Microwave promoted regeneration of carbonyl compounds from oximes using N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin

Article abstract of DOI:10.1155/2011/590923

An efficient, economically viable and operationally simple method was developed for deoximation of oximes (of ketones and aldehydes) to their corresponding carbonyl compounds using polymer beads of N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin. Polymeric reagent offered speedy conversion and substantial yields of products under mild condition and is recyclable. Deoximation was monitored by the use of ¹³C NMR.

Full text of DOI:10.1155/2011/590923

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
2011, 8(1), 288-292
http://www.e-journals.net
Microwave Promoted Regeneration of Carbonyl
Compounds from Oximes Using N, N-Dichloro
Poly(Styrene-co-divinylbenzene)Sulphonamide Resin
A.G. BELDAR and MAMTA SHARMA*
Synthetic Chemistry Division
Defence R & D Establishment, Jhansi Road, Gwalior- 474002, M.P., India
reekana@rediffmail.com
Received 10 May 2010; Accepted 20 July 2010
Abstract: An efficient, economically viable and operationally simple method
was developed for deoximation of oximes (of ketones and aldehydes) to their
corresponding carbonyl compounds using polymer beads of N, N-dichloro
poly(styrene-co-divinylbenzene)sulphonamide resin. Polymeric reagent offered
speedy conversion and substantial yields of products under mild condition and
is recyclable. Deoximation was monitored by the use of 13C NMR.
Keywords: Deoximation, N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide, Solid phase
reagent, Resin.
Introduction
Oximes play a significant role in the organic synthesis as carbonyl group protector and
enable the isolation and purification of ketoximes and aldoximes by selectively protecting
them1-17. A plethora of papers in the literature reveals the interest of researchers towards the
rapid development of novel techniques for regeneration of carbonyl compounds from
oximes under the mild conditions.
A wide variety of deoximation reagents have been developed so far such as manganese
triacetate18, dinitrogen tetraoxide19, trimethylsilyl chlorochromate20, titanium silicalite21,
pyridinium chlorochromate22, bismuth trichloride23, ammonium persulfate- silica gel24,
sodium periodate25. Among them some require strong acidic condition; some takes long
reaction time and give low product yield while some are poisonous and oxidative reagents
posses serious isolation difficulties.
Heterogenised reagents26-28 has evinced the attention of researchers because of their handling
ease, lower toxicity, non explosive and malodorous nature. Another important motive of
supported reagents is facile isolation of the pure product than their solution phase equivalents.
Few reports are available on the solid supported deoximating agents under mild condition29,30
.

Microwave Promoted Regeneration of Carbonyl Compounds
289
N-halo reagents are widely used in fine organic synthesis because of its highly reactive
N-X bond and various mode of its splitting. This polymeric resin proved to be a very strong
chlorinating agent and found to be easily regenerable and reusable. In earlier work
N,N-dichloro poly(styrene-co-divinylbenzene)sulphonamide has been reported as
decontaminant31 and as chlorinating reagent for synthesis of dialkyl chlorophosphates32. This
development encouraged us to explore the utility of polymeric beads in multi-dimensions.
Here we report an organic transformation: a conventional and microwave assisted clean, rapid
and efficient method for the regeneration of carbonyl compounds with the help of beads.
Experimental
IR spectra were recorded on FT-IR spectrometer Perkin-Elmer model 1720 on KBr disk. (for solids)
and neat for liquids. 13C{1H}NMR spectra were recorded in CDCl3 solvent on Bruker DPX
Advance FT-NMR instrument at 400 MHz and 100 MHz respectively using trimethylsilane as an
internal standard at 0.0 ppm. A house hold LG make oven was used for studies.
General procedure for deprotection of oximes
A mixture of oxime (2 mmol), carbon tetrachloride (8 mL) and N, N-dichloro poly(styrene-co-
divinylbenzene)sulphonamide resin (2 mmol) was refluxed or irradiated in the microwave
oven at power 600 W for specific time period (Table 1). When all the oxime was converted,
the intermediate was hydrolysed by adding water and washed with CCl4. Before adding CCl4
beads were separated out through filtration. The organic layer was dried with MgSO4 after
separation from aqueous layer. Carbon tetrachloride was evaporated to get desired product.
The yield and 13C NMR chemical shift values are summarized in the Table 1 and 2 respectively.
Table 1. Deoximation with N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide
produced via Scheme 1
Time Refluxb/ Yield,
Time Refluxb/ Yield
Entry Producta
Entry
9
Producta
M.W.c
55/60
%
96
M.W.c
65/120
%
81
O
O
1
O
2
50/60
75/90
92
89
10
11
75/90
89
85
O
O
O
3
75/120
HO
O
O
CHO
4
65/90
90/120
65/90
50/90
90
91
91
85
12
13
14
15
55/90
65/90
70/120
70/90
82
88
76
79
NH2
O
5
CHO
S
O
6
CHO
O
O
O
7
N
H
O
O
8
60/90
90
16
50/60
86
CO2Et
Cl
M.W.=Microwave, aProducts were characterized by their physical properties, comparison with
authentic samples and IR spectra. btime in minutes. Ctime in seconds

290
MAMTA SHARMA et al.
Results and Discussion
The microwave energy has given a new dimension and vision to organic reactions29. The
reaction of oximes with polymeric reagent in CCl4 provide carbonyl compound without any
side product, under the microwave radiations (Scheme 1). The completion time of reaction
was monitored by TLC and 13C{1H} NMR spectroscopy.
R1
R1
Polymericreagent
SO NH
2
C
O
2
C
N
CCl4, refluxedor MW*
R2
R2
OH
*Microwave
Scheme 1
We obtained almost all quantitative yields in short reaction times. The microwave
temperature for the reaction of various oximes with N, N-dichloro poly(styrene-co-
divinylbenzene)sulphonamide polymeric beads afforded the corresponding carbonyl
compounds in 55 to 90 sec. in excellent yields (Scheme 1, Table 1).The uniqueness of this
method is its simplicity and time saving. The process of a typical reaction was monitored by
appearance and disappearance of 13C NMR signal of carbonyl and oximino carbon
respectively (Figure 1).
Figure 1. Progress of a typical reaction as monitored by 13C{1H} NMR analysis at different
time intervals for entry 2.
Reason behind the use of NMR is here, that it provides direct analysis of reaction
mixture without the use of any tedious sample preparation method as it is required in GC-MS.
The carbon chemical shift changes with significant difference (~ ∆δ = 35 ppm) on conversion
of oxime (δ range of C=N is 145-170 ppm) into carbonyl (δ range of C=O is 190-227 ppm).
13C{1H} NMR chemical shifts of oximes and carbonyl compounds are presented in the Table 2.
The results of conversion of oximes to their corresponding carbonyl compounds are presented
in the Table 1. In order to evaluate the generality and applicability of this method a variety of
oximes were deprotected to their parent carbonyl compounds. The product of reaction with
polymeric reagent was isolated simply by filtering off the solid polymer and subsequently
evaporation of the solvent from filtrate. The advantages of this method are good yield, mild
condition, short reaction time and no side product. The recovered polymer was again
chlorinated and reused up to several times without any loss in activity.

Microwave Promoted Regeneration of Carbonyl Compounds
291
Table 2. 13C{1H} NMR chemical shifts of compounds
13C NMR values
of carbonyl
carbon
13C NMR
values of
oximino carbon
162.3
13C NMR values
Entry of carbonyl
carbon
13C NMR
values of
Entry
oximino carbon
173.6
163.7
1
2
3
4
5
6
7
8
197.1
8
212.7
217.2
217.1
198.61
195.89
201.1
162.2
162
9
10
11
12
13
14
15
169.9
160.4
163.8
217.8 * 201.2
192
210.7
164.8 163.2
151.9
145.1
207.8
194.5
209.7
163.9
160.5
212.3
142.6
192.6
161.9
216.1
144.7
a
*
Chemical shift of carbonyl carbon in ppm, acetyl group, chemical shit of oximino carbon
b
in ppm
Conclusion
In conclusion, N, N-dichloro poly(styrene-co- divinylbenzene)sulphonamide resin is a
efficient reagent to fulfil different required objectives of organic synthesis. Here in this work
it is proved to be an important and valuable reagent for the conversion of oximes to their
corresponding carbonyl compounds. The conversion was very efficient, with excellent yield,
and polymeric reagent can be recovered, activated and reused. The main advantage of the
method is that reactions were very clean and operationally simple. Therefore method is
attractive for organic chemist.
Acknowledgment
Authors are thankful to Dr. R. Vijayaraghavan, Director Defence Research & Development
Establishment (DRDE) Gwalior.
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