Amberlyst A-26: An efficient and reusable heterogeneous catalyst for a one-pot oxidation-Cannizarro reaction

Article abstract of DOI:10.3184/174751912X13551435784584

Amberlyst A-26 catalyses the efficient synthesis of α-hydroxy- arylacetic acids from aryl methyl ketones in the presence of SeO₂. After simple separation, the catalyst does not lose its activity and can be reused without significant loss in activity for at least four cycles.

Full text of DOI:10.3184/174751912X13551435784584

JOURNAL OF CHEMICAL RESEARCH 2013
RESEARCH PAPER 51
JANUARY, 51–52
Amberlyst A-26: an efficient and reusable heterogeneous catalyst for a
one-pot oxidation–Cannizarro reaction
Ming-Gui Shena,b, Shi-Bin Shanga,b*, Zhan-Qian Songa,b, Dan Wanga,b, Xiao-Ping Raoa,b, Hong
Gaoa,b and He Liua,b
aInstitute of Chemical Industry of Forest Products, CAF; National Engineering Lab. For Biomass Chemical Utilisation; Key and Open Lab.
On Forest Chemical Engineering, SFA; Key Laboratory of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, P. R. China
bInstitute of NewTechnology of Forestry, CAF, Beijing 100091, P. R. China
Amberlyst A-26 catalyses the efficient synthesis of α-hydroxy-arylacetic acids from aryl methyl ketones in the pres-
ence of SeO2. After simple separation, the catalyst does not lose its activity and can be reused without significant loss
in activity for at least four cycles.
Keywords: α-hydroxy-arylacetic acids, Amberlyst A-26, heterogeneous catalyst, reusable catalyst
α-Hydroxy-arylacetic acids are very useful intermediates for
the development of molecules of pharmaceutical or biological
interest. They are important synthons of many natural and
semisynthetic biologically active compounds such as prosta-
glandins,1 β-lactams,2,3 vanillic acid metabolites4 and homatro-
pine.5
Some classical methods for the synthesis of α-hydroxy-
arylacetic acids are reported in the literature. These include the
cyanidation of aromatic aldehydes,6 reaction of aromatic alde-
hyde with chloroform,7 chlorination of aryl methyl ketones8
and reaction of glyoxylic acids with benzene.9 In contrast
to the drastic reaction conditions, low yields and severe side
reactions of these methods, it is reported that ytterbium tri-
flate10 and rare earth perfluoroctanesulfonates11 can separately
catalyse the synthesis of α-hydroxy-arylacetic acid from aryl
methyl ketones in good to excellent yields. However, reusing
the ytterbium triflate required tedious work up procedures
such as filtration, purification and drying; as to rare earth
perfluoroctanesulfonate, the reuse procedure involved the use
of fluorous solvents.
From the environmental point of view, several practical and
economical aspects of organic reactions have to be developed
for their industrialisation. Therefore, the development of highly
active and easily reusable immobilised catalysts is of great
interest to chemists.12 To date, numerous reactions on polymer-
supported catalysts suggest that the polymer-supported cata-
lytic system is promising (see ref. 13 and refs therein). Ideally,
the catalytic synthesis is efficiently carried out, and the cata-
lyst can be easily separated from the reaction mixture by
simple filtration. Recently, Amberlyst resins such as A-1514–19
with the functional group [–SO3H] and A-2720 with the func-
tional group [–N(CH3)3+] have been widely reported in organic
synthesis because of their ease of handling, recoverability and
enhanced reaction rates.
Initially, the effects of catalyst amount and solvent were
examined. The results are summarised in Table 1. Acetophe-
none was selected as a model reactant for this study. We found
that treating acetophenone (10 mmol) and SeO2 (20 mmol)
in a solution of dioxane/H2O (3/1, 4 mL) with A-26 (1g)
as catalyst at 90 °C for 24 h gave the product in 95% yield
(Table 1, entry 1).
Under similar conditions, lower product yields of 88% and
73% were obtained when decreasing the catalyst amount from
1 g to 0.75 g and 0.5 g (Table 1, entries 2 and 3). No reaction
was observed in the absence of Amberlyst A-26 after 48h
(Table 1, entry 4). In contrast, other solvents were less effec-
tive and lower product yields of 35–80% were obtained for
reactions in dioxane, MeCN, H2O, toluene (Table 1, entries
5–8). The mixture of dioxane and H2O on 3:1 ratio as solvent
proved to be the most efficient and was selected as the solvent
for subsequent investigations.
The reaction was extended to the synthesis of other α-
hydroxy-arylacetic acids as summarised in Table 2. Moderate
to excellent yields (70–95%) of α-hydroxy-arylacetic acids
were obtained. The product from entry 1 was isolated and
identified as mandelic acid. When the reaction was finished,
and the reaction mixture was cooled to room temperature, the
solid phase containing catalyst Amberlyst A-26 and selenium
powder can be separated by filtration. Selenium powder can be
further removed by soaking with dilute nitric acid. Amberlyst
A-26 can be recycled by washing with dilute hydrochloric
acid and can be reused in the reaction. The recycled results
(Table 2, entry 1) indicate that the catalyst does not lose its
activity and can be reused without significant loss in activity
for up to four cycles. This one-pot oxidation-Cannizarro reac-
tion comprises two steps. In the first step, the methyl group is
oxidised to an aldehyde group by SeO2. In the second step,a
Cannizaro-type reaction forms the α-hydroxy acid. These two
reactions could be carried out in the same reaction vessel [10].
Amberlyst A-26 is an ideal catalyst for efficiently promoting
the two steps.
We now report an efficient way to synthesise α-hydroxy-
arylacetic acids from aryl methyl ketones catalysed by the
reusable heterogeneous catalyst Amberlyst A-26, a macro-
reticular anionic resin with [–N(CH3)3+] as functional group
(Scheme 1).
Table 1 The effect of catalyst amount and solventa
Entry
Catalyst/g
Solvent (vol/vol)
Time/h
Yield/%b
1
2
3
4
5
6
7
8
1
Dioxane/H2O (3/1)
Dioxane/H2O (3/1)
Dioxane/H2O (3/1)
Dioxane/H2O (3/1)
Dioxane
24
24
24
48
24
24
24
24
95
88
73
–
40
52
80
35
0.75
0.5
–
1
1
CH3CN
1
H2O
PhMe
1
Scheme 1
a Reaction conditions: Amberlyst A-26, acetophenone (10 mmol),
solvent (4 mL), SeO2 (20 mmol), 90 °C.
b Isolated yield.
* Correspondent. E-mail: shangsb@163.com

52 JOURNAL OF CHEMICAL RESEARCH 2013
Table 2 Amberlyst A-26 catalysed synthesis of α-hydroxy-arylacetic acidsa
Entry
Reactant
Product
Yieldb/%
M.p./°C
1
2
PhCOCH3
PhCH(OH)COOH
4-ClC6H4CH(OH)COOH
95, 94, 93, 93c
120–122 (lit.10 120–122)
118–120 (115–121)d
4-ClC6H4COCH3
92
89
90
85
88
82
81
81
80
70
3
3-ClC6H4COCH3
2-ClC6H4COCH3
3-ClC6H4CH(OH)COOH
112–114 (lit.10 112–114)
78–80 (lit.11 78–80)
4
2-ClC6H4CH(OH)COOH
5
2-BrC6H4COCH3
4-BrC6H4COCH3
4-CH3C6H4COCH3
3,4-(CH3)2C6H3COCH3
2,4-(CH3)2C6H3COCH3
2-Acetonaphthone
2-Acetylthiopene
2-BrC6H4CH(OH)COOH
178–180 (lit.11 179–180)
114–116 (lit.10 114–116)
120–122 (lit.10 120–122)
126–128 (lit.11 126–128)
120–122 (lit.11 120–122)
124 (lit.10 125–126)
6
4-BrC6H4CH(OH)COOH
7
4-CH3C6H4CH(OH)COOH
3,4-CH3C6H3CH(OH)COOH
2,4-CH3C6H3CH(OH)COOH
Hydroxy(2-naphthyl)acetic acid
Hydroxy(thien-2-yl)acetic acid
8
9
10
11
92–94 (lit.11 92–94)
a The reaction condition: Amberlyst A-26 (1 g), aryl methyl ketone (10 mmol), 1,4-dioxane (3 mL), H2O (1 mL), SeO2 (20 mmol), 90 °C,
24 h.
b Isolated yield.
c Recycled results.
d Across organics.
The solid phase containing the catalyst Amberlyst A-26 and sele-
nium powder, which had been separated by filtration, could be treated
with dilute nitric acid (50 mL, 1 M) to remove selenium powder. The
Amberlyst A-26, which remained, could then be washed with dilute
hydrochloric acid (50 mL, 1 M) and reused in the reaction.
In conclusion, Amberlyst A-26 is an efficient and reusable
heterogeneous catalyst for preparation of α-hydroxy-arylacetic
acids. The catalyst can be separated by simple filtration and the
reaction can be repeated many times.
Experimental
Received 30 August 2012; accepted 27 November 2012
Paper 1201492 doi: 10.3184/174751912X13551435784584
Published online: 15 January 2013
Chemicals used were obtained from commercial suppliers and used
without further purification. IR spectra were recorded on a Bomem
MB154S IR analyser. H NMR spectra were recorded with a Bruker
1
Advance RX500 spectrometer. Mass spectra were recorded on a
Saturn 2000GC/MS instrument.
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the environment. Due precautions should be taken.
Typical procedure for preparation of α-hydroxy-arylacetic acids: A
mixture of Amberlyst A-26 (1 g), the aryl methyl ketone (10 mmol),
1,4-dioxane (3 mL), H2O (1 mL) and SeO2 (20 mmol) was stirred at
90 °C for 24 h. Then the mixture was cooled to room temperature. The
solid phase containing the Amberlyst A-26 and selenium powder was
filtered off, the filtrate was filtered again through a short pad of celite
in order to immobilise the unreacted SeO2. The filtrate was diluted
with 1% aq. NaOH (10 mL) and extracted with CH2Cl2 (3 × 10 mL).
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column to give a white crystalline (eluent: CH2Cl2/MeOH = 90/10).
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comparison of their spectroscopic data with those of authentic sam-
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