A novel transformation of oximes into hydrazones by hydrazine hydrate

Article abstract of DOI:10.1081/SCC-200034750

We report a novel transformation of different substituted aryl, diaryl, and aralkyloximes into the respective hydrazones using hydrazine hydrate in ethanol at reflux in excellent yields.

Full text of DOI:10.1081/SCC-200034750

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A Novel Transformation of
Oximes into Hydrazones by
Hydrazine Hydrate
M. A. Pasha a & H. M. Nanjundaswamy b
a Department of Studies in Chemistry, Central
College Campus , Bangalore University ,
Bangalore, 560 001, India
b Chemical Examination Section , Public Health
Institute , Bangalore, India
Published online: 10 Jan 2011.
To cite this article: M. A. Pasha & H. M. Nanjundaswamy (2004) A Novel
Transformation of Oximes into Hydrazones by Hydrazine Hydrate, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 34:21, 3827-3831, DOI: 10.1081/SCC-200034750
To link to this article: http://dx.doi.org/10.1081/SCC-200034750
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 21, pp. 3827–3831, 2004
A Novel Transformation of Oximes into
Hydrazones by Hydrazine Hydrate
2
M. A. Pasha1, and H. M. Nanjundaswamy
*
1Department of Studies in Chemistry, Central College Campus,
Bangalore University, Bangalore, India
2Chemical Examination Section, Public Health Institute,
Bangalore, India
ABSTRACT
We report a novel transformation of different substituted aryl, diaryl, and
aralkyloximes into the respective hydrazones using hydrazine hydrate in
ethanol at reflux in excellent yields.
Key Words: Oximes; Hydrazine hydrate; Hydrazones.
*
Correspondence: M. A. Pasha, Department of Studies in Chemistry, Central College
Campus, Bangalore University, Bangalore 560 001, India; E-mail: m_af_pasha@
yahoo.co.in.
3827
DOI: 10.1081/SCC-200034750
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

3828
Pasha and Nanjundaswamy
Oximes, being highly stable and readily prepared compounds, are very
useful not only for isolation, purification, and characterization of carbonyl com-
pounds, but also for protection of a carbonyl group.[1] Numerous methods
have been developed for their oxidative,[2] reductive,[3] and hydrolytic[4]
conversion to carbonyl compounds. Dehydration to nitriles,[5] reduction to
amines,[6] and acylation of oximes[7] are also documented in the literature.
On the other hand, hydrazones are versatile intermediates and important
building blocks. They have been prepared by treating aryl hydrazines with car-
bonyl compounds using a variety of solvents in presence or absence of an
acidic catalyst.[8] Since oximes can be prepared from noncarbonyl starting
materials,[9–11] it would be very interesting to develop a method to convert
oximes into hydrazones, which would constitute the first procedure for obtain-
ing hydrazones from noncarbonyl compounds. This communication reports
the conversion of aryloximes into the corresponding hydrazones (Sch. 1).
In a typical experiment, benzophenone oxime (1.97 g, 10mmol), 99–100%
hydrazine hydrate (2 mL), and ethyl alcohol (15 mL) were heated under reflux
for 1 h (disappearance of the starting material on TLC), and the reaction
mixture was diluted with water and extracted with ether. Removal of ether
provided benzophenone hydrazone purified by silica gel column chromato-
graphy using 10% ethyl acetate in light petroleum to get benzophenone
hydrazone (1.82 g, 95%). The product was identified by its mp, IR, and
NMR spectra. Encouraged by this result, we extended this reaction to substi-
tuted oximes, in order to verify the suitability of the method for the conver-
sion of oximes into the respective hydrazones. The results are summarized in
Table 1. While diaryl and arylalkyl oximes furnish the expected hydrazones,
dialkyl oximes such as camphor oxime, carvone oxime, and cyclohexyl
oxime give a complex mixture of products under the above reaction
conditions. A plausible mechanism for the formation of hydrazones as
shown in Sch. 2 has been proposed for the reaction.
Scheme 1.

Transformation of Oximes into Hydrazones
3829
Table 1. Conversion of oximes into the corresponding hydrazones by hydrazine
hydrate/EtOH at reflux.
Entry
1
Oxime
Hydrazone
Time (h)
1.00
Yield (%)
95
2
3
1.20
1.20
92
94
4
5
1.25
1.20
95
93
6
7
1.50
1.25
86
88
Products were characterized by GC, IR, and 1H NMR; yields are based on TLC and GC
analysis.

3830
Pasha and Nanjundaswamy
Scheme 2.
CONCLUSION
In conclusion, we have developed the first method to convert oximes into
corresponding hydrazones.
ACKNOWLEDGMENTS
H. M. Nanjundaswamy wishes to thank Chemical Examiner and Joint
Director of Public Health Institute, Bangalore, India for their encouragement.
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Received in India June 14, 2004