Dess-Martin periodinane on silica: Rapid oxidation of alcohols using microwaves

Article abstract of DOI:10.1080/10426500307797

Adsorbed on silica gel. Dess-Martin periodinane can rapidly oxidize alcohols to the corresponding carbonyl compounds upon exposure to microwave under solvent-free condition.

Full text of DOI:10.1080/10426500307797

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Phosphorus, Sulfur, and Silicon and the Related
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Dess-Martin Periodinane on Silica: Rapid Oxidation of
Alcohols using Microwaves
a
a
a
b
Majid M. Heravi , Ladan Sangsefidi , Hossein A. Oskooie , Mitra Ghassemzadeh
&
b
Koroush Tabar-Hydar
a
Azzahra University , Tehran, Iran
b
Chemistry and Chemical Engineering Research Center of Iran , Tehran, Iran
Published online: 27 Oct 2010.
To cite this article: Majid M. Heravi , Ladan Sangsefidi , Hossein A. Oskooie , Mitra Ghassemzadeh & Koroush Tabar-Hydar
2003) Dess-Martin Periodinane on Silica: Rapid Oxidation of Alcohols using Microwaves, Phosphorus, Sulfur, and Silicon and
(
the Related Elements, 178:4, 707-709, DOI: 10.1080/10426500307797
To link to this article: http://dx.doi.org/10.1080/10426500307797
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Phosphorus, Sulfur and Silicon, 2003, Vol. 178:707–709
Copyright �C 2003 Taylor & Francis
1
042-6507/03 $12.00 + .00
DOI: 10.1080/10426500390197913
DESS-MARTIN PERIODINANE ON SILICA: RAPID
OXIDATION OF ALCOHOLS USING MICROWAVES
a
a
a
Majid M. Heravi, Ladan Sangsefidi, Hossein A. Oskooie,
b
b
Mitra Ghassemzadeh, and Koroush Tabar-Hydar
a
Azzahra University, Tehran, Iran and Chemistry and
Chemical Engineering Research Center of Iran, Tehran, Iranb
Received March 22, 2002)
(
Adsorbed on silica gel. Dess-Martin periodinane can rapidly oxidize
alcohols to the corresponding carbonyl compounds upon exposure to
microwave under solvent-free condition.
Keywords: Alcohols; carbonyl compounds; Dess-Martin periodinane;
microwave irradiation; solvent-free condition
Oxidation of alcohols to obtain carbonyl compounds or carboxylic acids
are important and fundamental transformations in synthetic organic
chemistry and several methods have been explored to accomplish this
1
2
conversion. The most well known is aggressive chromium (VI) oxide
and the milder non aqueous variants like dipyridine chromium (VI)
3
4
5
oxide, pyridinium chlorochromate, and pyridinium dichromate. In
spite of the many other reagents that are available, there is still a de-
6
mand for mild and selective reagents for the rapid oxidation of alcohols
to carbonyl compounds in an eco-friendly manner.
Dess-Martin periodinane (DMP), 1, [1,1,1-triacetoxy-1-dihydro-1,2-
benziodoxol-3(1H)-one] has received wide recognition as a mild selective
reagent for oxidation of primary and secondary alcohols to the corre-
7
sponding carbonyl compounds.
The microwave enhanced chemical reactions in general, and on inor-
ganic solid supports in particular, have gained popularity over the usual
8
homogeneous and heterogeneous reactions. In continuation of our in-
9
vestigations on organic reactions in solvent-fee condition, we report a
facile, selective, and rapid oxidation of alcohols to carbonyl compounds
Address correspondence to Majid M. Heravi, Department of Chemistry, School of
Sciences, Azzahra University, Vanak, Tehran, Iran. E-mail: mmheravi@azzahra.ac.ir
7
07

7
08
M. M. Heravi et al.
TABLE I Oxidation of Alcohols to Carbonyl Compounds
Dess-Martin periodinane
1
2
R R CHOH
�ꢀ
Silica gel, MW
Entry
Substrate
Time (sec)
120
Product
Yielda (%)
1
2
3
4
5
Benzyl alcohol
Benzaldehyde
77
78
86
82
85
4-Nitrobenzyl alcohol
4-Methylbenzyl alcohol
4-Methoxybenzyl alcohol
5-Methyl-2-nitrobenzyl
alcohol
60
120
120
120
4-Nitrobenzaldehyde
4-Methylbenzaldehyde
4-Methoxybenzaldehyde
5-Methyl-2-nitrobenzaldehyde
6
7
Benzhydrol
Cyclohexanol
120
60
Benzophenone
Cyclohexanone
97
99
aIsolated yield. Melting points for all derivatives agreed with literature values. All
compounds identified by their spectroscopic data with those of authentic samples.
using Dess-Martin periodinane supported onto silica gel in solventless
system, which is accelarated by exposure to microwave.
Since this reagent is no longer commercially available, it was pre-
1
0
pared according to the literature procedure. The reaction is conducted
by mixing the supported reagent with alcohol in a beaker. Microwave
irradiation of this solvent-free mixture provides an efficient, rapid, se-
lective, and simple method for oxidation of alcohols to carbonyl com-
pounds. To establish the generality of the method a variety of alcohols
were efficiently converted to the corresponding aldehydes and ketones
in a very short time (Table I). No overoxidation to carboxylic acid was
observed.
It is noteworthy that without using silica gel, the reaction does not
go to completion and considerable amounts of starting material are
recovered unchanged.
In conclusion, oxidation with silica gel supported Dess-Martin peri-
odinane in solventless system under microwave irradiation is a rapid,
manipulatively simple selective protocol when compared to the con-
ventional solution phase reaction which uses CH2Cl2 as solvent and
trifluroacetic acid as cocatalyst. The oxidative use of supported Dess-
Martin periodinane reagent under solvent-free conditions will generate
newer applications of this and related hypervalent iodine agents in or-
ganic synthesis.

Dess-Martin Periodinane on Silica
709
EXPERIMENTAL SECTION
All products were known compounds. Yields refer to isolated prod-
ucts. Dess-Martin periodinane was prepared according to referred
procedure.10
Oxidation of Alcohols to Carbonyl Compound:
General Procedure
Dess-Martin periodinane (1.05 g, 1.2 mmol) supported onto silica gel
(
1 mmol) was mixed with an appropriate alcohol (1 mmol) in a beaker.
The reaction mixture was placed in a household microwave oven and ir-
radiated for the specific time (Table I). After the completion of reaction
(
monitored by TLC, Petrol ether/ethyl acetate 8:2) CH2Cl2 (5 mL) was
added. The solid was filtered off, and was added to the filtrate sodium
hydroxide solution (1.3 M, 10 mL). The organic layer was washed with
sodium hydroxide solution (1.3 M, 10 mL) and water (20 mL). The or-
ganic layer was dried over Na2SO4 and evaporated to dryness to afford
the corresponding carbonyl compound (Table I).
(
Caution: Although supported DMP under microwave irradiation
was safe in our hand, it is advisable to carry out the reaction in an
efficient hood.)
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