Catalytic Oxidation of Alcohol to Carboxylic Acid with a Hydrophobic Cobalt Catalyst in Hydrocarbon Solvent

Article abstract of DOI:10.1002/asia.201700717

A hydrophobic cobalt catalyst was synthesized and proved to be effective in alcohol oxidation under the assistance of hydrocarbon solvent with oxygen as the terminal oxidant. A series of catalysts with different water contact angles was applied to investigate the hydrophobic effect. Further insight into the reaction process was gained by reaction kinetics, isotopic effect, etc. It showed that the hydrocarbon solvent participated in the alcohol oxidation, and with the aid of the in situ generated free radicals, the α-C?H bond was smoothly activated and the alcohol was converted to carbonyl compounds. The hydrophobic effect promoted the alcohol oxidation by affecting the solvent oxidation.

Full text of DOI:10.1002/asia.201700717

CHEMISTRY
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Accepted Article
Title: Catalytic oxidation of alcohol to carboxylic acid with hydrophobic
cobalt catalyst in hydrocarbon solvent
Authors: Song Shi, Meng Liu, Li Zhao, Min Wang, Chen Chen, Jin
Gao, and Jie Xu
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Chemistry - An Asian Journal
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Catalytic oxidation of alcohol to carboxylic acid with hydrophobic
cobalt catalyst in hydrocarbon solvent
a
a,b
a,b
a
*a
a
*a
Song Shi, Meng Liu, Li Zhao, Min Wang, Chen Chen, Jin Gao and Jie Xu
Dedication ((optional))
Abstract:
A
hydrophobic cobalt catalyst was synthesized and
pyrolysis of nitrogen-ligated cobalt(II) acetate supported on
commercial carbon could convert alcohol to ester in excellent
proved to be effective in the alcohol oxidation under the assistance
of hydrocarbon solvent with oxygen as the terminal oxidant. A series
of catalyst with different water contact angles was applied to
investigate the hydrophobic effect. Further insight in to the reaction
process was researched by reaction kinetics, isotopic effect, etc. It
showed that the hydrocarbon solvent participated in the alcohol
oxidation, and with the aid of the in-situ generated free radicals, the
α-C-H bond was smoothly activated and the alcohol was converted
to carbonyl compounds. The hydrophobic effect promoted the
alcohol oxidation through affecting the solvent oxidation.
[
13]
yield.
In this process, however, extra base is necessary. In
terms of economy and environmental friendliness, it is highly
desirable to employ catalyst with earth-abundant elements under
base-free conditions using molecular oxygen (ideally air) as the
terminal oxidant.
Hydrophobic effect has been proved to be effective in many
catalytic fields. The catalytic activity, product selectivity, and
catalyst stability are strongly related to the catalyst
[
14]
hydrophobicity. For example, hydrophobic modification of the
catalyst could enhance the selectivity of 5-hydroxymethylfurfural
[
15]
in the fructose dehydration process.
Our group proved the
hydrophobic effect could enhance the activity of the catalyst
Introduction
[16]
towards the hydrocarbon oxidation.
Nevertheless, to gain
more insight into the hydrophobic towards the catalyst field is
still an important work.
Selective oxidation of alcohol into carbonyl compound is of great
[
1]
importance at both laboratorial and industrial levels. In recent
years, the oxidation of primary alcohol has been frequently
In addition, the solvent in the present work was another
important factor. The solvent effect is one of the fundamental
phenomena in general chemistry, kinetics and catalysis. The
solvent may play a passive or an active role, as it may be
involved in the elementary reaction steps. In the present work,
the hydrocarbon solvent was proved to be participated in the
reaction, and with the aid of the in-situ generated free radicals,
the α-C-H bond was smoothly activated and the alcohol was
converted to carbonyl compounds. Herein, we firstly reported the
hydrophobic cobalt catalyst for the alcohol oxidation under the
assistance of hydrocarbon solvent. Hydrophobic effect was
proved to be effective in the catalytic process. This process
provided a new route for the alcohol oxidation.
[
2]
reported. Several groups tried different catalysts and reactors
[
3]
in selective oxidation of alcohols to aldehydes. Deep-oxidation
product of primary alcohol especially for the non-activated
aliphatic alcohol to carboxylic acid or ester is also an important
issue, which showed wide application in detergent, paint, and
[4]
cosmetic, etc. So far, most of the reported catalysts for the
synthesis of carboxylic acid from alcohol under mild conditions
are based on noble metals such as palladium, gold, and
[
5]
platinum, and bases are generally needed. Recently, through
modifying the support, we achieved the oxidation of primary
[
6]
aliphatic alcohols to acid in the absence of base. However,
noble metal platinum was still necessary. The limited availability
and high price of noble metals constrict their application in large-
scale industrial production. Catalysts that contain earth-
Results and Discussion
[
7]
[8]
[9]
[10]
abundant element such as Co, Fe, Mn, Cu
et al are
attractive both from environmental and economic consideration.
However, when these non-noble metals were used as the
heterogeneous catalysts, the efficiencies are generally lower
than the noble catalysts no matter in the activity or substrate
Catalytic results with hydrophobic catalyst
Utilizing a reverse-phase micro-emulsion method, a hydrophobic
silica-based cobalt-containing nanoparticle (Co-Pr-15) was
prepared with cobalt ions distributed in the matrix of silica and
propyl groups on its surface. The catalyst shows the morphology
of sphere with fluffy surfaces (Figure S1, S2). With organic
silane introduced while hydrolysis, the catalyst owed organic
groups on the surface demonstrated by the asymmetric and
symmetric stretching vibration absorption of the saturated C–H
[
11]
scope.
And a large excess of base additives or explosive
oxidizing agents (e.g., peroxy acids, and metal oxidants) are
[
12]
generally required to promote the activity and selectivity.
Examples reported by Matthias Beller’s group showed that the
[
[
a]
b]
State Key Laboratory of Catalysis, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, Dalian National Laboratory
for Clean Energy, Dalian 116023,P. R. China. E-mail:
xujie@dicp.ac.cn
University of Chinese Academy of Sciences, Beijing 100049, P. R.
China
-1
bond emerged at around 2930 cm in the spectrum of FT-IR
Figure S3) and showed hydrophobic character with water
(
o
contact angles (WCA) of 127 . The cobalt content determined by
ICP is only 2.27%. The three absorption peaks (525, 583, and
6
45 nm) in the UV-Vis were unambiguously assigned to the
Co(II) in tetrahedral environment. And another broad
absorption was centered at 356 nm, assigned to a Co(III)
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
a
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species (Figure S4). P-methylbenzyl alcohol was selected as the
model molecule to test the catalyst. During the catalytic
application, with ethylbenzene as the solvent, p-methylbenzyl
alcohol was nearly completely converted to p-methylbenzoic
acid (Table 1, Entry 1). As comparison, with commercial
hydrophilic catalysts Co
3 4 2 3
O and Co O , the alcohol conversion is
only about 60% conversion (Table S1).
These control experiments clearly showed the hydrophobic
catalyst gained the advantage in this catalytic process.
Correlating ln(Ct/Co) (C stands for concentration) against
reaction time (s) indicated a linear relationship and a first order
reaction with respect to p-methylbenzyl alcohol (Figure S5). The
apparent activation energy, Ea, determined from the Arrhenius
plot (Fig. S6,S7), is 69.2 kJ/mol. In order to show hydrophobic
effect, a series of catalysts with different amount of organic
group functionalized were used as the catalysts. C-H bond peak
appeared in the FT-IR spectra and intensity increased with the
increase in the ratio of n-propyltrimethoxysilane (PTMS):
tetraethyl orthosilicate (TEOS) (Figure S3). The hydrophobicity
increased with the increase of propyl group content, as
evidenced by the WCA. As expected, a positive correlation was
observed in Figure 1, with the increase of WCA, the reaction
rate of alcohols increased. This further confirmed the surface
hydrophobicity is favourable for oxidation, which will be further
discussed below.
Various substrates were tested in the oxidation. As seen in
Table 1, aromatic primary alcohols were converted to acids with
9
6-99% conversion and 89-99% selectivity. Aliphatic primary
alcohols were also converted with moderate conversion (54-
2%) and high selectivity to acid (80-85%). Secondary alcohols
were converted to the corresponding ketones (Table 1, entry
,10). These results illustrated that the reported method is
7
5
effective for the oxidation of a wide range of alcohols.
Figure 2. i) Reaction rates of different alcohols with ethylbenzene solvent ii)
Reaction rates of p-methylbenzyl alcohol with different hydrocarbon solvents
Reaction conditions, 1 mmol substrate, 50 mg catalyst, 10 mL solvent, 1.0
o
MPa O
2
, 120 C,
Various alcohols with different α-C-H bond dissociative energy
(
2
BDE) were also studied with ethylbenzene as the solvent (Fig.
[
17]
i, S8).
The reaction rates were plotted against their α-C-H
BDE in Fig. 2i. With ethylbenzene as the solvent, the reaction
rate decreased with the increase of α-C-H BDE of the alcohols.
This suggested the alcohol oxidation process is much related
with the α-C-H bond activation. A phenomenon should be
noticed that the C-H BDE in ethylbenzene is 87 Kcal/mol, while
for some alcohols, such as cyclohexanol (92.8 Kcal/mol), the α-
C-H BDE exceeds this value, which suggested this process
could not only activate the C-H bond weaker than the
Figure 1. Reaction rates of p-methylbenzyl alcohol with different hydrophobic
o
catalysts, Reaction conditions, 10 mL solvent, 1 mmol substrate, 120 C, 50
mg catalyst, 1.0 MPa O
2
The effect of the C-H BDE of alcohols
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hydrocarbon solvent but also active those alcohols whose C-H
bond stronger than the hydrocarbon solvent. It is a new route to
activate the C-H bond through first activating a relative weak C-
H bond to generate the free radicals and then activate a relative
strong C-H bond.
Table 1. Aerobic oxidation of different alcohols.
Conv.
%)
Select.
(%)
Entry
Reactants
Products
(
1
2
3
4
5
6
>
>
>
>
>
>
99
99
99
99
99
99
92
>99
96
>99
>99
99
89
-
Figure 3. Alcohol oxidation by different solvent. a,with tert-Butyl hydroperoxide
(TBHP) added
not be converted. When the radical initiator was added in
toluene solvent, p-methylbenzyl alcohol was converted to p-
methylbenzoic acid with 98% conversion (Figure 3). In addition,
the product distribution varied with the kind of hydrocarbon, p-
a
7
9
7
b
8
methylbenzoicacid
was
the
only
product
in
Trace
Trace
tetrahydronaphthalene and p-diethylbenzene solvent. While 36%
and 19% of p-tolualdehyde exist in tetrahydronaphthalene and
o-xylene solvent, respectively. This indicated the reactivity of the
hydrocarbon free radical affects the alcohol oxidation process.
b
9
-
10
7
2
96
82
80
85
11
12
13
43
48
54
The effect of the C-H BDE of hydrocarbon solvent
A series of hydrocarbon with different C-H bond energies were
[18]
o
applied as the solvents (Fig. 2ii, S9).
A negative correlation
Reaction conditions, 10 mL solvent, 1 mmol substrate, 120 C, 4 h, Catalyst:
tendency between the alcohol reaction rate and the C-H BDE of
the hydrocarbon solvents was observed. This tendency showed
that the oxidation rate of the hydrocarbon could affect the
alcohol oxidation rate, meaning these two steps are highly
related. Due to the difference in the C-H BDE of the solvent, the
types and the generation rates of the free radicals are different
for a certain catalyst. The final alcohol oxidation is related with
the types and the generation rates of the free radicals. For the
hydrocarbon solvents with high C-H BDE, though the free
radicals generated may gain higher ability to activate alcohols,
itself is also difficult to be activated thus resulting in a low
generation rate. The generation rate played the leading role in
the gambling resulting in the negative correlation tendency in
Figure 2ii.
5
2
0 mg Co-Pr-15, 1.0 MPa O , a, 3 mmol substrate, b, butylated
hydroxytoluene (BHT) added.
The effect of solvent
Similar results were obtained with other hydrocarbon as the
solvent such as tetralin, o-xylene and p-diethylbenzene (Figure
3
). When non-hydrocarbon solvent solvents including methanol,
acetonitrile and dichloromethane were used, the alcohol was not
converted. This indicated hydrocarbon solvent played an
important role in this process. Moreover, the hydrocarbon
solvents themself were oxidized into the corresponding ketones
and alcohols to some extent. The non-hydrocarbon solvent
stayed stable during oxidation process. In addition, when the
inert hydrocarbon such as toluene or cyclohexane was
employed in the reaction, the p-methylbenzyl alcohol could not
be oxidized under the same conditions (Figure 3). The above
results indicated that solvent oxidation affected the alcohol
oxidation process. It was well acknowledged that a free radical
mechanism usually involved for the selective oxidation of
hydrocarbon, indicating that the formation of hydrocarbon free
radical is a key factor for the alcohol oxidation. The C-H bond in
toluene and cyclohexane are too inert to be activated to carbon
radicals under the above conditions, and thus the alcohol could
The effect of peroxide
The peroxide formed in-situ during the hydrocarbon oxidation
may oxidize the alcohol. An experiment was performed to
investigate whether the alcohol was oxidized by the in-situ
formed peroxide (Figure 4). Without the catalyst, 1-phenyl-
ethylhydroperoxide (PEHP) is the major product for self-
oxidation of ethylbenzene. After ethylbenzene mainly converted
to PEHP, the catalyst and alcohol were added into the reaction
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resulting Hammett parameter ρ was only -0.07, suggesting that
the reaction was insensitive to substituent effect, which support
the free radicals process. Hot filtration of catalyst slowed down
the reaction rate but not completely stop the reaction (Figure
S10). The results indicated that the generation of radicals is
majorly caused by the catalyst and the slow oxidation of alcohols
after catalyst filtration was due to the already generated free
radicals in the solvent.
To study the effect of the free radical on the oxidation of alcohol,
reaction rates of alcohol and aldehyde as the reactants were
measured individually (Figure 6). The rate of aldehyde is 3.4
times faster than that of the alcohol under the same conditions,
meaning the rate-determining step is the oxidation of alcohol to
aldehyde. Reaction kinetic isotope effect (KIE) was investigated
to determine the bond dissociation in the rate-determining step
of alcohol oxidation (Table 2). The
CH PhCH OD and p-CH PhCD OD are 1.07 and 6.50,
respectively. The large value of k /k for p-CH PhCD OD shows
first KIE, meaning the α-C-H bond cleavage is the rate-
determining step. All these evidences proved the reaction
undergoes a free radicals process and the activation of α-C-H
bond of alcohol is the key step.
k
H
/k
D
value for p-
3
2
3
2
Figure 4. Alcohol oxidation by the peroxide Reaction conditions：10 mL
H
D
3
2
o
ethylbenzene，120 C，1.0 MPa O
2
，at the vertical line, 1 mmol substrate
and 50 mg catalyst was added in and O
2
was replaced by N
2
medium, and O
2
was replaced with N
2
, to insure PEHP as the
sole potential oxidant. The amount of PEHP decreased
immediately after the catalyst added. However, the alcohol was
not converted even PEHP was completely decomposed. This
result demonstrated that the alcohol is not oxidized by the in-situ
formed peroxide.
Table 2. Reaction rates and kinetic isotopic effects (KIEs) for aerobic
oxidation of p-methylbenzyl alcohol.
-1
Entry
1
Reactants
Reaction rates(S )
KIE(k
-
H D
/k )
-
4
6.18×10
5.73×10
-4
2
3
1.07
6.50
-4
0.95×10
Reaction conditions: 10 mL solvent, 1 mmol substrate, 120 °C, 50 mg
catalyst, 1.0 MPa O
2
Figure 5. Hammett plot for the oxidation of substituted benzyl alcohols
catalyzed by Co-Pr-15.
The investigation of reaction mechanism
Figure 6. Reaction rate of alcohol and aldehyde oxidation with Co-Pr-15.
A serious of experiments were performed to investigate the
mechanism reaction process. With BHT added into the reaction
medium to inhibit the free radical process (Table 1, Entry 8,9),
the oxidation of ethylbenzene, p-methylbenzyl alcohol and p-
tolualdehyde were all inhibited, implying both the alcohol and
aldehyde oxidation rely on the free radicals. In addition, a linear
relationship between lg(kX/kH) and Brown–Okamoto constant
σ+ (Figure 5) was established for the oxidation of substituted
The proposed mechanism
In this catalytic process, all these experiment results showed the
alcohol was activated by the free radicals. Based on the
experiment results and the references, a proposed mechanism
similar with the NHPI system was illustrated in Scheme 1. In
the presence of the catalyst, the hydrocarbon-based free
radicals were generated from the oxidation of hydrocarbon
[
19]
2
benzyl alcohols (X = p-Cl, p-NO , p-Me and p-OMe). The
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solvent. These radicals could react with alcohols and abstract
the α-C-H, leading to the formation of alcohol radicals. These
alcohol free radicals could react with oxygen and thus further
converted to the aldehyde, and the aldehyde was finally
converted to the acid smoothly. According to this proposed
mechanism, the reason of hydrophobic effect in promoting the
alcohol oxidation (vide supra) could be explained. In this
catalytic process, alcohol oxidation rate is highly related with the
generation rate of hydrocarbon free radicals. Under the same
conditions, the difference in the alcohol oxidation rate could be
only be the result of different generation rates of free radicals,
meaning the catalysts could influence the alcohol oxidation rate
through the control of free radicals generation rate. Previously, a
number of literatures reported the oxidation rate of hydrocarbon
increased with the hydrophobicity of catalysts, which suggested
a higher generation rate of free radicals. And in this catalytic
process, the hydrophobic catalyst owned higher oxidation rate of
the hydrocarbon than the hydrophilic one, which finally result in
a higher oxidation rate of the alcohols.
temperature, while agitation was ensured by an external magnetic stirrer.
Upon heating to the reaction temperature, the reactor was charged with
2 2
1.0 MPa of O and O was fed continuously to maintain constant
pressure. The reaction was carried out at 393 K for 4 h. Reaction
products were identified by Agilent 6890N GC/5973 MS detector and
quantitated with an internal standard (1,4-dichlorobenzene) method by
Agilent 6890D GC equipped with Innovex capillary column (50 m × 0.32
mm × 0.4 μm). The products were quantified via a double injection:
triphenylphosphine (1 M in THF) was added to one of the samples to
reduce the peroxide product to the alcohol. For the kinetic study, Liquid
samples (∼20 ul) were extracted periodically using the syringe. Typically,
8-15 points were used.
Synthesis of the catalyst:
First, two kinds of solution (solution A, B) were obtained. Solution A was
composed of 15 g of Np-7, 31.5 g of cyclohexane, and 8 g of n-butyl
alcohol; solution B was the metal ammonia complex water solution (0.13
2 2 2 3 2
g of Co(OAc) •4H O, 5.5 g of H O, and 2 g of NH •H O (21%));
Microemulsion was obtained with the blending of solutions A and B. To
this microemulsion, 2 g TEOS was added slowly under stirring. After 1
hour, the mixture of TEOS and PTMS was added and the ratio of TEOS
and PTMS was 5.6:1. The stirring was continued for 24 h. It was then
centrifuged, washed with hot ethanol to remove the surfactant and dried
at 353 K for 12 h. The catalyst was named as Co-Pr-15. The other
catalysts were synthesized with different ratio of TEOS and PTMS. The
catalysts were named as Co-Pr-5, Co-Pr-25, Co-Pr-35 with the ratio
19,3,1.85. The non-organic group containing Co-Pr-0 was synthesized
without PTMS.
3 2
Synthesis of p-CH PhCH OD
A 60% suspension of sodium hydride in mineral oil was washed with dry
pentane under an argon atmosphere, and the residual solvent was
removed under vacuum. Undiluted p-methylbenzyl alcohol was added to
the reaction flask slowly, and the resulting suspension was stirred for 1 h
Scheme 1. Propose mechanism catalyzed by the cobalt catalyst under the
assistance of hydrocarbon solvent.
at room temperature before being quenched with 2 equiv. of D O (99.9%
2
atom %D). The deuterated alcohol was extracted with dry ether, and the
organic layer was dried ver sodium sulfate before removing the solvent
under vacuum with a mechanical pump to afford the deuterated products.
Conclusions
3 2
Synthesis of p-CH PhCD OD
In summary, we have reported a highly active hydrophobic
cobalt catalyst in the alcohol oxidation under the assistance of
hydrocarbon solvent with oxygen as the terminal oxidant. In this
process, the hydrocarbon solvent not only played the role of the
reaction medium, but also supplied free radicals to active the α-
C-H bond of the alcohols. The hydrophobicity of the catalyst
favours the generation of hydrocarbon free radicals, thus
enhancing the oxidation rate of alcohols. The present work
provided a new strategy for the alcohol oxidation, which can
guide designing alcohol oxidation system.
To a stirred suspension of LiAlD
ºC was added a solution of methyl benzoate (3.00 g, 22 mmol) in THF
20 mL). The reaction was stirred at room temperature and was
4
(0.50 g, 12 mmol) in THF (40 mL) at
0
(
monitored by GC/MS until consumption of the benzoate. The resulting
solution was quenched at 0 ºC with D2O and was extracted with ethyl
acetate (3 x 20 mL). The combined organic layers were dried over
anhydrous sodium sulfate, filtered and concentrated under reduced
pressure.
Characterizations
Fourier transform infrared (FT-IR) spectra were collected between 4000
and 400 cm on a Bruker Tensor 27 spectrometer in KBr media. Water
Experimental Section
-1
contact angles were performed on contact angle measuring system JC
Catalytic oxidation of alcohol:
2000 C1. The nuclear magnetic resonance spectra were performed on a
Bruker DRX-400 spectrometer. ICP was measured on PerkinElmer ICP-
OES 7300DV. TEM images were performed on HITACHI HT7700.SEM
images were collected on Tecnai Quanta 200F. UV-Vis were collected on
SHIMADZU UV-2600.
Catalytic reactions were performed in a 50 mL of autoclave reactor with a
teflon insert inside. Typically, 10 mL hydrocarbon was added as the
solvent, 1 mmol alcohol and 50 mg of catalyst were placed in the reactor.
Then, after being sealed, the reactor was heated to the reaction
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Acknowledgements
This work was supported by National Natural Science
Foundation of China (Grant no. 21233008 and 21603218), the
Strategic Priority Research Program of Chinese Academy of
Sciences (XDB17020300).
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Chemistry - An Asian Journal
10.1002/asia.201700717
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An efficient method of alcohol
oxidation was developed through the
activation of the α-C-H bond by the in-
situ generated free radicals of
hydrocarbon oxidation.
Song Shi, Meng Liu, Li Zhao, Min Wang,
Chen Chen*, Jin Gao and Jie Xu*
Page No. – Page No.
Catalytic oxidation of alcohol to
carboxylic acid with hydrophobic
cobalt catalyst in hydrocarbon
solvent
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