Stepwise synthesis and selective dimerisation of bis- and trisloop tetra-urea calix[4]arenes

Article abstract of DOI:10.1002/chem.200701694

Tetra-urea calix[4]arenes substituted with four mono- or bisalkenyl residues have been converted into bis- or tetraloop compounds by intramolecular olefin metathesis, with use of a tetratosylurea calix[4]arene as template. The same strategy has now been used to synthesise trisloop compounds and bisloop compounds with adjacent loops, completing the series of the loop-containing tetra-urea derivatives. A tetra-urea calix[4]arene of the AABB type, where A stands for a bisalkenyl- and B for a monoalkenyl-substituted urea unit, was used as precursor for the three loops. It was easily synthesised from a tetraamino calix[4]-arene in which two adjacent amino groups were Boc-protected. The ABCB-type precursor for the two adjacent loops was prepared through protection of two opposite amino functions with trityl groups. The capabilities of the novel macrocyclic tetra-ureas for the selective formation of hydrogenbonded dimers were studied.

Full text of DOI:10.1002/chem.200701694

DOI: 10.1002/chem.200701694
Stepwise Synthesis and Selective Dimerisation ofBis- and Trisloop Tetra-urea
Calix[4]arenes
Yuliya Rudzevich,*[a] Yudong Cao,[a] Valentyn Rudzevich,[a, b] and Volker Bçhmer*[a]
Abstract: Tetra-urea calix[4]arenes
substituted with four mono- or bisal-
kenyl residues have been converted
into bis- or tetraloop compounds by in-
tramolecular olefin metathesis, with
use of a tetratosylurea calix[4]arene as
template. The same strategy has now
been used to synthesise trisloop com-
pounds and bisloop compounds with
adjacent loops, completing the series of
the loop-containing tetra-urea deriva-
tives. A tetra-urea calix[4]arene of the
AABB type, where A stands for a bi-
salkenyl- and B for a monoalkenyl-sub-
stituted urea unit, was used as precur-
sor for the three loops. It was easily
synthesised from a tetraamino calix[4]-
arene in which two adjacent amino
groups were Boc-protected. The
ABCB-type precursor for the two adja-
cent loops was prepared through pro-
tection of two opposite amino func-
tions with trityl groups. The capabilities
of the novel macrocyclic tetra-ureas for
the selective formation of hydrogen-
bonded dimers were studied.
Keywords: calixarenes · dimeriza-
tion · metathesis · self-assembly ·
template synthesis
Introduction
mer 1·2. This observation could be utilisable, for instance,
for the construction of “informational polymers” through
self-assembly.[4]
Calix[4]arenes substituted at the wide rim with four arylurea
functions (1) form dimeric capsules in aprotic, apolar sol-
vents, held together by a seam of hydrogen bonds involving
the urea functions of both calixarenes in an alternating pat-
tern. This dimerisation, first described by Rebek,[1] has
meanwhile been confirmed in numerous examples, including
several crystal structures.[2] A solution of two different aryl-
ureas of type 1 normally contains not only the two homo-
dimers but also the heterodimer (in a more or less statistical
ratio) which is additional evidence of the dimerisation.[3]
Tetra-tosylureas 2 also form homodimers, but surprisingly
a 1:1 mixture of 1 and 2 contains exclusively the heterodi-
[a] Dr. Y. Rudzevich, Dr. Y. Cao, Dr. V. Rudzevich, Dr. V. Bçhmer
Abteilung Lehramt Chemie
Fachbereich Chemie, Pharmazie und Geowissenschaften
Johannes Gutenberg-Universität Mainz
Duesbergweg 10–14, 55099 Mainz (Germany)
Fax : (+49)613-1392-5419
Although a reasonable explanation for this exclusive for-
mation of heterodimers was found only recently,[5] the preor-
ganisation achieved in this way has frequently been used for
intramolecular reactions between functional groups attached
to the urea residues of 1.[6] Bis- and tetra-loop compounds[7]
3 and 4, in which adjacent urea groups are covalently inter-
connected, were obtained by olefin metathesis[8] (followed
by hydrogenation) of tetra- or octaalkenyl derivatives 1b
E-mail: rudzevic@uni-mainz.de
vboehmer@mail.uni-mainz.de
[b] Dr. V. Rudzevich
Permanent address: Institute of Organic Chemistry
NAS of Ukraine, Murmanska str. 5
02094 Kyiv-94 (Ukraine)
Supporting information for this article is available on the WWW
1
under http://www.chemeurj.org/ or from the author: H and 13C NMR
spectra of compounds 5 and 6.
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Chem. Eur. J. 2008, 14, 3346 – 3354

FULL PAPER
and 1c with use of 2 as a template.[9] Compounds 3 and 4[10]
are not able to form homodimers, as this would require the
sterically unfavourable overlap of the loops. However, they
form heterodimers with tetra-ureas 1, as long as their urea
groups can pass through the loops. In a 1:1 mixture of 1 and
3 in an apolar solvent, exclusively the heterodimer 1·3 is
present, since this represents the only possible means of
having all urea functions involved in hydrogen bonding.
This means that new selectivities for the dimerisation of
tetra-ureas are possible. They have already been used for
the synthesis of different catenanes[11,12] and rotaxanes,[13,14]
and might be utilisable, for instance, for the controlled con-
struction of larger assemblies.[15]
a phenolic unit substituted with a bisalkenyl urea group and
B is a phenolic unit substituted with a monoalkenyl urea
group. Their synthesis, from a starting 1,2-bis Boc-protected
tetraamine 7, is straightforward (Scheme 1). Compound 7 is
acylated with an isocyanate I, prepared in situ from 3,5-di-
alkenyloxybenzoic acid, to afford 8. After deprotection, the
remaining two amino functions are acylated to provide 10,
with use of an activated urethane II as a milder reagent in
this step.
The synthesis of the ABAC-type calix[4]arenes 5 requires
more steps (Scheme 2). It is possible by use of the recently
described 1,3-protection of a tetraamino calix[4]arene.[17] In
a first step the 1,3-bistrityl tetraamine 11 is diacylated with a
monoalkenyl isocyanate III as
reagent to provide 12. (All at-
tempts to introduce two urea
fragments by acylation with
active urethanes failed, even at
increased temperatures. Under
these conditions the 1,3-ditrityl
monourea is formed as main
product.) Although the ditri-
tyl-diurea 12 slowly decompos-
es under the conditions used
for column chromatography
(probably due to the slightly
acidic silica gel),
a product
with about 95% purity (suffi-
cient for the further steps) can
be obtained by reprecipitation
with methanol from
a di-
chloromethane solution. The
subsequent removal of the
trityl groups under conditions
(TFA in dichloromethane) re-
cently described for a ditolyl
analogue[17] results in a mix-
ture of compounds. Obviously,
the m-alkenyloxy aryl residue
of the urea is nucleophilic
enough to react with the trityl
cation. This undesired substitu-
tion can be avoided by trap-
ping the trityl cation with 3,5-
dihydroxytoluene (IV, three-
fold excess). Reaction of dia-
To extend this pattern of selective recognition and to
complete the set of the multiloop tetra-urea derivatives, we
have prepared compounds 5 and 6, using tetra-tosylurea 2 as
template, and have studied their dimerisation and self-sort-
ing[16] properties.
mine 13 with the corresponding active urethane V allows the
triurea monoamine 14 to be obtained with high selectivity in
relation to the same acylation with p-tolylisocyanate. Finally,
the exhaustive acylation to afford 15 is easily achieved with
the freshly prepared isocyanate I.
Olefin metathesis followed by hydrogenation of the ini-
tially formed double bonds finally gives the desired bis- and
trisloop compounds 5 and 6. The use of the tetra-tosyl urea
2 as template avoids the potentially possible trans-cavity
bridging during metathesis, but does not exclude intercon-
Results and Discussion
Syntheses: Suitable precursors for compounds 6 are tetra-
urea calix[4]arenes of the AABB-type, where A symbolises
Chem. Eur. J. 2008, 14, 3346 – 3354
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3347

V. Bçhmer et al.
Scheme 1. Synthesis of the trisloop tetra-urea calix[4]arene 6: i) I, toluene; ii) AlCl3, CH2Cl2; iii) II, Et3N, THF, reflux; iv) 2, Grubbs first-generation cata-
lyst, CH2Cl2/C6D6; reduction (Pt2O).
nection between the monoalkenyl residues in 10. Neverthe-
less, the yield of this cyclisation step is “excellent”.
three loops, this number of possible combinations can be re-
duced by six (first rule). If, in addition, the bulky residues of
A–C cannot pass through the loops, only 11 possible dimers
remain (second rule), as illustrated in Figure 1. (For some of
these combinations several regioisomeric arrangements are
possible.)
In a stoichiometric mixture the number of combinations
achieved is further reduced to three, due to the fact that all
tetra-urea calix[4]arenes “want to form dimers”, since this is
obviously the most stable arrangement. Only in this way can
all urea functions be involved in a “hydrogen-bonded belt”,
in which each urea group acts simultaneously as hydrogen
bond donor and acceptor.
Self-assembly: The novel bis- and trisloop compounds 5 and
6 can form neither homo- (5·5, 6·6), nor heterodimers (5·6),
as this would require the sterically unfavourable overlapping
of loops. However, they easily form heterodimers in combi-
nations with “open chain” tetra-urea calix[4]arenes, if small
urea residues (e.g., tolylurea groups) to penetrate the loops
are present. In combination with the use of bulky substitu-
ents that cannot pass through the loops, this leads to novel
selectivities for the dimerisation of tetra-urea calix[4]ar-
enes.[18]
The underlying sorting process is based on two simple
rules:
Among the six tetra-ureas shown in Figure 1, the trisloop
compound F can dimerise only with A, which is thus “con-
sumed” in this way, and other dimers of A should not be
formed. The bisloop compound E has only B as a potential
partner (cf. Figure 2, where E=5a and B=16), and bisloop
D can combine only with C. It is important to note that all
six tetra-ureas do not even have to be present at the same
concentration, only the appropriate pairs A/F, B/E and C/D.
Thus, of the 11 possible dimeric combinations, only three
dimers will be formed in the stoichiometric mixture.
*
dimers with overlapping loops are not formed,
*
bulky residues do not penetrate the loops.
Statistically, six different tetra-urea calix[4]arenes can
form 21 homo- and heterodimers, if all pairwise combina-
tions can be achieved. With derivatives D–F, in which adja-
cent urea functions are covalently connected by two or
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Bis- and Trisloop Tetra-urea Calix[4]arenes
FULL PAPER
Scheme 2. Synthesis of the bisloop tetra-urea calix[4]arene 5: i) III, toluene; ii) IV, T FA, CHCl2; iii) V, CHCl3; iv) I, toluene; v) 2, Grubbs first-genera-
2
tion catalyst, CH2Cl2/C6D6; reduction (Pt2O).
The NMR spectra shown in
Figure 2 confirm these predic-
tions. The bisloop compound
5a shows a broad, unresolved
spectrum, typical for a mixture
of ill-defined assemblies (Fig-
ure 2a). The tetra-urea 16,
with two bulky urea residues,
forms two regioisomeric ho-
modimers (Figure 2b). The sto-
ichiometric mixture of the two
tetra-urea compounds shows a
sharp, well resolved spectrum,
corresponding to the heterodi-
mer 5a·16 (Figure 2c). In spite
of the spectrumꢁs complex and
complicated pattern, the ab-
sence of the homodimer 16·16
can be unambiguously de-
duced. This principle also
holds for the combination of
trisloop derivative 6a and
tetra-urea 17 with one bulky
residue (Figure 2d–f). Again,
the NMR spectrum shows the
formation of a single heterodi-
mer 6a·17 (Figure 2f), while
the homodimers 17·17 com-
Figure 1. Schematic representation of the possible combinations of tetra-urea calix[4]arenes A–F to form di-
meric capsules. Combinations for which regioisomeric arrangements are possible are marked with *.
pletely disappear.
Chem. Eur. J. 2008, 14, 3346 – 3354
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3349

V. Bçhmer et al.
Figure 2. Sections of the 1H NMR spectra (CDCl3, 258C) of: a) the bisloop derivative 5a, b) tetra-urea 16 (mixture of two regioisomeric homodimers),
c) stoichiometric mixture of 5a and 16 (heterodimer), d) trisloop derivative 6a, e) tetra-urea 17 (mixture of two regioisomeric homodimers), and f) stoi-
chiometric mixture of 6a and 17 (heterodimer).
identities of the reported compounds, as well as their purities, were un-
ambiguously established by their spectroscopic data.
Conclusion
1,3-Bis-[3-(hex-5-enyloxy)phenylureido]-2,4-bis-[triphenylmethylamino]-
calix[4]arene (12): Bis(trichloromethyl) carbonate (1.52 g, 5.12 mmol)
The recently described protection of two opposite amino
was added under nitrogen to a solution of 3-(hex-5-enyloxy)aniline[20]
(0.98 g, 5.12 mmol) in toluene (20 mL). The solution was stirred for half
an hour at room temperature, for 1 h at 508C and for 1 h at 808C and
was finally concentrated under reduced pressure (bath temperature
>708C). Toluene (20 mL) was added and evaporated again to remove
the residues of phosgene.
functions in tetra-amino calix[4]arenes (“1,3-protection”) by
trityl groups paves the way for the controlled synthesis of
tetra-urea calix[4]arenes, in which three urea functions are
covalently connected by aliphatic chains to form bisloop de-
rivatives. Trisloop derivatives were made analogously by use
of “1,2-protection” with Boc groups. Tetra-urea calix[4]ar-
enes with bulky urea groups are available by analogous
strategies. These novel derivatives create novel possibilities
for selective dimerisation, which may be utilisable, for in-
stance, for the construction of structurally uniform, self-as-
sembled dendrimers.[11]
Calix[4]arene 11[17] (2.00 g, 1.60 mmol) was added under nitrogen to the
solution of freshly prepared isocyanate in toluene (30 mL), and the reac-
tion mixture was stirred overnight. Methanol (10 mL) was added, and the
solvents were evaporated to a volume of ꢀ1–2 mL. The residue was
treated with methanol (50 mL), and the resulting solid was filtered off,
washed with methanol and dried in air to give compound 12 (2.45 g,
91%) as a light brown powder. If necessary, additional purification can
be performed by column chromatography (THF/hexane 1:5). M.p. 145–
1478C (decomposition); 1H NMR (400 MHz, [D6]DMSO, 258C): d=0.88
3
3
ACHTREUNG
(t, J
1.52 (m, 20H; CH2), 1.71 (m, 8H; CH2), 1.90 (m, 4H; CH2), 2.05 (m,
4H; CH2), 2.69 (d, 2J(H,H)=12.4 Hz, 4H; ArCH2Ar), 3.45 (t, 3J
(H,H)=
6.6 Hz, 4H; OCH2), 3.82 (m, 4H; OCH2), 3.93 (t, 3J
(H,H)=6.6 Hz, 4H;
OCH2), 4.13 (d, 2J
(H,H)=12.4 Hz, 4H; ArCH2Ar), 4.97 (m, 4H; CH=
CH2), 5.21 (s, 2H; Ph3CNH), 5.79 (m, 2H; CH=CH2), 5.87 (s, 4H; ArH),
6.51 (d”d, 3J(H,H)=8.3 Hz, 4J
(H,H)=2.1 Hz, 2H; PhH), 6.80 (s, 4H;
ArH), 6.86 (brd”d, 3J(H,H)=8.3 Hz, 4J
(H,H)=2.1 Hz, 2H; PhH), 6.99
(s, 30H; CPh3H), 7.15 (d”d, 3J(H,H)=8.3 Hz, 3J
(H,H)=8.3 Hz, 2H;
PhH), 7.31 (d”d, 4J(H,H)=2.1 Hz, 4J
(H,H)=2.1 Hz, 2H; PhH), 7.92 (s,
(H,H)=7.0 Hz, 6H; CH3), 0.89
N
Experimental Section
A
ACHTREUNG
Melting points are uncorrected. 1H and 13C NMR spectra were recorded
on a Bruker Avance DRX 400 spectrometer at 400 and 100.6 MHz, re-
spectively. Chemical shifts are reported as d values (ppm) with reference
to the residual solvent peaks. Decoupling and DEPTexperiments con-
firmed the assignments of the signals. ESI mass spectra were recorded on
a Waters/Micromass QTof Ultima 3 mass spectrometer. 1H and 13C NMR
spectra of compounds 5 and 6 are available as Supporting Information.
AHCTREUNG
AHCTREUNG
A
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
2H; NH), 8.38 ppm (s, 2H; NH); 13C{1H} NMR (100.6 MHz, [D6]DMSO,
258C): d=13.7 (CH3), 14.0 (CH3), 22.2 (CH2), 22.3 (CH2), 24.6 (CH2),
27.7 (CH2), 28.0 (CH2), 28.1 (CH2), 29.0 (CH2), 29.5 (CH2), 30.6 (CH2),
32.7 (CH2), 66.9 (OCH2), 70.8 (CPh3), 74.3 (OCH2), 74.7 (OCH2), 104.1
(CH), 107.4 (CH), 110.0 (CH), 114.8 (CH=CH2), 115.9 (CH), 117.9 (CH),
125.7 (CH), 127.1 (CH), 128.8 (CH), 129.3 (CH), 131.56 (C), 133.6 (C),
135.4 (C), 138.4 (CH=CH2), 140.7 (C), 141.3 (C), 145.7 (C), 146.6 (C),
All solvents were HPLC grade and were used without further purifica-
tion. Column chromatography was performed on silica gel 60 (0.035–
0.070 mm, Acros). Grubbs’ catalyst—bis-(tricyclohexylphosphine)benzyl-
idene ruthenium(IV) chloride—was purchased from Aldrich.
As previously verified,[19] data for elemental analyses of organic calixar-
enes are often misleading, due to inclusion of solvent molecules, and
cannot be considered appropriate criteria of purity. Nevertheless, the
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Bis- and Trisloop Tetra-urea Calix[4]arenes
FULL PAPER
151.2 (C), 152.2 (C), 159.0 ppm (C); MS (ESI): m/z (%): calcd for
C
chloromethane (3 mL) was added to the freshly prepared isocyanate, and
the reaction mixture was stirred at 708C for 4 h. Methanol (10 mL) was
added, and the solvents were evaporated. Purification by column chroma-
tography (CH2Cl2 followed by chloroform/acetone 30:1) afforded product
15a (0.14 g, 67%) as a white powder. M.p. 158–1608C (decomposition);
1H NMR (400 MHz, [D8]THF, 258C): d=0.96 (m, 12H; CH3), 1.36–1.59
(m, 24H; CH2), 1.69 (m, 8H; CH2), 1.94 (m, 8H; CH2), 2.08 (m, 8H;
112H126N6O8Na: 1707.28; found: 1707.0 (100) [M+Na]+.
1,3-Bis-[3-(hex-5-enyloxy)phenylureido]-2,4-diaminocalix[4]arene (13):
Trifluoroacetic acid (1.35 g, 11.9 mmol) was added to a solution of calix-
[4]arene 12 (1.0 g, 0.59 mmol) and 3,5-dihydroxytoluene (IV, 0.59 g,
4.75 mmol) in dichloromethane (60 mL). After stirring for 2 h the reac-
tion mixture was washed with water (2”20 mL), aqueous K2CO3 solution
(5%, 4”20 mL) and again with water (2”20 mL) and dried (MgSO4).
The resulting mixture was purified by column chromatography (chloro-
form/acetone 3:1) to give the product 13 (0.38 g, 53%) as a beige solid
CH2), 2.19 (s, 3H; TolCH3), 3.06 (d, 2J
3.84 (m, 16H; OCH2), 4.43 (d, 2J
(H,H)=13.2 Hz, 4H; ArCH2Ar), 4.94
(m, 8H; CH=CH2), 5.80 (m, 4H; CH=CH2), 6.04 (brs, 1H; p-PhH), 6.42
(d”d, 3J(H,H)=8.0 Hz, 4J(H,H)=1.8 Hz, 2H; PhH), 6.57 (d, 4J
(H,H)=
1.6 Hz, 2H; o-PhH), 6.69 (brd, 3J
(H,H)=8.0 Hz, 2H; PhH), 6.78 (s, 4H;
A
AHCTREUNG
A
N
ACHTREUNG
mass. M.p. 147–1508C (decomposition); 1H NMR (400 MHz,
AHCTREUNG
3
[D6]DMSO+CD3COOD (10%), 258C): d=0.87 (t, J
A
3
ArH), 6.83 (m, 4H; ArH), 6.92 (d, J
A
CH3), 0.89 (t, 3J
1.64–1.73 (m, 4H; CH2), 1.76–1.85 (m, 8H; CH2), 2.02–2.10 (m, 4H;
CH2), 3.03 (d, 2J(H,H)=13.4 Hz, 4H; ArCH2Ar), 3.66 (t, 3J
(H,H)=
6.2 Hz, 4H; OCH2), 3.83 (t, 3J
(H,H)=7.8 Hz, 4H; OCH2), 3.89 (t,
3J(H,H)=6.2 Hz, 4H; OCH2), 4.28 (d, 2J
(H,H)=13.4 Hz, 4H;
ArCH2Ar), 4.90–5.03 (m, 4H; CH=CH2), 5.73–5.85 (m, 2H; CH=CH2),
5.88 (s, 4H; ArH), 6.48 (d”d, 3J(H,H)=8.2 Hz, 4J
(H,H)=2.0 Hz, 2H;
PhH), 6.83 (brd”d, 3J(H,H)=8.2 Hz, 4J
(H,H)=2.0 Hz, 2H; PhH), 7.05
(s, 4H; ArH), 7.09 (d”d, 3J(H,H)=8.2 Hz, 3J
(H,H)=8.2 Hz, 2H; PhH),
7.16 (d”d, 4J(H,H)=2.0 Hz, 4J
(H,H)=2.0 Hz, 2H; PhH), 8.44 (s, {2H};
A
d, 3J(H,H)=8.0 Hz, 3J
A
ACHTREUNG
and o-PhH), 7.43 (s, 1H; NH), 7.52 (s, 1H; NH), 7.55 (s, 3H; NH), 7.58
(s, 1H; NH), 7.62 ppm (s, 2H; NH); 13C{1H} NMR (100.6 MHz, [D8]THF,
258C): d=14.6 (CH3), 20.8 (TolCH3), 23.8 (CH2), 26.4 (CH2), 29.49
(CH2), 29.51 (CH2), 29.8 (CH2), 30.88 (CH2), 30.91 (CH2), 32.1 (CH2),
34.4 (CH2), 68.12 (OCH2), 68.14 (OCH2), 75.9 (OCH2), 95.5 (CH), 97.7
(CH), 105.4 (CH), 108.3 (CH), 111.0 (CH), 114.9 (CH=CH2), 119.1 (CH),
119.3 (CH), 129.7 (CH), 129.8 (CH), 131.3 (C), 134.8 (C), 134.88 (C),
134.94 (C), 135.79 (C), 135.82 (C), 136.00 (C), 136.02 (C), 138.7 (C),
139.5 (CH=CH2), 142.4 (C), 142.8 (C), 152.6 (C), 152.7 (C), 152.8 (C),
153.2 (C), 153.3 (C), 153.5 (C), 160.7 (C), 161.4 ppm (C); MS (ESI): m/z
A
ACHTREUNG
AHCTREUNG
A
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
NH), 8.59 ppm (s, {2H}; NH) {the intensities of NH signals are lower be-
cause of deuterium exchange}; 13C{1H} NMR (100.6 MHz,
[D6]DMSO+CD3COOD (10%), 258C): d=14.2 (CH3), 14.3 (CH3), 22.7
(CH2), 22.8 (CH2), 25.2 (CH2), 28.1 (CH2), 28.6 (CH2), 29.7 (CH2), 30.0
(CH2), 31.0 (CH2), 33.3 (CH2), 67.5 (OCH2), 74.9 (OCH2), 75.0 (OCH2),
104.8 (CH), 107.9 (CH), 110.6 (CH), 115.2 (CH=CH2), 117.6 (CH), 118.8
(CH), 129.8 (CH), 133.8 (C), 135.2 (C), 135.4 (C), 136.3 (C), 138.9 (CH=
CH2), 141.4 (C), 151.2 (C), 152.5 (C), 152.9 (C), 159.6 ppm (C); MS
(ESI): m/z (%): calcd for C74H98N6O8: 1199.64; found: 1199.8 (100) [M]+,
1221.8 (73) [M+Na]+, 1239.8 (99) [M+K]+, 2399.5 (31) [2M]+, 2419.5
(5) [2M+Na]+, 2439.5 (10) [2M+K]+.
(%): calcd for C101H130N8O12
:
1648.21; found: 1649.1 (21) [M+H]+,
1671.0 (100) [M+Na]+.
2-[3,5-Di(oct-7-enyloxy)phenylureido]-1,3-bis-[3-(hex-5-enyloxy)phenyl-
ureido]-4-tolylureido-calix[4]arene (15b): This compound was prepared
as described for 15a; after column chromatography (CH2Cl2 followed by
chloroform/acetone 15:1) 15b was obtained in 68% yield. 1H NMR
(400 MHz, [D6]DMSO, 258C): d=0.93 (t, 3J
ACHTREUNG
AHCTREUNG
AHCTREUNG
1,3-Bis-[3-(hex-5-enyloxy)phenylureido]-2-tolylureido-4-amino-calix[4]-
arene (14): Et3N (0.5 mL) was added to a solution of diamino-calix[4]ar-
ene 13 (0.36 g, 0.30 mmol) and the p-nitrophenyl ester V[21] (0.09 g,
0.33 mmol) in chloroform (50 mL). The reaction mixture was stirred for
3 h at room temperature, and was then washed with aqueous K2CO3 solu-
tion (10%, 3”20 mL) and water (2”20 mL), dried (MgSO4) and concen-
trated. The residue was purified by column chromatography (THF/
hexane 2:3) to yield calix[4]arene 14 (0.30 g, 75%) as a light yellow
powder. M.p. 182–1858C; 1H NMR (400 MHz, [D6]DMSO, 258C): d=
A
N
ACHTREUNG
AHCTREUNG
AHCTREUNG
G
ACHTREUNG
3
AHCTREUNG
8.17 (s, 2H; NH), 8.19 (s, 1H; NH), 8.27 (s, 1H; NH), 8.31 ppm (s, 2H;
NH); 13C{1H} NMR (100.6 MHz, [D6]DMSO, 258C): d=13.9 (CH3), 20.2
(TolCH3), 22.2 (CH2), 24.7 (CH2), 25.2 (CH2), 27.9 (CH2), 28.08 (CH2),
28.12 (CH2), 28.14 (CH2), 28.5 (CH2), 29.3 (CH2), 30.6 (CH2), 32.8 (CH2),
33.0 (CH2), 66.9 (OCH2), 67.1 (OCH2), 74.7 (OCH2), 94.3 (CH), 96.6
(CH), 104.2 (CH), 107.2 (CH), 110.1 (CH), 114.5 (CH=CH2), 114.8 (CH=
CH2), 117.9 (CH), 118.0 (CH), 118.1 (CH), 128.9 (CH), 129.2 (CH), 130.1
(C), 133.2 (C), 133.3 (C), 133.4 (C), 134.2 (C), 134.3 (C), 134.4 (C), 137.2
(C), 138.4 (CH=CH2), 138.6 (CH=CH2), 140.9 (C), 141.4 (C), 150.9 (C),
151.0 (C), 151.1 (C), 152.2 (C), 152.3 (C), 152.4 (C), 158.9 (C), 159.8 ppm
(C); MS (ESI): m/z (%): calcd for C105H138N8O12Na: 1727.31; found:
1727.0 (100) [M+Na]+.
0.93 (t, 3J
4H; CH2), 1.89 (m, 8H; CH2), 2.07 (m, 4H; CH2), 2.21 (s, 3H; TolCH3),
2.96 (d, 2J(H,H)=12.8 Hz, 2H; ArCH2Ar), 3.10 (d, 2J
(H,H)=12.8 Hz,
2H; ArCH2Ar), 3.83 (m, 12H; OCH2), 4.25 (d, 2J
(H,H)=12.8 Hz, 2H;
ArCH2Ar), 4.33 (d, 2J
(H,H)=12.8 Hz, 2H; ArCH2Ar), 4.39 (brs, 2H;
NH2), 5.00 (m, 4H; CH=CH2), 5.82 (m, 2H; CH=CH2), 6.01 (s, 2H;
ArH), 6.48 (d”d, 3J(H,H)=8.3 Hz, 4J
(H,H)=2.4 Hz, 2H; PhH), 6.71 (d,
4J
(H,H)=2.3 Hz, 2H; ArH), 6.75 (m, 4H; ArH and PhH), 6.82 (s, 2H;
ArH), 7.03 (d, J
PhH), 7.26 (d, 3J
A
A
ACHTREUNG
AHCTREUNG
ACHTREUNG
A
ACHTREUNG
ACHTREUNG
3
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Bisloop calix[4]arene 5a:
1H; NH), 8.24 (s, 1H; NH), 8.32 ppm (s, 2H; NH); 13C{1H} NMR
(100.6 MHz, [D6]DMSO, 258C): d=13.9 (CH3), 20.2 (TolCH3), 22.2
(CH2), 22.3 (CH2), 24.7 (CH2), 27.8 (CH2), 27.9 (CH2), 28.1 (CH2), 29.2
(CH2), 29.3 (CH2), 30.6 (CH2), 32.8 (CH2), 66.9 (OCH2), 74.7 (OCH2),
104.2 (CH), 107.2 (CH), 110.1 (CH), 114.0 (CH), 114.8 (CH=CH2), 117.9
(CH), 118.1 (CH), 118.4 (CH), 118.6 (CH), 129.0 (CH), 129.3 (CH),
130.2 (C), 133.0 (C), 133.3 (C), 134.1 (C), 134.2 (C), 134.5 (C), 134.6 (C),
137.2 (C), 138.4 (CH=CH2), 141.0 (C), 147.3 (C), 151.1 (C), 151.2 (C),
152.3 (C), 152.5 (C), 159.0 ppm (C); MS (ESI): m/z (%): calcd for
C82H105N7O9Na: 1355.78; found: 1354.8 (100) [M+Na]+.
0.085 mmol) and tetratosylurea 2[23] (0.15 g, 0.093 mmol) in dichlorome-
thane/benzene 3:1 (280 mL) was stirred until it became clear. Nitrogen
was bubbled through the solution for 1 h, and Grubbsꢁ catalyst, (0.014 g,
0.017 mmol) was added under nitrogen. The reaction mixture was stirred
for 2 days. After addition of Et3N (3 mL) the solvents were evaporated,
and the residue was purified by column chromatography (THF/hexane
2:5 followed by THF/hexane 1:2). The obtained white solid was hydro-
genated in THF/toluene 5:1 (60 mL) in the presence of PtO2 (0.005 g,
0.022 mmol) as catalyst over 1.5 h. The catalyst was filtered off, solvents
were evaporated, and the residue was precipitated with methanol from
dichloromethane to yield compound 5a (0.11 g, 81%) as a white powder.
M.p. 290–3008C (decomposition); 1H NMR (400 MHz, [D8]THF, 258C):
2-[3,5-Di(hex-5-enyloxy)phenylureido]-1,3-bis-[3-(hex-5-enyloxy)phenyl-
ureido]-4-tolylureido-calix[4]arene (15a): Diphenyl phosphoryl azide
(DPPA, 0.061 g, 0.22 mmol) and Et3N (0.023 g, 0.22 mmol) were added
under nitrogen to a solution of 3,5-bis(hex-5-enyloxy)benzoic acid[22]
(0.061 g, 0.19 mmol) in toluene (20 mL), and the mixture was stirred at
708C for 4 h. A solution of calix[4]arene 14 (0.17 g, 0.13 mmol) in di-
d=0.96 (t, 3J
CH3), 1.25–1.57 (m, 40H; CH2), 1.67 (m, 8H; CH2), 1.86–2.03 (m, 8H;
CH2), 2.16 (s, 3H; TolCH3), 3.03 (d, 2J
(H,H)=13.0 Hz, 2H; ArCH2Ar),
3.07 (d, 2J
(H,H)=13.0 Hz, 2H; ArCH2Ar), 3.77 (m, 8H; OCH2), 3.93 (t,
N
A
AHCTREUNG
AHCTREUNG
Chem. Eur. J. 2008, 14, 3346 – 3354
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
3351

V. Bçhmer et al.
3
3J
(d, 2J
PhH), 6.44 (m, 4H; PhH and o-PhH), 6.54 (s, 2H; ArH), 6.58 (s, 2H;
ArH), 6.83 (m, 4H; PhH and TolH), 6.98 (d, 4J
(H,H)=2.1 Hz, 2H;
ArH), 7.02 (d”d, 3J(H,H)=8.2 Hz, 3J
(H,H)=8.2 Hz, 2H; m-PhH), 7.06
(d, 3J(H,H)=8.6 Hz, 2H; TolH), 7.19 (s, 2H; o-PhH), 7.22 (d, 4J
(H,H)=
A
G
7.45 (brs, 4H; NH), 8.17 ppm (brs, 2H; NH); MS (ESI): m/z (%): calcd
for C116H174N6O14Na: 1898.30; found: 1899.4 (100) [M+Na]+.
A
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1,2-Bis-[3,5-di(hex-5-enyloxy)phenylureido]-3,4-diamino-calix[4]arene
(9a): Aluminium chloride (0.12 g, 0.90 mmol) was added to a solution of
8a (0.48 g, 0.30 mmol) in dichloromethane (30 mL) and the mixture was
stirred for 4 h at room temperature. It was filtered through celite, washed
with saturated aqueous NaHCO3 (3”20 mL) and water (2”10 mL) and
dried (MgSO4). Evaporation of the solvent gave diamino-calix[4]arene
AHCTREUNG
A
ACHTREUNG
G
ACHTREUNG
2.1 Hz, 2H; ArH), 7.24 (s, 1H; NH), 7.33 (s, 1H; NH), 7.43 (s, 1H; NH),
7.48 (s, 1H; NH), 7.76 (s, 2H; NH), 7.77 ppm (s, 2H; NH); 13C{1H} NMR
(100.6 MHz, [D8]THF, 258C): d=14.5 (CH3), 14.7 (CH3), 20.8 (TolCH3),
23.7 (CH2), 23.9 (CH2), 26.6 (CH2), 26.7 (CH2), 29.4 (CH2), 29.5 (CH2),
29.6 (CH2), 29.7 (CH2), 29.8 (CH2), 30.0 (CH2), 30.1 (CH2), 30.7 (CH2),
31.08 (CH2), 31.10 (CH2), 32.12 (CH2), 67.8 (OCH2), 68.1 (OCH2), 75.8
(OCH2), 75.9 (OCH2), 76.0 (OCH2), 95.6 (CH), 97.5 (CH), 105.7 (CH),
108.3 (CH), 111.1 (CH), 118.8 (CH), 119.0 (CH), 119.3 (CH), 119.4
(CH), 129.6 (CH), 129.9 (CH), 130.9 (C), 134.7 (C), 134.85 (C), 134.95
(C), 135.00 (C), 136.9 (C), 138.7 (C), 142.5 (C), 142.7 (C), 152.0 (C),
152.1 (C), 153.1 (C), 153.2 (C), 153.3 (C), 160.7 (C), 161.4 ppm (C); MS
(ESI): m/z (%): calcd for C97H126N8O12Na: 1619.12; found: 1619.0 (100)
[M+Na]+.
9a (0.39 g, 92%) as
a
yellow powder. M.p. 153–1548C; 1H NMR
(400 MHz, [D8]THF, 258C): d=0.94 (m, 12H; CH3), 1.40 (m, 16H; CH2),
1.52 (m, 8H; CH2), 1.69 (m, 8H; CH2), 1.87 (m, 8H; CH2), 2.08 (m, 8H;
CH2), 2.51 (brs, 4H; NH2), 2.80 (d, 2J
ACHTREUNG
2.94 (d, 2J
A
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CH=CH2), 5.94 (m, 4H; ArH), 6.04 (s, 2H; p-PhH), 6.49 (s, 2H; ArH),
6.67 (s, 4H; o-PhH), 6.77 (s, 2H; ArH), 7.44 (brs, 2H; NH), 7.66 ppm
(brs, 2H; NH); 13C{1H} NMR (100.6 MHz, [D8]THF, 258C): d=14.6
(CH3), 23.76 (CH2), 23.79 (CH2), 26.4 (CH2), 29.4 (CH2), 29.5 (CH2), 29.8
(CH2), 30.9 (CH2), 32.1 (CH2), 32.2 (CH2), 34.4 (CH2), 68.2 (OCH2),
75.69 (OCH2), 75.73 (OCH2), 95.7 (CH), 97.8 (CH), 114.9 (CH=CH2),
115.8 (CH), 121.8 (CH), 122.3 (CH), 134.1 (C), 135.9 (C), 136.6 (C),
139.5 (CH=CH2), 142.9 (C), 149.8 (C), 153.8 (C), 161.4 ppm (C); MS
(ESI): m/z (%): calcd for C86H118N6O10Na: 1417.88; found: 1417.9 (100)
[M+Na]+.
Bisloop calix[4]arene 5b: Compound 5b was prepared and purified as
described for 5a; yield 77%; m.p. 290–3008C (decomposition); 1H NMR
(400 MHz, [D8]THF, 258C): d=0.96 (t, 3J
(H,H)=7.0 Hz, 6H; CH3), 0.97
G
(t, 3J
(H,H)=7.0 Hz, 6H; CH3), 1.22–1.54 (m, 48H; CH2), 1.68 (m, 8H;
E
CH2), 1.95 (m, 8H; CH2), 2.17 (s, 3H; TolCH3), 3.06 (d, 2J
A
2
12.8 Hz, 2H; ArCH2Ar), 3.07 (d, J
ACHTREUNG
(m, 8H; OCH2), 3.93 (m, 8H; OCH2), 4.44 (d, 2J
ArCH2Ar), 6.00 (t, 4J
8.2 Hz, 4J
ACHTREUNG
A
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1,2-Bis-[3,5-di(undec-10-enyloxy)phenylureido]-3,4-diamino-calix[4]arene
(9b): On application of the procedure described for the synthesis of 9a,
calix[4]arene 9b was obtained in 93% yield. M.p. 128–1308C; 1H NMR
(400 MHz, [D8]THF, 258C): d=0.94 (brs, 12H; CH3), 1.22–1.49 (m, 64H;
CH2), 1.69 (m, 8H; CH2), 1.87 (m, 8H; CH2), 2.03 (m, 8H; CH2), 2.55
A
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3
AHCTREUNG
A
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(H,H)=8.2 Hz, 3J
ACHTREUNG
3
(brs, 4H; NH2), 2.80 (d, 2J
2J(H,H)=13.2 Hz, 2H; ArCH2Ar), 3.02 (d, 2J
ArCH2Ar), 3.79 (m, 16H; OCH2), 4.27 (d, 2J
ArCH2Ar), 4.32 (d, 2J
(H,H)=13.2 Hz, 2H; ArCH2Ar), 4.39 (d,
2J
(H,H)=13.2 Hz, 1H; ArCH2Ar), 4.91 (m, 8H; CH=CH2), 5.78 (m, 4H;
(H,H)=13.2 Hz, 1H; ArCH2Ar), 2.94 (d,
(H,H)=13.2 Hz, 1H;
(H,H)=13.2 Hz, 1H;
A
ACHTREUNG
2H; TolH), 7.18 (s, 2H; o-PhH), 7.24 (s, 1H; NH), 7.32 (s, 1H; NH), 7.36
(s, 1H; NH), 7.45 (s, 1H; NH), 7.60 (s, 2H; NH), 7.65 ppm (s, 2H; NH);
13C{1H} NMR (100.6 MHz, [D8]THF, 258C): d=14.6 (CH3), 14.7 (CH3),
20.8 (TolCH3), 23.7 (CH2), 23.9 (CH2), 26.5 (CH2), 26.6 (CH2), 29.4
(CH2), 29.6 (CH2), 29.7 (CH2), 29.8 (CH2), 29.85 (CH2), 29.87 (CH2), 30.0
(CH2), 30.1 (CH2), 30.8 (CH2), 31.1 (CH2), 32.1 (CH2), 67.9 (OCH2), 68.0
(OCH2), 75.9 (OCH2), 75.97 (OCH2), 76.02 (OCH2), 95.3 (CH), 97.6
(CH), 105.5 (CH), 108.2 (CH), 110.9 (CH), 118.9 (CH), 119.1 (CH),
119.2 (CH), 129.7 (CH), 129.9 (CH), 131.1 (C), 134.96 (C), 135.01 (C),
135.04 (C), 136.7 (C), 138.8 (C), 142.5 (C), 142.8 (C), 152.1 (C), 152.2
(C), 152.9 (C), 153.0 (C), 153.2 (C), 160.7 (C), 161.4 ppm (C); MS (ESI):
A
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AHCTREUNG
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CH=CH2), 5.95 (m, 4H; ArH), 6.03 (s, 2H; p-PhH), 6.47 (s, 2H; ArH),
6.67 (brs, 4H; o-PhH), 6.80 (s, 2H; ArH), 7.49 (brs, 2H; NH), 7.69 ppm
(brs, 2H; NH); 13C{1H} NMR (100.6 MHz, [D8]THF, 258C): d=14.6
(CH3), 23.8 (CH2), 27.1 (CH2), 29.4 (CH2), 29.5 (CH2), 29.9 (CH2), 30.1
(CH2), 30.3 (CH2), 30.4 (CH2), 30.6 (CH2), 30.9 (CH2), 32.1 (CH2), 32.2
(CH2), 34.7 (CH2), 68.4 (OCH2), 75.7 (OCH2), 95.5 (CH), 97.7 (CH),
114.6 (CH=CH2), 115.8 (CH), 121.8 (CH), 122.3 (CH), 134.1 (C), 136.1
(C), 136.6 (C), 139.8 (CH=CH2), 142.9 (C), 149.9 (C), 153.8 (C),
161.5 ppm (C); MS (ESI): m/z (%): calcd for C106H158N6O10Na: 1698.19;
found: 1699.3 (100) [M+Na]+.
m/z (%): calcd for
[M+Na]+.
C101H134N8O12Na: 1675.23; found: 1675.0 (100)
1,2-Bis-[3,5-di(hex-5-enyloxy)phenylureido]-3,4-di-Boc-calix[4]arene
(8a): Compound 8a was synthesised as described for 15a from diamino
calix[4]arene 7[24] (0.48 g, 0.50 mmol) and the isocyanate freshly prepared
from 3,5-bis(hex-5-enyloxy)benzoic acid[22] (0.35 g, 1.11 mmol), DPPA
(0.36 g, 1.32 mmol) and Et3N (0.13 g, 1.32 mmol). Purification by column
chromatography (ethyl acetate/hexane 5:1) afforded 8a (0.65 g, 81%) as
a white solid. M.p. 151–1538C; 1H NMR (400 MHz, [D8]THF, 258C): d=
0.96 (m, 12H; CH3), 1.31–1.48 (m, 34H; C
CH2), 1.72 (m, 8H; CH2), 1.94 (m, 8H; CH2), 2.09 (m, 8H; CH2), 3.05 (d,
2J(H,H)=13.2 Hz, 4H; ArCH2Ar), 3.87 (t, 3J
(H,H)=6.2 Hz, 16H;
OCH2), 4.42 (d, 2J
(H,H)=13.2 Hz, 4H; ArCH2Ar), 4.95 (m, 8H; CH=
1,2-Bis-[3,5-di(hex-5-enyloxy)phenylureido]-3,4-bis-[3-(hex-5-enyloxy)-
phenylureido]calix[4]arene (10a): A solution of diamino-calix[4]arene 9a
(0.35 g, 0.25 mmol), p-nitrophenyl ester II[20] (0.19 g, 0.53 mmol) and
Et3N (0.5 mL) in THF (25 mL) was heated at reflux overnight. The resi-
due obtained after evaporation was dissolved in dichloromethane
(30 mL), washed with aqueous K2CO3 solution (5%, 4”20 mL) and
water (2”20 mL) and dried (MgSO4). The crude product was purified by
column chromatography (ethyl acetate/hexane 1:5) to afford calix[4]ar-
ene 10a (0.21 g, 46%) as a white solid. M.p. 208–2108C; 1H NMR
A
A
ACHTREUNG
(400 MHz, [D8]THF, 258C): d=0.96 (t, 3J
1.44 (m, 16H; CH2), 1.53 (m, 12H; CH2), 1.69 (m, 12H; CH2), 1.94 (m,
8H; CH2), 2.09 (m, 12H; CH2), 3.07 (d, 2J
(H,H)=12.8 Hz, 4H;
ArCH2Ar), 3.85 (m, 20H; OCH2), 4.44 (d, 2J
(H,H)=12.8 Hz, 4H;
ArCH2Ar), 4.94 (m, 12H; CH=CH2), 5.80 (m, 6H; CH=CH2), 6.03 (brt,
4J(H,H)=1.7 Hz, 2H; p-PhH), 6.41 (d”d, 3J(H,H)=8.1 Hz, 4J
(H,H)=
1.7 Hz, 2H; PhH), 6.58 (m, 4H; o-PhH), 6.66 (brd, 3J
(H,H)=8.1 Hz,
2H; PhH), 6.81 (s, 8H; ArH), 6.97 (d”d, 3J(H,H)=8.1 Hz, 3J
(H,H)=
A
ACHTREUNG
CH2), 5.80 (m, 4H; CH=CH2), 6.04 (s, 2H; p-PhH), 6.66 (s, 4H; o-PhH),
6.75 (brs, 8H; ArH), 7.46 (brs, 4H; NH), 8.16 ppm (brs, 2H; NH); MS
(ESI): m/z (%): calcd for C96H134N6O14Na: 1617.99; found: 1619.0 (100)
[M+Na]+.
AHCTREUNG
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1,2-Bis-[3,5-di(undec-10-enyloxy)phenylureido]-3,4-di-Boc-calix[4]arene
(8b): Compound 8b was prepared and purified analogously to 8a, yield
94%; m.p. 126–1288C; H NMR (400 MHz, [D8]THF, 258C): d=0.96 (m,
A
N
ACHTREUNG
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1
A
ACHTREUNG
12H; CH3), 1.22–1.51 (m, 82H; C
1.94 (m, 8H; CH2), 2.03 (m, 8H; CH2), 3.05 (d, 2J
ArCH2Ar), 3.86 (t, 3J(H,H)=6.3 Hz, 16H; OCH2), 4.42 (d, 2J
12.8 Hz, 4H; ArCH2Ar), 4.91 (m, 8H; CH=CH2), 5.78 (m, 4H; CH=
CH2), 6.03 (s, 2H; p-PhH), 6.66 (s, 4H; o-PhH), 6.76 (brs, 8H; ArH),
A
8.1 Hz, 2H; m-PhH), 7.23 (brs, 2H; o-PhH), 7.44 (s, 2H; NH), 7.46 (s,
2H; NH), 7.51 (s, 2H; NH), 7.55 ppm (s, 2H; NH); 13C{1H} NMR
(100.6 MHz, [D8]THF, 258C): d=14.6 (CH3), 23.8 (CH2), 26.4 (CH2), 29.5
(CH2), 29.8 (CH2), 30.9 (CH2), 32.1 (CH2), 34.4 (CH2), 68.1 (OCH2), 75.9
(OCH2), 95.5 (CH), 97.6 (CH), 105.3 (CH), 108.2 (CH), 111.0 (CH),
AHCTREUNG
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3352
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 3346 – 3354

Bis- and Trisloop Tetra-urea Calix[4]arenes
FULL PAPER
114.9 (CH=CH2), 119.1 (CH), 129.8 (CH), 135.0 (C), 135.9 (C), 139.5
(CH=CH2), 142.5 (C), 142.8 (C), 152.6 (C), 153.0 (C), 153.1 (C), 160.7
(C), 161.4 ppm (C); MS (FD): m/z (%): calcd for C112H148N8O14: 1829.11;
found: 1830.2 (100) [M+H]+.
Acknowledgement
Financial support by the Deutsche Forschungsgemeinschaft (Bo 523/14
and SFB 625) is gratefully acknowledged.
1,2-Bis-[3,5-di(undec-10-enyloxy)phenylureido]-3,4-[3-(hex-5-enyloxy)-
phenylureido]calix[4]arene (10b): Calix[4]arene 10b was prepared as de-
scribed for 10a. The crude product was recrystallised from dichlorome-
thane/methanol to afford 10b, yield 78%. M.p. 144–1468C; 1H NMR
[1] a) K. D. Shimizu, J. Rebek, Jr., Proc. Natl. Acad. Sci. USA 1995, 92,
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1996, 35, 1326–1329.
(400 MHz, [D8]THF, 258C): d=0.96 (brt, 3J
ACHTREUNG
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[2] a) O. Mogck, E. F. Paulus, V. Bçhmer, I. Thondorf, W. Vogt, Chem.
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[3] O. Mogck, V. Bçhmer, W. Vogt, Tetrahedron 1996, 52, 8489–8496.
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[8] For reviews on ring-closing metathesis, see: a) R. H. Grubbs, S. J.
Miller, G. C. Fu, Acc. Chem. Res. 1995, 28, 446–452; b) H.-G.
Schmalz, Angew. Chem. 1995, 107, 1981–1984; Angew. Chem. Int.
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[9] Examples of template synthesis of macrocycles, see: a) P. A. Chase,
M. Lutz, A. L. Spek, G. P. M. van Klink, G. van Koten, J. Mol. Catal.
A 2006, 254, 2–19; b) K. H. Song, S. O. Kang, J. Ko, Chem. Eur. J.
2007, 13, 5129–5134; c) N. Gimeno, R. Vilar, Coord. Chem. Rev.
2006, 250, 3161–3189; d) M. Bru, I. Alfonso, M. I. Burguete, S. V.
Luis, Angew. Chem. 2006, 118, 6301–6305; Angew. Chem. Int. Ed.
2006, 45, 6155–6159.
ACHTREUNG
2H; NH), 7.47 (s, 2H; NH), 7.51 (s, 2H; NH), 7.55 ppm (s, 2H; NH);
13C{1H} NMR (100.6 MHz, [D8]THF, 258C): d=14.6 (CH3), 23.8 (CH2),
26.4 (CH2), 27.1 (CH2), 29.5 (CH2), 29.8 (CH2), 29.9 (CH2), 30.1 (CH2),
30.3 (CH2), 30.4 (CH2), 30.6 (CH2), 30.9 (CH2), 32.2 (CH2), 34.4 (CH2),
34.7 (CH2), 68.1 (OCH2), 68.3 (OCH2), 75.9 (OCH2), 95.5 (CH), 97.6
(CH), 105.3 (CH), 108.3 (CH), 111.0 (CH), 114.6 (CH=CH2), 114.9 (CH=
CH2), 119.2 (CH), 129.8 (CH), 135.0 (C), 135.9 (C), 139.5 (CH=CH2),
139.8 (CH=CH2), 142.5 (C), 142.8 (C), 152.7 (C), 153.0 (C), 153.1 (C),
160.7 (C), 161.5 ppm (C); MS (ESI): m/z (%): calcd for C132H188N8O14Na:
2132.41; found: 2133.4 (100) [M+Na]+.
Trisloop calix[4]arene 6a: Compound 6a was prepared from calix[4]ar-
ene 10a (0.18 g, 0.11 mmol) as described for 5a. Purification by column
chromatography (THF/hexane 1:2) afforded 6a (0.12 g, 70%) as a white
solid. M.p. >3008C (decomposition); 1H NMR (400 MHz, [D8]THF,
258C): d=0.97 (brt, 3J
(H,H)=6.6 Hz, 12H; CH3), 1.22–1.51 (m, 56H;
G
CH2), 1.68 (m, 8H; CH2), 1.96 (m, 8H; CH2), 3.067 (d, 2J
ACHTREUNG
12.8 Hz, 2H; ArCH2Ar), 3.074 (d, 2J
ACHTREUNG
2
3.85 (m, 20H; OCH2), 4.44 (d, J
ACHTREUNG
4J
(H,H)=2.1 Hz, 2H; p-PhH), 6.40 (d”d, 3J
A
ACHTREUNG
AHCTREUNG
ACHTREUNG
AHCTREUNG
ACHTREUNG
[10] Cleavage of the urea links leads to huge macrocycles; see: Y. Cao,
L. Wang, M. Bolte, M. O. Vysotsky, V. Bçhmer, Chem. Commun.
2005, 3132–3134.
[11] a) M. O. Vysotsky, A. Bogdan, T. Ikai, Y. Okamoto, V. Bçhmer,
Chem. Eur. J. 2004, 10, 3324–3330; b) O. Molokanova, A. Bogdan,
M. O. Vysotsky, M. Bolte, T. Ikai, Y. Okamoto, V. Bçhmer, Chem.
Eur. J. 2007, 13, 6157–6170.
[12] For catenanes made with use of appropriate preorganisation: a) P.
Baeuerle, M. Ammann, M. Wilde, G. Goetz, E. Mena-Osteritz, A.
Rang, C. A. Schalley, Angew. Chem. 2007, 119, 367–372; Angew.
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Int. Ed. 2001, 40, 1538–1543.
7.47 (s, 4H; NH), 7.51 ppm (s, 4H; NH); 13C{1H} NMR (100.6 MHz,
[D8]THF, 258C): d=14.6 (CH3), 23.8 (CH2), 26.58 (CH2), 26.61 (CH2),
29.5 (CH2), 29.6 (CH2), 29.7 (CH2), 29.98 (CH2), 30.01 (CH2), 30.09
(CH2), 30.9 (CH2), 31.0 (CH2), 32.1 (CH2), 32.2 (CH2), 67.90 (OCH2),
67.94 (OCH2), 75.9 (OCH2), 76.0 (OCH2), 95.6 (CH), 97.3 (CH), 97.4
(CH), 105.5 (CH), 108.1 (CH), 111.0 (CH), 118.8 (CH), 118.88 (CH),
118.91 (CH), 119.1 (CH), 129.9 (CH), 135.0 (C), 135.1 (C), 135.8 (C),
142.5 (C), 142.8 (C), 152.5 (C), 152.9 (C), 153.0 (C), 160.7 (C), 161.4 (C),
161.5 ppm (C); MS (ESI): m/z (%): calcd for C106H143N8O14: 1752.07;
found: 1753.14 (100) [M+H]+.
Trisloop calix[4]arene 6b: Compound 6b was prepared and purified as
described for 6a, yield 73%; m.p. >3008C (decomposition); 1H NMR
(400 MHz, [D8]THF, 258C): d=0.97 (brt, 3J
(H,H)=6.6 Hz, 12H; CH3),
R
1.20–1.51 (m, 96H; CH2), 1.68 (m, 8H; CH2), 1.95 (m, 8H; CH2), 3.08 (d,
2J
2J
3J
ACHTREUNG
ACHTREUNG
A
ACHTREUNG
(s, 2H; o-PhH), 6.79 (m, 6H; ArH and PhH), 6.85 (s, 4H; ArH), 6.98
(d”d, 3J(H,H)=8.2 Hz, 3J
(H,H)=8.2 Hz, 2H; m-PhH), 7.10 (s, 2H; o-
A
ACHTREUNG
PhH), 7.44 (s, 2H; NH), 7.46 (s, 2H; NH), 7.51 (s, 2H; NH), 7.54 ppm (s,
2H; NH); 13C{1H} NMR (100.6 MHz, [D8]THF, 258C): d=14.6 (CH3),
23.8 (CH2), 26.8 (CH2), 26.9 (CH2), 29.5 (CH2), 29.8 (CH2), 29.87 (CH2),
29.91 (CH2), 29.97 (CH2), 30.00 (CH2), 30.1 (CH2), 30.2 (CH2), 30.3
(CH2), 30.9 (CH2), 32.1 (CH2), 32.2 (CH2), 68.1 (OCH2), 68.2 (OCH2),
75.9 (OCH2), 95.4 (CH), 97.6 (CH), 105.3 (CH), 108.1 (CH), 111.0 (CH),
119.0 (CH), 119.1 (CH), 119.2 (CH), 129.8 (CH), 134.97 (C), 135.00 (C),
135.8 (C), 142.5 (C), 142.8 (C), 152.6 (C), 152.9 (C), 153.0 (C), 160.7 (C),
161.5 ppm (C); MS (ESI): m/z (%): calcd for C126H182N8O14Na: 2054.37;
found: 2055.36 (100) [M+Na]+.
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Received: October 26, 2007
Published online: February 12, 2008
3354
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 3346 – 3354