Regeneration of carbonyl compounds by deoximation of piperidine-4-one oximes with quinolinium flurochromate in presence of montmorillonite K10 clay

Article abstract of DOI:10.14233/ajchem.2017.20787

The regeneration of oximes from 2,6-diphenyl piperidine-4-one oximes (PPO) and its alkyl substituted derivatives (3-alkyl PPO and 3,5- dimethyl PPO) by quinolinium flurochromate under microwave irradiation in the presence of montmorillonite K10 clay leads to the formation of ketone in a good yield.

Full text of DOI:10.14233/ajchem.2017.20787

Asian Journal of Chemistry; Vol. 29, No. 11 (2017), 2485-2487
A
SIAN
J
OURNAL OF HEMISTRY
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https://doi.org/10.14233/ajchem.2017.20787
Regeneration of Carbonyl Compounds by Deoximation of Piperidine-4-one Oximes
with Quinolinium Flurochromate in Presence of Montmorillonite K10 Clay
*
T. VIMALA and U.D. LINGESWARI
PG and Research Department of Chemistry, Seethalakshmi Ramaswami College, Tirichirappalli-620 002, India
*Corresponding author: E-mail: vimalsrc@gmail.com
Received: 17 May 2017;
Accepted: 30 June 2017;
Published online: 29 September 2017;
AJC-18577
The regeneration of oximes from 2,6-diphenyl piperidine-4-one oximes (PPO) and its alkyl substituted derivatives (3-alkyl PPO and 3,5-
dimethyl PPO) by quinolinium flurochromate under microwave irradiation in the presence of montmorillonite K10 clay leads to the
formation of ketone in a good yield.
Keywords: Piperidine 4-one oximes, Quinolinium flurochromate, Microwave irradiation, Montmorillonite K10 clay.
is a demand for the development of this process using readily
available reagents which operate under extremely mild reaction
conditions. Microwave reaction is a green method for efficient
deprotection [12,13]. Recent developments in microwave
accelerated and solvent free approach involves the exposure
of neat reactants to microwave irradiation in conjugation with
the use of supported reagents as catalyst give good yields.
Quinolinium flurochromate (QFC), in the Cr(IV) oxidant series
is one of the efficient and interesting oxidizing agent [14-17].
Quinolinium flurochromate is found to have several advantages
over similar oxidizing agents due to its special characteristics
such as less acidity, better solubility in non-aqueous solvents,
shorter reaction times and forming products in high yield. It
behaves as two electron oxidant in majority of the reactions
so far studied. A perusal of literature revels that no work has
been reported on the deprotection of 3-alkyl-2,6-diphenyl
piperidin-4-one oximes with QFC by microwave method.
INTRODUCTION
Oximes and semicarbazones of aldehydes and ketones
are highly crystalline compounds. Deprotection of these deriva-
tives is an efficient method for the isolation, purification and
characterization of carbonyl compounds [1-3]. Oximes not
only serve as the protecting groups for carbonyl compounds
but also have other uses such as the preparation of nitrites,
amides via Beckman rearrangement. In addition, oximes can
be prepared from non-carbonyl compounds and therefore
regeneration of carbonyl compounds from their oximes is an
important reaction. This is especially true with natural products.
Various methods are adopted for the deoximation process to
obtain aldehydes and ketones [4,5]. Oxidation, reduction and
hydrolysis are the common methods using organic and inorga-
nic reagents. Besides some surface templates processes and
photochemical processes are also used to give the required
products [6]. The solvent free deoximation of protected carbonyl
compounds by ammonium persulphate on silica [7] and regene-
ration of carbonyl compounds from aromatic semicarbazones
by ammonium persulphate impregnated on montmorillonite
K 10 clay in microwave or ultra sound irradiation [8] was also
reported. Poly[N-bromobenzene-1,3-disulphonamide] [9] is
used for the conversion of oximes and semicarbazones in solid
state to their corresponding carbonyl compounds [10,11].
However, most of the procedures used for this type of
reaction require a use of solid support or other axillaries,
solvents for the extraction from the solid supports, high tempe-
rature, long reaction time, expensive and not readily available
reagents and tedious work-up procedures. Consequently, there
EXPERIMENTAL
Quinoline was distilled at its boiling point. Chromium
trioxide, hydrofluoric acid, hydroxylamine hydrochlorite, silica
gel, dichloro methane, diethyl ether, petroleum ether,
montmorillonite clay K10 and ethyl acetate were used as such
(Analar grade).
Quinolinium flurochromate (QFC), a complex of chromic
acid, quinoline and hydrogen fluoride was prepared as reported
earlier [14]. Chromium(VI) oxide (15 g:0.15 mol) was dissol-
ved in water (25 mL) in a polythene beaker and 40 % hydro-
fluoric acid (11.3mL : 0.23 mol) added to it with stirring at

2486 Vimala et al.
Asian J. Chem.
room temperature. To this clear solution, distilled quinoline
(17.7 mL:0.15 mol) was added slowly with stirring. The mixture
was heated on a steam-bath for 0.5 h, then cooled to room
temperature and allowed to stand for 1 h. The bright red-orange
crystalline quinolinium flurochromate was isolated by filtration
and dried in vacuo for 1 h (m.p. 163 °Cand 162-163 °C). All
the oximes were prepared from the respective ketones by the
reported procedure [18,19].
and generally heat any material containing mobile electric
charges, such as polar molecules in a solvent or conducting
ions in a solid. Montmorillonite clay K10 known as a Brønsted
acid have a great impact on organic synthesis. These solid
supports with lamellar swelling structure and large surface area
enhance selectivity in synthetic organic chemistry. Avoding
organic solvents during the reaction in organic synthesis lead
to a clean, efficient and economical technology. In solid state
reaction, work-up is considerably simplified, cost is reduced
and increased amounts of reactants can be used in the same
equipment [20].
Microwave irradiation process: Microwave chemistry
is the science of applying microwave radiation to chemical
reactions. Microwave acts as high frequency electric fields
TABLE-1
m.p. (°C)
Literature
Irradiation
time (min)
Substrate
Product
Yield (%)
Observed
OH
O
N
PPO
10
70
104
103
N
H5C6
C6H5
N
H
H5C6
C6H5
H
O
OH
N
CH3
CH3
3-Me PPO
15
20
25
90
90
90
86-87
85
N
N
H
H5C6
H5C6
H5C6
H5C6
C6H5
OH
C6H5
C2H5
H
O
N
C2H5
3-Et PPO
107
106
114
N
C6H5
N
H
H5C6
C6H5
H
O
OH
N
CH3
CH3
CH3
CH3
3,3-diMe PPO
114-115
N
H
C6H5
N
H
H5C6
C6H5
OH
O
N
CH3
C6H5
H3C
CH3
H3C
3,5-diMe PPO
30
30
75
80
133-134
125-126
133
124
N
H5C6
N
H
H5C6
C6H5
H
O
OH
N
CH(CH3)2
CH(CH3)2
3-ipro PPO
N
H
N
H
H5C6
C6H5
H5C6
C6H5

Vol. 29, No. 11 (2017)
Regeneration of Carbonyl Compounds by Deoximation of Piperidine-4-one Oximes 2487
3-Alkyl-2,6-diphenyl piperidin-4-one oxime was mixed
with quinolinium flurochromate (4 mmol) with 2g of montmori-
llonite clay K10 and irradiated in microwave oven (LG. model
No. MH2043DW) for an appropriate time. The progress of
the reaction was monitored by thin layer chromatography.After
completion of the reaction the products were recovered by
passing the reaction mixture through column chromatography
of silica. (200-300 mesh, eluted with mixture of petroleum
ether and ethyl acetate).
are due to the carbonyl groups present in corresponding ketones.
Formation of ketone as a product is further confirmed by the
blue shift in λmax value of UV-visible spectrum of the product
ketones compared to oximes [21,22].
ACKNOWLEDGEMENTS
The authors are gratefully acknowledge the financial support
provided by the University Grants Commission, New Delhi,
India to carry out this work.
Separation of product by column chromatography: A
column of 5 × 1 cm was packed with silica gel by making
slurry with dichloromethane. It was dried in an oven and used
for eluting the products. The product dissolved in dichloro-
methane and diethyl ether (9:1). After repeated eluting and
washing the fractions obtained were collected together and
evaporated to get the solid ketone.
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