Unusual reaction of tetramethylcalix[4]resorcinolarene with 3,5-di-tert-butyl-4-hydroxybenzyl acetate [6]

Full text of DOI:10.1023/A:1020825106933

Russian Journal of General Chemistry, Vol. 72, No. 8, 2002, pp. 1320 1321. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 8, 2002,
pp. 1405 1406.
Original Russian Text Copyright
2002 by Bukharov, Nugumanova, Mukmeneva, Syakaev, Burilov, Pudovik, Konovalov.
LETTERS
TO THE EDITOR
Unusual Reaction of Tetramethylcalix[4]resorcinolarene
with 3,5-Di-tert-butyl-4-hydroxybenzyl Acetate
S. V. Bukharov, G. N. Nugumanova, N. A. Mukmeneva, V. V. Syakaev,
A. R. Burilov, M. A. Pudovik, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Kazan State Technological University, Kazan, Tatarstan, Russia
Received July 23, 2001
In the recent time, calix[4]resorcinolarenes and
their derivatives which have a cup-like structure and
are capable of binding both organic molecules and
ions attract increased interest [1 4]. The stability of
calixarene macrocycles and the possibility of modify-
ing them by organic and organometallic reagents
makes the chemistry of these compounds quite a
promising field of studies.
We were the first to reveal that calix[4]resorcinol-
arene (I) reacts with 3,5-di-tert-butyl-4-hydroxybenzyl
acetate (II) in the presence of perchloric acid to give
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)resorcinol
(III). A small amount of compound IV was also
isolated.
R
OH
R
R
OH
OH
HO
III
HO
HO
OH
OH
OH
Me
Me
Me
HO
OH
t-Bu
Bu-t
1
+
2
t-Bu
Bu-t
H+
Me
OH
3
4
5
CH2
OC(O)Me
OH
HO
7
I
II
8
10
HO
OH
9 Me
11
Me
Me
R
R
Me
OH
HO
HO
OH
R
OH
IV
t-Bu
Bu-t
R =
CH2
1070-3632/02/7208-1320$27.00 2002 MAIK Nauka/Interperiodica

UNUSUAL REACTION OF TETRAMETHYLCALIX[4]RESORCINOLARENE
1321
It should be noted that no macrocycle opening
occurs in the binary system calixarene perchloric
acid. Therefore, the formation of compound III is
the result of transalkylation of calixarene I with
the 3,5-di-tert-butyl-4-hydroxybenzyl cation generated
during the process.
(8H, Harom), 7.52 s (4H, Narom), 7.88 s (8H, OH).
13C NMR spectrum (CDCl3), C, ppm (J, Hz): 20.5 q
1
1
(C11, JCH 125.0), 28.3 d (C10, JCH 130.0), 29.4 t
(C5, JCH 90.0), 30.2 q (CMe3, JCH 120.0), 34.3 s
1
1
(CMe3), 114.0 s (C8), 121.6 d (C9, JCH 150.0),
1
125.0 d (C3, JCH 150.0), 125.5 s (C6), 128.9 s (C4),
1
136.5 s (C2), 149.0 s (C7), 152.6 s (C1). Found, %:
C 77.65; H 8.65. C92H120O12. Calculated, %: C 77.97;
H 8.47.
Reaction of tetramethylcalix[4]resorcinolarene
with 3,5-di-tert-butyl-4-hydroxybenzyl acetate.
To a solution of 1 g of calixarene I and 4.1 g of ester
II in 20 ml of acetone we added 0.08 ml of 72% per-
chloric acid. The mixture was kept for 24 h at 20 C
and poured into water, and the precipitate was washed
with water to neutral reaction and dried for 2 days
at 20 C. We thus obtained 3.4 g of a product which,
1
The H and 13C NMR spectra were recorded on
a Varian Gemini-200 spectrometer at 200 and
50 MHz, respectively, using the solvent (chloroform-d
and acetone-d6) signals as reference.
1
according to the H NMR data, was a mixture of
ACKNOWLEDGMENTS
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)resorcinol
(III) and 4,6,10,12,16,18,22,24-octahydroxy-5,11,17,-
19-tetrakis(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-dodecaene (IV) at a ratio of 70:30. Recrystalliza-
tion of the crude product from hexane gave 1.2 g
This study was financially supported by the Rus-
sian Foundation for Basic Research (project no. 02-
03-33037).
REFERENCES
1
(35%) of compound III with mp 153 154 C [5]. H
1. Izatt, R.M. and Christensen, J.J., Synthesis of Macro-
cycles: Design of Selective Complexing Agents, New
York: Wiley, 1987, p. 95.
NMR spectrum (CDCl3), , ppm: 1.42 s (54H, CMe3),
3.92 s (6H, CH2), 4.87 s (2H, OH), 5.09 s (1H, OH),
5.16 s (2H, OH), 6.93 s (1H, Harom), 7.12 s (6H,
Harom). Found, %: C 79.85; H 9.70. C51H72O5. Calcu-
lated, %: C 80.10; H 9.42. The mother liquor obtained
after separation of compound III was evaporated, and
the residue was subjected to column chromatography
on silica gel using hexane ether (8:2 to 1:1) as
eluent. We thus isolated 0.5 g (15%) of compound
2. Gutsche, C.D., Calyxarenes, Cambridge: Royal Soc.
Chem., 1989, p. 132.
3. Vicens, J. and Bohmer, V., Calyxarenes, a Versatile
Class of Macrocyclic Compounds, Dodrecht: Kluwer
Academic, 1991, p. 15.
4. Kal’chenko, V.I., Shivanyuk, A.N., Pirozhenko, V.V.,
and Markovskii, L.N., Zh. Obshch. Khim., 1994,
vol. 64, no. 9, p. 1562.
1
IV with mp 230 C (decomp.). H NMR spectrum
(acetone-d6), , ppm: 1.37 s (72H, CMe3), 1.73 d
3
(12H, CH3, JHH 7.0 Hz), 3.89 s (8H, CH2), 4.60 q
5. US Patent 4173541, 1979; Ref. Zh., Khim., 1980,
3
(4H, CH, JHH 7.0 Hz), 5.72 s (4H, OH), 7.18 s
no. 9P356P.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 8 2002