A novel calix[4]arene-dipyrrole conjugate designed for complexation of ion pairs

Article abstract of DOI:10.1515/znb-2007-0318

A novel calixarene derivative with dipyrromethane moieties on the lower rim was prepared. NMR spectroscopy revealed a high selectivity towards sodium cations and the ability to bind ion pairs.

Full text of DOI:10.1515/znb-2007-0318

A Novel Calix[4]arene-Dipyrrole Conjugate Designed for Complexation
of Ion Pairs
Jan Budkaa,b, Petra Curinovac, Rong Gua, Pavel Lhotakb, Ivan Stiborb, Jan Schramlc,
and Wim Dehaena
a Molecular Design and Synthesis, Department of Chemistry, University of Leuven,
Celestijnenlaan 200F, 3001 Leuven, Belgium
b Department of Organic Chemistry, Institute of Chemical Technology, Technicka 5,
166 28 Prague 6, Czech Republic
c Institute of Chemical Process Fundamentals, Czech Academy of Sciences, Rozvojova 135,
165 02 Prague 6, Czech Republic
Reprint requests to Prof. Dr. Wim Dehaen. E-mail: wim.dehaen@chem.kuleuven.be
Z. Naturforsch. 2007, 62b, 439 – 446; received September 5, 2006
Dedicated to Prof. Helgard G. Raubenheimer on the occasion of his 65th birthday
A novel calixarene derivative with dipyrromethane moieties on the lower rim was prepared. NMR
spectroscopy revealed a high selectivity towards sodium cations and the ability to bind ion pairs.
Key words: Calixarenes, Receptors, Ion Pairs
Introduction
Calix[n]arenes are a well-known group of macro-
cyclic oligophenols that are very useful due their
unique molecular structures and simple prepara-
tion. They are used as important building blocks
in supramolecular chemistry, where they have found
many applications in the design of sophisticated
molecular structures and assemblies. The relatively
easy derivatisation of the basic skeleton allows the syn-
thesis of receptors for recognition of anions, cations,
neutral molecules, chiral compounds and other sub-
strates [1, 2].
Great attention has been focused on derivatives ca-
pable to bind both anions and cations [3a – e]. For
such so-called ditopic receptors calix[n]arenes [3f – g],
(aza)crowns [3h – k], cyclodextrins [3l] and many other
scaffolds can be used [3m – 3y]. The aim of this work
is to build molecules which could employ the attributes
of both calix[4]arenes and oligopyrroles.
It is known from the literature that calix[4]arenes
with their cone conformation substituted at the lower
rim can interact with hard metal cations to form
complexes which are very stable both in solution
and in the solid state. Among the suitable deriva-
tives we can mention for example different esters [4]
and amides [5], and also calixarenes substituted by
(oligo)ethylene glycol ethers. Typical examples are
Fig. 1. Design of the target molecule and proposed binding
mode (schematically).
represented by calixarenes bearing 2-methoxyethoxy,
2-ethoxyethoxy [4a, 6c] and longer oligoethylene gly-
col chains [6], as well as a large family of bridged
calix-crowns and related compounds [7].
0932–0776 / 07 / 0300–0439 $ 06.00 © 2007 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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J. Budka et al. · A Novel Calix[4]arene-Dipyrrole Conjugate Designed for Complexation of Ion Pairs
Scheme 1. a) BrCH2COOEt,
K2CO3,
acetone,
reflux;
b) LiAlH4, diethyl ether, r. t.;
c) Cl3CCOCl, Et3N, heptane,
0
◦C; d) Na2CO3, phenol,
THF, reflux; e) CH3CH2-
OCH2CH2Br, NaH, DMF,
r. t.
On the other hand, calix[4]pyrroles [8] and also the tetra - tert - butyl - 25,26,27,28- tetrakis(2-hydroxyeth-
corresponding open-chain dipyrroalkanes are very ef- oxy)-calix[4]arene(2), was synthesised in two steps by
ficient anion receptors [8e, 9]. In previous work [10] (i) alkylation of 5,11,17,23-tetra-tert-butyl-calix[4]-
we reported the synthesis of reactive derivatives of arene (1) with ethyl bromoacetate, and (ii) re-
dipyrroheptane, which can be used for further reac- duction of the resulting “tetraacetate” with lithium
tions. One of the possibilities is the appending of aluminium hydride [11]. 5-(1-Propyl-1-(pyrrol-2-yl)-
dipyrroheptane units to the calix[4]arene skeleton.
butyl)-2-trichloroacetylpyrrole (4) was obtained by
Based on this knowledge we designed a molecule a modification of the published reaction of 4,4-
for co-operative complexation of both cations and an- bis(pyrrol-2-yl)heptane (3) and trichloroacetyl chlo-
ride [10]. The condensation of derivatives 2 and 4
ions, which is schematically depicted in Fig. 1. As
the basic building block we used calix[4]arene in the was achieved by a five day reflux period in THF
cone conformation bearing tert-butyl groups on the up- in the presence of sodium carbonate and phe-
per rim to improve the solubility in organic solvents. nol. For comparison of complexation abilities, the
corresponding model compound without dipyrrolic
The lower rim was substituted with four ethylene gly-
col units, forming a cryptand-like cage that was de- units, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis-
signed for cation complexation. The ethylene glycol (2-ethoxyethoxy)calix[4]arene (6), was prepared ac-
cording to the published procedure [4a].
units were terminated by four dipyrrol moieties poten-
tially playing the role of anion receptor.
Complexation study of derivative 5
Results and Discussion
Synthesis
Compound 5 was studied by 1H NMR spectroscopy
as a potential receptor for anions, alkali metal cations
Receptor 5 was prepared according to Scheme 1. and also for co-operative and/or simultaneous com-
The starting calix[4]arene derivative, 5,11,17,23- plexation of ion pairs. All measurements were per-
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J. Budka et al. · A Novel Calix[4]arene-Dipyrrole Conjugate Designed for Complexation of Ion Pairs
441
formed in CDCl3/CD3CN 4 : 1 (v/v) solutions at 25 ◦C.
Alkali metal cations were added in the form of
well-soluble salts, namely, sodium as the Kobayashi
reagent Na{B[3,5-(CF3)2C6H3]4}, potassium as the
similar salt K[B(4-Cl-C6H4)4] and lithium as the pi-
crate. All studied anions were used as the tetra-n-
butylammonium salts. All titration experiments were
performed with constant concentration of receptor (ap-
prox. 3 × 10−3 M). The association constants under
slow exchange conditions were calculated from con-
centrations of free ligand, free substrate and complex
1
as determined from integrals in the H NMR spectra
for several signals. In the case of fast exchange condi-
tions, the association constants were determined from
binding isotherms corresponding to 1 : 1 binding using
an original non-linear-fitting program [6c] and statis-
tically treated for several signals. To confirm the stoi-
chiometry of the complexes in all cases, job plots were
drawn from 1H NMR titration data.
Complexation of anions
The complexation ability toward anions was stud-
ied for tetra-n-butylammonium chloride, bromide, io-
dide, hydrogensulphate, dihydrogenphosphate and ni-
trate. In all cases there were no changes observed in
1
the H NMR spectra of receptor 5. Only after addi-
tion of nBu4N+ HSO4−, the colourless solution be-
came pink. The cause of this chromatic change is not
known.
Complexation of alkali metal cations
Calixarene-dipyrrole conjugate 5 possesses a very
Fig. 2. The complexation of sodium cations by compound 5
as followed by 1H NMR spectroscopy. The white arrow cor-
responds to the signals of the free ligand 5, the black arrow
to complex Na·5 and signals of the Kobayashi reagent are
marked by a cross.
similar structural motif if compared with the tetrato-
sylate of derivative 2, which was used for the synthesis
of the bis-calixarene named calix[4]tube [11]. Both the
tetratosylate and the calix[4]tube are known for their
pronounced selectivity towards potassium cations over
all other alkali metals.
spectra. Two broadened triplets of the ethylene gly-
col units (δ = 4.44 and 4.37 ppm) merged into a sim-
ple singlet (δ = 4.12 ppm) due to the complexation
with sodium. The complexation process is depicted in
Fig. 2.
Interestingly, derivative 5 showed no affinity to
potassium or lithium, but selectively formed a rel-
atively strong complex with the sodium cation. As
the complexation proceeded under slow exchange
conditions (1H NMR), the association constant (KNa
5000 M−1) was obtained by integration of the cor-
responding signals of the NH groups and the –CH2–
bridges of the calixarene framework. The predicted used for a study of potential co-operative complexa-
binding mode with sodium being kept inside the tion of anions. To a solution of the saturated sodium
cryptand cavity was clearly confirmed by the 1H NMR complex (1.1 eq. of sodium) was added a solution
Complexation of ion pairs
The above-mentioned sodium complex Na·5 was
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J. Budka et al. · A Novel Calix[4]arene-Dipyrrole Conjugate Designed for Complexation of Ion Pairs
chemical shift of the NH proton a is 8.85 ppm, of pro-
ton b 8.53 ppm). The black arrow indicate the signals
of the NH protons in complex Na·5, the grey one illus-
trates the changes in the new species. While the reso-
nance of the NH proton a moved from 8.91 to 9.04 ppm
(difference 39 Hz), the induced change for proton b is
not so remarkable (9 Hz only). The remarkably differ-
ent behaviour of both NH protons indicates the possi-
ble position of the bromide anion within the complex
Na·5·Br: it is situated closer to the inner cavity formed
by the NH-a protons, probably because of the elec-
trostatic attraction between the Br− anion and bound
Na+ cation. Unfortunately, due to these complicated
simultaneous processes, the complexation of the bro-
mide anion could not be quantified.
For comparison, we also performed extraction ex-
periments. Solid salt (NaCl, NaBr and NaI, re-
Fig. 3. The complexation of bromide anions by complex
Na·5 as followed by 1H NMR spectroscopy. White arrow:
free ligand 5, black arrow: complex Na·5, gray arrow: new
species, probably due to the creation of complex Na·5·Br.
spectively) was added to a solution of ligand 5
(CDCl3/CD3CN 4 : 1 v/v) in the NMR tube and the
mixture was sonicated overnight. In all cases no
1
change in the H NMR spectra of compound 5 was
of a tetra-n-butylammonium salt of different halides,
namely Cl−, Br− and I−. Titration by nBu4N+Cl− in-
duced the decomplexation of the sodium cation un-
der slow exchange conditions and precipitation of solid
NaCl. Iodide anions induced small changes (< 5 Hz) in
the part of the spectrum correspondingto the upper part
of molecule 5, especially in the shifts of the equatorial
hydrogen atoms of the –CH2– bridges, but no changes
in the shifts of the NH groups of the pyrrole units.
Really interesting is the behaviour of the Na·5
complex towards the bromide anion. Addition of
nBu4N+Br− caused two different simultaneous pro-
cesses: (i) kinetically slow decomplexation of sodium
cations and precipitation of NaBr and also (ii) kinet-
ically fast co-operative complexation of the bromide
anions by the sodium complex of derivative 5. The sig-
nals of both NH groups in Na·5 split into two signals.
While one of them can be assigned as the signal of
the free ligand 5, the other one does not correspond to
the signal of the original complex Na·5. The shifts of
these NH groups changed after each addition of bro-
mide, which indicated the formation of a new species
– probably the complex Na·5·Br. Interestingly, after
observed. Moreover, extraction from water solution
(water saturated with the appropriate sodium salt was
shaken with a CDCl3 solution of 5 overnight and the
organic phase was measured by NMR) induced no
change of shifts in the 1H NMR spectra.
Complexation study of derivative 6
The model compound, the tetrakis(2-ethoxyethoxy)
derivative 6, has already been published, but never
studied as an alkali metal cation receptor by 1H NMR
spectroscopy. Chang et al. described the extrac-
tion of various picrate salts and transport experi-
ments [4a]. The very similar 5,11,17,23-tetra-tert-
butyl-25,26,27,28-tetrakis(2-methoxyethoxy)-calix-
[4]arene was also used for extraction of alkali metal
salts and as a phase-transfer catalyst [6a].
1H NMR spectroscopy was used only for the com-
plexation studies of other tetrakis(2-ethoxyethoxy)
derivatives, that were partly substituted or unsubsti-
tuted on the upper rim, CDCl3/CD3OD 2 : 1 or 1 : 1
solutions being used [6c].
Our studies of the complexation abilities of deriva-
reaching the equilibrium, the ratio between free and tive 6 towards alkali metal cations and ion pairs were
bound ligand did not change upon further addition of performed under the same conditions as described in
the bromide salt. The remarkable changes in the sig- the previous part. In contrast to receptor 5, compound 6
nals of the NH-hydrogen atoms during the titration of possesses no complexation sites for anions. Hence, di-
Na·5 by nBu4N+Br− are depicted in Fig. 3. The sig- rect titrations with tetra-n-butylammonium salts were
nals of free ligand 5 are marked by a white arrow (the not performed.
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J. Budka et al. · A Novel Calix[4]arene-Dipyrrole Conjugate Designed for Complexation of Ion Pairs
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Table 1. Association constants of derivatives 5 and 6 towards Table 2. Association constants of alkali metal complexes of
alkali metal cations Kas [M−1].
derivatives 5 and 6 towards halide anions Kas [M−1].
Ligand
5
6
Li+
n.c.
12.000
Na+
K+
n. c.
Ligand
Na·5
Li·6
Cl−
d.c.
200
d.c.
d.c.
Br−
I−
5.000a
60.000a
a
n. c.
n. c.
n. c.
n. c.
> 105
n.c.
500
500
Na·6
K·6
n. c.: no complexation observed (complexation-induced shifts <
5 Hz); a slow exchange conditions; estimated errors < 15 %.
d. c.: decomplexation of cation; n. c.: no complexation observed
a
(complexation-induced shifts < 5 Hz); complicated simultaneous
processes – see text; estimated errors < 15 %.
Fig. 4. The complexation of sodium cations by compound 6
as followed by 1H NMR spectroscopy. The white arrow cor-
responds to the free ligand 6.
Fig. 5. The complexation of chloride anions by complex Li·6
as followed by 1H NMR spectroscopy. Black arrow: most
significant shift of the O–CH2–CH3 signals. The signals of
the tetra-n-butylammonium cation are marked by a cross.
Complexation of alkali metal cations
The study of the complexation abilities of the model
compound 6 showed again a different situation for
sodium in comparison to the other two studied cations der slow exchange conditions, whereas the complexes
(lithium, potassium): complex Na·6 was formed un- Li·6 and K·6 were formed under fast exchange con-
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444
J. Budka et al. · A Novel Calix[4]arene-Dipyrrole Conjugate Designed for Complexation of Ion Pairs
Fig. 6. Proposed bind-
ing mode of the ion pair
in the complex with lig-
and 6.
ditions. The corresponding association constants are
summarised in Table 1.
The complexation of sodium cations is depicted in
1
Fig. 4. The H NMR spectrum shows two doublets
of the CH2 bridges of the calixarene skeleton (δ =
3.14 and 4.47 ppm) and all signals of three different
–CH2O– groups. The most significant complexation-
induced chemical shift (Na+ cation) was observed for
the doublet of the equatorial hydrogen atoms of the
CH2 group (∆δ = 0.27 ppm), whereas the shift of the
signal of the axial hydrogen atoms was negligible.
Fig. 7. Numbering scheme for compound 5.
accompanied by another competitive process, namely
the decomplexation of sodium cations.
The study of the model calixarene 6 without
dipyrrolic units showed a different complexation of al-
kali metals cations. The simplest compound has lost
the selectivity for sodium and forms strong complexes
also with lithium and potassium. Interestingly, only
sodium cations are complexed by both receptors 5
and 6 under slow exchange conditions. Receptor 6
without any complexation site for anions, can co-
operatively bind bromide and iodide anions after cation
complexation.
Complexation of ion pairs
Robust complexes of derivative 6 with alkali metal
cations were also used for the study of co-operative
complexation of halide anions. Results are summarised
in Table 2. No complexation of iodide anions was ob-
served, the complexation-induced shifts being < 5 Hz.
The chloride anion was co-operatively bound only by
Li·6. The titration of Na·6 or K·6 by nBu4N+Cl− only
caused the decomplexation of the cations. In compar-
ison, Li·6 did not bind a bromide anion, which was
bound by both Na·6 and K·6. The process of co-
operative complexation of chloride anions by Li·6 is
depicted in Fig. 5. The largest shifts (up to 20 Hz) were
observed for the quartet of the O–CH2 unit of the ter-
minal ethoxy group, which indicates a binding mode
of both cation and anion as depicted in Fig. 6.
Experimental Section
Melting points were determined with a Boetius Block ap-
paratus and are uncorrected. ES mass spectra were measured
on a Micromass Mattro II instrument. 1H and 13C NMR
spectra were recorded on Varian Mercury 300 MHz, Bruker
Avance 300 MHz, and Bruker AMX3 400 spectrometers us-
ing tetramethylsilane as an internal standard. For the full as-
signment of the signals in the 1H NMR and 13C NMR spectra
of derivative 5, gCOSY, gHSQC, gHMBC and 1D NOESY
experiments were used.
Conclusion
5-(1-Propyl-1-(pyrrol-2-yl)-butyl)-2-trichloroacetylpyrrole
(4)
A novel calixarene-dipyrrole conjugate 5 was found
to be a very selective receptor for the sodium cation.
The possibility for co-operative complexation of both
cation and anion was confirmed for bromide anions
A solution of 0.46 g (2 mmol) of dipyrrole 3 and 0.22 g
(2 mmol) of triethylamine in 50 mL of heptane was cooled
in an ice-bath. Trichloroacetyl chloride (◦0.36 g, 2 mol) was
only. However, even in this case anion complexation is added and the mixture was stirred at 0 C for 30 minutes.
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J. Budka et al. · A Novel Calix[4]arene-Dipyrrole Conjugate Designed for Complexation of Ion Pairs
445
Then the solution was poured into 100 mL of water and ex- were collected, dried over magnesium sulphate and evapo-
tracted by 2 × 30 mL of ethyl acetate. The organic layers rated to dryness. The crude product was separated by col-
were collected, washed with 2×50 mL of water, dried over umn chromatography (silica gel, petroleum ether/ethyl ac-
magnesium sulphate and evaporated to dryness. The crude etate 10 : 1 to remove unreacted 4 and phenol, then the ratio
product was separated by column chromatography (silica was changed to 4 : 1) to give 96 mg (29 %◦) of derivative 5
gel, petroleum ether/ethyl acetate 8 : 1) to give 0.56 g (75 %) as a pale yellow powder (M. p. 112 – 115 C). – 1H NMR
◦
of derivative 4 (M. p. 98 – 100 C). – 1H NMR (300 MHz, (300 MHz, CDCl3, 25 ◦C): δ = 8.75 (s, 4 H, NH-a), 8.21 (s,
◦
CDCl3, 25 C): δ = 8.91 (brs, 1 H, NH), 7.80 (brs, 1 H, 4 H, NH-b), 6.77 (s, 8 H, ArH), 6.72 (t, J = 2.7 Hz, 4 H,
NH), 7.31 (brs, 1 H, pyrrole β-CH), 6.69 (brs, 1 H, pyr- H-pyrr-12), 6.56 (m, 4 H, H-pyrr-19), 6.07 – 6.03 (m, 12 H,
role α-CH), 6.23, 6.15 and 6.13 (3× brs, 1 H, pyrrole β- H-pyrr-13,17 and 18), 4.44 (m, 8 H, 4 × C(O)–O–CH2), 4.40
CH), 1.98 – 1.90 (m, 4 H, 2 × C–CH2), 1.15 – 1.10 (m, 4 (d, J = 12.9 Hz, 4 H, ax Ar–CH2–Ar), 4.17 (m, 8 H, O–CH2),
H, 2 × C–CH2–CH2), 0.86 – 0.90 (m, 6 H, 2 × CH3). – 3.07 (d, J = 12.6 Hz, 4 H, eq Ar–CH2–Ar), 1.92 – 1.87 (m,
13C NMR (75 MHz, CDCl3, 25 ◦C): δ = 172.9 (carbonyl-C), 16 H, 8 × C–CH2), 1.09 (m, 52 H, 4 ×tBu + 8 × C–CH2–
148.8, 134.8 and 122.2 (pyrrole α-C), 112.0, 118.0, 110.2, CH2), 0.84 (t, J = 6.9 Hz, 24 H, 8 × C–CH2–CH2–CH3). –
108.5, and 107.1 (pyrrole-CH), 44.0 (meso-C), 40.5 and 17.7 13C NMR (CDCl3, TMS, 75 MHz, 25 ◦C): δ = 161.0 (C-10),
(CH2), 14.8 (CH3). – MS-ES: m/z = 375.5 (calcd. 375.72 for 153.2 (C-5), 144.8 (C-3), 143.6 (C-14), 135.7 (C-16), 133.3
C17H21Cl3N2O, [M]+).
(C-6), 125.1 (C-4), 121.2 (C-11), 117.2 (C-19), 116.2 (C-12),
108.3 (C-13), 107.4 (C-17), 105.9 (C-18), 72.4 (C-9), 64.2
(C-8), 43.1 (C-15), 39.7 (C-20), 33.8 (C-2), 31.3 (C-1), 30.9
(C-7), 17.1 (C-21), 14.4 (C-22) (Numbering of carbon and
nitrogen atoms according to Fig. 7). – MS-ES: m/z = 1873.4
(calcd. 1850.51 for C116H152N8O12, [M+Na]+).
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-
(2-(5-(1-propyl-1-(pyrrol-2-yl)-butyl)pyrrol-2-yl-
carbonyloxy)ethoxy)calix[4]arene (5)
150 mg (0.18 mmol) of derivative 2, 67 mg (0.72 mmol,
4 eq.) of phenol and 285 mg (0.72 mmol, 4 eq.) of 5-
Acknowledgements
(1-propyl-1-(pyrrol-2-yl)-butyl)-2-trichloroacetyl-pyrrole
were dissolved in 60 mL of dry THF and 20 mg of Na2CO3 (bilateral project BIL03/09 between Flanders and Czech Re-
4
The authors thank the Flemish and Czech Government
public), the Grant Agency of the Czech Republic (Grant No.
was added. The mixture was refluxed for 120 h. After cool-
ing, the mixture was poured into 100 mL of water and ex- 203/06/0738), the University of Leuven and the Ministerie
tracted with 3 × 30 mL of ethyl acetate. The organic layers voor Wetenschapsbeleid for financial support.
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