AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE

Journal of Scientific & Industrial Research 745

Vol. 68, September 2009, pp. 745-768

Design and synthesis of calixarene

Y K Agrawal* J P Pancholi and J M Vyas
Institute of Research and Development, Gujarat Forensic Sciences University, Sector 18A, Gandhinagar 382 007, India

Received 06 October 2008; revised 01 June 2009; accepted 16 June 2009

Calixarenes are versatile macromolecules in the field of supramolecules because of its synthetic feasibility and extensive
analytical applications. This paper reviews synthesis of calixarenes and related derivatives containing heterocycles, polymers,
crown-ethers, and fullerenes. Various analytical applications of calixarenes are discussed.

Keywords: Calixarenes, Crown-ethers, Fullerenes, Polymers

Introduction upper rim substitution of calixarene is carried out by de-t-

Calixarene is a macrocycle or cyclic oligomer based
on a hydroxyl alkylation product of phenols and
aldehydes1. Calixarenes have hydrophobic cavities that
can hold smaller molecules or ions and belong to the
class of cavitands known as host-guest chemistry. In
1940s, Zinke & Ziegler2 discovered base-induced
reaction of p-alkylphenols with formaldehyde, which
yields cyclic oligomers. Then, synthesis of cyclic
oligomers was reported3. Calixarenes can be used as
ion sensitive electrodes or sensors4, optical sensors5,
chiral recognition devices for solid phase extraction,
as a stationary phase and modifiers6. Several books7-
12
and reviews13-17 covered synthesis, properties and
applications of calixarenes. Some studies18-20 reported
structures and properties of calixarene. This review
presents five types of calixarenes.
I. Modified Calixarenes
There are two places (phenolic hydroxyl groups
and p-positions) for modification of calixarenes.
Methylene bridges may be substituted with aromatic
system of phenolic units as a whole or may lead to
replacement of OH-function by other groups. Functional
groups introduced in a first step may be further modified
by subsequent reactions including migration. Usually
*Author for correspondence
E-mail: drykagrawal@yahoo.com
butylation of p-tert-butyl group followed by subsequent
reaction. Substitution of hydroxamic acid group21-24 and
bromination25 is reported. Similarly, p-bromination of
calix[4]arenemethylether26 and bromination of tetra-
methoxycalix[4]arene is also reported 27 . Ipso-
bromination28 has been carried out under a variety of
reaction parameters. Optimized conditions give p-
bromocalixarenes and methylene bridge brominated
calix[n]arene directly28. Single step, one-pot procedure
is also given (Scheme 1) for conversion of p-tert-
butylcalix[n]arenes (Table 1) to their p-acyl derivatives;
thus (2) and (3) has been prepared29. Ipso-substitution is
also possible with more than one substitution (Table 2)30.
Calixarenes having larger cavity size like calix[8]arenes
can also be ipso substituted31.
Calixarenes of varying cavity size can form variety
of host-guest type of inclusion complexes similar to
cyclodextrins. However, calixarene host molecules have
a unique composition that include benzene groups, which
provide À-À interaction and hydroxyl groups for hydrogen
bonding, which is generally water insoluble. Shinkai et al
synthesized water-soluble calixarenes having sulfonate
groups32. Calixarene cavity is capable for molecular
recognition in solution, and can be applid in remediation
of contaminated groundwater and industrial effluents.
Intercalation of water-soluble p-sulfonated calix[4]arene
(CS 4 ) in interlayer of Mg-Al and Zn-Al lactate
dehydrogenase (LDHS) (M2+/Al = 3) by co-precipitation
method33 showed adsorption ability for benzyl alcohol
(BA) and p-nitrophenol (NP) in aqueous solutions, which
746 J SCI IND RES VOL 68 SEPTEMBER 2009

Table 1—Substitutions for p-acyl derivatives prepared from p-t-butylcalixarene

R1 R2 R3 R4 (3) R4 (4)

OH H CO-C 6H5 CO-C 6H5 CO-C 6H5

OH t –Bu CO-C(CH3 )3 CO-C(CH3 )3 CO-C(CH3) 3
OMe t –Bu CO-CH3 t-Bu CO-4-NO 2C6 H4
CO-CH3CH2 t-Bu

Table 2—ipso-substitution group for calix[4]arene are also larger in Zn-Al/CS4/LDH than in Mg-Al/CS4/
LDH because of effective use of parallel arranged cavity
Compound R1 R2 R3 R4 only in Zn-Al/CS4/LDH. CS4/LDHs have possibility as
new organic-inorganic hybrid adsorbents.
1 H H H H
Makha & Rasston 34 synthesized water soluble
2 H H H Me
calixarenes using p-phenyl calix[n]arene and sulfonate
3 H COMe H Me
derivatives (Scheme 2), which have exciting possibilities
4 H H H COMe
as a phase transfer catalyst in transport processes. To
5 Me COMe H H
increase size of a hydrophobic cavity, calix[n]arenas
6 Me H H COMe
(Scheme 3) consist of different bulky groups. Functional
7 Me H H CoMe
groups present in adamantine fragment (9) and (10)

SO3H

R1 H2CO H2SO4
OR3 OH n=4,5,6,8
KOH ClSO3H
AlCl3
n RCOCl
n n
n
OH n OH
OH
R2 (6)
n= 4, 8, 6 R4 R4 (4) (5)
(1)
(2) (3)
Scheme 2
Scheme 1

R R

OH
CF3COOH
CH3
+
R
CH3 n CH3
OH
+ n CH3
CH3
CH3 n-1
OH OH
OH

(7) (8) (9) (10)

Scheme 3
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 747

R 1CH2BR

K2CO3, Na2CO3,CH3CN O OH OH O

R1 (12) R1

OH OH OH HO R 2CH2BR

Na2CO3 CH3CN

OH OH OH O
R1= p-MeC6H 4 R2= m-MeC6H 4
R2

(11) (13)

Scheme 4

NH 2
NO 2

SnCl2, 2H 2O
CH 2Cl2, r.t., 3h
EtOH, reflux
HNO 3 HOAc
O O O O
O O O O O O O O
R
R R R R R
R R R R R
R
(16)
(14) (15)
NO 2 N O2
NO 2 NO 2

CH 2Cl 2, r.t., 3h
+
HNO 3 HOAc O O O O
O O O O
R
R R R R
R R R
(18)
R=CH2CH 2CH3 (17)

R=CH2(CH2) 8CH3

SnCl2, 2H 2O EtOH, reflux SnCl2, 2H 2O EtOH, re flux

NH 2 NH 2 NH 2 NH 2

O O O O O O O
O
R R
R R R R R
R
(19)
(20)

Scheme 5
748 J SCI IND RES VOL 68 SEPTEMBER 2009
K 2C O 3
B r(C H 2 ) 3 B r
OH OH OH HO
(2 1)
Scheme 6
should provide possibility for further modification and
conformational organization of molecule35-37. Self-
assembly of tetradentate ligand 5,5-bipyrimidine with
c-methyl calix[4]resorcinarene is reported 38,39 . It
modulates volume and periphery of cavity in a predictable
fashion by changing size, flexibility and composition of
spacer between pyrimidyl units.
Introduction of bulky substituents as m-methyl
benzyl groups incorporate and remove protective groups
in synthesis of calixarenes with three different
substituents in molecule. In presence of sodium and
potassium carbonates, reaction of calixarene with p and
m-methyl benzyl bromides gives compounds (12) and
(13) that affect composition, current conformations, and
yield of products (Scheme 4) 40-43. Calix[4]arene
nucleoside base (19) and (20) receptors provide ion
pairing complex 44 (Scheme 5). Novel bis (8-
hydroxyquinoline)calix[4]arene (23) is a versatile building
block of supramolecular chemistry (Scheme 6). This
ligand is specially designed for photo physical applications
in metalo-supramolecular chemistry45-47. Liu et al48
synthesized bis(azo-phenol)calix[4]arenes (27), which
O OH OH O
(2 2 )
Br
Br
OH
K 2C O 3
C H 3C N
N
O OH OH O
O
O
N N
(2 3)
possesses multiple chromogenic donors (Scheme 7) and
is useful for alkali metal ions Na+, K+, Rb+ and Cs+. Bis
and tetrakistetrazole derivatives of calix[4]arene (32)
have ability to bind cations of transition metals
(Scheme 8). Result of structural investigation of
macrocycle and its complex with palladium dichloride is
also reported49-51.
Separation of amino acids is a key technology for
downstream processing in bio-industrial complex. Tabaksi
et al52 carried out a reaction of p-tert-butylcalix[4]arene
and p-h-calix[4]arene with (S)-(-)-1-phenylethylamine
(37) (Scheme 9), which forms useful host molecule for
quantitative extraction of ±-amino acid methyl esters and
±-phenylethylamines in a liquid–liquid extraction system.
Specified applications of calixarenes can be possible by
substitution of selected groups either on upper or lower
rim. Several picoline binding groups at upper or lower
rim of calix[n]arenes (39) (n = 4, 6, 8) have been
synthesized for extraction of actinides (Scheme 10)53.
Fluorescence chemosensors, calix[4]arene containing
tetraamide derivative (43) (Scheme 11)54, exhibit high
selectivity for H2PO4– over a wide range of anions;
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 749

t- t-B u t-B u t-B u t- t -B u t-B u t- B u

Bu Bu
t- t -B u t-B u t-B u
Bu C lC H 2C N L IA l H 4
an h y d ro u s ac eto n e O a nh y d ro u s T H F O
O OH OH O OH OH

OH OH OH HO NC H 2N
CN N H2
(2 4) (2 5 )
(2 6 )

OH C OH

N
a n hy d ro u s T H F
N

t- t -B u t-B u t-B u
Bu

O OH OH O

N N
CH
OH CH
HO

N
N
N
N

(2 7 )

Scheme 7— (THF, Tetrahydrofuran)

selectivity for H2PO4– is more than 2700-fold higher than
for F–.
Fluorescence-labeled calix[4]arene substituted with
peptides serve as a useful platform to produce artificial
receptors using peptides and various types of other
building blocks55.Upper rim, c-linked and cbz-protected
cone calix[4]arene bis-l-alanyl derivative have been
synthesized to prepare self-assembled nanotubes in solid
state through a two-dimensional network of hydrogen
bonds between amide chains of adjacent conformers56.
A new type of inherently chiral calix[5]arene has been
obtained from significant inherently chiral calix[5]arene
derivatives using (R)-BINOL and their racemates
(Scheme 12)57-59. Calix[8]quinone derivative (48) has
also been synthesized (Scheme 13) through a protection-
deprotection procedure60.
Two polyether moieties, two urea sites, and two
bipyridine units containing novel multi-responsive host
(54) has been synthesized and its ion binding sites are
arranged on calix[4]arene skeleton61. Compound (54)
(Scheme 14) recognizes Na+ and Ag+ simultaneously as
well as quantitatively and captures an anionic guest.
Ability of (54) to recognize anions including CF3SO3-
and BF4- remarkably increases using Na+ and Ag+. Yang
et al62 and Tilki et al63 synthesized oxo-calixarenes (57),
(58) (Scheme 15), which have unique applications in
molecular recognition studies and for enhancement of Ag+
and Hg+ ion selectivity by minimizing side arm effect.
However, extraction results of bisazocalix[4]arenes show
no selectivity toward heavy metal ions but effect of bis-
structure on color and selectivity of bisazocalix[4]arenes
have been discussed; dyeing behavior, performance on
solvent and framework effect are assessed63-65.
II. Bridged Calixarenes
Remarkable regio-selectivities have been observed
in bridging reactions of calixarenes. If a bridge contains
functional groups like S, N, O, then it is easy to get
750 J SCI IND RES VOL 68 SEPTEMBER 2009

Ar O O Ar Cl Ar Cl
Ar
NH2 HN
H2 N HN NH NH
ArC(O)Cl PCl 5

OH O O HO HO OH O O HO
OH O O
Pr Pr Pr Pr Pr Pr
(28) (29) (30)

Me2 Sn3 SnCl4

N N
N N N Ar Ar
N
N N
Ar N N Ar N N

OH O O HO OH O HO
O
Pr Pr Pr Pr
Ar=p-Cl-C6H 4
(32) (31)

Scheme 8

C2H5 O O OC2H5 OC H
2 5
HO HO OH OH
O O O
OH OH OH HO O
ethylbromoacetate O O O O O O
O O
K 2CO3/Acetone LiAlH4 /THF

R R
R R R
R R
R R R
(33) R R
R=H (34)
(35)
R=t-Butyl

TsCl Pyridine

CH3 TsO TsO OTs OTs

H CH3 H
HN H NH H CH3
NHCH3 NH
THF O
O O O
(S)-(-)-1-phenylethylamine
O O O O

R R
R R
R R (36)
R R
(37)

Scheme 9— (THF, Tetrahydrofuran)

 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 751

R
R

NaH, dry DMF

O
*
n
OH Br m-3 N
O
(38) O
R= H or OBn O (39) m-3 N
m= 4, 6, 8
R= H, OBn, or t -Bu O

Scheme 10— (DMF, Dimethyl formamide)

t-Bu
t-Bu
t-Bu t-Bu
t-Bu t-Bu
t-Bu
t-Bu O
H2 N NHBoc
O OH OH
O
OH OH
O Et 3N\ DCM O
NH
O O HN
Cl
O Cl
NHR RHN
(40) (41)

t-Bu DCM TFA

t-Bu
t-Bu
t-Bu
t-Bu
O t-Bu
t-Bu
OH OH t-Bu
O
O
O NH O
HN OH OH
SO2 Cl SO2Cl O
O
NH Et3 N\ DCM NH
HN O HN
SO 2 O2S
NH3 + H 3+N

(43) (42)

Scheme 11— (DCM, Dichloromethane; TFA, Trifluoroacetic acid)

752 J SCI IND RES VOL 68 SEPTEMBER 2009

i
ii
CH2
CH3 CH2
CH2
O CH3
HO O O CH3
OH O O O
O HO O O HO O O
O OEt OH O OH O
O
O O OH O O OH O
O O
(50)
(49)

(i) Me4N+ OH- THF, 8h (ii) (R)- BINOL,DCC,DMAP, rt, 10h

(51)

Scheme 12— (DCC, Dicyclohexyl carbodimide; DMAP, 4-

Dimethylaminopyridine)

Br Br
OH
OH
HO HO MeI, reflux, 48h
OH
OH
ACETONE,CS2 CO 3
O O
OH HO
DMF,CS2 CO3, 40h

HO HO
OH OH
OH
OH

OMe
MeO
OMe

(44) (45)
O O

MeO
OMe
OMe

OMe (46)
MeO
OMe OMe
MeO H2/Pd, CH2Cl2,
OMe Ti(CF3COO)3
OH HO
CF3 COOH/EtOH, r.t. 12h r.t. 1h
O O O
O
MeO
OMe
OMe
OMe MeO
OMe

(47)

(48)

Scheme 13— (DMF, Dimethyl formamide; MeI, Methyl iodide)

 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 753

O O O O
N N NH2
N3 OTs O
MeO2C O CO2Me
PPh3, CO2,Toluene/DMF, rt
K2CO3, CH3CN,reflux
OR O O RO O O
OH OH OH HO
O O NH HN
(52) O
O
O O NH HN

N3 N N N N
N3
(54)
R=H
R=CH2 CO2Me

(53)

Scheme 14

NO 2 O
O O O
NO 2
F F Pyridine ( highly dilute)
+ R3 NO 2 NO 2 R3
NO 2
+
CuI , K 2C O3 , reflux 1day NO 2
OH OH O O O
O

(55) (56) (57)

(58)

Scheme 15

R R
R
OH
R
HO
OH

HO N N OH O O
HO N N
OH R O
O R HO
OH
HO OH OH HO
OH
R=t-Bu
R
R=H
R
R R

(59) (60)

sterically shielded reagents. Size of macrocycles affects [1+1] condensation products (60). Resulting heterocycles
selectivity towards metal ions. Bigger cavity size are selective ligand for copper (I) ions and also show
calixarenes are more selective to heavy metal ions than remarkable synthetic selectivity66-68. These compounds
other calixarenes. Calix[5]arene and calix[8]arene react due to bulky group inside cavity could not be much
with bis(bromomethyl)-substituted heterocyclic such as elongated but elongation of calix[8]arenes could be
1,10-phenanthroline to give [2+1] dicalixarenes (59) and possible by bridging such calixarenes with ethers,
754 J SCI IND RES VOL 68 SEPTEMBER 2009

O
O OH
OH

CS 2C O 3 OH
OH HO
+
O
BrCH 2Cl

HO OH
OH OH
OH
o
DMF 80 C

(61)

62)

OH
HO
OH

OH HO

OH HO
OH

6 3)

D MF 80 oC
O
O O
OH
O
Cs 2CO 3
+ +
O
O O O
O O
BrCH 2 Cl
O

OH

(64) (65) (66)

Scheme: 16

2PCl3 6-

OH
HO O
OH Cl O
Cl
O
PCl5
OH HO
P+ P P+ O
CH2Cl2 O

HO Cl Cl
OH Cl
OH O O
O

(67)
(68)

H2 O

O
OH O
O O O O
O OH O O O
O O
OEt
P P P O
P P P O P P P O O
O
CH3
CH2 (OEt)3
O
+ O O O
OH O EtO
O O O
O CH3 O O
O O
O O

(71)
(69) (70)

Scheme:17
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 755

R
Br R
Br Se Se O
Se O
i Se OH R
OH O OH
O OH R
OH + OH
O O R
OH R OH
O
Se Se
R O
R R R
R
R R
(72) R R R
(74)
(73)
R=t-Bu
R=H

i= Disodium salts of 1, 3 propanediol, ethanol ,THF, reflux 6h

Scheme:18

t-Bu t-Bu

NH
N N O
O
O HO HO t-Bu
OH HO
O t-Bu
CH3 HO t-Bu
O t-Bu OH
+ O
t-Bu
t-Bu O N O
t-Bu t-Bu N
t-Bu
t-Bu
(75)
(76)

=
N

Scheme:19

MeO
R MeO
OMe
R
R OMe
OMe
R O R
(MeO)2CH2, HOAc O OMe
or O O OMe
O OMe HCHO +
reflux MeO
(79) O OMe MeO
O OMe

MeO (80) R
(81) R
MeO
R=Ph R=Ph
R= 4-Br-C6H4 R= 4-Br-C6H4
R=CMe3 R=CMe3

Scheme:20
756 J SCI IND RES VOL 68 SEPTEMBER 2009

MeO
R MeO
OMe
R
R OMe
OMe
R O R
(MeO)2CH2, HOAc O OMe
or O O OMe
O OMe HCHO +
reflux MeO
(79) O OMe MeO
O OMe

MeO (80) R
(81) R
MeO
R=Ph R=Ph
R= 4-Br-C6H4 R= 4-Br-C6H4
R=CMe3 R=CMe3

Scheme 21

R
R
MeO
MeO MeO
MeO
OMe O
O
R
MeO OMe
MeO OMe
K10 Clay +
O
O O
MeO O CH2OH
O
R
R R
(82) R
OMe
OMe
MeO (83)
MeO
(84)

I Ph

II CMe 3

Scheme 22

t-Bu t-Bu
t-Bu
t-Bu

O O O
N
H O
Me
Methansulfonic acid
4 H HN
O NH MeH N
EtOH/CH2 Cl2
N
Me
O Me Me
(85) (86)

Scheme 23
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 757

S S

X X
S
SnBu 3

S S
S

Pd 2 dba3 , P(t-Bu)3 , NMP

HO O
OH KI for X=Br and L ICl for X=I
O R

R (87)
HO O
R=CH 3 , X =I OH R
O
R (88)
R= n-C 3 H 7 , X=B r

R R O
HO
O OH
R O
HO
O OH

S
S

S
S
S S

S n
S

S S
S S
CH 3
(89) R=CH 3
S S
(90) R= n-C 3 H 7 S S

HO O
OH HO O
O OH
R O
R
R
R

Scheme 24— (NMP, N-methylpyrolidine)

phosphoryls and aza groups. Depending on length and
nature of bridges, they possess better encapsulating
properties toward alkali metal ions, rare earths and heavy
metal ions. Such calixarenes have been prepared from
p-tert-butylcalix[8]arenes by using two step alkylation
procedure69-74.
Mono to tetra-dioxamethylene bridged calix[8]arene
derivatives75 [(64), (65), (66)] have been synthesized
(Scheme 16). p-tert-Butylcalix[8]arene (67) with 5
equivalent of PCl5 in CH2Cl2 gives compound (68) whose
subsequent hydrolysis gives compound (69) (Scheme
17)76. Series of tweezer-like calix[4]arene derivatives
containing S, N and O atoms exhibit a good Ag +
selectivity against interfering ions. Zeng et al synthesized
two calix[4](diseleno)crown ethers (74) from compound
(72) and (73) (Scheme 18)77-79. Selenium schiff base81
and hydroxamic acid80 containing bis-calixarenes are
versatile compounds in calixarene chemistry, and show
silver-ion selectivity by two-phase extraction and
transportation. Bis-calix[4]arene (76) forms silver-
758 J SCI IND RES VOL 68 SEPTEMBER 2009
O O Styrene,DVB,Bz 2O,82 0C,24h
O O
R3
R1 R4
R2 a.R1=R2=R3=R4=H
(91) b.R1=R2=R3=Propyl, R4=H
c.R1=R2=R3=Propyl, R4=CH2C6H4CH=CH2
Scheme 25
selective PVC membrane due to electrostatic interaction
between metal ion and aza crown cavity composed of
oxygen and nitrogen atoms as donors (Scheme 19)81.
III. Hetero Calixarenes
Heterocalixarenes or calixhetarenes are built from
heterocyclic moieties. Another class is heteracalixarenes
(aza, oxa and thia-calixarenes), in which bridges between
phenol units contain heteroatoms (N, O or S). This review
reports hetero-calixarenes built from benzofuran moieties
and from other heterocycles. Formation of cone
conformers of calix[3]indoles has been discussed82. An
isomeric series has also been obtained with combination
of an indole with bis (hydroxymethyl)-2, 2’-di-
indolylmethane (Scheme 20)83.
3-Substituted 4, 6-dimethoxyindoles possess two
reactive sites for electrophilic substitution, and can react
with aryl aldehydes in presence of phosphoryl chloride
to give calix[3]indoles (77). As a part of expanding range
of calixarenes from outher activated heterocycles, calix
[3]benzofurans have been prepared from 3-substituted
4,6-dimethoxybenzofurans(79) (Scheme 21) and 2-7-
hydroxymethylbenzofurans (82) (Scheme 22) with
formaldehyde and arly- aldeydes in prence of acetic acid
and phosphoryl chloride84-85
Like indoles and furans, pyridines and pyrroles can
play a major role in heterocyclic calixarene chemistry.
Calix(4)pyrroles are effective and selective receptors
for anions and neutral guest species and find applications
as coordination complexes, catalytic materials, nano-
sponges, molecular machines, nano entities and semi
O
O O O
Pr Pr
Pr
t-Bu
m n z
(92)
conducting materials86. Bipyridyl group containing
calixarenes are useful for binding various metal ions.
Bipyridyl containing calixarenes87 are extensively used
to form complexes with various metal ions88-93. Two new
meso-indanyl-substituted calix[4]pyrrole receptors have
been synthesized94 using MCM-41. For expansion of
calixarenes, pseudo-dimer (86) of calix[4]arene and
calix[4]pyrroles (Scheme 23) have been synthesized as
a good anion receptors95.
IV. Polymeric Calixarenes
Polymer supported calixarenes have variety of
applications. Polyethyleneimine supported calix[6]arenes
can extract uranium from seawater96, polyacryloyl
chloride and chloromethyl polystyrene supported
calix[4]arenes have been used to extract iron97 and
lead98. Methacrylate99 acrylonitrile and styrene100 derived
calix[4]arenes have been polymerized to make calixarene
oligomers. Proton-doped segmented polymers, Poly(89)
and Poly(90), are based upon a calix[4]arene scaffold
and increase conductivity of calixarene polymers(Scheme
24)101. These compounds are attractive candidates for
design of sensing and actuating materials102.
Utility of calix[4]arenes for phase transfer
reactions, adsorbents or for fabricating membranes and
sensors, copolymer and homopolymer containing
calix[4]arene moieties on polymer backbone were
successfully synthesized from monomer and styrene103.
Both polymers show good selectivity towards Hg+ ion.
In a related study104, radical polymerization of styrene
has been carried out in presence of a novel calix[4]arene
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 759

OH OH HO OR2 OH OH R2O H H2
OH C C
OH

NaOH
+ HCHO
OH O OH HO

(93) (94) (95)

(96)

Scheme 26

a to c
Merrifield resin
a= NaH, toluene, reflux
O O O O O O O O
R2 b= NaH, THF, reflux
R1 R1 R1 R1 R1 R2 P
c= Cs2CO3, DMF, 1000C R1
(97) (98)

Scheme 27— (THF, Tetrahydrofuran; DMF, Dimethyl formamide)

Table 3—Substitution groups to prepare polymerizable Table 4—Substitution groups for merrifield
calixarene derivatives resin containing calixarene
R1 R2
95a CH2 CN CH2CN R1 R2 R1 R2
96a CH2 CN CH2CN H CH 2 H H
95b H CNC6 H4 NH 2 CH 2CO2 Et CH 2 Propyl H
96b CNC6 H5 NH2 CNC6 H4 NH 2 CH 2 CO2 H CH 2 CH2CO 2Et CH2 CO2Et
95c H CNC6 H4 NH 2 CH2 CO2 Na CH 2 CH2 CO2 H CH2 CO 2H
96c CNC6 H5 NH2 CNC6 H4 NH 2
CH 2 CO2 H C(O)OCH2 Propyl H

derivative bearing two distal benzyl-vinyl groups in lower
rim. Such terpolymer (92) exhibits good thermal stability
and good yield (Scheme 25)105. Nitrile functionality at
lower rim of calix[4]arenas, synthesized via nucleophilic
substitution reactions, have an effective binding character
for particular set of cations and can be useful for
laboratory, clinical, environmental, and industrial process
analysis106.
A novel benzyl-terminated dendron based sol-gel
coating has been developed for capillary micro extraction
(CME). Characteristic branched design of dendron
makes them structurally superior extraction media
compared to traditional linear polymeric counterparts107.
Other higher molecular weight moieties that are also
useful for many specialized applications like new
polymer-supported calix[6]arene hydroxamic acid have
been synthesized 108. Resin was used for
chromatographic separation of U (VI), Th (IV) and Ce
(IV). Versatile starting materials for synthesis of
polymerizable calixarene derivatives (95) have been
760 J SCI IND RES VOL 68 SEPTEMBER 2009

OH OH OH OH
OH OH
i ii iii

t-Bu 4 4 3N
(100) N 3S
(99) S
(101) (102)

(i). AlCl 3, Toluene,Phenol iv

(ii).NH(CH3)2, THF,CH3COOH,HCHO
H H2
(iii).N(C2H5) 3,DMSO, CH3I, 1-Propanethiol C C
n
(iv). DMF,Merrifield's resin,NaI, NaH

OH O

3S
S
(103)

Scheme 28 — (DMSO, Dimethylsulfoxide; DMF, Dimethyl formamide)

OMe OMe

PEG
GEP
Cl Cl HN
O O S O
O S O NaH Et3N O S O
O S O
Meo-PEG-OH Meo-PEG-NH2

-HCl -HCl
4
O 4 O
104a. R=OEt 4 O
O 106c. R=OEt 4
CH2 CH2 106d.R=NEt2
104b.R=NEt 2 CH2
CH2 O
O O
O R
R R
R
(104) (105) (106) (107)

Scheme 29— (PEG, Polyethyleneglycol)

synthesized for extraction of cations as well as for anions
(Table 3, Scheme 26). Depending on oxidative stability,
it is observed that ionophore (95a) is selective for Hg2+,
whereas ionophores [(95b) and (95c)] are selective for
both Cd2+ and Hg2+109. Immobilized calix[4]arene (98)
containing merrifield resin is a very useful polymeric
scaffold for synthesis of various lower rim derivatives
(Table 4, Scheme 27) demonstrated with preparation of
triacid110.
Thio-ether functionalized calix[4]arene based
polymeric resin compounds (102), which are versatile
starting materials for synthesis of polymerizable
calixarene derivatives111, are suitable for extraction of
toxic heavy metal cations as well as for dichromate anions
(Scheme 28). In case of more than one functionalization
of polymeric groups on calix[4]arenes (107), both
ligating and methoxy poly(ethylene glycol) groups are
introduced for formation of sulfonyl ester groups on wide
rim (Scheme 29), schiff base derivatives on narrow rim,
and thioether groups on both wide and narrow rims112,
which are non-toxic, non-flammable, biphasic and
hydrophilic. It can also be potentially useful for
simultaneous extraction of both metals and organics that
are commonly present in soil and water. Cyclo-
polymerizability of calix[4]arene monomer is also a
favorable interaction that occurs between two vinyl benzyl
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 761

OH OH O
O
OH OH O
O BPO

THF, heat

n
Poly 1

(108) (109)

Scheme 30— (BPO, Benzoyl peroxide)

OH O OH
Ts(OCH2CH2)2OH O
K2CO3, MeCN O OH
OHC OH OHC O
(111)
(110)
O OTs
O
TsCl, NaOH O OTs
THF, H2O OHC O
(112)

O O
O O
O O
OH OH Cs 2CO3, MeCN
O O
O O O O O
O O O

(113) O O

CHO

(114)

Scheme 31
762 J SCI IND RES VOL 68 SEPTEMBER 2009

O
Cl
NH

O O O
HO O
OH O O
O O O
OH OH NH 2 NH NH 2 NH NH O
O O
O O NH
O K 2CO 3, NaI,CH 3 CN, N 2 NH
O O O Toluene/Ethanol(1), 2N
NH NH NH
CH 3 CH3

(115) NH
(116)

(117)
O
Cl
NH

O O
O
OH OH O
O O
O OH OH
NH NH
K 2 CO3 , NaI,CH3 CN, N2 O
CH 3 CH 3
(118)

(119)

Scheme 32

O
n

OH OH OH HO O O O
TsO n OTs

NaH, DMF, Heat O O OH HO

n= 1, 2, 3

(120)

(121)

Scheme 33— (DMF, Dimethyl formamide)

units due to constrained conformation generated by synthesized dendrimers from an excellent ionophore 1, 3
calixarene moiety, which in turn drive intermolecular calix[4]crown that gives multi metal recognition central
cyclization. Poly1 (109) represents a new type of highly dendrimer (Scheme 31). Moreover, 2 nd generation
organized macromolecule useful for widespread dendrimers have also been synthesized from 1,3
applications associated with single-handed helical calix[4]benzocrown-6 as repeat units 115 . 1,3-
polymers113 (Scheme 30). Calix[4]arene bis-crown-6 containing six oxygen donor
atoms are also potential extractant for selective removal
V. Crown And Fullerene Bearing Calixarenes of cesium cation from radioactive liquid nuclear waste116.
Calix[n]crowns are macrocycles composed of To increase complexation ability and for better analytical
subunits of a calix[n]arene and crown ether joined via applications, one has to substitute calix[n]crown with
phenolic oxygen of calix component. Chen et al114 different hetero or bulky groups. Lee et al117 prepared a
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 763

OH O O HO
OH OH OH HO
n OH O O HO
X O nY
O O
K2CO3, N2, CH3CN O O
O O
OH O O HO

(122)

(124)
123a. n= 0, X=Br, Y=OTs
123b. n= 1, X=OTos, Y=OTs

Scheme 34

O2N O O O O
TsO(CH2CH2O)5Ts
Br
NaH, CH3CN O
K2CO3 , CH3CN O OH OH O O

O O
OH OH OH HO
(127)
(125) (126) O2N NO2
NO2 NO2
H2NNH2.H2O Raney Ni

O O CH2Cl2, Pyridine
O O
O O O O O
O O
O
Cl O
O O Cl O

O O

CH3 HN
NH CH3
O O H2N NH2
n
(129) (128)

Scheme 35
764 J SCI IND RES VOL 68 SEPTEMBER 2009

OC12H 25
OC12H25
CuCN, HMPA BocNH
I I
0
150 C, 3h LiAlH4, THF, 12h
BocNH
Boc 2O, NaOH
C12H25 O
OC12 H25 (131)
(130)

O
NH
TFA CH2 Cl2 , 3h
C12 H25O

OC12H 25

OC12 H25
H3 +N i-Pr2NEt, C6H 5Br, 12h,
Cl O NH

+
N+H 3 O

C12 H25O

(132) (133)

(134)

Scheme 36— (TFA, Trifluoroacetic acid)

CH 3 CHO N
Me
CH 3 i, ii C H3
iii CH 3
C H3
O O O O CH 3
O O O O
O O O
CH 3 CH3 CH 3 CH 3
O
CH 3 CH 3 CH 3 CH3
(135) C H3
(136) CH3 CH 3 CH 3
(137)

i) NBS, acetone, rt, 24 h ; ii) n-Bu-Li, THF, -78°C, 1 h, then DMF, -78°C to rt; iii) C60, N-methylglycine, toluene, 16 h
Scheme —37 (NBS, n-Bromosuccinimide; THF, Tetrahydrofuran; DMF, Dimethyl formamide)

new fluorogenic cone calix[4]triazacrown-5 (117) bearing To perform selective extraction of metals,
two pyrene amide groups and its structural analogues preparation of a series of p-sulfonated 1,2,3,4-
(119) (Scheme 32). Such fluorescent chemosensors are calix[4]arene-biscrowns (121) are reported120 for Cs+/
effective useful tool to analyze and clarify roles of Na+ selectivity (Scheme 33). Kerdpaiboon et al 121
charged chemical species in living system as well as to synthesized three new calix[4]quinines [(123a) 122,
measure amount of metal ions from sources (123b) 123, (124) 124 ] from corresponding double
contaminated118,119. calix[4]arenas and complexation studies were carried
 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE
out with alkali metal ions such as Li+, Na+, K+, and Cs+
(Scheme 34). Substitution of oligomers increases liquid
liquid extraction ability for calix[4]crown-6 monomers
[(128) and (129)] (Scheme 35)125 while aza crown based
two new calix[4]arene ionophores increases
complexation ablility with metal ions126. Apart from
crown ethers, covalent assemblies of fullerene and
calixarenes have also been investigated to study
polymeric nature appeared in solid phase127,128 using
calix[5]arenes (Scheme 36) 129 . Intramolecular
association, self complexation and de-complexation
properties using tetra-o-alkylated cone calix[4]arene
(137) skeleton have also been examined (Scheme
37)130,131.
Conclusions
Calixarenes are easy to synthesize and modify, and
can form polymer, dendritic network particles and liquid
crystalline systems. Development of new catalysts, non-
linear optics and removal of heavy metal ions and/or ura-
nyl ion is on.
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