Mild and convenient epoxidation of α,β-unsaturated ketones by amberlyst A-26 supported hydroperoxide

Article abstract of DOI:10.1081/SCC-100104010

The epoxidation of α,β-unsaturated ketones to the corresponding epoxy ketones, using amberlyst A-26 supported hydroperoxide, which is prepared in situ from (35%) hydrogen peroxide and amberlyst A-26(OH^-), is described. Reactions were carried out at room temperature and the corresponding epoxides were isolated in excellent yields.

Full text of DOI:10.1081/SCC-100104010

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MILD AND CONVENIENT
EPOXIDATION OF α,β-
UNSATURATED KETONES BY
AMBERLYST A-26 SUPPORTED
HYDROPEROXIDE
M. M. Lakouraj a , B. Movassagh b & K. Bahrami a
a Department of Chemistry , Razi University ,
Kermanshah, 67149, Iran
b Department of Chemistry , Razi University ,
Kermanshah, 67149, Iran
Published online: 09 Nov 2006.
To cite this article: M. M. Lakouraj , B. Movassagh & K. Bahrami (2001) MILD AND
CONVENIENT EPOXIDATION OF α,β-UNSATURATED KETONES BY AMBERLYST A-26
SUPPORTED HYDROPEROXIDE, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 31:8, 1237-1242, DOI:
10.1081/SCC-100104010
To link to this article: http://dx.doi.org/10.1081/SCC-100104010
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SYNTHETIC COMMUNICATIONS, 31(8), 1237–1242 (2001)
MILD AND CONVENIENT EPOXIDATION
OF a,b-UNSATURATED KETONES BY
AMBERLYST A-26 SUPPORTED
HYDROPEROXIDE
M. M. Lakouraj,* B. Movassagh,* and K. Bahrami
Department of Chemistry, Razi University,
Kermanshah 67149, Iran
ABSTRACT
The epoxidation of a,b-unsaturated ketones to the
corresponding epoxy ketones, using amberlyst A-26 sup-
ported hydroperoxide, which is prepared in situ from (35%)
hydrogen peroxide and amberlyst A-26(OHꢀ), is described.
Reactions were carried out at room temperature and the
corresponding epoxides were isolated in excellent yields.
Polymer-supported reagents and catalysts, especially the anion
exchange resins, have been widely applied in organic transformations.1
Recently, we described an efficient method for the selective conversion of
nitriles to amides using amberlyst A-26 supported hydroperoxide.2 In con-
nection, we have now investigated the synthetic potential of this reagent in
epoxidation of a,b-unsaturated ketones, and found that this reagent has
certain advantages over its homogeneous analog,3,4 in terms of convenient
* Corresponding authors.
1237
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1238
LAKOURAJ, MOVASSAGH, AND BAHRAMI
reaction condition, easier work-up, high yield, and selectivity. The epoxida-
tion reaction is carried out by stirring the unsaturated ketone and commer-
cial (35%) hydrogen peroxide in 1,4-dioxane with a catalytic amount of
amberlyst A-26 (OHꢀ form) at room temperature.
Reactions are very clean and the epoxides are obtained as a sole prod-
uct in good to excellent yields. The work-up of the reaction is accomplished
by simple filtration and evaporation of solvent, and finally purification is
involved. The representative examples illustrating the usefulness of this
method are represented in Table 1. Under the same conditions, a,b-unsatu-
rated aldehyde, cinnamaldehyde (1s), was converted to benzoic acid. The
epoxidation reaction of a,b-unsaturated carboxamides, esters, and car-
boxylic acids was also tried according to this procedure, but no epoxidation
was observed.
EXPERIMENTAL
All unsaturated ketones were prepared using general methods.5 The
products were characterized by comparison of their spectral and physical
data with those of known samples. IR spectra were obtained using a
Shimadzu 470 instrument. 1H NMR spectra were recorded on a JEOL
JNM-PMX 60 MHz and Bruker 80 MHz NMR spectrometer with TMS
as internal standard. Elemental analyses were performed on a FOSS-
Heraeus CHN-O-Rapid instrument. Amberlyst A-26 (OHꢀ form) was pur-
chased from Merck Company or prepared by simple exchange reaction of
chloride form of the resin with 1.0N NaOH aqueous solution.
General Procedure for Conversion of a,b-Unsaturated
Ketones to their Corresponding Epoxy Ketones with Amberlyst
A-26 Supported Hydroperoxide
To a solution of a,b-unsaturated ketones (2.42 mmoles) in 1,4-dioxane
(5ꢀ10 ml), amberlyst A-26 (0.24 mmol, of wet OHꢀ form) and hydrogen

a,b-UNSATURATED KETONES
1239
Table 1. Epoxidation of a,b-Unsaturated Ketones with QþOHꢀH2O2a
No.
R1
R2
Time(h)
Yield
M.p. (found/ꢂC)
a
b
c
d
e
f
Ph
Ph
Ph
Ph
6.5
8.0
4.5
7.5
7.5
6.0
6.0
6.0
6.0
6.0
7.0
5.0
12.0
5.0
6.0
5.0
10.0
6.0
6.0
96
90
94
88
86
85
96
93
91
93
90
94
94
91
95
93
70
94
94
84–85
75–78
4-MeC6H4
4-ClC6H4
Ph
118–120
67–70
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-BrC6H4
3-BrC6H4
3-BrC6H4
Ph
4-ClC6H4
4-BrC6H4
Ph
110–115
127–129
68–71
g
h
i
4-ClC6H4
4-BrC6H4
Ph
116–120
121–123
85–86
j
k
l
4-MeC6H4
4-ClC6H4
2-NH2C6H4
Ph
54–56
92–93
m
n
o
p
q
r
153–154
131–135
145–148
128–133
107–109
54
4-NO2C6H4
4-NO2C6H4
4-NO2C6H4
4-PhCH2OC6H4
Ph
4-MeC6H4
4-ClC6H4
Ph
Me
s
Ph
H
54
b
aSubstrate/H2O2/ A-26(OHꢀ) ratio 1:4:0.1; Isolated yields.
peroxide (35% w/v solution 9.7 mmoles) were added. After a few minutes,
the reaction mixture was stirred magnetically at room temperature
for 4–18 h. The progress of the reaction was monitored by TLC
(eluent: n-hexane/acetone, 2/1). On completion of the reaction, the reaction
mixture was filtered. The solid material was washed with 1,4-dioxane
(2ꢁ5 mL). The solvent was removed under diminished pressure, which
afforded their corresponding epoxides in good yields. The products were
recrystallized from petroleum benzene or diisopropyl ether.
Epoxidation of Benzalacetophenone as a Typical Procedure
To a solution of benzalacetophenone (1a) (0.5 g, 2.43 mmol) in 1,4-
dioxane (5 mL), amberlyst A-26 (0.24 g, 0.24 mmol of wet OHꢀ form) and
hydrogen peroxide (35% w/v solution, 9.7 mmol) were added. After a few

1240
LAKOURAJ, MOVASSAGH, AND BAHRAMI
minutes, the reaction mixture was stirred magnetically at room temperature.
Monitoring by TLC (eluent: n-hexane/acetone: 2/1) showed the completion
of the reaction after 6.5 h. The reaction mixture was filtered and the solid
material was washed with 1,4-dioxane (2ꢁ5 mL). Removal of the solvent
under reduced pressure afforded 1,3-diphenyl-2,3-epoxy-1-propanone (2a),
which recrystallized from diisopropyl ether to yield 0.521 g (96%).
Representative Physical and Spectral Data
1
Compound (2a). H NMR (CDCl3), ꢀ(ppm): 8.25–8.08(m, 2H), 7.7–
7.4(m, 8H), 4.31(d, 1H), 4.12(d, 1H). IR(KBr), ꢁ(cmꢀ1): 750(s), 770(s),
800(s), 890(m), 1005(s), 1240(m), 1405(s), 1450(s), 1580(m), 1590(m),
1687(s), 3000–3050(w). Anal. calc. for C15H12O2: C, 80.3; H, 5.4; N, 0%.
Found: C, 80.4%; H, 5.4%; N, <0.1%. M.p. ¼ 84ꢂ–85ꢂC, lit.6 m.p. ¼
88ꢂ–89ꢂC.
1
Compound (2b). H NMR (CDCl3), ꢀ(ppm): 8.1–7.92(m, 2H), 7.6–
7.3(m, 7H), 4.31(d, 1H), 4.12(d, 1H), 2.27(s, 3H). IR(KBr), ꢁ(cmꢀ1):
750(s), 800(s), 900(m), 1010(m), 1180(m), 1240(m), 1400(m), 1600(s),
1680(s), 3000–3050(w). M.p.¼75ꢂ–78ꢂC.
1
Compound (2c). H NMR (CDCl3), ꢀ(ppm): 8.24–8.05(m, 2H), 7.7–
7.35(m, 7H), 4.32(d, 1H), 4.1(d, 1H). IR(KBr), ꢁ(cmꢀ1): 715(s), 795(s),
800(m), 880(m), 1000(s), 1085(s), 1180(m), 1230(m), 1415(s), 1560(m),
1580(s), 1677(s), 3000–3050(w). M.p.¼118ꢂ–120ꢂC.
1
Compound (2d). H NMR (CDCl3), ꢀ(ppm): 8.25–8.07(m, 2H), 7.7–
7.1(m, 7H), 4.31(d, 1H), 4.12(d, 1H), 2.25(s, 3H). IR(KBr), ꢁ(cmꢀ1): 750(s),
780(s), 800(s), 880(m), 1000(s), 1060(m), 1100(m), 1240(m), 1380(s),
1500(m), 1590(s), 1680(s), 3000–3050(w). M.p.¼67ꢂ–70ꢂC.
1
Compound (2e). H NMR (CDCl3), ꢀ(ppm): 8.25–8.08(m, 2H), 7.7–
7.1(m, 6H), 4.32(d, 1H), 4.12(d, 1H), 2.25(s, 3H). IR(KBr), ꢁ(cmꢀ1):
750(s), 770(s), 800(s), 820(s), 900(m), 1010(s), 1090(s), 1180(m), 1235(m),
1290(s), 1400(s), 1580(s), 1674(s), 3000–3050(w). M.p.¼110ꢂ–115ꢂC.
1
Compound (2f). H NMR (CDCl3), ꢀ(ppm): 8.25–8.08(m, 2H), 7.7–
7.17(m, 6H), 4.32(d, 1H), 4.12(d, 1H), 2.25(s, 3H). IR(KBr), ꢁ(cmꢀ1):
760(s), 800(s), 820(s), 900(m), 1010(s), 1090(s), 1180(m), 1230(s), 1300(s),
1400(s), 1600(s), 1677(s), 3000(s)–3050(w). M.p.¼127ꢂ–129ꢂC.
Compound (2g). 1H NMR (CDCl3), ꢀ(ppm): 8.3–8.1(m, 2H), 7.7–
7.36(m, 7H), 4.32(d, 1H), 4.12(d, 1H). IR(KBr), ꢁ(cmꢀ1): 780(s), 800(s),
820(s), 840(s), 890(m), 1010(s), 1090(s), 1235(m), 1390(m), 1430(s),
1445(s), 1590(s), 1687(s), 3000–3050(w). M.p.¼68ꢂ–71ꢂC.
1
Compound (2h). H NMR (CDCl3), ꢀ(ppm): 8.3–8.1(m, 2H), 7.71–
7.4(m, 6H), 4.32(d, 1H), 4.12(d, 1H). IR(KBr), ꢁ(cmꢀ1): 760(s), 800(s),

a,b-UNSATURATED KETONES
1241
820(s), 890(m), 1000(m), 1090(s), 1230(m), 1400(m), 1420(m), 1580(s),
1677(s), 3000–3050(w). M.p.¼116ꢂ–120ꢂC.
1
Compound (2i). H NMR (CDCl3), ꢀ(ppm): 8.25–8.05(m, 2H), 7.71–
7.4(m, 6H), 4.32(d, 1H), 4.12(d, 1H). IR(KBr), ꢁ(cmꢀ1): 730(s), 800(s),
820(s), 880(m), 1000(s), 1060(m), 1235(m), 1400(s), 1430(m), 1480(m),
1580(s), 1677(s), 3000–3050(w). M.p.¼121ꢂ–123ꢂC.
Compound (2j). 1H NMR (CDCl3), ꢀ(ppm): 8.06–7.95(m, 2H),
7.65–7.15(m, 7H), 4.25(d, 1H), 4.05(d, 1H). IR(KBr), ꢁ(cmꢀ1): 780(s),
800(s), 840(s), 890(m), 1010(s), 1070(m), 1290(m), 1390(m), 1310(s),
1440(m), 1480(m), 1580(s), 1590(m), 1661(s), 3000–3050(w). M.p.¼85ꢂ–
86ꢂC.
1
Compound (2k). H NMR (CDCl3), ꢀ(ppm): 8.05–7.99(m, 2H), 7.6–
7.2(m, 6H), 4.31(d, 1H), 4.12(d, 1H), 2.25(s, 3H). IR(KBr), ꢁ(cmꢀ1): 730(s),
800(s), 890(m), 1000(m), 1060(m), 1120(m), 1180(s), 1240(s), 1280(m),
1400(s), 1600(s), 1677(s), 3000–3050(w). M.p.¼54ꢂ–56ꢂC.
1
Compound (2l). H NMR (CDCl3), ꢀ(ppm): 8.25–8.08(m, 2H), 7.7–
7.4(m, 6H), 4.32(d, 1H), 4.15(d, 1H). IR(KBr), ꢁ(cmꢀ1): 730(s), 770(s),
800(s), 830(s), 880(m), 1000(s), 1190(s), 1230(m), 1340(m), 1410(s),
1560(m), 1580(s), 1680(s), 3000–3050(w). M.p.¼92ꢂ–93ꢂC.
1
Compound (2m). H NMR (CDCl3), ꢀ(ppm): 7.6–7.4(m, 1H), 7.25–
7(m, 6H), 6.6–6.2(m, 2H), 6.1(broad, s, 2H), 4.31(d, 1H), 4.12(d, 1H).
Anal. calcd. for C15H12O2: C, 75.3%; H, 5.47%; N, 5.8%. Found: C,
75.1%; H, 5.5%; N, 5.7%. M.p.¼153ꢂ–154ꢂC.
1
Compound (2n). H NMR (CDCl3), ꢀ(ppm): 8.25–7.95(m, 2H), 7.3–
7.15(m, 7H), 4.1(d, 1H), 4(d, 1H). IR(KBr), ꢁ(cmꢀ1): 700(s), 740(m), 840(s),
1000(s), 1100(s), 1230(m), 1340(s), 1520(s), 1600(s), 1680(s), 3000–3050(w).
M.p.¼131ꢂ–135ꢂC.
1
Compound (2o). H NMR (CDCl3), ꢀ(ppm): 8.25–7.95(m, 2H), 7.83–
7.65(m, 2H), 7.4–7(m, 4H), 4.05 (d, 1H), 4.(d, 1H), 2.25(s, 3H). IR(KBr),
ꢁ(cmꢀ1): 730(s), 805(s), 880(m), 1000(s), 1100(m), 1180(s), 1240(m), 1340(s),
1520(s), 1600(s), 1690(s), 3000–3050(w). M.p.¼145ꢂ–148ꢂC.
1
Compound (2p). H NMR (CDCl3), ꢀ(ppm): 8.1–7.8(m, 2H), 7.75–
7.15(m, 6H), 4.05(d, 1H), 3.99(d, 1H). IR(KBr), ꢁ(cmꢀ1): 735(s), 800(s),
830(s), 860(m), 1000(s), 1080(s), 1235(m), 1340(s), 1520(s), 1590(s),
1690(s), 3000¼3050(w). M.p.¼128ꢂ–133ꢂC.
1
Compound (2q). H NMR (CDCl3), ꢀ(ppm): 8.2–8(m, 2H), 7.8–7.4(m,
12H), 4.42(s, 2H), 4.32(d, 1H), 4.12(d, 1H). IR(KBr), ꢁ(cmꢀ1): 800(s),
880(m), 1010(s), 1100(m), 1180(m), 1250(s), 1280(m), 1440(m), 1510(s),
1600(s), 1661(s), 2980–3050(w). M.p.¼107ꢂ–109ꢂC.
1
Compound (2r). H NMR (CDCl3), ꢀ(ppm): 7.42–7.22(m, 5H), 3.99(d,
1H), 3.48(d, 1H), 2.2(s, 3H). IR(KBr), ꢁ(cmꢀ1): 750(s), 790(s), 850(s), 880(s),
900(m), 1240(m), 1580(s), 1712(s), 2980¼3020(w). M.p.¼54ꢂC.

1242
LAKOURAJ, MOVASSAGH, AND BAHRAMI
ACKNOWLEDGMENTS
We are indebted to Professor B. Tamami for valuable discussion. This
investigation was supported by a grant from the Razi University Research
Council.
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Accepted July 7, 2000