Mendeleev
Communications
Mendeleev Commun., 2014, 24, 345
A convenient synthesis of cyclopropane malonyl peroxide
Alexander O. Terent’ev,* Vera A. Vil’, Olga M. Mulina, Kazimir K. Pivnitsky and Gennady I. Nikishin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
Fax: +7 499 135 8824; e-mail: alterex@yandex.ru
DOI: 10.1016/j.mencom.2014.11.010
Cyclopropane-1,1-dicarbonyl peroxide was prepared in 85% yield by the reaction of diethyl cyclopropane-1,1-dicarboxylate with the
urea hydrogen peroxide clathrate in the presence of methanesulfonic acid.
1
O
O
O
O
O
Cyclic diacyl peroxide oxidation known since the 1950s has
recently undergone a renaissance.2,3 Cyclopropane malonyl
peroxide 1 is the most widely used and the most active oxidizing
(CH2Br)2, NaOH
EtO
EtO
OEt
HO
OH
via formation of 3
agent among malonyl peroxides.2
(a),(b),(d),(f),(g)
2
The main preparative synthesis of compound 1 is based on
the reaction of cyclopropane-1,1-dicarboxylic acid 2 with urea
hydrogen peroxide clathrate in the presence of methanesulfonic
(
CH2Br)2
K CO
2
H2O2·CO(NH2)2
MeSO3H
3
2
(a),(f)
O
O
O
acid (Scheme 1).
H2O2·CO(NH2)2
MeSO3H
Diacid 2 was prepared in moderate (52–72%) yields in one-
pot by alkylation of diethyl malonate with 1,2-dibromoethane
in the presence of alkali and a phase-transfer catalyst via the
stages of formation and hydrolysis of cyclopropane diester 3.
Higher yield of diacid 2 can be achieved by two-step proce-
dure. First, diester 3 was obtained in 92% yield by alkylation
of diethyl malonate with 1,2-dibromoethane in the presence of
K CO and a phase-transfer catalyst. Second, diacid 2 was
prepared in high yield by hydrolysis of ester 3. However, this
two-step procedure is more laborious.
Here, we demonstrated that peroxide 1 can be directly prepared
in 85% yield by the reaction between diethyl cyclopropane-
,1-dicarboxylate 3 and urea hydrogen peroxide clathrate in the
presence of methanesulfonic acid. This reaction is a rare example
of the synthesis of peroxides from esters, since peroxides are
O
O
OEt
3
1
2(f),4
Scheme 1
5
,6
References
2
3
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1
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†
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8
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5
0, 10495; (c) C. Yuan, A. Axelrod, M. Varela, L. Danysh and D. Siegel,
The method developed in the present study provides an essentially
facile approach to the synthesis of peroxide 1. The reaction can
be scaled up to yield gram amounts providing total yield 78%
based on diethyl malonate 3, thus making cyclopropyl malonyl
peroxide 1 readily available in laboratory practice.
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†
Synthesis of cyclopropane-1,1-dicarbonyl peroxide 1. Caution:Although
7
we have encountered no difficulties in working with peroxides, precautions,
such as the use of shields, fume hoods, and the avoidance of transition
metal salts, heating and shaking, should be taken whenever possible.
Urea hydrogen peroxide clathrate (50.80 g, 0.540 mol) was added with
stirring to methanesulfonic acid (155.70 g, 105.13 ml), and the mixture
was stirred for 2 min. Then diethyl cyclopropane-1,1-dicarboxylate 3 (10.00 g,
6
7
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0
.054 mol) was added, and the mixture was stirred for 24 h. Water (200 ml)
and ethyl acetate (200 ml) were added, the organic layer was separated,
and the aqueous layer was extracted with ethyl acetate (4×50 ml). The
combined organic layers were washed with water (2×30 ml), a 5% aqueous
NaHCO solution (2×30 ml), and again with water (2×30 ml) and dried over
MgSO . The solvent was removed under water jet vacuum. Product 1 was
3
4
obtained as white crystals in 85% yield (5.88 g, 0.046 mol), mp 89–91°C
2(a)
1
13
(
lit., mp 90°C). H NMR (300.13 MHz, CDCl ) d: 2.11 (s, 4H). C NMR
3
(
75.48 MHz, CDCl ) d: 19.8, 23.6, 172.1.
Received: 20th August 2014; Com. 14/4449
3
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