Clean and Selective Oxidation of Alcohols with Oxone and Phase-Transfer Catalysts in Water

Article abstract of DOI:10.1134/S1070428020100206

Abstract: A new, simple, metal-free, and eco-friendly procedure has been proposed forthe oxidation of alcohols with Oxone (potassium peroxymonosulfate) in water inthe presence of six phase-transfer catalysts (PTC). Phase-transfer catalystswere found to display high catalytic activity in water solution. Furthermore,the oxidation of alcohols was also carried out with relatively good conversionand selectivity in water without any catalyst.

Full text of DOI:10.1134/S1070428020100206

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 10, pp. 1790–1794. © Pleiades Publishing, Ltd., 2020.
Clean and Selective Oxidation of Alcohols with Oxone
and Phase-Transfer Catalysts in Water
Y. X. Yanga,b,*, M. Kanga,b, X. Q. Ana,b, W. Zenga,b, Z. W. Yanga,b, and H. C. Maa,b
a Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Northwest Normal University,
Lanzhou, Gansu, 730070 China
b Key Laboratory of Eco-environmental Polymer Materials, College of Chemistry and Chemical Engineering,
Northwest Normal University, Lanzhou, Gansu, 730070 China
*e-mail: yangyaoxia2007@126.com
Received May 20, 2020; revised June 1, 2020; accepted June 14, 2020
Abstract—A new, simple, metal-free, and eco-friendly procedure has been proposed for the oxidation of
alcohols with Oxone (potassium peroxymonosulfate) in water in the presence of six phase-transfer catalysts
(PTC). Phase-transfer catalysts were found to display high catalytic activity in water solution. Furthermore, the
oxidation of alcohols was also carried out with relatively good conversion and selectivity in water without any
catalyst.
Keywords: alcohols, oxidation, phase-transfer catalyst, aldehydes, ketones
DOI: 10.1134/S1070428020100206
INTRODUCTION
cesses also generated equivalent amounts of metal
waste, which are environmentally undesirable. There-
fore, development of green, selective, and efficient
catalysts for the oxidation of alcohols is important for
both economic and environmental reasons.
The oxidation of alcohols to the corresponding
carbonyl compounds is a fundamental transformation
in organic synthesis and is of major importance in both
laboratory and industrial synthetic chemistry [1–3].
The oxidation of alcohols was traditionally carried out
with the use of large amounts of noxious transition
metal compounds such as chromates and permanga-
nates [4, 5] or organic solvent [6, 7] or complicated
reaction conditions were required [8–10]. In an attempt
to provide a more environmentally benign process for
alcohol oxidation, a variety of catalytic oxidation
procedures using water as the only solvent have been
investigated [11–15]. Bolm et al. [16] presented
a metal-free oxidation system for the oxidation of
alcohols using TEMPO/Oxone® in the presence of
a catalytic amount of Bu4NBr. Surendra et al. [17, 18]
reported a transition metal-free catalytic system for the
oxidation of alcohols with o-iodoxybenzoic acid (IBX)
or N-bromosuccinimide (NBS) catalyzed by β-cyclo-
dextrin in aqueous acetone. Thottumkara et al. [19]
reported a highly efficient oxidation of alcohols using
IBX/Oxone® oxidation system in aqueous acetonitrile.
Wu et al. [20] reported AlCl3/Oxone oxidation of alco-
hols in aqueous medium to attain excellent conversion
and selectivity. Moriyama et al. [21] described a halide-
catalyzed selective oxidation of alcohols with
KBr/Oxone in aqueous acetone. Some of these pro-
Oxone is a white crystalline solid which is easy to
handle, nontoxic, soluble in water, cheap, and stable.
Therefore, it has received much attention in the field of
oxidation of alcohols [22–24]. Phase-transfer catalysts
(PTC) facilitate reactant transport from one phase into
another phase where the reaction occurs. It is a special
form of heterogeneous catalysis, which is one of the
most useful methods in synthetic organic chemistry
[25, 26]. In an effort to provide a more convenient
procedure and environmentally benign process for the
oxidation of alcohols with commercially available
Oxone as oxidant we used a series of phase-transfer
catalysts and water as solvent.
Herein we report a green, simple, and efficient
method for the oxidation of alcohols to the correspond-
ing carbonyl compounds using Oxone as an oxidant
and six phase-transfer catalysts in aqueous solution.
RESULTS AND DISSUSSION
A number of substituted benzyl alcohols, benz-
hydrol, and its derivatives were oxidized with Oxone
in water at certain temperature in the presence of
1790

CLEAN AND SELECTIVE OXIDATION OF ALCOHOLS WITH OXONE
1791
Scheme 1.
0.5 equiv of phase-transfer catalysts (Scheme 1). The
catalysts used were tetrabutylammonium hydrogen sul-
fate (TBAHS), tetrapropylammonium hydrogen sulfate
(TPAHS), tetraethylammonium hydrogen sulfate
(TEAHS), tetramethylammonium hydrogen sulfate
(TMAHS), tetrabutylammonium chloride (TBAC), and
tetrabutylammonium bromide (TBAB). The results are
summarized in Table 1.
R1
O
Oxone/PTC, H2O, 4 h
HO
1a–1m
R2
R2
R1
2a–2m
For R1, R2, see Table 1.
reactions showed 100% selectivity, except for benzyl
alcohol (1a), 4-nitrobenzyl alcohol (1d), and 4-chloro-
benzyl alcohol (1e) (Table 2, entry nos. 1, 4, 5). The
oxidation of 4-chlorobenzhydrol (1g) and 4,4′-dime-
thoxybenzhydrol (1i) to the corresponding ketones in
water solution was characterized by excellent conver-
sion and selectivity. Cyclic alcohols could not be easily
oxidized to the corresponding cyclic ketones in this
oxidation system. Long-chain aliphatic alcohols were
also difficult to oxidize under the given conditions.
This may be due to the molecular structure of these
alcohols.
It was found that all PTCs were active catalysts for
the oxidation of alcohols. Benzyl alcohol, benz-
hydrol, and their derivatives were easily oxidized to
the corresponding carbonyl compounds in aqueous
solution with excellent conversion (Table 1, entry
nos. 1, 6, 10). In most cases, the oxidation selectivity
was 100%, except for benzyl alcohol (1a), 3-methyl-
benzyl alcohol (1b), and 2-methylbenzyl alcohol (1c),
and no other oxidation products were detected.
Considering the environmental impact, the oxida-
tion of alcohols in water without any catalyst was also
investigated. A series of alcohols, including substituted
benzyl alcohols, benzhydrols, and long-chain aliphatic
alcohols were oxidized with Oxone in water at certain
temperature. The results were summarized in Table 2.
Benzyl alcohols were oxidized to the corresponding
benzaldehydes and benzoic acids with a good conver-
sion (Table 2, entry nos. 1, 2). Most of the oxidation
In summary, we have proposed a green, efficient,
inexpensive, metal-free, and environmentally friendly
procedure for the oxidation of benzylic primary and
secondary alcohols to the corresponding aldehydes and
ketones in water using Oxone as oxidant and phase-
transfer catalyst with excellent conversion and selec-
tivity. Furthermore, the oxidation of alcohols was also
Table 1. Oxidation of alcohols with Oxone in the presence of different phase-transfer catalysts in watera
Phase-transfer
Entry no. Alcohol no.
R1
R2
Conversion, b % Selectivity,b % Product no.
catalyst
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
100
100
96
56
60
67
1
2
3
1a
1b
1c
Ph
H
2a
2b
2c
100
100
100
68
34
61
TBAB
74
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
91
67
95
75
100
100
94
3-MeC6H4
H
H
61
82
TBAB
84
78
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
69
84
78
83
83
100
100
91
2-MeC6H4
59
74
TBAB
96
55
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

YANG et al.
1792
Table 1. (Contd.).
Entry no. Alcohol no.
Phase-transfer
catalyst
R1
R2
Conversion,b % Selectivity,b % Product no.
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
73
60
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
73
4
5
1d
1e
1f
4-O2NC6H4
H
2d
2e
2f
65
46
TBAB
99
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
>99
100
>99
>99
74
4-ClC6H4
4-MeOC6H4
4-ClC6H4
H
TBAB
>99
50
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
69
69
6
H
46
65
TBAB
57
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
77
84
71
7
1g
1i
Ph
2g
2i
80
52
TBAB
67
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
69
100
69
8
4-MeOC6H4 4-MeOC6H4
76
82
TBAB
88
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
70
33
62
9
1j
3-PhOC6H4
H
2j
80
46
TBAB
90
TBAHS
TPAHS
TEAHS
TMAHS
TBAC
100
100
100
100
100
100
10
1m
Ph
Ph
2m
TBAB
a
Reaction conditions: solvent: H2O (3 mL), alcohol (1.5 equiv), Oxone (1 equiv), PTC (0.071 equiv), 4 h, 70°C.
According to the GC data.
b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

CLEAN AND SELECTIVE OXIDATION OF ALCOHOLS WITH OXONE
Table 2. Oxidation of alcohols with Oxone in water in the absence of a catalysta
1793
Entry no.
Alcohol no.
R1
R2
Conversion,b % Selectivity,b %
Product no.
1
2
1a
1b
1c
1d
1e
1f
Ph
H
98
52
64
48
96
44
84
71
91
41
7
57
100
100
83
2a
2b
2c
2d
2e
2f
3-MeC6H4
2-MeC6H4
4-O2NC6H4
4-ClC6H4
H
3
H
4
H
5
H
76
6
4-MeOC6H4
4-ClC6H4
H
100
100
100
100
100
100
100
7
1g
1h
1i
Ph
Ph
2g
2h
1i
8
4-MeC6H4
4-MeOC6H4
3-PhOC6H4
Me(CH2)6
9
4-MeOC6H4
10
11
12
1j
H
H
2j
1k
1l
2k
2l
(CH2)5
9
a
Reaction condition: solvent: H2O (3 mL), alcohol (2.0 equiv), Oxone (1 equiv), 4 h and 65°C.
According to the GC data.
b
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and similar selectivity in aqueous solution without any
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EXPERIMENTAL
https://doi.org/10.1021/acsami.9b07961
A typical reaction was carried out as follows:
alcohol (1.0 equiv), Oxone (1.5 equiv), and PTC
(0.5 equiv) were dissolved in 3 mL of water in a 10-mL
glass reactor. The mixture was stirred for 4 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.
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This work was supported by the Nature Science
Foundation of China (grant nos. 21563026, 21764012), by
the Science and Technology Program of Gansu Province
(no. 19JR2RA020), and by the Scientific Research Ability
Promotion Program of Young Teachers of Northwest Normal
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CONFLICT OF INTEREST
The authors declare that they have no conflict of interest.
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