Epoxidation of 1,4-diaroyl ethene derivatives in the presence of UHP or H2O2

Article abstract of DOI:10.1080/00397910903372333

Hydrogen peroxide (H₂O₂) or urea-hydrogen peroxide (UHP) in basic media react with carbon-carbon double bonds of 1,4-diaroyl ethenes to produce the corresponding epoxides. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910903372333

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Epoxidation of 1,4-Diaroyl Ethene
Derivatives in the Presence of UHP or
H2O2
Nosrat O. Mahmoodi a , Mohammad R. Yazdanbakhsh a & Fateme
Ghanbari a
a Department of Chemistry , Faculty of Sciences, University of
Guilan , Iran
Published online: 04 Oct 2010.
To cite this article: Nosrat O. Mahmoodi , Mohammad R. Yazdanbakhsh & Fateme Ghanbari
(2010) Epoxidation of 1,4-Diaroyl Ethene Derivatives in the Presence of UHP or H2O2 , Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
40:21, 3181-3185, DOI: 10.1080/00397910903372333
To link to this article: http://dx.doi.org/10.1080/00397910903372333
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Synthetic Communications1, 40: 3181–3185, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903372333
EPOXIDATION OF 1,4-DIAROYL ETHENE DERIVATIVES
IN THE PRESENCE OF UHP OR H2O2
Nosrat O. Mahmoodi, Mohammad R. Yazdanbakhsh, and
Fateme Ghanbari
Department of Chemistry, Faculty of Sciences, University of Guilan, Iran
Hydrogen peroxide (H2O2) or urea–hydrogen peroxide (UHP) in basic media react with
carbon–carbon double bonds of 1,4-diaroyl ethenes to produce the corresponding epoxides.
Keywords: 1,4-Diaroyl ethenes; epoxidation; hydrogen peroxide; UHP
Epoxides are well known as valuable building blocks that can be used as intermediates
and precursors for chemical production. Therefore, the epoxidation reaction is an
important transformation of carbon–carbon double bonds. Many epoxidation
reactions have been done on the carbon–carbon double bonds using sodium hypo-
chlorite,[1] sodium peroxide,[2] m-chloroperbenzoic acid,[3] oxone,[4] dimethyloxir-
ane,[5] hydrogen peroxide,[6] and urea–hydrogen peroxide (UHP).[7] Bentley et al.
reported epoxidation of chalcones with UHP in an organic solvent in the presence
of 1,8-diazabicycloundec-7-ene (DBU) and poly-(L)-leucine in 1997.[8] Recently, Jin
et al. reported epoxidation of chalcones with UHP under ultrasound irradiation.[7]
Some epoxidations have been done on a,b-unsaturated compounds including
hydrogen peroxide,[9] poly-L-leucine=H2O2 (Julia–Colonna epoxidation)[8] for ennan-
tiomeric epoxidation, NaOCl,[10] and H2O2=[cnMIm][PF6].[11]
RESULTS AND DISCUSSION
To contribute to these epoxide syntheses, we decided to transform some
1,4-diaroyl ethenes (1) to their epoxides (2) utillizing two available reagents and con-
sidering their reactions time and yields. So far, no published methodology in the
literature for epoxidation of 1,4-diaroyls had been reported. For this epoxidation,
our adopted two reagents were (1) H2O2=Na2CO3 and (2) urea–hydrogen peroxide
(UHP)=NaOH (Scheme 1). Hydrogen peroxide has an active oxygen content about
as high as molecular oxygen, and the waste product by employing this oxidant is
plain water. UHP is a white crystalline solid formed from urea and hydrogen
Received August 26, 2009.
Address correspondence to Nosrat O. Mahmoodi, Department of Chemistry, Faculty of Sciences,
University of Guilan, P. O. Box 1914, Iran. E-mail: mahmoodi@guilan.ac.ir
3181

3182
N. O. MAHMOODI, M. R. YAZDANBAKHSH, AND F. GHANBARI
Scheme 1. Two adopted reagents for epoxidation of 1,4-diaroyl ethenes.
peroxide.[7] This solid has a high hydrogen peroxide content and releases it in a
controlled manner, with green by-products. In comparison with many epoxidation
reactions that used MeOH,[12] toluene,[10] and CH2Cl2
procedure EtOH worked excellently.
as solvents, in our
[10]
The produced epoxides are symmetric and have two identical carbonyl groups;
these functional groups have potential for subsequent reactions and produce various
compounds. For example, like in some reactions that have been done on epoxy
ketones, they can be hydrolised,[13] converted to corresponding esters by Baeyer–
Villiger oxidation,[14] and undergo epoxy ring opening by nucleophilic addition.[15]
The 1,4-diaroyl compounds were prepared according to the literature[16] and
then underwent epoxidation. The mechanism for epoxidation by either H2O2 or
UHP is depicted in Scheme 2.
In either method, first OOHꢀ is formed in situ and then added to the unreactive
enone unit (1) to generate intermediate hydroperoxide enolate (3). This reactive
enolate, by excluding the OHꢀ, led to the formation of the epoxide (2) (Scheme 2).
Scheme 2. The mechanism for epoxidation of 1,4-diaroyl ethenes using either H2O2 or UHP.

EPOXIDATION OF 1,4-DIAROYL ETHENE DERIVATIVES
3183
Table 1. Epoxidation of 1,4-diaroyl ethenes
Substrate
Product
Reagent
Time (h)
Yield (%)
1a
2a
H2O2=Na2CO3
UHP=NaOH
H2O2=Na2CO3
UHP=NaOH
H2O2=Na2CO3
UHP=NaOH
H2O2=Na2CO3
UHP=NaOH
8
60
76
90
75
55
60
70
55
6
1b
1c
1d
2b
2c
2d
10
14
10
15
14
20
A few minutes after adding of reagents to the compound 1a, the color of
the solution changed from deep yellow to white. This demonstrated that the
intermediate (3) instantaneously was formed. Monitoring a reaction with thin-layer
chromatography (TLC) indicated that a trace of 1a still was present. However, for
2a after 6 h, TLC did not show any 1a. Table 1 shows that compound 1a has the
shortest and 1d has the longest reaction time.
As expected, both our adapted reagents attacked the double bond of 1a–d
from both side of 1 equally, so for the epoxids 2a–d, a mixture of symmetrical
racemic compounds was obtained.
CONCLUSION
In conclusion, for the first time some new epoxides were synthesized from
premade 1,4-diaroyl ethenes (1) through a safe and green procedure utillizing
available and cheap reagents. These epoxidation reagents are environmentally
friendly and useful for the industrial proposes.
EXPERIMENTAL
Melting points were measured on a Mettler Fp5 apparatus and are uncor-
rected. The infrared (IR) spectra were recorded on a Shimadzu IR-470 spectrophot-
ometer. The 1H NMR spectra were recorded on a Bruker 500-MHz instrument using
solvent as internal standard (CDCl3 at 7.31 ppm).
General Procedure for the Formation of Epoxides 2a–d Utilizing
H2O2/Na2CO3
To a solution of sodium carbonate (0.25 g) in water (1 ml), hydrogen peroxide
(30%, 0.25 ml) was added. This mixture was added to corresponding but-2-ene-1,4-
diones 1a–d (1 mmol) in ethanol (3 ml). The mixture was vigorously stirred at
room temperature; after completion of the reaction (monitored by thin-layer
chromatography, TLC, petroleum ether=ethyl acetate 3:1), the precipitate solid
was filtered and washed with water. Then solid was recrystallized from ethanol to
yield the desired compound.

3184
N. O. MAHMOODI, M. R. YAZDANBAKHSH, AND F. GHANBARI
General Procedure for the Formation of Epoxides 2a–d Utilizing UHP
An aqueous solution of NaOH (4%, 0.2 ml) and UHP (0.15 g) was added to
a solution of corresponding but-2-ene-1,4-diones 1a–d (1 mmol) in ethanol (5 ml).
The mixture was vigorously stirred at room temperature. After completion of the
reaction (monitored by TLC, petroleum ether=ethyl acetate 3:1), the precipitate solid
was filtered and washed with water. The solid was recrystallized from ethanol to
yield the desired compound.
The produced epoxides utilizing UHP have the same melting points, IR, and 1H
NMR spectra as the epoxides produced by H2O2=Na2CO3.
Selected Data
2,3-Epoxy-1,4-diphenyl-1,4-butanone 2a. Yield 60%, mp 130–131 ꢁC,
1
white solid. IR (KBr, n=cmꢀ1): 3080, 1670, 1600, 1240, 940, 880. H NMR (CDCl3,
500 MHz) d: 4.54 (s, 1H), 7.58 (t, 2H, J ¼ 8 Hz), 7.71 (t, 1H, J ¼ 7.4 Hz), 8.11 (d, 2H,
J ¼ 7.2 Hz). Anal. calcd. for C16H12O3; C, 76.18; H, 4.79; found: C, 76.20; H, 4.80.
2,3-Epoxy-1,4-(2,4-dimethyl)diphenyl-1,4-butanone 2b. Yield 85%, mp
80–81 ꢁC, white solid. IR (KBr, n=cmꢀ1): 3050, 2980, 1670, 1560, 1440, 1280,
1
1220, 890. H NMR (CDCl3, 500 MHz) d: 2.43 (s, 6H), 2.56 (s, 6H), 4.31 (s, 2H),
7.17 (d, 2H, J ¼ 7.4 Hz), 7.78 (d, 2H, J ¼ 8.1 Hz). Anal. calcd. for C20H20O3; C,
77.90; H, 6.54; found: C, 77.93; H, 6.56.
2,3-Epoxy-1,4-(4-chloro)diphenyl-1,4-butanone 2c. Yield 55%, mp
175–176 ꢁC, white solid. IR (KBr, n=cmꢀ1): 3050, 1670, 1590, 1400, 1090, 890.1H
NMR (CDCl3, 500 MHz) d: 4.47 (s, 1H), 7.56 (d, 2H, J ¼ 8.5 Hz), 8.06 (d, 2H,
J ¼ 8.5 Hz). Anal. calcd. for C16H10Cl2O3: C, 59.84; H, 3.14; Cl, 22.08; found: C,
59.86; H, 3.17; Cl, 22.11.
2,3-Epoxy-1,4-(4-bromo)-diphenyl-1,4-butanone 2d. Yield 65%, mp
1
187–188 ꢁC, white solid. IR (KBr, n=cmꢀ1): 3100, 3050, 1670, 1585, 1400, 890. H
NMR (CDCl3, 500 MHz) d: 4.46 (s, 1H), 7.73 (d, 2H, J ¼ 8.5 Hz), 7.98 (d, 2H,
J ¼ 8.5 Hz). Anal. calcd. for C16H10Br2O3: C, 46.86; H, 2.46; Br, 38.97; found: C,
46.89; H, 2.47; Br, 38.99.
ACKNOWLEDGMENT
This study was supported in part by the Research Committee of the University
of Guilan.
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