A Simple Efficient Click Synthesis of Novel Crown Ethers Containing 1,2,3-Triazole Moieties

Article abstract of DOI:10.1134/S1070428019110228

Novel crown ether derivative containing 1,4-disubstituted-1,2,3-triazole moieties were synthesized. At the first step of the synthesis 4,13-diaza-18-crown-6 and 4-aminobenzo-15-crown-5 were converted into terminal alkynes, which were then subjected to copper(I)-catalyzed alkyne-azide coupling (CuAAC) in methylene chloride. This coupling reaction was performed according to the concept of click chemistry, using an Amberlyst A-21-supported copper(I) iodide catalyst.

Full text of DOI:10.1134/S1070428019110228

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 11, pp. 1785–1790. © Pleiades Publishing, Ltd., 2019.
A Simple Efficient Click Synthesis of Novel Crown Ethers
Containing 1,2,3-Triazole Moieties
H. Elamaria, A. Ouerghuib,c,*, F. Ammaric, and C. Girarda
a Unit of Chemical and Biological Technologies for Health, UMR 8258 CNRS/U 1022 Inserm, National Chemical
Engineering Institute in Paris, Chimie Paristech – PSL Research University,
11 rue Pierre et Marie Curie, Paris, 75005 France
b Unit of Functional Physiology and Valorization of Bioresources (UR17ES27), Higher Institute of Biotechnology of Beja,
University of Jendouba, Beja, 9000 Tunisia
c Laboratory of Organic Chemistry and Applications (Unit 05/UR/12-05 ), Faculty of Sciences of Bizerte, University of Carthage,
Bizerte, 7021 Tunisia
*e-mail: ouerghiabid@gmail.com
Received June 30, 2019; revised August 25, 2019; accepted September 3, 2019
Abstract—Novel crown ether derivative containing 1,4-disubstituted-1,2,3-triazole moieties were synthesized.
At the first step of the synthesis 4,13-diaza-18-crown-6 and 4-aminobenzo-15-crown-5 were converted into
terminal alkynes, which were then subjected to copper(I)-catalyzed alkyne–azide coupling (CuAAC) in
methylene chloride. This coupling reaction was performed according to the concept of click chemistry, using an
Amberlyst A-21–supported copper(I) iodide catalyst.
Keywords: terminal alkynes, crown ethers, click chemistry, CuAAC, copper(I) catalysis, 1,2,3-triazoles
DOI: 10.1134/S1070428019110228
Heterocyclic compounds containing a triazole motif
play an important role in therapeutics [1]. These
compounds have several interesting biological
applications due to their antimicrobial [2–6], anti-
inflammatory [7], antifungal [8, 9] and antitumor
activity [10–12]. On the other hand, substituted 1,2,3-
triazoles are molecules for organic synthesis, because
they present as key structural units in many
pharmaceuticals. It is for this reason, heterocyclic
compounds containing triazole units are important in
several areas [13–17].
catalyst (Amberlyst A-21·CuI) prepared as described
in [26]. The use of Amberlyst A-21·CuI in this organic
synthesis was motivated by that our aim was to obtain
1,4-disubstituted-1,2,3-triazole derivatives but not their
mixtures with 1,5-isomers [15, 20] and the copper(I)
catalyst could be easily removed, not applying organic
solvents or nitrogen compounds [21]. Thus, using
Amberlyst A-21·CuI allows minimization of a loss of
the synthesized triazole derivatives and ensures high
synthetic yields [15, 22].
According to the LC/MS-ELSD data, 1,2,3-
triazole-containing crown ethers 2a–2f and 4a–4d
(Schemes 2 and 3) had a good purity ranging from 94
to 100%. These results are consistent with those
obtained by Jlalia et al. [15]. The efficiency of the
synthesis varied from 84 to 97%, which is better than
in the work of Tilliet et al. [18], where a macrocycle
derived from 4,13-diaza-18-crown-6 and containing
1,2,3-triazole moieties was synthesized in a yield not
exceeding 21%.
The present paper reports the synthesis of
novel 1,4-disubstituted-1,2,3-triazole derivatives of
4-aminobenzo-15-crown-5 and 4,13-diaza-18-crown-6
(Scheme 1). The CuAAC method used in this synthesis
was based on the concept of click chemistry [18, 19].
As the a first step, we converted 4,13-diaza-18-
crown-6 and benzo-15-crown-5 into terminal alkynes.
The second step involved a coupling reaction between
the synthesized alkynes with azides prepared by
known procedures [15, 20, 23–25]. The coupling
reaction was carried out at room temperature in the
presence of an Amberlyst A-21-supported copper(I)
The newly synthesized heterocyclic compounds
2a–2f and 4a–4d were characterized by IR and 1H and
13C NMR, elemental analysis, and LCMS.
1785

ELAMARI et al.
1786
Scheme 1.
O
O
O
O
O
O
N
N
N
Dichloromethane
rt, 16 h
Crown Ether
+
Crown Ether
N3
R
O
O
PS
NMe2
CuI
R
n
Amberlyst A-21-CuI
EXPERIMENTAL
Acetonitrile (spectrometric grade, low water) was
purchased from SDS France and used as received.
Dichloromethane (SDS France) was treated with
phosphorus pentoxide under reflux (1 h) and then
distilled.
Copper(I) iodide was purchased from Lancaster,
4,13-diaza-18-crown-6, 4-aminobenzo-15-crown-5,
propargyl chloroformate, propiolic acid, 1,3-dicyclo-
hexyl carbodiimide, and Amberlyst A21 resin (20–
50 mesh) were purchased from Sigma Aldrich.
The melting points were determined using a Kofler
apparatus in two steps: after initial estimation, the
device was calibrated against a reference standard with
a melting point close to the estimated value and then a
final measurement was made. The IR spectra were
recorded neat on a Jasco FT/IR-4100 in the ATR mode
Azides were prepared from sodium azide, benzyl
bromide, 3-chloropropanol, ethyl bromoacetate, phe-
nylboronic acid, p-tolylboronic acid, 2-bromoethyl
acetate and benzyl bromoacetate (after treatment with
ethyl trifluoroacetate) following published procedures
[15, 20, 23–25].
1
(PIKE-MIRacle) between 4000 and 400 cm–1. The H
and 13C NMR spectra were recorded on a Bruker
Scheme 2.
O
O
O
O
O
O
O
O
O
O
O
O
Propargyl chloroformate
HN
N
NH
N
Na2CO3, CH3CN
rt, 24 h
4,13-diaza-18-crown-6
1, yield 84%
N
R
N
N
O
O
O
O
O
O
N
N
R
N3
O
O
A-21-CuI, CH2Cl2, 16 h
N
N
N
R
2a_2f
2, R = C2H5OCOCH2 (a); HO(CH2)3 (b); AcOC2H4 (c); PhCH2 (d); 4-Me-Ph (e); Ph (f).
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A SIMPLE EFFICIENT CLICK SYNTHESIS OF NOVEL CROWN ETHERS
1787
Scheme 3.
H
O
O
N
O
O
NH2
O
O
Propiolic Acid
O
O
DCC, CH2Cl2
rt, 4 h
O
O
O
4-Aminobenzo-15-crown-5
3, yield 62%
H
N
N
O
N
R
N
R
N3
O
O
O
A-21-CuI, CH2Cl2, 16 h
O
O
4a_4d
4, R = C2H5OCOCH2 (a); AcOC2H4 (b); Ph-CH2OCOCH2 (c); PhCH2 (d).
Avance DRX instrument in CDCl3 (unless otherwise
specifies) at 300 (1H) and 75.5 (13C) MHz, respec-
tively, internal reference TMS. Liquid chromatog-
raphy–mass spectrometry was performed on a
Shimadzu LCSM-2010 A instrument equipped with a
SPD-M10 A PDA diode array detector (D2, lamp from
190 to 400 nm) and an ELSD-LT light scattering
detector. Liquid chromatography was performed on an
Alltech Alltima HP C8 3μm reversed-phase HPLC
column (53 × 7 mm ID) and a mobile phase comp-
rising MeCN, water, and 0.1% formic acid at a flow
rate of 1 mL/min; the MeCN/water gradient was as
follows: 0–1 min: 30% MeCN; 1–5 min: ramp from
30% to 100% MeCN; 5–12 min: 100% MeCN; 12–
14.99 min: ramp from 100% to 30% MeCN; and
14.99–20 min: 30% MeCN. The ESI mass spectra
were recorded in the m/z range 100–500 in the positive
ion mode (detector 1.5 kV, quadrupole 5 V). Elemental
analysis was performed on a Perkin-Elmer 2400 Series
II CHN analyzer.
3.59–3.70 m (12H, 6CH2), 4.72 d (2H, CH2). 13C NMR
spectrum (CDCl3), δ, ppm: 47.97, 48.04, 48.67, 52.88,
69.84, 69.88, 70.12, 70.16, 70.56, 70.60, 70.65, 70.71,
74.44, 78.51, 155.34. Found, %: C 56.211; H 7.029;
N 6.540; O 29.950. C20H30N2O8. C20H30N2O8. Calcu-
lated, %: C 56.328; H 7.090; N 6.569; O 30.013. Mass
spectrum: m/z 427 [M + H]+
N-(2,3,5,6,8,9,11,12-Octahydro-1,4,7,10,13-ben-
zopentaoxacyclopentadecyn-15-yl)prop-2-ynamide
(3). Propiolic acid, 350 mg (5 mmol), was added to a
solution of 1.41g (5 mmol) of 4-aminobenzo-15-
crown-5 in 10 mL of CH2Cl2. After slow agitation at
0°C for 30 min, 1.28 g of DCC (6.25 mmol) in CH2Cl2
(10 mL) was added. The mixture was stirred at room
temperature for 4 h and then cooled in ice water,
filtered through celite, and washed with 20 mL of 1M
HCl, 20 mL of saturated aqueous NaHCO3, and 20 mL
of water. After drying over MgSO4 and evaporation of
the solvent under vacuum, alkyne 3 was purified by
column chromatography in heptane–EtOAc, 13 : 7.
Yield 1.03 g (62%), beige solid, mp 146°C. IR spec-
trum, ν, cm–1: 3375 (NH), 3186 (CH), 2895–2857
7,16-Bis(prop-2-yn-1-yl)-1,4,10,13-tetraoxa-7,16-
diazacyclooctadecane-7,16-dicarboxylate (1). Pro-
pargyl chloroformate, 0.47 g (4 mmol) was slowly
added to a solution of 0.52 g (2 mmol) of diaza-18-
crown-6 in 15 mL of MeCN in the presence of 0.21 g
(2 mmol) of Na2CO3. The mixture was stirred for 24 h
at room temperature. Filtration and evaporation of the
solvents under vacuum gave macrocyclic alkyne 1 as a
white solid. Yield 0.71 g (84%), mp 108°C. IR spec-
1
(CH2), 2093 (C≡C), 1650 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 2.99 s (1H, C≡CH), 3.73 s (8H,
4CH2), 3.86–3.87 m (4H, 2CH2), 4.07 m (4H, 2CH2),
6.72 d (1H), 7.01 d.d (1H), 7.29 d (1H), 8.67 s (1H,
NH). 13C NMR spectrum (CDCl3), δ, ppm: 68.75,
69.31, 69.50, 70.35, 70.39, 70.84, 74.46, 77.78,
107.19, 112.96, 114.36, 131.46, 146.16, 149.05,
149.95. Found, %: C 60.821; H 6.290; N 4.170; O
28.113. C17H21NO6. Calculated, %: C 60.886; H 6.311;
1
trum, ν, cm–1: 3053–2945 (CH2), 1737 (C=O). H
NMR spectrum (CDCl3), δ, ppm: 2.48 t (1H, C≡CH),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019

ELAMARI et al.
1788
N 4.177; O 28.625. Mass spectrum: m/z 358 [M +
liquid. IR spectrum, ν, cm–1: 3100–2954 (CH2), 1738
(C=O), 1688 (N=N). 1H NMR (CDCl3), δ, ppm: 2.03 s
(3H, CH3), 3.49–3.57 m (12H, 6CH2), 4.43–4.58 m
(4H, 2CH2), 5.17 s (2H, CH2), 7.68 s (1H, C=CH). 13C
NMR spectrum (CDCl3), δ, ppm: 20.54, 47.71, 48.29,
48.87, 58.10, 62.15, 69.65, 69.79, 70.31, 124.42,
143.57, 155.77, 170.20. Found, %: C 49.07; H 6.324;
N 16.05; O 28.01. C28H44N8O12. Calculated, %: C
49.117; H 6.477; N 16.365; O 28.040. Mass spectrum:
m/z 686 [M + H]+.
Na]+.
Copper(I)-catalyzed alkyne–azide coupling
reaction (general procedure). Azide, 2.2 equiv, and
12 mg (0.016 mmol CuI, 8 mol %) of Amberlyst
A-21·CuI in 2 mL of CH2Cl2 were added to the
synthesized terminal alkyne, and the reaction mixture
was stirred at room temperature for 16 h, filtered, and
washed with 2 mL of CH2Cl2. The product was
obtained after evaporation of the solvent under
vacuum.
7,16-Bis[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]-
1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-
dicarboxylate (2d) was prepared from 0.213 g (0.5 mmol)
of alkyne 1 and 0.146 g (1.1 mmol) of benzyl azide
[15, 24, 25]. Yield 0.311g (90%), green solid, mp 88°C.
IR spectrum, ν, cm–1: 3120 (CH), 2941 (CH2), 1715
7,16-Bis{[1-(2-ethoxy-2-oxoethyl)-1H-1,2,3-tri-
azol-4-yl]methyl}1,4,10,13-tetraoxa-7,16-diaza-
cyclooctadecane-7,16-dicarboxylate (2a) was prepa-
red from 0.213 g (0.5 mmol) of alkyne 1 and 0.142 g
(1.1 mmol) of ethyl azidoacetate [15, 20, 25]. Yield
0.318 g (93%), white solid, mp 110°C. IR spectrum,
ν, cm–1: 3021–2970 (CH2), 2285 (CH3), 1741 (C=O),
1
(C=O), 1696 (N=N). H NMR spectrum (CDCl3),
δ, ppm: 2.44 s (3H, CH3), 3.56–3.65 m (12H, 6CH2),
5.28 s (2H, CH2), 7.33–7.62 m (4H), 8.07 s (1H,
C=CH). 13C NMR spectrum (CDCl3), δ, ppm: 21.12,
48.02–48.59, 58.40, 69.27, 69.47, 69.97, 120.49,
125.83, 129.19, 130.28, 138.60, 156.04. Found, %: C
58.865; H 6.380; N 15.989; O 18.187. C34H44N8O8.
Calculated, %: C 58.948; H 6.401; N 16.175; O
18.476. Mass spectrum: m/z 694 [M + H]+.
1
1699 (N=N). H NMR spectrum (CDCl3), δ, ppm:
1.23–1.29 m (3H, CH3), 3.50–3.59 m (12H, 6CH2),
4.21–4.25 m (2H, CH2), 5.13 d (2H, CH2), 5.20 s (2H,
CH2), 7.76 s (1H, C=CH). 13C NMR spectrum
(CDCl3), δ, ppm: 13.61, 47.48, 48.06, 50.42, 57.87, 62,
69.35, 69.50, 69.56, 70.06, 124.64, 124.95, 155.45,
165.70. C28H44N8O12. Calculated, %: C 49.118; H
6.477; N 16.365; O 28.041. Found, %: C 48.987; H
6.234; N 16.118; O 28.029. Mass spectrum: m/z 686
[M + H]+.
7,16-Bis{[1-(4-methylphenyl)-1H-1,2,3-triazol-4-
yl]methyl}1,4,10,13-tetraoxa-7,16-diazacycloocta-
decane-7,16-dicarboxylate (2e) was prepared from
0.213 g (0.5 mmol) of alkyne 1 and 0.133 g (1.1 mmol)
of 1-azido-4-methylbenzene [24]. Yield 0.304 g (88%),
brown liquid. IR spectrum, ν, cm–1: 3055 (CH), 2956
7,16-Bis{[1-(3-hydroxypropyl)-1H-1,2,3-triazol-
4-yl]methyl}1,4,10,13-tetraoxa-7,16-diazacyclo-
octadecane-7,16-dicarboxylate (2b) was prepared
from 0.213 g (0.5 mmol) of alkyne 1 and 0.111 g
(1.1 mmol) of 3-azidopropan-1-ol [15, 23]. The pro-
duct was obtained as a yellow solid. Yield 0.264 g
(84%), yellow solid, mp 94°C. IR spectrum, ν, cm–1:
3110–2945 (CH2), 1746 (C=O), 1704 (N=N). 1H NMR
spectrum (CDCl3), δ, ppm: 1.80 s (1H, OH), 2.11 s
(2H, CH2), 3.43–3.73 m (14H, 7CH2), 4.50 s (2H,
CH2), 5.18 s (2H, CH2), 7.70 s (1H, C=CH). 13C NMR
spectrum (CDCl3), δ, ppm: 31.01, 32.06, 46.57–48.06,
57.95–59.29, 69.24, 70.06, 124.14, 155.56. Found, %:
C 49.582; H 7.012; N 17.718; O 25.218. C26H44N8O10.
Calculated, %: C 49.673; H 7.054; N 17.824; O
25.449. Mass spectrum: m/z 630 [M + H]+.
1
(CH2), 1720 (C=O), 1676 (N=N). H NMR spectrum
(CDCl3), δ, ppm: 3.39–3.67 m (12H, 6CH2), 4.71 d
(2H, CH2), 7.47–7.58 m (3H), 7.75–7.78 m (2H),
8.11 s (1H, C=CH). 13C NMR spectrum (CDCl3),
δ, ppm: 48.30, 48.55, 58.64, 70.36, 70.40, 70.37,
120.76, 122.43, 137.26, 146.59, 155.60. Found, %: C
58.889; H 6.390; N 16.080; O 18.351. C34H44N8O8.
Calculated, %: C 58.948; H 6.401; N 16.175; O
18.476. Mass spectrum: m/z 694 [M + H]+.
7,16-Bis[(1-phenyl-1H-1,2,3-triazol-4-yl)methyl]-
1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-di-
carboxylate (2f) was prepared from 0.213 g (0.5 mmol)
of alkyne 1 and 0.131g (1.1mmol) of azidobenze-
ne [24]. Yield 0.311g (90%), brown liquid. IR
spectrum, ν, cm–1: 3135 (CH), 3033–2955 (CH2), 1723
7,16-Bis({1-[2-(acetyloxy)ethyl]-1H-1,2,3-triazol-
4-yl}methyl)1,4,10,13-tetraoxa-7,16-diazacycloocta-
decane-7,16-dicarboxylate (2c) was prepared from
0.213 g (0.5 mmol) of alkyne 1 and 0.142 g (1.1 mmol)
of 1-azidoethyl acetate [25]. Yield 0.314g (92%), beige
1
(C=O), 1682 (N=N). H NMR spectrum (CDCl3), δ,
ppm: 3.49–3.55 m (12H, 6CH2), 5.18 s (2H, CH2),
5.28 s (2H, CH2), 7.25–7.34 m (5H), 7.54 s (1H,
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A SIMPLE EFFICIENT CLICK SYNTHESIS OF NOVEL CROWN ETHERS
1789
C=CH). 13C NMR spectrum (CDCl3), δ, ppm: 47.39,
47.92, 55.30, 57.50, 69.26, 69.96, 127.61, 123.23,
123.30, 128.22, 128.80, 133.95, 138.54, 143.34,
143.39, 155.61. Found, %: C 57.658; H 6.047; N
16.657; O 19.178. C32H40N8O8. Calculated, %: C
57.822; H 6.065; N 16.857; O 19.255. Mass spectrum:
m/z 666 [M + H]+.
3293 (NH), 3003 (CH), 2864 (CH2), 1753 (C=O),
1650 (N=N). H NMR spectrum (CDCl3), δ, ppm:
1
3.80 s (8H, 4CH2), 3.93–3.97 m (4H, 2CH2), 4.16–
4.23 m (4H, 2CH2), 5.30 s, 2H), 6.86–6.92 d.d (1H)
7.38–7.50 m (6H), 8.30 s (1H, C=CH), 8.86 s (1H,
NH). 13C NMR spectrum (CDCl3), δ, ppm: 50.39,
51.20, 67.58, 68.32, 68.79, 69.46, 69.69, 70.40, 70.56,
71.07, 106.68, 112.34, 114.87, 127.26, 128.59, 128.71,
128.98, 131.65, 134.39, 143.93, 145.95, 149.41,
157.34, 165.67; Found, %: C 59.304; H 5.470; N
10.538; O 24.297. C26H30N4O8. Calculated, %: C
59.308; H 5.742; N 10.640; O 24.308. Mass spectrum:
m/z 549 [M + Na]+.
Ethyl 2-{4-[(2,3,5,6,8,9,11,12-octahydro-
1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-
carbamoyl]-1H-1,2,3-triazol-1-yl}acetate (4a) was
prepared from 67 mg (0.2 mmol) of alkyne 3 and
28 mg (0.22 mmol) of ethyl azidoacetate [25, 20, 15].
Yield 90.10 mg (97%), brown solid, mp 182°C. IR
spectrum, ν, cm–1: 3296 (NH), 2941 (CH), 2875 (CH2),
1752 (C=O), 1654 (N=N). 1H NMR spectrum (CDCl3),
δ, ppm: 1.34 t (3H, CH3), 3.79 s (8H, 4CH2), 3.93–
3.96 m (4H, 2CH2), 4.15–4.22 m (4H, 2CH2), 4.32 q
(2H, CH2), 5.26 s (2H, CH2), 6.89 d (1H), 7.11 d.d
(1H), 7.49 d (1H), 8.29 s (1H, C=CH), 8.87 s (1H,
NH). 13C NMR spectrum (CDCl3), δ, ppm: 14.09, 51.24,
62.38, 68.35–71.51, 106.79, 112.40, 114.91, 127.14,
131.61, 143.96, 146.05, 149.47, 157.37, 165.60.
Found, %: C 54.198; H 6.069; N 12.049; O 27.489.
C21H28N4O8. Calculated, %: C 54.305; H 6.076; N
12.062; O 27.557. Mass spectrum: m/z 465 [M + H]+.
1-Benzyl-N-(2,3,5,6,8,9,11,12-octahydro-
1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-
1H-1,2,3-triazole-4-carboxamide (4d) was prepared from
67 mg (0.2 mmol) of alkyne 3 and 28.5 mg (0.22 mmol)
of benzyl azide [15, 24, 25]. Yield 89.95 mg (96%),
yellow solid, mp 200°C. IR spectrum, ν, cm–1: 3299
(NH), 3048 (CH), 2937 (CH2), 1659 (C=O), 1610
1
(N=N). H NMR spectrum (CDCl3), δ, ppm: 3.74 s
(8H, 4CH2), 3.93–3.96 m (4H, 2CH2), 4.16–4.21 m
(4H, 2CH2), 5.62 s (2H, CH2), 6.88–6.91 m (1H),
7.09–7.13 m (1H), 7.32–7.47 m (6H), 8.05 s (1H,
C=CH), 8.86 s (1H, NH). 13C NMR spectrum (CDCl3),
δ, ppm: 54.80, 68.99, 69.62, 69.83, 70.61, 70.77,
71.19, 71.24, 106.93, 112.52, 115.04, 125.65, 128.40,
129.32, 129.47, 131.71, 133.78, 143.95, 146.14,
149.58, 157.68. Found, %: C 61.413; H 5.998; N
11.768; O 20.118. C24H28N4O6. Calculated, %: C
61.528; H 6.024; N 11.958; O 20.490. Mass spectrum:
m/z 469 [M + H]+.
2-{4-[(2,3,5,6,8,9,11,12-Octahydro-1,4,7,10,13-
benzopentaoxacyclopentadecin-15-yl)-carbamoyl]-
1H-1,2,3-triazol-1-yl}ethyl acetate (4b) was prepared
from 67 mg (0.2 mmol) of alkyne 3 and 28 g (0.22 mmol)
of 1-azidoethyl acetate [25]. Yield 87.31 mg (94%),
beige solid, mp 182°C. IR spectrum, ν, cm–1: 3385
(NH), 2933 (CH), 2870 (CH2), 1746 (C=O), 1662
1
(N=N). H NMR spectrum (CDCl3), δ, ppm: 2.10 s
CONCLUSIONS
(3H, CH3), 3.79 s (8H, 4CH2), 3.93–3.96 m (4H,
2CH2), 4.15–4.23 m (4H, 2CH2), 4.52 t (2H, CH2),
4.72 t (2H, CH2), 6.89 d (1H), 7.11 d.d (1H), 7.48 d
We realized a click synthesis of some novel 1,2,3-
triazole derivatives. These heterocyclic compounds
were synthesized from 4,13-diaza-18-crown-6 or
4-aminobenzo-15-crown-5 and azides in the presence
of an easily prepared Amberlyst A-21-supported
copper(I) catalyst with high purities and very good
yields. Following the approach of Jlalia et al. [15],
developed for the synthesis of 1,2,3-triazole
derivatives, starting from small molecules, we found
that the same approach is also suitable for supra-
molecular chemistry.
13
(1H), 8.22 s (1H, C=CH), 8.89 s (1H, NH). C NMR
spectrum (CDCl3), δ, ppm: 20.98, 49.93, 62.44, 69.14-
71.38, 107.04, 112.67, 115.12, 126.53, 131.85, 144.07,
146.33, 149.73, 157.80 170.61. Found, %: C 54.119; H
6.054; N 12.047; O 27.478. C21H28N4O8. Calculated, %:
C 54.305; H 6.076; N 12.062; O 27.557. Mass spec-
trum: m/z 465 [M + H]+.
Benzyl 2-{4-[(2,3,5,6,8,9,11,12-octahydro-
1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-
carbamoyl]-1H-1,2,3-triazol-1-yl}acetate (4c) was
prepared from 67 mg (0.2 mmol) of alkyne 3 and 42 g
(0.22 mmol) of benzyl azidoacetate [25]. Yield 96.88 mg
(92%), beige solid, mp 168°C. IR spectrum, ν, cm–1:
CONFLICT OF INTEREST
The authors declare no conflict of interest.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019

ELAMARI et al.
13. Hajri, A. and Marzouki, M.L., Heterocycl. Commun.,
1790
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