Synthesis of novel chiral Schiff base and amino alcohol derivatives of calix[4]arene and chiral recognition properties

Article abstract of DOI:10.1016/j.molstruc.2011.10.053

In the present study, the synthesis and liquid phase extraction properties towards some amino acid methylesters and amino alcohols of Schiff base and amino alcohol substituted calix[4]arene are reported. The Schiff base substituted calix[4]arene 5 has bee

Full text of DOI:10.1016/j.molstruc.2011.10.053

Journal of Molecular Structure 1007 (2012) 235–241
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Journal of Molecular Structure
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Synthesis of novel chiral Schiff base and amino alcohol derivatives
of calix[4]arene and chiral recognition properties
⇑
Serkan Erdemir
Selcuk University, Department of Chemistry, 42031 Konya, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
In the present study, the synthesis and liquid phase extraction properties towards some amino acid
methylesters and amino alcohols of Schiff base and amino alcohol substituted calix[4]arene are reported.
The Schiff base substituted calix[4]arene 5 has been synthesized via condensation reaction involving
5,17-diformyl-11,23-di-tert-butyl-25,27-di[3-(4-formylphenoxy)propoxy]-26,28 dihydroxycalix[4]arene
4 and (R)-(ꢀ)-2-phenylglycine methyl ester in CHCl3:MeOH. To give the amino alcohol substituted
calix[4]arene 6, the synthesized chiral compound 5 was reduced by LiAlH4. The new chiral Schiff base
and amino alcohol derivatives of calix[4]arene have been characterized by a combination of FT-IR, 1H
NMR, 13C NMR, FAB-MS and elemental analysis. Also, the extraction behaviors of 5 and 6 towards some
selected amino acid methylesters and amino alcohols have been studied by liquid–liquid extraction.
Ó 2011 Elsevier B.V. All rights reserved.
Received 16 September 2011
Received in revised form 30 October 2011
Accepted 30 October 2011
Available online 11 November 2011
Keywords:
Calix[4]arene
Chiral
Amino acid methylesters
Amino alcohol
Liquid phase extraction
1. Introduction
inherently chiral derivatives [8] in which an asymmetric substitu-
tion of the macrocycle is associated to its intrinsic three-dimen-
Calixarenes, cyclic oligomers of phenolic units linked through
the ortho positions, are a fascinating class of macrocycles. They
are synthetic macrocycles readily available by condensation of p-
tert-butylphenol with formaldehyde under alkaline conditions.
From these starting materials, a large number of sophisticated
compounds have been prepared. To date, various calixarenes that
possess ketone, amine, ester, amide, carboxylic acid or other func-
tional groups have been synthesized for separation, recognition,
discrimination and catalysis. A number of books were published
concerning synthesis, structural features and host–guest interac-
tions [1]. More specifically, the subject of chemical recognition
and separation of ions was addressed in several publications [2].
On the other hand, only few reviews concerning calixarenes for
biochemical recognition are available, e.g. on peptido- and glyco-
conjugates and the role of hydrogen-bonding interactions [3], on
neoglyco conjugates with large rigidified cavities [4] and on syn-
thetic receptors [5]. Among them, chiral recognition, the process
in which an enantiomerically pure host molecule, such as a chiral
calixarene, selectively binds one of the enantiomers, is one of the
most essential reaction processes occurring in living systems [6].
Therefore chiral calixarenes [7] have attracted increasing research
interest because of their potential in enantio discrimination pro-
cesses. They can be obtained either by attaching chiral moieties
at one of the calix rims (upper or lower) [1] or by synthesizing
sional nature. From a practical point of view, the first approach
appears to be preferable because inherent chirality always requires
a difficult resolution on an appropriate scale [9]. Therefore, a large
number of chiral calixarenes have been prepared by using chiral
units, such as single amino acids [10], peptides [11], amino alco-
hols [12], sugars [13], tartaric acid esters [14], binaphthyl [15],
glycidyl [16], menthone [17], and guanidinium groups [18].
Herein we report the synthesis of novel chiral calix[4]arene
platform with Schiff base and amino alcohol derivatives on their
lower and upper rim for quantitative extraction of some amino
acid methylesters and amino alcohols in a liquid–liquid extraction
system.
2. Experimental
2.1. Materials and general methods
Melting points were determined on a Gallenkamp apparatus in
a sealed capillary and are uncorrected. 1H NMR and 13C NMR spec-
tra were recorded on a Varian 400 MHz spectrometer in CDCl3. FT-
IR spectra were recorded on a Perkin Elmer spectrum 100. UV–vis
spectra were obtained on a Shimadzu 160A UV–visible recording
spectrophotometer. FAB-MS spectra were taken on a Varian MAT
312 spectrometer. Elemental analyses were performed on a Leco
CHNS-932 analyzer. Optical rotations were measured on an Atago
AP-100 digital polarimeter. Analytical TLC was performed on pre-
coated silica gel plates (SiO2, Merck PF254), while silica gel 60
⇑
Tel.: +90 3322233858; fax: +90 3322230106.
E-mail address: serdemir82@gmail.com
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2011.10.053

236
S. Erdemir / Journal of Molecular Structure 1007 (2012) 235–241
(Merck, particle size 0.040–0.063 mm, 230–240 mesh) was used
for preparative column chromatography. Generally, solvents were
dried by storing them over molecular sieves (Aldrich; 4 Å, 8–12
mesh). Acetone and CHCl3 were distilled from CaSO4 and CaCl2,
respectively. All aqueous solutions were prepared with deionized
water that had been passed through a Millipore Milli-Q Plus water
purification system.
cially available purity were used in this study:
methylester hydrochloride ( -Phe-OMe), -phenylalanine methyl-
ester hydrochloride ( -Phe-OMe), -alanine methylester hydrochlo-
ride ( -AlaOMe), -alanine methylester hydrochloride ( -AlaOMe),
-tryptophan methylester hydrochloride ( -TrpOMe), -tryptophan
methylester hydrochloride ( -TrpOMe), -phenylglycinol ( Phegly),
-phenylglycinol -Phegly), (R)-(5)-(hydroxymethyl)-2-pyrolidi-
L-phenylalanine
L
D
D
L
L
D
D
L
L
D
D
L
L
D
(L
The following amino acid methylester hydrochlorides and ami-
no alcohols obtained from Aldrich or Merck at the highest commer-
none [(R)-Hyd-Me-Pyr], (S)-(5)-(hydroxymethyl)-2-pyrolidinone
[(S)-Hyd-Me-Pyr] (Figs. 1 and 2).
H
H
H2N
H2N
O
O
.HCl
H3C
.HCl
H3C
O
O
CH3
CH3
D-Alanine methylester hydrochloride
L-Alanine methylester hydrochloride
H2N
H
.HCl
CH3
H2N
H
O
.HCl
CH3
O
O
O
D-Phenylalanine methylester hydrochloride
L-Phenylalanine methylester hydrochloride
H2N
H
H2N
H
O
O
CH3
CH3
O
O
.HCl
.HCl
N
H
N
H
D-Tryptophan methylester hydrochloride
L-Tryptophan methylester ahydrochloride
Fig. 1. The chemical structures of amino acid methylesters used in experiments.
H
H2N
OH
OH
H
NH2
L-Phenylglycinol
D-Phenylglycinol
H
OH
OH
O
H
N
H
O
N
H
(R)-5-(Hydroxymethyl)-2-pyrolidinone (S)-5-(Hydroxymethyl)-2-pyrolidinone
Fig. 2. The chemical structures of amino alcohols used in experiments.

S. Erdemir / Journal of Molecular Structure 1007 (2012) 235–241
237
2.2. Syntheses
2.2.4. Compound 6
To a stirred suspension of compound 5 (0.7 g, 0.46 mmol) in
THF (100 mL) under dry N2 gas was added LiAlH4 (0.172 g,
4.65 mmol) in three steps at room temperature. Then, the reaction
mixture was refluxed for 3 h. The solution was filtrated and the fil-
trate was evaporated under reduce pressure. The residue was dis-
solved in CH2Cl2 (50 mL) and to the solution was added NaOH 1 M.
The organic phase was separated and dried over MgSO4. After
evaporation of the solvent, the crude product was recrystallized
Compounds 1 and 2 were prepared according to the literature
methods [19,20]. Other compounds (3–6) were synthesized by
adapting known synthetic procedures.
2.2.1. Compound 3
To
a mixture of 2 (1 g, 1.12 mmol) and K2CO3 (0.34 g,
2.47 mmol) in acetonitrile (100 mL), p-hydroxybenzaldehyde
(0.30 g, 2.46 mmol) was added and the reaction mixture was stir-
red at reflux for 2.5 days. After cooling, the solvent was removed
under reduced pressure. The remaining solid was taken up CH2Cl2
(100 mL) and washed with 1 M HCl (2 ꢁ 50 mL) and water (50 mL).
The organic layer was dried over MgSO4 and evaporated to give a
white powder. The product was crystallized from CH2Cl2:hexane
(1:3) to obtain pure 3 (85%). mp: 198–201 °C. FT-IR: 1678 cmꢀ1
(C@O). 1H NMR (CDCl3): d 1.00 (s, 18H, C(CH3)3), 1.29 (s, 18H,
C(CH3)3), 2.36 (p, 4H, J = 6.2 Hz, CH2CH2CH2), 3.34 (d, 4H,
J = 13.1 Hz, ArCH2Ar), 4.13 (t, 4H, J = 6.2 Hz, OCH2CH2CH2), 4.24
(d, 4H, J = 13.1 Hz, ArCH2Ar), 4.48 (t, 4H, J = 6.2 Hz, CH2CH2CH2O),
6.86 (s, 4H, ArH), 7.04–7.09 (m, 8H, ArH), 7.61 (s, 2H, ArOH), 7.81
(d, 4H, J = 8.6 Hz, ArH), 9.85 (s, 2H, CHO). FAB-MS m/z: (996.10)
[M+Na]+. Anal. Calcd. for C64H76O8 (973.28): C, 78.98; H, 7.87.
Found: C, 79.01; H, 7.90.
in MeOH:CH2Cl2 (2:1). Yield 65%.%. mp; 126–129 °C. ½a D22
= ꢀ13.3
ꢂ
(c 0.5, CHCl3); FT-IR: 3293 cmꢀ1 (OH). 1H NMR (CDCl3): d 1.02 (br
s, 18H, C(CH3)3), 2.35–2.40 (m, 4H, CH2CH2CH2), 3.28–3.82 (m,
28H, ArCH2Ar + CH2CH2CH2O + CH2OH + NHCH2), 4.18 (m, 4H,
OCH2CH2CH2), 4.23 (m, 4H, ArCH2Ar), 4.38 (m, 4H, CHPh), 6.85–
6.97 (m, 12H, ArH), 7.11–7.13 (m, 4H, ArH), 7.28–7.37 (m, 22H, Ar-
H + ArOH). 13C NMR (CDCl3): d 161.6, 156.7, 149.8, 149.7, 148.5,
148.2, 138.9, 138.8, 138.7, 132.3, 130.6, 129.9, 129.7, 128.8,
128.6, 128.3, 128.1, 127.8, 127.2, 126.4, 126.3, 126.2, 115.0,
114.8, 73.2, 70.6, 69.2, 69.1, 67.8, 67.7, 53.4, 53.1, 45.9, 34.5,
31.5, 30.2. FAB-MS m/z: (1424.63) [M+Na]+. Anal. Calcd. for
C90H104N4O10 (1401.81): C, 77.11; H, 7.48. Found: C, 77.14; H, 7.50.
2.3. Analytical procedure
Picrate extraction experiments were performed following
Pedersen’s procedure [21]. A 10 mL of a 2.0 ꢁ 10ꢀ5 M aqueous pic-
rate (the picrate solutions were prepared as our previous study
[22]) and 10 mL of 1 ꢁ 10ꢀ3 M solution of calixarene 5 or 6 in
CH2Cl2 were vigorously agitated in a stoppered glass tube with a
mechanical shaker for 2 min, then magnetically stirred in a
thermostated water-bath at 25 °C for 1 h, and finally left standing
for an additional 30 min. The concentration of the picrate ion,
which remained in the aqueous phase was then determined spec-
trophotometrically. Blank experiments showed that no picrate
extraction occurred in the absence of calixarene. The percent
extraction (E%) has been calculated as:
2.2.2. Compound 4
Compound 3 (1.0 g, 1.03 mmol) and hexamethylenetetramine
(HMTA, 5.94 g, 42.36 mmol) were taken in trifluoroacetic acid
(TFA, 60 mL). The reaction mixture was refluxed until the starting
material (compound 3) had disappeared (TLC). On completion,
the mixture was quenched with cold water and extracted with
dichloromethane. The organic layer was washed with water and
dried over Na2SO4. Evaporation of the solution gave a white solid
residue, which was crystallized from a mixture of acetone:hexane
(2:3) to give product 4 in 75% yield. mp: 155–158 °C. FT-IR:
1679 cmꢀ1 (CH@O). 1H NMR (CDCl3): d 0.98 (s, 18H, C(CH3)3),
2.42 (p, 4H, J = 6.2 Hz, CH2CH2CH2), 3.47 (d, 4H, J = 13.3 Hz, ArCH2-
Ar), 4.18 (t, 4H, J = 6.2 Hz, OCH2CH2CH2), 4.22 (d, 4H, J = 13.3 Hz,
ArCH2Ar), 4.45 (t, 4H, J = 6.2 Hz, CH2CH2CH2O), 6.86 (s, 4H, ArH),
7.03 (d, 4H, J = 8.6 Hz, ArH), 7.62 (s, 4H, ArH), 7.78 (d, 4H,
J = 8.6 Hz, ArH), 8.62 (s, 2H, ArOH), 9.80 (s, 2H, CHO), 9.82 (s, 2H,
CHO). FAB-MS m/z: (939.91) [M+Na]+. Anal. Calcd. for C58H60O10
(917.09): C, 75.96; H, 6.59. Found: C, 76.01; H, 6.61.
E% ¼ ðA0 ꢀ AÞ=A0 ꢁ 100
ð4Þ
where A0 and A are the initial and final concentrations of the ammo-
nium picrate before and after the extraction, respectively. All mea-
surements were performed in triplicate and an average was taken
as final result.
2.2.3. Compound 5
3. Results and discussion
To a solution of 4 (0.8 g, 0.87 mmol) in CHCl3 (50 mL) was added
a solution of (R)-(ꢀ)-2-phenylglycine methyl ester hydrochloride
and triethylamine (1 mL, excess) in MeOH (10 mL) and refluxed
for 24 h. The reaction mixture was allowed to cool to room temper-
ature, and filtered. Evaporation of the solvent and subsequent puri-
fication of the mixture by recrystallization from CHCl3:MeOH (1:3)
We have interested in the synthesis of novel chiral calix[4]ar-
ene-based ionophores having Schiff base and amino alcohol moie-
ties and also investigated the extraction properties of chiral
calix[4]arene Schiff base 5 and amino alcohol 6 derivatives towards
some selected
a-amino acid methylesters and amino alcohols
afforded pure 5. Yield 78%. mp; 115–119 °C. ½a D22
ꢂ
= ꢀ9.8 (c 0.5,
through the two-phase solvent extraction system. The synthesis
of 1–6 depicted in Scheme 1 have been carried out as follows: After
compounds 1 and 2 have been synthesized according to previous
literature methods [19,20], compound 2 was reacted with p-
hydroxybenzaldehyde in dry acetonitrile in the presence of potas-
sium carbonate at reflux for 2.5 days in order to obtain 3 in 85%
yield. The characterization of compound 3 was made by a combi-
nation of FT-IR, 1H NMR and elemental analysis. The FT-IR spectra
show an aldehyde band at 1678 cmꢀ1, and 1H NMR exhibits singlet
at 9.85 ppm corresponding to the aldehyde protons. To obtain the
tetra aldehyde derivative 4 of calix[4]arene, compound 3 was re-
acted with hexamethylenetetramine (HMTA) in trifluoroacetic acid
(TFA) and it afforded compound 4 in 75% yield. 1H NMR spectra
confirmed the composition of 4 due to observing peaks at 9.80
and 9.82 ppm, which correspond to the aldehyde protons and the
CHCl3); FT-IR: 1686 and 1636 cmꢀ1 (C@N), 1737 cmꢀ1 (C@O). 1H
NMR (CDCl3):
d 0.96–1.02 (m, 18H, C(CH3)3), 2.40 (p, 4H,
J = 5.2 Hz, CH2CH2CH2), 3.41–3.46 (m, 4H, ArCH2Ar), 3.72 (s, 6H,
OCH3), 3.74 (s, 6H, OCH3), 4.14 (m, 4H, OCH2CH2CH2), 4.17–4.23
(m, 4H, ArCH2Ar), 4.45 (m, 4H, CH2CH2CH2O), 5.13 (s, 2H, CHPh),
5.15 (s, 2H, CHPh), 6.85–6.95 (m, 8H, ArH), 7.25–7.37 (m, 12H,
ArH), 7.48–7.50 (m, 8H, ArH), 7.57–7.61 (m, 4H, ArH), 7.71 (d,
4H, J = 8.2 Hz, ArH), 8.16 (s, 2H, CHN), 8.19 (s, 2H, CHN), 8.36 (s,
2H, ArOH). 13C NMR (CDCl3): d 172.1, 171.9, 163.8, 163.2, 161.5,
156.5, 149.7, 149.6, 148.4, 148.2, 138.8, 138.7, 138.6, 132.2,
130.6, 129.8, 129.7, 128.8, 128.7, 128.2, 128.0, 127.8, 127.0,
126.3, 126.2, 126.1, 115.0, 114.7, 73.0, 64.8, 52.7, 52.6, 52.5, 45.8,
34.4, 31.4, 30.1. FAB-MS m/z: (1528.61) [M+Na]+. Anal. Calcd. for
C94H96N4O14 (1505.79): C, 74.98; H, 6.43. Found: C, 75.01; H, 6.46.

238
S. Erdemir / Journal of Molecular Structure 1007 (2012) 235–241
CHO
O
CHO
O
Br
Br
OH OH
HO
OH
OH OH
O
O
i
OH OH
O
O
1
2
3
ii
OH
HO
HN
NH
H2C
H
H
CHO
O
CHO
CH2
O
O
O
OHOH
O
O
COOCH3
N
OH OH
O
H3COOC
N
O
H
H
HC
CH
CH2
H
H2C
HN
NH
OHC
CHO
H
HO
OH
O
O
4
iii
iv
OHOH
O
O
6
CH
H
HC
N
N
H
H3CO OC
COOCH3
5
Scheme 1. Schematic representation of synthesis of chiral calix[4]arene derivatives 5 and 6. Reagents and conditions: (i) p-hydroxybenzaldehyde, K2CO3, acetonitrile, 85%;
(ii) HMTA, TFA, reflux, 75%; (iii) (R)-(ꢀ)-2-phenylglycine methyl ester hydrochloride, methanol: toluene, reflux, 78%; (iv) LiAlH4, THF, reflux, 65%.
disappearance of t-butyl groups at 1.29 ppm belong to compound 3
(Fig. 3). The chiral Schiff base derivative of calix[4]arene 5 was pre-
pared from the reaction of compound 4 with (R)-(ꢀ)-2-phenylgly-
cine methyl ester in CHCl3:MeOH. From 1H NMR data, 5 exhibits
two singlet at 8.16, 8.19 ppm, respectively, which indicates the
presence of HC@N (Fig. 4) This conclusion has also been confirmed
by strong C@N bands at 1686–1637 cmꢀ1 and ester band at
1737 cmꢀ1 in the FT-IR spectra of chiral Schiff base derivative. Sub-
sequent reduction of these ester and Schif base groups of 5 by lith-
ium aluminum hydride yielded amino alcohol derivative 6 in 65%
yield. Completion of the reaction was followed by FT-IR spectros-
copy, which showed the disappearance of the band due to C@N
bands at 1686–1637 cmꢀ1 and ester band at 1737 cmꢀ1 and
appearance of the band due to alcohol hydroxyl groups at
3293 cmꢀ1. Also, the formation of 6 was confirmed by the disap-
pearance of the HC@N protons belong to compound 4 at 8.16
and 8.19 ppm in 1H NMR spectra (Fig. 5). Compounds 5 and 6 are
asymmetric due to the formation of chiral sub-units onto the lower
and upper rim of calix[4]arene. The splitting patterns of protons
(see Experimental) reflect the presence of the chiral moieties in
the molecules [23].
Extraction studies were performed in order to examine the
extraction behavior of a-amino acid methylesters and amino alco-
hols from the aqueous phase into the organic phase (CH2Cl2) by
using novel chiral calix[4]arene derivatives 5 and 6. The results
of the picrate extraction studies are summarized in Tables 1 and
2. These data have been obtained by using dichloromethane solu-
tion of the ligands to extract ammonium picrates from aqueous
solution. The equilibrium concentration of ammonium picrate in
an aqueous phase was then determined spectrophotometrically.
From the extraction data given Tables 1 and 2, it has been observed
that compound 1 and 4 transfer all amino acid and amino alcohol
species from aqueous phase into organic phase in trace amounts,
and chiral calix[4]arene Schiff base 5 and amino alcohol 6 recog-
nize all amino acid and amino alcohol species in high yields.
According to our experience and knowledge from our previous

S. Erdemir / Journal of Molecular Structure 1007 (2012) 235–241
239
Fig. 3. The 1H NMR spectra of compound 4.
Fig. 4. The 1H NMR spectra of compound 5.
Fig. 5. The 1H NMR spectra of compound 6.

240
S. Erdemir / Journal of Molecular Structure 1007 (2012) 235–241
Table 1
Extraction percentage of selected amino acid methylesters with 4, 5 and 6.a
Ligand
L
-AlaOMe
D
-AlaOMe
L
-PheOMe
D-PheOMe
D-TrpOMe
L-TrpOMe
1b
4
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
5
6
54.4 1.1
55.1 0.8
57.2 0.9
56.8 1.0
69.4 1.4
61.2 1.2
76.4 1.3
57.4 1.1
75.3 1.1
73.9 1.4
77.1 1.2
72.5 1.3
a
Aqueous phase, [ammonium picrate] = 2.0 ꢁ 10ꢀ5 M; organic phase, dichloromethane, [ligand] = 1.0 ꢁ 10ꢀ3; at 25 °C, for 1 h.
b
Chloroform was used as organic phase.
Table 2
Extraction percentage of selected amino alcohols with 4, 5 and 6.a
Ligand
(R)-Hyd-Me-Pyr
(S)-Hyd-Me-Pyr
D-Phegly
L-Phegly
1b
4
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
5
6
66.5 1.3
69.5 1.4
79.3 1.4
89.2 1.5
65.2 1.2
68.9 1.1
70.9 1.3
80.0 1.2
a
Aqueous phase, [ammonium picrate] = 2.0 ꢁ 10ꢀ5 M; organic phase, dichloro-
methane, [ligand] = 1.0 ꢁ 10ꢀ3; at 25 °C, for 1 h.
b
Chloroform was used as organic phase.
study and the other studies [22,24,25], increased extraction prop-
erties of chiral calix[4]arene Schiff base and amino alcohol (5 and
6) can be explained by multiple hydrogen bonding between 5–6
and amino acids or amino alcohols. In addition, the guests are sta-
Fig. 6. LogD versus log[L] for the extraction of
into dichloromethane phase at 25 °C.
L
-Phegly by 6 from an aqueous phase
bilized by CH–p interactions with the aromatic walls of the hydro-
½R—NH3PicðLÞxꢂ
phobic cavity of the chiral calix[4]arenes (5 and 6). An expectation
of this study is also to observe chiral discrimination between ami-
no acids or amino alcohols by using these new chiral calix[4]arene
derivatives as a ligand. From the results, this goal is relatively true,
especially for phenylglycinols because of their extraction abilities
being different according to each other, when compared to other
species.
The extraction data for 6 has been analyzed by a classical slope
analysis method. Assuming the extraction of an ammonium cation
ðR—NHþ3 Þ by the receptor 6 according to the following equilibrium:
Kex
¼
ð1Þ
ꢀ
x
½R—NHþ3 ꢂ½Pic ꢂ½Lꢂ
Eq. (1) can be rewritten as
log DA ¼ log Kex½Picꢀꢂ þ x log½Lꢂ
ð2Þ
where the distribution ratio DA is defined as ratio of the concentra-
tions of the ammonium cation ðR—NHþ3 Þ in the two phases:
DA ¼ ½R—NH3PicðLÞ ꢂorg=½R—NHþ3 ꢂaq
ð3Þ
x
½R—NHþ3 ꢂaq þ ½Picꢀꢂaq þ x½Lꢂorg ꢀ ½R—NH3PicðLÞ ꢂ
Consequently a plot of logDA versus log[L] leads to a straight
line, whose slope allows the stoichiometry of the extracted species
to be determined.
x
org
The extraction constant Kex is defined by
2Pic-
HO
OH
HO
HO
HN
OH
NH
+
N
H
H
NH
H
HN
H
H
CH2
O
H2C
CH2
O
H2C
O
O
OH
O
OH
O
O
OH OH
O
+ Pic-
+
2
N
HO
H
H2C
CH2
H2C
CH2
HN
NH
H
OH
HN
NH
H
HO
H
OH
H
HO
H
OH
N+
Fig. 7. Proposed interaction model between 6 and ammonium cation (L-Phegly).

S. Erdemir / Journal of Molecular Structure 1007 (2012) 235–241
241
[5] J.H. Hartley, T.D. James, C.J. Ward, J. Chem. Soc. Perkin Trans. 1 (19) (2000)
3155.
[6] (a) R. Crossley, Chirality and the Biological Activity of Drugs, CRC, New York,
1995;
(b) G. Blaschke, H.P. Kraft, K. Fickentscher, F. Kohler, Arzeneim-Forsch. 29
(1979) 1640.
[7] For a general review on chiral calixarenes: M.O. Vysotsky, C. Schmidt, V.
Bohmer, in: G. Gokel (Ed.), Advances in Supramolecular Chemistry, vol. 7, Jai
Press, Stanford, 2000, p. 139.
Fig. 6 shows the extraction into dichloromethane at different
concentrations of 6 for the ammonium ion. A linear relationship
between logDA versus log[L] is observed with a slope for ammo-
nium ion by 6, which equals 0.66, suggesting that 6 forms a 1:2
complex with an ammonium cation. According to these data, the
proposed interaction model between 6 and L-Phegly is depicted
in Fig. 7. The analytical data of 6 shows that the complexation reac-
tion takes place according to the following equilibrium:
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ðLÞorg þ 2ðR—NHþ3 PicꢀÞaq ꢀ ðLðR—NHþ3 PicꢀÞ2Þorg
According to the experimental data, if the Eq. (2) rearrangement
for 6, logKex has the value 2.92 0.2.
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4. Conclusions
Novel chiral Schiff base and amino alcohol derivatives of ca-
lix[4]arene were synthesized with convenient reactions in order
to examine the extraction and chiral discrimination ability towards
some selected amino acids and amino alcohols. The enantioselec-
tive recognition ability of the receptors was studied by UV/vis
absorption spectroscopy. Although the chiral calix[4]arene Schiff
base and amino alcohol derivatives (5 and 6) were excellent
extractants for all used amino acid and amino alcohol species,
the chiral discrimination between amino acid and amino alcohol
molecules could not be obtained. It should be noted that the hydro-
phobic cavity of chiral calix[4]arenes and hydrogen bonding led us
to recognize these amino acids and amino alcohols. This work
should be useful with regards to the synthesis of chiral and enan-
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Acknowledgment
We thank the Research Foundation of The Selcuk University
(BAP) for financial support of this work.
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