Efficient Baeyer-Villiger oxidation of ketones using molecular iodine/H2O2 as heterogeneous catalytic system

Article abstract of DOI:10.1080/00397910701572589

The use of molecular iodine as a catalyst for the oxidation of ketones using hydrogen peroxide in the presence of acetic acid at room temperature is reported. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701572589

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Efficient Baeyer–Villiger Oxidation of
Ketones using Molecular Iodine/H2O2 as
Heterogeneous Catalytic System
Digambar D. Gaikwad a , Satish A. Dake b , Ravibhushan S. Kulkarni b
Wamanrao N. Jadhav b , Shankar B. Kakde c & Rajendra P. Pawar b
,
a Department of Chemistry, Vaidayanath College, Parli Vaijnath, India
b Organic Chemistry Synthesis Laboratory, Dnyanopasak College, Parbhani,
India
c College of Pharmaceutical Sciences, Berhampur, Orissa, India
Published online: 10 Dec 2007.
To cite this article: Digambar D. Gaikwad , Satish A. Dake , Ravibhushan S. Kulkarni , Wamanrao N. Jadhav ,
Shankar B. Kakde & Rajendra P. Pawar (2007) Efficient Baeyer–Villiger Oxidation of Ketones using Molecular
Iodine/H2O2 as Heterogeneous Catalytic System, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 37:23, 4093-4097, DOI: 10.1080/00397910701572589
To link to this article: http://dx.doi.org/10.1080/00397910701572589
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Synthetic Communicationsw, 37: 4093–4097, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701572589
Efficient Baeyer–Villiger Oxidation
of Ketones using Molecular Iodine/H2O2
as Heterogeneous Catalytic System
Digambar D. Gaikwad
Department of Chemistry, Vaidayanath College, Parli Vaijnath, India
Satish A. Dake, Ravibhushan S. Kulkarni, and Wamanrao N. Jadhav
Organic Chemistry Synthesis Laboratory, Dnyanopasak College,
Parbhani, India
Shankar B. Kakde
College of Pharmaceutical Sciences, Berhampur, Orissa, India
Rajendra P. Pawar
Organic Chemistry Synthesis Laboratory, Dnyanopasak College,
Parbhani, India
Abstract: The use of molecular iodine as a catalyst for the oxidation of
ketones using hydrogen peroxide in the presence of acetic acid at room temperature
is reported.
Keywords: acetic acid, ketones, hydrogen peroxide, molecular iodine
INTRODUCTION
Baeyer–Villiger oxidation of ketones is an important tool in ester/lactone
synthesis. The reaction was first reported for the conversion of cyclic
Received May 3, 2007
Address correspondence to Rajendra P. Pawar, Organic Chemistry Synthesis Lab-
oratory, Dnyanopasak College, Parbhani 431401, India. E-mail: rppawar@yahoo.com
4093

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D. D. Gaikwad et al.
ketones to the corresponding lactones using Caro’s acid.[1] The use of
Baeyer–Villiger oxidation in several stereoselective organic syntheses is
known.[2,3] Baeyer–Villiger oxidation has been studied in the presence of tri-
fluroperacetic acid, and perbenzoic acid, and meta-chloroperbenzoic acid,
which produces a large amount of waste.[3,4] Several other catalysts are also
reported, such as heterogeneous catalysts based on solid acid,[5] zeolites,[6]
titanium silicate,[7] Se,[8] arsenic (As),[9] and homogeneous catalysts based
on platinum (Pt),[10] zirconium (Zr),[11] rhenium (Re),[12] selenium (Se),[13]
As,[14] and molybdinum (Mo).[15] The oxidation was also studied with
molecular oxygen catalyzed by a metal complex or supported metal
complex.[16] A selective oxidation is also known to oxidize the substrate by
activating the .C55O group of the lactones instead of H2O2 activation
using Sn/Zeolite catalyst.[17]
The use of molecular iodine in several organic synthesis reactions
attracted considerable attention because it is a nontoxic, readily available,
inexpensive, and mild Lewis acid catalyst. The molecular iodine used in
several organic transformations, such as synthesis of benzothiophenes[18]
and bis-indoles,[19] deprotection of acetals,[20] esterification,[21] transesterifi-
cation,[22] and Michael addition.[23] Recently, the use of iodine for the
synthesis of b-keto-enol esters[24] and multicomponent dihydropyrimidinone
synthesis[25] also has been reported.
In a typical procedure, to a mixture of molecular iodine and 40%
hydrogen peroxide in acetic acid acetophenone in acetic acid was added.
The mixture was stirred at room temperature for 1 h. The progress of
the reaction was checked by thin-layer chromatography (TLC, hexane–
ethyl acetate 8:2). After completion of the reaction, an aqueous workup
afforded the corresponding ester. To evaluate the use of this procedure,
different ketones were oxidized. The reaction proceeded very cleanly at
room temperature, and no undesirable side reactions were observed. In
the absence of molecular iodine catalyst, the reaction did not proceed,
even after 10 h (Scheme 1).
We have demonstrated an efficient and mild protocol for the oxidation of
different ketones to give corresponding esters at room temperature in acetic
acid using a catalytic amount of molecular iodine in excellent yields
(Table 1). Similarly, the aldehydes using the same procedure afforded corre-
sponding acids in 12 h of stirring at room temperature.
Scheme 1. R1 and R2 ¼ H/Alkyl/Aryl.

Baeyer–Villiger Oxidation of Ketones
4095
Table 1. Baeyer–Villiger oxidation in the presence of H2O2 and AcOH-I2
Entry
1
Substrate (1)
Product (2)
Time
1 h
Yield (%)
80
2
3
4
5
15 min
35 min
10 min
20 min
90
85
95
90
6
10 min
93
7
8
1 h
1 h
80
85
9
1 h
70
10
11
12 h
12 h
50
50
EXPERIMENTAL
All the melting points were determined in open capillaries and are uncor-
rected. TLC routinely checked the purity of the synthesized esters on silica-
gel-coated plates.
Preparation of Phenyl Acetate
To a mixture of molecular iodine (50 mg), hydrogen peroxide (40%, 4 ml,
0.117 mol), and acetic acid (0.5 ml, 0.016 mol) was added. The mixture was
stirred for half an hour at room temperature. Acetophenone (2 ml,
0.0188 mol) in 3 ml of acetic acid was added to the mixture and stirred for
1 h at room temperature. The progress of the reaction was checked by TLC

4096
D. D. Gaikwad et al.
(hexane–ethyl acetate 8:2). After completion of the reaction, the mixture was
poured on ice-cooled water. The reaction mixture was extracted with
4 Â 25 ml diethyl ether. The organic layer was dried over anhydrous
sodium sulphate and the ether was evaporated under vaccum to afford the
crude product. The obtained crude product was further purified by column
chromatography using hexane–ethyl acetate 8:2 as an eluent. Yield ¼ 80%.
The products obtained were identified by comparing data with authentic
1
samples, TLC, H NMR, and IR spectral spectroscopy.
Data
Entry 1: IR (cm21) 3062, 2850, 1685, 1444, 1263, 1178, and 1080. 1H NMR
2.59d (3H, s, CH3), 7.4–7.6d (3H, m, Ar-H), 7.9–8.0d (2H, d, Ar-H).
Entry 2: IR (cm21) 3068, 2845, 1685, 1484, 1261, 1182, and 1050. 1H NMR
2.56d (3H, s, CH3), 7.38d (2H, d, Ar-H), 7.80d (2H, d, Ar-H).
ACKNOWLEDGMENTS
The authors are thankful to P. L. More, principal, Dnyanopasak College,
Parbhani, for providing the necessary facilities.
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