Simple and efficient method for the synthesis of δ-chloroesters from tetrahydrofuran and acyl chlorides in the presence of catalytic iodine

Article abstract of DOI:10.1080/00397910601163778

Acyl chlorides and dry tetrahydrofuran (THF) in the presence of catalytic amounts of iodine at 25°C give δ-chloroesters in excellent yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910601163778

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Simple and Efficient Method for the Synthesis
of δ‐Chloroesters from Tetrahydrofuran and
Acyl Chlorides in the Presence of Catalytic
Iodine
a
a
M. A. Pasha & K. Manjula
a
Department of Studies in Chemistry , Central College Campus, Bangalore
University , Bangalore, India
Published online: 24 Feb 2007.
To cite this article: M. A. Pasha & K. Manjula (2007) Simple and Efficient Method for the Synthesis of
δ‐Chloroesters from Tetrahydrofuran and Acyl Chlorides in the Presence of Catalytic Iodine, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:6,
927-932, DOI: 10.1080/00397910601163778
To link to this article: http://dx.doi.org/10.1080/00397910601163778
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Synthetic Communications , 37: 927–932, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910601163778
Simple and Efficient Method for the
Synthesis of d-Chloroesters from
Tetrahydrofuran and Acyl Chlorides in the
Presence of Catalytic Iodine
M. A. Pasha and K. Manjula
Department of Studies in Chemistry, Central College Campus, Bangalore
University, Bangalore, India
Abstract: Acyl chlorides and dry tetrahydrofuran (THF) in the presence of catalytic
amounts of iodine at 258C give d-chloroesters in excellent yields.
Keywords: acyl chlorides, d-chloroesters, iodine, tetrahydrofuran (THF)
INTRODUCTION
The preparation of d-chloroesters are important in organic synthesis and find
application in the syntheses of natural products where a four-carbon chain is
required. These d-chloroesters are also used as intermediates in the synthesis of
valuable pharmaceuticals. It has been known for some time that tetrahydrofuran
[1]
[2]
undergoes cleavage in the presence of Lewis acids such as ZnCl , BCl3,
2
[3]
[4]
[5]
and Bi(III)halides; organolanthanide complexes; and iodides. However,
quite a few of the reported methods have limitations mainly with respect to
yield, cost, and availability of the reagents. Some of the systems require longer
duration, stringent conditions, work at reflux temperature of the solvent or at
higher temperatures, environmentally toxic catalysts, and cumbersome method-
ologies. Thus, the search for new catalysts and methods is still of practical
Received in India August, 14 2006
Address correspondence to M. A. Pasha, Department of Studies in Chemistry,
Central College Campus, Bangalore University, Bangalore 560 001, India. E-mail:
m_af_pasha@yahoo.co.in
9
27

9
28
M. A. Pasha and K. Manjula
importance. In this article, we describe our successful work on iodine as a catalyst
for the cleavage of tetrahydrofuran in the presence of acyl chlorides at 258C.
RESULTS AND DISCUSSION
An earlier report from our laboratory describes synthesis of d-chloroesters
[6]
from tetrahydrofuran and acyl chloride in the presence of zinc dust.
Because the reaction takes a long time for completion, the reaction has been
studied under sonication. In continuation with our work, we are reporting a
novel method of synthesis of d-chloroesters from tetrahydrofuran using a
catalytic amount of iodine and acid chlorides in the absence of any additional
solvent at 258C as shown in Scheme 1.
To standardize the reaction, different amounts of iodine were used to get
d-chloro esters from THF and benzoyl chloride; the results are summarized in
Table 1. From the table, it is clear that the reaction can be carried out in the
presence of catalytic amounts of iodine and that it is not possible without
iodine (entries 7 and 8).
EXPERIMENTAL
[7]
Different acyl chlorides were prepared by standard procedures and purified
before use. All reagents were purchased from BDH and S. D. Fine chemicals,
and all the chemicals and solvents were distilled before use. Reactions were
monitored on thin-layer chromatography (TLC) by comparison with the
authentic samples. A Nicolet 400D FT-IR spectrophotometer was used for
IR spectral analysis. NMR spectra were recorded on a 400-MHz Bruker instru-
ment. The chemical shift values (d ppm) reported are relative to TMS in
CDCl as solvent. Yields refer to the isolated yields of the products and are
3
based on 10 mmol of starting acyl chloride.
General Procedure for the Preparation of CH COO(CH ) Cl
3 2 4
Acetyl chloride (0.78 g, 10 mmol) and tetrahydrofuran (10 ml) were taken
in a 25-ml round-bottom flask. Iodine (0.063 g, 0.25 mmol) was added to
Scheme 1.

d-Chloroesters
929
Table 1. Reaction of THF and benzoyl chloride in the presence of different amounts
of iodine at 258C
Amount of
iodine
(mmol)
Entry
1
Product
Time
Yield (%)
78
10
30 min
2
3
4
5
6
7
8
7.5
5
30 min
30 min
30 min
30 min
30 min
5 min
80
80
82
85
90
94
—
2.5
1
0.1
0.05
Nil
No reaction
24 h
this and stirred at 258C for 3 min. The progress of the reaction was
monitored by TLC; after completion of the reaction, 25 ml of ether
was added. The organic layer was washed with saturated Na S O
2 3
2
(
10 mL) followed by water (3 ꢀ 10 ml), dried over anhydrous Na SO , con-
2
4
centrated in vacuo, and purified by column chromatography (5% ethyl
acetate–petroleum ether) to afford pure 4-chlorobutyl acetate (1.44 g, 96%).
1
The IR and H NMR spectral data of the d-chloroesters are presented in
Table 2.

9
30
M. A. Pasha and K. Manjula
To extend the reaction of THF with different acyl halides in the presence
of iodine to get d-chloroesters, the reaction of THF with alkyl, aryl, and allyl sub-
stituted acyl chlorides was studied. The reactions were carried out under
normal conditions, and the results are summarized in Table 3. From Table 3,
it is clear that aroyl chlorides containing both electron- withdrawing and
electron-donating groups react equally efficiently to give d-chloroesters in
excellent yields in less than 15 min.
1
Table 2. Spectral data (IR and H NMR) of d-chloroesters
IR [y
2
(cm )]
1
1
Entry
1
Product
(CH Cl
H NMR (CDCl
3
) [d (ppm)]
CH )],
.97 [s, 3H (CH CO-)], 3.42
CH
3
CO
2
2
)
4
1740, 762
1.60–1.80 [m, 4H(CH
2
2
1
3
[
t, 2H(CH
t, 2H (CH
2
Cl), J ¼ 6 Hz), 4.00
[
2
O-), J ¼ 6 Hz].
2 2
2
3
C
6
H
5
CO
2
(CH
2
)
4
Cl
1724, 721
1750, 762
1.97 [m, 4H(CH
H (CH
CH )], 3.60 [t,
2
2
Cl), J ¼ 4.1 Hz], 4.35
[
t, 2H(CH O-), J ¼ 4.1 Hz],
2
7
.41–8.04 [m, 5H(C
6
H
5
)].
)],
COO-g],
ClCH
2
CO
2
(CH
2
)
4
Cl
1.6–1.9 [m, 4H(CH
2
CH
2
2
3
.05 [s, 2HfClCH
2
.5 [t, 2HfCH CH Clg,
2
2
J ¼ 6 Hz], 4.05 [t, 2H(CH
2
O-),
J ¼ 6 Hz].
4
5
6
7
ClC
6
H
4
CO
2
(CH
2
)
4
Cl
1719, 740
1718, 756
1729, 726
1770, 768
2 2
1.95 [m, 4H(CH CH )], 3.60
[
m, 2H(CH
H(CH O-)], 7.57–7.92
2
Cl)], 4.37 [m,
2
2
[
dd, 4H(C
6
H
4
), J ¼ 10 Hz].
CH )], 3.55
Cl)], 4.34
O-)], 7.55–7.91
BrC
6
H
4
CO
2
(CH
2
)
4
Cl
1.91 [m, 4H(CH
2
2
[
[
[
m, 2H(CH
m, 2H(CH
2
2
dd, 4H(C H ), J ¼ 8.2 Hz].
6
4
NO C H CO (CH ) Cl
2 4
1.90 [m, 4H(CH CH )], 3.59
2 2
2
6
4
2
[
m, 2H(CH
2
Cl)], 4.36 [m,
O-)], 8.16–8.24 [dd,
H(C H ), J ¼ 8 Hz].
2
4
H(CH
2
6
4
C
6
H
5
1.89 [m, 4H(CH
2 2
CH )], 3.61
CH 55 CHCO (CH ) Cl
2 4
[m, 2H(CH Cl)], 4.36 [m,
2
2
2
H(CH
2
O-)], 6.45 [d,
1
HfCH(OCO-) ¼ CH-g,
J ¼ 16 Hz], 7.7 [d, 1HfCH
) ¼ CHg, J ¼ 16 Hz],
.38–7.56 [m, 5H(C )].
6 5
(C H
7
6 5
H

d-Chloroesters
Table 3. Reaction of acyl chlorides with THF in presence of iodine at 258C
931
a
Yield
(%)
Entry
1
Acid chloride
Product
Time
3
96
94
2
5
3
4
5
5
90
92
5
6
10
10
90
89
7
15
92
a 1
Products are identified by the IR and H NMR spectral analysis.
CONCLUSION
In conclusion, we have presented novel, rapid, efficient, economically viable
protocol for the preparation of d-chloroesters from THF and acyl chlorides
using catalytic amounts of nontoxic, readily available, and inexpensive
iodine.
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9
32
M. A. Pasha and K. Manjula
2
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3
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4
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5
6
7
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1
553–1556.
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