A convenient and inexpensive method for conversion of thiocarbonyl compounds to their oxo derivatives using oxone under solvent-free conditions

Article abstract of DOI:10.1081/SCC-120016359

A series of thioamides, thioureas and thioesters are transformed to their corresponding carbonyl compounds in good to excellent yields with oxone under solid phase conditions, while thioketones remained unchanged under these conditions.

Full text of DOI:10.1081/SCC-120016359

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A Convenient and Inexpensive Method for Conversion
of Thiocarbonyl Compounds to Their Oxo Derivatives
Using Oxone Under Solvent-Free Conditions
Iraj Mohammadpoor-Baltork a , Majid M. Sadeghi a & Karim Esmayilpour a
a Department of Chemistry , Isfahan Univeristy , Isfahan, Iran
Published online: 17 Aug 2006.
To cite this article: Iraj Mohammadpoor-Baltork , Majid M. Sadeghi & Karim Esmayilpour (2003) A Convenient and Inexpensive
Method for Conversion of Thiocarbonyl Compounds to Their Oxo Derivatives Using Oxone Under Solvent-Free Conditions,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 33:6, 953-959,
DOI: 10.1081/SCC-120016359
To link to this article: http://dx.doi.org/10.1081/SCC-120016359
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 6, pp. 953–959, 2003
A Convenient and Inexpensive Method for
Conversion of Thiocarbonyl Compounds to
Their Oxo Derivatives Using Oxone Under
Solvent-Free Conditions
*
Iraj Mohammadpoor-Baltork, Majid M. Sadeghi, and
Karim Esmayilpour
Department of Chemistry, Isfahan Univeristy,
Isfahan, Iran
ABSTRACT
A series of thioamides, thioureas and thioesters are transformed to
their corresponding carbonyl compounds in good to excellent yields
with oxone under solid phase conditions, while thioketones remained
unchanged under these conditions.
The transformation of thioamides to their corresponding amides is
an important reaction in synthetic organic chemistry. Amides are
valuable chemical intermediates in some organic reactions; they can be
*Correspondence: Iraj Mohammadpoor-Baltork, Department of Chemistry,
Isfahan University, Isfahan 81744, Iran; E-mail: imbaltork@sci.ui.ac.in.
953
DOI: 10.1081/SCC-120016359
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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954
Mohammadpoor-Baltork, Sadeghi, and Esmayilpour
hydrolyzed to carboxylic acids, dehydrated to nitriles and degraded to
amines in Hofmann rearrangement. Many methods and reagents such as
t-butyl hypochlorite,[1] diaryl selenoxide,[2] dimethyl selenoxide,[3] diaryl
telluroxide,[4] benzeneseleninic anhydride,[5] singlet-oxygen,[6] thiophos-
[8]
gene,[7] sodiumperoxide, dimethyl sulfoxide/iodine,[9] m-chloroperben-
zoic acid,[10] NOBF4,[11] N-nitrosamines,[12] soft NOþ species,[13]
trifluoroacetic
anhydride,[14]
clayfen,[15]
p-nitrobenzaldehyde/
TMSOTf,[16] 2-nitrobenzenesulfonyl chloride/potassiumsuperoxide,
manganese dioxide,[18] clayfen or clayan/MW[19] and caro’s acid sup-
ported on silica gel,[20] have been reported for the conversion of thiocar-
bonyl compounds to their parent carbonyl compounds. However, some
of these methods have certain limitations such as long reaction times,
toxic or expensive reagents and tedious procedures.
[17]
Oxone is a cheap, easily handled and stable ternary composite
of KHSO5, KHSO4, and K2SO4 in a 2:1:1 molar ratio. Recently we
have introduced oxone as an efficient reagent for deprotection of
trimethylsily and tetrahydropyranyl ethers, ethylene acetals and
ketals.[21] We now report a convenient method for the conversion of
thioamides, thioureas and thioesters to their oxo derivatives with oxone
under solid phase conditions.
As shown in Table 1, a variety of thioamides and thioureas
were treated with oxone under solid phase conditions afforded the corre-
sponding carbonyl compounds in good to excellent yields (Entries 1–31).
Thioesters were also transformed to esters in good yields (Entries 32–35).
However, thioketones are resistant towards this reagent and remained
intact in the reaction mixture (Entries 36–39). Deprotection of
larger amounts (8–10 mmol) of some thioamides to their corresponding
amides was also investigated. The results were comparable to those
of small scale experiments, therefore, it seems that the methodology is
also applicable for operation on molar scale. It was found that in these
reactions sulfur is converted to sulfate and replaced by oxygen.
In conclusion, we have developed
a mild and convenient
procedure for the conversion of thioamides, thioureas and thioesters to
their carbonyl compounds using oxone as a commercial available, non-
toxic and inexpensive reagent under solvent-free conditions.
EXPERIMENTAL
All of the products were identified by comparison of their physical
and spectral data with those of authentic samples. The starting thiocar-
bonyl compounds are either commercially available or were prepared
according to described procedures.[22–25]

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Conversion of Thiocarbonyl Compounds
955
Table 1. Transformation of thiocarbonlyl compounds to carbonyl compounds
with oxone.
Oxone/
subs.
Time
(min.)
Yield
(%)a
Run
R1
R2
R3
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
Me
Me
Et
1
1
1
1.5
1.5
2
1.5
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
5
5
5
95
96
81
85
82
85
99
90
98
95
92
90
90
75
77
88
90
85
78
86
82
90
99
95
73
75
95
90
96
85
NH2
NH2
NH2
PhNH
H2NC¼Sb
PhN¼N
Ph
Ph
Ph
Ph
Ph
NH2
Ph
Ph
H
PhNH
Ph
PhCH2
2-MeOC6H4
2-MeC6H4
4-MeOC6H4
4-MeC6H4
4-BrC6H4
4-NO2C6H4
Ph
10
20
10
20
15
25
10
15
30
35
20
25
25
30
20
25
25
20
30
15
20
25
25
10
25
30
20
Ph
Ph
Ph
4-MeC6H4
4-NO2C6H4
4-NO2C6H4
4-NO2C6H4
4-NO2C6H4
2-ClC6H4
4-MeC6H4
Me
Ph
2-MeOC6H4
2-MeC6H4
2-ClC6H4
4-MeC6H4
1-Naphthyl
4-BrC6H4
4-NO2C6H4
Ph
2-MeC6H4
Ph
Ph
Me
Et
Me
3,5-(NO2)2C6H3
3,5-(NO2)2C6H3
Me
4-NO2C6H4
3,5-(NO2)2C6H3
3,5-(NO2)2C6H3
(continued )

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956
Mohammadpoor-Baltork, Sadeghi, and Esmayilpour
Table 1. Continued.
Oxone/
subs.
Time
(min.)
Yield
(%)a
Run
R1
R2
R3
31
32
—
—
—
—
1.5
3
20
20
90
80
33
34
—
—
—
—
3
3
25
30
75
60
35
36
37
38
—
—
—
—
—
—
—
3
3
3
3
35
60
60
60
58
0
0
0
39
—
—
3
60
0
aIsolated yields.
bOxamide was obtained from the reaction mixture.
General Procedure for the Conversion of Thiocarbonyl
Compounds to Their Corresponding Carbonyl Compounds
A mixture of substrate (1 mmol) and oxone (1–3 mmol) in a mortar
was prepared. The mixture was ground with a pestle for the length of
time according to Table 1. The progress of the reaction was monitored

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Conversion of Thiocarbonyl Compounds
957
by TLC. The mixture was extracted with CH2Cl2. The solvent was
evaporated and the crude product was either recrystallized fromethanol
or subjected to column chromatography using silica gel.
ACKNOWLEDGMENT
We are thankful to the Isfahan University Research Council
for partial support of this work.
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Received in the Netherlands April 10, 2002

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