Synthesis of a Novel calix[4]resorcinarene-Chitosan hybrid

Article abstract of DOI:10.13005/ojc/340103

Synthesis of a novel calix[4]resorcinarene-chitosan hybrid using vanillin as raw material has been conducted. The synthesis was carried out in four steps i.e. (1) allylation of vanillin, (2) HCl-catalyzed condensation allyl vanillin with resorcinol, (3) c

Full text of DOI:10.13005/ojc/340103

ISSN: 0970-020 X
CODEN: OJCHEG
2018, Vol. 34, No.(1):
Pg. 30-37
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Synthesis of a Novel Calix[4]resorcinarene-Chitosan Hybrid
PRIO SANTOSO1*, CHAIRIL ANWAR2, JUMINA2, DWI SISWANTA2, SUHARSO3
and KEISUKE OHTO4
1Department of Chemistry, Faculty of Sciences, Institut Teknologi Sumatera,
Lampung 35365, Indonesia.
2Department of Chemistry, Faculty of Mathematics and Natural Sciences,
University of Gadjah Mada, Yogyakarta 55281, Indonesia.
3Department of Chemistry, Faculty of Mathematics and Natural Sciences,
University of Lampung, Lampung 35145, Indonesia.
4Saga University, 1-Honjo, Saga 840-8502, Japan.
*Corresponding author E-mail: santosoprio99@gmail.com
http://dx.doi.org/10.13005/ojc/340103
(Received: November 26, 2017; Accepted: January 01, 2018)
ABSTRACT
Synthesis of a novel calix[4]resorcinarene-chitosan hybrid using vanillin as raw material
has been conducted. The synthesis was carried out in four steps i.e. (1) allylation of vanillin,
(2) HCl-catalyzed condensation allyl vanillin with resorcinol, (3) chloromethylation of
C-4-allyloxy-3-methoxyphenylcalix[4] resorcinarene with paraformaldehyde and HCl in the
presence of ZnCl2 to yield tetrakis-chloromethyl-C-4-allyloxy-3 methoxyphenylcalix[4]resorcinarene, and
(4) reaction of tetrakis-chloromethyl-C-4-allyloxy-3-methoxyphenylcalix[4] resorcinarene with
chitosan to yield calixarene-chitosan hybrid. Structure elucidation of products were performed
using FT-IR, 1H-NMR, 13C-NMR, GC-MS, XRD, and SEM. The product of calixarene-chitosan
hybrid was obtained as dark red solid with m.p. > 300 °C in 78% yield.
Keywords: Calixarene modification synthesis, Chitosan hybrid,
Novel calix[4]resorsinarenes, Vanillin.
INTRODUCTION
purposes, including: sunscreen,2 extraction,3
inhibitor of calcium carbonate4,5 and calcium
sulphate6 scale formation, a stationary phase
of HPLC,7,8 drug delivery,9 antioxidant and
anti-toxoplasma,10 dye fibers,11 biosensors,12 and
adsorbent 13,14. Calixarene is compound group of
Calixarene has attracted the attention of
scientists since it was first introduced in 19781
because it can be utilized in various fields.
Calixarene has been studied its use for various
This is an
Open Access article licensed under a Creative Commons Attribution-NonCommercial-ShareAlike
4.0 International License (https://creativecommons.org/licenses/by-nc-sa/4.0/ ), which permits unrestricted
NonCommercial use, distribution and reproduction in any medium, provided the original work is properly cited.

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SANTOSO et al., Orient. J. Chem., Vol. 34(1), 30-37 (2018)
synthetic oligomer containing aromatic ring in a synthesized through bond formation of secondary
cyclic sequence linked by a methylene group1. One amine between the amine group of chitosan with
derivate of this compound that has been studied is chloromethyl group of tetrakis-chloro methyl-C-4-
calix[4]resorcinarene15-17. Calix[4]resorcinarene alyloxy-3 methoxyphenylcalix[4]resorcinarene at R2
(Fig. 1) consists of 4 units of resorcinol in the form of group. Cl atom on the alkyl halide is better leaving
cyclic linked by a methylene bridge. It can be group than –OCH3 at the carbonyl group, so the
synthesized by reaction of resorcinol with an hybrid formation reactions in this research would
aldehyde under acidic conditions.
be easier to happen and has a high yield.
MATERIALS AND METHODS
Materials and equipments
Chemicals used in this research were
vanillin, resorcinol, allyl bromide, chitosan,
paraformaldehyde, zinc chloride (ZnCl2), Pb,
ethanol, methanol, acetone, N,N-dimethyl
formamide (DMF), dichloromethane, hydrochloric
acid (HCl 37%), sodium sulfate (Na2SO4) anhydrate,
ethyl acetate (EtOAc), and distilled water. All
chemicals except distilled water were purchased
from E. Merck KG. Distilled water was obtained from
Laboratory of Fundamental Chemistry, University
of Gadjah Mada.
Fig. 1. Structure of calix[4]resorcinarene
A number of studies have shown that
research developments of calixarene more focused
on modifying the calixarene structure by adding a
variety of new functional groups. Timmerman and
his colleagues have been succes to synthesize and
modify a wide variety of calix[4]resorcinarene by
varying groups at R1 and R218. Groups at R1 can be
varied by using aldehyde different as the reagent
forming of calix[4]resorcinarene. While groups at
R2 can be varied via electrophilic substitution
reaction of calix[4]resorcinarene. Because a position
between OH in the aromatic ring of resorcinol has
high electron density so it is very reactive to the
presence of an electrophilic.19
Equipment used in this research were
laboratory glassware, hot plate with magnetic stirrer,
Büchner funnel, Buchi R-124 Rotary Vap System
(Marshall Scientific), analytical mass balance
(Mettler AT 200, Mettler Instrument Corp. Switzerland),
infra-red spectrophotometer (IR, Shimadzu-Prestige
21, Japan), proton nuclear magnetic resonance
spectrometer (1H-NMR, JEOL JNM-MY60 and JEOL
MY-500 MHz, USA), carbon nuclear magnetic
resonance spectrometer (13C-NMR, JEOL MY-500
MHz, USA), gas chromatography-mass spectrometer
(GC-MS, Shimadzu QP-5000, Japan), X ray
diffraction (XRD Shimadzu 6000, Japan) and scanning
electron microscope (SEM, Jeol JSM T300, USA).
In this research, the new calixarene
produced was derived from reaction between
resorcinol and vanillin as a source of aldehyde
functional group. In addition, modification
of calixarene structure was performed by
Procedures
As much as 15 mL of ethanol was added
into 100 mL of three-necked-flask. Then, 0.38 g
(16.40 mmol) of sodium metal was added and stirred
reacting chitosan with calix[4]resorcinarene at R2 until it was dissolved completely to produce sodium
ethoxide. After that, 1.25 g (4.10 mmol) of vanillin
was added and refluxed for 1 hour. Then, as much
as 1.99 g (16.40 mmol) of allyl bromide was added
portion by portion into the mixture of sodium
ethoxide and vanillin.The mixture was then refluxed
for 24 hours. The solution was evaporated, washed
with 30 mL of NaOH 0.1 M and extracted with
position formed a calix[4]resorcinarene-chitosan
hybrid. Anggraini has been successfully produced
calix[4]resorcinarene-chitosan hybrid from chitosan and
C-4-methoxycarbonilmethoxy-3-methoxyphenylcalix
[4]resorcinarene through amide bond formation at
R1 group20. The product has sufficiently low yield,
which is 28%. In this research, the hybrid was

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SANTOSO et al., Orient. J. Chem., Vol. 34(1), 30-37 (2018)
20 mL of dichloromethane three times. The
combined organic layer was washed with distilled
water and dried with Na2SO4 anhydrate, filtered and
evaporated. The product 1 was obtained as brown
yellowish liquid in 72% yield; FT-IR (KBr) v
(cm-1): 1682 (C=O aldehyde), 1589 and 1512
(C=C aromatic), 1134 (C-O-C); 1H-NMR (500 MHz,
CDCl3) δ(ppm): 9.83 (1H,s,-HC=O), 7.40 (1H,d,ArH),
7.03 (1H,s,ArH), 6.97 (1H,d,ArH), 6.00 (1H,m,-CH=),
5.33 and 5.31 (2H,d of d, H2C= allyl), 4.69
(2H,d,-CH2- allyl), 3.92 (3H,s,-CH3); 13C-NMR (126
MHz, CDCl3) δ(ppm): 191 (Ar-C=O), 154, 150, 130,
127, 112, 109 (Ar), 132 (-CH= allyl), 119
(H2C= allyl), 70 (-CH2- allyl), 56 (-CH3); GC-MS:
rt = 30 min, purity 87%, m/z 192 g/mol.
The formed solid was then filtered, washed with
distilled water and dried in the oven.The dried solid
was recrystallized with methanol-water.The product
3 was obtained as a light brown solid in 71% yield
with m.p. > 250 °C (decomposed). FT-IR (KBr) v (cm-1):
3426 (OH), 1605 and 1504 (C=C aromatic),
1
1450 (-CH2-), 1080 (C-O-C); H-NMR (500 MHz,
CD3OD): 8.51 (2H,s,OH), 6.17-6.56 (4H,s,ArH),
5.55-5.85 (1H,m,-CH=), 5.15-5.55 (2H,d of d,H2C=),
4.85 (1H,s,-CH methylene bridge), 4.45 (2H,d,-CH2-),
3.42 (3H,s,-CH3), 3.10 (2H,s,-CH2-Cl) ; 13C-NMR
(126 MHz, CD3OD) δ(ppm): 153, 148, 145, 139, 135,
117, 115, 112, 113, 102 (Ar), 137 (-CH= allyl),
114 (H2C= allyl), 69 (-CH2- allyl), 55 (-CH3), 40
(-CH methylene group), 34 (-CH2-Cl).
Synthesis of C-4-allyloxy-3methoxyphenylcalix
[4]resorcinarene (2)
Synthesis calix[4]resorcinarene-chitosan hybrid (4)
Mixture of chitosan (0.43 g, 2.40 mmol),
In 100 mL three-necked flask equipped
tetrakis-chloromethyl-C-4-allyoxy-3-methoxyphenyl
calix[4] resorcinarene (0.32 g, 0.24 mmol) and DMF
(30 mL) in the 100 mL three-necked-flask was
refluxed for 24 hours. Product was cooled, filtered
and washed with distilled water until the solid was
formed. The formed solid was filtered and dried.
The product 4 was obtained as a dark red solid
with m.p. > 250 °C (decomposed) in 78% yield.
FT-IR (KBr) v (cm-1): 3426 (OH), 1605 and 1512
(C=C aromatic), 1142 (C-O-C).
with water condenser, 0.87 g (4.54 mmol) of
4-allyloxy-3-methoxy benzaldehyde and 0.50 g
(4.54 mmol) of resorcinol were dissolved in 20 mL
of ethanol. Then, concentrated hydrochloric acid
(0.5 mL) was added into the solution. The mixture
was refluxed for 24 h and evaporated. The solid
was washed using the mixture of distilled water
and ethanol (1:1) and dried. The product 2 was
obtained as a white solid with m.p. 235-236 °C
in 64% yield; FT-IR (KBr) v (cm-1): 3426 (OH),
1612 and 1512 (C=C aromatic), 1134 (C-O-C);
1H-NMR (500 MHz, CD3OD): 6.53 (1H,s,ArH), 6.47
(1H,d,ArH), 6.29 (1H,d,ArH), 6.25 (1H,s,ArH),
6.20 (1H, s, ArH), 5.61-5.77 (1H, m, -CH=), 5.21-
5.39 (2H, d of d,H2C=), 4.61 (1H, s,-CH methylene
group), 4.54 (2H, d, -CH2-), 3.57 (3H, s, -CH3); 13C-
NMR (126 MHz, CD3OD) δ(ppm): 154, 150, 147,
140, 132, 124, 122, 115, 114, 104 (Ar), 136 (-CH=
allyl), 117 (H2C= allyl), 71 (-CH2- allyl), 56 (-CH3),
43 (-CH methylene group).
RESULTS AND DISCUSSION
Synthesis of calix[4]resorcinarene-
chitosan hybrid compound was carried out in four
steps i.e. allylation of vanillin, condensation
allyl vanillin with resorcinol to yield 4-allyloxy-3-
methoxyphenylcalix[4]resorsinarene, chloromethylation
of C-4-allyloxy-3-methoxyphenylcalix[4], and
reaction of tetrakis-chloro methyl-C-4-allyloxy-3-
methoxyphenylcalix[4]resorcinarene with chitosan
to yield calix[4]resorcinarene-chitosan hybrid.
Synthesis scheme of calix[4]resorcinarene-chitosan
hybrid was presented in Figure. 2.
Synthesis of tetrakis-chloromethyl-C-4-allyoxy-
3-methoxyphenylcalix[4]resorcinarene (3)
Into 100 mL three-necked flask,
C-4-allyloxy-3methoxyphenylcalix[4]resorcinarene
(1.44 g, 1.27 mmol) was dissolved in 35 mL of DMF.
Then, paraformaldehyde (0.23 g, 7.67 mmol), ZnCl2
(1.50 g, 11 mmol) and concentrated hydrochloric
acid (8 mL) were added to the solution, respectively.
The mixture was heated at 120 oC for 22 hours.The
trituration of the cool reaction mixture using distilled
water was then carried out to give the precipitate.
Allylation of vanillin produce 4-allyloxy-3-
methoxybenzaldehyde compound was performed
by inserting Na into ethanol in a 100 mL three neck
flask. The mixture was stirred until all the Na reacts
generate sodium ethanolic. The sodium ethanolic
is a strong base so it will take H+ from the group

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SANTOSO et al., Orient. J. Chem., Vol. 34(1), 30-37 (2018)
of phenol contained in vanillin (4-hydroxy-3-methoxy
benzaldehyde) produced strong nucleophile.
The nucleophile will attack the C atoms which
charged positive partial binding Br in allyl bromide.
This reaction is predicted through SN2 mechanism.
This is due to a nucleophile formed in this reaction
is a strong nucleophile and alkyl halides involved
in the reaction are primary alkyl halide which very
open to attack by a nucleophile. Compound of
4-allyloxy-3-methoxybenzaldehyde was obtained
as brown yellowish liquid in 72% yield. Then it
was characterized with IR spectrometer, H-NMR,
13C-NMR and GC-MS. FT-IR spectra showed
absorption of C=O aldehyde, C=C aromatic, and
C-O-C groups. The most important information of
the FT-IR spectra is the loss absorption of OH group
at 3200-3400 cm-1. This indicates that OH group at
vanillin has been allylated.
1
Fig. 2. Synthesis scheme of calix[4]resorcinarene-chitosan hybrid from vanillin
Based on 1H-NMR spectra, there are nine
hydrogens are in a different environments. Singlet
signal at 9.83 ppm showed one proton aldehyde
group.Three signals at 7.40 ppm (duplet), 7.03 ppm
(singlet) and 6.97 ppm (duplet) showed protons
aromatic group. Multiplet signal at 6.00 ppm shift
shows 1 proton -CH = the allyl group. Two protons
of H2C = were shown at 5.33 ppm (duplet of duplet)
and 5.31 ppm (duplet of duplet). Two protons of
-CH2- the allyl group were shown by duplet signal
at 4.69 ppm and three protons of -CH3 were shown
by shift at 3.92 ppm. Characterization of vanillin
allylation product was resumed with 13C-NMR
spectrometer. Spectra of 13C-NMR showed that the
compound of 1 contained 11 C atoms in different
environments. C atom of carbonyl was shown by
signal at 191 ppm. Six C atoms of aromatic group
were shown by signal at 154, 150, 130, 127, 112
and 109 ppm. Three C atoms of allyl (-CH=, H2C=, -CH2-)
were shown by signal at 132, 119 and 70 ppm. One
C atom of methoxy was shown by at 56 ppm. The
last characterization product of vanillin allylation
was performed using GC-MS. The use of GC-MS
aimed to determine purity and confirmed the relative
molecular mass of product. Based on data from
GC-MS, product has 87% purity, 192 g/mol
molecular weight and 30 min. retention time.
Synthesis of C-4-allyloxy-3methoxypheny
lcalix[4]resorcinarene compound was conducted by
reacting resorcinol and 4-allyloxy-3-methoxy
benzaldehyde results of previous phase synthesis
using HCl for catalyst in ethanol. The mixture
was refluxed at 78 °C for 24 hours. Formation of
C-4-allyloxy-3-methoxyphenylcalix[4]resorcinarene
was preceded by protonation of the carbonyl group

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SANTOSO et al., Orient. J. Chem., Vol. 34(1), 30-37 (2018)
4-allyloxy-3-methoxy benzaldehyde to form
carbonyl group which is positively charged. The
existence of positive charge causes double bond
of carbonyl group conjugated to the oxygen atom. It
causes carbon atom of the carbonyl group to be
positively charged. Then carbon atom which
positively charged will be attacked by a double bond
of carbon atom number 4 on the benzene ring of
resorcinol. A second carbocation formed again after
releasing a water molecule. The next step was
cyclization through attack of second carbocation
by electron double bond of carbon atom number 4
on the benzene ring of resorcinol. This happened
repeatedly until formed calix[4]resorcinarene.
Compound of C-4-allyloxy 3-methoxy phenylcalix
[4]resorcinarene was obtained as a as a white solid
with m.p. 235-236 °C in 64% yield. Furthermore, to
ensure that the compound of 2 has formed, structure
group. Protons at 6.20 and 6.53 ppm with the
appearance show proton of resorcinol aromatic ring.
Protons at 6.25, 6.29, and 6.47 ppm with the
appearance singlet, duplet, and duplet respectively
show protons of allyl vanillin aromatic ring.
Further characterization using 13C-NMR
spectrometer shows that all of the carbons appear
in the appropriate area. The carbon of methylene
bridge appears at 43 ppm, the carbon of methoxy
seems at 56 ppm, the carbons of allyl are indicated
at 71, 117, and 136 ppm. The carbons for aromatic
benzene ring which come from vanillin can be
identified at 114, 115, 122, 140, 147, and 150 ppm.
While, the carbons of aromatic benzene ring from
resorcinol can be seen at 104, 124, 132, and
154 ppm.The data of carbon shift of C-4-allyloxy-3-
methoxyphenilcalix[4]resorcinarene compound
have a shift similar to the shift shown in chem draw
1
elucidation was conducted by FT-IR, H-NMR and
13C-NMR spectrometry.
1
software. Based on data from FT-IR, H-NMR and
13C-NMR spectrometer can be concluded that the
C-4-allyloxy-3-methoxyphenilcalix[4]resorcinarene
has been formed.
Based on the data from FT-IR spectra, it
was obtained information that the compound
C-4-allyloxy-3-methoxyphenylcalix[4]resorcinarene
which was synthesized containing OH groups. This
was shown by absorption band at 3426 cm-1.
Absorption bands at 1512 and 1612 cm-1 indicate
the presence of C=C aromatic groups. The
presence of ether groups (C-O-C) was shown by
an absorption band at 1134 cm-1. Absorption band
at 1682 cm-1 shows the aldehyde carbonyl group
(C=O) in 4-allyloxy-3-methoxybenzaldehyde as the
reactants have been lost. This indicates that the
formation of bonds between carbon atom number
4 and 6 in resorcinol with carbon atom atom of
carbonyl at the 4-allyloxy-3-methoxybenzaldehyde
formed methylene bridge.
Tetrakis-chloromethyl-C-4-allyloxy-3-
methoxyphenylcalix[4]resorcinarene was produced
through two reaction stages. The first stage is an
electrophilic substitution reaction, while the second
stage is a nucleophilic substitution reaction with
zinc chloride as a catalyst in both reactions.Tetrakis-
chloromethyl-C-4-allyloxy-3-methoxyphenylcalix[4]
resorcinarene was synthesized by reacting
C-4-allyloxy-3-methoxyphenylcalix [4]resorcinarene
with paraformaldehyde, zinc chloride and concentrated
hydrochloric acid in N,N-dimethylformamide. The
compound of Tetrakis-chloromethyl-C-4-allyloxy-3-
methoxyphenylcalix[4] resorcinarene was obtained
as a light brown solid in 71% yield with m.p. > 250 °C
(decomposed). Increasing of melting point of
compound 3 compared to compound 2 was
predicted by increasing of polarity due to the
inclusion chloromethyl and increasing of relative
molecular mass from 1137 g mol-1 to 1331 g mol-1.
Furthermore compound 3 was characterized by IR,
1H-NMR, and 13C-NMR spectrometer.
Further characterization by 1H-NMR
spectrometer was obtained information that there
are at least 10 types of protons that can be identified
in different environments in the C-4-allyloxy-3-
methoxyphenylcalix[4]resorcinarene synthesized.
Singlet proton at 3.57 ppm shows proton at methoxy
group (-OCH3). Singlet proton at 4.54 ppm shows
proton of -CH2- allyl group. Singlet protons at
4.61 ppm shows proton of methylene bridge.
Protons at 5.21-5.39 ppm with the appearance
duplet of duplet indicated proton of =CH2
allyl group. Protons at 5.61-5.77 ppm with the
appearance multiplet show proton of -CH= allyl
Based on identify of IR spectra performed,
it was obtained information the OH group absorption
that appeared in the 3426 cm-1. The absorbance of
C=C aromatic group existed at 1504 and 1605 cm-1.

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SANTOSO et al., Orient. J. Chem., Vol. 34(1), 30-37 (2018)
then the cation will be attacked by amine group of
chitosan to form a hybrid product. Calix[4]resorcinarene-
chitosan hybrid was obtained as dark red solid
with m.p > 300 °C (decomposed) in 78% yield.
Furthermore, it was characterized by FT-IR
spectrometer, XRD, and SEM. 1H-NMR and
13C-NMR spectrometer was not used for the
characterization of hybrid product because of it was
The absorbance of C-O-C group was displayed at
1142 cm-1. The absorbance of –CH2– at 1450 cm-1
indicated that chloromethylation reaction of
C-4-allyloxy-3-methoxyphenylcalix[4] resorcinarena
have done successfully. Further characterization of
1
chloromethylation product was done by H-NMR
and 13C-NMR spectrometer.
From the result of 1H-NMR, least 8 protons
were in a different environments. Success of
chloromethylation reaction was shown by presence
of chemical shift at 3.10 ppm in the form singlet
proton which indicates proton of chloromethyl group.
This is similar to the result proton chloromethyl of
tetrakis-chloromethyl-C-4methoxyphenylcalix
[4]resorcinarene which was synthesized by Utomo,
et al., (2011)20. The next characterization using
13C-NMR showed that all of the carbons appear in
the appropriate area with the chloromethyl carbon
at 34 ppm19.The methylene bridge carbon identified
at 40 ppm, the methoxy carbon existed at 55 ppm,
and the carbons of allyl group appeared at 69, 115,
and 137 ppm. The carbons of resorcinol aromatic
ring appeared at 102, 103, 135, and 153 ppm. While
carbons of vanillin aromatic ring appeared at 112,
114, 117, 139, 145, and 148 ppm. Based on FT-IR,
1H-NMR and 13C-NMR spectra can be stated that
the compound of tetrakis-chloromethyl-C-4-allyloxy-3-
methoxyphenylcalix[4]resorcinarene has been formed.
1
not soluble in solvents commonly used in H-NMR
and 13C-NMR spectrometer.
Based on FT-IR spectrometer, it was gained
OH group absorbance at 3426 cm-1. Absorbance of
C=C aromatic appeared at 1512 and 1605 cm-1.
Absorbance of C-O-C group arised at 1142 cm-1.
The data was supported by data from XRD and SEM
to compare hybrid with calixarene and chitosan
constituent. Based on X-ray diffraction pattern in Fig. 3,
it was found information that calix[4]resorcinaren-
chitosan hybrid and chitosan have a semi-crystalline
form. Tetrakis-chloromethyl-C-4-allyloxy-3methoxycalix
[4]resorcinarene has amorphousform.FromFig.3also
show that calix[4]resorcinarene-chitosan decreased
crystallinity caused by destruction of hydrogen
bonds from amine groups of chitosan. Kumirska
et al., reported that destruction of hydrogen
bonds in chitosan will decrease crystallinity
21
of compounds
.
Synthesis of calix[4]resorcinarene-
chitosan hybrid was conducted by reactingtetrakis-
chloromethyl-C-4-allyloxy-3-methoxyphenylcalix
[4]resorcinarene with chitosan using N,N-dimethyl
formamide solvent. The use of chitosan excessive
number of moles was expected that all Cl atoms of
chloromethyl group substituted by an amine
group of chitosan. Synthesis reaction of
calix[4]resorcinarene-chitosan was predicted
through SN1 mechanism. It is due to carbocation
formed in this reaction will be stabilized by
conjugation of electrons from the aromatic ring and
solvation by the N, N-dimethylformamide solvent
which is polar.Moreover, NH2 nucleophile of chitosan
was steric condition. Initially, C-4-allyloxy-3-methoxyphenyl
calix[4]resorcinarene releases Cl- ionformingcarbocation
Fig. 3. X-ray diffraction pattern (a) chitosan, (b)
calix[4]resorcinarene-chitosan hybrid, and (c)
tetrakis-chloromethyl-C-4-allyloxy-3-
methoxyphenylcalix[4]resorcinarene

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SEM analysis was carried out to see the
surface profile difference of calix[4]resorcinarene-
chitosan with chitosan and calixarene constituent.
Result of SEM analysis was presented in Fig. 4.
From this Fig, it can be seen that there was a
difference between surface profile of calix[4]
resorcinarene-chitosan with chitosan and calixarene
constituent. In addition, result of SEM image
analysis shows that tetrakis-chloromethyl-C-4-
allyloxy-3-methoxyphenylcalix[4]resorcinarene has
been distributed or bound to chitosan. Based on
results of FT-IR spectrometer, XRD and SEM
analysis were predicted that calix[4]resorcinarene-
chitosan hybrid have been formed. Mechanism of
hybrid formation was presented in Figure. 5.
(a)
(b)
(c)
Fig. 4. SEM image of (a) tetrakis-chloromethyl-C-4-
allyloxy-3-methoxy phenylcalix[4]resorcinarene,
(b) chitosan, and (c) calix[4] resorcinarene
chitosan hybrid
Fig. 5. Reaction mechanism of calix[4]resorcinarene-chitosan hybrid formation
Product was obtained as dark red solid with
m.p. > 300 °C in 78% yield.
CONCLUSIONS
Calix[4]resorcinarene-chitosan hybrid
(4) has been synthesized through vanillin allylation,
aromatic electrophilic substitution followed by
cyclization, chloromethylation, and unimolecular
nucleophilic substitution as well as characterized
by FT-IR, 1H-NMR, 13C-NMR, XRD and SEM.
ACKNOWLEDGEMENT
The authors would like to thank the
Directorate of Research and Community Service,
Directorate General for Research and Development,
Ministry of Research, Technology and Higher
Education which has provided funds of this research.

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