl3
have the structure of 5-(1-anilino-2-nitroethyl)imid-
azoles characterized by a triplet at δ 5.04–5.18 and
a multiplet at 4.69–4.96 ppm due to CHNH and
CH NO protons, respectively. The spectral pattern
fragment regularly decreases, the intensity ratio with
the doublet at δ 6.25 ppm remaining constant. The NH
2
2
2
becomes more complicated in going to strongly polar
protons appear as a broadened singlet at δ 4.75 ppm,
which considerably broadens (up to a halfwidth of
more than 100 Hz at high conversions) with time due
to exchange with protons of water present in the
solvent (see figure, curve 2). The above findings are
consistent with the presumed slow dissociation of
adducts 6a–6d in a strongly polar solvent to form
initial 1-aryl-5-(2-nitroethenyl)imidazoles 1a and 1b
and anilines 5a–5d, i.e., retro-Michael reaction. We
have found no published data on analogous behavior of
aniline addition products to nitrostyrenes.
DMSO-d : additional signals appear at δ 6.00–6.06 and
6
6
.49–6.57 ppm, while the appearance of signals at
δ 4.77–5.50 ppm changes. Joint analysis of the COSY
and HSQC data for compound 6c showed that the NH
signal in DMSO-d shifts downfield to δ 6.01 ppm,
6
but remains a narrow doublet. The difference in the
chemical shifts of nonequivalent methylene protons
increases, and the CH signal shifts from δ 5.16 to
4
.92 ppm, while the spin–spin coupling in the
NHCHCH fragment remained the same as in CDCl .
2
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 3 2017

POLYFUNCTIONAL IMIDAZOLES: XІІІ.
409
2
1
6
.8
6.6
6.4
6.2
6.0
5.8
5.6
5.4
5.2
5.0
4.8
4.6
δ, ppm
1
H NMR spectra of compound 6c in DMSO-d
6
recorded (1) immediately after dissolution and (2) after 14 days.
The reaction of compounds 1a and 1c–1f with
sodium azide in DMSO at 60°C in the absence of
a catalyst followed the [2+3]-cycloaddition path with
formation of 87–94% of imidazolyltriazoles 7a–7f.
The products can be regarded as new 1,2,3-triazole
derivatives with a wide application potential in
medicinal chemistry, agrochemistry, and materials
chemistry [21].
DMSO-d . The mass spectra were obtained using
an Agilent 1100 instrument.
6
Compounds 3a–3e (general procedure). A mixture
of 5 mmol of 1-aryl-5-(2-nitroethenyl)imidazole 1a–1d
and 5 mmol of thiol 2a–2c in 5 mL of methanol was
stirred for 12 h at room temperature. The precipitate
was filtered off and recrystallized from methanol.
{
[1-(4-Chloro-1-phenyl-1H-imidazol-5-yl)-
With account taken of the data in [22, 23], we can
state that azide ion adds to the activated double bond
of 1 to give anionic intermediate A which undergoes
cyclization to intermediate B. The subsequent elimina-
tion of nitrite ion yields compounds 7 (Scheme 3).
Unlike the reaction of azide ion with nitrostyrenes
2
-nitroethyl]sulfanyl}acetic acid (3a). Yield 70%,
1
mp 136–137°C. H NMR spectrum, δ, ppm: 3.35 d and
.47 d (1H each, CH COOH, J = 14.4 Hz), 4.67 t (1H,
3
2
CH, J = 7.2 Hz), 5.14–5.27 m (2H, CH NO ), 7.52–
2
2
13
7
.64 m (5H, Harom), 7.89 s (1H, 2-H). C NMR spec-
trum, δ , ppm: 33.10 (CH ), 34.65 (CH), 75.05 (CH ),
C
2
2
[
24], no aryltriimidazoles are formed as by-products.
5
2
1
1
%
21.92 (C ), 125.59 (C ); 126.47, 127.81, 129.74,
37.53 (Carom); 134.67 (C ), 170.56 (COOH). Found,
: C 45.41; H 3.72; N 12.53. m/z 342 [M + 1] .
4
EXPERIMENTAL
+
C H ClN O S. Calculated, %: C 45.69; H 3.64;
N 12.29. M 341.78.
1
3
12
3
4
The IR spectra were recorded in KBr on a UR-20
1
13
spectrometer. The H (400.0019 MHz) and C NMR
spectra (125.7126 MHz) were recorded on a Varian
Gemini-400 spectrometer using tetramethylsilane as
internal standard. The spectra of 3a–3e and 7a–7e were
recorded in DMSO-d , and of 6a–6d, in CDCl and
4-Chloro-5-{1-[(4-chlorophenyl)sulfanyl]-2-
nitroethyl}-1-phenyl-1H-imidazole (3b). Yield 69%,
1
mp 154–155°C. H NMR spectrum, δ, ppm: 4.71 t
(1H, CH, J = 7.8 Hz), 5.06–5.11 m and 5.34–5.39 m
6
3
Scheme 1.
Cl
Cl
Cl
Cl
NO2
N
N
N
N
N3
NO2
NO2
N
N
NH
N
N
N
–NO2
N
N
N
N
N
N
Ar
Ar
N
Ar
Ar
1
a, 1c–1f
A
B
7a–7e
1
, Ar = 4-FC
6
H
4
7 6 4 6 4 6 4
(e), 1-C10H (f); 7, Ar = Ph (a), 3-MeC H (b), 4-ClC H (c), 4-FC H (d), naphthalen-1-yl (e).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 3 2017

4
10
CHORNOUS et al.
(
2
(
1H each, CH ), 7.23–7.60 m (9H, Harom), 7.90 s (1H,
N-[1-(4-Chloro-1-phenyl-1H-imidazol-5-yl)-
2-nitroethyl]-3-methoxyaniline (6a). Yield 63%,
mp 143–144°C. H NMR spectrum, δ, ppm: 3.70 s
2
1
3
-H). C NMR spectrum, δ , ppm: 40.52 (CH), 74.98
C
5
2
1
CH ), 121.47 (C ), 125.34 (C ); 126.62, 128.18,
2
1
28.95, 129.38, 129.80, 134.49, 134.64, 137.32
(3H, CH O), 4.00 br.s (1H, NH), 4.80–4.89 m (2H,
3
4
(
Carom); 134.70 (C ). Found, %: C 52.06; H 3.46;
CH ), 5.18 t (1H, CH, J = 6.6 Hz), 6.03 s (1H, Harom),
2
+
N 10.49. m/z 395 [M + 1] . C H Cl N O S. Calculat-
ed, %: C 51.79; H 3.32; N 10.66. M 394.28.
6.07 d (1H, Harom, J = 8.0 Hz), 6.35 d (1H, Harom, J =
8.0 Hz), 7.06 t (1H, Harom, J = 7.8 Hz), 7.13 d (1H,
1
7
13
2
3
2
H
arom, J = 7.6 Hz), 7.41–7.53 m (5H, Harom, 2-H).
4
-Chloro-1-(2-chlorophenyl)-5-{1-[(4-chloro-
1
3
C NMR spectrum, δ , ppm: 46.37 (CH), 55.16
C
phenyl)sulfanyl]-2-nitroethyl}-1H-imidazole (3c).
Yield 67%, mp 161–163°C. H NMR spectrum, δ,
ppm: 4.41 t and 4.58 t (1H, CH, J = 7.0 Hz), 4.98–
.05 m and 5.26–5.33 m (1H each, CH ), 7.23–7.80 m
8H, Harom), 7.94 s and 7.98 s (1H, 2-H). C NMR
spectrum, δ , ppm: 41.03 and 41.22 (CH), 75.06 and
5.49 (CH ), 121.62 and 121.77 (C ), 125.79 and
25.90 (C ); 128.08, 128.32, 128.47, 128.66, 128.79,
28.86, 129.53, 129.64, 130.45, 130.59, 130.86,
31.39, 136.23, 136.58, 138.07, 138.39 (Carom); 134.71
and 134.95 (C ). Found, %: C 47.77; H 2.66; N 9.89.
m/z 429 [M + 1] . C H Cl N O S. Calculated, %:
1
(CH O), 75.60 (CH ); 100.63, 105.37, 107.16, 126.60,
3 2
1
28.89, 129.99, 130.18, 136.42, 145.87, 160.89
5
2
4
(
Carom); 123.42 (C ), 130.38 (C ), 134.76 (C ). Found,
5
(
2
+
1
3
%
: C 57.78; H 4.66; N 15.18. m/z 373 [M + 1] .
C H ClN O . Calculated, %: C 57.99; H 4.60;
18 17
4
3
C
5
N 15.03. M 372.81.
-Bromo-N-[1-(4-chloro-1-phenyl-1H-imidazol-
-yl)-2-nitroethyl]aniline (6b). Yield 58%, mp 178–
7
1
1
1
2
2
4
5
1
179°C. H NMR spectrum, δ, ppm: 4.03 br.s (1H, NH),
.69–4.80 m (2H, CH ), 5.09 t (1H, CH, J = 6.4 Hz),
4
4
2
+
1
7
12
3
3
2
6.53 d (2H, Harom, J = 7.6 Hz), 6.90 d (2H, Harom, J =
C 47.63; H 2.82; N 9.80. M 428.73.
7
7
.6 Hz), 7.28–7.38 d (3H, H ), 7.52 s (1H, 2-H),
.83 d (2H, Harom, J = 7.8 Hz). C NMR spectrum, δ ,
arom
1
3
(
{1-[4-Chloro-1-(3-methylphenyl)-1H-imidazol-
C
5
6
(
-yl]-2-nitroethyl}sulfanyl)acetic acid (3d). Yield
9%, mp 128°C. H NMR spectrum, δ, ppm: 2.40 s
3H, CH ), 3.34–3.42 m (2H, CH COOH), 4.68 t (1H,
ppm: 46.62 (CH), 74.07 (CH
129.33, 130.72, 130.91, 131.44, 135.88, 142.42
(Carom); 124.13 (C ), 130.16 (C ), 135.89 (C ). Found,
%: C 48.71; H 3.21; N 13.06. m/z 422 [M + 1] .
2
); 116.81, 126.40,
1
5
2
4
3
2
+
CH , J = 7.2 Hz), 5.13–5.24 m (2H, CH, CH ), 7.30–
2
2
13
7
.49 m (4H, Harom), 7.85 s (1H, 2-H). C NMR spec-
C H14BrClN O . Calculated, %: C 48.42; H 3.35;
17 4 2
trum, δ , ppm: 19.36 (CH ), 33.52 (CH ), 34.81 (CH),
N 13.29. M 421.68.
C
3
2
5
2
7
1
1
4.86 (CH ), 122.23 (C ), 125.41 (C ); 126.98, 127.80,
28.41, 128.59, 130.64, 138.09 (Carom); 134.15 (C ),
2
N-[1-(4-Chloro-1-phenyl-1H-imidazol-5-yl)-2-
4
nitroethyl]-4-methylaniline (6c). Yield 68%, mp 175–
69.83 (COOH). Found, %: C 47.51; H 4.05; N 12.04.
1
1
3
76°C. H NMR spectrum, δ, ppm: 2.23 s (3H, CH ),
3
+
m/z 356 [M + 1] . C H ClN O S. Calculated, %:
1
4
14
3
4
.95 br.s (1H, NH), 4.74–4.89 m (2H, CH ), 5.16 t
2
C 47.26; H 3.97; N 11.81. M 355.80.
-[1-(Benzylsulfanyl)-2-nitroethyl]-4-chloro-
-(4-chlorophenyl)-1H-imidazole (3e). Yield 73%,
(
1H, CH, J = 6.2 Hz), 6.42 d (2H, Harom, J = 7.8 Hz),
5
6.94 d (2H, Harom, J = 7.6 Hz), 7.26 d (2H, Harom, J =
1
7.6 Hz), 7.41 s (1H, 2-H), 7.44–7.51 m (3H, Harom).
1
13
mp 105°C. H NMR spectrum, δ, ppm: 3.74–3.87 m
C NMR spectrum, δ
C 3
, ppm: 20.47 (CH ), 47.92 (CH),
(
(
2H, CH ), 4.27 t (1H, CH, J = 7.2 Hz), 5.21–5.26 m
75.75 (CH
130.04, 134.81, 142.18 (Carom); 123.58 (C ), 130.11
2
); 115.03, 126.59, 128.79, 129.55, 129.96,
2
5
2H, CH ), 7.17–7.24 m (7H, H ), 7.48 d (2H, Harom
,
2
arom
1
3
2
4
J = 7.6 Hz), 7.84 s (1H, 2-H). C NMR spectrum, δ ,
ppm: 33.41 (CH ), 34.84 (CH), 74.98 (CH ), 121.70
(
1
Found, %: C 53.18; H 3.60; N 10.07. m/z 409 [M + 1] .
C H Cl N O S. Calculated, %: C 52.95; H 3.70;
N 10.29. M 408.31.
(C ), 136.20 (C ). Found, %: C 60.81; H 4.68; N 15.84.
C
+
m/z 357 [M + 1] . C H ClN O . Calculated, %:
2
2
18 17
4
2
5
2
C ), 127.70 (C ); 127.88, 128.01, 128.61, 128.84,
29.83, 133.25, 136.88, 137.37 (Carom); 134.29 (C ).
C 60.69; H 4.80; N 15.70. M 356.81.
4
N-{1-[4-Chloro-1-(3-methylphenyl)-1H-imidazol-
+
5
6
2
-yl]-2-nitroethyl}-4-methoxyaniline (6d). Yield
8%, mp 175–176°C. H NMR spectrum, δ, ppm:
1
1
8
15
2
3
2
.34 s (3H, CH ), 3.72 s (3H, CH O), 3.90 br.s (1H,
3
3
Compounds 6a–6d (general procedure). A mixture
of 5 mmol of 1-aryl-5-(2-nitroethenyl)imidazole 1a or
NH), 4.82–4.96 m (2H, CH ), 5.04 t (1H, CH, J =
2
6.0 Hz), 6.47 d (2H, Harom, J = 7.2 Hz), 6.70 d (2H,
Harom, J = 7.6 Hz), 6.79 s (1H, Harom), 6.83–6.88 m
1
c and 5 mmol of aniline 5a–5d in 7 mL of methanol
1
3
was stirred for 24 h at room temperature. The precip-
itate was filtered off and recrystallized from methanol.
(1H, Harom), 7.32–7.44 m (3H, Harom, 2-H). C NMR
spectrum, δ , ppm: 20.32 (CH ), 46.52 (CH), 54.71
C
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 3 2017

POLYFUNCTIONAL IMIDAZOLES: XІІІ.
411
3
5′
4
(
CH O), 74.87 (CH ); 99.72, 104.44, 107.33, 125.49,
(Carom, J = 9.8 Hz), 128.74 (C ), 131.42 (C ),
3
2
CF
4
′
1
1
1
26.32, 127.40, 128.91, 129.83, 130.14, 136.85,
132.42 (C ), 132.44 (C ), 133.43 (Carom), 160.89
arom
5
2
1
45.23, 159.32 (C ); 122.64 (C ), 130.67 (C ),
(Carom, J = 246.0 Hz). Found, %: C 49.95; H 2.53;
arom
CF
4
+
34.49 (C ). Found, %: C 59.26; H 4.88; N 14.23.
N 26.40. m/z 264 [M + 1] . C H ClFN . Calculated,
%: C 50.11; H 2.68; N 26.56. M 263.66.
11
7
5
+
m/z 387 [M + 1] . C H ClN O . Calculated, %:
1
9
19
4
3
C 58.99; H 4.95; N 14.48. M 386.84.
4
-[4-Chloro-1-(naphthalen-1-yl)-1H-imidazol-5-
Compounds 7a–7e (general procedure). A mixture
of 5 mmol of 1-aryl-5-(2-nitroethenyl)imidazole 1a
or 1c–1f and 0.36 g (5 mmol) of sodium azide in
yl]-1H-1,2,3-triazole (7e). Yield 92%, mp 186–187°C.
H NMR spectrum, δ, ppm: 7.21 d (1H, Harom, J =
1
7.6 Hz), 7.49–7.73 m (8H, H , 5-H, 2′-H), 14.99 br.s
arom
1
3
2′
1
0 mL of DMSO was stirred for 4 h at 60°C. The mix-
(1H, NH). C NMR spectrum, δ , ppm: 119.63 (C ),
121.78 (C ); 125.52, 126.14, 126.95, 127.90, 127.97,
C
5
ture was cooled and poured into 50 mL of ice water,
and the precipitate was filtered off, dried in air, and
recrystallized from 70% ethanol.
128.34, 129.90, 130.03, 133.50, 138.04 (Carom); 129.09
5
′
4′
4
(
C ), 132.02 (C ), 134.61 (C ). Found, %: C 60.67;
+
H 3.53; N 23.44. m/z 296 [M + 1] . C H ClN . Cal-
4
-(4-Chloro-1-phenyl-1H-imidazol-5-yl)-1H-
15 10
5
1
1
,2,3-triazole (7a). Yield 90%, mp 147°C. H NMR
culated, %: C 60.92; H 3.41; N 23.68. M 295.73.
spectrum, δ, ppm: 7.30–7.35 m (2H, Harom), 7.43–
REFERENCES
7
1
1
1
.49 m (3H, Harom), 7.92 s (1H, 5-H), 8.02 s (1H, 2′-H),
1
3
5.27 br.s (1H, NH). C NMR spectrum, δ , ppm:
C
2
′
5
1
. Grozav, A.N., Chornous, V.A., and Vovk, M.V., Russ. J.
Org. Chem., 2016, vol. 52, p. 873.
18.74 (C ), 122.51 (C ); 125.63, 127.81, 129.15,
36.44 (Carom); 129.30 (C ), 132.03 (C ), 135.07 (C ).
5
′
4′
4
+
2
. Calderari, G. and Seebach, D., Helv. Chim. Acta, 1985,
Found, %: C 53.63; H 3.41; N 28.65. m/z 246 [M + 1] .
vol. 68, p. 1592.
C H ClN . Calculated, %: C 53.78; H 3.28; N 28.51.
11
8
5
3
4
. Rajappa, S., Tetrahedron, 1981, vol. 37, p. 1453.
M 245.67.
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4
-[4-Chloro-1-(3-methylphenyl)-1H-imidazol-
vol. 86, p. 751.
5
-yl]-1H-1,2,3-triazole (7b). Yield 87%, mp 125°C.
1
5. Trost, B.M. and Lavoie, A.C., J. Am. Chem. Soc., 1983,
H NMR spectrum, δ, ppm: 2.36 s (3H, CH ), 7.08 d
3
vol. 105, p. 5075.
(
1H, Harom, J = 7.2 Hz), 7.21–7.35 m (3H, Harom),
6
. Cordova, A., Acc. Chem. Res., 2004, vol. 37, p. 102.
7
.92 s (1H, 5-H), 8.03 s (1H, 2′-H), 15.26 br.s (1H,
1
3
7. Okamoto, Y., Yokota, M., Kawazoe, S., Kubota, H.,
Nagaoka, H., Arakida, Y., and Takeuchi, M., Chem.
Pharm. Bull., 2006, vol. 54, p. 603.
NH). C NMR spectrum, δ , ppm: 20.69 s (CH ),
C
3
2
′
5
118.50 (C ), 122.79 (C ); 126.32, 128.77, 129.00,
5
′
1
29.46, 133.23, 138.48 (C ); 129.94 (C ), 132.71
arom
4
′
4
8. Ramirez-Osuna, M., Chavez, D., Hernandez, L.,
(
C ), 134.15 (C ). Found, %: C 55.22; H 3.71;
+
Molins, E., Somanathan, R., and Aguirre, G., Molecules,
005, vol. 10, p. 295.
N 27.13. m/z 260 [M + 1] . C H ClN . Calculated, %:
1
2
10
5
2
C 55.50; H 3.88; N 26.97. M 259.70.
-[4-Chloro-1-(4-chlorophenyl)-1H-imidazol-
-yl]-1H-1,2,3-triazole (7c). Yield 94%, mp >250°C.
9
. Fromtling, R.A., Clin. Microbiol. Rev., 1988, vol. 1,
4
p. 187.
5
1
0. Bloch, R., Chem. Rev., 1998, vol. 98, p. 1407.
1
H NMR spectrum, δ, ppm: 7.37 d (2H, Harom, J =
.0 Hz), 7.53 d (2H, Harom, J = 8.0 Hz), 8.02 s (1H,
1
1. Kobayashi, S. and Ishitani, H., Chem. Rev., 1999,
8
5
vol. 99, p. 1069.
1
3
-H), 8.07 s (1H, 2′-H), 15.25 br.s (1H, NH). C NMR
1
1
1
2. Lucet, D., Le Gall, T., and Mioskowski, C., Angew.
Chem., Int. Ed., 1998, vol. 37, p. 2580.
2
′
5
spectrum, δ , ppm: 119.44 (C ), 121.07 (C ); 127.89,
1
(
C
5
′
29.34, 133.44, 137.92 (C ); 129.11 (C ), 132.02
arom
3. Ballini, R. and Petrini, M., Tetrahedron, 2004, vol. 60,
4
4′
C ), 132.77 (C ). Found, %: C 47.39; H 2.36;
p. 1017.
+
N 25.16. m/z 281 [M + 1] . C H Cl N . Calculated, %:
1
1
7
2
5
4. Japarpour, M., Rezaeifard, A., and Aliabadi, M., Lett.
Org. Chem., 2009, vol. 6, p. 94.
C 47.17; H 2.52; N 25.00. M 280.12.
4
-[4-Chloro-1-(4-fluorophenyl)-1H-imidazol-5-
15. Yadav, J.S., Reddy, A., Rao, Y.G., Narsaiah, A.V., and
yl]-1H-1,2,3-triazole (7d). Yield 89%, mp 202–203°C.
H NMR spectrum, δ, ppm: 7.28–7.43 m (4H, Harom),
Reddy, B.V.S., Synthesis, 2007, p. 3447.
1
16. Choudhary, G. and Peddinti, R.K., Green Chem., 2011,
7
.99 s (1H, 5-H), 8.04 s (1H, 2′-H), 14.98 br.s (1H,
vol. 13, p. 276.
1
3
NH). C NMR spectrum, δ , ppm: 116.16 d (Carom,
17. Hui, X.-P., Yin, C., Ma, J., and Xu, P.F., Synth.
Commun., 2009, vol. 39, p. 676.
C
2
2′
5
JCF = 22.6 Hz), 118.80 (C ), 120.44 (C ), 128.51 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 3 2017

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0. Chornous, V.A., Grozav, A.N., Mel’nik, O.Ya., Piro-
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 3 2017