Synthesis of derivatives of p-tert-butylcalix[4]arene containing on lower rim fragments of 2-aminoalkylbenzimidazoles

Article abstract of DOI:10.1134/S107042801009023X

Reactions of calix[4]arene carboxymethoxy derivatives with 2-aminoalkylbenzimidazoles in the presence of dicyclohexylcarbodiimide and hydroxybenzotriazole afforded a series of p-tert-butylcalix[4]arene derivatives containing on the lower rim N-(2-benzimidazolylalkyl)carbamoylmethoxy fragments. The reaction carried out in the absence of hydroxybenzOtriazole resulted in macrocycles containing one N-(2-benzimidazolylalkyl)carbamoyl fragment and a fragment of N-(acyl)dicyclohexylisourea.

Full text of DOI:10.1134/S107042801009023X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 9, pp. 1403−1408. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.A. Alekseeva, A.P. Luk’yanenko, S.S. Basok, A.V Mazepa, A.I. Gren’, 2010, published in Zhurnal Organicheskoi Khimii, 2010,
Vol. 46, No. 9, pp. 1399−1404.
Synthesis of Derivatives of p-tert-Butylcalix[4]arene Containing
on Lower Rim
Fragments of 2-Aminoalkylbenzimidazoles
E. A. Alekseeva, A. P. Luk’yanenko, S. S. Basok, A. V. Mazepa, and A. I. Gren’
Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine,
Odessa, 65080 Ukraine
e-mail: Alyeksyeyeva@rambler.ru
Received September 21, 2009
Abstract—Reactions of calix[4]arene carboxymethoxy derivatives with 2-aminoalkylbenzimidazoles in the presence
of dicyclohexylcarbodiimide and hydroxybenzotriazole afforded a series of p-tert-butylcalix[4]arene derivatives
containing on the lower rim N-(2-benzimidazolylalkyl)carbamoylmethoxy fragments. The reaction carried out in
the absence of hydroxybenzOtriazole resulted in macrocycles containing one N-(2-benzimidazolylalkyl)carbamoyl
fragment and a fragment of N-(acyl)dicyclohexylisourea.
DOI: 10.1134/S107042801009023X
Derivatives of calixarenes containing on the lower or
upper rim of the macrocycle amide and heteroaromatic
fragments are capable of binding cations of certain met-
als, of bringing these complexes through hydrophobic
membranes, and some among such compounds exhibit
a biological activity with respect to pathogenic bacteria
and simulate enzymes action [1–8].Among new efficient
receptors underlain by calixarenes exhibiting such proper-
ties derivatives are promising containing imidazole and
benzimidazole fragments [9–11].
at the ratio calixarene–benzimidazole 1 : 4 [12]. In
all events mono- and di(benzimidazolylcarbamoyl)
derivatives were isolated in the ratio 2:1 (the conversion
of initial calixarene 65–70%); therewith the increase
in the number of the carbon atoms in the position 2 of
2-aminoalkylbenzimidazoles resulted in the hgher yield
of compounds containing a single benzimidazole group
(Scheme 1).
The second procedure consisted in the reaction
of acid chloride III with 2-aminoalkyl-substituted
benzimidazoles [13, 14]. In this case independent of
the reagents ratio and the reaction time the acylation
proceeded also ambiguously. Compounds formed
in the reaction of calixarene carbonyl chloride III
with 2-(aminoalkyl)benzimidazoles containing one
carboxy group and one amide fragment in the course
of purification by crystallization from lower alcohols
readily transformed into the corresponding derivatives
possessing an ester group. The prolonged boiling of
calixarene II with unsubstituted benzimidazole (6 equiv
per each ester group) in xylene did not provide the
target products, whereas the reaction of acid chloride
III with benzimidazole gave calixarene XII containing
one benzimidazole fragment, although in a low yield.
This compound is unstable in acid medium, the formed
Aiming at preparation of benzimidazolyl deriv-
atives of p-tert-butylcalix[4]arene (I) we considered
the possibility to use two methods of reaction
between bis[(methoxycarbonyl)methoxy]- II and
bis[(chlorocarbonyl)methoxy]- III derivatives of
calixarene I with 2-aminoalkyl-substituted benz-
imidazoles. This way would introduce into the molecule
of the macrocycle an additional binding site, a carbamoyl
group [12–14].
The preparation of the calixarene derivatives
containing benzimidazole fragments by the first
procedure occurred by boiling bis[(methoxycarbonyl)
methoxy]-p-tert-butylcalix[4]arene (II) with 2-amino-
alkyl-substituted benzimidazoles in mixed solvents
methanol–toluene, ethanol–benzene, xylene–methanol
1403

ALEKSEEVA et al.
1404
Scheme 1.
R = CH2 (IV, VIII), (CH2)2 (V, IX), CH (VI, X), (CH2)4 (VII, XII).
amide group decomposed even at washing its solution in
chloroform with 10% HCl solution.
The reaction between calixarene XIII and 2-amino-
alkylbenzimidazoles in the presence of dicyclohexyl-
carbodiimide (DCC) and hydroxybenzotriazole (HBTA)
proved to be more effective approach to the preparation
of p-tert-butylcalix[4]arenas substituted with two benz-
imidazole fragments. By the same procedure we obtained
from mono- XV and tetra- XIV carboxy-substituted
calixarenes mono- (XVI) and tetra-cis-[(benzimidazol-
2-ylmethyl)carbamoyloxy]- (XVII), mono- (XVIII) and
tetracis[(benzimidazol-2-ylethyl)carbamoyloxy]- (XIX)
calixarenes (Scheme 2). The yields of the target com-
pounds were 75% for tetraderivatives XVII, XIX and
80–85% for mono- and disubstituted calixarenes.
In order to increase the yield of the symmetrically
substituted calixarene benzimidazolyl derivatives we
considered the possibility to use the carbodiimide method
by an example of reaction between dicarboxymethoxy-
p-tert-butylcalix[4]arene (XIII) with 2-aminoalkyl-
benzimidazoles [15]. But in this case alongside the
disubstituted compounds with two benzimidazole frag-
ments we also obtained macrocycles where along with
the N-(2-benzimidazolylalkyl)carbamoyl substituent an
N-cyclohexyl-N-(N’-cyclohexyl-carbamoyl)carbonylme-
thoxy fragment was present.
These data suggest that the reaction involving the
carboxy groups in the calixarene molecule is a step-wise
process where first one carboxy group is activated, then
the second. In no experiments the obtained calixarene
contained two N-acylurea residues. The reaction of
calixarene XIV containing four carboxy groups with
aminoalkylbenzimidazoles furnished a mixture of
compounds conteining two or three benzimidazole frag-
ments and consequently two or one N-acylurea residue,
whereas acylation of 2-aminoalkylbenzimidazoles with
mono(carboxymethoxy)-p-tert-butylcalix[4]arene (XV)
alongside the target product a calixarene was obtained in
minor quantity with an N-cyclohexyl-N-(N’-cyclohexyl-
carbamoyl)carbonylmethoxy substituent.
The structure of compounds obtained was proved by
1H NMR spectroscopy. The 1H NMR spectra of the ob-
tained disubstituted calix[4]-arene derivatives contained
2 singlets from the protons of the tert-butyl groups with
the integral intensity 18H each, two doublets from the
protons of the methylene bridges of intensity 4H each,
J 12.7–13.7 Hz, and two singlets from the protons of the
aromatic part of the macrocycle with the intensity 4H
each. In the spectra of the monosubstituted calixarenes
the protons of the tert-butyl groups appeared as three
singlets (1:2:1), the protons of the methylene bridges,
as four doublets of intensity 2H each (J 11.4–13.3 Hz),
aromatic protons of the macrocycle, as two doublets and
two singlets. The tetraderivatives XVII, XIX have in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

SYNTHESIS OF DERIVATIVES OF p-tert-BUTYLCALIX[4]ARENE
1405
Scheme 2.
R = CH2COOH (XIV); n = 1 (XVII), 2 (XIX).
1
the H NMR spectra a singlet (36H) from the protons
pounds obtained were established by 1H NMR method on
a spectrometer Varian VXR-300 (300 MHz) from ~10%
solutions in CDCl3, internal reference TMS. Mass spectra
were obtained by FAB method on a mass spectrometer
VG 70-70EQ using a Xe atoms beam of the energy 8 kV,
electron impact (70 eV) mass spectra were registered on
an instrument MKh-1321.
of the tert-butyl groups, 2 doublets from the methylene
protons, and a singlet from the aromatic protons of the
calixarene skeleton. This spectral pattern indicates that
the obtained compounds exist in the cone conformation
and makes it possible to conclude that no conformational
isomerization of the macrocycle occurs during the modi-
fication of the functional group on the lower rim of the
p-tert-butylcalix-[4]arene.
Bis[(methoxycarbonyl)methoxy]-p-tert-butyl-calix[4]
arene (II), bis[(chlorocarbonyl)methoxy]-p-tert-bu-
tylcalix[4]arene (III), di(carboxymethoxy)-p-tert-bu-
tylcalix[4]arene (XIII), tetra(carboxymethoxy)-p-tert-
butylcalix[4]arene (XIV), and mono(carboxymethoxy)-p-
tert-butylcalix[4]arene (XV) were obtained by procedures
[12–14, 16, 17].
Therefore the comparison of approaches to the intro-
duction into the molecule of p-tert-butylcalix[4]arene of
amidoalkylbenzimidazole fragments demonstrated that
the most efficient procedure for the preparation of the
benzimidazolyl-substituted macrocycles from the corre-
sponding carboxy derivatives was the carbodiimide method
of acylation in the presence of hydroxybenzotriazole.
Reaction of bis[(methoxycarbonyl)methoxy]-p-tert-
butylcalix[4]arene (II) with 2-aminoalkylbenzimid-
azoles. A dispersion of 0.79 g (1 mmol) of calix[4]arene
II, 12 mmol of an appropriate 2-aminoalkylbenzimid-
azole in 55 ml of a mixture methanol–xylene, 1:10, was
boiled at stirring over 48–52 h. The solvent was removed
EXPERIMENTAL
The structure and prevailing conformations of com-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

ALEKSEEVA et al.
1406
at a reduced pressure, the dry residue was treated with hot
hexane or heptane (4 × 15 ml). The solution obtained was
concentrated to 15 ml and cooled. Unreacted calixarene
II was filtered off. The solution was evaporated at the
reduced pressure, the disubstituted compounds VIII–XI
were separated from monobenzimidazolyl-substituted
calixarenes by the fractional crystallization from the
mixture methanol–water, 5 : 1.
was added of 2.3 mmol of an appropriate 2-aminoalkyl-
benzimidazole dihydrochloride and 0.61 ml (4.4 mmol)
of triethylamine in 10 ml of chloroform. After 20 h the
reaction mixture was filtered, the filtrate was evaporated,
the dry residue was dissolved in 50 ml of chloroform and
the solution was washed with water (2 × 20 ml). The
organic layer was evaporated at a reduced pressure. The
crude feaction products were purified by crystallization
(from methanol–water, 5:1).
Reaction of bis[(chlorocarbonyl)methoxy]-p-tert-
butylcalix[4]arene (III) with 2-aminoalkylbenzimid-
azoles. To a dispersion of 2.3 mmol of 2-aminoalkyl-
benzimidazole dihydrohloride, 0.95 ml (6.9 mmol) of
triethylamine in 30 ml of anhydrous chloroform was
added dropwise at stirring a solution of 0.8 g (1 mmol)
of calixarene ІІІ in 20 ml of anhydrous chloroform.
The reaction mixture was boiled at stirring for 18 h. On
completion of the reaction the triethylamine hydrochlo-
ride was filtered off, the solvent was evaporated at a
reduced pressure, the dry residue was dissolved in 50 ml
of chloroform and the solution was several times washed
with water. The organic layer was evaporated at a reduced
pressure. The purification and separation of the reaction
products was carried out as described above.
5,11,17,23-Tetra-tert-butyl-25-[(methoxycarbonyl)
methoxy]-27-[(benzimidazol-2-yl-methyl)
carbamoylmethoxy]-26,28-dihydroxycalix[4]arene
1
(IV). H NMR spectrum, δ, ppm: 0.97 s [9H, (CH3)3C],
0.98 s [9H, (CH3)3C], 1.26 s [9H, (CH3)3C], 1.30 s [9H,
(CH3)3C], 3.32 d (2H, ArCH2Ar, J 13.38 Hz), 3.55 s
(2H, CH2COCH3), 4.07 d (2H, ArCH2Ar, J 13.69 Hz),
4.38 s (2H, CH2COCH3), 4.45 d (2H, ArCH2Ar,
J 13.07 Hz), 4.53 d (2H, ArCH2Ar, J 12.76 Hz), 4.62 s
(2H, CH2CONH), 4.71 s (2H, CH2NH), 6.80 d (2H,ArH),
6.83 s (2H,ArH), 6.98 d (2H,ArH), 7.02 s (2H,ArH), 7.12
m (2H,ArHbenzim), 7.35 m (2H,ArHbenzim), 7.53 br.s (3H,
OH, NH), 8.91 br.s (1H, NH). Mass spectrum: m/z 908
[M + 1]+.
5,11,17,23-Tetra-tert-butyl-25,27-bis[(benz-imidaz-
Reaction of di(carboxymethoxy)-p-tert-butylca-
lix[4]arene (XIII) with 2-aminoalkylbenzimidazoles.
To a dispersion of 2.3 mmol of 2-aminoalkylbenzimid-
azole dihydrochloride, 0.61 ml (4.4 mmol) of triethyl-
amine in 10 ml of chloroform was added at stirring 0.76 g
(1 mmol) of calixarene XIII in 10 ml of chloroform,
10 min after the addition of calixarene into the reaction
mixture was added 0.47 g (2.3 mmol) of N,N-dicyclohex-
ylcarbodiimide. The reaction progress was monitored by
TLC and mass spectrometry. After 10–15 h the reaction
mixture was filtered, the filtrate was evaporated, the dry
residue was dissolved in 50 ml of chloroform and the
solution was washed with water (2 × 20 ml). The organic
layer was evaporated at a reduced pressure. The reaction
products containing the acylurea fragment were separated
from the disubstituted compounds by fractional crystal-
lization from hexane or heptane.
ol-2-ylmethyl)carbamoylmethoxy]-26,28-dihydroxy-
1
calix[4]arene (VIII). H NMR spectrum, δ, ppm: 0.97 s
[18H, (CH3)3C], 1.28 s [18H, (CH3)3C], 3.27 d (4H, Ar-
CH2Ar, J 13.38 Hz), 3.95 d (4H, ArCH2Ar, J 13.38 Hz),
4.39 d (4H, CH2CO), 4.85 s (4H, CH2NH), 6.81 s (4H,
ArH), 7.03 s (4H, ArH), 7.19 m (4H, ArHbenzim), 7.48 m
(4H, ArHbenzim), 7.55 br.s (4H, OH, NH), 9.02 br.s (2H,
NH). Mass spectrum: m/z 1023 [M + 1]+.
5,11,17,23-Tetra-tert-butyl-25-[(methoxycarbonyl)
m e t h o x y ] - 2 7 -[ ( b e n z i m i d a z o l - 2 - y l e t h y l ) -
carbamoylmethoxy]-26,28-dihydroxycalix[4]arene
1
(V). H NMR spectrum, δ, ppm: 0.94 s [9H, (CH3)3C],
0.96 s [9H, (CH3)3C], 1.24 s [9H, (CH3)3C], 1.28 s [9H,
(CH3)3C], 3.28 d (2H, ArCH2Ar, J 13.35 Hz), 3.44 t
(2H, CH2CH2NH), 3.7 s (2H, CH2COCH3), 4.1 d (2H,
ArCH2Ar, J 13.69 Hz), 4.3 s (2H, CH2COCH3), 4.38 m
(4H, ArCH2Ar, CH2CH2NH), 4.47 d (2H, ArCH2Ar, J
12.67 Hz), 4.52 s (2H, CH2CONH), 6.82 d (2H, ArH),
6.86 s (2H, ArH), 6.94 d (2H, ArH), 7.05 s (2H, ArH),
7.12 m (2H,ArHbenzim), 7.39 m (2H,ArHbenzim), 7.55 br.s
(3H, OH, NH), 8.97 br.s (1H, NH). Mass spectrum: m/z
922 [M + 1]+.
Reaction of di(carboxymethoxy)-p-tert-butylca-
lix[4]arene (XIII) with 2-aminoalkylbenzimidazoles in
the presence of hydroxybenzotriazole. To a dispersion
of 0.76 g (1 mmol) of calixarene XIII, 0.3 g (2.25 mmol)
hydroxybenzotriazole in 30 ml of chloroform cooled to
0°C was added at stirring 0.46 g (2.25 mmol) of dicyclo-
hexylcarbodiimide. The reaction mixture was stirred at
room temperature for another 30 min, and a dispersion
5,11,17,23-Tetra-tert-butyl-25,27-bis[(benz-imidaz-
ol-2-ylethyl)carbamoylmethyloxy]-26,28-dihydroxy-
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SYNTHESIS OF DERIVATIVES OF p-tert-BUTYLCALIX[4]ARENE
1407
1
azol-2-ylbutyl)carbamoylmethoxy]-26,28-dihydroxy-
calix[4]arene (XI). H NMR spectrum, δ, ppm: 1.12 s
calix[4]arene (IX). H NMR spectrum, δ, ppm: 1.01 s
1
[18H, (CH3)3C], 1.26 s [18H, (CH3)3C], 3.28 d (4H, Ar-
CH2Ar, J 13.69 Hz), 3.35 t (4H, CH2CH2NH), 3.99 d (4H,
ArCH2Ar, J 13.07 Hz), 4.46 t (4H, CH2CH2NH), 4.53 s
(4H, CH2CO), 6.89 s (4H, ArH), 7.00 s (4H, ArH), 7.15
m (4H,ArHbenzim), 7.46 m (4H,ArHbenzim), 7.64 br.s (4H,
OH, NH), 9.0 br.s (2H, NH). Mass spectrum: m/z 051
[M + 1]+.
[18H, (CH3)3C], 1.24 s [18H, (CH3)3C], 1.60–1.80 m (8H,
NHCH2CH2CH2CH2), 2.9 m (4H, NHCH2CH2CH2CH2),
3.24 m (4H, NHCH2CH2CH2CH2), 3.45 d (4H, ArCH2Ar,
J 13.76 Hz), 4.28 d (4H, ArCH2Ar, J 13.38 Hz), 4.45 s
(4H, CH2CO), 6.89 s (4H,ArH), 7.03 s (4H,ArH), 7.12 m
(4H, ArHbenzim), 7.34 m (4H, ArHbenzim), 7.65 br.s (4H,
OH, NH), 9.1 br.s (2H, NH). Mass spectrum: m/z 1107
[M + 1]+.
5,11,17,23-Tetra-tert-butyl-25-[(methoxycarbonyl)
methoxy]-27-[(benzimidazol-2-ylpropyl)
carbamoylmethoxy]-26,28-dihydroxycalix[4]arene
5,11,17,23-Tetra-tert-butyl-25-[(benzimidazol-2-
1
ylmethyl)carbamoylmethoxy]-26,27,28-trihydroxycal-
(VІ). H NMR spectrum, δ, ppm: 0.97 s [9H, (CH3)3C],
1
ix[4]arene (XVI). H NMR spectrum, δ, ppm: 1.15 s [9H,
1.01 s [9H, (CH3)3C], 1.18 s [9H, (CH3)3C], 1.22 s [9H,
(CH3)3C], 1.85 m (2H, NHCH2CH2CH2), 2.78 m (2H,
NHCH2CH2CH2), 3.22 m (2H, NHCH2CH2CH2), 3.35 d
(2H, ArCH2Ar, J 13.69 Hz), 3.53 s (2H, CH2COCH3),
3.98 d (2H,ArCH2Ar, J 13.48 Hz), 4.25 d (2H,ArCH2Ar,
J 12.76 Hz), 4.32 s (2H, CH2COCH3), 4.40 d (2H, Ar-
CH2Ar, J 12.69 Hz), 4.46 s (2H, CH2CONH), 6.86 d (2H,
ArH), 6.9 s (2H,ArH), 7.03 d (2H,ArH), 7.1 m (4H,ArH,
ArHbenzim), 7.34m(2H,ArHbenzim), 7.59br.s(3H, OH, NH),
8.74 s (1H, NH). Mass spectrum: m/z 936 [M + 1]+.
(CH3)3C], 1.18 s [18H, (CH3)3C], 1.19 s [9H, (CH3)3C],
4.06 d (2H,ArCH2Ar, J 12.76 Hz), 4.18 d (2H,ArCH2Ar,
J 13.56 Hz), 4.25 d (2H, ArCH2Ar, J 12.76 Hz), 4.34 d
(2H, ArCH2Ar, J 11.5 Hz), 4.42 s (2H, CH2CO), 4.68 s
(8H, CH2NH), 7.02 d (2H, ArH), 7.06 s (2H, ArH), 7.1 d
(2H, ArH), 7.12 s (2H, ArH), 7.25 m (2H, ArHbenzim),
7.42 m (1H,ArHbenzim), 7.70 m (1H,ArHbenzim), 8.49 br.s
(1H, NH), 8.58 s (1H, OH), 8.59 s (2H, OH), 8.62 s (1H,
NH). Mass spectrum: m/z 836 [M + 1]+.
5,11,17,23-Tetra-tert-butyl-25-[(benzimidazol-2-
ylethyl)carbamoylmethoxy]-26,27,28-trihydroxy-
calix[4]arene (XVIII). 1H NMR spectrum, δ, ppm:
1.13 s [9H, (CH3)3C], 1.15 s [18H, (CH3)3C], 1.17
s [9H, (CH3)3C], 3.88 t (2H, CH2CH2NH), 4.00 d
(2H, ArCH2Ar, J 13.21 Hz), 4.12 d (2H, ArCH2Ar,
J 13.45 Hz), 4.22 d (2H, ArCH2Ar, J 12.76 Hz), 4.31 d
(2H, ArCH2Ar, J 11.49 Hz), 4.37 t (2H, CH2CH2NH),
4.62 s (2H, CH2CO), 7.01 d (2H, ArH), 7.04 s (2H,
ArH), 7.09 d (2H, ArH), 7.12 s (2H, ArH), 7.25 m
(1H, ArHbenzim), 7.41 m (1H, ArHbenzim), 7.70 m (1H,
ArHbenzim), 8.33 br.s (1H, NH), 8.51 s (1H, OH),
8.59 s (2H, OH), 8.61 s (1H, NH). Mass spectrum:
m/z 850 [M + 1]+.
5,11,17,23-Tetra-tert-butyl-25,27-bis[(benz-imidaz-
ol-2-ylpropyl)carbamoylmethoxy]-26,28-dihydroxy-
1
calix[4]arene (X). H NMR spectrum, δ, ppm: 1.14 s
[18H, (CH3)3C], 1.27 s [18H, (CH3)3C], 1.87 m (4H,
NHCH2CH2CH2), 2.84 m (4H, NHCH2CH2CH2), 3.65 m
(4H, NHCH2CH2CH2), 3.52 d (4H,ArCH2Ar, J 13.6 Hz),
4.2 d (4H, ArCH2Ar, J 13.38 Hz), 4.48 s (4H, CH2CO),
6.92 s (4H,ArH), 7.06–7.17 m (8H,ArH,ArHbenzim), 7.1 s
(ArH), 7.35 m (4H, ArHbenzim), 7.69 br.s (4H, OH, NH),
8.72 br.s (2H, NH). Mass spectrum: m/z 1079 [M + 1]+.
5,11,17,23-Tetra-tert-butyl-25-[(methoxycarbonyl)
methoxy]-27-[(benzimidazol-2-ylbutyl)-carbamo-
ylmethoxy]-26,28-dihydroxycalix[4]arene (VІІ).
1H NMR spectrum, δ, ppm: 0.95 s [9H, (CH3)3C],
1.05 s [9H, (CH3)3C], 1.17 s [9H, (CH3)3C], 1.23 s
[9H, (CH3)3C], 1.57–1.78 m (4H, NHCH2CH2CH2CH2),
2.85 m (2H, NHCH2CH2CH2CH2), 3.25 m (2H,
NHCH2CH2CH2CH2), 3.32 d (2H, ArCH2Ar, J 13.38
Hz), 3.6 s (2H, CH2COCH3), 3.76 d (2H, ArCH2Ar,
J 13.38 Hz), 4.23 d (2H, ArCH2Ar, J 12.76 Hz), 4.36 s
(2H, CH2COCH3), 4.41 d (2H, ArCH2Ar, J 12.78 Hz),
4.32 s (2H, CH2CONH), 6.90 d (2H, ArH), 6.95 s (2H,
ArH), 7.01 d (2H, ArH), 7.05 s (2H, ArH), 7.1 m (2H,
ArHbenzim), 7.35 m (2H, ArHbenzim), 7.6 br.s (3H, OH,
NH), 8.64 s (1H, NH). Mass spectrum: m/z 950 [M + 1]+.
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetra-cis-
[(benzimidazol-2-ylmethyl)carbamo-ylmethoxy]ca-
1
lix[4]arene (XVII). H NMR spectrum, δ, ppm: 1.04 s
[36H, (CH3)3C)], 3.04 d (4H,ArCH2Ar, J 11.74 Hz), 4.28
d (4H, ArCH2Ar, J 11.74 Hz), 4.36 s (8H, CH2CO),
4.67 m (8H, CH2NH), 5.18 s (4H, NHCO), 6.71 s (8H,
ArH), 7.18 m (8H, ArHbenzim), 7.49 m (8H, ArHbenzim),
8.90 br.s (4H, NH). Mass spectrum: m/z 1397 [M + 1]+.
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetra-
cis-[(benzimidazol-2-ylethyl)carbamoylmethoxy]
calix[4]arene (XIX). 1H NMR spectrum, δ, ppm:
1.02 s [36H, (CH3)3C], 3.01 t (8H, CH2CH2NH),
5,11,17,23-Tetra-tert-butyl-25,27-bis[(benz-imid-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010

ALEKSEEVA et al.
1408
p. 7837.
3.04 d (4H, ArCH2Ar, J 11.98 Hz), 3.66 t (8H,
CH2CH2NH), 4.25 d (4H, ArCH2Ar, J 11.98 Hz),
4.44 s (8H, CH2CO), 5.20 s (4H, NHCO), 6.74 s (8H,
ArH), 7.10 m (8H, ArHbenzim), 7.40 m (8H, ArHbenzim),
8.66 br.s (4H, NH). Mass spectrum: m/z 1453 [M + 1]+.
9. Ebbing, M.H.K., Villa, M.-J., Valpuesta, J.-M., Prados, P.,
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