Selective upper-rim adamantylation of calix[4]arenes

Article abstract of DOI:10.1023/A:1012423128245

Lower-rim mono- and diacylated calix[4]arenes [acyl = C₆H₅caret;CO, 3,5-(NO₂)₂C₆H₃CO] undergo selective adamantylation with 3-Y-1-adamantanols (Y = H, i-Pr, 4-MeC₆H₄) in trifluoroacetic acid at the free phenolic fragments of the macroring. The reaction provides a convenient preparative route to di-, tri-, and tetraadamantylated calix[4]arenes.

Full text of DOI:10.1023/A:1012423128245

Russian Journal of Organic Chemistry, Vol. 37, No. 5, 2001, pp. 612 619. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 5, 2001,
pp. 656 662.
Original Russian Text Copyright
2001 by Shokova, Khomich, Kovalev.
Selective Upper-Rim Adamantylation of Calix[4]arenes*
E. A. Shokova, A. N. Khomich, and V. V. Kovalev
Faculty of Chemistry, Moscow State University, Vorob’evy gory, Moscow, 119899 Russia
Received December 23, 1999
Abstract Lower-rim mono- and diacylated calix[4]arenes [acyl = C6H5CO, 3,5-(NO2)2C6H3CO] undergo
selective adamantylation with 3-Y-1-adamantanols (Y = H, i-Pr, 4-MeC6H4) in trifluoroacetic acid at the free
phenolic fragments of the macroring. The reaction provides a convenient preparative route to di-, tri-, and
tetraadamantylated calix[4]arenes.
Design of new molecular receptors is one of the
most important problems of organic chemistry. From
this viewpoint, very promising compounds are calix-
[n]arenes (n usually equals 4, 6, or 8) which have
been extensively studied in the last two decades.
give 70% of the corresponding triadamantyl derivative
[7, 8]. Diadamantyl derivatives were isolated only as
mixtures of 1,2- and 1,3-isomers. On the other hand,
such derivatives with functional groups in the
adamantane fragments, especially those with distal
Valuable properties of calixarenes originate from the arrangement of the adamantyl substituents, attract
presence of a hydrophobic aromatic cavity and the attention as building blocks in supramolecular syn-
possibility for both upper- and lower-rim modification
by appropriate functional groups. As a result, these
compounds can be widely used as models for simula-
tion of biochemical processes, molecular recognition,
membrane transfer, and enzymatic catalysis. In this
connection, important problems are both synthesis of
new types of calixarenes and development of proce-
dures for their selective functionalization.
thesis, specifically for creation of selective receptors
for metal cations and organic molecules.
In all the above cases [5 8], the adamantylation
was performed with calixarenes having free hydroxy
groups. We now propose a general procedure for
selective adamantylation of calix[4]arenes, which is
based on the difference in the reactivity of alkylated
(or acylated) and free phenolic fragments in calix[4]-
arenes with respect to carbocationic adamantyl inter-
mediates in trifluoroacetic acid.
The reactions were carried out in excess TFA using
chloroform as co-solvent. As starting compounds we
used calix[4]arenes selectively alkylated or acylated at
the lower rim: 25,27-dipropoxy, 25,27-bis(benzyloxy),
25,27-bis(benzoyloxy), 25,26,27-tris(benzoyloxy),
25-(3,5-dinitrobenzoyloxy), and 25,27-bis(3,5-dinitro-
benzoyloxy) derivatives I VI with unsubstituted
para-positions and 5,17-di-tert-butyl-26,28-bis(3,5-di-
nitrobenzoyloxy)calix[4]arene (VII) (Scheme 1).
1,3-Dipropyl ether I turned out to be resistant to
TFA, but its reaction with 1-adamantanol was not
selective: it resulted in exhaustive adamantylation at
the para-positions of both phenolic and ether frag-
ments with formation of tetraadamantyl derivative
VIII (Scheme 2). We did not succeed in selectively
obtaining the desired 5,17-bis(1-adamantyl) derivative
by varying the reaction conditions such as TFA
amount and temperature; in all cases intractable mix-
tures of partially and exhaustively admantylated
Prior to our studies, adamantylcalix[n]arenes were
not reported. The first representatives were obtained
in 1993 [4]. In 1994 we developed a new procedure
for modification of calix[4]arene via reaction with
1-hydroxyadamantane and 3-alkyl-1-hydroxyada-
mantanes in trifluoroacetic acid (TFA). This reaction
gives exhaustively adamantylated derivatives [5].
Later on, the procedure was applied to calix[6]arene
[6]. In 1996 97 we showed that 3-substituted 1-hy-
droxyadamantanes as adamantylating agents provide
the possibility for upper-rim functionalization of
calix[4 or 6]arenes by adamantyl fragments containing
various groups [6, 7]. Finally, with the use of 1-hy-
droxyadamantanes having electron-acceptor substit-
uents in position 3 we succeeded in finding conditions
for selective adamantylation of calix[4]arene. The
latter reacted with 3-(4-methylsulfonylphenyl)-1-
hydroxyadamantane in trifluoroacetic acid/xylene to
____________
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 99-03-33071).
1070-4280/01/3705-0612$25.00 2001 MAIK Nauka/Interperiodica

SELECTIVE UPPER-RIM ADAMANTYLATION OF CALIX[4]ARENES
613
Scheme 1.
I, R = Pr; II, R = CH2Ph; III, R = X = H; VI, R = NO2, X = H; VII, R = NO2, X = t-Bu.
products were formed. 1,3-Dibenzyl ether II under-
goes dealkylation in TFA even at room temperature.
Its reaction with 1-adamantanol yields p-tetrakis-
(1-adamantyl)calix[4]arene (IX) (Scheme 2).
tions of phenolic rings we obtained the corresponding
dibromide whose adamantylation gave 11,23-di-
adamantyl derivative (X).
The reaction of partially acylated 1,3-bis(benzoyl-
oxy)calix[4]arene (III) with 3-Y-substituted 1-hy-
droxyadamantanes (Y = H, iso-C3H7, 4-CH3C6H4) in
TFA gave calixarenes XIa XIc having two adamantyl
Thus, lower-rim alkylation does not allow us to
effect selective upper-rim adamantylation of calix-
arenes. By selective bromination of I at the para-posi-
Scheme 2.
I, R = Pr; II, R = CH2Ph; VIII, R = Pr; IX, R = H.
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614
SHOKOVA et al.
Scheme 3.
III, R = X = H; VI, R = NO2, X = H; VII, R = NO2, X = t-Bu; XIa, R = X = Y = H (90%); XIb, R = X = H, Y = i-Pr (89%);
XIc, R = X = H, Y = 4-MeC6H4 (63%); XII, R = NO2, X = Y = H (76%); XIV, R = NO2, X = t-Bu, Y = H (86%); XVa, X =
Y = H (92%); XVb, X = H, Y = i-Pr (77%); XVc, X = H, Y = 4-MeC6H4 (81%); XVII, X = t-Bu, Y = H (89%).
groups in the para-positions of the phenol rings. It
should be emphasized that the adamantylation was
selective in a narrow temperature range, from 45 to
55 C. At higher temperature the reaction was accom-
panied by partial debenzoylation of the initial ester
to produce complex reaction mixtures. At lower tem-
perature the reaction was very slow. Less active tris-
(benzoyloxy)calix[4]arene IV almost did not react
with adamantanols below 75 C, while above that
temperature debenzoylation occurred.
3,5-Dinitrobenzoyloxy derivatives V VII are more
resistant to hydrolysis in acid medium. No deacylation
occurred in TFA even under reflux. The reaction of
25,27-bis(3,5-dinitrobenzoyloxy)calix[4]arene (VI)
with 1-adamantanol gave 76% of upper-rim diada-
mantylated calixarene XII (Scheme 3). Under similar
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 5 2001

SELECTIVE UPPER-RIM ADAMANTYLATION OF CALIX[4]ARENES
615
Scheme 4.
conditions, from monoacyl derivative V we obtained
80% of product XIII having three adamantyl groups
at the upper rim. 5,17-Di-tert-butyl-26,28-bis(3,5-di-
nitrobenzoyloxy)calix[4]arene (VII) obtained by selec-
tive dealkylation of the corresponding tetra-tert-butyl
derivative reacted with 1-adamantanol to afford calix-
[4]arene XIV with distal tert-butyl and adamantyl
groups.
The acyl protection can readily be removed from
the synthesized adamantylcalix[4]arenes by alkaline
hydrolysis. As a result, compounds XV XVII were
obtained (Scheme 3).
The product of selective upper-rim 1,3-diadaman-
tylation, calix[4]arene XII, was used as starting
compound for synthesis of calix[4]arenes XIX XXI
with four or three differently substituted adamantyl
fragments on the upper rim. In the first case, further
adamantylation of calix[4]arene XII was performed
after hydrolysis. In the second case, we used a proce-
dure utilizing imidazole [9] to remove one of the two
acyl groups in XII, and the resulting monoacyl deriva-
tive XVIII was subjected to further adamantylation.
Our results show that the reaction in trifluoroacetic
acid of 3-substituted 1-hydroxyadamantanes with
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616
SHOKOVA et al.
calix[4]arenes selectively acylated at the lower rim chloroform or methylene chloride. The extract was
provides a selective synthetic route to upper-rim
adamantylated derivatives.
dried over MgSO4 and evaporated, and the residue
was subjected to column chromatography using 1:1
hexane chloroform as eluent.
EXPERIMENTAL
5,11,17,23-Tetrakis(1-adamantyl)-25,27-di-
propoxycalix[4]arene (VIII) was synthesized from
100 mg (0.2 mmol) of calixarene I, 120 mg
(0.8 mmol) of 1-adamantanol, and 0.6 ml (8 mmol)
of trifluoroacetic acid; reaction temperature 60 65 C,
reaction time 8 h. The reaction mixture was evaporat-
ed, 5 10 ml of water was added to the residue, and
the mixture was left overnight. The precipitate was
filtered off and washed with water and methanol.
Yield of VIII 130 mg (62%), mp 210 212 C, Rf 0.59
1
The H and 13C NMR spectra were recorded on
a Varian VRX-300 spectrometer in CDCl3 (75.4 MHz
for 13C) using tetramethylsilane as internal reference.
Preparative column chromatography was performed
on Silicagel 40/60 m. Silufol-254 and DC Alufolien
Kieselgel 60 F256 plates (Merck) were used for thin-
layer chromatography; spots were visualized by UV
irradiation. Initial calixarenes and adamantylating
agents were synthesized by known methods: calix[4]-
arene [10, 11], 25,27-dipropoxycalix[4]arene (I) [12],
5,17-dibromo-25,27-dipropoxycalix[4]arene [13],
25,27-bis(benzyloxy)calix[4]arene (II) [14], 25,27-bis-
(benzoyloxy)calix[4]arene (III) [15], 25,26,27-tris-
(benzoyloxy)calix[4]arene (IV) [11], 25,27-bis(3,5-di-
nitrobenzoyloxy)calix[4]arene (VI) [9], 5,7-di-tert-
butyl-26,28-bis(3,5-dinitrobenzoyloxy)calix[4]arene
(VII) [9, 16], 1-adamantanol [17, 18], 3-isopropyl-1-
adamantanol [19]; 3-(4-methylphenyl)-1-adamantanol
[20]. 25-(3,4-Dinitrobenzoyloxy)calix[4]arene (V) was
synthesized from calix[4]arene and 3,5-dinitrobenzoyl
chloride in acetonitrile in the presence of 1-methyl-
imidazole by analogy with the synthesis of p-tert-
butyl derivative reported in [9]. The yield of V was
75%. The solvents used in this work were purified and
dehydrated by standard procedures.
(chloroform hexane, 1 : 2). 13C NMR spectrum
(CDCl3), , ppm: CAd: 35.40, 35.26 (C1), 43.66, 43.21
(C2), 29.10, 28.89 (C3), 36.92, 36.79 (C4); Ccavity
:
150.69, 149.64, 146.65, 141.47, 132.68, 127.83
(Carom), 124.88, 124.38 (CHarom); 31.50 (ArCH2Ar);
CR: 78.08 (OCH2CH2CH3), 23.36 (OCH2CH2CH3),
10.72 (OCH2CH2CH3). Found, %: C 85.31; H 8.57.
C74H92O4. Calculated, %: C 85.01; H 8.87.
5,11,17,23-Tetrakis(1-adamantyl)calix[4]arene
(IX) was synthesized from 100 mg (0.17 mmol) of
calixarene II, 104 mg (0.68 mmol) of 1-adamantanol,
and 0.5 ml (6.62 mmol) of trifluoroacetic acid; reac-
tion temperature 60 65 C, reaction time 9 h. The
mixture was treated as described above for compound
VIII. Yield of IX 158 mg (99%). The constants and
1H and 13C NMR spectral parameters of the product
were identical to those given in [5].
5,17-Dibromo-11,23-bis(1-adamantyl)-26,28-di-
propoxycalix[4]arene (X) was synthesized from
100 mg (0.15 mmol) of 5,17-dibromo-26,28-di-
propoxycalix[4]arene, 91 mg (0.6 mmol) of 1-ada-
mantanol, and 0.48 ml (6.4 mmol) of trifluoroacetic
acid; reaction temperature 70 75 C, reaction time
12 h. After removal of the solvent, the solid residue
was washed with boiling methanol and was subjected
to column chromatography using 1:9 carbon tetra-
chloride hexane as eluent. Yield of X 106 mg (76%),
mp 365 367 C, Rf 0.54 (chloroform hexane, 1:2).
1H NMR spectrum (CDCl3), , ppm: 8.26 s (2H, OH),
7.13 s (4H, Harom), 6.86 s (4H, Harom), 4.24 d.d
(4H, ArCH2Ar), 3.91 t (4H, OCH2CH2CH3), 3.28 d.d
(4H, ArCH2Ar), 2.05 1.95 m (7H, OCH2CH2CH3,
CH, adamantane), 1.60 1.75 m (24H, CH2, adaman-
tane), 1.21 t (6H, OCH2CH2CH3). 13C NMR spec-
trum (CDCl3), C, ppm: CAd: 35.61 (C1), 42.81 (C2),
28.74 (C3), 36.55 (C4); Ccavity: 152.26, 149.94,
147.87, 132.02, 130.51 (CHarom), 130.33 (Carom),
125.33 (CHarom), 110.41 (Carom), 31.50 (ArCH2Ar);
Typical procedure for adamantylation of calix-
arenes. A flask was charged with required amounts
of calixarene, adamantylating agent, and chloroform.
The flask was filled with argon, and trifluoroacetic
acid and lithium perchlorate as catalyst were added.
The reactant ratio calixarene adamantylating agent
TFA was as a rule 1:3 4:40 60. The amount of
chloroform (by volume) was the same as the amount
of TFA. Lithium perchlorate was taken in an amount
2
of 6 10 mol per mole of calixarene. The reaction
mixture was heated (oil bath) to a required tempera-
ture in a stream of argon. The progress of the reaction
was monitored by TLC, following the disappearance
of the initial calixarene. When the reaction was com-
plete, the mixture was evaporated to dryness.
Typical procedure for removal of acyl protection
from adamantylated calixarenes XI XIV and XX.
A mixture of acylated calixarene (0.15 mmol), sodium
hydroxide (1 g), THF (30 ml), ethanol (10 ml), and
water (4 ml) was refluxed for 18 20 h and evaporated.
Dilute hydrochloric acid, 15 ml, was added to the
solid residue, and the products were extracted into
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SELECTIVE UPPER-RIM ADAMANTYLATION OF CALIX[4]ARENES
617
CR: 78.16 (OCH2CH2CH3), 23.29 (OCH2CH2CH3),
10.72 (OCH2CH2CH3). Found, %: C 69.19; H 6.84;
Br 16.91. C54H62Br2O4. Calculated, %: C 69.38;
H 6.68; Br 17.09.
5,17-Bis(1-adamantyl)-25,27-bis(benzoyloxy)-
calix[4]arene (XIa) was synthesized from 1 g
(1.6 mmol) of calixarene III, 0.98 g (6.4 mmol) of
1-adamantanol, and 5 ml (66 mmol) of trifluoroacetic
acid. Reaction temperature 55 C, reaction time 10 h.
After removal of the solvent, the solid residue was
(C2), 36.80 (C3), 42.39 (C4, C10), 29.47 (C5, C7),
35.71 (C6), 42.04 (C8, C9); Ccavity + CR: 164.51
(OCOPh), 150.54, 145.40, 142.24, 133.60 (Carom),
132.43, 130.30 (CHarom), 129.09 (Carom), 129.01,
128.85 (CHarom), 127.30 (Carom), 126.57, 125.37
(CHarom), 33.14 (ArCH2Ar). Found, %: C 84.78;
H 7.01. C76H72O6. Calculated, %: C 84.41; H 6.71.
5,17-Bis(1-adamantyl)-25,27-bis(3,5-dinitroben-
zoyloxy)calix[4]arene (XII) was synthesized from
0.81 g (1 mmol) of calixarene VI, 0.45 g (3 mmol)
refluxed with methanol, and the precipitate was fil- of 1-adamantanol, and 3.9 ml (50 mmol) of trifluoro-
tered off and dried. Yield of XIa 1.3 g (90%),
mp 318 320 C, Rf 0.61 (chloroform hexane, 2:1).
13C NMR spectrum (CDCl3), C, ppm: CAd: 35.22
acetic acid; reaction temperature 65 C, reaction time
30 h. After evaporation of the reaction mixture, the
residue was washed with boiling methanol and was
subjected to column chromatography using hexane
chloroform as eluent. Yield of XII 1.45 g (76%),
mp 243 245 C, Rf 0.62 (chloroform hexane, 2:1).
(C1), 43.13 (C2), 28.86 (C3), 36.63 (C4); Ccavity + CR:
164.66 (OCOPh), 150.39, 145.46, 142.93 (Carom),
133.56 (CHarom), 132.54 (Carom), 130.33 (CHarom),
129.10 (Carom), 129.04, 128.84 (CHarom), 127.17
(Carom), 126.57, 125.35 (CHarom), 33.27 (ArCH2Ar).
Found, %: C 82.91; H 6.99. C62H60O6. Calculated, %:
C 82.64; H 6.71.
13C NMR spectrum (CDCl3), C, ppm: CAd: 35.61
(C1), 43.51 (C2), 29.01 (C3), 36.78 (C4); Ccavity + CR:
163.55 (OCOAr), 149.96, 148.75, 144.52, 144.21
(Carom), 132.75 (CHarom), 131.81 (CHarom), 129.35
(Carom), 127.67, 127.53 (CHarom), 125.70 (Carom),
123.08 (CHarom), 32.01 (ArCH2Ar). Found, %:
C 68.71; H 5.50; N 5.01. C62H56N4O14. Calculated,
%: C 68.88; H 5.22; N 5.18.
5,11,17-Tris(1-adamantyl)-25-(3,5-dinitroben-
zoyloxy)calix[4]arene (XIII) was synthesized from
0.15 g (0.2 mmol) of calixarene V, 0.21 g (1.5 mmol)
of 1-adamantanol, and 0.3 ml (3.8 mmol) of trifluoro-
acetic acid; reaction temperature 60 C, reaction time
12 h. After evaporation of the reaction mixture, the
residue was washed with boiling methanol. Yield of
XIII 0.20 g (80%), mp 260 262 C, Rf 0.38 (chloro-
25,27-Bis(benzoyloxy)-5,17-bis(3-isopropyl-1-
adamantyl)calix[4]arene (XIb) was synthesized as
described above for compound XIa from 0.1 g
(0.16 mmol) of calixarene III, 0.12 g (0.62 mmol) of
3-isopropyl-1-adamantanol, and 1 ml (13 mmol) of
trifluoroacetic acid. Yield of XIb 140 mg (89%),
mp 323 325 C, Rf 0.70 (chloroform hexane, 2:1).
13C NMR spectrum (CDCl3), C, ppm: CAd: 37.55
[(CH3)2CH], 16.40 [(CH3)2CH], 35.01 (C1), 45.43
(C2), 36.37 (C3), 42.81 (C4, C10), 29.25 (C5, C7),
35.39 (C6), 38.21 (C8, C9); Ccavity + CR: 164.71
(OCOPh), 150.47, 145.49, 142.92, 133.61 (Carom),
132.54 (CHarom), 130.35 (CHarom), 129.13 (Carom),
129.04, 128.89 (CHarom), 127.24 (Carom), 126.63,
125.42 (CHarom), 33.24 (ArCH2Ar). Found, %:
C 82.61; H 7.58. C68H72O6. Calculated, %: C 82.89;
H 7.37.
form hexane, 2:1). 13C NMR spectrum (CDCl3),
,
ppm: CAd: 35.52, 34.92 (C1), 43.04, 42.80 (C2C),
29.01, 28.54 (C3), 36.80, 36.41 (C4); Ccavity + CR:
159.82 (OCOPh), 149.11, 148.53, 148.42, 143.83,
132.65, 132.16 (Carom), 130.34, 129.50, 128.91
(CHarom), 127.57, 127.41 (Carom), 125.61 (CHarom),
125.46 (Carom), 124.38, 122.30, 122.02 (CHarom),
35.40, 31.72 (1:1, ArCH2Ar). Found, %: C 76.71;
H 6.51; N 2.91. C65H68N2O9. Calculated, %: C 76.45;
H 6.71; N 2.74.
25,27-Bis(benzoyloxy)-5,17-bis[3-(4-methyl-
phenyl)-1-adamantyl]calix[4]arene (XIc) was syn-
thesized as described above for compound XIa from
0.25 g (0.4 mmol) of calixarene III, 0.39 g (1.6 mmol)
of 3-(4-methylphenyl)-1-adamantanol, and 2 ml
(26 mmol) of trifluoroacetic acid. After evaporation
of the reaction mixture, the residue was washed with
boiling methanol and was subjected to column
chromatography using hexane chloroform as eluent.
Yield of XIc 270 mg (63%) (500 mg before chrom-
atographic treatment), mp 208 210 C, Rf 0.65
(chloroform hexane, 2 : 1). 13C NMR spectrum
(CDCl3), C, ppm: CAd: 20.79 (PhCH3), 147.62,
134.99, 128.73, 124.68 (CH3C6H5); 36.37 (C1), 49.08
11,23-Bis(1-adamantyl)-5,17-di-tert-butyl-26,28-
bis(3,5-dinitrobenzoyloxy)calix[4]arene (XIV) was
synthesized from 0.92 g (1 mmol) of calixarene VII,
0.45 g (3 mmol) of 1-adamantanol, and 3.9 ml
(50 mmol) of trifluoroacetic acid, following the proce-
dure described above for compound XII. Yield of
XIV 1.03 g (80%), mp 216 218 C. Found, %:
C 70.70; H 5.85; N 4.98. C70H72N4O14. Calculated,
%: C 70.45; H 6.08; N 4.70.
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SHOKOVA et al.
5,17-Bis(1-adamantyl)calix[4]arene (XVa) was
(ArCH2Ar). Found, %: C 83.71; H 8.75. C56H68O4.
obtained by alkaline hydrolysis of compound XIa.
Yield of XVa 92%, mp 241 243 C, Rf 0.51 (chloro-
Calculated, %: C 83.54; H 8.51.
5,17-Bis(1-adamantyl)-25-(3,5-dinitrobenzoyl-
oxy)calix[4]arene (XVIII). A solution of 0.3 g
(4.4 mmol) of imidazole in 8 ml of acetonitrile was
added to a solution of 0.4 g (0.37 mmol) of calixarene
XII in 8 ml of chloroform. The mixture was stirred
for 30 min at room temperature, 3 ml of 1 N hydro-
chloric acid was added, and the mixture was stirred
for an additional 20 min. The product was extracted
into chloroform, and the extracts were washed with
water until neutral reaction, dried over MgSO4, and
evaporated. The residue was washed with boiling
methanol. Yield of XVIII 240 mg (73%), mp 265
267 C, Rf 0.29 (chloroform hexane, 2:1). 13C NMR
spectrum (CDCl3), C, ppm: CAd: 35.01 (C1), 42.91
form hexane, 1:2). 13C NMR spectrum (CDCl3),
,
C
ppm: CAd: 35.46 (C1), 43.15 (C2), 28.87 (C3), 36.65
(C4); Ccavity: 148.51, 146.63, 144.84 (Carom), 128.86
(CHarom), 128.37, 127.37 (Carom), 125.28, 122.16
(CHarom), 32.12 (ArCH2Ar). Found, %: C 83.55;
H 7.90. C48H52O4. Calculated, %: C 83.20; H 7.56.
5,17-Bis(3-isopropyl-1-adamantyl)calix[4]arene
(XVb) was obtained by alkaline hydrolysis of com-
pound XIb. Yield of XVb 77%, mp 237 239 C.
13C NMR spectrum (CDCl3), , ppm: CAd: 37.55
[(CH3)2CH], 16.40 [(CH3)2CH], 35.01 (C1), 45.43
(C2), 36.37 (C3), 42.81 (C4, C10), 29.25 (C5, C7),
35.39 (C6), 38.21 (C8, C9); Ccavity: 148.55, 146.33,
144.55 (Carom), 128.26 (CHarom), 128.38, 127.23
(Carom), 125.20, 122.00 (CHarom), 32.32 (ArCH2Ar).
Found, %: C 83.21; H 8.51. C54H64O4. Calculated, %:
C 83.46; H 8.30.
5,17-Bis[3-(4-methylphenyl)-1-adamantyl]calix-
[4]arene (XVc) was obtained by alkaline hydrolysis
of compound XIc. Yield of XVc 81%, mp 243
245 C. 13C NMR spectrum (CDCl3), C, ppm: CAd:
20.78 (CH3Ph), 147.60, 134.99, 128.74, 124.70
(CH3C6H5), 36.55 (C1), 48.85 (C2), 36.80 (C3), 42.27
(C4, C10), 29.46 (C5, C7), 35.73 (C6), 42.27 (C8, C9);
Ccavity: 148.45, 146.77, 144.17 (Carom), 128.88
(CHarom), 128.24, 127.49 (Carom), 125.32, 122.20
(CHarom), 32.12 (ArCH2Ar). Found, %: C 85.54;
H 7.18. C62H64O4. Calculated, %: C 85.28; H 7.39.
(C2), 28.58 (C3), 36.42 (C4); Ccavity + CR: 159.90
(OCOPh), 149.11, 148.53, 148.42, 143.83, 132.65,
132.16 (Carom), 130.34, 129.50, 128.91, 128.19
(CHarom), 127.57, 127.41 (Carom), 125.61 (CHarom),
125.46 (Carom), 124.38, 122.30, 122.02 (CHarom),
35.40, 31.72 (1:1, ArCH2Ar). Found, %: C 74.28;
H 6.31; N 3.40. C55H54N2O9. Calculated, %: C 74.47;
H 6.14; N 3.16.
5,17-Bis(1-adamantyl)-11,23-bis[3-(4-methyl-
phenyl)-1-adamantyl]calix[4]arene (XIX) was syn-
thesized from 0.28 g (0.4 mmol) of calixarene XVa,
0.39 g (1.6 mmol) of 3-(4-methylphenyl)-1-adaman-
tanol, and 2 ml (26 mmol) of trifluoroacetic acid,
following the procedure described below for com-
pound XXI. Yield of XIX 0.33 g (75%), mp 223
225 C, Rf 0.72 (chloroform hexane, 1:2). 13C NMR
spectrum (CDCl3), C, ppm: CAd: 35.47 (C1), 43.11
5,11,17-Tris(1-adamantyl)calix[4]arene (XVI)
was obtained by alkaline hydrolysis of compound
XIII. Yield of XVI 91%, mp 259 261 C, Rf 0.80
(chloroform hexane, 1 : 2). 13C NMR spectrum
(CDCl3), C, ppm: CAd: 35.45 (C1), 43.12, 43.06
(C2), 28.83 (C3), 36.79 (C4); C3-Tol-1-Ad: 20.75
(CH3C6H4), 147.66, 134.90, 128.68, 124.58
(CH3C6H4); 36.70 (C1), 48.90 (C2), 36.56 (C3), 42.28
(C4, C10), 29.55 (C5, C7), 35.84 (C6), 42.28 (C8, C9);
Ccavity: 146.71, 146.22, 144.66, 144.18, 127.82,
(2:1, C2), 28.87 (C3), 36.68 (C4); Ccavity: 148.73,
146.58, 146.24, 144.71, 144.65 (Carom), 128.79
(CHarom), 128.45, 127.67, 127.65, 127.28 (Carom),
125.45, 125.17, 122.04 (CHarom), 32.53, 32.17 (1:1,
ArCH2Ar). Found, %: C 84.55; H 7.98. C58H66O4.
Calculated, %: C 84.22; H 8.04.
11,23-Bis(1-adamantyl)-5,17-di-tert-butylcalix-
[4]arene (XVII) was obtained by alkaline hydrolysis
of compound XIV. Yield of XVII 89%, mp 186
188 C, Rf 0.59 (chloroform hexane, 1:2). 13C NMR
spectrum (CDCl3), C, ppm: CAd: 35.45 (C1), 43.10
(C2), 28.88 (C3), 36.70 (C4); Ct-Bu: 33.94, 31.38;
Ccavity: 146.61, 146.52, 144.25, 144.18, 127.64,
127.55 (Carom), 125.43 (CHarom), 32.59 (ArCH2Ar).
Found, %: C 86.51; H 7.98. C82H92O4. Calculated, %:
C 86.27; H 8.12.
5,17-Bis(1-adamantyl)-11-[3-(4-methylphenyl)-
1-adamantyl)]-25-(3,5-dinitrobenzoyloxy)calix[4]-
arene (XX) was synthesized from 89 mg (0.1 mmol)
of compound XVIII, 100 mg (0.4 mmol) of 3-(4-
methylphenyl)-1-adamantanol, and 1 ml (13 mmol)
of trifluoroacetic acid; reaction temperature 60 C,
reaction time 12 h. The mixture was then treated as
described above for compound XIII. Yield of XX
81 mg (73%). The product was immediately brought
into alkaline hydrolysis.
127.53 (Carom), 125.85, 125.36 (CHarom), 32.59
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 5 2001

SELECTIVE UPPER-RIM ADAMANTYLATION OF CALIX[4]ARENES
619
5,17-Bis(1-adamantyl)-11-[3-(4-methylphenyl)-1-
adamantyl]calix[4]arene (XXI) was obtained by
alkaline hydrolysis of compound XX. Yield of XXI
60 mg (90%), mp 263 265 C. 13C NMR spectrum
7. Kovalev, V., Shokova, E., Khomich, A., and Luzi-
kov, Yu., New J. Chem., 1996, vol. 20, no. 4,
pp. 483 492.
8. Shokova, E., Khomich, A., and Kovalev, V., Tetra-
hedron Lett., 1996, vol. 37, no. 4, pp. 543 546.
(CDCl3), C, ppm: CAd: 35.44 (C1), 43.11 (C2), 28.84
(C3), 36.66 (C4); C3-Tol-1-Ad: 20.77 (CH3C6H4),
147.67, 134.88, 128.64, 124.55 (CH3C6H4); 36.50
9. See, K.A., Fronczek, F.R., Watson, W.H.,
Kashyap, R.P., and Gutsche, C.D., J. Org. Chem.,
1991, vol. 56, no. 26, pp. 7256 7268.
(C1), 48.72 (C2), 36.75 (C3), 42.31 (C4, C10), 29.52
9
(C5, C7), 35.84 (C6), 42.24 (C8, ); Ccavity: 148.78,
10. Gutsche, C., Iqbal, M., and Stewart, D., J. Org.
Chem., 1986, vol. 51, no. 5, pp. 742 745.
146.57, 146.31, 144.75, 144.06 (Carom), 128.80
(CHarom), 128.48, 127.73, 127.19 (Carom), 125.42,
125.14, 121.98 (CHarom), 32.44, 32.18 (1 : 1,
ArCH2Ar). Found, %: C 85.39; H 8.15. C65H72O4.
Calculated, %: C 85.11; H 7.91.
11. Gutsche, C. and Lin, L., Tetrahedron, 1986, vol. 42,
no. 6, pp. 1633 1640.
12. Arduini, A., Fabbi, M., Mantovani, M., Mirone, L.,
Pochini, A., Secchi, A., and Ungaro, R., J. Org.
Chem., 1995, vol. 60, no. 5, pp. 1454 1457.
13. Linnane, P., James, T.D., and Shinkai, S., J. Chem.
Soc., Chem. Commun., 1995, no. 19, pp. 1997 1998.
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