Transesterification via Baeyer-Villiger oxidation utilizing potassium peroxydisulfate (K2S2O8) in acidic media

Article abstract of DOI:10.1007/s00706-010-0338-9

Baeyer-Villiger oxidation of ketones with potassium peroxydisulfate (K ₂S₂O₈) and sulfuric acid generates the anticipated esters or lactones. These products are transformed into new esters (or hydroxy esters) in the presence of alcohols via transesterification under Baeyer-Villiger reaction conditions in one pot. Springer-Verlag 2010.

Full text of DOI:10.1007/s00706-010-0338-9

Monatsh Chem (2010) 141:889–891
DOI 10.1007/s00706-010-0338-9
ORIGINAL PAPER
Transesterification via Baeyer–Villiger oxidation utilizing
potassium peroxydisulfate (K2S2O8) in acidic media
•
S. Zarrabi N. O. Mahmoodi O. Marvi
•
Received: 4 August 2009 / Accepted: 30 May 2010 / Published online: 15 June 2010
Ó Springer-Verlag 2010
Abstract Baeyer–Villiger oxidation of ketones with potas-
sium peroxydisulfate (K2S2O8) and sulfuric acid generates the
anticipated esters or lactones. These products are transformed
into new esters (or hydroxy esters) in the presence of alcohols
via transesterification under Baeyer–Villiger reaction condi-
tions in one pot.
that are identical to those of ester hydrolysis (by the
acyl-oxygen fission mechanisms) and frequently fail when
the alkoxy group is tertiary due to steric hindrance. This
process generates a new ester, and if lactones are used as
starting material they are easily opened by treatment with
alcohols to give open-chain hydroxy esters [7, 8].
Baeyer–Villiger reaction involves formation of esters
(from acyclic ketones) or lactones (from cyclic ketones), so
its products can be used for transesterification under
appropriate conditions. Baeyer–Villiger oxidation is usu-
ally carried out with peroxy compounds such as peracids
[9–11] and ROOH [12, 13]. Acids, bases, enzymes, and
metal-containing reagents are known to catalyze Baeyer–
Villiger oxidation [14, 15].
Keywords Potassium peroxydisulfate (K2S2O8) Á
Transesterification Á Baeyer–Villiger oxidation Á
Hydroxy esters
Introduction
Transesterification is an equilibrium process in which an
existing ester is transformed into a desired one through
interchange of the alkoxy group [1]. Since transesterifi-
cation is an equilibrium process, an acidic [2, 3] or basic
[4, 5] catalyst is usually required to promote the desired
reaction. Transesterification occurs by mechanisms [6]
Results and discussion
Recently, we reported a general route for direct synthesis
of lactones by utilizing a peroxydisulfate oxidative system
[16–20]. Herein we describe an application of potassium
peroxydisulfate (K2S2O8) in sulfuric acid solution in the
presence of ketones and excess alcohols to prepare the
relevant esters (or hydroxy esters) via transesterification of
Baeyer–Villiger oxidation products (Scheme 1).
Peroxydisulfate salts are powerful and useful oxidizing
agents [21, 22]. Potassium peroxydisulfate (also known as
potassium persulfate) in acidic solution generates perox-
odisulfuric acid with the chemical formula H2S2O8.
Hydrolysis of peroxodisulfuric acid gives peroxomono-
sulfuric acid (H2SO5), which is often called Caro’s acid
and is the real oxidant in this reaction [23]. The mechanism
of Baeyer–Villiger oxidation involves nucleophilic addi-
tion of the peroxymonosulfate anion to the protonated
carbonyl group, formation of a Criegee intermediate, loss
S. Zarrabi (&)
Department of Chemistry, Faculty of Sciences,
Islamic Azad University, Lahijan Branch, Lahijan, Iran
e-mail: saeid_zarrabi@yahoo.com
N. O. Mahmoodi
Department of Chemistry, Faculty of Science,
Guilan University, Rasht, Iran
O. Marvi
Department of Chemistry, Payame Noor University (PNU),
Roodsar, Guilan, Iran
123

890
S. Zarrabi et al.
O
O
Because of the presence of excess alcohol and acidic
conditions, esters and lactones undergo transesterification
to produce the relevant new esters and hydroxy esters,
respectively. By use of different ketones and alcohols,
various esters were obtained in high yields except with
t-butanol because of steric hindrance (Table 1).
K2S2O8 / H2SO4
r. t. / 12-16 h
R3
+
+
R3OH
ROH
R1
R2
R1
O
O
O
K2S2O8 / H2SO4
r. t. / 18-20 h
R
( )n
HO
O
( )n
n = 1, 2
Herein is described an efficient and mild method for the
oxidation and transesterification of ketones to the relevant
esters in one step at room temperature using K2S2O8 and
40% sulfuric acid in the presence of alcohols. This pro-
cedure affords high product yields, especially of hydroxy
esters, in a clean one-pot reaction using readily available
reagents.
Scheme 1
of HSO4- with simultaneous formation of a dioxirane ring
[24], and finally intramolecular rearrangement to give an
ester or lactone [25, 26] (Scheme 2).
Scheme 2
O
S
O
S
O
S
O
S
O
S
O
S
H2O
H2SO4
+
OH
KO
O
O
OK
HO
O
O
OH
HO
OH
HOO
O
O
O
O
O
O
O
S
HOO
OH
O
O
O
O
H
O
O
R1
O
R2
OSO3H
R2
R1
R2
R1
O
R1
R2
H2SO4
Table 1 Baeyer–Villiger
oxidation of linear and cyclic
ketones utilizing K2S2O8/H2SO4
and subsequence
transesterification in the
presence of different alcohols
Entry
Ketone
Alcohol
EtOH
Product
Time
(h)
Yieldc
(%)
O
O
O
O
O
O
O
1a
2a
12
12
14
12
20
14
12
15
15
18
18
18
20
20
20
84
92
98
97
54
95
98
97
97
81
97
98
95
99
96
O
O
O
O
n-PrOH
i-PrOH
O
O
3a
O
4a
n-BuOH
t-BuOH
Cyclohexanol
MeOH
O
O
5a
O
6a
O
O
O
O
O
7a
O
O
8a
n-PrOH
n-BuOH
MeOH
O
O
9a
O
O
10b
11b
12b
13b
14b
15b
O
O
O
O
O
O
HO
HO
HO
HO
HO
HO
O
O
EtOH
O
a
The reaction products were
identified by GC–MS analysis
[27]
O
n-PrOH
MeOH
O
O
b
Identification of products was
O
done by comparison of their IR,
1H NMR, and mass spectra with
data in Refs. [28–32]
O
EtOH
O
O
c
Determined by GC analysis of
the reaction mixture
n-PrOH
O
123

Transesterification via Baeyer–Villiger oxidation
Experimental
891
3. Shishido K, Irie O, Shibuya M (1992) Tetrahedron Lett 33:4589
4. Stanton MG, Gagne MR (1997) J Org Chem 62:8240
5. Vasin VA, Razin VV (2001) Synlett 658
6. Koskikallio EA, Patai S (1969) The chemistry of carboxylic acids
and esters. Wiley, New York
General procedure for the Baeyer–Villiger oxidation
7. Anand RC, Sevlapalam N (1994) Synth Commun 24:2743
8. Kondaveti L, Al-Azemi TF, Bisht KS (2002) Tetrahedron
Asymmetry 13:129
9. Butkus E, Stoncius S (2001) J Chem Soc Perkin Trans 1 1885
10. Yakura T, Kitano T, Ikeda M, Uenishi J (2002) Tetrahedron Lett
43:6925
11. Kosaka N, Hiyama T, Nozaki K (2004) Macromolecules 37:4484
12. Fukuda O, Sakaguchi S, Ishii Y (2001) Tetrahedron Lett 42:3479
13. Tenbrink GJ, Arends IWCE, Sheldon RA (2004) Chem Rev
104:4105
14. Bolm C, Palazzi C, Francio G, Leitner W (2002) Chem Commun
1588
15. Jimenez-Sanchidrian C, Ruiz JR (2008) Tetrahedron 64:2011
16. Mahmoodi NO, Jazayri M (2001) Synth Commun 31:1467
17. Mahmoodi NO, Salehpour M (2003) J Heterocycl Chem 40:875
18. Mahmoodi NO, Salehpour M (2003) Russ J Org Chem 39:1760
19. Mahmoodi NO, Dadvar P (2006) Asian J Chem 18:1973
20. Mahmoodi NO, Tabatabaeian K, Kosari M, Zarrabi S (2008)
Chin Chem Lett 19:1431
21. Behrman EC, Chen S, Behrman EJ (2002) Tetrahedron Lett
43:3221
22. Anniyappan M, Muralidharan D, Perumal PT (2002) Tetrahedron
58:5069
23. Lee JD (1996) Concise inorganic chemistry, 5th edn. Blackwell
Science, UK
24. Snowden M, Bermudez A, Kelly DR, Radkiewicz-Poutsma JL
(2004) J Org Chem 69:7148
25. Okuno Y (1997) Chem Eur J 3:212
26. Renz M, Meunier B (1999) Eur J Org Chem 737
27. Spectral Database for Organic Compounds SDBS. http://riodb01.
ibase.aist.go.jp/sdbs/ Accessed March 1999
28. El Fangour S, Guy A, Despres V, Vidal JP, Rossi JC, Durand T
(2004) J Org Chem 69:2498
29. Schneider HJ, Ahlhelm A, Mueller W (1984) Chem Ber 117:3297
30. Terent’ev AO, Platonov MM, Kutkin AV (2006) Cent Eur J
Chem 4:207
31. Capon B, Grieve DMcLA (1982) Tetrahedron Lett 23:4823
32. Xu G, Micklatcher M, Silvestri MA, Hartman TL, Burrier J,
Osterling MC, Wargo H, Turpin JA, Buckheit RW, Cushman M
(2001) J Med Chem 44:4092
The oxidizing agent was prepared by adding potassium
peroxydisulfate (4.32 g, 16 mmol) to sulfuric acid (40%,
15 cm3) under stirring at room temperature. The ketone
(8 mmol) and excess alcohol (5 cm3) were added to the
oxidant and the reaction mixture was stirred for 12–20 h.
After the completion of the reaction (monitored by GC),
the solution was diluted with 15 cm3 water, filtered, and
extracted with diethyl ether (2 9 20 cm3). The organic
layer was washed with 5% sodium bicarbonate, then with
distilled water, dried over magnesium sulfate, filtered, and
concentrated in vacuum. Simple esters (Table 1, entries
1–9) were injected into the GC–MS system without further
purification, but hydroxy esters (entries 10–15) were first
purified by using a short silica gel column (eluent: n-hex-
ane/ethyl acetate 9:1). Pure hydroxy esters were obtained
after evaporation of the solvent.
The relevant products were detected via their retention
times as measured by GC–MS analysis on a Hewlett-
Packard 6890 GC instrument (helium as carrier gas) fur-
nished with an HP-5MS (30 m 9 0.25 mm 9 0.25 lm)
column and Hewlett-Packard 5973N MSD instrument. The
IR spectra were recorded on an FTIR-8900S spectropho-
1
tometer as neat films on sodium chloride plates. The H
NMR spectra were recorded on a Bruker 500 MHz
instrument. The structures of simple esters (entries 1–9)
were determined by comparing their mass spectra and
fragmentation patterns with a GC–MS instrument library
search (Wiley 275) and those of the authentic compounds
[27]. The structures of hydroxy esters (entries 10–15) were
1
determined by their IR, H NMR, and mass spectra frag-
mentation pattern [28–32].
Acknowledgment Financial support from the Research Committee
of University of Guilan is gratefully appreciated.
References
1. Otera J (1993) Chem Rev 93:1449
2. Chavan SP, Subbarao YT, Dantale SW, Sivappa R (2001) Synth
Commun 31:289
123