tert-butyl hypoiodite for deoximation

Article abstract of DOI:10.1080/00397910500290599

tert-Butyl hypochlorite and tert-butyl hypobromide react with aldoximes and convert them into hydroximinoyl chloride and bromide, respectively; however, under the same reaction conditions, tert-butyl hypoiodite deoximates aldoximes and ketoximes to give corresponding aldehydes and ketones in high yield (>94%) in a short reaction time (～20 min). Copyright Taylor & Francis, Inc.

Full text of DOI:10.1080/00397910500290599

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tert‐Butyl Hypoiodite for
Deoximation
Vikas N. Telvekar a
a Department of Pharmaceutical Sciences and
Technology , University Institute of Chemical
Technology, University of Mumbai , Mumbai, India
Published online: 22 Aug 2006.
To cite this article: Vikas N. Telvekar (2005) tert‐Butyl Hypoiodite for Deoximation,
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 35:21, 2827-2829
To link to this article: http://dx.doi.org/10.1080/00397910500290599
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Synthetic Communicationsw, 35: 2827–2829, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500290599
tert-Butyl Hypoiodite for Deoximation
Vikas N. Telvekar
Department of Pharmaceutical Sciences and Technology, University
Institute of Chemical Technology, University of Mumbai, Mumbai, India
Abstract: tert-Butyl hypochlorite and tert-butyl hypobromide react with aldoximes
and convert them into hydroximinoyl chloride and bromide, respectively; however,
under the same reaction conditions, tert-butyl hypoiodite deoximates aldoximes and
ketoximes to give corresponding aldehydes and ketones in high yield (.94%) in a
short reaction time (ꢀ20 min).
Keywords: Deoximination, oximes, tert-butyl hypoiodite
INTRODUCTION
There is a continued interest in the development of procedures for the effective
generation of carbonyl compounds from the corresponding oximes, espe-
cially under mild conditions. There are several oxidative methods available
for regeneration of carbonyl compounds from their corresponding oximes.
These methods include use of Bismuth nitrate pentahydrate,[1] peroxomono-
sulfuric acid supported on silica gel,[2] tert-butyl hydroperoxide,[3] iodine in
acetonitrile,[4] ammonium persulfate ion,[5] chromium trioxide–silica gel–
microwave irradiation,[6] sodium periodate,[7] nickel diperiodate,[8] periodic
acid,[9] and hypervalent iodine compounds.[10] In spite of the many reagents
available, there is still scope for newer reagents. Here we report use of tert-
butyl hypoiodite in carbon tetrachloride for the oxidative regeneration
of carbonyl compounds from their oximes. Previously it was reported that
tert-butyl hypochlorite and tert-butyl hypobromite in carbon tetrachloride
Received in India May 25, 2005
Address correspondence to Vikas N. Telvekar, Department of Pharmaceutical
Sciences and Technology, University Institute of Chemical Technology, University
of Mumbai, Matunga, Mumbai 400 019, India. E-mail: vikastelvekar@rediffmail.com
2827

2828
V. N. Telvekar
react with oxime to produce hydroximinoyl chloride and bromide respecti-
vely, with no reported deoximation.[11]
tert-Butyl hypoiodite was prepared by the reactionof tert-butyl hypochlorite
with iodine in dry carbon tetrachloride in situ. Oximes were synthesized as per
the literature report.[12] The deoximation was carried out by addition of stock
solution of the reagent to a stirred solution of the oximes in carbon tetrachloride.
More than 94% pure carbonyl compounds were recovered from the organic layer
after the usual workup. Examples illustrating conversion of oximes to parent
carbonyl compounds are listed in Table 1. The rate of deoximation was neither
affected by electron-withdrawing or electron-donating substituents at the para-
position. Even the sterically hindered camphor oxime could be successfully
converted into camphor in high yield. It was observed that benzaldehyde
methoxime (entry 15) did not undergo deoximation.
GENERAL PROCEDURE
The reagent tert-butyl hypoiodite (0.48 g of tert-butyl hypochlorite and 1.12 g
of iodine in 20 mL of dry carbon tetrachloride) were added to a stirred solution
Table 1. Transformation of oximes to the corresponding carbonyl compounds using
tert-butyl hypoioditea
Entry
Carbonyl compoundb
Benzaldehyde
Time (min)
Yield (%)c
1
2
15
20
96
94
96
93
96
96
94
96
95
96
96
95
94
96
—
4-Nitrobenzaldehyde
4-Methoxybenzaldehyde
4-Chlorobenzaldehyde
4-Methyl benzaldehyde
Cyclohexanone
3
20
15
4
5
15
15
6
7
Acetophenone
15
20
8
4-Methoxyacetophenone
4-Chloroacetophenone
4-Fluroacetophenone
4-Methylacetophenone
Benzil
9
20
20
10
11
12
13
14
15
15
15
15
Camphor
Octanal
Benzyldehyde O-methyloxime
20
No reaction
aAll reactions were carried out at rt in dry CCl4 under N2 atmosphere.
1
bStructures confirmed by IR, H NMR, and mp/bp.
cYields are of the isolated products.

tert-Butyl Hypoiodite for Deoximation
2829
of 4-methylbenzaldoxime (0.5 g, 3.70 mmol) in carbon tetrachloride (20 mL)
dropwise at room temperature under a stream of nitrogen. The stirring was
continued until the oxime disappeared (TLC). The reaction mixture was
diluted with addition of methylene dichloride and water. The organic layer
was separated, washed with 5% cold sodium thiosulphate solution and
water (50 mL), dried over sodium sulphate, and concentrated to give almost
pure 4-methyl benzaldehyde (0.426 g, 96%).
ACKNOWLEDGMENT
We gratefully acknowledge the UICT for financial support under the UICT
Golden Jubilee Fund.
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