Solvent-free rapid deprotection of ketone and aldehyde oximes using periodic acid

Article abstract of DOI:10.1080/00397910500212833

Ketone and aldehyde oximes can be readily converted to the corresponding carbonyl compounds in high yields under solvent-free conditions when treated with periodic acid. Oximes bearing aliphatic C=C bonds can be selectively deoximated. The advantages of this protocol include a rapid reaction rate and a simple workup procedure. No volatile organic solvents are required in the reaction processes. Copyright Taylor & Francis, Inc.

Full text of DOI:10.1080/00397910500212833

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Solvent‐Free Rapid
Deprotection of Ketone
and Aldehyde Oximes using
Periodic Acid
a
a
a
Zheng Li , Run‐Bo Ding , Yu‐Lin Xing & Sheng‐Yi
a
Shi
a
Gansu Key Laboratory of Polymer Materials,
College of Chemistry and Chemical Engineering,
Northwest Normal University, Lanzhou, Gansu, China
Published online: 18 Aug 2006.
To cite this article: Zheng Li , Run‐Bo Ding , Yu‐Lin Xing & Sheng‐Yi Shi (2005):
Solvent‐Free Rapid Deprotection of Ketone and Aldehyde Oximes using Periodic Acid,
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 35:19, 2515-2520
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Synthetic Communications , 35: 2515–2520, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500212833
Solvent-Free Rapid Deprotection of Ketone
and Aldehyde Oximes using Periodic Acid
Zheng Li, Run-Bo Ding, Yu-Lin Xing, and Sheng-Yi Shi
Gansu Key Laboratory of Polymer Materials, College of Chemistry
and Chemical Engineering, Northwest Normal University, Lanzhou,
Gansu, China
Abstract: Ketone and aldehyde oximes can be readily converted to the corresponding
carbonyl compounds in high yields under solvent-free conditions when treated with
periodic acid. Oximes bearing aliphatic C 55 C bonds can be selectively deoximated.
The advantages of this protocol include a rapid reaction rate and a simple workup
procedure. No volatile organic solvents are required in the reaction processes.
Keywords: Aldehyde oxime, deoximation, ketone oxime, periodic acid, solvent-free
INTRODUCTION
[1]
Oximes are frequently used to protect carbonyl compounds in the course of
[2]
synthesis and are extensively used for purification of carbonyl compounds.
In addition, oximes also have other applications such as the preparation of
[3]
[4]
nitriles and amides via Beckmann rearrangement or to activate carbonyl
[5]
groups. At the same time, oximes can be prepared from noncarbonyl
compounds, and the regeneration of carbonyl compounds from oximes rep-
[6]
resents a potential route for syntheses of ketones and aldehydes. Hence,
regeneration of carbonyl compounds from the corresponding oximes is a
very important transformation in organic chemistry.
In view of the importance of deoximation, a good number of methods based
[
on microwave assistance and photochemical, electrochemical, and ion
7]
[8]
[9]
Received in Japan March 28, 2005
Address correspondence to Zheng Li, Gansu Key Laboratory of Polymer Materials,
College of Chemistry and Chemical Engineering, Northwest Normal University,
Lanzhou, Gansu 730070, China. Fax: 86-931-7971989; E-mail: lizheng@nwnu.edu.cn
2
515

2516
Z. Li et al.
[
10]
liquid catalytic
used for deoximation is oxidative reaction using several oxidants, such as pyr-
reactions have been developed. The most popular approach
[
11]
[12]
idinium fluorochromate/Al O ,
potassium permanganate/Al O ,
2 3
2
3
[13]
N-chloro-3-methyl-2,6-diphenylpiperidin-4-one,
[14]
bismuth compounds,
ammonium
2-iodylbenzoic
[15]
N,N-dibromo-N,N-1,2-ethanediylbis(p-toluenesulphonamide),
[
7a]
[2]
N-haloamides, dimethyl dioxirane,
[16]
persulfate/SiO ,
2
[17]
acid,
[18]
[19]
Dess–Martin periodinane,
and manganese triacetate.
However,
these reagents suffer from different disadvantages such as requirements for
refluxing temperature, long reaction times, difficulties in isolation of products,
formation of overoxidation products, and use of volatile organic solvents.
Many reagents are not selective for oximes in the presence of an aliphatic
C 55 C bond.
Solvent-free organic synthesis is of current interest because of its many
advantages, such as reduced pollution, low cost, simplicity in process and hand-
ling, and potential applications in combinatorial chemistry and chemical
[20]
industry. In this article, we report a solvent-free, rapid, and mild
oxidative method for selective deoximation using periodic acid as an oxidant.
RESULTS AND DISCUSSION
The reactions were carried out by mixing 0.5 equivalents of periodic acid with
different oximes in an agate mortar (6-cm diameter) and grinding with a pestle
at room temperature. It was found that 0.5 equivalents of periodic acid for the
reactions was the optimized ratio for excellent yields, and an excess of reagent
and longer reaction time sometimes resulted in lower yields resulting from
overoxidation. The results illustrated in Table 1 indicate that the reaction is
suitable for a variety of aliphatic, aromatic, heterocyclic ketone and
aldehyde oximes (Scheme 1).
The deprotection of aromatic oximes normally required longer reaction times
than aliphatic oximes. In addition, aldoximes needed shorter time compared with
ketoximes. All substrates, even the hindered oximes, were converted to corre-
sponding carbonyl compounds in high yields. Oxidative cleavage of most
ketoximes was slow enough that it can allow selective cleavage of aldoximes
in the presence of ketoximes. For oximes, including steric congestion near
carbonyl carbon, the reaction times were prolonged remarkably. However, func-
tional groups such as hydroxy, halo, nitro, and methoxy did not have a dramatic
effect on the rate of oxidative deoximation because the reaction rate was fast
enough in almost all cases, including the substrates bearing either electron-
donating or electron-withdrawing groups. In addition, unlike other oxidative
methods, the major drawback of overoxidation of the aldoximes to their
carboxylic acids was not observed.
Encouraged by these results, we studied the reaction of a series of special
oximes. We found that periodic acid was compatible with oximes involving
aliphatic C 55 C bonds (entry 18). Therefore, dibenzylidene-acetone oxime

Ketone and Aldehyde Oxime Deprotection
2517
Table 1. Solvent-free deoximation using periodic acid
Time
(min)
Yield
c
(%)
a
b
Entry
Substrate
Product
1
2
3
0.5
1
96
98
96
1
4
5
4
4
94
95
6
5
92
7
8
15
18
95
94
9
20
18
89
91
1
0
1
1
1
1
1
2
3
4
18
16
14
2
86
94
92
96
(
continued)

2518
Z. Li et al.
Table 1. Continued
Time
(min)
Yield
c
(%)
a
b
Entry
Substrate
Product
15
16
17
1.5
14
98
88
91
16
1
1
8
9
12
89
94
3.5
20
3.5
89
2
2
1
2
2.5
3
92
96
23
25
92
a
b
All substrates were synthesized according to known literature procedures.
All products were characterized by comparison of their melting points, and IR and
1
H NMR spectra with those of authentic samples.
c
Yields refer to isolated products.
Scheme 1.

Ketone and Aldehyde Oxime Deprotection
2519
underwent deoximation very efficiently without rearrangement or cleavage of
the aliphatic C 55 C bonds and the reaction was essentially chemoselective. In
addition, oximes, including heterocycles, did not have a great difference in
rate and yield compared with other aromatic oximes, and no by-product
formation was observed.
In conclusion, the ketoximes and aldoximes can be expeditiously depro-
tected to afford corresponding carbonyl compounds under solvent-free and
room temperature conditions in high yields. This is a more environmental
benign, chemselective protocol over the existing methodologies and also is
a good alternative to deoximation.
EXPERIMENTAL
General Procedure for Deprotection of Oximes using Periodic Acid
Oxime (2 mmol) and periodic acid (1 mmol) were mixed in an agate mortar
until a homogeneous mixture was formed. Then, the mixture was thoroughly
ground with a pestle for an appropriate time (Table 1) until the starting
material disappeared. The completion of reaction was monitored by TLC
using petroleum ether, ethyl acetate, and acetone (5 : 1 : 1) as eluent. The
resulting mixture was extracted with 10 mL of acetone, and the extract was
evaporated to give the product.
For entries 1, 2, 3, 14, 15, and 22, the liquid products were isolated by
distillation after the completion of the reactions.
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