Polyvinylpyrrolidone/thionyl chloride as a new polymeric reagent for facile conversion of epoxides to β-chlorohydrins

Article abstract of DOI:10.1081/SCC-120015389

Epoxides undergo rapid ring opening with cross-linked polyvinylpyrrolidone/thionyl chloride complex, under mild reaction condition to afford chlorohydrins in high yields.

Full text of DOI:10.1081/SCC-120015389

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POLYVINYLPYRROLIDONE/THIONYL CHLORIDE AS A
NEW POLYMERIC REAGENT FOR FACILE CONVERSION OF
EPOXIDES TO β-CHLOROHYDRINS
Bahman Tamami a , Iraj Ghazi a & Hossein Mahdavi a
a Chemistry Department , College of Sciences , Shiraz University , Shiraz, 71454, Iran
Published online: 23 Aug 2006.
To cite this article: Bahman Tamami , Iraj Ghazi & Hossein Mahdavi (2002) POLYVINYLPYRROLIDONE/THIONYL CHLORIDE
AS A NEW POLYMERIC REAGENT FOR FACILE CONVERSION OF EPOXIDES TO β-CHLOROHYDRINS, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:24, 3725-3731, DOI: 10.1081/
SCC-120015389
To link to this article: http://dx.doi.org/10.1081/SCC-120015389
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 24, pp. 3725–3731, 2002
POLYVINYLPYRROLIDONE/THIONYL
CHLORIDE AS A NEW POLYMERIC
REAGENT FOR FACILE CONVERSION OF
EPOXIDES TO b-CHLOROHYDRINS
*
Bahman Tamami, Iraj Ghazi, and Hossein Mahdavi
Chemistry Department, College of Sciences,
Shiraz University, Shiraz 71454, Iran
ABSTRACT
Epoxides undergo rapid ring opening with cross-linked
polyvinylpyrrolidone/thionyl chloride complex, under mild
reaction condition to afford chlorohydrins in high yields.
Epoxides are versatile intermediates in organic synthesis. No reaction
of epoxides has been more thoroughly studied and more widely used in
synthesis than the addition of nucleophilic agent to epoxides to form
1,2-disubstituted products.[1–3] Vicinal halohydrins have attained consider-
able importance in organic synthesis[4] andover the years many reagents
have been reportedin the literature for conversion of epoxieds to
such compounds, e.g.: electrophilic cleavage with hydrohalic acids[5] or
*Corresponding author. E-mail: tamami@chem.susc.ac.ir
3725
DOI: 10.1081/SCC-120015389
Copyright & 2002 by Marcel Dekker, Inc.
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3726
TAMAMI, GHAZI, AND MAHDAVI
Lewis acids such as BF3,[6] chlorosilanes,[7] haloborane reagents,[8,9] pyri-
[11–15]
dine-HCl,[10] Lewis acidmetal halides,
silica-gel supportedlithium
halides,[16,17] ammonium halides in the presence of metal salts,[18]
FeCl3 Á 6H2O supportedon SiO ,[19] monochloroborane-dimethyl sulfide,[20]
2
Tin(II) halides,[21] anddilithium tetrachlro-cuprate.
Most of the above
[22]
methods are not always fully satisfactory and suffer at least from one of the
following disadvantages: (1) formation of some unwanted by-products, (2)
relatively long reaction times, (3) low yield, (4) expensive reagents, or (5)
tedious work-up procedure. Considering these facts, there is still a need for
new reagents for this conversion. Poly(N-vinylpyrrolidone) (PVP) has wide
applications in pharmaceuticals, cosmetics, foods, adhesives, and textile
industries.[23] It has also been usedas phase-transfer catalyst andcosolvent
in organic reactions.[24] However, there are very few reports on its appli-
cation as a polymeric support for reagents usedin functional group
transformations in organic synthesis. In view of this, we recently reported
the use of PVP/thionyl-chloride complex in dehydration of aldoximes
to nitriles,[25] andnow we report a new, easy, andefficient conversion of
epoxides to b-chlorohydrins with this polymeric reagent.
The polymeric reagent was easily preparedby the reaction of thionyl
chloride with two equivalents of cross-linked poly(N-vinylpyrrolidone)[26] in
dichloromethane at room temperature. This kind of mechanism has also
been proposedin the reaction of thionyl chloride and
N-methylpyrroli-
done[27] or, N,N-dimethyl formamide.[28] In the first step, poly(N-vinyl-
pyrrolidone)-thionyl chloride complex (I) is probably formed, which is
convertedinto (II) by reaction with other pyrrolidone units. The reaction
of a stoichiometric amount of polymeric reagent (II) and different epoxides
at room temperature with subsequent addition of water afford the corres-
ponding chlorohydrins probably via (III), (Sch. 1).
The general applicability of this procedure was clarified for a variety of
epoxides, as summarized in Table 1. In all of the cases, the reaction pro-
ceeded to give the desired chlorohydrin derivatives in high yields, within a
short time. Ring opening reaction was highly regioselective in giving the
corresponding 1-halo-2-alkanols, demonstrating the predominant attack
of the chloride anion from the less hindered side of the epoxide as well as
the electronic factor due to the presence of the heteroatom (Entries 2, 5, 6, 8)
in the chain. The only exception is the case of styrene oxide wherein
2-halo-2-phenyl-ethanol was obtained, suggesting that the preferential
cleavage of the benzylic C–O bondprovieds stabilizedcation species
during the reaction. The ring opening reaction of cyclic epoxides such as
cyclohexene oxide and cyclooctene oxide was completely anti-stereoselective
giving only the trans isomers (Entries 3, 4). Entry 7 gives two products in the
ratio of 65/35 due to the absence of the heteroatom in the chain.

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CONVERSION OF EPOXIDES TO b-CHLOROHYDRINS
3727
Scheme 1.
In comparison with the previously reportedreagent for transforming
epoxides into the corresponding b-chlorohydrins, our method offers consid-
erable advantages: (1) reaction work-up is very easy and product isolation
consists of simple filtration of spent polymeric reagent andevaporation of
the solvent, (2) short reaction times, (3) available andinexpensive reagents,
(4) high yields of products especially for conversion of cyclooctene oxide to
2-chloro cyclooctanol in comparison to other reports,[16] and(5) regenera-
tion andreuse of the cross-linkedpolymer. It shouldbe citedthat efforts to
carry out the transformation of epoxides into chlorohydrins with thionyl
chloride alone were not successful and due to its very high reactivity,
a mixture of unidentified products obtained.
In conclusion, we believe that the present procedure for conversion of
epoxides to chlorohydrins provides an easy, mild, efficient, and general
methodology and can be added to the currently available methodologies.
It shouldbe mentionedthat the applications of polyvinylpyrroliodne/
thionylchloride complex for other functional group transformation are
also in progress in our laboratory.

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3728
TAMAMI, GHAZI, AND MAHDAVI
Table 1. Conversion of Epoxides into Their Corresponding Chlorohydrins Using
the Polymeric Reagent
Reaction
Time
(min)
Yielda
(%)
Entry
1
Substrate
Product
10
95
2
3
4
15
70
92
93
88
960
5
20
95
6
7
20
94
90
180
8e
15
92
aYields refer to isolated yields. Products were characterized by comparison of their
[16]
IR andNMR spectra with those of known samples,
except for Entries 4–6.
b1H-NMR (CDCl3), ꢀ 1.35–2.07 (complex, 12H), 3.01 (s, 1H), 3.78 (m, 1H), 4.02
(m, 1H).
13C-NMR (CDCl3), ꢀ 22.42, 23.09, 23.27, 24.93, 25.05, 31.23, 69.91, 75.22.
c1H-NMR (CDCl3), ꢀ 1.17 (d, 6H), 3.49–3.6 (complex, 6H), 3.91 (m, 1H).
13C-NMR (CDCl3), ꢀ 22.22, 46.17, 69.03, 70.63, 72.55.
d1H-NMR (CDCl3), ꢀ 3.52 (m, 5H), 3.90 (m, 3H), 5.29–5.24 (complex, 2H), 5.82
(m, 1H).
13C-NMR (CDCl3), ꢀ 46.31, 70.51, 71.18, 72.62, 117.76, 134.48.
eBy regeneratedpolymer.

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CONVERSION OF EPOXIDES TO b-CHLOROHYDRINS
3729
EXPERIMENTAL
Polyvinylpyrrolidone (K60) and thionyl chloride were purchased from
Fluka. Epoxides were prepared from Fluka or Merck. Polyvinylpyrrolidone
(K60) was cross-linkedin aqueous solution by potassium persulfate at
80ꢀC.[29] Products were characterized by comparison of their IR and
1H NMR spectra with those of known samples. IR spectra were recorded
on a Perkin Elmer IR-157G instrument. NMR spectra were recorded on a
Bruker DPX 250 MHz spectrometer. The purity determination of the
substrates andreaction monitoring were accomplishedby TLC on silica
gel plates or GC.
General Procedure for the Conversion of Epoxides into
Chlorohydrins Using the Polymeric Reagent
To a stirredsuspension of cross-linkedpolyvinylpyrrolidone (0.45 g,
ꢁ 4 mmole) preswelledin dichloromethane (10 mL), at room temperature
was slowly added freshly distilled thionyl chloride (0.25 g, 2.1 mmole). The
reaction mixture was stirredat room temperature for a few minutes to effect
complete reaction. Epoxide (2 mmole) solution in dichloromethane (2 mL)
was then slowly added and stirred at room temperature. Progress of the
reaction was followedby TLC (petroleum ether–ethyl acetate) or GC. On
its completion upon addition of 1–2 drops of water, the polymer was
1
separatedby filtration andwashedwith CH 2Cl2. The TLC and H NMR
pure products (88–95%) were obtained by evaporation of CH2Cl2 from
the filtrate under reduced pressure. The original polymer was obtained by
washing the spent regent with water andacetone several times anddrying at
70ꢀC in a vacuum oven.
ACKNOWLEDGMENT
We wouldlike to acknowledge the partial support of this work by
Shiraz University Research Council andMinistry of Science, Research
andTechnology.
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CONVERSION OF EPOXIDES TO b-CHLOROHYDRINS
3731
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Receivedin the Netherlands November 26, 2001

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