Oligophenylcalix4|arenes as potential precursors for funnelenes and calix[4]triphenylenes: Syntheses and preliminary cyclodehydration studies

Article abstract of DOI:10.1002/ejoc.200600463

The concept for a new class of nonplanar polyaromatic hydrocarbons - the funnelenes - is presented. Retrosynthetic considerations lead to polyphenyl- and oligophenylcalix[4]-arenes as potential precursors. In this paper we describe the synthesis of these

Full text of DOI:10.1002/ejoc.200600463

FULL PAPER
DOI: 10.1002/ejoc.200600463
Oligophenylcalix[4]arenes as Potential Precursors for Funnelenes and
Calix[4]triphenylenes: Syntheses and Preliminary Cyclodehydration Studies
Michael Mastalerz,[a] Gerald Dyker,*[a] Ulrich Flörke,[b] Gerald Henkel,[b] Iris M. Oppel,[a]
and Klaus Merz[a]
Keywords: Calixarenes / Funnelenes / Palladium / Nanostructures / Supramolecular chemistry
The concept for a new class of nonplanar polyaromatic hy- studies on a model compound which leads to a hexabenzoco-
drocarbons − the funnelenes − is presented. Retrosynthetic
considerations lead to polyphenyl- and oligophenylcalix[4]-
arenes as potential precursors. In this paper we describe the
synthesis of these calixarenes and the first cyclodehydration
ronene derivative.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
Polycyclic aromatic hydrocarbons (PAHs) can be re-
garded as partial structures of, and therefore as model com-
pounds for, graphite, fullerenes and carbon nanotubes. Pre-
parative studies in modern hydrocarbon chemistry are fre-
quently aimed at the synthesis of large plane graphite
sheets[1] and of geodesic fullerene substructures,[2] such as
corannulene[3] or sumanene.[4] Carbon nanotubes are re-
ceiving particularly broad interest because of their manifold
amazing physical and electronic properties.[5] Small cyclic
fragments of carbon nanotubes are objects of theoretical
calculations,[6] however, the so called cyclacenes, for exam-
ple, have not yet been synthesised.[7]
Figure 1. Computer-generated model (MM2-optimised) of the
functionalised funnelene 1.
We envisioned a new class of large extended aromatic
carbon π-systems with a conical topology (Figures 1 and
2), which we called funnelenes (1 and 2) because of their
funnel-like shape, and it seemed obvious that calix[4]ar-
enes,[8] which can easily be rigidified in the cone conforma-
tion, could be suitable starting materials for funnelenes.
As a result of retrosynthetic analysis the cyclodehy-
dration (dashed lines in Scheme 1) of the oligophenylic ca-
lixarenes 3 and 4 would be a straightforward synthetic ap-
proach to the funnelenes.
Figure 2. Computer-generated model (MM2-optimised) of the
functionalised funnelene 2.
In this paper we describe the synthesis of the oligophen-
ylcalixarenes and preliminary studies on cyclodehydration
reactions with an alkoxy-substituted model compound.
Results and Discussion
Compound 3 is accessible with excellent yields of up to
85% by a fourfold Diels–Alder reaction of the tetraethyn-
ylcalixarene 5[9] with tetracyclone (6), followed by CO ex-
trusion (Scheme 2), and was characterised by NMR spec-
troscopy and an X-ray crystal structure analysis.
[a] Fakultät für Chemie, Ruhr-Universität Bochum,
Universitätsstrasse 150, 44780 Bochum, Germany
E-mail: gerald.dyker@ruhr-uni-bochum.de
[b] Fakultät für Chemie, Universität Paderborn,
Warburger Str. 100, 33098 Paderborn, Germany
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
Suitable crystals were obtained by diffusion of methanol
into a dichloromethane solution of 3 (Figures 3 and 4);[10]
they were found to crystallise in the monoclinic space group
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Scheme 1. The polyphenylic calixarenes 3 and 4 as precursors for funnelene syntheses by cyclodehydration. Dashed lines indicate the
necessary formation of C–C bonds (R = alkyl).
Scheme 2. Diels–Alder reaction of the tetraethynylcalixarene 5 with tetracyclone (6).
C2/c. Dichloromethane molecules are loosely bound in the 6.35 ppm, with an integral of eight protons, and the signal
lattice voids: when the crystals are removed from the of 6-H of the oligophenyl substituents appears at δ =
mother liquor they rapidly lose their crystalline brightness 7.31 ppm, with an integral of four protons.
due to the decomposition of the clathrate. Statistically, 2.91
Most interestingly, the tetrakis(phenylethynyl)calixarene
dichloromethane molecules are clathrated for each calixar- 7 reacts selectively with two equivalents of tetracyclone (6)
ene. The calixarene is fixed in a pinched cone conformation in diphenyl ether at 190 °C to give 8 in 72% yield
and the peripheral phenyl units are slightly twisted with re- (Scheme 3). Neither higher reaction temperatures (269 °C)
spect to one another. The R value of 7.6% can be explained nor a change of the solvent (benzophenone, 305 °C) gave
by disordered propyl moieties and phenyl rings, and the loss the fourfold Diels–Alder product 9, probably for reasons of
of solvent molecules.
steric hindrance.
In the 1H NMR spectrum of 8 two doublets for the
1
In the H NMR spectrum the bridging methylene pro-
tons appear at δ = 2.60 (equatorial) and 4.15 ppm (axial), methylene protons, each of which integrates for four pro-
whereas the equatorial protons are influenced by the pe- tons, appear at δ = 2.67 and 4.05 ppm. Two sets of signals
ripheral phenyl units and therefore undergo a relative up- are also observed for the propyloxy substituents, and two
field shift compared to other cone calix[4]arenes. Two sing- singlets for the m-aryl protons of the calixarene scaffold res-
lets are diagnostic in the aromatic region: the signal of the onances at δ = 5.97 and 6.53 ppm (4 H each). The sp-hy-
m-protons of the calixarene scaffold appear at δ = bridized carbon atoms of the phenylethynyl substituents
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Potential Precursors for Funnelenes and Calix[4]triphenylenes
FULL PAPER
Figure 3. Crystal structure of compound 3 with thermal ellipsoids. Hydrogen atoms have been omitted for clarity.
Figure 4. Packing of 3 in the unit cell. View along the crystallographic b-axis. Hydrogen atoms and solvent molecules have been omitted
for clarity.
can be clearly seen as two signals at δ = 116.7 and ture procedures, to give calixarenes 11a and 11b in good
124.35 ppm in the 13C NMR spectrum. Upon attempting and moderate yields respectively.[11] The calixarenes 12a–
to grow crystals from dichloromethane/methanol molecules 12d were obtained in good yields upon subsequent haloge-
of the alcohol became clathrated and could not be removed nation (Scheme 4).[12,13]
even after heating the substance in a kugelrohr oven for
several hours. This was confirmed both by recording a H biphenylboronic acid (13) in a palladium-catalysed Suzuki
NMR spectrum of the crystalline substance and by elemen- reaction to give the oligophenylcalixarenes 4a, 4b, 14a and
The halocalixarenes 12a–12d were cross-coupled with 2-
1
tal analysis.
14b (Scheme 5 and Table 1).[14]
The retrosynthetic analysis of the smaller funnelene 2
We obtained a mixture of the twofold (14a), threefold
suggests the oligophenylcalixarenes 4a and 4b as suitable (14b) and tetra-coupled (14c) products in the ratio 15:62:23,
1
precursors. For their synthesis we started with the fixation as determined from the diagnostic H NMR signals, from
of calixarene 10 in a cone conformation and subsequent the coupling reaction of the tetrabromide 12a with the bo-
halogenation in the 4-position, essentially following litera- ronic acid 13. The product mixture could not be further
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Scheme 3. Diels–Alder reaction of tetrakis(phenylethynyl)calixarene 7 with tetracyclone (6).
Scheme 4. a) DMF, NaH, RBr, 60–70 °C, 2 h. b) bromination: NBS, 2-butanone, room temperature, 3 d (12a), 24 h (12c); iodination: 1.
Ag(OOCCF3), CHCl3, 15 min; 2. I2, 20 min.
separated by flash chromatography; instead, fractional crys-
tallisation from toluene/pentane allowed us to enrich the fusion of pentane into a saturated solution of 4a in toluene.
threefold product 14b up to a purity of 93%. This compound crystallises in the monoclinic space group
Suitable single crystals of 4a were grown by slow dif-
Under the same reaction conditions (refluxing THF) the P21 and contains one clathrated molecule of toluene per
tetraiodo compound 12b gave the desired fourfold product calixarene.[10] The calixarene molecules are in a pinched-
4a selectively, but with only a moderate yield of 49%. Carry- cone conformation where two of the peripheral phenyl rings
ing out the reaction in a screw-capped vessel at 120 °C al- are exo- and two are endo-oriented to the cavity (see Sup-
lowed the yield of the desired fourfold coupling product to porting Information).
be increased up to 83%. Similar results were obtained for
The synthesis of calixarene 16 was achieved in a very
the coupling reactions with tetrahalocalixarenes 12c and 12d. good yield by Suzuki cross-coupling of the monobromide
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Potential Precursors for Funnelenes and Calix[4]triphenylenes
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Scheme 5. Suzuki cross-coupling reaction of halocalixarenes 12a–12d with 2-biphenylboronic acid (13). See Table 1 for conditions and
yields.
Table 1. Suzuki cross-coupling reactions of halocalixarenes 12a– ditions. O-Alkylation was achieved by a procedure de-
12d and 15 with boronic acid 13.[a]
scribed in the literature,[14c] and a Sonogashira cross-coup-
ling reaction with phenylacetylene gave the tolane 19 in
good yields. Subsequent Diels–Alder reaction with tetracy-
clone 6 led to 20. Different standard procedures for the oxi-
dative cyclodehydration reactions were tested, for example
reaction with AlCl3/CuCl2 in CS2, FeCl3 in dichlorometh-
ane/nitromethane[1,18] and MoCl5 in dichloromethane.[19]
The best results were obtained with FeCl3 in dichlorometh-
ane/nitromethane. Because of the very low solubility of the
hexabenzocoronene (HBC) 21 in usual solvents, the analysis
was restricted to IR and UV/Vis spectroscopy and
MALDI-TOF mass spectrometry.[20] Chlorinated and par-
tially dehydrogenated products were detected as minor by-
products of 21 in the MALDI-TOF mass spectrum of the
crude product. Purification by Soxhlet extraction gave pure
21 (no peaks of by-products were observed in the MALDI-
TOF mass spectrum) in 41% yield. The UV/Vis spectrum
of a benzene solution of 21 reveals three absorptions at λ =
391, 360 and 344 nm, which are typical for the unsubsti-
tuted HBC.[21]
Entry
1[b]
Calixarene Temp. [°C]
Time
26 h
Products (yield %)
12a
67[c]
14a (14)
14b (59)
4a (22)
4a (83)
4a (49)
4b (91)
4b (31)
16 (87)
2
3
4
5
6
12a
12b
12c
12d
15
120[d]
67[c]
21 h
16 h
20 h
16 h
24 h
120[d]
67[c]
120[d]
[a] Reaction conditions: THF as solvent, a 2  aqueous potassium
carbonate solution as base and 6 mol-% [Pd(PPh3)4] as catalyst
were heated under argon. [b] After flash chromatographic purifica-
tion the yields were determined by the ratio of integrals of diagnos-
1
tic H NMR signals of the calixarene mixture. [c] Reflux tempera-
ture. [d] The reaction was carried out in a screw-capped vessel.
15[15] with the boronic acid 13 under the same conditions
as for compound 4a (Scheme 5 and Table 1).
1
In the H NMR spectrum of compound 16 the signals
of the aryl protons Ha, Hb and Hc (Figure 5) in the proxim-
ity of the triphenylene unit are found in the relatively up-
field region at δ = 5.86, 6.25 and 6.31 ppm, probably due
to an anisotropic ring-current effect of the peripheral
phenyl unit, thus indicating that this substituent is prefera-
bly endo oriented due to CH–π interactions (see Fig-
ure 5).[16] Neither the addition of N-methylpyridinium io-
First attempts to cyclodehydrate calixarene 16 under the
same conditions (FeCl3 in CH2Cl2/CH3NO2) gave only re-
covered starting material. In the case of MoCl5 an unse-
lected cleavage of the propyloxy moieties takes place to give
the hydroxycalixarenes 23a and 23b (Scheme 7) as a 1:1
mixture.[22]
Although the insoluble crude materials we obtained from
dide to the NMR solution of 16 nor a solvent change to the reaction of oligophenylcalixarenes 3, 4a and 4b with
[D8]toluene caused a downfield shift of these signals. FeCl3 in nitromethane/dichloromethane exhibit strong fluo-
The X-ray crystal structure of 16[10] (see Supporting In- rescence, we could not detect any signals in the MALDI-
formation) confirms the hypothesis of intramolecular CH– TOF mass spectrum that could be evidence for the funnel-
π interactions. Suitable crystals grown from toluene/pentane enes 1 and 2. In the mass spectrum of the crude product of
showed no clathrated solvent molecules. The peripheral 3 with FeCl3 signals corresponding to the loss of 20, 48 and
phenyl unit is endo oriented, with an average distance to 60 hydrogens were observed, besides cleavage of the O-alkyl
one of the proximal meta-protons of about 3.48 Å, in agree- bonds; 64 hydrogen atoms must be eliminated for the for-
ment with the typical range of CH–π interactions.[16,17]
mation of the funnelene 1. In the case of 4a the mass spec-
The model compound 20 (Scheme 6) was synthesised trum of the crude product is best interpreted in terms of
from commercially available bromophenol 17 as a test sub- partial dehydration in combination with cleavage of O-alkyl
strate for the cyclodehydration under various reaction con- bonds, which is typical for the formation of spiro-annulated
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1
Figure 5. Aromatic region of the H NMR spectrum of 16 in CDCl3 (400 MHz).
Scheme 6. Synthesis and cyclodehydration of model compound 20.
products.[14g] Indeed, the strong absorption observed at
Conclusions
1667 cm–1 in the IR spectrum of the crude material is typi-
cal for the carbonyl bond of a spiro-annulated substruc-
ture.[14g,23]
A new class of polyhydrocarbon compounds − the fun-
nelenes − has been conceptually introduced and an access
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Potential Precursors for Funnelenes and Calix[4]triphenylenes
FULL PAPER
Scheme 7. Preliminary cyclodehydration experiments of 16 to approach the synthesis of an inherently chiral calix[4]triphenylene.
were dissolved in diphenyl ether (3 mL) and heated for 4 d at
190 °C. After cooling to room temperature the diphenyl ether was
removed by bulb-to-bulb distillation (200 °C, 5.0×10–1 mbar) to
give 400 mg of a dark-purple solid. TLC (light petroleum ether/
ethyl acetate, 5:1): Rf = 0.28, 0.35, 0.44 (8), 0.53. Separation by
column chromatography (light petroleum ether/ethyl acetate, 10:1;
Rf = 0.12) and drying in vacuo gave 65 mg (77%) of calixarene 8
as a pale-yellow solid. Recrystallisation from CH2Cl2/MeOH (1:1)
gave 61 mg (72%) of pale-yellow crystals (1:1 complex with meth-
to these substances from polyphenyl- and oligophenylcalix-
arenes fixed in the cone conformation as potential precur-
sors evaluated. Although the cyclodehydration of a model
compound has been successfully achieved, first attempts to
use these conditions for the complete cyclodehydration of
the calixarene 16 failed. Future work will focus on deriva-
tives of the oligophenylcalixarenes with increased solubility
in order to simplify the purification and analysis of the
cyclodehydration products.
anol) with m.p. Ͼ320 °C. IR (KBr): ν = 3078 cm–1, 3055, 3023,
˜
2953, 2921, 2859, 2203, 1594, 1484, 1469, 1453, 1398, 1383, 1297,
1227, 1195, 1180, 1156, 1125, 1102, 1070, 1016, 984, 953, 906, 875,
867, 812, 766, 750, 734, 719, 688, 563, 547. UV/Vis (CH3CN): λmax.
Experimental Section
1
(lgε) = 207 nm (6.4, sh), 239 (6.1), 273 (5.8, sh), 306 (5.5, sh). H
General Remarks: Melting points (uncorrected values) were deter-
mined with a Kofler Heizmikroskop, model Reichert Thermovar.
Elemental analysis was performed with a Carlo–Erba Elemental
Analyser 1106 or a Vario EL. Infrared spectroscopy was performed
with a Bruker Vector 22, a Bruker Equinox 55, a Perkin–Elmer
983G or a Perkin–Elmer 841. UV/Vis spectra were recorded with
a Perkin–Elmer Lambda 40 apparatus or a Varian Carey 1. 1H and
13C NMR spectra were recorded with a Bruker DPX 200, a Bruker
WM 300, a Bruker DRX 400 or a Bruker DRX 500 spectrometer.
MALDI-TOF spectra were recorded with a Bruker Daltonics flex
analysis (α-cyanocinnamic acid as matrix). Mass spectrometry was
performed with a Varian MAT 311 A, AMD 604, Varian MAT
CH5 or a VG Autospec instrument. SiO2 plates (Polygram SIL G/
UV 254) from Macherey–Nagel were used for TLC. All compounds
were purified by flash chromatography on Kieselgel 60 (Merck,
0.030–0.60 mm). All commercially available products were used
without further purification. The compounds 5,[9] 7,[9] 11,[11] 12a,[12]
12b[13] and 18[14c] were synthesised as previously described in litera-
ture.
NMR (500.1 MHz, CDCl3): δ = 0.74 (t, J = 7.4 Hz, 6 H,
OC2H4CH3), 0.99 (t, J = 7.4 Hz, 6 H, OC2H4CH3), 1.50 (m, J =
7.8 Hz, 4 H, OCH2 CH2 CH3 ), 1.75 (m, J = 7.3 Hz, 4 H,
OCH2CH2CH3), 2.67 (d, J = 13.6 Hz, 4 H, Ar-CH2-Ar), 3.44 (t, J
= 6.9 Hz, 4 H, OCH2CH2CH3), 3.47 (s, 3 H, CH3OH) 3.79 (t, J =
8.2 Hz, 4 H, OCH2CH2CH3), 4.05 (d, J = 13.5 Hz, 4 H, Ar-CH2-
Ar), 5.97 (s, 4 H, Ar-H), 6.53 (s, 4 H, Ar-H), 6.85 (m, 44 H, Ar-
H), 7.04 (“t”, “J” = 7.8 Hz, 4 H, Ar-H), 7.10 (“d”, “J” = 7.0 Hz,
4 H, Ar-H), 7.16 (“d”, “J” = 8.6 Hz, 4 H, Ar-H), 7.22 (“d”, “J” =
7.6 Hz, 4 H, Ar-H), 7.35 (“d”, “J” = 8.3 Hz, 4 H, Ar-H) ppm. 13
C
NMR (125.8 MHz, CDCl3): δ = 10.03 (q, OCH2CH2CH3), 10.70
(q, OCH2 CH2 CH3 ), 21.89 (t, OCH2 CH2 CH3 ), 23.43 (t,
OCH2CH2CH3), 30.82 (t, Ar-CH2-Ar), 50.95 (t, OCH2CH2CH3),
75.57 (t, OCH2CH2CH3), 87.29 (s, Ar-C-C-ArЈ), 91.07 (s, Ar-C-
C-ArЈ), 116.67 (s, ArЈC-CC-Ar), 124.35 (s, ArC-CC-ArЈ), 124.68,
125.13, 125.17, 126.29, 126.57, 126.64, 126.96, 127.22, 127.30,
128.25, 130.79, 131.46, 131.50, 131.55, 131.60, 131.65, 132.13 (all
d, ArC-H), 133.10, 134.17 (s, ArC-CH2-Ar), 134.65 (s, ArC-CH2-
Ar), 139.96, 140.06, 140.26, 140.75, 140.85, 140.88, 140.91, 140.93,
141.17 (all s), 154.93 (s, ArC-O-), 155.71 (s, ArC-O-) ppm. MS (EI,
70 eV, 400 °C): m/z (%) 1706 (4) [M+ + 2], 1705 (7) [M+ + 1], 1704
(9) [M+], 1703 (7), 592 (5), 564 (5), 91 (9), 78 (8), 69 (7), 44 (100),
cone-17,23-Bis[1-(2,3,4,5,6-pentaphenyl)phenyl)-5,11-bis(phenyl-
ethynyl)-25,26,27,28-tetrakis(propyloxy)calix[4]arene (8): Calixar-
ene 7 (49 mg, 0.049 mmol) and tetracyclone 6 (352 mg, 0.92 mmol)
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43 (11), 42 (48), 41 (71), 40 (16), 39 (46), 38 (10), 37 (8).
C128H104O4·CH3OH (1738.2): calcd. C 89.13, H 6.26; found C
89.09, H 6.25.
(4) [M – 3C12H24]+. C76H120O4 (1097.8): calcd. C 83.15, H 11.02;
found C 83.10, H 10.90.
cone-5,11,17,23-Tetrabromo-25,26,27,28-tetrakis(dodecyloxy)calix-
[4]arene (12c): NBS (1.61 g, 9.03 mmol) was added to a solution of
calixarene 11b (1.03 g,1.06 mmol) in 2-butanone (20 mL) and the
mixture stirred for 24 h at room temperature. 2-Butanone (25 mL)
was then added and the mixture washed with aqueous 10 %
Na2S2O3 (10 mL), water (2×20 mL) and brine (20 mL), and dried
with MgSO4. The solvents were removed by rotary evaporation and
methanol (8 mL) was added. The precipitate was collected by fil-
tration, washed with methanol (3×2 mL) and dried in vacuo to
give 1.234 g (82%) of calixarene 12c as a colourless solid with m.p.
cone-25,26,27,28-Tetrakis(propyloxy)-5,11,17,23-tetrakis[1-(2,3,4,5-
tetraphenyl)phenyl]calix[4]arene (3): A solution of calixarene 5
(60 mg, 0.087 mmol) and tetracyclone 6 (550 mg, 1.43 mmol) in di-
phenyl ether (3 mL) was heated for 3 d at 190 °C. After cooling to
room temperature the diphenyl ether was removed by bulb-to-bulb
distillation (200 °C, 5.0×10–1 mbar) to give 620 mg of a dark pur-
ple solid. TLC (light petroleum ether/ethyl acetate, 10:1): Rf = 0.15,
0.26 (6), 0.41, 0.53 (3), 0.62. Separation by column chromatography
(light petroleum ether/ethyl acetate, 10:1; Rf = 0.26) gave calixarene
3 (157 mg, 85 %) as a pale-yellow solid after drying in vacuo
(200 °C, 5.0 ×10–1 mbar). Recrystallisation from CH2Cl2/MeOH
(6 mL) and drying in vacuo (200 °C, 5.0×10–1 mbar) gave 148 mg
(80%) of calixarene 3 as colourless crystals with m.p. Ͼ 320 °C. IR
56 °C. IR (KBr): ν = 2917 cm–1, 2850, 1570, 1456, 1381, 1296, 1253,
˜
1196, 1159, 994, 921, 855, 721. UV/Vis (n-hexane): λmax. (lgε) =
286 nm (3.8), 278 (3.8). 1H NMR (400.1 MHz, CDCl3): δ = 0.89
[t, J = 6.8 Hz, 12 H, OCH2CH2(CH2)9CH3], 1.27 [m, 72 H,
OCH2CH2(CH2)9CH3] 1.85 [“t”, J = 7.0 Hz, 8 H, OCH2CH2-
(CH2)9CH3], 3.08 (d, J = 13.5 Hz, 4 H, Ar-CH2-Ar), 3.83 [t, J =
7.5 Hz, 8 H, OCH2CH2(CH2)9CH3], 4.34 (d, J = 13.6 Hz, 4 H, Ar-
CH2-Ar), 6.80 (s, 8 H, Ar-H) ppm. 13C NMR (100.6 MHz, CDCl3):
δ = 14.1 [q, OCH2(CH2)10CH3], 22.7, 26.3, 29.5, 29.8 (two superim-
posed signals), 29.9 (three superimposed signals), 30.2, 30.8 [all t,
OCH2(CH2)10CH3], 32.0 (t, Ar-CH2-Ar), 75.6 [t, OCH2-
(CH2)10CH3], 115.2 (s, ArC–Br), 131.1 (d, ArC-H), 136.5 (s, ArC–
CH2-Ar), 156.7 (s, ArC–O-) ppm. MS (FAB): m/z (%) 1412 (2) [M
+ H]+. C76H116Br4O4 (1413.4): calcd. C 64.59, H 8.27; found C
64.13, H 8.57.
(KBr): ν = 3056 cm–1, 3033, 2961, 2932, 2875, 1600, 1495, 1468,
˜
1441, 1430, 1383, 1220, 1186, 1151, 1072, 1027, 1009, 966, 761,
698. UV/Vis (CH3CN): λmax. (lgε) = 207 nm (5.3, sh), 249 (5.0), 277
(4.9, sh). 1H NMR (500.1 MHz, CDCl3): δ = 0.93 (t, J = 7.5 Hz, 12
H, OCH2CH2CH3), 1.81 (m, J = 7.5 Hz, 8 H, OCH2CH2CH3),
2.61 (d, J = 12.3 Hz, 4 H, Ar-CH2-Ar), 3.72 (t, J = 7.7 Hz, 8 H,
OCH2C2H5), 4.15 (d, J = 12.3 Hz, 4 H, Ar-CH2-Ar), 6.35 (s, 8 H,
Ar-H), 6.63 (“t”), 6.72 (m, together 36 H, ArЈЈ-H), 6.86 (ЈtЈ), 6.90
(m, together 24 H, ArЈЈ-H), 6.97 (m, 8 H, ArЈЈ-H), 7.04 (m, 12 H,
ArЈЈ-H), 7.32 (s, 4 H, ArЈ-H) ppm. 13C NMR (125.8 MHz, CDCl3):
δ = 10.41 (q, OCH2CH2CH3), 22.89 (t, OCH2CH2CH3), 31.40 (t,
Ar-CH2-Ar), 76.46 (t, OCH2CH2CH3), 125.14, 125.21, 125.41,
125.94 126.51, 126.84, 127.58, 129.96, 130.08, 130.73, 131.48,
131.71 (all d, ArC-H), 133.39, 134.79 (s, ArC–CH2-Ar), 138.46,
139.28, 140.16, 140.22, 140.41, 140.72, 141.16, 141.18, 141.64 (all
s), 154.90 (s, ArC–O-) ppm. MS (EI, 70 eV, 380 °C): m/z (%) 2112
(1) [M+], 44 (37), 42 (69), 41 (100), 40 (63), 39 (59), 38 (13), 37 (8).
C160H128O4 (2114.7): calcd. C 90.87, H 6.10; found C 91.28, H 5.90.
cone-25,26,27,28-Tetrakis(dodecyloxy)-5,11,17,23-tetraiodocalix[4]-
arene (12d): A solution of calixarene 11b (785 mg, 0.72 mmol) in
dry chloroform (25 mL) was added dropwise to a boiling suspen-
sion of silver trifluoroacetate (642 mg, 2.91 mmol) in dry chloro-
form (25 mL). The mixture was refluxed for an additional 15 min.
Iodine (983 mg, 3.87 mmol) was then added in small portions and
refluxed for 20 min. After cooling to room temperature, the mix-
ture was filtered through a pad of Celite 535. The filtrate was
washed with 10 % aqueous Na2S2O3 (60 mL), water (4×20 mL)
and brine (25 mL), and dried with MgSO4. Solvents were removed
by rotary evaporation to give a yellow oil. Purification by flash
chromatography (5 g silica gel, light petroleum ether) and subse-
quent drying in vacuo (60 °C, 0.8 mbar) gave 974 mg (85%) of ca-
cone-25,26,27,28-Tetrakis(dodecyloxy)calix[4]arene (11b): Sodium
hydride (3.65 g, 152 mmol) was suspended in dry DMF (85 mL),
calix[4]arene 10 (2.00 g, 4.73 mmol) was added in portions and the
reaction mixture was heated for 30 min at 50 °C. After cooling to
room temperature 1-bromododecane (10 mL, 41.1 mmol) was
added dropwise and the reaction mixture was heated for 2 h at
65 °C. After cooling to room temperature ice/water (100 mL) was
added and the mixture extracted with dichloromethane (3×50 mL).
The organic layer was washed with water (3×50 mL), 1  aqueous
ammonia chloride solution (2 ×50 mL) and brine (50 mL), and
dried with MgSO4. Dichloromethane was removed by rotary evap-
oration to give a yellow solution, from which colourless needles
precipitated overnight. The needles were collected by filtration,
washed with methanol (3×4 mL) and dried in vacuo to give 2.05 g
(40%) of calixarene 11b as colourless needles with m.p. 60–62 °C.
lixarene 12d as a colourless solid with m.p. 59 °C. IR (KBr): ν =
˜
2917 cm–1, 2850, 1563, 1455, 1402, 1380, 1295, 1249, 1195, 1160,
1072, 994, 966, 919, 877, 858, 839, 802, 763, 721, 677, 648, 611,
585, 561, 531. UV/Vis (n-hexane): λmax. (lgε) = 290 nm (3.5), 280
1
(3.6). H NMR (400.1 MHz, CDCl3): δ = 0.89 ppm [t, J = 6.8 Hz,
12 H, OCH2CH2(CH2)9CH3], 1.27–1.35 [m, 72 H, OCH2CH2-
(CH2)9CH3], 1.84 [“t”, J = 7.0 Hz, 8 H, OCH2CH2(CH2)9CH3],
3.04 (d, J = 13.6 Hz, 4 H, Ar-CH2-Ar), 3.84 [t, J = 7.6 Hz, 8 H,
OCH2CH2(CH2)9CH3], 4.28 (d, J = 13.6 Hz, 4 H, Ar-CH2-Ar),
7.00 (s, 8 H, Ar-H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 14.14
[q, OCH2(CH2)10CH3], 22.74, 26.29, 29.45, 29.78, 29.83, 29.92
IR (KBr): ν = 3063 cm–1, 2919, 2850, 1586, 1466, 1378, 1292, 1245,
˜
1193, 1157, 1127, 1091, 1069, 1043, 1021, 995, 957, 913, 831, 800,
1
760, 721, 632, 602. H NMR (400.1 MHz, CDCl3): δ = 0.90 [t, J
(three superimposed signals), 30.16, 30.44 [all t, OCH2(CH2)10
-
= 6.8 Hz, 12 H, OCH2 CH2 (CH2 )9 CH3 ], 1.29 [m, 72 H,
OCH2CH2(CH2)9CH3] 1.91 [“t”, J = 6.5 Hz, 8 H, OCH2CH2-
(CH2)9CH3], 3.15 (d, J = 13.5 Hz, 4 H, Ar-CH2-Ar), 3.88 [t, J =
7.5 Hz, 8 H, OCH2CH2(CH2)9CH3], 4.46 (d, J = 13.0 Hz, 4 H, Ar-
CH2-Ar), 6.56–6.61 (m, 12 H, Ar-H) ppm. 13C NMR (100.6 MHz,
CDCl3): δ = 14.1 (q, OCH2(CH2)10CH3], 22.7, 26.4, 29.5, 29.8 (two
superimposed signals), 29.9 (two superimposed signals), 30.0, 30.4,
CH3], 31.99 (t, Ar-CH2-Ar), 75.57 [t, OCH2(CH2)10CH3], 86.11 (s,
ArC–I), 136.88 (d, ArC-H), 137.19 (s, ArC-CH2-Ar), 156.45 (s,
ArC-O-) ppm. MS (FAB): m/z (%) 1601 (0.5) [M + H]+.
C76H116I4O4·C5H12 (1673.5): calcd. C 58.13, H 7.71; found C 57.73,
H 7.71.
cone-5-Bromo-11,17,23-tris[(2-phenyl)phenyl]-25,26,27,28-tetrakis-
31.1 [all t, OCH2(CH2)10CH3], 32.0 (t, Ar-CH2-Ar), 75.2 [t, (propyloxy)calix[4]arene (14b): Calixarene 12b (602 mg, 0.38 mmol)
OCH2(CH2)10CH3], 121.9 (d, ArC-H), 128.1 (d, ArC-H), 135.2 (s, and 2-diphenylboronic acid (1.112 g, 5.62 mmol) were dissolved in
ArC-CH2-Ar), 156.7 (s, ArC-O-) ppm. MS (FAB): m/z (%) 1097 a mixture of THF (18 mL) and an aqueous 2  potassium carbon-
(12) [M + H]+, 928 (3) [M – C12H24]+, 762 (5) [M – 2C12H24]+, 591 ate solution (18 mL). Tetrakis(triphenylphosphane)palladium(0)
4958
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 4951–4962

Potential Precursors for Funnelenes and Calix[4]triphenylenes
FULL PAPER
(194 mg, 160 µmol) was then added and the reaction mixture re-
fluxed for 26 h. After cooling to room temperature the layers were
separated and dichloromethane (10 mL) added to the organic layer.
The organic layer was washed with water (2 × 10 mL), brine
(10 mL) and dried with MgSO4. The solvents were then removed
by rotary evaporation to give a brown residue. TLC (light petro-
leum ether/ethyl acetate, 8:1): Rf = 0.55, 0.45 (14a, 14b, 4a), 0.30,
0.18, 0.03, 0.55. Separation by column chromatography (light pe-
troleum ether/ethyl acetate, 20:1) gave 712 mg of the ternary ca-
lixarene mixture (14a, 14b, 4a). Further fractional crystallisation
allowed calixarene 14b to be enriched to a grade of purity Ͼ93%.
2959, 2929, 2873, 1596, 1463, 1432, 1384, 1322, 1285, 1226, 1179,
1161, 1115, 1074, 1043, 1008, 965, 884, 777, 761, 743, 700, 615. UV/
Vis (CH2Cl2): λmax. (lgε) = 272 nm (sh, 4.4), 234 (4.9). 1H NMR
( 4 0 0 . 1 M H z , C D C l 3 ) : δ = 0 . 9 7 ( t , J = 7 . 5 H z , 1 2 H ,
OCH2CH2CH3), 1.88 (m, J = 7.5 Hz, 8 H, OCH2CH2CH3), 2.74
(d, J = 12.5 Hz, 4 H, Ar-CH2-Ar), 3.77 (t, J = 7.5 Hz, 8 H,
OCH2C2H5), 4.24 (d, J = 12.5 Hz, 4 H, Ar-CH2-Ar), 6.31 (s, 8 H,
Ar-H), 6.92–7.03 (m, 24 H, ArЈ-H), 7.19 (dt, J = 1.7, 6.9 Hz, 4 H,
ArЈ-H), 7.30–7.31 (m, 8 H, ArЈ-H) ppm. 13C NMR (100.6 MHz,
C D C l 3 ) : δ = 1 0 . 1 p p m ( q , O C H 2 C H 2 C H 3 ) , 2 2 . 8 ( t ,
OCH2CH2CH3), 30.7 (t, Ar-CH2-Ar), 76.7 (t, OCH2CH2CH3),
125.8, 126.4, 126.9, 127.2, 129.4, 129.8, 130.2 (all d, ArC-H), 133.5
(s), 134.5 (s, ArC-CH2-Ar), 140.0, 140.5, 141.6 (all s), 154.9 (s, ArC-
O-) ppm. MS (FAB): m/z (%) 1201 (58) [M + H]+. C88H80O4
(1201.6): calcd. C 87.96, H 6.71; found C 87.66, H 6.38.
Yield: 291 mg (39 %) with m.p. 220–225 °C. IR (KBr): ν =
˜
3053 cm–1, 3021, 2960, 2932, 2873, 1948, 1596, 1572, 1484, 1463,
1432, 1384, 1322, 1287, 1225, 1196, 1180, 1164, 1113, 1074, 1045,
1034, 1008, 965, 904, 880, 864, 777, 762, 743, 699, 637, 614, 598,
1
559. UV/Vis (CH2Cl2): λmax. (lgε) = 273 nm (sh, 4.5), 231 (5.1). H
cone-25,26,27,28-Tetrakis(dodecyloxy)-5,11,17,23-tetrakis[(2-
phenyl)phenyl]calix[4]arene (4b). a) From Tetraiodocalixarene 12d:
Calixarene 12d (910 mg, 0.57 mmol) and 2-diphenylboronic acid
(967 mg, 4.88 mmol) gave 298 mg (31%) of calixarene 4b under the
same conditions described for 4a.
NMR (400.1 MHz, CDCl3): δ = 0.86 (t, J = 7.3 Hz, 6 H,
OCH2CH2CH3), 1.01 (t, J = 7.3 Hz, 3 H, OCH2CH2CH3), 1.06
(t, J = 7.3 Hz, 3 H, OCH2CH2CH3), 1.81 (sext, J = 7.4 Hz, 4 H,
OCH2CH2CH3), 1.91 (m, 4 H, OCH2CH2CH3), 2.85 (d, J =
13.0 Hz, 2 H, Ar-CH2-Ar), 2.86 (d, J = 13.0 Hz, 2 H, Ar-CH2-Ar),
3.53 (t, J = 7.0 Hz, 2 H, OCH2C2H5), 3.60 (t, J = 7.3 Hz, 2 H,
OCH2C2H5), 4.00 (m, 4 H, two superimposed signals, OCH2C2H5),
4.27 (d, J = 13.0 Hz, 2 H, Ar-CH2-Ar), 4.30 (d, J = 13.0 Hz, 2 H,
Ar-CH2-Ar), 5.92 (s, 2 H, ArH), 6.16 (s, 2 H, BrArH), 6.71 (d, J
= 2.0 Hz, 2 H, ArH), 6.80 (d, J = 2.0 Hz, 2 H, ArH), 6.95–7.05
(m, ArH), 7.09 (t, J = 7.5 Hz, ArH), 7.18 (d, J = 7.0 Hz, ArH),
7.28–7.41 (m, ArH) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 9.59
(q, OCH2CH2CH3), 10.38 (q, OCH2 CH2CH3 ), 10.58 (q,
O C H 2 C H 2 C H 3 ) , 2 2 . 4 5 ( t , O C H 2 C H 2 C H3 ) , 2 3 . 0 6 ( t ,
OCH2CH2CH3), 23.11 (t, OCH2CH2CH3), 30.77 (t, Ar-CH2-Ar),
30.88 (t, Ar-CH2-Ar), 76.02 (t, OCH2CH2CH3), 76.06 (t,
OCH2CH2CH3), 76.94 (t, OCH2CH2CH3), 114.56 (s, ArC-Br),
125.56, 126.35, 126.60, 126.66, 126.93, 126.99, 127.06, 127.19,
127.83, 128.87, 129.45, 129.49, 129.89, 129.93, 130.26, 130.44,
130.61 (all d, all ArC-H), 131.50, 134.61, 134.97, 135.05, 135.19,
135.90, 139.98, 140.14, 140.22, 140.93, 141.37, 141.66, 141.97 (all
s), 153.92, 154.40 (both s, both ArC-O-), 156.02 (s, BrArC-O-)
ppm. MS (FAB): m/z (%) 1201 (23) (impurity of 4a), 1129 (22)
[M+]. C76H71BrO4 (1128.3): calcd. C 80.90, H 6.34; found C 80.53,
H 6.58.
b) From Tetrabromocalixarene 12c: Calixarene 12c (334 mg,
0.23 mmol) and 2-diphenylboronic acid (327 mg, 1.65 mmol), un-
der the same conditions as described for 4a, gave 355 mg (91%) of
calixarene 4b as a colourless solid with m.p. 88–93 °C. IR (KBr): ν
˜
= 3056 cm–1, 3021, 2919, 2849, 1595, 1464, 1433, 1380, 1323, 1285,
1231, 1176, 1116, 1079, 1009, 888, 762, 744, 722, 700, 615, 558.
UV/Vis (n-hexane): λmax. (lgε) = 262 nm (sh, 4.7), 243 (4.7). 1H
NMR (400.1 MHz, CDCl3): δ = 0.90 [t, J = 6.8 Hz, 12 H,
OCH2(CH2)10CH3], 1.29, 1.36 [both br. “s”, 72 H, OCH2CH2-
(CH2)9CH3], 1.86 [br. “t”, 8 H, OCH2CH2(CH2)9CH3], 2.74 (d, J
= 13.0 Hz, 4 H, Ar-CH2 -Ar), 3.80 [t, J = 7.2 Hz, 8 H,
OCH2CH2(CH2)9CH3], 4.24 (d, J = 13.0 Hz, 4 H, Ar-CH2-Ar),
6.31 (s, 8 H, ArH), 6.89–7.04 (m, 24 H, ArЈH), 7.20 (dt, J = 1.7, J
= 6.9 Hz, 4 H, ArЈH), 7.29–7.34 (m, 8 H, ArЈH) ppm. 13C NMR
(100.6 MHz, CDCl3): δ = 14.14 [q, OCH2CH2(CH2)9CH3], 22.75
[t, OCH2CH2(CH2)9CH3], 26.47, 29.49, 29.82, 29.89, 29.93, 30.05,
30.20 [all t, OCH2CH2(CH2)9CH3], 31.08 (t, Ar-CH2-Ar), 32.01 [t,
OCH2CH2(CH2)9CH3], 75.19 [t, OCH2CH2(CH2)9CH3], 126.17,
126.71, 127.21, 127.48, 129.69, 130.15, 130.50 (all d, ArC-H),
133.82 (s), 134.79 (s, ArC-CH2-Ar), 140.27, 140.84, 141.86 (all s),
154.22 (s, ArC-O-) ppm. MS (FAB): m/z (%) 1706 (1.7) [M+].
C124H152O4 (1706.6): calcd. C 87.27, H 8.98; found C 86.89, H 9.15.
cone-5,11,17,23-Tetrakis[(2-phenyl)phenyl]-25,26,27,28-tetrakis(pro-
pyloxy)calix[4]arene (4a). a) From Iodocalixarene 12b: Calixarene
12b (415 mg,0.38 mmol) and 2-diphenylboronic acid (600 mg,
3.03 mmol) were dissolved in a mixture of THF (10 mL) and an
aqueous 2  potassium carbonate solution (10 mL). Tetrakis(tri-
phenylphosphane)palladium(0) (105 mg, 90 µmol) was then added
and the reaction mixture refluxed for 16 h. After cooling to room
temperature the layers were separated and dichloromethane
(10 mL) was added to the organic layer. The organic layer was
washed with water (2 × 10 mL), brine (10 mL) and dried with
MgSO4. Solvents were removed by rotary evaporation to give a
brown residue. TLC (light petroleum ether/ethyl acetate, 8:1): Rf =
0.03, 0.18, 0.30, 0.45 (4a), 0.55. Separation by column chromatog-
raphy (PE/EA, 20:1) gave 223 mg (49%) of calixarene 4a.
cone-5-[(2-Phenyl)phenyl]-25,26,27,28-tetrakis(propyloxy)calix[4]ar-
ene (16): Calixarene 15 (656 mg, 0.98 mmol) and 2-diphenylboronic
acid (318 mg, 1.61 mmol) were dissolved in a mixture of THF
(20 mL) and an aqueous 2  potassium carbonate solution (20 mL)
in a screw-capped vessel. Tetrakis(triphenylphosphane)palla-
dium(0) (132 mg,110 µmol) was then added and the reaction mix-
ture heated at 120 °C for 21 h. After cooling to room temperature
dichloromethane (50 mL) was added and the layers separated. The
organic layer was washed with water (2×50 mL) and brine (50 mL)
and dried with magnesium sulfate. Solvents were removed by rotary
evaporation to give 1.020 g of an orange-coloured solid. Dichloro-
methane (15 mL) was added and the insoluble material filtered off.
The dichloromethane was removed by rotary evaporation, meth-
anol (15 mL) was added to the residue and the mixture ultra-soni-
cated. The resulting solid was collected by filtration, washed with
methanol (3×2 mL) and dried in vacuo to give 726 mg (99%) of
calixarene 16 as a colourless solid with a high grade of purity
(Ͼ95 %). Purification by flash chromatography (light petroleum
ether/ethyl acetate, 15:1, Rf = 0.40) and subsequent drying in vacuo
b) From Tetrabromocalixarene 12a: Calixarene 12a (399 mg,
0.44 mmol) and 2-diphenylboronic acid (752 mg, 3.79 mmol) were
dissolved in a mixture of THF (10 mL) and an aqueous 2  potas-
sium carbonate solution (10 mL) in a 50-mL, screw-capped vessel.
Tetrakis(triphenylphosphane)palladium(0) (132 mg, 110 µmol) was
added and the reaction mixture heated to 120 °C for 21 h. After
workup, 440 mg (83%) of calixarene 4a was isolated as colourless
crystals with m.p. 178–186 °C. IR (KBr): ν = 3055 cm–1, 3021, (0.6 mbar, 120 °C) gave 635 mg (87%) of calixarene 16 as a colour-
˜
Eur. J. Org. Chem. 2006, 4951–4962
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4959

M. Mastalerz, G. Dyker, U. Flörke, G. Henkel, I. M. Oppel, K. Merz
FULL PAPER
less solid with m.p. 169–171 °C. IR (KBr): ν = 3020 cm–1, 2963,
(light petroleum ether/ethyl acetate, 10:1): Rf = 0.09, 0.18, 0.27,
0.36 (20). Separation by column chromatography (light petroleum
ether/ethyl acetate, 20:1) and washing of the resulting solid with
light petroleum ether gave 960 mg (52%) of 20 as a colourless solid
˜
2920, 2874, 1587, 1456, 1432, 1383, 1288, 1248, 1225, 1211, 1194,
1156, 1088, 1067, 1034, 1008, 967, 884, 844, 798, 756, 743, 701,
668, 627, 498. UV/Vis (n-hexane): λmax. (lgε) = 265 nm (sh, 4.1),
1
216 (4.8). H NMR (400.1 MHz, CDCl3): δ = 0.91 (t, J = 7.5 Hz,
with m.p. 243–245 °C. IR (KBr): ν = 3055 cm–1, 3024, 2961, 2927,
˜
3 H, OCH2CH2CH3), 0.93 (t, J = 7.4 Hz, 3 H, OCH2CH2CH3), 2329, 1941, 1600, 1495, 1441, 1403, 1384, 1278, 1221, 1186, 1134,
1.06 (t, J = 7.3 Hz, 6 H, OCH2CH2CH3), 1.87 (sext, J = 7.2 Hz, 4 1070, 1028, 1011, 966, 906, 878, 814, 779, 755, 736, 698, 611. UV/
H, OCH 2 CH2 CH3 ) , 1 . 9 5 ( “ s ex t” , “ J ” = 7 . 7 Hz , 4 H,
OCH2CH2CH3), 2.97 (d, J = 13.4 Hz, 2 H, ArЈCH2Ar), 3.14 (d, J
= 13.4 Hz, 2 H, ArЈCH2 ArЈЈ), 3.69 (t, J = 7.0 Hz, 4 H,
Vis (CH3CN): λmax. (lgε) = 216 nm (4.6), 243 (4.6), 271 (4.0, sh).
1H NMR (400.1 MHz, CDCl3): δ = 0.97 (t, J = 7.3 Hz, 3 H,
OCH2CH2CH3), 1.66 (sext, J = 7.3 Hz, 2 H, OCH2CH2CH3), 1.87
OCH2CH2CH3), 3.95 (t, J = 7.8 Hz, 2 H, OCH2CH2CH3), 3.98 (t, (s, 6 H, Ar-CH3), 3.47 (t, J = 7.3 Hz, 2 H, ArOCH2C2H5), 6.38 (s,
J = 7.8 Hz, 2 H, OCH2CH2CH3), 4.37 (d, J = 13.2 Hz, 2 H, ArЈ-
CH2Ar), 4.44 (d, J = 13.4 Hz, 2 H, ArЈCH2ArЈЈ), 5.86 (d, J =
6.6 Hz, 2 H, ArЈ-3-H), 6.25 (d, J = 6.3 Hz, 2 H, ArЈ-5-H), 6.31 (t,
2 H, ArH), 6.81 (m, 25 H, ArЈH) ppm. 13C NMR (100.6 MHz,
CDCl3): δ = 10.6 (q, OCH2CH2CH3), 15.8 (t, OCH2CH2CH3), 23.5
(t, Ar-CH3), 73.6 (t, OCH2CH2CH3), 125.0, 125.1, 126.4, 126.5 (all
J = 7.5 Hz, 2 H, ArЈ-4-H), 6.74 (s, 2 H, Ar-3/5-H), 6.81 (t, J = s), 128.5 (s), 131.4, 131.5, 132.1 (all d), 135.6 (s), 140.0, 140.1, 140.2
7.5 Hz, 1 H, ArЈЈ-4-H), 6.98 (d, J = 7.4 Hz, 2 H, ArЈЈ-3/5-H), 7.22– (all d), 140.4 (s), 140.7 (s), 140.8 (s, five superimposed signals),
7.25 (m, 6 H, diphenyl-H), 7.30–7.33 (m, 1 H, diphenyl-H), 7.36–
7.42 (m, 3 H, diphenyl-H) ppm. 13C NMR (100.6 MHz, CDCl3): δ
= 9.99, 10.03, 10.71 (all q, all OCH2CH2CH3), 23.08, 23.13, 23.47
(all t, all OCH2CH2CH3), 30.88 (t, Ar-CH2ArЈ), 31.03 (t, ArЈ-
CH2ArЈЈ), 76.50, 76.56, 76.87 (all t, all OCH2CH2CH3), 121.79 (d,
ArЈЈ-C-4), 121.98 (d, ArЈ-C-4), 126.12 (d, diphenyl-C), 126.88 (s,
Ar-C-4), 127.12 (d, diphenyl-C), 127.49 (d, ArЈ-C-5), 127.88 (d,
ArЈ-C-3), 127.94 (d, diphenyl-C), 128.71 (d, ArЈЈ-C-3/5), 130.01 (d,
diphenyl-C), 130.36 (d, Ar-C-3/5), 130.53 (d, diphenyl-C), 133.54
(s, ArЈC-CH2-Ar), 133.61 (s, ArЈC-CH2-ArЈЈ), 135.91 (s, ArC-CH2-
ArЈ), 136.61 (s, ArЈЈC-CH2-ArЈ), 140.87 (s, diphenyl-C), 141.23 (s,
diphenyl-C), 142.16 (s, diphenyl-C), 155.51 (s, ArЈC-O-), 156.42 (s,
ArC-O-), 157.66 (s, ArЈЈC-O) ppm. MS (FAB): m/z (%) 768 (11)
[M + Na+], 745 (100) [M + H+]. C52H56O4 (745.01): calcd. C 83.83,
H 7.57; found C 83.77, H 7.83.
153.3 (s, ArC-O-) ppm. MS (FAB): m/z (%) 622 (11) [M + 2]+, 621
(36) [M + 1]+, 620 (33) [M]+, 578 (6). C47H40O·1/4CH2Cl2 (642.06):
calcd. C 88.39, H 6.36; found C 88.60, H 6.36.
1,3-Dimethyl-2-(propyloxy)hexa-peri-hexabenzocoronene (21): Poly-
phenyl 20 (130 mg, 0.21 mmol) was dissolved in dry dichlorometh-
ane (100 mL) and degassed with argon (15 min). A solution of
iron(III) chloride (1.36 g, 8.40 mmol) in dry nitromethane (20 mL)
was added dropwise with a syringe and the mixture stirred for an
additional 50 min at room temperature. During the whole reaction
time a moderate stream of argon was bubbled through the reaction
mixture. Methanol (100 mL) was added, the volume reduced to
about 20 mL by rotary evaporation and water (50 mL) added. The
resulting precipitate was filtered off and washed with water
(6×5 mL) and methanol (6 ×3 mL) to give, after drying, about
80 mg of a green-yellow solid. Impurities were removed by column
chromatography (10 g silica gel and 500 mL petroleum ether/
CH2Cl2, 5:2). The dried silica gel was extracted with a Soxhlet ap-
paratus and dichloromethane (20 h). The dichloromethane was
then removed by rotary evaporation to give, after drying in vacuo,
52 mg (41%) of 21 as a yellow solid with m.p. Ͼ 300 °C. IR (KBr):
2,6-Dimethyl-4-(phenylethynyl)propyloxybenzene (19): A solution of
bromophenol ether (18; 624 mg, 2.57 mmol) and phenylacetylene
(680 mg, 6.66 mmol) in trimethylamine (10 mL) was degassed with
argon for 10 min then [PdCl2(PPh3)2] (92 mg, 0.13 mmol) and CuI
(45 mg, 0.24 mmol) were added and the reaction mixture heated for
24 h at 90 °C. After cooling to room temperature dichloromethane
ν = 3083 cm–1, 2962, 2923, 2848, 1456, 1371, 1313, 1261, 1180,
˜
(25 mL) was added and the mixture washed with water (4×25 mL) 1155, 1075, 882, 801, 759, 739. UV/Vis (benzene): λmax. (lgε) =
and brine (25 mL). Dichloromethane was removed by rotary evapo-
ration to give a brown residue. TLC (light petroleum ether/CH2Cl2,
4:1): Rf = 0.03, 0.12 (19), 0.33. Purification by flash chromatog-
raphy (light petroleum ether/CH2Cl2, 10:1) gave 533 mg (79%) of
328 nm (sh, 4.0), 344 (4.4), 360 (4.8), 391 (4.3), 403 (sh, 3.8) ppm.
MS (MALDI-TOF): m/z (calcd.) 608.21 (100), 609.21 (53), 610.22
(14); m/z (found) 608.81 (100), 609.68 (55), 610.84 (13).
syn,syn-28-Hydroxy-5-[(2-phenyl)phenyl]-25,26,27-tris(propyloxy)ca-
lix[4]arene (23b) and syn,syn-26-Hydroxy-5-[(2-phenyl)phenyl]-
25,27,28-tris(propyloxy)calix[4]arene (23a): MoCl5 (153 mg,
0.56 mmol) was added to a cooled (0 °C) solution of calixarene 16
(100 mg, 0.13 mmol) in dry dichloromethane (10 mL) under argon
and the mixture stirred at 0 °C for 1.75 h. Saturated aqueous
NaHCO3 solution (25 mL) was added, the layers separated and the
aqueous layer extracted with dichloromethane (25 mL). The com-
bined organic layers were washed with water (25 mL) and brine
(25 mL) and dried with magnesium sulfate. Dichloromethane was
removed by rotary evaporation to give 83 mg of a brown solid.
Separation by flash chromatography (light petroleum ether/ethyl
acetate, 50:1) and subsequent recrystallization from 2-propanol
gave, from the mother liquor, 53 mg (58%) of a 1:1 mixture[22] of
23a and 23b as a colourless solid with m.p. 94–98 °C. 1H NMR
(400.1 MHz, CDCl3): δ = 0.93 (t, 6 H, OCH2CH2CH3), 1.10 (“t”,
12 H, OCH2CH2CH3), 1.88 (“sept”, 8 H, OCH2CH2CH3), 2.27
(sext, 4 H, OCH2CH2CH3), 3.05 (d, J = 12.8 Hz, 2 H, ArCH2Ar),
3.11 (d, J = 13.4 Hz, 2 H, ArCH2Ar), 3.21 (d, J = 13.2 Hz, 2 H,
ArCH2Ar), 3.29 (d, J = 13.9 Hz, 2 H, ArCH2Ar), 3.67–3.75 (m, 8
H, OCH2CH2CH3), 3.82–3.87 (m, 4 H, OCH2CH2CH3), 4.31 (d, J
= 14.1 Hz, 2 H, ArCH2Ar), 4.34 (d, J = 12.9 Hz, 2 H, ArCH2Ar),
19 as a pale-yellow solid with m.p. 58–61 °C. IR (KBr): ν =
˜
3051 cm–1, 2957, 2924, 2872, 2328, 2212, 1725, 1594, 1491, 1441,
1383, 1337, 1277, 1238, 1201, 1120, 1068, 1025, 963, 915, 886, 866,
816, 754, 691, 609, 525, 414. UV/Vis (CH3CN): λmax. (lg ε) =
207 nm (4.3), 284 (4.3), 301(4.3). 1H NMR (400.1 MHz, CDCl3): δ
= 1.11 (t, J = 7.5 Hz, 3 H, OCH2CH2CH3), 1.86 (sext, J = 7.1 Hz,
2 H, OCH2CH2CH3), 2.30 (s, 6 H, Ar-CH3), 3.76 (t, J = 7.3 Hz, 2
H, ArOCH2C2H5), 7.23 (s, 2 H, ArH),7.35 (m, 3 H, ArЈH), 7.52
(m, 2 H, ArЈH) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 10.6 (q,
OCH2CH2CH3), 16.2 (t, OCH2CH2CH3), 23.7 (t, Ar-CH3), 74.0 (t,
OCH2CH2CH3), 88.2 (s, ArCCArЈ), 89.5 (s, ArCCArЈ), 118.2 (s),
123.6 (s), 128.0 (d), 128.3 (d), 131.2 (s), 131.5 (d), 132.1 (d), 156.5
(s, ArC-O-) ppm. MS (EI): m/z (%) 265 (10) [M + 1]+, 264 (48)
[M]+, 223 (18), 222 (100), 221 (17), 189 (5), 115 (5), 59 (7), 43 (9),
41 (9), 27 (7). C19H20O (264.37): calcd. C 86.32, H 7.62; found C
86.24, H 7.76.
2,6-Dimethyl-4-[(2,3,4,5,6-pentaphenyl)phenyl]propyloxybenzene
(20): A solution of tolane (19; 783 mg, 2.97 mmol) and tetracyclone
(6; 1.229 g, 3.20 mmol) in diphenyl ether (4 mL) was heated for 3 d
at 190 °C. After cooling to room temperature, methanol (5 mL)
was added to precipitate about 1.1 g of an off-white solid. TLC
4960
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 4951–4962

Potential Precursors for Funnelenes and Calix[4]triphenylenes
FULL PAPER
SMART 1000 (Mo-Kα radiation). All structures were solved by
direct methods and refined by full-matrix least-squares using
SHELXTL-97 and PLATON/SQUEEZE.[24,25] All non-hydro-
gen atoms were refined using anisotropic thermal parameters.
Crystal data for 3: T = 153(2) K, C160H128O4·2.91CH2Cl2, M
= 2607.19, monoclinic space group C2/c, a = 20.3689(8), b =
26.8405(10), c = 28.3061(11) Å, β = 103.768(1)°, V =
4.38 (d, J = 13.2 Hz, 2 H, ArCH2Ar), 4.41 (d, J = 13.2 Hz, 2 H,
3
ArCH2Ar), 4.58 (s, 1 H, -OH), 4.61 (s, 1 H, -OH), 5.89 (dd, J =
4
3
4
7.1, J = 2.0 Hz, 2 H, ArЈ-3-H), 6.02 (dd, J = 6.7, J = 2.4 Hz, 2
H, ArЈЈ-3-H), 6.35–6.41 (m, 8 H, ArЈ-4/5-H und ArЈЈ-4/5-H), 6.79
(s, 1 H, Ar-mH), 6.87 (s, 1 H, Ar-mH), 7.11 (d, 2 = H, J = 7.3 Hz,
ArЈЈЈ-4-H), 7.17–7.26 (m, 12 H, ArЈЈЈ-H and biphenyl-H), 7.39–
7.50 (m, 8 H, biphenyl-H) ppm. 13C NMR (100.6 MHz, CDCl3): δ
= 9.63, 10.83 (both q, both -OCH2CH2CH3), 22.38, 23.46, 25.41
(all t, all -OCH2CH2CH3), 30.52, 30.62, 30.77, 30.81 (all t, all Ar-
CH2-Ar), 76.57, 76.61, 77.51 (all t, all -OCH2CH2CH3), 119.30,
122.88, 122.93, 122.97, 125.98, 126.09, 126.90, 127.22, 127.28,
127.47, 127.68, 127.80, 127.94, 128.05, 128.14, 128.42, 129.21,
129.76, 129.99, 130.05, 130.42, 130.50, 130.84, 130.89, 131.37 (d),
132.49, 132.53, 132.80, 133.24, 133.31, 136.46, 136.73, 137.28,
140.81, 140.89, 140.97, 141.20, 141.97, 142.20 (all s), 152.07,
153.36, 154.33, 154.42, 155.63, 156.97 (all s, all ArCO) ppm. MS
(FAB): m/z (%) 703 (79) [M + H+], 661 (10) [M – C3H6]+.
15030.6(10) Å3, Z = 4, Dc = 1.152 gcm–3, µ = 0.266 mm–1
,
1.52° Ͻ Θ Ͻ 28.6°, reflections collected/unique 47790/17152
[R(int) = 0.0494], data/restraints/parameters 17152/0/871, GOF
0.935, final R [I Ͼ 2σ(I)] R1 = 0.0764, wR2 (all data) = 0.2359,
residual density 0.799 and –0.445 eÅ–3. Crystal data for 4a: T
= 293(2) K, C88H80O4·2C7H8, M = 1385.79, monoclinic space
group P21, a = 18.4007(19), b = 23.644(3), c = 19.1697(19) Å,
β = 105.871(9)°, V = 8022.1(15) Å3, Z = 4, Dc = 1.147 gcm–3, µ
= 0.521 mm–1, 3.04° Ͻ Θ Ͻ 65.78°, reflections collected/unique
74457/13658 [R(int) = 0.0961], data/restraints/parameters
13658/0/1790, GOF 1.1117, final R [I Ͼ 2σ(I)] R1 = 0.0697,
wR2 (all data) = 0.1812, residual density 0.734 and
–0.628 e Å–3. Crystal data for 16: T = 213(2) K, C52H58O4,
M = 746.95, orthorhombic space group Pna21, a = 20.253(5),
b = 14.889(3), c = 28.256(5) Å, V = 8520(3) Å3, Z = 8, Dc =
1.158 gcm–3, µ = 0.072 mm–1, 1.55° Ͻ 2Θ Ͻ 25.00°, reflections
collected/unique 21404/6690 [R(int) = 0.0560], data/restraints/
Supporting Information (see also the footnote on the first page of
this article): 1H NMR spectrum of calixarene 3. 1H NMR spectrum
of calixarene 8. Crystal structures of 4a and 16. MALDI-TOF
mass spectra of benzocoronene 21, the solid (crude material) re-
sulting from the cyclodehydration of calixarene 3 and the solid
(crude material) resulting from the cyclodehydration of calixarene
4a.
parameters 6690/1/887, GOF 1.133, final R [I Ͼ 2σ(I)] R1
=
0.0695, wR2 (all data) = 0.2098, residual density 0.395 and
–0.276 e Å–3. CCDC-199298 (for 3), -609003 (for 4a) and
-608548 (for 16) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
[11]
This work was supported by the Fonds der Chemischen Industrie.
A generous donation of palladium chloride from Degussa AG is
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Eur. J. Org. Chem. 2006, 4951–4962
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4961

M. Mastalerz, G. Dyker, U. Flörke, G. Henkel, I. M. Oppel, K. Merz
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Received: May 29, 2006
Published Online: September 7, 2006
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