CuO nanoparticles-catalyzed a novel method to the synthesis of symmetrical diselenides from aryl halides: selenoamide as an organic Se-donor reagent

Article abstract of DOI:10.1007/s11696-018-0450-6

A new method is reported for the synthesis of symmetrical diaryldiselenides from aryl halides using selenoamide as an organic Se-donor reagent in the presence of copper (II) oxide nanoparticles. CuO nanoparticles were found to be an efficient and inexpensive catalyst for ligand-free C-Se bond formation with a series of symmetrical diaryldiselenides obtained in good to excellent yield.

Full text of DOI:10.1007/s11696-018-0450-6

Chemical Papers
https://doi.org/10.1007/s11696-018-0450-6
ORIGINAL PAPER
CuO nanoparticles‑catalyzed a novel method to the synthesis
of symmetrical diselenides from aryl halides: selenoamide
as an organic Se‑donor reagent
1
2
1
Mohammad Soleiman‑Beigi · Issa Yavari · Fatemeh Sadeghizadeh
Received: 7 December 2017 / Accepted: 14 March 2018
©
Institute of Chemistry, Slovak Academy of Sciences 2018
Abstract
A new method is reported for the synthesis of symmetrical diaryldiselenides from aryl halides using selenoamide as an
organic Se-donor reagent in the presence of copper (II) oxide nanoparticles. CuO nanoparticles were found to be an eꢀcient
and inexpensive catalyst for ligand-free C-Se bond formation with a series of symmetrical diaryldiselenides obtained in
good to excellent yield.
Keywords Diaryldiselenides · Selenoamide · Se-donor · Copper (II) oxide · Nanoparticles
Introduction
and Griꢀn 1973; Lewicki et al. 1976, 1978), the reaction of
benzyl alcohols with NaBH Se (Panduranga et al. 2016)
2
3
Over the last few decades, organoselenium compounds
have shown versatile application as organic intermediates
and reagents in organic synthesis (Wirth 2000; Devillanova
and reaction of metal diselenides with organoylhalides
(Gladysz et al. 1978; Syper and Miochowski 1988; Ping
and Xunjun 1993) have been reported for the synthesis of
organic diselenides. In recent decades the cross-coupling
reactions aryl halide with elemental selenium in the present
of transition metals have been studied for diselenide bond
formation (Krief 1995; Li et al. 2013; Botteselle et al. 2012;
Kassaee et al. 2013; Singh et al. 2010). Some of these pro-
cedures are ineꢀcient due to the use of expensive reagents,
diꢀculty in workup and long reaction time (Kumar and Eng-
man 2006; Jamier et al. 2010). In all the previously reported
investigations describing the synthesis of diaryldiselenides,
there has been no report on the use of organic source of
selenium in the reactions. Herein, we report the utilization of
an organic Se-donor reagent used for the coupling reaction
with arylhalide compounds.
2
007; Derek and Risto 2011; Godoi et al. 2011; Freuden-
dahl et al. 2009). In addition to their synthetic application,
organoselenium compounds have received a lot of attention
due to their wide range of biological activities (Nogueira
et al. 2004; Mugesh et al. 2001, 1998; Iwaoka and Tomoda
1
994). Organic compounds containing Se–Se bonds have
shown anti-inꢁammatory (Savegnago et al. 2007), anti-ulcer
(
Savegnago et al. 2006), antioxidant (Ibrahim et al. 2012),
anticancer activities (Kim et al. 2015). Diꢂerent approaches
such as oxidation of selenols (Prabhu and Chandrasekaran
1
997) or selenolates (Krief et al. 1988), reactions of alde-
hydes with sodium hydrogen selenide in the presence of an
amine and sodium borohydride (Krief et al. 1999; Klayman
Currently, there has been an increasing demand towards
using nanostructured metallic catalysts in organic reactions,
especially in coupling reactions (Fihri et al. 2011; Swapna
et al. 2011a, b; Xu et al. 2011). Among the various nanopar-
ticulate metal oxides, CuO nanoparticles have emerged as
an eꢂective catalyst in several transformations (Jammi et al.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11696-018-0450-6) contains
supplementary material, which is available to authorized users.
*
Mohammad Soleiman-Beigi
SoleimanBeigi@yahoo.com
2
009; Rout et al. 2007a, b; Reddy et al. 2009; Zhang et al.
1
2
2011; Alves et al. 2009), because of its captivating proper-
ties such as large speciꢃc surface areas and high activities
in many catalytic processes. In continuation of our eꢂorts
to introduce sulfur-transfer reagents (Soleiman-Beigi et al.
Department of Chemistry, Ilam University, PO.
Box 69315-516, Ilam, Iran
Department of Chemistry, Tarbiat Modares University,
PO. Box 14115-175, Tehran, Iran
Vol.:(0
1
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Chemical Papers
2
012, 2013, 2015a, b, c, d, 2016), we now report a method
The reaction continued at 110 °C under atmospheric condi-
tions. After completion of the reaction [about 10 h; TLC
(EtOAc/hexane, 1:20) monitoring. CH Cl (20 mL) was
used for the direct synthesis of symmetrical diaryldisele-
nides (3) using N, N-di ethyl selenoformamide (2) as new
organic Se-donor reagent (Scheme 1).
2
2
added and the mixture was washed with H O (2×15 mL).
2
The combined organic fractions were dried (Na SO ) and
2
4
concentrated under reduced pressure. The residue was puri-
ꢃed by preparative chromatography (silica gel), hexane/
EtOAc, 20:1] to give the product.
Experimental
Materials
Diphenyl diselenide (3a)
The reactions were performed under normal atmosphere
condition. All reagents and solvents used in this work were
obtained from Merck and were used without further puriꢃca-
tion. Analytical thin layer chromatography was performed
The product was obtained (ethyl acetate/n-hexane, 1:20)
1
as a yellow solid in 91% yield. mp: 59–62 °C. H NMR
(
CDCl , 500 MHz) : 7.19–7.30 (m, 6 H), 7.55–7.61 (m, 4
3
13
using Merck silica gel GF plates. Plate chromatography
2
54
H). C NMR (125.7 MHz, CDCl ) : 128.05, 129.64, 131.87,
3
was performed using silica gel 60 PF
. All products
2
54+366
133.31. GC-Mass (EI, m/z): 314.0 [M+]. Elemental analysis
are known and were characterized by comparison of their
calculated for C H Se : % =C, 46.18; H, 3.23. Found: C,
1
2
10
2
1
13
spectral ( H NMR, C NMR, and GC-Mass) and physi-
cal data with those of authentic samples. The NMR spectra
were recorded at on a Bruker Avance NMR spectrometer in
4
6.47; H, 3.03.
Bis (4‑nitrophenyl) diselenide (3b)
CDCl solution with TMS as internal standard. All shifts
3
are given in ppm and all coupling constants (J values) were
The product was obtained (ethyl acetate/n-hexane, 1:5) as
reported in Hertz (Hz).
1
a yellow solid in 94% yield. H NMR (CDCl , 500 MHz) :
3
13
7
.70 (d, J=8.8 Hz, 4 H), 8.11 (d, J=8.8 Hz, 4 H). C NMR
Chemicals
(
125.7 MHz, CDCl ) : 125.01, 129.98, 138.62, 147.02.
3
Synthesis of CuO nanoparticles
Bis (2‑methylphenyl)diselenide (3c)
CuO nanoparticles were synthesized as described in (Azam
et al. 2012). Cu (NO ) ·3H O and citric acid was dissolved
The product was obtained (ethyl acetate/n-hexane, 1:20) as
3
2
2
1
a yellow oil in 83% yield. H NMR (CDCl , 500 MHz) :
3
in 100 mL deionized water to form 0.1 M concentration
1
3
2
.41 (s, 6 H), 7.46–6.59 (m, 6 H), 7.88–7.90 (m, 2 H).
C
(
2.41 g Cu (NO ) ·3H O and 1.92 g citric acid), the solution
3 2 2
NMR (125.7 MHz, CDCl ) : 21.69, 126.68, 128.42, 129.76,
3
was stirred with a magnetic stirrer at 100 °C. Stirring contin-
ued until gel formation (approximately 1 h). Subsequently,
the gel was allowed to burn at 200 °C until a light ꢁuꢂy mass
was obtained. The obtained light ꢁuꢂy mass was further
annealed for 2 h at 400 °C to obtain the highly crystalline
CuO nanoparticles.
1
30.29, 132.39, 138.70.
Bis (4‑methylphenyl) diselenide (3d)
The product was obtained (ethyl acetate/n-hexane, 1:20) as a
1
yellow oil in 79% yield. H NMR (CDCl , 500 MHz) : 2.34
3
(
s, 6 H), 7.02 (d, J=8.5 Hz, 4 H), 7.47 (d, J=8.6 Hz, 4 H).
General procedure for the preparation of diaryldiselenides
Bis(4‑methoxyphenyl) diselenide (3e)
Symmetrical organic diselenides synthesis: typical experi-
mental procedure. CuO nanoparticles (10 mol%) were added
to stirred solution of iodobenzene (2.0 mmol), selenoamide
The product was obtained (ethyl acetate/n-hexane, 1:5) as
1
a yellow solid in 75% yield. mp: 133–136 °C. H NMR
(
2.0 mmol) and KOH (3 mmol) in 4 mL DMF/H O (20:1).
2
(
CDCl , 500 MHz) : 3.71 (s, 6 H), 6.54 (d, J=8.2 Hz, 4 H),
3
1
3
7
5
.88 (d, J=8.3 Hz, 4 H). C NMR (125.7 MHz, CDCl ) :
3
5.69, 115.49, 124.62, 137.39, 159.70.
Bis (2‑methoxyphenyl) diselenide (3f)
The product was obtained (ethyl acetate/n-hexane, 1:10) as a
Scheme 1 The synthesis of diaryldiselenides using N, N-di ethyl
yellow oil in 67% yield. MS (EI, m/z): 372 [M+]. Elemental
selenoformamide
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Chemical Papers
analysis calculated for C H O Se : % =C, 45.18; H, 3.79.
oxide nanopowder (up to 10 mol%) led to increased rate of
the reaction; however, further increasing the catalyst load-
ing (˃10 mol%) had no eꢂect on the product yield (Table 1,
entries 1–3). We performed the model reaction in the
absence of base, however, this failed to aꢂord the desired
product. Several bases including KOH, K CO , Et N and
1
4
14
2
2
Found: C, 44.66; H, 3.51.
Bis (1‑naphthalene) diselenide (3g)
The product was obtained (ethyl acetate/n-hexane, 1:20) as
2
3
3
1
a yellow oil in 90% yield. H NMR (CDCl , 300 MHz) :
t-BuOK were used in the reaction, with KOH giving the best
results (Table 1, entries 4–7). Subsequently, we evaluated the
inꢁuence of the solvent in the reaction, dimethylformamide
(DMF) was found to be the most eꢂective solvent in the
diaryldiselenides synthesis (Table 1, entries 8–11). Low-
ering the temperature from 110 to 25 °C led to a reduced
yield, whereas increasing the temperature to 130 °C failed
to improve the yield (Table 1, entries 12–14). Thus, the
optimized reaction conditions used were: 10 mol% of CuO
nanopowder as the catalyst, 3 mmol of KOH as the base,
2 mmol of arylhalide, and 2 mmol of selenoamide in DMF
(See Table 1).
3
3
.35-7.40 (m, 2 H), 7.61–7.70 (m, 4 H), 7.85–7.93 (m, 6
1
3
H), 8.42 (d, J=8.7 Hz, 2 H). C NMR (100 MHz, CDCl )
3
:
123.04, 126.31, 126.85, 127.24, 127.49, 128.09, 128.48,
1
30.06, 132.14, 134.77.
Bis (2‑naphthalene) diselenide (3h)
The product was obtained (ethyl acetate/n-hexane, 1:20) as
1
a yellow oil in 87% yield. H NMR (CDCl , 500 MHz) :
3
3
2
.37–7.40 (m, 4 H), 7.48–7.51 (m, 4 H), 7.76 (d, J=8.4 Hz,
1
3
H), 7.88 (d, J = 8.3 Hz, 2 H), 8.39 (s, 2 H). C NMR
(
125.7 MHz, CDCl ) : 123.15, 125.91, 126.69, 127.14,
We then used the optimized conditions to construct a
series of diselenide derivatives from selenoamide 2 and vari-
ous alkyl halide compounds 1. The desired products 3a–k
were obtained in good to excellent yields and the results are
summarized in Table 2. Aryl chlorides and aryl tosylates
served as low yielding substrates when compared to aryl
iodides and aryl bromides. In addition, this catalytic system
provided good to excellent results using both electron-rich
and electron-poor arylhalide compounds, however electron-
withdrawing groups gave better yields as when compared
electron-donating groups. For instance, we obtained the
desired diselenide derivatives using 4-nitro-bromobenzene,
4- methoxyIodobenzene and 2- methoxyIodobenzene in 94,
75 and 67% yield after 3, 24 and 24 h, respectively (Table 2).
In addition, to investigate the scope of this reaction, we
examined the reaction using heteroaryl halides (Table 2, 3k).
Although we cannot clearly determine the catalytic
reaction pathway for this protocol, a plausible mecha-
nism for the reaction is given in Scheme 2. Since that
selenium may have behavior similar to that established
for sulfur, the initial event is the formation of complex
4 through oxidative addition of Ar–X to CuO which is
attached by selenoamide (1) to afford the complex 5
3
1
28.09, 128.49, 128.93, 131.46, 132.84, 134.63. MS (EI,
m/z): 412 [M+].
Bis(4‑chlorophenyl) diselenide (3i)
The product was obtained (ethyl acetate/n-hexane, 1:20) as
1
a yellow oil in 72% yield. H NMR (CDCl , 500 MHz) :7.21
3
(
d, J=8.5 Hz, 2 H), 7.55 (d, J=8.4 Hz, 4 H).
Bis(thiophen‑2‑yl) diselenide (3 k)
The product was obtained (ethyl acetate/n-hexane, 1:10) as
1
a dark orange oil in 90% yield. H NMR (CDCl , 300 MHz)
3
:
7.02–7.03 (m, 2 H), 7.24–7.27 (m, 2 H), 7.49-7.51 (m, 2
H). MS (EI, m/z): 326 [M+].
, 2‑Bis (4‑boromophenyl) diselenide (3j)
1
The product was obtained (ethyl acetate/n-hexane, 1:5) as a
1
dark orange oil in 81% yield. H NMR (CDCl , 300 MHz) :
3
7
.27- 47 (m, 8 H). MS (EI, m/z): 470 [M+].
(
Soleiman-Beigi et al. 2013; Sperotto et al. 2010). Then
Results and discussion
potassium arylselenolate is produced by hydrolyze 5 in
the aqueous basic conditions. Finally, arylselenolate is
converted to the desired product under optimal reaction
conditions (Ming-De et al. 1995; Soleiman-Beigi et al.
2015; Lenardo et al. 2007).The morphology, crystal-
linity, and chemical properties of the synthesized CuO
nanoparticle investigated by X-ray diffractometry (XRD),
scanning electron microscope (SEM) and Fourier trans-
form infrared (FT-IR) spectra, respectively. According
to SEM (Fig. 1a) the catalyst was made up of uniform
nanometer sized particles and the average size of prepared
The reaction between iodobenzene (2 mmol) and selenoam-
ide (2 mmol), in the presence of copper (II) oxide nano-
powder (5 mol %) and KOH (3 mmol) in DMF at 110 °C
was chosen as a model for the synthesis of symmetrical
diaryldiselenides (Table 1, entry 1). To optimize the reac-
tion conditions, we have studied various bases, solvents and
temperatures as well as the catalyst loading. Initially the
amount of copper (II) oxide nanopowder was controlled
and it was found that increasing the amount of copper (II)
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Scheme 2 Plausible mechanism
for the synthesis of diaryldis-
elenides
Table 1 Optimization of reaction conditiona
Entry
CuO (xmol%)
Base (3 mmol)
Solvent
Temp (°C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
5
10
15
10
10
10
10
10
10
10
10
10
10
10
KOH
KOH
KOH
–
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMSO
Toluene
PEG
110
110
110
110
110
110
110
110
110
110
110
25
3
3
3
24
3
3
3
3
3
3
75
91
91
N.R
85
56
74
71
62
K CO
2
3
Et N
3
t-BuOK
KOH
KOH
KOH
KOH
KOH
KOH
KOH
10
11
12
13
14
57
H O
3
Trace
Trace
88
2
DMF
DMF
DMF
24
24
3
80
130
91
Reactions were carried out at 1 mmol scale; using 2.0 mmol of PhI 2 mmol of Selenoamide 3 mmol of base in 4 mL solvent, under air
CuO is about 40 nm. The XRD pattern can be indexed
to the monoclinic phase of CuO crystals (Fig. 1b). The
FT-IR analysis of CuO show vibrations of Cu–O bond
2007), Also, the successful incorporation of Cu metal and
a uniform distribution of the particles was confirmed by
EDX analysis (Fig. 1d).
−
1
in the waves numbers 477, 522 and 603 cm and broad
−
1
absorption peak at around 3442 cm which is attributed
to the presence water molecules. All of the data are simi-
lar to that of other CuO nanoparticle samples previously
mentioned in the literatures (Azam et al. 2012; Zhu et al.
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Chemical Papers
Table 2 Screening of diꢂerent substrates
Conclusions
is easily prepared and nontoxic without harmful by-prod-
uct formation. Normal atmospheric conditions, eꢀcient,
an inexpensive and easily prepared catalyst, ligand-free
systems, short reaction times, and high yields are other
advantages of this protocol.
In conclusion, we have introduced a new organic Se-donor
reagent used for the synthesis of diselenides via the cross-
coupling of various aryl halides and selenoamide, which
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3

Chemical Papers
Fig. 1 a SEM Image of CuO (NPs), b XRD pattern of the CuO (NPs), c FT-IR spectra for the CuO (NPs), d EDX spectrum of the CuO (NPs)
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