Synthesis of rctt, rccc, and rcct diastereomers of calix[4] methylresorcinarenes based on p-tolualdehyde. X-ray diffraction study of the rcct isomer. Formation of rctt and rccc cavitands in a cone conformation

Article abstract of DOI:10.1007/s11172-006-0154-x

The reaction of 2-methylresorcinol with p-tolualdehyde afforded rctt and rccc diastereomers of calix[4]methylresorcinarene and an insignificant amount of the rcct isomer. The structure of the latter was established by X-ray diffraction analysis. The macro

Full text of DOI:10.1007/s11172-006-0154-x

2550
Russian Chemical Bulletin, International Edition, Vol. 54, No. 11, pp. 2550—2557, November, 2005
Synthesis of rctt, rccc, and rcct diastereomers
of calix[4]methylresorcinarenes based on pꢀtolualdehyde.
Xꢀray diffraction study of the rcct isomer. Formation
of rctt and rccc cavitands in a cone conformation
A. V. Prosvirkin,a E. Kh. Kazakova,aꢀ A. T. Gubaidullin,a I. A. Litvinov,a
M. Gruner,b W. D. Habicher,bꢀ and A. I. Konovalova
aA. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843 2) 75 2253. Eꢀmail: ella@iopc.knc.ru
bDresden University of Technology, Institute of Organic Chemistry,
Mommsenstrasse 13, Dꢀ01062 Dresden, Germany
Fax: (+351) 3463 4093. Eꢀmail: Wolf.Habicher@chemie.tuꢀdresden.de
The reaction of 2ꢀmethylresorcinol with pꢀtolualdehyde afforded rctt and rccc diastereoꢀ
mers of calix[4]methylresorcinarene and an insignificant amount of the rcct isomer. The
structure of the latter was established by Xꢀray diffraction analysis. The macrocycle in the
rcct isomer adopts a 1,2ꢀdiplanar conformation, in which one pair of adjacent resorcinol
fragments is nearly orthogonal to another pair of resorcinol fragments. The supramolecular
organization of the diastereomer in the crystal was studied. The tolyl fragments form the outer
surface of the layers composed of the macrocycles, which are separated by "interlayers" of
solvent molecules. Cavitands adopting a cone conformation were prepared from the rctt and
rccc diastereomers by linking the adjacent phenoxy groups through methylene bridges. The
structure of the rctt cavitand was confirmed by 2D NMR spectroscopy.
Key words: calixarene, calix[4]methylresorcinarenes, cavitands, supramolecular structure,
stereoꢀ and regioselectivity, isomerization, hydrogen bond.
Macrocyclic condensation products of resorcinol with
densation affords rccc and rctt diastereomers (1 : 4). The
ratio of diastereomers usually depends on the structure
of the aldehyde. The condensation with longꢀchain aliꢀ
phatic aldehydes gives predominantly the rccc isomer
(60—80%),2 that with aromatic aldehydes yields a mixꢀ
ture of the rccc and rctt isomers,2,3 whereas the condensaꢀ
tion of aromatic aldehydes with 2ꢀmethylresorcinol afꢀ
fords exclusively the rctt isomer.4 In the present study, we
examined the structure and isomeric composition of a
new calix[4]methylresorcinarene derived from 2ꢀmethylꢀ
resorcinol and pꢀtolualdehyde.
aldehydes are known as calix[4]resorcinarenes, which
can exist as four diastereomers. If all four substituꢀ
ents in the calixarene fragment are mutually cis, this
compound (according to Hoegberg1) is defined as the
rccc isomer. Other diastereomers are rcct, rctt, and
rtct isomers.
Results and Discussion
We synthesized and characterized new isomers of
calix[4]methylresorcinarenes based on 2ꢀmethylresorcinol
and pꢀtolualdehyde (Scheme 1). The reaction afforded
two main products in a ratio of 6 : 1, whose molecular
mass (M = 904) corresponds to that for the tetramer. The
resulting isomers differ in solubilities. The rctt diastereoꢀ
mer (1) precipitates from the reaction mixture and is parꢀ
Studies of the diastereomeric compositions of acetyl
derivatives of calix[4]resorcinarenes1 showed that the conꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2470—2477, November, 2005.
1066ꢀ5285/05/5411ꢀ2550 © 2005 Springer Science+Business Media, Inc.

Synthesis of rcttꢀ and rcccꢀcalix[4]resorcinarenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005 2551
Scheme 1
Fig. 1. Mutual arrangement of molecule 3 and two acetonitrile
solvate molecules. Hydrogen atoms are ignored, except for the
hydrogen atoms of the hydroxy and methyl groups of the acetoꢀ
nitrile molecules.
tially soluble on heating only in DMSO, whereas the
rccc diastereomer (2) remains in the filtrate and, after
isolation in pure form, is readily soluble in ethanol and
acetone.
In addition, several crystals of rcct isomer 3 were isoꢀ
lated from the reaction mixture. Its structure was estabꢀ
lished by Xꢀray diffraction. Earlier, this isomer has not
been observed in analogous reactions. In this connection,
we report the results of Xꢀray diffraction study of this
compound.
In the crystal structure of 3, there are one resorcinarene
molecule and two solvate molecules of acetonitrile per
asymmetric unit (Fig. 1)
The conformation of the macrocycle in the crystal can
be described as 1,2ꢀalternate or chair (two adjacent resorꢀ
cinol groups are in opposite orientation relative to two
other resorcinol groups) (Fig. 2).
Let us take the plane passing through the bridging
C(1), C(8), C(15), and C(22) atoms as the arbitrary basis
plane. Then the dihedral angles between the benzene
,
,
rings
and
and the above plane are 34.0(1), 49.3(1),
79.6(1), and 32.7(1)°, respectively (see Fig. 2). This moꢀ
lecular geometry is favorable for the formation of numerꢀ
ous intramolecular hydrogen bonds in the macrocyꢀ
clic core.
A system of weak directed interactions in the crystal
involves both classical O—H...O and O—H...N hydrogen

2552
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005
Prosvirkin et al.
Table 1. Hydrogen bonds and angles in the crystal structure of
compound 3
C(31)
O(19)
C(18)
Bond
typea
D—H...A triad
H...A/Å
[D...A]/Å
Angle
D—H...A
/deg
O(17)
C(19)
C(17)
O(24)
C(24)
C(23)
C(20)
C(22)
O(12)
C(25)
C(16)
C(15)
C(13)
C(14)
C(21)
IntraHB O(3)—H(3)...O(26)
IntraHB C(1)—H(1)...O(3)
IntraHB C(1)—H(1)...O(26)
IntraHB C(8)—H(8)...O(10)
IntraHB C(15)—H(15)...O(12)
IntraHB C(29)—H(291)...O(3)
IntraHB C(30)—H(301)...O(10)
IntraHB C(31)—H(313)...O(19)
IntraHB C(32)—H(322)...O(24)
InterHB O(26)—H(26)...N(63)
InterHBb O(5)—H(5)...O(24)
InterHBc O(12)—H(12)...N(66)
InterHBc O(17)—H(17)...O(12)
InterHBd O(19)—H(19)...O(5)
InterHBe O(24)—H(24)...O(3)
InterHBd C(22)—H(22)...O(5)
InterHB f C(61)—H(613)...O(19)
1.96
[2.858(4)]
2.53
[2.907(4)]
2.32
[2.817(4)]
2.48
[2.921(4)]
2.48
[2.933(5)]
2.34
[2.784(6)]
2.33
[2.790(5)]
2.33
[2.770(5)]
2.45
[2.916(5)]
1.92
[2.809(11)]
1.97
[2.748(3)]
1.97
[2.933(7)]
1.96
[2.833(3)]
2.02
[2.937(3)]
1.89
[2.862(3)]
2.51
[3.330(4)]
2.57
156.6
102.8
110.8
104.7
108.4
107.6
108.9
106.8
109.5
160.4
138.5
141.4
149.2
134.1
161.1
143.5
152.9
C(32)
O(26)
C(28)
C(1)
C(26)
C(2)
C(11)
C(30)
C(10)
C(9)
C(7)
C(6)
C(3)
C(4)
C(8)
O(3)
O(10)
C(5)
O(5)
C(29)
Fig. 2. Atomic numbering scheme and intramolecular hydrogen
bonds in molecule 3. Hydrogen atoms are ignored, except for
the hydrogen atoms involved in hydrogen bonding.
bonds and weaker C—H...O hydrogen bonds, as well as
C—H...π and π...π interactions (Table 1). Many of these
interactions are biꢀ and trifurcate.
All other hydroxy groups are involved in intermolecuꢀ
lar contacts corresponding to hydrogen bonds. The
macrocycles are linked to each other through the
O(5)—H(5)...O(24) and O(19)—H(19)...O(5) hydrogen
bonds to form chains along the [100] crystallographic
direction. The chains, in turn, are linked to each other
along the [011] direction through the bifurcate
O(24)—H(24)...O(3) and O(17)—H(17)...O(12) hydroꢀ
gen bonds. These weak interactions are responsible for
the formation of a supramolecular structure as a layer
parallel to the [011] crystallographic plane (Fig. 3).
The solvate molecules of acetonitrile are linked to the
calixarene molecules through the O(12)—H(12)...N(66)
and O(26)—H(26)...N(63) hydrogen bonds. In addition,
these molecules are probably involved in weak C—H...π
interactions. However, the main function of these molꢀ
ecules is to fill the cavities in the crystal packing, thus
decreasing the unitꢀcell volume, which is potentially acꢀ
cessible to the solvent, to the minimum value of 16 Å3
(the volume of the water molecule is 40 Å3).
[3.44(2)]
a IntraHB and InterHB are intraꢀ and intermolecular hydrogen
bonds, respectively. The molecules are related by the symmetry
operations: b 1 + x, y, z; c 1 – x, 1 – y, –z ; d –1 + x, y, z; e 1 – x,
–y, 1 – z; f –x, 1 – y, 1 – z.
bonds in the crystal formation is not always completely
satisfied.
It should be noted that analysis of intermolecular conꢀ
tacts (which was carried out with the use of the PLATON
program5) based on the formal criteria for hydrogen bondꢀ
ing in a donor—hydrogen...acceptor (D—H...A) system,
viz., d(D...A) < R(D) + R(A) + 0.50 Å, d(H...A) < R(H) +
R(A) – 0.12 Å, and ∠D—H...A > 100.0° (where R are the
van der Waals radii of the corresponding atoms), revealed
no involvement of the H(10) atom of one of the hydroxy
group in contacts of any type. This may be attributed only
to the steric factor. This fact is additional evidence that
the principle of the maximum saturation of hydrogen
In the crystal structure, π...π interactions occur beꢀ
tween pairs of the resorcinol fragments C(23)—C(28) of
the adjacent molecules related by the symmetry operation
(1 – x, –y, 1 – z) (the shortest distance between the
planes of the rings is 3.64 Å and the dihedral angle is 0°).
The pꢀtolyl fragments belonging both to the same molꢀ
ecule and to adjacent molecules are coplanar with each
other (in the former case, the interplanar distance is
4.60 Å; in the latter case, the interplanar distance is smaller
(3.34 Å), but the distance between the centers of the rings
is larger (5.77 Å)).

Synthesis of rcttꢀ and rcccꢀcalix[4]resorcinarenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005 2553
one C—H...π interaction with the resorcinol fragment of
molecule 3 (the distance is 2.86 Å and the angle is 166°).
The tolyl fragments form the outer surface of the
aboveꢀconsidered layers (Fig. 4). Hence, these fragments
and the solvate molecules located in these layers form
"interlayers" between the adjacent layers packed in the
crystal structure. Thus, the alternating spatial separation
of the regions having predominantly hydrophilic and
hydrophobic properties is observed in the crystal packing
of 3, as in other structures studied earlier.6,7
H(17)
H(19)
H(12)
The minor condensation product of 2ꢀmethylresorꢀ
cinol with pꢀtolualdehyde was identified as rccc isomer 2
by 1H and 13C NMR spectroscopy and mass spectrometry
as well as by analogy with the published data.2—5
H(24)
H(3)
H(5)
1
The H NMR spectra of isomeric calixarenes 1 and 2
are similar to the spectra of analogous isomers described
earlier,2—4 but differ substantially from each other. In the
spectrum of product 2, the signals for the protons of the
tolyl residues at δ 7.01 and 6.85 are observed as two douꢀ
blets, the integrated intensity of each signal correspondꢀ
ing to eight protons. The methine protons are represented
by one resonance singlet at δ 5.78 with an integrated
intensity corresponding to four protons. Two groups of
signals each corresponding to 12 protons at δ 2.42 and 2.20
are assigned to the methyl groups of the tolyl and resorciꢀ
nol fragments, respectively. This simple spectral pattern is
indicative of high symmetry of the structure and is comꢀ
pletely analogous to that usually observed for rccc isomers.
The spectrum of the major condensation product 1 is
totally different. All protons of the tolyl substituents are
represented by double sets of signals. Two lowꢀfield douꢀ
blets at δ 7.40 and 7.17 with integrated intensities of 4 H
Fig. 3. Formation of infinite layers of hydrogenꢀbonded molꢀ
ecules in the crystal of 3.
The environment of two solvent molecules differs. Two
resorcinol fragments of the macrocycle and the pꢀtolyl
fragment form a pseudoplane, and one of the acetonitrile
solvate molecules lies in this plane. The methyl group of
this solvent molecule is directed inside the cavity. The
hydrogen atoms of this group are directed toward three
benzene rings, which is favorable for the formation of
three C—H...π interactions. The distances between the
hydrogen atoms and the centers of the rings are in the
range of 2.35—3.01 Å, and the angles vary from 101°
to 170°. The second solvent molecule is involved only in
each were assigned (according to the published data2—5
to protons of two tolyl fragments that are orthogonal to
)
Fig. 4. Molecular packing in the crystal of 3 projected along the a axis.

2554
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005
Prosvirkin et al.
Scheme 2
the arbitrary plane of the macrocycle passing through the
bridging carbon atoms. Another pair of doublets at higher
field (at δ 7.13 and 7.07) with the same integrated intenꢀ
sity belongs to another pair of protons of the tolyl groups
arranged parallel to the arbitrary plane of the macrocycle.
The spectrum shows two sets of signals for the methine
protons at δ 6.40 and 5.00 with the intensity of 2 H, which
does not contradict the proposed mutual trans orientation
of the substituents and is convincingly confirmed by the
fact that the protons of the methyl groups of the tolyl
fragments are also observed as two sets of signals at δ 2.40
and 2.30.
The signals for the protons of the methyl groups and
the aromatic paraꢀprotons of the resorcinol fragments are
grouped in a different way. They give three groups of
signals, one of which has a double intensity. The methyl
groups give signals at δ 2.13 (3 H), 1.93 (3 H), and
2.03 (6 H). The first two signals each have an intensity of
3 H, and their chemical shifts are most different. The
signal with an intermediate chemical shift has an intensity
of 6 H. Three signals for the protons of the resorcinol
fragments at δ 7.20 (s, 1 H), 7.02 (s, 2 H), and 6.90
(s, 1 H) are characterized by the same intensity ratio. The
double intensities of the signals of the resorcinol fragꢀ
ments with intermediate chemical shifts indicate that two
resorcinol rings have an equivalent environment.
This spectral pattern agrees well with the structure of
rctt isomer 1. This isomer is presented in Scheme 1 as
a molecular model constructed with the use of the
HyperChem program. Two opposite resorcinol rings are
nearly orthogonal to the arbitrary plane of the macrocycle
passing through the bridging carbon atoms. This is consisꢀ
tent with the noticeable difference in the chemical shifts
of the protons bound to these carbon atoms.
Cavitands based on calixarenes are readily formed by
linking the adjacent hydroxy groups only from structures,
in which these groups are spatially close to each other. In
most cases, these calixarenes adopt a cone conformaꢀ
tion.8 However, it has been demonstrated4 that rctt isoꢀ
mers also form cavitands.
Product 4 was prepared in 36.8% yield by linking
rccc isomer 2 with BrCH2Cl (Scheme 2). This product
was isolated in pure form by chromatography and was
1
characterized by H and 13C NMR spectroscopy and
mass spectrometry. The elucidation of the structures of
cavitands synthesized from rccc isomers presents no diffiꢀ
culty because these compounds are symmetrical and have
been well characterized. The structure is confirmed by the
absence of a broad signal of hydroxy groups in the
1H NMR spectrum of the product, which was observed in
the spectrum of starting calixarene 2 (δ 3.06). The specꢀ
trum contained two new doublets (δ 5.90 and 4.34) for the
protons of the methylene bridge formed as a result of
linking.
Product 5 was synthesized analogously from rctt isoꢀ
mer 1 in lower yield (14.3%) (see Scheme 2). After chroꢀ
matographic purification, the product with M = 952 was
isolated. Its structure was established by 2D NMR specꢀ
troscopy, because the closure of rctt isomer 1 by a methylꢀ
ene bridge to form a cavitand could not be expected a priori
since it was not evident whether steric conditions are
sufficient for the complete linking of all hydroxy groups
giving rise to a cavitand.

Synthesis of rcttꢀ and rcccꢀcalix[4]resorcinarenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005 2555
The structure of cavitand 5 was confirmed by analysis
of its 2D COSY (Fig. 5), HSQC, and ROESY spectra,
which allowed us to identify signals for the protons of the
Me group (the atomic numbering scheme corresponds to
that used for cavitand systems) of the tolyl substituent,
which appear as two singlets (δ 2.38 and 2.33). The proꢀ
tons of the methylene bridge, H(12) and H(13), are obꢀ
served as four doublets (δ 6.01, 5.67, 4.47, and 4.37), and
the methine protons are nonequivalent and appear as two
singlets (δ 6.46 and 5.00) denoted as Heq(1) and Hax(1).
The mutual trans arrangement of pairs of the aromatic
substituents with respect to the arbitrary plane of the
macrocycle is confirmed by the fact that the ROESY specꢀ
trum has signals attributed to exchange interactions in the
oxygenꢀcontaining rings of the cavitand between the muꢀ
tually cis methine protons Heq(1) and the protons of the
methylene bridge, Ha(12) and Hb(12,) which links the
resorcinol oxygen atoms. This is evidence that these groups
are closely spaced. The absence of analogous interactions
in two other oxygenꢀcontaining rings between the mutuꢀ
10
ax 11A
11C
8e
3A
7ax
3B
3C
13a
12b
1e
12a
1ax
8ax 7e
10e 11B
13b
δ
2
3
4
5
6
7
7
6
5
4
3
2
δ
1
Fig. 5. COSY H—1H spectrum of cavitand 5.

2556
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005
Prosvirkin et al.
Physical Chemistry of the Kazan Research Center of the Rusꢀ
sian Academy of Sciences and the Institute of Organic Chemisꢀ
try of the Dresden University of Technology.
ally trans protons Hax(1) and the corresponding protons
of the methylene bridge, Ha(13) and Hb(13), is evidence
that these fragments are far apart.
Xꢀray diffraction analysis of compound 3 was carried out on
an automated fourꢀcircle EnrafꢀNonius CADꢀ4 diffractometer.
Crystals of 3, C60H56O8•2C2H3N, are triclinic. At 20 °C,
a = 11.217(4), b = 13.567(3), c = 19.09(1) Å, α = 83.28(4),
Thus, the reaction of 2ꢀmethylresorcinol with pꢀtoluꢀ
aldehyde, unlike analogous reactions with other aromatic
aldehydes, afforded two main diastereomers (rctt and rccc)
rather than one rctt isomer. In addition, we demonstrated
that not only the rccc isomer but also the rctt isomer can
be linked to form cavitands adopting a cone conformaꢀ
tion in spite of the fact that the latter isomer adopts a
chair conformation containing two differently oriented
aryl substituents.
β = 78.39(3), γ = 69.33(3)–°, V = 2660.5(4) Å3, Z = 2, dcalc
=
1.23 g cm–3, space group Р1.
The unit cell parameters and intensities of 7682 reflections,
of which 5071 reflections were with I ≥ 3σ, were measured at
20 °C (λ(CuꢀKα) = 1.5418 Å, graphite monochromator,
ω/2θ scanning technique, θ ≤ 57.22°). The intensities of three
check reflections showed no decrease in the course of Xꢀray data
collection. The absorption correction was ignored because of
the small absorption coefficient (µCu = 6.09 cm–1). The strucꢀ
ture was solved by direct methods using the SIR program9 and
refined first isotropically and then anisotropically, except for the
atoms of two solvate molecules, which were refined isotropically.
Subsequently, all hydrogen atoms were located from difference
electron density maps. The contributions of the hydrogen atoms
to the structure amplitudes were taken into account with fixed
positional and thermal parameters in the final steps of the leastꢀ
squares refinement. The final reliability factors were as follows:
R = 0.062, Rw = 0.076 using 5071 independent reflections with
F 2 ≥ 3σ. All calculations were carried out using the MolEN
program package10 on an AlphaStation 200 computer. The
atomic coordinates and displacement parameters were deposꢀ
ited with the Cambridge Structural Database. Selected geometꢀ
Experimental
1
The H and 13C NMR spectra were recorded on a Bruker
ACꢀ300 spectrophotometer (300.1 MHz for 1H and 75 MHz
for 13C). The 2D NMR spectra were measured on a Bruker
DRXꢀ500 instrument operating at 500.1 and 125.7 MHz, reꢀ
spectively; Me4Si was used as the internal standard. The mass
spectra were obtained on a MALDIꢀTOF Kratos Kompact
MALDI II mass spectrometer (Shimadzu Europa GmbH,
Duisburg, Germany), N2ꢀLaserquelle (λ = 337 nm), with the
use of 1,8,9ꢀtrihydroxyanthracene and pꢀnitroaniline as the maꢀ
trices. The melting points were determined on a Boetius hotꢀ
stage apparatus. Elemental analysis was carried out in microanaꢀ
lytical laboratories at the A. E. Arbuzov Institute of Organic and
Table 2. Selected geometric parameters of molecule 3
Bond
d/Å
Bond angle
ω/deg
Torsion angle
τ/deg
O(3)—C(3)
O(5)—C(5)
1.379(4)
1.392(4)
1.377(5)
1.396(4)
1.381(4)
1.390(4)
1.398(5)
1.386(5)
1.05(2)
1.141(7)
1.520(5)
1.521(6)
1.542(5)
1.517(6)
1.514(4)
1.534(5)
1.532(5)
1.495(6)
1.520(6)
1.514(4)
1.517(5)
1.503(4)
1.542(5)
1.524(5)
1.516(4)
1.516(5)
C(2)—C(1)—C(27)
C(2)—C(1)—C(33)
C(2)—C(1)—H(1)
C(27)—C(1)—C(33)
C(27)—C(1)—H(1)
C(33)—C(1)—H(1)
C(9)—C(8)—H(8)
C(6)—C(8)—C(9)
C(6)—C(8)—C(40)
C(6)—C(8)—H(8)
C(9)—C(8)—C(40)
C(40)—C(8)—H(8)
C(13)—C(15)—C(16)
C(13)—C(15)—C(47)
C(13)—C(15)—H(15)
C(16)—C(15)—C(47)
C(16)—C(15)—H(15)
C(47)—C(15)—H(15)
C(23)—C(22)—H(22)
C(20)—C(22)—C(23)
C(20)—C(22)—C(54)
C(20)—C(22)—H(22)
C(23)—C(22)—C(54)
C(54)—C(22)—H(22)
N(63)—C(62)—C(61)
N(66)—C(65)—C(64)
111.1(3)
113.8(3)
110.2(3)
116.2(3)
105.4(3)
99.0(3)
103.5(3)
116.5(2)
110.9(3)
110.7(3)
109.6(3)
104.8(3)
109.0(3)
115.8(3)
108.3(3)
112.6(3)
110.9(3)
99.9(3)
106.8(3)
111.3(3)
111.7(2)
106.9(3)
112.4(3)
107.4(4)
167.0(2)
179.3(6)
H(3)—O(3)—C(3)—C(2)
H(5)—O(5)—C(5)—C(4)
–5.5(5)
–60.8(4)
78.8(4)
–163.2(2)
179.1(3)
–160.9(2)
–122.7(3)
105.3(3)
96.6(3)
O(10)—C(10)
O(12)—C(12)
O(17)—C(17)
O(19)—C(19)
O(24)—C(24)
O(26)—C(26)
N(63)—C(62)
N(66)—C(65)
C(1)—C(2)
C(1)—C(27)
C(1)—C(33)
C(4)—C(29)
C(6)—C(8)
H(10)—O(10)—C(10)—C(9)
H(12)—O(12)—C(12)—C(11)
H(17)—O(17)—C(17)—C(16)
H(19)—O(19)—C(19)—C(18)
H(24)—O(24)—C(24)—C(23)
H(26)—O(26)—C(26)—C(25)
C(27)—C(1)—C(2)—C(3)
C(2)—C(1)—C(33)—C(34)
C(27)—C(1)—C(33)—C(34)
C(6)—C(8)—C(9)—C(10)
C(6)—C(8)—C(40)—C(45)
C(9)—C(8)—C(40)—C(45)
C(13)—C(15)—C(47)—C(48)
C(16)—C(15)—C(47)—C(48)
C(14)—C(13)—C(15)—C(16)
C(19)—C(20)—C(22)—C(23)
C(20)—C(22)—C(54)—C(55)
C(23)—C(22)—C(54)—C(55)
41.6(4)
172.5(3)
–95.9(4)
–25.8(5)
104.2(4)
–12.3(5)
114.0(4)
–66.6(4)
71.4(4)
C(8)—C(9)
C(8)—C(40)
C(11)—C(30)
C(13)—C(15)
C(15)—C(16)
C(15)—C(47)
C(18)—C(31)
C(20)—C(22)
C(22)—C(23)
C(22)—C(54)
C(25)—C(32)
–106.3(4)
19.6(5)

Synthesis of rcttꢀ and rcccꢀcalix[4]resorcinarenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 11, November, 2005 2557
ric parameters are given in Table 2. The molecular structures
were drawn and intermolecular interactions were calculated usꢀ
ing the PLATON program.5
J = 7.4 Hz); 7.13 and 7.07 (both d, 4 H each, J = 8.2 Hz); 7.02
(s, 2 H); 6.92 and 6.46 (both s, 2 H each); 6.01 (d, 2 H, J =
6.9 Hz); 5.67 (d, 2 H, J = 6.96 Hz); 5.00 (s, 2 H); 4.47 (d, 2 H,
J = 6.9 Hz); 4.37 (d, 2 H, J = 6.96 Hz); 2.38 and 2.33 (both s,
6 H each); 2.13 (s, 3 H); 2.03 (s, 6 H); 1.93 (s, 3 H). 13C NMR
(CDCl3), δ: 155.2, 154.4, 153.8, 153.1, 137.5, 137.4, 137.3,
137.0, 136.2, 135.9, 135.7, 135.2, 131.1, 129.0, 128.7, 128.5,
127.1, 126.8, 125.5, 124.2, 123.97, 98.5, 97.7, 56.3, 41.9, 21.07,
20.98, 10.6, 10.5, 10.4. MS, m/z (Irel (%)): 952 [M – 1]+ (100),
calcd. M = 953.
Calix[4]methylresorcinarenes 1 (rctt) and 2 (rccc). Concenꢀ
trated HCl (25 mL) was added with stirring and cooling
(ice—water) to a solution of 2ꢀmethylresorcinol (13.8 g,
0.112 mol) and pꢀtolualdehyde (12.25 g, 0.100 mol) in ethanol
(200 mL). The reaction mixture was stirred at room temperature
for 3 days. The white precipitate that formed was filtered off and
washed with ethanol (3×50 mL). Compound 1 was obtained in a
yield of 20.2 g (80.3%), m.p. 360 °C (decomp.). Water (300 mL)
was added to the filtrate. The yellow precipitate was filtered off
and washed with water. Compound 2 was obtained in a yield of
3.12 g (12.4%), m.p. 360 °C (decomp.).
We thank Professor V. Boehmer (Johannes Gutenberg
University of Mainz, Germany) for help in interpreting
2D NMR spectra.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos 03ꢀ03ꢀ96258
and 02ꢀ03ꢀ32280) and the Academy of Sciences of
Tatarstan (Grant 07ꢀ7.4ꢀ207).
Compound 1. Found (%): C, 79.10; H, 6.00. C60H56O8. Calꢀ
1
culated (%): C, 79.62; H, 6.23. H NMR (DMSOꢀd6), δ: 7.40
(d, 4 H, J = 7.4 Hz); 7.20 (s, 1 H); 7.17 (d, 4 H, J = 7.4 Hz); 7.13
(d, 4 H, J = 8.2 Hz); 7.07 (d, 4 H, J = 8.2 Hz); 7.02 (s, 2 H); 6.90
(s, 1 H); 6.40 (s, 2 H); 5.00 (s, 2 H); 2.40 (s, 6 H); 2.30 (s, 6 H);
2.13 (s, 3 H); 2.03 (s, 6 H); 1.93 (s, 3 H). 13C NMR (DMSOꢀd6),
δ: 155.1, 154.9, 153.8, 153.0, 137.9, 137.5, 137.4, 136.2, 136.0,
135.5, 135.2, 131.1, 129.1, 128.7, 128.5, 127.2, 126.9, 126.7,
125.4, 124.2, 123.9, 56.1, 42.0, 21.1, 20.8, 10.6, 10.5, 10.4. MS,
m/z (Irel (%)): 904 [M – 1]+ (100), calcd. M = 905.
References
1. A. G. S. Hoegberg, J. Org. Chem., 1980, 45, 4498.
2. L. M. Tunstad, J. A. Tucker, E. Dalcanale, J. Weiser, J. A.
Bryant, J. C. Sherman, R. C. Helgeson, C. B. Knobler, and
D. J. Cram, J. Org. Chem., 1989, 54, 1305.
3. Y. Yamakawa, M. Ueda, R. Nagahata, K. Takeuchi, and
M. Asai, J. Chem. Soc., Perkin Trans. 1, 1998, 4135.
4. O. Middel, W. Verboom, R. Hulst, H. Kooijman, A. L.
Spek, and D. N. Reinhoudt, J. Org. Chem., 1998, 63, 8259.
5. A. L. Spek, Acta Crystallogr., Sect. A, Fund. Crystallogr.,
1990, 46, 34.
6. A. T. Gubaidullin, Intern. Union of Crystallography
XVIII Congress and General Assembly (Glasgow, August 4—13,
1999), Collected Abstract, Glasgow (Scotland, UK),
1999, 393.
7. V. F. Mironov, A. T. Gubaidullin, A. A. Shtyrlina, I. A.
Litvinov, R. R. Petrov, A. I. Konovalov, T. A. Zyablikova,
R. Z. Musin, and E. N. Varaksina, Zh. Org. Khim., 2002, 72,
1868 [Russ. J. Org. Chem., 2002, 72 (Engl. Transl.)].
8. H. Boerrigter, W. Verboom, and D. N. Reinhoudt, J. Org.
Chem., 1997, 62, 7148.
Compound 2. Found (%): C, 78.90; H, 6.20. C60H56O8. Calꢀ
1
culated (%): C, 79.62; H, 6.23. H NMR (acetoneꢀd6), δ: 7.01
(d, 8 H, J = 8.0 Hz); 6.85 (d, 8 H, J = 8.0 Hz); 6.08 (s, 4 H); 5.78
(s, 4 H); 3.06 (br.s, 8 OH); 2.42 (s, 12 H); 2.20 (s, 12 H).
13C NMR (acetoneꢀd6), δ: 154.9, 137.5, 137.0, 135.4, 131.2,
129.6, 128.1, 125.4, 55.6, 21.9, 9.1. MS, m/z (Irel (%)): 904
[M – 1]+ (100), calcd. M = 905.
Calix[4]methylresorcinareneꢀbased cavitand (4, rccc). A soꢀ
lution of calix[4]methylresorcinarene 2 (3.1 g, 3.4 mmol) and
BrCH2Cl (4 mL, 61.25 mmol) in DMF (150 mL) and K2CO3
(11 g, 80 mmol) were stirred at 70 °C for 4 days. After removal of
the solvent in vacuo, CH2Cl2 (60 mL) was added, and the soluꢀ
tion was washed with 2 M HCl (3×25 mL). After silica gel
column chromatography (CH2Cl2 as the eluent), a paleꢀpink
powder of 4 was isolated in a yield of 1.2 g (36.8%), m.p. 360 °C
(decomp.). Found (%): C, 80.10; H, 5.90. C64H56O8. Calcuꢀ
1
lated (%): C, 80.64; H, 5.92. H NMR (CDCl3), δ: 7.11 and
6.97 (both d, 8 H each, J = 8.0 Hz); 6.73 and 6.29 (both s,
4 H each); 5.90 and 4.34 (both d, 4 H each, J = 6.9 Hz); 2.22
and 2.01 (both s, 12 H each). 13C NMR (CDCl3), δ: 154.8,
137.5, 137.1, 135.4, 131.2, 129.6, 128.1, 125.4, 96.9, 55.4, 22.1,
10.4. MS, m/z (Irel (%)): 952 [M – 1]+ (100), calcd. M = 953.
Calix[4]methylresorcinareneꢀbased cavitand (5, rctt) was preꢀ
pared analogously from calix[4]methylresorcinarene 1 in 14.3%
yield, m.p. 360 °C (decomp.). Found (%): C, 79.80; H, 5.80.
9. A. Altomare, G. Cascarano, C. Giacovazzo, and D. Viterbo,
Acta Crystallogr., Sect. A, 1991, 47, 744.
10. L. H. Straver and A. J. Schierbeek, MolEN. Structure Deterꢀ
mination System. Vol. 1. Program Description, Nonius B. V.,
1994, 180 p.
C
64H56O8. Calculated (%): C, 80.64; H, 5.92. 1H NMR
(CDCl3), δ: 7.38 (d, 4 H, J = 7.4 Hz); 7.19 (s, 1 H); 7.17 (d, 4 H,
Received January 10, 2003;
in revised form September 22, 2005