Partial oxidation of alcohols to aldehydes and ketones under mild conditions

Article abstract of DOI:10.1081/SCC-120034155

A number of aldehydes and ketones were prepared by partial oxidation of alcohols in air catalyzed by RuO₂/ZSM-5 which can be easily prepared with the industrial grade ZSM-5 and RuCl₃·xH₂O.

Full text of DOI:10.1081/SCC-120034155

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Partial Oxidation of Alcohols to Aldehydes and
Ketones Under Mild Conditions
a
a
a
a
a
Guang Qian , Rui Zhao , Gaomeng Lu , Yanxing Qi & Jishuan Suo
a
Lanzhou Institute of Chemical Physics, The Chinese Academy of Sciences, Lanzhou,
30000, P.R. China
7
Published online: 20 Aug 2006.
To cite this article: Guang Qian , Rui Zhao , Gaomeng Lu , Yanxing Qi & Jishuan Suo (2004): Partial Oxidation of
Alcohols to Aldehydes and Ketones Under Mild Conditions, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 34:10, 1753-1758
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SYNTHETIC COMMUNICATIONS
Vol. 34, No. 10, pp. 1753–1758, 2004
Partial Oxidation of Alcohols to Aldehydes
and Ketones Under Mild Conditions
*
Guang Qian, Rui Zhao, Gaomeng Lu, Yanxing Qi,
and Jishuan Suo
Lanzhou Institute of Chemical Physics, The Chinese Academy of
Sciences, Lanzhou, P.R. China
ABSTRACT
A number of aldehydes and ketones were prepared by partial oxidation of
alcohols in air catalyzed by RuO /ZSM-5 which can be easily prepared
2
.
with the industrial grade ZSM-5 and RuCl xH O.
3 2
Key Words: RuO
Benzyl alcohol.
2
/ZSM-5; Alcohol oxidation; Air atmosphere;
INTRODUCTION
Aerobic alcohol oxidation is one of the most important reactions in
organic synthesis, since it can transform functional group (Sch. 1). Traditional
*
Correspondence: Yanxing Qi, Lanzhou Institute of Chemical Physics, The Chinese
Academy of Sciences, Lanzhou 730000, P.R. China; Fax: þ86-931-8277787;
E-mail: fpierc@ns.lzb.ac.cn.
1
753
DOI: 10.1081/SCC-120034155
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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1
754
Qian et al.
methods for performing such transformations generally involve the use of
stoichiometric quantities of inorganic oxidants. However, from both an
economic and environmental viewpoint there is a growing demand for atom
efficient, catalytic methods that employ clean oxidants such as O (air) and
2
[
1]
H O . In this field, many catalytic systems have been designed. Although
2
2
some homogenous transition metal complexes systems have achieved high
[
2–10]
activity and selectivity, most of the systems have their natural shortages.
For example, it is difficult to recycle and separate catalyst. In recent years,
[11–18]
several efficient heterogeneous catalytic systems have been developed
but their applications are limited because they generally need pure oxygen,
or activated alcohols. The search for a green, mild, and stable aerobic catalytic
system is still an interesting subject.
Recently, Zhan et al. reported high activities for the aerobic alcohol
19]
[
oxidation on an RuO –FAU.
However, they only evaluated their catalyst
by a limited number of substrates. In our research, we directly synthesized
2
RuO in the industrial grade ZSM-5 zeolite by one-step method rapidly, and
2
RuO /ZSM-5 was used as catalyst for partial oxidation of alcohols to alde-
2
hydes and ketones in air atmosphere.
RESULTS AND DISCUSSION
a
The partial oxidation results are shown in Table 1. Benzyl alcohol was
oxidized to benzaldehyde with high selectivity and conversion under the
given reaction conditions (entry 2). However, only 16.1% of benzyl alcohol
was converted to benzaldehyde within 16 hr when pure hydrous RuO was
2
used as a catalyst under the same reaction conditions (entry 1).
Scheme 1.
a
All the oxidation reactions were carried out in the air of 0.83 atm, which is a normal
atmospheric pressure in Lanzhou, China. The experiments carried out in the air of
1
.0 atm indicated the pressure 0.83 atm is not essential for these results. For examples,
in the air of 1.0 atm, farfuryl alcohol was oxidized to furfural with 67% conversion and
9% selectivity in 5.5 hr, and cyclohexanol was oxidized to cyclohexanone with 20%
9
conversion and 99% selectivity in 18 hr. Clearly, these results do not differ greatly from
the results obtained in the experiments carried out in the air of 1.0 atm.

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Partial Oxidation of Alcohols to Aldehydes and Ketones
1755
/ZSM-5 catalyst.
Conversion Selectivity
Table 1. Aerobic oxidation results of alcohols using RuO
2
Entry
Time
16
Substrate
Product
(mol%)
(mol%)
a
1
16.1
99
2
3
16
20
100
81
99
95
4
5
6
7
8
9
5.5
12
24
5.5
32
6
65.5
86
99
91
85
61
75
99
99
92
100
67
98
16
1
1
0
1
18
18
20
55
1
2
26
55
80
1
1
1
3
4
5
10
36
16
32
55
99
92
99
b
100
c
1
1
a
6
16
52
13.1
50.5
99
99
d
7
0
.06 mmol hydrous RuO
Oxidation result for the fifth run.
2
was used as catalyst.
b
c
Alcohol (1 mmol), RuO
Alcohol (23 mmol), RuO
2
/ZSM-5 (0.1 g), H
/ZSM-5 (0.2 g), 808C.
2
O (4 mL), 808C.
d
2

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Qian et al.
With 2-phenyl ethanol used as a substrate, acetophenone was achieved
under the same conditions with 81% conversion and 95% selectivity in
20 hr. GC–MC indicated that the main by-product is styrene (entry 3).
Farfuryl alcohol was oxidized to furfural with 65.5% conversion and 99%
selectivity in 5.5 hr. Prolonging the reaction time could increase the conver-
sion, but decrease the selectivity; farfuryl alcohol was oxidized to furfural
with 100% conversion and 86% selectivity under the same conditions in
28 hr (entries 4–6).
With unsaturated alcohols used as the substrate, the corresponding alde-
hydes were detected by GC (entries 7 and 8). The main by-products were car-
boxylic acids (by GC–MC).
Compared to RuO , which only can catalyze activated alcohols
2
[
1]
oxidation; RuO /ZSM-5 also displays good activity in the oxidation of
2
unactivited alcohols (entries 9–14). For example, hexadecanol was oxidized
to hexadecanal with 55% conversion and 92% selectivity in 36 hr.
It was found that the partial oxidation could be performed without using
any solvent. For example, neat benzyl alcohol was oxidized to benzaldehyde
with a conversion of 50.5% and selectivity of 99% in 52 hr (entry 17). In
addition, the conversion is significantly dropped to 13.1% under the same con-
ditions when H O was used as solvent (entry 16).
2
After reacting with alcohols, RuO /ZSM-5 can be separated from the
2
reaction mixture by filtrating, and the recovered catalyst can be used for partial
oxidation more than four times without any decrease in either conversion or
selectivity (entry 15).
EXPERIMENTAL PART
Catalyst Preparation
.
A measured amount of RuCl3 xH O was added into a flask containing
2
2.0 g of ZSM-5, 0.5 g of NaOH and 35.0 g of H O. The mixture was stirred
2
at 808C for 1.5 hr, and the resultant black powder was separated from the
solution by filtrating and then washed completely with water. The synthesized
samples were dried at room temperature for further characterization and appli-
cation. Inductively coupled plasma (ICP) analysis indicated that concentration
of RuO incorporated in the zeolite is 0.6 mmol/g.
2
General Procedure for Partial Oxidation
The oxidation reaction was carried out in a flask (with a condenser)
containing 1 mmol of alcohol, 4 mL of toluene, and 0.1 g of RuO /ZSM-5
2

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Partial Oxidation of Alcohols to Aldehydes and Ketones
1757
catalyst. The oxidation reactions were conducted in 80 8C oil bath with
magnetic stirring in air. The oxidation products were analyzed and quantified
by gas chromatography and identified by either GC-MC or GC with standard
samples.
CONCLUSIONS
A number of aldehydes and ketones were prepared by partial oxidation of
alcohols in air catalyzed by RuO /ZSM-5. This catalyst shows high stability,
2
reactivity and selectivity, and this procedure has advantages of easy work-up
and good industrial applicability.
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Received in Japan October 6, 2003

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