One-pot synthesis of 5-Alkylfuran-2(5H)-ones

Article abstract of DOI:10.1080/00397910500514493

5-Alkylfuran-2(5H)-ones can be efficiently obtained using a one-pot approach, starting from methyl 3-nitropropanoate and aldehydes, in ethyl acetate, with Amberlyst A-21 as catalyst, in 60-90% overall yield. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910500514493

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One‐Pot Synthesis of 5‐Alkylfuran‐2(5H)‐ones
a
a
a
Si Hong Wang , Guan Rong Tian & Jie Ma
a
Department of Chemistry, Yanbian University, Yan Ji, Ji Lin, China
Version of record first published: 24 Feb 2007.
To cite this article: Si Hong Wang, Guan Rong Tian & Jie Ma (2006): One‐Pot Synthesis of
5‐Alkylfuran‐2(5H)‐ones, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 36:9, 1229-1233
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Synthetic Communications , 36: 1229–1233, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500514493
One-Pot Synthesis of 5-Alkylfuran-2(5H)-
ones
Jie Ma, Si Hong Wang, and Guan Rong Tian
Department of Chemistry, Yanbian University, Yan Ji, Ji Lin, China
Abstract: 5-Alkylfuran-2(5H)-ones can be efficiently obtained using a one-pot
approach, starting from methyl 3-nitropropanoate and aldehydes, in ethyl acetate,
with Amberlyst A-21 as catalyst, in 60–90% overall yield.
Keywords: 5-Alkylfuran-2(5H)-ones, Amberlyst A-21, Henry reaction, methyl
3-nitropropanoate, one-pot synthesis
The furan-2(5H)-one ring system is common in many biologically active
natural products. Furan-2(5H)-ones also exhibit high reactivity toward
different reagents because of the presence of the a,b-unsaturated carbonyl
moiety; therefore, they serve as useful building blocks in organic
synthesis. They can be synthesized using a variety of compounds and
[
1]
methods.
Nitro compounds are among the fundamental classes of substances in
organic chemistry. Peculiar to aliphatic nitroalkanes is the formation of new
carbon–carbon double bonds through the elimination of nitrous acid.
Because of the great applicability of the Henry reaction, transformations
[
2]
have been extensively developed.
anionic resin with 2N(CH ) as a functional group, is an excellent and
Amberlyst A-21, a macroreticular
3
2
highly superior heterogeneous catalyst.
In this context, we present a new one-pot approach to the preparation of
5
-alkylfuran-2(5H)-ones. Our procedure is based on the Henry reaction, as
Received in Japan July 28, 2005
Address correspondence to Guan Rong Tian, Department of Chemistry, Yanbian
University, Yan Ji, Ji Lin 133002, China. E-mail: grtn@ybu.edu.cn
1
229

1
230
J. Ma, S. H. Wang, and G. R. Tian
Scheme 1.
depicted in Scheme 1. The key point of our method is the simultaneous
behavior of the nitro group as an electron-withdrawing group and as a good
[
2]
leaving group.
on Amberlyst A-21 in ethyl acetate directly to produce 5-alkylfuran-
(5H)-ones.
Alumina as a catalyst in ethyl acetate and Amberlyst A-21 as a catalyst in
Thus, methyl 3-nitropropanoate reacts with aldehydes
[
3]
2
dichloromethane were also attempted, but the yield of 5-alkylfuran-2 (5H)-
ones was not better than with the previously mentioned method. The
proposed reaction path should proceed via a Henry reaction–lactonization–
elimination. See the results listed in Table 1.
In conclusion, our procedure allows the one-pot synthesis of 5-alkylfuran-
(5H)-ones in good yield, on Amberlyst A-21 in ethyl acetate, under mild
2
conditions, using simple chemicals.
EXPERIMENTAL
[
4] 1
The methyl 3-nitropropanoate was prepared according to the literature.
1
H
3
NMR and C NMR spectra were recorded on a Bruker AV 300 spectrometer.
EI-MS spectra (70 eV) were taken on a Shimadzu GC-MS-QP2010. Only
þ
molecular ions [M ] are given. IR spectra were obtained on a PE-1730
spectrometer.
Table 1. The results of one-pot synthesis
Yield (%)
Amberlyst
A-21/EtOAc
Al
2
O
3
/
EtOAc
Amberlyst
A-21/CH Cl
Entry
R
Result
2
2
[
[
[
5]
a
b
c
d
e
f
Methyl
Ethyl
Brown oil
Brown oil
Brown oil
Yellow oil
Yellow oil
Yellow oil
86.9
71.4
63.2
63.8
61.8
66.7
68.5
54.3
54.0
42.0
52.5
50.0
35.7
6]
7]
Isopropyl
Propyl
Butyl
[
[
[
6]
6,8]
5a,8]
Pentyl
Hexyl
[
6]
g
Brown oil

One-Pot Synthesis of 5-Alkylfuran-2(5H)-ones
1231
General Procedure for One-Pot Preparation of 5-Alkylfuran-2(5H)-
ones
A 25-mL two-necked flask was charged with Amberlyst A-21 (3 g) and ethyl
acetate (5 mL); then a mixture of methyl 3-nitropropanoate (2.25 mmol) and
an aldehyde (2.25 mmol) was added and vigorously stirred for 5 min. After
standing for 24 h, Amberlyst A-21 was washed with ethyl acetate
(
3 ꢀ 30 mL), dried (Na SO ), and evaporated at reduced pressure to give
2
4
the title compounds.
5
-Methylfuran-2(5H)-one (2a)
21 1
IR (film): 3090, 1753 cm . H NMR (d, CDCl ): 1.46 (3H, d, J ¼ 7.0 Hz),
3
5
.16 (1H, m), 6.11 (1H, dd, J ¼ 5.6, 1.8 Hz), 7.47 (1H, dd, J ¼ 5.6, 1.0 Hz).
1
3
C NMR (d, CDCl ): 18.8, 79.6, 121.3, 157.3, 173.0. MS (EI): m/z ¼ 98.
3
5
-Ethylfuran-2(5H)-one (2b)
21 1
IR (film): 3090, 1753 cm . H NMR (d, CDCl ): 1.05 (3H, t, J ¼ 6.0 Hz),
3
1
.72–1.86 (2H, m), 5.08 (1H, m), 6.14 (1H, d, J ¼ 5.4 Hz), 7.74 (1H, dd,
1
3
J ¼ 5.4, 1.0 Hz). C NMR (d, CDCl ): 8.9, 26.2, 84.3, 121.6, 156.2, 173.2.
3
MS (EI): m/z ¼ 112.
5
-Isopropylfuran-2(5H)-one (2c)
21 1
IR (film): 3090, 1753 cm . H NMR (d, CDCl ): 0.99 (6H, d, J ¼ 6.0 Hz),
3
2
.00 (1H, m), 4.85 (1H, d, J ¼ 6.0 Hz), 6.14 (1H, dd, J ¼ 6.0, 1.8 Hz), 7.47
1
3
(1H, dd, J ¼ 6.0, 1.3 Hz). C NMR (d, CDCl ): 17.5, 17.8, 31.6, 88.0,
3
1
22.2, 155.0, 173.2. MS (EI): m/z ¼ 126.
5
-Propylfuran-2(5H)-one (2d)
21 1
IR (film): 3090, 1753cm . H NMR (d, CDCl ): 0.97 (3H, t, J ¼ 7.3 Hz),
3
1
.46–1.53 (m, 2H), 1.71–1.75 (2H, m), 5.07–5.12 (1H, m), 6.13 (1H, dd,
1
3
J ¼ 5.7, 1.9 Hz), 7.46 (1H, dd, J ¼ 5.7, 1.3 Hz). C NMR (d, CDCl ): 13.8,
3
1
7.2, 35.0, 83.2, 125.8, 156.8, 170.7. MS (EI): m/z ¼ 126.
5
-Butylfuran-2(5H)-one (2e)
2
1
1
IR (film): 3090, 1753 cm
.
H NMR (d, CDCl ): d ¼ 0.88 (3H, t,
3
J ¼ 6.3 Hz), 1.22–1.44 (4H, m), 1.67–1.77 (2H, m,), 5.03–5.07 (1H, m),

1
232
J. Ma, S. H. Wang, and G. R. Tian
1
3
6
.08 (1H, dd, J ¼ 5.7, 1.9 Hz), 7.46 (1H, dd, J ¼ 5.7, 1.3 Hz). C NMR
(
d, CDCl ): 13.7, 22.3, 27.3, 32.8, 83.6, 121.3, 156.6, 173.3. MS (EI):
3
m/z ¼ 140.
5-Pentylfuran-2(5H)-one (2f)
2
1 1
IR (film): 3090, 1753 cm . H NMR (d, CDCl ): 0.88 (3H, t, J ¼ 6.0 Hz),
3
5
1
1
.03–5.07 (1H, m), 6.11 (1H, dd, J ¼ 5.7, 2.0 Hz), 7.47 (1H, dd, J ¼ 5.7,
1
.4 Hz). C NMR (d, CDCl ): 13.9, 22.4, 24.6, 31.4, 33.1, 83.5, 121.5,
3
3
56.3, 173.2. MS (EI): m/z ¼ 154.
5-Hexylfuran-2(5H)-one (2g)
21 1
IR (film): 3090, 1753 cm . H NMR (d, CDCl ): 0.87 (3H, t, J ¼ 6.0 Hz),
3
1
.31–1.45 (8H, m), 1.67–1.80 (2H, m), 5.01–5.05 (1H, m), 6.09 (1H, dd,
1
3
J ¼ 5.4, 2.0 Hz), 7.46 (1H, dd, J ¼ 5.4, 1.4 Hz). C NMR (d, CDCl ): 13.9,
3
2
2.4, 24.9, 25.1, 31.5, 33.3, 83.4, 121.5, 156.2, 173.1. MS (EI): m/z ¼ 168.
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