Modular chemistry. Double- and multi-1,3-alternate-calixcrowns

Article abstract of DOI:10.1016/S0040-4039(02)02657-6

Double- and multi-1,3-alternate-calixcrowns were prepared by multistep syntheses.

Full text of DOI:10.1016/S0040-4039(02)02657-6

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 44 (2003) 805–809
Modular chemistry. Double- and multi-1,3-alternate-calixcrowns
Sung Kuk Kim,a Wonbo Sim,a Jacques Vicensb,* and Jong Seung Kima,*
aDepartment of Chemistry, Konyang University, Nonsan 320-711, South Korea
bECPM, Becquerel, F-67087 Strasbourg, Ce´dex 2, France
Received 17 September 2002; accepted 21 November 2002
Abstract—Double- and multi-1,3-alternate-calixcrowns were prepared by multistep syntheses. © 2003 Elsevier Science Ltd. All
rights reserved.
Because of their easy functionalization calixarenes have
been combined in various ways to larger molecules
(double- and multi-calixarenes) containing more than
one calixarene unit.1 Due to the special geometry of the
calix[4]arene in the 1,3-alternate conformation allowing
metal cation tunnelling through the p-basic tube of the
calix unit2 chemists have prepared ‘nano-tubes’ consist-
ing of two or more calixarene units in the 1,3-alternate
conformation. In 1992, Asfari et al.3 reported the reac-
tion of p-tert-butyl calix[4]arene with an excess of
tetraethylene glycol ditosylate and K2CO3 leading to
the double calix[4]biscrown-5 (1) in which the two
calix[4]crown-5 are crowned constraining the calix-
arenic units into the 1,3-alternate conformation.3 Selec-
tivity of complexation was observed for K+ and Rb+,
the cation being located in the central cavity of the
tritopic receptor.3 Subsequently, Asfari et al.4 obtained
similar structures from a mesitol-derived calix[4]arene
known to exist in the 1,3-alternate conformation. More
recently, Kim et al.5 obtained a dimeric structure by
reacting 1,3-dipropyl calix[4]arene with N-tosyl tetra-
another by crown elements giving rise to polytopic
ethylene glycol dimesylate and Cs2CO3.5 The calixarene
receptors with tubular structures.
units were shown to be in the 1,3-alternate conforma-
tion.5 Nano-tubes consisting of two6–8 or three6
Synthesis of dimers 2–4. Scheme 1 shows the synthesis
calix[4]arene units in the 1,3-alternate conformation
of dimers 2–4. 1,3-Calix[4]monocrown-5 (9)11 or 1,3-
have also been constructed by linkages at the para
calix[4]monocrown-6 (10)11 was reacted with 3 equiv. of
position instead of the phenolic oxygens.
diethylene glycol monotosylate in the presence of 2
equiv. of Cs2CO3 in refluxing acetonitrile for 24 h under
As part of our work on calix[4]crown compounds2,9,10
we report in this letter the synthesis of 1,3-calix[4]crown
polymers: dimers 2–4, trimers 5 and 6, tetramer 7 and
pentamer 8 in which all the calixcrown units are in the
N2.12
Chromatography on a silica column (eluent: ethyl ace-
tate) gave diglycolic 1,3-calix[4]monocrowns 11 (90%
yield) and 12 (92% yield) in the 1,3-alternate conforma-
1,3-alternate conformation and are linked to one
tion with singlets at 3.83 and 3.77 ppm for the
1
ArCH2Ar protons in their respective H NMR spectra.
Tosylation of the hydroxyl groups was carried out with
4 equiv. of tosyl chloride (TsCl) in THF in the presence
of 10 equiv. of NaOH dissolved in water. Chromatog-
Keywords: calixarenes; nanotubes; polytopic receptors; alkali cations.
* Corresponding authors. E-mail: vicens@chimie.u-strasbg.fr;
jongskim@konyang.ac.kr
0040-4039/03/$ - see front matter © 2003 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(02)02657-6

806
S. K. Kim et al. / Tetrahedron Letters 44 (2003) 805–809
Scheme 2. Synthesis of trimers 5 and 6.
Scheme 1. Synthesis of dimers 2–4.
raphy on a silica column using (eluent: ethyl acetate/
hexane (3:1)) gave calix ditosylates 13 (80% yield) and
14 (78% yield). 1H NMR showed the 1,3-alternate
conformation was maintained during tosylation. Next,
9 was reacted with 1 equiv. of 13 or 14 and 3 equiv. of
Cs2CO3 in refluxing acetonitrile for 24 h to afford
respectively symmetrical (the two calix crowns units are
the same) dimer 2 (41% yield) by recrystallization from
ethyl acetate:chloroform (4:1) and unsymmetrical 3
(35% yield) separated by chromatography on a silica
column (eluent: ethyl acetate) followed by recrystallisa-
tion from diethyl ether:chloroform (4:1). Similarly
dimer 4 was obtained in 20% yield by running a similar
reaction between 10 and 14.
Synthesis of trimers 5 and 6. According to Scheme 2,
calix[4]arene13 was reacted with 2 equiv. of diethylene
glycol monotosylate in the presence of 1 equiv. of
K2CO3 in refluxing acetonitrile for 24 h to produce
diglycolic calix 15 (44% yield) after recrystallization
from CH2Cl2/ethyl acetate (1:5). 15 Was reacted once
again with diethylene glycol monotosylate but using
Cs2CO3 to afford tetraglycolic calix 16 which was trans-
formed into its tetratosylate 17 as previously done to
obtain 13. The 1,3-alternate conformation of 16 and 17
was deduced from the presence of singlets at 3.78 and
4.18 ppm for the ArCH2Ar protons in their respective
1H NMR spectra. Acting as a central unit 17 was
reacted with 9 or 10 to afford trimers 5 (25% yield) and
6 (34% yield) after a work up similar to the one of
dimers 2–4.
Scheme 3. Synthesis of tetramer 7.
protons with a 1:1 integration ratio indicative of both
cone and 1,3-alternate conformation. The 13C NMR
spectra reflected both conformations with two signals at
38.8 ppm (1,3-alternate) and 32.2 ppm (cone).14 20 Was
prepared by reacting 13 with 1 equiv. of 15 in the
presence of 3 equiv. of Cs2CO3 to give 19 (35% yield)
which was then tosylated into 20 (78% yield). Double
calix 18 was therefore reacted with 20 to produce
tetramer 7 (81% yield). The tetrameric structure of 7
was in agreement with the analytical data.
Synthesis of pentamer 8. According to Scheme 4, tetra-
tosylate 17 and double calix 18 were reacted to produce
pentamer 8 (31% yield). The analytical data of all the
products were in agreement with the proposed struc-
tures. The structures of dimers 2–4, trimers 5 and 6,
tetramer 7 and pentamer 5 were deduced from mass
spectra. The high symmetry of their molecular structure
Synthesis of tetramer 7. According to Scheme 3,
calix[4]arene13 was reacted with 1 equiv. of calix ditosy-
late 13 in the presence of 1 equiv. of K2CO3 in refluxing
acetonitrile for 24 h to produce double calix 18 (40%
yield) after chromatography on silica (eluent: ethyl
acetate/hexane (1:1)) and recrystallization from ethyl
acetate. The spectrum of 18 showed one AB system
with two doublets at 4.40 and 3.52 ppm with J=12.72
Hz and one singlet at 3.92 ppm for the ArCH2Ar
1
was reflected in the H NMR and 13C NMR spectra
which presented very simple patterns.

S. K. Kim et al. / Tetrahedron Letters 44 (2003) 805–809
807
References
1. Saadioui, M.; Bo¨hmer, V. In Calixarenes 2001; Asfari, Z.;
Bo¨hmer, V.; Harrowfield, J.; Vicens, J., Eds.; Kluwer
Academic Publishers: Dordrecht, Holland, 2001; pp. 130–
154.
2. Casnati, A.; Ungaro, R.; Asfari, Z.; Vicens, J. In Calix-
arenes 2001, Asfari, Z.; Bo¨hmer, V.; Harrowfield, J.;
Vicens, J., Eds.; Kluwer Academic Publishers: Dordrecht,
Holland, 2001; pp. 365–384. See also Kim, J. S.; Yang, S.
H.; Rim, J. A.; Vicens, J.; Shinkai, S. Tetrahedron Lett.
2001, 42, 8047.
3. Asfari, Z.; Abidi, R.; Arnaud, F.; Vicens, J. J. Incl.
Phenom. 1992, 13, 163–169.
4. Asfari, Z.; Pappalardo, S.; Vicens, J. J. Incl. Phenom.
1992, 13, 189–192.
5. Kim, J. S.; Shon, O. J.; Ko, J. W.; Cho, M. H.; Yu, I. Y.;
Vicens, J. J. Org. Chem. 2000, 65, 2386–2392.
6. Ikeda, A.; Shinkai, S. J. Chem. Soc., Chem. Commun.
1994, 2375–2376.
Scheme 4. Synthesis of pentamer 8.
Table 1. % Extraction of alkali metal picrates by ligands
2–8a
% Extraction
Ligand
Na+
K+
Rb+
Cs+
54.44
101.14
113.31
38.89
89.95
38.01
34.82
2
3
4
5
6
7
8
16.42
14.18
17.46
9.41
1.94
5.07
155.76
130.76
72.75
157.72
15.03
136.91
121.1
72.52
143.78
46.48
132.85
116.45
144.8
122.47
23.58
a Conditions: 2–8, 0.1 mM in 1,2-dichloroethane; metal picrate, 0.2
mM in water. The intensities of the extracted picrates (umax=373
nm) from the water into the organic layer were measured.
7. Kanamathareddy, S.; Gutsche, C. D. J. Org. Chem. 1995,
60, 6070–6075.
8. Perez-Aldemar, J.-A.; Abreaham, H.; Sanchez, C.;
Rinassen, K.; Prados, P.; de Mendoza, J. Angew. Chem.,
Int. Ed. Engl. 1996, 35, 1009–1011.
9. Thue´ry, P.; Nierlich, M.; Lamare, V.; Dozol, J. F.;
Asfari, Z.; Vicens, J. J. Incl. Phenom. Macro. Chem. 2000,
36, 375–408.
10. Kim, J. S.; Lee, W. K.; Kim, J. G.; Suh, I. H.; Yoon, J.
Y.; Lee, J. H. J. Org. Chem. 2000, 65, 7215.
11. Kim, J. S.; Lee, W. K.; Sim, W.; Ko, J. W.; Cho, M. H.;
Ra, D. Y.; Kim, J. W. J. Incl. Phenom. Macro. Chem.
2000, 37, 359.
Two-phase extraction studies. Table 1 gives extraction
data of alkali metal picrates from water to 1,2-
dichloroethane by ligands 2–8. K+ and Rb+ were better
extracted by 2, 5, 7 and 8. This is probably due to
complexation of these cations in the crown-5 loop, the
cavity size of which (five oxygen atoms) is known to be
appropriate for them as described for 1,3-
calix[4]crowns-5.2
Similarly, Cs+ was better extracted by 4 and 6 for
similar reasons, since 1,3-calix[4]crowns-6 are known to
be suitable for this cation.2 Ligand 3 which is a hybrid
structure containing both crown-5 and crown-6 units
was observed to extract the three cations in almost the
same percentage range. Concerning Cs+/Na+ selectivity
the highest one was observed for trimer 6 to be equal to
46.4. The second observation is that as some extraction
percentages are higher than 100% (bold numbers), one
can assume the formation of binuclear 1:2 ligand:metal
complexes.
12. Melting points (mps) were taken with a Mel-Temp of
Fisher–Johns apparatus without any correction. 1H and
13C NMR spectra were recorded with a 400 MHz (Bruker
ARX-600) and a 100 MHz spectrometer, respectively, the
chemical shifts (l) reported in ppm downfield from the
internal standard, tetramethylsilane. FAB+ mass spectra
was obtained from JEOL-JMS-HX 110A/110A High
Resolution Tandem Mass Spectrometry in Korea Basic
Science Institute in Daejon, Korea. All the chemicals
were of commercial value and used without any further
purification. All the reactions were run under N2. Com-
pound 11. 911 (2.00 g; 3.43 mmol), diethyleneglycol
monotosylate (2.68 g; 10.3 mmol), Cs2CO3 (3.32 g; 10.2
mmol), acetonitrile (100 mL) were refluxed for 24 h. After
removing the solvents, the brownish solid residue was
dissolved in 5% aqueous HCl (100 mL) and CH2Cl2 (50
mL). The organic layer was washed three times with
water (50 mL) and dried over anhydrous MgSO4. After
filtration and evaporation, the crude residue was chro-
matographed on silica gel using ethyl acetate as eluent to
give 11 as a yellowish oil. Yield: 90%. 1H NMR (400
MHz, CDCl3): l 7.15 (d, 4H, Ar-Hm, J=6.82 Hz), 7.09
(d, 4H, Ar-Hm, J=6.80 Hz), 6.94–6.91 (m, 4H, Ar-Hp),
3.71–3.23 (m, 32H, -OCH2CH2O-), 3.83 (s, 8H, Ar-CH2
-Ar), 2.27 (s, 2H, -OH). 13C NMR (100 MHz, CDCl3):
156.8, 156.5, 134.7, 134.1, 130.6, 130.5, 124.1, 123.6, 73.4,
71.4, 71.3, 70.5, 70.3, 68.8, 62.1, 38.7, 38.6, 38.5, 31.6.
FAB MS m/z (M+) calcd 758.2, found 758.6. Compound
12. Same procedure as for 11: 1011 (3.19 mmol),
In this paper we have described the construction of
polymers made of 1,3-alternate calix[4]crowns by multi-
step procedure. Preliminary extraction studies indicated
the formation of 1:2 ligand/metal complexes. The bind-
ing properties of polytopic receptors 2–8 are currently
under investigation and will be presented in more detail
in due course.
Acknowledgements
This research was supported by a Grant from the
Korea Science and Engineering Foundation (R01-2000-
000-00047-0). We also gratefully thank KBSI in Daejon
for the instrumentation support (1H, 13C NMR, and
mass spectroscopy).

808
S. K. Kim et al. / Tetrahedron Letters 44 (2003) 805–809
diethyleneglycol monotosylate (9.57 mmol), acetonitrile
(100 mL), reflux 24 h. Yellowish oil. Yield: 92%. 1H
NMR (400 MHz, CDCl3): l 7.14 (d, 4H, Ar-Hm, J=7.43
Hz), 7.10 (d, 4H, Ar-Hm, J=7.52 Hz), 6.94–6.86 (m, 4H,
Ar-Hp), 3.73–3.46 (m, 36H, -OCH2CH2O-, -OH), 3.77 (s,
8H, Ar-CH2-Ar). 13C NMR (100 MHz, CDCl3): 156.9,
156.7, 134.6, 134.5, 131.0, 130.0, 124.0, 123.9, 73.5, 71.9,
71.8, 71.4, 70.5, 70.3, 62.0, 38.3. FAB MS m/z (M+) calcd
803.1, found 802.9. Compound 13. To a solution of 11
(2.00 g; 2.64 mmol), TsCl (2.01 g; 10.5 mmol) in THF
(100 mL) in an ice bath was added dropwise a NaOH
solution (0.85 g, 26.4 mmol) in 5 mL of water. After 24
h stirring at rt, the solvents were removed to give a
yellowish oil. The crude product was extracted with
CH2Cl2 (100 mL) and water (100 mL). The organic layer
was dried over anhydrous MgSO4. After filtration and
evaporation, the crude mixture was chromatographed on
silica gel (ethyl acetate/hexane (3:1) as eluent) to give 13
as a colorless oil. Yield: 80%. 1H NMR (400 MHz,
CDCl3): l 7.80 (d, 4H, Ar-H-tosyl, J=7.92 Hz), 7.34 (d,
4H, Ar-H-tosyl, J=7.92 Hz), 7.09 (d, 4H, Ar-Hm, J=
7.45 Hz), 6.99 (d, 4H, Ar-Hm, J=7.47 Hz), 6.90 (t, 2H,
Ar-Hp, J=7.45 Hz), 6.76 (t, 2H, Ar-Hp, J=7.47 Hz),
4.09–3.07 (m, 32H, -OCH2CH2O-), 3.81 (s, 8H, Ar-CH2-
Ar), 2.43 (s, 6H, Ar-CH3-tosyl). FAB MS m/z (M+) calcd
1067.27, found 1066.2. Compound 14. Same procedure as
for 13: 12 (2.49 mmol), TsCl (7.47 mmol), NaOH (24.9
mmol) in water (5 mL). Yellowish oil. Yield: 78%. 1H
NMR (400 MHz, CDCl3): l 7.81 (d, 4H, Ar-H-tosyl,
J=7.88 Hz), 7.33 (d, 4H, Ar-H-tosyl, J=7.88 Hz), 7.08
(d, 4H, Ar-Hm, J=7.42 Hz), 7.01 (d, 4H, Ar-Hm, J=7.47
Hz), 6.83 (t, 2H, Ar-Hp, J=7.42 Hz), 6.72 (t, 2H, Ar-Hp,
J=7.47 Hz), 4.13–3.19 (m, 36H, -OCH2CH2O-), 3.74 (s,
8H, Ar-CH2 -Ar), 2.43 (s, 6H, Ar-CH3-tosyl). 13C NMR
(100 MHz, CDCl3): 156.9, 156.5, 145.1, 134.1, 133.4,
130.2, 130.1, 128.3, 122.8, 122.5, 71.5, 71.3, 70.1, 70.0,
69.6, 69.5, 68.9, 37.9. FAB MS m/z (M+) calcd 1111.32,
found 1110.1. Dimer 2. Same procedure as for 11: 9 (0.55
g, 0.94 mmol), 13 (1.00 g, 0.94 mmol), Cs2CO3 (0.93 g,
2.85 mmol), acetonitrile (100 mL), reflux 24 h. Brownish
solid residue. Recrystallization from ethyl acetate/CHCl3
(4:1) gave 2 as a white solid. Mp 380°C (dec.). Yield:
41%. 1H NMR (400 MHz, CDCl3): l 7.18 (d, 8H, Ar-Hm,
J=7.40 Hz), 7.09 (d, 8H, Ar-Hm, J=7.46 Hz), 7.03 (t,
4H, Ar-Hp, J=7.40 Hz), 6.92 (t, 4H, Ar-Hp, J=7.46 Hz),
(1.56 mmol), Cs2CO3 (4.68 mmol), acetonitrile (100 mL),
reflux 24 h. White solid. Mp 384°C (dec.). Yield: 20%. H
1
NMR (400 MHz, CDCl3): l 7.19 (d, 8H, Ar-Hm, J=7.43
Hz), 7.09 (d, 8H, Ar-Hm, J=7.30 Hz), 7.03 (t, 4H, Ar-Hp,
J=7.30 Hz), 6.92 (t, 4H, Ar-Hp, J=7.43 Hz), 3.91 (m,
16H, Ar-CH2–Ar), 3.69–2.57 (m, 52H, -OCH2CH2O-).
13C NMR (100 MHz, CDCl3): 157.2, 156.1, 134.3, 129.4,
129.2, 123.3, 122.7, 71.4, 71.0, 69.9, 69.7, 69.3, 66.4, 38.4.
FAB MS m/z (M+) calcd 1392.6, found 1392.6. Com-
pound 15. Same procedure as for 11. Calix[4]arene13 (3.00
g, 7.07 mmol), diethyleneglycol mono-p-toluenesulfonate
(3.86 g, 14.8 mmol), K2CO3 (0.98 g, 7.07 mmol), acetoni-
trile (100 mL) were refluxed for 24 h. White solid. Recrys-
tallization from CH2Cl2/ethyl acetate (1:5) gave 15 as a
white solid. Mp 191–193°C. Yield: 44%. 1H NMR (400
MHz, CDCl3): l 9.00 (s, 2H, Ar-OH), 7.05 (d, 4H,
Ar-Hm, J=5.04 Hz), 7.01 (d, 4H, Ar-Hm, J=4.52 Hz),
6.81 (t, 2H, Ar-Hp, J=5.04 Hz), 6.66 (t, 2H, Ar-Hp,
J=4.52 Hz), 4.74 (broad s, 2H, -OH), 4.43 (d, 4H,
Ar-CH2-Ar, J=13.12 Hz), 4.17 (broad s, 8H,
-
OCH2CH2O-), 3.81 (broad s, 8H, -OCH2CH2O-), 3.40
(d, 4H, Ar-CH2-Ar, J=13.12 Hz). 13C NMR (100 MHz,
CDCl3): 152.6, 151.9, 134.7, 131.5, 129.7, 129.1 126.5,
120.6, 76.3, 74.2, 70.3, 62.7, 31.7. FAB MS m/z (M+)
calcd 600.70, found 601.2. Compound 16. Same procedure
as for 11. 15 (2.00 g, 3.33 mmol), diethylene-glycol mono-
p-toluenesulfonate (2.82 g, 6.66 mmol), Cs2CO3 (3.25 g,
9.99 mmol), acetonitrile (100 mL), reflux 24 h. White
solid. Recrystallization from CH2Cl2/ethyl acetate (1:5)
1
gave 12 as a white solid. Mp 198–201°C. Yield: 73%. H
NMR (400 MHz, CDCl3): l 7.13 (d, 8H, Ar-Hm, J=6.69
Hz), 6.91 (t, 4H, Ar-Hp, J=6.69 Hz), 3.82 (s, 8H, Ar-
CH2-Ar), 3.78 (broad s, 4H, -OH), 3.72 (broad s, 16H,
-OCH2CH2O-), 3.62 (broad s, 16H, -OCH2CH2O-). FAB
MS m/z (M+) calcd 776.9, found 777.3. Compound 17.
Same procedure as for 13. 16 (2.00 g, 2.52 mmol), TsCl
(2.16 g, 11.4 mmol), THF (100 mL), NaOH (1.01 g, 25.2
mmol) dissolved in water (5 mL). Colorless oil. Column
chromatography on silica gel using CH2Cl2/methanol
1
(19:1) as eluent gave 17 as a colorless oil. Yield: 85%. H
NMR (400 MHz, CDCl3): l 7.80 (d, 8H, Ar-H-tosyl,
J=7.20 Hz), 7.32 (d, 8H, Ar-H-tosyl, J=7.20 Hz), 6.97
(d, 8H, Ar-Hm, J=7.14 Hz), 6.64 (t, 4H, Ar-Hp, J=7.14
Hz), 4.18 (s, 8H, Ar-CH2-Ar), 3.66–3.46 (m, 32H, -
OCH2CH2O-), 2.42 (s, 12H, Ar-CH3). 13C NMR (100
MHz, CDCl3): 156.5, 145.5, 134.2, 133.7, 130.5, 128.6,
122.7, 71.0, 70.9, 70.0, 69.3, 36.7, 22.3. FAB MS m/z
(M+) calcd 1393.6, found 1393.5. Trimer 6: 17 (3.00 g,
2.15 mmol), 9 (2.51 g, 4.30 mmol), Cs2CO3 (4.21 g, 12.9
mmol), acetonitrile (100 mL) were refluxed for 24 h. After
evaporation, the resulting solid was dissolved in CHCl3
(100 mL) and 5% aqueous HCl (100mL). The organic
layer was washed three times with water and dried over
anhydrous MgSO4. After filtration and evaporation the
obtained white solid was recrystallized from CHCl3/ethyl
acetate (1:2) to give 6 as a white solid. Mp 348–351°C
3.91 (s, 16H, Ar-CH2-Ar), 3.60–2.54 (m, 48H,
-
OCH2CH2O-). 13C NMR (100 MHz, CDCl3): 156.7,
156.1, 134.3, 129.2, 129.1 129.0, 123.3, 122.6, 73.0, 70.9,
70.1, 69.2, 68.5, 66.4, 38.3. FAB MS m/z (M+) calcd.
1305.5, found 1305.3. Dimer 3. Same procedure as for 11.
10 (0.94 mmol), 13 (0.94 mmol), Cs2CO3 (2.82 mmol),
acetonitrile (100 mL), reflux 24 h. Brownish residue.
Column chromatography on silica gel using ethyl acetate
as an eluent followed by recrystallization from diethyl
ether/CHCl3 (4:1) gave 4 as a white solid. Mp 395°C
1
(dec.). Yield: 35%. H NMR (400 MHz, CDCl3): l 7.19
1
(d, 8H, Ar-Hm, J=7.38 Hz), 7.11–7.01 (m, 8H, Ar-Hm;
4H Ar-Hp), 6.95–6.89 (m, 4H, Ar-Hp), 3.90 (s, 16H,
Ar-CH2 -Ar), 3.68–2.54 (m, 52H, -OCH2CH2O-); 13C
NMR (100 MHz, CDCl3): 156.7, 156.1, 134.3, 129.2,
129.1 129.0, 123.3, 122.6, 73.0, 71.0, 69.9, 69.3, 68.5, 66.3,
38.3. FAB MS m/z (M+) calcd 1348.6, found 1349.5.
Dimer 4. Same procedure as for 11. 10 (1.56 mmol), 14
(dec.). Yield: 25%. H NMR (400 MHz, CDCl3): l 7.18
(dd, 16H, Ar-Hm, J=38, J=7.12), 7.11–7.00 (m, 8H,
Ar-Hm; 8H, Ar-Hp), 6.95 (t, 4H, Ar-Hp, J=7.75 Hz),
3.97–3.87 (m, 24H, Ar-CH2-Ar), 3.59–3.53 (m, 16H,
-OCH2CH2O-diethyleneglycol spacers; 16H, -OCH2-
CH2O-crown-5), 3.39 (t, 8H, -OCH2CH2O-crown-5, J=
6.13 Hz), 3.07 (t, 8H, - OCH2CH2O-crown-5, J=6.38

S. K. Kim et al. / Tetrahedron Letters 44 (2003) 805–809
809
Hz), 2.56–2.53 (m, 16H, -OCH2CH2O- diethyleneglycol
spacers). 13C NMR (100 MHz, CDCl3): 156.8, 156.3,
156.1, 134.4, 129.1, 128.7, 123.4, 122.7, 73.0, 71.0, 70.2,
69.3, 68.6, 66.5, 38.4. FAB MS m/z (M+) calcd 1868.9,
found 1869.9. Trimer 7: Same procedure as for 16: with
the same molar quantities. White solid. Mp 381–392°C
(dec.). Yield: 34%. 1H NMR (400 MHz, CDCl3): l
7.21–7.18 (dd, 16H, Ar-Hm, J=6.09 Hz, J=6.35 Hz),
7.10–7.02 (m, 8H, Ar-Hm; 8H, Ar-Hp), 6.92 (t, 4H,
Ar-Hp, J=6.69 Hz), 3.94 (d, 24H, Ar-CH2-Ar, J=13.24
Hz), 3.68 (s, 8H, -OCH2CH2O-crown-6), 3.62–3.54 (m,
16H, -OCH2CH2O-diethyleneglycol spacers; 16H,
-OCH2CH2O-crown-6), 3.38 (t, 8H, -OCH2CH2O-crown-
6, J=3.79 Hz), 3.23 (t, 8H, -OCH2CH2O-crown-6, J=
5.84 Hz), 2.59–2.51 (m, 16H, -OCH2CH2O- diethylene-
glycol spacers). 13C NMR (100 MHz, CDCl3): 157.6,
156.7, 156.5, 134.7, 129.7, 129.1, 123.3,123.0, 71.8, 71.4,
70.3, 70.1, 69.7, 38.8. FAB MS m/z (M+) calcd 1958.3,
found 1958.5. Compound 18: Same procedure as for 11:
calix[4]arene (2.00 g, 4.71 mmol), 13 (5.03 g, 4.71 mmol),
K2CO3 (0.65 g, 4.71 mmol), acetonitrile (100 mL), reflux
24 h. Brownish solid. Column chromatography on silica
gel using ethyl acetate/hexane (1:1) as eluent and recrys-
tallization from ethyl acetate gave 18 as a white solid. Mp
321–329°C (dec.). Yield: 40%. 1H NMR (400 MHz,
CDCl3): l 8.34 (broad s, 2H, Ar-OH), 7.13–6.92 (m,
12H, Ar-Hm; 4H, Ar-Hp), 6.81–6.78 (m, 2H, Ar-Hp),
6.66–6.62 (m, 2H, Ar-Hp), 4.40 (d, 4H, Ar-CH2-Ar,
J=14.31 Hz), 4.18–4.17 (broad t, 4H, -OCH2CH2O-),
3.95–3.92 (m, 8H, Ar-CH2-Ar; 4H, -OCH2CH2O-), 3.63–
3.41 (m, 4H, Ar-CH2-Ar; 16H, -OCH2CH2O-), 3.17–3.09
(m, 8H, -OCH2CH2O-). 13C NMR (100 MHz, CDCl3):
157.1, 156.9, 153.8, 152.3, 134.6, 129.8, 129.1, 126.3,
123.6, 120.0, 75.4, 73.5, 71.4, 70.9, 70.4, 68.9, 68.4, 38.8,
32.2, 30.3. FAB MS m/z (M+) calcd 1147.4, found 1147.5.
Compound 19: Same procedure as for 18: 13 (3.33 mmol),
15 (3.33 mmol), Cs2CO3 (9.99 mmol), acetonitrile (100
mL), reflux 24 h. White solid. Mp 358–365°C (dec.).
Yield: 35%. 1H NMR (400 MHz, CDCl3): l 7.22–7.19
(m, 8H, Ar-Hm), 7.11–7.02 (m, 8H, Ar-Hm; 4H, Ar-Hp),
6.93 (t, 4H, Ar-Hp, J=7.60 Hz), 3.93 (broad s, 16H,
Ar-CH2-Ar), 3.65–3.40 (m, 32H, -OCH2CH2O-), 3.21 (t,
4H, -OCH2CH2O-crown-5, J=4.77 Hz), 3.04 (t, 4H,
-OCH2CH2O-crown-5, J=6.53 Hz), 2.66–2.57 (m, 8H,
-OCH2CH2O-diethyleneglycol spacers). FAB MS m/z
(M+) calcd 1323.6, found 1323.9. Compound 20: Same
procedure as for 13: 19 (1.51 mmol), TsCl (4.53 mmol),
THF (100 mL), NaOH (15.1 mmol) in water (5 mL).
Colorless oil. Yield: 78%. 1H NMR (400 MHz, CDCl3): l
7.82–7.80 (d, 4H, Ar-H-tosyl, J=7.76 Hz), 7.35–7.33 (d,
4H, Ar-H-tosyl, J=7.76 Hz), 7.19–7.17 (m, 8H, Ar-Hm),
7.10 (d, 4H, Ar-Hm, J=7.39 Hz), 7.05–6.99 (m, 4H,
Ar-Hm; 4H, Ar-Hp), 6.94 (t, 2H, Ar-Hp, J=7.39 Hz),
6.82 (t, 2H, Ar-Hp, J=7.41 Hz), 4.04 (broad s, 4H,
-OCH2CH2O-), 3.97–3.82 (m, 16H, Ar-CH2 –Ar), 3.60–
3.03 (m, 36H, -OCH2CH2O-), 2.57–2.56 (m, 8H,
-OCH2CH2O-diethyleneglycol spacers). 13C NMR (100
MHz, CDCl3): 156.8, 156.1, 145.1, 134.3, 133.4, 130.2,
130.1, 129.3, 129.2, 128.9, 128.3, 123.2, 122.9, 122.6, 73.0,
70.9, 70.1, 69.2, 68.8, 66.4, 60.7, 38.6, 38.3, 38.1, 22.2,
21.4. Tetramer 7: 20 (1.00 g, 0.61 mmol), 18 (0.70 g, 0.61
mmol), Cs2CO3 (0.60 g, 1.83 mmol), acetonitrile (100 mL)
were refluxed for 24 h. Work-up procedure was the same
as for 6. White solid. Mp 338–345°C (dec.). Yield: 81%.
1H NMR (400 MHz, CDCl3): l 7.19 (broad s, 12H,
Ar-Hm), 7.09–7.03 (m, 20H, Ar-Hm; 4H, Ar-Hp), 6.95–
6.91 (m, 12H, Ar-Hp,), 3.95–3.87 (m, 32H, Ar-CH2-Ar),
3.57–3.54 (m, 24H, -OCH2CH2O-diethyleneglycol spac-
ers; 16H, -OCH2CH2O-crown-5), 3.39 (broad s, 8H,
-OCH2CH2O-crown-5), 3.06 (broad s, 8H, -OCH2CH2O-
crown-5), 2.56–2.50 (m, 24H, -OCH2CH2O- diethylene-
glycol spacers). 13C NMR (100 MHz, CDCl3): 157.1,
156.6, 156.5, 134.7, 130.1, 129.6, 129.4, 129.1, 123.7,
123.3, 73.4, 71.3, 70.5, 69.6, 68.9, 66.8, 38.7. FAB MS
m/z (M+) calcd 2434.9, found 2433.8. Pentamer 8: 17
(1.00 g, 0.72 mmol), 18 (1.65 g, 1.44 mmol), Cs2CO3 (0.94
g, 2.87 mmol), acetonitrile (100 mL) were refluxed for 24
h. Work-up procedure was same as for 6. White solid.
Mp 369–385°C (dec.).Yield: 37%. 1H NMR (400 MHz,
CDCl3): l 7.18 (broad s, 20H, Ar-Hm), 7.09 (m, 20H,
Ar-Hm; 10H, Ar-Hp), 6.93 (m, 10H, Ar-Hp), 3.95 (broad
m, 40H, Ar-CH2-Ar), 3.55 (broad s, 32H, -OCH2CH2O-
diethyleneglycol spacers; 16H, -OCH2CH2O-crown-5),
3.39 (broad s, 8H, -OCH2CH2O-crown-5), 3.05 (broad s,
8H, -OCH2CH2O-crown-5), 2.53 (broad m, 32H,
-OCH2CH2O- diethyleneglycol spacers). 13C NMR (100
MHz, CDCl3): 155.6, 133.8, 133.6, 128.8, 123.5, 72.3,
70.3, 69.6, 68.8, 68.2, 40.6, 40.4, 40.2, 40.0,39.8, 39.5,
37.8. FAB MS m/z (M+) calcd 2999.6, found 2999.1.
13. Gutsche, C. D.; Levine, J. A.; Sujeeth, P. K. J. Org.
Chem. 1985, 50, 5802–5806.
14. Jaime, C.; de Mendoza, J.; Prados, P.; Nieto, P. M.;
Sanchez, C. J. Org. Chem. 1991, 56, 3372–3376.