Synthesis of 3,5-di-tert-butyl-4-hydroxyphenylsulfanylmethyl-substituted tetramethylcalix[4]resorcinarenes

Full text of DOI:10.1134/S1070428010070250

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 7, pp. 1097–1098. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © G.N. Nugumanova, T.A. Barsukova, S.V. Bukharov, A.R. Burilov, V.V. Syakaev, N.A. Mukmeneva, 2010, published in Zhurnal
Organicheskoi Khimii, 2010, Vol. 46, No. 7, pp. 1096–1097.
SHORT
COMMUNICATIONS
Synthesis of 3,5-Di-tert-butyl-4-hydroxyphenylsulfanylmethyl-
Substituted Tetramethylcalix[4]resorcinarenes
G. N. Nugumanovaa, T. A. Barsukovaa, S. V. Bukharova, A. R. Burilovb,
V. V. Syakaevb, and N. A. Mukmenevaa
a Kazan State Technological University, ul. K. Marksa 68, Kazan, 420015 Tatarstan, Russia
e-mail: guliang1@rambler.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received January 4, 2010
DOI: 10.1134/S1070428010070250
Dialkylaminomethyl-substituted calix[4]resorcin-
arenes have been reported long ago [1], but further
transformations of these compounds were reported in
a few publications [2–4], and the described transforma-
tions did not involve the dialkylaminomethyl group
therein. An exception was the formation of the corre-
sponding ammonium salts [5, 6] and thioamides [7].
Products of nucleophilic replacement of dialkylamino
group in the above calix[4]resorcinarenes were not
reported. On the other hand, deamination of phenolic
Mannich bases is their typical reaction [8].
affect the yield of III. By contrast, the reaction of
benzenethiol II with calixarene Ia preliminarily stored
for 3 months gave a mixture of products of partial
replacement of the dimethylamino groups (according
1
to the H NMR data) even after heating for 66 h. The
reactivity of calix[4]resorcinarene Ia can be restored
after prolonged storage by washing with dimethyl
sulfoxide and then with water, followed by drying in
air. Presumably, the reactivity of aminomethyl calix-
arene derivatives Ia and Ib depends on their supra-
molecular organization.
Deamination of freshly prepared dialkylamino-
methyl-substituted calix[4]resorcinarenes Ia and Ib by
the action of 2,6-di-tert-butyl-4-sulfanylphenol (II)
resulted in the formation of previously unknown calix-
arene III containing sterically hindered phenylsulfanyl
fragments (yield 68–72%). We also found that the
duration of storage of initial compound Ib does not
According to [9], molecules of calix[4]resorcin-
arene Ia in crystal are linked to dimers where dimeth-
ylaminomethyl groups of neighboring molecules enter
the macroring cavity in each other; therefore, these
groups become spatially inaccessible for nucleophilic
attack. Such associates are likely to dissociate by the
action of solvent, whereas prolonged drying favors the
OH
1
t-Bu
Bu-t
2
3
4
NR2
S
5
6
OH
HO
OH
t-Bu
Bu-t
HO
OH
7
+
4
8
–4HNR2
1
10
11Me
9
Me
SH
4
4
Ia, Ib
II
III
R = Me (a), Et (b).
1097

NUGUMANOVA et al.
1098
formation of the dimers. Compound Ib in crystal does
not give rise to analogous dimers.
This study was performed in the framework of the
Federal Target Program “Scientific and Scientific–
Pedagogical Personnel in Innovation Russia,” 2009–
2013, state contract no. P478.
5,11,17,19-Tetrakis(3,5-di-tert-butyl-4-hydroxy-
phenylsulfanylmethyl)-2,8,14,20-tetramethylpenta-
cyclo[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-4,6,10,12,-
16,18,22,24-octaol (III). A mixture of 0.6 g of calix-
arene Ia, 0.8 g of thiol II, and 20 ml of o-xylene was
stirred for 14 h at 125°C in a stream of argon. The
solvent was removed under reduced pressure, and the
residue was washed with hexane. Yield 0.82 g (68%),
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1
off-white powder, mp >168°C (decomp.). H NMR
spectrum (CDCl3), δ, ppm: 1.23 s (72H, CMe3), 1.68 d
3
(12H, Me, J = 7.29 Hz), 4.07 s (8H, CH2S), 4.50 q
3
(4H, CH, J = 7.29 Hz), 5.17 s (4H, OH), 7.06 s (8H,
3-H), 7.26 s (4H, 9-H), 7.60 s (8H, OH). 13C NMR
spectrum (CDCl3), δC, ppm: 20.18 q (C11, JCH
=
127.15 Hz), 28.18 d (C10, JCH = 126.79 Hz), 30.15 q
(CMe3, J = 126.07 Hz), 31.21 t (C5, JCH = 143.33 Hz),
34.40 s (CMe3), 111.04 s (C8), 122.55 s (C6), 126.10 s
(C4), 127.90 (C9, JCH = 160 Hz), 129.86 d (C3, J =
160 Hz), 136.89 s (C2), 149.74 s (C7), 154.21 s (C1).
Found, %: C 72.84; H 9.12; O 10.01; S 8.03.
C92H120O12S4. Calculated, %: C 71.50; H 7.77;
O 12.44; S 8.29.
Calixarene III was also synthesized in a similar
way from 0.6 g of compound Ib and 0.74 g of thiol II
in 20 ml of o-xylene. Yield 0.80 g (72%).
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1
The H and 13C NMR spectra were recorded on
a Bruker Avance-600 spectrometer operating at 600
and 150 MHz, respectively.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 7 2010