Zinc chloride anhydrous as new and effective catalyst for conversion of ketones and aldehydes to corresponding gem-dihydroperoxides

Article abstract of DOI:10.1002/jccs.201100605

Zinc chloride anhydrous has been used as an efficient and new catalyst for conversion of ketones and aldehydes to corresponding gem-dihydroperoxides by aqueous hydrogen peroxide (30%) in room temperature with excellent yields and notable reaction times.

Full text of DOI:10.1002/jccs.201100605

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Zinc Chloride Anhydrous as New and Effective Catalyst for Conversion of Ketones
and Aldehydes to Corresponding Gem-dihydroperoxides
a
Kaveh Khosravi * and Samira Kazemi
b
a
Department of Chemistry, Faculty of Science, University of Arak, Zip Cod 38156-879 Arak, Iran
Department of Chemistry, Shahr-e-Rey Branch, Islamicazad University, Tehran, Iran
b
(Received: Oct. 15, 2011; Accepted: Nov. 28, 2011; Published Online: Dec. 12, 2011; DOI: 10.1002/jccs.201100605)
Zinc chloride anhydrous has been used as an efficient and new catalyst for conversion of ketones and alde-
hydes to corresponding gem-dihydroperoxides by aqueous hydrogen peroxide (30%) in room temperature
with excellent yields and notable reaction times.
Keywords: Zinc chloride anhydrous; Gem-dihydroperoxides; Hydrogen peroxide; Ketones; Alde-
hydes.
INTRODUCTION
Gem-dihydroperoxides are stable derivatives of ke-
Zinc chloride anhydrous as a moderate-strength Lewis
2
acid has been widely applied in organic synthesis.
4,25
1
tones and aldehydes, have been remarkable compounds
2
because of their relevance to peroxidic anti malarial drugs.
RESULTS AND DISCUSSION
Also, these compounds are important intermediates in the
synthesis of a number of classes of peroxides including
In continuous of our work for synthesis of gem-di-
2
hydroperoxides, we have used ZnCl anhydrous as solid,
6
2
3
4
5
tetraoxanes, silateraoxans, spirobisperoxyketals, bisper-
mild and effective catalyst for synthesis of gem-dihydro-
6
oxyketals, 1,2,4,5-tetraoxa cycloalkanes. Gem-dihydro-
7
peroxides from ketones and aldehydes at room temperature
(Scheme I).
peroxides have also been employed as initiators for radical
8
polymerization ractions, as precursors for synthesis of di-
9
carboxylic acid esters and as reagents for oxidation reac-
Scheme I
1
tions such epoxidation of a,b-unsaturated ketones, en-
0
antioselective oxidation of 2-substituted 1,4-naphtoqui-
11
12
nones, oxidation of sulfides and as suitable oxidants in
1
2
other organic reactions. There are three major methods
for synthesis of gem-dihydroperoxides: 1) ozonolysis of
ketone eneol ethers or a-olefines in presence of aqueous
In the beginning of our work, we have selected cyclo-
7
,13
2
hexanone to study the effect of amount of ZnCl on the re-
H
2
O
2
,
2) Reaction of ketals with H
2
O
2
in the presence of
1
4
15
action times and its yields (Scheme II) (Table 1). Also, refer
to results; MeCN has been selected as best solvent.
tungstic acid, or BF
tones using an acidic solvent. However, many of these
methods have defects including use of concentrated H
and excess acid, low yields, limited substrate range and
3 2
.Et O
and 3) peroxidation of ke-
1
6
2
O
2
Scheme II
1
7
production of mixtures of peroxidic products. Also, poor
selectivity of ozonolysis and the presence of ozone sensi-
tive groups in the substrates is further limitation in ozono-
lysisi reaction. For avoid these limitations, recently, reac-
tions of ketones and aldehydes with H
2 2
O in presence of
Lewis acids in organic solvents have been reported. Sev-
1
8
19
CAN reagent, CSA,
20
eral Lewis acids such as I
2
2
,
1
22
23
and PMA have been used for
NaHSO
4
.SiO
2
,
Re
2
O
7
Several aliphatic and aromatic ketones and aldehydes
this conversion.
have been treated with aqueous H
2
O
2
by this methodology
*
Corresponding author. E-mail: khosravi.kaveh@gmail.com
J. Chin. Chem. Soc. 2012, 59, 641-644
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
641

Article
Khosravi and Kazemi
(
Table 2).
It is notable that aliphatic ketones were converted to
Table 1. Optimization of amount of catalyst
Entry
ZnCl (mol %)
2
Ra (%)
Time (h)
corresponding gem-dihydroperoxides faster than aromatic
ketones and aldehydes, in excellent yields (Table 2, entries
of a, b, c, d, e, and f). Also, aliphatice aldehydes were con-
verted to 1,1-hydroxyhydroperoxides (Table 2, entries of t
and w) (Scheme III).
1
2
3
4
5
2
40
65
85
90
80
8
7
7
3
3
5
10
15
20
Scheme III
2 4
ganic layers was dried by Mg SO and was concentrated in
vacuum. The residue was collected as the products. The
known products were characterized by their physical and
1
spectral (IR, H NMR and C NMR) analysis and com-
13
1
8,19,20,21,22,24,26
pared with the reported data.
Aromatic ketones and aldehydes also were converted
to gem-dihydroperoxides but reaction times of these sub-
strates are longer than aliphatic substrates (Table 2).
The spectrum information for new compounds (l, m,
n, p and q entries) is reported in below:
(4-Bromophenyl)methylene-1,1-dihydroperoxide (l)
m.p. 88-90 °C; IR (KBr) nmax: 3426, 3085, 2909,
1608, 1528, 1411, 1353, 1236, 1195, 1083, 973, 856, 828,
CONCLUSION
1
753, 706, 601; H NMR (CDCl , 90 MHz) d : 6.26 (s, 1H),
In conclusion, the present work offers that this meth-
odology is simple, available, nontoxic and inexpensive for
synthesis of gem-dihydroperoxides in mild condition. The
reactions time and purity of products are notable.
3
H
1
7.00-7.90 (m, PhH, 4H), 9.96 (br, s, 2H); C NMR (CDCl ,
3
3
22.5 MHz) d : 111.00, 120.00, 130.50, 132.50, 141.00;
C
Anal. Calcd for C H O Br: C, 35.74; H, 2.97. Found: C,
7
7
4
3
5.96; H, 3.06.
EXPERIMENTAL
(4-Fluorophenyl)methylene-1,1-dihydroperoxide (m)
Caution: Although we did not encounter any prob-
lem with peroxides, peroxides are potentially explosive
and should be handled with precautions; all reactions
should be carried out behind a safety shield inside a fume
hood and transition metal salts or heating should be avoided.
Chemicals used in this work were purchased from
Fluka and Merk chemical companies and used without pu-
rification. IR spectra were recorded on a Perkin Elmer GX
m.p: 110-112 °C; IR (KBr) nmax: 3464, 3085, 2909,
1
6
7
2
625, 1601, 1564, 1453, 1353, 1303, 1071, 1025, 844, 720,
-
1
1
85 cm ; H NMR (CDCl
.14-8.14 (m, PhH, 4H), 9.21 (br, s, 2H); C NMR (CDCl
2.5 MHz) d : 112.00, 118.50, 128.50, 137.00, 161.62;
F: C, 48.27; H, 4.02. Found: C,
3 H
, 90 MHz) d : 6.14 (s, 1H),
1
3
3
,
C
Anal. Calcd for C
7.98; H, 4.18.
7 7 4
H O
4
(
2-Methoxyphenyl)methylene-1,1-dihydroperoxide (n)
1
13
FT IR spectrometer from KBr pellets. H and C NMR
spectra were measured for samples in CDCl with a JEOL
FX 90Q instrument at 90 and 22.5 MHz respectively, using
Me Si as internal standard. Melting points were measured
Oil, decomposed after 1 day; IR (KBr): nmax: 3226,
3
3
1
085, 2853, 1647, 1603, 1493, 1465,1372, 1245, 1177,
-
1 1
3 H
017, 844, 758 cm ; H NMR (CDCl , 90 MHz) d : 4.05
4
(
s, 3H), 6.04 (s, 1H), 6.84-8.18 (m, PhH 4H), 9.35 (br, s,
1
3
on a SMPI apparatus.
2
H); C NMR (CDCl
18.50, 123.00, 128.50, 139.10, 157.45; Anal. Calcd for
: C, 51.61; H, 5.37. Found: C, 52.32; H, 6.05.
3 C
, 22.5 MHz) d : 57.50, 102.00,
General procedure for conversion of ketones and al-
dehydes to gem-dihydroperoxies
1
8 10 5
C H O
To a mixture of aromatic substrate (1 mmol) and
1-(1,1-Dihydroperoxyethyl)-4-methoxybenzene (p)
ZnCl
2
(0.02 gr, 0.15 mmol) in MeCN (4 mL) was added
Oil. IR (KBr) nmax: 3408, 3005, 2861, 1635, 1620,
H
2
O
2
(aq) 30% (3 mL) and the mixture was stirred at room
1434, 1382, 1332, 1226, 1172, 1091, 952, 919, 892, 849,
1 1
-
temperature for an appropriate time (Table 2). After com-
pletion of the reaction as monitored by TLC, the solution
was quenched with 15 mL of water. Then, the products
were extracted by EtOAC (3 × 5 mL). The mixture of or-
3 H
792, 669, 603 cm ; H NMR (CDCl , 90 MHz) d : 1.70 (s,
3H), 3.55 (s, 3H), 7.32 (d, 2H), 7.97 (d, 2H), 9.00 (br, s,
1
2H); C NMR (CDCl , 22.5 MHz) d : 16.50, 50.63,
3
3
C
109.74, 116.00, 128.65, 135.70, 160.00; Anal. Calcd for
642
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J. Chin. Chem. Soc. 2012, 59, 641-644

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Zinc Chloride Anhydrous
J. Chin. Chem. Soc. 2012, 59, 641-644
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
643

Article
Khosravi and Kazemi
C
9
H
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O
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: C, 54.45; H, 6.25. Found: C, 53.87; H, 6.32.
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1
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ACKNOWLEDGMENT
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J. Chin. Chem. Soc. 2012, 59, 641-644