Surface-mediated highly efficient oxidation of alcohols by bismuth nitrate

Article abstract of DOI:10.1081/SCC-100105397

Montmorillonite impregnated with bismuth nitrate was found to be an excellent reagent for the oxidation of a variety of alcohols in excellent yield.

Full text of DOI:10.1081/SCC-100105397

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SURFACE-MEDIATED HIGHLY EFFICIENT OXIDATION OF
ALCOHOLS BY BISMUTH NITRATE
a
a
b
Susanta Samajdar , Frederick F. Becker & Bimal K. Banik
a
Department of Molecular Pathology , The University of Texas, M. D. Anderson Cancer
Center , Box 89, 1515 Holcolmbe Blvd., Houston, TX, 77030, U.S.A.
b
Department of Molecular Pathology , The University of Texas, M. D. Anderson Cancer
Center , Box 89, 1515 Holcolmbe Blvd., Houston, TX, 77030, U.S.A.
Published online: 09 Nov 2006.
To cite this article: Susanta Samajdar , Frederick F. Becker & Bimal K. Banik (2001) SURFACE-MEDIATED HIGHLY
EFFICIENT OXIDATION OF ALCOHOLS BY BISMUTH NITRATE, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:17, 2691-2695, DOI: 10.1081/SCC-100105397
To link to this article: http://dx.doi.org/10.1081/SCC-100105397
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SYNTHETIC COMMUNICATIONS, 31(17), 2691–2695 (2001)
SURFACE-MEDIATED HIGHLY
EFFICIENT OXIDATION OF ALCOHOLS
BY BISMUTH NITRATE
Susanta Samajdar, Frederick F. Becker,
and Bimal K. Banik*
The University of Texas, M. D. Anderson Cancer Center,
Department of Molecular Pathology, Box 89,
1515 Holcolmbe Blvd., Houston, TX 77030, USA
ABSTRACT
Montmorillonite impregnated with bismuth nitrate was found
to be an excellent reagent for the oxidation of a variety of
alcohols in excellent yield.
Oxidation of organic compounds is one of the fundamental chemical
transformations. Therefore, oxidation chemistry in organic or in aqueous
solution continues to attract considerable attention. New versatile and selec-
tive reagents to achieve the oxidation of alcohols are constantly being
1
sought and as a result, many oxidizing agents have been developed.
Some of the methods described for these reactions have significant limita-
tions, such as, long reaction times, secondary reactions, low yield, the
requirement for a number of solvents and strong acid medias, relative
unavailability of the reagents, anhydrous conditions and in some cases
stringent reaction conditions. To overcome these shortcomings, oxidation of
*
Corresponding author.
2
691
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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SAMAJDAR, BECKER, AND BANIK
2
a
2b
alcohols under solid phase and by catalytic reactions are very promising.
We have been engaged in the synthesis and biological evaluation of several
polyaromatic compounds and in a preliminary study have shown the antic-
3
ancer activity of several of these derivatives. Recently, we also develop a
4
simple oxidation method of benzylic methylenes to the ketones mediated by
sodium bismuthate in acid media. The versatility of this method has been
exploited through the facile oxidation of allylic and benzylic alcohols to the
4
b
corresponding aldehydes.
Disposal of solvent and acid-base waste is a significant problem for
chemical research and therefore, we also were interested in surface-mediated
oxidation chemistry of alcohols and report here a highly efficient oxidation
method of a wide variety of alcohols by montmorillonite impregnated with
5
bismuth nitrate. Montmorillonite has been used previously for the oxidation
6
of secondary benzylic alcohols in the presence of ‘‘clayfen’’ (montmorillo-
7
nite-ferric nitrate) under the influence of microwave irradiation. The notable
advantages of our method include a general procedure for the oxidation of
benzylic alcohol, allylic alcohol and aliphatic alcohol without any micro-
6
i
wave irradiation or pre-treatment for the preparation of the solid support.
The montmorillonite-induced oxidation of the alcohols is shown in the
Table 1. Saturated alcohols (entries 1–3), benzylic alcohols (entries 4–6) and
8
allylic alcohols (entry 7 and 8) underwent facile oxidation in excellent yield
(
69–99%) (Scheme 1).
Similar oxidation of 2-phenylethanol (entry 4) with silica gel or acidic
alumina gave a complex mixture of products. However, oxidation of
-phenylethanol (entry 4) with montmorillonite induced condition afforded
2
acetophenone in 89% yield. Thus, we believe that the nature of the support,
not the acidity is an important factor for the successful oxidation described
in this present investigation. Although, oxidation of benzylic alcohols was
reported by clayfen under microwave irradiation method, we found a facile
oxidation of the same substrates by bismuth nitrate at room temperature
within a few minutes without using microwave. The solid support being the
same, this strongly suggests that bismuth nitrate is a superior oxidizing
agent compared to ferric nitrate. Also this reagent in combination with
montmorillonite was shown to be effective for the oxidation of allylic alco-
hol and saturated alcohol. No lactones acids or epoxides could be detected
Scheme 1.

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Table 1. Bi(NO
3
)
3
Mediated Oxidation of Alcohols
ꢀ
BP/MP ( C)
Time
(min)
Yield
a
Entry Substrate Product
(%) Observed
Lit.
in the reaction mixture. However, all attempts to oxidize the primary
alcoholic substrates to generate the corresponding aldehydes failed.
In conclusion, we have demonstrated a facile synthetic method for the
oxidation of several alcohols to the ketones by bismuth nitrate supported on
montmorillonite.
ACKNOWLEDGMENTS
We gratefully acknowledge the funding support received for this
research project from the Golden Family Fund for cancer research and

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SAMAJDAR, BECKER, AND BANIK
NIH Cancer Center Support Grant, 5-P30-CA16672-25, in particular the
shared resources of the Pharmacology and Analytic Center Facility.
REFERENCES
1
. For oxidation with chromium based reagents, see: (a) Cainelli, G.;
Cardillo, G. Chromium Oxidations in Organic Chemistry; Springer-
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6
. Laszlo et al. studied reactions with montmorillonite in the presence of
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Cornelis, A.; Laszlo, P. Synthesis 1980, 849.

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7
8
. Varma, R.S.; Dahuya, R. Tetrahedron Lett. 1997, 38, 2043.
. A representative procedure is as follows: The alcohol (1 mmol) and
montmorillonite KSF (500 mg, Aldrich) was added to a suspension of
bismuth nitrate (1 mmol) in THF (5 mL). The solvent was then evapo-
rated under reduced pressure and dried in the vacuum pump for ꢁ5 min.
The mixture was then repeatedly washed with dichloromethane
(
ꢁ25 mL) and it was concentrated to afford the crude product.
Pure product was isolated after column chromatography and by crystal-
lization.
All compounds described in this paper gave satisfactory physico-chemi-
cal data.
Received in the USA November 21, 2000

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