International Journal of Organic Chemistry, 2011, 1, 6-14
doi:10.4236/ijoc.2011.11002 Published Online March 2011 (
Copyright © 2011 SciRes. IJOC
Synthesis, Characterization of Cellulose Grafted N-Oxide
Reagent and Its Application in Oxidation of Alkyl/Aryl
Inderjeet Kaur*, Poonam K. Dhiman
Department of C hemi st ry , H. P. University, Shimla, India
Received March 19, 2011; revised March 28, 2011; accepted April 2, 2011
Oxidation of aliphatic and aromatic halides by N-oxide functionalities supported on 4-vinyl pyridine, (4-VP),
grafted cellulose is reported in the present manuscript. Synthesis of graft copolymer of cellulose and poly
4-vinyl pyridine, poly(4-VP), has been carried out using ceric ions as redox initiator. Post-grafting treatment
of CellO-g-poly(4-VP) with 30% H2O2 in acetic acid gives Cellulose-g-poly(4-VP) N-oxide, the polymeric
supported oxidizing reagent. The polymeric support, CellO-g-poly(4-VP) N-oxide, has been used for oxida-
tion of different alkyl/aryl halide such as 1-bromo-3-methyl butane, 2-bromo propane, 1-bromo heptane and
benzyl chloride. The polymeric reagent was characterized by IR and thermo-gravimetric analysis. The oxi-
dized products were characterized by FTIR and H1NMR spectral methods. The reagent was reused for the
oxidation of a fresh alkyl/aryl halides and it was observed that the polymeric reagent oxidizes the compounds
successfully but with little lower product yield.
Keywords: Cellulose, 4-Vinyl Pyridine, Graft Co-Polymerization, Cellulose Supported N-Oxide, Oxidation,
Thermo-gravimetric Analysis
1. Introduction
Preparation of chemically modified polymer surfaces
with controllable structures is an area of current research,
having both theoretical and practical interest [1]. The
objective is to devise mild techniques of primary surface
functionalization with a high degree of chemo- and
topological selectivity. The primary functional groups on
the surface should be capable of undergoing a variety of
organic chemical transformations under mild conditions,
thus enabling creation of novel secondary surface func-
Efficient methods for the conversion of alcohols to al-
dehydes, ketones or carboxylic acids under mild condi-
tions have been developed, using TEMPO (2,2,6,
6-tetramethyl-1-piperidinyloxy), (I), as a catalyst and
stoichiometric amounts of inexpensive, safe and easy to
handle oxidants such as bleach [2], [bis(acetoxy) iodo]
benzene (BAIB) [3], trichloroisocyanuricacid (TCCA)
[4], oxone [5] or iodine [6].
However, separation of the products from TEMPO
could require lengthy workup procedures, especially
when reactions are run on large scale [7]. To solve this
problem, TEMPO residue has been successfully immobi-
lized to polymeric supports both inorganic [8] and or-
ganic polymers [9], affording heterogeneous catalysts
which are readily separated from the reaction mixtures
but are usually far less versatile than the homogeneous
TEMPO [10]. The use of heterogeneous catalysts in the
liquid phase, however, offers several advantages over
homogeneous ones, such as ease of recovery and recy-
cling, atom utility and enhanced stability [11]. TEMPO
anchored to poly (ethylene glycol) (PEG) has been pre-
pared by Pozzi et al. [12] and its catalytic activity in the
chemoselective oxidation of alcohols with stoichiometric
amounts of organic or inorganic oxidants has been inves-
tigated. The PEG-TEMPO is a new metal free catalyst
and exhibits high activity. It can be easily removed from
the reaction mixture and can be reutilized number of
Miyazawa and Endo [13] reported the synthesis of
soluble and insoluble polystyrene type polymers featur-
ing TEMPO residue and used it in combination with po-
tassium ferricyanide in alkaline water/acetonitrile as sol-
vent for the oxidation of benzyl alcohol to benzaldehyde
at room temperature. Leadbeater and Scott [14] prepared
a resin-bound cobalt phosphine complex and assessed its
use in catalytic oxidation and acid anhydride synthesis.
Gopinathan et al. [15] described a simple, mild and high
yielding procedure for the iodination of allylic, benzylic
and other primary alcohols using a combination of iodine
imidazole on polymer supported triphenylphosphine.
Poly(ethylene glycol) based aqueous biphasic systems
(PEG-ABSs) have been investigated as tunable reaction
media to control the oxidation of cyclohexene to adipic
acid with hydrogen peroxide [16].
Divinyl benzene cross-linked polystyrene supported
β-diketone linked complexes of Mn (II) have been pre-
pared, characterized and their role as catalysts in the
oxidation of alcohols by Cr (VI) has been invesitigated
[17]. New reagents and polymer supported versions are
highlighted which facilitate the use of hypervalent iodine
compounds in oxidation and rearrangement reactions
[18]. A three-step preparation of a polymer-supported
iodoxybenzoic acid (PSIBX) reagent from poly(p-methyl
styrene) has been reported and it was used for the effi-
cient oxidation of a series of alcohols to the correspond-
ing aldehydes [19]. An efficient procedure for the highly
selective oxidation of leucomycines to the corresponding
16-membered 9- and 13-oxomacrolides using hyperva-
lent iodine reagents in solution and on solid support has
been reported [20].
A polymer support, (1-hydroxy-1,2-benziodoxol-
3(1H)-one-1-oxide), was synthesized and used to oxidize
alcohols selectively to the corresponding ketones and
aldehydes [21].
It is well known that pyridine has wide applicability in
organic synthesis by itself or in conjunction with other
reagents. Both poly(2-vinyl pyridine) and poly(4-vinyl
pyridine) form complexes with various transition metal
ions [22,23]. Therefore, it seems that in case of grafted
pyridines, the presence of pendant reactive pyridyl group
nitrogen on the repeating unit of polyvinyl pyridine will
make the grafted polymer useful as a reagent. Recently
we reported on the oxidation and reduction reactions
using polymer supported reagents developed from cellu-
lose grafted with 4-vinyl pyridine [24].
Thus, it is evident from literature that different poly-
meric supports carrying specific functional groups are
used for specific reactions. In view of this, in the present
manuscript, synthesis of simple polymeric support from
cellulose graft copolymerized with 4-vinyl pyridine i.e.
Cellulose-g-poly (4-vinyl pyridine) carried out by post
grafting reaction is discussed. The respective polymeric
reagent was utilized for oxidation of some alkyl halides
such as 1-bromo-3-methyl butane, 2-bromo propane and
1-bromo heptane and aryl halide such as benzyl chloride.
Structure – reactivity relationship between the reactant
and the reagent has been evaluated and discussed.
2. Experimental
2.1 Synthesis of Cellulose Based Poly(4-VP)
The details of the synthesis of 4-vinyl pyridine grafted
cellulose has been discussed in our previous papers
Optimum conditions pertaining to maximum percent-
age of grafting have been evaluated as a function of
concentration of the initiator, monomer, and nitric acid,
amount of water, time and temperature. Maximum per-
centage of grafting (585%) was obtained using 0.927
moles/L of 4-VP and 0.018 moles/L of ceric ammonium
nitrate (CAN) in 120 min. at 45˚C.
2.2 Synthesis of Cellulose Based N-oxide Reagent
1) Material s a nd Me thod
CellO-g-poly (4-VP), referred to as Resin I, was used
as the base polymer. Acetic acid (Reagent Grade) and
30% H2O2 (S.D. Fine Chem. Ltd.) were used as received.
Benzene-Methanol in different proportions was used as
the solvent for TLC.
2) Procedure
A suspension of 1 gm of Resin I in 8 mL acetic acid
was treated with 5.3 mL of H2O2 (30%) and kept at room
temperature under stirring for 4h. After the stipulated
time, the reagent, CellO-g-poly(4-VP) N-oxide, referred
to as Resin II, was collected and dried.
2.3 Oxidation of Alkyl/Aryl Halides
The following general method was followed for the oxi-
dation reactions:
Freshly prepared CellO-g-poly(4-VP) N-oxide, Resin
II, 0.500 g in 10 mL of benzene was placed in a round
bottomed flask and to this was added 5 mL of the reac-
tant i.e. alkyl/aryl halide. The reaction mixture was
heated under reflux and continuous stirring. The progress
of the reaction was monitored on TLC. After the comple-
tion of the reaction, the resin was filtered off and the
products were separated by fractional distillation.
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3. Characterization
The characterization of CellO-g-poly(4-VP) N-oxide was
carried out by FTIR spectroscopy and thermo gravimet-
ric analysis (TGA) and was compared to that of cellulose
and CellO-g-poly(4-VP). FTIR spectra have been ob-
tained on Beckman spectrophotometer. TGA have been
taken on LINSEIS, L 81-11 Germany made, in air at the
heating rate of 10 ˚C/min. The oxidation products of al-
kyl/aryl halides to respective aldehydes/ketones have
been characterized by IR and NMR spectroscopic meth-
ods. H1NMR was obtained on JEOL FT-NMR AL 300
MHz Spectrophotometer.
3.1 FTIR Spectroscopy Figure 1. FTIR spectrum of CellO-g-poly(4-VP)N-oxide.
The FTIR data of CellO-g-poly(4-VP) N-oxide (Figure
1), in addition to the regular bands due to νC-H str. at
2952.3 cm–1 and νC-O str. at 1352 - 1032 cm–1 of cellulose
and νC=C and νC=N str. at 1644 - 1381 cm–1 of pyridine
ring of grafted poly(4-VP) (Ta ble 1), shows a character-
istic peak for the ammonium salt i.e. at 2392.3 cm–1
which confirms that CellO-g-poly(4-VP) is converted
into ammonium salt with oxide anion attached to it. In
case of quaternization, the signal for νC=N is shifted from
1575.1 cm–1 to 1644.3 cm–1 and a new strong signal at
1209.2 cm–1 due to N-oxide has appeared, thus proving
the chemical transformation. Similar observations were
made by Zupan, Sket and Johar [25] during the studies
on synthesis and preparation of cross-linked 4-vinyl pyri-
dine-styrene-halogen complexes.
while the 4-VP grafted cellulose shows double stage of
In case of the primary thermogram of cellulose the
thermal degradation of cellulose proceeds essentially
through two types of reactions. At lower temperatures i.e.
between 120˚C - 250˚C, there is a gradual degradation,
which includes depolymerization, hydrolysis, oxidation,
dehydration and decarboxylation. At higher temperatures
(250˚C - 397˚C), a rapid volatilization occurs losing H2O,
CO2 and CO molecules with the formation of glucosan.
The percent residue is 13.08%.
Thermal decomposition of grafted cellulose i.e.
CellO-g-poly(4-VP) proceeds in two stages. The first
stage of decomposition lying between 170˚C - 205˚C
during which the pendant grafted chains of poly(4-VP)
are degraded with up to 35% weight loss beyond which
the second stage of decomposition starts and goes upto
375˚C and continues up to 584.5˚C with further loss of
45% weight. High percentage (26.67%) of residue is left
after the decomposition.
3.2 Thermo-gravimetric Analysis
The primary thermograms of cellulose, CellO-g-poly
(4-VP) and CellO-g-poly(4-VP) N-oxide are compared.
The initial decomposition temperature (IDT), final de-
composition temperature (FDT) and decomposition
temperature (DT) at every 10% weight loss are presented
in Table 2. It is observed from the thermo grams that
unmodified cellulose shows a single stage of decomposition
In case of CellO-g-poly(4-VP) N-oxide (Figure 2), it
is observed from the primary thermogram that the cellu-
lose graft N-oxide shows a single stage decomposition as
observed for cellulose. During the initial rise in tem-
perature from 80˚C to 283.3˚C, from where the initial
Table 1. FTIR spectroscopy of CellO-g-poly(4-VP).
Sample Structure C-H
v, cm–1
v, cm–1
v, cm–1
v, cm–1
v, cm–1
1430.7 (def.)
1376.0 (def.)
CellO-g-poly(4-VP) 3043.2
Figure 2. Primay thermogram of CellO-g-poly(4-VP) N-oxide.
Table 2. Thermogravimetric data of cellulose and cellulose g-poly (4-VP) N-Oxide.
DT at every 10% wt. Loss (˚C)
Sample IDT (˚C)
FDT (˚C)
Loss) 10% 20% 30% 40% 50% 60% 70% 80% 90%
Cellulose 319.35
(65.62%) 330.65 339.68 346.45 350.97 353.23 366.77 393.87 500.00 - 13.08%
(32.11%) 271.43 315.7348.57462.85- - - - - 52.66%
decomposition begins, the decomposition is very slow
with a small loss in weight (10%). There may be some
loss due to moisture desorption during this phase. Be-
yond the initial decomposition, (283.3˚C), the degrada-
tion is fast with a large temperature difference between
each 10% wt, loss (44.27˚C between 10% to 20%,
32.87˚C between 20 to 30% and 117.28˚C between 30%
to 40% wt. loss). The temperature difference between
each 10% weight loss of cellulose up to 70% is very low,
lying between 2.26˚C to 27.10˚C and moving from 70%
weight loss to 80% weight loss this difference increases
to 106.13˚C indicating the formation of stable glucosan.
In case of the grafted sample, although the decomposi-
tion values are very low as compared to that for unmodi-
fied cellulose, the temperature difference between each
10% weight loss is very high, beyond 30% wt. loss the
value difference lies between 47.5˚C to 105˚C.
Final decomposition begins at 354.3˚C with only
32.11% wt. loss. The percent residue left is very high
Higher DT values, large temperature difference be-
tween each 10% wt. loss and high percent residue indi-
cate a very good thermal stability of CellO-g-poly(4-VP)
N-oxide as compared to cellulose and CellO-g-poly
4. Results and Discussion
4.1 Synthesis of Polymeric Support
Synthesis of graft co-polymer of cellulose essentially
involves generation of active sites on the cellulose back-
bone upon which a suitable monomer is polymerized. In
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the present work grafting onto cellulose is carried out in
the presence of 4-VP, by chemical method using CAN as
redox initiator. The detailed mechanism has been dis-
cussed elsewhere [24]. In general the mechanism of the
transition metal ion induced grafting process, where
glycol groups are involved, using Ce(IV) salt, can be
represented as follows:
The presence of radicals on the cellulose backbone has
been confirmed by ESR measurements [26]. Monomer is
also known to form complex with ions, which dissociate
to give monomer radical that propagates to give poly-
meric chains. These growing polymeric chains attach to
the radical site on cellulose to give graft copolymer or
terminate to give homopolymer.
The effect of different reaction parameters such as
[CAN], [HNO3], [4-VP], amount of water, temperature,
and reaction time on percentage of grafting of 4-VP onto
cellulose has been studied and maximum percentage of
grafting (585%) was obtained at the following reaction
Table 3. Optimum conditions for grafting 4-vinyl pyridine
onto cellulose.
0.200 0.018 0.797 20 45 120 0.927
On treatment 4-vinyl pyridine grafted cellulose,
CellO-g-poly(4-VP), with H2O2/AcOH polymeric re-
agent, CellO-g-poly(4-VP) N-oxide was obtained and
was used for the oxidation reactions.
4.2 Oxidation Reactions
Oxidations of alkyl/aryl halides were carried out by
CellO-g-poly(4-VP) N-oxide. The time of reaction, per-
cent yield and Rf values for reactants and products are
presented in Table 4.
Few reagents are available for the direct oxidation of
alkyl halides into carbonyl compounds. Perhaps the best
known reagent for this transformation is DMSO. Johnson
and Pelter [27] showed that DMSO at 150˚C oxidized
1-iodooctane rapidly to aldehyde in 74% yield. Lower
yields were obtained with secondary iodides or primary
chlorides. By adding silver tetrafluoroborate to the reac-
tion mixture Ganem and Boeckman [28] obtained 83%
yield of octanal from 1-bromooctane. Another reagent
which is available but is seldom used for this type of
transformation is trimethylamine oxide [29]. This reagent
is potentially very interesting but it affords only 30% -
50% yields of highly contaminated aldehydes from cor-
responding primary alkyl iodides. It also requires scru-
pulously anhydrous conditions.
Significant improvements in oxidation were achieved
by using insoluble polymer, cross-linked polystyrene
containing amine oxide group (I).
Table 4. Oxidation of alkyl/aryl halides using CellO-g-poly (4-VP) N-oxide, Resin II, as PS-oxidizing reagent: (Resin II = 500
mg, Solvent = 10 mL, Reactant = 5 mL).
Rf values
Reactant Product Time (hrs.)
Reactant Product Yield
Benzyl chloride Benzaldehyde 18 ------ 0.75 53.4%
1-Br-3-methyl butane 3-Methyl butanal 24 0.47 0.22 30%
2-Bromopropane Acetone 16 ------ ------ 40%
1-Br-heptane Heptanal 38 0.90 0.40 60%
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Frechet and co-workers [30] used five fold excess of
the polymeric N-oxide (I) for the oxidation of
1-bromoheptane and benzyl chloride to yield 87% and
95% of corresponding aldehydes at 70˚C. In the present
work, N-oxide functionality supported on a polymeric
backbone, CellO-g-poly(4-VP), to carry out oxidation of
alkyl/aryl halides has been used. The percent yield of the
corresponding aldehydes from 1-bromoheptane and
benzyl chloride using CellO-g-poly(4-VP) N-oxide was
60% and 53.4% obtained in 38 h and 18 h respectively
which was less than that obtained by using polymeric
N-oxide (I). The low yield may be due to the reason that
nitrogen carrying the oxygen is a part of the aromatic
ring and thus behaves differently from its alkyl N-oxide
(I) counterpart.
4.3 FTIR Spectroscopy of Oxidized Products
The FTIR spectra of benzaldehyde (Figure 3) obtained
upon oxidation of benzyl chloride, 3-methyl butyralde-
hyde (Figure 4) from 1-bromo-3-methyl butane, acetone
from 2-bromopropane and heptanal from 1-bromoheptane
show characteristic peaks for aldehydes/ketones between
1637.2 - 1733.3 cm–1 due to νC=O str.. The aldehydic
function of 3-methyl butyraldehyde and heptanal show a
doublet for νC-H str. in the region between 2859 - 2962
cm1. Several bands in the range 1023 - 1386 cm–1 due to
C-CHO skeletal structure are also observed.
4.4. H1NMR Studie s
In the H1NMR spectrum of the benzaldehyde obtained
by the oxidation of benzyl chloride, a characteristic
singlet at 10.00 δ for aldehydic protons is observed in
addition to the aromatic protons.
3-Methyl butyraldehyde obtained by the oxidation of
1-bromo-3-methyl butane, have four types of equivalent
protons (marked as a, b, c and d).
The H1NMR spectrum accordingly reveals a doublet at
0.97 δ due to CH3 (a) protons, a multiplet at 1.35 δ due to
CH (b) proton and CH2 (c) protons (not splitted) and a
triplet at 10.00 δ for aldehydic proton (d).
Figure 3. FTIR spectrum of benzaldehyde.
Figure 4. FTIR spectrum of 3-methyl butyraldehyde.
The H1NMR spectrum of acetone, (Figure 5), obtained
upon oxidation of 2-bromo propane shows a singlet at
1.20 δ, equivalent to 6H due to the methyl protons (a)
attached to the carbonyl group.
The H1NMR spectra of heptanal obtained by the oxi-
dation of 1-bromo heptane is shown in Figure 6. Char-
acteristic triplet at 10.00 δ for aldehydic proton and
peaks between 0.90 δ to 2.47 δ for alkyl chain of
heptanal are observed. The splitting of the peaks is not so
clear due to the overlapping of the peaks.
From the above studies it is, thus, clear that successful
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Figure 5. H1 NMR spectrum of acetone.
Figure 6. H1 NMR spectrum of heptanal.
oxidations of alkyl/aryl halides using CellO-g-poly(4-VP)
N-oxide as PS-oxidizing reagent has been achieved.
5. Reusability of PS-oxidizing Reagents
In order to check that whether the polymeric support is
reusuable after the reaction, the PS-oxidizing reagents
were reused after drying for the oxidation of benzyl
chloride. It was observed that the reagent efficiently oxi-
dized the reactant although the yield of the oxidation
product was little low (46%) as compared to the yield
(53.4%) obtained from freshly prepared polymeric re-
The PS-oxidizing reagent could also be easily regen-
erated by washing with very dilute HCl solution, fol-
lowed by very dilute NaOH solution and rinsing with
water. The washed polymers were treated with subse-
quent simple organic reagents to introduce respective
functional moieties such as N-oxide and then used for
further oxidation reactions. Table 5 shows the % yield of
the products obtained by oxidation of benzyl chloride
using the used CellO-g-poly(4-VP) N-oxide reagent and
the regenerated CellO-g-poly(4-VP) N-oxide polymeric
support. The data shows that the percent yield is less
with the used PS-oxidizing reagent but it is almost re-
gained after regenerating the polymeric support with
respective oxidizing groups.
6. Conclusion
The synthesis of simple polymeric support from cellulose
graft copolymerized with 4-vinyl pyridine i.e. cellu-
lose-g-poly(4-vinyl pyridine) by carrying out post graft-
ing reaction is discussed. The respective polymeric re-
agent i.e. CellO-g-poly(4-VP) N-oxide is utilized for
oxidation of different alkyl/aryl halide such as
1-bromo-3-methyl butane, 2-bromo propane, 1-bromo
heptane and benzyl chloride. The support can be reused
and can also be easily regenerated for further oxidations.
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