Facile synthesis of novel (1-Aryl/alkyl-1H-1,2,3-triazol- 4-yl)methyl-2-bromo-4-methylthiazole-5-carboxylates by Cu(I) catalyzed click reaction

Article abstract of DOI:10.1134/S1070363216070306

A number of novel thiazole-triazole heterocycles bearing (1-aryl/alkyl-1H-1,2,3-triazol-4-yl)methyl- 2-bromo-4-methylthiazole-5-carboxylates was synthesized through the click reaction. The structure of all new synthesized compounds was established by

Full text of DOI:10.1134/S1070363216070306

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 7, pp. 1722–1729. © Pleiades Publishing, Ltd., 2016.
Facile Synthesis of Novel (1-Aryl/alkyl-1H-1,2,3-triazol-
4-yl)methyl-2-bromo-4-methylthiazole-5-carboxylates
by Cu(I) Catalyzed Click Reaction1
K. Sudhakar, G. Thirupathi, A. Balakishan, S. Narsima chary, and S. Ravi
Rural Development Society, R&D Centre,Punjagutta, Hyderabad, 500082 India
e-mail: ksudhakariict@gmail.com
Received March 5, 2016
Abstract—A number of novel thiazole-triazole heterocycles bearing (1-aryl/alkyl-1H-1,2,3-triazol-4-yl)methyl-
2-bromo-4-methylthiazole-5-carboxylates was synthesized through the click reaction. The structure of all new
synthesized compounds was established by 1H and 13C NMR spectroscopy and mass spectrometry methods.
Keywords: thiazole, 1,2,3-triazole, click reaction
DOI: 10.1134/S1070363216070306
One of the trends in contemporary organic
chemistry is the development of new biologically
active heterocyclic compounds, which should satisfy
the following criteria: be non-toxic, lower dosage,
effectively bind specific receptor sites. Among variety
of heterocyclic compounds the nitrogen-containing
thiazoles and triazoles are very important classes
[1, 2], which are well known for their broad spectrum
of remarkable biological and pharmaceutical activities
[3–6]. Thiazoles and triazoles link to various
heterocylic ring systems through various linkages; they
have attracted great attention recently. Thus, 1,3-
thiazole scaffolds [7] have found application in drug
development for the treatment of hypertension [8],
allergies [9], schizophrenia [10], bacterial inflamma-
tion [11–13], and HIV [14] infections. Thiazoles are
non-carcinogenic by their nature [15] and therefore
they are easily metabolized by ordinary biochemical
reactions. Moreover, thiazole derivatives possess
antibacterial activity [16, 17] due to the presence of
toxophoric unit.
For introduction of 1,2,3-triazole groups to organic
molecules, the copper-catalyzed Huisgen-type alkyne-
azide cycloaddition (CuAAC) is the most common
click reaction that has recently been used and found
wide application in organic synthesis, molecular biology,
medicinal chemistry and materials and polymer
science because of its versatility, regioselectivity, and
high efficiency under physiological conditions [26].
Considering the biological properties exhibited by
these two types of heterocycles, the elaboration of new
methods of the synthesis of thiazole-triazole dyads
aimed specifically at developing potentially improved
therapeutic agents is a challenge of high priority.
However, biheterocyclic compounds contained thiazole
and triazole moieties have not reported yet. Some of
pharmacologically important thiazole- or triazole-
linked heterocycles [27, 28] are shown in the figure.
To find simple and efficient procedure for the syn-
thesis of triazole- and thiazole-based heterocyclic
compounds with different substituents is of great
importance for both synthetic and medicinal chemists.
It was found by us that even at room temperature a
regioselective synthesis of novel 1,2,3-triazole deri-
vatives of thiazole in relatively high yields could
successfully been carried out by 1,3-dipolar cyclo-
addition with the use of CuSO4 and sodium ascorbate
as the catalysts, and a mixture t-BuOH–H2O (1 : 1) as
the solvent.
Compounds containing a 1, 2, 3-triazole moiety de-
monstrated various biological activities such as
antiHIV-type I protease [18], antimicrobial [19], anti-
allergic [20], antihyperglycemic [21], and adrenergic
receptor agonists [22]. In addition, they are
commercially used as photostabilizers and dyes [23],
anticorrosive agents [24], and agrochemicals [25].
Initially, ethyl acetoacetate 1 was treated with N-
bromosuccinimide (NBS) in dichloromethane with the
1 The text was submitted by the authors in English.
1722

FACILE SYNTHESIS OF NOVEL (1-ARYL/ALKYL-1H-1,2,3-TRIAZOL-...
1723
N
OH
CN
N
Cl
O
S
N NO2
HN
O
S
O
S
HN
Cl
O
N
Febuxosat
Flurazole
F
Clothianidin
O
N
O
N
N
N
N
S
N
F
N
NH2
O
COOH
O
Rufinamide
Pharmacologically important thiazole- or triazole-linked heterocycles.
Tazobactum
formation of ethyl 2-bromo-3-oxobutanoate 2 that
reacted with thiourea to afford ethyl 2-amino-4-
methylthiazole-5-carboxylate 3. Bromination of 2-
amino-4-methylthiazole-5-ethylcarboxylate 3 with hydro-
gen bromide, copper bromide and catalytic amount of
potassium bromide in the presence of sodium nitrite
gave ethyl 2-bromo-4-methylthiazole-5-carboxylate 4.
Treatment of 4 with sodium hydroxide in ethanol
afforded 2-bromo-4-methylthiazole-5-carboxylic acid
5 [29]. In order to get the precursor prop-2-yn-1-yl
2-bromo-4-methylthiazole-5-carboxylate 6 to target
compounds 1-aryl/alkyl-1H-1, 2, 3-triazol-4-yl)methyl
Scheme 1. Synthesis of (1-aryl/alkyl-1H-1,2,3-triazol-4-yl)methyl 2-bromo-4-methylthiazole-5-carboxylates 7a–7l.
O
O
O
O
O
O
O
O
2
1
3
N
S
N
S
O
O
Br
Br
NH2
4
3
2
1
4
O
O
O
R
OH
N
O
O
N
N
6
5
S
N
S
N
S
N
Br
Br
6
Br
7a−7l
5
Reaction coditions: (1) NBS (1 mmol), DCM, room temperature, 16 h; (2) thiourea (3 mmol), EtOH, 70ºC, 2 h;
(3) aq. NaNO2 (1.2 mmol), CuBr (1 mmol), HBr (3 mmol), KBr (0.2 mmol); (4) aq. NaOH (1 mmol), EtOH, 0–25ºC, 1 h;
(5) SOCl2 (1.1 mmol), 100ºC, 1 h, propargyl alcohol (1.2 mmol), TEA (2 mmol), DCM, 0ºC, 3 h; (6) aryl/alkyl azides
(1.1 mmol), CuSO4 (1.5 mmol), Na-ascorbate (0.2 mmol), tert-butanol/H2O (1 : 1), 1 h.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

1724
SUDHAKAR et al.
2-bromo-4-methylthiazole-5-carboxylates 7a–7l, com-
pound 5 was heated under reflux in thionyl chloride at
100oC, followed by treatment with propargyl alcohol
in the presence of triethylamine at 0oC. The click
reaction of newly synthesized prop-2-yn-1-yl 2-bromo-
4-methylthiazole-5-carboxylate 6 with aryl or alkyl
azides with the use of catalytic system CuSO4–sodium
ascorbate and t-BuOH–H2O (1 : 1) as a solvent at room
temperature provided (1-aryl/alkyl-1H-1, 2, 3-triazol-
4-yl)methyl 2-bromo-4-methylthiazole-5-carboxylates
7a–7l in 78–90% yield (Scheme 1 and table).
DCM was removed under reduced pressure. Crude
residue was diluted with ethanol, and thiourea (3 mmol)
was added; the reaction mixture was heated at 70°C for
2 h. After cooling to room temperature, the reaction
mixture was filtered and diluted with chilled water.
Then the solution was neutralized with NaHCO3
saturated solution. The obtained precipitate was
filtered off and dried to provide compound 3 as pale
yellow solid in 76% yield, mp 179–181°C.
Ethyl 2-bromo-4-methylthiazole-5-carboxylate
(4). Compound 3 (1 mmol) in HBr (3 mL) was added
to cold aqueous solution of CuBr (1 mmol) and KBr
(0.2 mmol) followed by dropwise addition of
preliminary cooled aqueous solution of NaNO2
(10 mL) for 1 h. The reaction mixture was stirred at
60oC for 2 h. The reaction progress was monitored by
TLC until the starting material completely dis-
appeared. The reaction mixture was diluted with water,
the obtained precipitate was filtered off to give ethyl 2-
bromo-4-methylthiazole-5-carboxylate 4 as off-white
The structures of 7a–7l were proved by the spectral
1
analysis. In the H NMR spectrum of compound 7a a
characteristic signal at δ 8.13, singlet (1H, triazole-H)
and 2.70, singlet (3H, –CH3) were observed. The 13C
NMR spectrum of 7a showed signals, which were in
the agreement with the proposed structure; the mass
spectrum of 7a contained a main peak at m/z 379 [M + H]+.
In summary, we elaborated simple and efficient
protocol for the synthesis of novel (1-aryl/alkyl-1H-
1,2,3-triazol-4-yl)methyl 2-bromo-4-methylthiazole-5-
carboxylates 7a-–7l by the treatment of new prop-2-
1
solid in 62% yield. H NMR spectrum (CDCl3), δ,
ppm: 4.28 q (2H), 2.81 s (3H), 1.33 t (3H). Mass
spectrum (ESI-MS): m/z 251 [M + H]+.
yn-1-yl 2-bromo-4-methylthiazole-5-carboxylate
6
with aryl or alkyl azides under the click reaction condi-
tions. This procedure required mild reaction condi-
tions, shorten reaction time, use of nontoxic catalyst
and provided good yields of the target compounds. The
biological activity of all the new synthesized
compounds will be reported hereafter.
2-Bromo-4-methylthiazole-5-carboxylic acid (5).
A solution of ethanolic NaOH (5 N, 15 mL) was
added to a solution of compound 4 (1 mmol) in ethanol
(20 mL) and the reaction mixture was stirred at room
temperature for 14 h; the reaction progress was
monitored by TLC. The reaction mixture was cooled
and neutralized with conc. HCl. The organic layer was
extracted with EtOAc and dried over anhydrous
Na2SO4. The solvent was removed under reduced pres-
sure to obtain crude product. The crude product was
purified by column chromatography using silica gel
(60–120 mesh) eluting with ethyl acetate and petro-
leum ether to obtain 2-bromo-4-methylthiazole-5-
EXPERIMENTAL
All the reagents and solvents were of reagent grade
and used without further purification. Column chromato-
graphy was performed on Merck silica gel, 60–1
1
20 mesh. H NMR spectra were recorded on a Bruker
spectrometer operating at 400 MHz, 13C NMR spectra
were obtained at 100 MHz with tetramethylsilane as an
internal reference, and the chemical shifts (δ) are
reported in ppm. The mass spectral analysis was
accomplished using electrospray ionization (ESI) tech-
nique. The IR spectra were recorded on a Shimadzu
FT-IR-8400s spectrophotometer in KBr. Elemental
analysis was done on a Thermo Finnigan Flash EA
microanalyzer.
1
carboxylic acid 5 as off-white solid in 76% yield. H
NMR spectrum (CDCl3), δ, ppm: 13.19 s (1H), 2.54 s
(3H). Mass spectrum (ESI-MS): m/z 223 [M + H]+.
Prop-2-yn-1-yl 2-bromo-4-methylthiazole-5-car-
boxylate (6). A solution of compound 5 (1 mmol) in
SOCl2 (1.1 mmol) was stirred at 100oC for 1 h. Then
the reaction mixture was cooled to 0oC, diluted with
CH2Cl2, and triethyl amine (1.5 mmol) and propargyl
alcohol (1.2 mmol) were added. The resulting solution
was stirred for 2 h at 0oC. After completion of the
reaction, CH2Cl2 was removed under vacuum, the
residue obtained was diluted with chilled water and
extracted with EtOAc (2 × 30 mL). The combined
Ethyl 2-amino-4-methylthiazole-5-carboxylate (3).
NBS (1 mmol) was added to a solution of ethyl
acetoacetate 1 (1 mmol) in DCM at 0°C. The reaction
mixture was stirred at room temperature for 12 h, then
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

FACILE SYNTHESIS OF NOVEL (1-ARYL/ALKYL-1H-1,2,3-TRIAZOL-...
Yields and melting points of compounds 7a–7l
1725
Comp.
no.
Product
Time, h
2.0
Yielda, %
88
mp, ºC
194–198
7a
N
N
O
O
N
N
S
Br
CH3
CH3
Cl
7b
1.0
90
186–189
N
O
N
N
O
S
N
Br
O
7c
1.0
91
149–151
N
N
O
O
N
N
S
Br
7d
1.5
86
166–168
N
O
N
N
O
N
S
Br
7e
NO2
2.0
82
188–190
N
N
O
O
N
N
S
Br
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

1726
SUDHAKAR et al.
Table (Contd.)
Comp.
no.
Product
Time, h
1.0
Yielda, %
84
mp, ºC
7f
163–165
Cl
N
N
O
O
N
N
S
Br
7g
2.0
81
177–179
NO2
N
O
N
N
O
N
S
Br
7h
1.5
84
206–208
OCH3
N
O
NO2
N
N
O
S
N
Br
7i
7j
2.0
2.0
85
82
84–86
96–98
N
O
N
N
O
N
S
Br
O
N
N
O
N
N
S
Br
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

FACILE SYNTHESIS OF NOVEL (1-ARYL/ALKYL-1H-1,2,3-TRIAZOL-...
1727
Table (Contd.)
Comp.
no.
Product
Time, h
2.0
Yielda, %
78
mp, ºC
115–118
O
N
N
N
7k
O
O
O
N
N
N
S
Br
1.0
83
154–157
O
N
N
NO2
7l
O
N
S
Br
a Isolated yield.
1
organic layers were dried over anhydrous Na2SO4, the
solvent was removed under reduced pressure. The
crude product was purified by column chromatography
using silica gel (60–120 mesh) eluting with ethyl
acetate and petroleum ether (2 : 8) to afford prop-2-yn-
1-yl 2-bromo-4-methylthiazole-5-carboxylate 6 as
colorless solid in 82% yield. 1H NMR spectrum
(CDCl3), δ, ppm: 4.88 s (2H), 2.72 s (3H), 2.54 s (1H).
Mass spectrum (ESI-MS): m/z 261 [M + H]+.
cm–1: 1703 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 8.13 s (1H), 7.74 d (J = 7.7 Hz, 2H), 7.54–7.46
m (3H), 5.51 s (2H), 2.70 s (3H). 13C NMR spectrum
(CDCl3), δ, ppm: 160.8, 159.9, 155.1, 140.2, 136.8,
129.8, 129.0, 123.3, 122.4, 120.6, 58.3, 17.4. Mass
spectrum (ESI-MS): m/z 379 [M + H]+. Found, %: C
44.31; H 2.96; N 14.72. C14H11BrN4O2S. Calculated,
%: C 44.34; H 2.92; N 14.77.
[1-(p-Tolyl)-1H-1,2,3-triazol-4-yl]methyl 2-bromo-
4-methylthiazole-5-carboxylate (7b). IR spectrum, ν,
cm–1: 1699 (C=O). 1H NMR spectrum (CDCl3), δ, ppm:
8.04 s (1H), 7.81–7.76 m (2H), 7.50–7.34 m (2H), 5.40
s (2H), 2.59 s (3H), 2.36 s (3H). 13C NMR spectrum
(CDCl3), δ, ppm: 160.6, 159.1, 155.0, 140.6, 138.4,
135.2, 133.3, 131.8, 128.6, 120.8, 58.1, 29.3, 16.8.
Mass spectrum (ESI-MS): m/z 393 [M + H]+. Found,
%: C 45.78; H 3.30; N 14.29. C15H13BrN4O2S. Cal-
culated, %: C 45.81; H 3.33; N 14.25.
General procedure for the synthesis of (1-aryl/
alkyl-1H-1,2,3-triazol-4-yl)methyl 2-bromo-4-methyl-
thiazole-5-carboxylates (7a–7l). Thiazole propargyl
ester 6 (1 mmol) and the corresponding aryl or alkyl
azides 2a–2e (1 mmol) were dissolved in 8 mL of a
mixture t-BuOH-–H2O (1 : 1). The reaction mixture
was stirred at room temperature for 10 min, then
CuSO4·5H2O (1 mmol) and sodium ascorbate
(0.2 mmol) were added. The reaction mixture was
stirred at room temperature until the starting material
was consumed as proven by TLC analysis. White
precipitate was formed, when the reaction was com-
pleted. The precipitate was filtered off, washed with
chilled water and dried to give (1-aryl/alkyl -1H-1,2,3-
triazol-4-yl)methyl 2-bromo-4-methylthiazole-5-car-
boxylates 7a–7l as light brown solids in 80–92% yield.
[1-(4-Methoxyphenyl)-1H-1,2,3-triazol-4-yl]methyl
2-bromo-4-methylthiazole-5-carboxylate (7c). IR
1
spectrum, ν, cm–1: 1719 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 8.08 s (1H), 7.82 d (J = 7.7 Hz, 2H),
7.38–7.46 m (2H), 5.44 s (2H), 4.32 s (3H), 2.58 s
(3H). 13C NMR spectrum (CDCl3), δ, ppm: δ 161.1,
159.2, 158.9, 155.4 138.2, 136.8, 129.3, 122.1, 120.9,
118.3, 58.0, 54.9, 16.8. Mass spectrum (ESI-MS): m/z
409 [M + H]+. Found, %: C 44.01; H 3.15; N 13.72.
(1-Phenyl-1H-1, 2, 3-triazol-4-yl)methyl 2-bromo-
4-methylthiazole-5-carboxylate (7a). IR spectrum, ν,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 7 2016

1728
SUDHAKAR et al.
C15H13BrN4O3S. Calculated, %: C 44.02; H 3.20; N
13.69.
112.6, 58.8, 54.3, 17.3. Mass spectrum (ESI-MS): m/z
454 [M + H]+. Found, %: C 39.60; H 2.62; N 15.39.
C15H12BrN5O5S. Calculated, %: C 39.66; H 2.66; N
15.42.
[1-(4-Chlorophenyl)-1H-1,2,3-triazol-4-yl]methyl
2-bromo-4-methylthiazole-5-carboxylate (7d). IR
1
spectrum, ν, cm–1: 1714 (C=O). H NMR spectrum
(1-Hexyl-1H-1,2,3-triazol-4-yl)methyl 2-bromo-4-
methylthiazole-5-carboxylate (7i). IR spectrum, ν,
(CDCl3), δ, ppm: 8.03 s (1H), 7.74–7.55 m (2H), 7.51–
7.38 m (2H), 5.42 s (2H), 2.62 s (3H). 13C NMR
spectrum (CDCl3), δ, ppm: 160.0, 159.8, 158.9, 154.2,
139.3, 134.2, 133.8, 129.0, 121.3, 120.7, 57.2, 16.4,
16.3. Mass spectrum (ESI-MS): m/z 413 [M + H]+.
Found, %: C 40.62; H 2.49; N 13.55. C14H10BrClN4O2S.
Calculated, %: C 40.65; H 2.44; N 13.54.
1
cm–1: 1711 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 7.66 s (1H), 5.36 s (2H), 4.37 t (J = 5.8 Hz, 2H),
2.57 s (3H), 1.95–1.84 m (4H), 1.48–1.28 m (4H), 0.96
t (J = 7.4 Hz, 3H). 13C NMR spectrum (CDCl3), δ,
ppm: 175.7, 162.2, 157.6, 142.7, 123.7, 113.1, 68.1,
57.9, 50.1, 32.2, 19.7, 17.6, 14.3, 13.4. Mass spectrum
(ESI-MS): m/z 387 [M + H]+. Found, %: C 43.40; H
4.91; N 14.42. C14H19BrN4O2S. Calculated, %: C
43.42; H 4.94; N 14.47.
[1-(4-Nitrophenyl)-1H-1,2,3-triazol-4-yl]methyl
2-bromo-4-methylthiazole-5-carboxylate (7e). IR
1
spectrum, ν, cm–1: 1713 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 8.13 s (1H), 7.74 d (J = 7.7 Hz, 2H),
7.54 d (J = 7.6 Hz, 2H), 5.58 s (2H), 2.69 s (3H). 13C
NMR spectrum (CDCl3), δ, ppm: 164.2, 161.8, 154.8,
140.9, 137.9, 132.8, 129.2, 123.4, 121.8, 120.1, 57.9,
17.3. Mass spectrum (ESI-MS): m/z 424 [M + H]+.
Found, %: C 39.60; H 2.42; N 16.49. C14H10BrN5O4S.
Calculated, %: C 39.64; H 2.38; N 16.51.
(1-Octyl-1H-1,2,3-triazol-4-yl)methyl 2-bromo-4-
methylthiazole-5-carboxylate (7j). IR spectrum, ν,
1
cm–1: 1722 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 7.72 s (1H), 5.41 s (2H), 4.35 t (J = 5.5 Hz, 2H),
2.59 s (3H), 1.81–1.75 m (2H), 1.15–1.33 m (10H),
0.85 t (J = 7.0 Hz, 3H). 13C NMR spectrum (CDCl3), δ,
ppm: 174.8, 161.8, 157.1, 142.0, 123.9, 112.9, 67.7,
58.2, 49.8, 32.6, 19.8, 19.3, 18.3, 17.8, 14.6, 13.6.
Mass spectrum (ESI-MS): m/z 415 [M + H]+. Found,
%: C 46.22; H 5.66; N 13.44. C16H23BrN4O2S.
Calculated, %: C 46.27; H 5.58; N 13.49.
[1-(3-Chlorophenyl)-1H-1,2,3-triazol-4-yl]methyl
2-bromo-4-methylthiazole-5-carboxylate (7f). IR
1
spectrum, ν, cm–1: 1723 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 8.06 s (1H), 7.78–7.62 m (3H), 7.75–
7.49 m (1H), 5.49 s (2H), 2.56 s (3H). 13C NMR
spectrum (CDCl3), δ, ppm: 161.9, 159.9, 154.3, 138.2,
136.4, 133.9, 132.8, 128.9, 128.3, 127.4, 123.9, 120.8,
59.4, 18.1. Mass spectrum (ESI-MS): m/z 413 [M + H]+.
Found, %: C 40.59; H 2.41; N 13.58. C14H10BrClN4O2S.
Calculated, %: C 40.65; H 2.44; N 13.54.
[1-(2-Morpholino-2-oxoethyl)-1H-1,2,3-triazol-4-
yl]methyl 2-bromo-4-methylthiazole-5-carboxylate
(7k). IR spectrum, ν, cm–1: 1636 (C=O), 1704 (C=O).
1H NMR spectrum (CDCl3), ppm: 7.85 s (1H), 5.38 s
(2H), 5.24 d (J = 7.2 Hz, 2H), 3.67–3.63 m (2H), 3.62–
3.56 m (2H), 3.55–3.50 m (2H), 3.49–3.43 m (2H)
2.58 s (3H). 13C NMR spectrum (CDCl3), δ, ppm:
171.8, 163.4, 161.1, 143.5, 136.8, 133.4, 125.4, 66.6,
66.3, 65.9, 57.4, 47.9, 45.8, 17.7. Mass spectrum (ESI-
MS): m/z 430 [M + H]+. Found, %: C 39.01; H 3.72; N
16.23. C14H16BrN5O4S. Calculated, %: C 39.08; H
3.75; N 16.28.
[1-(3-Nitrophenyl)-1H-1,2,3-triazol-4-yl]methyl
2-bromo-4-methylthiazole-5-carboxylate (7g). IR
1
spectrum, ν, cm–1: 1716 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 8.14 s (1H), 7.87–7.75 m (3H), 7.64–
7.58 m (1H), 5.52 s (2H), 2.58 s (3H). 13C NMR
spectrum (CDCl3), δ, ppm: 163.8, 161.7, 154.3, 141.2,
138.6, 133.9, 132.6, 129.1, 128.8, 123.8, 121.6, 113.2,
61.2, 18.0. Mass spectrum (ESI-MS): m/z 424 [M + H]+.
Found, %: C 39.61; H 2.44; N 16.48. C14H10BrN5O4S.
Calculated, %: C 39.64; H 2.38; N 16.51.
[1-(4-Nitrobenzyl)-1H-1,2,3-triazol-4-yl]methyl
2-bromo-4-methylthiazole-5-carboxylate (7l). IR
1
spectrum, ν, cm–1: 1728 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 8.25 d (J = 8.78 Hz, 2H), 7.68 s
(1H), 7.43 d (J = 8.78 Hz, 2H), 5.66 s (2H), 5.41 s
(2H), 2.67 s (3H). 13C NMR spectrum (CDCl3), δ,
ppm: 163.9, 160.8, 155.6, 154.1, 139.2, 136.1, 129.1,
123.8, 122.6, 120.6, 58.8, 54.2, 18.1. Mass spectrum
(ESI-MS): m/z 438 [M + H]+. Found, %: C 45.78; H
3.28; N 14.28. C15H13BrN4O2S. Calculated, %: C
45.81; H 3.33; N 14.25.
[1-(4-Methoxy-2-nitrophenyl)-1H-1,2,3-triazol-4-
yl]methyl 2-bromo-4-methylthiazole-5-carboxylate
(7h). IR spectrum, ν, cm–1: 1708 (C=O). 1H NMR spec-
trum (CDCl3), δ, ppm: 8.01 s (1H), 7.68 s (1H), 7.54–
7.48 m (2H), 5.61 s (2H), 4.28 s (3H), 2.58 s (3H). 13C
NMR spectrum (CDCl3), δ, ppm: 166.7, 162.8, 159.9,
154.3, 141.6, 138.7, 133.8, 130.2, 122.3, 121.8, 120.2,
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FACILE SYNTHESIS OF NOVEL (1-ARYL/ALKYL-1H-1,2,3-TRIAZOL-...
1729
p. 1679.
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