One-pot synthesis of 1-(E)-phenylethenyl-1,2,3-triazoles by sequential click-elimination reaction from 2-azido-1-phenyl-1-(Phenylseleno)ethane

Article abstract of DOI:10.1080/10426507.2013.769987

A new convenient one-pot, two-step procedure involving sequential click chemistry and oxidation-elimination reaction for the preparation of 1,4-disubstituted 1,2,3-triazoles bearing 1-(E)-phenylethenyl group from 2-azido-1-phenyl-1-(phenylseleno)ethane is described. The prominent features of this protocol are mild reaction conditions, operational simplicity, and good to high yields of products, as well as avoidance of the isolation of the selenated intermediate. Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional figures.

Full text of DOI:10.1080/10426507.2013.769987

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One-Pot Synthesis of 1-(E)-
Phenylethenyl-1,2,3-Triazoles
by Sequential Click-Elimination
Reaction from 2-Azido-1-Phenyl-1-
(
Phenylseleno)Ethane
a b
c
a
Hai-You Su , Shou-Ri Sheng , Xiao-Lan Zhang , Xiao-Ying Ding
&
a
Ming-Zhong Cai
a
Institutes of Chemistry and Chemical Engineering , Jiangxi Normal
University , Nanchang , P.R. China
b
Key Laboratory of Functional Small Organic Molecule, Ministry of
Education , Jiangxi Normal University , Nanchang , P.R. China
c
Department of Chemistry , Shangrao Normal College , Shangrao ,
P.R. China
Accepted author version posted online: 05 Apr 2013.Published
online: 20 Sep 2013.
To cite this article: Hai-You Su , Shou-Ri Sheng , Xiao-Lan Zhang , Xiao-Ying Ding & Ming-Zhong Cai
(2013) One-Pot Synthesis of 1-(E)-Phenylethenyl-1,2,3-Triazoles by Sequential Click-Elimination
Reaction from 2-Azido-1-Phenyl-1-(Phenylseleno)Ethane, Phosphorus, Sulfur, and Silicon and the
Related Elements, 188:11, 1591-1598, DOI: 10.1080/10426507.2013.769987
To link to this article: http://dx.doi.org/10.1080/10426507.2013.769987
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Phosphorus, Sulfur, and Silicon, 188:1591–1598, 2013
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2013.769987
ONE-POT SYNTHESIS OF
-(E)-PHENYLETHENYL-1,2,3-TRIAZOLES BY
SEQUENTIAL CLICK-ELIMINATION REACTION FROM
-AZIDO-1-PHENYL-1-(PHENYLSELENO)ETHANE
1
2
1
2
3
Hai-You Su, Shou-Ri Sheng, Xiao-Lan Zhang,
1
1
Xiao-Ying Ding, and Ming-Zhong Cai
Institutes of Chemistry and Chemical Engineering, Jiangxi Normal University,
Nanchang, P.R. China
1
2
Key Laboratory of Functional Small Organic Molecule, Ministry of Education,
Jiangxi Normal University, Nanchang, P.R. China
3
Department of Chemistry, Shangrao Normal College, Shangrao, P.R. China
GRAPHICAL ABSTRACT
Abstract A new convenient one-pot, two-step procedure involving sequential click chemistry
and oxidation-elimination reaction for the preparation of 1,4-disubstituted 1,2,3-triazoles bear-
ing 1-(E)-phenylethenyl group from 2-azido-1-phenyl-1-(phenylseleno)ethane is described. The
prominent features of this protocol are mild reaction conditions, operational simplicity, and
good to high yields of products, as well as avoidance of the isolation of the selenated interme-
diate.
Supplementary materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental
files: Additional figures.
Keywords 1-(E)-Phenylethenyl-1,2,3-triazoles; one-pot; 2-azido-1-phenyl-1-(phenylseleno)
ethane; click chemistry; oxidation-elimination
Received 12 December 2012; accepted 22 January 2013.
Financial support from the National Natural Science Foundation of China (No. 21062007) and the Research
Program of Jiangxi Province Department of Education (Nos. GJJ10385, GJJ10733, and GJJ11380) is gratefully
acknowledged.
Address correspondence to Dr. Shou-Ri Sheng, Jiangxi Normal University, Institutes of Chemistry and
Chemical Engineering, Nanchang 330022, P.R. China. E-mail: shengsr@jxnu.edu.cn
1
591

1
592
H.-Y. SU ET AL.
INTRODUCTION
Heterocyclic compounds are important structural units useful in medicinal chem-
1
istry and valuable as synthetic organic building blocks. Among the various heterocycles,
the 1,2,3-triazole class of heterocycles has attracted considerable interest because of its
2
3
4
biological activities including antimicrobial, antiallergic, and anti-HIV properties, and
5
–7
8–10
14
its wide applications in many fields such as organic synthesis, material science,
Since the discovery from the research groups of Sharpless
and Meldal, the copper (I)-catalyzed 1,3-dipolar Huisgen cycloaddition reaction between
azides and terminal alkynes (CuAAC), “click-chemistry” has received growing interest in
the regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles efficiently.
11–13
and medicinal chemistry.
15
16
1
7–23
Because of
their importance, numerous structurally different 1,2,3-triazoles have been developed. But,
2
4–26
less attention has been focused on the synthesis of styryl-substituted 1,2,3-triazoles.
Therefore, the synthesis of functionalized 1,2,3-triazoles containing a styryl group via a
simple, step-economic, less hazardous methodology is still in demand.
It is well known that organoselenium reagents have been increasingly used as a
powerful tool for the introducing new functional groups into organic substrates under ex-
tremely mild conditions.27 For instance, the phenylseleno group is readily converted to a
leaving group giving access to a carbon–carbon double bond via oxidation followed by
β-elimination. On the other hand, one-pot sequential multicomponent reactions (MCRs),
which combine two or more completely different reactions in a single transformation,
provide significant advantage over conventional stepwise synthesis avoiding tedious chro-
matographic purifications. For this reason, more recent sequential one-pot processes have
been utilized in rapid and convergent construction of 1,2,3-triazole molecules without the
isolation of intermediates.2
8–32
However, to our knowledge, there are few reported exam-
ples of the synthesis of 1,4-disubstituted 1,2,3-triazoles containing 1-phenylethyenyl group
2
5,27
except 1-(E)-phenylethenyl-4-phenyl-1,2,3-triazole.
As part of an ongoing research
33
program focused on the use organic selenium reagents in organic synthesis, we report
herein a one-pot, two-step route to the synthesis of 1-(E)-phenylethyenyl-1,2,3-triazoles
using 2-azido-1-phenyl-1-(phenylseleno)ethane (1) as original material by sequential click
and oxidation-elimination reactions, as depicted in Scheme 1.
Scheme 1
RESULTS AND DISCUSSION
In order to find the most suitable conditions for our purpose, copper (I) iodide as a
catalyst in combination with different solvents at room temperature, were initially investi-
gated using compound 134 and phenylacetylene (2a) as model substrates for the synthesis
of 1-(1-phenyl-1-phenylselenoethyl)-4-phenyl-1,2,3-triazole (3a), and the results are sum-
marized in Table 1. First of all, dichloromethane was chosen as the solvent, but no product
was obtained after the reaction proceed at room temperature even for 24 h in the presence

SYNTHESIS OF 1-(E)-PHENYLETHENYL-1,2,3-TRIAZOLES
1593
Table 1 Optimization conditions for the reaction of 1 and 2aa
Entry
Cu (I) catalyst
Solvent
Base
Time
Yield (%)b
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CH2Cl2
CH2Cl2
THF
t-BuOH
DMSO
CH3CN
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
CH3CN/H2O (4:1)
—
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Pyridine
i-Pr2NEt
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
24 h
24 h
24 h
24 h
24 h
15 h
10 h
15 h
15 h
24 h
24 h
24 h
6 h
—
48
50
42
70
88
94
75
70
75
65
60
62
1
1
1
1
1
1
1
1
1
CuSO4 /Na ascorbate
CuBr
CuCl
CuI
CuI
CuI
CuI
CuI
–
c
d
10 h
10 h
24 h
10 h
24 h
80 , 94
e
95
f
70
g
94
0
aReaction conditions: 1 (1.0 mmol), 2a (1.2 mmol), catalyst (10 mol%), base (1.2 mmol), solvent (5 mL), r.t.
b
Isolated yield based on 1 after column chromatography.
.0 equivalent of triethylamine was used.
.5 equivalent of triethylamine was used.
.5 mmol of 2a was used.
mol% of CuI was used.
5 mol% of CuI was used.
c
1
1
1
d
e
f
5
g
1
of 10 mol% copper (I) iodide (Table 1, entry 1). It was reported that organic bases could
promote the “click reaction,”15 when 1.2 equivalent of triethylamine was added to the re-
action system, the reaction gave a 48% yield of the corresponding compound 3a (Table 1,
entry 2), which is in accordance with the reported results that organic bases could promote
7
the generation of the active copper acetylide complex, mediating the “click” reaction.
Encouraged by this result, other polar solvents such as tetrahydrofuran (THF), t-BuOH,
CH3CN, and dimethyl sulfoxide (DMSO) were further examined. After several experi-
ments, it was found that CH3CN seems to be the best solvent to furnish good yield (88%)
(Table 1, entry 6). However, replacement of CH3CN with CH3CN/H2O (4:1) co-solvent
gave the desired product 3a in better yield (94%) within 10 h of reaction (Table 1, entry 7).
Thus, the CH3CN/H2O (4:1) was chosen as the typical co-solvent in subsequent optimiz-
ing experiments. Second, other organic bases such as diisopropylethylamine (DIPEA) and
pyridine were introduced into the reaction and resulted in a drop of yields (Table 1, entries
8
and 9). Furthermore, reactions with other copper (I)-catalysts including CuSO4·5H2O/Na
ascorbate, CuBr, and CuCl generated the desired product 3a in lower yield (Table 1, entries
0–12).
It is notable that the yield of 3a dramatically dropped to 62% when the reaction time
1
was decreased from 10 to 6 h (Table 1, entry 13). When 1.0 equivalent of triethylamine
was utilized, the reaction gave rise to a reduction of the yield, while adding 1.5 equivalent
of triethylamine to the reaction system, 3a was obtained with quite similar results (Table 1,
entry 14). Additionally, if the quantity of the 2a was increased from 1.2 to 1.5 equivalents,

1
594
H.-Y. SU ET AL.
Table 2 Yields of 1-(E)-phenylethenyl-1,2,3-triazoles (4a–4i)
Entry
R
Product
Yield (%) a
1
2
3
4
5
6
7
8
9
C6H5
4-C2H5C6H4
4a
4b
4c
4d
4e
4f
4g
4h
4i
90
91
89
88
86
83
84
85
82
2-CH3OC6H4OCH2
2-CH3C6H4OCH2
2-ClC6H4OCH2
2-NO2C6H4OCH2
4-NO2C6H4OCH2
2-Naphthoxymethyl
n-C4H9
aIsolated yield based on 1 after column chromatography.
the yield of 3a was not improved significantly (Table 1, entries 7 and 15). Nevertheless,
reducing the amount of CuI to 5 mol%, the 3a yield dropped to 70% (Table 1, entry 16),
whereas using 15 mol% CuI, the yield of the product 3a was not increased (Table 1, entry
17). Clearly, the reaction did not proceed in the absence of CuI (Table 1, entry 18).
Subsequently, oxidation-elimination of 3a with 30% hydrogen peroxide was per-
formed in CH3CN at room temperature to afford 1-(E)-phenylethenyl-4-phenyl-1,2,3-
triazole (4a) in 90% yield. Indeed, although selenated intermediate 3a can be isolated
and purified by chromatography, we have found it most convenient to carry out the oxida-
tion of the material in one-pot. Therefore, the one-pot preparation of 4a was carried out
again by treating 1 with phenylacetylene (2a) (1.2 equiv) in CH3CN/H2O (4:1) at room
temperature for 10 h in the presence of triethylamine (1.2 equiv), followed by the addition
excess of 30% hydrogen peroxide. After stirring for a further 1 h at room temperature
(monitoring by TLC), 4a was isolated in 90% yield as an exclusive product in one-pot,
two-step (Table 2, entry 1).
In order to prove the applicability of the conditions for the preparation of dif-
ferent triazoles bearing 1-substituted phenylethenyl group at position 1, the methodol-
ogy was extended to a series of terminal alkynes including aryl-, aryloxymethyl-, and
n-butylacetylenes. As shown in Table 2, both aromatic and aliphatic alkynes underwent the
reaction smoothly under the optimized reactions, and the corresponding 1,4-disubstituted
triazoles (4a–4i) were obtained exclusively in good to excellent yields (82% to 91%).
It should be pointed out that the (E) configuration of the double bond of all
products (4a–4i) was established from the coupling constants of the olefinic protons in
1
their NMR spectra. For example, in the H NMR spectrum of 1-(E)-phenylethenyl-4-(4-
nitrophenoxymethyl)-1,2,3-triazole (4g), the coupling constants (J = 14.8 Hz) between the
two olefinic protons at δ = 7.77 and 7.22 ppm were observed, which indicated its exclusive
1
production of E-isomer. In addition, the H NMR spectrum of 4g exhibited a typical singlet
at δ = 7.99 ppm for the triazolyl C5–H proton, and its IR spectrum showed a weak C C
–
1
–1
absorption at 1654 cm and a strong unsaturated C H stretch at 951 cm , corresponding
–
1
its (E) configuration, and the characteristic band at 1510 cm indicated the presence of a
nitro group.
Further, it is worthy to mention that the phenylseleno moiety, introduced in the starting
material, is eliminated as benzeneseleninic acid in the oxidation step. After neutralization

SYNTHESIS OF 1-(E)-PHENYLETHENYL-1,2,3-TRIAZOLES
1595
and acidification by addition of concd HCl to the alkaline aqueous extract, the water-
soluble benzeneseleninate was converted into benzeneseleninic acid. After treatment with
35,36
hydrazine monohydrate, diphenyl diselenide can be recovered
in 62% yield.
In summary, a novel one-pot tandem procedure for the synthesis of 1,4-disubstituted
,2,3-triazoles containing 1-(E)-phenylethenyl group have been developed by the reaction of
-azido-1-phenyl-1-(phenylseleno)ethane with terminal alkynes in the presence of copper
1
2
(I) iodide and triethylamine in CH3CN-H2O co-solvent, followed by treatment of 30%
H2O2. This convenient synthesis using sequential click chemistry and oxidation-elimination
reaction gives the corresponding target compounds in good to excellent yields with simple
work-up, mild reaction conditions, and without the isolation of the selenated intermediate.
Further studies on this subject are currently in progress.
EXPERIMENTAL
Melting points were measured with an XT-4 melting point apparatus and were uncor-
rected. IR spectra were recorded on a Perkin-Elmer SP One FT-IR spectrophotometer. Mass
spectra (EI, 70 eV) were recorded on a HP5989B mass spectrometer. Microanalyses were
performed with a Carlo Erba 1106 Elemental Analyzer. The NMR spectra were taken on a
1
13
Bruker 400 spectrometer operating at 400 MHz for H and 100 MHz for C, respectively,
with TMS as an internal standard, and the chemical shifts are reported in δ units. The values
of chemical shifts (δ) are given in ppm and coupling constants (J) in Hz. 2-Azido-1-phenyl-
34
1
-(phenylseleno)ethane (1) was prepared according to the literature procedures. The other
chemicals (AR grade) were obtained from commercial sources and used without further
purification. All reactions were monitored by thin-layer chromatography (TLC), which was
performed on silica gel 60 F254 (0.25 mm thickness), precoated aluminum sheets. Column
chromatography was performed on silica gel (60–120 mesh) using ethyl acetate/hexane
1
13
mixtures as the eluent. Selected H and C NMR spectra for the products are presented in
the Supplemental Materials (Figures S1–S18).
Preparation of Triazoles (4a–4i): General Procedure
To a solution of 2-azido-1-phenyl-1-(phenylseleno)ethane (1) (302 mg, 1.0 mmol) in
CH3CN/H2O (4:1, 5 mL) was added terminal alkyne (2) (1.2 mmol), Et3N (1.2 mmol) and
CuI (19 mg, 10 mol%), and the reaction mixture was stirred at room temperature. After
completion of the reaction (10–12 h, as monitored by TLC), the mixture was cooled to
◦
0
C, 30% hydrogen peroxide (1.0 mL, 11.6 mmol) was added, the reaction mixture was
then warmed to room temperature and stirred for 1–1.5 h until the reaction was finished as
determined by TLC. Finally, the resulting mixture was extracted with ether (3 ×10 mL),
and the combined organic layers were washed with brine (3 mL), dried over anhydrous
sodium sulfate, and concentrated under vacuum to give a crude product that was purified
by column chromatography eluted with ethyl acetate/hexane to afford 4a–4i.
◦
1
-(E)-Phenylethenyl-4-phenyl-1,2,3-triazole (4a). Pale yellow solid, mp 95–96 C
◦
1
(
(
1
lit.26 96–98 C). H NMR: δ = 7.79–7.77 (m, 2 H), 7.72 (s, 1 H), 7.42–7.32 (m, 8 H), 5.80
13
s, 1 H), 5.48 (s, 1 H). C NMR: δ = 146.6, 142.0, 133.7, 129.2, 128.9, 128.0, 127.8, 127.4,
26.4, 124.8, 118.8, 108.4. IR (film): ν = 3061, 2925, 2854, 1644, 1577, 1456, 1429, 1267,
–1
1
233, 1074, 1021, 898, 808, 763, 692 cm .
-(E)-Phenylethenyl-4-(4-ethylphenyl)-1,2,3-triazole (4b). Pale yellow viscous oil.
H NMR: δ = 7.90 (s, 1 H), 7.71–7.68 (m, 2 H), 7.41–7.29 (m, 5 H), 7.19–7.12 (m, 2 H),
1
1

1
596
H.-Y. SU ET AL.
1
3
5
1
1
7
.78 (s, 1 H), 5.47 (s, 1 H), 2.60 (q, J = 7.2 Hz, 2 H), 1.20 (t, J = 7.2 Hz, 3 H). C NMR: δ =
47.7, 144.6, 143.1, 134.7, 129.9, 128.9, 128.4, 127.7, 127.4, 125.8, 119.5, 109.3, 28.7,
5.5. IR (film): ν = 3028, 2964, 2928, 1642, 1496, 1445, 1265, 1230, 1017, 896, 839, 800,
–
1
+
72, 693 cm . EIMS: m/z (%) = 275 [M ]. Anal. Calcd for C18H17N3: C, 78.52; H, 6.22;
N, 15.26. Found: C, 78.39; H, 6.38; N, 15.15.
1
-(E)-Phenylethenyl-4-(2-methoxyphenoxymethyl)-1,2,3-triazole (4c). White
◦
1
solid, mp 123–124 C. H NMR: δ = 7.96 (s, 1 H), 7.75 (d, J = 14.8 Hz, 1 H), 7.47 (d, J
7.6 Hz, 2 H), 7.41–7.31 (m, 3 H), 7.15 (d, J = 14.8 Hz, 1 H), 7.07 (d, J = 7.6 Hz, 1
=
13
H), 6.97–6.88 (m, 3 H), 5.35 (s, 2 H), 3.88 (s, 3 H). C NMR: δ = 149.6, 147.5, 144.8,
1
33.5, 129.0, 128.8, 126.8, 122.9, 122.0, 121.9, 120.9, 120.3, 114.3, 111.9, 63.1, 55.9. IR
(
KBr): ν = 3153, 3115, 2953, 1654, 1590, 1570, 1503, 1465, 1456, 1439, 1393, 1359,
–
1
1
3
5
325, 1288, 1251, 1177, 1123, 1054, 1026, 1010, 956, 875, 750 cm . EIMS: m/z (%) =
+
07 [M ]. Anal. Calcd for C18H17N3O2: C, 70.34; H, 5.58; N, 13.67. Found: C, 70.20; H,
.74; N, 13.55.
1
-(E)-Phenylethenyl-4-(2-methylphenoxymethyl)-1,2,3-triazole (4d). Pale yellow
◦
1
solid, mp 129–130 C. H NMR: δ = 7.90 (s, 1 H), 7.77 (d, J = 14.4 Hz, 1 H), 7.48 (d, J =
7
.2 Hz, 2 H), 7.41–7.32 (m, 3 H), 7.19–7.13 (m, 3 H), 6.97 (d, J = 8.4 Hz, 1 H), 6.92 (d,
13
J = 14.4 Hz, 1 H), 5.28 (s, 2 H), 2.04 (s, 3 H). C NMR: δ = 156.4, 145.2, 133.5, 130.8,
1
29.0, 128.9, 127.0, 126.9, 126.8, 123.0, 122.1, 121.1, 120.0, 111.5, 62.2, 16.3. IR (KBr):
–
1
ν = 3136, 3096, 2927, 1655, 1493, 1454, 1383, 1350, 1239, 1050, 1021, 950, 752 cm .
+
EIMS: m/z (%) = 291 [M ]. Anal. Calcd for C18H17N3O: C, 74.20; H, 5.88; N, 14.42.
Found: C, 74.03; H, 5.96; N, 14.32.
1
-(E)-Phenylethenyl-4-(2-chlorophenoxymethyl)-1,2,3-triazole (4e). Pale yellow
◦
1
solid, mp 106–107 C. H NMR: δ = 7.98 (s, 1 H), 7.76 (d, J = 14.8 Hz, 1 H), 7.47 (d,
J = 7.2 Hz, 2 H), 7.41–7.32 (m, 4 H), 7.26–7.19 (m, 2 H), 7.15 (d, J = 15.6 Hz, 1 H),
6
1
2
.92–6.89 (m, 1 H), 5.34 (s, 2 H). 13C NMR: δ = 153.7, 144.4, 133.5, 130.4, 129.0, 128.9,
27.9, 126.8, 123.2, 122.9, 122.2, 120.3, 116.2, 114.3, 63.4. IR (KBr): ν = 3104, 3086,
–
1
931, 1654, 1587, 1485, 1388, 1350, 1242, 1161, 1133, 1049, 1018, 969, 856, 750 cm .
+
EIMS: m/z (%) = 311 [M ]. Anal. Calcd for C17H14ClN3O: C, 65.49; H, 4.53; N, 13.48.
Found: C, 65.34; H, 4.68; N, 13.35.
1
-(E)-Phenylethenyl-4-(2-nitrophenoxymethyl)-1,2,3-triazole (4f). Pale yellow
◦
1
solid, mp 134–135 C. H NMR: δ = 8.04 (s, 1 H), 7.87 (dd, J = 8.0, 1.2 Hz, 1 H), 7.76
(
7
1
d, J = 14.8 Hz, 1 H), 7.58–7.54 (m, 1 H), 7.48 (d, J = 7.2 Hz, 2 H), 7.41–7.30 (m, 4 H),
13
.22 (d, J = 14.8 Hz, 1 H), 7.10–7.06 (m, 1 H), 5.42 (s, 2 H). C NMR: δ = 151.4, 143.6,
40.2, 134.3, 133.4, 129.0, 128.8, 126.8, 125.7, 122.8, 122.4, 121.2, 120.7, 115.4, 63.7. IR
(
7
KBr): ν = 3071, 2957, 1658, 1606, 1517, 1347, 1275, 1251, 1168, 1044, 993, 957, 862,
–
1
+
75, 750, 693 cm . EIMS: m/z (%) = 322 [M ]. Anal. Calcd for C17H14N4O3: C, 63.35;
H, 4.38; N, 17.38. Found: C, 63.19; H, 4.56; N, 17.26.
1
-(E)-Phenylethenyl-4-(4-nitrophenoxymethyl)-1,2,3-triazole (4g). Pale yellow
◦
1
solid, mp 149–150 C. H NMR: δ = 8.22–8.19 (m, 2 H), 7.99 (s, 1 H), 7.77 (d, J =
4.8 Hz, 1 H), 7.48 (d, J = 7.6 Hz, 2 H), 7.42–7.33 (m, 3 H), 7.22 (d, J = 14.8 Hz, 1
1
13
H), 7.11–7.07 (m, 2 H), 5.36 (s, 2 H). C NMR: δ = 163.0, 143.1, 141.9, 133.3, 129.0,
1
1
9
28.8, 126.8, 126.0, 122.7, 122.6, 120.6, 114.9, 62.3. IR (KBr): ν = 3080, 2930, 2875, 1654,
607, 1591, 1510, 1495, 1459, 1348, 1297, 1249, 1176, 1153, 1113, 1048, 1018, 1006,
–
1
+
51, 868, 846, 751, 696 cm . EIMS: m/z (%) = 322 [M ]. Anal. Calcd for C17H14N4O3:
C, 63.35; H, 4.38; N, 17.38. Found: C, 63.21; H, 4.53; N, 17.24.
-(E)-Phenylethenyl-4-(2-naphthoxymethyl)-1,2,3-triazole (4h). White solid, mp
1
◦
1
1
58–159 C. H NMR: δ = 7.97 (s, 1 H), 7.97–7.74 (m, 4 H), 7.48–7.44 (m, 3 H), 7.40–7.34

SYNTHESIS OF 1-(E)-PHENYLETHENYL-1,2,3-TRIAZOLES
1597
1
3
(
m, 5 H), 7.23–7.20 (m, 1 H), 7.19 (d, J = 14.8 Hz, 1 H), 5.40 (s, 2 H). C NMR: δ =
1
1
1
3
5
56.1, 144.6, 134.4, 133.5, 129.7, 129.2, 129.1, 128.9, 127.7, 126.9, 126.8, 126.6, 124.0,
22.9, 122.1, 120.1, 118.7, 107.3, 62.0. IR (KBr): ν = 3055, 2917, 1658, 1627, 1599, 1511,
–
1
461, 1390, 1260, 1218, 1183, 1119, 1043, 951, 837, 818, 749, 694 cm . EIMS: m/z (%) =
+
27 [M ]. Anal. Calcd for C21H17N3O: C, 77.04; H, 5.23; N, 12.84. Found: C, 76.88; H,
.38; N, 12.71.
1
1
-(E)-Phenylethenyl-4-(n-butyl)-1,2,3-triazole (4i). Colorless oil. H NMR: δ =
7
(
0
1
1
.98 (s, 1 H), 7.75 (d, J = 14.8 Hz, 1 H), 7.42–7.38 (m, 2 H), 7.34–7.27 (m, 3 H), 7.15
d, J = 14.8 Hz, 1 H), 2.70 (t, J = 7.2 Hz, 2 H), 1.68–1.60 (m, 2 H), 1.41–1.39 (m, 2 H),
13
.98 (t, J = 7.6 Hz, 3 H). C NMR: δ = 147.2, 135.9, 133.9, 128.7, 128.1, 126.9, 125.7,
18.8, 32.3, 26.0, 22.6, 14.1. IR (film): ν = 3050, 2923, 1655, 1625, 1600, 1464, 1390,
–
1
+
263, 1222, 1180, 1119, 1040, 950, 835, 750, 695 cm . EIMS: m/z (%) = 227 [M ]. Anal.
Calcd for C14H17N3: C, 73.98; H, 7.54; N, 18.49. Found: C, 73.83; H, 7.69; N, 18.36.
Recovery of Diphenyl Diselenide
To the alkaline aqueous extract from the oxidation procedure (containing the ben-
zeneseleninate anion) was added conc HCl, after which, the resulting suspension was
evaporated and the residue was suspended in methanol (30 mL), and hydrazine monohy-
drate (3.5 mmol, 0.16 mL) was added gradually to the suspension and stirred until diphenyl
diselenide was formed, as indicated by the yellow color. The mixture was then concentrated
in vacuo, poured into water (30 mL) and extracted with ether (3 × 10 mL). The organic
layer was dried over anhydrous sodium sulfate and evaporated. Diphenyl diselenide was
recovered as a pure compound in 62% yield.
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