Benzylation of tetraalkylcalix[4]resorcinols

Article abstract of DOI:10.1007/s11172-009-0021-7

New amphiphilic benzylated calix[4]resorcinols were synthesized by the reaction of tetra-alkylcalix[4]resorcinols with 3,5-di(tert-butyl)-4- hydroxybenzyl acetate. The reaction pathway and the type of the products formed are determined by the structure of

Full text of DOI:10.1007/s11172-009-0021-7

Russian Chemical Bulletin, International Edition, Vol. 58, No. 1, pp. 138—144, January, 2009
138
Benzylation of tetraalkylcalix[4]resorcinols
E. M. Kasymova,a A. R. Burilov,a N. A. Mukmeneva,b S. V. Bukharov,b G. N. Nugumanova,b A. R. Ibragimova,a
A. P. Timosheva,a L. Ya. Zakharova,a L. A. Kudryavtseva,a M. A. Pudovik,a 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: pudovik@iopc.knc.ru
bKazan State Technological University,
68 ul. K. Marksa, 420015 Kazan, Russian Federation
New amphiphilic benzylated calix[4]resorcinols were synthesized by the reaction of tetraꢀ
alkylcalix[4]resorcinols with 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl acetate. The reaction pathway
and the type of the products formed are determined by the structure of the alkyl substituent at
the lower rim of tetraalkylcalix[4]resorcinols and the nature of acid used as a catalyst of the
process. Selfꢀorganization of some synthesized compounds in nonpolar media was studied.
Key words: calix[4]resorcinols, benzylation, selfꢀorganization.
The chemistry of calix[4]resorcinols is one of the most
the calixresorcinol matrix. Continuing these studies, we
attempted to reveal whether the nature of alkyl substituꢀ
ents arranged at the lower rim of the molecule affects the
number of introduced 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl
groups. Indeed, this dependence was found.
The reaction of tetraalkylcalix[4]resorcinols 2a—c with
3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl acetate (1) in the presꢀ
ence of formic acid affords new tetrabenzylated calix[4]ꢀ
resorcinols 3a—c and tribenzylated resorcinol 4 (Scheme 1).
Compound 4 was not isolated in the individual state.
According to the 1H NMR spectral data, its amount in the
reaction mixture ranged from 5 to 20%, which was conꢀ
firmed by TLC.
intensively developed areas of the chemistry of macroꢀ
cyclic polyphenol compounds. Calix[4]resorcinols are
macrocyclic tetramers distinguished by simplicity of prepaꢀ
ration and a possibility of further functionalization both
at the orthoꢀposition of the aromatic ring and involving the
hydroxy groups.1 Calixarenes widely used as molecular
matrices for the creation of preorganized threeꢀdimenꢀ
sional receptors are at present theoretically and practiꢀ
cally significant.2,3 Amphiphilic calixarenes functionalized
by alkyl substituents in solutions form nanosized aggreꢀ
gates capable of efficient and highly selective binding
of guests of various nature. These ensembles are widely
demanded in modern technologies and as nanocontainers,
sensors, nanoreactors, etc.4 The study of the antioxidative
properties of tetramethylcalix[4]resorcinol showed that it
is possible to create a new group of highly efficient inhibiꢀ
tors of thermooxidative destruction of calix[n]areneꢀbased
polymers.3 From this point of view, modification of
calix[4]resorcinols by the introduction of sterically
hindered phenol fragments into the aromatic rings is
of doubtless interest.
Recently5 we have found that the reaction of tetramethylꢀ
calix[4]resorcinol with 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl
acetate (1) in the presence of mineral or organic acids can
proceed via two routes to form electrophilic substitution
products (tetrabenzylated calix[4]resorcinol) and a product
of decomposition of the calixresorcinol framework (triꢀ
benzylated resorcinol). It was found that the use of formic
acid as an acidic reactant made it possible to direct the
reaction mainly via the first route, namely, benzylation of
The introduction of four 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxyꢀ
benzyl groups to the orthoꢀposition of the benzene rings
of calix[4]resorcinol (with respect to the hydroxy groups)
substantially enhances solubility in nonpolar organic
solvents.
1
Based on the H NMR spectral data, we concluded
that the Cꢀbenzylated calix[4]resorcinols have the cone
conformation. This conclusion follows, particularly, from
the fact that the chemical shifts of signals from the
methine protons (quartets) in the benzylated and nonꢀ
benzylated calixarenes are identical and lie in the region
of δ 4.5, and the nonbenzylated calixarene exists in the
cone conformation according to the Xꢀray diffraction
data.6,7 It is known8 that the change of the cone conforꢀ
mation by 1,3ꢀalternate in phenolic calixarenes results in
the downfield shift of the signal of the methylene protons
by ~1 ppm. The 2D ROESY spectrum of compound 3а
(Fig. 1) in chloroform contains only trivial crossꢀpeaks
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 138—144, January, 2009.
1066ꢀ5285/09/5801ꢀ0138 © 2009 Springer Science+Business Media, Inc.

Benzylation of tetraalkylcalix[4]resorcinols
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
139
Scheme 1
2, 3: R = Et (a), Pr (b), C5H11 (c); 3, 4: R´ =
Scheme 2
1 (4 equiv.)
R = C7H15 (2d, 5a), C8H17 (2e, 5b), C9H19 (2f, 5c); R´ =
(5a—c)

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
Kasymova et al.
Ha ↔ But, OH ↔ But, confirming the cone conformation.
It is interesting that the crossꢀpeaks CH3 ↔ But are also
observed. This interaction cannot be intramolecular beꢀ
cause of the long distance between the protons of the
methyl and tertꢀbutyl groups. It is most likely that this
interaction is due to intermolecular coupling and can be
explained by the headꢀtoꢀtail packing.
Monobenzylated calixarene 6 is formed as the single
product of the reaction of calix[4]resorcinol containing
the undecyl fragment at the lower rim of the molecule
with acetate 1 (Scheme 3).
Scheme 3
The further increase in the alkyl substituent size imꢀ
pedes benzylation. The reaction of calix[4]resorcinols conꢀ
taining the heptyl, octyl, and nonyl fragments at the
lower rim of the macromolecule with acetate 1 in the
presence of formic acid affords compounds 5a—c having
only two 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl fragments.
This follows from the data of MALDIꢀTOF mass specꢀ
1 (4 equiv.)
1
trometry (peak values of molecular ions), H and 13C
NMR spectroscopy, and elemental analysis. Based on the
1
data of the H NMR spectra exhibiting the double numꢀ
ber of signals from the aromatic protons, we assumed that
compounds 5a—c represent a mixture of two regiomers
(Scheme 2).
δ
0.0
2.0
4.0
6.0
R = C11H23 (2g, 6)
It should specially be mentioned that we failed to
detect the macrocycle opening products in the case of
formation of dibenzylated and monobenzylated calix[4]ꢀ
resorcinols.
7.00 6.00 5.00 4.00 3.00 2.00 1.00 δ
The synthetic results obtained are likely due to the
susceptibility of calix[4]resorcinols to form organized
structures.4 The ability to form selfꢀassociates increases
with elongation of the alkyl radical. In this case, calix[4]ꢀ
resorcinols are in a denser packing, which is not destroyed
even upon strong dilution. Due to this, the attack of the
bulky electrophilic species, viz., 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀ
hydroxybenzyl carbocation, is impeded, which reflects
the degree of benzylation of the calixarene matrix. Taking
into account the aforesaid, we studied the selfꢀorganizaꢀ
tion of benzylated calix[4]resorcinols.
The method of selfꢀorganization of calixarenes in
solution depends on their structure, concentration, and
Fig. 1. The 2D ROESY spectrum of compound 3a.

Benzylation of tetraalkylcalix[4]resorcinols
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
141
nature of the solvent. Among the listed factors, the
calixarene structure plays the determining role. It has preꢀ
viously4 been shown that the formation of polycapsules,
nanotubes, and polycylinders involves the calixarene
matrix. The selfꢀorganization of amphiphilic calixarenes
and calixresorcinols was studied to most detail.9—11
Depending on the cavity size and conformation, these
compounds can form aggregates with lamellar molecular
packing, classical micelles, or monomolecular micelles.
We studied the selfꢀorganization of benzylated calix[4]ꢀ
resorcinols 3c, 5a,c, 6, and 7 by dielcometry and dynamic
light scattering.
of ε can be considered as a critical concentration that
characterizes structural rearrangements in the system. The
critical concentration (Ccr) depends on the length of the
alkyl radical of calixarene: for compounds 3c and 7 Ccr is
~3•10–5 mol L–1, whereas for compounds 5a,c and 6 this
value lies in the region of (6—8)•10–5 mol L–1. Since the
elongation of the alkyl radical impedes the associative
process, it should be assumed that no typical aggregates
are formed in the concentration range studied. It is most
likely that the break in the dielcometric dependences
indicates preorganization in the system, which can be
identified with sufficient probability by sensitive dielcometric
titration.
Selfꢀorganization of benzylated calixarenes 3c, 5a,c,
6, and 7 was studied by dynamic light scattering. This
method determines sizes of colloidal particles with the
radius not less than 2—4 nm with good accuracy. We
ε
4.86
7
4.84
4.82
1
1
2
3
4
C•104/mol L–1
ε
ε
ε
4.84
4.82
6
The formation of nanostructures in calixarene soluꢀ
tions can involve various intermolecular interactions
including dispersion interactions, π—πꢀinteractions, and
probably, hydrogen bonding, in spite of strong shielding
of the resorcinol and phenolic hydroxy groups. The
geometry factor can play a substantial role in selfꢀorganiꢀ
zation. The results of studies of calixresorcinarene selfꢀ
organization in solutions by dielcometric titration are
shown in Fig. 2. This method is very fruitful when using
nonpolar solvents and the application of tensioꢀ and
conductometry methods is restricted.12 Low cooperativity
of the process and insignificant changes in the properties
of the medium are specific features of selfꢀorganization
of amphiphilic compounds in nonaqueous media. High
sensitivity of the dielectric constant (ε) to changes in the
structural organization of components in the solution or
to the formation of supramolecular structures makes it
possible to successfully use this method for indicating
association processes in various media.12,13 In particular,
the formation of organized structures in chloroform soluꢀ
tions of calixarenes has earlier12—15 been analyzed.
2
3
4
C•104/mol L–1
4.86
4.84
4.82
5c
1
2
3
4
C•104/mol L–1
4.86
5a
4.84
1
2
3
4
C•104/mol L–1
ε
4.86
4.84
4.82
3c
According to available data (see Fig. 2), the effective
ε value for calixarene solutions increases with an increase
in their concentration and after the dependence reached a
plateau. In the framework of the formed methodology,13
the concentration of the compound corresponding to the
beginning of saturation of the concentration dependence
1
2
3
4
C•104/mol L–1
Fig. 2. Dependences of the dielectric constant (ε) of solutions of
calix[4]resorcinols 3c, 5a,c, 6, and 7 in chloroform on their
concentration at 25 °C.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
Kasymova et al.
R/nm
shown that the reaction route and ability to selfꢀorganizaꢀ
tion depend on the nature of the alkyl substituent at the
lower rim of tetraalkylcalix[4]resorcinols.
60
Experimental
50
40
30
20
1H and 13C NMR spectra were recorded in DMSOꢀd6 on a
Bruker MSLꢀ400 instrument (400.13 and 100.62 MHz, respecꢀ
tively). The δ values were calculated relative to signals of the
solvent. Mass spectra were obtained on a MALDI 2 V5.2.0
instrument (1,8,9ꢀtrihydroxyanthracene as a matrix).
The dielectric constants of a series of solutions were deterꢀ
mined on a setup consisting of an E12ꢀ1 instrument operating in
the beating mode and a measuring cell being a temperatureꢀ
controlled condenser. Light scattering was studied on a PhotoCor
Complex photon correlation light scattering spectrometer.
A He—Ne gas laser served as the laser radiation source (power
10 mW, wavelength 633 nm). The experimental details were
described elsewhere.16
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,11,17,23ꢀtetrakisꢀ
[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl]ꢀ2,8,14,20ꢀtetraethylpentaꢀ
cyclo[19.3.1.13,7.19,13.115,19]octacosaꢀ1(25),3,5,7(28),9,11,
13(27),15,17,19(26),21,23ꢀdodecaene (3a). Formic acid (55 mL)
was added with stirring to a mixture of calix[4]resorcinol 2a
(2.0 g, 3.3 mmol), 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl acetate
(1) (3.70 g, 13.3 mmol), and acetone (45 mL). The reaction
mixture was stored for 24 h at 20 °C, water (100 mL) was added,
the pH value of the solution was brought to 5—6 by the addition
of sodium bicarbonate, and the precipitate formed was filtered
off. According to the 1H NMR spectral data, the precipitate was
calixarene 3a with an admixture of tribenzylated resorcinol 4,
Rf 0.38 (4) and 0.20 (3a) (acetone—pentane (7 : 3) mixture).
Product 3a was isolated by chromatography on silica gel
(pentane—acetone (7 : 3) mixture). The yield was 1.53 g (33%),
0
0.005 0.010 0.015
C/mol L–1
Fig. 3. Concentration dependence of the effective hydrodynamic
radius (R) of aggregates 5c.
measured the average hydrodynamic radius for solutions
of benzylated calixarenes 3c, 5a,c, 6, and 7 in chloroꢀ
form. Aggregates only for compound 5c (Fig. 3, radius
13 nm) were found in the critical concentration range
(C > 0.0001 mol L–1) by dynamic light scattering. No
aggregation was observed for other calixarenes studied in
a wide concentration range. The aggregate size increases
up to ~60 nm with an increase in the concentration of
calixarene 5c (see Fig. 3). Thus, the aggregation ability
of dibenzylated amphiphilic calixarene 5c differs from
that of other compounds studied. Probably, the decisive
role belongs to the structural factor, because the aggregaꢀ
tion behavior is optimized along the length of the hydroꢀ
phobic groups at the lower rim together with the presence
of two benzyl fragments in the series of compounds 5a—c.
The results obtained make a new contribution to the
study of selfꢀorganization of amphiphilic compounds
based on the calixarene matrix in nonpolar media.
Although the mechanism of selfꢀorganization of the comꢀ
pounds under study remains unclear, a considerable role
of the geometric factor along with the energy component
in the formation of organized structures can be assumed
with sufficient reliability. Taking into account the
2D ROESY spectral data (see Fig. 1), we can suggest that
the soꢀcalled supramolecular polymers, i.e., nanochains
composed of several calixarene fragments, are formed
in the studied systems.
1
3
m.p. 200 °C. H NMR, δ: 0.93 (t, 12 H, Me, JH,H = 6.97 Hz);
1.38 (s, 72 H, CMe3); 2.18 (m, 8 H, CH2); 3.93 (s, 8 H, CH2);
4.23 (t, 4 H, CH, 3JH,H = 7.0 Hz); 5.09 (s, 4 H, OH); 6.53 (s, 8
H, OH); 6.99 (s, 8 H, Ha); 7.34 (s, 4 H, Hb). 13C NMR, δ: 12.07
1
1
(q, Me, JC,H = 125.0 Hz); 27.19 (t, CH2, JC,H = 125.0 Hz);
1
1
28.4 (d, C(10), JC,H = 130.0 Hz); 29.65 (t, C(5), JC,H = 90.0
Hz); 30.9 (s, CMe3); 33.07 (q, CMe3, 1JC,H = 120.0 Hz); 113.66
1
(s, C(8)); 121.4 (d, C(9), JC,H = 150.0 Hz); 124.14 (d, C(3),
1JC,H = 150.0 Hz); 124.26 (s, C(6)); 128.46 (s, C(4)); 136.23 (s,
C(2)); 149.22 (s, C(7)); 152.2 (s, C(1)). IR (KBr), ν/cm–1
:
3440, 3640 (OH). Found (%): C, 78.59; H, 8.50. C96H128O12.
Calculated (%): C, 78.26; H, 8.70.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,11,17,23ꢀtetrakisꢀ
[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl]ꢀ2,8,14,20ꢀtetrapropylpentaꢀ
cyclo[19.3.1.13,7.19,13.115,19]octacosaꢀ1(25),3,5,7(28),9,11,
13(27),15,17,19(26),21,23ꢀdodecaene (3b) was synthesized
similarly to compound 3a from calixarene 2b (2.00 g, 3.1 mmol)
and benzylic acetate 1 (3.39 g, 12.4 mmol). After chromatography
on silica gel (pentane—acetone (7 : 3) mixture), the yield
of product 3b was 1.32 g (28%), Rf 0.18 (pentane—acetone
1
(7 : 3) mixture), m.p. 205 °C. H NMR, δ: 0.90 (t, 12 H, Me,
3JH,H = 6.97 Hz); 1.39 (s, 72 H, CMe3); 1.68, 2.18 (both m, 8 H
each, CH2); 3.95 (s, 8 H, CH2); 4.33 (t, 4 H, CH, 3JH,H = 7.0 Hz);
5.09 (s, 4 H, OH); 6.53 (s, 8 H, OH); 6.99 (s, 8 H, Ha); 7.34
(s, 4 H, Hb). Found (%): C, 78.72; H, 8.70. C100H136O12.
Calculated (%): C, 78.95; H, 8.95.
In summary, the reactions of tetraalkylcalix[4]resorꢀ
cinols with 3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl acetate
were studied. The synthesized benzylated calix[4]resorcinols
are capable of selfꢀorganization in nonpolar media. It was

Benzylation of tetraalkylcalix[4]resorcinols
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
143
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,11,17,23ꢀtetrakisꢀ
[3,5ꢀdi(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl]ꢀ2,8,14,20ꢀtetrapentylpentaꢀ
cyclo[19.3.1.13,7.19,13.115,19]octacosaꢀ1(25),3,5,7(28),9,11,
13(27),15,17,19(26),21,23ꢀdodecaene (3c) was synthesized
similarly from calixarene 2c (2.00 g, 2.6 mmol) and benzylic
acetate 1 (2.89 g, 10.4 mmol). After chromatography on silica
gel (pentane—acetone (7 : 3) mixture), the yield of product 3c
was 1.28 g (30%), Rf 0.22 (pentane—acetone (7 : 3) mixture),
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,17ꢀbis[3,5ꢀdiꢀ
(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl]ꢀ2,8,14,20ꢀtetranonylpentacycloꢀ
[19.3.1.13,7.19,13.115,19]octacosaꢀ1(25),3,5,7(28),9,11,13(27),
15,17,19(26),21,23ꢀdodecaene (5c) was synhesized similarly
from calixarene 2f (1.00 g, 1.0 mmol) and benzylic acetate 1
(1.12 g, 4.0 mmol). After chromatography on silica gel (pentane—
acetone (7 : 3) mixture), compound 5c was obtained in a yield of
0.6 g (41%), Rf 0.2 (pentane—acetone (7 : 3) mixture), m.p. 215 °C.
1H NMR, δ: 0.89 (t, 12 H, Me, 3JH,H = 7.0 Hz); 1.29 (m, 48 H,
(CH2)6Me); 1.43 (s, 36 H, CMe3); 1.89 (m, 8 H, CH2Me); 2.17
(m, 8 H, CH2CH); 3.93 (s, 8 H, CH2); 4.28 (t, 4 H, CHCH2,
3JH,H = 7.0 Hz); 5.28 (s, 2 H, OH); 6.09 (s, 8 H, OH); 6.57 (s,
2 H, Hd); 6.64 (s, 4 H, Ha); 6.96 (s, 2 H, Hb); 7.22 (s, 2 H, Hs).
1
m.p. 190 °C. H NMR, δ: 0.89 (t, 12 H, Me, 3JH,H = 6.97 Hz);
1.37 (s, 72 H, CMe3); 1.57 (m, 24 H, CH2); 2.20 (m, 8 H,
CH2CH); 3.91 (s, 8 H, CH2); 4.51 (t, 4 H, CH, 3JH,H = 7.0 Hz);
5.09 (s, 4 H, OH); 6.28 (s, 8 H, OH); 6.97 (s, 8 H, Ha); 7.25
1
(s, 4 H, Hb). 13C NMR, δ: 13.09 (q, Me, JC,H = 150.0 Hz);
1
1
21.51 (m, (CH2)3); 26.60 (t, CH2CH, JC,H = 125.0 Hz); 28.39
13C NMR, δ: 14.07 (q, C(19), JC,H = 125.0 Hz); 22.67 (m,
1
1
1
(d, C(10), JC,H = 130.0 Hz); 29.63 (t, C(5), JC,H = 90.0 Hz);
(CH2)6); 29.38 (t, CH2CH, JC,H = 90.0 Hz); 30.27 (d, C(10),
1
1
31.83 (q, CMe3, JC,H = 120.0 Hz); 33.52 (s, CMe3); 111.65
(s, C(8)); 119.52 (d, C(9), JC,H = 150.0 Hz); 121.71 (d, C(3),
1JC,H = 130.0 Hz); 31.94 (t, C(5), JC,H = 90.0 Hz); 34.34 (q,
1
1
CMe3, JC,H = 120.0 Hz); 35.58 (s, CMe3); 116.0 (s, C(8),
1JC,H = 150.0 Hz); 126.47 (s, C(6)); 128.9 (s, C(4)); 134.22 (s,
C(2)); 147.15 (s, C(7)); 150.29 (s, c(1)). Found (%): C, 79.32;
H, 9.50. C108H152O12. Calculated (%): C, 79.02; H, 9.27.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,17ꢀbis[3,5ꢀdiꢀ
(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl]ꢀ2,8,14,20ꢀtetraheptylpentacycloꢀ
[19.3.1.13,7.19,13.115,19]octacosaꢀ1(25),3,5,7(28),9,11,13(27),
15,17,19(26),21,23ꢀdodecaene (5a). Formic acid (25 mL) was
added to a mixture of calixarene 2d (1.00 g, 1.1 mmol), acetate 1
(1.26 g, 4.5 mmol), and acetone (35 mL). The reaction mixture
was stored for 24 h at 20 °C, water (100 mL) was added, and the
pH of the solution was brought to 5—6 by the addition of sodium
bicarbonate. The precipitate formed was separated, washed with
water, and purified by chromatography on silica gel (pentane—
acetone (7 : 3) mixture), Rf 0.60 (benzene—acetone (9 : 1)
C(12)); 121.6 (m, C(9), C(11)); 124.81 (d, C(3), 1JC,H = 150.0 Hz);
125.36 (s, C(6)); 130.10 (s, C(4)); 136.24 (d, C(14),
1JC,H = 150.0 Hz); 136.49 (s, C(2)); 150.09 (s, C(7), C(13)); 158.11
(s, C(1)). MS, m/z: 1451 [M + Na]. Found (%): C, 78.50;
H, 9.70. C94H140O10. Calculated (%): C, 78.99; H, 9.80.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5ꢀ[3,5ꢀdi(tertꢀbutyl)ꢀ
4ꢀhydroxybenzyl]ꢀ2,8,14,20ꢀtetraundecylpentacycloꢀ
[19.3.1.13,7.19,13.115,19]octacosaꢀ1(25),3,5,7(28),9,11,13(27),
15,17,19(26), 21,23ꢀdodecaene (6). Formic acid (20 mL) was
added to a mixture of calixarene 2g (1.0 g, 0.9 mmol), benzylic
acetate 1 (1.01 g, 3.6 mmol), and acetone (30 mL). The reaction
mixture was stored for 24 h at 20 °C, water (100 mL) was added,
and the pH of the solution was brought to 5—6 by the addition of
sodium bicarbonate. The precipitate formed was separated,
washed with water, and purified on silica gel (pentane—acetone
(7 : 3) mixture). Compound 6 was obtained in a yield of 0.7 g
(58%), Rf 0.16 (pentane—acetone (7 : 3) mixture), m.p. 205 °C.
1H NMR, δ: 0.87 (m, 12 H, Me); 1.24 (m, 72 H, (CH2)9Me);
1.37 (s, 18 H, CMe3); 2.11 (m, 8 H, CH2CH); 3.91 (s, 2 H,
CH2); 4.35 (m, 4 H, CH); 5.31 (s, 1 H, OH); 6.49 (s, 3 H, Hd)
6.96 (s, 2 H, Ha); 6.99 (s, 1 H, Hb); 7.19 (s, 3 H, Hs); 7.8 (s, 8 H,
1
mixture). The yield was 1.4 g (57%), m.p. 196 °C. H NMR, δ:
0.88 (t, 12 H, Me, 3JH,H = 7.0 Hz); 1.28 (m, 32 H, (CH2)4CH2); 1.38
(m, 36 H, CMe3); 1.43 (m, 8 H, CH2Me); 2.16 (m, 8 H, CH2CH);
3.93 (s, 4 H, CH2); 4.28 (t, 4 H, CHCH2, 3JH,H = 7.0 Hz); 5.08
(s, 2 H, OH); 6.11 (s, 8 N, OH); 6.29 (s, 2 H, Hd); 6.51 (s, 4 H,
Ha); 6.96 (s, 2 H, Hb); 7.02 (s, 2 H, Hs). 13C NMR, δ: 14.05 (q,
1
Me, JC,H = 125.0 Hz); 22.67 (m, (CH2)5); 29.38 (t, CH2CH,
1
1
1JC,H = 90.0 Hz); 30.27 (d, C(10), JC,H = 130.0 Hz); 31.9 (t,
OH). 13C NMR, δ: 14.1 (q, Me, JC,H = 125.0 Hz); 22.68 (t,
1
1
C(5), JC,H = 90.0 Hz); 34.35 (q, CMe3, JC,H = 120.0 Hz);
(CH2)10); 29.34 (t, CH2CH, 1JC,H = 150.0 Hz); 29.71 (d, C(10),
1
35.57 (s, CMe3); 114.0 (s, C(8), C(12)); 121.6 (m, C(9), C(11));
1JC,H = 130.0 Hz); 31.93 (t, C(5), JC,H = 90.0 Hz); 35.56 (q,
1
1
124.81 (d, C(3), JC,H = 150.0 Hz); 125.36 (s, C(6)); 130.14
CMe3, JC,H = 120.0 Hz); 30.89 (s, CMe3); 124.0 (s, C(8),
(s, C(4)); 136.26 (d, C(14), 1JC,H = 150.0 Hz); 136.51 (s, C(2));
149.46 (s, C(7), C(13)); 158.0 (s, C(1)). MS, m/z: 1339 [M + Na].
Found (%): C, 78.52; H, 9.50. C86H124O10. Calculated (%):
C, 78.42; H, 9.42.
C(12)); 125.6 (m, C(9), C(11)); 126.7 (d, C(3), 1JC,H = 150.0 Hz);
1
130.11 (s, C(6)); 155.9 (s, C(4)); 157.93 (d, C(14), JC,H
=
= 150.0 Hz); 187.76 (s, C(2)); 189.16 (s, C(7), C(13)); 207.39
(s, C(1)). MS, m/z: 1345 [M + Na]. Found (%): C, 78.52;
H, 10.30. C87H134O9. Calculated (%): C, 78.97; H, 10.12.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,17ꢀbis[3,5ꢀdiꢀ
(tertꢀbutyl)ꢀ4ꢀhydroxybenzyl]ꢀ2,8,14,20ꢀtetraoctylpentacycloꢀ
[19.3.1.13,7.19,13.115,19]octacosaꢀ1(25),3,5,7(28),9,11,13(27),
15,17,19(26),21,23ꢀdodecaene (5b) was synthesized similarly to
compound 5a from calixarene 2a (1.00 g, 1.06 mmol) and
benzylic acetate 1 (1.18 g, 4.24 mmol). After chromatography
on silica gel (pentane—acetone (7 : 3) mixture), product 5b was
obtained in a yield of 0.8 g (54%), Rf 0.58 (benzene—acetone
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 05ꢀ03ꢀ32136).
References
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Recognition and Physiological Action, Cambridge, 1998.
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(9 : 1) mixture), m.p.. 202 °C. H NMR, δ: 0.89 (t, 12 H, Me,
3JH,H = 7.0 Hz); 1.28 (m, 40 H, (CH2)5Me); 1.39 (m, 36 H,
CMe3); 1.70 (m, 8 H, CH2Me); 2.17 (m, 8 H, CH2CH); 3.93
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Found (%): C, 78.52; H, 9.50. C90H132O10. Calculated (%):
C, 78.72; H, 9.62.

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Received December 12, 2006;
in revised form March 14, 2008