Ring opening of epoxides with carboxylates and phenoxides in micellar media catalyzed with Ce(OTf)4

Article abstract of DOI:10.1081/SCC-120005998

Efficient ring opening reaction of epoxides with carboxylates and phenoxide anions catalyzed with ceric triflate is performed in micellar media. This new method is a useful procedure for the preparation of β-carboxy and phenoxy alcohols from epoxides under mild reaction conditions.

Full text of DOI:10.1081/SCC-120005998

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RING OPENING OF EPOXIDES WITH CARBOXYLATES AND
PHENOXIDES IN MICELLAR MEDIA CATALYZED WITH
Ce(OTf)4
N. Iranpoor a , H. Firouzabadi b , A. Safavi a & M. Shekarriz c
a Chemistry Department , College of Sciences , Shiraz University , Shiraz, 71454, Iran
b Chemistry Department , College of Sciences , Shiraz University , Shiraz, 71454, Iran
c Research Center of Oil Industry , Tehran, Iran
Published online: 16 Aug 2006.
To cite this article: N. Iranpoor , H. Firouzabadi , A. Safavi & M. Shekarriz (2002) RING OPENING OF EPOXIDES WITH
CARBOXYLATES AND PHENOXIDES IN MICELLAR MEDIA CATALYZED WITH Ce(OTf)4 , Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 32:15, 2287-2293, DOI: 10.1081/SCC-120005998
To link to this article: http://dx.doi.org/10.1081/SCC-120005998
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 15, pp. 2287–2293, 2002
RING OPENING OF EPOXIDES WITH
CARBOXYLATES AND PHENOXIDES IN
MICELLAR MEDIA CATALYZED WITH
Ce(OTf )4
*
*
N. Iranpoor, H. Firouzabadi, A. Safavi, and
M. Shekarrizy
Chemistry Department, Shiraz University, College of
Sciences, Shiraz 71454, Iran
ABSTRACT
Efficient ring opening reaction of epoxides with carboxylates
and phenoxide anions catalyzed with ceric triflate is per-
formed in micellar media. This new method is a useful proce-
dure for the preparation of b-carboxy and phenoxy alcohols
from epoxides under mild reaction conditions.
It is well established that micelles as media for chemical reactions,
present interesting features which are influenced by the micellar environ-
mental factors.[1] These factors can result changes in the reaction rate,
mechanism, regio, and stereochemistry, and the scope of the reaction.[2–6]
Despite the extensive studies on the analytical applications and catalytic
activity of micelles,[7–11] the occurrence of organic reactions and especially
*Corresponding authors. E-mail: iranpoor@chem.susc.ac.ir
yCurrent address: Research Center of Oil Industry, Tehran, Iran.
2287
DOI: 10.1081/SCC-120005998
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2288
IRANPOOR ET AL.
Lewis acid catalysis in micellar media are rarely studied.[12] Most classical
Lewis acids used are unstable in aqueous media and are hydrolyzed easily
and therefore, study on the catalytic activity of stable Lewis acids in
aqueous and micellar media is a useful investigation.
The ring opening reaction of epoxides by nucleophiles is an interesting
approach in organic synthesis.[13] This reaction with nucleophiles such as
CNꢀ,[14–16] N3ꢀ,[17] NO3ꢀ,[18] and halides[19] have been performed in both
organic and aqueous organic solvents. The reactions of epoxides with
carboxylic acids are generally limited to the reaction of acetic acid catalyzed
with different Lewis acids.[18b,20a] The use of NaOAc/HOAc[20c] and benzoic
acid/Co(salen)/i-Pr2NH[20d] are also reported.
Ring opening reaction of epoxides with phenols has also been
performed, but the reaction usually occurs in the presence of tertiary
amines or under alkaline conditions at 80–130ꢁC.[21] We now wish to
report an efficient method for the ring opening of epoxides with carboxylates
and phenoxide anions in micellar media at room temperature using ceric
triflate [Ce(OTf)4], as the catalyst (Scheme).
Scheme.
When we performed the reaction of styrene oxide with sodium acetate
in water or in aqueous acetonitrile and in the presence of 0.1 molar equiva-
lents of Ce(OTf)4, a very slow reaction occurred in both cases (Table 1,
Entries 1, 2). Therefore, in order to increase the rate of reaction, the
effect of different micellar media on the progress of the reaction was
examined. We first studied the effect of cetyltrimethylammonium bromide
(CTAB) as a cathionic, sodium dodecyl sulfate (SDS) as an anionic and
triton X-100 as a neutral micelle on the ring opening reaction of styrene
oxide with sodium acetate. The results obtained for these reactions are
shown in Table 1.
Results of Table 1 show that in the absence of either micelle (Table 1,
Entries 1, 2) or the catalyst (Table 1, Entry 5), the reaction of styrene oxide

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RING OPENING OF EPOXIDES IN MICELLAR MEDIA
2289
Table 1. Effects of Different MicellesI for the Conversion of Styrene Oxide to
2-Phenyl-2-acetoxy-1-ethanol with Sodium Acetate Catalyzed with 0.1 Molar
Equivalents of Ce(OTf)4 at Room Temperature
Entry
Reaction Media
Time (h)
Yield %II
1
2
3
4
5
6
7
8
9
10
WaterIII
10
7
0.5
3
3
7
3
0.5
7
8
15
87
80
25
43
60V
65V
40
20% aq. CH3CNIII
SDS (8.1 ꢃ 10ꢀ2 M)
SDS (8.1 ꢃ 10ꢀ3 M)
SDS (8.1 ꢃ 10ꢀ2 M)IV
CTAB (1.3 ꢃ 10ꢀ3 M)
CTAB (1.3 ꢃ 10ꢀ2 M)
CTAB (8.1 ꢃ 10ꢀ3 M)
Triton X-100 (3.0 ꢃ 10ꢀ4 M)
Triton X-100 (6.0 ꢃ 10ꢀ4 M)
7
55
IThe CMC of SDS ¼ 8.1 ꢀ 10ꢁ3 M,[11b] CTAB ¼ 1.3 ꢀ 10ꢁ3 M,[11b] Triton X ¼ 3.0 ꢀ
10ꢁ4 M (2%).[11c]
IIIsolated yield.
IIIThe reaction was performed in the absence of micelle.
IVThe reaction was performed in the absence of Ce(OTf)4.
VThe formation of b-bromohydrine (15–35%) was also occurred in this micellar
solution.
with sodium acetate is very slow. However, the rate of reaction is increased
in micellar media at critical micelle concentration (CMC) or above it.
In SDS micellar solution, the reaction was completed after 30 min and 87%
of the corresponding product was obtained (Table 1, Entry 3). In micellar
solution of cetyltrimethylammonium bromide either at or above the critical
micelle concentration, (Table 1, Entries 6, 7), the reaction of styrene oxide
was found to be some how slower than in SDS solution and was not
completed. However, when the reaction was performed in the same concen-
tration as SDS solution (Table 1, Entry 8), the reaction was completed
after 30 min but, the formation of b-bromohydrine which occurs through
the reaction of bromide ion with epoxide, increases as the concentration of
the micellar solution is increased. Similarly, the solution of triton X-100
both at and above its critical micelle concentration, (Table 1, Entries 8, 9),
was found not to be a suitable micellar media, since the reactions were not
completed after several hours.
Due to the cheapness and more clean reaction of styrene oxide in
SDS micellar solution, we choose SDS solution (ꢂ 0.1 M) as a suitable reac-
tion media for the ring opening of epoxides with different carboxylates. The
reaction of epoxides carrying electron-releasing or withdrawing groups with

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2290
IRANPOOR ET AL.
sodium acetate and propionate occurred efficiently at room temperature and
their corresponding b-carboxy alkanols were obtained in high yields. It was
interesting to apply this method for ring opening of epoxides with a
less reactive carboxylate such as sodium benzoate. When sodium benzoate
was reacted with styrene oxide under the same reaction conditions as
applied for sodium acetate, the reaction furnished the corresponding
2-phenyl-2-benzoxy-1-ethanol in 84% yield after 30 min (Table 2, Entry 7).
However, this reaction in the absence of micelle did not proceed at all
and styrene oxide was remained intact. The results obtained for the reaction
of epoxides with carboxylates are shown in Table 2.
Due to the importance of the reaction of epoxides with phenols
from biological points of view,[21c] and in order to avoid the strong alkaline
conditions for this important synthetic transformation, we decided to
apply our method for the ring opening of epoxides with phenoxide
anions. We first studied the reaction of different substituted epoxides with
Table 2. Reaction of Epoxides with Carboxylates and Phenoxides Catalyzed with
Ce(OTf)4 in SDS (0.1M) at Room Temperature
Mole Ratio of
Sub./Cat./
NaNu
Reference
Time YieldI to the
Entry Epoxide Nuclephile
Product (h)
(%) Product.
II
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1a
1b
1c
1d
1a
1b
1c
1a
1b
1d
1a
1b
1c
1e
1e
CH3CO2Na
CH3CO2Na
CH3CO2Na
CH3CO2Na
C2H5CO2Na
C2H5CO2Na
C2H5CO2Na
PhCO2Na
PhCO2Na
PhCO2Na
PhONa
PhONa
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
1/0.1/1.5
ꢀ
2
0.5
1
1
4
5
5
1
0.5
2
85 18b, 20
87 18b, 20
85 18b, 20
88 18b, 20
80 22, 23
88 24, 23
83 23
90 20e
84 25
87 25
92 26
2b
3c
3d
III
ꢀ
2b
3c
IV
ꢀ
2b
3d
V
ꢀ
3
3
1
4
2b
3c
3e
3e
90 27
85 28
89 21c
91 21c
PhONa
4-ClC6H4ONa
4-MeOC6H4ONa
1
IIsolated Yield.
II2-Hydroxycyclohexyl acetate.
III2-Hydroxycyclohexyl propionate.
IV2-Hydroxycyclohexyl benzoate.
V2-Hydroxycyclohexyl phenyl ether.

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RING OPENING OF EPOXIDES IN MICELLAR MEDIA
2291
sodium phenoxide in 0.1 molar solution of SDS and in the presence of
0.1 molar equivalents of Ce(OTf )4 as catalyst. The reactions occurred at
room temperature and the corresponding b-phenoxy alkanols were obtained
in high yields (Table 2). The reaction was then successfully performed with
electron-withdrawing substituted phenols such as 4-chloro, and 4-methoxy
phenols (Table 2, Entries 13, 14).
In conclusion, using a combination of micellar media and Ce(OTf )4
as an stable Lewis acid in aqueous media provides a new, efficient and
simple method for ring opening of epoxides with both aliphatic and
aromatic carboxylates and also with electron-donating and -withdrawing
substituted phenoxide anions at room temperature. The possibility of
using carboxylates instead of their carboxylic acids at room temperature,
and the absence of strong alkaline conditions for ring opening of epoxides
with phenol are the strong practical points of this method.
EXPERIMENTAL
Products were characterised by comparison of their physical data with
those of known samples. All yields refer to isolated products. IR spectra
were recorded on Perkin Elmer 781 spectrometers. NMR spectra were
recorded on Bruker DPX 250.
Catalytic Ring Openig of Styrene Oxide with Sodium Benzoate in
the Presence o f Ce(OTf) in SDS Solution as Typical Procedure
4
A solution of cyclohexene oxide (98 mg, 1 mmol) in SDS (0.1 M, 3 mL)
was prepared. Sodium benzoate (217 mg, 1.5 mmol) and ceric triflate
(73.6 mg, 0.1 mmol) were added to this solution. The reaction mixture was
stirred at room temperature for 1 h. The mixture was extracted with CHCl3
(4 ꢃ 10 mL) and solid NaCl was added during the extraction to remove the
emulsion. The organic layer was dried with anhydrous Na2SO4. The solvent
was evaporated and the resulting mixture was applied on a short column of
silica gel. Elution with petroleum ether gave 2-hydroxycyclohexyl benzoate
in 90% yield, m.p. 104–106ꢁC, Lit.[20d] 105.5–107.5ꢁC.
ACKNOWLEDGMENT
We are thankful to Shiraz University Research Council for partial
support of this work.

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2292
IRANPOOR ET AL.
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RING OPENING OF EPOXIDES IN MICELLAR MEDIA
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Received in the UK January 4, 2001

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