Synthesis of novel 1,4-disubstituted 1,2,3-triazoles bearing organosilicon-sulfur groups via the click reaction sonocatalyzed by LaCuxMn1-xO3nanoparticles

Article abstract of DOI:10.1080/00397911.2016.1217339

A highly efficient and environmentally friendly one-pot procedure for the synthesis of 1,2,3-triazoles by 1,3-dipolar cycloaddition of benzyl halides, terminal alkynes, and sodium azide over LaCu_xMn_1-xO₃perovskite oxides was developed. LaCu_0.7Mn_0.3O₃was found to be active with low catalyst loading under ultrasonic irradiation in aqueous media. The reaction was performed efficiently in the presence of the nanocatalyst in the absence of any additive or base with a noticeable reduction in the reaction time. The catalyst could be recycled and reused at least five times without any significant effect on the results of the reaction. Moreover, a series of novel organosilicon-sulfur substituted 1,2,3-triazole derivatives was synthesized using carbon disulfide and tris(trimethylsilyl)methylithium.

Full text of DOI:10.1080/00397911.2016.1217339

Synthetic Communications
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Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Synthesis of Novel 1,4-disubstituted 1,2,3-triazoles
Bearing Organosilicon-sulfur Groups via the
Click Reaction Sonocatalyzed by LaCuxMn1-xO3
Nanoparticles
Kazem D. Safa & Hanieh Mousazadeh
To cite this article: Kazem D. Safa & Hanieh Mousazadeh (2016): Synthesis of Novel
1,4-disubstituted 1,2,3-triazoles Bearing Organosilicon-sulfur Groups via the Click
Reaction Sonocatalyzed by LaCuxMn1-xO3 Nanoparticles, Synthetic Communications, DOI:
10.1080/00397911.2016.1217339
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Date: 20 August 2016, At: 01:30

Synthesis of Novel 1,4-Disubstituted 1,2,3-triazoles Bearing Organosilicon-sulfur
Groups via the Click Reaction Sonocatalyzed by LaCuxMn1-xO3 Nanoparticles
Kazem D. Safa1, Hanieh Mousazadeh1
1Organosilicon Research Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz,
Iran
Corresponding author: Kazem D. SafaE-mail: dsafa@tabrizu.ac.ir
Abstract
A high efficient and environmentally friendly one-pot procedure for the synthesis of
1,2,3-triazoles by 1,3-dipolar cycloaddition of benzyl halides, terminal alkynes and
sodium azide over LaCuxMn1-xO3 perovskite oxides was developed. LaCu0.7Mn0.3O3 was
found to be active with low catalyst loading under ultrasonic irradiation in aqueous
media. The reaction was performed efficiently in the presence of the nanocatalyst in the
absence of any additive or base with a noticeable reduction in the reaction time. The
catalyst could be recycled and reused at least five times without any significant effect on
the results of the reaction. Moreover, a series of novel organosilicon-sulfur substituted
1,2,3-triazole derivatives was synthesized using carbon disulfide and
tris(trimethylsilyl)methylithium.
Graphical abstract
1

KEYWORDS: 1,2,3-Triazole, LaCu0.7Mn0.3O3 perovskite, Organosilicon, Carbon
disulfide, Ultrasonic irradiation
INTRODUCTION
Organosilicon compounds provide opportunities to design and control stability,
solubility, and pharmacokinetic properties.[1] The incorporation of organosilicon moieties
into known drug scaffolds changes the geometric and electronic aspects, chemical
reactivity and lipophilicity of the molecule.[2] Lipophilicity can provide several biological
benefits, including an increase bioavailability and better tissue and cell penetration.
Organosilicon compounds of sulphur-containing ligands have known to be important due
to their useful applications as pharmaceutical agents, e.g. anticarcinogenic, antibacterial,
antifungal, insecticidal and acaricidal activities.[3,4] However, the chemistry of these
compounds is still underdeveloped. As five-membered heterocyclic compounds, 1,2,3-
triazoles have received increasing attention over the past few years, because of their wide
range of applications in pharmaceuticals, agrochemicals, dyes, photographic materials,
corrosion inhibition, photostabilizers and etc.[5–8] The copper(I) catalyzed Huisgen
cycloaddition reaction has been recognized as a regioselective method for the synthesis of
1,4-disubstituted 1,2,3-triazoles.[9,10] Recently, various catalytic systems such as copper
nano particles[11], copper immobilized on various supports,[12–15] Cu(I) directly[9,10] or
Cu(II) in the presence of reductants [16] and etc, have been reported for the synthesis of
1,2,3-triazoles. However, few reports have been dedicated to mixed metal oxides in
organic synthesis. Metal oxide[17] catalysts appear to be a promising alternative to noble
metal catalysts in organic syntheses. Metal oxides are developed both for their acid-base
2

and redox properties and constitute the largest family of catalysts in heterogeneous
catalysis.[18] The catalytic activity of some of the mixed metal oxides is better than
component oxides in various reactions due to increasing acidic and basic sites, and
increasing surface area.[19]
Among the metal oxides, perovskites as mixed metal oxides have received wide attention,
due to their low-cost, appropriate redox properties, stability of mixed oxidation, high
thermal stability and high catalytic activity. This material is introduced by the general
formula of ABO3, where A is lanthanide or alkaline earth metal ion and B is a transition
metal ion. The partial substitution of cations in both places A and B, provided
multicomponent oxides (A1−xA′xB1−yB′yO3) with unusual valence in cation sites that
usually increased catalytic activity of the perovskite systems.[20, 21] For example, the
synergistic effect manganese oxide and copper ions in the LaMn0.5Cu0.5O3 increased the
activity of perovskite system in the oxidation of CO.[22] The attractive catalytic activity of
perovskite-type oxides related to their acid-base, adsorption as well as redox
properties.[23] In this work, we described the effect of the mole fractions of Mn and Cu on
the catalytic performance of LaCuxMn1-xO3 perovskite oxides in the 1,3-dipolar azide-
alkyne cycloaddition reaction. Our results demonstrate that the LaCu0.7Mn0.3O3
perovskite is an efficient, environmentally heterogeneous nanocatalyst for the synthesis
of 1,4-disubstituted 1,2,3-triazoles in high yields in aqueous media. The 1,3-dipolar
cycloaddition reaction of benzyl halides, terminal alkynes and sodium azide over
LaCu0.7Mn0.3O3 nanocatalyst was followed in aqueous media under ultrasonic irradiation.
3

Moreover, a series of novel 1,2,3-triazoles bearing organosilicon-sulfur groups was
synthesized using carbon disulfide and tris(trimethylsilyl)methylithium.
RESULTS AND DISCUSSION
LaCuxMn1-xO3 nano perovskite oxides were prepared by sol-gel procedure.[24–26] In this
sense, the results of the investigations showed that the ratio of x = 0.7 of mixed metal
oxides is the ideal ratio for 1,3-dipolar azide-alkyne cycloaddition reaction. The structure
of the nanocatalyst was characterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM). According to the Scherrer’s equation from the XRD pattern and the
result of SEM photograph, the average particle size of LaCu0.7Mn0.3O3 nano perovskite is
around 20 nm. The EDX spectrum of the perovskite system confirmed the presence of
copper and manganese (Fig. 1).
Initially, we explored the catalytic activity of LaCu0.7Mn0.3O3 perovskite in the 1,3-
dipolar cycloaddition reaction of phenylacetylene, benzyl bromide and sodium azide in
aqueous media. As shown in Table 1, incorporation of Mn into the LaCuO3 improved the
catalytic activity of the perovskite system and the optimum catalytic activity was
obtained for LaCu0.7Mn0.3O3 (3 mol %) at room temperature under ultrasound-irradiation
condition. It is noteworthy that the corresponding 1,2,3-triazole 1a was obtained in high
yield after 5 min. When the Cu catalyst loading increased to 5 mol %, the reaction was
completed without any observable change in the cycloaddition reaction time. The use of
ultrasound irradiation as compared to conventional stirring or heating conditions
significantly decreased reaction times. Acoustic cavitation-induced sonochemistry lead to
4

high local temperatures and pressures and increase in the rate of reaction.[27] On the other
hand, decreasing the ratio of copper in catalyst system resulted in an increase in the
cycloaddition reaction time. The cycloaddition reaction was not completed using
LaMnO3 even after 24 hours reaction time. Similarly, no 1,2,3-triazole was isolated in the
absence of copper mixed catalyst system even after 2 h of sonication.
LaCu0.7Mn0.3O3 as a heterogeneous nanocatalyst can be recovered by simple filtration
and reused at least five times without any loss in acceptable catalytic activity (Table 1,
entry 9).
In order to further investigate, the reaction was also carried out for a series of other
substrates under the optimized conditions and the related products were obtained (Table
2, entries 1-18). The results showed that the reaction in the presence of electron
withdrawing substituents (Table 2, entries 4, 12, 18) and less reactive benzyl chlorides
(Table 2, entries 2, 9) processed in good yield. Also benzyl and alkyl halides, aromatic
and hydroxyl functionalized alkynes obtained the desired products in high yield,
revealing the efficacy of the catalytic system. The known products are confirmed by
making a comparison with melting point in the literature.[28–31]
Additionally, a series of novel 1,2,3-triazoles bearing organosilicon-sulfur groups was
synthesized using carbon disulfide and tris(trimethylsilyl)methylithium. Recently,
successful synthesis of a variety of organosilicon-sulfur derivatives was reported in our
laboratory.[ 32–35] The tris(trimethylsilyl)methyllithium substance was organized using
5

published methodologies (Scheme 1).[36] The reaction of the hydroxyl group of 1,2,3-
triazole derivatives 1h-q with phosphorus tribromide (PBr3) obtained the desired
bromomethyl derivatives 2h–q in good yields (Scheme 2).[37] After this successful
synthesis, the crude products 2h-p were added dropwise to the stirred solution of carbon
disulfide and tris(trimethylsilyl)methyllithium in tetrahydrofuran at 0 °C. The 1,2,3-
triazole substitute thioalkynes 3h-p (Table 3, entries 1-9) were obtained in good yield at 0
°C. Nucleophilic attack of tris(trimethylsilyl)methyllithium at the carbon of carbon
disulfide at –46 °C furnished the other organosilicon-sulfur containing triazoles 4h, 4i, 4j
and 4q in high yields and short reaction times (Table 3, entries 9-13).
CONCLUSION
A one-pot procedure was introduced for the synthesis of 1,4-disusbtitude 1,2,3-triazoles
through 1,3-dipolar cycloaddition of benzyl halides, terminal alkynes and sodium azide
using LaCu0.7Mn0.3O3 recyclable nanocatalyst in aqueous media. The LaCu0.7Mn0.3O3 as
an effective and inexpensive catalyst showed high catalytic activity with low catalyst
loading under ultrasonic irradiation in aqueous media. Using this methodology, the
corresponding 1,2,3-triazole derivatives obtained in high yields and very short reaction
times. In continuous, the organosilicon-sulfur substituted 1,2,3-triazole derivatives were
synthesized using carbon disulfide and tris(trimethylsilyl)methylithium in high yields.
These synthetic compounds are valuable intermediates in synthetic chemistry, chemical
biology, and material science.
EXPERIMENTAL
6

Chemicals were either prepared in our laboratory or purchased from Merck, Fluka and
Aldrich. 1H and 13CNMR spectra of all samples were obtained using Bruker 400 MHz
spectrometer in CDCl3. Elemental analyses were performed on Elementar Vario EL III
apparatus. The reactions were carried out using an ultrasonic processor probe
(SONOPULS Ultrasonic homogenizers). The structure of the nanocatalyst was
characterized by X-ray diffraction (Bruker AXS model D8Advance diffractometer using
CuKα radiation ( = 1.542 A°), with the Bragg angle ranging from 10° to 70° and
scanning electron microscopy using LEO 1430VP instrument. The elemental chemical
composition of the prepared catalyst was determined by EDX (VEGA\\TESCAN-LMU,
Czech Republic).
Typical Procedure For The Preparation Of Lacuxmn1-Xo3 Oxides
LaCuxMn1-xO3 oxides were prepared by the sol-gel method. The citric acid was added to
an aqueous stirred solution of La(NO3)3.6H2O, Cu(NO3)2.3H2O and Mn(NO3)2.4H2O in
the stoichiometric amount at 70 °C. The ratio of citric acid to nitrates was 0.4 for
complete complexation of the cations. The solution was heated to 80 °C and the extra
water was evaporated. Then, the gel-like substance was dried at 200 °C overnight and
calcined at 700 °C for 3 h.[24–26]
Typical Procedure For The Preparation Of 1-Benzyl-4-Phenyl-1H-1,2,3-Triazole
(1a)
In a 20 ml thick-walled flax a mixture of sodium azide (1.2 mmol), benzyl halide (1
mmol), terminal alkyne (1 mmol), LaCu0.7Mn0.3O3 (3% mol) and 2 ml water was added.
7

The flask was attached to a 12-mm-tip-diameter Probe. The reaction mixture was then
sonicated at room temperature at 20 % power of the processor. After completion the
reaction (TLC monitoring), the crude product was extracted using EtOAC. The recovered
catalyst by simple filtration was washed three times with ethanol and dried under
vacuum. The product was identified as 1-benzyl-4-phenyl-1H-1,2,3-triazole (1a) by
spectral data.
A yellowish white solid, m.p. 128-130 °C [34]; 1H NMR (400 MHz, CDCl3): δ 5.57 (s, 2H,
CH2), 7.26-7.48 (m, 8H, Ar), 7.68 (s, 1H, triazole), 7.79-7.81 (m, 2H, Ar); 13C NMR (100
MHz, CDCl3): δ 52.83, 118.55, 124.43, 126.74, 126.89, 127.43, 127.51, 127.84, 129.36,
133.55, 146.84 ppm; Anal. Calcd for C15H13N3: C, 76.57; H, 5.57; N, 17.86%; Found: C,
76.54; H, 5.61; N, 17.83%.
Preparation Of Tris(Trimethyl)Methyllithium
The reagent was prepared as described by Grobel and coworkers [36].
Typical Procedure For The Synthesis Of 4-((2-(Trimethylsilyl)Ethynylthio)Methyl)-
1-Benzyl-1H-1,2,3-Triazole (3h)
Carbon disulfide (1.2 mmol) was added dropwise to a stirred solution of (Me3Si)3CLi (1
mmol) in THF at 0 °C under an argon atmosphere. Immediately, an orange-red solution
was formed. Then bromomethyl derivative 2h (1 mmol) was added in this temperature.
The reaction was completed within 10 min (TLC monitoring) and the color of the
solution changed to red dark. Finally, the mixture was extracted with CH2Cl2 and was
8

purified by preparative column chromatography using (n-hexane/EtOAc 3:1) to give the
pure products 3h.
A yellow sticky solid (96%); 1H NMR (400 MHz, CDCl3): δ 0.08 (s, 9H, SiMe3), 4.53 (s,
2H, CH2), 5.48 (s, 2H, CH2), 7.19-7.22 (m, 2H, Ar), 7.33-7.36 (m, 3H, Ar), 7.44 (s, 1H,
triazole); 13C NMR (100 MHz, CDCl3): δ -1.22 (SiMe3), 30.89, 53.14, 90.86, 101.33,
121.19, 126.92, 127.01, 127.66, 127.79, 128.07, 128.13, 143.29; Anal. Calcd for
C15H19N3SSi: C, 59.76; H, 6.35; N, 13.94%; Found: C, 59.83; H, 6.39; N, 13.89%.
Typical Procedure For The Synthesis Of 3-(1-Benzyl-1H-1,2,3-Triazol-4-Yl)-1-
Mercapto-1,1-Bis(Trimethylsilyl)Propane-2-Thione (4h)
Carbon disulfide (1.2 mmol) was added dropwise to a stirred solution of (Me3Si)3CLi (1
mmol) in THF at -46 °C under an argon atmosphere. Then bromomethyl derivative 2h (1
mmol) was added in this temperature. The reaction was followed by TLC and completed
within 5 min. Finally, the mixture was extracted with CH2Cl2 and was purified by
preparative column chromatography using (n-hexane/EtOAc 10:2) to give the pure
products 4h.
A yellow sticky solid (95%); 1H NMR (400 MHz, CDCl3): δ 0.078 (s, 18H, SiMe3), 3.11
(bs, 1H, S-H), 4.53 (s, 2H, CH2), 5.48 (s, 2H, CH2), 7.19-7.22 (m, 2H, Ar) 7.33-7.36 (m,
3H, Ar) 7.44 (s, 1H, triazole); 13C NMR (100 MHz, CDCl3): δ -1.22 (SiMe3), 30.89,
53.13, 57.07, 121.19, 126.92, 127.01, 127.66, 127.79, 128.07, 128.127, 143.26, 230.53;
9

Anal. Calcd for C18H29N3S2Si2: C, 53.02; H, 7.17; N, 10.31%; Found: C, 53.16; H, 7.23;
N, 10.33%.
SUPPLEMENTARY INFORMATION
Supporting information associated with this article can be found via the “Supplementary
Content” section of this article’s webpage.
ACKNOWLEDGMENTS
We thank Dr. A. Niaei for supplying some of the starting materials and his helpful
comments.
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12

Table 1. Optimization of the reaction conditionsa
Entry Catalyst (mol %) Ultrasound irradiation Time
(min)/yieldb (%)
Stirring conditions
Temp. (°C)/time
(h)/yieldb (%)
1
2
3
4
5
6
7
8
9
LaCuO3 (3)
30
70
70
70
70
70
100
70
70
70
70
12 h 72
LaCu0.5Mn0.5O3 (3) 10
90
2 h
2 h
2 h
2 h
6 h
92
96
95
96
85
LaCu0.7Mn0.3O3 (3)
LaCu0.7Mn0.3O3 (5)
5
5
98
98
LaCu0.7Mn0.3O3 (3) 10
LaCu0.3Mn0.7O3 (3) 20
98
87
LaMnO3 (3)
Neat
2 h
2 h
5
Trace
Trace
95
24 h Trace
24 h Trace
LaCu0.7Mn0.3O3 (3)
(Recycled)
2 h
96
aReactions were carried out on a scale of 1.0 mmol of benzyl bromide, 1.0 mmol of
phenylacetylene, 1.2 mmol of sodium azide, and 2 ml of H2O.
bIsolated yield.
13

Table 2. LaCu0.7Mn0.3O3 catalyzed 1,3-dipolar azide-alkyne cycloaddition reactiona
Entry Alkyl halide
Alkyne Product 1
Yield
R1
X
R2
Ph
Ph
Ph
Ph
Ph
Ph
Ph
(%)b
98
1
2
3
4
5
6
7
C6H5CH2
Br
Cl
Br
Br
Br
Br
Br
1a
1b
1c
1d
1e
1f
C6H5CH2
95
C6H5CH2CH2
4-O2NC6H4CH2
C6H5COCH2
CH3(CH2)4CH2
5-(benzyloxy)-2 methyl-4-pyran-4-
one
92
90
92
90
85
1g
8
C6H5CH2
Br
Cl
Br
Br
Br
Br
Br
Br
Br
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
93
92
92
92
85
93
92
94
92
1h
1i
9
C6H5CH2
10
11
12
13
14
15
16
C6H5CH2CH2
4-BrC6H4CH2
4-O2NC6H4CH2
2-ClC6H4CH2
3-ClC6H4CH2
2,6-ClC6H3CH2
CH3(CH2)4CH2
1j
1k
1l
1m
1n
1o
1p
14

17
18
CH3(CH2)10CH2
4-BrC6H4CH2
Br
Br
CH2OH
90
90
1q
1r
4-
CHOC6H4OCH2
aReactions were carried out on a scale of 1.0 mmol of alkyl halide, 1.2 mmol of sodium
azide, and 1.0 mmol of alkyne, La3Cu0.7Mn0.3O3 (3% mol) in 2 ml H2O.
bIsolated yield.
15

Table 3. 1,2,3-triazoles bearing organosilicon-sulfur groups
Entry Substrate
(2h-p) / R1
Product / (3h-p)
Time Yield (%)c
(min)
1a
2a
3a
4a
C6H5CH2
10
15
10
96
92
94
95
SiMe3
N
S
N
N
3h
SiMe3
4-O2NC6H4CH2
4-BrC6H4CH2
2-ClC6H4CH2
O2N
N
S
N
N
3i
SiMe3
Br
N
S
N
N
3j
SiMe3
N
S
N
10
10
N
Cl
3k
3l
5a
3-ClC6H4CH2
92
90
SiMe3
N
S
N
N
Cl
6a
2,6-ClC6H3CH2
15
15
SiMe3
Cl
N
S
N
N
Cl
3m
3n
7a
CH3(CH2)2CH2
CH3(CH2)4CH2
85
SiMe3
N
S
N
N
8a
89
SiMe3
N
S
N
15
N
3o
16

9a
CH3(CH2)10CH2
83
SiMe3
N
S
N
N
20
5
( )7
3p
4h
4i
10b
11b
12b
13b
C6H5CH2
95
92
94
96
S
SH
N
N
SiMe3
SiMe3
N
S
SH
SiMe3
SiMe3
O2N
4-O2NC6H4CH2
4-BrC6H4CH2
C6H5CH2CH2
10
5
N
N
N
S
SH
SiMe3
Br
N
N
N
SiMe3
4j
S
SH
5
N
N
N
SiMe3
SiMe3
4q
aReactions were carried out in CS2 /(Me3Si)3CLi /THF /0 °C,
bin CS2/(Me3Si)3CLi /THF /-46 °C.
cIsolated yield.
17

Scheme 1. Synthesis of the tris(trimethylsilyl)methyllithium.
18

Scheme 2. Synthesis of the 1,2,3-triazoles bearing organosilicon-sulfur groups.
19

Figure 1 The SEM image (a), the XRD pattern (b) and the EDX of image (c)
LaCu0.7Mn0.3O3 nano perovskite.
20