[2]Catenane Assembly from Calix[4]arene Crown Ethers

Article abstract of DOI:10.1021/jo000196l

A variety of novel calix[4]arene-incorporating crown ethers with or without intramolecular hydrogen bonding have been prepared by two efficient methods and utilized as donor rings to assemble calix[4]arene [2]catenanes based on π-stacking interaction between hydroquinone and bipyridinium units. Treatment of calix[4]arene crown ethers 4, 10a, or 10b, whose cone conformation was fixed by intramolecular hydrogen bonding within the calix[4]arene moiety, with dicationic salt 15·2PF₆ and dibromide 16 afforded the corresponding [2]catenanes 17a·4PF₆, 17b·4PF₆, and 17b·4PF₆in 20%, 53%, and 55% yields, respectively, whereas from the reactions of 15·2PF⁶and dibromide 16 in the presence of conformationally flexible 11 or 12 with a cone conformation kept by two propyl groups, [2]catenanes 18-4PF₆ and 19-4PF₆ were obtained in 12% and 6% yields. [2]Catenanes 21a· 4Cl, 21b·4Cl, and 21c·4Cl, incorporating calix[4]arene in both the donor and acceptor rings, were also successfully assembled from 10a or 10b, 16, and dicationic salts 20a·2PF₆ or 20b·2PF₆. The dynamic ¹H NMR and absorption spectra of the [2]catenanes have been investigated, which revealed a strongest donor-acceptor interaction in 17a·4PF₆ and that the cone [2]catenanes 17a-c·4PF₆ can isomerize to the partial cone isomer at high temperature. The difference of the dynamic properties of these catenanes was discussed. The results demonstrate that catenation is one new general method to change the conformational distributions of calix[4]arenes.

Full text of DOI:10.1021/jo000196l

5136
J . Org. Chem. 2000, 65, 5136-5142
[2]Ca ten a n e Assem bly fr om Ca lix[4]a r en e Cr ow n Eth er s
Zhan-Ting Li,*,† Xiu-Lian Zhang,† Xiong-Dong Lian,† Yi-Hua Yu,† Yi Xia,† Cheng-Xue Zhao,‡
Zhang Chen,† Zhi-Ping Lin,† and Huan Chen‡
Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences, 354 Fenglin Lu,
Shanghai 200032, China, and School of Chemistry and Chemical Engineering, Shanghai J iaotong
University, 800 Dongchuan Lu, 200240 Shanghai, China
ztli@pub.sioc.ac.cn
Received February 11, 2000
A variety of novel calix[4]arene-incorporating crown ethers with or without intramolecular hydrogen
bonding have been prepared by two efficient methods and utilized as donor rings to assemble calix-
[4]arene [2]catenanes based on π-stacking interaction between hydroquinone and bipyridinium units.
Treatment of calix[4]arene crown ethers 4, 10a , or 10b, whose cone conformation was fixed by
intramolecular hydrogen bonding within the calix[4]arene moiety, with dicationic salt 15‚2P F 6
and dibromide 16 afforded the corresponding [2]catenanes 17a ‚4P F 6, 17b‚4P F 6, and 17c‚4P F 6 in
20%, 53%, and 55% yields, respectively, whereas from the reactions of 15‚2P F 6 and dibromide 16
in the presence of conformationally flexible 11 or 12 with a cone conformation kept by two propyl
groups, [2]catenanes 18‚4P F 6 and 19‚4P F 6 were obtained in 12% and 6% yields. [2]Catenanes 21a ‚
4Cl, 21b‚4Cl, and 21c‚4Cl, incorporating calix[4]arene in both the donor and acceptor rings, were
also successfully assembled from 10a or 10b, 16, and dicationic salts 20a ‚2P F 6 or 20b‚2P F 6. The
dynamic 1H NMR and absorption spectra of the [2]catenanes have been investigated, which revealed
a strongest donor-acceptor interaction in 17a ‚4P F 6 and that the cone [2]catenanes 17a -c‚4P F 6
can isomerize to the partial cone isomer at high temperature. The difference of the dynamic
properties of these catenanes was discussed. The results demonstrate that catenation is one new
general method to change the conformational distributions of calix[4]arenes.
In tr od u ction
self-assembling efficiency and dynamic properties of the
corresponding catenanes. Therefore we had decided to
further explore the possibility of incorporating the calix-
[4]arene moiety into the donor rings, not only to inves-
tigate the scope and limitations of cali[4]xarene catenane
assembly, but also to study the effect of calixarene
moieties on the dynamic properties of the corresponding
catenanes and the effect of catenation on calixarene
conformational distribution. In the present work we
Following crown ethers and cyclodextrins, calixarenes1
and their derivatives are enjoying a burgeoning role in
host-guest and supramolecular chemistry.2 In particular
calix[4]arenes and their derivatives provide a versatile
platform of well-defined shape for construction of sophis-
ticated and functional structures.3,4 For example, calix-
[4]arene moieties have been incorporated into multiple
systems,5,6 connected to porphyrins,7 crown ethers,8
fullerenes,9 and cyclodextrins.10 We recently reported the
synthesis of one new class of calix[4]arene [2]catenanes,11
in which the calix[4]arene moiety was incorporated into
the tetracationic acceptor rings, by using the donor-
acceptor interaction principle12 and found that the exist-
ence of the calix[4]arene moiety has significant effect on
(6) (a) Shimizu, K. D.; Rebek, J ., J r. Proc. Natl. Acad. Sci. U.S.A.
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meester, J . Chem. Eur. J . 1997, 3, 1823. (d) Mogck, O.; Pons, M.;
Bo¨hmer, V.; Vogt, W. J . Am. Chem. Soc. 1997, 119, 5726. (d) Castellano,
R. K.; Rebek, J ., J r. J . Am. Chem. Soc. 1998, 120, 3657. (e) Neri, P.;
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M. F.; Petringa, A. J . Org. Chem. 1998, 63, 9703. (b) Reynier, N.; Dozol,
J .-F.; Saadioui, M.; Asfari, Z.; Vicens, J . Tetrahedron Lett. 1998, 39,
6461.
† Chinese Academy of Sciences.
‡ Shanghai J iaotong University.
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Bo¨hmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713. (c) Gutsche,
C. D. Calixarene Revisited; RSC: Cambridge, 1998.
(2) (a) Lehn, J .-M. Supramolecular Chemistry: Concepts and Per-
spectives; VCH: Weinheim, 1995. (b) Comprehensive Supramolecular
Chemistry; Atwood, J . L., Davies, J . E. V., MacNicol, D. D., Vo¨gtle, F.,
Eds.; Pergamon: Oxford, U.K., 1996; 11 Vols.
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Trans. 1 1998, 179.
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1088. (b) Lhota´k P.; Shinkai, S. J . Synth. Org. Chem. J pn. 1995, 53,
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Lett. 1994, 31, 7131. (b) Takeshita, M.; Suzuki, T.; Shinkai, S. J . Chem.
Soc., Chem. Commun. 1994, 2587. (c) Casnati, A.; Pochini, A.; Ungaro,
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Van Hoek, A.; Nolte, R. J . M.; Engbersen, J . F. J .; Reinhoudt, D. N. J .
Am. Chem. Soc. 1999, 121, 28. (b) Buegler, J .; Engbersen, J . F. J .;
Reinhoudt, D. N. J . Org. Chem. 1998, 63, 5339.
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10.1021/jo000196l CCC: $19.00 © 2000 American Chemical Society
Published on Web 07/29/2000

[2]Catenane Assembly from Calix[4]arene Crown Ethers
J . Org. Chem., Vol. 65, No. 17, 2000 5137
Sch em e 1a
Sch em e 2a
a
Key: (i) ClCH2CH2OTs, K2CO3, MeCN, 80 °C, 65%; (ii) K2CO3,
MeCN, 80 °C, 36%; (iii) MeI, NaH, THF, 40 °C, 95%; (iv) n-PrBr,
K2CO3, THF, 65 °C, 35%.
a
Key: (i) ClCH2CH2OCH2CH2OH, K2CO3, MeCN, 80 °C, 74%;
(ii) TsCl, pyridine, CHCl3, 0 °C, 82%; (iii) K2CO3, MeCN, 80 °C,
34% (10a ) and 40% (10b); (iv) MeI, NaH, THF, 40 °C, 98%; (v)
n-PrBr, K2CO3, THF, 65 °C, 38%.
report the assembly and spectral investigation of eight
novel calix[4]arene [2]catenanes, in all of which one calix-
[4]arene moiety is incorporated into the donor ring.
Sch em e 3a
Resu lts a n d Discu ssion
Syn th esis of Ca lix[4]a r en e Cr ow n Eth er s. A va-
riety of calix[4]arene crown ethers with different func-
tional groups at the lower and/or upper rims of the
calix[4]arene moiety have been synthesized. In all these
compounds, the calix[4]arene unit is linked to two hy-
droquinone units through two ether chains with the same
length. Two methods have been developed for preparation
of calix[4]arene crown ethers with two free hydroxyl
groups at the lower rim. The route that leads to com-
pounds 4-6 is outlined in Scheme 1. Thus, calix[4]arene
1 was first converted to 2 with 2-chloroethyl tosylate.
Compound 2 then reacted with diol 3 with potassium
carbonate as a base, to afford calix[4]arene crown ether
4. Compound 4 reacted with methyl iodide or propyl
bromide in the presence of sodium hydride, giving
compounds 5 or 6, respectively.
Treatment of calix[4]arene 1 or 7 with ditosylate 9 in
acetonitrile in the presence of potassium carbonate could
result in the formation of calix[4]arene crown ethers 10a
or 10b. Compound 9 could be prepared conveniently
starting from 3 through intermediate 8. Under the
similar conditions as for preparing 5 and 6, compounds
11 and 12 were also prepared from 10a (Scheme 2). Calix-
[4]arene crown ether 10a could also be prepared through
another route (Scheme 3). Thus, calix[4]arene 1 first
reacted with excessive (2-chloroethoxy)ethanol to afford
intermediate 13, which was then ditosylated to give calix-
[4]arene derivative 14. Treatment of compound 14 with
diol 3 in the presence of potassium carbonate resulted
in the formation of 10a . It is worthwhile to note that
conversion of 13 to 14 was selective and the phenol
hydroxyl was not tosylated during the reaction.
a
Key: (i) ClCH2CH2OCH2CH2OH, K2CO3, MeCN, 80 °C, 74%;
(ii) TsCl, pyridine, CHCl3, 0 °C, 71%; (iii) 3, K2CO3, MeCN, 80 °C,
42%.
tional isomers at rapid equilibrium. The cone conforma-
tion of 6 and 12 were inferred from their 1H NMR
spectra.14,15
The possibility to prepare the tetraalkylated calix[4]-
arene derivatives from reactions of the readily available
1,3-dimethoxyl or 1,3-dipropoxy derivatives16 of 1 or 7
with compound 3 were also investigated, but no expected
products were generated. These reactions only gave
undissolved oligomers. This observation, together with
the fact that 4, 10a , and 10b could be prepared in
acceptable yields, demonstrates that the hydrogen bond-
ing at the lower rim of the calix[4]arene moiety is
indispensable for efficient formation of the macrocyclic
crown ethers, which may be attributed to the preorga-
nized U-shaped feature of the cone calix[4]arene deriva-
tives.
[2]Ca ten a n es Self-Assem bly. Catenations have been
performed under the standard reaction conditions for the
π-stacking principle.12 Thus, dicationic salt 15‚2P F 6
reacted with 16 in the presence of excessive 4, 10a or
10b in MeCN at room temperature for 7 days, to afford
[2]catenanes 17a -c‚4P F 6 in 20%, 53%, or 55% yields
after column chromatography and anionic exchange with
The calix[4]arene moiety of compounds 4, 10a and 10b
was exclusively in the cone conformation, as indicated
by their 1H NMR spectra, all of which exhibited the
typical AB system for the ArCH2Ar protons.13 As ex-
pected, compounds 5 and 11 were mixtures of conforma-
(14) The propyl group is the smallest alkyl group to suppress the
ring inversion within calix[4]arenes, see: Iwamoto, K.; Araki, K.;
Shinkai, S. J . Org. Chem. 1991, 56, 4955.
(15) Ikeda, A.; Tsudera, T.; Shinkai, S. J . Org. Chem. 1997, 62, 3568.
(16) Groenen, L. C.; Ruel, B. H.; Casnati, A.; Timmerman, P.;
Verboom, W.; Harkema, S.; Pochini, A.; Ungaro, R.; Reinhoudt, D. N.
Tetrahedron Lett. 1991, 32, 2675.
(13) Molins, M. A.; Nieto, P. M.; Sanchez, C.; Prodos, P.; de Mendoza,
J .; Pons, M. O. J . Org. Chem. 1992, 57, 6924.

5138 J . Org. Chem., Vol. 65, No. 17, 2000
Li et al.
Sch em e 4
Sch em e 5
ammonium hexafluorophosphate (Scheme 4). The calix-
[4]arene moieties in all the [2]catenanes were in the cone
1
conformation as indicated by their H NMR spectra. No
catenanes, in which calix[4]arene was in other conforma-
tions, were obtained from the reactions. The remarkably
higher yields of 17b‚4P F 6 and 17c‚4P F 6, compared with
17a ‚4P F 6, demonstrated that the spatial separation
between the hydroquinone units in 10a and 10b were
more suitable for efficient π-stacking than that in 4. Since
CPK molecular model analysis showed that, if hydrogen
bonding in calix[4]arene was not considered, both 4 and
10a and 10b displayed very changeable spatial separa-
tions between the hydroquinones, the above observations
implied that the hydrogen bonding in 4, 10a , and 10b
played a significant role to hold the hydroquinones to a
relatively fixed distance.
Stirring a solution of 15‚2P F 6, 16, and 5 or 6 in
acetonitrile or N,N-dimethylformamide at room temper-
ature for a long time (21 days) did not afford any
detectable amount of catenane products, whereas treat-
ment of 15‚2P F 6 and 16 with excessive 11 or 12 could
result in formation of [2]catenanes 18‚4P F 6 or 19‚4P F 6
in 12% or 6% yields, respectively (Scheme 5). These
results once again demonstrated that the hydrogen
bonding within the calix[4]arene moiety was crucial to
efficient donor-acceptor interaction. The low assembling
efficiency of 18‚4P F 6 might be the result of rapid con-
formational isomerization of the calix[4]arene moiety,
which was unfavorable for efficient π-stacking by produc-
ing spatial hindrance and raising the flexibility of the
donor ring. The low yield of 19‚4P F 6 from the precursor
12, relative to that of 17b‚4P F 6 and 17c‚4P F 6 from 10a
and 10b, reflected the unique function of the hydrogen
bonding within the calix[4]arene unit to promote self-
assembly. It was reasonable to assume that the ring of
the cone 12, formed by large alkyl groups, was more
flexible than that of the cone 10a , induced by intramo-
lecular hydrogen bonding. The spatial hindrance from the
propyl groups in 12 should be, if any, small since a CPK
model investigation showed that their spatial distance
to hydroquinones was long enough. As expected, the
calix[4]arene in 18‚4P F 6 was a mixture of conformational
isomers at rapid equilibrium, while the cone conformation
of the calix[4]arene moiety in 19‚4P F 6 was kept un-
changed.
Three [2]catenanes 21a ‚4Cl, 21b‚4Cl, and 21c‚4Cl,
which had one calix[4]arene unit in both the donor and
acceptor rings, were assembled in 14%, 12%, and 15%
yields as pale yellow solids from the reactions of dicat-
ionic precursors 20a ‚2P F 6 or 20b‚4P F 611b with 16 in the
presence of excessive 10a or 10b albeit after a prolonged
time (Scheme 6). The yields are acceptable considering
that both donor and acceptor precursors are more flexible
than the model reaction precursors,12 probably reflecting
the preorganization feature of U-shaped 20a ‚2P F 6 or
20b‚4P F 6, which had been proved to promote formation
of calix[4]arene [2]catenanes.11b The 1H NMR spectra
showed that, for all these three [2]catenanes, the cone
conformation of the calix[4]arene subunits in both the
donor and acceptor rings were unchanged. Under the
same reaction conditions, no similar catenanes were
obtained from 4.
1H NMR Sp ectr a . The solution-state properties of the
calix[4]arene [2]catenanes have been investigated by
1
1
dynamic H NMR spectroscopy. The H NMR spectra of
17a -c‚4P F 6, 18‚4P F 6, and 19‚4P F 6 display temperature
dependence between 223 and 393 K as a result of the
dynamic processes shown in Figure 1. The first process
involves the circumrotation of the tetracationic cyclo-
phane through the cavity of the macrocyclic calix[4]arene
polyether and the second one involves the circumrotation
of the calix[4]arene polyether through the cavity of the
tetracationic cyclophane. The kinetic and thermodynamic
data associated with the two processes are showed in
Table 1.17 It can be found that, although all the activation
barriers to both processes are reduced compared to that
of the “parent” [2]catenane,12 [2]catenane 17a ‚4P F 6
exhibits a higher activation barrier value associated to
the second process, implying that the donor-acceptor
interaction in this [2]catenane is stronger.
(17) The coalescence method (Sandstroom, J . Dynamic NMR Spec-
troscopy; Academic Press: New York, 1982) uses the expression Kc )
π(∆ν)/21/2 to approximate the rotation rate at the coalescence temper-
ature Tc, where ∆ν is the limiting chemical shift difference (Hz)
between coalescing signals in the absence of exchange. Free energy of
*
activation ∆Gc was calculated with the Eyring equation.

[2]Catenane Assembly from Calix[4]arene Crown Ethers
J . Org. Chem., Vol. 65, No. 17, 2000 5139
Sch em e 6
The possibility of conformational change of the calix-
[4]arene units in these [2]catenanes at high temperature
have also been explored by H NMR spectroscopy. The
F igu r e 1. Dynamic processes associated with calix[4]arene
[2]catenanes.
1
1H NMR spectrum of 17a ‚4P F 6 in DMSO-d6 began to
exhibit signals of the partial cone conformer at above 115
°C, which could be inferred by the typical signals for the
aromatic protons of the calix[4]arene moiety (Figure
2).13-15 The ratio of the partial cone conformer with the
cone conformer rose and reached to a value of ∼0.35 at
130 °C, according to their signal intensities. When the
temperature decreased, the partial cone conformer isomer-
ized to the cone one gradually. Similar isomerization was
also observed for [2]catenanes 17b‚4P F 6 and 17c‚4P F 6
albeit emerging at the higher temperature of ∼125 °C.
The ratio of the partial cone isomer with the cone one
could reach ∼0.15 and 0.20 for these two compounds at
the available temperature of 130 °C. No signals of the
1,3-alternate conformer were observed for all the three
[2]catenanes. Between the investigated temperature
range, no such isomerization was observed for free calix-
[4]arene crown ethers 4, 10a , and 10b, therefore the
conformational isomerization in 17a -c‚4P F 6 must have
been induced by the tetracationic cyclophane in these
compounds. The lower isomerizaiton temperature dis-
played by 17a ‚4P F 6 shows that there exists a larger
spatial interaction between its tetracationic cyclophane
and calix[4]arene moiety, as a result of its smaller donor
ring. Such conformational isomerization has also been
found in [2]catenanes, in which one calix[4]arene was
incorporated into the acceptor ring, although in those
systems the 1,3-alternate conformer could also be
generated.11b Therefore these results appear to indicate
that catenation represents one new unique method to
affect or control the conformation of calix[4]arene deriva-
tives, which may find applications for future supramo-
lecular design.
F igu r e 2. Conformational isomerization of 17a -c‚4P F 6.
within both the donor and acceptor did not isomerize to
other conformers at ∼120 °C when they began to decom-
pose. These results may reflect the expanded cavity size
and higher flexibility of the two components of these [2]-
catenanes and consequently catenation does not have
substantial effect on the hydrogen bonding within both
the donor and acceptor calix[4]arenes.
Electr on ic Absor p tion Sp ectr a . The charge-transfer
behavior of all the calix[4]arene [2]catenanes has been
investigated by UV-absorption spectroscopy. A summary
of their absorption data, characteristic of the donor-
acceptor interactions between the bipyridinium and
hydroquinone units, is presented in Table 2. It can be
observed that all the molar extinction coefficients at the
charge-transfer absorption maxima are smaller than
those of the “parent” [2]catenane (λmax 478 nm, ꢀ 700 M-1
cm-1),12 indicating a reduced donor-acceptor interaction
within these calix[4]arene [2]catenanes. This observation
is consistent with the above 1H NMR investigations.
However, although the assembling efficiency of 17a ‚4P F 6
is not so high as that of 17b‚4P F 6 or 17c‚4P F 6, it exhibits
the highest molar extinction coefficients. This may be
attributed to the narrower spatial separation between the
hydroquinones of its donor component and consequently
more efficient donor-acceptor interaction with the dipy-
ridinium unit. The fact that [2]catenanes 21a -c‚4Cl
exhibit much lower values reflects that there exists very
weak π-stacking interaction in these catenanes.
Although some distinct chemical shifts were also
displayed for [2]catenanes 21a -c‚4Cl, no coalescence
temperature could be observed between the investigated
temperature range to determine the exchange rates and
free energy barriers. The cone calix[4]arene moieties

5140 J . Org. Chem., Vol. 65, No. 17, 2000
Li et al.
Ta ble 1. Kin etic a n d Th er m od yn a m ic P a r a m eter s for th e Dyn a m ic P r ocesses of F igu r e 1 Associa ted w ith Som e
Ca lix[4]a r en e [2]Ca ten a n es
b
catenane
probe proton
∆ν (Hz)a
kc (s-1
)
Tcc (K)
∆Gqd (kcal mol-1
)
processe
solvent
17a ‚4P F 6
R-CHf
60
70
725
45
86
1050
50
1072
65
55
1120
73
906
96
133
155
1610
100
190
2332
111
2380
144
122
2487
162
2011
213
228
233
338
223
238
328
223
333
230
233
328
228
326
236
325
11.0
11.2
14.9
10.9
11.3
14.2
10.8
14.3
11.1
11.3
14.1
10.9
14.2
11.2
14.1
1
1
2
1
1
2
1
2
1
1
2
1
2
1
2
CD3OD
CD3OD
CD3SOCD3
CD3OD
CD3OD
CD3SOCD3
CD3OD
CD3OD
CD3OD
CD3OD
CD3OD
CD3OD
CD3OD
CD3OD
CD3OD
N+CH2
OC6H4O
R-CHf
17b‚4P F 6
N+CH2
OC6H4O
R-CHf
17b‚4Cl
OC6H4O
17c‚4P F 6
R-CHf
N+CH2
OC6H4O
R-CHf
18‚4P F 6
19‚4P F 6
OC6H4O
R-CHf
OC6H4O
1025
2276
a
b
d
Error ( 2 Hz. Error ( 5 s-1 c Error ( 1 K. Error ( 0.2 kcal mol-1 e Shown in Figure 1. f Related to the pyridine protons.
. .
Ta ble 2. Ch a r ge-Tr a n sfer Absor p tion s of Ca lix[4]a r en e
[2]Ca ten a n es, Recor d ed in Meth a n ol a t Room
Tem p er a tu r e
(4.91 g, 21.0 mmol) in acetonitrile (100 mL) added. The mixture
was stirred under reflux for 48 h and the solvent removed.
The residue was triturated in chloroform (300 mL). After
workup, the product was purified by column chromatography
(chloroform/petroleum ether 1:1) to afford compound 2 (5.02
λmax
ꢀ
λmax
ꢀ
catenane (nm) (M-1 cm-1
)
catenane (nm) (M-1 cm-1
)
1
g, 65%) as a white solid: Mp: >280 °C. H NMR (CDCl3): δ
17a ‚4P F 6 460
550
415
360
165
170
17b‚4P F 6 455
420
410
375
160
0.97 (s, 18 H, CH3), 1.27 (s, 18 H, CH3), 3.32 (d, 4 H, J ) 12.9
Hz, ArCH2Ar), 3.76 (t, 4 H), 4.05 (t, 4 H), 4.23 (d, J ) 12.9 Hz,
4H, ArCH2Ar), 6.80 (s, 4 H), 7.07 (s, 4H), 7.47 (s, 2 H, OH).
EIMS: m/z 772 (M+). Anal. Calcd for C48H62Cl2O4: C, 74.49;
H, 8.09. Found: C, 74.03; H, 7.82.
17b‚4Cl
18‚4P F 6
21a ‚4Cl
21c‚4Cl
455
458
467
470
17c‚4P F 6
19‚4P F 6
21b‚4Cl
452
464
466
[25,27-Dih ydr oxy-5,11,17,23-tetr a(ter t-bu tyl)-26,28-[4,4′-
[b is[1,13-(1,4,7,10,13-p en t a oxa )t r id ecylen e]p h en ylen e]-
1,1′-oxy]eth oxyca lix[4]a r en e (4). A suspension of calix[4]-
arene 2 (7.72 g, 10.0 mmol), 312 (3.78 g, 10.0 mmol), potassium
iodide (3.32 g, 20.0 mmol), and potassium carbonate (2.76 g,
20.0 mmol) in acetonitrile (200 mL) was refluxed for 4 days.
The solvent was then removed in vacuo and the residue
quenched with 2 N hydrochloric acid (50 mL) and chloroform
(300 mL). The organic phase was washed with water and brine
and dried (MgSO4). The solvent was then distilled off, and the
resulting residue subjected to column chromatography on silica
gel (methylene chloride/ethyl acetate 5:1) to afford 4 (3.88 g,
36%) as a white solid. Mp: >260 °C. 1H NMR (CDCl3): δ 0.98
(s, 18 H), 1.28 (s, 18 H), 3.32 (d, 4 H, J ) 13.0 Hz, ArCH2Ar),
3.70 (m, 4 H), 3.82 (m, 4 H), 3.95 (m, 4 H), 4.00 (m, 4 H), 4.15
(m, 4 H), 4.36 (d, 4 H, J ) 13.0 Hz, ArCH2Ar), 6.65 (m, 8 H),
6.75 (s, 4 H), 7.02 (s, 4 H), 7.36 (s, 2 H). EIMS: m/z 1078 (M+).
Anal. Calcd for C68H86O11: C, 75.65; H, 8.05. Found: C, 75.32;
H, 8.14.
[25,27-Dim eth oxy-5,11,17,23-tetr a(ter t-bu tyl)-26,28-[4,4′-
[b is[1,13-(1,4,7,10,13-p en t a oxa )t r id ecylen e]p h en ylen e]-
1,1′-oxy]eth oxyca lix[4]a r en e (5). To a solution of 4 (1.08 g,
1.00 mmol) in dried tetrahydrofuran (50 mL) was added
sodium hydride (60%) (0.80 g, 20.0 mmol). The mixture was
stirred at room temperature for 1 h and then methyl iodide
(0.66 mL, 1.50 g) added with a syringe. The solution was
warmed at 40 °C with stirring for 24 h and then quenched
water carefully. After workup, the resulting residue was
purified by flash chromatography on silica gel (dichloromethane/
ethyl acetate 5:1), to give pure compound 5 (1.05 g) as a white
solid in 95% yield. Mp: 233-236 °C. 1H NMR (CDCl3): δ 1.05-
1.25 (m, 36 H), 3.33 (m, 4 H), 3.68-3.95 (m, 14 H), 4.15-4.36
(m, 12 H), 6.89 (m, 16 H). EIMS: m/z 1106 (M+). Anal. Calcd
for C70H90O11: C, 75.90; H, 8.21. Found: C, 76.00; H, 8.35.
Con clu sion s
A series of novel crown ethers incorporating calix[4]-
arene units have been prepared and utilized to assemble
a variety of calix[4]arene [2]catenanes. The hydrogen
bonding within the calix[4]arene moiety of the donor
rings facilitates the formation of catenane structures and
introduction of methyl groups at the calix[4]arene lower
rim will greatly reduce the assembling efficiency. The
calix[4]arene crown ether in which the cone conformation
is kept by large alkyl groups also exhibits much less
efficient templating ability. Incorporation of the calix[4]-
arene moiety into the donor ring generally reduces the
activation barrier to the dynamic processes within the
[2]catenanes, especially within [2]catenanes consisting
of two calix[4]arene-incorporating rings. The conforma-
tional isomerization exhibited by [2]catenanes 17a -c‚
4P F 6 demonstrates that catenation represents one new
principle to change or control the conformational distri-
butions of calix[4]arene derivatives.
Exp er im en ta l Section
Gen er a l Meth od s a n d Ma ter ia ls. See ref 11b.
25,27-Bis(2-ch lor oeth oxy)-26,28-d ih yd r oxy-5,11,17,23-
t et r a (ter t-b u t yl)ca lix[4]a r en e (2). A solution of chloro-
ethanol (16.0 g, 200 mmol) in chloroform (150 mL) was added
slowly with stirring to a solution of toluene-p-sulfonyl chloride
(38.0 g, 200 mmol) and pyridine (100 mL) in chloroform (300
mL), which was cooled to 0 °C. The solution was then warmed
to room temperature and stirred for 48 h and then poured into
ice-water (500 mL). The aqueous phase was extracted with
chloroform (100 mL×3) and the combined organic phase
washed and dried. After workup, 28.0 g of 2-chloroethyl
[25,27-Dip r oxy-5,11,17,23-t et r a (ter t-b u t yl)-26,28-[4,4′-
[b is[1,13-(1,4,7,10,13-p en t a oxa )t r id ecylen e]p h en ylen e]-
1,1′-oxy]eth oxyca lix[4]a r en e (Con e) (6). A solution of 4
(2.16 g, 2.00 mmol) and sodium hydride (60%, 0.80 g, 20.0
mmol) in dried tetrahydrofuran (150 mL) was stirred at room
temperature for 1 h and then propyl bromide (1.22 g, 10 mmol)
added. The solution was warmed to 65 °C with stirring and
kept at this temperature for 48 h. After cooled to room
temperature, 2 N hydrochloric acid was added dropwise to
1
tosylate was obtained in 60% yield. H NMR (CDCl3): δ 2.38
(s, 3 H), 4.07 (t, 2 H), 4.20 (t, 2 H), 7.22 (d, 2 H), 7.40 (d, 2 H).
EIMS: m/z 234 (M+). Anal. Calcd for C9H11ClO3S: C, 46.06;
H, 4.69. Found: C, 45.82; H, 4.81. A suspension of calix[4]-
arene 1 (6.48 g, 10.0 mmol) and potassium carbonate (3.04 g,
22.0 mmol) in acetonitrile (200 mL) was stirred at room
temperature for 1 h and a solution of 2-chloroethyl tosylate

[2]Catenane Assembly from Calix[4]arene Crown Ethers
J . Org. Chem., Vol. 65, No. 17, 2000 5141
quench the reaction. After workup and purification by flash
chromatography on silica gel (dichloromethane/ethyl acetate
10:1), 6 was obtained (0.87 g, 35%) as a white solid. Mp: >270
°C. 1H NMR (CDCl3): δ 0.94 (s, 18 H), 1.06 (t, 6 H), 1.26 (s, 18
H), 1.89 (m, 4 H), 3.10 (d, 4 H, J ) 13.0 Hz, ArCH2Ar), 3.70-
4.02 (m, 24 H), 4.16 (m, 4 H), 4.35 (d, 4 H), 6.60 (s, 4 H), 6.74
(d, d, 8 H), 7.16 (m, 4 H). FABMS: m/z 1162 (M+). Anal. Calcd
for C74H98O11: C, 76.38; H, 8.51. Found: C, 75.96; H, 8.42.
1,11-Bis[4-[2-(2-h yd r oxyeth oxy)eth oxy]p h en oxy]-3,6,9-
tr ioxa u n d eca n e (8). 2-(2-Chloroethoxy)ethanol (18.0 g, 145
mmol) was added to a suspension of potassium carbonate (20.0
g, 145 mmol), potassium iodide (24.1 g, 145 mmol), and 3 (16.0
g, 42.3 mmol) in acetonitrile (300 mL). The slurry was then
refluxed with stirring for 7 days and, after cooling to room
temperature, filtered. The solid was washed well with aceto-
nitrile and the solvent was removed in vacuo. The residue was
triturated in ethyl acetate and the solution washed with water,
brine, and dried (MgSO4). After the solvent was evaporated
in vacuo, the residue was purified by flash chromatography
on silica gel (methanol/chloroform, 1:20) to afford 17.3 g of
compound 8 (74%) as a colorless solid. Mp: 68-69 °C (lit.18
mp 66-68 °C). 1H NMR (CDCl3): δ 1.89 (s, 2 H), 3.72 (m, 8
H), 3.77 (m. 12 H), 3.85 (m, 8 H), 4.08 (m, 4 H), 6.84 (s, 8 H).
EIMS: m/z 554 (M+).
6.64-6.84 (m, 12 H), 6.90 (d, 4 H), 7.07 (d, 4 H), 7.86 (s, 2 H).
EIMS: m/z 942 (M+). Anal. Calcd for C56H62O13: C, 71.32; H,
6.64. Found: C, 70.94; H, 6.57.
[25,27-Dim eth oxy-5,11,17,23-tetr a(ter t-bu tyl)-26,28-[4,4′-
[b is[1,13-(1,4,7,10,13-p en t a oxa )t r id ecylen e]p h en ylen e]-
1,1′-oxy]eth oxyeth oxyca lix[4]a r en e (11). This compound
was prepared as a white solid in 98% yield by using the
procedure as described above for 5. Mp: 292 °C. 1H NMR
(CDCl3): δ 1.00-1.28 (m, 36 H), 3.31 (m, 4 H), 3.71 (m, 14 H),
3.86-3.95 (m, 8 H), 4.10-4.38 (m, 12 H), 6.70-7.02 (m, 16
H). EIMS: m/z 1194 (M+). Anal. Calcd for C74H98O13: C, 74.33;
H, 8.28. Found: C, 74.04; H, 8.32.
[25,27-Dip r oxy-5,11,17,23-t et r a (ter t-b u t yl)-26,28-[4,4′-
[b is[1,13-(1,4,7,10,13-p en t a oxa )t r id ecylen e]p h en ylen e]-
1,1′-oxy]eth oxyeth oxyca lix[4]a r en e (Con e) (12). This com-
pound was prepared as a white solid in 38% yield by using a
similar procedure as described above for 6. Mp: 200-202 °C.
1H NMR (CDCl3): δ 0.90 (s, 18 H), 1.03 (t, 6 H), 1.26 (s, 18 H),
1.99 (m, 4 H), 3.13 (d, 4 H, J ) 13.0 Hz, ArCH2Ar), 3.72 (m,
16 H), 3.89 (m, 8 H), 4.00 (m, 8 H), 4.20 (m, 4 H), 4.35 6.65 (s,
4 H), 6.74 (d, d, 8 H), 7.02 (m, 4 H). FABMS: m/z 1250 (M+).
Anal. Calcd for C78H106O13: C, 74.83; H, 8.55. Found: C, 74.60;
H, 8.42.
25,27-Bis(2-h yd r oxyeth oxy)eth oxy-26,28-d ih yd r oxy-5,-
11,17,23-tetr a (ter t-bu tyl)ca lix[4]a r en e (13). A suspension
of calix[4]arene 1 (6.46 g, 10.0 mmol), 2-(2-chloroethoxy)-
ethanol (4.96 g, 40.0 mmol), and K2CO3 (2.76 g, 20.0 mmol) in
MeCN (300 mL) was refluxed for 6 days. After workup and
purification by column chromatography on silica gel (methyl-
ene chloride/ methanol 20:1), compound 13 (6.10 g) was
1,11-Bis[4-[2-(2-tolu en e-p-su lfon yleth oxy)eth oxy]p h e-
n oxy]-3,6,9-tr ioxa u n d eca n e (9). Tosyl chloride (12.2 g, 64.2
mmol) in chloroform was added slowly with stirring to a
solution of compound 8 (11.9 g, 21.5 mmol) and triethylamine
(18.2 g, 160 mmol) in chloroform (300 mL), while the solution
was maintained at ∼0 °C. The reaction mixture was then
allowed to warm to room temperature and stirred for 48 h.
The solution was washed with 2 N hydrochloric acid, water,
and brine and finally dried (MgSO4). The solvent was evapo-
rated and the residue obtained purified by column chroma-
tography (ethyl acetate/chloroform 1:3) to give compound 9
(15.1 g) in 82% yield as a colorless oil, which solidified slowly
1
obtained as a white solid in 74% yield. Mp: 142-144 °C. H
NMR (CDCl3) δ 1.11 (s, 18 H, CH3), 1.23 (s, 18 H, CH3), 3.35
(d, 4 H, J ) 12.8 Hz, ArCH2Ar), 3.81 (m, 8 H), 4.14 (m, 8 H),
4.27 (b, 2 H), 4.40 (d, 4 H, J ) 12.8 Hz, ArCH2Ar), 7.01 (s, 4
H), 7.03 (s, 4 H), 8.90 (s, 2 H). EIMS: m/z 824 (M+). Anal.
Calcd for C52H72O8‚1.5H2O: C, 73.28; H, 8.89. Found: C, 72.98;
H, 8.56.
1
to a colorless solid. Mp: 58-60 °C. H NMR (CDCl3): δ 2.46
25,27-Bis(2-tolu en e-p-su lfon yleth oxy)eth oxy-26,28-d i-
h ydr oxy-5,11,17,23-tetr a(ter t-bu tyl)calix[4]ar en e (14). Tol-
uene-p-sulfonyl chloride (1.70 g, 9.00 mmol) in dichlo-
romethane (30 mL) was added slowly to a solution of compound
13 (3.75 g, 4.55 mmol) and pyridine (3.0 mL) in chloroform
(50 mL) at 0 °C with stirring. The solution was then allowed
to warm to room temperature and, after stirring for 72 h,
washed with 2 N of hydrochloric acid, water, and brine and
finally dried (MgSO4). The solvent was then removed. The oily
residue was subjected to column chromatography (ethyl acetate/
dichloromethane 1:10) to give 14 (3.55 g, 71%) as a colorless
solid. Mp: 122-124 °C. 1H NMR (CDCl3) δ 0.95 (s, 18 H), 1.20
(s, 18 H), 2.38 (s, 6 H), 3.88 (m, 8 H), 4.04 (m, 4 H), 4.21 (m,
4 H), 4.26 (d, 4 H, J ) 13.2 Hz, ArCH2Ar), 6.78 (s, 4 H), 7.05
(s, 4 H), 7.20 (s, 2 H), 7.22 (d, 4 H), 7.74 (d, 4 H). FABMS: m/z
1132 (M+). Anal. Calcd for C66H84O12S2: C, 70.00; H, 7.54.
Found: C, 69.77; H, 7.54.
(s, 6 h, CH3), 3.76 (m, 16 H), 3.87 (m, 4 H), 4.02 (t, 4 H), 4.13
(t, 4 H), 4.23 (t, 4 H), 6.86 (dd, 8 H), 7.35 (d, 4 H), 7.83 (d, 4
H). FABMS: m/z 862 (M+). Anal. Calcd for C42H54O15S2: C,
58.44; H, 6.32. Found: C, 58.35; H, 6.30.
[25,27-Dih ydr oxy-5,11,17,23-tetr a(ter t-bu tyl)-26,28-[4,4′-
[b is[1,13-(1,4,7,10,13-p en t a oxa )t r id ecylen e]p h en ylen e]-
1,1′-oxy]eth oxyeth oxyca lix[4]a r en e (10a ). Meth od A. A
suspension of 1 (6.48 g, 10.0 mmol), 9 (8.62 g, 10.0 mmol), and
potassium carbonate (2.76 g, 20.0 mmol) in acetonitrile (200
mL) was refluxed for 4 days. The solvent was then removed
in vacuo and the residue quenched with 2 N hydrochloric acid
(50 mL) and chlorform. The organic phase was washed with
water and then dried (MgSO4). The solvent was then distilled
off and the resulting residue subjected to column chromatog-
raphy on silica gel (methylene chloride/ethyl acetate 5:1) to
1
give 10a (3.96 g, 34%) as a white solid. Mp: 285 °C. H NMR
(CDCl3): δ 0.96 (s, 18 H), 1.30 (s, 18 H), 3.31 (d, 4 H, J ) 13.5
Hz, ArCH2Ar), 3.71 (m, 8 H), 3.84 (m, 4 H), 3.97 (m, 4 H), 4.06
(m, 8 H), 4.15 (m, 4 H), 4.38 (d, 4 H, J ) 13.5 Hz, ArCH2Ar),
6.68 (m, 8 H), 6.73 (s, 4 H), 7.06 (s, 4 H), 7.34 (s, 2 H). EIMS:
m/z 1166 (M+). Anal. Calcd for C72H94O13: C, 74.06; H, 8.13.
Found: C, 74.22; H, 8.19. Meth od B. A suspension of 3 (1.89
g, 5.00 mmol), 14 (5.50 g, 5.0 mmol), and potassium carbonate
(1.38 g, 10.0 mmol) in acetonitrile (200 mL) was refluxed for
48 h. After workup, 10a was obtained in 42% yield.
[25,27-Dih yd r oxy-26,28-[4,4′-[bis[1,13-(1,4,7,10,13-p en -
taoxa)tr idecylen e]ph en ylen e]-1,1′-oxy]eth oxyeth oxycalix-
[4]a r en e (10b). This compound was prepared in 40% yield
as a white solid from the reaction of calix[4]arene 7 and
compound 9, as described for preparing 10a by method A.
Mp: 272 °C. 1H NMR (CDCl3): δ 3.37 (d, 4 H, J ) 13.5 Hz,
ArCH2Ar), 3.71 (m, 8 H), 3.84 (m, 4 H), 3.97 (m, 4 H), 4.07 (m,
12 H), 4.18 (m, 4 H), 4.42 (d, 4 H, J ) 13.5 Hz, ArCH2Ar),
[2]Ca ten a n e 17a ‚4P F 6. To the solution of calix[4]arene
crown ether 4 (1.62 g, 1.50 mmol) in acetonitrile (50 mL) was
added dicationic salt 15‚2P F 6 (210 mg, 0.33 mmol) and
dibromide 16 (103 mg, 0.40 mmol). After the solution was
stirred at 25 °C for 7 days, the solvent was removed in vacuo.
The remaining residue was triturated in CH2Cl2 and filtrated.
The residue was subjected to column chromatography on silica
gel (MeOH-2 N NH4Cl-MeNO2 7:2:1). The orange product
fractions were combined and taken to dryness. The residue
obtained was dissolved in warm water, saturated NH4PF6
solution was added until no more precipitate formed. The
precipitate was filtrated, washed with water, and dried. It was
then recrystallyzed from MeOH-Me2CO-H2O to give 17a ‚4P F 6
1
(144 mg, 20%) as an orange solid. Mp: 250 °C dec. H NMR
(CD3OD): δ 0.92 (s, 18 H), 1.33 (s, 18 H), 3.22 (d, 4 H), 3.42
(m, 8 H), 4.10 (m, 16 H), 4.34 (d, 4 H), 4.52 (m, 4 H), 5.99 (s,
8 H), 6.24 (br 8 H), 6.73 (s, 4 H), 7.25 (s, 4 H), 7.90 (s, 8 H),
8.00 (d, 8 H), 9.22 (d, 8 H). ESMS (m/z): 2034 (M - PF6)+,
945 (M - 2PF6)2+, 582 (M - 3PF6)3+. Anal. Calcd for
(18) Amabilino, D. B.; Anelli, P.-L.; D. B.; Ashton, P. R.; Brown, G.
R.; Co´rdova, E.; God´ınez, L. A.; Hayes, W.; Kaifer, A. E.; Philp, D.;
Slawin, A. M. Z.; Spencer, N.; Stoddart, J . F.; Tolley, M. S.; Williams,
D. J . J . Am. Chem. Soc. 1995, 117, 11142.
C
104H118N4O11F24P4‚2H2O: C, 56.36; H, 5.53; N, 2.50. Found:
C, 56.04; H, 5.64; N, 2.47.

5142 J . Org. Chem., Vol. 65, No. 17, 2000
Li et al.
[2]Ca ten a n e 17b‚4P F 6. This orange solid was obtained in
52% from the reaction of 15‚2P F 6 and 16 (7 days) in the
presence of compound 10a by using the procedure described
[2]Ca ten a n e 21a ‚4Cl: A solution of dication salt 20a ‚2P F 6
(240 mg, 0.20 mmol), 16 (63.0 mg, 0.24 mmol), and 10a (1.74
g, 1.50 mmol) in MeCN (50 mL) was stirred at 25 °C for 21
days. After workup, 21a ‚4Cl (68 mg) was obtained as a pale
1
above for 17a ‚4P F 6. Mp: >268 °C dec. H NMR (CD3OD): δ
1
0.91 (s, 18 H), 1.31 (s, 18 H), 3.20 (d, 4 H), 3.35-3.52 (m, 16
H), 3.56-4.12 (m, 16 H), 4.30 (d, 4 H), 4.50 (m, 4 H), 5.95 (s,
8 H), 6.20 (br, 4 H), 6.79 (s, 4 H), 7.15(s, 4 H), 7.95 (s, 8 H),
yellow solid in 14% yield. Mp: 249 °C dec. H NMR (CD3OD/
CD3CN): δ 0.94 (s, 18 H), 1.04 (s, 18 H), 1.24 (s, 18 H), 1.30
(s, 18 H), 3.00 (m, 4 H), 3.31 (d, 4 H), 3.34 (m, 4 H), 3.72-3.75
(m, 12 H), 3.92 (m, 4 H), 3.95-4.01 (m, 16 H), 4.10 (m, 4 H),
4.35 (m, 8 H), 5.85 (m, 4 H), 6.20 (s, 4 H), 6.75 (m, 8 H), 6.75
(s, 4 H), 6.82 (s, 4 H), 7.26 (s, 4 H), 7.30 (s, 4 H), 7.87 (s, 4 H),
7.90 (d, 4 H), 7.96 (d, 4 H), 9.23 (d, 4 H), 9.26 (d, 4 H). ESMS:
m/z 1192 (M - 2Cl)2+, 1175 (M - 3Cl)2+, 783 (M - 3Cl)3+, 578
(M - 4Cl)4+. Anal. Calcd for C150H184Cl4N4O17‚2H2O: C, 72.25;
H, 7.62; N, 2.25. Found: C, 72.10; H, 7.68; N, 2.09.
[2]Ca ten a n e 21b‚4Cl. This catenane was obtained from the
reaction of 20b‚2P F 6 and 16 in the presence of 10a in 12%
yield as a pale yellow solid. Mp: 268 °C dec. 1H NMR (CD3-
OD): δ 0.95 (s, 18 H), 1.24 (s, 18 H), 3.04 (m, 4 H), 3.34 (d, d,
8 H), 3.72 (m, 12 H), 3.95 (m, 4 H), 3.98 (m, 16 H), 4.11 (m, 4
H), 4.39 (m, 8 H), 5.83 (m, 4 H), 6.21 (s, 4 H), 6.78 (m, 8 H),
6.78 (m, 8 H), 6.82 (d, 4 H), 7.30 (s, 4 H), 7.32 (s, 4 H), 7.90 (s,
4 H), 7.95 (d, 4 H), 7.99 (d, 4 H), 9.20 (d, 4 H), 9.26 (d, 4 H).
ESMS: m/z 1080 (M - 2Cl)2+, 522 (M - 4Cl)4+. Anal. Calcd
for C134H152Cl4N4O17‚3H2O: C, 70.39; H, 6.91; N, 2.49. Found:
C, 70.10; H, 7.00; N, 2.19.
8.01 (d, 8 H), 9.26 (d, 8 H). ESMS (m/z): 1184 (2M - 3Cl)3+
,
878 (M - 2Cl)2+, 860 (M - 3Cl)2+, 562 (M - 4Cl)3+. Anal. Calcd
for C108H126Cl4N4O13‚H2O: C, 70.18; H, 6.99; N, 3.03. Found:
C, 70.00; H, 6.72; N, 2.87. This [2]catenane was converted to
17b‚4P F 6 via anionic exchange with saturated aqueous NH4-
1
PF6 solution. Mp: >270 °C dec. H NMR (CD3CN): δ 0.95 (s,
18 H), 1.31 (s, 18 H), 3.22 (d, 4 H), 3.38-4.12 (m, 32 H), 4.35
(d, 4 H), 4.50 (m, 4 H), 5.90 (s, 8 H), 6.19 (br, 4 H), 6.69 (s, 4
H), 7.22 (s, 4 H), 7.95 (s, 8 H), 7.96 (d, 8 H), 9.29 (d, 8 H).
ESMS: m/z 2120 (M - PF6)+, 988 (M - 2PF6)2+
.
[2]Ca t en a n e 17c‚4P F 6. This compound was obtained in
55% yield as an orange solid from the reaction of 15‚2P F 6 and
16 (7 days) in the presence of compound 10b. Mp: >280 °C
1
dec. H NMR (CD3CN): δ 3.24 (d, 4 H), 3.35-4.22 (m, 32 H),
4.30 (d, 4 H), 4.55 (m, 4 H), 5.98 (s, 8 H), 6.25 (br, 4 H), 6.69
(d, 4 H), 7.15-7.28 (m, 8 H), 7.95 (s, 8 H), 7.96 (d, 8 H), 9.29
+
(d, 8 H). ESMS: m/z 1898 (M - PF6) +, 1752 (M - 2PF6)
,
876 (M - 2PF6)2+. Anal. Calcd for C92H94N4O13F24P4‚H2O: C,
53.59; H, 4.70; N, 2.72. Found: C, 53.23; H, 4.76; N, 2.66.
[2]Ca ten a n e 18‚4P F 6. This compound was prepared in 12%
yield (14 days) as an orange solid from 15‚2P F 6 and 16 in the
presence of excessive 11. Mp: >298 °C dec. 1H NMR (CD3-
CN): δ 1.04 (s, 18 H), 1.30 (s, 18 H), 3.40 (m. 4 H), 3.70-3.88
(m, 30 H), 4.08 (s, 8 H), 4.46 (br, 4 H), 5.68 (s, 8 H), 6.89 (s, 8
H), 7.25 (s, 2 H), 7.62 (m, 8 H), 7.74 (m, 8 H), 8.78 (d, 8 H).
ESMS: m/z 2150 (M - PF6) +, 1002 (M - 2PF6)2+, 620 (M -
3PF6)3+. Anal. Calcd for C110H130N4O13F24P4‚2H2O: C, 56.64;
H, 5.80; N, 2.40. Found: C, 56.32; H, 5.89; N, 2.34.
[2]Ca ten a n e 21c‚4Cl. This catenane was obtained from the
reaction of 20b‚2P F 6 and 16 in the presence of 10b in 15%
1
yield as a pale yellow solid. Mp: >288 °C dec. H NMR (CD3-
OD): δ 3.06 (m, 4 H), 3.35 (d, d, 8 H), 3.70 (m, 12 H), 3.90 (m,
4 H), 3.95 (m, 16 H), 4.20 (m, 4 H), 4.38 (m, 8 H), 5.86 (m, 4
H), 6.60 (s, 4 H), 6.78 (m, 8 H), 6.80 (m, 12 H), 6.85 (d, 4 H),
7.33 (d, 4 H), 7.36 (d, 4 H), 7.92 (s, 4 H), 7.90 (d, 4 H), 7.95 (d,
4 H), 9.15 (d, 4 H), 9.23 (d, 4 H). ESMS: m/z 1970 (M - Cl)+,
968 (M - 2Cl)2+. Anal. Calcd for C118H120Cl4N4O17‚2H2O: C,
69.34; H, 6.04; N, 2.74. Found: C, 69.10; H, 6.21; N, 2.59.
[2]Ca ten a n e 19‚4P F 6. This compound was prepared in 6%
yield (28 days) as an orange solid from 15‚2P F 6 and 16 in the
presence of excessive 12. Mp: >258 °C dec. 1H NMR (CD3-
CN): δ 0.90 (s, 18 H), 1.02 (t, 6 H), 1.29 (s, 18 H), 2.04 (m, 4
H), 3.25 (d, 4 H), 3.35-4.15 (m, 36 H), 4.35 (d, 4 H), 5.90 (s, 8
H), 6.30 (br, 8 H), 6.63 (s, 4 H), 7.25 (s, 4 H), 7.68 (s, 8 H),
Ack n ow led gm en t. This work is partially supported
by the Natural Sciences Foundation of China and
Chinese Academy of Sciences, which are greatly ap-
preciated. We thank Professor Xi-Kui J iang for his
encouragement of this work.
7.90 (d, 8 H), 9.24 (d, 8 H). ESMS: m/z 1030 (M - 2PF6)2+
,
639 (M - 3PF6)3+. Anal. Calcd for C114H138N4O13F24P4‚3H2O:
C, 56.89; H, 6.04; N, 2.33. Found: C, 56.62; H, 6.09; N, 2.30.
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