Synthesis, structural characterization and metal inclusion properties of 18-, 20- and 22-membered oxaazacyclophanes and oxaazacalix[4]arene analogues: Macrocyclic amine and schiff base receptors with variable NxO y donor sets

FULL PAPER

DOI: 10.1002/ejoc.201001312

Synthesis, Structural Characterization and Metal Inclusion Properties of

18-, 20- and 22-Membered Oxaazacyclophanes and Oxaazacalix[4]arene

Analogues: Macrocyclic Amine and Schiff Base Receptors with Variable N_xO_y

Donor Sets

Ramón Moreno-Corral,^[a]Herbert Höpfl,^[b]Lorena Machi-Lara,^[a]and Karen O. Lara*^[a]

Keywords: Schiff bases / Macrocycles / Cyclophanes / Calixarenes / Metal complexes

A series of oxaazacyclophanes and oxaazacalix[4]arene ana- been analysed by single-crystal X-ray diffraction. Two of the

logues with 18-, 20- and 22-membered rings have been syn-

thesized from diamine and dialdehyde building blocks and

structurally characterized by spectroscopic methods. One di-

amine precursor and four macrocycles have additionally

oxaazacalix[4]arene analogues were employed for metal ion

complexation studies based on UV/Vis absorption spec-

troscopy, showing both compounds to be able to form com-

plexes with Cu²⁺and Zn²⁺

.

oxygen donors is an expanding domain of research with

promising and diverse applications.^[18–20]

1. Introduction

During the past few decades much effort has been dedi-

cated to the design of macrocyclic receptors possessing spe-

cific structural features, as a result of their importance in

the fields of supramolecular and coordination chemis-

try.^[1–4]Accordingly, macrocycles have played a key role in

the understanding of certain molecular processes, especially

those relating to bioactive molecules such as porphyrins,

corrins and antibiotics.^[5–8]In addition, macrocyclic com-

pounds have important applications in, among other fields,

analytical chemistry, pharmaceutics, food chemistry, hydro-

metallurgy, agriculture and materials science.^[9–12]

One representative group of macrocycles is the cy-

clophane family. Special attention has been drawn to oxa-

azacyclophanes, because they are versatile hosts for the re-

cognition of organic and inorganic ions and mole-

cules.^[13–14]Depending on the number, position and orienta-

tion of the donor groups included in a macrocycle structure,

as well as its ring size, highly selective ligands for certain

metal ions can be obtained.^[15–17]Although there are many

reports on this topic in the literature, the coordination

chemistry of ditopic macrocycles with mixed nitrogen–

From the synthetic point of view, these compounds can

be obtained by a variety of methods, which typically involve

either the high-dilution principle or the template effect, in

order to increase the yield of the cyclization step.^[21–22]In

the metal template synthesis approach, however, stable

metal-complexed macrocycles can be generated, and re-

moval of the metal can be a problem in this case.^[23]

A third synthetic method for macrocyclic enclosure is the

high-pressure procedure. Although it is the least common

method, there are several reports describing its efficacy in

macrocycle synthesis, especially when suitable building

blocks are employed for the cyclization.^[24–26]We recently

reported on the preparation of a series of Schiff base diox-

adiazamacrocycles in moderate to high yields by this

method, from combinations of dialdehyde precursors and

diamines.^[27,28]However, the structural characterization of

these compounds showed that in some of the macrocycles

the orientation of the lone pair electrons on the nitrogen

atoms was not suitable for metal complexation.^[28]

We now report on the synthesis and structural charac-

terization of a series of oxaazacyclophanes and oxaaza-

calix[4]arene analogues, the preparation of which from di-

amine and dialdehyde building blocks has been optimized

by exploration of the high-pressure, high-dilution and metal

template methods. In view of the structural characteristics

of the macrocycles, some of them might be employable as

hosts for small organic compounds and metal ions. In order

to verify this hypothesis, two of these and their oxaaza-

calix[4]arene analogues were employed for titration experi-

[a] Departamento de Investigación en Polímeros y Materiales,

Universidad de Sonora,

Rosales y Encinas s/n, Col. Centro, 83000 Hermosillo, Sonora,

México

Fax: +52-662-2592216

E-mail: karenol@polimeros.uson.mx

[b] Centro de Investigaciones Químicas,

Universidad Autónoma del Estado de Morelos,

Av. Universidad 1001, Cuernavaca 62209, México

Supporting information for this article is available on the

WWW under http://dx.doi.org/10.1002/ejoc.201001312.

ments with Cu²⁺, Ni²⁺and Zn²⁺

.

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Oxaazacyclophanes and Oxaazacalix[4]arene Analogues

Treatment of equimolar amounts of the diamines 6–9

with isophthalaldehyde in ethanol under high-dilution con-

ditions to give the corresponding cyclic Schiff bases only

succeeded in the cases of 7 and 9. In situ reduction by ad-

dition of sodium borohydride to the reaction solutions af-

forded the corresponding 18-membered oxaazamacrocycles

14 and 15 (Scheme 2) in moderate yields.

In an attempt to achieve reactivity of diamine 6 towards

isophthalaldehyde, zinc perchlorate was employed as tem-

plate to give the diimine 16 (Scheme 2). However, this reac-

tion gave only low yields and in the case of the diamine 8

it did not take place. In order to test a third synthetic pro-

cedure, the diamines 6 and 8 were therefore combined with

the appropriate alkyl dihalides in equimolar proportions

2. Results and Discussion

2.1. Synthetic Procedures

The diamines 6–9 were prepared by the synthetic pro-

cedure shown in Scheme 1. Treatment of 2-(acetylamino)-

phenol (1) with suitable alkyl dihalides in a 2:1 molar ratio

gave the corresponding ethers 2–5, which were then depro-

tected to afford the corresponding diamine derivatives 6–9.

Compounds 1–2, 5–7 and 9 had been reported in the litera-

ture previously,^[29–35]but the diamines 3, 4 and 8 had not.

The dialdehyde building blocks 10–13 were prepared by

an analogous Williamson ether synthesis with salicylalde-

hyde in place of the N-protected amine 1. All of the dialde-

hyde compounds had been reported previously.^[28,36,37]

Scheme 1. Synthesis of the diamine (6–9) and dialdehyde (10–13) building blocks.

Scheme 2. Synthesis of the oxaazacyclophanes 14–16.

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Scheme 3. Synthesis of the oxaazacyclophanes 17 and 18.

Scheme 4. Synthesis of the oxaazacyclophanes 19–23.

2.2. Structural Characterization

under high-dilution conditions to give the 18- and 20-mem-

bered dioxadiaza macrocycles 17 and 18 (Scheme 3) in

moderate to good yields.

All compounds described here were characterized by ele-

1

With the dialdehyde building blocks 10, 11 and 13, on mental analysis, IR and H/¹³C NMR spectroscopy (stan-

the other hand, the high-dilution reaction sequence shown dard one- and two-dimensional techniques) and mass spec-

in Scheme 1 (Method 1) was explored. When 10, 11 and trometry. In all cases the spectroscopic data were consistent

13 were each combined with m-xylylenediamine in ethanol with the assigned structures (see the Experimental Section).

under high-dilution conditions, followed by in situ treat- In the cases of compounds 7, 14, 15, 17 and 19, the molecu-

ment with sodium borohydride, the 20- and 22-membered lar structures were additionally established by single-crystal

m-xylylene derivatives 21–23 (Scheme 4) could be isolated X-ray diffraction analysis. The most relevant crystallo-

in good yields. In order to explore an alternative method graphic data are given in the Experimental Section (see

for the preparation of macrocycles, the high-pressure Table 4, below).

method was employed for the dialdehydes 10 and 12 in

The molecular structure of the diamine intermediate 7 is

combination with m- and p-xylylenediamine, respectively. In shown in Figure 1. As expected, the amino functions are

this case the macrocyclic Schiff bases 19 and 20 (Scheme 4) not syn-oriented as in the macrocyclic ring structure. In-

were obtained in good to moderate yields.

teratomic distances and angles are in the expected ranges.

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Oxaazacyclophanes and Oxaazacalix[4]arene Analogues

In the crystal structure the diamine molecules are linked Table 1. Hydrogen bonds in the crystal structure of 7·H₂O (Å and

°).^[a]

through hydrogen bonding interactions with crystal lattice

water molecules to give a 1D chain along the c axis, based

on an interesting tetrameric assembly formed between two

water and four diamine molecules (Figure 2). Within these

D–H···A

d(D–H)

d(H···A)

d(D···A)

ЄDHA

O31–H···N2

O31–H···N1ⁱ

0.84

0.86

2.05

2.12

2.09

2.50

2.87

2.96

2.91

3.23

165

174

160

144

chains each water molecule is connected to three diamines N1ⁱⁱ–H···O31ⁱⁱ

N3ⁱⁱⁱ–H···O31

by O_w–H···N_pyr, O_w–H···N_amineand N_amine–H···O_whydro-

gen bonding interactions (Table 1). The chains are linked

through further N_amine–H···O_winteractions to give an over-

all 3D hydrogen-bonded network.

[a] Symmetry operators: i) –x, 2 – y, –z; ii) –x, 2 – y, 1 – z; iii) –x,

1 – y, 1 – z.

oriented towards the cavity of the macrocycle. In contrast,

the diimine 19 has the E configuration (Figure 4, b), and

the lone pair electrons on the nitrogen atoms are oriented

towards the periphery of the macrocycle (exo), whereas the

lone pair electrons of the oxygen atoms are oriented into

the cavity (endo). This finding is in agreement with our re-

cently published report on structurally related diimine

macrocycles,^[28]which have been analysed by molecular

modelling and X-ray diffraction analysis.

“Calixarene” is the term coined for a series of macro-

cyclic phenol condensates connected through methylene

bridges and capable of assuming basket-shaped (or calyx-

shaped) conformations.^[38]A variety of calixarenes and their

Figure 1. Perspective view of the molecular structure of the precur-

sor 7·H₂O. Displacement ellipsoids are drawn at the 50% prob-

ability level. Hydrogen atoms are shown as small spheres of arbi-

trary radius.

The molecular structures of compounds 14, 15, 17 and analogues have been obtained: a) by derivatizations on the

19 are shown in Figure 3 and Figure 4, revealing that for upper and/or lower rims of conventional calix[n]arenes,

the macrocyclic diamines 14, 15 and 17 the NH hydrogen b) by the replacement of their phenylene units with hetero-

atoms and the lone pair electrons of the oxygen atoms are cyclic moieties (such as furan, thiophene, pyridine, imid-

Figure 2. Fragment of the crystal structure of diamine 7·H₂O showing a) the tetrameric assembly within b) the 1D hydrogen-bonded

chain. Symmetry operators: i) –x, 2 – y, –z; ii) –x, 2 – y, 1 – z; iii) x, y, 1 + z.

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Figure 3. Perspective views and space-filling models of the molecular structures of compounds a) 14 and b) 15. Displacement ellipsoids

are drawn at the 50% probability level. Hydrogen atoms are shown as small spheres of arbitrary radius.

logues. Calix[4]arenes exhibit four different conformations,

termed cone, partial cone, 1,2-alternate and 1,3-alternate.^[38]

In the solid state, the two independent molecules in the

crystal lattice of compound 14 have flattened 1,3-alternate

conformations, in which the cavities are partially occupied

by water molecules. The oxygen atoms of the water mole-

cules show a total of six short D···A contacts in the 2.88–

3.35 Å range, of which five correspond to hydrogen bonds

with the nitrogen and oxygen atoms of the macrocyclic ring

and one to a C–H···O_winteraction (Figure 5). The large

number of possible interactions is interesting, because a co-

ordinated water molecule generally occupies a tetrahedral

coordination environment with a maximum of four hydro-

gen bonding interactions. This structure indicates that the

water molecules are scrambling around the cavity of the

oxaazacalix[4]arene analogue, probably each having at least

two different orientations.

Figure 4. a) Perspective views and space-filling models of the mo-

lecular structures of compounds a) 17 and b) 19. Displacement el-

lipsoids are drawn at the 50 and 30% probability level, respectively.

Hydrogen atoms are shown as small spheres of arbitrary radius.

azole, indole, etc.),^[39]or c) by linking the aromatic rings

with atoms other than carbon (such as nitrogen, oxygen,

Figure 5. In the solid state, compound 14 forms inclusion com-

silicon and sulfur, among others).^[40]

plexes with crystal lattice water molecules. Displacement ellipsoids

are drawn at the 50% probability level. Hydrogen atoms are shown

and 19, they could be considered oxaazacalix[4]arene ana- as small spheres of arbitrary radius.

From the structural characteristics of compounds 14, 17

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Oxaazacyclophanes and Oxaazacalix[4]arene Analogues

Table 2. Selected geometrical parameters for the description of size, cavity and conformation of the macrocycle components in compounds

14, 15, 17 and 19.

[b]

[c]

O···O [Å]

O···N [Å]

N···N [Å]

centr···centr^[a][Å]

C_ar–N–CH₂–C_ar[°]

C_Ar–O–CH₂–C_Ar[°]

14^[d]

5.17

5.19

5.05

4.96

5.04

2.60/2.63

2.62/2.63

2.63/2.61

2.61/2.61

3.96/3.97

5.24

5.39

5.36

4.96

5.62

6.72/9.50

6.72/9.65

–/9.26

8.25/6.52

9.00/7.97

+174.6/+172.2

–170.5/–167.6

–172.2/+166.1

+69.8/+85.1

–176.0/–177.4

+177.3/–178.7

+177.4/+174.6

–85.1/–69.8

15

17^[e]

19

–115.5/+117.3

+78.0/+76.7

[a] The first value corresponds to the centroid···centroid distance between the phenylene groups and the second to the centroid···centroid

distance between the 2-aminophenoxy groups. [b] C_H–N–CH₂–CH_arin the case of compound 19. [c] C_ar–O–CH₂–CH₂in the case of

compound 15. [d] The crystal structure of this compound has two independent molecules in the asymmetric unit. [e] The molecules are

disordered around crystallographic inversion centres within the crystal structure.

The molecular structure of 15 has a very similar confor-

Of the structures analysed by X-ray diffraction analysis,

mation to the previous case (Figure 3, b). In compounds 17 the crystal structures of compounds 15 and 19 show an

and 19 the meta-phenylene rings are in or almost in the interesting supramolecular organization. In compound 15

same plane (angle between the mean planes of the meta- the macrocycles are arranged in pillars in 1D chains along

phenylene rings: 0.0° for 17 and 12.2° for 19), so that the the b axis. In these strands, the –CH₂CH₂OCH₂CH₂–

conformations of these oxaazacalix[4]arene analogues are groups are embedded within the cavities of neighbouring

best described as chair conformations (Figure 4).

macrocycles (Figure 6). In the crystal structure of com-

The geometric and topological properties of the macro-

cycles can be analysed in greater detail in terms of the series

of intra-annular distances and torsion angles summarized

in Table 2. The O···O, O···N, N···N and centroid···centroid

distances between opposite aromatic rings allow the recep-

tor shape to be outlined. For the diamine derivatives 14, 15

and 17 the spatial orientations of the NH groups are best

described by the C_ar/C_H–NH–CH₂–C_artorsion angles,

which together with the C_ar–CH₂–O–CH₂torsion angles

provide valuable information on the molecular conforma-

tions. The values of these torsion angles show that the con-

formational changes between the two types of macrocycles

(14 and 15 vs. 17 and 19) arise from rotation of the 2-ami-

nophenoxy groups around the O–CH₂and N–CH₂bonds

groups together with rotation of the meta-phenylene rings

around the C_ar–CH₂bonds. As a consequence, the

centroid···centroid distances between the meta-phenylene

Figure 7. In the crystal structure of compound 19, the macrocycles

are arranged in pillars to give 1D chains along the c axis through

inclusion of the -OCH₂C₄H₄CH₂O- and -NCH₂C₄H₄CH₂N-

groups within the cavities of neighbouring macrocycles.

groups

increase

significantly,

whereas

the

centroid···centroid distances between the 2-aminophenoxy

groups decrease (Table 2).

Figure 6. In the crystal structure of compound 15, the macrocycles are arranged in pillars to give 1D chains along the b axis through

inclusion of the -CH₂CH₂OCH₂CH₂- group within the cavity of a neighbouring macrocycle.

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pound 19, a similar 1D supramolecular arrangement arises presence of copper and zinc ions caused small changes in

from the inclusion of the –OCH₂C₄H₄CH₂O– and the absorption spectra, but no spectral change was detected

–NCH₂C₄H₄CH₂N– groups into neighbouring macrocycles in the presence of nickel. Because the spectral changes were

(Figure 7).

not very significant, it was not possible to determine the

binding constants. The low-affinity binding for the metal

ions can be attributed to the coordinative nature of the sol-

vent (acetonitrile), which thus competes for the binding

sites at the metal centre. The UV/Vis spectra of the free

macrocycles 14 and 17 and their corresponding metal com-

plexes with Cu²⁺, Ni²⁺and Zn²⁺in dichloromethane (10^–4

to 10^–6m solutions) were recorded and significant spectral

changes for the ligands were observed in the presence of

Cu²⁺and Zn²⁺. In particular, a new strong absorption band

appeared for each receptor, at approximately 380 nm for the

copper complexes and at approximately 390 nm for the zinc

complexes (see Figures 8 and 9). If it is taken into account

that Zn²⁺is a closed-shell metal ion, the new absorption

band around 390 nm in the spectra of copper and zinc com-

plexes of the macrocycles can only be attributed either to

intraligand charge transfer transition of mixed ππ*/nπ*

character^[41]or to charge transfer between a cyclophane

molecule and metal acetonitrile complexes [M(CH₃CN)_n].

This latter due to acetonitrile was employed as co-solvent,

typically at 3% v/v (see Experimental Section: Solution

Studies by UV/Vis Electronic Absorption). As was also ob-

served for the titrations in acetonitrile, the presence of

nickel ions did not cause changes in the absorption spectra

of compounds 14 and 17. This may be attributed to the

rigidity of the structures of the cyclophane ligands, which

reduces their ability to adapt themselves to the stereochemi-

cal requirements of Ni²⁺, which are much stricter than

those of Cu²⁺and Zn²⁺, producing a decrease in the

thermodynamic stability of the nickel complexes.

2.3. Complexation Studies in Solution

From the chemical structures of the oxaazacalix[4]arene

analogues 14 and 17 (see Figures 3 and 4), it can be ex-

pected that these multipoint coordination ligands might be

capable of forming stable complexes with certain metals.

For that reason, we carried out preliminary experiments to

investigate the UV/Vis spectroscopic properties of these

compounds. Characteristic absorption bands and molar ab-

sorptivity coefficients for compounds 14 and 17 are summa-

rized in Table 3.

Table 3. Characteristic absorption bands and molar absorptivity

coefficients for compounds 14 and 17 in different solvents.

Solvent

λ_max[nm] ε_max[dm³mol^–1cm^–1]

14

17

acetonitrile

246

289

275

293

249

292

287

14500

5830

methylene chloride

acetonitrile

7014

20540

10207

23229

methylene chloride

The coordination capabilities of the oxaazamacrocyclic

ligand 14 towards Cu²⁺, Ni²⁺and Zn²⁺ions were first in-

vestigated by UV/Vis spectroscopy in acetonitrile. The UV/

Vis spectra of the macrocycle and of its corresponding

metal complexes were recorded in 10^–3to 10^–5m solutions.

As summarized in Table 3, in acetonitrile the free macro-

Titration plots of the absorbance at 380 or 390 nm

cycle exhibits two strong broad absorption bands at 246 showed different behaviour for the two metal ions: for the

and 289 nm, which correspond to π–π* and n–π* transi- copper complexes a hyperbolic shape characteristic of 1:1

tions of benzene rings and amine groups, respectively. The stoichiometry was observed, whereas the zinc complexes

Figure 8. Variation of the absorption spectra (in CH₂Cl₂) in the presence of Cu²⁺(10^–6to 10^–4m) for: a) macrocycle 14, and b) macrocycle

17. Insets: plots of the absorbance at 380 and 390 nm, respectively, with respect to the concentration of Cu²⁺. For both solutions the

concentration of the macrocycle was 3ϫ10^–5m. Solid lines are the fitting curves in accordance with Equation (1).

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Oxaazacyclophanes and Oxaazacalix[4]arene Analogues

Figure 9. Variation of the absorption spectra (in CH₂Cl₂) in the presence of Zn²⁺(10^–6to 10^–4m) for: a) macrocycle 14, and b) macrocycle

17. Insets: plots of the absorbance at 392 and 390 nm, respectively, with respect to the concentration of Zn²⁺. For both solutions the

concentration of the macrocycle was 3ϫ10^–5m.

generated a sigmoid shape, suggesting that the ligands were

3. Conclusions

not forming complexes with definite compositions. The

The above discussion shows that the diamine and dialde-

spectral changes accompanying complex formation and the

hyde building blocks used here allow macrocyclic structures

titration plots are shown in Figures 8 and 9.

to be prepared easily and in good yields by the high-pres-

The hyperbolic behaviour observed in the titration plots

sure, high-dilution or metal template methods. The solid-

of the copper complexes indicates a 1:1 ligand/metal stoi-

state characterization of one diimine and three diamine

chiometry, so the data were fitted in accordance with Equa-

macrocycles by X-ray diffraction analysis indicates that

tion (1).^[42,43]

these compounds are good candidates for receptors for

metal ions or small molecules. Titration studies with cop-

A_obs= (A₀+ A_ϱK[G]_T)/(1 + K[G]_T)

(1)

per(II), nickel(II) and zinc(II) nitrate have shown that some

of the macrocyclic hosts described are indeed capable of

metal complexation. On the other hand, it is important to

emphasize that some of the cyclic diamines described in this

report could also serve as receptors for anions, in particular

if the nitrogen atoms were protonated. In this respect, we

are currently working on anion complexation studies of

some of these macrocyclic hosts. We are also working on

the preparation of further oxaazyclophanes with additional

binding sites, in order to generate hosts with a more specific

capability for guest complexation in organic and aqueous

media.

where A_obsis the observed absorbance, A₀is the absorbance

of free ligand, A_∞is the maximum absorbance induced

by the presence of a given metal ion, [G]_Tis the total con-

centration of the metal ion and K is the binding constant.

This gave K = 4600 m^–1for 14-Cu²⁺and K = 10200 m^–1for

17-Cu²⁺

.

On the other hand, in order to observe the d–d transi-

tions of the copper complexes, additional UV/Vis measure-

ments were carried out in dichloromethane at a higher li-

gand concentration ([17] = 5.0ϫ10^–4m). A solution of a

17/Cu²⁺mixture at a molar ratio [Cu]/[L] = 1 showed a new

broad band in the absorption spectrum, its centre at about

770 nm, characteristic of copper complexes with octahedral

geometry (see the Supporting Information).^[44]The two

oxygen and two nitrogen atoms on the macrocycle ring are

Experimental Section

General: All solvents were of analytical reagent grade and reagents

from Sigma–Aldrich were used without further purification. For

coordinated to the metal cation, and the six-coordination spectrophotometric measurements HPLC-grade solvents were

used. The 1D and 2D NMR spectra were recorded with a Bruker

Advance 400 instrument. Chemical shifts (δ) are reported as values

in ppm in relation to TMS (δ¹H = 0 ppm and δ¹³C = 0 ppm). IR

spectra were recorded with Bruker Vector 22 and Perkin–Elmer

Spectrum GX FTIR spectrophotometers. Mass spectrometry was

conducted with a high-resolution Jeol MStation 700 mass spec-

trometer and use of the FAB⁺technique. Elemental analyses were

carried out with an Elementar Vario ELIII instrument. Melting

points are uncorrected. The UV/Vis absorption spectra were mea-

sured with an Agilent 8435 UV/Vis spectrophotometer (Agilent

Technologies).

sphere is believed to be completed by two acetonitrile mole-

cules (for the titration experiments, stock solutions of Cu²⁺

,

Ni²⁺and Zn²⁺were prepared from the corresponding ni-

trates in acetonitrile; see the Experimental Section: Solution

Studies by UV/Vis Electronic Absorption.).

Finally, in order to confirm the possibility of multiple

equilibria for zinc complexes, a Job experiment was per-

formed for the 14/Zn²⁺system, which confirmed a ligand-

to-metal stoichiometry of 1:2 (see the Supporting Infor-

mation).

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Table 4. Crystallographic data^[a]for compounds 7, 14, 15, 17 and 19.

7

14

15

17

19

Formula

C₁₉H₁₉N₃O₂·H₂O C₂₇H₂₅N₃O₂·0.175 H₂O C₂₄H₂₆N₂O₃

C₂₈H₂₆N₂O₂

422.51

P2₁/c

C₃₀H₂₆N₂O₂

446.53

P2₁

MW [gmol^–1]

339.39

426.65

390.47

P2₁/n

¯

P1

¯

P1

Space group

Temperature [K]

a [Å]

b [Å]

c [Å]

α [°]

β [°]

100(2)

14.729(2)

4.9912(7)

27.837(4)

90

98.351(2)

90

2024.7(5)

4

0.085

173(2)

8.0946(14)

7.8455(13)

17.134(3)

90

101.389(3)

90

1066.7(3)

2

0.083

1.315

5244

1874 (0.03)

1498

151

293(2)

9.746(3)

13.056(4)

9.796(3)

90

106.831(5)

90

1193.0(6)

2

0.078

7.5478(11)

10.5612(15)

10.9098(16)

76.035(3)

80.438(3)

89.909(3)

831.6(2)

2

0.093

1.355

4362

2817 (0.02)

2372

9.0783(14)

12.1441(19)

21.050(3)

103.970(2)

96.166(3)

90.441(3)

2237.7(6)

4

0.081

1.266

16742

7823 (0.03)

6549

γ [°]

V [Å³]

Z

M [mm^–1]

ρ_calcd.[gcm^–3]

Collected reflections

Independent reflections (R_int

Observed reflections^[b]

Variables

1.281

1.243

18053

3539 (0.05)

3098

270

0.059

11431

2206 (0.05)

1878

307

0.065

)

244

0.049

0.133

607

0.062

0.134

R^[b,c]

0.055

0.116

[d,e]

R_w

0.148

0.151

[a] λ_Mo-Kα= 0.71073 Å. [b] F_oϾ4σ(F_o). [c] R = Σ||F_o| – |F_c||/Σ|F_o|. [d] All data. [e] R_w= [Σw(F_o– F_c) /Σw(F_o²)²]^1/2

.

2

2 2

X-ray Crystallographic Studies: X-ray diffraction analyses were per-

formed with a Bruker-APEX diffractometer and CCD area detec-

tor (λ_Mo-Kα= 0.71073 Å, graphite monochromator). Frames were

collected through ω- and φ-rotation at 10 s per frame

(SMART).^[45a]The measured intensities were reduced to F²and

corrected for absorption with SADABS (SAINT-NT).^[45b]Correc-

tions were made for Lorentz and polarization effects. Structure

solution, refinement and data output were carried out with the

SHELXTL-NT program package.^[45c–45d]Non-hydrogen atoms

were refined anisotropically, whereas hydrogen atoms were placed

in geometrically calculated positions by use of a riding model. O–

H and N–H hydrogen atoms were localized by use of difference

Fourier maps and refined by fixing the bond lengths to 0.84 and

0.86 Å, respectively; the isotropic temperature factors were re-

strained to values 1.5 times those of the corresponding oxygen/

nitrogen atoms. Compounds 7 and 14 crystallized as solvates

(7·H₂O and 14·0.175H₂O). In 14·0.175H₂O, the asymmetric unit

contains two independent macrocyclic molecules, in which the cavi-

ties are occupied partially by water molecules (occ = 0.10 and 0.25).

Because of the low occupancy, the O_w–H hydrogen atoms could

not be localized by difference Fourier maps in the latter case. In

the crystal structure of compound 17, the macrocycles are disor-

dered over two positions around crystallographic inversion centres

(occ = 0.50), which introduces apparent inversion symmetry. EXYZ

and EADP instructions were used for the refinement of this struc-

ture. Crystals of compound 19 diffracted only weakly, so the data/

parameter ratio was low (7.2). Despite this, the data were of suf-

ficient quality to allow determination of the molecular structure

and discussion of the molecular geometry. Figures were created

with SHELXTL-NT and DIAMOND.^[46]Hydrogen bonding inter-

actions in the crystal lattice were calculated with the WINGX pro-

gram package.^[47]The most relevant crystallographic data are given

in Table 4.

Solution Studies by UV/Vis Electronic Absorption: For the titration

experiments receptor concentrations of 3ϫ10^–5m were employed.

Stock solutions of Cu²⁺, Ni²⁺and Zn²⁺were prepared from the

corresponding nitrates in acetonitrile. For the determination of the

ligand/metal stoichiometry by a continuous variation experiment

(Job’s method), the total concentrations employed for all solutions

were 6ϫ10^–5m. Spectrometric titration curves were fitted with the

aid of the Microcal Origin 8.1 program.^[48]

Syntheses

Compound 1: This compound was prepared by a modification of

the procedure reported previously.^[29]A solution of acetic anhy-

dride (0.11 g, 14.7 mmol) in methanol (3 mL) was added slowly to

a suspension of 2-aminophenol (0.70 g, 6.42 mmol) in water

(20 mL). The reaction mixture was then stirred for 5 h at room

temperature. The reaction was monitored by TLC (hexane/acetone

60:40) until a single product was observed and the starting material

had disappeared. The reaction mixture was filtered in order to re-

move the solvent. A pale yellow solid was obtained after filtration,

recrystallization from EtOH and drying in vacuo; yield 0.95 g,

1

98%; m.p. 218–220 °C. H NMR (400 MHz, [D₆]DMSO, 25 °C): δ

= 9.73 (s, 1 H, 8-H), 9.30 (s, 1 H, 1-H), 7.68 (dd, J = 1.4, J = 8 Hz,

1 H, 6-H), 6.93 (dt, J = 1.4, J = 8 Hz, 1 H, 4-H), 6.86 (dd, J = 1.4,

J = 8 Hz, 3-H), 6.75 (dt, J = 1.4, J = 8 Hz, 1 H, 5-H), 2.09 (s, 3

H, 10-H) ppm. ¹³C NMR (400 MHz, [D₆]DMSO, 25 °C): δ = 169.5

(C-9), 148.3 (C-6), 126.9 (C-3), 125.1, 122.9 (C-2, C-7), 119.4 (C-

4), 116.4 (C-5), 24.1 (C-10) ppm. IR (KBr): ν = 3403 (s), 3084 (s),

˜

2882 (m), 2747 (m), 2619 (m), 1659 (s), 1284 (s), 755 (s). FAB⁺-

MS: m/z (%)

= 152 (45) [M +

H]⁺, 136 (75), 108 (26).

C₈H₉NO₂·EtOH (197.23): calcd. C 60.90, H 7.67, N 7.10, O 24.33;

found C 60.86, H 7.66, N 7.08.

CCDC-787531 (for 7), -787532 (for 14), -787533 (for 15), -787534

(for 17), and -787535 (for 19) contain the supplementary crystallo-

graphic data for this paper. These data can be obtained free of

charge from The Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif.

2156

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Eur. J. Org. Chem. 2011, 2148–2162

Oxaazacyclophanes and Oxaazacalix[4]arene Analogues

Compound 2: This compound was prepared by a modification of

the procedure reported previously.^[30]A solution of 1 (3.36 g,

17.04 mmol) in anhydrous DMF (5 mL) was added to a suspension

of K₂CO₃(in excess) in the same solvent (25 mL). The suspension

was kept under nitrogen and stirred at 80 °C for 30 min. A solution

of 1,3-bis(bromomethyl)benzene (2.25 g, 8.52 mmol) in anhydrous

DMF (5 mL) was then added slowly to the mixture and the re-

sulting suspension was stirred at 80 °C. The reaction was monitored

by TLC (hexane/acetone 60:40) until a single product was observed

and the starting material had disappeared. The suspension was fil-

tered in order to remove the potassium salt. The filtrate was evapo-

rated in vacuo to dryness and acetone was added until a precipitate

appeared. A light brown solid was obtained after filtration, acetone

washing and drying in vacuo; yield 3.05 g, 93%; m.p. 183–184 °C.

¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 8.34 (dd, J = 2.1, J =

7.3 Hz, 2 H, 5-H), 7.74 (s, 2 H, 3-H), 7.52 (d, J = 7.5 Hz, 2 H, 12-

H), 7.45 (m, 2 H, 13-H, 14-H), 6.90 (m, 4 H, 6-H, 7-H), 6.92 (dd,

J = 2.2, J = 7.2 Hz, 2 H, 8-H), 5.29 (s, 4 H, 10-H), 2.17 (s, 6 H, 1-

H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 165.59 (C-2),

144.4 (C-4), 134.7 (C-9), 126.8 (C-11), 125.5 and 123.9 (C-13 and

C-14), 124.9 (C-12), 121.2 (C-7), 119.2 (C-6), 117.8 (C-5), 109.3 (C-

Compound 4: This compound was prepared in a manner similar to

that described above, from 1 (5.20 g, 26.4 mmol) and 1,4-bis(brom-

omethyl)benzene (3.60 g, 13.2 mmol). The product was obtained as

a light brown solid; yield 5.2 g, 98%; m.p. 197–200 °C. ¹H NMR

(400 MHz, CDCl₃, 25 °C): δ = 8.38 (d, J = 7.48 Hz, 2 H, 5-H),

7.78 (s, 2 H, 3-H), 7.47 (s, 4 H, 12-H), 7.02 (m, 4 H, 6-H, 7-H),

6.96 (d, J = 7.65 Hz, 2 H, 8-H), 5.29 (s, 4 H, 10-H), 2.17 (s, 6 H,

1-H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 167.0 (C-2),

137.1 (C-4), 136.7 (C-9), 127.9 (C-11), 128.0 (C-12), 123.7 (C-7),

121.7 (C-6), 120.2 (C-5), 111.8 (C-8), 70.6 (C-10), 24.9 (C-1) ppm.

IR (KBr): ν = 3293 (s), 1657 (m), 1260 (s), 1119 (w), 802 (w) cm^–1.

˜

FAB-MS: m/z (%) = 405 (95) [M + H]⁺, 363 (10), 307 (17), 289

(15), 254 (83), 212 (35). C₂₄H₂₄N₂O₄(404.46): calcd. C 71.27, H

5.98, N 6.93, O 15.82; found C 71.26, H 5.95, N 6.93.

8), 68.2 (C-10), 22.4 (C-1) ppm. IR (KBr): ν = 3301 (s), 1662 (s),

˜

1600 (s), 1545 (s), 1494 (s), 1446 (s), 1252 (m), 1117 (w), 746 (w),

693 (w) cm^–1. FAB-MS: m/z (%) = 405 (32) [M + H]⁺, 270 (15),

254 (35), 212 (27). C₂₄H₂₄N₂O₄(404.46): calcd. C 71.27, H 5.98, N

6.93, O 15.82; found C 71.26, H 5.98, N 6.95.

Compound 5: This compound was prepared in a manner similar to

that described for compound 2 (by a modification of the procedure

reported previously),^[31]from compound 1 (3.89 g, 19.70 mmol)

and bis(2-chloroethyl) ether (1.41 g, 9.85 mmol). The product was

obtained as a dark green solid; yield 3.34 g, 91%; m.p. 130–134 °C.

¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 8.34 (d, J = 7.48 Hz, 2

H, 5-H), 7.94 (s, 2 H, 3-H), 7.01 (m, 4 H, 6-H, 7-H), 6.93 (dd, J =

3.0, J = 7.11 Hz, 2 H, 8-H), 4.24 (m, 4 H, 10-H), 3.92 (m, 4 H, 11-

H), 2.08 (s, 6 H, 1-H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C):

δ = 168.0 (C-2), 146.9 (C-4), 127.0 (C-9), 123.9 and 122.5 (C-6 and

C-7), 120.6 (C-5), 112.0 (C-8), 70.0 (C-11) 69.0 (C-10), 24.6 (C-

1) ppm. IR (KBr): ν = 3290 (s), 1640 (m), 1200 (s), 1109 (w), 802

˜

(w) cm^–1. FAB-MS: m/z (%) = 373 (100) [M + H]⁺, 331 (44), 313

(12), 222 (11), 136 (85), 109 (38). C₂₀H₂₄N₂O₅(372.41): calcd. C

64.50, H 6.50, N 7.52, O 21.48; found C 64.51, H 6.42, N 7.55.

Compound 3: This compound was prepared in a manner similar to

that described for compound 2, from 1 (3.36 g, 17.04 mmol) and

2,6-bis(chloromethyl)pyridine (1.47 g, 8.33 mmol). The product

was obtained as a white solid; yield 2.97 g, 86%; m.p. 226–228 °C.

¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 8.37 (dd, J = 3.6, J =

6.9 Hz, 2 H, 5-H), 7.95 (s, 2 H, 3-H), 7.77 (t, J = 7.8 Hz, 1 H, 13-

H), 7.36 (d, J = 7.8 Hz, 2 H, 12-H), 7.00 (m, 4 H, 6-H, 7-H), 6.90

(dd, J = 3.5, J = 6.9 Hz, 2 H, 8-H), 5.29 (s, 4 H, 10-H), 2.17 (s, 6

H, 1-H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 155.5 (C-

2), 145.6 (C-4), 136.9 (C-13), 127.5 (C-9), 122.7 (C-11), 121.0 (C-

12), 119.6 and 119.4 (C-6 and C-7), 117.76 (C-5), 111.1 (C-8), 70.5

(C-10), 23.9 (C-1) ppm. IR (KBr): ν = 3303 (m), 1663 (s), 1248 (m),

˜

1123 (w), 774 (w), 774 (w), 750 (w) cm^–1. FAB-MS: m/z (%) = 406

(97) [M + H]⁺, 388 (5), 364 (10), 362 (5), 346 (4), 256 (53), 254

(51), 212 (26). C₂₃H₂₃N₃O₄(405.45): calcd. C 68.13, H 5.72, N

10.36, O 15.78; found C 68.14, H 5.75, N 10.40.

Compound 6: This compound was prepared by a modification of

the procedure reported previously.^[30]A solution of compound 2

(3.00 g, 7.42 mmol) in ethanol (30 mL) and a solution of NaOH

(6.86 g, 49.63 mmol) in water (10 mL) were mixed, stirred and

heated at reflux (80 °C) for several days. The reaction was moni-

tored by TLC (hexane/acetone 60:40) until a single product was

observed and the starting material had disappeared. The reaction

mixture was evaporated in vacuo to dryness in order to remove the

solvent. A chloroform/water extraction (70:30) was performed, the

phases were separated, and the solvent was removed from the or-

ganic phase. The product was obtained as an orange solid; yield

1

1.82 g, 77%; m.p. 62–65 °C. H NMR (400 MHz, CDCl₃, 25 °C):

δ = 7.55 (s, 1 H, 12-H), 7.45 (m, 3 H, 10-H, 11-H), 6.86 (m, 4 H,

4-H, 6-H), 6.7 (m, 4 H, 3-H, 5-H), 5.13 (s, 4 H, 8-H), 3.78 (s, 4 H,

1-H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 146.41 (C-7),

Eur. J. Org. Chem. 2011, 2148–2162

www.eurjoc.org

2157

R. Moreno-Corral, H. Höpfl, L. Machi-Lara, K. O. Lara

FULL PAPER

137.66 (C-2), 136.57 (C-9), 128.86 (C-11), 127.16 (C-10), 126.61 (C- Compound 9: This compound was reported previously.^[33–35]It was

12), 121.61 (C-4), 118.43 (C-3), 115.30 (C-5), 112.18 (C-6), 70.25 prepared in a manner similar to that described for compound 6,

(C-8) ppm. IR (KBr): ν = 3476 (m), 3438 (m), 3037 (w), 2931 (w), from 5 (2.80 g, 6.91 mmol) and NaOH (6.86 g, 49.23 mmol). The

˜

1283 (m), 1140 (m), 783 (m), 747 (m) cm^–1. FAB-MS: m/z (%) =

321 (42) [M + H]⁺, 212 (98), 211 (45), 195 (14), 167 (15), 149 (28),

136 (10). C₂₀H₂₀N₂O₂(320.39): calcd. C 74.98, H 6.29, N 8.74, O

9.99; found C 75.47, H 6.35, N 8.98.

product was obtained as a pale orange solid; yield 1.79 g, 81%;

m.p. 64.7 °C. H NMR (400 MHz, CDCl₃, 25 °C): δ = 6.79 (m, 4

1

H, 4-H, 5-H), 6.67 (m, 4 H, 3-H, 6-H), 4.15 (m, 4 H, 8-H), 3.88

(m, 4 H, 9-H), 3.72 (s, 2 H, 1-H) ppm. ¹³C NMR (400 MHz,

CDCl₃, 25 °C): δ = 146.5 (C-7), 137.1 (C-2), 121.9 (C-5), 118.3 (C-

4), 115.9 (C-3), 114.0 (C-6), 70.5 (C-8), 68.6 (C-9) ppm. IR (KBr):

ν = 3462 (w), 3420 (m), 3270 (s), 1276 (m), 1212 (m), 790 (m) cm^–1.

˜

FAB-MS: m/z (%) = 289 (68) [M + H]⁺, 250 (28), 210 (15), 180

(17). C₁₆H₂₀N₂O₃(288.34): calcd. C 66.65, H 6.99, N 9.72, O 16.65;

found C 66.67, H 7.01, N 9.78.

Compound 7: This compound was reported previously.^[32]It was

prepared in a manner similar to that described for compound 6,

from 3 (3.80 g, 9.38 mmol) and NaOH (6.86 g, 49.23 mmol). The

product was obtained as an orange solid; yield 2.06 g, 68%; m.p.

63–66 °C. ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 7.33 (t, J =

7.76 Hz, 1 H, 11-H), 7.43 (d, J = 7.76 Hz, 2 H, 10-H), 6.83 (m, 4

H, 4-H, 5-H), 6.76 (dd, J = 1.59, J = 8.04 Hz, 2 H, 3-H), 6.70 (m,

2 H, 6-H), 5.25 (s, 4 H, 8-H), 3.92 (s, 4 H, 1-H) ppm. ¹³C NMR

(400 MHz, CDCl₃, 25 °C): δ = 155.0 (C-7), 146.1 (C-2), 137.7 (C-

11), 136.5 (C-9), 121.8 (C-5), 120.2 (C-10), 118.5 (C-6), 115.4 (C-

Compound 10: This compound was previously reported by our re-

search group.^[28]

Compound 11: This compound was prepared by a modification of

the procedure reported previously.^[36]A solution of salicylaldehyde

(0.56 g, 4.59 mmol) in anhydrous DMF (6 mL) was added to a sus-

pension of K₂CO₃(in excess) in the same solvent. The suspension

was kept under a flow of nitrogen and stirred at 80 °C for 30 min.

A solution of 2,6-bis(chloromethyl)pyridine (0.28 g, 2.29 mmol) in

anhydrous DMF (20 mL) was then added slowly to the mixture

and the resulting suspension was stirred at 80 °C. The reaction was

monitored by TLC (hexane/acetone 60:40) until a single product

was observed and the starting material had disappeared. The sus-

pension was filtered in order to remove the potassium salt. The

filtrate was evaporated in vacuo to dryness and acetone was added

until a precipitate appeared. A light pink solid was obtained after

filtration, acetone washing and drying in vacuo; yield 0.63 g, 79%;

m.p. 183–186 °C. ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 10.55

(s, 2 H, 1-H), 7.81 (dd, J = 1.71, 7.65 Hz, 2 H, 3-H), 7.75 (t, J =

7.77 Hz, 1 H, 11-H), 7.47 (m, 4 H, 5-H, 10-H), 7.09 (m, 4 H, 4-H,

6-H), 5.35 (s, 4 H, 8-H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C):

δ = 189.5 (C-1), 160.5 (C-11), 156.0 (C-9), 138.0 (C-7), 136.0 (C-

3), 129.0 (C-10), 125.2 (C-2), 121.4 and 120.5 (C-4 and C-5), 113.0

4), 112.4 (C-3), 71.1 (C-8) ppm. IR (KBr): ν = 3438 (m), 3365 (m),

˜

3060 (w), 1280 (m), 1114 (w), 741 (s), 633 (w) cm^–1. FAB-MS: m/z

(%)

= 322 (100) [M +

H]⁺, 214 (85), 196 (8), 120 (18).

C₁₉H₁₉N₃O₂·1/4EtOH (350.91): calcd. C 71.88, H 5.89, N 11.97,

O 10.26; found C 71.86, H 5.83, N 11.92.

Compound 8: This compound was prepared in a manner similar to

that described for compound 6, from 4 (2.80 g, 6.91 mmol) and

NaOH (6.86 g, 49.23 mmol). The product was obtained as a pale

orange solid; yield 1.79 g, 81%; m.p. 110–114 °C. ¹H NMR

(400 MHz, CDCl₃, 25 °C): δ = 7.42 (s, 4 H, 10-H), 6.79 (m, 4 H,

4-H, 5-H), 6.70 (m, 4 H, 3-H, 6-H), 5.09 (s, 4 H, 8-H), 3.99 (s, 4

H, 1-H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 146.5 (C-

7), 137.1 (C-2), 136.6 (C-9), 127.9 (C-10), 121.7 and 118.4 (C-4 and

(C-6), 70.9 (C-8) ppm. IR (KBr): ν = 2854 (w), 1687 (s), 1241 (s),

˜

1108 (w), 849 (w), 779 (m) cm^–1. FAB-MS: m/z (%) = 348 (98) [M

+ H]⁺, 325 (36), 245 (15), 226 (35), 220 (16). C₂₁H₁₇NO₄·1/2H₂O

(358.39): calcd. C 70.94, H 5.06, N 3.91, O 20.09; found C 70.62,

H 5.13, N 3.95.

C-5), 115.3 and 112.2 (C-3 and C-6), 70.2 (C-8) ppm. IR (KBr): ν

˜

= 3463 (w), 3436 (m), 3370 (m), 1276 (m), 1212 (m), 793 (m) cm^–1.

FAB-MS: m/z (%) = 321 (31) [M + H]⁺, 288 (6), 239 (6), 210 (28),

211 (100), 212 (92). C₂₀H₂₀N₂O₂(320.39): calcd. C 74.98, H 6.29,

N 8.74, O 9.99; found C 74.89, H 6.29, N 8.76.

Compound 12: This compound was previously reported by our re-

search group.^[28]

2158

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Eur. J. Org. Chem. 2011, 2148–2162

Oxaazacyclophanes and Oxaazacalix[4]arene Analogues

Compound 13: This compound was prepared by a modification of

the procedure reported previously,^[37]in a manner similar to that

described for compound 11, from salicylaldehyde (3 g, 4.49 mmol)

and bis(2-chloroethyl) ether (1.7 g, 12 mmol). The product was ob-

tained as a pale pink solid; yield 2.27 g, 59%; m.p. 59–61 °C. ¹H

NMR (400 MHz, CDCl₃, 25 °C): δ = 10.50 (s, 2 H, 1-H), 7.76 (dd,

J = 2.1, J = 8.0 Hz, 2 H, 3-H), 7.45 (t, J = 8.0 Hz, 2 H, 5-H), 6.95

(m, 4 H, 4-H, 6-H), 4.20 (m, 4 H, 8-H), 3.93 (m, 4 H, 9-H) ppm.

¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 189.8 (C-1), 161.2, 135.7,

1.38 mmol) and isophthalaldehyde (0.13 g, 0.95 mmol). The prod-

uct was obtained as a yellow pale solid; yield 0.24 g, 44%; m.p.

210–212 °C. H NMR (400 MHz, CDCl₃, 25 °C): δ = 7.72 (s, 2 H,

11-H), 7.30 (m, 3 H, 13-H, 14-H), 6.89 (dd, J = 1.4, J = 7.62 Hz,

2 H, 4-H), 6.70 (m, 6 H, 5-H, 6-H, 7-H), 4.49 (s, 2 H, 2-H), 4.28

(d, 4 H, 1-H), 4.16 (m, 4 H, 9-H), 3.84 (m, 4 H, 10-H) ppm. ¹³C

NMR (400 MHz, CDCl₃, 25 °C): δ = 146.0 (C-12), 140.2 (C-8),

138.2 (C-3), 128.5 (C-14), 127.8 (C-13), 126.7 (C-11), 121.4, 116.6,

109.8, 109.7 (C-4 to C-6, C-7), 70.0 (C-10), 67.1 (C-9), 48.0 (C-

1

125.2, 121.9, 113.6, 112.9 (C-2 to C-7), 70.6 (C-9), 24.9 (C-8) ppm. 1) ppm. IR (KBr): ν = 3433 (s), 3033 (w), 2917 (m), 1612 (s), 1590

˜

IR (KBr): ν = 3293 (s), 1657 (m), 1260 (s), 1119 (w), 802 (w) cm^–1.

(s), 1519 (w), 1492 (s), 1486 (s), 1458 (s), 1363 (m), 1306 (s), 1219

˜

FAB-MS: m/z (%) = (%), 315 (32) [M + H]⁺, 267 (8), 231 (10), 148 (s), 1152 (m), 1061 (m), 1032 (s), 809 (s), 755 (s) cm^–1. FAB-MS:

(80), 121 (58). C₁₈H₁₈O₅(314.33): calcd. C 68.78, H 5.77, O 25.45;

found C 68.80, H 5.78.

m/z (%) = 391 (80) [M + H]⁺, 314 (42), 286 (35), 209 (60), 181 (82).

C₂₄H₂₆N₂O₃(390.45): calcd. C 73.82, H 6.71, N 7.17, O 12.29;

found C 73.75, H 6.68, N 7.19.

Macrocycle 14:

A

solution of isophthalaldehyde (0.13 g,

0.95 mmol) in anhydrous ethanol (60 mL) was added dropwise to

a solution of compound 7 (0.31 g, 0.95 mmol) in the same solvent

(100 mL). The solution was kept under nitrogen and stirred at

79 °C. The reaction was monitored by TLC (hexane/acetone 60:40)

until a single product was observed and the starting material had

disappeared. Sodium borohydride (0.14 g, 3.8 mmol) was then

added. The reaction progress was monitored by TLC (hexane/ace-

tone 60:40) until completion. The reaction mixture was evaporated

to dryness, a chloroform/water extraction (70:30) was then per-

Macrocycle 16: A solution of 6 (0.31 g, 0.98 mmol) in anhydrous

acetonitrile (10 mL) was added to a solution of isophthalaldehyde

(0.13 g, 0.98 mmol), and a catalytic amount of zinc perchlorate was

then added. The reaction was monitored by TLC (hexane/acetone

60:40) until a single product was observed and the starting material

had disappeared. The suspension was filtered in order to remove

formed, the phases were separated, and the solvent was removed the solvent, and a yellow solid was obtained after acetone washing

from the organic phase to give the compound as an orange solid;

yield 0.13 g, 33%; m.p. 242–244 °C. H NMR (400 MHz, CDCl₃,

and drying in vacuo; yield 0.14 g, 35%; m.p. 140–144 °C. ¹H NMR

(400 MHz, CDCl₃, 25 °C): δ = 9.46 (s, 2 H, 1-H), 8.61 (s, 2 H, 13-

1

25 °C): δ = 7.73 (t, J = 7.0 Hz, 1 H, 12-H), 7.62 (s, 1 H, 13-H), H), 8.33 (s, 1 H, 12-H), 7.66 (d, J = 7.2 Hz, 2 H, 3-H), 7.53 (t, J

7.35 (d, J = 7.0 Hz, 2 H, 11-H), 7.23 (m, 3 H, 15-H, 16-H), 6.92

(m, 4 H, 5-H, 6-H), 6.70 (m, 4 H, 4-H, 7-H), 5.05 (s, 4 H, 9-H),

4.34 (s, 2 H, 2-H), 4.22 (s, 4 H, 1-H) ppm. ¹³C NMR (400 MHz,

CDCl₃, 25 °C): δ = 155.9, 146.3, 139.9, 138.4, 137.6, 128.4, 127.1,

123.9, 121.8 (C-3, C-5, C-8, C-10 to C-16), 116.6, 110.3, 110.0 (C-

= 6.8 Hz, 1 H, 11-H), 7.38 (d, J = 7.2 Hz, 2 H, 10-H), 7.23 (m, 7

H, 4-H, 6-H, 15-H, 16-H), 7.09 (t, J = 7.2 Hz, 2 H, 5-H), 5.20 (s,

4 H, 8-H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 157.9 (C-

1), 153.3 (C-7), 142.3 (C-10), 137.9 (C-15), 137.5 (C-16), 133.1 (C-

9), 128.5 (C-11), 128.2, 127.9, 127.5, 125.5 (C-2 to C-4), 122.7 (C-

4, C-6, C-7), 71.4 (C-9), 48.2 (C-1) ppm. IR (KBr): ν = 3421 (s), 12), 118.5 (C-14), 117.1 (C-13), 116.8 (C-6), 73.1 (C-8) ppm. IR

˜

2860 (m), 2300 (m), 1600 (s), 1512 (s), 1247 (m), 742 (m) cm^–1. (KBr): ν = 3063 (w), 3006 (w), 2928 (w), 2870 (m), 1615 (m), 1478

˜

FAB-MS: m/z (%) = 424 (73) [M + H]⁺, 318 (18), 226 (55), 212 (5),

(m), 1368, 763 (m) cm^–1. FAB-MS: m/z (%) = 419 (25) [M + H]⁺,

197 (8), 191 (63), 105 (10). C₂₇H₂₅N₃O₂·0.175H₂O (426.66): calcd. 392 (5), 209 (15), 210 (12), 120 (18). C₂₈H₂₂N₂O₂(418.49): calcd.

C 76.01, H 5.99, N 9.85, O 8.16; found C 76.26, H 6.51.

C 80.36, H 5.30, N 6.69, O 7.65; found C 80.34, H 5.31, N 6.70.

Macrocycle 15: This compound was prepared in a manner similar

to that described for macrocycle 14, from compound 9 (0.40 g,

Macrocycle 17: A solution of 1,3-bis(bromomethyl)benzene (0.43 g,

1.56 mmol) in anhydrous acetone (60 mL) was added dropwise to

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R. Moreno-Corral, H. Höpfl, L. Machi-Lara, K. O. Lara

FULL PAPER

a suspension of compound 7 (0.50 g, 1.56 mmol) and Na₂CO₃(in

excess) in the same solvent (100 mL). The suspension was kept un-

der nitrogen and stirred at 80 °C for 24 h. The reaction was moni-

tored by TLC (hexane/acetone 60:40) until a single product was

observed and the starting material had disappeared. The suspen-

sion was filtered in order to remove the sodium salt. The filtrate

was evaporated in vacuo to dryness and acetone was added until a

precipitate appeared. An orange solid was obtained after filtration,

acetone washing and drying in vacuo; yield 0.3 g, 45%; m.p.

walled borosilicate glass tube. A considerable amount of yellow

crystals appeared during the reaction and were removed by fil-

tration, washed with ethanol and dried under vacuum; yield 0.10 g,

67%; m.p. 80–84 °C. ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 8.88

(s, 2 H, 2-H), 7.97 (dd, J = 1.74, 7.7 Hz, 2 H, 4-H), 7.49 (s, 1 H,

13-H), 7.44 (m, 1 H, 12-H), 7.34 (d, J = 7.1 Hz, 2 H, 11-H), 7.30

(m, 4 H, 14-H, 16-H, 17-H), 6.95 (m, 4 H, 5-H, 6-H), 6.82 (dd, J

= 1.8, 7.61 Hz, 2 H, 7-H), 5.21 (s, 4 H, 9-H), 4.79 (s, 4 H, 1-H) ppm.

¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 158.4 (C-2), 157.5 (C-8),

Ͼ300 °C. ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 7.71 (s, 1 H, 14- 139.0 (C-10), 137.8 (C-15), 131.8 (C-6), 128.7 and 127.7 (C-16 and

H), 7.64 (s, 1 H, 13-H), 7.22 (m, 6 H, 11-H, 12-H, 16-H, 17-H), C-17), 127.6 and 126.3 (C-3, C-12, C-11), 125.0 (C-13, C-14), 124.7

6.88 (m, 4 H, 4-H, 5-H), 6.62 (m, 4 H, 6-H, 7-H), 4.95 (s, 4 H, 9- (C-4), 121.0 (C-5), 112.0 (C-7), 69.7 (C-9), 65.7 (C-1) ppm. IR

H), 4.32 (s, 2 H, 2-H), 4.20 (s, 4 H, 1-H) ppm. ¹³C NMR (400 MHz,

CDCl₃, 25 °C): δ = 145.03 (C-8), 138.90 (C-10), 137.08 (C-3),

(KBr): ν = 3069 (m), 2928 (m), 3034 (w), 2809 (m), 1635 (s), 1598

˜

(s), 1483 (s), 1298 (m), 1027 (s), 753 (s) cm^–1. FAB-MS: m/z (%) =

136.41 (C-15), 127.44, 127.40 (C-14, C-17), 127.31 (C-12), 127.16 447 (52) [M + H]⁺, 391 (100), 371 (9), 279 (13), 220 (32).

(C-16), 126.80 (C-11), 125.4 (C-13), 120.56 (C-5), 115.57 (C-6), C₃₀H₂₆N₂O₂(446.54): calcd. C 80.69, H 5.87, N 6.27, O 7.17; found

109.01 (C-7), 108.84 (C-4), 68.96 (C-9), 47.09 (C-1) ppm. IR (KBr):

C 80.69, H 6.27, N 6.31.

ν = 3420 (m), 2865 (m), 2316 (m), 1600 (s), 1512 (s), 1245 (m),

˜

1210 (m), 741 (s) cm^–1. FAB-MS: m/z (%) = 423 (9) [M]⁺, 345 (32),

313 (38), 319 (30), 286 (58), 219 (15). C₂₈H₂₆N₂O₂(422.52): calcd.

C 79.59, H 6.20, N 6.63, O 7.57; found C 79.26, H 6.09.

Macrocycle 20: This compound was prepared in a manner similar

to that described for macrocycle 19, from [4-(aminomethyl)phenyl]-

methanamine (0.04 g, 0.28 mmol) and compound 12 (0.10 g,

0.28 mmol). The product was obtained as a yellow solid; yield

0.04 g, 35%; m.p. 140–144 °C. ¹H NMR (400 MHz, CDCl₃, 25 °C):

δ = 8.70 (s, 2 H, 2-H), 7.79 (dd, J = 2.5, 8.1 Hz, 2 H, 4-H), 7.39

(dt, J = 3.0, 8.1 Hz, 2 H, 5-H), 7.32 (s, 4 H, 11-H) 7.29 (s, 4 H, 12-

H), 7.03 (m, 4 H, 6-H, 7-H), 5.11 (s, 4 H, 9-H), 4.90 (s, 4 H, 1-

H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 157.9 (C-2),

157.8 (C-8), 137.2 and 136.3 (C-10 and C-13), 131.6 (C-6), 129.1

(C-12), 128.9 (C-4), 127.7 (C-3), 126.8 (C-11), 121.3 (C-5), 113.1

Macrocycle 18: This compound was prepared in a manner similar

to that described for macrocycle 17, from compound 8 (0.51 g,

1.56 mmol) and 1,4-bis(bromomethyl)benzene (0.43 g, 1.56 mmol).

The product was obtained as a pale brown solid; yield 0.13 g, 19%;

1

m.p. Ͼ300 °C. H NMR (400 MHz, CDCl₃, 25 °C): δ = 7.21 (s, 4

H, 11-H), 7.17 (s, 4 H, 12-H), 6.84 (m, 4 H, 4-H, 5-H), 6.65 (m, 4

H, 6-H, 7-H), 4.97 (s, 4 H, 9-H), 4.12 (s, 4 H, 1-H), 4.0 (s, 2 H, 2-

H) ppm. ¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 140.8 (C-8),

137.2 (C-10), 135.9 (C-3), 133.1 (C-13), 128.3 (C-11), 122.4 (C-12),

120.2 (C-6), 117.2 (C-5), 115.8 (C-4), 111.1 (C-7), 68.9 (C-9), 47.2

(C-7), 70.0 (C-9), 63.7 (C-1) ppm. IR (KBr): ν = 3398 (w), 3071

˜

(w), 3034 (w), 2896 (m), 2880 (m), 2824 (m), 1905 (w), 1573 (s),

1473 (s), 1455 (s), 1367 (s), 1161 (s), 1142 (m), 1003 (s), 963 (m),

862 (m), 799 (m) cm^–1. FAB-MS: m/z (%) = 447 (25) [M + H]⁺,

446 (9), 289 (12), 223 (18), 92 (44), 78 (38). C₃₀H₂₆N₂O₂(446.54):

calcd. C 80.69, H 5.87, N 6.27, O 7.17; found C 80.69, H 5.50, N

6.30.

(C-1) ppm. IR (KBr): ν = 3421 (s), 3061 (w), 2868 (m), 2360 (m),

˜

1600 (s), 1246 (s), 1005 (s), 844 (m), 726 (s) cm^–1. FAB-MS: m/z

(%) = 423 (80) [M + H]⁺, 422 (42), 331 (12), 287 (15), 225 (64),

197 (84), 135 (38), 91 (23). C₂₈H₂₆N₂O₂·2H₂O (458.55): calcd. C

73.34, H 6.59, N 6.11, O 13.96; found C 73.38, H 6.50, N 6.12.

Macrocycle 19: This compound was prepared from 10 (0.12 g,

0.33 mmol) and [3-(aminomethyl)phenyl]methanamine (0.05 g,

Macrocycle 21: This compound was prepared in a manner similar

to that described for macrocycle 14, from [3-(aminomethyl)phenyl]-

0.33 mmol). The reaction mixture was stirred in ethanol (25 mL) methanamine (0.19 g, 1.39 mmol), compound 10 (0.48 g,

under high pressure for 24 h at 70 °C with employment of a heavy- 1.39 mmol) and sodium borohydride (0.14 g, 3.8 mmol). The prod-

2160

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Oxaazacyclophanes and Oxaazacalix[4]arene Analogues

1

uct was obtained as a white solid; yield 0.44 g, 70%; m.p. 147–

149 °C. H NMR (400 MHz, CDCl₃, 25 °C): δ = 7.51 (s, 1 H, 14-

solid was obtained; yield 1.19 g, 56%; m.p. 143–146 °C. H NMR

1

(400 MHz, CDCl₃, 25 °C): δ = 7.27 (m, 4 H, 5-H, 6-H), 7.19 (m, 3

H), 7.35 (m, 3 H, 12-H, 13-H), 7.30 (d, J = 8.5 Hz, 2 H, 17-H), H, 8-H, 12-H), 7.08 (d, J = 6.54 Hz, 2 H, 7-H), 6.92 (t, J = 8.15 Hz,

7.22 (m, 2 H, 15-H, 18-H), 7.15 (dd, J = 2.8, 8.0 Hz, 2 H, 5-H),

7.09 (dt, J = 1.58, 8.0 Hz, 2 H, 7-H), 6.94 (m, 4 H, 6-H, 8-H), 5.02

(s, 4 H, 10-H), 3.84 (s, 4 H, 3-H), 3.67 (s, 4 H, 1-H) ppm. ¹³C NMR

(400 MHz, CDCl₃, 25 °C): δ = 157.0 (C-9), 140.5 (C-11), 137.4 (C-

1 H, 15-H), 6.80 (d, J = 8.15 Hz, 2 H, 14-H), 4.06 (m, 4 H, 10-H),

3.82 (m, 4 H, 3-H), 3.79 (m, 4 H, 11-H), 3.75 (m, 4 H, 1-H) ppm.

¹³C NMR (400 MHz, CDCl₃, 25 °C): δ = 157.8 (C-9), 136.6 (C-

13), 128.9 (C-15), 128.7 (C-12), 128.3 (C-5), 127.6 (C-7), 126.2 (C-

16), 130.3 (C-7), 128.8 (C-14), 128.7 (C-15), 128.3 (C-4, C-6), 127.8 14), 122.42 (C-4), 120.1 (C-6), 112.2 (C-8), 69.42 (C-11), 68.22 (C-

(C-12), 127.0 (C-13), 126.9 (C-17), 126.8 (C-18), 120.9 (C-5), 111.7

10), 56.34 (C-1), 52.6 (C-3) ppm. IR (KBr): ν = 3310 (m), 3058 (s),

˜

(C-8), 70.2 (C10), 53.3 (C-1), 50.2 (C-3) ppm. IR (KBr): ν = 3314

2874 (m), 2342 (s), 1598 (s), 1210 (m), 782 (m), 752 (m) cm^–1. FAB-

˜

(w), 3059 (w), 2878 (w), 1586 (w), 1490 (m), 1448 (m), 1238 (m),

MS: m/z (%) = 419 (95) [M + H]⁺, 298 (12), 225 (12), 120 (30), 105

754 (m) cm^–1. FAB-MS: m/z (%) = 451 (90) [M + H]⁺, 346 (32), (60). C₂₆H₃₀N₂O₃(418.53): calcd. C 74.61, H 7.22, N 6.69, O 11.47;

254 (60), 241 (45), 225. C₃₀H₃₀N₂O₂(450.57): calcd. C 79.97, H found C 74.65, H 7.21, N 6.69.

6.71, N 6.22, O 7.10; found C 79.71, H 6.58, N 6.23.

Supporting Information (see footnote on the first page of this arti-

cle): UV/Vis spectra of 17 and 17 in the presence of Cu²⁺(1:1 molar

ratio) and the Job plot for the 14-Zn²⁺system.

Macrocycle 22: This compound was prepared in a manner similar

to that described for macrocycle 14, from [3-(aminomethyl)phenyl]-

methanamine (0.19 g, 1.4 mmol), compound 11 (0.49 g, 1.4 mmol)

Acknowledgments

and sodium borohydride (0.14 g, 3.8 mmol). A white solid was ob-

tained; yield 0.22 g, 35%; m.p. 169–171 °C. ¹H NMR (400 MHz,

This work received support from the Consejo Nacional de Ciencia

y Tecnologia (CONACyT) in the form of a postgraduate fellowship

CDCl₃, 25 °C): δ = 7.63 (t, J = 7.8 Hz, 1 H, 13-H), 7.29 (d, J =

7.8 Hz, 2 H, 12-H), 7.18 (d, J = 8.1 Hz, 2 H, 16-H), 7.16 (m, 2 H,

for RMC and through project number CB-54675. We thank Mario

5-H), 6.95 (m, 7 H, 6-H, 7-H, 8-H, 17-H), 6.75 (s, 1 H, 14-H), 5.03

Sánchez for helpful discussions.

(s, 4 H, 10-H), 3.75 (s, 4 H, 3-H), 3.50 (s, 4 H, 1-H) ppm. ¹³C NMR

(400 MHz, CDCl₃, 25 °C): δ = 157.2, 156.3, 140.5, 137.5, 130.7,

129.4, 128.5, 128.0, 127.0, 126.7, 122.0, 121.5 (C-4 to C-7, C-9, C-

11 to C-17), 112.8 (C-8), 71.9 (C-10), 53.5 (C-1), 50.2 (C-3) ppm.

[1] N. Singh, M. S. Hundal, G. Hundal, M. Martinez-Ripoll, Tet-

rahedron 2005, 61, 7796–7806.

[2] P. Rajakumar, A. M. A. Rasheed, Tetrahedron 2005, 61, 5351–

5362.

[3] H. J. Kim, Y. Jin, J. Seo, J.-E. Lee, J. Y. Lee, S. S. Lee, Inorg.

Chem. Commun. 2006, 9, 1040–1044.

[4] A. G. Algarra, M. G. Basallote, R. Belda, S. Blasco, C. E. Cas-

tillo, J. M. Linares, E. García-España, L. Gil, M. A. Máñez,

C. Soriano, B. Verdejo, Synth. Eur. J. Inorg. Chem. 2009, 62–

75.

IR (KBr): ν = 3419 (m), 3059 (s), 2874 (m), 2342 (s), 1597 (s), 1230

˜

(s), 786 (m), 757 (s) cm^–1. FAB-MS: m/z (%) = 452 (95) [M + H]⁺,

393 (18), 378 (7), 327 (8), 322 (38), 250 (12), 136 (84).

C₂₉H₂₉N₃O₂·1/2H₂O (460.58): calcd. C 75.63, H 6.57, N 9.12, O

8.68; found C 75.63, H 6.59, N 9.01.

[5] W. Radecka-Paryzek, V. Patroniak, J. Lisowski, Coord. Chem.

Rev. 2005, 249, 2156–2175.

[6] E. A. Katayev, J. L. Sessler, V. N. Khrustalev, Y. A. Ustynyuk,

J. Org. Chem. 2007, 72, 7244–7252.

[7] E. Brunet, O. Juanes, J. C. Rodriguez-Ubis, Curr. Chem. Biol.

2007, 1, 11–39.

[8] C. Lodeiro, F. Pina, Coord. Chem. Rev. 2009, 253, 1353–1383.

[9] B. Verdejo, J. Aguilar, A. Domenéch, C. Miranda, P. Navarro,

H. R. Jiménez, C. Soriano, E. García-España, Chem. Commun.

2005, 3086–3088.

[10] P. K. T. Lin, A. N. Araujo, M. C. B. S. M. Montenegro, R.

Pérez-Olmos, J. Agric. Food Chem. 2005, 53, 211–215.

[11] V. Gasperov, S. G. Galbraith, L. F. Lindoy, B. R. Rumbel, B. W.

Skelton, P. A. Tasker, A. H. White, Dalton Trans. 2005, 139–

145.

[12] A. Arbuse, M. Font, M. A. Martínez, X. Fontrodona, M. J.

Prieto, V. Moreno, X. Sala, A. Llobet, Inorg. Chem. 2009, 48,

11098–11107.

Macrocycle 23: This compound was prepared in a manner similar

to that described for macrocycle 14, from compound 13 (1.62 g,

5.16 mmol),

[3-(aminomethyl)phenyl]methanamine

(0.70 g,

5.16 mmol) and sodium borohydride (0.73 g, 19 mmol). A white

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FULL PAPER

[13]

[34] H. Sharghi, M. A. Nasseri, K. Niknam, J. Org. Chem. 2001,

66, 7287–7293.

M. A. Sierra, D. Pellico, M. Gómez-Gallego, M. J. Mancheño,

R. Torres, J. Org. Chem. 2006, 71, 8787–8793.

[35] W. Qin, Y. Zhang, W. Liu, M. Tan, N. Tang, Synth. React.

Inorg. Met.-Org. Nanomet. Chem. 2003, 33, 883–897.

[36] H. Keypour, A. A. Dehghani-Firouzabadi, M. Shayesteh, S.

Salehzadeh, J. Chem. Res. 2008, 10, 587–588.

[37] N. Arumugam, R. Raghunathan, Tetrahedron Lett. 2006, 47,

8855–8857.

[14]

M. I. Burguete, E. García-España, L. López-Diago, S. V. Luis,

J. Miravet, D. Sroczynski, Org. Biomol. Chem. 2007, 5, 1935–

1944.

A. Bianchi, K. Bowman-James, E. García-España (Eds.), The

Supramolecular Chemistry of Anions, John Wiley & Sons, New

York, 1997, p. 124.

I. M. Atkinson, A. R. Carroll, J. A. Janssen, L. F. Lindoy,

O. A. Matthews, G. V. Meehan, J. Chem. Soc. Perkin Trans. 1

1997, 295–301.

[15]

[16]

[38] For reviews on calixarene-based hosts, see: a) J. Vicens, V.

Böhmer (Eds.), Calixarenes: A versatile class of macrocyclic

compounds, Kluwer Academic Publisher, Dordrecht, The Ne-

therlands, 1991; b) C. D. Gutsche, Calixarenes in: Monographs

in Supramolecular Chemistry (Ed.: J. F. Stoddart), The Royal

Society of Chemistry, Cambridge, 1998; c) A. W. Coleman,

A. N. Lazar, E. Da Silva, Calixarenes and their analogues: cat-

ion complexation, in: Encyclopedia of Supramolecular Chemistry

(Eds.: J. L. Atwood, J. W. Steed), Taylor & Francis, New York,

2004, pp. 137–144; d) L. Baldini, A. Casnati, F. Sansonse, R.

Ungaro, Chem. Soc. Rev. 2007, 36, 254–266; e) S. J. Dalgarno,

P. K. Thallapally, L. J. Barbour, J. L. Atwood, Chem. Soc. Rev.

2007, 36, 236–245.

[39] For syntheses, structures and interactions of heterocalixarenes,

see: S. Kumar, D. Paul, H. Singh, Arkivoc 2006, 9, 17–25.

[40] a) J. L. Katz, M. B. Feldman, R. R. Conry, Org. Lett. 2005, 7,

91–94; b) H. Tsue, K. Ishibashi, R. Tamura, Top. Heterocycl.

Chem. 2008, 17, 73–96; c) J. L. Katz, B. A. Tschaen, Org. Lett.

2010, 12, 4300–4303.

[17]

[18]

[19]

C. Platas, R. Bastida, A. Blas, D. E. Fenton, A. Macias, A.

Rodríguez, T. Rodríguez-Blas, Polyhedron 1998, 17, 1759–1765.

L. Cronin, Annu. Rep. Prog. Chem. Sect. A: Inorg. Chem. 2003,

99, 289–347.

J. R. Price, M. Fainerman-Melnikova, R. R. Fenton, K. Gloe,

L. F. Lindoy, T. Rambusch, B. W. Skelton, P. Turner, A. H.

White, K. Wichmann, Dalton Trans. 2004, 3715–3726.

L. Cronin, Annu. Rep. Prog. Chem. Sect. A: Inorg. Chem. 2005,

101, 319–347.

N. E. Borisova, M. D. Reshetova, Y. A. Ustynyuk, Chem. Rev.

2007, 107, 46–79, and references cited therein.

[20]

[21]

[22]

A. H. M. Elwahy, G. S. Masaret, J. Heterocycl. Chem. 2007, 44,

1475–1484.

[23] J. L. Atwood, J. W. Steed, Encyclopedia of Supramolecular

Chemistry, CRC, Florida, USA, 2004, p. 830–843.

[24] T. Zielinski, M. Achmatowicz, J. Jurczak, Tetrahedron: Asym-

metry 2002, 13, 2053–2059.

[25] M. M. Gruza, A. Pokrop, J. Jurczak, Tetrahedron: Asymmetry

2005, 16, 1939–1946.

[26] J. G. Marrero, L. M. Harwood, Tetrahedron Lett. 2009, 50,

[41] V. Béreau, Inorg. Chem. Commun. 2004, 7, 829–833.

[42] K. A. Connors, Binding constants: The measurement of molecu-

lar complexes stability, John Wiley & Sons, New York, 1987,

p. 24.

[43] H.-J. Schneider, A. K. Yatsimirsky, Principles and methods in

supramolecular chemistry, John Wiley & Sons, UK, 2000,

p. 142, p. 151.

3574–3576.

[27] V. Reyes-Márquez, K. O. Lara, M. Sánchez, J. C. Gálvez-Ruiz,

Arkivoc 2008, 5, 115–123.

[28] V. Reyes-Márquez, M. Sánchez-Vázquez, H. Höpfl, K. O.

Lara, J. Inclusion Phenom. Macrocyclic. Chem. 2009, 65, 305–

315.

[44] C. Anda, C. Bazzicalupi, A. Bencini, A. Bianchi, P. Fornasari,

C. Giorgi, B. Valtancoli, C. Lodeiro, A. J. Parola, F. Pina, Dal-

ton Trans. 2003, 1299–1307.

[45] a) Bruker Analytical X-ray Systems, SMART, Bruker, Molecu-

lar Analysis Research Tool, versions 5.057 and 5.618, 1997 and

2000; b) Bruker Analytical X-ray Systems, SAINT + NT, ver-

sions 6.01 and 6.04, 1999 and 2001; c) G. M. Sheldrick,

SHELX86, Program for Crystal Structure Solution, University

of Göttingen, Germany, 1986; d) Bruker Analytical X-ray Sys-

tems, SHELXTL-NT, versions 5.10 and 6.10, 1999 and 2000.

[46] K. Brandenburg, Diamond, version 3.1c, 1997.

[47] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837–838.

[48] Origin (OriginLab, Northampton, MA).

[29] K.-L. Li, Z.-B. Du, C.-C. Guo, Q.-Y. Chen, J. Org. Chem. 2009,

74, 3286–3292.

[30] A. H. M. Elwahyand, A. A. Abbas, Tetrahedron Lett. 2006, 47,

1303–1306.

[31] A. P. Avdeenko, A. M. Surmii, L. P. Atyasova, S. I. Burmistrov,

Vop. 1982, 67, 3–6.

[32] E. Wagner-Wysiecka, E. Luboch, M. S. Fonari, Pol. J. Chem.

2008, 82, 1319–1330.

[33] Y. Zhang, W. Liu, M. Tan, K. Yu, J. Chem. Res. 2001, 10, 416–

417.

Received: September 20, 2010

Published Online: March 7, 2011

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www.eurjoc.org

Eur. J. Org. Chem. 2011, 2148–2162

Article Doi

Synthesis, structural characterization and metal inclusion properties of 18-, 20- and 22-membered oxaazacyclophanes and oxaazacalix[4]arene analogues: Macrocyclic amine and schiff base receptors with variable NxO y donor sets

DOI: 10.1002/ejoc.201001312

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