Calix[4]arenes containing a ureido functionality on the lower rim as highly efficient receptors for anion recognition

Article abstract of DOI:10.1039/c6nj01271j

The introduction of nosyl moieties onto the lower rim of the calix[4]arene skeleton led to the formation of compounds immobilised in cone conformations. Subsequent reduction of the nitro group and reaction with aryl isocyanates enabled the construction of

Full text of DOI:10.1039/c6nj01271j

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Calix[4]arenes Containing Ureido Functionality on the Lower Rim
as Highly Efficient Receptors for Anion Recognition
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
c
Tomáš Klejch, Jan Slavíček, Oldřich Hudeček, Václav Eigner, Natalia Andrea Gutierrez, Petra
c
a
Cuřínová, and Pavel Lhoták*
DOI: 10.1039/x0xx00000x
The introduction of nosyl moieties onto the lower rim of the calix[4]arene skeleton led to compounds
immobilised in the cone conformations. Subsequent reduction of the nitro group and reaction with aryl
isocyanates enabled the construction of new calixarene-based ligands for anion recognition. As proven by
NMR and UV/vis titration experiments, diaryl urea moieties with electron-withdrawing substituents on both
www.rsc.org/
-
-
-
sides represent very efficient tools for the complexation of selected anions (AcO , BzO , H
competitive solvents such as DMSO-d
2 4
PO ) even in highly
6
.
bonding interactions from amide, sulfonamide, urea and/or
4
thiourea moieties most efficiently complex anions. The
Introduction
1
tuneable shape of the calix[4]arene cavity can then operate as
a molecular platform enabling an elaborated arrangement of
functional groups in precisely defined mutual positions. As a
result, calix[4]arene allows for the construction of highly
Calix[n]arenes are macrocyclic compounds, well-known for
their complexation abilities and are easily obtainable by base-
catalysed condensation of p-substituted phenols with
formaldehyde. These compounds have been attracting
attention for decades as one can easily select the appropriate
size of the cavity depending on the application. Moreover, in
the case of calix[4]arene, the 3D shape of the macrocycle can
be deliberately tuned to obtain one of the four basic
conformations (atropoisomers), known as cone, partial cone,
5
preorganised anion receptors possessing a cooperative effect
of the various functional groups.
X
X
1,2-alternate and 1,3-alternate. All of these features make
calix[4]arene a logical choice for the role of molecular scaffolds
in the design of molecular receptors.
O
O
N
N
H
H
H
H
N
N
(
CH
2
)
n
2 n
(CH )
O
O
N
N
H
H
N
N
The role of anions in various biological systems and their
function in living organisms is well recognized. Due to their
ubiquity, the study of anion complexation and/or recognition
has become an integral part of modern supramolecular
chemistry as can be demonstrated by the vast number of
O
O
H
H
X
X
2
3
papers, review articles and books recently published on this
Fig.
1 General design of calix[4]arene-based ureido receptors for anion
topic. Because of the importance of anions in many biological recognition.
and industrial processes, including environmental pollution,
there are ongoing efforts to design and develop new synthetic
receptors and sensors for the recognition of anions.
Typical examples of calixarene-based anion receptors are
depicted in Fig. 1. Calix[4]arene immobilised in the cone
Of the many types of receptors for anion recognition conformation is completed by neutral groups (such as ureido
currently known, those using highly directional hydrogen moieties) capable of hydrogen bonding interactions with
6
anions. As shown in our previous work, both the upper rim
(aromatic subunits) and the lower rim (phenolic oxygens) of
the calix[4]arene skeleton can be used for the design of
receptors. The upper rim appended ureido functionality
represents a diaryl urea motif which usually exhibits better
a
results (in term of K values) than the corresponding alkyl aryl
ureas on the lower rim (Fig. 1). In both cases, the complexation
ability of the receptors can be enhanced by the introduction of
electron-withdrawing groups onto the aryl moiety, but,
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because of the design, this substitution can only be done on
one side of the ureido moiety.
Results and discussion
8
Starting dipropoxycalix[4]arene
1
was reacted with p-
Recently, we reported a straightforward regioselective
derivatization of the calix[4]arene skeleton based on
protection/deprotection of the lower rim with nosyl (p-
nitrobenzenesulfonyl chloride according to literature
7
c
precedence (NaH/DMF, r.t.) to give sulfonylated compound
2
7
in 87% yield (Scheme 1). The nitro groups were then smoothly
nitrobenzenesulfonyl) groups. We realised that the nosyl
reduced by reaction of
2
with SnCl
2
·2H
2
O in refluxing EtOH.
was isolated in 98%
Cl , r.t.) with p-
substituted phenyl isocyanates bearing electron-withdrawing
substituents (CF , NO ) or with phenyl isocyanate to give the
target receptors 4a 4c in good yields.
group represents a suitable structural motif that (i) possesses a
The corresponding amino derivative
3
3
strongly electron-withdrawing substituent (-SO -), and (ii)
yield. Finally, this compound was reacted (CH
2
2
enables the introduction of the diarylureido moiety onto the
lower rim of calixarenes. In this paper we report on the
synthesis and the complexation abilities of novel receptors
based on the application of nosyl groups in the design of
functional molecules capable of the recognition of biologically
relevant anions, such as dihidrogenphosphate or carboxylates.
3
2
-
Scheme 1 Preparation of anion receptors based on calix[4]arene-urea conjugates.
To compare the complexation ability and to evaluate the Hz. Also the presence of one triplet for the methyl (from
cooperation effects of the two ureido clefts, the corresponding propyl) at 0.69 ppm, together with two singlets from the NH
monosubstituted analogues 8a and 8b were prepared bonds from the ureido moieties, is in line with the predicted
analogously. Thus, tripropoxy derivative
nosyl chloride to give mononosylated calixarene
Reduction with hydrazine and Raney nickel led to amino value (1215.3078) for the [M+Na] ion.
5
was reacted with structure. HR MS (Orbitrap) analysis of 4a displayed a signal at
6
in 63% yield. 1215.3095, that was in good agreement with the calculated
+
1
derivative
reaction with isocyanates in 48% and 81% yields, respectively.
The structures of the products were determined using the presence of two pairs of doublets for the -CH
7
(98%) that was transformed into 8a and 8b by
Similarly, the H NMR spectrum (CDCl
supported the lower symmetry of this compound. Thus, the
- bridges
combination of NMR and HR MS techniques. Thus, the H NMR moieties (2.90, 3.15, 4.15 and 4.40 ppm) corresponded to the
spectrum of 4a (in DMSO-d ) reflected the expected C2v expected symmetry of the monosubstituted cone
symmetry of the cone conformation as demonstrated by the conformation.
presence of the pair of characteristic doublets for equatorial The structure of 8b was unequivocally confirmed by X-ray
and axial protons from -CH - bridging moieties at 3.02 and 4.05 crystallography. It crystallised in the monoclinic system (CH Cl
ppm, possessing a typical geminal interaction constant J = 13.2 - MeOH mixture), space group P2 /c. Calix[4]arene adopted a
3
) of 8a clearly
2
1
6
C
s
2
2
2
1
2
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ARTICLE
distinctive pinched cone conformation (Fig 2a,b) with two
The diaryl ureido part of 8b is highly planar and it is clearly
phenyl rings (one of them bearing the ureido functional group) distorted out of the cavity. As follows from Fig 2a,b the long
pointing inside the cavity. The corresponding interplanar axis of the diaryl urea fragment is almost perpendicular to the
angles
the four carbon atoms of the CH
subunits were 68.08° and 75.62°. The other two moieties together by hydrogen bonding interactions between the N-H
Φ
between the main plane of the molecule defined by vertical axis of the calix[4]arene molecule. The crystal packing
2
bridges and the phenolic of 8b is characterised by an infinite assembly of molecules held
pointed outside from the cavity (
Φ
.=151.28° and 139.38°).
bonds from the urea moieties and the oxygen atom (S=O) from
sulfonate groups (Fig 2c). The corresponding N-H···O distances
were 2.240 and 2.271 Å. Moreover, the planarized diaryl urea
fragments formed dimers with an interplanar distance of 3.38
Å indicating the contribution of π-π interactions.
The complexation ability of novel ligands 4a-c and 8a,b
1
towards selected anions was studied by standard H NMR
titration techniques. All anions used for titrations were in the
form of tetrabutylammonium (TBA) salts to avoid possible
complexation of bulky cations by the calixarene cavity. The
selection of anions took into consideration various possible
a)
-
-
-
-
geometries, such as spherical (Cl ), trigonal (NO , BzO , AcO )
3
-
-
or tetragonal (HSO , H PO ) shapes. The aliquots of anions
4
2
4
were gradually added into the solution of ligands in DMSO-d6
to obtain calixarene:anion ratios of up to 1:10-15.
b)
a)
c)
b)
Fig 3 H NMR titration curves of 4a (a) and 8a (b) with BzO (DMSO-d
98 K).
1
-
6
, 300 MHz,
2
Although DMSO is an example of a highly competitive
solvent towards hydrogen bonding interactions, the addition
of anion aliquots led to pronounced downfield shifts of the
ureido NH signals, demonstrating strong complexation under
fast exchange conditions. Thus, the addition of benzoate anion
d)
Fig. 2 Single crystal X-ray structures of compound 8b: (a) side view, (b) from
above the cavity, (c) packing motif showing hydrogen bonding interactions, (d) to a solution of 8a in DMSO-d resulted in huge complexation
6
packing motif with
clarity).
π-π interactions (calixarene units were removed for better
induced shifts (CIS) of both ureido NH protons from 9.5 to ca
9
3.2 ppm (see Fig. 3b). The corresponding Job plot analyses of
1
8
a
and 8b revealed the formation of complexes with 1:1
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-
stoichiometry for all anions measured (see Fig. 4 for 8b/ BzO isotherms obtained from the CIS values of NH ureido protons
1
0
system). The corresponding complexation constants, collected using the original nonlinear curve-fitting program (OPIUM).
in Table 1, were determined by analysing the binding
a)
1
6
Table 1. Binding constants of receptors 4 and 8 toward selected anions ( H NMR titration, 300 MHz, DMSO-d , 298 K)
-
-
-
-
4
-
-
Compound
BzO
AcO
NO
3
HSO
H
2
PO
4
Cl
b)
b)
b)
b)
b)
b)
b)
b)
b)
4
a
b
20 ± 3
27 ± 7
2.4 ± 0.3
1.5 ± 0.4
7 ± 0.7
135 ± 54
210 ± 16
2.7 ± 0.4
b)
b)
b)
4
108 ± 44
79 ± 17
0.5 ± 0.1
4 ± 0.4
b)
b)
b)
b)
b)
b)
4c
22 ± 6
29 ± 3
0.12 ± 0.03
≈ 0
0.17 ± 0.05
97 ± 5
95 ± 6
˃˃3·10
˃˃3·10
0.34 ± 0.07
105 ± 5
4
4
8
a
b
5000 ± 160
9400 ± 520
9400 ± 760
8
12700 ± 720
120 ± 10
250 ± 22
140 ± 10
a)
b)
5
All anions used as TBA salts. 1:2 stoichiometry (calix:anion), given as (K
1
·K
2
)/10 .
-
As documented by Table 1, spherical Cl was only relatively Cl , NO and HSO4 exhibit lower overall complexations
-
-
-
3
-
weakly bound by 8b (KCl = 140 M ), the same is true for constants K and are relatively weakly bound by ditopic
1
-
-
trigonal NO
3
and tetrahedral HSO
4
with the complexations receptors 8a
-
8b
As the complexation of H
the other hand, planar carboxylates like BzO and AcO formed reliably measured by NMR techniques, we have carried out
.
-1
-1
-
constants KNO3 = 120 M and KHSO4 = 250 M , respectively. On
2
4
PO was in fact too strong to be
-
-
-1
-1
much stronger complexes (KBzO- = 12700 M , KAcO- = 9400 M ). UV/vis titration experiments using nitro and trifluoromethyl
-
Surprisingly, the strongest binding was observed for the H
2
PO
4
derivatives 4a, 4b, 8a and 8b. The low concentration of the
-
5
-1
anion. In this case, the NMR titration experiments were found host molecules (< 10 mol·l ) allowed for the assignment of
to reach the borderlines of applicability of this method for the both the overall and the stepwise constants that are collected
1
1
evaluation of the complexation constants. As the titrations in Table 2. In both cases the corresponding nitro derivatives
were carried out at millimolar concentration of receptors 8a or exhibited stronger complexation ability for the
, the values of the KH2PO4 could be assigned only dihydrogenphosphate anion. All four receptors possessed very
8
b
1
2
4
-1
4
-1
approximately as >>3·10 M .
1
high complexation constants (K > 4.5·10 M ), despite the fact
that DMSO is a highly competitive solvent towards hydrogen
bonding interactions.
-
4
Table 2. Binding constants of receptors 4a,b and 8a,b towards H
2
PO
(UV/vis
a)
titrations, DMSO, 298 K).
c)
Compound
K
1
K
4
3
6
5
4a
4b
8a
8b
7.7 x 10 ± 3.4 x 10
7.3 x 10 ± 3.7 x 10
5
4
7
6
3.5 x 10 ± 1.1 x 10
3.0 x 10 ± 9.0 x 10
4
2
3
b)
4.5 x 10 ± 9.3 x 10
na
5
b)
1.8 x 10 ± 2.9 x 10
na
a)
b)
c)
TBA salt used. na = not applicable. K = K
1
× K
2
.
-
-
1
6
Fig 4 Job plot for 8b/BzO and 4b/BzO systems ( H NMR titration, DMSO-d , 300
MHz, 298 K).
Conclusions
The complexation with bis-urea derivatives 4a-c resulted in
the formation of complexes with 1:2 stoichiometry
calix:anion) as confirmed by the Job plot analyses for all
The introduction of nosyl moieties onto the lower rim of
the calix[4]arene skeleton led to compounds immobilised in
the cone conformations. Subsequent reduction of the nitro
group and reaction with aryl isocyanates enabled the
construction of new calixarene-based ligands for anion
recognition. As proven by NMR and UV/vis titration
experiments, the N,N’-diarylurea moieties substituted at both
para positions with electron-withdrawing substituents
represent very efficient tools for the complexation of selected
a
(
1
anions used. Consequently, the H NMR titration experiments
led to evaluation of the overall binding constants K (defined by
stepwise binding constants K and K as K = K × K ). As shown
1
2
1
2
in Table 1 there are several general trends: (i) receptor 4c
without an electron-withdrawing substituent possesses the
lowest K values as compared to those of 4a (CF ) or 4b (NO2)
3
with the exception of carboxylates where the affinities of 4a
and 4c were more or less comparable. (ii) 4a and 4b show
-
-
-
anions (AcO , BzO , H PO ) even in a highly competitive solvent
4
2
-
extremely high overall constant towards H PO (KH2PO4- =
like DMSO-d .
6
2
4
7
.35·10 and 2.1·10 , respectively). (iii) by way of contrast, the
7
1
4
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Synthesis
Experimental
Starting compounds
1
and
5
were prepared exactly according
8
Materials and instrumentations
,13
to recently published procedures.
All chemicals were purchased from commercial sources and
used without further purification. Solvents were dried and 25,27-bis(p-nitrophenylsulfonyl)-26,28-dipropoxy-calix[4]arene (2)
distilled using conventional methods. Melting points were
A mixture of 26,28-dipropoxy-calix[4]arene-25,27-diol
1 (5.00
measured on Heiztisch Mikroskop-Polytherm A (Wagner &
Munz, Germany) and are not corrected. NMR spectra were
g, 9.80 mmol) and sodium hydride (1.1 g, 27.50 mmol, 60%
suspension in mineral oil) was stirred for 30 min at 0 °C in
anhydrous DMF (200 ml). Then, p-nitrobenzenesulfonyl
chloride (8.70 g, 38.3 mmol, 97% purity) was added and the
reaction mixture was stirred at room temperature for 7 days.
The resulting mixture was acidified with 1M HCl (aq) and
1
performed on Varian Gemini 300 ( H: 300 MHz, C: 75 MHz),
13
1
Varian Unity Inova 500 ( H: 500 MHz, C: 125 MHz, F 470
13
19
TM
1
13
MHz), and on Bruker Avance III ( H: 500 MHz, C: 125 MHz).
spectrometers. Deuterated solvents used are indicated in each
case. Chemical shifts (δ) are expressed in ppm and are
referenced to the residual solvent signal or TMS as an internal
standard as indicated; coupling constants (J) are in Hz. Signal
extracted with CH
layers were washed with water (300 ml), brine (300 ml) and
dried over MgSO . Organic solvent was removed under
reduced pressure, and the oily residue was dissolved in CH Cl
30 ml) and precipitated by addition of methanol (150 ml). The
precipitate was filtered off, washed with methanol and dried
to give 7.58 g of title compound as a yellowish powder
87%).
2 2
Cl (3 × 100 ml). The combined organic
1
1
1
13
4
assignments were supported by H– H COSY, H– C HMQC,
1
13
1
1
1
H– C HMBC and H– H NOESY 2D NMR and 1D H-DPFGSE
2
2
(
NOE experiments using the standard pulse sequences provided
by Bruker and Varian. The right position of chemical shift of
2
1
3
19
3
CF carbon of receptor 8a was determined using the C- F
(
gHSQC pulse sequence provided by Varian. The HRMS analyses
were performed using ESI on a LTQ Orbitrap Velos (Thermo
Scientific) spectrometer equipped with an Orbitrap detector.
The IR spectra were measured on an FT–IR spectrometer
Nicolet 740 or Bruker IFS66 spectrometers equipped with a
heatable Golden Gate Diamante ATR–Unit (SPECAC) in KBr.
1
H NMR (CDCl
Hz, Ar-H), 8.15 – 7.96 (m, 4H, J = 8.49 Hz, Ar-
J = 7.9 Hz, Ar- ), 6.91 (t, 2H, J = 7.5 Hz, Ar-
J = 7.6 Hz, Ar- ), 6.19 (d, 4H, J = 7.6 Hz, Ar-
J = 13.8 Hz, Ar-CH
3
, 300 MHz, 298 K)
δ
(ppm): 8.40 (d, 4H, J = 8.8
H
), 7.07 (d, 4H,
H
H
), 6.40 (t, 2H,
H
H), 3.98 (d, 4H,
2
-Ar); 3.81 (t, 4H, J = 8.4 Hz, -OCH
H, J = 13.8 Hz, Ar-CH -Ar), 1.96 – 1.74 (m, 4H, -CH
.87 (t, 6H, J = 7.47 Hz, -CH CH ). All characterizations
2
-), 2.83 (d,
4
0
2
2
-CH -CH ),
2
3
1
00 Scans for one spectrum were co–added at a spectral
-
3
–
1
2
resolution of 4 cm . The purity of substances and the courses
of the reactions were monitored by TLC using TLC aluminium
sheets with Silica gel 60 F254 (Merck) and analysed at 254
13
including C NMR, IR and MS spectra are in agreement with
7
previously published data.
and/or 365 nm. Preparative TLC chromatography was carried 25,27-bis(p-aminophenylsulfonyl)-26,28-dipropoxy-calix[4]arene
out on 20 × 20 cm glass plates covered by Silica gel 60 GF254 (3)
(
Merck).
A 100 mL flask was charged with compound
mmol) and ethanol (50 ml). The mixture was heated to obtain
a clear solution and then SnCl .2H O (2.60 g, 11.6 mmol) was
2 (1.00 g, 1.14
Titration experiments
2
2
The UV-Vis titration experiments were carried out using Cintra
added. The reaction mixture was stirred at 80 °C for 4 days.
The reaction was quenched by pouring the mixture into ice
water which was basified to pH 9-10 using 1M aq. KOH. The
2
0 spectrometer (GBC Scientific Equipment Ltd.). The starting
concentration of the calixarene-based receptors in DMSO was
-6
-5
held in the region 4·10 - 2·10 mol/l. Tetrabutylammonium
phosphate solution in DMSO was added in portions into the
UV cuvette until at least 10 equiv. of the anion was added. All
UV spectra were taken in the wavelength region from 200 to
aqueous phase was extracted with CH
combined organic layers were washed with saturated solution
of NaCl, dried over MgSO and the solvent was evaporated in
vacuo to yield 0.91 g (98%) of the title compound as a
2 2
Cl (3 x 25 mL), the
4
7
00 nm, with steps of 0.48 nm. The stability constants of the
1
yellowish powder, m.p.: 140-147
3
°C. H NMR (CDCl , 400 MHz,
resulting complexes were evaluated by employing the
0
freeware program OPIUM,
2
98 K) δ (ppm): 7.62 (d, 2H, J = 8.8 Hz, Ar-
J = 7.3 Hz, Ar-
H), 7.07 (d, 4H,
H), 6.67 (d, 4H,
H), 6.16 (d, 4H,
1
using the whole parts of
H
), 6.90 (t, 2H, J = 7.3 Hz, Ar-
), 6.34 (t, 2H, J = 7.7 Hz, Ar-
absorption curves where the changes in absorbance were the
most significant. For each calixarene derivative, the
appropriate computational model was chosen according to the
Job plot. In the case where the 1:2 stoichiometry model was
J = 8.7 Hz, Ar-
H
J = 7.6 Hz, Ar-CH
2
-Ar), 4.14 (d, 4H, J = 13.8 Hz, Ar-CH
3.71 (m, 4H, -O-CH -CH ), 2.93 (d, 4H, J = 14.4 Hz, Ar-CH
.91 – 1.72 (m, 4H, O-CH CH -), 0.80 (t, 6H, J = 7.47 Hz, -CH
, 100 MHz, 298 K) (ppm): 157.6, 151.7,
44.3, 136.4, 134.5, 130.6, 129.1, 127.9, 124.9, 122.3, 113.8,
2
-Ar), 3.85
-
2
2
-
2
-Ar),
1
2
-
2
2
-
used, both the values of K
were obtained.
1
The HNMR titration measurements were performed in DMSO-
1
(for 1:1 binding) and K (overall)
13
CH
3
). C NMR (CDCl
3
δ
1
1
1
-1
10.0, 76.5, 31.9, 22.9, 9.8. IR (KBr)
ν (cm ): 3386; 1625; 1355;
168. HRMS-ESI (C46 ) m/z (% int.) calcd.: 841.25878
-
3
6
d at concentrations of ~1·10 mol/l. The concentration of
46 2 8 2
H N O S
calixarene receptors was held constant to avoid potential
problems with changes of chemical shifts induced by dilution.
+
+
[M+Na] , found: 841.25941 [M+Na] (100)..
The stability constants and their errors were evaluated using 25,27-bis(4-(p-trifluormethylphenylureido)-phenylsulfonyl)-26,28-
the self-made computation program ESTAC.
dipropoxycalix[4]arene (4a)
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A 10 mL flask charged with amino derivative
3
(100 mg, 0.12 was used to remove impurities and the second eluent
Cl /MeOH = 1:1) gave the pure product 4c as slightly
Then, p-trifluormethylphenyl isocyanate (114 mg, 0.61 mmol) brown solid in 39% yield (75 mg), m.p: 219.3 – 220.5 °C. H
was added and the mixture was stirred for 2 days at room NMR (DMSO-d , 400 MHz, 298 K) (ppm): 9.40 (s, 2H, N- ),
temperature under an inert atmosphere. The reaction was 8.91 (s, 2H, N- ), 7.80-7.74 (m, 8H, Ar- ), 7.47 (d, J = 7.83 Hz,
mmol) and 2 mL of CH
2
Cl
2
was degassed with argon for 5 min. (CH
2
2
1
6
δ
H
3
H
H
3
3
quenched with 2 ml of MeOH and the mixture was stirred for 2 4H, Ar-
H
H
), 7.30 (t, J = 8.00 Hz, 4H, Ar-
3
), 7.01 (t, J = 7.43 Hz, 2H, Ar-
H
), 7.17 (d, J = 7.83 Hz,
3
), 6.89 (t, J = 7.63, 2H,
hours. The solvents was removed under reduced pressure and 4H, Ar-
H
3
3
the residue was purified by column chromatography on silica Ar-
gel (eluent: CH Cl :MeOH = 100:1) to give 110 mg of product 4.05 (d, J = 13.69 Hz, 4H; Ar-CH
(78%) as a colourless microcrystals, m.p. > 300 °C. H NMR 4H; OCH
DMSO-d , 300 MHz, 298 K) (ppm): 9.51 (s, 2H, N- ), 9.31 (s, (m, 8H; OCH
H, N- ), 7.80 (m, 8H, Ar- ), 7.66 (m, 8H, Ar- ), 7.18 (d, 4H, (CDCl /CD OD = 7:1, v/v, 100 MHz, 298 K)
J = 7.3 Hz, Ar- ), 6.89 (t, 2H, J = 7.3 Hz, Ar-
J = 7.6 Hz, Ar- ), 6.28 (d, 4H, J = 7.6 Hz, Ar-
J = 13.2 Hz, Ar-CH -Ar), 3.64 (t, 4H, J = 8.5 Hz, -O-CH
H, J = 13.2 Hz, Ar-CH -Ar), 1.70 (m, 4H, -CH CH -CH
H, J = 7.3 Hz, -CH CH , 75 MHz, 298 K)
H
), 6.45 (t, J = 7.63, 2H, Ar-
H
), 6.28 (d, J = 7.43, 4H, Ar-
H
),
2
3
2
2
2
-
Ar ax), 3.65 (t, J = 8.41 Hz,
), 3.02 (d, J = 13.69 Hz, 4H; Ar-CH -Ar eq), 1.74–1.64
1
2
4a
2
2
3
13
) ppm. C NMR
(
6
δ
H
2
CH
2
), 0.72 (t, J = 7.44 Hz, 6H; CH
3
2
H
H
H
3
3
δ (ppm): 161.28,
H
H
), 6.46 (t, 2H, 156.63, 149.22, 148.05, 142.20, 140.02, 138.27, 132.01,
H
H), 4.05 (d, 4H, 133.64, 132.82, 131.90, 129.02, 127.20, 126.32, 123.24,
2
2
-), 3.02 (d, 121.57, 80.40, 35.72, 26.77, 13.54 ppm, (C=O signal was not
-1
4
6
2
2
-
2
3
), 0.71 (t, clearly visible). IR (KBr) (cm ): 2924, 1665, 1594, 1447, 1173.
ν
1
3
2
-
3
),. C NMR (DMSO-d
6
δ
MS-ESI (C60H N O S ) m/z (% int.) calcd.: 1079.33301
56 4 10 2
+
+
(ppm): 156.8, 151.9, 145.4, 143.3, 142.9, 135.5, 134.2, 129.6, [M+Na] , found: 1079.33374 [M+Na] (100).
1
1
6
29.2, 127.9, 127.3, 126.1, 125.0, 122.7, 122.6, 122.2, 118.3,
1
9
25-(p-nitrophenylsulfonyl)-26,27,28-dipropoxy-calix[4]arene (6)
(cm ): 3372; 1723; 1168. HRMS-ESI A mixture of 26,27,28-tripropoxy-calix[4]arene (0.466 g,
) m/z (% int.) calcd.: 1215.30778 [M+Na] , 0.868 mmol) and sodium hydride (0.138 g, 3.47 mmol, 4
6
18.0, 76.0, 31.1, 22.4, 9.5. F NMR (DMSO-d , 282 MHz): δ = -
-
1
0.89. IR (KBr)
ν
5
+
(C
62
H
54
F
6
N
4
O
10
S
2
+
found: 1215.30946 [M+Na] (100).
equivs, 60% suspension in mineral oil) was stirred for 30 min at
°C in anhydrous DMF (25 ml). Then, p-nitrobenzenesulfonyl
0
25,27-bis(4-(p-nitrofenylureido)-phenylsulfonyl)-26,28-
chloride (0.77 g, 3.47 mmol, 4 equivs, 97% purity) was added
and the reaction mixture was stirred at room temperature for
dipropoxycalix[4]arene (4b)
The same procedure as described for the preparation of 5 days. The resulting mixture was acidified with 1 M aq. HCl
compounds 4a starting from derivative (116 mg, 0.141 (50 ml) and extracted with CH Cl (3 × 50 ml). The combined
mmol), dry CH Cl (1O ml), and p-nitrophenyl isocyanate (116 organic layers were washed with water (100 ml), brine (100
mg, 0.705 mmol). The crude product was purified by ml), and dried over MgSO . Organic solvent was removed in
precipitation from MeOH/CH Cl mixture to yield 94 mg (67%) vacuo, and the oily residue was dissolved in CH Cl (20 ml) and
of 4b as a yellow powder, m.p: 280 – 286 °C. H NMR (DMSO- precipitated by the addition of methanol (100 ml). The
2
2
2
2
2
4
2
2
2
2
1
d
6
, 300 MHz, 298 K)
δ
H
(ppm): 9.63 (s, 4H, N-
); 7.73 (m, 4H, Ar- ), 7.32 (d, 4H, J = 7.6 a yellow powder (63%), m.p: 280 – 286 °C. H NMR (DMSO-d
), 6.46 (t, 2H, J = 7.3 Hz, 300 MHz, 298 K) (ppm): 9.63 (s, 4H, N- ), 8.22 (m, 4H, Ar-
), 4.06 (d, 4H, J = 13.5 Hz, Ar- 7.82 (m, 8H, Ar- ); 7.73 (m, 4H, Ar- ), 7.32 (d, 4H, J = 7.6 Hz,
-Ar), 3.64 (t, 4H,J = 7.9 Hz, -OCH ), 3.02 (d, 4H, J = 13.8 Hz, Ar- ), 6.90 (t, 2H, J = 7.6 Hz, Ar- ), 6.46 (t, 2H, J = 7.3 Hz, Ar- ),
Ar-CH -Ar), 1.70 (m, -OCH CH -), 0.71 (t, 6H, J = 7.3 Hz, - 6.28 (d, 4H, J = 7.3 Hz, Ar- ), 4.06 (d, 4H, J = 13.5 Hz, Ar-CH
CH CH , 75.4 MHz, 298 K) (ppm): 156.5, Ar), 3.64 (t, 4H,J = 7.9 Hz, -OCH ), 3.02 (d, 4H, J = 13.8 Hz, Ar-
51.6, 145.7, 145.1, 143.3, 141.6, 135.9, 134.2, 129.6, 129.2, CH -Ar), 1.70 (m, -OCH CH -), 0.71 (t, 6H, J = 7.3 Hz, -CH CH ).
, 75.4 MHz, 298 K) (ppm): 156.5, 151.6,
(cm ): 3352, 1724, 1542, 1332, 1195, 1170. 145.7, 145.1, 143.3, 141.6, 135.9, 134.2, 129.6, 129.2, 127.9,
H), 8.22 (m, 4H, Ar- filtration of precipitate yielded 0.404 g of title compound 6 as
1
H
), 7.82 (m, 8H, Ar-
H
6
,
Hz, Ar-
Ar- ), 6.28 (d, 4H, J = 7.3 Hz, Ar-
CH
H
), 6.90 (t, 2H, J = 7.6 Hz, Ar-
H
δ
H
H),
H
H
H
H
2
2
H
H
H
2
2
2
H
2
-
1
3
2
3
). C NMR (DMSO-d
6
δ
2
1
1
2
2
2
2
2
3
1
3
27.9, 127.6, 125.12, 125.09, 122.7, 118.2, 117.9, 76.0, 31.1,
C NMR (DMSO-d
6
δ
-
1
2.4, 9.5. IR (KBr)
ν
MS-ESI (C60
H
56
N
6
O
14
S
2
) m/z (% int.) calcd.: 1164.34777 127.6, 125.12, 125.09, 122.7, 118.2, 117.9, 76.0, 31.1, 22.4,
-1
(cm ): 3352, 1724, 1542, 1332, 1195, 1170. MS-
+
+
+
] , 1169.30316 [M+Na] , 1185.27710 [M+K] , found: 9.5. IR (KBr)
[
M+NH
4
ν
+
+
(30), 1169.30241 [M+Na] (100), ESI (C60
+
) m/z (% int.) calcd.: 1169.30316 [M+Na] ,
1
164.34770 [M+NH
4
]
H
56
N
6
O
14
S
2
+
185.27647 [M+K] (10).
+
found: 1169.30241 [M+Na] (100).
1
2
5,27-bis(4-(phenylureido)phenylsulfonyl)-26,28-
dipropoxycalix[4]arene (4c)
Phenyl isocyanate (0.15 g, 1.26 mmol) was added to the mixture and a catalytic amount (10 mg) of Raney nickel was
solution of amine (0.15 g, 0.02 mmol) dissolved in dry THF added. The reaction mixture was heated to 65 °C and
15 mL) under an inert atmosphere of nitrogen. The resulting hydrazine hydrate (0.5 ml) was added. The mixture was stirred
mixture was stirred for 7 days, poured into water (60 mL) and for 10 min at the same temperature, then cooled to rt and
extracted with CH Cl (3 x 20 mL). The combined organic layers filtered through a short pad of celite. Evaporation of the
were washed with brine, dried over MgSO and evaporated to filtrate gave 0.291 g of product (98%) as an off-white
dryness. The mixture was purified by flash column powder, m.p.: 172-174 C. H NMR (CDCl , 300 MHz, 298 K)
chromatography (Al ; CH Cl /MeOH = 160:1), first eluent (ppm): 7.61 (d, 2H, J = 8.6 Hz, Ar- ), 7.12 (d, 2H, J = 7.0 Hz, Ar-
25-(p-aminophenylsulfonyl)-26,27,28-tripropoxy-calix[4]arene (7)
Nitro derivative
6 (0.31 g) was dissolved in MeOH:THF (1:1)
1
(
2
2
4
7
1
°
3
δ
2
O
3
2
2
H
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 7 of 9
NP lee wa s eJ od uo r nn oa tl aod fj uC s ht em ma ri sg it nr ys
View Article Online
DOI: 10.1039/C6NJ01271J
Journal Name
), 7.06 (d, 2H, J = 7.4 Hz, Ar-
ARTICLE
H
H
), 6.91 (t, 2H, J = 7.4 Hz, Ar-
), 6.38 (t, 2H, J = 7.4 Hz, Ar- ), 6.20 Ar-
), 4.43 (d, 2H, J = 13.3 6.27 (d, 2H, J = 7.8 Hz, Ar-
), 4.30 (d, 2H J = 12.9 Hz, Ar-CH
2
H
),
H
), 7.84 (m, 4H, Ar-
), 6.88 (t, 2H, J = 7.4 Hz. Ar-
), 6.17 (m, 2H, Ar-
-Ar), 4.11 (d, 2H, J
H
), 7.74 (d, 2H, J = 9 Hz, Ar-
), 6.46 (t, 2H, J = 7.8 Hz, Ar-
), 6.09 (d, 2H, J =
H
), 7.13 (m, 4H,
6
.64 (d, 2H, J = 8.6 Hz, Ar-
H
H
H
H
H
),
(
m, 2H, Ar-
H
), 6.10 (d, 2H, J = 7.4 Hz, Ar-
H
H
H
Hz, Ar-CH
2
-Ar), 4.32 (s, 2H, -NH
2
), 4.19 (d, 2H, J = 14.1 Hz, Ar- 7.8 Hz, Ar-
H
1
2
1
2
CH
.84 (td, 2H, J = 11.0 Hz, J = 5.5 Hz, -CH
J = 6.7 Hz, O-CH -CH ), 3.16 (d, 2H, J = 13.7 Hz, Ar-CH
d, 2H, J = 13.7 Hz, Ar-CH Ar), 1.88 (m, 6H, -CH -CH
t, 3H, J = 7.4 Hz, -CH CH ), 0.86 (t, 3H, J = 7.4 Hz, -CH
, 75 MHz, 298 K)
2
-Ar), 4.05 (td, 2H, J = 11.0 Hz, J = 5.5 Hz, CH
2
-
CH
), 3.66 (t, 2H, CH
-Ar), 2.95 3.58 (t, 2H, J = 6.3 Hz, O-CH
2
-CH
3
), = 13.3 Hz, Ar-CH
-CH -), 3.71 (dt, 2H, J = 10.6 Hz, J = 5.5 Hz, O-CH
-CH -), 3.17 (d, 2H, J = 12.9 Hz, Ar-
-Ar), 3.02 (d, 2H, J = 14.1 Hz, Ar-CH -Ar), 1.79 (m, 8H,-CH
-CH ), 1.05 (t, 3H, J = 7.4 Hz, -CH CH ), 0.78 (t, 6H, J = 7.4
, 100 MHz, 298 K) (ppm):
2
-Ar), 3.91 (dt, 2H, J = 10.6 Hz, J = 5.5 Hz, O-
1
2
1
2
3
2
-CH
2
-CH
3
2
2
2 2
-CH -),
2
2
2
2
2
(
(
2
-
2
2
-
CH
3
), 1.10 CH
CH ). CH
2
2
2
2
-
2
-
3
2
-
3
3
2
-
3
1
3
13
C NMR (CDCl
3
δ
(ppm): 157.7, 155.0, 151.8, Hz, -CH
2
-CH
3
). C NMR (DMSO-d
6
δ
1
1
2
1
44.4, 136.9, 136.3, 134.7, 132.9, 130.6, 129.3, 128.6, 127.8, 157.03, 154.61, 151.67, 145.73, 145.73, 145.08, 143.36,
27.3, 124.9, 123.7, 121.9, 113.6, 76.5, 76.4, 31.9, 30.8, 23.4, 141.46, 136.24, 135.50, 134.42, 132.55, 129.64, 128.58,
-
1
2.9, 10.8, 9.8. IR (KBr)
ν (cm ): 3384, 2960, 2964, 2360, 2339, 127.74, 127.17, 125.15, 122.26, 121.63, 118.63, 117.93, 76.79,
-1
623; 1594; 1455; 1088; 767. HRMS-ESI (C43
+
H
6
47NO S) m/z (% 75.95, 23.03, 22.49, 10.71, 9.61. IR (KBr) ν (cm ): 3358, 2961,
+
int.) calcd.: 728.30163 [M+Na] , 744.27472 [M+K] , found: 2923, 2350, 1727, 1593, 2638, 1498, 2332, 1303, 1195, 1170,
+
28.30194 [M+Na] (100), 744.27557 [M+K] (25).
+
7
51 3 2 7
1088, 1004, 857, 768. MS-ESI (C51H F N O S) m/z (% int.)
+
calcd.: 892.32382 [M+Na] , 908.29776 [M+K] , found:
+
25-(4-(p-trifluoromethylphenylureido)-phenylsulfonyl)-26,27,28-
+
+
92.32367 [M+Na] (100), 908.29712 [M+K] (40).
8
tripropoxycalix[4]arene (8a)
Crystallographic measurements
Using the same procedure as described for the preparation of
compounds 4a, starting from
trifluoromethylphenyl isocyanate (61.4 mg, XXX mmol, 2.5 (λ = 1.54054 Å) radiation at 180 K. The structure was in
equiv.) were reacted in dry DMF (2 mL). The crude product was monoclinic system, P2 /c space group with lattice parameters
purified by preparative TLC using CH Cl as eluent to yield 56 a = 21.5008 (10) Å, b = 12.8677 (6) Å, c = 16.1684 (7) Å,
mg (48%) of 8a as an off white powder, m.p: 148 – 152 °C. H β = 91.2161 (19) °, Z = 4, V = 4472.2 (4) Å , D
7 (92.5 mg, 0.131 mmol) and p- The structure 8b was measured using D8 VENTURE with Cu-Kα
1
2
2
1
3
-3
c
= 1.292 g cm ,
-
1
NMR (CDCl
Ar- ), 7.58 (d, 4H, J = 8.45 Hz, Ar-
), 7.20 (bs, 1H, N- ), 7.11 (dd, 2H, J = 7.5 Hz, J = 1.6 Hz, Ar- was solved by direct methods and refined by full matrix least
3
, 500 MHz, 298 K) δ (ppm): 7.79 (d, 2H, J = 8.3 Hz, μ(Cu-Kα) = 1.14 mm . The data reduction and absorption
1
4
H
H, 7.53 (d, 2H, J = 8.5 Hz, Ar- correction were done with Apex3 software. The Structure
1
2
15
H
H
H
1
2
16
), 7.01 (dd, 2H, J = 7.5 Hz, J = 1.3 Hz, Ar-
), 6.40 (t, 1H, J = 7.6 Hz, Ar-
J = 7.7 Hz, Ar-H), 6.14 (m, 1H, Ar- ), 6.08 (d, 2H, J = 7.5 Hz, Ar- reflections (Θmax = 68.3 °), 624 parameters and 74 restrains.
), 4.41 (d, 2H, J = 13.3 Hz, Ar-C
Ar-C -Ar), 4.06 (m, 2H, -OCH ), 3.79 (m, 2H, -OCH
H, J = 7.4 Hz, -OC ), 3.15 (d, 2H, J = 13.5 Hz, Ar-C
d, 2H, J = 13.9 Hz, Ar-C -Ar), 1.8-1.6 (m, 6H, -OCH
t, 3H, J = 7.4 Hz, -CH CH ), 0.84 (t, 6H, J = 7.5 Hz, -CH
, 125 MHz, 298 K) (ppm): 157.6, 155.0, 151.0, to common practice the hydrogen atoms attached to the
44.2, 144.0, 140.9, 136.9, 135.9, 134.6, 132.9, 129.9, 129.6, carbon atoms were placed geometrically with Uiso(H) in the
H
), 6.89 (t, 2H, squares on F squared value using Crystals software to final
J = 7.5 Hz, Ar-
H
H
), 6.19 (d, 2H, values R = 0.085 an R = 0.193 using 8114 independent
w
H
1
7
H
2
H -Ar), 4.14 (d, 2H, J = 13.8 Hz, The MCE software was used for visualization of electron
H
2
H
H
), 3.65 (t, density maps. The positions of disordered functional groups
2
H
2
H -Ar), 2.89 were found in difference Fourier maps; the bond lengths and
2
(
(
H
2
2
CH
2
-
), 1.07 angles were restrained. The overall occupancy of the
1
3
2
3
2
CH
3
).
C
disordered functional groups was constrained to 1. According
NMR (CDCl
3
δ
1
1
3
1
29.4, 128.5, 128.1, 127.3, 126.4 (q, J = 3.9 Hz), 125.5 (q, J = range of 1.2-1.5 Ueq of parent atom (C). The structure was
2.9Hz), 125.4, 123.9 (q, J = 271.2Hz), 122.0, 121.9, 119.3, deposited into Cambridge Structural Database under number
9
18.3, 76.8, 76.5, 31.9, 30.9, 23.5, 23.0, 10.8, 9.8. F NMR CCDC 1471641.
1
-1
(
CDCl
3
, 282 MHz): δ = -62.10. IR (KBr) ν (cm ): 3383, 2903,
360, 1958, 1538, 1323, 1167, 1068, 771. MS-ESI
2
+
Acknowledgements
(
51 51 3 2 7
C H F N O S) m/z (% int.) calcd.: 915.32613 [M+Na] ,
+
31.30007 [M+K] , found: 915.32629 [M+Na] (100),
+
9
This research was supported by the Czech Science Foundation
+
31.29834 [M+K] (25).
9
(
13-21704S and 14-03636S).
25-(4-(p-nitrophenylureido)-phenylsulfonyl)-26,27,28-
tripropoxycalix[4]arene (8b)
Notes and references
Using the same procedure as described for the preparation of
1
2
For books on calixarenes, see: (a) C. D. Gutsche Calixarenes
An introduction 2nd Edition, The Royal Society of Chemistry,
Thomas Graham House, Cambridge, 2008. (b) J. Vicens, J.
Harrowfield, L. Backlouti, Eds. Calixarenes in the Nanoworld,
Springer, Dordrecht, 2007. (c) L. Mandolini, R. Ungaro,
Calixarenes in Action, Imperial College Press, London, 2000.
For some recent selected reviews on anion recognition, see:
compounds 4a, starting derivative
7 (55.5 mg, 0.079 mmol)
and p-nitrophenyl isocyanate (32.3 mg, 0.197 mmol, 2.5
equiv.) were reacted in dry DMF (5 mL). The crude product was
purified by column chromatography on silica gel (eluent:
petroleum ether : ethyl acetate = 3:1 v/v) to yield 35 mg (81%)
1
of 8b as a yellow powder, m.p: 275 – 278 °C. H NMR (DMSO-
(a) P. A. Gale, Chem. Commun. 2011, 47, 82. (b) I. Ravikumar,
P. Ghosh, Chem. Soc. Rev. 2012, 41, 3077. (c) M. Wenzel, J. R.
d
6
, 300 MHz, 298 K)
δ
(ppm): 8.22 (s, 1H, N-
H
), 8.20 (s, 1H, N-
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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New Journal of Chemistry
Page 8 of 9
View Article Online
DOI: 10.1039/C6NJ01271J
ARTICLE
Journal Name
Hiscock, P. A. Gale, Chem. Soc. Rev. 2012, 41, 480. (d) N.
Busschaert, C. Caltagirone, W. Van Rossom, P. A. Gale, Chem.
Pojarová, P. Curinova, P. Lhotak, New J. Chem. 2008, 32
1597.
,
Rev., 2015, 115, 8038. (e) V. Blazek Bregovic, N. Basaric, K.
Mlinaric-Majerski, Coord. Chem. Rev. 2015, 295, 80. (f) M. J.
Langton, C. J. Serpell, P. D. Beer, Angew. Chem. Int. Ed. 2016,
7
7(a) O. Hudecek, P. Curinova, J. Budka, P. Lhoták,
Tetrahedron 2011, 67, 5213-5218; (b) O. Hudecek, J. Budka,
V. Eigner, P. Lhotak, Tetrahedron 2012, 68, 4187. (c) O.
Hudecek, J. Budka, H. Dvorakova, P. Curinova, I. Cisarova, P.
Lhoták, New J. Chem. 2013, 37, 220.
55, 1974.
3
K. Bowman-James, A. Bianchi, E. Garcia-Espana, (Eds) Anion
Coordination Chemistry, Wiley-VCH Verlag, 2012. (b) P. A.
Gale, W. Dehaen, (Eds.) Anion Recognition in Supramolecular
8
9
S. Kennedy, S. J. Dalgarno, Chem. Commun. 2009, 35, 5275.
Z. D. Hill, P. MacCarthy, J. Chem. Educ. 1986, 63, 162.
Chemistry in Topics in Heterocyclic Chemistry, Vol. 24, 10 The binding constants were calculated using the computer
Springer Verlag, 2010. (c) R. Vilar, (Ed.) Recognition of Anions
in Structure and Bonding, Vol. 129, Springer Verlag, 2008.
program OPIUM (Kyvala M.) freely available at:
http://www.natur.cuni.cz/~kyvala/opium.html.
See e.g.: (a) V. Amendola , L. Fabbrizzi, L. Mosca, Chem. Soc. 11 P. Thordarson, Chem. Soc. Rev. 2011, 40, 1305.
4
5
Rev. 2010, 39, 3889. (b) P. Dydio, D. Lichosyt, J. Jurczak, 12 It is well known that the NMR measurements below 20% and
Chem. Soc. Rev. 2011, 40, 2971. (c) M. O. Odago, A. E.
Hoffman, R. L. Carpenter, D. C. T. Tse, S.-S. Sun, A. J. Lees,
Inorg. Chim. Acta, 2011, 374, 558.
For selected reviews on calixarene-based receptors for
anions, see: (a) B. Mokhtari, K. Pourabdollah, Asian J. Chem.
above 80% complexation ratio (x) yield uncertain values. In
the case where [8a 1 mM as an example, the
complexation ratio between 0.2 and 0.8 corresponds to K
values between 300 and 20 000 M . For more details, see: K.
Hirose in Analytical Methods in Supramolecular Chemistry,
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New Journal of Chemistry
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DOI: 10.1039/C6NJ01271J
Graphical Abstract
Calix[4]arenes Containing Ureido Functionality on the Lower
Rim as Highly Efficient Receptors for Anion Recognition
Tomáš Klejch, Jan Slavíček, Oldřich Hudeček, Václav Eigner, Natalia Andrea Gutierrez, Petra
Cuřínová, and Pavel Lhoták
Calix[4]arenes bearing diaryl urea moieties with electron-withdrawing substituents on both sides
-
-
-
represent very efficient tools for the complexation of selected anions (AcO , BzO , H PO ) even in
2
4
6
highly competitive solvents such as DMSO-d .