Supported copper (I) catalyst from fish bone waste: An efficient, green and reusable catalyst for the click reaction toward N-substituted 1,2,3-TRIAZOLES

Article abstract of DOI:10.1002/aoc.3946

An eco-efficient, green, and multi-gram procedure is presented for one-pot multicomponent synthesis of N-substituted 1,2,3-triazoles by using waste fishbone powders supported CuBr (FBPs-CuBr) as catalyst. FBPs-CuBr is found to be an efficient heterogeneous catalyst and a series of 1,2,3-triazoles are obtained in moderate to excellent yields in water under MW irradiation (70–98%). It can be separated conveniently by a simple filtration and reused at least seven consecutive runs with a slight drop in the product yields. Furthermore, the desired product still could be obtained in 80% yield when the scale of the reaction was increased to 40.0 mmol.

Full text of DOI:10.1002/aoc.3946

Received: 2 February 2017
DOI: 10.1002/aoc.3946
Revised: 26 May 2017
Accepted: 29 May 2017
F U L L PA P E R
Supported copper (I) catalyst from fish bone waste: An efficient,
green and reusable catalyst for the click reaction toward N‐
substituted 1,2,3‐TRIAZOLES
Xingquan Xiong
| Zhongke Tang | Zhaohong Sun | Xiaoqing Meng | Sida Song | Zhilong Quan
College of Materials Science and
Engineering, University of Huaqiao,
Xiamen, 361021, China
An eco‐efficient, green, and multi‐gram procedure is presented for one‐pot multi-
component synthesis of N‐substituted 1,2,3‐triazoles by using waste fishbone pow-
ders supported CuBr (FBPs‐CuBr) as catalyst. FBPs‐CuBr is found to be an efficient
heterogeneous catalyst and a series of 1,2,3‐triazoles are obtained in moderate to
excellent yields in water under MW irradiation (70–98%). It can be separated con-
veniently by a simple filtration and reused at least seven consecutive runs with a
slight drop in the product yields. Furthermore, the desired product still could be
obtained in 80% yield when the scale of the reaction was increased to 40.0 mmol.
Correspondence
Xingquan Xiong, College of Materials
Science and Engineering, University of
Huaqiao, Xiamen 361021, China.
Email: xxqluli@hqu.edu.cn
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 21004024;
Natural Science Foundation of Fujian prov-
ince, Grant/Award Number: 2016 J01063;
New Century Excellent Talents in University
of Fujian province, Grant/Award Number:
2012FJ‐NCET‐ZR03; Young and Middle‐
aged Teacher in Science and Technology
Research of Huaqiao University, Grant/
Award Number: ZQN‐YX103; Science &
Technology Project of Quanzhou, Grant/
Award Number: 2014Z126
KEYWORDS
green synthesis, heterogeneous catalyst, MW irradiation, N‐substituted 1,2,3‐triazoles, waste fishbone
powders
1 | INTRODUCTION
catalyst, which make the separation and recovery of copper
catalyst very difficult. In addition, it is probable that the
As important five‐membered nitrogen heterocycles, 1,2,3‐
triazoles have several biological activities, including
antiviral, antifungal, and antitubercular activities.[1–4]
Therefore, they represent an important class of biomole-
cules and have received widespread attention not only from
academic research but also from industrial production and
application. Recently, it has been reported that N‐
substituted 1,2,3‐triazoles have more potential uses than
simple 1,2,3‐triazole derivatives.[5] However, for the prepa-
ration of N‐substituted 1,2,3‐triazoles though copper (I)‐cat-
alyzed azide alkyne cycloaddition (CuAAC),[6,7] the
starting materials, such as functional alkynes and organic
azides were not easily available and expensive.
Furthermore, the synthesis of N‐substituted 1,2,3‐triazoles
proceed in the presence of copper salts as homogeneous
obtained 1,2,3‐triazoles can be contaminated by the copper
metal in homogeneous catalytic system. So far, many chal-
lenges remain and much work still needs to be done.
Therefore, an efficient and simple way to synthesize N‐
substituted 1,2,3‐triazoles is still necessary.
In order to overcome the above shortcomings,
immobilizing the copper salts as heterogeneous catalysts in
CuAAC reaction via silica,[8–11] magnetic nanoparti-
cles,[12–18] polymers,[19–25] zeolites,[26–29] and charcoal[30,31]
have been reported. These heterogeneous catalysts offer
several advantages, such as simplification of reaction
procedures, easy separation of products, and easy recovery
of catalyst. However, a series of laborious, tedious, and
time consuming steps are needed during the procedures of
catalyst preparation.
Appl Organometal Chem. 2017;e3946.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 10
https://doi.org/10.1002/aoc.3946

2 of 10
XIONG ET AL.
In recent years, low‐cost and green synthesis of sup-
ported catalysts from agricultural wastes and biomass has
been found to be of increasing interest. Using agricultural
wastes as support materials of catalysts, such as rice husk
powders and oyster shell waste,[32–34] not only helps to
reuse and recycle waste materials, but also reduces the costs
of the supported catalysts. Xiamen is a coastal city of
southeast China, and marine fish is one of the most popular
seafood in the city. The majority of waste generated by fish
processing factory comes from the heads and bones.
Although abundant waste fishbones are generated there
every day, most of them are abandoned without any
pretreatment. Therefore, disposal of fishbone waste in
Xiamen is associated with environmental problems. The rea-
sonably utilizing of the surplus waste fishbones has become
a new subject of construction of harmonious society at
present based on the view of sustainable development.
Because fishbone powders contain collagen, noncollagen
proteins, carbohydrate, and phosphopeptide, etc., they can
be used as an adsorbent for the removal of heavy metal salts
from sewage and waste aqueous solution.[35,36] Very
recently, Akhlaghinia and co‐workers have reported the
one‐pot synthesis of 1,4‐disubstituted 1,2,3‐triazoles via a
three‐component reaction between terminal alkynes, organic
bromides, and NaN3 in H2O by using cuttlebone supported
heterogeneous catalyst cuttlebone@CuCl2. The obtained
results showed that this protocol was an attractive and envi-
ronmentally compatible process for the regioselective syn-
thesis of 1,4‐disubstituted 1,2,3‐triazoles.[37]
In continuation of our efforts to develop green, highly effi-
cient and practical chemical methods as well as our interest on
the application of heterogeneous catalysts in organic reactions
under MW irradiation,[13,38–41] we report here an environ-
mentally benign and highly efficient one‐pot three‐component
coupling of amines, propargyl bromide and organic azides
catalyzed by FBPs‐CuBr for the preparation of N‐substituted
1,2,3‐triazoles under MW irradiation in water. To the best of
our knowledge, this is the first work that prepares
N‐substituted 1,2,3‐triazoles catalyzed by biowaste supported
FBPs‐CuBr with one‐pot three‐component and scale‐up
synthetic strategy. It not only synthesizes N‐substituted 1, 2,
3‐triazoles with low cost, but also reduces the amount of fish
bone waste and improves environmental conditions.
FIGURE 1 (a) fish bone waste; (b) milled FBPs after rinsed
thoroughly with hot water; (c) FBPs‐CuBr catalyst prepared from fish
bone waste
2 | RESULTS AND DISCUSSION
hammer and then the crushed fish bones were ground into
powders with a pestle and mortar, and then screened over
100 mesh sieve (Figure 1b). CuBr was added into FBPs in
DMF under the protection of N2 atmosphere. The obtained
mixture was stirred at room temperature. The solid products
separated from mother liquor through vacuum filtration and
then washed with distilled water to obtain FBPs‐CuBr cata-
lyst (Figure 1c).
2.1 | Preparation and characterization of
FBPs‐CuBr catalyst
Fleshy and oily materials were removed from raw fish bones
with hot deionized water using ultrasonic irradiation until
water was clear. The fishbones were put into ethanol to soak
and dried. The dried fishbones were roughly crushed using a

XIONG ET AL.
3 of 10
1023 cm−1. Similarly, the –CO3 bending vibration absorp-
tion peaks at 1428 and 880 cm−1 were also shifted to lower
wave numbers 1425 and 875 cm−1. The lowering in frequency
of the above peaks indicates the formation of the metal–ligand
bond. So, it is clear from the above comparison that FBPs‐
CuBr has been prepared successfully.
2−
FBPs‐CuBr has been characterized using various
methods, such as FT‐IR, TGA, ICP‐AES, XRD and SEM/
EDX. At first, FBPs and FBPs‐CuBr were characterized using
FT‐IR spectroscopy (Figure 2). The spectrum of FBPs
showed a broad band between 3600 and 3000 cm−1 (Figure 2a).
It included O–H stretch vibration of HPO42−, carbohydrate and
adsorbed water. The peaks at near 2925 cm−1 and 2852 cm−1
were characteristic bands of –CH2– stretching vibration. The
bands 1030 and 750 cm−1 characterized the bending vibration
of phosphate (O–P). The peaks observed at 1650 and
1535 cm−1 were characteristic bands of amide I or amide II
bands, respectively. Additionally, the O–P group is also found
at 1024 cm−1 for FBPs. When FBPs complexed with CuBr,
the –C–H stretching peaks of –CH2– appeared at 2925 and
2852 cm−1 were shifted to lower wave numbers 2921 and
2844 cm−1, respectively. The characteristic bands of amide
bands appeared at 1650 cm−1 was shifted to lower wave num-
ber 1647 cm−1. The bending vibration of phosphate (O–P)
appeared at 1030 cm−1 was shifted to lower wave number
The XRD patterns of FBPs and FBPs‐CuBr are presented
in Figure 3. The obtained XRD patterns of FBPs and FBPs‐
CuBr displayed the following diffraction peaks (2θ[o]):
25.9, 32.4, 40.1, and 47.1, which can be correlated to the
hkl indices (002), (211), (310), and (222), respectively, of
hydroxyapatite (JCPDS card number: 09–0432). As shown in
Figure 3b, three additional peaks at 2θ = 27.0o, 45.1o, 53.2o,
and 72.5o corresponding to the (111), (220), (311) and (331)
planes of CuBr were observed in the pattern of the FBPs‐
CuBr composite, indicating CuBr has been successfully load
on the fishbone powders though chemical bonding and phys-
ical adsorption.
The thermal behaviors of FBPs and FBPs‐CuBr are fur-
ther investigated by TGA. As shown in Figure 4a and 4b, a
slow weight loss occurred over 30–100 °C (about 1.4 wt.%)
was observed, which could be assigned to the evaporation
of the residual or absorbed water and solvent from the surface
of the FBPs and FBPs‐CuBr samples. On further heating over
a temperature range between 250 °C and 600 °C, it was found
that 30% and 43% weight losses occurred for FBPs and
FBPs‐CuBr samples, respectively. These resulted from the
decomposition of protein molecules and other organic sub-
stances. It was worth mentioning that FBPs‐CuBr possessed
good thermal stability (up to 250 °C), which meets the
demands for potential applications in catalysis.
Figure 5 showed the EDX mapping images of Cu (red)
element, which were from the fresh FBPs‐CuBr (a) and the
recycled catalyst after 7 consecutive trials (b), respectively.
Figure 5a showed the homogeneous distribution of Cu in
the fresh FBPs‐CuBr catalyst, which meant that CuBr dis-
tributed homogeneously in the FBPs instead of forming
FIGURE 2 FT‐IR spectra of FBPs (a) and FBPs‐CuBr (b)
FIGURE 3 XRD patterns of FBPs (a) and FBPs‐CuBr (b)
FIGURE 4 TGA curves of FBPs (a) and FBPs‐CuBr (b)

4 of 10
XIONG ET AL.
FIGURE 5 EDX elemental mapping images of the surface of FBPs‐CuBr (a) and the recycled catalyst after 7 consecutive trials (b)
any fine particles. Obviously, Figure 5b showed the Cu of
the recycled catalyst after 7 cycles was lower than the fresh
catalyst.
The copper contents of FBPs‐CuBr and the reused cata-
lyst after seven recycling were found to be 2.85 wt% and
0.71 wt% by ICP‐AES, respectively. It can be further
confirmed that the copper contents of catalyst is decreased
by the following tests.
XPS analysis is further carried out to determine the
composition and the surface electronic state of FBPs‐CuBr
and FBPs‐CuBr after 7 recycling (Figure 6). The XPS
spectrum of the Cu2p core level region for the FBPs‐CuBr

XIONG ET AL.
5 of 10
TABLE 1 Investigation of various copper salts catalysts in the one‐
pot synthesis of 4‐((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)morpholine
under MW and conventional heating conditionsa
Entry
Catalyst
Cu2O
Timeb/Timec(min) Yieldd/Yielde (%)
1
2
3
4
5
30/240
30/240
36/57
54/56
CuBr
Cu(OAc)2
FBPs‐cu(OAc)2
FBPs‐CuBr
30/240
51/53
30/240
30/240/30c
39/45
96/82/31e
a0.5 mmol of morpholine, 1.5 mmol of BrCH2C ≡ CH, 1.5 mmol of BnN3, FBPs‐
CuBr (5.50 mg, 0.002 mmol Cu), water (5.0 mL), MW, 400 W, 80 °C;
FIGURE 6 XPS Cu2p spectra of FBPs‐CuBr (a) and FBPs‐CuBr
after 7 recycling (b)
b,cReaction time under MW and conventional heating condition, respectively;
d,eIsolated yield of 1, 2, 3‐triazole under MW and conventional heating condition,
respectively.
catalyst displays main peaks at 932.4 and 952.6 eV, which
can be attributed to the binding energy of Cu2p3/2 and
Cu2p1/2, respectively (Figure 6a). These values correspond
to the Cu(I) binding energies of CuBr. The binding energies
of Cu2p3/2 in FBPs‐CuBr and the recycled FBPs‐CuBr were
both found to be around 932.4 eV, suggesting no obvious
change in chemical valence of Cu(I) in the supported catalyst
after 7 recycling. Especially to deserve to be mentioned, the
alkyne‐alkyne coupling product was not observed. Herein,
the stability of catalyst and the effect of basicity were very
vital in the three component reaction. The basicity could
drive the rapid formation of propargyl amines and avoid
self‐coupling product of terminal alkynes. The stability of
catalyst could lead to the regioselectivity (1,4‐disubstitution)
of the three‐component CuAAC reaction.
could be obtained in low yield of 39% (Table 1, entry 4).
To our delight, FBPs‐CuBr was found to be the most effec-
tive catalyst in terms of isolated yield of the corresponding
product (96%, entry 5).
Subsequently, we investigated the activity of the
catalysts with respect to time for the formation of the
desired 1,2,3‐triazole under conventional heating condi-
tion. When the supported copper salts, such as
FBPs‐Cu(OAc)2 and FBPs‐CuBr were used as catalysts,
the yields were found to be 45% and 82% after 240 min
at 80 °C, respectively (Table 1). In addition, when
FBPs‐CuBr was used as catalyst, the reaction has only a
31% yield after 30 min. Compared with the traditional
heating method, the use of MW irradiation could dramat-
ically reduce the reaction time.
In order to further study the regioselectivity (1,4‐ or 1,5‐
disubstitution) of the three‐component CuAAC reaction, the
obtained product has been characterized using NOE tech-
nique. In the H − H NOESY spectrum of the obtained
product in CDCl3, the correlation between the triazole proton
(Hb) and the adjacent benzyl proton (Hc) was observed
(Figure 7). suggesting 4‐((1‐benzyl‐1H‐1, 2, 3‐triazol‐4‐yl)
methyl)morpholine is the only 1,4‐disubstitution isomer
obtained from the three‐component CuAAC reaction by
using FBPs‐CuBr as catalyst.
2.2 | Effect of the copper source
1
1
In order to determine the optimal catalyst for CuAAC reac-
tion, the catalytic activities of copper salts and supported cat-
alysts were examined in a model reaction using morpholine,
propargyl bromide and benzyl azide at 80 °C. The results
are summarized in Table 1.
It can be seen that when CuAAC reaction was carried
out using homogeneous copper catalysts, such as Cu2O,
CuBr and Cu(OAc)2 for 30 min at 80 °C under MW irradi-
ation, the desired 1,2,3‐triazole could be obtained in 36%,
54% and 51% isolated yield, respectively (Table 1, entries
1–3). Unfortunately, these homogeneous copper catalysts
cannot be recycled. In order to recycle the copper salts,
the supported catalysts, such as FBPs‐Cu(OAc)2 and
FBPs‐CuBr were employed as heterogeneous catalysts.
The obtained results showed that when the reaction was
carried out using FBPs‐Cu(OAc)2 as the catalysts for
30 min at 80 °C under MW irradiation, the desired product
2.3 | One‐pot synthesis of N‐substituted 1,2,3‐
triazoles
Prompted by the aforementioned excellent result of FBPs‐
CuBr, we further investigate the practicality of the catalyst.
Using the optimized reaction condition, the one‐pot three‐
component CuAAC reaction was further expanded to a
broader range of various organic amines, propargyl bromide
and benzyl azide using FBPs‐CuBr as catalyst in order to

6 of 10
XIONG ET AL.
1
1
FIGURE 7 2D H − H NOESY
spectrum of the prepared 1,2,3‐triazole by
using FBPs‐CuBr catalyst
evaluate the scope and limitations of the method. The
obtained results are summarized in Table 2. It was found that
most of the reactions proceeded smoothly to give the desired
1,2,3‐triazoles in moderate to excellent yields, which obvi-
ously indicated the generality and scope of the reaction with
respect to various organic amines.
TABLE 2 Synthesis of N‐substituted 1,2,3‐triazoles under the optimized reaction conditiona
Entry
Amine
Propargyl bromide
Azide
Yield(%)b
85[8]
1
2
70[9]
3
4
5
6
85
82
98
93
7
8
9
95
90
84
aReagents and conditions: R1R2NH (0.50 mmol), BrCH2C ≡ CH (0.50 mmol), BnN3 (0.50 mmol), FBPs‐CuBr (5.50 mg, 0.002 mmol Cu), water (5.0 mL), MW, 400 W,
80 °C, 30 min.
bIsolated yield.

XIONG ET AL.
7 of 10
The yields of the three‐component CuAAC reaction of
annular secondary amines are higher than open chain sec-
ondary amines. Similarly, as for the open chain organic
amines, the yield of diethylamine is higher than
dibutylamine. However, there are obvious difference in
reactivity was observed for the examined reactants with
varied electronic properties. For example, the organic
amines with electron withdrawing groups (such as
succinimide) can react with propargyl bromide/benzyl azide
and give moderate yield (Table 2, entry 2, 70%). When
using piperazine as starting in the reaction, it is very easy
to prepare the corresponding disubstituted bis‐1, 2, 3‐tri-
azole in 85% yield under the same reaction condition
(Table 2, entry 3). Interestingly, this methodology could
also be extended to the primary aliphatic and aromatic
amines. For example, n‐butylamine, phenyl amine, and
benzyl amine, the corresponding disubstituted bis‐1,2,3‐
triazoles could also be obtained in excellent yields under
the optimized reaction condition (Table 2, entries 6–8).
The copper contents of the obtained 1,2,3‐triazoles were
detected by atomic absorption spectroscopy (AAS). The
exact amount of copper in the isolated final 1,2,3‐triazoles
(Table 2, entries 1 and 2) were found to be 93 ppm and
147 ppm, respectively. At the same time, the copper contents
(Table 2, entries 1 and 2) present in the aqueous phase after
extraction with ethyl acetate (10.0 mL × 3) were found to
be 850 ppm and 965 ppm, respectively.
FIGURE 8 Recycling activity of FBPs‐CuBr for the synthesis of
1,2,3‐triazole by using morpholine, propargyl bromide and benzyl
azide as starting materials
TABLE 3 Scale‐up synthesis of 4‐((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)
methyl) morpholine
Entry
Scale (mmol)
H2O (mL)
Isolated yield (%)
1
2a
0.5
0.5
5
5
5
96
94
94
90
85
84
82
80
3
20
20
40
40
80
120
4b
5
6c
5
10
10
20
40
7
8
a‐cCatalyst recycled and used for the fifth run.
2.4 | Recycle use of FBPs‐CuBr
For a heterogeneous catalyst, it is very important to investi-
gate its ease of recoverability and reusability. In order to
make the FBPs‐CuBr catalytic system greener and econom-
ical, we focused on recoverability and reusability of FBPs‐
CuBr on three‐component CuAAC reaction of morpholine,
propargyl bromide and benzyl azide under the optimized
reaction condition. After completion of each run, ethyl
acetate was added to dilute the reaction mixture and
FBPs‐CuBr was recovered from the reaction mixture by a
simple filtration. After a simple wash using ethyl acetate
and dried, the catalyst was reused directly for the next run
under the same condition. The obtained results were shown
in Figure 8. The obtained results showed that FBPs‐CuBr
still kept moderate catalytic activity and the desired product
could be obtained in 79% yield after 7 cycles. The result
could be explained by the protein, carbohydrate and
phosphopeptide molecules on the FBPs surfaces, which
play a key role in the chelation of CuBr.
was found to be 0.71 wt %, which lower than the fresh
catalyst (2.85 wt %). The decrease of yields should be
due to the normal loss of the Cu(I) catalyst during the
work‐up stage.
2.5 | Scale‐up synthesis of 4‐((1‐benzyl‐1H‐
1,2,3‐triazol‐4‐yl) methyl) morpholine
Finally, in order to evaluate the feasibility of applying this
methodology in a preparative scale, a multi‐scale experi-
ment for synthesis of 4‐((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)
methyl) morpholine was carried out in the presence of
morpholine, propargyl bromide and benzyl azide in water
under the optimized reaction condition.
The obtained results were summarized in Table 3. The
experimental results showed that the amplification reactions
were found to proceed smoothly and the desired product
was obtained in good yields (80–96%). When the scales
of the reaction were 5 and 10 mmol, the catalyst could be
recycled and reused at least 5 times and still maintained
good yield (˃84%). At last, when the scale of the reaction
was 40 mmol, the yield was 80%.
The percentage of copper contents of the fresh and
the recycled FBPs‐CuBr after seven consecutive trials
were determined by ICP‐AES analysis. The ICP‐AES
results showed that the weight percentage of copper
content of the recycled FBPs‐CuBr after seven cycles

8 of 10
XIONG ET AL.
4 | EXPERIMENTAL
4.1 | Materials and instrumentation
All chemicals were purchased from Aladdin Reagent Company
(Shanghai, China). The progress of the reaction was monitored
by thin layer chromatography using silica gel plates.
The IR spectra were obtained using
a
FT‐IR
(4000 ~ 400 cm−1) spectrometer (Nicolet Nexus FT‐IR spec-
trometer, USA) at 4 cm−1 resolution and 32 scans. Samples
were prepared using the KBr disc method. NMR spectra were
acquired in CDCl3 on a Bruker DMX‐400 spectrometer at
1
400 MHz for H NMR, the chemical shifts are given in δ
values from TMS as an internal standard. Powder X‐ray dif-
fraction (XRD) was used to characterize the crystalline
structure of FBPs‐CuBr on Bruker D8 Advance (Germany)
using Cu Kα radiation. Thermo gravimetric analyzer (TGA)
was run on TA instruments TA (USA) DSC2910/SDT2960,
samples were heated from 25 to 700 °C at ramp 10 °C/min
under N2. Scanning electron microscopy/energy dispersive
X‐ray spectroscopy (SEM/EDX) was used on the Oxford
instruments 7021. The copper contents of N‐substituted
1,2,3‐triazoles prepared by using CuBr and FBPs‐CuBr as
catalyst were determined by atomic absorption spectropho-
tometry (AAS) using standard methods with a Varian
AA275 atomic absorption spectrophotometer (USA).
SCHEME 1 A plausible mechanism for the synthesis of N‐
substituted 1,2,3‐triazole catalyzed by FBPs‐CuBr under MW
irradiation
2.6 | Tentative reaction mechanism
A plausible mechanistic pathway for the Cu(I)‐catalyzed
three‐component reaction to form N‐substituted 1,2,3‐
triazoles was illustrated in Scheme 1. In the first step, the
reaction between a nucleophilic organic amine and propargyl
bromide carried out to form propargyl amine by a fast substi-
tution reaction in the presence of Et3N. Subsequently, the
desired copper(I)‐acetylide complex was generated by activa-
tion of FBPs‐CuBr catalyzed C–H bond of terminal alkyne
under MW‐assisted condition. At last, the copper(I)‐acetylide
complex was added to organic azide to give the correspond-
ing N‐substituted 1,2,3‐triazoles (Scheme 1).
4.2 | Preparation of FBPs‐CuBr catalyst
Fleshy and oily materials were removed from raw fish bones
with hot deionized water using ultrasonic irradiation until
water was clear. The fishbones were put into ethanol to soak
for 12 h, dried at 80 °C for 12 h. The dried fishbones were
roughly crushed using a hammer and then the crushed fish
bones were ground into powders with a pestle and mortar,
and then screened over 100 mesh sieve (Figure 1 B).
CuBr (0.3 g) was added into FBPs (2.0 g) in DMF
(10.0 mL) under the protection of N2 atmosphere. The
obtained mixture was stirred for 24 h at room temperature.
The solid products separated from mother liquor through
vacuum filtration and then washed with distilled water to
obtain FBPs‐CuBr catalyst.
3 | CONCLUSIONS
In summary, we have successfully developed a new and
inexpensive FBPs‐CuBr as heterogeneous catalyst from
readily available waste FBPs for the first time. FBPs‐CuBr
showed highly catalytic activity with efficient recycling for
the one‐pot multicomponent synthesis of N‐substituted
1,2,3‐triazoles from organic amines, propargyl bromide, and
benzyl azide under MW irradiation in water. When the scale
of the CuAAC reaction was increased to 10.0 mmol, the
desired 1,2,3‐triazole still could be obtained in 84% yield
after 5 recycles. Importantly, when the scale of the reaction
was increased to 40.0 mmol, the product still could be
obtained in 80% yield. This protocol realizes green, eco‐effi-
cient, and multi‐gram synthesis of N‐substituted 1,2,3‐
triazoles with good yields under mild conditions.
4.3 | Synthesis of N‐substituted 1,2,3‐triazoles
catalyzed by FBPs‐CuBr
N‐substituted 1,2,3‐triazoles was prepared by one‐pot method
in two steps: nucleophile substitution reaction between
organic amines and propargyl bromide, and the CuAAC reac-
tion between obtained terminal alkynes and benzyl azide.
At first, the nucleophile substitution reaction was carried
out as follows: a mixture of water (5.0 ml), Et3N (1.5 mmol),
organic amine (0.5 mmol) and propargyl bromide (0.5 mmol)

XIONG ET AL.
9 of 10
was stirred vigorously for 10 min at 80 °C under MW
irradiation (400 W). Then, benzyl azide (0.5 mmol) and
FBPs‐CuBr (5.50 mg, 0.002 mmol Cu) were added into the
reaction system, the mixture was further heated and stirred
under the same conditions until complete consumption of
the starting substrates monitored by TLC. Subsequently, the
reaction mixture was cooled to room temperature and FBPs‐
CuBr was isolated by simple filtration, the residual mixture
was extracted with ethyl acetate (10.0 mL × 3). The combined
organic extracts were washed with saturated brine, and dried
(anhydrous MgSO4). After removal of ethyl acetate under
reduced pressure, the residue was purified by flash chroma-
tography on silica‐gel to give the desired product.
(m, 14H), 6.87–6.86 (m, 2H), 6.77–6.75 (m, 1H), 5.45 (s,
4H), 4.66 (s, 4H); 13C NMR (100 MHz, CDCl3) δ:
134.71, 129.27, 129.08, 128.66, 127.84, 122.00, 54.09,
46.95; MS (ESI): m/z calc. For C25H25N7: 435.22 [M]+,
found: 436.14 [M + H]+.
N,N‐bis((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)(phenyl)
methanamine (Table 2, entry 7): FTIR (KBr disc) cm−1: 3120
(m), 3065 (m), 3041 (w), 2930 (m), 2834 (m), 1494 (m),
1
1434 (s), 1382 (s), 1319 (s), 740 (s), 700 (m); H NMR
(400 MHz, CDCl3) δ: 7.50–7.28 (m, 17H), 5.52 (s, 4H),
3.74 (s, 4H), 3.65 (s, 2H); 13C NMR (100 MHz, CDCl3) δ:
134.85, 129.08, 129.05, 128.66, 128.28, 127.94, 127.04,
123.10, 57.74, 54.08, 47.58; MS (ESI): m/z calc. For
C27H27N7: 449.23 [M]+, found: 450.15[M + H]+.
N,N‐bis((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)butan‐1‐
amine (Table 2, entry 8): FTIR (KBr disc) cm−1: 3136 (s),
3065 (w), 2930 (w), 1597 (s), 1510 (m), 1446 (w), 1367
(m), 1224 (m), 1057 (m), 756 (s), 716 (w); 1H NMR
(400 MHz, CDCl3) δ: 7.52–7.28 (m, 12H), 5.22 (s, 4H),
3.73 (s, 4H), 2.46 (s, 2H), 1.27 (s, 4H), 0.85 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 134.85, 129.07, 128.64,
127.95, 122.95, 54.08, 53.34, 47.84, 20.45, 13.95; MS
(ESI): m/z calc. For C24H29N7: 415.25 [M]+, found: 416.15
[M + H]+.
4.4 | Spectroscopic data of the N‐substituted 1,
2, 3‐triazoles
1,4‐bis((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)piperazine
(Table 2, entry 3): FT‐IR (KBr disc) cm−1: 3034 (w), 2940
(w), 2874 (m), 2821 (w), 2803 (w), 2785 (w), 2741 (w),
2692(w), 1639 (m), 1550 (m), 1493 (m), 1457 (m), 1373
(m), 1324 (m), 1284 (m), 1208 (m), 1160 (m), 1128 (m),
1048 (m), 1008 (m), 928 (m), 867 (m), 830 (m), 760 (s);
1H NMR (400 MHz, CDCl3) δ: 7.44–7.37 (m, 12H), 5.52
(s, 4H), 3.70 (s, 4H), 2.59 (s, 8H); 13C NMR (100 MHz,
CDCl3) δ: 134.60, 129.13, 128.76, 128.14, 54.16, 53.15,
52.54; MS (ESI): m/z calc. For C24H28N8: 428.24 [M]+,
found: 429.52 [M + H]+.
4‐((1‐(2‐(2‐(2‐methoxyethoxy)ethoxy)ethyl)‐1H‐1,2,3‐
triazol‐4‐yl)methyl)morpholine (Table 2, entry 9): FTIR
(KBr disc) cm−1: 3137 (w), 2875 (s), 2817 (s), 1977 (w),
1648 (w), 1551 (s), 1453 (m), 1351 (m), 1328 (m), 1284
(w), 1115 (s), 1049 (m), 1004 (m), 915 (m), 862 (w), 800
N‐((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)‐N‐
1
butylbutan‐1‐amine (Table 2, entry 4): FT‐IR (KBr disc) cm
−1: 3144 (w), 3080 (w), 3041 (w), 2953 (s), 2874 (m), 2811
(w), 1470 (s), 1382 (m), 1327 (m), 1216 (m), 1057 (m),
(w), 711 (w); H NMR (400 MHz, CDCl3) δ: 7.70 (s, 1H),
4.54 (t, J = 5.1 Hz, 2H), 3.88 (t, J = 5.1 Hz, 2H), 3.73–
3.71 (m, 4H), 3.68 (s, 2H), 3.63–3.61 (m, 6H), 3.55 (dd,
J = 5.7, 3.2 Hz, 2H), 3.38 (s, 3H), 2.55–2.52 (m, 4H); 13C
NMR (100 MHz, CDCl3) δ: 143.67, 123.95, 71.90, 70.51,
69.47, 66.80, 59.02, 53.61, 53.30, 50.19. MS (ESI): m/z calc.
For C14H26N4O4: 314.20 [M]+, found: 315.45 [M + H]+.
1
724 (s); H NMR (400 MHz, CDCl3) δ: 7.36–7.23 (m, 6H),
5.51 (s, 2H), 3.73 (s, 2H), 2.46–2.33 (m, 4H), 1.42 (dt,
J = 15.0, 7.4 Hz, 4H), 1.30–1.20 (m, 4H), 0.85 (t,
J = 7.3 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ: 146.26,
134.94, 131.99, 130.86, 130.12, 54.04, 53.54, 49.03, 29.21,
20.57, 13.99; MS (ESI): m/z calc. For C18H28N4: 300.23
[M]+, found: 301.53 [M + H]+.
ACKNOWLEDGEMENTS
4‐((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)morpholine
(Table 2, entry 5): FT‐IR (KBr disc) cm−1: 3152 (m), 3096
(w), 3033 (w), 2969 (m), 2850 (m), 2811 (m), 1462 (m),
This work was financially supported by the National Natural
Science Foundation of China (21004024), the Natural
Science Foundation of Fujian province (2016 J01063), the
Program for New Century Excellent Talents in University
of Fujian province (2012FJ‐NCET‐ZR03), the Promotion
Program for Young and Middle‐aged Teacher in Science
and Technology Research of Huaqiao University (ZQN‐
YX103) and Science & Technology Project of Quanzhou
(2014Z126).
1
1335 (m), 1279 (m), 1216 (m), 1130 (s), 732 (m); H NMR
(400 MHz, CDCl3) δ: 7.41–7.28 (m, 6H), 5.53 (s, 2H),
3.79–3.68 (m, 4H), 3.66 (s, 2H), 2.51 (s, 4 H); 13C NMR
(100 MHz, CDCl3) δ: 134.63, 129.13, 128.77, 128.11,
122.56, 66.78, 54.16, 53.70, 53.37; MS (ESI): m/z calc. For
C14H18N4O: 258.15 [M]+, found: 258.86 [M]+.
N,N‐bis((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)
benzenamine (Table 2, entry 6): FTIR (KBr disc) cm−1
:
REFERENCES
3128 (m), 3073 (m), 3041 (w), 2953 (m), 2938 (m), 2866
(w), 2803 (w) 1462 (m), 1327 (s), 1224 (s), 1128 (s), 732
(s), 708 (w); 1H NMR (400 MHz, CDCl3) δ: 7.35–7.28
[1] N. Siddiqui, W. Ahsan, M. S. Alam, R. Ali, S. Jain, B. Azad, J.
Akhtar, Int. J. Pharm. Sci. Rev. Res. 2011, 8, 161.

10 of 10
XIONG ET AL.
[2] S. G. Agalave, S. R. Maujan, V. S. Pore, Chem. – Asian J. 2011, 6,
[25] X. Q. Xiong, Y. B. Jiang, S. Y. Xiao, L. Shi, S. D. Song, Chem. J.
Chinese U. 2016, 37, 1863.
2696.
[3] K. L. Hsu, K. Tsuboi, J. W. Chang, L. R. Whitby, A. E. Speers, H.
[26] S. Chassaing, M. Kumarraja, A. S. S. Sido, P. Pale, J. Sommer,
Pugh, B. F. Cravatt, J. Med. Chem. 2013, 56, 8270.
Org. Lett. 2007, 9, 883.
[4] V. K. Tiwari, B. B. Mishra, K. B. Mishra, N. Mishra, A. S. Singh,
[27] S. Chassaing, A. S. S. Sido, A. Alix, M. Kumarraja, P. Pale, J.
X. Chen, Chem. Rev. 2016, 116, 3086.
Sommer, Chem. – Eur. J. 2008, 4, 6713.
[5] L. Daz, J. Bujons, J. Casas, A. Llebaria, A. Delgado, J. Med. Chem.
2010, 53, 5248.
[28] P. Kuhn, A. Alix, M. Kumarraja, B. Louis, P. Pale, J. Sommer, Eur.
J. Org. Chem. 2009, 423.
[6] V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew.
Chem., Int. Ed. 2002, 41, 2596.
[29] V. Bénéteau, A. Olmos, T. Boningari, J. Sommer, P. Pale,
Tetrahedron Lett. 2010, 51, 3673.
[7] X. Q. Xiong, L. Cai, Z. K. Tang, China J. Org. Chem. 2012, 32,
[30] H. Sharghi, R. Khalifeh, M. M. Doroodmand, Adv. Synth. Catal.
2009, 351, 207.
1410.
[8] T. Miao, L. Wang, Synthesis 2008, 3, 363.
[31] M. Nasrollahzadeh, B. Jaleh, P. Fakhri, A. Zahraei, E. Ghadery,
RSC Adv. 2015, 5, 2785.
[9] A. Coelho, P. Diz, O. Caamano, E. Sotelo, Adv. Synth. Catal. 2010,
352, 1179.
[32] F. Shirini, S. Akbari‐Dadamahaleh, A. Mohammad‐Khah, J. Mol.
Catal. A: Chem. 2011, 363–364, 10.
[10] R. P. Jumde, C. Evangelisti, A. Mandoli, N. Scotti, R. Psaro,
J. Catal. 2015, 324, 25.
[33] S. Jairama, P. Kolar, S. S. Ratna, J. A. Osborne, J. P. Davis,
Bioresour. Technol. 2012, 104, 329.
[11] P. Diz, P. Pernas, A. E. Maatougui, C. R. Tubio, J. Azuaje, E.
Sotelo, F. Guitián, A. Gil, A. Coelho, Appl. Catal. A: Gen. 2015,
502, 86.
[34] X. Q. Xiong, H. X. Chen, R. J. Zhu, Chin. J. Catal. 2014, 35, 2006.
[35] L. Agwaramgbo, N. Magee, S. Nunez, K. Mitt, J. Environ.
Protection 2013, 4, 1251.
[12] X. Q. Xiong, L. Cai, Catal. Sci. Technol. 2013, 3, 1301.
[13] M. Tajbakhsh, M. Farhang, S. M. Baghbanian, R. Hosseinzadeh,
[36] L. Agwaramgbo, N. Lathan, S. Edwards, S. Nunez, J. Environ.
Protection 2013, 4, 741.
M. Tajbakhs, New J. Chem. 2015, 39, 1827.
[14] F. M. Moghaddam, S. E. Ayati, RSC Adv. 2015, 5, 3894.
[37] S. S. E. Ghodsinia, B. Akhlaghinia, R. Jahanshahi, RSC Adv. 2016,
6, 63613.
[15] A. Pourjavadi, M. Tajbakhsh, M. Farhang, S. H. Hosseini, New J.
Chem. 2015, 39, 4591.
[38] X. Q. Xiong, L. Cai, Z. K. Tang, Chin. J. Org. Chem. 2012, 32,
1410.
[16] A. Pourjavadi, A. Motamedi, S. H. Hosseini, M. Nazari, RSC Adv.
2016, 6, 19128.
[39] X. Q. Xiong, H. X. Chen, Z. K. Tang, Y. B. Jiang, RSC Adv. 2014,
4, 9830.
[17] K. Bahrami, M. S. Arabia, New J. Chem. 2016, 40, 3447.
[18] R. Jahanshahia, B. Akhlaghinia, RSC Adv. 2016, 6, 29210.
[40] X. Q. Xiong, L. Cai, Y. B. Jiang, Q. Han, ACS Sustainable Chem.
Eng. 2014, 2, 765.
[19] L. Bonami, W. Van Camp, D. Van Rijckegem, F. E. D. Prez,
[41] Y. B. Jiang, Y. L. Wang, Q. Han, R. J. Zhu, X. Q. Xiong, Chin. J.
Org. Chem. 2014, 34, 2068.
Macromol. Rapid Commun. 2009, 30, 34.
[20] S. Wallyn, M. Lammens, R. K. O'Reilly, F. D. Prez, J. Polym. Sci.,
Part A: Polym. Chem. 2011, 49, 2878.
[21] J. Albadi, M. Keshavarz, F. Shirini, M. Vafaie‐nezhad, Catal.
Commun. 2012, 27, 17.
How to cite this article: Xiong X, Tang Z, Sun Z,
Meng X, Song S, Quan Z. Supported copper (I)
catalyst from fish bone waste: An efficient, green and
reusable catalyst for the click reaction toward N‐
substituted 1,2,3‐TRIAZOLES. Appl Organometal
Chem. 2017;e3946. https://doi.org/10.1002/aoc.3946
[22] R. B. Nasir Baig, R. S. Varma, Green Chem. 2013, 15, 1839.
[23] B. S. P. Anil Kumar, K. Harsha Vardhan Reddy, K. Karnakar, G.
Satish, Y. V. D. Nageswar, Tetrahedron Lett. 2015, 56, 1968.
[24] W. B. Yu, L. X. Jiang, C. Shen, W. M. Xu, P. F. Zhang, Catal.
Commun. 2016, 79, 11.