An expedient synthesis of oxazolones using a cellulose supported ionic liquid phase catalyst

Article abstract of DOI:10.1039/c6ra03873e

A novel cellulose supported ionic liquid phase catalyst containing hydroxide ions ([CellFemImi]OH) has been synthesized by covalent anchoring of 1-N-ferrocenylmethyl imidazole in the functionalized cellulose matrix followed by an anion metathesis reaction. The [CellFemImi]OH was characterized by various techniques including FT-IR, FT-Raman, ¹³C solid state NMR, X-ray diffraction, energy dispersive X-ray (EDX) analysis, field emission scanning electron microscopy (FESEM) and thermogravimetric analysis. The [CellFemImi]OH was effectively employed as a heterogeneous catalyst in the synthesis of oxazolones by cyclocondensation of aryl aldehydes with hippuric acid in the presence of acetic anhydride.

Full text of DOI:10.1039/c6ra03873e

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An expedient synthesis of oxazolones using cellulose supported ionic liquid
phase catalyst
Rajanikant Kuranea, Sharanabasappa Khanapurea, Dolly Kalea, Rajashri Salunkhea and Gajanan
Rashinkara*
aDepartment of Chemistry, Shivaji University, Kolhapur, 416004, M.S., India
Eꢀmail: gsr_chem@unishivaji.ac.in
∗Corresponding author Tel.: +91 231 260 9169; fax: +91 231 2692333.

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An expedient synthesis of oxazolones using cellulose supported ionic liquid
phase catalyst
Rajanikant Kuranea, Sharanabasappa Khanapurea, Dolly Kalea, Rajashri Salunkhea and Gajanan
Rashinkara*
aDepartment of Chemistry, Shivaji University, Kolhapur, 416004, M.S., India
Eꢀmail: gsr_chem@unishivaji.ac.in
∗Corresponding author Tel.: +91 231 260 9169; fax: +91 231 2692333.
Abstract
A novel cellulose supported ionic liquid phase catalyst containing hydroxide ion
([CellFemImi]OH) has been synthesized by covalent anchoring of 1ꢀNꢀferrocenylmethyl
imidazole in the functionalized cellulose matrix followed by anion metathesis reaction. The
[CellFemImi]OH was characterized by various techniques including FTꢀIR, FTꢀRaman, 13C
Solid state NMR, Xꢀray diffraction, energy dispersive Xꢀray (EDX) analysis, field emission
scanning electron microscopy (FESEM) and thermogravimetric analysis. The [CellFemImi]OH
was effectively employed as heterogeneous catalyst in the synthesis of oxazolones by
cyclocondensation of aryl aldehydes with hippuric acid in the presence of acetic anhydride.
Keywords: Cellulose, Oxazolones, Ferrocene, Reusability.

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Introduction
The green chemistry necessitates a paradigm shift from traditional chemical processes to
more sustainable catalytic processes.1 Tremendous strides have been made to achieve the goal of
greater sustainability through applications of green chemistry principles. The concept of
supported ionic liquid phase (SILP) catalysis involving immobilization of ionic liquids (ILs) onto
a surface of a porous high area support material constitute one of the most promising tools in the
in the chemist's tool box for realizing sustainable chemical processes.2 This new class of
advanced materials dramatically reduces the amount of ILs used, retaining their properties. There
are potentially multiple advantages employing SILP catalysts in organic synthesis. These include
ease of separation of products as well as catalyst recycling along with significant advances in
activity and selectivity. In addition, the processes applying SILP catalysts can be performed in
continuous mode using fix bed reactors.3 The SILP catalysts are usually prepared by depositing
ILs on the surface of high area porous material either by covalent bonding or van der Waals
interactions.4 The majority of the supports used in SILP catalysis are either porous silica gels or
polymer based materials.5 In addition, carbon nanotubes,6 active carbon cloth,7 chitosan,8
magnetic nanoparticles9 and carbon nanofibers supported on sintered metal fibers10 have also
been sporadically employed as supports. Over the past few years, intense research in this field
has greatly expanded the scope of SILP catalyzed reactions by designing structurally diverse
SILP catalyst based on various supports.11 Although tremendous progress has been already
made, the field of SILP catalysis is still in its infancy and extension of this technology using
SILP catalysts from bio renewable feedstock is yet to be fully exploited.
Cellulose is the most abundant and environmentally benign renewable biopolymer in the
ecosphere.12 It is composed of long linear polymeric chain made up of repeating units of βꢀDꢀ

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glucose linked by 1,4ꢀglycosidic bonds. Cellulose has an unusual structure in which every other
glucose monomer is flipped over and packed tightly as extended long chains. This imparts
cellulose rigidity and high tensile strength. Owing to multiple hydrogen bonding interactions
between the individual chains, cellulose is insoluble in water and most common solvents.13
A
unique attribute of cellulose is its structure that can be easily modified with the help of surface
hydroxyl groups. In addition to aforementioned properties, its high surface area, nonꢀtoxicity,
stability in common organic solvents, unlimited availability as a renewable agroꢀresource,
limited carbon footprint and excellent biodegradability makes cellulose the most potential
feedstock for producing materials for catalytic applications.14 The tempting properties of
cellulose spurred us to investigate its compatibility in the synthesis of SILP catalysts.
Oxazolones are privileged scaffolds that are compatible in the synthesis of natural or
artificial bioactive molecules on account that they may serve as protected amino acids.15 They
also act as carbon centered nucleophiles in enantioselective organocatalysis.16 They are main
intermediates in the synthesis of various fine chemicals, amino acids, carboxylic acids, peptides,
herbicides, fungicides, skin sensitizers and photosensitizes.17 Their derivatives exhibits important
properties such as antimicrobial, antifungal and anticancer activities.18a,b Oxazolone grafted
MNPs are used as efficient drug delivery agents, particularly for cancer treatment18c and act as
antiꢀinflammatory,18d antiallergic18e and efficient cell permeable agents18f. In addition, they serve
as anticonvulsants,18g antiangeogenetics18h and antioxidants18i. The unique structural properties as
well as their biological and pharmaceutical relevance have motivated research aimed at the
development of efficient strategies to access these compounds. Oxazolones are synthesized under
mild conditions by the reaction of Nꢀacylated amino acid derivatives with dehydrating reagents
which usually consist of activated anhydrides or carbodiimides.19 Although there are several

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methods for the synthesis of oxazolones, the classical and most widely used strategy includes
Erlenmeyer reaction which involves cyclodehydration of hippuric acid followed by condensation
with an aldehyde in the presence of acetic anhydride.20 Several catalysts such as,
[Et3NH][HSO4],21a
TsCl/DMF
under
microwave,21b
POCl3,21c
CuSO45H2O/[(Ph3P)(NCMe)]SbF6,21d alum,21e Yb(OTf)3,21f Bi(OAc)3,21g Fe2O3ꢀnanoparticles,21h
ferrocene bisꢀimidazoline bisꢀpalladacycle,21i molecular iodine,21j montmorillonite Kꢀ10,21k nano
crystalline TiO2,21l etc. have been used to accomplish this condensation. However, there is still a
plenty of room to conceive new wellꢀdesigned, inexpensive and sustainable approache in
addition to current catalytic methodologies.
In continuation of our work on the development of green methodologies using SILP
catalysts,22 we report herein an expedient synthesis of oxazolones using cellulose supported ionic
liquid phase catalyst.
Results and discussion
In the synthesis of cellulose supported ionic liquid phase catalyst (Scheme 1), aluminum
oxide was dispersed on the cellulose (1) with a good degree of adhesion to form CellꢀAl2O3
composite (2) using literature procedure.23 The inherent ability of surface AlꢀOH groups of 2 to
form stable AlꢀOꢀSi bonds with SiꢀOR groups of (3ꢀchloropropyl)triethoxysilane allowed the
synthesis of chloropropyl cellulose (3) with a good degree of organofunctionalization. The
ferrocenylmethyl imidazole (4) was then covalently anchored in the cellulose matrix with the
help of tethered chloropropyl group by quaternization reaction to yield azolium salt acronymed
as [CellFemImi]Cl (5). The anion metathesis reaction of 5 with aqueous solution of ammonia

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resulted in the desired cellulose supported ionic liquid phase catalyst acronymed as
[CellFemImi]OH (6).
The reactions involved in the synthesis of [CellFemImi]OH (6) catalyst were monitored
by using FTIR and FTRAMAN spectroscopy. The reaction of 3 with 4 was supervised by
FTRAMAN spectroscopy. The intensities of peaks at 605 cmꢀ1 (CꢀCl stretching) and 1291 cmꢀ1
(wagging band of CH2ꢀCl) decreased considerably whereas the peaks at 466 cmꢀ1 (stretching
band of FeꢀCp), 1234 cmꢀ1, 1338 cmꢀ1, 1438 cmꢀ1 (stretching modes of imidazolium ring) and
3115 cmꢀ1 (CꢀH stretching of Cp ring) appeared after 72 h reflecting the confinement of 4 on
cellulose matrix. The anion metathesis reaction was monitored by using FTIR spectroscopy. The
FTIR spectrum of the 6 displayed characteristic stretching band of medium intensity of OꢀH
group at 3345 cmꢀ1 and a peak of weak intensity at 703 cmꢀ1 revealing the considerable
replacement of Clꢀ by OHꢀ during the anion metathesis reaction. The formation of 6 was further
corroborated by recording 13C CPꢀMAS spectrum which displayed peaks at 138.5 (s,
imidazolium Cꢀ2), 127 (s, imidazolium Cꢀ4), 120 (s, imidazolium Cꢀ5), 113 (bs, Cꢀ1 of
cellulose), 90 (bs, Cꢀ4 of cellulose), 72ꢀ76 (m, Cꢀ2,3,5 of cellulose), 67 (bs, Cꢀ6 of cellulose), 70
(s, non substituted Cp ring carbons of ferrocene), 78 (s, substituted Cp ring carbons of
ferrocene), 49 (s, 1C, =NꢀCH2ꢀCH2ꢀCH2), 28 (s, 1C, =NꢀCH2ꢀCH2ꢀCH2), 8.0 (s, 1C, ꢀCH2ꢀSi)
confirming the proposed structure.
An EDX elemental analysis of 5 revealed grafting of 0.46 mmol of ferrocenylmethyl
imidazolium units gꢀ1 catalyst. The quantification of hydroxyl groups in 6 was done using
volumetric titration analysis24 and was found to be 0.31 mmol gꢀ1 catalyst.
The FESEM investigations were carried out to study size and morphology of
[CellFemImi]OH (6). The FESEM image of 6 is shown in figure 1. The FESEM image clearly

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shows fibrous morphology of catalyst particles with length in the range of several hundred
nanometers up to a few micrometers.
The Xꢀray diffraction (XRD) pattern of chloropropyl cellulose, 5 and [CellFemImi]OH
(6) is shown in figure 2. The XRD profiles displayed major reflections at 2θ = 14.6°, 16.3°, 22.7°
and 34.4° resembling XRD pattern of cellulose confirming that microcrystallinity is maintained
in chloropropyl cellulose, 5 and 6. In addition, the decreased peak intensities in 5 and 6 revealed
surface destruction of cellulose due to confinement of ionic liquid like unit.25
The thermal stability profile of [CellFemImi]OH (6) was analyzed by using TGAꢀDSC
analysis in the temperature range of 25ꢀ1000 °C (Figure 3). The initial weight loss of 6.1% is
attributed to the loss of physisorbed water associated with ionic liquid like unit through the
hydrogen bonding. The second steep weight loss of ~61% in the temperature range of 280ꢀ330
oC is ascribed to collective loss of ionic liquid like unit and combustible organic materials from
crystalline cellulose. The subsequent weight loss of 16.60% is assigned to the decomposition of
cellulose units through the formation of levoglucosan and other volatile compounds. The
observations are in good agreement with the TGA profile of cellulose reported in the literature.26
Our next task was to evaluate catalytic efficiency of [CellFemImi]OH (6) in the synthesis
of oxazolones. Initially, to optimize the reaction conditions, hippuric acid (7, 1 mmol), 4ꢀ
nitrobenzaldehyde (8c, 1 mmol) and acetic anhydride (3 mmol) were chosen as model substrates
for the synthesis of oxazolones in the presence of a catalytic amount of 6 (100 mg) in various
solvents at room temperature (Table 1). The model reaction afforded corresponding (4E)ꢀ4ꢀ(4ꢀ
nitrobenzylidene)ꢀ2ꢀphenyloxazolꢀ5ꢀ(4H)ꢀone (9c) in significantly lower yields in CH2Cl2,
CHCl3, CH3CN, THF and water (Table 1, entries 1-4 and 12). Ethanol was found to be the best

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solvent as it furnished the corresponding product in excellent yield in much shorter time (Table
1, entry 6).
The effect of catalyst loading on the model reaction was also investigated. As shown in
Table 1, the yield of product increased by increasing quantity of catalyst from 50 to 100 mg
(Table 1, entries 5,6). However, further increase in the amount of the catalyst did not showed
significant effect on the product yield and reaction time (Table 1, entries 7,8). Thus, 100 mg of
6 was selected as optimal catalyst loading for further studies.
The generality of the protocol was established by carrying out reactions of several
diversified aldehydes with hippuric acid and acetic anhydride under optimized reaction
conditions. It was interesting to note that all the aromatic aldehydes containing various
substituents (Table 2, entries a-l) reacted efficiently affording the corresponding oxazolones in
excellent yields (Table 2). It is noteworthy to mention that there was no influence of electronic
nature of substituents on the aryl ring on the yield of products as aromatic aldehydes with
electronic donating as well as electron withdrawing groups resulted in the formation of products
1
in nearly quantitative yields. The identity of all the products was ascertained on the basis of H
13
NMR, C NMR, FTIR and mass spectroscopy. The spectroscopic data is in consistent with the
proposed structures and in harmony with the literature values.27
A plausible mechanism for the formation of oxazolones catalyzed by [CellFemImi]OH
(6) is shown in figure 4. Initially, 2ꢀphenylꢀ5ꢀoxazolone is generated by cyclocondensation of
hippuric acid in the presence of acetic anhydride as dehydrating agent. The catalyst plays a dual
role during catalysis. It activated carbonyl group of aromatic aldehydes by the hydrogen bonding
through C2 proton of imidazolium cation as well as acts as a base generating carbanion of 2ꢀ

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phenylꢀ5ꢀoxazolone. The further nucleophilic attack of carbanion of activated carbonyl group
followed by dehydration results in the formation of desired oxazolone.
The leaching of [CellFemImi]OH (6) was studied via ICPꢀAES. A small amount of
organic moieties (< 1.6 %) were detected leaching into the solvent indicating that most of the
ionic liquid like unit remains hooked upon the support. The observed minute leaching could be
due to small fraction of ionic liquid like units resided on the outer surface of crystalline cellulose
particles. This suggests that ionic liquid like unit containing catalytically active hydroxyl anion is
significantly entrenched in crystalline framework of cellulose making 6 leaching defiant for a
highꢀquality reclamation and reusability.
To determine heterogeneity of [CellFemImi]OH (6), hot filtration test was carried out for
the model reaction. After 50 % conversion (GC), the reaction mass was divided, with one half
separated (by simple filtration) into a separate reaction flask. The reaction mixture containing 6
furnished to a completion whereas filtered portion did not exhibit any improvement in the yield
of product beyond 50 % even after prolonged reaction time confirming the heterogeneous nature
of 6.
In order to assess recyclability and reusability of [CellFemImi]OH (6), the model
reaction was performed under optimized conditions. An important feature of 6 was its easy and
reliable separation from the reaction mixture. The catalyst was separated from reaction mass by
simple filtration and reused after reactivation that involved washing with the reaction solvent to
o
remove any adhered species and drying at 60 C. It is noteworthy to mention that the 6 showed
appreciating recycling performance as the corresponding yields started at 89 % and reached 84 %
at the fifth run without extended reaction time (Figure 5). The slight loss in the yields of the
products even after reactivation is likely to be due to agglomeration of support particles into

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larger crystallites which limits reaching of reacting molecules to the active catalytic site. The
mechanical stability of 6 was confirmed from its post catalytic FTIR and CP/MAS 13C
13
spectroscopy analysis. The FTIR and CP/MAS C spectra of spent catalyst were similar to that
of fresh catalyst confirming the intactness of organic functional groups in the 6.
Present study demonstrates the potential application of SILP catalyst based on refined
cellulose as support. This work is model study for its extension to make generalized methods
using SILP catalysts for organic transformations through use of natural resources such as raw
wood dust, crustacean shells, etc besides the use of refined cellulose. Recently, some efforts have
already been made in this direction.28 Our further research work is focused to design and develop
new SILP catalysts using above mentioned natural resources to bring various organic
transformations under the umbrella of this novel approach to make synthetic chemistry more
sustainable.
Conclusion
In conclusion, we have successfully synthesized a novel cellulose supported ionic liquid
phase catalyst containing hydroxide ion and employed in the synthesis of oxazolones by the
cyclocondensation of aryl aldehydes with hippuric acid and acetic anhydride. Use of eco benign
solvent, excessive product yields, ease of separation and reusability of catalyst makes this
protocol a high quality alternative over the other reported methodologies.

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Experimental
General
Melting points were determined in an open capillary and are uncorrected. All reactions
were carried out under air atmosphere in dried glasswares. Infrared spectra were measured with a
PerkinꢀElmer one FTIR spectrophotometer. The samples were examined as KBr discs~5% w/w.
1
Raman spectroscopy was done by using Bruker FTRAMAN (MultiRAM) spectrometer. H
NMR and 13C NMR spectra were recorded on a Bruker AC (300 MHz for 1H NMR and 75 MHz
13
for C NMR) spectrometer using CDCl3 as solvent and tetramethylsilane (TMS) as an internal
standard. Chemical shifts (δ) are expressed parts per million (ppm) values with tetramethylsilane
(TMS) as the internal reference and coupling constants are expressed in hertz (Hz). CP/MAS 13C
NMR spectrum were recorded on Bruker 500 type FTꢀNMR spectrometer under prescribed
operating conditions. Mass spectra were recorded on a Shimadzu QP2010 GCMS. The thermal
gravimetric analysis (TGA) curves were obtained by using the instrument TA SDT Q600 in the
o
o
o
presence of static air at a linear heating rate of 10 C/min from 25 C to 1000 C. XRD pattern
was taken by using Brucker D2 Phaser. FESEM was done using HITACHI Sꢀ4800. Elemental
analyses were performed on EURO EA3000 vectro model. All the chemicals were obtained from
local suppliers as were used without further purification and 1-Nꢀferrocenylmethyl imidazole
was synthesized using reported procedure.29
Preparation of the Cell-Al2O3 composite (2)
The CellꢀAl2O3 composite (2) was prepared as per the reported procedure.[21] A mixture
of cellulose (15 gm) and aluminum chloride hexahydrate (15 gm) in water (200 ml) was stirred
for 12 hours. The mixture was filtered and the solid was exposed to ammonia gas, washed with

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water and dried under vacuum at room temperature. The amount of aluminum was determined
by calcining 0.300 g of 2 to 600 °C for 8 h and the residue weighed as Al2O3, which was found
to be 3.27 wt %, corresponding to 0.69 mmol gꢀ1 aluminium.
Preparation of chloropropyl cellulose (3)
A mixture of 2 (10 gm) and (3ꢀchloropropyl)triethoxysilane (9.6 gm, 40 mmol) in toluene
(30 ml) was refluxed for 24 h. The mixture was filtered and the resultant solid was washed with
copious amount of toluene and dried in vacuum at room temperature. FTIR (KBr, thin film): υ =
3366, 2901, 1428, 1372, 1281, 1236, 1031, 898, 703, 629, 513 cmꢀ1; FTRAMAN (KBr): υ =
2898, 1481, 1375, 1117, 1094, 898, 610, 566, 515, 431 cmꢀ1; Elemental analysis observed: %C
74.03, %O 22.04, %Al 1.84, %Cl 2.09; Loading: 0.59 mmol functional group gꢀ1 of cellulose.
Preparation of [CellFemImi]Cl (5)
A mixture of 4 (5.0 g) and 1ꢀNꢀferrocenylmethyl imidazole 5 (2.65 g, 10 mmol) in DMF
(25 ml) was heated at 80 °C. After 48 h, the solid was filtered, washed with DMF (3x50 ml),
MeOH (3x50 ml), CH2Cl2 (3x50 ml) and dried in vacuum at room temperature to afford of
[CelFemImi]Cl (5). FTIR (KBr, thin film): υ = 3346, 2963, 2901, 1456, 1428, 1371, 1281, 1112,
1059, 703, 665, 560 cmꢀ1; FTRAMAN (KBr): υ = 3235, 2898, 1471, 1330, 1240, 1081, 1089,
987, 768, 605, 555, 443 cmꢀ1; Elemental analysis observed: %C 61.2, %N 1.28, %Al 1.2, %Si
0.23, %Fe 0.27; Loading: 0.46 mmol functional group gꢀ1 of cellulose.
Preparation of [CellFemImi]OH (6)
[CellFemImi]Cl (3.0g) was suspended in 30 ml of an aqueous solution of NH3. The
system was stirred for 48 h at room temperature, Afterwards the polymer was filtered and

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washed with MeOH (3×20 ml), MeOH:H2O (1:1) (3× 20 ml), H2O (3× 20 ml) and MeOH (3× 20
ml) and dried under vacuum at 50 0C for 48 h to afford [CellFemImi]OH (6). FTIR (KBr, thin
film): ν = 3345, 3280, 2964, 2901, 2853, 1633, 1480, 1455, 1372, 1356, 1318, 1281, 1163, 1112,
1059, 1033, 664, 560, 441 cm−1; FTRAMAN (KBr): υ = 3235, 3115, 2899, 1523, 1475, 1438,
13
1371, 1234, 1085, 466 cmꢀ1; C CPꢀMAS NMR (500 MHz.): δ 138.5 (s), 127 (s), 120 (s), 113
(bs), 90 (bs,), 72ꢀ76 (m), 67 (bs), 70 (s), 78 (s), 49 (s), 28 (s), 8.0 (s); Elemental analysis
observed: %C 61.31, %N 1.19, %Al 1.21, %Si 0.21, %Fe 0.28; Loading: 0.31 mmol OHꢀgroups
gꢀ1 cellulose matrix.
General procedure for the synthesis of oxazolones
A mixture of aryl aldehyde (1 mmol), hippuric acid (1 mmol) and acetic anhydride (3
mmol) in presence of 6 (100 mg, 0.106 mmol) was stirred in ethanol at room temperature. After
the completion of reaction, the reaction mass was filtered and the solid washed with ethanol to
afford crude product which was purified by column chromatography (nꢀhexane/EtOAc = 8:2).
Spectral data
4ꢀ(4ꢀBenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9a)
o
Yellow solid; M. P. 165 °C (lit., 166 C)27; FTIR (KBr, thin film): υ = 3450, 3415, 1796, 1659,
1545, 1475, 859, 760 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 7.27 (s, 1H), 7.42ꢀ7.58 (m, 6H), 8.20ꢀ
8.24 (m, 4H) ppm; 13C NMR (CDCl3, 75 MHz): δ 166.0, 160.9, 135.5, 131.7, 131.2, 129.8,
129.2, 128.9, 128.7, 128.0 ppm; Mass (EI) m/z: 249 [M]+; Anal. Calcd. for C16H11NO2: %C
77.10, %H 4.45, %N 5.62, observed: %C 77.06, %H 4.42, %N 5.65.
4ꢀ(3ꢀNitrobenzylidene)ꢀ 2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9b)
o
Pale yellow solid; M. P. 173 °C (lit., 175 C)27; FTIR (KBr, thin film): υ = 3410, 1810, 1650,
1536, 1430, 860, 721 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 9.29 (t, J =1.6 Hz, 1H), 8.44 (d, J =

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7.7 Hz, 1H), 8.26 (dd, J = 2.4, 8.1 Hz, 1H), 8.19ꢀ8.22 (m, 2H), 7.67 (m, 2H), 7.55 (m, 2H), 7.26
(s, 1H) ppm; 13C NMR (CDCl3, 75 MHz): δ 166.1, 160.1, 148.0, 136.0, 131.1, 129.7, 129.4,
129.1, 128.7, 121.1, 120.4, 112.2 ppm; Mass (EI) m/z: 294 [M]+; Anal. Calcd. for C16H10N2O4:
%C 65.31, %H 3.43, %N 9.52, observed: %C 65.35, %H 3.41, %N 9.54.
4ꢀ(4ꢀNitrobenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9c)
o
Pale yellow solid; M. P. 241 °C (lit., 239 C)27; FTIR (KBr, thin film): υ = 3460, 1756, 1652,
1
1547, 1465, 854, 765 cmꢀ1; H NMR (CDCl3, 300 MHz): δ 8.29ꢀ8.32 (m, 2H), 8.34ꢀ8.37 (m,
2H), 8.24 (dd, J = 1.2, 8.6 Hz, 2H), 7.71ꢀ7.73 (m, 1H), 7.61 (dd, J = 4.7, 10.9 Hz, 2H), 7.27 (s,
1H) ppm; 13C NMR (CDCl3, 75 MHz): δ 166.3, 160.4, 147.3, 141.1, 131.4, 131.0, 129.7, 129.1,
128.8, 127.1, 121.2, 112.3 ppm; Mass (EI) m/z: 294 [M]+; Anal. Calcd. for C16H10N2O4: %C
65.31, %H 3.43, %N 9.52, observed: %C 65.29, %H 3.40, %N 9.49.
4ꢀ(2ꢀChlorobenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9d)
o
Yellow solid; M. P. 163 °C (lit., 162 C)27; FTIR (KBr, thin film): υ = 3445, 3305, 1802, 1659,
1
1547, 1401, 851, 735 cmꢀ1; H NMR (CDCl3, 300 MHz): δ 8.94 (dd, J = 1.7, 7.9 Hz, 1H), 8.18
13
(d, J= 7.5 Hz, 2H), 7.79 (t, J = 7.6 Hz, 1H), 7.67 (m, 2H), 7.58 (m, 3H), 7.50 (s, 1H) ppm; C
NMR (CDCl3, 75 MHz): δ 166.4, 160.7, 133.3, 131.8, 131.1, 129.6, 129.4, 129.2, 128.7, 128.6,
127.6, 126.2, 112.4 ppm; Mass (EI) m/z: 284 [M]+; Anal. Calcd. for C16H10ClNO2: %C 67.74,
%H 3.55, %N 4.94, observed: %C 67.70, %H 3.50, %N 4.97.
4ꢀ(4ꢀChlorobenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9e)
o
Pale yellow solid; M. P. 196 °C (lit., 198 C)27; FTIR (KBr, thin film): υ = 3457, 3360, 1799,
1658, 1597, 1450, 1295, 1071, 855, 760 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 8.17 (m, 4H), 7.65
(dd, J = 2.7, 8.6 Hz, 1H), 7.55 (dd, J = 4.9, 10.7 Hz, 2H), 7.47 (dd, J = 2.1, 8.9 Hz, 2H), 7.19 (s,
1H) ppm; 13C NMR (CDCl3, 75 MHz): δ 166.2, 160.4, 133.7, 133.4, 131.4, 131.1, 129.7, 129.1,

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128.8, 128.6, 127.6, 112.2 ppm; Mass (EI) m/z: 284 [M]+; Anal. Calcd. for C16H10ClNO2: %C
67.74, %H 3.55, %N 4.94, observed: %C 67.70, %H 3.50, %N 4.97.
4ꢀ(4ꢀBromobenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9f)
o
Yellow solid; M. P. 203 °C (lit., 204 C)27; FTIR (KBr, thin film): υ = 3466, 3075, 1804, 1670,
1547, 1444, 1297, 1044, 840, 753 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 8.11 (d, J = 7.5 Hz, 2H),
8.04 (d, J = 8.6 Hz, 2H), 7.61 (dd, J = 8.6, 15.4 Hz, 3H), 7.60 (t, J = 7.7 Hz, 2H), 7.18 (s, 1H)
ppm; 13C NMR (CDCl3, 75 MHz): δ 166.1, 160.7, 134.0, 131.8, 131.2, 129.7, 129.1, 128.7,
128.5, 122.2, 112.7 ppm; Mass (EI) m/z: 328 [M]+; Anal. Calcd. for C16H10BrNO2: %C 58.56,
%H 3.07, %N 4.27, observed: %C 58.59, %H 3.09, %N 4.29.
4ꢀMethylbenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9g)
o
Pale yellow solid; M. P. 146 °C (lit., 148 C)27; FTIR (KBr, thin film): υ = 3470, 3325, 2910,
1809, 1659, 1520, 1434, 1270, 1034, 870, 745 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 8.13 (dd, J =
1.3, 8.5 Hz, 2H), 8.12 (d, J = 8.3 Hz, 2H), 7.63 (m, 1H), 7.55 (m, 2H), 7.29 (d, J = 8.2 Hz, 2H),
7.25 (s, 1H), 2.39 (s, 3H) ppm; 13C NMR (CDCl3, 75 MHz): δ 166.2, 160.3, 137.3, 132.0, 131.4,
131.0, 129.7, 129.4, 128.9, 128.7, 126.1, 112.2, 24.1 ppm; Mass (EI) m/z: 263 [M]+; Anal. Calcd.
for C17H13NO2: %C 77.55, %H 4.98, %N 5.32, observed: %C 77.52, %H 5.02, %N 5.35.
4ꢀ(4ꢀFluorobenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9h)
o
Pale yellow solid; M. P. 185 °C (lit., 183 C)27; FTIR (KBr, thin film): υ = 3401, 3315, 1804,
1
1668, 1522, 847, 740 cmꢀ1; H NMR (CDCl3, 300 MHz): δ 8.45 (dd, J = 5.9, 8.8 Hz, 2H), 8.17
(d, J = 8.3 Hz, 2H), 7.76 (dd, J = 7.1, 14.4 Hz, 1H), 7.67 (t, J = 7.5 Hz, 2H), 7.22 (s, 1H), 7.19 (t,
13
J = 8.6 Hz, 2H). ppm; C NMR (CDCl3, 75 MHz): δ 166.1, 162.3, 160.4, 131.8, 131.2, 130.7,
129.6, 129.1, 128.8, 128.2, 115.1, 112.3 ppm; Mass (EI) m/z: 267 [M]+; Anal. Calcd. for
C16H10FNO2: %C 71.91, %H 3.77, %N 5.24, observed: %C 71.89, %H 3.79, %N 5.22.

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4ꢀ(4ꢀMethoxybenzylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9i)
o
Yellow solid; M. P. 161 °C (lit., 159 C)27 ; FTIR (KBr, thin film): υ = 3456, 3401, 3035, 2950,
1805, 1760, 1652, 1545, 1076, 803, 775 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 8.19 (ddd, J = 2.2,
13
4.1, 8.4 Hz, 4H), 7.56 (m, 1H), 7.55 (m, 2H), 7.24 (s, 1H), 7.01 (m, 2H), 3.91 (s, 3H) ppm; C
NMR (CDCl3, 75 MHz): δ 166.4, 160.7, 159.7, 131.4, 131.0, 129.5, 129.1, 128.7, 127.4, 127.1,
114.0, 112.1, 55.7 ppm; Mass (EI) m/z: 279 [M]+; Anal. Calcd. for C17H13NO2: %C 73.11, %H
4.69, %N 5.02, observed: %C 73.14, %H 4.72, %N 5.05.
4ꢀ(2ꢀThiophenecarboxylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9k)
o
Yellow solid; M. P. 174 °C (lit., 176 C)27; FTIR (KBr, thin film): υ = 3411, 3055, 2905, 1798,
1756, 1658, 1554, 1090, 823, 757 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 8.05 (dd, J = 1.2, 8.4 Hz,
2H), 7.46 (dd, J = 0.8, 5.1 Hz, 1H), 7.38 (m, 2H), 7.32 (m, 2H), 7.22 (s, 1H), 7.13 (dd, J = 3.8,
5.0 Hz, 1H) ppm; 13C NMR (CDCl3, 75 MHz): δ 167.4, 161.9, 137.6, 135.4, 135.2, 132.8, 131.3,
128.9, 128.5, 128.1, 124.6, 123.9 ppm; Mass (EI) m/z: 255 [M]+; Anal. Calcd. for C14H9NO2S:
%C 65.87, %H 3.55, %N 5.49, %S 12.56, observed: %C 65.41, %H 3.12, %N 5.10, %S 12.21.
4ꢀ(2ꢀFuranylidene)ꢀ2ꢀphenylꢀ5ꢀ(4H)ꢀoxazolone (Table 2, product 9j)
o
Yellow solid; M. P. 171 °C (lit., 169 C)27; FTIR (KBr, thin film): υ = 1787, 1653, 1599, 1558,
1492, 1454, 1329, 1232, 1156, 1023, 989, 856 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 8.16 (t, J =
1.5, 7.2 Hz, 2H), 7.70 (d, J = 1.5 Hz, 1H), 7.58ꢀ7.65 (m, 2H), 7.53 (t, 2H), 7.19 (s, 1H), 6.68 (dd,
J = 1.8, 1.5 Hz, 1H) ppm; 13C NMR (CDCl3, 75 MHz): δ 167.1, 163.0, 150.5, 146.6, 133.2,
130.4, 128.9, 128.2, 125.5, 120.1, 118.3, 113.8 ppm; Mass (EI) m/z: 239 [M]+; Anal. Calcd. for
C14H9NO3: %C 70.29, %H 3.79, %N 5.86, observed: %C 69.89, %H 3.46, %N 5.26.

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3ꢀ((6E)ꢀ(5ꢀoxoꢀ2ꢀphenyloxazolꢀ4ꢀ(5H)ꢀylidene)methyl) benzaldehyde (Table 2, product 9l)
Yellow solid; M. P. 135 °C; FTIR (KBr, thin film): υ = 3062, 2926, 2855, 1789, 1654, 1450,
1325, 1295, 1157, 1097, 981, 884, 799 cmꢀ1; 1H NMR (CDCl3, 300 MHz): δ 10.13 (s, 1H), 8.72
(s, 1H), 8.46 (d, J = 7.8 Hz, 1H), 8.20 (t, J = 7.2, 1.5 Hz, 2H), 7.98 (d, J = 7.8 Hz, 1H), 7.64ꢀ7.70
13
(m, 2H), 7.57 (t, J = 7.5, 7.2 Hz, 2H), 7.29 (s, 1H) ppm; C NMR (CDCl3, 75 MHz): δ 191.6,
167.1, 164.5, 137.5, 136.9, 134.6, 134.4, 134.2, 133.8, 133.7, 133.5, 131.1, 129.6, 129.4, 129.0,
128.6, 125.2 ppm; Mass (EI) m/z: 279 [M]+; Anal. Calcd. for C17H11NO3: %C 73.64, %H 4.00,
%N 5.05, observed: %C 73.14, %H 3.66, %N 4.85.
Acknowledgment
The authors thank UGC, New Delhi for financial assistance [F.No.40ꢀ96/2011(SR)].
References
1
P. T. Anastas, J. C. Warner, Green Chemistry: Theory and Practice, Oxford University
Press: New York, 1998, p 30.
2
(a) J. D. Patil, S. A. Patil and D. M. Pore, RSC Adv., 2015, 5, 21396; (b) P. Forte, A.
Sachse, M. Maes, A. Galarneau and D. De Vos, RSC Adv., 2014, 4, 1045; (b) C. V.
Doorslaer, J. Wahlen, P. Mertens, K. Binnemans and D. De Vos, Dalton Trans., 2010,
39, 8377; (c) C. P. Mehnert, Chem. A. Eur. J., 2005, 11, 81; (d) S. S. Shinde, B. Se Lee
and D. Y. Chi, Tetrahedron Lett., 2008, 49, 27.
3
4
(a) C. P. Mehnert, R. A. Cook, N. C. Dispenziere and M. Afeworki, J. Am. Chem. Soc.,
2002, 124, 12932; (b) A. Riisager, K. M. Eriksen, P. Wasserscheid and R. Fehrmann,
Catal. Lett., 2003, 90, 149.
P. Wasserscheid, J. Ind. Eng. Chem., 2007, 13, 325.

RSC Advances
Page 18 of 30
View Article Online
DOI: 10.1039/C6RA03873E
5
(a) H. Li, P. S. Bhadury, B. Song and S. Yang, RSC Adv., 2012, 2, 12525; (b) M. I.
Burguete, H. Erythropel, E. GarciaꢀVerdugo, S. V. Luis and V. Sans, Green. Chem.,
2008, 10, 401; (c) M. I. Burguete, H. Erythropel, E. GarciaꢀVerdugo, S. V. Luis and V.
Sans, Green. Chem., 2008, 10, 401; (d) G. Rashinkar and R. Salunkhe, J. Mol. Catal. A:
Chem., 2010, 316, 146; (e) V. Sans, N. Karbass, M. I. Burguete, V. Compan, E. Garciaꢀ
Verdugo, S. V. Luis and M. Pawlak, Chem. A. Eur. J., 2011, 17, 1894.
L. RodríguezꢀPérez, E. Teuma, A. Falqui, M. Gómez and P. Serp, Chem. Commun.,
2008, 4201.
6
7
J. Mikkola, P. Virtanen, H. Karhu, T. Salmia and D. Y. Murzin, Green. Chem., 2006, 8,
197.
8
N. Clousier, R. Moucel, P. Naik, P. J. Madec, A. C. Gaumont and I. Dez, C. R. Chimie,
2011, 14, 680.
9
Y. Qiao, H. Li, L. Hua, L. Orzechowski, K. Yan, B. Feng, Z. Pan, N. Theyssen, W.
Leitner and Z. Hou, ChemPlusChem, 2012, 77, 1128.
10
11
W. Xia, D. Su, A. Birkner, L. Ruppel, Y. Wang, C. Woll, J. Qian, C. Liang, G.
Marginean, W. Brandl and M. Muhler, Chem. Mater., 2005, 17, 5737.
(a) A. H. Tamboli, A. A. Chaugule, F. A. Sheikh, W. J. Chung and H. Kim, Chin. J.
Catal. 2015, 36, 0; (b) S. Martin, R. Porcar, E. Peris, M. I. Burguete, E. G. Verdugo and
S.V. Luis, Green. Chem., 2014, 16, 1639; (c) U. Hintermair, G. Francio and W. Leitner,
Chem. Eur. J., 2013, 19, 4538; (d) B. Karimi and M. Vafaeezdeh, Chem. Commun., 2012,
48, 3327; (e) N. A. Khan, Z. Hasan and S. H. Jhung, Chem. Eur. J., 2014, 20, 376; (f) B.
Ni, A. D. Headley, Chem. Eur. J., 2010, 16, 4426; g) A. Riisager, R. Fehrmann, M.
Haumann and P. Wasserscheid, Eur. J. Inorg. Chem., 2006, 695.

Page 19 of 30
RSC Advances
View Article Online
DOI: 10.1039/C6RA03873E
12
13
14
J. Zhang, T. J. Elder, Y. Pu and A. J. Ragauskas, Carbohyd. Polym., 2007, 69, 607.
S. Sen, J. D. Martin and D. S. Argyropoulos, ACS Sustain. Chem. Eng., 2013, 1, 858.
(a) A. Mohammadinezhad, M. A. Nasseri and M. Salimi, RSC Adv., 2014, 4, 39870; (b)
P. V. Chavan, K. S. Pandit, U. V. Desai, M. A. Kulkarni and P. P. Wadgaonkar, RSC
Adv., 2014, 4, 42137; (c) A. Shaabani, Z. Hezarkhani and S. Shaabani, RSC Adv., 2014,
4, 64419; (d) D. Baruah, U. P. Saikia, P. Pahari, D. K. Dutta and D. Konwar, RSC Adv.,
2014, 4, 59338; (e) F. Quignard and A. Choplin, Chem. Commun., 2001, 21.
A. A. Pereira, P. P. deCastro, A. C. de Mello, B. R. V. Ferreira, M. N. Eberlin and G. W.
Amarante, Tetrahedron, 2014, 70, 3271.
15
16
17
H. Jiang, M. W. Paixao, D. Monge and K. A. Jørgensen, J. Am. Chem. Soc., 2010, 132,
2775.
(a) M. Parveen, A. Ali, S. Ahmed, A. M. Malla, M. Alam, P. S. Pereira Silva, M. R. Silva
and D. U. Lee, Spectrochim. Acta Part A: Mol. Biomol. Spectrosc., 2013, 104, 538; (b) C.
Cativiela, J. A. Mayoral, A. Avenoza, M. Gonzalez and M. A. Roy, Synthesis, 1990, 12,
1114; (c) P. A. Conway, K. Devine and F. Paradisi, Tetrahedron, 2009, 65, 2935; (d) A.
Natsch, H. G. feller, F. Kuhn, T. Granier and D. W. Roberts, Chem. Res. Toxicol., 2010,
23, 1913; (e) I. FunesꢀArdoiz, M. BlancoꢀLomas, P. J. Campos and D. Sampedro,
Tetrahedron, 2013, 69, 9766.
18
(a) S. Moorkoth, K. K. Srinivasan and D. Bukka, Elixir Pharmacy, 2013, 54, 12315; (b)
J. Penalva, R. Puchades, A. Maquieira, S. Gee and B. D. Hammock, Biosens.
Bioelectron., 2000, 15, 99; (c) Y. Prayin, B. Rutnakornpituk, U. Wichai, T. Vilaivan and
M. Rutnakornpituk, J. Nanopart. Res., 2014, 16:2357, 1; (d) T. Nakanishi, K. Yamanaka,
M. Kakeda, K. Tsuda and H. Mizutani, Arch. Dermatol. Res., 2013, 305, 241; (e) M.

RSC Advances
Page 20 of 30
View Article Online
DOI: 10.1039/C6RA03873E
Hatao, T. Hariya, Y. Katsumura and S. Kato, Toxicol., 1995, 98, 15; (f) B. Balan and D.
Bahulayan, Helv. Chim. Acta., 2013, 96, 2251; (g) H. H. Georgey, Egypt. J. Chem., 2007,
50, 455; (h) M. Francoise, P. Sierra, A. Pierre, M. Burbridge and N. Guilbaud, Bioorg.
Med. Chem. Lett., 2002, 12, 1463; (i) A. ElꢀMekabaty, O. M. O. Habib, H. M. Hassan
and E. B. Moawad, Pet. Sci., 2012, 9, 389.
19
20
A. K. Mukerjee, Heterocycles, 1987, 26, 1077.
K. V. J. Ahluwalia, ErlenmeyerꢀPlochl Azalactone and amino acid synthesis,
Comprehensive Practical Organic Chemistry: Preparations And Quantitative analysis,
2000; 82.
21
(a) M. Parveen, F. Ahmad, A. M. Malla, S. Azaz, M. R. Silva and P. S. P. Silva, RSC
Adv., 2015, 5, 52330; (b) H. Moghanian, M. Shabanian and H. Jafari, C. R. Chimie, 2012,
15, 346; (c) A. R. Khosropour, M. M. Khodaei and S. J. Hoseini Jomor, J. Heterocycl.
Chem., 2008, 45, 683; (d) F. M. Istrate, A. K. Buzas, I. D. Jurberg, Y. Odabachian and F.
Gagosz, Org. Lett., 2008, 10, 925; (e) B. R. Madje, M, B. Ubale, J. V. Bharad and M. S.
Shingare, S. Afr. J. Chem., 2010, 63, 158; (f) M. R. P. Norton Matos, P. M. P. Gois,
Maria L. E. N. Mata, E. J. Cabrita and C. A. M. Afonso, Synth. Commun., 2003, 33,
1285; (g) K. A. Monk, D. Sarap and R. S. Mohan, Synth. Commun., 2000, 30, 3167; (h)
S. J. Ahmadi, S. Sadjadi and M. Hosseinpour, Ultrason. Sonochem., 2013, 20, 408; (i) M.
Weber, W. Frey and R. Peters, Chem. Eur. J., 2013, 19, 8342; (j) M. B. Madhusudana
Reddy and M. A. Pasha, Synth. Commun., 2010, 40, 1895; (k) N. N. Karade, S. G.
Shirodkar, B. M. Dhoot and P. B. Waghmare, J. Chem. Res., 2005, 2005, 46; (l) P.
Anandgaonker, G. Kulkarni, S. Gaikwad and A. Rajbhoj, Chin. J. Catal., 2014, 35, 196.

Page 21 of 30
RSC Advances
View Article Online
DOI: 10.1039/C6RA03873E
22
(a) R. Kurane, J. Jadhav, S. Khanapure, R. Salunkhe and G. Rashinkar, Green Chem.,
2013, 15, 1849; (b) M. Jagadale, P. Bhange, R. Salunkhe, D. Bhange, M. Rajmane and G.
Rashinkar, Appl. Cat. A: Gen., 2016, 511, 95; (c) G. Rashinkar and R. Salunkhe, J. Mol.
Cat. A: Chem., 2010, 316, 146.
23
24
A. M. Lazarin, Y. Gushikem and S. C. deCastro,. J. Mater. Chem., 2000, 10, 2526.
(a) V. K. Ahluwalia and R. Aggarwal, Comprehensive Practical Organic Chemistry:
Preparations And Quantitative Analysis. Universities Press (India) Pvt. Limited, 2005
;
(b) A. Kumbhar, S. Jadhav, R. Shejwal, G. Rashinkar and Rajshri Salunkhe, RSC
Adv., 2016, 6, 19612.
25
26
Q. Pang, L. Wang, H. Yang, L. Jia, X. pan and C. Qui, RSC Adv., 2014, 4, 41212.
a) Y. Wu, Z. Fu, D. Yin, Q. Xu, F. Lu, C. Lu v L. Mao, Green Chem., 2010, 12, 696; b)
O. W. Guirguis and M. T. H. Moselhey, Nat. Sci., 2012, 4, 57.
27
28
29
(a) T. Cleary, T. Rawalpally, N. Kennedy and F. Chavez, Tetrahedron Lett., 2010, 51,
1533; (b) S. Paul, P. Nanda, R. Gupta and A. Loupy, Tetrahedron Lett., 2004, 45, 425;
(c) T. Cleary, J. Brice, N. Kennedy and F. Chavez, Tetrahedron Lett., 2010, 51, 625.
(a) B. B. F. Mirjalili and R. Z. Reshquiyea, RSC Adv., 2015, 5, 15566; (b) E. Tahanpesar,
S. Elhami and M. Mohammadi, IJSRES., 2015, 3, 0038; (c) N. Yan, X. Chen, Nat., 2015,
524, 155.
(a) J. K. Lindsay and C. R. Hauser, J. Org. Chem., 1956, 22, 355; (b) Y. Gao, B.
Twamley and J. M. Shreeve, Inorg. Chem., 2004, 43, 3406.

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Scheme 1 Synthesis of [CellFemImi]OH catalyst

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Figure 1 FESEM of [CellFemImi]OH

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Figure 2 XRD patterns of chloropropyl cellulose, 5 and 6

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Figure 3 TGA profile of [CellFemImi]OH

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Table 1 Optimization of reaction conditions in the synthesis of oxazolꢀ5ꢀonesa
CHO
O
N
[CellFemImi]OH
N
H
COOH
+
Ac2O, solvent, rt
O
O2N
O
NO2
8c
7
9c
(4E)ꢀ4ꢀ(4ꢀNitrobenzylidene)ꢀ2ꢀphenyloxazolꢀ5ꢀ(4H)ꢀone
Entry
Solvent
Catalyst
(mg)
Time
(h)
Yieldb
(%)
1
2
CH2Cl2
CHCl3
100
100
100
100
50
20
18
15
14
8
40
30
48
34
61
89
90
90
63
51
52
42
3
CH3CN
THF
4
5
Ethanol
Ethanol
Ethanol
Ethanol
Methanol
DMF
6
100
150
200
100
100
100
100
4
7
4
8
4
9
12
15
16
15
10
11
12
1, 4ꢀdioxane
Water
aOptimal reaction conditions: 7 (1 mmol.), 8 (1 mmol.), Ac2O (3 mmol), solvent (5 ml) and [CellFemImi]OH
b
(100 mg). Isolated yields after column chromatography.

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Table 2 [CellFemImi]OH catalyzed synthesis of oxazolonesa
O
Ar
N
[CellFemImi]OH
Ac2O, EtOH, rt
CHO
Ar
N
COOH
+
H
O
O
8 a-l
9 a-l
Entry
Ar
8
Product
9
Time
(h)
Yieldb Melting
(%)
point (oC)
165[32]
173[32]
241[32]
N
a
b
c
C6H4ꢀ
4
5
5
89
O
O
O2N
N
3ꢀNO2ꢀC6H4ꢀ
4ꢀNO2ꢀC6H4ꢀ
85
O
O
N
89
O
O2N
O
Cl
N
d
e
2ꢀClꢀC6H4ꢀ
4ꢀClꢀC6H4ꢀ
4
4
84
87
163[32]
198[32]
O
O
N
O
Cl
O

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N
f
4ꢀBrꢀC6H4ꢀ
4ꢀMeꢀC6H4ꢀ
4ꢀFꢀC6H4ꢀ
5
5
6
4
6
89
86
88
86
82
203[32]
O
O
Br
Me
F
N
g
146[32]
185[32]
161[32]
171[32]
O
O
N
h
i
O
O
4ꢀMeOꢀ
C6H4ꢀ
N
O
O
MeO
O
N
j
k
l
*
O
O
O
S
N
6
5
80
85
174[32]
*
S
O
O
OHC
N
3ꢀCHOꢀC6H4
135
O
O
aOptimal reaction conditions: 7 (1 mmol.), 8 (1 mmol.), Ac2O (3 mmol), EtOH (5 ml) and [CellFemImi]OH (100 mg.).
bIsolated yields after column chromatography.

Page 29 of 30
RSC Advances
View Article Online
DOI: 10.1039/C6RA03873E
Ph
Ph
H
O
O
O
O
OH
O
O
N:
ꢀH2O
N
O
OH-
H
OH-
OH-
OH-
OH-
OH-
OH-
H
Cellulose
Ph
Ar
H
OH-
OH-
O
O
[CellFemImi]OH
O
OH
OH-
OH-
H
OH-
Ar
ꢀH2O
OH-
OH-
OH-
Cellulose
OH-
OH-
OH-
Catalyst recovered for next cycle
O
O
Ar
Ph
Figure 4 Plausible mechanism for the synthesis of oxazolones using [CellFemImi]OH