Calixarene and hemicarcerand-like compounds obtained by self-assembly of 3-aminophenylboronic acid...

Accepted Manuscript

Calixarene and hemicarcerand-like compounds obtained by self-assembly of 3-

aminophenylboronic acid and salicylaldehyde derivatives

Victor Barba, Paola Ramos, Danae Jiménez, Abraham Rivera, Ariel Meneses

PII: S0020-1693(13)00073-X

DOI: http://dx.doi.org/10.1016/j.ica.2013.02.033

Reference: ICA 15352

To appear in: Inorganica Chimica Acta

Received Date: 19 December 2012

Revised Date: 20 February 2013

Accepted Date: 25 February 2013

Please cite this article as: V. Barba, P. Ramos, D. Jiménez, A. Rivera, A. Meneses, Calixarene and hemicarcerand-

like compounds obtained by self-assembly of 3-aminophenylboronic acid and salicylaldehyde derivatives,

Inorganica Chimica Acta (2013), doi: http://dx.doi.org/10.1016/j.ica.2013.02.033

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers

we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and

review of the resulting proof before it is published in its final form. Please note that during the production process

errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

http://dx.doi.org/10.1016/j.ica.2013.02.033

http://dx.doi.org/http://dx.doi.org/10.1016/j.ica.2013.02.033

Calixarene and hemicarcerand-like compounds obtained by self-assembly of 3-

aminophenylboronic acid and salicylaldehyde derivatives

Victor Barba,* Paola Ramos, Danae Jiménez, Abraham Rivera and Ariel Meneses

Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av.

Universidad 1001, C.P. 62209 Cuernavaca, Morelos, México.

Abstract: One-pot synthesis of calixarene and hemicarcerand like compounds can be

modulated by use of mono- or bis-salicylaldehyde derivatives respectively, reacting with 3-

aminophenylboronic acid. Thus, the first part of this work is focused on the synthesis of

calix-like compounds derived from salicylaldehyde units including different substituents on

the aromatic moiety. Seven different calix structures are described and their structural

analysis has been carried out by spectroscopic techniques. The second part corresponds to

the description of bis-salicylaldehyde derivatives, synthesis and reactivity towards the 3-

aminophenylboronic acid leading to the formation of hemicarcerand-like compounds.

Aliphatic and aromatic chains were inserted as linkers between the two salicylaldehyde

units in order to evaluate the influence on the formation of the hemicarcerands compounds.

Both, calixarene and hemicarcerand compounds resulted from condensation reactions,

wherein the formation of N-B coordination bonds plays a significant role on the

macrocyclization process.

Keywords: Calixarenes, hemicarcerands, macrocycles, trimeric compounds, boronic acids

Corresponding author: Tel/fax +52 777 3297997

E-mail address: [email protected]

1. Introduction

Calixarene chemistry has received considerable attention for long time ago, and it is really

interesting to find that the large number of applications for calix-like compounds still

continues increasing [1-8]. At the beginning, calixarenes derived mainly from phenol units

were synthesized and properties as inclusion and recognition analyzed [9-12]. Nonetheless,

heteroaromatic macrocycles are more frequently part of the calix-like compounds for

several interesting reasons as: a) easy accessibility, b) rich molecular diversity, c) unique

conformation, and d) cavity modulation [13-19]. These factors make them useful

macrocycles for research in supramolecular chemistry. Thus, heterocalixaromatics with

well-defined conformations and fascinating cavity properties are powerful tools for the

construction of supramolecular arrays and frequently are used as syntons for the

construction of Metal-Organic Frameworks [20-23]. It is known that multicomponent

molecular self-assembly of heterocalixaromatics coupled with metals forms soft materials

having diverse applications in material science. Even if the synthesis of sulphur, nitrogen-

and oxygen-bridged calixarenes looks very difficult; several reports have recently appeared

describing the formidable synthetic challenges involved and denoting thus, the rapid and

tremendous development of the supramolecular chemistry of this new generation of

macrocycles [24-28].

Beside all the heterocalixarenes modifications described before, we have introduce a new

strategy to construct heterocalixarenes using nitrogen-boron coordination bonds. Thus, we

have reported that boron macrocycles having boron-nitrogen coordinative bonds are easily

formed by the reaction of salicylaldehyde derivatives and 3-aminophenylboronic acid

(Scheme 1, up) [29]. The reaction occurs in one-pot synthesis leading to the formation of

trimeric compounds in good yields. The 15-membered macrocycles are surrounded by three

aromatic units and connected by three N-B coordinative bonds having a cone-cone

conformation, relating these with a calix-like form. These boroncalix[3]arenes have been

found to be useful for molecular encapsulation of neutral molecules, amines and

ammonium salts [30].

By the way, using hydroxyketones instead of salicylaldehyde derivatives the macrocyclic

compounds are also obtained but having a partial-cone conformation which is not useful

for recognition process [31]. It is important to remark that during the reaction, an

alcoholysis reaction occurs forming the ester group depending of the alcohol used, the

alcohoxy group is oriented always outside from the macrocycle. In fact in alcohol absence,

the condensation reaction takes place between two B-OH units forming B-O-B bridges

joining two calixarene units [32].

In another hand, bis-calixarenes can be obtained also in one pot synthesis from bis-

salicylaldehyde derivatives with 3-aminophenylboronic acid in moderate yields (Scheme 1,

down) [33]. In these cases the N-B coordination bond, the imine group formation and the

alcoholysis reaction, are the main factors responsible for the macrocyclization pathway. In

a previous report, a CH2 group connects the two salicylaldehyde units leading to

hemicarcerand-like compounds in good yields. The X-ray analysis reveals the inclusion of

two benzene molecules in its cavity, given evidence that these compounds acts as molecular

containers.

The principal topics in the construction of macrocycles based on boronic esters are: a)

modify the ring size, b) change the conformational flexibility and c) increase the thermal

stability. It is know that these factors are relevant in the formation on new Covalent

Organic Frameworks which are convenient for potential applications as porous materials

[34-37]. Herein, we describe the synthesis and characterization of calix- and

hemicarcerand-like compounds in order to determine additional structural factors that have

influence in their formation. The synthesis was done from salicylaldehyde derivatives and

3-aminophenylboronic acid. In the first part, the preparation of boroncalixarenes is

described and later, the formation of hemicarcerands is discussed. In all cases, compounds

were analyzed using techniques as infrared, nuclear magnetic resonance, mass spectrometry

and elemental analysis in order to get a complete characterization.

2. Results and discussion

In order to expand the number of molecular receptors type boroncalix[3]arenes, herein we

have synthesized the trimeric boron compounds 1-4. The direct reaction between the 5-

bromo-, 5-methyl or 4-(diethylamine) salicylaldehyde derivatives with 3-

aminophenylboronic acid (Scheme 2), offers the new calix-like compounds in moderate

yields, stables under moisture to room temperature and having high melting points (>260

C). Compounds 1-3 were obtained using methanol as solvent leading to the boron esters

having the OMe group attached to the boron atom, in case of compound 4 ethanol was used

as solvent leading to an ethoxy group joined to the boron atom. As describe in our previous

reports [32], the use of different alcohols during the reaction change the alcohoxy group

attached to the boron atom, changing thus the physico-chemical properties; for instance

larger chains leads to increase solubility in less polar solvents.

In all four cases, the IR spectra showed a band in the range of 1617 - 1632 cm-1, assigned to

the stretching of the v(C=N) group indicating the presence of the imine group. The

macrocyclic nature of the derivatives was suggested by mass spectrometry, a FAB+ analysis

reveals that the highest peak corresponds to the trimeric molecular ion, except for

compound 1 wherein the observed peak corresponds to the loss of a methoxy group from a

trimeric compound [M-OMe]+, actually these peak has been identify as a characteristic

pattern in analogous calix-like derivatives [30].

The NMR spectra for 1-4 showed signals for only a third part of the molecule, indicating

the C3 symmetric nature which is characteristic for a cone-cone conformation for this type

of molecules [30,32]. The 1H spectra showed a single signal to down fields (8.20-8.80 ppm)

while the 13C spectra shown a single signal in the range of 161.4-163.3 ppm, denoting thus

the formation of the HC=N moiety. The chemical shift of the hydrogen atoms

corresponding to the MeO group are shifted at 3.16 to 3.40 ppm, the corresponding signals

in 13C for the same group were found at 45.3 - 48.0 ppm. By the way, for compound 4 the

EtO moiety showed signals at 1H in 3.56 (q) and 1.18 (t) ppm, whereas in 13C spectra

signals at 48.0 and 15.6 ppm were observed. The 11B NMR confirms the tetrahedral

character of the boron atoms having chemical shifts at 2.0-4.5 ppm as observed for

analogous compounds [30,32].

As mention above, boroncalixarenes have been used to trap neutral guest [30] and thus, in

order to increase the hydrophobic nature of the cavity for the calix-like compounds, the 2-

hydroxynaphtaldehyde was used for the condensation with the 3-aminophenylboronic acid

in ethanol leading to the formation of compound 5 (Scheme 3). It was obtained in good

yield but the solubility decreased with respect to its parent compounds 1-4 in all common

organic solvents, in fact making the reaction under methanol, a highly insoluble yellow

solid is obtained in good yield. For compound 5, the mass spectra gave evidence for the

trimeric product formation, a peak at m/z = 903 was observed which corresponds to the

molecular ion, additionally, the peak at m/z = 858 reveals the loss of an EtO moiety. The IR

shows the characteristic band for the imine group at 1625 cm-1 and the 1H spectrum showed

a single signal at 8.91 ppm assigned to the proton of the iminic group. In the 13C spectrum a

single signal at 163.7 ppm was observed assigned to the same group. The 11B chemical shift

was observed at 5 ppm denoting the tetrahedral character for the boron atom.

One of the main problems to use these compounds as molecular receptors is the low

solubility, even in water for possible biological applications. So, in order to increase the

hydrophilic character surrounded the calix structure, we decide to introduce phosphate

groups in the periphery of the macrocycle. Thus, the condensation reaction was done using

pyridoxal 5’-phosphate with the boronic acid. Under methanol reflux compound 6 is

obtained whereas using ethanol as solvent it is possible to isolate the compound 7 (Scheme

3). In both cases the presence of the phosphate at the periphery of the upper rim, introduce

a high solubility in polar solvents as alcohols or water. Actually, all the previous

boroncalix-like compounds described are insoluble in water. This characteristic could help

us to expand the analysis of these systems as molecular receptors in biological systems.

Nevertheless, as a consequence of the OH groups presents at the pyridoxal which are

susceptible for condensation reactions, the yields for the trimeric compounds formation are

relatively lower compared with 1-5 (23 and 28 % for 6 and 7, respectively). Additionally, a

white insoluble solid is isolated as byproduct in both cases, perhaps being part of a

polymeric chain which was impossible to characterize. Mass spectrometry analysis

confirms the trimeric nature for these derivatives. The IR spectra show bands at 1642 and

1631 cm-1 for 6 and 7, respectively. The 1H NMR showed that the imine proton is shifted to

lower fields in comparison with the analogous compounds, a single signal was observed at

9.27 in both cases, the corresponding signal at 13C spectra was observed at 160.1 and 160.2

ppm, for 6 and 7, respectively. 31P NMR spectra of these calixarenes including the

phosphate groups showed a broad signal at �: 6.6 and 6.5 ppm respectively, which are in

accordance with the records reported for compounds having this group [38].

Following the strategy described at Scheme 1 for the construction of the hemicarcerands, at

the beginning the synthesis of bis-salicylaldehyde derivatives was carried out. Ligand 8 was

produced from the 5-methylsalicylaldehyde and formaldehyde in acetic acid in very little

yield (9.6%) [39]. The new ligand possess a methylene moiety connecting the two

salicylaldehyde units at position 3. The ligand 8 was allowed to react with 3-

aminophenylboronic acid to get the macrocyclic structure 12. As expected, 3 equivalents of

ligand 8 reacts with 6 equivalents of the boron acid to give a trimeric compound (Scheme

4), in a similar way that the observed using a similar ligand having the methylene unit at

position 5 [33]. The product is very little soluble in common organic solvents and was

obtained in moderate yield (68%). The IR shows the stretching band v(C=N) at 1625 cm-1

which is shifted to lower wavenumber in comparison with the stretching band for the

carbonyl group of the ligand (1645 cm-1). Mass spectrometry reveals the macrocyclic

structure showing a peak corresponding to the molecular ion with the loss of an OMe

group, as observed for related compounds. The high symmetry for this molecule was notice

from the 1H, 13C and 11B NMR spectra, in all three cases only a six part of the molecule was

noticed. By NMR it was possible identify the iminic group, in 1H the chemical shift for the

hydrogen atom was observed as single signal at 8.19 ppm, whereas in 13C, the

corresponding carbon atom showed the signal at 163.5 ppm. The methanolysis reaction also

was evidenced since the observation of signals at 3.36 ppm and 38.2 ppm from proton and

carbon spectra, respectively. The 11B spectrum shows a broad signal at 1.0 ppm giving

evidence for the tetrahedral character of the boron atom.

In addition, large alkyl chains separating the two salicylaldehyde units where introduced in

order to increase the size of the cavity for the hemicarcerand-like derivatives. Therefore,

the ligands 9-11 were synthesized using 2,4-dihydroxybenzaldehyde and the corresponding

alkyl dibromide (1,2-dibromoethane, 1,3-dibromopropane and �,�’-dibromo-p-xylene).

The reaction was carried out under reflux using KHCO3 as base in accordance to a method

previously reported [40]. These compounds were obtained in low yields (6, 10 and 12 %)

mainly because of the presence of two hydroxyl groups in the aromatic ring giving little

selectivity to form the required compounds, additionally a solid white was obtained which

was difficult to characterize. In all three cases the ligands were characterized by 1H and 13C

NMR as well as IR and mass spectrometry. For instance, from the mass spectra, the

observed peaks at m/z= 302, 316 and 378 corresponds to the molecular ion for compounds

9-11 confirming the formation of the products. In addition, for compound 10 in was

possible to get suitable crystals for the X-ray analysis [41], the molecular structure is

showed at Figure 1 wherein the alternate conformation between the carbonyl groups is

observed. This conformation is very important in the formation of the hemicarcerand- like

compounds [33]. At the supramolecular level, the molecules are ordered in a zig-zag

conformation leading to extended sheets (Figure 2).

The ligands 9-11 were allowed to react with the 3-aminophenylboronic acid in order to get

macrocyclic hemicarcerand-like compounds (Scheme 5). The reactions were done using

ethanol as solvent for 13 and 14, and methanol for 15. It is noteworthy to remark that using

methanol for 13 and 14, and ethanol for 15, the reaction leads to the formation of insoluble

white solids having high melting points (> 360 °C). First evidence of the macrocyclic

structure formation was provide by the mass spectrometry, wherein for compounds 13 and

14 the peak corresponding to the molecular ion was observed at m/z= 1681 and 1723,

respectively. The Figure 3 shows part of the FAB-MS spectrum for compound 14,

indicating that the isotopic pattern correlated with the calculated. Moreover, in all three

cases the corresponding peak characteristic for the loss of an OR group was observed at m/z

= 1636 (M-OEt), 1677 (M-OEt) and 1794 (M-OMe) for 13, 14 and 15 respectively. In the

IR analysis, the presence of the stretching band v(C=N) at 1622, 1618 and 1621 cm-1

confirmed the imine group formation. These molecules have high symmetry as noticed

from the NMR spectra, signals corresponding to only a sixth part of the whole molecule

were observed. For instance, at 1H a single signal at 8.88, 8.89 and 8.87 ppm was observed

for the iminic hydrogen of 13, 14 and 15, respectively. The chemical shift of the 13C for the

same group was observed at 163.9 for compounds 13 and 15 and 11B chemical shift was

registered at 1.0 and 2.0 ppm for 13 and 15, respectively. Compound 14 was very little

soluble and was impossible to get the 13C and 11B NMR spectra. Unfortunately, we were

unable to get crystals suitable for the X-ray diffraction analysis; therefore a mechanical

molecular model was used at the MM+ level of theory [42] for compounds 13, 14 and 15 in

order to have an idea of the whole geometry for this type of complexes (Figure 4). From

there, it was noticed that the presence of large linkers change the whole structure

conformation reducing the cavity size, and at the same time reducing the possibility for

host-guest possible applications.

3. Conclusions

We have carried out the formation of boroncalix[3]arenes having different physical

properties by changing the functional groups of the salicylaldehyde moiety. For instance,

the introduction on the naphthalene moiety gives more hydrophobic effect, while the

presence of phosphate fragments leads to give a higher hydrophilic behavior. By the way,

the formation of hemicarcerand-like compounds was also done, wherein the insertion of

short or large aliphatic fragments connecting two salicylaldehyde moieties have not

influence on the hemicarcerand like compounds formation but in the whole geometry as

observed from the mechanical molecular model. Further investigations as molecular

containers for neutral molecules are current in our lab.

4. Experimental part

4.1. Materials

All reagents and solvents were acquired from commercial suppliers and used without

further purification.

4.2. Instrumentation

The 1H, 13C and 119Sn NMR spectra were recorded at room temperature using a Varian Unit

400 spectrophotometer. As standard references were used TMS (internal, 1H, � = 0.00 ppm,

13C, � = 0.0 ppm) and BF3.Et2O (external, 11B, � = 0.0 ppm). The 2D COSY and HETCOR

experiments have been carried out for the unambiguous assignment of the 1H and 13C

signals present at the NMR spectra. Infrared spectra have been recorded on a Bruker Vector

22 FT-IR spectrophotometer. Mass spectra were obtained with Jeol JMS 700 equipment.

Melting points were determined with a Büchi B-540 digital apparatus.

4.3. X-ray crystal-structure determination

X-ray diffraction studies for compound 10 were performed on a Bruker-APEX

diffractometer with a CCD area detector, using Mo Kα-radiation, (λ = 0.71073 Å) and a

graphite monochromator. Frames were collected at T = 293 K. The measured intensities

were reduced to F2. Structure solution, refinement and data output were carried out with the

SHELXTL-NT program package [43]. All non-hydrogen atoms were refined

anisotropically. Hydrogen atoms were placed in geometrically calculated positions using a

riding model.

4.4. General method for the preparation of calix-like complexes 1-7

Compounds 1-7 were synthesized from the equimolecular reaction of the corresponding

salicylaldehyde derivative with 3-aminophenylboronic acid monohydrate using 10 mL of

benzene as solvent and 2 mL of the corresponding alcohol (methanol or ethanol). The

reaction mixtures were stirred for 4 h under reflux. After that, part of the solvent and the

water formed through the triple condensation reaction were removed using a Dean-Stark

trap. The final products were recovered by filtration and purified by recrystallization in a

solvent mixture MeOH/CHCl3 (1:3 ratio).

Compound 1 was prepared from 0.30 g (1.93 mmol) of 3-aminophenylboronic acid

monohydrate and 0.38 g (1.92 mmol) 5-bromosalicylaldehyde in 10 mL of benzene and 10

mL of methanol. The product was obtained as a yellow powder. Yield: 0.52 g (85%);

m.p.decomp > 300 °C. IR (KBr) v (cm-1): 3547 (m), 3055 (w), 2819 (w), 1625 (C=N, s),

1547 (s), 1474 (s), 1371 (m), 1299 (m), 1202 (m), 1120 (w), 944 (w), 877 (w), 824 (w), 706

(w), 561 (w). EI-MS m/z (%): 917 ([M+-OMe], 13), 619 (15), 481 (55), 453 (25), 379 (87),

378 (35), 257 (22), 241 (100), 167 (24), 139 (35), 104 (51), 79 (47), 41 (38). 1H NMR (400

MHz, DMSO-d6) �: 8.20 (3H, s, H-7), 7.89 (3H, d, J = 2.6, H-6), 7.78 (3H, s, H-9), 7.75-

7.73 (3H, m, H-12), 7.55 (3H, dd, J = 7.4, 2.6 Hz, H-4), 7.45 (3H, d, J = 7.4 Hz, H-13),

7.44 (3H, d, J = 2.2 Hz, H-11), 6.95 (3H, d, J = 7.4 Hz, H-3), 3.35 (9H, s, CH3O) ppm. 13C

NMR (100 MHz, DMSO-d6) �: 161.4 (C-7), 159.2 (C-2), 146.8 (C-8), 135.3 (C-4), 133.8

(C-6), 133.0 (C-12), 128.5 (C-11), 127.0 (C-9), 122.7 (C-13), 121.1 (C-1), 119.0 (C-3),

109.8 (C-5), 45.3 (CH3O) ppm. 11B NMR (64 MHz, DMSO-d6) �: 2.0 ppm (h1/2 = 2400

Hz). Elemental Anal. Calc. for C42H33B3N3Br3O6: C 53.21, H 3.50, N 4.43 %. Found: C

52.99, H 3.37, N 4.25 %.


monohydrate and 0.26 g (1.91 mmol) 5-methylsalicylaldehyde in 30 mL of benzene and 3

mL of methanol. The product was obtained as a yellow powder. Yield: 0.24 g (54%); m.p.=

298-300 °C. IR (KBr) v (cm-1): 3434 (m), 2920 (m), 1632 (C=N, s), 1562 (s), 1487 (m),

1382 (s), 1294 (m), 1220 (w), 1161 (w), 1082 (w), 983 (w), 951 (w), 884 (w), 821 (w), 786

(w), 567 (w). FAB+-MS m/z (%):753 ([M+H]+, 15), 712(34), 691 (25), 690 (15), 677 (15),

592 (15), 471 (25), 457 (17), 307 (56), 264 (100), 263 (30), 220 (13). 1H NMR (400 MHz,

DMSO-d6) �: 8.80 (3H, s, H-7), 7.77 (3H, s, H-9), 7.72 (3H, d, J = 2 Hz, H-6), 7.45 (3H, t,

J = 6.8 Hz, H-12), 7.45 (3H, dt, J = 6.8 Hz, 1.6, H-13), 7.43 (3H, dt, J = 6.8 Hz, 1.6, H-11),

7.23 (3H, dd, J = 8.4, 2.0 Hz, H-4), 6.87 (3H, d, J = 8.4 Hz, H-3), 3.40 (9H, s, CH3O), 2.28

(9H, s, CH3arom) ppm. 13C NMR (100 MHz, DMSO-d6) �: 162.8 (C-7), 158.0 (C-2), 147.3

(C-8), 133.9 (C-4), 132.6 (C-6), 132.1 (C-12), 128.5 (C-11), 127.6 (C-5), 127.0 (C-9),

122.6 (C-13), 119.0 (C-1), 116.4 (C-3), 46.00 (CH3O), 20.0 (CH3arom). 11B NMR (64 MHz,

DMSO-d6) �: 2 ppm (h1/2 = 2181 Hz). Elemental Anal. Calc. for C45H42B3N3O6: C 71.75, H

5.62, N 5.57 %. Found: C 71.49, H 5.58, N 5.45 %.


monohydrate and 0.46 g (2.41 mmol) 4-diethylamine salicylaldehyde in 50 mL of benzene

and 50 mL of methanol. The product was obtained as a yellow powder. Yield: 0.63 g

(85%); m.p. = 260-262 °C. IR (KBr) v (cm-1): 3365 (m), 2973 (C-H, m), 1705 (w), 1618

(C=N, s), 1510 (s), 1445 (s), 1409 (s), 1350 (s), 1222 (s), 1141 (s), 1076 (m), 1009 (m), 932

(m), 709 (w), 526 (w). FAB+-MS m/z (%): 924 ([M]+, 12), 909 (25), 893 ([M-MeO]+, 100),

879 (95), 878 (59), 865 (35), 849 (20), 835 (12), 819 (8). 1H NMR (200 MHz, DMSO-d6)

�: 8.68 (3H, s, H-7), 7.69 (3H, s, H-3), 7.62 (3H, d, J = 7.3 Hz, H-13), 7.35 (3H, t, J = 7.3

Hz, H-12), 6.96 (3H, d, J = 7.2 Hz, H-6), 6.59 (3H, dd, J = 7.2, 2.0 Hz, H-5), 6.32 (3H, d, J

= 7.3 Hz, H-11), 6.06 (3H, s, H-9), 3.40 (12H, q, J = 4.0 Hz, -CH2N), 3.16 (9H, s, CH3O),

1.11 (18H, t, J = 4.0 Hz, CH3CH2N) ppm. 13C NMR (50 MHz, DMSO-d6) �: 162.3 (C-7),

161.5 (C-2), 153.3 (C-4), 147.1 (C-8), 132.1 (C-13), 129.3 (C-12), 128.9 (C-6), 127.2 (3),

116.1 (C-5), 108.0 (C-1), 104.5 (C-11), 98.3 (C-9), 48.0 (CH3O), 44.4 (-CH2N), 13.8

(CH3CH2N). 11B NMR (64 MHz, DMSO-d6) �: 3.6 ppm (h1/2 = 1453 Hz). Elemental Anal.

Calc. for C54H63B3N6O6: C 70.15, H 6.86, N 10.38 %. Found: C 70.06, H 6.67, N 10.24 %.


monohydrate and 0.46 g (2.41 mmol) 4-diethylamine salicylaldehyde in 50 mL of benzene

and 50 mL of ethanol. The product was obtained as a yellow powder. Yield: 0.67 g (87%);

m.p.= 282-285 °C. IR (KBr) v (cm-1): 3428 (w), 2971 (w), 1617 (C=N, s), 1511 (s), 1445

(m), 1409 (m), 1349 (m), 1238 (m), 1140 (m), 1076 (w), 1011 (w), 1004 (m), 967 (w), 789

(w), 709 (w). FAB+-MS m/z (%): 966 ([M]+, 8), 938 (10), 922 ([M-EtO]+, 100) 894 (22),

893 (41), 865 (27), 864 (21), 848 (10), 835 (6), 819 (6), 818 (5). 1H NMR (200 MHz,

DMSO-d6) �: 8.72 (3H, s, H-7), 7.67 (3H, s, H-3), 7.61 (3H, d, J = 7.2 Hz, H-13), 7.27

(3H, t, J = 7.2 Hz, H-12), 6.87 (3H, d, J = 6.8 Hz, H-6), 6.58 (3H, d, J = 6.8 Hz, H-5), 6.39

(3H, d, J = 7.2 Hz, H-11), 6.01 (3H, s, H-9), 3.56 (6H, q, J = 5.6 Hz, CH3CH2O), 3.33

(12H, q, J = 4.7 Hz, CH3CH2N), 1.18 (9H, t, J = 5.6 Hz, CH3CH2O), 1.09 (18H, t, J = 4.7

Hz, CH3CH2N) ppm. 13C NMR (100 MHz, DMSO-d6) �: 163.3 (C-7), 161.1 (C-2), 152.1

(C-4), 147.0 (C-8), 132.4 (C-13), 128.1 (C-12), 128.7 (C-6), 126.9 (3), 116.3 (C-5), 107.8

(C-1), 104.2 (C-11), 99.3 (C-9), 48.0 (CH3CH2O), 45.2 (CH3CH2N), 15.6 (CH3CH2O), 14.7

(CH3CH2N). 11B NMR (64 MHz, DMSO-d6) �: 4.5 ppm (h1/2 = 2367 Hz). Elemental Anal.

Calc. for C57H69B3N6O6: C 70.82, H 7.19, N 8.69 %. Found: C 70.71, H 7.11, N 8.49 %.


monohydrate and 0.36 g (2.12 mmol) 2-hydroxynaphtaldehyde in 50 mL of benzene and 50

mL of ethanol. The product was obtained as a yellow powder. Yield: 0.51 g (80%); m.p.=

380-383 °C. IR (KBr) v (cm-1): 3429 (w), 2969 (C-H, w), 1625 ( C=N, s), 1548 (s), 1460

(s), 1401 (m), 1345 (m), 1239 (m), 1062 (m), 1004 (m), 954 (m), 861 (m), 793 (w), 679

(m). FAB+-MS m/z (%): 903 ([M]+, 5), 858 ([M-CH3CH2O]+, 10), 829 (2), 562 (1), 307

(17), 289 (10), 154 (100), 136 (73), 90 (23), 78 (18). 1H NMR (200 MHz, DMSO-d6) �:

8.91 (3H, s, H-C=N), 7.94-7.02 (24H, m, Harom), 3.62 (6H, q, J = 4.2 Hz, CH2), 1.16 (9H, t, J

= 4.2 Hz, CH3) ppm. 13C NMR (50 MHz, DMSO-d6) �: 163.7 (CC=N), 158.7 (Carom-O),

146.2, 135.1, 132.4, 132.2, 130.1, 129.1, 128.0, 126.8, 126.6, 123.9, 123.7, 122.3, 121.5

(Carom), 46.1 (CH2), 14.7 (CH3). 11B NMR (64 MHz, DMSO-d6)�: 5 ppm (h1/2 = 2486 Hz).

Elemental Anal. Calc. for C57H48B3N3O6: C 75.77, H 5.35, N 4.65 %. Found: C 75.56, H

5.27, N 4.58 %.


monohydrate and 0.20 g (0.8092 mmol) pyridoxal 5’-phosphate hydrate in 3 mL of benzene

and 30 mL of methanol. The product was obtained as a yellow powder. Yield: 0.07 g (23

%); m.p.decomp = 210 °C. IR (KBr) v (cm-1): 3442(s), 20741(w), 1642(C=N, s), 1387(m),

1249(m), 1034(w), 926(w), 698(w), 503(m). FAB+-MS m/z (%): 1037 ([M -OMe, -H2O]+,

2), 934(1), 807(4), 646(26), 645(9), 332(7), 202(100). 1H NMR (400 MHz, DMSO-d6) �:

9.27 (3H, s, H-7), 8.10 (3H, s, H-4), 7.96 (3H,s, H-9), 7.77 (3H, d, J = 7.6 Hz, H-13), 7.62

(3H, d, J = 7.6 Hz, H-11), 7.47 (3H, t, J = 7.6 Hz, H-12), 5.55 (6H, br, OH), 5.18 (6H, d, J

= 7.2 Hz, H-6), 2.45 (9H, s, CH3O), 2.08 (9H, s, CH3arom) ppm. 13C NMR (100 MHz,

DMSO-d6) �: 160.1 (C-7), 153.5 (C-2), 149.6 (C-4), 145.8 (C-3), 138.5 (C-8), 134.0 (C-5),

129.3 (C-9), 128.8 (C-11), 128.2 (C-12), 122.6 (C-13), 120.1 (C-1), 62.2 (C-6), 38.3

(CH3O), 18.7 (CH3arom) ppm; 11B NMR (64 MHz, DMSO-d6) �: 1.0 ppm (h1/2= 2008 Hz). 31P NMR (162 MHz , DMSO-d6) �: - 6.6 ppm. Elemental Anal. Calc. for C45H46B3N6P3O18:

C 49.84, H 4.27, N 7.75 %. Found: C 49.86, H 4.17, N 7.64 %.


monohydrate and 0.20 g (0.8092 mmol) pyridoxal 5’-phosphate hydrate in 3 mL of benzene

and 30 mL of ethanol. The product was obtained as a yellow powder. Yield: 0.08 g (28 %);

m.p. decomp = 240 °C. IR (KBr) v (cm-1): 3455(s), 2927(w), 1631(C=N, s), 1391(m),

1166(w), 1027(w), 699(w), 504(m); FAB+-MS m/z (%): 1128 ([M]+, 5), 1014(5), 915(5),

810(5), 758(10), 643(10), 615(5), 524(10), 460(5), 391(20), 307(100), 289(70), 219(50). 1H

NMR (400 MHz, DMSO-d6) �: 9.27 (3H, s, H-7), 8.05 (3H, s, H-4), 7.95 (3H, s, H-9), 7.78

(3H, d, J= 7.2 Hz, H-13), 7.63 (3H, dt, J=7.2 Hz, 1.2 Hz, H-11), 7.48 (3H, t, J=7.6 Hz, H-

12), 5.20 (6H, d, J=6.8 Hz, H-6), 3.50 (6H, br, OH), 3.43 (6H, q, J= 7 Hz, CH3CH2O), 2.46

(9H, S, CH3arom), 1.04 (9H, t, J= 7 Hz, CH3CH2O) ppm. 13C NMR (100 MHz, DMSO-d6) �:

160.2 (C-7), 153.3 (C-2), 149.5 (C-4), 145.9 (C-3), 138.8 (C-8), 133.8 (C-5), 129.0 (C-9),

128.7 (C-11), 128.2 (C-12), 127.8 (C-10), 122.5 (C-13), 119.8 (C-1), 62.1 (C-6), 38.9

(CH3CH2O), 18.9 (CH3arom), 14.8 (CH3CH2O) ppm; 11B NMR (64 MHz, DMSO-d6) �: 3.5

ppm (h1/2= 2106 Hz). 31P NMR (162 MHz , DMSO-d6) �: - 6.5 ppm. Elemental Anal. Calc.

for C48H54B3N6P3O18: C 51.09, H 4.82, N 7.44 %. Found: C 51.06, H 4.71, N 7.58 %.

4.5. Preparative method for ligands 8-11

Ligand 8 was prepared following a synthetic method described before [39] from 1.00 g of

2-hydroxy-5-methylbenzaldehyde and 0.44 g of p-formaldehyde using 25 mL of acetic acid

and 3 drops of sulfuric acid. Yield 9.6% (0.13g), m.p. = 150-153 °C. IR (KBr) v (cm-1):

3429 (w), 2919 (w), 1645 (C=O, s), 1457 (m), 1382 (m), 1329 (m), 1301 (m), 1265 (m),

1218 (m), 1164 (w), 1035 (w), 991 (w), 739 (w), 715 (w), 598 (w). EI-MS m/z (%): 284

([M]+, 100), 256 (12), 237 (25), 208 (28), 165 (34), 149 (76), 120 (70), 91 (54), 77 (28), 65

(13). 1H NMR (400 MHz, CDCl3) �: 11.08 (2H, s, OH), 9.76 (2H, s, H-7), 7.22 (2H, d, J =

1.8 Hz, H-6), 7.14 (2H, d, J = 1.8 Hz, H-4), 3.91 (2H, s, H-8), 2.22 (6H, s, CH3) ppm.

13C NMR (100 MHz, CDCl3) �: 196.8 (C-7), 157.2 (C-2), 139.3 (C-6), 131.9 (C-4), 129.0

(C-3), 128.6 (C-5), 120.5 (C-1), 28.1 (C-8), 20.5 (CH3) ppm. Elemental Anal. Calc. for

C17H16O4: C 71.75, H 5.62 %. Found: C 70.92, H 5.60 %.

Ligands 9-11 were synthesized according to the reported method [40] from two equivalents

of 2,4-dihydroxybenzaldehyde, one equivalent of the corresponding dibromoalkyl

derivative and two equivalents of KHCO3 using acetone as solvent. After 72 h under reflux,

the mixture was filtered and the product was extracted from the solid washing twice with

CH2Cl2, evaporation of the solvent allows isolate the pure compounds.

Compound 9 was prepared from 1.00 g (7.24 mmol) of 2,4-dihydroxybenzaldehyde and

0.68 g (3.62 mmol) of 1,2-dibromoethane in 50 mL of acetone. The product was obtained

as a white powder. Yield: 0.06 g (6 %); m.p. = 165-169 °C. IR (KBr) v (cm-1): 3423 (m),

2930 (m), 2864 (m), 1728 (s), 1638 (C=O, s), 1469 (m), 1376 (m), 1333 (m), 1285 (s),

1124 (m), 1074 (w), 1034 (w), 969 (w), 747 (m), 629 (m). EI-MS m/z (%): 302 (M+, 100),

164 (46), 150 (23), 137 (25), 136 (20), 111 (15), 110 (9), 65 (15). 1H NMR (200 MHz,

CDCl3) �: 11.42 (2H, s, OH), 9.67 (2H, s, H-7), 7.39 (2H, d, J = 7.6 Hz, H-6), 6.52 (2H, dd,

J = 7.6, 2.4 Hz, H-5), 6.40 (2H, d, J = 2.4 Hz, H-3), 4.32 (4H, s, CH2) ppm. 13C NMR (50

MHz, CDCl3) �: 194.6 (C-7), 165.6 (C-4), 164.6 (C-2), 135.5 (C-6), 115.7 (C-1), 108.9 (C-

5), 101.5 (C-3), 66.7 (CH2) ppm. Elemental Anal. Calc. for C16H14O6: C 63.57, H 4.66 %.

Found: C 63.52, H 4.62 %.


0.70 g (3.48 mmol) of 1,3-dibromopropane in 50 mL of acetone. The product was obtained

as a white powder. Yield: 0.11 g (10 %); m.p. = 117-120 °C. IR (KBr) v (cm-1): 3405 (m),

2947 (w), 2881(w), 1634 (C=O, s), 1506 (w), 1464 (w), 1374 (m), 1331 (m), 1225 (s), 1183

(m), 1117 (m), 1046 (m), 989 (m), 763 (w), 631 (w). EI-MS m/z (%): 316 (M+, 9), 151 (5),

87 (9), 71(100), 43 (26). 1H NMR (400 MHz, CDCl3) �: 11.40 (2H, s, OH), 9.65 (2H, s, H-

7), 7.37 (2H, d, J = 7.7 Hz, H-6), 6.47 (2H, dd, J = 7.7, 2.2 Hz, H-5), 6.37 (2H, d, J = 2.2

Hz, H-3), 4.14 (4H, t, J = 6.0 Hz, OCH2), 2.24 (2H, qn, J = 6.0 Hz, OCH2CH2) ppm. 13C

NMR (50 MHz, CDCl3) �: 194.5 (C-7), 166.0 (C-4), 165.0 (C-2), 135.5 (C-6), 115.9 (C-1),

108.8 (C-5), 101.4 (C-3), 64.8 (OCH2), 29.8 (OCH2CH2) ppm. Elemental Anal. Calc. for

C17H16O6: C 64.55, H 5.09 %. Found: C 64.49, H 4.92 %.


1.06 g (4.01 mmol) of �,�’-dibromo-p-xilene in 50 mL of acetone. The product was

obtained as a white powder. Yield: 0.18 g (12 %); m.p. = 195-199 °C. IR (KBr) v (cm-1):

3446 (m), 2951 (w), 2865 (w), 1738 (m), 1639 (C=O, s), 1506 (m), 1378 (m), 1223 (s),

1179(m), 1117 (m), 1000 (m), 810 (m), 628 (w), 547 (w). EI-MS m/z (%): 378 (M+, 18)

293 (5), 241(100), 143 (10), 104 (60), 69 (8). 1H NMR (400 MHz, DMSO-d6) �: 10.01

(2H, s, H-7), 7.62 (2H, d, J = 7.6 Hz, H-6), 7.48 (4H, s, CHarom), 6.63 (2H, dd, J = 7.6, 2.4

Hz, H-5), 6.55 (2H, d, J = 2.4, H-3), 5.19 (4H, s, CH2), 3.26 (2H, s, OH) ppm. 13C NMR

(100 MHz, DMSO-d6) �: 190.8 (C-7), 164.7 (C-4), 163.0 (C-2), 136.0 (CCH2), 132.0 (C-6),

127.9 (CHarom), 116.3 (C-1), 107.8 (C-5), 101.7 (C-3), 69.3 (CH2) ppm. Elemental Anal.

Calc. for C22H18O6: C 69.83, H 4.79 %. Found: C 69.69, H 4.67 %.

4.6. General method for the preparation of hemicarcerand complexes 12-15

Compounds 12-15 were synthesized by reacting 3-aminophenylboronic acid monohydrate

with the corresponding bis-salicylaldehyde derivative (2:1 ratio) using a mixture of 5 mL of

benzene and 20 mL of the corresponding alcohol (methanol or ethanol) as solvent. The

reaction mixtures were stirred for 4 h under reflux. After that, part of the solvent and the

water formed through the triple condensation reaction were removed using a Dean-Stark

trap. The final products were recovered by filtration and purified by washing with the same

alcohol used for the reaction.


monohydrate and 0.030 g (0.09 mmol) of ligand 8 in methanol. The product was obtained

as a yellow powder. Yield: 0.043 g (68 %); m.p. decomp = 300 °C. IR (KBr) v (cm-1): 3427

(w), 2921 (w), 1625 (C=N, s), 1564 (s), 1459 (m), 1416 (m), 1368 (m), 1319 (m), 1221 (m),

1168 (w), 1104 (w), 986 (w), 898 (w), 789 (w), 679 (w), 563 (w). FAB+-MS m/z (%): 1511

([M-OMe]+, 7), 1422 (2), 1322 (2), 1222 (2), 1063 (2), 870 (2), 766 (2), 613 (4), 460 (16),

390 (8), 307 (100), 289 (60), 161 (32). 1H NMR (200 MHz, DMSO-d6) �: 8.19 (6H, H-7),

7.81 (6H, s, H-9), 7.77 - 7.70 (6H, m, H-12), 7.46 (6H, d, J = 6.6 Hz, H-13), 7.36 (6H, d, J

= 6.6 Hz, H-11), 7.31 (6H, s, H-6), 7.08 (6H, s, H-4), 3.96 (6H, s, CH2), 3.36 (18H, s,

CH3O), 2.23 (18H, s, CH3arom) ppm. 13C NMR (50 MHz, DMSO-d6) �: 163.5 (C-7), 156.4

(C-2), 146.8 (C-8), 134.5 (C-6), 132.7 (C-4), 130.8 (C-12), 128.6 (C-11), 128.3 (C-3),

127.5 (C-5), 127.1 (C-9), 122.7 (C-13), 118.3 (C-1), 38.2 (CH3O), 28.1 (CH2), 20.2

(CH3arom) ppm. 11B NMR (64 MHz, DMSO-d6) �: 1.0 ppm (h1/2 = 3852 Hz). Elemental

Anal. Calc. for C93H84B6N6O12: C 71.41, H 5.48, N 5.44 %. Found: C 71.37, H 5.41, N 5.27

%. 1542.57


monohydrate and 0.020 g (0.066 mmol) of ligand 9 in ethanol. The product was obtained as

a yellow powder. Yield: 0.006 g (16 %); m.p. > 360 °C. IR (KBr) v (cm-1): 3451 (s), 1622

(C=N, s), 1539 (w), 1389 (w), 1303 (w), 1183 (w), 1119 (w), 993 (w), 584 (w). FAB+-MS

m/z (%): 1681 ([M]+, 5), 1652 (5), 1636 ([M-OEt]+, 55), 1635 (38), 1606 (5), 1591 (5),

1562 (4), 460 (48), 307 (100), 289 (61), 219 (25). 1H NMR (200 MHz, DMSO-d6) �: 8.88

(6H, s, H-7), 8.19 (6H, s, H-9), 7.77 (6H, d, J = 8.0 Hz, H-11), 7.68 (6H, t, J = 8.0 Hz, H-

12), 7.56 (6H, d, J = 8.8 Hz, H-6), 7.42 (6H, d, J = 8.0 Hz, H-13), 6.61 (6H, dd, J = 8.8, 2.4

Hz, H-5), 6.56 (6H, d, J = 2.4 Hz, H-3), 4.40 (12H, s, CH2CH2O), 3.49-3.29 (12H, m,

CH3CH2O), 1.05 (18H, t, J = 7.0 Hz, CH3CH2O) ppm. 13C NMR (50 MHz, DMSO-d6) �:

163.9 (C-7), 163.2 (C-4), 162.7 (C-2), 147.5 (C-8), 134.8 (C-11), 133.0 (C-6), 129.2 (C-

12), 127.4 (C-9), 123.2 (C-13), 113.9 (C-1), 107.9 (C-5), 102.1 (C-3), 67.2 (CH2CH2O),

56.8 (CH3CH2O), 19.3 (CH3CH2O) ppm. 11B NMR (64 MHz, DMSO-d6) �: 1.0 ppm (h1/2 =

1920 Hz). Elemental Anal. Calc. for C96H90B6N6O18: C 68.60, H 5.39, N 5.00 %. Found: C

68.32, H 5.22, N 4.89 %.


monohydrate and 0.029 g (0.09 mmol) of ligand 10 in ethanol. The product was obtained as

a yellow powder. Yield: 0.014 g (27 %); m.p. > 360 °C. IR (KBr) v (cm-1): 3861 (w), 3439

(s), 2857 (w), 1618 (C=N, s), 1542 (w), 1382 (w), 1299 (w), 1112 (w), 988 (w), 905 (w),

835 (w), 787 (w), 558 (w). FAB+-MS m/z (%): 1723 (M+, 5) 1681 (4), 1677 ([M-OEt]+, 19),

1649 (4), 1632 (6), 1631 (5), 1604 (4), 704 (5), 524 (15), 443 (11), 307 (100), 266 (99), 240

(54). 1H NMR (400 MHz, DMSO-d6) �: 8.89 (6H, s, H-7), 8.18 (6H, s, H-9), 7.76 (6H, d, J

= 8.8 Hz, H-11), 7.68 (6H, t, J = 8.8 Hz, H-12), 7.55 (6H, d, J = 9.6 Hz, H-6), 7.40 (6H, d,

J = 8.8 Hz, H-13), 6.58 (6H, dd, J = 9.6, 2.4 Hz, H-5), 6.53 (6H, d, J = 2.4 Hz, H-3), 4.20

(12H, t, J = 5.2 Hz, CH2CH2O), 3.35-3.25 (12H, m, CH3CH2O), 1.23 (18H, s, CH3CH2O),

0.90-0.81 (6H, m, CH2CH2O) ppm. Elemental Anal. Calc. for C99H96B6N6O18: C 69.02, H

5.61, N 4.87 %. Found: C 68.97, H 5.52, N 4.80 %.


monohydrate and 0.10 g (0.26 mmol) of ligand 11 in methanol. The product was obtained

as a yellow powder. Yield: 0.109 g (68 %); m.p. > 360 °C. IR (KBr) v (cm-1): 3429 (s),

2369 (w), 1621 (C=N, s), 1542 (w), 1388 (m), 1180 (w), 1122 (w), 1002 (w), 797 (w), 704

(w), 475 (w). FAB+-MS m/z (%): 1794 ([M-OMe]+, 7), 1632 (15), 1542 (16), 1030 (28),

814 (15), 624 (17), 448 (12), 307 (100), 272 (38). 1H NMR (400 MHz, DMSO-d6) �: 8.87

(6H, s, H-7), 8.18 (6H, s, H-9), 7.76 (6H, d, J = 7.1 Hz, H-11), 7.70 (6H, t, J = 7.1 Hz, H-

12), 7.55 (6H, d, J = 8.5 Hz, H-6), 7.50 (12H, s, CHarom), 7.41 (6H, d, J = 7.1 Hz, H-13),

6.63 (6H, d, J = 8.5 Hz, H-5), 6.58 (6H, s, H-3), 5.19 (12H, s, CH2O), 3.37 (18H, s, CH3O)

ppm.13C NMR (100 MHz, DMSO-d6) �: 163.9 (C-7), 163.1 (C-4), 162.7 (C-2), 147.5 (C-

8), 137.0 (CCH2), 134.7 (C-11), 133.0 (C-6), 129.2 (C-12), 128.6 (CHarom), 127.5 (C-9),

123.1 (C-13), 113.8 (C-1), 108.1 (C-5), 102.5 (C-3), 69.9 (CH2O), 31.4 (CH3O) ppm. 11B

NMR (64 MHz, DMSO-d6) �: 2 ppm (h1/2 = 1920 Hz). Elemental Anal. Calc. for

C108H90B6N6O18: C 71.08, H 4.97, N 4.60 %. Found: C 70.97, H 5.01, N 4.57 %.

Acknowledgments

The authors thank Consejo Nacional de Ciencia y Tecnología (CONACyT) for financial

support. Project number: 157743.

References

[1] N. Basílio, V. Francisco, L. García-Río, J. Org. Chem., 77 (2012) 10764-10772.

[2] C. Talotta, C. Gaeta, P. Neri, Org. Lett., 14 (2012) 3104-3107.

[3] L. Erra, C. Tedesco, I. Immediata, L. Gregoli, C. Gaeta, M. Merlini, C. Meneghini, M.

Brunelli, A. N. Fitch, P. Neri, Langmuir, 28 (2012) 8511-8517.

[4] A. F. Danil de Namor, W. Aparicio-Aragon, N. Nwogu, A. El Gamouz, O. E. Piro, E. E.

Castellano, J. Phys. Chem. B, 115 (2011) 6922-6934.

[5] S. Sayin, M. Yilmaz, J. Chem. Eng. Data, 56 (2011) 2020-2029.

[6] X. Chen, R. A. Boulos, P. K. Eggers, C. L. Raston, Chem. Commun., 48 (2012) 11407-

11409.

[7] S. M. Taylor, R. D. McIntosh, S. Piligkos, S. J. Dalgarno, E. K. Brechin, Chem.

Commun., 48 (2012) 11190-11192.

[8] S. B. Nimse, T. Kim, Chem. Soc. Rev., 42 (2013) 366-386.

[9] S. G. Bott, A. W. Coleman, J. L. Atwood, J. Am. Chem. Soc., 108 (1986)1709-1710.

[10] A. Arduini, A. Pochini, S. Raverberi, R. Ungaro, J. Chem. Soc., Chem. Commun.,

(1984) 981-982.

[11] C. Alfieri, E. Dradi, A. Pochini, R. Ungaro, G. D. Andreetti, J. Chem. Soc., Chem.

Commun., (1983) 1075-1077.

[12] D. Xie, C. D. Gutsche, J. Org. Chem., 62 (1997) 2280-2284.

[13] D. S. Black, D. C. Craig, R. Rezaie, Chem. Commun., (2002) 810-811.

[14] M.-X. Wang, H.-B. Yang, J. Am. Chem. Soc., 126 (2004) 15412-15422.

[15] C.-H. Lee, H. Miyaji, D-W. Yoon, J. L. Sessler, Chem. Commun., (2008) 24-34.

[16] V. Král, P. A. Gale, P. Anzenbacher Jr., K. Jursíková, V. Lynch, J. L. Sessler, Chem.

Commun., (1998) 9-10.

[17] P. A. Gale, J. L. Sessler, V, Král, Chem. Commun., (1998) 1-8.

[18] Y. Chen, D.-X. Wang, Z.-T. Huang. M.-X. Wang, J. Org. Chem., 75 (2010) 3786–

3796.

[19] M.-X. Wang, Chem. Commun., (2008) 4541-4551.

[20] M.-L. Ma, X.-Y. Li, X.-L. Zhao, F. Guo, B. Jiang, K. Wen, Cryst. Eng. Comm., 13

(21) 1752-1754.

[21] N. Das, P. J. Sanz Miguel, A. Khutia, M. Lazar, B. Lippert, Dalton Trans., (2009)

9120-9122.

[22] E. Khomich, M. Kashapov, I. Vatsouro, E. Shokova, V. Kovalev, Org. Biomol. Chem.,

4 (2006) 1555-1560.

[23] X. Chen, M. Ji, D. R. Fisher, C. M. Wai, Inorg. Chem., 38 (1999) 5449-5452

[24] M.-X. Wang, Acc. Chem. Res. 45 (2012) 182-195.

[25] J.-M. Raimundo, Z. Chen, O. Siri, Chem. Commun., 47 (2011) 10410-10412.

[26] K.-B. Jung, S. K. Kim, V. M. Lynch, D.-G. Cho, J. L. Sessler, Chem. Commun., 48

(2012) 2495-2497.

[27] X.-Y. Li, K.-Y. Yu, X.-L. Zhao, M.-L. Ma, F. Guo, X.-Q. Mi, B. Jiang, K. Wen Cryst.

Eng. Comm., 14 (2012) 7869-7871.

[28] J. Morales-Sanfrutos, M. Ortega-��oz, J. Lopez-Jaramillo, F. Hernandez-Mateo, F.

Santoyo-Gonzalez, J. Org. Chem., 73 (2008) 7768-7771.

[29] V. Barba, H. Höpfl, N. Farfán, R. Santillan, H.I. Beltran, L.S. Zamudio, Chem.

Commun., 24 (2004) 2834-2835.

[30] V. Barba, R. Villamil, R. Luna, C. Godoy-Alcántar, H. Höpfl, H. I. Beltran, L. S.

Zamudio-Rivera, R. Santillan, N. Farfán. Inorg. Chem., 45, 2006, 2553-2561.

[31] V. Barba, E. Gallegos, R. Santillan, N. Farfán, J. Organomet. Chem., 622 (2001) 259-

264.

[32] V. Barba, R. Hernández, H. Höpfl, R. Santillan, N. Farfán, J. Organomet. Chem., 694

(2009) 2127-2133.

[33] V. Barba, I. Betanzos. J. Organomet. Chem., 692 (2007) 4903-4908.

[34] N, Nishimura, K. Kobayashi, J. Org. Chem. 75 (2010) 6079-6085.

[35] N. Fujita, S. Shinkai, T. D. James, Chem. Asian J., 3 (2008) 1076-1091.

[36] R. Nishiyabu, Y. Kubo, T. D. James, J. S. Fossey, Chem. Commun., 47 (2011) 1124-

1150.

[37] K. Severin, Dalton Trans., (2009) 5254-5264.

[38] Y. C. Kim, S. G. Brown, T. K. Harden, J. L. Boyer, G. Dubyak, B. F. King, G.

Burnstock, K. A. Jacobson, J. Med. Chem. 44 (2001) 340-349.

[39] Z. Li, C. Jablonski, Chem. Commun., 16 (1999) 1531-1532.

[40] V. Reyes-Márquez, M. Sánchez, H. Höpfl, K. O. Lara, J. Incl. Phenom. Macrocycl.

Chem., 65 (2009) 305-315.

[41] Crystal data for 10 (C17H16O6): CCDC number 916398, Orthorhombic, space group

P2(1)2(1)2, a = 6.787(3)), b =23.691(10), c = 4.5084(19) A˚ , a = b = c = 90.00°, V =

724.9(5) Å3, T = 100 K, Z = 2, 2341 reflections measured, 773 unique, (Rint = 0.04), R1

[I > 2�I] = 0.04, wR2 = 0.08 for all data.

[42] Geometry optimization was done using HyperChem 8.0.7.

[43] Bruker Analytical X-ray Systems. SHELXTL-NT Version 6.10, 2000.

Schemes and Figures

O

OHR

B(OH)2

NH2

3 3

Double cone conformation

OH

O

HO

OX

B(OH)2

NH2

+3

6

Boroncalix[3]arenes

DoubleCalixarene

Linkers Doublecalixarene

X

X

X

Boronhemicarcerands

Scheme 1: Strategy to synthesized calix- (up) and hemicarcerand- (Down) like compounds

B(OH)2

NH2

3O

OH+ 3

OBN

OB

N

OB

N

OR'

R'O

R'O4 h

R'OH/Benzene

R R

R

R

∆

R R'1: 5-Br Me2: 5-Me Me3: 4-(Et2N) Me4: 4-(Et2N) Et

1

23

4

5

6 78 9

10

1112

13

Scheme 2: Synthesis of calix-like compounds

OBN

OB

N

OB

N

OEt

EtO

EtON

OBN

OB

N

OB

N

OR'

R'O

R'O

OPO

HOHO

N

OP

O OHOH

N

OP

O

OHHO

56: R = Me7: R = Et

1

23

4

5

6

78 9

10

1112

13

Scheme 3: Naphthalene and pyridoxal derivatives calix-like compounds

1 2

3

45

6

7

8

91011

1213

NO

OB

N

B

OH OH

CH3 CH3

O OB(OH)2

NH2

3 + 6MeOH/Benzene

4 h

CH3

CH3

OMe

MeO

∆

3128

12

3

45

6

78

Scheme 4: Formation of hemicarcerand derived from bis-salicylaldehyde having CH2

groups as linkers

1

23

4

5 6

7O O

O OOHHO

R

+ 6

B(OH)2

NH2

R'OH/C6H6∆ 4 h

3

ONOB

OR'

O NO B

OR'

R

9-11

R R'13: -CH2CH2- Et14: -CH2CH2CH2- Et15: p-CH2C6H4CH2- Me

3

1

23

4

5 6

7

8

910

11

1213

Scheme 5: Synthesis of hemicarcerands having large chain linkers

Figure 1: Molecular structure for compound 10, ellipsoids are in a 50% of probability.

Selected bond distances (Å) and angles (°): C1-O1 1.356(4), C7-O2 1.239(4), C5-O3

1.362(4), C8-O3 1.449(4), C8-C9 1.508(4), C9-C8-O3 105.7(2), C8-O3-C5 118.6(3).

Figure 2: Side view of the unit cell for compound 10 showing a zig-zag ordering.

Figure 3: Part of the FAB+-MS Spectrum for compound 14 showing the molecular ion.

Inset, calculate isotopic pattern.

Figure 4: Molecular models for compounds 13, 14 and 15, illustrating the cavity distortion

arrangement.

�

��

�

�

One-pot synthesis of calixarene and hemicarcerand like compounds can be modulated by

use of mono- or bis-salicylaldehyde derivatives respectively reacting with��

�� . Both, calixarene and hemicarcerand compounds are result from

condensation reactions, wherein the formation of N-B coordination bonds plays a

significant role on the formation of macrocyclic products.

�

�

�

Graphical abstract

��

�

�

�

�

�

�

��

�

��

��

�� !�� !��

��

Date post:	08-Dec-2016
Category:	Documents
Upload:	ariel
View:	213 times
Download:	0 times

Calixarene and hemicarcerand-like compounds obtained by self-assembly of 3-aminophenylboronic acid...

Documents