Regeneration of carbonyl compounds from phenylhydrazones under microwave irradiation

Article abstract of DOI:10.1080/10426500214118

An environmentally benign, efficient, and mild methodology for the cleavage of phenylhydrazones using potassium ferrate under microwave irradiation in solvent-free conditions is described.

Full text of DOI:10.1080/10426500214118

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Regeneration of Carbonyl Compounds from
Phenylhydrazones Under Microwave Irradiation
Majid M. Heravi a , Mahmood Tajbakhsh b , Setareh Habibzadeh b & Mitra Ghassemzadeh c
a Department of Chemistry, School of Sciences , Azzahra University , Vanak, Tehran, Iran
b Department of Chemistry , University of Mazandaran , Babolsar, Iran
c Chemistry and Chemical Engineering Research Center of Iran , Tehran, Iran
Published online: 27 Oct 2010.
To cite this article: Majid M. Heravi , Mahmood Tajbakhsh , Setareh Habibzadeh & Mitra Ghassemzadeh (2002) Regeneration
of Carbonyl Compounds from Phenylhydrazones Under Microwave Irradiation, Phosphorus, Sulfur, and Silicon and the Related
Elements, 177:10, 2299-2302, DOI: 10.1080/10426500214118
To link to this article: http://dx.doi.org/10.1080/10426500214118
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2299–2302
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DOI: 10.1080/10426500290106013
REGENERATION OF CARBONYL COMPOUNDS
FROM PHENYLHYDRAZONES UNDER
MICROWAVE IRRADIATION
Majid M. Heravi,a Mahmood Tajbakhsh,b Setareh Habibzadeh,b
and Mitra Ghassemzadehc
Department of Chemistry, School of Sciences,
Azzahra University, Vanak, Tehran, Iran;a Department of
Chemistry, University of Mazandaran, Babolsar, Iran;b and
Chemistry and Chemical Engineering Research Center of Iran,
Tehran, Iranc
(Received October 17, 2001; accepted December 4, 2001)
An environmentally benign, efficient, and mild methodology for
the cleavage of phenylhydrazones using potassium ferrate under
microwave irradiation in solvent-free conditions is described.
Keywords: Carbonyl compounds; microwave irradiation; phenylhydra-
zones; potassium ferrate; solventless system
Protection and subsequent deprotection of a functional group is almost
inevitable in multistage organic synthesis.1 Phenylhydrazones serve as
important synthetic intermediates and they can be preferably used for
isolation, purification and characterization of aldehydes and ketones.2
Developing mild, efficient, ecofriendly and selective cleavage of phenyl-
hydrazones continues to be a significant aspect of organic chemical
transformation.
There has been considerable attention in the creation and develop-
ment of ever green and solventless methods3 in organic methodology
dictated by stringent environment protection laws.4 Organic solvents
are not only expensive but are often flammable, toxic and environmen-
tally hazardous. Microwave irradiation in organic synthesis is a useful
7
technique nowadays.5 Dry media using microwave thermolysis have
attracted much attention, because it omits the use of hazardous and
Address correspondence to M. M. Heravi, Department of Chemistry, Tarbiat Modarres
University, P.O. Box 14115-175, Tehran, Iran. E-mail: mmheravi@azzahra.ac.it
2299

2300
M. M. Heravi et al.
relatively expensive organic solvents and the reaction can be conducted
in open vessels.8
Potassium ferrate (K2FeO4) is a sixvalent iron compound which can
be easily and economically prepared by oxidizing ferric nitrate with
sodium hypochlorite and the subsequent treatment with potassium
hydroxide.9 It has been recently used by P. Laszlo and his coworker
for oxidizing organic substrates in nonaqueous media.10
Reagents adsorbed on mineral supports have gained popularity in
organic synthesis due to their selectivity, ease of manipulation11,12 and
especially make them suitable and safe to be placed in a microwave
oven.13
Association of ferric salts with zeolite14 16 and clay17 and conduction
of their reactions under microwave irradiation in solvent free conditions
had been pioneered in our laboratory. Armed with these experiences in
this communication we wish to report that clay supported potassium
ferrate can efficiently and rapidly cleave phenylhydrazones under mi-
crowave irradiation in a solventless system.
As illustrated in Table I regeneration of carbonyl compounds
from their diphenyl-hydrazones was performed by mixing substrate
and supported reagent with the ratio 1:3 and irradiation under
microwave.
It is noteworthy to mention that in the absence of clay the reactions
remain incomplete even with higher ratio of reagent (1:5) and even
longer reaction time. Most seriously in the absence of clay the molten
ferric salt adhered to the walls of the vessel, making the work up cum-
bersome. However, the reactions proceed efficiently and rapidly when
potassium ferrate is mixed with equivalent weights of montmorillonite
K-10. The work up procedure involves addition of solvent, mere filtra-
tion and evaporation of the solvent to afford a pure product in high
yield.
In conclusion the use of nontoxic potassium ferrate permits the
regeneration of carbonyl compounds from their hydrazones. The
advantages of this method are mild, eco-friendly conditions, short
reaction time, easy work up and high yields. We believe this
procedure will find its place in organic methodology. The only
drawback of this method is that the yields of the reaction for
nonbenzylic derivatives are low. Potassium ferrate was prepared
according to a modified procedure and supported onto montmorillonite
K-10.10 All substrates were synthesized by a known literature proce-
dure. All products were known compounds and characterized by com-
parison of their physical and spectroscopic data with those of authentic
samples.

Carbonyl Compounds
2301
TABLE I Oxidative Cleavage of Phenylhydrazones Using Potassium Ferrate
Under Microwave Irradiation in Solvent-Free Conditions
Reaction time
(min)
Yieldc
(%)
Entry
1
Substratea
Productb
8
6
92
94
2
3
11
87
4
5
6
8
10
10
90
89
85
7
8
87
aAll substrates were synthesized according to reported procedures.
bAll products were known compounds.
cYields refer to isolated products.
REGENERATION OF CARBONYL COMPOUNDS FROM
THEIR PHENYLHYDRAZONES
General Procedure
A mixture of an appropriate phenylhydrazone (1 mmol) and clay sup-
ported potassium ferrate were mixed intimately in a pyrex beaker. The
beaker was then placed in a household microwave oven and irradiated
at an output of 900W. The progress of the reaction was monitored by
TLC using pet ether-ethyl acetate 8:2 as eluent. After completion of the
reaction, CH2Cl2 (5 mL) was added and the residue was filtered off. The
organic solvent was evaporated to dryness to afford the corresponding
carbonyl compound (Table I).

2302
M. M. Heravi et al.
Caution
Although the reactions were smooth and safe in our hands, precaution
for using a microwave oven is advised. It is recommended to use the
microwave oven in an efficient and standard hood.
REFERENCES
[1] T. W. Green and P. G. M. Wuts, Protective Groups in Organic Synthesis (John Wiley,
New York, 1991), 2nd ed.
[2] S. R. Sander and W. Karo, Organic Functional Groups Preparation (Academic Press,
London, 1989), 2nd ed, vol. 3.
[3] K. Tanaka and F. Toda, Chem. Rev., 100, 1025 (2000).
[4] C. B. Khouv, C. B. Darth, J. A. Lalenger, and M. E. Davis, J. Catal., 149, 195 (1994).
[5] S. Caddick, Tetrahedron 38, 10403 (1995).
[6] R. A. Abramovitch, Org. Prep. Proceed. Int., 23, 623 (1991).
[7] D. M. P. Mingos and D. R. Baghu Orust, Chem. Soc. Rev., 20, 1 (1990).
[8] J. P. Barnier, A. Loupy, P. Pigeon, M. Ramdani, and P. Jac Quglt, J. Chem. Soc.,
Perkin Trans I, 397 (1993).
[9] G. W. Thompson, L. T. Ockerman, and J. M. Schreyer, J. Am. Chem. Soc., 73, 1379
(1951).
[10] L. Delaude and P. Laszlo, J. Org. Chem., 61, 6360 (1996).
[11] A. Mc Killop and D. W. Young, Synthesis, 401 and 481 (1979).
[12] M. M. Balogh and P. Laszlo, Organic Chemistry Using Clays (Springer Verlag,
Berlin, 1993).
[13] H. M. Meshram, G. Sumithra, G. S. Reddy, Y. S. S. Ganesh, and J. S. Yadav, Synth.
Commun. 29(16), 2807 (1999).
[14] M. M. Heravi, D. Ajami, K. Aghapoor, and M. Ghassemzadeh, J. Chem. Soc., Chem.
Commun., 893 (1999).
[15] M. M. Heravi, D. Ajami, M. Ghassemzadeh, and K. Tabar-Hydar, Synth. Commun.
31, 2079 (2001).
[16] B. Mohajerani, M. M. Heravi, and D. Ajami, Monatsh. Chem., 2001, in press.
[17] M. M. Heravi, D. Ajami, M. M. Mojtahedi, and M. Ghassemzadeh, Tetrahedron Lett.,
40, 561 (1999).