Synthesis and some properties of tetrakis-3,5-di-tert-butyl-4- hydroxybenzylated calix[4]resorcinols

Article abstract of DOI:10.1134/S1070363207030206

A method for the synthesis of new calix[4]resorcinols tetra-3,5-di-tert- butyl-4-hydroxybenzyl derivatives is developed. Their interaction with methyldichlorophosphonate, dimethyldichlorosilane in the presence of a base leads to formation of organophospho

Full text of DOI:10.1134/S1070363207030206

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 3, pp. 458 468.
Pleiades Publishing, Ltd., 2007.
Original Russian Text E.M. Kasymova, A.R.Burilov, N.A. Mukmeneva, S.V. Bukharov, G.N. Nugumanova, M.A. Pudovik, A.V. Chernova, R.R. Shagi-
dullin, A.I. Konovalov, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 3, pp. 494 504.
Synthesis and Some Properties
of Tetrakis-3,5-di-tert-butyl-4-hydroxybenzylated
Calix[4]resorcinols
E. M. Kasymovaa, A. R. Burilova, N. A. Mukmenevab, S. V. Bukharovb,
G. N. Nugumanovab, M. A. Pudovika, A. V. Chernovaa,
R. R. Shagidullina, and A. I. Konovalova
a Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, ul. Acad. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
Fax: (843 2) 75 2253
e-mail: pudovik@iopc.knc.ru
b Kazan State Technological University, Kazan, Tatarstan, Russia
Received November 16, 2006
Abstract A method for the synthesis of new calix[4]resorcinols tetra-3,5-di-tert-butyl-4-hydroxybenzyl
derivatives is developed. Their interaction with methyldichlorophosphonate, dimethyldichlorosilane in the
presence of a base leads to formation of organophosphorus-organosilicon cavitands. Acetylation of hydroxy-
benzylated calix[4]resorcinols with acetic anhydride leads to products of either incomplete or full acetylation
depending on experimental conditions.
DOI: 10.1134/S1070363207030206
One of perspective and intensively developing lines
of investigation in organic chemistry comprises re-
search in the field of calix[n]arens and in particular
calix [4]resorcinols [1 4]. It is caused by an ease of
their synthesis, opportunity of C- and O-functionalisa-
tion, ability to form complexes of host guest type
with organic compounds of various structure and
metal ions. Combination of properties mentioned
above makes use of this class compounds perspective
for creation of new type complexing agents, metal
ions extractants and new catalytic systems. One of the
peculiarities of calix[4]resorcinols is their tendency to
selfassociation leading to a formation of supramole-
cular ensembles. As a consequence, they are low
soluble in organic solvents, have diffuse melting
points and in some cases reduced reactivity. We have
assumed that introduction of bulky groups into calixa-
rene molecules should prevent their aggregation and
as a consequence would substantially improve solu-
bility in organic solvents and enhance their reactivity.
We choose a bulky 3,5-di-tert-butyl-4-hydroxybenzyl
fragment as a substituent which is of interest from one
more point of view. Investigation of antioxidant
properties of tetramethylcalix[4]resorcinol and some
of its derivatives has shown an opportunity of creation
a new group of highly effective inhibitors of polymers
thermal-oxidative degradation on the basis of calix-
arenes [5, 6]. In that aspect modification of tetraal-
kylcalix[4]resorcinols by introduction of sterically
hindered phenol fragments into their aromatic rings
could be a perspective method to increase their anti-
oxidizing activity.
In the present work we investigated an interaction
of calix[4]resorcinols Ia Id with 3,5-di-tert-butyl-4-
hydroxybenzylacetate (II), which application allows
to introduce under mild conditions sterically hindered
phenol fragments into the molecules of various
compounds [7].
Interaction of compound Ia with benzylacetate II
in acetone solution in the presence of chloric acid
leads to formation of two products: 2,4,6-tris(3,5-di-
tert-buty-4-hydroxybenzyl)resorcinol (III) and
4,6,10,12,16,18,22,24-octahydroxy-5,11,17,19-tetra-
kis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]octa-
cosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-
dodecaen (IVa) in a ratio of 70:30%. The major
product, substituted resorcinol III, is isolated and
characterized by spectral methods and also by com-
parison of its constants with published data [8].
Change the ratio of reagents Ia and II to 1:12 has
led to increase of a product III yield up to 95%. Thus,
we found a new direction of calixarene reaction with
458

SYNTHESIS AND SOME PROPERTIES OF TETRAKIS-3,5-DI-tert-BUTYL-4-HYDROXYBENZYLATED 459
OH
1
Bu-t
HO 2
3
Ha
4
H25C
6
OH
HO
HO
OH
HO
7
8
OH
R1
HO
HO
HO
R1
HO
OH
OH
OH
R1
9
R
R
R
R
R
R
t-Bu
HO
R1
OH
R1
Bu-t
nHCOOH
+
4
+
Hb
R
4MeCOOH
R
OH
H2C
O
HO
OH
OH
H3C
O
R1
IVa IVd
Ia Id
II
III
I, IV, R = Me (a), Et (b), Pr (c), C5H11 (d),
Bu-t
R1 =
CH2
OH .
Bu-t
electrophilic reagents, leading to a full destruction of
a macro cyclic matrix and formation of tris-benzylated
resorcinol.
tetra-benzylated calixarene IVa synthesis we used
formic acid instead of chloric acid as the acidic
catalyst. This replacement influenced essentially the
synthetic result of reaction: the calixarene IVa yield
increased from 30 up to 80%.
With the purpose of optimization the method of
OH
OH
t-Bu
Bu-t
t-Bu
HCOO
Bu-t
HCOOH
II
CH3COOH +
CH2+
O
H
O
A
V
As we suggest, this influence of formic acid is
connected with the course of starting compound II
transacylation reaction and formation of benzylfor-
mate V [9]. As formate group seems to be better
leaving group than the acetate one, benzylformate V
is the best benzylating agent in comparison with
benzylacetate. Analysis of homonuclear correlation
1H NMR spectra showed that C-benzylated calix[4]-
resorcinol IVa has a cone conformation (see figure).
This conclusion follows from the fact that compound
IVa methine proton quartet is located in the field of
4.5 ppm, same as calixarene Ia methine proton quar-
tet, having according to X-ray structural analysis a
cone conformation [10]. According to published
data, a change of a cone conformation by 1,3-
alternant in phenol calixarenes leads to displacement
of methine protons signal by 1 ppm [11]. In the 2D
ROESY spectrum of compound IVa in chloroform
(see figure) only trivial cross-peaks Ha t-Bu,
OH t-Bu are present, that confirm realization of a
cone conformation.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

460
KASYMOVA et al.
ppm
CH3
C
CH3
C
OH
CH3
CH3
CH3
CH3
2.0
4.0
6.0
Ha
Ha
H2C
OH
C
HO
H
Hb
CH3
4
8.0
ppm
7.00 6.00 5.00 4.00 3.00 2.00 1.00
2D ROESY spectrum of compound IVa.
1
Analysis of hydroxyl groups stretching vibrations
region in calixresorcinol IVa IR spectra allows to
make certain conclusions concerning character of
hydrogen bonds with participation of OH groups and
hence on the supramolecular structure of this com-
pound. In the spectrum of compound IVa crystal
sample the hydroxyl groups stretching vibrations are
displayed in the form of two major absorption bands,
3595 cm in the solution spectrum corresponds to
absorption of hydroxyl groups of this fragment con-
nected from behind by OH O H (so-called pseudo-
free hydroxyls [14]) which can form with involvement
of their protons the additional intramolecular hydro-
gen bonds with -electrons located near benzyl rings
[14]. Growth of free
bonds intensity, as well as
noted above change in OthHe band contours observed in
the spectra of compound IVa under crystal-solution
transition, confirm the fact that a part of di-tert-butyl-
phenol hydroxyls in a solid phase participates in
intermolecular hydrogen bonds breaking off under the
substance dilution.
1
narrow with a maximum at 3642 cm , having a
1
shoulder at 3615 cm , and wide asymmetrical at
1
3435 cm with a number of shoulders. In the spectra
of calixarene IVa solutions in CCl4 position of main
OH. bands maxima practically does not change. At
the same time, passing on from the crystal sample
4
spectrum to the spectra of solutions (© 10 ) an ob-
For specification of possible number and position
of bands components at 3640 and 3430 cm a de-
composition of these bands contours in a version of
Local Least Squares algorithm and Lorentz Gauss
bands configuration is carried out. In the spectrum of
the solid sample the results of decomposition are the
following: in the free
component at 3619 cm alongside with major peak
at 3641 cm . Band
into five components with approximate maxima at
3546, 3494, 3438, 3330, and 3145 cm . After dec-
omposition of a solution spectrum alongside with
singlet at 3644 cm
nents at 3597, 3551, 3524, 3492, 3461, 3429, 3386,
1
vious change of the peak intensity ratio of the bands
1
at 3640 and 3430 cm is observed in favor of a high-
frequency component. The peak intensity ratio D3640
/
D3430 increases from 0.7 for crystals up to 1.02 for
solutions. Simultaneously the contours of both bands
become a little simpler: the high-frequency band
region there is a second
OH
1
1
shoulder at 3615 cm disappears and a weak maxi-
1
1
1
mum at 3597 cm appears, and the absorption of the
bound 3435 cm is resolved
OH
1
lowfrequency band shoulder at 3495 cm decreases.
1
Further dilution of the solution down to the concentra-
5
tion of 3 10 M leaves unchanged the spectral pat-
1
tern in the region of OH. Mentioned above allows to
(
free) there are 8 compo-
OH
1
assign the band at 3640 cm to vibrations of 2,6-di-
1
tert- butylphenol fragment free hydroxyl group as it
and 3280 cm in the field of
(bound).
OH
is observed in the region typical of the sterically
hindered phenols [12]. Absorption at 3430 cm
should be attributed to calix[4]resorcinol backbone
resorcinol hydroxyls connected by intramolecular
hydrogen bonds OH OH [13]. The weak peak at
1
In the spectra of compounds IVa diluted solutions
in CCl4 (down to 3 10 5 M) the absence of resorcinol
backbone free OH groups bands, which by analogy to
resorcinol and data [15] for calixarenes are expected
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

SYNTHESIS AND SOME PROPERTIES OF TETRAKIS-3,5-DI-tert-BUTYL-4-HYDROXYBENZYLATED 461
1
to be located in the region of 3616 3620 cm , indi-
cates the retaining in molecules IVa, both in a crystal
and solutions, of the above-described intramolecular
hydrogen bonds on the upper rim of calix[4]resorcinol
rings, i.e. a primary cone conformation. It is ob-
vious that in case of alternant forms along with the
bound OH groups the above-mentioned free hydroxyls
bands should be observed. Retaining the complex
structured character of the band at 3430 cm also in
solutions confirms the cone asymmetry and hetero-
geneity that can be a consequence of the presence of
bulky tert-butyl substituents in the molecule.
1
Bu-t
O
t-Bu
H
O
t-Bu
OH
O
H
H
O
OH
Bu-t
Me
Me
Me
Me
O
HO
t-Bu
HO
H
H
O
O
Bu-t
H
t-Bu
Bu-t
OH
As it was already mentioned above, the formation
of benzylated resorcinol III appeared to be unexpected
for us as there were no publications on the oppor-
tunity of calixarene ring cleavage under the action of
electrophilic reagents. By special experiments it has
been found out that in double system: calixarene I
chloric or formic acid the splitting of macrocycle does
not occur. It could be assumed, that formation of
compound III is a result of calixarenes I and/or IV
complete benzylation by benzyl carbocation (A),
generated in the reaction conditions. Actually, when
acetone solution of compounds IVa and II in the ratio
of 1:8 was standing during 24 hours in the presence
Developed on an example of tetramethyl derivative
Ia the method of calixarene matrix benzylation have
been extended also to other calixarenes. Interaction of
tetraethyl(propyl-, pentyl-) calix[4]resorcinols Ib Id
with benzylacetate II in the presence of formic acid
leads to formation of tetrabenzylated calix[4]resor-
cinols IVb IVd with high yields and to small
amounts of tris-benzylated resorcinol III. As expected,
compounds IVa IVd are well soluble in nonpolar
organic solvents and have narrow melting points, that
indirectly confirm the breaking of their aggregation.
The prepared tetrabenzylated calix[4]resorcinols
IVa IVd are studied in phosphorilation, silylation and
acetylation reactions. Recently the researchers have
paid a great attention to calixarenes phosphorilated
derivatives, which are of interest as complexing
agents, extractants of metal ions, basic compounds
for synthesis of new types of spatially organized
structures: carceplex, tubes, etc. [16]. With the
purpose of preparation of phosphorous containing
cavitands we studied phosphorylation of calixarenes
IVa IVd by methyldichlorophosphonate in the pres-
ence of a base. As a result the compounds Va Vd
were obtained and their structure were confirmed by
1
of chloric or formic acid in H NMR spectrum of the
reaction mixture the signals of calixarene IVa 1.74 d
3
3
(12H, Me, JHH 7.0 Hz), 4.60 q (4H, CH, JHH
7.0 Hz), 6.34 s (8H, OH) practically disappeared, and
the signals of nonequivalent methylene and hydroxyl
(in the benzyl fragment) groups of compound III:
3.80 s (4H, CH2), 3.92 s (2H, CH2), 4.85 s (2H, OH),
5.09 s (1H, OH) were observed. Thus, it is possible to
conclude, that formation of the product III in reaction
of calixarene I with benzylacetate II probably occurs
as a result of compound IVa calixarene ring splitting
under the action of benzyl carbocation (A) and the
acid catalyst.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

462
KASYMOVA et al.
1
the data of IR, H, 31P NMR spectroscopy, mass spec-
trometry and elemental analysis. It should be noted
that obtained spectral and analytical data indicate the
presence of hydrochloride triethylamine admixture in
the synthesized compounds, probably as a part of
molecular complex which is not possible to avoid.
OH
Bu-t
Bu-t
Ha
O
O
H2C
O
PMe
O
MeP
O
O
R
R
8Et3N
R1
R1
IVa IVd + 4MeP(O)Cl2
Hb
8Et3N HCl
R
R
O
O
O
PMe
MeP
O
O
R1
O
Va Vd
Bu-t
OH
Bu-t
R1 =
.
IV, V, R = Me (a), Et (b), Pr (c), C5H11 (d),
CH2
According to published data, phenols silylation can
be carried out with use of some halogen- or nitrogen
containing organosilicon compounds [17]. It was
found, that at interaction of calixarenes IVa IVd with
dimethylchlorosilane in toluene in the presence of tri-
ethylamine (24 h, 100 C) organosilicon cavitands
VIa VId were formed, which structure
1
was proven by IR the H, 13C NMR spectroscopy and
mass spectrometry data.
OH
Bu-t
t-Bu
Ha
Me
Me
H2C
O
Si Me
Me Si
O
O
O
R1
O
R
R
4Me2SiCl2,8Et3N
R1
O
IVa IVd + 4MeP(O)Cl2
Hb
100 C, 24 h
R
R
O
Si Me
Me
O
Me Si
Me
R1
VIa VId
Bu-t
OH
VI, R = Me (a), Et (b), Pr (c), C5H11 (d), R1 =
.
CH2
Bu-t
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

SYNTHESIS AND SOME PROPERTIES OF TETRAKIS-3,5-DI-tert-BUTYL-4-HYDROXYBENZYLATED 463
OH
Bu-t
t-Bu
Ha
H2C
OSiMe3
Me3SiO
OSiMe3
Me3SiO
R
R
R
(Me3Si)2,NH
R1
VIa, VIb, VId
Hb
R1
R
OSiMe3
Me3SiO
Me3SiO
OSiMe3
R1
VIIa, VIIb, VIId
VII, R = Me (a), Et (b), Pr (c), C5H11 (d),
Bu-t
R1 =
CH2
OH .
Bu-t
As a result of resorcinols IVa, IVb, and IVd
silylation by hexamethyldisilazane the octasilylderi-
vatives VIIa, VIIb, and VIId were prepared.
these conditions, acylation of calixarene matrix
hydroxyl groups occurs with the formation of com-
pounds VIIIa VIIId. In their IR spectra there is an
1
absorption band in the region of 3640 cm character-
Interaction of calix[4]resorcinols IVa IVd with
acetic anhydride in the presence of pyridine catalytic
quantity was carried out at double excess of the
acylating agent at long heating (24 h, 70 C). Under
istic of the benzyl fragment hydroxyl group in the
molecules of compounds IVa IVd, and also a band
1
of stretching vibrations at 1780 cm , characteristic of
carbonyl group.
IVa IVd
8Ac2O
48 h, 70 C
12Ac2O
48 h, 100 C
R1
R2
OAc
AcO
OAc
AcO
R
OAc
R2
OAc
AcO
OAc
R1
AcO
R2
R
R
R
R
R
R1
Hb
Hb
R
R
AcO
OAc
AcO
AcO
OAc
AcO
OAc
R1
R2
IXa, IXb, IXd
VIIIa VIIId
Bu-t
Bu-t
OAc
Bu-t
R1 =
.
VIIIa VIIId, IXa IXd, R + Me (a), Et (b), Pr (c), C5H11 (d),
CH2
OH , R2 =
CH2
Bu-t
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

464
KASYMOVA et al.
It was possible to carry out complete acylation of
(pentane acetone, 7:3). Yield 2.6 g (33%) of com-
calixarenes IVa, IVb, and IVd in acetic anhydride as
pound IVa, mp 230 C (decomp.). IR spectrum (¤Br),
1
a solvent at long heating of the reaction mixture (48 h,
, cm : 3440, 3640 (OH). 1H NMR spectrum
1
100 C). In the H NMR spectrum of compound IXa a
(CDCl3), , ppm, (J, Hz): 1.39 s (72H, CMe3), 1.77 d
3
singlet peak is observed in the field of 2.15 ppm
corresponding to acyl groups methyl protons whereas
singlet signals of OH groups protons (at 5.07 and
6.84 ppm) are absent. In the IR a spectrum of com-
pound IXa there are no bands of stretching vibrations,
characteristic of hydroxyl groups. It should be noted
that in the ivestigated reactions tetrabenzylated calix-
arenes IVa IVd displayed rather low reactivity in
comparison with starting calixarenes Ia Id, that can
be caused by the presence of bulky 3,5-ditert-butyl-4-
hydrobenzyl groups in ortho-positions of calixarene
backbone.
(12H, Me, JHH 7.0), 3.89 s (8H, CH2), 4.60 q (4H,
3
CH, JHH 7.0), 5.08 s (4H, OH), 6.34 s (8H, OH),
7.0 s (8H, Ha), 7.33 s (4H, Hb). 13C NMR spectrum
1
(CDCl3), , ppm, (J, Hz): 20.5 q (C11, JCH 125.0),
28.3 d (C10, 1JCH 130.0), 29.4 t (C5, 1JCH 90.0), 30.2 q
1
(CMe3, JCH 120.0), 34.3 s (CMe3), 114.0 s (C8),
1
1
121.6 d (C9, JCH 150.0), 125.0 d (C3, JCH 150.0),
125.5 s (C6), 128.9 s (C4), 136.5 s (C2), 149.0 s (C7),
152.6 s (C1). Found, %: C 77.69; H 8.65. C92H120O12.
Calculated, %: C 77.97; H 8.47.
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetraethylpentacyclo[19.3.1.13,7.19,13.115,19]octa-
cosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-
dodecaen (IVb) was prepared similarly to the pre-
vious one from 2.0 g of calixarene Ib, 4.2 g of ben-
zylacetate II, 45 ml of acetone, 55 ml of formic acid.
EXPERIMENTAL
1
The H, 13C, and 31P NMR spectra were measured
on Bruker MSL-400 spectrometer at 400.13, 100.62,
and 166.93 MHz, respectively, relative to residual
protons of deuterated solvent (D-acetone, CDCl3) and
external reference 85% H3PO4. The mass spectra were
obtained on MALDI-2 V-5.2.0 spectrometer (1,8,9-
trihydroxyanthracene matrix).
1
Yield of IVb 1.5 g (31%), mp 200 C. H NMR spec-
trum (CDCl3), , ppm (J, Hz): 0.93 d (12H, Me, 3JHH
6.97), 1.38 s (72H, CMe3), 2.18 m (8H, CH2), 3.93 s
3
(8H, CH2), 4.23 t (4H, CH, JHH 7.0), 5.09 s (4H,
OH), 6.53 s (8H, OH), 6.99 s (8H, Ha), 7.34 s (4H,
2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-
resorcinol (III). 0.08 ml of 72% chloric acid was
added to a solution of 1.0g of calixarene Ia and 4.1 g
of benzylacetate II in 20 ml of acetone. The reaction
mixture was kept for 24 hours at 20 C and then
poured into water. The precipitate formed was filtered
off, washed with water to pH 7 and dried for 48 h at
Hb). 13C NMR spectrum (CDCl3), , ppm (J, Hz):
1
12.07
q
(C12, JCH 125.0), 27.19
t
(C11,
1JCH 125.0), 28.4 d (C10, JCH 130.0), 29.65 t (C5,
1
1JCH 90.0), 33.07 q (CMe3, JCH 120.0), 30.9 s
1
(CMe3), 113.66 s (C8), 121.4 d (C9, JCH 150.0),
1
124.14 d (C3, JCH 150.0), 124.26 s (C6), 128.46 s
1
1
(C4), 136.23 s (C2), 149.22 s (C7), 152.2 s (C1).
Found, %: C 78.59; H 8.50. C96H128O12. Calculated,
%: C 78.26; H 8.70.
20 C. According to H NMR spectroscopy data the
reaction product obtained (3.4 g) was a mixture of
compounds III and IV in a ratio of 70:30%. After
recristallisation from hexane 1.2 g (35%) of com-
pound III was obtained, mp 153 154 C (151 154 C
[8]). Found, %: C 79.85; H 9.70. C51H72O5 Calculated,
%: C 80.10; H 9.42.
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetrapropylpentacyclo[19.3.1.13,7.19,13.115,19]-
octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,
23-dodecaen (IVc) was prepared similarly to the
previous one from 2.0 of calixarene Ic, 3.81 g of
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]-
octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),
21,23-dodecaen (IVa). A mixture 3.0 g calixarene Ia,
6.9 g benzylacetate II, 55 ml acetone and 65 ml of
formic acid was kept for 24 h at 20 C, poured into
100 ml of water, and a solution of sodium bicarbonate
was added to povide pH 5 6. The precipitate formed
was filtered off, washed with water and dried in air.
We obtained 7.75 g of powder, which according to 1H
NMR spectroscopy data was a mixture of compounds
III and IVa. The main reaction product IVa was
isolated by column chromatography on silica gel
1
benzylacetate II. Yield 1.3 g (31%), mp 205 C. H
NMR spectrum (CDCl3), , ppm (J, Hz): 0.90 t (12H,
3
Me, JHH 6.97), 1.39 s (72H, CMe3), 1.68 m (8H,
CH2), 2.18 m (8H, CH2), 3.95 s (8H, CH2), 4.33 t
3
(4H, CH, JHH 7.0), 5.09 s (4H, OH), 6.53 s (8H,
OH), 6.99 s (8H, Ha), 7.34 s (4H, Hb). Found, %: C
78.72; H 8.70. C100H136O12. Calculated, %: C 78.95;
H 8.95.
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetrapenthylpentacyclo[19.3.1.13,7.19,13.115,19]-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

SYNTHESIS AND SOME PROPERTIES OF TETRAKIS-3,5-DI-tert-BUTYL-4-HYDROXYBENZYLATED 465
octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,
23-dodecaen (IVd) was prepared similarly to the
previous one from 2.0 of calixarene Id and 3.25 g of
Ha, 4H, Hb). 31P NMR spectrum, P, ppm: 22.62,
18.40. Found, %: C 70.56; H 7.99; P 6.94. C100H132
O16P4. Calculated, %: C 70.07; H 7.76; P 7.23.
1
benzylacetate II. Yield 1.28 g (30%), mp 190 C. H
33,34,35,36-Tetrakis(3,5-di-tert-butyl-4-hydroxy-
benzyl)-3,11,19,27-tetramethyl-2,4,10,12,18,20,26,
28-octaoxy-3,11,19,27-tetraphospha-37,38,39,40-
NMR spectrum (CDCl3), , ppm, (J, Hz): 0.89 t (12H,
3
Me, JHH 6.97), 1.37 s (72H, CMe3), 1.57 m (24H,
CH2), 2.20 m (8H, CH2CH), 3.91 s (8H, CH2), 4.51 t
tetrapropylnonacyclo[29,3,1,121,25,113,17,15,9]-
3
(4H, CH, J 7.0), 5.09 s (4H, OH), 6.28 s (8H, OH),
tetracosa-[16,32,124,30,116,22,18,14]1(32),5,7,9(36),
13,15,17(35),21,23,25(34),30,29(33)-dodecaen (Vc)
was prepared similarly to the previous one from 1.0 g
of calixarene IVc, 0.5 g of triethylamine and 0.4 g of
methyldichlorophpsphonate. Yield 0.5 g (58%), mp
6.97 s (8H, Ha), 7.25 s (4H, Hb). 13C NMR spectrum
1
(CDCl3), , ppm (J, Hz): 13.09 q (C15, JCH 150.0),
21.73 t (C12 14, 1JCH 125.0), 25.49 q (C11, 1JCH 125.0),
1
1
27.47 d (C10, JCH 130.0), 29.7 t (C5, JCH 90.0),
1
31.83 q (CMe3), JCH 120.0), 33.39 s (CMe3),
1
150 C. H NMR spectrum (CDCl3), , ppm. (J, Hz):
111.65 s (C8), 119.52 d (C9, 1JCH 150.0), 122.36 d (C3,
0.88 t (12H, Me, 3J 6.9), 1.34 m (72H, CMe3), 1.60 m
1JCH 150.0), 126.5 s (C6), 128.9 s (C4), 134.22 s (C2),
147.15 s (C7), 150.29 s (C1). Found, %: C 79.32;
H 9.50. C108H152O12. Calculated, %: C 79.02; H 9.27.
(8H, CH2), 1.80 m (12H, MeP), 2.20 m (8H, CH2),
3
3.82 s (8H, CH2Ph), 4.42 t (4H, CH, J 6.9), 5.92 s
(4H, OH), 6.08 m (8H, Ha, 4H, Hb). 31P NMR spec-
trum, P, ppm: 22.64, 18.43. Found, %: C 70.34; H
8.10; P 6.81. C104H140O12P4. Calculated, %: C 70.57;
H 7.97; P 7.00.
33,34,35,36-Tetrakis(3,5-di-tert-butyl-4-hyd-
roxybenzyl)-3,11,19,27-tetramethyl-2,4,10,12,18,20,
26,28-octaoxy-3,11,19,27-tetraphospha-37,38,39,40-
tetramethylnonacyclo[29,3,1,121,25,113,17,15,9]-
tetracosa[16,32,124,30,116,22,18,14]1(32),5,7,
9(36),13,15,17(35),21,23,25(34),30,29(33)-dodecaen
(Va). 0.06 g of methyldichlorophpsphonate was added
to a mixture of 0.2 g of calixarene IVa, 10 ml of
anhydrous acetonitrile, 0.1 g triethylamine. The reac-
tion mixture was kept for 32 h at 80 C, triethylamine
hydrochloride was separated, the solvent was removed
and the residue was reprecipitated to hexane from
chloroform and dried in vacuum (5 h, 20 C, 04 mm
33,34,35,36- Tetrakis(3,5- di-tert-butyl-4-hyd-
roxybenzyl)-3,11,19,27-tetramethyl-2,4,10,12,18,
20,26,28-octaoxy-3,11,19,27-tetraphospha-37,38,39,
40-tetrapenthylnonacyclo[29,3,1,121,25,113,17,15,9]-
tetracosa[16,32,124,30,116,22,18,14]1(32),5,7,9(36),13,
15,17(35),21,23,25(34),30,29(33)-dodecaen (Vd) was
prepared similarly to the previous one from 1.0 of
calixarene IVd, 0.5 g of triethylamine, 0.5 g of
methyldichlorophpsphonate. Yield 0.57 ' (52%), mp
1
147 150 C. H NMR spectrum (CDCl3), , ppm (J,
1
Hz): 0.88 m (12H, Me), 1.36 m (72H, CMe3), 1.63 m
(24H, CH2), 1.81 m (12H, MeP ), 2.21 m (8H, CH2),
Hg). Yield 0.1 g (43%), mp 145 147 C. H NMR
spectrum (acetone-d6), , ppm, (J, Hz): 0.88 br.m.
(12H, Me), 1.38 s (72H, CMe3), 1.80 m (12H, MeP),
3.93 s (8H, CH2Ph), 4.55 q (4H, CH, 3JHH 6.9), 6.45 s
(4H, OH), 6.98 7.21 m (8H, Ha, 4H, Hb). 31P NMR
spectrum, P, ppm: 22.63, 18.48. Found, %: C 70.03;
H 8.11; P 7.19. C96H124O16P4. Calculated, %:, C
69.55; H 7.54; P 7.47. m/z 1679 (M + Na), 1793 (M +
Et3N HCl).
3
3.93 s (8H, CH2Ph), 4.52 t (4H, CH, J 6.9), 5.95 s
(4H, OH), 6.08 m (8H, Ha, 4H, Hb). 31P NMR spec-
trum, P, ppm: 23.30, 18.90. Found, %: C 72.04; H
9.09; P 6.25. C112H156O16P4. Calculated, %: C 71.46;
H 8.35; P 6.58. m/z 1903 (M + Na), 1919 (M + K),
2017 (M + Et3N HCl).
33,34,35,36-Tetrakis(3,5-di-tert-butyl-4-hydroxy-
benzyl)-3,11,19,27-octamethyl-2,4,10,12,18,20,26,28-
octaoxy-3,11,19,27-tetrasila-37,38,39,40-tetramethyl-
33,34,35,36-Tetrakis(3,5-di-tert-butyl-4-hydroxy-
benzyl)-3,11,19,27-tetramethyl-2,4,10,12,18,20,26,
28-octaoxy-3,11,19,27-tetraphospha-37,38,39,40-
nonacyclo[29,3,1,121,25,113,17,15,9]tetracosa[16,32
,
124,30,116,22,18,14]1(32),5,7,9(36),13,15,17(35),21,23,
25(34),30,29(33)-dodecaen (VIa). 0.16 g of triethyl-
amine were added dropwise to 0.2 g of calixarene Ia
in 10 ml toluene at a constant stirring under argon.
0.14 g of dimethylchlorosylane were added to a reac-
tion mixture, then it was kept for 24 h at 100 C, tri-
ethylamine hydrochloride precipitate was filtered off.
The solvent was removed and reaction product was
recrystallized with hexane from chloroform and dried
in vacuum of oil pump (2 h, 60 C, 0.01 mm Hg.).
tetraethylnonacyclo[29,3,1,121,25,113,17,15,9]-
tetracosa-[16,32,124,30,116,22,18,14]1(32),5,7,9(36),
13,15,17(35),21,23,25(34),30,29(33)-dodecaen (Vb)
was prepared similarly to the previous one from 1.0 of
calixarene IVb, 0.5 g of triethylamine and 0.4 g of
methyldichlorophpsphonate. Yield 0.6 g (52%), mp
1
143 C. H NMR spectrum (acetone-d6), , ppm (J,
Hz): 0.89 m (12H, Me), 1.38 m (72H, CMe3), 1.83 m
(12H, MeP), 2.17 m (8H, CH2), 3.85 s (8H, CH2Ph),
3
1
4.56 t (4H, CH, J 6.9), 6.50 s (4H, OH), 7.08 m (8H,
Yield 0.10 g (48%), mp 159 C. H NMR spectrum
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

466
KASYMOVA et al.
(CDCl3), , ppm (J, Hz): 0.08 m (24H, SiMe2),
IVd, 0.1 g of triethylamine and 0.08 g of dimethyl-
1
0.87 m (12H, Me), 1.41 m (72H, CMe3), 3.59 s (8H,
chlorosilane. Yield 0.13 g (52%), mp 170 C. H
3
CH2Ph), 4.50 q (4H, CH, JHH 6.9), 5.01 s (4H, OH),
NMR spectrum (CDCl3), , ppm, (J, Hz): 0.08 s (24H,
3
7.17 m (8H, Ha, 4H, Hb). Found, %: C 73.84; H 9.01;
Si 6.44. C100H136O12Si4. Calculated, %: C 73.13; H
8.35; Si 6.84. m/z 1663 (M + Na).
SiMe2), 0.85 t (12H, Me, JHH 6.90), 1.42 m (72H,
CMe3), 1.70 m (24H, (CH2)3), 2.18 m (8H, CH2CH),
3
3.57 s (8H, CH2Ph), 4.52 t (4H, CH, JHH 6.9), 5.01 s
(4H, OH), 7.15 7.23 m (8H, Ha, 4H, Hb). 13C NMR
33,34,35,36-Tetrakis(3,5-di-tert-butyl-4-hydroxy-
benzyl)-3,11,19,27-octamethyl-2,4,10,12,18,20,26,28-
octaoxy-3,11,19,27-tetrasila-37,38,39,40-tetraethyl-
spectrum (CDCl3), , ppm (J, Hz): 0.75 q (SiMe2,
1JCH 125.0), 11.56 q (C15,1JCH 140.0), 21.73 t (C12 14
,
1
1JCH 125.0), 25.49 q (C11, JCH 125.0), 27.47 d (C10,
nonacyclo[29,3,1,121,25,113,17,15,9]tetracosa[16,32
,
1
1JCH 130.0), 30.7 t (C5, JCH 90.0), 33.97 q (CMe3,
124,30,116,22,18,14]1(32),5,7,9(36),13,15,17(35),21,23,
25(34),30,29(33)-dodecaen (VIb) was prepared si-
milarly to the previous one from 0.5 of calixarene
IVb, 0.27 g of triethylamine and 0.18 g of dimethyl-
chlorosilane. Yield 0.32 g (53%), mp 157 C. 1H NMR
spectrum (CDCl3), , ppm. (J, Hz): 0.08 s (24H,
SiMe2), 0.85 m (12H, Me), 1.38 m (72H, CMe3),
2.17 m (8H, CH2CH) 3.59 s (8H, CH2Ph), 4.47 t (4H,
1JCH 120.0), 35.4 s (CMe3), 115.65 s (C8), 125.52 d
1
1
(C9, JCH 150.0), 128.36 d (C3, JCH 150.0), 130.5 s
(C6), 135.9 s (C4), 144.22 s (C2), 150.15 s (C7),
155.29 s (C1). Found, %: C 75.18; H 9.58; Si 5.74.
C116H168O12Si4. Calculated, %: C 74.63; H 9.07; Si
6.02. m/z 1887 (M + Na).
4,6,10,12,16,18,22,24-Octatrimethysiloxy-5,11,
17,23-tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,
3
CH, JHH 6.9), 5.01 s (4H, OH), 7.14 m (8H, Ha, 4H,
Hb). 13C NMR spectrum (CDCl3), , ppm (J, Hz):
0.87 q (SiMe21, 1JCH 120.0), 12.52 q (C12, 1JCH 125.0),
14,20-tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]-
octacosa-1(25),3,7(28),9,11,13(27),15,17,19(26),21,
23-dodecaen (VIIa). A mixture of 0.2 g of compound
IVa, 5 ml of anhydrous toluene and 0.7 g of hexa-
methyldisilazane was heated for 36 h at 90 C, solvent
was removed, the residue was recrystallized with
hexane from chloroform, solvent was removed, the
residue was dried in vacuum of oil pump (4 h, 40 C,
1
25.65 t (C11, JCH 125.0), 29.38 d (C10, JCH 130.0),
1
1
30.34 t (C5, JCH 90.0), 35.57 q (CMe3, JCH 120.0),
34.28 s (CMe3), 125.47 s (C8), 130.14 d (C9, JCH
1
150.0), 131.26 d (C3, JCH 150.0), 131.8 s (C6),
1
135.35 s (C4), 148.21 s (C2), 151.82 s (C7), 157.93 s
(C1). Found, %: C 73.98; H 8.88; Si 6.14. C104H144
O12Si4. Calculated, %:, C 73.54; H 8.54; Si 6.61. m/z
1695.5.
1
0.4 mm Hg). Yield 0.15 g (53%), mp 143 C. H
NMR spectrum (acetone-d6), , ppm: 0.06 s (72H,
SiMe3), 1.36 m (72H, CMe3), 1.76 m (12H, Me,),
3.94 s (8H, CH2Ph), 4.41 m (4H, CH), 6.2 s (4H,
OH), 7.21 m (8H, Ha), 7.51 s (4H, Hb). Found, %:
C 70.36; H 9.58; Si 10.74. C116H184O12Si8. Calculated,
%: C 69.82; H 9.29; Si 11.26.
33,34,35,36-Tetrakis(3,5-di-tert-butyl-4-hydroxy-
benzyl)-3,11,19,27-octamethyl-2,4,10,12,18,20,26,28-
octaoxy-3,11,19,27-tetrasila-37,38,39,40-tetrapropyl-
nonacyclo[29,3,1,121,25,113,17,15,9]tetracosa-[16,32
,
124,30,116,22,18,14]1(32),5,7,9(36),13,15,17(35),21,23,
25(34),30,29(33)-dodecaen (VIc) was prepared si-
milarly to the previous one from 0.2 of calixarene
IVc, 0.27 g of triethylamine and 0.2 g of dimethyl-
chlorosilane. Yield 0.09 g (46%), mp 161 C. 1H NMR
spectrum (CDCl3), , ppm (J, Hz): 0.08 s (24H,
SiMe2), 0.84 m. (12H, Me), 1.41 s (72H, CMe3),
1.69 m (8H, CH2Me), 2.19 m (8H, CH2CH) 3.59 s
4,6,10,12,16,18,22,24-Octatrimethysiloxy-5,11,
17,23-tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,
14,20-tetraethylpentacyclo[19.3.1.13,7.19,13.115,19]-
octacosa-1(25),3,7(28),9,11,13(27),15,17,19(26),21,
23-dodecaen (VIIb) was prepared similarly to the
previous one from 1.0 g of calixarene IVb and 7 ml
of hexamethyldisilazane. Yield 0.16 g (59%), mp
1
157 C. H NMR spectrum (acetone-d6), , ppm, (J,
3
(8H, CH2Ph), 4.50 t (4H, CH, JHH 6.9), 5.01 s (4H,
Hz): 0.07 s (72H, SiMe3), 0.91 m (12H, Me), 1.41 m
(72H, CMe3), 2.32 m (8H, CH2CH) 3.93 s (8H,
OH), 7.19 m (8H, Ha, 4H, Hb). Found, %: C 73.20;
H 11.03; Si 6.82. C108H152O12Si4. Calculated, %:, C
73.92; H 10.94; Si 6.40.
3
CH2Ph), 4.30 t (4H, CH, JHH 7.00), 6.45 s (4H, OH),
7.13 m (8H, Ha, 4H, Hb). 13CNMR spectrum (CDCl3),
1
33,34,35,36-Tetrakis(3,5-di-tert-butyl-4-hydroxy-
benzyl)-3,11,19,27-octamethyl-2,4,10,12,18,20,26,28-
octaoxy-3,11,19,27-tetrasila-3,7,38,39,40-tetrapen-
, ppm, (J, Hz): 0.75 q (SiMe3, JCH 125.0), 11.52 q
1
1
(C12, JCH 125.0) 25.65 t (C11, JCH 140.0), 29.38 d
1
1
(C10, JCH 130.0), 30.34 t (C5, JCH 90.0), 34.57 q
tylnonacyclo[29,3,1,121,25,113,17,15,9]tetracosa-[16,32
,
(CMe3, JCH 120.0), 33.78 s (CMe3), 125.47 s (C8),
1
1
24,30,116,22,18,14]1(32),5,7,9(36),13,15,17(35),21,23,
130.14 d (C9, 1JCH 150.0), 131.26 d (C3, 1JCH 150.0),
131.8 s (C6), 135.35 s (C4), 148.21 s (C2), 151.82 s
(C7), 157.93 s (C1). Found, %: C 70.61; H 9.81; Si
25(34),30,29(33)-dodecaen (VId) was prepared
similarly to the previous one from 0.2 of calixarene
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

SYNTHESIS AND SOME PROPERTIES OF TETRAKIS-3,5-DI-tert-BUTYL-4-HYDROXYBENZYLATED 467
10.26. C120H192O12Si8. Calculated, %:, C 70.26; H
9.43; Si 10.95.
1JCH 150.0), 130.03 s (C6), 135.97 s (C4), 149.21 s
(C2), 151.82 s (C7), 152.37 s (C1), 168.71 s [C(O)].
Found, %: C 73.44; H 8.20. C112H144O20. Calculated,
%:, C 73.94; H 7.81.
4,6,10,12,16,18,22,24-Octatrimethysiloxy-5,11,
17,23-tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,
14,20-tetrapentylpentacyclo[19.3.1.13,7.19,13.115,19]-
octacosa-1(25),3,7(28),9,11,13(27),15,17,19(26),21,
23-dodecaen (VIId) was prepared similarly to the
previous one from 1.0 of calixarene IVd and 6 ml of
hexamethyldisilazane. Yield 0.21 g (61%), mp 146 C.
1H NMR spectrum (acetone-d6), , ppm (J, Hz):
0.08 s (72H, SiMe3), 0.85 m (12H, Me), 1.41 m (72H,
CMe3), 1.96 m [24H, (CH2)3], 2.30 m (8H, CH2CH),
4,6,10,12,16,18,22,24-Octaacetyloxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetrapropylpentacyclo[19.3.1.13,7.19,13.115,19]octa-
cosa-1(25),3,7(28),9,11,13(27),15,17,19(26),21,23-
dodecaen (VIIIc) was prepared similarly to the pre-
vious one from 1.0 of calixarene IVc, 6 ml of acetic
anhydride and 0.6 ml of pyridine. Yield 0.20 g (33%),
1
mp 150 C. H NMR spectrum (CDCl3), , ppm (J,
3
3
3.59 s (8H, CH2Ph), 4.50 t (4H, CH, JHH 6.9), 6.11 s
Hz): 0.87 t (12H, Me, J 6.97), 1.36 s (72H, CMe3),
(4H, OH), 7.14 s (8H, Ha), 7.23 s (4H, Hb). Found, %:
C 70.81; H 9.78; Si 10.26. C120H192O12Si8. Calculated,
%: C 70.26; H 9.43; Si 10.95.
1.50 m (8H, CH2), 1.71 s [24H, OC(O)Me], 2.19 m
(8H, CH2), 3.58 m (8H, CH2), 4.32 m (4H, CH), 5.0 s
(4H, OH), 6.85 s (8H, Ha), 7.33 s (4H, Hb). Found,
%: C 74.13; H 8.82. C116H152O20. Calculated, %: C
74.65; H 8.21.
4,6,10,12,16,18,22,24-Octaacetyloxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]octa-
cosa-1(25),3,7(28),9,11,13(27),15,17,19(26),21,23-
dodecaen (VIIIa). A mixture of 0.5 of calixarene
IVa, 6.57 ml of acetic anhydride and 0.66 ml of py-
ridine was heated for 24 h at 70 C. Acetic anhydride
was removed in vacuum of water-jet pump (1 h, 40 C,
0.01 mm Hg), the residue was dissolved in chloroform,
the organic phase was separated water-jet air pump,
dried over MgSO4 and poured into 150 ml of pentane.
Precipitated product was dried in vacuum (3 h, 50 C,
0.04 mm Hg). Yield 0.21 g (34%) of compound
4,6,10,12,16,18,22,24-Octaacetyloxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
tetrapentylpentacycl[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,7(28),9,11,13(27),15,17,19(26),21,23-dode-
caen (VIIId) was prepared similarly to the previous
one from 1 g of calixarene IVd, 6 ml of acetic an-
hydride and 0.6 ml of pyridine. Yield 0.21 g (35%),
mp 153 C. 1H NMR spectrum (CDCl3), , ppm:
0.85 m (12H, Me), 1.27 s (72H, CMe3), 1.50 m [24H,
(CH2)3], 1.71 s [24H, OC(O)Me], 2.17 m (8H, CH2),
3.83 m (8H, CH2), 4.23 m (4H, CH), 5.0 s (4H, OH),
6.95 s (8H, Ha), 7.33 s (4H, Hb). 13C NMR spectrum
VIIIa, mp 155 C. 1H NMR spectrum (CDCl3),
,
ppm (J, Hz): 0.87 t (12H, Me, 3JHH 6.97), 1.35 s (72H,
CMe3), 1.75 s [24H, OC(O)Me], 3.58 m (8H, CH2),
4.35 m (4H, CH), 5.0 s (4H, OH), 6.85 s (8H, Ha),
7.33 s (4H, Hb). Found, %: C 73.98; H 8.11. C108H136
O20. Calculated, %:, C 74.32; H 8.02. m/z 1775
(M + Na)
1
(CDCl3), , ppm (J, Hz): 11.54 q (C15, JCH 150.0),
1
20.89 q [(CH3C(O), 1JCH 130.0], 21.73 t (C12 14, JCH
1
1
125.0), 25.49 q (C11, JCH 125.0), 29.84 t (C5, JCH
1
90.0), 30.67 d (C10, JCH 130.0), 32.82 s (CMe3),
34.68 q (CMe3, JCH 120.0), 125.55 s (C8), 126.24 d
1
(C9, JCH 150.0), 127.2 d (C3, JCH 150.0), 130.03 s
1
1
4,6,10,12,16,18,22,24-Octaacetyloxy-5,11,17,23-
tetra(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-
(C6), 134.6 s (C4), 137.26 s (C2), 148.82 s (C7),
152.37 s (C1), 168.71 s [C(O)]. Found, %: C 73.12;
H 9.04. C124H168O20. Calculated, %: C 73.27; H 8.56.
m/z 2016 (M + K).
tetraethylpentacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,7(28),9,11,13(27),15,17,19(26),21,23-dode-
caen (VIIIb) was prepared similarly to the previous
one from 1 g of calixarene IVb, 6 ml of acetic an-
hydride and 0.6 ml of pyridine. Yield 0.23 g (38%),
4,6,10,12,16,18,22,24-Octaacyl-5,11,17,23-tetra-
(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-tetra-
1
mp 148 C. H NMR spectrum (CDCl3), , ppm (J,
Hz): 0.87 t (12H, Me, 3JHH 6.97), 1.35 s (72H, CMe3),
1.77 s [24H, OC(O)Me], 2.21 m (8H, CH2), 3.62 m
(8H, CH2), 4.40 m (4H, CH), 5.0 s (4H, OH), 6.85 s
(8H, Ha), 7.33 s (4H, Hb). 13C NMR spectrum
methylpentacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,7(28),9,11,13(27),15,17,19(26),21,23-dode-
caen (IXa). A mixture of 0.3 g of calixarene IVa and
7 ml of acetic anhydride was heated for 48 h at 100 C.
When acetic anhydride was removed the residue was
dissolved in 10 ml methylene chloride and this solu-
tion was poured into100 ml of hexane. Precipitated
product was dried in vacuum water-jet air pump (2 h,
100 C, 0.4 mm Hg). Yield 0.15 g (60%) of compound
1
(CDCl3), , ppm (J, Hz): 13.02 q (C12, JCH 125.0),
1
1
20.89 q (CH3C(O), JCH 130.0), 28.32 t (C11, JCH
1
1
140.0), 29.84 t (C5, JCH 90.0), 30.67 d (C10, JCH
1
130.0), 32.82 s (CMe3), 34.68 q (CMe3, JCH 120.0),
125.55 s (C8), 126.24 d (C9, 1JCH 150.0), 127.2 d (C3,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007

468
KASYMOVA et al.
IXa, mp 151 C. 1H NMR spectrum (CD3OD), , ppm,
(J, Hz): 0.89s (12H, Me), 1.33 s (72H, CMe3), 1.76 s
[24H, OC(O)Me], 2.10 m [12H, OC(O)Me], 3.62 s
(8H, CH2), 4.11 q (4H, CH, JHH 6.9), 6.9 m (8H,
Ha), 7.17 s (4H, Hb). Found, %: C 72.92; H 8.12.
3. Gutsche, C.D., Calyxarenes. Cambridge: Royal So-
ciety of Chemistry, 1989, p. 132.
4. Vicens, J. and Bohmer, V., Calyxarenes, a Versatile
Class of Macrocyclic Compounds, Dodrecht: Kluwer
Acad. Publ., 1991, p. 15.
3
C
116H144O24. Calculated, %: C 72.48; H 7.55.
5. Ehrhardt, D., Gummi, Fasern Kunststoffe, 1992,
4,6,10,12,16,18,22,24-Octaacyl-5,11,17,23-tetra-
vol. 45, no. 5, p. 231.
(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-tetra-
6. Ehrhardt, D., Gummi, Fasern Kunststoffe, 1992,
ethylpentacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,7(28),9,11,13(27),15,17,19(26),21,23-dode-
caen (IXb) was prepared similarly to the previous one
from 1.0 of calixarene IVb and 10 ml of acetic an-
vol. 45, no. 7, p. 358.
7. Bukharov, S.V., Nugumanova, G.N., and Mukmene-
va, N.A., Zh. Obshch. Khim., 1998, vol. 68, no. 12,
p. 1977.
1
hydride. Yield 0.16 g (64%), mp 200 C. H NMR
spectrum (CDCl3), , ppm (J, Hz): 0.88 t (12H, Me,
3JHH 7.02), 1.34 m (72H, CMe3), 1.79 m [24H,
OC(O)Me], 2.15 m [12H, OC(O)Me], 2.35 m (8H,
CH2CH), 3.84 s (8H, CH2), 4.22 t (4H, CH, 3JHH 7.0),
6.9 s (8H, Ha), 7.19 s (4H, Hb). Found, %: C 73.20; H
7.80. C120H152O24. Calculated, %: C 72.85; H 7.74.
m/z 1999 (M + Na).
8. Bukharov, S.V., Litvinov, I.A., Gubaydullin, A.T.,
Nugumanova, G.N., and Mukmeneva, N.A., Zh.
Obshch. Khim., 2002, vol. 72, no. 2, p. 290.
9. Brunetti, H. and Schmidt, A., USA Patent 3821334,
C. A., 1973, vol. 78. 15828k.
10. Hogberg, A.G., J. Org. Chem., 1980, vol. 45, no. 22,
p. 4498.
4,6,10,12,16,18,22,24-Octaacyl-5,11,17,23-tetra-
(3,5-di-tert-butyl-4-hydroxybenzyl)-2,8,14,20-tetra-
pentylpentacyclo[19.3.1.13,7.19,13.115,19]octacosa-
1(25),3,7(28),9,11,13(27),15,17,19(26),21,23-dode-
caen (IXd) was prepared similarly to the previous one
from 1.0 g of calixarene IVd and 10 ml of acetic
11. Tunstad, L.M., Tucker, J.A., Dalcanale, E., Weiser, J.,
Bruant, J.A., Sherman, J.C., Helgeson, R.C., Knob-
ler, C.B., and Cram, D.J., J. Org. Chem., 1989,
vol. 54, no. 6, p. 1305.
12. Belamy, L., Novie dannie po IK spektram slozhnih
molekul (New Data on IK spectra of Complex
Molecules), Moscow: Mir, 1971, p. 112.
1
anhydride. Yield 0.10 g (51%), bp 167 C. H NMR
spectrum (CDCl3), , ppm (J, Hz): 0.85 t (12H, Me,
3JHH 6.97), 1.34 m (72H, CMe3), 1.62 m [24H,
OC(O)Me], 2.03 s [12H, OC(O)Me], 2.17 m [24H,
(CH2)3], 2.38 m (24H, CH2CH), 3.84 s (8H, CH2),
13. Kovalenko, V.I., Chernova, A.V., Shagidullin, R.R.,
Doroshkina, G.M., Borisoglebskaya, E.A., and Ni-
kitin, V.G., Abstaract of Papers, V Vserossiyskaya
konferentsiya Structura i dinamika molekulyarnyh
system (Russian Conf. Structure and dynamics of
Molecular Systems ), Kazan Moscow, 1998, part 1,
p. 126.
3
4.22 t (4H, CH, JHH 7.0), 6.9 s (8H, Ha), 7.19 s (4H,
Hb). Found, %: C 74.27; H 8.81. C132H176O24. Cal-
culated, %: C 73.85; H 8.26.
ACKNOWLEDGMENTS
14. Lutz, B.T, Astarboa, G., Van der Maas, J.H, Jans-
sen, R.G., Verboom, W., Reinhoudt, D.N., Vibra-
tional Spectroscopy, 1995, vol. 10, p. 29.
This research was financially supported by the
Russian Foundation for Basic Research (project
no. 05-03-32136).
15. Groenen, L.C., Steinuender, E., Lutz, B.T.G., Van der
Maas, J.H., Reinhoudt, D.N., J. Chem. Soc. Perkin
Trans 2, 1992, p. 1893.
REFERENCES
16. Antipin, I.S., Kazakova, E.H., Habiher, V.D., and
Konovalov, A.I., Usp. Khim., 1998, vol. 67, no. 4,
p. 995.
1. Asfari, Z., Bohmer, V., Harrowfield, J., and Vicens, J.,
Calixarenes, Dordrecht: Kluwer Academic Publ.,
2001, p. 43.
2. Izatt, R.M. and Christensen, J.J., Synthesis of
Macrocycles: Design of Selective Complexing Agents,
New York: Wiley, 1987, p. 95.
17. Neda, I., Siedentop, T., Vollbrecht, A., Thoennesse, H.,
Jones, P.G., and Schmutzler, R., Chem. Sci., 1998,
vol. 53, p. 841.
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