Selective oxidation of alcohols to nitriles with high-efficient Co-[Bmim]Br/C catalyst system

Article abstract of DOI:10.1007/s11696-021-01593-z

An efficient method for catalyzing the ammoxidation of aromatic alcohols to aromatic nitriles was developed, in which a new heterogeneous catalyst based on transition metal elements was employed, the new catalyst was named Co-[Bmim]Br/C-700 and then characterized by X-ray photo-electronic spectroscopy, transmission electron microscope and X-ray diffraction. The reaction was carried out by two consecutive dehydrogenations under the catalysis of Co-[Bmim]Br/C-700, which catalytically oxidized the alcohol to the aldehyde, and then the aldehyde was subjected to ammoxidation to the nitrile. The catalyst system was suitable for a wide range of substrates and nitriles obtained in high yields, especially, the conversion rate of benzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol and 4-nitrobenzyl alcohol reached 100%. The substitution of ammonia and oxygen for toxic cyanide to participate in the reaction accords with the theory of green chemistry.

Full text of DOI:10.1007/s11696-021-01593-z

Chemical Papers
https://doi.org/10.1007/s11696-021-01593-z
ORIGINAL PAPER
Selective oxidation of alcohols to nitriles with high‑efcient
Co‑[Bmim]Br/C catalyst system
Yu‑Yan Xia1 · Qing‑Yang Lv1 · Hua Yuan1 · Jia‑Yi Wang1
Received: 11 September 2020 / Accepted: 8 March 2021
© Institute of Chemistry, Slovak Academy of Sciences 2021
Abstract
An efcient method for catalyzing the ammoxidation of aromatic alcohols to aromatic nitriles was developed, in which a new
heterogeneous catalyst based on transition metal elements was employed, the new catalyst was named Co-[Bmim]Br/C-700
and then characterized by X-ray photo-electronic spectroscopy, transmission electron microscope and X-ray difraction. The
reaction was carried out by two consecutive dehydrogenations under the catalysis of Co-[Bmim]Br/C-700, which catalyti-
cally oxidized the alcohol to the aldehyde, and then the aldehyde was subjected to ammoxidation to the nitrile. The catalyst
system was suitable for a wide range of substrates and nitriles obtained in high yields, especially, the conversion rate of
benzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol and 4-nitrobenzyl alcohol reached 100%. The substitution
of ammonia and oxygen for toxic cyanide to participate in the reaction accords with the theory of green chemistry.
Keywords Alcohol · Aldehyde · Ammoxidation · Co-[Bmim]Br/C · Nitrile
Introduction
chemistry perspective. The defects of the cyanation of halo-
genated hydrocarbons and the dehydration of amides and
aldehyde oximes force us to seek suitable raw materials for
sustainable and economical synthesis of nitrile. Compared
with aldehydes, alcohol is a more basic chemical raw mate-
rial, which is often used as raw material to prepare alde-
hydes, nitriles, amides, acids and other chemical products
(Iida and Togo 2007; Ishida et al. 2012; Chakraborty et al.
2017; Zultanski et al. 2016; Hashemi et al. 2019.
The nitrile group, one of the most important functional
groups in organic chemistry, widely exists in natural prod-
ucts and synthetic intermediates (Kim et al. 2012; Soleim-
ani et al. 2011). Organic nitriles have been widely used in
the synthesis of pharmaceuticals, agrochemicals and fne
chemicals due to its unsaturated structure and higher reac-
tive cyano groups (Fleming et al. 2010; Bezerra et al. 2008).
There are many conventional methods to synthesize nitrile,
such as Sandmeyer reaction (Sundermeier et al. 2003; Mar-
tin and Kalevaru 2010), dehydration of aldehydes or aldoxi-
mes (Yan et al. 2017; Zhang et al. 2015; Moussa et al. 2010),
cyanation of aryl halides (Hatsuda and Seki 2005; Song et al.
2013; Beletskaya et al. 2004) and transition-metal-catalyzed
C–H functionalization of arenes (Mori et al. 2001; Biondini
et al. 2005). However, multistep processes, highly toxic cya-
nide (or metal cyanide) and large amounts of by-products
were involved in these aforementioned methods (Lücke et al.
2004; Reddy et al. 2009), which is contrary to the green
In recent years, synthesizing nitriles through the catalytic
aerobic oxidation of alcohols have become one of the pre-
ferred strategies for green oxidation. Precious metal cata-
lysts have occupied the major market of selective oxidation
from alcohols or aldehydes to nitriles (Oishi et al. 2010;
Wu, Hartwig 2006). In 2009, Mizuno (Oishi et al. 2009)
et al. reported the heterogeneous Ru(OH)x/Al2O3 catalyzed
oxidation of alcohols to nitriles (120 °C and 6 atm air) with
high yield. However, the development of large-scale applica-
tions and industrial production of precious metal catalysts
has been limited due to the increased cost of nitriles. In
order to save resources and reduce the costs in the produc-
tions, the precious metal-based catalysts are being gradually
replaced by transition metal (Co, Fe, Ni, Cu)-based cata-
lysts (Dornan et al. 2013; Hyodo et al. 2016; Kim and Stahl
2013; Yin et al. 2013), because of their high-abundance,
low-price and low-toxicity. Through long-term development,
* Hua Yuan
yuanhua@wit.edu.cn
1
Key Laboratory for Green Chemical Process of Ministry
of Education, Wuhan Institute of Technology,
Wuhan 430073, China
Vol.:(0123456789)
1 3

Chemical Papers
state-of-the-art Co-based (Bezerra et al. 2008) catalysts for
aerobic oxidation reactions have been an integral part of
chemical research. Generally speaking, in industrial pro-
cesses, compared to homogeneous cobalt complexes (Jang
et al. 2015; Ren et al. 2019), heterogeneous cobalt-based
catalysts ZIF (Xu et al. 2016; Sun et al. 2019) are preferred
due to their stability, easy of separation and recycling. For
example, Beller et al. (Jagadeesh et al. 2014) reported the
synthesis of aromatic nitrile by ammonium oxidation of aro-
matic alcohol in the Co-phenanthroline/C system. In addi-
tion, many other cobalt-based catalysts are found to be both
efcient and convenient such as Cox@N–C system (Nakat-
suka et al. 2017), Co3O4-N@C (Jagadeesh et al. 2013; Zhang
et al. 2014), and N-doped cobalt graphene layer (Chen et al.
2015; Pendashteh et al. 2017; Wei et al. 2015).
(1.83 g) and [Bmim]Br (metal Co:[Bmim]Br 1:3 mol ratio)
were placed in a 100 mL beaker and stirred at room tempera-
ture for 10 min to obtain Co-DES (Co-[Bmim]Br). Then,
Vulcan XC72R carbon powder (2.0 g) and ethanol (40 mL)
were added to it, stirred at 25 °C for 12 h, after that etha-
nol was removed slowly under vacuum to obtain Co-DES.
Finally, Co-DES was dried in an oven at 80 °C for 12 h and
then calcined in a tube furnace at 700 °C (nitrogen atmos-
phere) for 2 h to obtain Co-[Bmim]Br/C-700.
The procedure for preparing Co/C-700 and Co-[Bmim]
Br-700 was the same as that for Co-[Bmim]Br/C-700, but
there was no [Bmim]Br or Vulcan XC72R carbon impreg-
nated in the mixture, respective. The Co-[Bmim]Br/C-700
catalyst was immersed in the prepared 0.5 mol/L H2SO4
solution and stored in an oven at 80 °C for 6 h. After that, the
catalyst was fltered and washed repeatedly with deionized
water for three times. The catalyst prepared by this method
was named as Co-[Bmim]Br/C-700 (H+).
Deep eutectic solvents (DESs) consist of hydrogen bond
acceptor (HBR) and hydrogen bond donor (HBD) with a
certain stoichiometric ratio (Zhang et al. 2012). It has a low
freezing temperature (Tf) and owns the advantages of simple
preparation, cheap and non-toxic. There is an easy way to
prepare DESs which can be obtained by simply mixing HBR
and HBD (such as polyhydric alcohols) together. Besides,
DESs gather many advantages such as (1) low price, (2) easy
storage (i.e., chemical inertness with water) and (3) easy to
prepare (Qureshi et al. 2014). However, because of a large
amount of usage, DESs used as solvents or catalysts are usu-
ally limited by several drawbacks such as high viscosity and
homogeneity (which makes them difcult to separate) (Pour-
javadi and Habibi 2017). However, immobilized catalysts
can solve this problem. When metal-containing DES was
loaded on the surface of porous support materials, the sup-
ported metal-containing DES materials can both sufcient
contact with the substrate in the solution and be easily recy-
cled. Recently, Zhao et al. (2018) developed the Co–N–C
catalyze system that converted alcohol to aldehyde under
heterogeneous conditions (120 °C and 6 atm air). Based on
it, the possibility of continuous secondary dehydrogenation
by in situ alcohol to nitrile was explored. In this study, aim-
ing at transforming alcohols to nitriles efciently, an immo-
bilized catalyst was used. It means the direct use of toxic
cyanide can be avoided, and water was the only by-product.
Results and discussion
To study the structural feature of Co-[Bmim]Br/C sam-
ples, several characterization techniques were performed
including XPS, XRD, TEM and SEM. First, in order to
explore the chemical and electronic states of the N ele-
ment, the XPS high-resolution spectrum analysis of N1s
was performed on Co-[Bmim]Br/C. The results are shown
in Fig. 1 and Table 1. The N1s spectrum can be deconvo-
luted into three peaks (Fig. 1), which can be assigned as
graphitic N (401 eV), Co–N center (399.3 eV) and pyridinic
N (398.6 eV), respectively. Moreover, when the pyrolysis
Experimental
Preparation of the catalyst
All of the Co-[Bmim]Br/C catalysts were prepared through
in situ pyrolysis methods. The catalysts were labeled as Co-
[Bmim]Br/C-T (where T refers to the pyrolysis temperature,
which was set to 600, 700, 800, 900 °C respectively). For
example, the typical preparation procedure of Co-[Bmim]
Br/C-700 was described as follows: First, Co(NO3)·6H2O
Fig. 1 XPS spectra in N1s region for diferent catalysts. Co-[Bmim]
Br/C-600 (a), Co-[Bmim]Br/C-700 (b), Co-[Bmim]Br/C-800 (c), Co-
[Bmim]Br/C-900 (d)
1 3

Chemical Papers
Table 1 Percentage of diferent N in the catalyst
the proportion of the Co–N center decreased, the catalytic
activity of the reaction decreased Tables 1 and 2. Therefore,
it was believed that the presence of the Co–N center was the
key to the catalysis.
Catalysts
Graphitic N/%
Co–N/%
Pyridinic/%
Co-[Bmim]Br/C-600
Co-[Bmim]Br/C-700
Co-[Bmim]Br/C-800
Co-[Bmim]Br/C-900
42.93
43.82
47.74
74.85
21.16
31.32
27.12
12.29
35.90
24.85
25.13
12.85
To explore the diferences in catalytic properties of dif-
ferent catalysts, the diferent catalysts were further ana-
lyzed by XRD. XRD spectra of the catalysts with diferent
pyrolysis temperatures were shown in (Fig. 2a). The XRD
powder pattern was recorded on a Stoe STADI P difrac-
tometer, equipped with a linear position sensitive detector
(PSD) using Cu Kα radiation (λ = 1.5406 Å). Processing
and assignment of the powder patterns were done by using
the software WinXpow (Stoe) and the Powder Difraction
File (PDF) database of the International Centre of Difrac-
tion Data (ICDD). For all samples, a broad peak at around
2θ=25° was attributed to the (002) plane difraction peaks
of the graphite structure. Co-[Bmim]Br/C-400 and Co-
[Bmim]Br/C-500 only owned the graphene structure of the
carbon support peaks, but no characteristic peaks for metal-
lic Co. As the pyrolysis temperature increases, the XRD
pattern of Co-[Bmim]Br/C-600, Co-[Bmim]Br/C-700, Co-
[Bmim]Br/C-800 and Co-[Bmim]Br/C-900 all showed three
peaks at around 2θ = 44.1°, 51.4° and 75.9°, which were
close to the (111), (200) and (220) crystalline planes of the
face-centered cubic structure of metallic cobalt (PDF#15-
0806). That indicated the existence of metallic cobalt and
proved that increasing the pyrolysis temperature can sig-
nifcantly increased the peak intensity of the metallic cobalt,
which also meant a higher crystallinity of metallic cobalt.
The appearance of metallic cobalt was due to the reduction
of the Co-containing precursor at high temperatures, as Co
element was prone to undergo reduction as the temperature
increased.
Table 2 Aerobic oxidative synthesis of benzonitrile over diferent
catalysts
Entry Catalyst
Pyrolysis
Conversion Selectivity
(℃, h, nitrogen) (%)
(%)
1
−
−
−
−
−
−
<1
16
98
3
<1
39
<1
3
29
1
<1
33
2
[Bmim]Br
3a
Co(NO3)2·6H2O
Co-[Bmim]Br
Co-[Bmim]Br/C
Co(NO3)2·6H2O 700, 2, N2
Co/C 700, 2, N2
Co-[Bmim]Br/C 400, 2, N2
Co-[Bmim]Br/C 500, 2, N2
Co-[Bmim]Br/C 600, 2, N2
Co-[Bmim]Br/C 700, 2, N2
Co-[Bmim]Br/C 800, 2, N2
Co-[Bmim]Br/C 900, 2, N2
4a
5a
6a
7b
99
9
8b
28.1
28.2
85.5
100
98.3
63.7
90
39.2
71.2
97.4
100
98.3
92.1
<1
35
9b
10b
11b
12b
13b
14b,c Co-[Bmim]Br/C 700, 2, N2
15b,c Co-TBAB/C
700, 2, N2
60
Co=Co(NO3)2·6H2O. [Bmim]Br=1-butyl-3-methylimidazolium bro-
mide. C=carbon support (Vulcan XC 72R).
aHomogeneous catalysis reaction conditions: 2.5 mmol phenylmetha-
nol, 0.63 mmol Co(NO3)2·6H2O, 2.00 mmol ligand, 100 µL aq. NH3
(28–30 % NH3 basis), 5 bar O2, 20 mL t-amyl alcohol.
Catalytic performance tests of various catalysts, includ-
ing Co(NO3)2-[Bmim]Br and Co-[Bmim]Br/C-T are sum-
marized in Table 2. In the exploratory experiment of the
active component of the catalyst, the ammoxidation of
benzyl alcohol was used as the model reaction (Table 2,
120 °C, 5 bar O2). The blank experiment under identical
conditions indicated that the noncatalytic autoxidation of
benzyl alcohol gave below 1% conversion (Table 2, entry
1). The catalytic performance of the one-component catalyst
was also not good enough (Table 2, entries 2, 3), suggesting
that metallic cobalt played a major role in conversion rate.
Non-pyrolyzed complexes Co-[Bmim]Br or Co-[Bmim]Br/C
exhibited almost no catalytic activities (Table 2, entries 4, 5),
and pyrolyzed Co(NO3)2∙6H2O gave low benzonitrile selec-
tivity of 33 % (Table 2, entry 6). As for the pyrolyzed Co/C,
it exhibited good conversion but poor selectivity (Table 2,
entry 7). It can be seen that the Co-[Bmim]Br/C-T materials
displayed various catalytic activities in the ammoxidation
of benzyl alcohol (Table 2, entries 8–13). However, signif-
cant conversion was observed in the presence of Co-[Bmim]
bHeterogeneous catalysis reaction conditions: 2.5 mmol phenylmetha-
nol, 20 mg catalyst (4.5 mol % Co), 100 µL aq. NH3 (28–30 % NH3
basis), 5 bar O2, 20 mL t-amyl alcohol.
cSame as footnote b without aq. NH3.
dTBAB. Yields were determined by GCMS and GC
temperature enhanced (e.g., 1.2 for 600 °C, 1.8 for 700 °C
and 1.9 for 800 °C) (Table 1), the ratio of graphitic nitrogen
to pyridinic nitrogen in Co-[Bmim]Br/C-T increased. This
phenomenon indicated that higher temperature led to higher
graphitization degree. Besides, with the increase of pyroly-
sis temperature, the content of Co–N increased frstly and
decreased then. Therefore, the Co–N center was considered
to be an intermediate state in which pyridine N was con-
verted to graphite N. The combination of Co–N center and
cobalt was considered to be necessary for the high catalytic
property of the catalyst (Noyori et al. 2001). In combination
with Tables 1 and 2, Co-[Bmim]Br/C-700 had the highest
content of Co–N center and the best catalytic activity. As
1 3

Chemical Papers
Table 3 Catalytic aerobic oxidative synthesis of structurally diverse nitiriles over Co-N/C-700 catalyst
Entry
1
Substratea
Time (h)
20
T(℃)
Product
Conv./Select.b(%)
100/100
120
2
20
110
90/85
3
4
20
20
130
130
98/96
100/100
5
20
120
100/100
6
7
8
20
20
20
120
120
120
96/94
98/96
100/100
9
20
20
120
120
100/98
56/56
10
11
20
120
89/89
12
13
20
20
120
125
88/84
98/98
14
15
28
28
125
125
13/8
<1
16
17
18
28
28
28
140
140
125
<1
<1
<1
a1 mmol alcohol, 5 mol % Co-[Bmim]Br/C, 300 ml aq. NH3, 20 ml t-amyl alcohol, 140 ℃, 5 bar O2. Yields determined by GC analysis with
n-Hexadecane as an internal standard. Aromatic aldehydes were the main byproducts.
Br/C-700 demonstrating the best catalytic activity. Besides,
Co-[Bmim]Br/C-800 also exhibited high catalytic per-
formance to give benzonitrile in 98.3 % yield at 120 °C
(Table 2, entry 12). Notably, all further catalytic tests were
performed in the presence of aq. ammonia and molecular
oxygen.
Co-[Bmim]Br/C-400 or Co-[Bmim]Br/C-500. With the
appearance of metallic cobalt, the conversion rate of the
substrate was greatly improved. Compared with Co-[Bmim]
Br/C-500, the conversion and selectivity of Co-[Bmim]
Br/C-600 catalyzed reaction were improved. Therefore, the
presence of metallic cobalt indicates that the conversion of
the substrate and the selectivity of product can be greatly
improved. In addition, in the catalytic reaction of Co-[Bmim]
According to the results of Table 2, the conversion of
benzyl alcohol was only 28 % in the reaction catalyzed by
1 3

Chemical Papers
Fig. 2 XRD patterns of diferent catalysts. Co-[Bmim]Br/C-400
(a), Co-[Bmim]Br/C-500 (b), Co-[Bmim]Br/C-600 (c), Co-[Bmim]
Br/C-700 (d), Co-[Bmim]Br/C-800 (e), Co-[Bmim]Br/C-900 (f), Co-
[Bmim]Br/C-700 (H+) (g)
Fig. 3 HRTEM images of Co-[Bmim]Br/C-700
Br/C-900 with the best crystallinity, the conversion rate of
benzyl alcohol was only 63.7 %. However, Co-[Bmim]Br/C-
700 showed the best catalytic activity in the reaction. It can
be seen that the crystallinity of Co was not the main factor
determining the catalytic activity. As shown in Fig. 2(b), the
XRD spectra of Co-[Bmim]Br/C-700 (H+) after acid treat-
ment only had a weak Co spectrum peak, but the selectivity
of benzonitrile was still 78 %. It is verifed again that the
crystallinity of Co was not the main factor that determines
the catalytic activity. From the HRTEM (Fig. 3(a)) and the
SEM (Fig. S(1)) images, we could observe cobalt species,
and as the pyrolysis temperature increases, the carbon balls
agglomerate more severely. In addition, it can be seen from
Fig. 3(a) that spherical materials with diameters between
30 and 40 nm were stacked on top of each other, on which
loaded cloud-like irregular materials, and no large agglomer-
ates appeared. From Fig.3(b), the graphitic carbon could be
seen. The analysis showed that the agglomerates were the
agglomeration of metal components under high tempera-
ture environment. However, due to the extremely high atom
1 3

Chemical Papers
1/2 O2
H2O
1/2 O2
H2O
CN
OH
NH
O
NH3
R
R
R
R
Catalyst
Catalyst
Fig. 4 Possible reaction pathway for the synthesis of nitriles from alcohols. R=aromatic; aliphatic; heterocyclic; allylic.
utilization rate of the DES solvent and the relatively stable
chemical structure support, no large-diameter agglomerates
were found, and all of which were aggregated in the form
of clouds.
In the model reaction, the Co-[Bmim]Br/C-700 catalysts
showed the best activity, and it was applied to a range of
structurally diverse benzyl alcohols under similar reaction
conditions. The results were summarized in Table 3, it was
demonstrated that benzyl alcohols usually reacted at 120 °C
for 20 h, while aliphatic alcohols at high temperature for 28 h,
it was proved that benzyl alcohols were easier to be oxidized
than aliphatic alcohols. A wide range of aromatic alcohols
and heterocyclic alcohols that efectively underwent the two
consecutive dehydrogenations under O2 in t-amyl alcohol were
selectively converted into the corresponding nitriles of good
yields. Substrates with electron donating groups (Table 3,
entries 2–4) and electron withdrawing groups (Table 3, entries
5–8) can be converted to the corresponding substituted benzo-
nitriles with excellent yields. Also, 2-pyridinemethanol can be
converted to the corresponding nitrile in high conversion and
high selectivity (98 %) (Table 3, entry 9). Halogenated ben-
zonitriles usually serve as precursors in pesticides and agro-
chemicals, such as 2, 6-dichlorobenzontirile (DCBN), which
was an important intermediate and can also be used in engi-
neering plastics, electronic materials and dyes. In our study,
DCBN was obtained 56 % yield (Table 3, entry 10). Next,
cyano-substituted heterocycles and aryl nitriles bearing het-
erocyclic backbones were synthesized in 84–98 % conversion
or selectivity (Table 3, entries 11–13). Aliphatic primary alco-
hols can hardly be converted to the corresponding nitrile in a
very low yield (Table 3, entries 14–18). Based on the previous
experiments, we propose the following general reaction path-
way for the synthesis of nitriles from alcohols catalyzed under
molecular oxygen and aq. ammonia (Fig. 4). Initially, catalytic
aerobic oxidation of alcohol to the corresponding aldehyde
was observed (Song et al. 2018). In some cases, the respective
aldehyde can be observed during the progress of the reaction.
Next, the aldehyde underwent condensation with ammonia and
formed the corresponding imine. Notably, the imine was unsta-
ble and would be immediately oxidized to nitrile as the fnal
product (Gunanathan et al. 2013). In this reaction sequence,
water was produced as the only by-product. Certain aromatic
alcohols including cinnamyl alcohol, 4-methoxybenzyl alco-
hol, etc. may also generate benzonitrile as by-product during
the reaction. It was speculated that this situation was mainly
due to the too long break of the branch.
Fig. 5 Reusability of Co-[Bmim]Br/C-700
Recycling test of catalyst
As shown in Fig. 5, our supported Co nanoparticles are stable
and can be used up to four times without signifcant inactiva-
tion, with benzonitrile yields of 100%, 96%, 96% and 93%
after 1, 2, 3 and 4 rounds of runs respectively. The recycling
of Co-[Bmim]Br/C-700 catalyst experiments was carried out
using benzyl alcohol, as model substrate applying standard
procedure under following reaction conditions: benzyl alcohol
(2.5 mmol), 80 mg catalyst (4.5 mol% Co), aq. NH3 (28–30%
NH3 basis, 100 µL), O2 (5 bar), t-amyl alcohol (20 mL),
120–140 °C, 20 h. After the completion of the reaction, in
each run the catalyst was separated by flter, washed with etha-
nol and dried 12 h. Then, the dried catalyst was directly used
for the next run without further treatment. Conversion and
selectivity were determined by GC and GCMS analysis using
n-hexadecane as standard.
Conclusions
In this work, the aerobic oxidation of alcohols with ammo-
nia and molecular oxygen to nitriles were demonstrated. Co-
[Bmim]Br/C-700 showed the best activity, high selectivity
and good conversion. A total of 10 nitriles were obtained with
good to excellent yields via the aerobic oxidation from alco-
hols. The prepared Co-[Bmim]Br/C-T catalysts were heterog-
enous and reusable. The future work will focus on the reac-
tion mechanism of alcohol to nitrile. Additionally, this aerobic
green oxidative method has been applied in the preparation of
primary aldehydes.
1 3

Chemical Papers
Supplementary Information The online version contains supplemen-
amide synthesis. Appl Catal A 425–426(28):85–90. https://doi.
org/10.1016/j.apcata.2012.03.006
tary material available at https://doi.org/10.1007/s11696-021-01593-z.
Jagadeesh RV, Junge H, Pohl M, Radnik J, Brückner A, Beller M
(2013) Selective oxidation of alcohols to esters using heteroge-
neous Co3O4–N@C catalysts under mild conditions. J Am Chem
Soc 135(29):10776–10782. https://doi.org/10.1021/ja403615c
Jagadeesh RV, Junge H, Beller M (2014) Green synthesis of nitriles
using non-noble metal oxides-based nanocatalysts. Nature Com-
mun 5:1–8. https://doi.org/10.1038/ncomms5123
Acknowledgements This work was supported by the Natural Science
Foundation of Hubei Province (Grant No. 2016CFA079).
References
Jang W, Kim SE, Yang CM, Yoon S, Park M, Lee J, Kim Y, Kim M
(2015) Cobalt/nitrophenolate-catalyzed selective conversion of
aldoximes into nitriles or amides. Catal Commun 60(5):120–
123. https://doi.org/10.1016/j.catcom.2014.11.025
Beletskaya IP, Sigeev AS, Peregudov AS, Petrovskii PV (2004) Cata-
lytic sandmeyer cyanation as a synthetic pathway to aryl nitriles.
J Organ Chem 689(23):3810–3812. https://doi.org/10.1016/j.
jorganchem.2004.07.019
Kim J, Stahl SS (2013) Cu/Nitroxyl-Catalyzed aerobic oxidation of
primary amines into nitriles at room temperature. ACS Catal
3(7):1652–1656. https://doi.org/10.1021/cs400360e
Bezerra CWB, Zhang L, Lee K, Liu H, Marques ALB, Marques
EP, Wang H, Zhang J (2008) A review of Fe–N/C and Co–N/C
catalysts for the oxygen reduction reaction. Electrochim Acta
53(15):4937–4951. https://doi.org/10.1016/j.electacta.2008.02.
012
Kim J, Kim HJ, Chang S (2012) Synthesis of aromatic nitriles
using nonmetallic Cyano-group sources. Angew Chem Int Ed
51(48):11948–11959. https://doi.org/10.1002/anie.201206168
Lücke B, Narayana KV, Martin A, Jähnisch K (2004) Oxidation and
ammoxidation of aromatics. Adv Synth Catal 346(12):1407–
1424. https://doi.org/10.1002/adsc.200404027
Biondini D, Brinchi L, Germani R, Goracci L, Savelli G (2005)
Dehydrogenation of amines to nitriles in aqueous Micelles. Eur
J Org Chem 14:3060–3063. https://doi.org/10.1002/ejoc.20050
0047
Martin A, Kalevaru VN (2010) Heterogeneously catalyzed ammoxi-
dation: a valuable tool for one-step synthesis of nitriles. Chem-
CatChem 2(12):1504–1522. https://doi.org/10.1002/cctc.20100
0173
Chakraborty S, Das UK, Ben-David Y, Milstein D (2017) Manga-
nese catalyzed α-olefnation of nitriles by primary alcohols. J
Am Chem Soc 139(34):11710–11713. https://doi.org/10.1021/
jacs.7b06993
Mori K, Yamaguchi K, Mizugaki T, Ebitani K, Kaneda K (2001)
Catalysis of a hydroxyapatite-bound Ru complex: efcient het-
erogeneous oxidation of primary amines to nitriles in the pres-
ence of molecular oxygen. Chem Commun 5:461–462. https://
doi.org/10.1039/B009944I
Chen F, Surkus A, He L, Pohl M, Radnik J, Topf C, Junge K, Beller
M (2015) Selective catalytic hydrogenation of heteroarenes with
N-Graphene-modifed cobalt nanoparticles (Co3O4–Co/NGr@α-
Al2O3). J Am Chem Soc 137(36):11718–11724. https://doi.org/
10.1021/jacs.5b06496
Moussa Z, Ahmed SA, ElDouhaibi AS, Al-Raqa SY (2010) NMR
Studies and electrophilic properties of triphenylphosphine–tri-
fuoromethanesulfonic anhydride; a remarkable dehydrating
reagent system for the conversion of aldoximes into nitriles.
Tetrahedron Lett 51(14):1826–1831. https://doi.org/10.1016/j.
tetlet.2010.01.119
Dornan LM, Cao Q, Flanagan JCA, Crawford JJ, Cook MJ, Muldoon
MJ (2013) Copper/TEMPO catalyzed synthesis of nitriles from
aldehydes or alcohols using aqueous ammonia and with air as
the oxidant. ChemInform 49(54):6030–6032. https://doi.org/10.
1039/c3cc42231c
Nakatsuka K, Yoshii T, Kuwahara Y, Mori K, Yamashita H (2017)
Controlled synthesis of carbon-supported co catalysts from
single-sites to nanoparticles: characterization of the structural
transformation and investigation of their oxidation catalysis.
Phys Chem Chem Phys 19(7):4967–4974. https://doi.org/10.
1039/c6cp06388h
Fleming FF, Yao L, Ravikumar PC, Funk L, Shook BC (2010)
Nitrile-containing pharmaceuticals: efcacious roles of the
nitrile pharmacophore. J Med Chem 53(22):7902–7917. https://
doi.org/10.1021/jm100762r
Gunanathan C, Milstein D (2013) Applications of acceptor less dehy-
drogenation and related transformations in chemical synthesis.
Science 341:249–260. https://doi.org/10.1126/science.1229712
Hashemi AN, Eshghi H, Lamei K (2019) Uniform silver nanoparti-
cles on tunable porous N-doped carbon nanospheres for aerobic
oxidative synthesis of aryl nitriles from benzylic alcohols. Appl
Organomet Chem 33(4):e4835. https://doi.org/10.1002/aoc.4835
Hatsuda M, Seki M (2005) A practical synthesis of highly functional-
ized aryl nitriles through cyanation of aryl bromides employing
heterogeneous Pd/C: in quest of an industrially viable process.
Tetrahedron 61(41):9908–9917. https://doi.org/10.1016/j.tet.
2005.06.061
Noyori R, Yamakawa M, Hashiguchi S (2001) Metal-Ligand bifunc-
tional catalysis: a nonclassical mechanism for asymmetric hydro-
gen transfer between alcohols and carbonyl compounds. J Org
Chem 66(24):7931–7944. https://doi.org/10.1021/jo010721w
Oishi T, Yamaguchi K, Mizuno N (2009) Catalytic oxidative synthesis
of nitriles directly from primary alcohols and ammonia. Angew
Chem Int Ed 48(34):6286–6288. https://doi.org/10.1002/anie.
200900418
Oishi T, Yamaguchi K, Mizuno N (2010) An efcient one-pot synthesis
of nitriles from alcohols or aldehydes with NH
3 catalyzed by a
supported ruthenium hydroxide. Top Catal 53:479–486. https://
doi.org/10.1007/s11244-010-9475-y
Hyodo K, Kitagawa S, Yamazaki M, Uchida K (2016) Iron-catalyzed
dehydration of aldoximes to nitriles requiring neither other rea-
gents nor nitrile media. Chem Asian J 11(9):1348–1352. https://
doi.org/10.1002/asia.201600085
Pendashteh A, Palma J, Anderson M, Marcilla R (2017) NiCoMnO4
nanoparticles on N-doped graphene: highly efcient bifunctional
electrocatalyst for oxygen reduction/evolution reactions. Appl
Catal B 201:241–252. https://doi.org/10.1016/j.apcatb.2016.08.
044
Iida S, Togo H (2007) Direct oxidative conversion of alcohols and
amines to nitriles with molecular iodine and DIH in aq NH3.
Tetrahedron 63(34):8274–8281. https://doi.org/10.1002/chin.
200749096
Pourjavadi A, Habibi Z (2017) Gold Nanoparticles supported on ionic
liquid-modifed cellulose as an efcient and recyclable catalyst
for the oxidation of alcohols to aldehydes/ketones and reduction
of nitroarenes. Appl Organomet Chem 31(11):e3783. https://doi.
org/10.1002/aoc.3783
Ishida T, Watanabe H, Takei T, Hamasaki A, Tokunaga M, Haruta
M (2012) Metal oxide-catalyzed ammoxidation of alcohols to
nitriles and promotion efect of gold nanoparticles for one-pot
1 3

Chemical Papers
Qureshi ZS, Deshmukh KM, Bhanage BM (2014) Applications of ionic
liquids in organic synthesis and catalysis. Clean Technol Environ
16(8):1487–1513. https://doi.org/10.1007/s10098-013-0660-0
Reddy KR, Maheswari CU, Venkateshwar M, Prashanthi S, Kantam
ML (2009) Catalytic oxidative conversion of Alcohols, aldehydes
and amines into nitriles using KI/I2—TBHP system. Tetrahedron
Lett 50(18):2050–2053. https://doi.org/10.1016/j.tetlet.2009.02.
057
Wu LY, Hartwig JF (2006) Mild palladium-catalyzed selective monoar-
ylation of nitriles. J Am Chem Soc 127(45):15824–15832. https://
doi.org/10.1021/ja053027x
Xu SL, Cai TH, Yun Z (2016) Cobalt-containing mesoporous
ZSM-5 zeolite catalyzed C=C bond cleavage of alkenes to
form nitriles. Synlett 27(2):221–224. https://doi.org/10.1002/
chin.201624079
Yan G, Zhang Y, Wang J (2017) Recent advances in the synthesis
of aryl nitrile compounds. Adv Synth Catal 359(23):4068–4105.
https://doi.org/10.1002/adsc.201700875
Ren SS, Wang YY, Yang F, Sun HJ, Li X (2019) Dehydration of
primary amides to nitriles catalyzed by [CNC]-pincer hydrido
cobalt(III) complexes. Catal Commun 120:72–75. https://doi.org/
10.1016/j.catcom.2018.12.002
Yin W, Wang C, Huang Y (2013) Highly practical synthesis of nitriles
and heterocycles from alcohols under mild conditions by aerobic
double dehydrogenative catalysis. Org Lett 15(8):1850–1853.
https://doi.org/10.1021/ol400459y
Soleimani E, Khodaei MM, Batooie N, Baghbanzadeh M (2011)
Water-prompted synthesis of alkyl nitrile derivatives via Knoev-
enagel condensation and Michael addition reaction. Green Chem
13(3):566–569. https://doi.org/10.1039/c0gc00739k
Zhang QH, Oliveira Vigier K, Royer S, Jérôme F (2012) Deep eutectic
solvents: syntheses, properties and applications. Chem Soc Rev
41(21):7108–7146. https://doi.org/10.1039/c2cs35178a
Zhang G, Li C, Liu J, Zhou L, Liu R, Han X, Huang H, Hu H, Liu Y,
Kang Z (2014) One-step conversion from metal–organic frame-
works to Co3O4@N-doped carbon nanocomposites towards highly
efcient oxygen reduction catalysts. J Mater Chem A 2(22):8184–
8189. https://doi.org/10.1039/C4TA00677A
Song RJ, Wu JC, Liu Y, Deng GB, Wu CY, Wei WT, Li JH (2013)
Copper-catalyzed oxidative cyanation of aryl halides with nitriles
involving carbon—carbon cleavage. Synlett 23(17):2491–2496.
https://doi.org/10.1055/s-0032-1317191
Song S, Wang YZ, Yan N (2018) A remarkable solvent efect on reduc-
tive amination of ketones. Mol Catal 454:87–93. https://doi.org/
10.1016/j.mcat.2018.05.017
Zhang X, Sun JJ, Ding YH, Yu L (2015) Dehydration of aldoximes
using PhSe(O)OH as the pre-catalyst in air. Org Lett 17(23):5840–
5842. https://doi.org/10.1021/acs.orglett.5b03011
Sun K, Sun J, Lu G, Cai C (2019) Enhanced catalytic activity of cobalt
nanoparticles encapsulated with an N-doped porous carbon shell
derived from hollow ZIF-8 for efcient synthesis of nitriles from
primary alcohols in water. Green Chem 21(16):4334–4340.
https://doi.org/10.1039/C9GC01893J
Zhao X, Zhou Y, Jin A, Huang K, Liu F, Tao D (2018) Co-N-C cata-
lysts synthesized by pyrolysis of co-based deep eutectic solvents
for aerobic oxidation of alcohols. New J Chem 42(19):15871–
15878. https://doi.org/10.1039/C8NJ03446J
Sundermeier M, Mutyala S, Zapf A, Spannenberg A, Beller M (2003)
A convenient and efcient procedure for the palladium-catalyzed
cyanation of aryl halides using trimethylsilylcyanide. J Organomet
Chem 684(1):50–55. https://doi.org/10.1016/S0022-328X(03)
00503-5
Zultanski SL, Zhao J, Stahl SS (2016) Practical synthesis of amides via
copper/ABNO-catalyzed aerobic oxidative coupling of alcohols
and amines. J Am Chem Soc 138(20):6416–6419. https://doi.org/
10.1021/jacs.6b03931
Wei J, Hu Y, Liang Y, Kong B, Zhang J, Song J, Bao Q, Simon GP,
Jiang SP, Wang H (2015) Nitrogen-doped nanoporous carbon/
graphene nano-sandwiches: synthesis and application for efcient
oxygen reduction. Adv Funct Mater 25(36):5768–5777. https://
doi.org/10.1002/adfm.201502311
Publisher’s Note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional afliations.
1 3