A new, mild, and rapid transformation of acylals to bisulfites in one-pot synthesis by bismuth (III) nitrate pentahydrate

Article abstract of DOI:10.1080/104265090921119

Direct conversion of acylals to the corresponding bisulfites can be easily performed in the presence of bismuth (III) nitrate pentahydrate in ethanol at room temperature in good yields. Copyright Taylor & Francis Inc.

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Phosphorus, Sulfur, and Silicon
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A New, Mild, and Rapid
Transformation of Acylals to
Bisulfites in One-Pot Synthesis
by Bismuth (III) Nitrate
Pentahydrate
Mohammad Mehdi Khodaei a & Davood Kordestani a
a Department of Chemistry, Razi University,
Kermanshah, Iran
Version of record first published: 16 Aug 2006.
To cite this article: Mohammad Mehdi Khodaei & Davood Kordestani (2005): A New,
Mild, and Rapid Transformation of Acylals to Bisulfites in One-Pot Synthesis by Bismuth
(III) Nitrate Pentahydrate, Phosphorus, Sulfur, and Silicon and the Related Elements,
180:11, 2403-2405
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Phosphorus, Sulfur, and Silicon, 180:2403–2405, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090921119
A New, Mild, and Rapid Transformation of Acylals to
Bisulfites in One-Pot Synthesis by Bismuth (III) Nitrate
Pentahydrate
Mohammad Mehdi Khodaei
Davood Kordestani
Department of Chemistry, Razi University, Kermanshah, Iran
Direct conversion of acylals to the corresponding bisulfites can be easily performed
in the presence of bismuth (III) nitrate pentahydrate in ethanol at room temperature
in good yields.
Keywords Acylals; bisulfites; Bi(NO3)3.5H2O; direct transformation; mild conditions;
one-pot synthesis
INTRODUCTION
Protection and deprotection of functional groups are common in multi-
step synthetic organic reactions.1 Direct transformation of a protecting
group of a carbonyl compound into another also is a useful conversion.
Thus, the development of new methods for direct transformation in
one-pot would be of significant utility. Among protecting groups for
aldehydes, bisulfite addition products, which have been shown to be
α-hydroxy alkanesulfonates, are useful due to their easy preparation,
stability, and compatibility in neutal solutions. However, they are usu-
ally not stable under acidic or basic conditions.2 Bisulfite addition
products of aldehydes are highly crystalline and used not only for
the isolation and characterization, but also for purification of carbonyl
compounds.
The application of Bi (III) salts as catalysts in organic synthesis has
been investigated extensively.3 Very recently, we have reported some of
their applications in organic transformations.4
Received September 24, 2004; accepted October 26, 2004.
We are grateful to the Research Council of Razi University for partial financial support
of this work.
Address correspondence to Mohammad Mehdi Khodaei, Razi University, Department
of Chemistry, Kermanshah 67149, Iran. E-mail: mmkhoda@razi.ac.ir
2403

2404
M. M. Khodaei and D. Kordestani
Thus, the conversion of acylals or 1,1-diacetates to bisulfite addition
products of aldehydes in the presence of Bi(NO3)3.5H2O could be an
important transformation in organic synthesis.
RESULTS AND DISCUSSION
The report on this transformation is absent in the literature and a
practical method for its performance is desired. We wish to report a
novel, convenient, and mild direct transformation of acylals to bisulfites
with bismuth (III) nitrate pentahydrate at room temperature in one-pot
and in short reaction times (Scheme 1).
Bi(NO3)3.5H2O
ArCH(OAC)2 −−−−−−−−−−−−−−−−−−−→ ArCH(OH)SO3Na
aq.NaHSO3(40%),EtOH,rt
SCHEME 1
An efficient transformation of acylals of benzaldehyde having dif-
ferent substituent groups was performed in the presence of 0.5 molar
ratio of Bi(NO3)3.5H2O and the results are shown in Table I. p-Methyl
benzaldehyde,1,1-diacetate as a model compound converted to the bisul-
fite addition product of p-methyl benzaldehyde at room temperature in a
75% yield. However, under similar reaction conditions, transformation
of p-chlorobenzaldehyde,1,1-diacetate into the corresponding bisulfite
gave only 50% of the desired product.
TABLE I Direct Transformation of 1,1-Diacetates to Bisulfites With
Sodium Bisulfite and Bi(NO3)3.5H2O as a Catalyst
Entry
Product
Time (min)
Yield(%)
1
2
3
4
5
6
7
8
9
10
11
12
13
4-CH3 C6H4 CH(OH)SO3Na
4-Cl C6H4 CH(OH)SO3Na
2-AcO C6H4 CH(OH)SO3Na
4-O2N C6H4 CH(OH)SO3Na
4-CH3O C6H4 CH(OH)SO3Na
4-F C6H4 CH(OH)SO3Na
C6H5 CH(OH)SO3Na
2,4-(CH3O)2 C6H3 CH(OH)SO3Na
2-Br C6H4 CH(OH)SO3Na
4-Br C6H4 CH(OH)SO3Na
3-Cl C6H4 CH(OH)SO3Na
2,4-(Cl)2 C6H3 CH(OH)SO3Na
C6H5 CH CH CH(OH)SO3Na
5
60
10
10
5
10
10
10
15
15
10
15
10
75
40
50
60
65
70
70
65
75
75
60
65
70

Transformation of Acylals to Bisulfites
2405
In summary, we have developed a new method for the one-pot con-
version of acylals to bisulfites in the presence of catalytic amounts of
Bi(NO3)3.5H2O. The advantages of this protocol, such as mild reaction
conditions, short reaction times, and using relatively nontoxic, inexpen-
sive, and commercially available catalyst, are worthy of mention and
make this method an attractive and useful methodology.
EXPERIMENTAL
Products are known compounds and were characterized by comparison
of their spectral data (1H NMR, IR) with those reported in the literature.
Monitoring of the reactions were accomplished by TLC on precoated
silica gel 60 F254 sheets. All yields refer to isolated products.
General Procedure for the Transformation of 1,1-Diacetates
to the Corresponding Bisulfites
To a solution of aryl acylal (1 mmol) in 1 mL of aqeous ethanol, 0.5 mmol
of bismuth(III)nitrate pentahydrate was added and the solution stirred
magnetically at room temperature until the acylal was deprotected and
the corresponding aldehyde was regenerated (5–60 min). Then 40%
aqueous sodium bisulfite solution was added to this solution and the
reaction was completed in less than 1 min appearing with the white
crystals. The crystals were filtered and washed with ethanol. The prod-
uct was dissolved in distilled water at 0◦C and the aqueous solution
was filtered. Evaporation of water afforded the pure product in 50–75%
yields.
REFERENCES AND NOTES
[1] T. Oriyama, M. Kimura, and G. Koga, Bull. Chem. Soc. Jpn., 67, 885 (1994) and
references cited in therein.
[2] (a) C. J. Cymerman ana D. P. G. Hamon, J. Org. Chem., 30, 4168 (1965): (b) P. R.
Young, W. P. Jencks, J. Am. Chem. Soc., 100, 1228 (1978).
[3] Mohammadpor-Baltork, Aliyan, H.; A. R. Khosropour, Tetrahedron, 57, 5851 (2001)
and references cited therein.
[4] M. M. Khodaei, A. R. Khosropour, and K. Ghozati, Tretrahedron Lett., 45, 3525 (2004)
and references cited therein.