Mendeleev Commun., 2007, 17, 330–331
References
Table 1 Yields of calixcrowns 2–5.
1
C. Alfieri, E. Dradi, A. Pochini, R. Ungaro and G. D. Adreetti, J.
Chem. Soc., Chem. Commun., 1983, 1075.
Yields of calixcrowns (%)
Lg
2
P. J. Dijkstra, J. A. Brunink, K.-E. Bugge, D. N. Reinhoudt, S. Harkema,
R. Ungaro, F. Ugozzoli and E. Ghidini, J. Am. Chem. Soc., 1989, 111,
7567.
V. Lamare, J.-F. Dozol, F. Ugozzoli, A. Casnati and R. Ungaro, Eur. J.
Org. Chem., 1998, 1559.
T. Jin, J. Chem. Soc., Perkin Trans. 2, 2002, 151.
B. Pipoosananakaton, M. Sukwattanasinitt, N. Jaiboon, N. Chaichit and
Th. Tuntulani, Tetrahedron Lett., 2000, 41, 9095.
A. P. Marchand, H.-S. Chong, T. P. Kumar, Z. Huang, S. Alihodzic,
W. H. Watson and K. Ejsmont, Tetrahedron, 2002, 58, 10205.
Z. Asfari, S. Wenger and J. Vicens, Supramol. Sci., 1994, 1, 103.
J. Dozol, H. Rouquette, R. Ungaro and A. Casnati, US Patent, 5926687,
B01D, 1999.
2
3
4
5
I
60
70–75
70
85
90
70
85
90
87
85
95
90
TsO
Br
MsO or PhSO3
3
65–70
3 + 4 + 5: 60–65
4
5
However, the reaction between H-calix[4]arene 9 and di-
iodides of oligo(oxa)alkanes or ditosylates of oligo(ethylene
glycols) yielded only calix[4]arene-crown-4(5,6) ethers 10–12
(65–75%).
Thereupon, the alkylation of calixarene 1 with mesylates and
phenylsulfonates of oligo(ethylene glycols) resulted in only
crowned compounds but with a large amount of unconverted
p-tert-butylcalix[4]arene (about 30–35%) (Scheme 1, Table 1).
All calix[4]arene-crown ethers were isolated by simple re-
crystallization from alcohols without column chromatography
or HPLC.†
6
7
8
9
Y. He, Y. Xiao, L. Meng, Zh. Zeng, Z. Wu and Ch.-T. Wu, Tetrahedron
Lett., 2002, 43, 6249.
10 H. Yamamoto, T. Sakaki and S. Shinkai, Chem. Lett., 1994, 469.
11 A. Arduini, A. Casnati, L. Dodi, A. Pochini and R. Ungaro, J. Chem.
Soc., Chem. Commun., 1990, 1597.
12 K. Iwamoto, K. Araki and S. Shinkai, Tetrahedron, 1991, 47, 4325.
Thus, the method proposed for the preparation of p-tert-butyl-
calix[4]crowns in a cone conformation leads to desired products
in good yields. We found that the formation of calixbis(crown)
and doubly(calix)-doubly(crown) as by-products depends on the
structure of the bridging chain and the nature of the leaving
group in the alkylating agent. In the interaction of calix[4]arene
with diiodides of oligo(oxa)alkanes or ditosylates of oligo-
(ethylene glycols), only the calixarene-crowns were formed.
Received: 2nd April 2007; Com. 07/2901
5: mp 235–236 °C. 1H NMR d: 0.80 (s, 18H, But), 1.21 (s, 18H, But),
3.40 (d, 4H, ArCH2Ar, J 13.5 Hz), 3.70–4.21 (m, 24H, OCH2CH2O),
4.45 (d, 4H, ArCH2Ar, J 13.5 Hz), 6.84 (s, 4H, ArH), 7.10 (s, 4H, ArH),
7.30 (s, 2H, OH). FAB-MS, m/z: 895 (M + H)+. Found (%): C, 75.07;
H, 8.84. Calc. for C56H78O9 (%): C, 75.13; H, 8.78.
6: mp 156 °C. 1H NMR, d: 1.20 (s, 36H, But), 1.23 (s, 36H, But), 3.34
(d, 8H, ArCH2Ar, J 12.3 Hz), 3.93 (s, 8H, OCH2CH2O), 4.14–4.23 (m,
16H, OCH2CH2O), 4.37 (d, 8H, ArCH2Ar, J 12.3 Hz), 7.00 (s, 8H, ArH),
7.09 (s, 8H, ArH), 8.50 (s, 4H, OH). FAB-MS, m/z: 1521 (M + H)+.
Found (%): C, 78.62; H, 8.77. Calc. for C100H132O12 (%): C, 78.70; H, 8.72.
7: mp 184–186 °C. 1H NMR, d: 1.19 (s, 18H, But), 1.20 (s, 18H, But),
3.18 (d, 2H, ArCH2Ar, J 14 Hz), 3.34 (d, 2H, ArCH2Ar, J 14 Hz), 3.98
(s, 8H, OCH2CH2O), 4.16–4.21 (m, 16H, OCH2CH2O), 4.40 (d, 2H,
ArCH2Ar, J 14 Hz), 4.65 (d, 2H, ArCH2Ar, J 14 Hz), 7.00 (s, 4H, ArH),
7.09 (s, 4H, ArH). FAB-MS, m/z: 876 (M + H)+. Found (%): C, 76.60;
H, 8.78. Calc. for C56H76O8 (%): C, 76.68; H, 8.73.
†
1H NMR spectra were recorded on a Varian VXR-300 (300 MHz)
spectrometer using CDCl3 as a solvent and TMS as an internal standard.
Mass spectra were recorded on MX-1321 and VG 70-70EQ spectro-
meters; FAB mass spectra were measured on a VG 70-70EQ mass
spectrometer using m-nitrobenzyl alcohol as a matrix.
General procedure for the calixarene-crowns: a suspension of p-tert-butyl-
calix[4]arene 1 (4 mmol, 2.96 g) or calix[4]arene 9 (4 mmol, 1.69 g) and
K2CO3 (9.2 mmol, 1.27 g) in dry MeCN (80 ml) was stirred for 30 min;
then, the solution of a corresponding alkylation agent (8.8 mmol) in 50 ml
of MeCN was added dropwise for 45 min. After stirring for 12–14 (in
case of the iodide ion), 8–12 (tosyloxy or bromide ion) or 18–20 h (mesyl
or phenylsulfonate), the reaction was stopped; the inorganic precipitate
was filtered off; the solution was vacuum concentrated to leave a residue,
which was dissolved in CHCl3, washed with 10% HCl and water and
then dried over MgSO4. The evaporation of the solvent afforded a white
solid crude product, which was purified by crystallization from alcohols.
The doubly crowned compounds were isolated from the crude mixture
by trituration in hot hexane or heptane and then purified by recrystal-
lization from alcohol–water. Monocrowned calixarenes were purified by
recrystallization from methanol or ethanol.
8: mp 195–197 °C. 1H NMR, d: 1.17 (s, 18H, But), 1.19 (s, 18H, But),
3.20 (d, 2H, ArCH2Ar, J 14.2 Hz), 3.60 (d, 2H, ArCH2Ar, J 14.2 Hz),
3.70–4.30 (m, 32H, OCH2CH2O), 4.50 (d, 2H, ArCH2Ar, J 14.7 Hz),
4.75 (d, 2H, ArCH2Ar, J 14.7 Hz), 6.87 (s, 4H, ArH), 7.00 (s, 4H, ArH).
FAB-MS, m/z: 966 (M + H)+. Found (%): C, 74.58; H, 8.82. Calc. for
C60H84O10 (%): C, 74.65; H, 8.77.
2: mp 262–264 °C. 1H NMR, d: 0.95 (s, 18H, But), 1.29 (s, 18H, But),
3.27 (d, 4H, ArCH2Ar, J 13.53 Hz), 4.00–4.15 (m, 12H, OCH2CH2O),
4.37 (d, 4H, ArCH2Ar, J 13.53 Hz), 6.79 (s, 4H, ArH), 7.05 (s, 4H,
ArH), 7.39 (s, 2H, OH). FAB-MS, m/z: 763 (M + H)+. Found (%): C,
78.78; H, 8.81. Calc. for C50H66O6 (%): C, 78.70; H, 8.72.
3: mp 250–252 °C. 1H NMR, d: 0.94 (s, 18H, But), 1.34 (s, 18H, But),
3.35 (d, 4H, ArCH2Ar, J 13.0 Hz), 3.80–4.15 (m, 16H, OCH2CH2O),
4.43 (d, 4H, ArCH2Ar, J 13.0 Hz), 6.8 (s, 4H, ArH), 7.15 (s, 4H, ArH),
7.20 (s, 2H, OH). FAB-MS, m/z: 807 (M + H)+. Found (%): C, 77.31;
H, 8.80. Calc. for C52H70O7 (%): C, 77.38; H, 8.74.
4: mp 240–242 °C. 1H NMR, d: 0.85 (s, 18H, But), 1.25 (s, 18H, But),
3.20 (d, 4H, ArCH2Ar, J 13.2 Hz), 3.65–4.10 (m, 20H, OCH2CH2O),
4.31 (d, 4H, ArCH2Ar, J 13.2 Hz), 6.75 (s, 4H, ArH), 6.98 (s, 4H, ArH),
7.00 (s, 2H, OH). FAB-MS, m/z: 851 (M + H)+. Found (%): C, 76.12;
H, 8.81. Calc. for C54H74O8 (%): C, 76.20; H, 8.76.
10: mp 381–382 °C. 1H NMR, d: 3.32 (d, 4H, ArCH2Ar, J 12.48 Hz),
3.91 (s, 4H, OCH2CH2O), 4.20–4.28 (m, 8H, OCH2CH2O), 4.40 (d, 4H,
ArCH2Ar, J 12.48 Hz), 6.60 (t, 2H, ArH, J 7.3 Hz), 6.85 (t, 2H, ArH,
J 7.3 Hz), 7.04 (d, 4H, ArH, J 7.5 Hz), 7.08 (d, 4H, ArH, J 7.5 Hz), 8.84
(s, 2H, OH). FAB-MS, m/z: 539 (M + H)+.
11: mp 268 °C. 1H NMR, d: 3.35 (d, 4H, ArCH2Ar, J 13.2 Hz), 3.80–
4.15 (m, 16H, OCH2CH2O), 4.43 (d, 4H, ArCH2Ar, J 13.2 Hz), 6.68
(t, 2H, ArH, J 7.5 Hz), 6.75 (t, 2H, ArH, J 7.5 Hz), 6.95 (d, 4H, ArH,
J 7.5 Hz), 7.04 (d, 4H, ArH, J 7.5 Hz), 7.87 (s, 2H, OH). FAB-MS, m/z:
584 (M + H)+.
1
12: mp 230–232 °C. H NMR, d: 3.38 (d, 4H, ArCH2Ar, J 13.4 Hz),
3.80 (s, 4H, OCH2CH2O), 3.85–3.94 (m, 4H, OCH2CH2O), 4.00–4.10 (m,
12H, OCH2CH2O), 4.43 (d, 4H, ArCH2Ar, J 13.4 Hz), 6.65 (t, 2H, ArH,
J 7.5 Hz), 6.72 (t, 2H, ArH, J 7.5 Hz), 6.88 (d, 4H, ArH, J 7.5 Hz), 7.04
(d, 4H, ArH, J 7.5 Hz), 7.52 (s, 2H, OH). FAB-MS, m/z: 627 (M + H)+.
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