01 Electrochemical - Performance - of - ABNO - For - Oxidation

molecules
Article
Electrochemical Performance of ABNO for Oxidation
of Secondary Alcohols in Acetonitrile Solution
Pengfei Niu 1,2 , Xin Liu 1,2 , Zhenlu Shen 1, * and Meichao Li 1,2, *
1 College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China;
niu_pengfei@yeah.net (P.N.); lx370682@163.com (X.L.)
2 Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310032, China
* Correspondence: zhenlushen@zjut.edu.cn (Z.S.); limc@zjut.edu.cn (M.L.);
Tel.: +86-571-8832-0416 (Z.S.); +86-571-8832-0568 (M.L.)

Received: 2 December 2018; Accepted: 27 December 2018; Published: 28 December 2018
Abstract: The ketones was successfully prepared from secondary alcohols using
9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO) as the catalyst and 2,6-lutidine as the base in acetonitrile
solution. The electrochemical activity of ABNO for oxidation of 1-phenylethanol was investigated
by cyclic voltammetry, in situ Fourier transform infrared spectroscopy (FTIR) and constant current
electrolysis experiments. The resulting cyclic voltammetry indicated that ABNO exhibited much
higher electrochemical activity when compared with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)
under the similar conditions. A reasonable reaction mechanism of the electrocatalytic oxidation of
1-phenylethanol to acetophenone was proposed. In addition, a series of secondary alcohols could be
converted to the corresponding ketones at room temperature in 80–95% isolated yields.
Keywords: electrochemical; ABNO; secondary alcohols; in situ FTIR; ketones
1. Introduction
The carbonyl compounds are important intermediates for synthesis of fine chemicals, such as
fragrances, pharmaceuticals, and food additives, and the worldwide demand for carbonyl compounds
is increasing every year [1–3]. Presently, the preparation of aldehydes and ketones by selective
oxidation of the corresponding primary and secondary alcohols is one of the most fundamental
functional group transformations in organic chemistry [4–7]. The stoichiometric or excess amounts of
oxidants containing chromium reagents, manganese reagents, or hypervalent iodine are often required
among the traditional protocols [8–10]. Unfortunately, these oxidants would generate equivalent
wastes and pose a risk to the environment [11,12]. It is well known that green chemistry is a crucial
principle of chemical research and its application in organic synthesis has attracted more and more
attention [13]. From both environmentally benign and sustainable viewpoints, it is a great desire to
develop a green and efficient catalyst for the synthesis of the corresponding carbonyl compounds.
Recently, a stable nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) has been
successfully applied to synthesize aldehydes, nitriles, and imines because of its cleaness and
inexpensiveness [14–16]. Several combinations of TEMPO and transition metals, especially Fe and Cu,
have been widely used for the synthesis of aldehydes from alcohols [17–29]. Despite of using molecular
oxygen as the terminal oxidant, the transition-metal catalyst still exists in these processes. Subsequently,
our group developed several catalytic oxidation systems for synthesizing the carbonyl compounds
without transition metals, such as TEMPO/HBr/tert-butyl nitrite (TBN)/O2 , TEMPO/TBN/O2 ,
TEMPO/2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)/TBN/O2 , etc [30–32]. Although a lot
of meaningful works about the preparation of aldehydes from primary alcohols catalyzed by TEMPO
were studied both in homogeneous and heterogeneous conditions, due to the high steric hindrance
Molecules 2019, 24, 100; doi:10.3390/molecules24010100 www.mdpi.com/journal/molecules

Molecules 2019, 24, x 2 of 14
TEMPO/TBN/O2, TEMPO/2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)/TBN/O2, etc [30–32].

Although
Molecules a 24,
2019, lot100
of meaningful works about the preparation of aldehydes from primary alcohols 2 of 14
catalyzed by TEMPO were studied both in homogeneous and heterogeneous conditions, due to the
high steric hindrance arising from four methyl group in TEMPO, the synthesis of ketones from
arising
secondary from four methyl
alcohols is stillgroup in TEMPO,
a serious challenge the[33–36].
synthesis of ketones from secondary alcohols is still a
serious challenge [33–36].
Subsequently, several less hindered nitroxyl radicals, such as 2-azaadamantan-N-oxyl
Subsequently,
(AZADO), 1-Me-AZADO,several lessand hindered
5-F-AZADO, nitroxyl
haveradicals, such as
been utilized by2-azaadamantan-N-oxyl
Iwabuchi and co-workers (AZADO),
[37–39].
1-Me-AZADO, and 5-F-AZADO, have been utilized by Iwabuchi
Owing to their less steric hindrance around the reaction center, AZADO and its derivatives and co-workers [37–39]. Owing to
their less steric hindrance around the reaction center, AZADO and its
exhibited high activity at a low loading for the preparation of carbonyl compounds from selective derivatives exhibited high activity
at a low loading
oxidation of highfor the preparation
hindered alcoholsofascarbonyl
compared compounds
with TEMPO from [40].
selective oxidation
However, AZADOsof highshould
hindered be
alcohols
synthesized through long and complicated processes. Another nitroxyl long
as compared with TEMPO [40]. However, AZADOs should be synthesized through and
radical,
complicated processes. Another nitroxyl
9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO) radical,
has the 9-azabicyclo[3.3.1]nonane-N-oxyl
similar activity with AZADOs (ABNO) and it couldhas thebe
similar activity with AZADOs and it could be prepared via only
prepared via only four steps [41]. It put forward the possibility to prepare the corresponding four steps [41]. It put forward the
possibility to prepare the
carbonyl compounds from corresponding
primary and carbonyl
secondary compounds
alcohols with fromABNO primary andcatalyst
as the secondary alcohols
under mild
with ABNOPreviously,
conditions. as the catalyst under mild conditions.
the ABNO/TBN/O 2 system for Previously,
the aerobic the ABNO/TBN/O
oxidation 2 system
of secondary for the
alcohols in
aerobic oxidation of secondary alcohols in water has been developed
water has been developed [42]. This reaction should be performed at 80 °C under 0.3–0.5 Mpa of [42]. This reaction should be
performed ◦
oxygen. at 80 C under 0.3–0.5 Mpa of oxygen.
As we
As we allall know,
know, the the electrochemical
electrochemical method method in in synthesis
synthesis possesses
possesses the the advantages
advantages of of friendly
friendly
environment,
environment, low cost, and high atom utilization, paving a new way for production of manymany
low cost, and high atom utilization, paving a new way for production of fine
fine chemicals
chemicals [43–46].
[43–46]. In 2012, InRaja
2012, Raja
et al. et al. disclosed
disclosed an electrochemical
an electrochemical method the
method to achieve to preparation
achieve the
preparation of aromatic
of aromatic aldehydes aldehydes
with sodium withnitrate sodium nitrate asredox
as an effective an effective
mediator redox mediator
in biphasic in biphasic
medium [47].
medium
However, the primary alcohols substituted with strong electron-withdrawing group, such asgroup,
[47]. However, the primary alcohols substituted with strong electron-withdrawing -nitro
such as -nitro
and some of and some of
secondary secondary
alcohols gavealcohols gave low
low product product
yields. yields.
Lately, we Lately,
prepared we aprepared
series of a
series of TEMPO-modified polymer electrodes, which could be
TEMPO-modified polymer electrodes, which could be used successfully for the selective oxidationused successfully for the selective
oxidation
of alcoholsof toalcohols
aldehydes to [48–50].
aldehydes It is[48–50].
well known It isthat
welltheknown
detailed that the detailed
information information
of the of the
electrochemical
electrochemical
behaviour of organic behaviour
compounds of organic compounds
is crucial is crucial for
for electrochemical electrochemical
synthesis. synthesis.
Stahl’s group reported Stahl’s
that
group
4-acetamido-TEMPO (ACT) possessed of the superior activity than AZADO and ABNO at highand
reported that 4-acetamido-TEMPO (ACT) possessed of the superior activity than AZADO pH
ABNO at high pH with
with electrocatalytic electrocatalytic
studies about the studies about the nitroxyl/oxoammonium
nitroxyl/oxoammonium redox potential [51]. redox In potential
continuation[51].
In continuation
with our previous withwork
our previous
about the work about the
synthesis synthesis offrom
of aldehydes aldehydes from
alcohols, wealcohols,
try to studywe trythe to
study the electrochemical performance of ABNO as the catalyst for
electrochemical performance of ABNO as the catalyst for the selective oxidation of secondary the selective oxidation of secondary
alcohols
alcohols in in the
the presence
presence of of 2,6-lutidine
2,6-lutidine in in acetonitrile
acetonitrile solution.
solution. In In this
this work,
work, thethe electrochemical
electrochemical
behaviour
behaviour of ABNO for the oxidation of 1-phenylethanol to acetophenone on the Pt electrode
of ABNO for the oxidation of 1-phenylethanol to acetophenone on the Pt electrode was was
studied
studied to to aa better
better understanding
understanding of of the
the catalytic
catalytic properties
properties (Scheme
(Scheme 1). 1).
Scheme 1.
Scheme The electrochemical
1. The electrochemical synthesis
synthesis of
of ketones
ketones from
from secondary
secondary alcohols.
alcohols.
2. Results and Discussion

2. Results and Discussion
2.1. Cyclic Voltammetric Study for Oxidation of 1-Phenylethanol
2.1. Cyclic Voltammetric Study for Oxidation of 1-Phenylethanol
The cyclic voltammograms for the oxidation of 1-phenylethanol in 0.1 M NaClO4 -CH3 CN solution
The
using ABNO cyclic
as voltammograms
the catalyst werefor the oxidation
shown in Figure of
1. 1-phenylethanol in 0.1
We first started out M NaClO4in
investigation -CH 3CN
0.1 M
solution using ABNO as the catalyst were shown in Figure 1. We first started out investigation in 0.1
NaClO4 -CH3 CN solution containing 1-phenylethanol (1.0 mmol) and 2,6-lutidine (1.0 mmol) at
M NaClO4-CH3CN solution containing 1-phenylethanol (1.0 mmol) and 2,6-lutidine (1.0 mmol) at Pt
Pt electrode (Figure 1a). No obvious reaction peaks appeared in the range of scanning potential
electrode (Figure 1a). No obvious reaction peaks appeared in the range of scanning potential
between −0.1 and 0.8 V. As shown in Figure 1b, a pair of reversible redox peaks was well centered at
between −0.1 and 0.8 V. As shown in Figure 1b, a pair of reversible redox peaks was well centered at
about 0.25 V in the presence of ABNO (0.1 mmol). The oxidation peak at 0.3 V corresponded to the
about 0.25 V in the presence of ABNO (0.1 mmol). The oxidation peak at+ 0.3 V corresponded to the
one-electron oxidation of nitroxyl radical to oxoammonium ion (ABNO ) rather than the response
of 1-phenylethanol or 2,6-lutidine [51]. By the addition of 1-phenylethanol, the reaction was so weak
one-electron oxidation of nitroxyl radical to oxoammonium ion (ABNO+) rather than the response of
Molecules 2019, 24,oxidation
one-electron
1-phenylethanol 100 or 2,6-lutidine
of nitroxyl radical
[51]. to oxoammonium
By the ion (ABNO+) rather
addition of 1-phenylethanol, than thewas
the reaction so3weak
of 14
response of
1-phenylethanol
that we could notordetect 2,6-lutidine [51]. change
the obvious By the addition
about theofoxidation
1-phenylethanol, the reaction
peak current wasHowever,
(Figure 1c). so weak
that wethe
when could
basenot detect thewas
2,6-lutidine obvious
addedchange
to theabout the oxidation
reaction solution, peak current (Figure
the apparent increase1c).
of However,
oxidation
that we could not detect the obvious change about the oxidation peak current (Figure 1c). However,
when current
peak the basefrom 2,6-lutidine
1.37 mA was to added
1.51 mAto the
wasreaction
observedsolution, the1d).
(Figure apparent increase
It certified thatof the
oxidation
active
when the base 2,6-lutidine was added to the reaction solution, the apparent increase of oxidation peak
peak current from
oxoammonium 1.37reacted
cations mA towith 1.511-phenylethanol
mA was observed (Figure
on the 1d).
surface of It
thecertified
workingthat the active
electrode and
current from 1.37 mA to 1.51 mA was observed (Figure 1d). It certified that the active oxoammonium
oxoammonium
2,6-lutidine was cations reacted
beneficial with 1-phenylethanol
to facilitate on the surface of[52].
the oxidation of 1-phenylethanol the working electrode and
cations reacted with 1-phenylethanol on the surface of the working electrode and 2,6-lutidine was
2,6-lutidine was beneficial to facilitate the oxidation of 1-phenylethanol [52].
beneficial to facilitate the oxidation of 1-phenylethanol [52].
0.15
0.15 d
0.10 d
c
0.10 b
c
b
I / mA
0.05
I / mA
0.05
a
0.00
a
0.00
-0.05
-0.05
-0.2 0.0 0.2 0.4 0.6 0.8
+
E /0.2V ( vs. Ag
-0.2 0.0 0.4 / Ag )0.6 0.8
E / V ( vs. Ag / Ag+)
Figure 1. Cyclic voltammograms of Pt electrode in 0.1 M NaClO4-CH3CN solution with (a)
Figure1.1. Cyclic
Figure voltammograms
Cyclic(1.0
1-phenylethanol voltammograms of
of Pt
Pt electrode
mmol) and 2,6-lutidine electrode in
(1.0 mmol);in 0.1(b)MM
0.1 NaClO
NaClO
active 4 -CH
4-CH 33CN
oxoammonium CN solution
cationswith
solution with (a)
(ABNO)(a)
1-phenylethanol
1-phenylethanol
(0.1 (1.0 mmol)
(1.0 mmol)
mmol); (c) ABNO and 2,6-lutidine
and 2,6-lutidine
(0.1 mmol) (1.0 mmol);
(1.0 mmol); (b)
and 1-phenylethanol (b) active
(1.0active oxoammonium
mmol);oxoammonium
and, (d) ABNO cations
cations (ABNO)
(0.1(ABNO)
mmol),
(0.1
(0.1mmol);
mmol);(c)
(c)ABNO
1-phenylethanol ABNO (0.1
(0.1mmol)
(1.0 mmol) mmol)
and and
and1-phenylethanol
(1.0 mmol) at(1.0
1-phenylethanol
2,6-lutidine mmol);
(1.0scan
the rateand,
mmol); of 50(d)
and, (d) ABNO
mV·s ABNO
−1. (0.1
(0.1 mmol),
mmol),
1-phenylethanol
1-phenylethanol(1.0
(1.0mmol)
mmol)andand2,6-lutidine
2,6-lutidine(1.0
(1.0mmol)
mmol)atatthe thescan
scanrate
rateofof5050mV ·s−−1
mV·s
1.
.
For comparison, other experiments for oxidation of 1-phenylethanol in 0.1 M NaClO4-CH3CN
For comparison, other experiments for oxidation of 1-phenylethanol in 0.1 M NaClO4 -CH3 CN
For using
solution comparison,
TEMPOother experiments
as the for oxidation
catalyst under the similarofconditions
1-phenylethanol in 0.1
have been M NaClOAs
conducted. 4-CH 3CN
shown
solution using TEMPO as the catalyst under the similar conditions have been conducted. As shown
solution
in Figureusing
2, theTEMPO as theatcatalyst
redox peaks under
about 0.34 andthe0.22
similar conditions
V could be seenhave been
in the conducted.
presence As shown
of TEMPO (0.1
in Figure 2, the redox peaks at about 0.34 and 0.22 V could be seen in the presence+ of TEMPO
in Figurewhich
mmol), 2, thewere
redoxcorresponded
peaks at about to 0.34
one and 0.22 Vtransfer
electron could be seenTEMPO
from in the presence
to TEMPO of TEMPO (0.1
[53].+When
(0.1 mmol), which were corresponded to one electron transfer from TEMPO to TEMPO [53].
mmol), which were
1-phenylethanol andcorresponded to oneadded
2,6-lutidine were electron transfer
to the from
above TEMPO
reaction to TEMPO
solution + [53]. When
sequentially, the
When 1-phenylethanol and 2,6-lutidine were added to the above reaction solution sequentially,
1-phenylethanol
corresponding andvoltammograms
cyclic 2,6-lutidine were wereadded
almost tooverlapped
the above and
reaction solutioninsequentially,
were omitted Figure 2 hence.the
the corresponding cyclic voltammograms were almost overlapped and were omitted in Figure 2 hence.
corresponding cyclic voltammograms were almost overlapped and were omitted in Figure 2 hence.
0.15
0.15
0.10
0.10
0.05
I / mA
0.05
I / mA
0.00
0.00
-0.05
-0.05
-0.10
-0.2 0.0 0.2 0.4 0.6 0.8
-0.10 +
E /0.2V ( vs. Ag
-0.2 0.0 0.4 / Ag )0.6 0.8
+
E / V ( vs. Ag / Ag )
Figure Cyclic voltammogram
Figure 2.2. Cyclic voltammogram of Pt Pt electrode
electrode in in 0.1
0.1 MM NaClO
NaClO 4 -CH
4-CH 3 CN
3CN solution
solution with
with
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) (0.1 mmol) at the scan rate of 50 mV · s −−1
1.
Figure 2. Cyclic voltammogram (TEMPO)
2,2,6,6-tetramethylpiperidine-1-oxyl of Pt electrode
(0.1 mmol) in at0.1
the M
scanNaClO
rate of4-CH 3CN solution with
50 mV·s
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) (0.1 mmol) at the scan rate of 50 mV·s−1.
ToTofuther
futher investigate the electrochemical
investigate the electrochemicalbehavior
behaviorofofABNO
ABNO forfor 1-phenylethanol
1-phenylethanol oxidation,
oxidation, the
the cyclic voltammograms
cyclicTovoltammograms
futher investigate with various
thevarious
with scan
electrochemical rates
scan rates were
behavior studied
of ABNO
were studied and
andfor shown in Figure
1-phenylethanol
shown in Figure 3A.3A. Due
Due to
tothe
oxidation, the
high
highsolution
cyclicsolutionresistance
voltammograms in
resistancewithCH
in CH CN solution,
various
3 the
scan rates
3CN solution,
peak-to-peak separation
were studied separation
the peak-to-peak between
and shownbetween the
in Figure oxidation
the3A. and
Due to and
oxidation the
reduction
reduction peaks
high solution
peaks was
wasabout
resistance in 100
about 1003mV
CH mV at
CN at the
the scan
solution, the
scan rate of
of 50 mV·s−1−separation
peak-to-peak
rate 50 mV·s
1 , which was slightly more than the
, which wasbetween
slightlythe oxidation
more than theand
59
59 mV separation
reduction [54].about
peaks was Nevertheless,
100 mV at with
the the
scanincreasing
rate of 50of scanning
mV·s −1, which rate, there
was was amore
slightly less shift
thanin the
the 59
oxidation peak, suggesting that the electrochemical reaction of ABNO still had good reversibility [55].
Molecules 2019, 24, 100 4 of 14

mV separation [54]. Nevertheless, with the increasing of scanning rate, there was a less shift in the
oxidation peak, suggesting that the electrochemical reaction of ABNO still had good reversibility
[55].excellent
The The excellent
linearlinear correlation
correlation between
between the oxidation
the oxidation peak peak current
current (Ip) the
(Ip ) and andsquare
the square root
root of scanof
scan rate (Figure 3B) exhibited that the electrode reaction was also a diffusion-controlled process,
rate (Figure 3B) exhibited that the electrode reaction was also a diffusion-controlled process, which
which provided
provided further further evidence
evidence for reacting
for reacting on the surface
on the surface of working
of working electrodeelectrode
[56]. [56].
0.3 50 mV.s-1 0.28

100 mV.s-1
150 mV.s-1
A B
0.26
200 mV.s-1
0.2 250 mV.s-1
0.24
Ip /mA
0.1 0.22
I/mA
R2=0.9996
0.20
0.0
0.18
-0.1
0.16
-0.2 0.14
-0.2 0.0 0.2 0.4 0.6 0.8 6 8 10 12 14 16
E / V ( vs. Ag / Ag+) v1/2/mV1/2⋅s-1/2
Figure 3. (A) Cyclic voltammograms

Figure 3. voltammograms for the oxidation of 1-phenylethanol
1-phenylethanol (1.0 mmol) withwith ABNO
ABNO
(0.1
(0.1 mmol)
mmol) and 2,6-lutidine (1.0
and 2,6-lutidine (1.0 mmol)
mmol) in
in 0.1
0.1MMNaClO
NaClO 4 -CH
4-CH 3 CN
3CN solution
solution at various
at various scanscan rates.
rates. (B)
(B) Linear
Linear plotplot between
between the the oxidation
oxidation peak
peak current
current (Ip)(Iand
p ) and
the the square
square rootroot of scan
of scan rate.
rate.
2.2. In situ FTIR Spectroscopic Analysis

2.2. In situ FTIR Spectroscopic Analysis
In situ FTIR spectroscopy is one of the most useful techniques in electrochemistry today, and it can
In situ FTIR spectroscopy is one of the most useful techniques in electrochemistry today, and it
be used to study the organic reaction at the electrode surface. Figure 4 showed the in situ FTIR spectra
can be used to study the organic reaction at the electrode surface. Figure 4 showed the in situ FTIR
that were obtained during the oxidation of 1-phenylethanol in the presence of ABNO and 2,6-lutidine
spectra that were obtained during the oxidation of 1-phenylethanol in the presence of ABNO and
in 0.1 M NaClO4 -CH3 CN solution at the scanning potentials varying from 0 to 800 mV. When the
2,6-lutidine in 0.1 M NaClO4-CH3CN solution at the scanning potentials varying from 0 to 800 mV.
sample potential reached to 200 mV, some weak bands emerged gradually. With the increasing of
When the sample potential reached to 200 mV, some weak bands emerged gradually. With the
potential, the corresponding infrared spectra signals could be seen clearly at approximately 400 mV.
increasing of potential, the corresponding infrared spectra signals could be seen clearly at
The downward bands at 1646, 1629, and 1587 cm−1 were contributed to ring stretching vibration of
approximately 400 mV. The downward bands −
at 1646, 1629, and 1587 cm−1 were contributed to ring
1
2,6-lutidinium cation [57]. The band at 1176 cm was related to C-H in-plane bending of 2,6-lutidinium
stretching vibration of 2,6-lutidinium cation [57]. The band at 1176 cm−1 was related to C-H in-plane
cation [58,59]. It confirmed that 2,6-lutidine got a hydrogen proton to become 2,6-lutidinium cation
bending of 2,6-lutidinium cation [58,59]. It confirmed that 2,6-lutidine got a hydrogen proton to
during the electrocatalytic process [60,61]. Meanwhile, three negative-going bands at 1685, 1360,
become 2,6-lutidinium cation during the electrocatalytic process [60,61]. Meanwhile, three
and 1267 cm−1 were detected, which were attributed to C=O stretching vibration, C-H deformation
negative-going bands at 1685, 1360, and 1267 cm−1 were detected, which were attributed to C=O
vibration in the methyl group, and skeleton vibration of acetophenone, respectively [62]. Moreover, a
stretching vibration, C-H deformation vibration in the methyl group, and skeleton vibration of
weak but important upward band of N-O stretching vibration, showing the participation of ABNO in
acetophenone, respectively [62]. Moreover, a weak but important upward band of N-O stretching
this reaction, was observed at 1369 cm−1 [49]. The other band located at 1129 cm−1 was assigned to
vibration, showing the participation of ABNO in this reaction, was observed at 1369 cm−1 [49]. The
ClO4 − ions of supporting electrolyte [63,64]. However, with the interference of the nearby signal peaks
other band located at 1129 cm−1 was assigned to ClO4− ions of supporting electrolyte [63,64].
at about 1280 and 1627 cm−1 , the ring stretching modes of 2,6-lutidinium cation and N+ =O−1stretching
However, with the interference of the nearby signal peaks at about 1280 and 1627 cm , the ring
vibration of oxoammonium ion could not be obviously found [48]. From the above results, we could
stretching modes of 2,6-lutidinium cation and N+=O stretching vibration of oxoammonium ion could
get the conclusion that 1-phenylethanol was oxidized to acetophenone with ABNO as the catalyst and
not be obviously found [48]. From the above results, we could get the conclusion that
2,6-lutidine as the base.
1-phenylethanol was oxidized to acetophenone with ABNO as the catalyst and 2,6-lutidine as the
To further observe the spectral changes with increasing time, the in situ time-resolved FTIR spectra
base.
experiment was carried out during the oxidation of 1-phenylethanol on Pt disk electrode with ABNO
as the catalyst at 400 mV. The resulting spectra were displayed in Figure 5. The seven negative signals
at 1685, 1360, and 1267 cm−1 and at 1645, 1629, 1587, and 1176 cm−1 , illustrated to acetophenone and
2,6-lutidinium cation, respectively, could still be seen clearly [58,59,62]. The intensity of these bands
significantly increased with the increasing of time. Meanwhile, no new bands emerged, which showed
that no new reaction occurred on the electrode surface.
Molecules 2019, 24, 100 5 of 14
Figure 4. In situ FTIR spectra collected on Pt disk electrode during the oxidation of 1-phenylethanol
(1.0 mmol) in the presence of ABNO (0.1 mmol) and 2,6-lutidine (1.0 mmol) in 0.1 M NaClO4-CH3CN
solution in a short time interval 10 s.
To further observe the spectral changes with increasing time, the in situ time-resolved FTIR
spectra experiment was carried out during the oxidation of 1-phenylethanol on Pt disk electrode
with ABNO as the catalyst at 400 mV. The resulting spectra were displayed in Figure 5. The seven
negative signals at 1685, 1360, and 1267 cm−1 and at 1645, 1629, 1587, and 1176 cm−1, illustrated to
acetophenone and 2,6-lutidinium cation, respectively, could still be seen clearly [58,59,62]. The
Figure 4.
Figure 4. In situ FTIR spectra collected on Pt disk electrode during the oxidation of 1-phenylethanol
intensity of these bands significantly increased with the increasing of time. Meanwhile, no new
presence of
(1.0 mmol) in the presence of ABNO
ABNO (0.1(0.1 mmol)
mmol) and
and 2,6-lutidine
2,6-lutidine (1.0
(1.0mmol)
mmol)in
in0.1
0.1MMNaClO -CH33CN
NaClO44-CH
bands emerged, which showed that no new reaction occurred on the electrode surface.
To further observe the spectral changes with increasing time, the in situ time-resolved FTIR
spectra experiment was carried out during the oxidation of 1-phenylethanol on Pt disk electrode
with ABNO as the catalyst at 400 mV. The resulting spectra were displayed in Figure 5. The seven
negative signals at 1685, 1360, and 1267 cm−1 and at 1645, 1629, 1587, and 1176 cm−1, illustrated to
acetophenone and 2,6-lutidinium cation, respectively, could still be seen clearly [58,59,62]. The
intensity of these bands significantly increased with the increasing of time. Meanwhile, no new
bands emerged, which showed that no new reaction occurred on the electrode surface.
Figure 5. In situ time-resolved FTIR spectra collected on Pt disk electrode during the oxidation of
presence of ABNO (0.1 mmol) and 2,6-lutidine (1.0 mmol) in 0.1 M
1-phenylethanol (1.0 mmol) in the presence
NaClO44-CH
-CH33CN
CNsolution
solution at
at 400
400 mV.
mV.
For comparision,
comparision,the theininsitu
situFTIR
FTIRspectra
spectracollected during
collected thethe
during oxidation of 1-phenylethanol
oxidation in the
of 1-phenylethanol in
presence of 2,6-lutidine with TEMPO as the catalyst and without any catalyst in 0.1
the presence of 2,6-lutidine with TEMPO as the catalyst and without any catalyst 4in 0.13 M M NaClO -CH CN
solution
NaClO4-CHunder
3CNthe similarunder
solution conditions were obtained.
the similar conditionsThe spectra
were at 400The
obtained. mVspectra
were put together
at 400 and
mV were
presented in Figure 6. As shown in Figure 6a, no additional bands were observed except for the band
of supporting electrolyte at Pt electrode without any catalyst. In addition, with the addition of TEMPO
Figure 5. In situ time-resolved FTIR spectra collected on Pt disk electrode during the oxidation of
as the catalyst in the reaction solution, all of the characteristic bands changed weakly (Figure 6b).
1-phenylethanol (1.0 mmol) in the presence of ABNO (0.1 mmol) and 2,6-lutidine (1.0 mmol) in 0.1 M
Only with ABNO as the catalyst in the reaction solution, the intensity of the bands enhanced markedly,
NaClO4-CH3CN solution at 400 mV.
which was identify with cyclic voltammograms results (Figure 6c). Thus, ABNO could act as an efficient
catalyst
Forfor the oxidation
comparision, theofinsecondary
situ FTIR alcohols instead ofduring
spectra collected TEMPO theunder the same
oxidation conditions [65,66].
the presence of 2,6-lutidine with TEMPO as the catalyst and without any catalyst in 0.1 M
NaClO4-CH3CN solution under the similar conditions were obtained. The spectra at 400 mV were
except for
except for the
the band
band ofof supporting
supporting electrolyte
electrolyte at
at Pt
Pt electrode
electrode without
without any
any catalyst.
catalyst. In
In addition,
addition, with
with
the addition of TEMPO as the catalyst in the reaction solution, all of the characteristic
the addition of TEMPO as the catalyst in the reaction solution, all of the characteristic bands bands
changed weakly
changed weakly (Figure
(Figure 6b).
6b). Only
Only with
with ABNO
ABNO as as the
the catalyst
catalyst in
in the
the reaction
reaction solution,
solution, the
the intensity
intensity of
of
the bands enhanced markedly, which was identify with cyclic voltammograms
the bands enhanced markedly, which was identify with cyclic voltammograms results (Figure 6c). results (Figure 6c).
Thus, ABNO
Thus, ABNO
Molecules could
2019, 24,could
100 act as
act as an
an efficient
efficient catalyst
catalyst for
for the
the oxidation
oxidation of
of secondary
secondary alcohols
alcohols instead
instead of
of
6 of 14
TEMPO under
TEMPO under the
the same
same conditions
conditions [65,66].
[65,66].
Figure 6.
Figure
Figure 6. Comparison
6. Comparison
Comparison of of in
of in situ
insitu FTIR
situFTIR spectra
FTIRspectra collected
spectracollected on
collectedon PtPtdisk
onPt disk electrode
diskelectrode during
electrode during
during the
the oxidation
the of
oxidation
oxidation of
1-phenylethanol
of 1-phenylethanol
1-phenylethanol (1.0 mmol)
(1.0
(1.0 mmol)
mmol) in the
ininthe presence
thepresence of 2,6-lutidine
presenceofof2,6-lutidine (1.0
2,6-lutidine(1.0 mmol)
(1.0mmol) at 400
mmol)atat400 mV.
400 mV. (a) without
mV. (a) without any
without any
any
catalyst,(b)
catalyst,
catalyst, (b) with
(b) with TEMPO
with TEMPO (0.1
TEMPO (0.1 mmol)
(0.1 mmol) as
mmol) as the
as thecatalyst,
the catalyst,(c)
catalyst, (c)with
(c) withABNO
with ABNO(0.1
ABNO (0.1mmol)
(0.1 mmol)as
mmol) asthe
as thecatalyst.
the catalyst.
catalyst.
Based
Based on
Based on the
on the above
the above observation
above observation and
observation and relevant
and relevant literatures,
relevant literatures, aaa plausible
literatures, plausible mechanism
plausible mechanism for
mechanism for the
for the
the
oxidation
oxidation of 1-phenylethanol was
was presented
presented in
in Scheme
Scheme 2.2. The
The catalyst
catalyst ABNO
ABNO
oxidation of 1-phenylethanol was presented in Scheme 2. The catalyst ABNO could be oxidized to could
could be be oxidized
oxidized to
to generate the active oxoammonium cations (ABNO + ) via one electronic transfer process
generate the
generate the active
active oxoammonium
oxoammonium cations cations (ABNO
(ABNO+)) via
+ via one
one electronic
electronic transfer
transfer process
process onon the
the anode
anode
on the anode electrode [36,67]. Subsequently, 1-phenylethanol reacted with ABNO + to give
electrode [36,67]. Subsequently, 1-phenylethanol reacted with ABNO + to give
electrode [36,67]. Subsequently, 1-phenylethanol reacted with ABNO to give acetophenone and
+ acetophenone and
acetophenone and 9-hydroxy-9-azabicyclo[3.3.1]nonane
9-hydroxy-9-azabicyclo[3.3.1]nonane (ABNOH), (ABNOH),
accompanied by accompanied
one hydrogen
9-hydroxy-9-azabicyclo[3.3.1]nonane (ABNOH), accompanied by one hydrogen proton generation by one
proton hydrogen
generation
proton
[42,68]. generation
[42,68]. Meanwhile,
Meanwhile, [42,68].
ABNOH
ABNOH Meanwhile,
was ABNOHto
was regenerated
regenerated towas
ABNO
ABNO regenerated to ABNO
[51,69]. The
[51,69]. The [51,69]. The
base 2,6-lutidine
base 2,6-lutidine gotbase
got the
the
2,6-lutidine
hydrogen got the
proton hydrogen
to form proton to
2,6-lutidinium form 2,6-lutidinium
cation during the cation during
oxidation the
reactionoxidation
hydrogen proton to form 2,6-lutidinium cation during the oxidation reaction [48]. In addition, H [48]. In reaction
addition, [48].
H22
In addition,
was H
generated was
as thegenerated
side as
product the
onside
the product
cathode on the cathode
electrode
was generated2 as the side product on the cathode electrode [54]. [54]. electrode [54].
Scheme
Scheme2.
Scheme 2. A
2. A plausible
A plausible mechanism
plausible mechanism for
mechanism for the
for the oxidation
the oxidation of
oxidation of 1-phenylethanol
1-phenylethanol in the
in the presence
the presenceof
presence ofABNO
of ABNOand
ABNO and
and
2,6-lutidine
2,6-lutidine (M).
(M).
2,6-lutidine (M).
2.3. Preparation Electrolysis
Inspired by these results, the scope of this electrochemical method for the oxidation of secondary
alcohols was explored. As shown in Table 1, 1-phenylethanol could be converted completely to
acetophenone in 98% GC internal standard yield (entry 1). Due to the volatility of acetophenone
during the process of purification and concentration, the isolated yield was relatively low (80%).
Meanwhile, we tried to calculate the faradaic efficiency in this electrochemical process. The faradaic
2.3.
2.3. Preparation
Preparation
2.3. Preparation
2.3. Electrolysis
Electrolysis
Preparation Electrolysis
Electrolysis
2.3.
2.3. Preparation
Preparation
2.3. Preparation
2.3. Electrolysis
Electrolysis
Preparation Electrolysis
Electrolysis
Inspired
Inspired
Inspired by
Inspired by
by these
by these
these results,
these results,
results, the
results, the
the scope
the scope
scope of
scope of
of this
of this electrochemical
this electrochemical
this electrochemical method
electrochemical method
method for
method for
for the
for the oxidation
the oxidation
the oxidation of
oxidation of
of
of
Inspired
Inspired
Inspired
Inspired by
by these
these
by these
by these results,
results,
results,
results, the
the
the As
the scope
scope
scope
scope of
of
of this
of this
this
electrochemical
electrochemical
electrochemical method
method
method for
method for
for
for the
the
the be
the oxidation
oxidation
oxidation
oxidation of
of
of
of
secondary
secondary
secondary
secondary alcohols
alcohols
alcohols
alcohols was
was
was
was explored.
explored.
explored.
explored. As
As
As shown
shown
shown
shown in
inin
in Table
Table
Table
Table 1,
1,
1,
1, 1-phenylethanol
1-phenylethanol
1-phenylethanol
1-phenylethanol could
could
could
could be
be
be converted
converted
converted
converted
secondary alcohols
secondary
secondary
secondary alcohols was
alcohols
alcohols was explored.
was
was explored. As
explored.
explored. As shown
As
As shown in
shown
shown in Table
in
in Table 1,
Table
Table 1, 1-phenylethanol
1,
1, 1-phenylethanol could
1-phenylethanol
1-phenylethanol could be
could
could be converted
be
be converted
converted
converted
completely
completely
completely to to acetophenone
to acetophenone
acetophenone in in 98%
in 98%
98% GC GC internal
GC internal
internal standardstandard
standard yield yield (entry
yield (entry
(entry 1). 1). Due
1). Due
Due to to
to thethe volatility
the volatility
volatility of of
of
completely
completely
completely
completely to
to
to
to acetophenone
acetophenone
acetophenone
acetophenone in
in 98%
98%
in 98%
in 98% GC
GC internal
internal
GC internal
GC internaland standard
standard
standard
standard yield
yield (entry
(entry
yield (entry
yield (entry 1).
1). Due
Due
1). Due
1). Dueyield to
to the
the
to the
to the volatility
volatility
volatility
volatility of
of
of
of
acetophenone
acetophenone
Molecules
acetophenone
acetophenone 2019, 24, during
during
100
during
during the
the
the
the process
process
process
process of
of
of
of purification
purification
purification
purification and
and
and concentration,
concentration,
concentration,
concentration, the
the
the
the isolated
isolated
isolated
isolated yield
yield
yield was
was
was
was relatively
relatively
7
relatively
relatively of 14
acetophenone
acetophenone
acetophenone
acetophenone during
during
during
during the
the
the
the process
process
process
process of
of
of
of purification
purification
purification
purification and
and
and
and concentration,
concentration,
concentration,
concentration, the
the
the
the isolated
isolated
isolated
isolated yield
yield
yield
yield was
was
was
was relatively
relatively
relatively
relatively
low
low (80%).
low (80%). Meanwhile,
(80%). Meanwhile,
Meanwhile, we we tried
we tried
tried to to calculate
to calculate
calculate the the faradaic
the faradaic efficiency
faradaic efficiency
efficiency in in this
in this electrochemical
electrochemical process. process.
process.
low
low
low
low (80%).
(80%).
(80%).
(80%). Meanwhile,
Meanwhile,
Meanwhile,
Meanwhile, we
we
we
we tried
tried
tried
tried to
to
to
to calculate
calculate
calculate
calculate the
the
the
the faradaic
faradaic
faradaic
faradaic efficiency
efficiency
efficiency
efficiency in
in
in
in this
this
this
electrochemical
electrochemical
electrochemical process.
process.
process.
process.
The
The
The faradaic
faradaic
faradaicwith efficiencies
efficiencies
efficiencies with
with 1-phenylethanol
1-phenylethanol
1-phenylethanol were
were
wereat about
about
about 81.4%
81.4%
81.4% at
at 6 6 h,
h,
at 6conversion
6 h, with
with
h, with
with 92% 92%
92%
92% conversion
conversion
conversion and
and
and
The
The
The
The faradaic
faradaic
efficiencies
faradaic
faradaic efficiencies
efficiencies
efficiencies
efficiencies with
with
1-phenylethanol
with
were about 81.4%
1-phenylethanol
1-phenylethanol were
were
were
were about
about
about
about 81.4%
81.4%
6 h, with
81.4%
81.4% 92% at
at
at
at 666 substrate
h,
h,
h, with
with
with 92%
92%
92% conversion
andconversion
99% selectivity.
conversion
conversion and
and
and
and
99%
99%
99%
99% selectivity.
selectivity.
selectivity.
selectivity. With
With
With
With the
the
the
the reaction
reaction
reaction
reaction proceeding,
proceeding,
proceeding,
proceeding, the
the
the
the concentration
concentration
concentration
concentration of
of
of
of the
the
the
the substrate
substrate
substrate was
was
was
was decreased
decreased
decreased
decreased and
and
and
and
99%
99%
99%
99% selectivity.
selectivity.
Withselectivity.
the reaction
selectivity. With
With
With
With the
the
proceeding, reaction
reaction
the reaction
the proceeding,
proceeding,
the concentration
reaction proceeding,
proceeding, the
the
of the
the
the concentration
concentration
substrate was
concentration
concentration of
of the
the substrate
substrate
decreased
of about
of the substrate
the substrate andwas was
was decreased
decreased
the reaction
was decreased
decreased and
and
slowed
anda
and
the
the
the reaction
reaction
reaction slowed
slowed
slowed down
down
down gradually.
gradually.
gradually. The
The
The faradaic
faradaic
faradaic efficiency
efficiency
efficiency was
was
was about
about 61.8%
61.8%
61.8% at
at
at 8.5
8.5
8.5 h.
h.
h. Similarly,
Similarly,
Similarly, aaaa
the
the
down
the
the reaction
reaction
reaction
reaction slowed
slowed
gradually.slowed
slowed The down
down
down
down gradually.
gradually.
faradaic efficiency
gradually.
gradually. Thewas
The
The
The faradaic
faradaic
faradaic
faradaic efficiency
aboutefficiency
61.8% at was
efficiency
efficiency was
8.5 h.
was
was about
about
Similarly,
about
about 61.8%aat
61.8%
61.8%
61.8% atseries
at
at 8.5 h.
8.5
8.5
8.5 h.of
h.
h. Similarly,
Similarly,
secondary
Similarly,
Similarly, aa
series
series
series of
series of
of secondary
secondary
of secondary
secondary benzyl benzyl
benzyl alcohols
alcohols
benzyl alcohols
alcohols with with
with
with both both
both electro-donating
electro-donating
electro-donating and and
and electron-withdrawing
electron-withdrawing
series
series
benzyl
series
series of
of
of secondary
secondary
alcohols
secondary
of secondary with benzyl
benzyl
both
benzyl
benzyl alcohols
alcohols
electro-donating
alcohols
alcohols with
with
withand
within both
electro-donating
both
electro-donating and
and
substituents
and
in phenyl
electron-withdrawing group
substituents
substituents
substituents in
substituents in
in phenyl
phenyl
in phenyl
phenyl group group
group
group were were
were provided
provided
were provided
provided in in good
good
in good
good to to
to excellent
excellent
to excellent isolated
isolated
excellent isolated
isolated yields yields
yields (entires
(entires
yields (entires
(entires 2–11). 2–11).
2–11).
2–11). For For
For
For
substituents
substituents
were provided
substituents
substituents in
in
in
in phenyl
phenyl
in good group
phenyl
phenyl group
group
to
group were
were
excellent
were
were provided
provided
isolated
provided
provided in
in
yields
in
in good
good
(entires
good
good to
to
to
to excellent
excellent isolated
isolated
2–11). Forisolated
excellent
excellent example,
isolated yields
yields (entires
(entires
four (entires
yields
yields secondary
(entires 2–11).
2–11). For
For
benzylic
2–11).
2–11). For
For
example,
example,
example, four four
four secondary
secondary
four secondary
secondary benzylic benzylic
benzylic alcohols
alcohols
benzylic alcohols
alcohols with with
with electro-donating
electro-donating
electro-donating group group
group
group were were
were converted
converted
were converted
converted into into
into the
the
into the the
example,
example,
alcohols with
example,
example, four
four
four secondary
electro-donating
secondary
secondary benzylic
benzylic
benzylic group alcohols
werewith
alcohols
alcohols with
converted
electro-donating
electro-donating group
into the corresponding
group
group were
were
were converted
ketones with
converted
converted into
into
into the
good
the
the
corresponding
corresponding
corresponding
corresponding ketones
ketones
ketones
ketones with
with
with
with good
good
good
good isolated
isolated
isolated
isolated yields
yields
yields
yields under
under
under
under the
the
the
the standard
standard
standard
standard conditions
conditions
conditions
conditions (entries
(entries
(entries
(entries 5–8).
5–8).
5–8).
5–8).
corresponding
corresponding
isolated yields under
corresponding
corresponding ketones
ketones
ketones
ketones with
with
thewithstandard
with good
good isolated
isolated
goodconditions
good isolated yields
isolated yields
yields
(entriesunder
yields under
under the
the
5–8). Meanwhile,
under standard
standard
the standard
the standard conditions
conditions
halide substituents
conditions
conditions (entries
(entries
(entries
(entries 5–8).
5–8).
products
5–8).
5–8).
Meanwhile,
Meanwhile,
Meanwhile, halide halide substituents
halide substituents
substituents products products
products such such
such as as chloro-acetophenone
as chloro-acetophenone
chloro-acetophenone (o-, (o-,
(o-, m-, m-,
m-, and and
and p-), p-),
p-),
Meanwhile,
Meanwhile, halide
halide
such as chloro-acetophenone
Meanwhile,
Meanwhile, substituents
substituents
halide substituents
halide substituents products
products
(o-, m-,products such
such
and p-), 4-bromo-acetophenone
products such were
such as
chloro-acetophenone
as and 4-fluoro-acetophenone
chloro-acetophenone (o-,
(o-, m-,
m-,
(o-, isolated
(o-, m-, and
m-, and
and
and p-),
p-),
were
p-),
p-),
4-bromo-acetophenone
4-bromo-acetophenone and and
and 4-fluoro-acetophenone
4-fluoro-acetophenone
4-fluoro-acetophenone were were
were all all
all obtained
obtained
all obtained
obtained in in
in excellent
excellent
in excellent
excellent isolated isolated
isolated yields yields
yields
yields
all obtained in excellent isolated
4-bromo-acetophenone and
and
yields (entries 2–4,10,11).
4-fluoro-acetophenone
4-fluoro-acetophenone were
were
were all
all
all obtained
Furthermore,
obtained
obtained in
in
in excellent
1-(4-nitrophenyl)ethanol
excellent
excellent isolated
isolated
isolated yields
could
yields
yields
(entries
(entries
(entries
(entries 2–4,10,11).
2–4,10,11).
2–4,10,11).
2–4,10,11). Furthermore,
Furthermore,
Furthermore,
Furthermore, 1-(4-nitrophenyl)ethanol
1-(4-nitrophenyl)ethanol could
could
could
could afford
afford
afford
afford the
the
the
the target
target
target
target product
product
product
product efficiently
efficiently
efficiently
efficiently
(entries
(entries
afford
(entries
(entries 2–4,10,11).
2–4,10,11).
the target
2–4,10,11).
2–4,10,11). Furthermore,
Furthermore,
product efficiently
Furthermore, 1-(4-nitrophenyl)ethanol
(entry
Furthermore, 1-(4-nitrophenyl)ethanol 9). When
1-(4-nitrophenyl)ethanol could
could
1-phenylpropan-1-ol
could
could afford
afford
afford
afford thefullthe
the
the wastarget
target
chosen
target
target product
product
productas the efficiently
efficiently
substrate,
efficiently
product efficiently
(entry
(entry
(entry 9). 9). When
9). When 1-phenylpropan-1-ol
When 1-phenylpropan-1-ol
1-phenylpropan-1-ol was was chosen
was chosenchosen as as the
as the substrate,
substrate, aaaaa full
the substrate, conversion
full conversion
conversion with with
with 88% 88%
88%
(entry
(entry
(entry
(entry 9).
9).
a full conversion
9).
9). When
When
When
When 1-phenylpropan-1-ol
1-phenylpropan-1-ol
with 88% isolated yield
1-phenylpropan-1-ol
1-phenylpropan-1-ol was
was
was
was chosen
chosen
could
chosen
chosen as
as
be achieved
as
as the
the
the
the substrate,
substrate,
(entry 12).aaOther
substrate,
substrate, full
full
full
full conversion
conversion
excellent results
conversion
conversion with
with
with
with 88%
88%
were
88%
88%
isolated
isolated
isolated yield
isolated yield
yield
yield couldcould
could
could be be
be achieved
achieved
be achieved
achieved (entry (entry
(entry
(entry 12). 12).
12). Other
Other
12). Other excellent
excellent
Other excellent results
results
excellent resultsresults were were
were
were also also
also obtained,
obtained,
also obtained,
obtained, including including
including
including
isolated
isolated
also obtained,
isolated
isolated yield
yield
yield
yield could
could
including
could
could be
be
be
be achieved
achieved
achieved
achieved (entry
(entry
1-phenyl-1-butanol
(entry
(entry 12).
12).
12).
12). Other
Other
and
Other
Other excellent
excellent results
results
1-(p-tolyl)propan-1-ol
excellent
excellent results
results were
were
were
were also
also
(entries
also
also obtained,
obtained,
13 and 14).
obtained,
obtained, including
including
Notably,
including
including
1-phenyl-1-butanol
1-phenyl-1-butanol
1-phenyl-1-butanol
1-phenyl-1-butanol and
and
and
and 1-(p-tolyl)propan-1-ol
1-(p-tolyl)propan-1-ol (entries
(entries
(entries
(entries 13
13
13
13 and
and
and
and 14).
14).
14).
14). Notably,
Notably,
Notably,
Notably, the
the
the
the conversion
conversion
conversion
conversion of
of
of
of
1-phenyl-1-butanol
1-phenyl-1-butanol
the conversion
1-phenyl-1-butanol
1-phenyl-1-butanol of and
and
and
and 1-(p-tolyl)propan-1-ol
2-methyl-1-phenylpropan-1-ol
1-(p-tolyl)propan-1-ol (entries
(entries
could
(entries
(entries 13
13
reach
13
13 and
and
to
and
and 98% 14).
14).
14).
14). by Notably,
Notably,
prolonging
Notably,
Notably, the
the
the
the the conversion
conversion
reaction
conversion
conversion timeof
of
of
of
2-methyl-1-phenylpropan-1-ol could could
could
could reachreach
reach
reach to to
to 98%
98%
to 98%
98% by by
by prolonging
prolonging
by prolonging
prolonging the the
the reaction
reaction
the reaction
reaction time time
time
time to to
to 11
11
to 1111 hhhh (entry
(entry
h (entry
(entry 15).15).
15).
15).
to 11 h (entry 15). The selectivity
2-methyl-1-phenylpropan-1-ol could
could
could toreach
reach
reach to
to
to 98%
2-methylpropiophenone
98%
98% by
by
by prolonging
prolonging
prolonging the
was
the
the reaction
92% andtime
reaction
reaction time
timethe to to
main
to 11
11
11 (entry
hhby-product
(entry
(entry 15).
15).
15).
The
The
The
The selectivity
selectivity
selectivity
selectivity to
toto
to 2-methylpropiophenone
2-methylpropiophenone was
was
was
was 92%
92%
92%
92% and
and
and
and the
the
the
the main
main
main
main by-product
by-product
by-product
by-product was
was
was
was benzaldehyde.
benzaldehyde.
benzaldehyde.
benzaldehyde.
The
The
The
The selectivity
selectivity
wasselectivity
benzaldehyde.
selectivity to
to
Next, the polycyclic and
2-methylpropiophenone was
was 92%
92%
washeterocyclic
was 92%
92% and
and the
the
andsmoothly
and the
the main
main
substrates by-product
by-product
mainconverted
main were smoothly
by-product
by-product was
was
was
was benzaldehyde.
benzaldehyde.
converted to
benzaldehyde.
benzaldehyde.
Next,
Next,
Next, the the polycyclic
the polycyclic
polycyclic and and heterocyclic
and heterocyclic
heterocyclic substratessubstrates
substrates were were
were smoothly
smoothly converted
converted to to
to thethe corresponding
the corresponding
corresponding
Next,
Next,
Next,
Next, the
the
thewith
the polycyclic
polycyclic
the correspondingpolycyclic
polycyclic and
and
ketones heterocyclic
heterocyclic
andisolated
and with satisfying
heterocyclic
heterocyclic substrates
substrates
substratesisolated
substrates were
were
were
wereyieldssmoothly
smoothly converted
converted
(entriesconverted
smoothly
smoothly 16–18). Into
converted to
to the
the
toorder corresponding
corresponding
to explore the
the corresponding
the corresponding
ketones
ketones
ketones with satisfying
with satisfying
satisfying isolated yields
isolated yields (entries
yields (entries
(entries 16–18).16–18).
16–18). In In order
In order
order to to explore
to explore
explore the the applicability
the applicability
applicability of of the
of the
the
ketones
ketones
applicability
ketones
ketones with
with
with
with satisfying
satisfying
of the protocol
satisfying
satisfying isolated
isolated
isolated
isolated yields
yields
for unactivated
yields
yields (entries
(entries
(entries
(entriessecondary16–18).
16–18).
16–18).
16–18). In
In order
order
aliphatic
In
In order
order to
to explore
explore
alcohols,
to
to explore
explore the
the
cycloheptanol
the
the applicability
applicability
applicability
applicability and 2-octanolof
of
of
of the
the
the
the
protocol
protocol
protocol
protocol for
for
for
for unactivated
unactivated
unactivated
unactivated secondary
secondary
secondary
secondary aliphatic
aliphatic
aliphatic
aliphatic alcohols,
alcohols,
alcohols,
alcohols, cycloheptanol
cycloheptanol
cycloheptanol
cycloheptanol and
and
and
and 2-octanol
2-octanol
2-octanol
2-octanol were
were
were
were tested.
tested.
tested.
tested.
protocol
protocol
were tested.
protocol
protocol for
for unactivated
unactivated
for unactivated
for unactivated secondary
secondary
Fortunately, secondary
the high GC
secondary aliphatic
aliphatic
yields of
aliphatic
aliphatic alcohols,
cycloheptanol
their corresponding
alcohols,
cycloheptanol and
and
ketones
and
and 2-octanol
2-octanol
were received
2-octanol
2-octanol were
were
were
were tested.
tested.
in 98%
tested.
tested.
Fortunately,
Fortunately,
Fortunately, the the high
the high
high GC GC yields
GC yields
yields of of their
of their corresponding
their corresponding
corresponding ketones ketones
ketones were were
were receivedreceived
received in in 98%
in 98%
98% and and
and 90%,90%,
90%,
Fortunately,
Fortunately,
and 90%, respectively
Fortunately,
Fortunately, the
the
the high
the high
high
high GC
GC yields
yields
(entries
GC
GC yields
yields19 andof
of
of their
their corresponding
corresponding
20). corresponding
of their
their corresponding ketones ketones
ketones
ketones were were
were
were receivedreceived
received
received in in
in
in 98%98%
98%
98% and and
and
and 90%,90%,
90%,
90%,
respectively
respectively
respectively (entries
(entries
(entries 19 19
19 and
and
19 and 20).
20).
and 20).20).
respectively
respectively
respectively
(entries
(entries
(entries 19
19
19
19 and
and
and
and 20).
20).
20).
20).
Table 1. Electrochemical conversion of various secondary alcohols to ketones aaa.
Table
Table
Table
Table 1.
1. Electrochemical
Electrochemical
1. Electrochemical
1. conversion
conversion
Electrochemical conversion
Electrochemical of
of
conversion of
conversion various
various
of various
of secondary
secondary
various secondary
various alcohols
alcohols
secondary alcohols
secondary to
to
alcohols to
alcohols to ketones
ketones
ketones aaaaaaaaaaaaa
to ketones
ketones
Table 1.
Table
Table
Table 1.
1.
1. Electrochemical
Electrochemical
Electrochemical conversion
conversion
conversion of
of
of various
various
various secondary
secondary
secondary alcohols
alcohols
alcohols to
to
to ketones
ketones
ketones
b (%) c (%)
Entry
Entry
Entry
Substrate
Substrate
Substrate
Product
Product
Product Conversion
Conversion
Conversion bbb (%) Selectivitybbbbbb(%)
Selectivity (%) Yield
(%) Yield Yield (%)
ccccc (%)
b (%) Selectivity
b
Entry
Entry
Entry
Entry Substrate
Substrate
Substrate
Substrate Product
Product
Product
Product Conversion
Conversion
Conversion
Conversion bbb (%)
(%)
(%) Selectivity
Selectivity
Selectivity bb (%)
b (%)
(%) Yield
Yield
Yield ccc (%)(%)
(%)
Conversion bbbb (%) Selectivity
Selectivity bbbb (%)
(%) Yield
Yield cccc (%)
b
b b b
b b c
c c
Entry
Entry Substrate
Substrate
OH
OH
OH Product
Product
O
O
O Conversion (%)
(%) Selectivity (%) Yield (%)
(%)
OH
OH OH
OH O
O O
O
OH
OH
OH O
O
O
OH
OH O
O
11111 >99
>99
>99
>99
>99 >99
>99
>99
>99
>99 80 (98)
80 80
80 (98)
(98)
(98)
1111 >99
>99
>99
>99 >99
>99
>99
>99
80
80
80 (98)
(98)
80 (98)
80 (98)
(98)
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
2222222 >99
>99
>99
>99
>99 98
98
98
98 94
94
94 94
22 >99
>99
>99
>99
98
98
98
98
98
94
94
94
94
94
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl O
O
O
O
O
O
O
O
O
O
O
O
3333333 >99
>99
>99
>99 97
97
97
97 88
88
88 88
33 >99
>99
>99
>99
97
97
97
97
97
88
88
88
88
88
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
OH
OH
OH Cl
Cl
Cl
Cl O
O
O
OH
OH
OH
OH O
O
O
O
OH
OH
OH O
O
O
OH
OH O
O
4 >99
>99 96 87
444444 >99
>99
>99
>99
>99 96
96
96
96
96
96
87
87 87
87
87
87
44 Cl
Cl Cl
Cl
>99
>99 96
96 87
87
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
OH Cl
Cl
Cl
ClO
Cl
Cl
OH
OH
OH
OH Cl
Cl
O
OO
O
OH
OH
OH O
O
O
OH
OH
OH
OH O
O
OO
55 >99
>99
>99
>99 97
97 92
92
5555555 >99
>99
>99
>99
>99
97
97
97
97
97
97
97
92 92
92
92
92
92
92
666 >99
>99
>99
>99 97
97
97 93
93
93
666666 >99
>99
>99
>99
>99 97
97
97
97
97
97
93
93
93
93
93 93
OH
OH
OH
OH
OH O
O
O
O
O
OH
OH
OH O
O
O
OH
OH
OH
OH O
O
O
O
7777 >99
>99
>99
>99 98
98
98 95
95
95
77777 >99
>99
>99
>99
>99
98
98
98
98
98
98
95
95
95
95
95 95
OH
OH
OH
OH
OH O
O
O
O
O
OH
OH
OH O
O
O
OH
OH
OH
OH O
O
O
O
8888 >99
>99
>99
>99 97
97
97 89
89
89
88
82019, 24, >99
>99
>99
>99
97
97
97
97
89
89
89
89
Molecules882019,
Molecules 24, xxOO
O O
O
O
>99 97
97 89 89 88 of
of 14
14
O
O
O
O O
O
O
O
O
O
O O
O
O
O
O O
O
999 >99
>99
>99 96
96
96 90
90 90
10
10 >99
>99 97
97 85
85
11
11 >99
>99 97
97 92
92
O
O
Molecules 2019, 24, 100 8 of 14
Molecules
Molecules
Molecules
Molecules 2019,
2019, 24,
2019,
2019, 24, xxxxx
24,
24, x 8888 of
of 14
of
of 14
14
14
Molecules
Molecules 2019,
2019,
Molecules 2019, 24,
24,
2019, 24,
24, xxx 88 ofof 14
14
Molecules
Molecules
Molecules 2019,
2019, 24,
24, x 8888 of
of 14
of
of
14
14
14
Table 1. Cont.
99999 >99
>99
>99
>99
>99 96
96
96
96 90
90
90
90
999999
Entry Substrate Product >99
>99
>99 b (%)
>99
Conversion
96
96
96
96 b (%)
Selectivity
90
90
90
90 c (%)
Yield
>99
>99 96
96
96 90
90
90
10
10
10
10 >99
>99
>99
>99
>99 97
97
97
97 85
85
85 85
10
10
10
10 >99
>99
>99
>99
97
97
97
97 85
85
85
85
10
10
10 >99
>99 97
97
97 85
85
85
11
11
11
11
11 >99
>99
>99
>99
>99 97
97
97
97
97 92
92
92 92
92
11
11 >99
>99
>99
>99 97
97 92
92
11
11
11 >99 97
97
97 92
92
92
O
O
O
O
O
O
O
O
O
12
12 O
O
O 99
99 99
99 88
88
12
12
12
12 99
99
99 99
99
99
99 88
88 88
88
12
12
12
12 99
99
99
99 99
99
99
99 88
88
88
88
12 99 99 88
13
13
13
13
13 98
98
98
98 98
98
98
98
98 92
92
92 92
92
13
13
13
13 98
98
98
98 98
98
98
98 92
92
92
92
13
13 98
98 98
98 92
92
14
14
14
14 >99
>99
>99
>99 97
97
97
97 93
93
93
93
14
14
14
14 >99
>99
>99
>99
>99
97
97
97
97 93 93
93
93
14
14
14 >99
>99 97
97
97 93
93
93
15
15
15
15
dd
15ddddddddddddd 98
98
98
98
98 92
92
92
92
92 89
89
89
89 89
89
15
15
15
15 dddd 98
98
98 92
92
92
92 89
89
89
15
15 98
98 92
92 89
89
16
16
16 >99
>99
>99
>99 99
99
99 90
90
90
16
16
16
16
16 >99
>99
>99
>99
99
99
99
99
99 90
90
90
9090
90
16
16
16 >99
>99 99
99
99 90
90
OH
OH
OH
OH
OH
OH
OH
OH
OH
17
17
17
17
OH
OH
OH >99
>99
>99
>99 99
99
99
99 95
95
95
95
17
17
17 >99
>99
>99
>99 99
99
99 95
95
9595
17
17
17
17 >99
>99 99
99
99
99 95
95
95
18
18
18
18
18 >99
>99
>99
>99
>99 99
99
99
99
99 80
80
80
80
80
18
18 >99
>99
>99
>99 99
99 80
80
18
18
18
18 >99 99
99
99
99 8080
80
80
19
19
19
19 99
99
99
99 99
99
99
99 98
98 ee
98 eeeeeeeeeeee
98
19
19
19
19 99
99
99
99 99
99
99
99 98
98
9898
98 eeee e
19
19 99 99
99 98
20
20
20
20 92
92
92
92 98
98
98
98 90
90 ee
90 eeeeeeeeeeee
90
20
20
20
20 92
92
92
92 98
98
98
98 90
90
90
90 eeee e
20
20
aaa Electrolytic
92
92 98
98 (1.0 mmol), 9090
Electrolytic
aaaaa Electrolytic
Electrolytic conditions:
conditions:
conditions:
conditions: substrate
substrate
substrate
substrate (1.0
(1.0
(1.0
(1.0 mmol),
mmol),
mmol),
mmol), ABNO
ABNO
ABNO
ABNO (0.1
(0.1
(0.1
(0.1 mmol),
mmol),
mmol),
mmol), 2,6-lutidine
2,6-lutidine
2,6-lutidine
2,6-lutidine (1.0
(1.0
(1.0 mmol),
mmol),
mmol), 0.1
0.1 0.1 M
0.1 M
M
M
a a Electrolytic
Electrolytic
Electrolytic
aaaaaaaa Electrolytic
Electrolytic conditions:
conditions:
conditions:
conditions: substrate
substrate
substrate
substrate (1.0
(1.0
(1.0 mmol),
mmol),
mmol),
(1.0 mmol),
mmol), ABNO
ABNO
ABNO
ABNO (0.1
(0.1
(0.1 mmol),
mmol),
mmol),
(0.1 current
mmol), 102,6-lutidine
2,6-lutidine
2,6-lutidine
2,6-lutidine (1.0
(1.0
(1.0
(1.0 mmol), mmol),
mmol),
mmol),
mmol), 0.1
0.1 0.1
0.1 M
M
M
M
NaClO Electrolytic
NaClO
a
NaClO 4 4
Electrolytic-CH
-CH
-CH 3 3 CN
CN
CNconditions:
conditions:
solution
solution
solution substrate
substrate
(15
(15
(15 mL),
mL),
mL), (1.0
(1.0
undivided
undivided
undividedmmol), ABNO
ABNO
cell,
cell,
cell, (0.1
(0.1
constant
constant
constant mmol),
mmol),
current
current 2,6-lutidine
2,6-lutidine
10
10 mA,
mA,
mA, (1.0
(1.0
electrolysis
electrolysis
electrolysis mmol),
time
time
time 0.1 0.1
8.5
8.5 8.5 M
M
h,
h,
h,
NaClO
NaClO -CH
444444-CH 333333conditions:
CN
CN solution
solution substrate
(15
(15 (1.0 mmol),
mL),
mL), undivided
undivided ABNO (0.1constant
cell,
cell, mmol), 2,6-lutidine
constant current
current 10
10(1.0 mmol),
mA,
mA, 0.1 M NaClO
electrolysis
electrolysis 4 -CH
time
time 8.5 3 CN
8.5 h,
h,
NaClO
NaClO NaClO
NaClO 4 -CH
4444-CH-CH
-CH 3333CN CN
CN
CN solution
solution
solution
solution (15
(15
(15
(15 mL),
mL),
mL),
mL), undivided
undivided
undivided
undivided cell,
cell,
cell,
cell, constant
constant
constant
constant current
current
current
current 10
10
10
10 mA,
mA,
mA,
mA, electrolysis
electrolysis
electrolysis
electrolysis time
time
time
time 8.5
8.5 8.5
8.5 h,
h,
h,
h,
room NaClO
solution
room
room
room
4 -CH
temperature.
44 (15 mL),
temperature.
4 4
temperature.
3
3
temperature.33 33CN solution
b
undivided
bb
b
b
b
b
(15
Determined
cell,
Determined
Determined
Determined mL),
constantundivided
by
by
by
by GC
current
GC
GC
GC with
10
with
with
with cell,
mA,peak
peak
peak
peakconstant
area
electrolysis
area
area
area current 10
normalization
time 8.5 h,
normalization
normalization
normalizationroommA,
method.
method.
method.
method.electrolysis
temperature. c
c
c b
cccc Isolatedtime
Determined
Isolated
Isolated
Isolated yield.8.5
yield.
yield. h,
by
yield.
roomroom temperature.
temperature. bbb ccc Isolated
GC
room with peak
temperature. area b b Determined
b Determined
normalization
b Determined by
by
method.
by cGC
GC with
with
Isolated
GC with peak
peak
yield.
peak area
area
Values
area normalization
normalization
in parentheses
normalization method.
method.
were determined
method. Isolated
cccccccc Isolated
by GC
Isolated yield.
internal yield.
yield.
room
ValuesValues
Values
Values temperature.
room temperature.
in
in
in
in parentheses
parentheses
parentheses
parentheses
b
b b
b Determined
Determined
were
were
were
were by
determinedby GC
determined
determined
determined GC by
by
by
bywith
with
GC
GC
GC
GC peak
internal
internal
internal
internal area
peak area normalization
normalization
standard
standard
standard
standard method.
method.
method.
method. method.
dmethod.
d
d
dd Electrolysis
Electrolysis
Electrolysis
Electrolysis Isolated
time
time
time
time 11
11
11
11 yield.yield.
h.
h.
h.
h.
eee
eeee
Values
Values
Values
standard in
in
in parentheses
parentheses
parentheses
method. were
d Electrolysis
were
were determined
determined by
time 11 h. e Yields
determined by
by GC
GC
GC internal
internal
wereinternal standard
standard
standard
calculated based onmethod.
method.
method. ddd Electrolysis
d
Electrolysis
Electrolysis
the GC dddddconversion and time
time
time 11
11
11
selectivity. h.
h.
h. eee
ValuesValues in
in parentheses
parentheses were
were determined
determined by
by GC
GC internal
internal standard
standard method.
method. d Electrolysis
d Electrolysis time
time 11
11 h.
h. eeeeeeee
YieldsValues
Values
Yields were
were
Yields were in
in parentheses
calculated
parentheses
were calculated calculated were
based
were
based
calculated based determined
on the
determined
based on on the
on the GC
GC
the GC by
by GC
conversion
GC internal
and
internal
conversion
GC conversion
conversion and and standard
selectivity.
standard
selectivity.
and selectivity.
selectivity. method.
method. d Electrolysis
d Electrolysis time
time 11
11 h.
h.
Yields
Yields
Yields
Yields were
were
were calculated
calculated
calculated based
based
based on
on
on the
the
the GC
GC
GC conversion
conversion
conversion and
and
and selectivity.
selectivity.
selectivity.
Yields Yields were
Yields were calculated
were calculated based
calculated based on
based on the
on the GC
the GC conversion
GC conversion and
conversion and selectivity.
and selectivity.
selectivity.
3. Materials and Methods
3.
3. Materials
3.
3. Materials and
Materials
Materials and Methods
and
and Methods
Methods
Methods
3.
3.
3. Materials
Materials
3. Materials
Materials and and
and Methods
Methods
and Methods
Methods
3.1. Catalyst Preparation and Reagents
3.1.
3.1.
3.1.
3.1.
3.1. Catalyst
Catalyst
Catalyst
Catalyst
Catalyst Preparation
Preparation
Preparation
Preparation
Preparation and
and
and
and
and Reagents
Reagents
Reagents
Reagents
Reagents
3.1.
3.1. Catalyst
Catalyst
3.1. Catalyst
3.1. Catalyst Preparation
Preparation
Preparation and
and Reagents
Reagents
and Reagents
Reagents
3.1.
3.1. ABNOPreparation
Catalyst
Catalyst Preparation
was synthesized
Preparation and
and
and Reagents
in our laboratory according to the available procedures [41]. Other
Reagents
ABNO
ABNO
ABNO
ABNO was
was
was
was synthesized
synthesized
synthesized
synthesized in
in
in
in our
our
our
our laboratory
laboratory
laboratory
laboratory according
according
according
according to
to
to
to the
the
the
the available
available
available
available procedures
procedures
procedures
procedures [41].
[41].
[41].
[41]. Other
Other
Other
Other
ABNO
ABNO
chemicals
ABNO
ABNO andwas
was
was
was synthesized
synthesized
solvents
synthesizedwere
synthesized in
in
purchased
in our
in our
our laboratory
laboratory
from the
our laboratory
laboratory according
according
supplier to
according
according to
to
and the
the
to thewere
the available
available procedures
procedures
used asprocedures
available
available received. In
procedures [41].
[41]. Other
Other
thisOther
[41].
[41]. work,
Other
chemicals
chemicalsABNO
ABNO
chemicals and
and
and was
was synthesized
synthesized
solvents
solvents
solvents were
were
were in
in
purchased
purchased
purchased our
our laboratory
laboratory
from
from
from the
the
the according
according
supplier
supplier
supplier to
to
and
and
and the
the
were
were
were available
available
used
used
used as
as
as procedures
procedures
received.
received.
received. In
In
In [41].
[41].
this
this
this Other
Other
work,
work,
work,
chemicals
the racemic
chemicals
chemicals and
and
and solvents
secondary
solvents
solvents were
alcohols
were
were purchased
purchased
purchased were used.from
from
from the
the
the supplier
supplier
supplier and
and
and were
were
were used
used
used as
as
as received.
received.
received. In
In
In this
this
this work,
work,
work,
chemicals
chemicals and solvents were
were purchased from
from the the supplier
supplier and and werewere used
used as as received.
received. In In this
this work,
the
the
the
the
the
the racemicand
racemic
racemic
racemic
racemic
racemic
solventsalcohols
secondary
secondary
secondary
secondary
secondary
secondary
alcohols
alcohols
alcohols
alcohols
alcohols
purchased
were
were used.
were
were
were
were
used.
used.
used.
used.
used.
work,
the
the racemic
racemic secondary
secondary
3.2. Cyclic Voltammetry Study alcohols
alcohols were
were used.
used.
3.2.
3.2.
3.2.
3.2.
3.2. Cyclic
Cyclic
Cyclic
Cyclic
Cyclic Voltammetry
Voltammetry
Voltammetry
Voltammetry
Voltammetry Study
Study
Study
Study
Study
3.2.
3.2. Cyclic
Cyclic
3.2. Cyclic
3.2. Cyclic Voltammetry
Voltammetry
Voltammetry
The cyclic
Voltammetry Study
Study
Study study was carried out by using CHI620B electrochemical workstation
voltammetric
Study
3.2.
3.2. Cyclic
Cyclic Voltammetry
Voltammetry Study
Study
(CHThe The
The
The
The cyclic
cyclic
cyclic
cyclic
Instrument voltammetric
Inc., Austin, study
voltammetric
voltammetric
voltammetric study
study
study
TX, was
was
was
was
USA) carried
carried
carried
carried
with an “L” out
out
out
out by
by
by
by
type using
using
using
using CHI620B
CHI620B
CHI620B
CHI620B
Pt electrode as electrochemical
electrochemical
electrochemical
electrochemical
the working electrode. workstation
workstation
workstation
workstation
A big
The
The
The cyclic
cyclic voltammetric
voltammetric
cyclic voltammetric
cyclic voltammetric study
study
study
study was
was
was
was carried
carried
carried
carried out
out by
by
outtype
out by using
by using
using
using CHI620B
CHI620B
CHI620B
CHI620B electrochemical
electrochemical
electrochemical
electrochemical workstation
workstation
workstation
workstation
(CH
(CH
(CH The
The cyclic
cyclic
Instrument
Instrument
Instrument voltammetric
voltammetric
Inc.,
Inc.,
Inc., Austin,
Austin,
Austin, study
study
TX,
TX,
TX, USA)
USA)
USA)was
was carried
carried
with
with
with an
an
an out
out
“L”
“L”
“L” by
by
type
type using
using
Pt
Pt
Pt+ CHI620B
CHI620B
electrode
electrode
electrode as
as
as electrochemical
electrochemical
the
the
the working
working
working workstation
workstation
electrode.
electrode.
electrode. A
A
A big
big
big
square
(CH
(CH
(CH platinum
Instrument
Instrument
Instrument sheet
Inc.,
Inc.,
Inc., (1.5
Austin,
Austin,
Austin, cm
TX,
TX,
TX, in length)
USA)
USA)
USA) with
with
with and
an
an
an a
“L”
“L”
“L” Ag/Ag
type
type
type Pt
Pt
Pt electrode
electrode
electrode
electrode as(0.1
as
as the
the
the M AgNO
working
working
working in acetonitrile)
electrode.
electrode.
3
electrode. A
A
A big
big
big
(CH
(CH
square
square
square Instrument
Instrument
platinum
platinum
platinum Inc.,
Inc.,
sheet
sheet
sheet Austin,
Austin,
(1.5
(1.5
(1.5 cm
cm
cm TX,
TX,
in
in
in USA)
USA)
length)
length)
length) with
with
and
and
and an
anaa “L”
“L”
Ag/Ag
Ag/Ag
aathe
Ag/Ag type
type Pt
Pt
++++ electrode electrode
electrode
electrode
electrode (0.1
(0.1
(0.1 as
Mas
M
M the
the
AgNO
AgNO
AgNO working
working
3 3 in
in
in electrode.
electrode.
acetonitrile)
acetonitrile)
acetonitrile) A
A big
big
were
were
were
square
were
square
square
square platinum
employed
platinum
platinum
platinum sheet
as
sheet
sheetthe
sheet (1.5
counter
(1.5
(1.5
(1.5 cm
cm
cm
cm in
in
in
in length)
electrode
length)
length)
length) and
and
and
and
and a Ag/Ag
reference
Ag/Ag
aaa Ag/Ag
Ag/Ag
Ag/Ag electrode
++++ electrode
++++++ electrode
one,
electrode (0.1
(0.1
(0.1
(0.1 M
M
M
M AgNO
respectively.
AgNO
AgNO
AgNO The
333 in
3
3333 in
in
in acetonitrile)
experiments
acetonitrile)
acetonitrile)
acetonitrile) were
were
were
were
were
square
square
employed platinum
platinum sheet
sheet (1.5
(1.5 cm
cm in
in length)
length) and
and a Ag/Ag electrode
electrode (0.1
(0.1 M
M AgNO
AgNO in
in acetonitrile)
acetonitrile) were
were
performed as
employed as the
the Mcounter
NaClO4electrode
counter electrode and
and the
the atreference
reference one,
one, of respectively.
respectively. The
The 33 experiments
experiments were
3 3
employed
employed
employed
employed
employed
employed
as
as
as
as
as
the
the
in 0.1
as the
the
the
theM
counter
counter
counter
counter
counter
counter
electrode
electrode
-CH
electrode
electrode
electrode
electrode
and
and
3 CN solution
and
and
and
the
the
the
the
the
and thethe
reference
reference
the scan rate
reference
reference
reference
reference
one,
one,
one,
one,
one,
one, mV·s−1 at room
respectively.
respectively.
50
respectively.
respectively.
respectively.
respectively.
The
The
The
The
The
experiments
experiments
temperature.
experiments
experiments
experiments
The temperature.
experimentsAll
were
were
All
were
were
were
wereof
employed
employed
employed
performed
performed as
as
as
in
in the
the
the
0.1
0.1 M counter
counter
counter
NaClO
NaClO electrode
electrode
electrode
444-CH
-CH 333CN CN and
and
and
solution
solution the
the at
at reference
reference
reference
the
the scan
scan + one,
one,
one,
rate
rate of
of respectively.
respectively.
respectively.
50
50 mV·s
mV·s −1
−1
−1 at
at The
The
The
room
room experiments
experiments
experiments
temperature. were
were
were
All of
of
performed
the potentials
performed
performed in
in
in 0.1
in
0.1
0.1 MM
this
M NaClO
article
NaClO
NaClO -CH
were
44-CH
4 -CH 33CN
3 CN
CN solution
referred
solution
solutionto at
the
at
at the
the
the scan
Ag/Ag
scan
scan rate
rate
rate of
electrode
of
of 50
50
50 mV·s
(0.1
mV·s
mV·s
−1
−1
M
−1
−1
−1 at
at
at room
AgNO
room
room temperature.
in
temperature.
temperature.
3temperature. All
acetonitrile).
All
All of
of
of
performed
performed
performed
the potentials in
in 0.1
in 0.1
0.1
in M
M NaClO
M NaClO
NaClO 44-CH
444-CH
-CH 33CN
333333CN
CN solution
solution
solution at
at the
at the
the scan
scan rate
rate
scan++++++ electrode
rate of
of 50
of 50 mV·s
50 mV·s
mV·s
−1 at
−1
−1 at
−1
−1 room
at room
room temperature.
temperature. All
All of
All of
of
in this article
article444were referred to
to the Ag/Ag (0.1
(0.1 MM AgNO
−1 333 in acetonitrile).
the
the
the potentials
potentials
potentials in
in this
this
this article
article were
were
were referred
referred
referred to
to the
the
the Ag/Ag
Ag/Ag
Ag/Ag electrode
electrode
electrode (0.1
(0.1 M
M AgNO
AgNO
AgNO in
in
in
3333 in
acetonitrile).
acetonitrile).
acetonitrile).
the
the potentials
potentials in
in this
this article
article were
were referred
referred to
to the
the Ag/Ag
Ag/Ag ++++ electrode
electrode (0.1
(0.1 M
M AgNO
AgNO in acetonitrile).
acetonitrile).
the
the potentials
potentials inin this
this article
article were
were referred
referred to
to the
the Ag/Ag
Ag/Ag + electrode
++ electrode
the potentials in this article were referred to the Ag/Ag electrode (0.1 M AgNO333 in acetonitrile).
+ (0.1
(0.1 M
M AgNO
AgNO 3
33 in
3 in acetonitrile).
acetonitrile).
3.3.
3.3.
3.3.
3.3.
3.3. In
In
In
In
In Situ
Situ
Situ
Situ
Situ FTIR
FTIR
FTIR
FTIR
FTIR Spectroscopic
Spectroscopic
Spectroscopic
Spectroscopic
Spectroscopic Study
Study
Study
Study
Study
3.3.
3.3. In
In
3.3. In
3.3. Situ
Situ
In Situ FTIR
FTIR
Situ FTIR Spectroscopic
Spectroscopic
FTIR Spectroscopic
Spectroscopic Study Study
Study
Study
3.3.
3.3. In
In Situ
Situ FTIR
FTIR Spectroscopic
Spectroscopic Study
Study
Molecules 2019, 24, 100 9 of 14
3.3. In Situ FTIR Spectroscopic Study

The in situ infrared spectroscopy experiments were performed on 263 A Potentiostat/Galvanostat
and Nicolet 670 FTIR spectrometer (Thermo Fisher Nicolet, Waltham, MA, USA), equipped with a
refrigerated MCT-A detector and KBr beam splitter. The disk electrode of Pt (0.6 cm in diameter) was
used as the working electrode. A three-electrode spectro-electrochemical cell equipped with CaF2
window as the IR window was used for collecting the interferograms. Each single-beam spectrum was
collected and two hundred interferograms were coadded at a spectral resolution of 8 cm−1 . The sample
potentials varied in a stepwise fashion from 0 to 800 mV and the reference potential was fixed at
−100 mV [70–72].
3.4. Preparation Electrolysis Experiments

The preparative electrolysis experiments were conducted with in an undivided cell containing
0.1 M NaClO4 -CH3 CN solution (15 mL), alcohol substrate (1.0 mmol), ABNO (0.1 mmol),
and 2,6-lutidine (1.0 mmol) at a constant current of 10.0 mA with moderate magnetic stirring for
8.5 h in the atmosphere. Two square platinum sheets were employed as the anode and cathode,
respectively. The electrolytic reaction was monitored by gas chromatography (GC) on a GC-2010
system (Shimadzu, Kyoto, Japan) equipped with a SH-Rtx-Was polar column and a flame ionization
detector (FID). Both the injector and detector were maintained at 220 ◦ C, the carrier gas is nitrogen,
and the flow rate is 1.2 mL/min. The initial oven temperature of 100 ◦ C was held for 2 min and
then ramped up at 15 ◦ C per min to 220 ◦ C. This final temperature was held for 8 min. After the
reaction was finished, the resulting mixture was concentrated in a rotary evaporator (Heidolph,
Schwabach, Germany) and purified by column chromatography on silica gel using petroleum and
ethyl acetate 15:1) as eluent to afford the products. The products were confirmed by GC-MS, 1 H-NMR,
and 13 C-NMR. NMR spectroscopy was carried out on a Bruker Avance III spectrometer (Bruker,
Fällanden, Switzerland). The GC-MS analysis was measured on Thermo Trace ISQ instrument (Thermo
Fisher Nicolet, Waltham, MA, USA) with TG 5MS capillary column.
Acetophenone (colorless oil, yield 80%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.94–7.92 (m, 2H), 7.55–7.51
(m,1H), 7.44–7.41 (m, 2H), 2.57 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 198.0, 136.9, 132.9, 128.4, 128.1,
26.4. GC-MS (EI): m/z: 120.14 [M+ ].
1-(4-Chlorophenyl)ethanone (colorless oil, yield 94%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.89–7.87 (m, 2H),
7.42–7.41 (m, 2H), 2.57 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 196.7, 139.5, 135.4, 129.7, 128.8, 26.5.
GC-MS (EI): m/z: 154.03 [M+ ].
7.83–7.81 (m, 1H), 7.54–7.51 (m, 1H), 7.42–7.39 (m, 1H), 2.59 (s, 3H). 13 C-NMR (125 MHz, CDCl3 )
δ 196.6, 138.6, 134.9, 133.0, 129.9, 128.3, 126.4, 26.6. GC-MS (EI): m/z: 154.17 [M+ ].
7.43–7.37 (m, 2H), 7.34–7.31 (m, 1H), 2.65 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 200.4, 139.1, 132.0,
131.3, 130.6, 129.4, 126.9, 30.7. GC-MS (EI): m/z: 154.11 [M+ ].
1-(4-Fluorophenyl)ethanone (colorless oil, yield 85%): 1 H-NMR (500 MHz, CDCl3 ) δ 8.00–7.96 (m, 2H),
7.15–7.10 (m, 2H), 2.58 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 196.4, 165.8 (d, J = 254.8 Hz), 133.6 (d,
J = 2.4 Hz), 130.9 (d, J = 9.3 Hz), 115.6 (d, J = 21.9 Hz), 26.5. GC-MS (EI): m/z: 138.06 [M+ ].
1-(4-Bromophenyl)ethanone (white solid, yield 92%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.83–7.80 (m, 2H),
7.61–7.59 (m, 2H), 2.58 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 196.9, 135.8, 131.9, 129.8, 128.3, 26.5.
GC-MS (EI): m/z: 197.98, 200.04 [M+ ].
1-(4-Methylphenyl)ethanone (colorless oil, yield 92%): 1 H-NMR (500 MHz, CDCl3) δ 7.86–7.84(m, 2H),
7.28–7.24 (m, 2H), 2.56 (s, 3H), 2.40 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 197.7, 143.8, 134.7, 129.2,
128.4, 26.4, 21.5. GC-MS (EI): m/z: 134.15 [M+ ].
Molecules 2019, 24, 100 10 of 14
1-(3-Methylphenyl)ethanone (colorless oil, yield 93%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.77–7.74(m, 2H),
128.7, 128.4, 125.5, 26.6, 21.2. GC-MS (EI): m/z: 134.10 [M+ ].
1-(2-Methylphenyl)ethanone (colorless oil, yield 95%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.71–7.69(m, 1H),
7.40–7.36 (m, 1H), 7.28–7.24 (m, 2H), 2.58 (s, 3H), 2.54 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 201.7,
138.3, 137.6, 132.0, 131.5, 129.3, 125.6, 29.5, 21.5. GC-MS (EI): m/z: 134.09 [M+ ].
1-(4-Methoxyphenyl)ethanone (colorless oil, yield 89%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.94–7.91 (m, 2H),
113.6, 55.4, 26.3. GC-MS (EI): m/z: 150.14 [M+ ].
1-(4-Nitrophenyl)ethanone (yellow crystal powder, yield 90%): 1 H-NMR (500 MHz, CDCl3 ) δ 8.28–8.27
(m, 2H), δ 8.11–80.08 (m, 2H), δ 2.66 (s, 3H); 13 C-NMR (125 MHz, CDCl3 ) δ 196.3, 150.3, 141.3, 129.2,
123.7, 26.9. GC-MS (EI): m/z: 165.05 [M+ ].
Propiophenone (colorless oil, yield 88%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.99–7.97 (m, 2H), 7.58–7.55(m,
1H), 7.49–7.45 (m, 2H), 3.04–3.00 (m, 2H), 1.24 (t, J = 7.2 Hz, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 200.9,
137.0, 132.9, 128.6, 128.0, 31.8, 8.3. GC-MS (EI): m/z: 134.16 [M+ ].
Phenylbutanone (colorless oil, yield 92%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.95–7.93 (m, 2H), 7.54–7.50(m,
1H), 7.44–7.41 (m, 2H), 2.94–2.91 (m, 2H), 1.79–1.72 (m, 2H), 0.99 (t, J = 7.4 Hz, 3H). 13 C-NMR (125 MHz,
CDCl3 ) δ 200.2, 137.0, 132.7, 128.4, 127.9, 40.3, 17.6, 13.7. GC-MS (EI): m/z: 148.17 [M+ ].
2-Methylpropiophenone (colorless oil, yield 89%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.98–7.96 (m, 2H),
7.58–7.54 (m, 1H), 7.49–7.46 (m, 2H), 3.60–3.54 (m, 1H), 1.23 (d, J = 6.9 Hz, 6H). 13 C-NMR (125 MHz,
CDCl3 ) δ 204.5, 136.3, 132.8, 128.6, 128.3, 35.3, 19.1. GC-MS (EI): m/z: 148.18 [M+ ].
1-(4-Methylphenyl)propan-2-one (colorless oil, yield 93%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.87 (d,
J = 8.2 Hz, 2H), 7.28–7.25 (m, 2H), 3.00–2.96 (m, 2H), 2.41 (s, 3H), 1.22 (t, J = 7.3 Hz, 3H). 13 C-NMR
(125 MHz, CDCl3 ) δ 200.5, 143.5, 134.4, 129.2, 128.1, 31.6, 21.5, 8.3. GC-MS (EI): m/z: 148.16 [M+ ].
1-Tetralone (white solid, yield 90%): 1 H-NMR (500 MHz, CDCl3 ) δ 8.04–8.03 (m, 1H), 7.48–7.45 (m, 1H),
7.30 (t, J = 7.5 Hz, 1H), 7.25 (d, J = 7.6 Hz, 1H), 2.97 (t, J = 6.1 Hz, 2H), 2.67–2.64 (m, 2H), 2.17–2.12 (m,
2H). 13 C-NMR (125 MHz, CDCl3 ) δ 198.3, 144.4, 133.3, 132.6, 128.7, 127.1, 126.6, 39.1, 29.7, 23.2. GC-MS
(EI): m/z: 146.17 [M+ ].
Benzophenone (white solid, yield 95%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.82 (d, J = 7.4 Hz, 4H), 7.60 (t,
J = 7.4 Hz, 2H), 7.49 (t, J = 7.6 Hz, 4H). 13 C-NMR (125 MHz, CDCl3 ) δ 196.7, 137.6, 132.4, 130.0, 128.2.
GC-MS (EI): m/z: 182.00 [M+ ].
1-(Thiophen-2-yl)ethanone (yellow oil, yield 80%): 1 H-NMR (500 MHz, CDCl3 ) δ 7.69–7.68 (m, 1H),
7.63–7.62 (m, 1H), 7.12–7.10 (m, 1H), 2.55 (s, 3H). 13 C-NMR (125 MHz, CDCl3 ) δ 190.6, 144.5, 133.7,
132.4, 128.0, 26.8. GC-MS (EI): m/z: 125.97 [M+ ].
Cycloheptanone (colorless oil, yield 57%): 1 H-NMR (500 MHz, CDCl3 ) δ 2.49–2.47 (m, 4H), 1.70–1.64 (m,
8H); 13 C-NMR (125 MHz, CDCl3 ) δ 215.3, 43.8, 30.4, 24.3. GC-MS (EI): m/z: 112.11 [M+ ].
4. Conclusions
In conclusion, the electrochemical behaviour of the nitroxyl radical ABNO for the oxidation
of 1-phenylethanol in acetonitrile solution have been studied. The electrochemical measurements
revealed that ABNO showed reversible redox behavior and it had lower potential than TEMPO.
The oxoammonium ion (ABNO+ ) was generated by single-electron oxidation. According to the in situ
FTIR spectra results, the base 2,6-lutidine received a hydrogen proton to become 2,6-lutidinium cation,
which was a crucial process during the synthesis of acetophenone from 1-phenylethanol. Under mild
Molecules 2019, 24, 100 11 of 14
reaction conditions, a variety of substrates, including aromatic, heteroaromatic, and aliphatic secondary
alcohols could be converted to the corresponding ketones with good to excellent isolated yields.
Author Contributions: Funding acquisition, M.L.; Investigation, P.N. and X.L.; Supervision, Z.S. and M.L.;
Writing–original draft, P.N.; Writing–review & editing, Z.S. and M.L.
Funding: This research was funded by the National Natural Science Foundations of China (21773211 and
21776260), and the Natural Science Foundation of Zhejiang Province (LY17B060007).
Conflicts of Interest: The authors declare no conflict of interest.
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Sample Availability: Not available.
© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

01 Electrochemical - Performance - of - ABNO - For - Oxidation

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01 Electrochemical - Performance - of - ABNO - For - Oxidation

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molecules

Keywords: electrochemical; ABNO; secondary alcohols; in situ FTIR; ketones

Molecules 2019, 24, 100; doi:10.3390/molecules24010100 www.mdpi.com/journal/molecules

TEMPO/TBN/O2, TEMPO/2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)/TBN/O2, etc [30–32].

2. Results and Discussion

Molecules 2019, 24, 100 4 of 14

0.3 50 mV.s-1 0.28

Figure 3. (A) Cyclic voltammograms

2.2. In situ FTIR Spectroscopic Analysis

3.3. In Situ FTIR Spectroscopic Study

3.4. Preparation Electrolysis Experiments

Sample Availability: Not available.

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