Metal-Free and Efficient Epoxidation of α,β-Unsaturated Ketones with 1,1,2,2-Tetrahydroperoxy-1,2-Diphenylethane as a Powerful Solid Oxidant

Article abstract of DOI:10.1002/jccs.201700026

1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane was used for the efficient and metal-free epoxidation of various α,β-unsaturated ketones, carried out under mild alkaline conditions at room temperature.

Full text of DOI:10.1002/jccs.201700026

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Metal-Free and Efficient Epoxidation of α,β-Unsaturated Ketones with 1,1,2,2-
Tetrahydroperoxy-1,2-Diphenylethane as a Powerful Solid Oxidant
a
a
b
*
Kaveh Khosravi , Shirin Naserifar and Boshra Mahmoudi
aDepartment of Chemistry, Faculty of Science, Arak University, Arak 38156-8-8349, Iran
bChemical Engineering Department, Faculty of Engineering, Soran University, Soran, Erbil 440018, Iraq-Kurdistan
(Received: January 21, 2017; Accepted: March 10, 2017; DOI: 10.1002/jccs.201700026)
1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane was used for the efficient and metal-free epoxidation
of various α,β-unsaturated ketones, carried out under mild alkaline conditions at room
temperature.
Keywords: 1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane; Metal-free; Epoxidation;
α,β-Unsaturated ketones.
INTRODUCTION
Epoxidation of carbon–carbon double bonds in
peroxide (UHP)19,20 under alkaline conditions. All the
mentioned oxidants have some deficiencies such as sol-
vent toxicity, expensive catalysts, long reaction times,
and low yields.
α,β-unsaturated ketones has been receiving much atten-
tion due to the various applications of epoxy ketones in
organic synthetic chemistry1,2 and their considerable
promise in the synthesis of various pharmaceutical com-
pounds.3,4 In addition, their industrial uses in surfac-
tants or detergents (tensides), antistatic or anticorrosion
agents, laundry detergents, lubricating oils, textiles, and
cosmetics production5,6 have gained great importance.
Hence, much effort has been devoted to finding highly
efficient methodologies for their synthesis. In recent
years, α,β-unsaturated ketones have received considera-
ble interest due to their wide utilization in perfume for-
mulations and in the production of flavoring
substances.7,8 Many procedures have been developed to
yield epoxides using a multitude of oxidants and cata-
lytic systems. The most frequently used oxidant has
been hydrogen peroxide since it is nontoxic and availa-
ble at low cost, and also because it produces water as
the only byproduct.5,9 But because of its low oxidation
potential, catalytic-based systems are required, or its
hydroperoxide form is applied to carry out the reac-
tions. A number of other oxidants have been employed
to afford the corresponding epoxy ketones, such as
sodium hypochlorite,10 m-chloroperbenzoic acid,11
sodium chlorite,12 oxone,13 trichloroisocyanuric
acid,14 dimethyldioxirane,15 t-butyl hydroperoxide,16,17
peroxide-ammonium fluoride,18 and urea-hydrogen
During the studies to find a noble oxidant, gem-
dihydroperoxides were found to possess sufficient oxida-
tive power in converting several materials to their corre-
sponding products. Basically, gem-dihydroperoxides
were considered because of their relevance to peroxide-
based antimalarial drugs.21,22 Soon it was proven that
these compounds have the potential to serve as oxidants,
but their callous synthesis23 was an obstacle hindering
their application as oxidants. In recent years, several
methodologies have been elaborated for the easy prepa-
ration of gem-dihydroperoxides.24 Moreover, these com-
pounds have important utility as oxidizing agents in a
variety of procedures including epoxidation of
α,β-unsaturated ketones,25 as precursors for the synthesis
of dicarboxylic acid esters,26 and as initiators for radical
polymerization reactions,27 enantioselective oxidation of
2-substituted 1,4-naphtoquinones,28 and oxidation of sul-
fides and benzothiazoles.29 Also, they function as inter-
mediates to yield numerous peroxides: for instance,
tetraoxanes,30,31
endoperoxides,32
silateraoxanes,33
spirobisperoxyketals,34,35 bisperoxyketals,36 and 1,2,4,5-
tetraoxacycloalkanes.37,38
As an extension of our interest in evaluating the
oxidative potential of gem-dihydroperoxides,24,25,29,39
we were intrigued by the investigation through the
*Corresponding author. Email: khosravi.kaveh@gmail.com, k-khosravi@araku.ac.ir
J. Chin. Chem. Soc. 2017
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1

Article
Khosravi et al.
In addition, different bases such as 1,4-diazabicyclo
[2.2.2]octane (DABCO), MgO, Hexamethylenetetramine
(HMTA), and NaOH were applied, and the effects were
studied carefully. On the basis of experimental evidences,
KOH was identified as the best base for this reaction by
which the corresponding epoxide (2a) was produced in high
yield (Table 1, entry 1) while in presence of HTMA the
reaction yield decreased to 10% (Table 1, entry 4). Also, to
establish the oxidant’s efficiency, the model reaction was car-
ried out with UHP as a solid peroxide (Table 1, entry 17).
According to the obtained results, t1,1,2,2-tetrahydroperoxy-
1,2-phenylethane (THPDPE) was the best oxidant. Based
on the mentioned results above, the optimized reaction
conditions were found as follows: α,β-unsaturated ketones
(1 mmol), 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane
(0.5 mmol), aq. KOH (1 M, 1 mL), and 1,4-dioxane
(4 mL). To understand the scope of the reaction, the
reactions of different α,β-unsaturated ketones under
the optimized conditions were investigated, and the
results are summarized in Table 2.
Scheme 1. Synthesis of 1,1,2,2-tetrahydroperoxy-1,2-
phenylethane.
synthesis (Scheme 1)40 and application of 1,1,2,2-tetra-
hydroperoxy-1,2-diphenylethane as a solid and efficient
oxidant in the facile and metal-free transformation of
α,β-unsaturated ketones to their corresponding epoxides
under mild alkaline conditions at room temperature
(Scheme 2).
RESULTS AND DISCUSSION
In an effort to determine the optimized reaction
conditions, we studied several parameters using a model
epoxidation reaction of E-chalcone (a) with 1,1,2,2-
tetrahydroperoxy-1,2-diphenylethane under mild alka-
line conditions in various solvents at room temperature
(Table 1).
A plausible mechanism for the reaction is pro-
posed, as shown in Scheme 3. Epoxy ketones were pre-
pared by the treatment of α,β-unsaturated ketones with
THPDPE under mild alkaline conditions via the Weitz–
Scheffer reaction. First, OH− deprotonates THPDPE.
Then ROO− attacks the enone unit in the chalcone, and
peroxidic enolate is generated as an intermediate.
Finally, the intermediate undergoes SN2 cyclization and
the corresponding epoxide is produced.
Experimental evidence showed that all the chal-
cone derivatives were converted to their corresponding
epoxy ketones in high yields. Obviously, reactivity of
the double bond in chalcones is decreased because of its
conjugation with the aryl ring, as cyclohex-2-en-1-one
and mesityl oxide being a cyclic and acyclic aliphatic α,
β-unsaturated and unconjugated ketone, respectively,
yielded their corresponding epoxy ketone faster than
their conjugated aromatic analogs (Table 2, entries 2t
and 2u). Based on our results shown in Table 2,
electron-withdrawing substituents led to shorter reac-
tion times (Table 2, entries 2e, 2f, 2n, 2o, and 2q),
whereas electron-donating substituents led to longer
reaction times (Table 2, entries 2b, 2c, and 2g). Also,
electron-donating atoms to carbonyl group such as oxy-
gen and nitrogen clearly caused longer reaction times
(Table 2, entries 2v and 2w). Looking at the mechanism
presented in Scheme 3, it is noticeable that the more
Initially, we investigated the effect of the mole per-
cent of the oxidant on the reaction. As shown in
Table 1, the best result in terms of yield was obtained
when using 0.5 mmol of the oxidant (Table 1, entry 1).
Then, the effect of the solvent on the epoxidation
reaction was studied. It was found that nonpolar n-
hexane was not a proper solvent since only a trace
amount of the epoxide (2a) was obtained (Table 1,
entry 10). Also, the reaction was carried out using H2O,
CH2Cl2, and CHCl3 and the desired epoxides (2a) were
obtained in 5%, 15%, and 20% yield, respectively
(Table 1, entries 7, 11, 12). Other polar solvents were
found to enhance the reaction conditions to better the
yields and gave the desired product (2a) in 60% yield in
dimethyl ether (DME) (Table 1, entry 6), in 90% yield
in ethanol (EtOH) (Table 1, entry 8), and in 90% yield
in acetonitrile (MeCN) (Table 1, entry 9). However, the
reaction was carried out in 1,4-dioxane to afford an
even better yield of 97% within 0.5 h (Table 1, entry 1).
Scheme 2. Epoxidation of chalcones by 1,1,2,2-tetra-
hydroperoxy-1,2-phenylethane.
2
www.jccs.wiley-vch.de
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2017

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Epoxidation of α,β-Unsaturated Ketones
Table 1. Optimization of reaction conditions for epoxidation of (E)-chalcone1
O
Entry
Base
Solvent
Oxidant (mmol)
Time (h)
Yield (%)2
1
2
3
4
5
6
7
8
KOH
NaOH
DABCO
HMTA
MgO
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
DME
H2O
EtOH
MeCN
n-Hexane
CH2Cl2
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.5)
THPDPE (0.3)
THPDPE (0.4)
THPDPE (0.8)
THPDPE (1)
0.5
1
4
4
4
2
6
1.5
2
10
6
5
2
1.3
0.5
0.5
3
97
56
15
10
25
60
5
90
90
Trace
15
20
80
90
94
92
50
9
10
11
12
13
14
15
16
CHCl3
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
17
1
UHP (0.5)
(E)-chalcone (3a) (1.0 mmol, 0.22 g), Base (aq.) (1 M, 1 mL), solvent ( 4 mL), rt.
2
Isolated yields.
positive the C–C and C–O, the easier the addition of
gem-dihydroperoxide,9 is a solid and stable oxidant
since it can be stored for several months without any
reactivity loss at room temperature.
ROO−. Therefore, the results observed are proved as
due to the electronic effects mentioned above. It is note-
worthy that both double bonds present in (E)-3-(4-cin-
namoylphenyl)-1-phenylprop-2-en-1-one
as
a
CONCLUSION
dichalcone were successfully transformed into its corre-
sponding noble bis-epoxide (Table 2, entry 2s). Moreo-
ver, the results of this procedure for the synthesis of
phenyl(3-phenyloxiran-2-yl)methanone (Table 2, prod-
uct 2a) were compared with those of some other
reported methodologies in Table 3. As shown in
Table 3, although the reactions we carried out in other
oxidants such as 1,1-dihydroperoxycyclohexane,
DHPDMDO, t-BuOOH, H2O2, and UHP, the
obtained yields are lower and the required reaction
times are longer. The results presented in Table 3 prove
that our oxidant has better efficiency and potential to
carry out the epoxidation reaction. Furthermore,
THPDPE in contrast with 1,1-dihydroperoxycyclohex-
ane, which is a very sticky oil and also a less stable
In summary, we have developed a simple, efficient,
metal-free, and environmentally friendly epoxidation
route of α,β-unsaturated ketones under mild reaction
conditions and short reaction times. No metal catalyst
requirement, nontoxicity, low cost, easy procedure, high
yields, short reaction times, and mild conditions are the
main advantages of the present methodology.
EXPERIMENTAL
Solvents, reagents, and chemical materials were
obtained from Aldrich and Merck chemical companies
and purified prior to use. NMR spectra were recorded
on a Bruker (300 MHz) spectrometer using tetramethyl-
silane (TMS) as internal standard. Infrared spectra were
recorded on a PerkinElmer GX FT IR spectrometer
J. Chin. Chem. Soc. 2017
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
3

Article
Khosravi et al.
Yield (%)2
Table 2. Epoxidation of (E)-chalcones by THPDPE under optimized conditions1
Product
Ar1
Ar2
Time (h)
2a
2b
2c
2d
2e
2f
2g
2h
2i
2j
2k
2l
2m
2n
2o
2p
2q
2r
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
4-MeO-C6H4
4-Cl-C6H4
4-Me-C6H4
4-Cl-C6H4
2-Naphthyl
2-Furyl
2-Thionyl
2-Thionyl
4-Cl-C6H4
4-Me-C6H4
2-Naphthyl
4-Cl-C6H4
C6H4
0.5
2
1.5
1
97
88
91
94
98
95
92
95
97
96
91
90
89
89
90
87
91
94
96
4-MeO-C6H4
4-Me-C6H4
4-Cl-C6H4
4-NO2-C6H4
3-NO2-C6H4
C6H5
0.8
0.9
1.6
1.5
1.1
0.9
1.5
0.9
1.2
0.9
0.8
1.8
1
C6H5
4-Cl-C6H4
4-Cl-C6H4
4-Cl-C6H4
4-Cl-C6H4
4-Cl-C6H4
2,6-diCl-C6H3
2,6-diCl-C6H3
4-Br-C6H4
4-NO2-C6H4
2-Naphthyl
C6H4
1.3
2.8
2s3
–
–
–
–
0.1
0.2
92
82
2t
2u
C6H5
C6H5
OMe
NH2
4
4
77
80
2v
2w
1
α, β-unsaturated ketones (1 mmol), 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane (0.5 mmol, 0.155 g), aq. KOH (1 M, 1 mL),
1,4-dioxane (4 mL).
2
3
Isolated yields.
Amount of oxidant, KOH, and solvent doubled.
(KBr pellets). Microanalyses were performed by an ele-
mental analyzer (Elemental, Vario EL III) at Arak Uni-
versity. The microanalyses results agreed favorably with
the calculated values. The reactions were monitored by
thin-layer chromatography (TLC) using silica gel F254
aluminum sheets (Merck).
4
www.jccs.wiley-vch.de
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2017

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Epoxidation of α,β-Unsaturated Ketones
Physical and spectra data for TDHPDPE
White solid, 89% yield, Mp: 100–102ꢀC. IR (KBr
pellet): 3304, 2924, 1614, 1513, 1457, 1375, 1115, 1033,
1
929; H NMR (CDCl3, 90 MHz): δH = 7.32–7.99 (m,
10H), 8.81 (br, s, 4H, OOH); 13C NMR (DMSO-d6,
75 MHz): δc = 129.02, 129.7, 131.2, 133.3, 167.7; Anal.
Calcd for C14H14O8: C, 54.20; H, 4.55 %; Found: C,
54.15; H, 4.63%.
General procedure for the synthesis of chalcones
Chalcones were synthesized by the base-catalyzed
Claisen–Schmidt condensation reaction of appropri-
ately substituted acetophenones and aldehydes as
described in the literature.43
Scheme 3. Suggested mechanism for the epoxidation
of α,β-unsaturated ketones.
Caution
Although we did not encounter any problems with
1,1,2,2-1,1,2,2-tetrahydroperoxy-1,2-diphenylethane, it
should be borne in mind that all peroxides are poten-
tially explosive and should be handled with great care;
all reactions should be carried out behind a safety shield
inside a fume hood, and heating should be avoided.
General procedure for the epoxidation of
α,β-unsaturated ketones
To a stirred solution of chalcones (1 mmol) in 1,4-
dioxane (4 mL), THPDPE (0.5 mmol, 0.15 g) was
added. Then, KOH (1 M, 1 mL) was added to this stir-
red solution. The mixture was stirred at room tempera-
ture for an appropriate time (Table 2). After the
completion of the reaction as monitored by TLC, the
mixture was quenched with Na2SO3 solution (2 M,
1 mL), diluted with water (5 mL), and extracted with
EtOAc (3 × 5 mL). Then, the organic layer was sepa-
rated, dried over anhydrous Mg2SO4, and evaporated
under reduced pressure. The residue was purified by
silica-packed column chromatography (hexane–EtOAc)
to afford pure epoxides (Table 2). All products were
characterized on the basis of their melting points, ele-
mental analysis, as well as IR, 1H NMR, and 13C
NMR spectral analyses7,44 (see Appendix S1, Support-
ing information).
General procedure for the synthesis of THPDPE
Benzil (1 mmol, .0.210 g) was added to acetoni-
trile (5 mL), followed by the addition of SbCl3
(0.2 mmol, 0.046 g) as the catalyst of the reaction. To
this stirred solution, H2O2 30% (2 mL, 19.5 mmol) was
added, and the mixture was stirred for 24 h at room
temperature. After completion of the reaction, as moni-
tored by TLC, water (5 mL) was added to the solution
and the mixture was extracted using ethyl acetate
(3 × 5 mL) and dried using MgSO4. After evaporation
of the solvent under reduced pressure, the pure crystal-
line product was obtained.40
Physical and spectroscopic data for some selected
and new products are given below:
Table 3. Comparing the efficiency of the present work with some reported methods for the synthesis of phenyl(3-phenyloxiran-2-
yl)methanone
Entry
1
Oxidant
Conditions
rt
Time (h)
0.5
Yields (%)
97
Ref
1,1,2,2-Tetrahydroperoxy-1,2-
This work
diphenylethane
1,1-Dihydroperoxycyclohexane
DHPDMDO
t-BuOOH
H2O2
9
25
41
40
42
1
2
3
4
5
6
7
rt
rt
2
2
3
2
95
96
93
99
88
91
Diaryl-2-pyrrolidinemethanols
Phase-transfer catalyst, 20ꢀC
Barium aluminate nanopowder
Ultrasonic
H2O2
UHP
17 (Reflux)
0.25
J. Chin. Chem. Soc. 2017
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
5

Article
Khosravi et al.
1
Compound 2g.
White solid, Mp: 66–68ꢀC. IR νmax
727, 669; H NMR (300 MHz, acetone-d6) δH: 2.41 (s,
3H, (CH3)), 4.12 (s, 1H, (epoxy ring)), 4.54 (s, 1H,
(epoxy ring)), 7.34–7.43 (m, 4H, (Ar–H)), 7.58–7.61 (d,
2H, (Ar–H)), 7.96–7.98 (d, 2H, (Ar–H)). 13C NMR:
(75 MHz, acetone-d6) δC: 20.7, 57.9, 60.1, 122.2, 128.3,
129.4, 131.6, 133.4, 135.7, 144.7, 191.8. Anal. Calcd
(%) for C16H13BrO2: C, 60.59; H, 4.13; Found: C:
61.23; H: 4.45.
/cm−1 (KBr pellet): 3055, 3005, 2976, 2935, 1655, 1602,
1572, 1444, 1334, 1257, 1224, 1184, 1016, 972, 829,
1
761, 694; H NMR (300 MHz, acetone-d6) δH: 3.89 (s,
3H, (OMe)), 4.09 (s, 1H, (epoxy ring)), 4.50 (s, 1H,
(epoxy ring)), 7.04–7.06 (d, 2H, (Ar–H)), 7.40–7.45 (m,
5H, (Ar–H)), 8.05–8.08, (d, 2H, (Ar–H)). 13C NMR:
(75 MHz, acetone-d6) δC: 55.16, 58.49, 60.21, 114.0,
126.0, 128.5, 128.7, 128.9, 130.6, 136.3, 163.6, 190.8.
Anal. Calcd (%) for C16H14O3: C, 75.58; H, 5.55;
Found: C: 76.20; H: 5.41.
Compound 2s.
White solid, Mp: 200–202ꢀC. IR
νmax/cm−1 (KBr pellet): 3070, 3026, 2926, 2852, 1689,
1602, 1425, 1327, 1294, 1184, 1132, 1072, 1026,
935, 707, 669, 551; 1H NMR (300 MHz, DMSO-d6)
δH: 4.18 (s, 2H, (epoxy ring)), 4.82 (s, 2H, (epoxy ring)),
7.35–8.03 (m, 14H, (Ar–H)). 13C NMR: (75 MHz,
DMSO-d6) δC: 58.6, 61.1, 119.1, 120.0, 122.0, 125.0,
127.1, 128.6, 129.4, 130.5, 134.5, 135.0, 136.1, 140.0,
192.0. Anal. Calcd (%) for C24H18O4: C, 77.82; H,
4.90; Found: C: 78.41; H: 4.59.
Compound 2i.
White solid, Mp: 73–75ꢀC. IR νmax
/cm−1 (KBr pellet): 3088, 3026, 2924, 2856, 1658, 1602,
1
1493, 1440, 1311, 1292, 1186, 1089, 1014, 891, 731; H
NMR (300 MHz, acetone-d6) δH: 2.41 (s, 3H, (CH3)),
4.13 (s, 1H, (epoxy ring)), 4.60 (s, 1H, (epoxy ring)),
7.35–7.48 (m, 6H, (Ar–H)), 7.97–7.99 (d, 2H, (Ar–H)).
13C NMR: (75 MHz, acetone-d6) δC: 20.7, 57.9, 60.1,
127.8, 128.3, 128.6, 129.4, 133.3, 134.0, 135.3, 144.8,
191.8. Anal. Calcd (%) for C16H13ClO2: C, 70.46; H,
4.80; Found: C: 71.35; H: 5.16.
ACKNOWLEDGMENTS
The authors thank Arak University for scientific
and instrumental support.
Compound 2j.
White solid, Mp: 117–119ꢀC. IR νmax
/cm−1 (KBr pellet): 3090, 3043, 2958, 2926, 2852, 1678,
1589, 1429, 1402, 1234, 1087, 1091, 1010, 883, 823,
Supporting information
Additional supporting information is available in
the online version of this article.
1
734; H NMR (300 MHz, acetone-d6) δH: 4.175–4.179
(d, 1H, (J = 1.2 Hz), (epoxy ring)), 4.612–4.616 (d, 1H,
(J = 1.2 Hz), (epoxy ring)), 7.46–7.60 (m, 6H, Ar–H),
8.02–8.11 (m, 2H (Ar–H)). 13C NMR: (75 MHz,
acetone-d6) δC: 58.2, 60.2, 127.8, 128.6, 129.0, 130.0,
131.2, 133.0, 134.1, 135.0, 139.5, 191.5. Anal. Calcd
(%) for C15H10Cl2O2: C, 61.46; H, 3.44; Found: C:
62.15; H: 3.30.
REFERENCES
1. H. Jin, H. Zhao, F. Zhao, S. Li, W. Liu, G. Zhou,
K. Tao, T. Hou, Ultrason. Sonochem. 2009, 16, 304.
2. J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless,
J. Am. Chem. Soc. 1997, 119, 6189.
3. C. M. R. Low, Ultrason. Sonochem. 1995, 2, 153.
4. B. M. Adger, J. V. Barkley, S. Bergeron, M. W. Cappi,
B. E. Flowerdew, M. P. Jackson, R. McCague,
T. C. Nugent, S. M. Rorberts, J. Chem. Soc. 1997, 1, 3501.
5. W. W. Leung, R. M. Savizky, Ind. Eng. Chem. Res. 2010,
49, 12327.
6. F. Ullmann, Ullmann’s Encyclopedia of Industrial Chemis-
try, 6 ed., Wiley-VCH, Weinheim, 1998.
7. M. A. Zolfigol, G. Chehardoli, M. Shiri, Reactive Funct.
Polym. 2007, 67, 723.
8. K. H. Schulte-Elte, D. Kastne, S. A. Firmenich, EP 1985,
11, 181475.
9. K. Jakka, J. Liu, C.-G. Zhao, Tetrahedron Lett. 2007,
48, 1395.
Compound 2n.
White solid, Mp: 100–102ꢀC. IR
νmax/cm−1 (KBr pellet): 3086, 2922, 2852, 1656, 1606,
1
1413, 1303, 1219, 1176, 1062, 972, 860, 773, 721; H
NMR (300 MHz, acetone-d6) δH: 4.342–4.347 (d, 1H,
J = 1.5 Hz, (epoxy ring)), 4.545–4.551 (d, 1H,
J = 1.8 Hz, (epoxy ring)), 7.32–7.50 (m, 4H, (Ar–H)),
8.05–8.07 (d, 1H, (Ar–H)), 8.31–8.32 (d, 1H, (Ar–H)).
13C NMR: (75 MHz, acetone-d6) δC: 56.6, 57.7, 128.6,
128.8, 130.8, 131.7, 134.3, 135.4, 135.7, 142.2, 186.1.
Anal. Calcd (%) for C13H8Cl2O2S: C, 52.19; H, 2.70; S,
10.72; Found: C: 52.56; H: 3.11; S, 11.02.
Compound 2p.
White solid, Mp: 117–119ꢀC. IR
10. D. Y. Kim, Y. J. Choi, H. Y. Park, C. U. Joung,
K. O. Koh, J. Y. Mang, K. Y. Jung, Synth.Commun.
2003, 33, 435.
νmax/cm−1 (KBr pellet): 3026, 2918, 2856, 1658, 1604,
1487, 1440, 1294, 1186, 1107, 1062, 952, 891, 842, 802,
6
www.jccs.wiley-vch.de
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2017

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Epoxidation of α,β-Unsaturated Ketones
11. M. B. Andrus, B. W. Poehlein, Tetrahedron Lett. 2000,
41, 1013.
12. X. L. Geng, Z. Wang, X. Q. Li, C. Zhang, J. Org. Chem.
2005, 70, 9610.
29. (a) D. Azarifar, K. Khosravi, Eur. J. Chem. 2010, 1, 15;
(b) K. Khosravi, S. Kazemi, J. Chin. Chem. Soc. 2012,
59, 557.
30. J. Iskra, D. Bonnet-Delpon, J. P. Begue, Tetrahedron
Lett. 2003, 44, 6309.
13. N. Hashimoto, A. Kanda, Org. Process. Res. Dev. 2002,
6, 405.
14. J. X. Ye, Y. C. Wang, J. P. Chen, X. M. Liang, Adv.
Synth. Catal. 2004, 346, 691.
31. A. V. Terent’ev, A. V. Kutkin, Z. A. Starikova,
M. Y. Antipin, Y. N. Ogibin, G. I. Nikishina, Synthesis
2004, 14, 2356.
32. T. Ito, T. Tokuyasu, A. Masuyama, M. Nojima,
K. J. McCullough, Tetrahedron 2003, 59, 525.
33. A. O. Terent’ev, M. M. Platonov, A. I. Tursina,
V. V. Chemyshev, G. I. Nikishin, J. Org. Chem. 2008,
73, 3169.
15. A. L. Baumstark, D. B. Harden, J. Org. Chem. 1993,
58, 7615.
16. V. K. Yadav, K. K. Kapoor, Tetrahedron Lett. 1994,
35, 9481.
17. S. D. Brukem, C. W. Murtiashaw, J. O. Saunders,
J. A. Oplinger, M. S. Dike, J. Am. Chem. Soc. 1984,
106, 4558.
34. P. Ghorai, P. H. Dussault, C. Hu, Org. Lett. 2008,
10, 2401.
35. Q. Zhang, Y. Li, Y.-K. Wu, Chin. J. Chem. 2007, 25, 1304.
36. Y. Hamada, H. Tokuhara, A. Masuyama, M. Nojima,
H. S. Kim, K. Ono, N. Ogura, Y. Wataya, J. Med.
Chem. 2002, 45, 1374.
18. M. Miyashita, T. Suzuki, A. Yoshkoshi, Chem. Lett.
1987, 16, 285.
19. C. L. Fan, W. Lee, N. Teng, Y. Sun, K. Chen, J. Org.
Chem. 2003, 68, 9816.
37. H. S. Kim, Y. Nagai, K. Ono, K. Begum, Y. Wataya,
Y. Hamada, K. Tsuchiya, A. Masuyama, M. Nojima,
K. J. McCullough, J. Med. Chem. 2001, 44, 2357.
38. A. Masuyama, J. M. Wu, M. Nojima, H. S. Kim,
Y. Wataya, Mini. Rev. Med. Chem. 2005, 5, 1035.
39. (a) D. Azarifar, B. Mahmoudi, J. Iran. Chem. Soc. 2016,
13, 645; (b) K. Khosravi, S. Naserifar, B. Mahmoudi,
K. Khalaji, Phosphorus Sulfur. 2017, 192, 316.
40. J.-T. Li, X.-F. Liu, Y. Yin, C. Du, Org. Commun.
2009, 2, 1.
41. A. Lattanzi, A. Russo, Tetrahedron 2006, 62, 12264.
42. N. Kazemi, M. Ghashang, A. A. Hassanzadeh-Tabrizi,
Nanosci. Nanotechnol.-Asia 2014, 4, 88.
43. M. G. Ahmed, U. K. R. Romman, S. M. Ahmed,
K. Akhter, Bangladesh J. Sci. Ind. Res. 2007, 42, 45.
44. (a) K. Khosravi, S. Naserifar, J. Iran. Chem. Soc. 2017,
14, 323; (b) B. Boyer, A. Hambardzoumian, J.-P. Roque,
Tetrahedron 1999, 55, 6147.
20. H. Yi, G. Zou, Q. Li, Q. Chen, J. Tanga, M. Hea, Tetra-
hedron Lett. 2005, 46, 5665.
21. B.
Das,
M.
Krishnaiah,
B.
Veeranjaneyulu,
B. Ravikanth, Tetrahedron Lett. 2007, 48, 6286.
22. Y. Q. Tang, Y. X. Dong, J. L. Vennerstrom, Med. Res.
Rev. 2004, 24, 425.
23. K. mitek, M. Zupan, S. Stavber, J. Iskra, Org. Lett. 2006,
8, 2491, and references cited therein.
24. (a) K. Khosravi, F. Pirbodaghi, S. Kazemi, A. Asgari,
J. Iran. Chem. Soc. 2015, 12, 1333; (b) K. Khosravi,
S. Kazemi, J. Chin. Chem. Soc. 2012, 59, 641.
25. D. Aarifar, K. Khosravi, Synlett 2010, 18, 2755.
26. A. O. Terent’ev, M. M. Platonov, A. V. A. Kutkin, Cent.
Eur. J. Chem. 2006, 4, 207.
27. (a) H. Hansma, A. Schroeder, AKZO N. V. Belg.
Patent 868, 681, 1978; (b) Chem. Abstr. 1979, 90, 153037a.
28. A. Bunge, H.-J. Hamann, E. McCalmont, J. Liebscher,
Tetrahedron Lett. 2009, 50, 4629.
J. Chin. Chem. Soc. 2017
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
7