A Simple and Effective Method for Catalytic Oxidation of Alcohols Using the Oxone/Bu4NHSO4 Oxidation System

Article abstract of DOI:10.1134/S1070428020030240

Abstract: A simple and efficient procedure is reported for the oxidation of alcohols tocarbonyl compounds with Oxone (potassium peroxymonosulfate) in the presence oftetrabutylammonium hydrogen sulfate as catalyst with excellent conversion andhigh selectivity using chloroform as solvent at room temperature. The efficiencyof several phase-transfer catalysts in the oxidation of benzyl alcohols andbenzydrol was studied. The proposed catalytic system was also evaluated in theoxidation of alcohols in water at room temperature.

Full text of DOI:10.1134/S1070428020030240

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 3, pp. 521–523. © Pleiades Publishing, Ltd., 2020.
A Simple and Effective Method for Catalytic Oxidation
of Alcohols Using the Oxone/Bu NHSO Oxidation System
4
4
a,b,
a,b
a,b
a,b
a,b
a,b
Y. X. Yang *, X. Q. An , M. Kang , W. Zeng , Z. W. Yang , and H. C. Ma
a
Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education,
Northwest Normal University, Lanzhou, 730070 China
b
Key Laboratory of Eco-environmental Polymer Materials of Gansu Province & College of Chemistry
and Chemical Engineering, Northwest Normal University, Lanzhou, 730070 China
*
e-mail: yangyaoxia2007@126.com
Received November 25, 2019; revised December 16, 2019; accepted December 18, 2019
Abstract—A simple and efficient procedure is reported for the oxidation of alcohols to carbonyl compounds
with Oxone (potassium peroxymonosulfate) in the presence of tetrabutylammonium hydrogen sulfate as catalyst
with excellent conversion and high selectivity using chloroform as solvent at room temperature. The efficiency
of several phase-transfer catalysts in the oxidation of benzyl alcohols and benzydrol was studied. The proposed
catalytic system was also evaluated in the oxidation of alcohols in water at room temperature.
Keywords: alcohols, oxidation, aldehydes, ketones, tetrabutylammonium hydrogen sulfate
DOI: 10.1134/S1070428020030240
Oxone is a white crystalline solid containing
potassium peroxymonosulfate (KHSO ·KHSO ·
transfer catalysts (TBAHS, TPAHS, TEAHS, TMAHS,
TBAC, and TBAB) were also examined to evaluate
their performance in this oxidation reaction. Further-
more, the catalytic oxidation procedure was investigat-
ed using water as solvent.
5
4
K SO ) as oxidizing species. It is a commercially
2
4
available oxidant that easily oxidizes many functional
groups. Oxone is easy to handle, nontoxic, soluble in
water, and relatively inexpensive, and it generates
nonpolluting by-products; therefore, it is an attractive
green reagent [1]. Oxone as a stable oxidant has been
widely studied in synthetic organic chemistry, e.g., in
epoxidation of olefins [2], esterification of alcohols
A series of alcohols, including substituted benzyl
alcohols, benzhydrols, and long-chain aliphatic alco-
hols were oxidized with Oxone in chloroform at room
temperature in the presence of 1.5 equiv of tetrabutyl-
ammonium hydrogen sulfate (Scheme 1). The results
are summarized in Table 1. It is seen that benzyl
alcohols were oxidized to the corresponding benzalde-
hydes with excellent conversion (Table 1, entry
nos. 1–3, 6–9). The conversion of benzhydrol to benzo-
phenone was 88%. Long-chain aliphatic alcohols could
also be oxidized to the corresponding aldehydes, but
the conversion was low. Furthermore, no over-oxida-
tion of aldehydes to carboxylic acids was observed
under the given conditions. A probable catalytic cycle
for the oxidation of benzyl alcohols with Oxone was
proposed in [13].
[
3], oxidation and halogenation of C–H bond [4],
oxidation of sulfides [5], organotrifluoroborates [6],
and alcohols [7, 8], as well as in other oxidation pro-
cesses [9]. Furthermore, it was also used in the manu-
facturing industry [10].
The oxidation of alcohols to aldehydes and ketones
is one of the most common classes of oxidation
reactions in organic chemistry [11, 12]. Aldehydes and
ketones represent important intermediates for the
preparation of various other chemicals. Many excellent
catalytic systems have been already reported for the
oxidation of alcohols. To provide a more convenient
procedure and environmentally benign process for the
oxidation of alcohols, herein we report the use of
Oxone as an oxidant and tetrabutylammonium hydro-
gen sulfate as a phase transfer catalyst (PTC) in the
oxidation of primary and secondary alcohols to the
corresponding carbonyl compounds. Six other phase
Scheme 1.
Oxone/Bu NHSO
4
4
OH
O
CHCl , room temp., 8 h
3
R1
R2
a–1p
R1
R2
1
2a–2p
1
2
For R , R , see Table 1.
5
21

522
YANG et al.
a
b
Table 1. Oxidation of alcohols with Oxone/Bu NHSO using chloroform and water as solvents
4
4
c
Conversion, %
Entry no.
Alcohol no.
R1
R2
Product no.
chloroform
water
14
74
13
34
1
2
3
4
5
6
7
8
9
1a
1b
1c
1d
1e
1f
1g
1h
1i
Ph
4-ClC H
H
H
H
H
Ph
Ph
H
H
H
H
H
H
H
Ph
100
100
100
23
2a
2b
2c
2d
2e
2f
2g
2h
2i
6
4
3-MeC H
6
4
4
2-MeC H
6
d
Ph
88
–
4-ClC H
100
100
100
100
25
84
31
36
39
6
4
4-MeOC H
3-PhOC H
4-O NC H
PhCH2
6
4
6
4
2
6
4
d
1
0
1j
–
2j
1
1
1k
1l
1m
1n
1o
1p
Me(CH2)10
Me(CH2)14
Me(CH2)16
4-MeC H
21
36
62
7
5
4
2k
2l
2m
2n
2o
2p
1
1
1
1
1
2
3
4
5
6
d
–
–
–
12
90
9
6
4
d
4-MeOC H
4-MeOC H
4
6
4
6
d
(CH2)5
a
b
c
d
Reaction conditions: solvent CHCl (3 mL), alcohol (1 equiv), Oxone (0.88 equiv), Bu NHSO (1.5 equiv), 8 h, 25°C.
3
4
4
Reaction conditions: solvent H O (2 mL), alcohol (1 equiv), Oxone (2 equiv), Bu NHSO (1.5 equiv), 10 h, room temperature.
2
4
4
According to the GLC data.
No data.
Table 2. Oxidation of alcohols 1b, 1f, 1g, and 1h with Oxone in the presence of different phase-transfer catalystsa
b
b
Alcohol no.
Phase-transfer catalyst
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
Conversion, %
Selectivity, %
Product
1
1
1
1
b
>99
51
11
–
31
23
>99
>99
97
3
44
51
>99
64
24
4
64
42
>99
73
72
13
36
35
100
100
100
–
2b
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
TBAB
f
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
2f
TBAB
g
h
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
2g
2h
TBAB
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
TBAB
a
Reaction conditions: solvent: CH Cl (3 mL), alcohol (1 equiv), Oxone (1 equiv), PTC (1.5 equiv), 10 h, room temperature.
According to the GLC data.
2
2
b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 3 2020

A SIMPLE AND EFFECTIVE METHOD FOR CATALYTIC OXIDATION OF ALCOHOLS
523
We also examined the efficiency of other phase-
transfer catalysts in the oxidation of 4-chlorobenzyl
alcohol (1b), 4-chlorobenzhydrol (1f), 4-methloxy-
benzyl alcohol (1g), and 3-phenoxybenzyl alcohol
FUNDING
This work was supported by the Nature Science
Foundation of China (project nos. 21563026, 21764012) and
by the Scientific Research Ability Promotion Program of
Young Teachers of Northwest Normal University (project
no. NWNU-LKQN-18-18).
(1h). The catalysts used were tetrabutylammonium
hydrogen sulfate (TBAHS), tetrapropylammonium hy-
drogen sulfate (TPAHS), tetraethylammonium hydro-
gen sulfate (TEAHS), tetramethylammonium hydrogen
sulfate (TMAHS), tetrabutylammonium chloride
CONFLICT OF INTEREST
The authors declare no conflict of interest.
REFERENCES
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Relatively good catalytic was also observed for TPAHS
under the same conditions. However, TMAHS had
basically no catalytic activity in the oxidation of these
alcohols. Thus, the longer alkyl radical in tetraalkyl-
ammonium salt favors better catalytic activity in this
oxidation process.
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1
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a 10-mL glass reactor. The mixture was stirred for 8 h,
and the substrate conversion and product formation
were monitored by GLC. The products were identified
by comparing with authentic samples using GC or
GC/MS analysis.
1
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 3 2020