Epoxidation of olefins at low temperature using m-chloroperbenzoic acid

Article abstract of DOI:10.1081/SCC-120004069

Epoxidation of olefins using m-chloroperbenzoic acid in dichloromethane without catalyst at low temperature is described.

Full text of DOI:10.1081/SCC-120004069

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EPOXIDATION OF OLEFINS AT LOW TEMPERATURE USING
m-CHLOROPERBENZOIC ACID*
R. Srinivasan a , M. Chandrasekharam a , P. V. S. N. Vani a , A. Seema Chida a & A. K. Singh b
a Fine Chemicals Laboratory, Division of Organic Chemistry-III, Indian Institute of Chemical
Technology, Hyderabad, 500 007, India
b Fine Chemicals Laboratory, Division of Organic Chemistry-III, Indian Institute of Chemical
Technology, Hyderabad, 500 007, India
Version of record first published: 17 Oct 2011.
To cite this article: R. Srinivasan , M. Chandrasekharam , P. V. S. N. Vani , A. Seema Chida & A. K. Singh (2002): EPOXIDATION
OF OLEFINS AT LOW TEMPERATURE USING m-CHLOROPERBENZOIC ACID*, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 32:12, 1853-1858
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SYNTHETIC COMMUNICATIONS, 32(12), 1853–1858 (2002)
EPOXIDATION OF OLEFINS AT LOW
TEMPERATURE USING
m-CHLOROPERBENZOIC ACID*
R. Srinivasan, M. Chandrasekharam, P. V. S. N. Vani,
A. Seema Chida, and A. K. Singhy
Fine Chemicals Laboratory, Division of Organic
Chemistry-III, Indian Institute of Chemical Technology,
Hyderabad-500 007, India
ABSTRACT
Epoxidation of olefins using m-chloroperbenzoic acid in
dichloromethane without catalyst at low temperature is
described.
Key Words: Olefins; m-Chloroperbenzoic acid; Epoxides
Epoxides[1a] are important building blocks for the preparation of opti-
cally active diols[1b] and amino alcohols,[1c,d] aziridines,[1e] thieranes[1f] etc.
The increasing attention has been paid to prepare volatile epoxides like 1,2-
and cis & trans 2,3-butylene oxides apart from other epoxides, because of
their commercial uses.[1g,h] The reports on epoxidation of alkenes using
peracids with copper/vanadium/iron salts as catalyst at low temperature
*IICT communication number 4472.
yCorresponding author.
1853
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1854
SRINIVASAN ET AL.
Scheme 1.
are known in literature.[1i,j] In this paper we report the epoxidation of vari-
ety of substrates at low temperature without using any catalyst.
Initially, we have done preliminary experiments on unsubsti-
tuted butylenes to convert to the corresponding volatile butyleneoxides.
When epoxidation has been attempted using m-CPBA in 1,4-dioxane
according to the reported procedure,[1k] the yield of product is not good.
Monoperoxyphthalic acid in ether gave a poor yield of compound 2.
Although the same reaction was performed with m-CPBA in ether at
ꢀ4–0ꢁC, the yield was not improved. Then it was conducted in dichloro-
methane (DCM) at various temperatures i.e., 0–5ꢁC, ꢀ4–0ꢁC and ꢀ11–0ꢁC
and the optimum yields were obtained at ꢀ50–(ꢀ10)ꢁC for 6 h (Scheme 1).
To generalize the above results, the similar study was conducted on
functionalised acyclic, and cyclic olefins and the results are complied in
Table 1. Analytical data of all compounds are matching with the literature
report.[1k,2a–i]
By considering the advantage of this reaction condition at low tem-
perature, we prepared the volatile butyleneoxides from the butylenes, which
are commercially important for drug intermediates. Also we have success-
fully utilized this condition for the conversion of other olefins with alcohol,
and acetate groups to their corresponding epoxides.
EXPERIMENTAL
General Procedure for Epoxidation
Butylene (300 g, 5.357 mol) was collected in a precooled (ꢀ50ꢁC)
round bottom flask (10L) fitted with overhead mechanical stirrer, a cold

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EPOXIDATION OF OLEFINS
1855

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SRINIVASAN ET AL.

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EPOXIDATION OF OLEFINS
1857
finger maintained at ꢀ78ꢁC and diluted with cold DCM (0.5 L). m-CPBA
(1347 g, 5.464 mol, 70%) in DCM (5.5 L) was added dropwise with stirring
over a period of an hour. Stirring was continued at the same temperature for
about 4 h and it was allowed to rise to ꢀ10ꢁC during a period of 2 h. The
insoluble material was filtered off and washed with cold DCM (3 ꢂ 0.3 L).
The washings were combined and it was subsequently washed with 10%
Na2SO3 solution (2 ꢂ 1 L), 5% NaOH solution (2 ꢂ 1 L), satd. NaCl sol-
ution (3 ꢂ 1 L) and dried over anhydrous Na2SO4. Removal of DCM and
distillation of compounds 11, 12 and 13 were carried out by using reflux
divider with timer. All other compounds (14–20) were purified by silica gel
column chromatography.
ACKNOWLEDGMENT
The authors thank Dr. K. V. Raghavan, Director, IICT for his
encouragement.
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1858
SRINIVASAN ET AL.
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1
3. Compound 15: H NMR (200 MHz, CDCl3): d 1.29 (s, 3H, CH3); 1.31
(s, 3H, CH3); 2.05 (s, 3H, COCH3); 2.85 (dd, J ¼ 7.9 & 4.7 Hz, 1H,
O-CH); 3.95 (dd, J ¼ 12.6 & 7.1 Hz, 1H, OOC-CH2); 4.22 (dd,
J ¼ 12.6 & 4.7 Hz, 1H, OOC-CH2).
Received in the Netherlands June 27, 2001