Zeofen, an eco-friendly catalyst for deoximation under microwave irradiation in solventless system

Article abstract of DOI:10.1081/SCC-120014039

An environmentally benign process for the conversion of oximes to carbonyl compounds upon treatment with zeofen under microwave irradiation in a solvent-free condition is described.

Full text of DOI:10.1081/SCC-120014039

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ZEOFEN, AN ECO-FRIENDLY CATALYST FOR
DEOXIMATION UNDER MICROWAVE IRRADIATION IN
SOLVENTLESS SYSTEM
Majid M. Heravi a , Dariush Ajami b , Bagher Mohajerani c , Kourosh Tabar-Hydar b & Mitra
Ghassemzadeh b
a Department of Chemistry , School of Sciences , Azzahra University , Vanak, Tehran, Iran
b Chemistry & Chemical Engineering Research Center of Iran , P.O. Box 14335-186, Tehran,
Iran
c Petroleum Research Center of Iran , Tehran, Iran
Published online: 16 Aug 2006.
To cite this article: Majid M. Heravi , Dariush Ajami , Bagher Mohajerani , Kourosh Tabar-Hydar & Mitra Ghassemzadeh (2002)
ZEOFEN, AN ECO-FRIENDLY CATALYST FOR DEOXIMATION UNDER MICROWAVE IRRADIATION IN SOLVENTLESS SYSTEM, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:21, 3325-3330, DOI:
10.1081/SCC-120014039
To link to this article: http://dx.doi.org/10.1081/SCC-120014039
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 21, pp. 3325–3330, 2002
ZEOFEN, AN ECO-FRIENDLY
CATALYST FOR DEOXIMATION UNDER
MICROWAVE IRRADIATION IN
SOLVENTLESS SYSTEM
Majid M. Heravi,1, Dariush Ajami,2
*
Bagher Mohajerani,3 Kourosh Tabar-Hydar,2
and Mitra Ghassemzadeh2
1Department of Chemistry, School of Sciences,
Azzahra University, Vanak, Tehran, Iran
2Chemistry & Chemical Engineering Research Center of
Iran, P.O. Box 14335-186, Tehran, Iran
3Petroleum Research Center of Iran, Tehran, Iran
ABSTRACT
An environmentally benign process for the conversion of
oximes to carbonyl compounds upon treatment with zeofen
under microwave irradiation in a solvent-free condition is
described.
*Corresponding author. E-mail: mmheravi@azzahra.ac.ir
3325
DOI: 10.1081/SCC-120014039
Copyright & 2002 by Marcel Dekker, Inc.
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3326
HERAVI ET AL.
Prompted by stringent environment protection laws in recent years,
there has been considerable growth in attention to the development of green
and solventless procedure in organic methodology.[1]
Organic solvents are not only expensive but are often flammable, toxic,
environmental hazardous. Microwave irradiation in organic synthesis is a
useful technique nowadays.[2] Dry media using microwave thermolysis has
attracted much attention.[3]
In the last decade oximes have received much interest, being not only
used to purify and isolate carbonyl compounds but also to protect and
activate carbonyl group.[4] Since oximes can also be produced at non-
activated hydrocarbon[5] sites its importance has been assumed added.
The hydrolytic stability of oximes has inspired the development of several
reagents,[6] each of which has its own merits and drawbacks.
We have recently introduced zeofen as a versatile oxidizing reagent[7]
and reported methods for oxidative cleavage of oximes.[8] To prepare
zeofen, Fe(NO3)3 ꢀ 9H2O (0.80 g, 2 mmol) and a weight equivalent of
HZSM-5 zeolite[9] were crushed together so as to form an intimate mixture
(zeofen). This new reagent can be stored in a dark bottle and its stable
without suffering from the problem of slow decomposition that clayfen
does.[10] In this communication we wish to extend the utility of zeofen as
a green chemical in deoximation reaction under microwave irradiation in
solvent free condition.
Cleavage of oxime to regenerate the carbonyl compounds has received
much attention over recent years. Classic reagents of this type are trimethyl-
ammonium chlorochromate,[6a] pyridinium chlorochromate,[6c] chromium
trioxidechlorotrimethylsilane,[6d] manganes triacetate,[6i] activated MnO2,[6j]
ammonium chlorochromate[8d] and bis-trimethylsilyl-chromate.[8c]
The most serious disadvantage of oxidants based on chromium[11] and
manganese[12] is that they are corrosive and they are irritants for the skin
and for sensitive body parts such as the eyes. Chromium compounds are
especially notorious carcinogens.[13] Design of new, less hazardous chemical
procedures have become a priority for the synthetic chemists.
Reagents adsorbed on mineral supports have gained popularity in
organic synthesis due to their selectivity and ease of manipulation.[14]
Association of ferric salts with zeolite[7a–c] and clay[15] had been pioneered
in our laboratory leading to the design of zeofen. We used zeofen for oxida-
tion of alcohols to carbonyl compounds,[7a] deprotection of silyl[7b] and
tetrahydropyranyl ethers.[7c] In this article we wish to report its utility to
rapid deoximation under solventless system. The deoximation reactions
were carried out by mixing four equivalent of zeofen with a neat oxime in
a beaker under microwave irradiation. For example benzaldoxime (Table 1,
Entry 1) was oxidatively cleaved in almost quantitative yield in 4 min in

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ZEOFEN AS DEOXIMATION CATALYST
3327
Table 1. Cleavage of Carbonyl Compounds Using Zeofen Under Microwave
Irradiation in Solventless System
Entry
1
Substratea
Carbonyl Compoundb
Time (min)
4
Yieldc (%)
95
2
3
4
5
5
5
92
90
88
5
6
4
5
91
90
7
8
9
7
7
82
80
74
10
aAll substrates were synthesized according to known procedures. bAll products were
known compounds and characterized by comparison of their physical and spectro-
c
scopic data. Yields refer to isolated products.

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3328
HERAVI ET AL.
substrate/reagent ratio of 1 : 4. The reaction remained incomplete when
lower amounts of the zeolfen was used. To assess the generality of this
solid state deoximation, a variety of oximes (Table 1) were reacted yielding
the corresponding carbonyl compounds in excellent yields at very short
reaction time.
In summary the present procedure for the oxidative cleavage of oximes
is efficient, convenient and high yielding which occurs at short time. The
notable advantage of this method is eco-friendly condition. To be environ-
mentally benign, by development of a continuous microwave reaction,[16]
this method could find application.
EXPERIMENTAL
The reagent zeofen was prepared according to reported method.[7a] All
products were known compounds and characterized by comparison of their
physical and spectroscopic data with those of authentic samples.
Conversion of Oximes to Carbonyl Compounds. General Procedure
A mixture of appropriate oxime (1 mmol) and zeofen (4 mmol) was
placed in a beaker and subjected to microwave irradiation at an output of
900 W. The progress of reaction was monitored by TLC using petrolether;
ethyl acetate 8 : 2 as eluents. After completion of the reaction (Table 1) the
reaction mixture was cooled to room temperature and charged on a silica gel
column (60 mesh) and eluted (Pet ether–ethyl acetate 8 : 2) to afford the
corresponding carbonyl compound (Table 1).
Caution
Although this reaction worked safely in our hands, using a microwave
oven in an efficient hood is advised.
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cited therein.

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ZEOFEN AS DEOXIMATION CATALYST
3329
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˚
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3330
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Received in Japan June 26, 2001