Synthesis of a shape-persistent macrocycle with intraannular sulfonate groups

Article abstract of DOI:10.1002/ejoc.200390077

The synthesis of a shape-persistent macrocycle with two intraannular sulfonate groups is described. The cylization step is the oxidative acetylene coupling of large phenylethynyl oligomers which are covalently connected to a template. The synthesis of the templated acetylenes at the template as well as the cyclization step give high product yields showing that the template-directed approach is superior to statistical oligocyclizations. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejoc.200390077

FULL PAPER
Synthesis of a Shape-Persistent Macrocycle with Intraannular
Sulfonate Groups
Matthias Fischer[a][‡] and Sigurd Höger*[a][‡‡]
Keywords: Cyclization / Macrocycles / Template synthesis
The synthesis of a shape-persistent macrocycle with two in-
traannular sulfonate groups is described. The cylization step
is the oxidative acetylene coupling of large phenylethynyl
oligomers which are covalently connected to a template. The
synthesis of the templated acetylenes at the template as well
as the cyclization step give high product yields showing that
the template-directed approach is superior to statistical oligo-
cyclizations.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
change, keeping the molecular backbone and the functional
groups unchanged. In addition, if the macrocycles are ar-
ranged in stacks and their interior is properly designed,
one-dimensional ion conductance might be observed in the
solid state.
Introduction
Shape-persistent macrocycles with diameters in the nano-
meter range have attracted much interest during the last few
years.[1Ϫ5] Apart from the synthetic challenge, the supramo-
Despite this possibly fascinating new application of
lecular organization of these compounds in solution as well shape-persistent macrocycles it should be mentioned that
as in the bulk is a topic of ongoing research.[6Ϫ11] Their
interior offers the possibility of arranging functional groups
at defined positions in a convergent arrangement, which is
otherwise difficult to achieve.[12Ϫ14] Shape-persistent macro-
cycles with properly arranged functional groups allow the
specific interaction with appropriate organic guest molec-
ules or inorganic ions.[15Ϫ19] They may also be used as the
basis for the formation of porous materials because their
covalent construction avoids the problem of lattice inter-
penetration often observed with supramolecular 2- and 3-
D aggregates.[20Ϫ28] Here again, the possibility to arrange
functional groups at defined positions in a convergent ar-
rangement may give rise to the construction of organic mat-
erials as functional analogues of zeolites. Although during
the last years several shape-persistent macrocycles con-
taining functional groups have been reported, ionic com-
pounds are still relatively rare.[16,29] Since in this case the
counterion can influence the solid-state and solution struc-
ture, it opens the possibility of controlling the supramole-
cular organization of these materials by simple ion ex-
the combination of shape persistence of phenylene or phen-
ylene-ethynylene macrocycles (Staab et al.)[30,31] and the
concept of intraannular functional groups (Vögtle et
al.)[32Ϫ34] can already be found in spherands (Cram et
al.).[35Ϫ36]
One relatively easy synthetic route to shape-persistent
macrocycles is the oxidative intermolecular oligomerization
of rigid bis(acetylenes) under high-dilution conditions.[37]
As we have shown previously, even higher yields can be ob-
tained by coupling covalently templated tetra- or
hexaacetylenes.[38Ϫ41] In this case, the local concentration
of the terminal acetylenes is very high while their overall
concentration in the solution is still low by using the
pseudo-high-dilution technique. In addition, the template
can act as a protective group for the polar functionalities of
the molecule. Removing the template releases the functional
groups, which can then be used as binding sites for the re-
cognition of other molecules or can be further func-
tionalized (Scheme 1).
[‡]
New address: RohMax Oil Additives, Rx-FEA-CC,
Kirschenallee, 64293 Darmstadt, Germany
[‡‡]
New address: Polymer-Institut, Universität Karlsruhe
Hertzstr. 16, 76187 Karlsruhe, Germany
Fax: (internat.) ϩ 49-721/608-4421
E-mail: hoeger@chemie.uni-karlsruhe.de
[a]
Max Planck Institute for Polymer Research,
Ackermannweg 10, 55128 Mainz, Germany
Fax: (internat.) ϩ 49-6131/379-100
Scheme 1. Intraannular functionalized macrocycles by template-
directed diacetylene formation and subsequent template removal
E-mail: hoeger@mpip-mainz.mpg.de
Eur. J. Org. Chem. 2003, 441Ϫ446  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ193X/03/0203Ϫ0441 $ 20.00ϩ.50/0
441

M. Fischer, S. Höger
FULL PAPER
Here we report the synthesis of the shape-persistent mac-
rocycle 1 with two intraannular sulfonate groups. The key
step in this synthesis is the template-directed cyclization of
rigid bis(acetylenes) in which a bis(phenol) acts as the cova-
lent template and at the same time as a protective group for
the polar sulfonate moieties of the macrocycle.
Results and Discussion
The synthesis of 1 is outlined in Scheme 2. Base-catalyzed
alkylation of 4-tert-butyl-2,6-diiodophenol (3) with pro-
panesultone gave the potassium sulfonate 4 in 93% yield.
This compound was transformed into the corresponding
sulfonyl chloride 5 in 76% yield with thionyl chloride/di-
methylformamide. Reaction of 5 with 2,2-bis(4-hydroxy-
phenyl)propane under basic conditions gave the templated
tetraiodide 6 (81%). Fourfold HagiharaϪSonogashira reac-
tion of 6 with 7 formed the triisopropylsilyl-(TIPS-)pro-
tected tetraacetylene 8 in 92% yield. As we have shown be-
fore, the quadruple Pd-catalyzed coupling reaction leads to
a product whose molecular weight and physical properties
differ greatly from those of the starting materials and the
by-products, so that 8 could be isolated in high yield.[39]
Subsequently, the TIPS groups were removed by reaction
with tetrabutylammonium fluoride to form the templated
tetraacetylene 9 (90%).
Scheme 2. Synthesis of the macrocycle 1: a) propanesultone,
KOtBu; b) SO2Cl2, DMF; c) bis(4-hydroxyphenyl)propane, NEt3;
d) Pd0/CuI, NEt3; e) Bu4NF; f) CuI/CuII/pyridine; g) Bu4NOH
The oxidative acetylene coupling was carried out by
slowly adding a solution of the tetraacetylene in pyridine to
a slurry of CuCl2/CuCl in the same solvent over a period
of 4 d. The crude product of the reaction mixture was ana-
lyzed by gel permeation chromatography (GPC) indicating
that the amount of 2 in the crude product exceeds 90% (Fig-
ure 1, a). Column-chromatographic purification gave 2 in
an isolated yield of 90%.[42]
The deprotection of the aryl sulfonates turned out to be
somewhat problematic initially. Dissolving 2 in THF and
stirring with 10% aqueous NaOH solution at 90 °C did not
cleave the ester to any significant degree. Attempts to pre-
Therefore, the activity of the hydroxide was increased by
pare a macrocycle with a more labile template group (10) reaction with tetrabutylammonium hydroxide (40 wt.% in
failed.[43]
442
H2O) in THF to give the tetrabutylammonium disulfonate
Eur. J. Org. Chem. 2003, 441Ϫ446

Synthesis of a Shape-Persistent Macrocycle with Intraannular Sulfonate Groups
FULL PAPER
Figure 1. a) GPC of the crude cyclization product and of pure 2;
b) HPLC of 1 and 2
1
1 in 85% yield.[44] The H NMR spectrum of 1 (Figure 2,
a) shows the signals of the macrocyclic backbone at δ ϭ
7.4Ϫ7.7 (aϪf) and 1.3 ppm (n,o) and the aliphatic CH2
groups of the spacer between the rigid backbone of the mo-
lecule and the sulfonate group at δ ϭ 4.4 (g), 3.2 (i) and 2.5
Figure 2. a) 1H NMR spectrum of 1; b) MALDI-TOF spectrum
of 1
(h) ppm. The signals of the tetrabutylammonium group are
found at δ ϭ 3.4 (j), 1.7 (k), 1.4 (l) and 1.0 (m) ppm. The
signals of the template are absent, indicating that the depro-
tection is complete. Quantitative deprotection could also be
confirmed by analytical high performance liquid chromato-
graphy(HPLC) (Figure 1, b). Mass spectrometric analysis
(MALDI-TOF) of 1 shows an isotope-resolved signal pat-
tern at m/z ϭ 1776.4, corresponding to the mass of the mac-
rocyclic sulfonate and 3 Kϩ (Figure 2, b). Not surprisingly
for a sulfonate, elemental analysis indicates the presence of
four water molecules per macrocycle, even after drying in
vacuo.
Compound 1 is stable in air at room temperature and
dissolves well in organic solvents like 1,2-dichloroethane or
dimethylformamide. Within the investigated concentration
regime (0.25Ϫ20 mg/ml) no concentration-dependent signal
shift could be observed, thus there is no indication for any
aggregation of the macrocycles in these solvents.
ing of the product with LiCl in DMF was unsuccessful.[45]
A possible explanation for the low solubility of the Li com-
pound is that the metal cation is coordinated by several
sulfonate groups of different macrocycles leading to a phys-
ically crosslinked network. Future experiments with analog-
ous macrocycles containing additional oligoalkyl substitu-
ents at the exterior will show if this 3-D network formation
can be avoided and tractable ion-conductive materials can
be obtained.
In conclusion, we have synthesized the first shape-persist-
ent macrocycle consisting of two intraannular sulfonate
groups in a large internal void. Due to the use of a cova-
lently bound template in the cyclization reaction and during
the preparation of the precursors, the yields in each reaction
step are very high. These results show again that the tem-
plate-directed synthesis of shape-persistent macrocycles is
superior to statistical cyclooligomerization reactions. In
addition, the deprotection of the aryl sulfonate moieties has
been optimized and works now under mild conditions lead-
ing to soluble ionic shape-persistent macrocycles.
Due to our interest in tubular stacks of macrocycles with
possible Li-ion conductivity, we investigated if an exchange
of the counterion would lead to new functional materials,
eventually by further addition of Li salts. However, ex-
change of the organic cation by lithium decreased the solu-
bility of the macrocycle dramatically and did not lead to a
completely cation-exchanged product. Even repeated heat-
Eur. J. Org. Chem. 2003, 441Ϫ446
443

M. Fischer, S. Höger
FULL PAPER
ciently pure for the next step. An analytical sample was obtained
by chromatography on silica gel eluting with ethyl acetate (Rf ϭ
0.69). M.p. 94 °C. 1H NMR (250 MHz, CDCl3): δ ϭ 7.71 (s, 2 H),
4.12 (m, 4 H), 2.59 (m, 2 H), 1.25 (s, 9 H) ppm. 13C NMR
(62.5 MHz, CDCl3): δ ϭ 155.28, 151.09, 136.72, 91.93, 72.11,
48.89, 34.08, 31.12, 26.03 ppm. MS (FD): m/z ϭ 542.2 [Mϩ], 1084.1
[2 Mϩ]. C13H17ClI2O3S (542.60): calcd. C 28.78, H 3.16; found C
28.73, H 2.96.
Experimental Section
General Remarks: Reactions requiring an inert gas environment
were conducted under argon, and the glassware was oven-dried
(140 °C). THF was distilled from potassium prior to use. Triethyl-
amine and pyridine were distilled from CaH2 and stored under ar-
gon. Commercially available chemicals were used as received. Com-
pounds 3 and 7 are described elsewhere.[39,46] 1H and 13C NMR
spectra were recorded with a Bruker DPX 250 or AC 300 spectro-
meter (250 and 300 MHz for 1H, 62.5 and 75.48 MHz for 13C).
Chemical shifts are given in ppm, referenced to residual proton
resonances of the solvents. Thin-layer chromatography was per-
formed on aluminum plates precoated with Merck 5735 silica gel
60 F254. Column chromatography was performed with Merck silica
gel 60 (230Ϫ400 mesh). The gel permeation chromatograms were
measured in THF (flow rate 1 mL minϪ1) at room temperature,
using a combination of three styragel columns (porosity 103, 105,
106) and a UV detector operating at λ ϭ 254 nm. The molecular
weight was obtained from polystyrene-calibrated SEC columns.
RP-HPLC was performed using an HP 1100 gradient chromato-
graphy system. The chromatograms were measured in methanol/
water (80:20) over 20 min (start phase: methanol; flow rate 1 mL
minϪ1) at room temperature, using a reversed-phase column and a
UV detector operating at λ ϭ 340 nm. The matrix-assisted laser
desorption ionization time-of-flight (MALDI-TOF) mass spectro-
metry measurements were carried out with a Bruker reflex spectro-
meter (Bruker, Bremen), which incorporates a 337-nm nitrogen
laser with a 3-ns pulse duration (106Ϫ107 W/cm, 100 mm spot dia-
meter). The instrument was operated in a linear mode with an acce-
lerating potential of 33.65 kV. The mass scale was calibrated with
polystyrene (Mp ϭ 2300), using a number of resolved oligomers.
Samples were prepared by dissolving the macrocycle in THF at a
concentration of 10Ϫ4 mol/L. In all cases, 1,8,9-trihydroxyanthra-
cene (Aldrich, Steinheim) was used as the matrix. Field desorption
spectra were recorded with a VG ZAB 2-SE FPD machine. Mic-
roanalyses were performed by the University of Mainz. Melting
points were measured with a Reichert hot-stage apparatus and
are uncorrected.
Compound 6: Triethylamine (0.6 mL, 8.3 mmol) was slowly added
to a solution of 5 (2.3 g, 4.3 mmol) and 2,2-bis(4-hydroxyphenyl)-
propane (0.5 g, 2.1 mmol) in THF (10 mL) at 0 °C. The solution
was stirred for 1 h at 0 °C and then at room temperature overnight.
The formed precipitate was removed by filtration and the filtrate
was concentrated under reduced pressure. The yellow, oily residue
was purified by chromatography on silica gel eluting with CH2Cl2/
hexanes (2:1) (Rf ϭ 0.51) to give 6 (2.2 g, 81%) as yellow solid.
1
M.p. 77Ϫ80 °C. H NMR (250 MHz, CDCl3): δ ϭ 7.70 (s, 4 H),
7.22 (br. s, 8 H) 4.07 (t, Jϭ 5.7 Hz, 4 H), 3.67 (m, 4 H), 2.53 (m,
4 H), 1.65 (s, 6 H), 1.25 (s, 18 H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ ϭ 154.67, 150.87, 138.45, 136.28, 129.62, 127.51, 123.09,
120.91, 90.61, 71.88, 70.07, 47.98, 32.21, 30.54, 24.81 ppm. MS
(FD): m/z ϭ 1242.5 [Mϩ], 2485.2 [2 Mϩ]. C41H48I4O8S2 (1240.58):
calcd. C 39.70, H 3.90; found C 40.04, H 3.93.
Compound 8: [Pd(PPh3)2Cl2] (30 mg) and CuI (22 mg) were added
to a solution of 6 (0.92 g, 0.74 mmol) and 7 (1.47 g, 3.33 mmol) in
triethylamine (12 mL) under argon. The mixture turned dark after
a few minutes and was stirred overnight at room temperature and
then at 50 °C for 1 h. After cooling to room temperature, diethyl
ether (150 mL) and water (150 mL) were added, the organic phase
was separated and extracted with water (2 ϫ 75 mL), 10% acetic
acid (5 ϫ 75 mL), water (2 ϫ 75 mL), 10% aqueous NaOH
(3 ϫ 75 mL), water (2 ϫ 75 mL) and brine (75 mL). Drying with
MgSO4 and evaporation of the solvent yielded an oily residue,
which was purified by chromatography on silica gel eluting with
CH2Cl2/hexanes (1:2) (Rf ϭ 0.36) to give 8 (1.68 g, 92%) as a light
yellow foamy solid. M.p. 167 °C. 1H NMR (250 MHz, CDCl3):
δ ϭ 7.11 (d, Jϭ 8.8 Hz, 4 H), 7.04 (d, Jϭ 8.8 Hz, 4 H), 7.42Ϫ7.48
(m, 32 H), 4.44 (t, Jϭ 5.4 Hz, 4 H), 3.69 (m, 4 H), 2.50 (m, 4 H),
1.55 (br. s, 6 H), 1.32 (s, 18 H), 1.31 (s, 36 H), 1.13 (s, 28 H) ppm.
13C NMR (75.5 MHz, CDCl3): δ ϭ 157.91, 151.75, 149.26, 147.20,
147.16, 133.01, 132.61, 131.93, 131.66, 131.46, 129.32, 129.01,
128.48, 123.73, 123.58, 122.95, 122.89, 121.83, 116.90, 106.87,
93.53, 91.47, 90.88, 89.12, 87.71, 71.47, 48.16, 42.78, 34.90, 34.63,
31.40, 31.31, 30.98, 25.21, 23.55, 18.91, 11.54 ppm. MS (FD):
m/z ϭ 2483.5 [Mϩ]. C165H196O8S2Si2 (2483.87): calcd. C 79.79, H
7.95; found C 79.69, H 8.00.
Potassium 3-(4-tert-Butyl-2,6-diiodophenoxy)propanesulfonate (4):
4-tert-Butyl-2,5-diiodophenol (3) (30.8 g, 76.6 mmol) was dissolved
in tBuOH (100 mL) at 35 °C. KOtBu (1  in tBuOH, 76.6 mL,
76.6 mmol) and then propanesultone (6.7 mL, 76.6 mmol) were ad-
ded. A fine precipitate formed immediately. The mixture became
slowly more viscous and could not be stirred after 15 min. After
an additional hour at 35 °C, the solvent was removed under re-
duced pressure and the residue was recrystallized from methanol
(250 mL) to give 4 (37.5 g, 93%) as a colorless solid. M.p. 262 °C
(dec.). 1H NMR (250 MHz, [D6]DMSO): δ ϭ 7.75 (s, 2 H), 3.87
(t, Jϭ 6.3 Hz, 2 H), 2.65 (m, 2 H), 2.09 (m, 2 H), 1.22 (s, 9 H)
ppm. 13C NMR (62.5 MHz, [D6]DMSO): δ ϭ 155.23, 150.91,
136.69, 91.67, 72.52, 48.83, 34.01, 31.04, 26.28 ppm. MS (FD):
m/z ϭ 561.8 [Mϩ]. C13H17I2KO4S (562.25): calcd. C 27.77, H 3.05;
found C 27.48, H 2.95.
Compound 9: Tetrabutylammonium fluoride (1  solution in THF,
9.3 mL, 9.3 mmol) was added to a solution of 8 (1.65 g, 0.66 mmol)
in THF/water (39:1, 40 mL). The solution was stirred at room tem-
perature for 4 h. After evaporation of most of the solvent, diethyl
ether (300 mL) and water (200 mL) were added and the organic
phase was extracted with water (3 ϫ 100 mL) and brine (100 mL).
Drying with MgSO4 and evaporation of the solvent yielded an oily
3-(4-tert-Butyl-2,6-diiodophenoxy)propane-1-sulfonyl Chloride (5): residue which was treated several times with small portions of
SO2Cl2 (3.0 g, 24.9 mmol, 1.8 mL) was slowly added to a suspen-
sion of 4 (14.0 g, 24.9 mmol) in THF/DMF (2:1, 300 mL) at room
temperature. The solid dissolved and, after the heat evolution had
stopped (approx. 1 h), the solution was heated to 60 °C for 2 h.
After cooling to room temperature, the mixture was poured slowly
onto ice/water (1 L). The product was then filtered off and washed
three times with ice-cold water and then with petroleum ether.
After drying, 5 (10.3 g, 76%) was obtained as a fawn powder suffi-
methanol to give 9 (1.11 g, 90%), after drying in vacuo, as a light-
yellow foamy solid. M.p. 155 °C. 1H NMR (250 MHz, CD2Cl2):
δ ϭ 7.12 and 7.05 (d, Jϭ 8.8 Hz, each 4 H), 7.42Ϫ7.48 (m, 32 H),
4.42 (t, Jϭ 5.4 Hz, 4 H), 3.67 (m, 4 H), 2.88 (s, 4 H), 2.46 (m, 4
H), 1.55 (br. s, 6 H), 1.31 (s, 18 H), 1.30 (s, 36 H) ppm. 13C NMR
(75.5 MHz, CD2Cl2): δ ϭ 158.32, 152.76, 149.98, 147.93, 147.82,
133.49, 133.00, 132.29, 132.07, 131.87, 129.32, 129.40, 128.85,
124.01, 123.68, 122.91, 122.89, 121.83, 117.40, 106.87, 93.90, 91.66,
444
Eur. J. Org. Chem. 2003, 441Ϫ446

Synthesis of a Shape-Persistent Macrocycle with Intraannular Sulfonate Groups
FULL PAPER
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31.31, 30.98, 25.81, 23.55, 18.91 ppm. MS (FD): m/z ϭ 1859.6
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[7]
[8]
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Compound 2: A solution of 9 (1.10 g, 0.59 mmol) in pyridine
(50 mL) was added to a suspension of CuCl (8.44 g, 85.2 mmol)
and CuCl2 (1.68 g, 7.4 mmol) in pyridine (300 mL) over 96 h at
room temperature. After completion of the addition, the mixture
was stirred for an additional day, then poured into CH2Cl2
(300 mL) and water (200 mL). The organic phase was extracted
with water, 25% NH3 solution (in order to remove the copper salts),
water, 10% acetic acid, water, 10% aqueous NaOH and, finally,
brine. After drying with MgSO4, the solvent was evaporated to
about 20 mL, and the coupling products precipitated by the addi-
tion of methanol (200 mL) and collected by filtration. Recrystal-
lization from ethyl acetate followed by chromatography on silica
gel eluting with CH2Cl2/hexanes (1:1) (Rf ϭ 0.74) gave 2 (0.99 g,
90%) as slightly yellow solid. M.p. Ͼ 220 °C. 1H NMR (250 MHz,
CDCl3): δ ϭ 7.51Ϫ7.56 (m, 32 H), 7.28 (d, Jϭ 8.8 Hz, 4 H), 7.20
(d, Jϭ 8.8 Hz, 4 H), 4.42 (t, Jϭ 5.4 Hz, 4 H), 3.75 (m, 4 H), 2.56
(m, 4 H), 1.72 (s, 6 H) 1.34 (s, 18 H), 1.32 (s, 36 H) ppm. 13C NMR
(75.5 MHz, CD2Cl2): δ ϭ 159.05, 152.98, 150.18, 148.11, 147.41,
133.39, 133.03, 132.19, 132.05, 131.85, 129.21, 128.85, 123.99,
123.94, 123.78, 122.44, 121.83, 117.61, 93.85, 91.46, 89.99, 88.28,
81.97, 74.40, 72.24, 49.34, 43.49, 35.48, 35.13, 31.40, 31.31, 30.98,
25.94 ppm. MS (MALDI-TOF): m/z ϭ 1964.3 [M ϩ Ag]ϩ; 1878.1
[M ϩ Na]ϩ. C129H112O8S2 (1854.45): calcd. C 83.55, H 6.09; found
C 83.38, H 5.99.
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Compound 1: Tetrabutylammonium hydroxide (1.6 mL, 40% in
water) was added to a solution of 2 (220 mg, 0.12 mmol) in THF
(20 mL). The mixture was stirred overnight at 40 °C and then the
solution was concentrated to a small volume. Methanol was added
to the oily residue (10 mL), the suspension stirred for 4 h and the
product collected by filtration to give 1 (190 mg, 85%) as a yellow
solid. M.p. Ͼ 220 °C. 1H NMR (250 MHz, CDCl3): δ ϭ 7.61Ϫ7.44
(m, 32 H), 4.37 (t, Jϭ 5.7 Hz, 4 H), 3.30 (m, 16 H) 3.17 (m, 4 H),
2.48 (m, 4 H), 1.61 (m, 16 H), 1.41 (m, 16 H) 1.32 (s, 18 H), 1.31
(s, 36 H) 0.97 (t, Jϭ 7.2 Hz, 24 H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ ϭ 158.16, 152.34, 149.56, 148.17, 147.50, 133.48, 132.97,
132.06, 131.94, 131.80, 129.14, 128.76, 123.59, 123.29, 122.49,
121.78, 116.97, 93.47, 91.23, 89.27, 87.93, 81.97, 77.47, 71.77,
48.31, 42.89, 34.95, 34.66, 31.40, 31.31, 25.38, 16.93, 13.08,
11.29 ppm. MS (MALDI-TOF): m/z ϭ 1776.3 [MDianionϩ 3 Kϩ]ϩ.
C146H170N2O8S2·4 H2O (2217.2): calcd. C 79.08 H 8.11; found C
79.11 H 8.38.
[23]
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Acknowledgments
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445

M. Fischer, S. Höger
FULL PAPER
[42]
[45]
[46]
1
We also performed the statistical dimerization of the p-cresol-
High-temperature H NMR spectra of the soluble parts of the
material in DMSO still showed the presence of about 20Ϫ30%
of the signal intensity of the initial tetrabutylammonium ions.
S. Rosselli, A.-D. Ramminger, T. Wagner, G. Lieser, S. Höger,
in preparation.
protected bis(acetylenes) and obtained the corresponding mac-
rocyclic dimer in 30% isolated yield after recrystallization (the
crude cyclization product contained about 60Ϫ70% of the mac-
rocyclic dimer).
[43]
The electron-withdrawing effect of the sulfone group led to a
Received July 25, 2002
cleavage of the aryl sulfonate group by fluoride ions when we
tried to prepare the template-free tetraacetylene.
Attempts to use a mixture of NaOH and 18-crown-6 led to
[O02427]
[44]
undefined side products.
446
Eur. J. Org. Chem. 2003, 441Ϫ446