Preparation of orthogonal π-conjugated aryl alkynes and cyclophanes

Article abstract of DOI:10.1016/S0040-4020(00)00741-9

A series of anthracene based orthogonal π-conjugated aryl alkynes was prepared using palladium-catalyzed couplings. Thia- and azacyclophanes were prepared from anthracene based orthogonal π-conjugated aryl alkynes. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4020(00)00741-9

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 8335±8344
Preparation of Orthogonal p-Conjugated Aryl Alkynes
and Cyclophanes
*
Geoffrey T. Crisp and Peter D. Turner
Department of Chemistry, University of Adelaide, Adelaide 5005, South Australia, Australia
Received 2 June 2000; revised 31 July 2000; accepted 17 August 2000
AbstractÐA series of anthracene based orthogonal p-conjugated aryl alkynes was prepared using palladium-catalyzed couplings. Thia- and
azacyclophanes were prepared from anthracene based orthogonal p-conjugated aryl alkynes. q 2000 Elsevier Science Ltd. All rights
reserved.
Introduction
rings is enforced in oligomeric systems, are rare. The
emission spectra of such compounds exhibit features that
are related to the ability of closely spaced chromophores to
interact electronically through space.4 By controlling the
distance between adjacent strands of oligomeric cyclo-
phanes it should be possible to model interchromophore
contacts in bulk p-conjugated polymers. We required a
series of p-conjugated cyclophanes in order to investigate
the relationship between aromatic rings in close proximity
and their optoelectronic properties and report herein
methodologies for the preparation of precursors to oligo-
meric cyclophanes. We have previously reported the
preparation of the monomeric precursors to the orthogonal
Cyclophane structures continue to generate interest due to
their unique physical properties and their ability to act as
model compounds for the study of intramolecular processes1
and host±guest chemistry.2 Cyclophanes containing
extended p-conjugation have been investigated as mimics
for the solid-state interactions involving photoexcitation3
and for electron transfer processes involving extended
orthogonal p-systems.4 The spatial proximity of extended
p-conjugated frameworks in¯uences the optical and
electronic properties of the resulting bulk materials. Well-
de®ned systems, where the cofacial overlap of aromatic
Scheme 1.
Keywords: cyclophanes; arylalkenes; p-conjugated.
* Corresponding author. Tel.: 161-8-83035497; fax: 161-8-83034358; e-mail: geoffrey.crisp@adelaide.edu.au
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00741-9

8336
G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
Scheme 2.
p-conjugated aryl alkynes.5 In this paper we report their
conversion to cyclophanes and extended p-conjugated
aryl alkynes.
The coupling of methyl ester 4 with 1 was performed using
Pd(PPh3)4 and CuI in a mixture of benzene and triethyl-
amine at 508, since at lower temperatures the mono-coupled
complex precipitated from solution and prevented further
progress of the reaction. The product 12 was isolated in
99% after puri®cation on normal phase silica gel. Attempted
coupling of dimethyl ester 5 with 1 under these standard
conditions gave little coupled product, however, changing
the solvent to DMSO and using DBU as the base gave 13 in
a quantitative yield. Coupling of silyloxy protected 6 with 1
could be achieved under the standard conditions but the
desired product 14 was only isolated in a low 16% after
puri®cation using reverse phase silica. Both 7 and 8 could
be coupled with 1 under the standard conditions and the
respective products 15 and 16 were isolated using reverse
phase silica in 60 and 43% (Scheme 1).
Results and Discussion
In order to compare the ground state electronic properties of
p-conjugated aryl alkynes with their cyclophane analogues,
a series of model compounds was initially prepared. Thus,
4-iodotoluene 2 was coupled to 1,8-diethynylanthracene 16
using standard palladium-catalyzed coupling conditions7
(Pd(PPh3)4, CuI, piperidine in acetonitrile) to give the
desired bis-coupled material 9 in 92% (Scheme 1, base
and solvent as indicated). The product was readily soluble
in halogenated solvents and could be puri®ed by chroma-
tography on normal phase silica gel without streaking.
4-Iodophenol 3 was then coupled to 1 using these same
conditions, and upon workup, the resultant bis-coupled
product 10 streaked signi®cantly on both normal phase
silica and alumina. The introduction of the phenolic
hydroxyl group had had a dramatic effect on the solubility
of the product. To improve the isolated yield of 10 the crude
reaction material was silylated with thexyldimethylsilyl
chloride (TDSCl) and the resulting product 11 (R1ˆ
R2ˆH, YˆOTDS) was isolated in 52% (Scheme 1).
Reduction of diester 12 with LAH in THF at 0±258 gave the
desired diol in 81% after an acidic workup and puri®cation
on reverse phase silica. This diol was not characterized
but converted directly into the corresponding bromo-
8
methyl compound 17 with dppe and Br2 in 79%
(Scheme 2). The alkyne functionality was not affected
by either of these two steps. Reaction of 17 with
sodium sul®de adsorbed on alumina (2.5 mmol/g)9
gave the desired cyclophane 18 in 50% after puri®cation
on reverse phase silica.
Scheme 3.
Scheme 4.

G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
8337
Scheme 5.
In order to increase the solubility of the p-conjugated aryl
alkynes, 1,8-diiodo-10-methoxyanthracene 1910 was used as
the orthogonal template. The aryl substrates 20 and 21 both
contained unprotected benzyl alcohols and coupled readily
with 19 using the standard palladium-catalyzed coupling
conditions to give 22 and 23 in a quantitative yield (Scheme
3). Compounds 22 and 23 were converted into the corre-
sponding bromomethyl derivatives by the addition of PPh3
and NBS to a THF solution of either at low temperature.11
No addition to the alkyne group was observed under these
conditions and the required products 24 and 25 were
isolated in 56 and 64%, respectively (Scheme 3).
The preparation of a bis-strapped cyclophane was then
attempted as outlined in Scheme 6. Coupling of 1 with
2,6-bis(morpholinylmethyl)-4-iodophenol 315 in the
presence of Pd(PPh3)4, CuI in piperidine gave the bis-
coupled product 32 after one hour in 95%. The Mannich
base 32 was heated at re¯ux in acetic anhydride with a
small amount of acetic acid5 to give the hexa-acetate 33 in
a modest 34% after puri®cation by chromatography on
normal phase silica.
Complete hydrolysis of the acetate groups of 33 could not be
achieved under basic conditions (guanidine/MeOH12,
K2CO3/H2O/MeOH or LiOH/H2O/MeOH). Under acidic
conditions the reaction proceeded beyond complete
hydrolysis to give the mono-strapped cyclophane 34 in
56% through the displacement of a protonated hydroxy-
methyl group by the oxygen of an adjacent hydroxymethyl
This procedure was applied to the preparation of the
extended complex 28 through the palladium-catalyzed
coupling of bis(hydroxymethyl)alkyne 265 with 19 and
subsequent transformation of the hydroxyl groups of 27 to
bromides with dppe and Br2 as shown in Scheme 4. The
tetra(bromomethyl) derivative 28 was obtained in 89%
from 19 over the two steps.
1
substituent. The H NMR spectrum for 34 showed two
singlets at d 4.88 and d 5.07 of equal intensity for the two
types of benzylic methylene protons, and two doublets at d
7.93 and d 7.65 (Jˆ1.8 Hz) corresponding to the two
distinct aromatic protons of the benzylic ring. The 13C
NMR spectrum for 34 showed the expected 14 aromatic
signals, and the accurate mass was in agreement with the
calculated value. Cyclophane 34 was the sole product
isolated from the reaction, with no bis-strapped cyclophane
being observed. The cyclophane streaked extensively on
normal phase silica gel and had limited solubility in
common organic solvents, resulting in the modest isolated
yield.
The bis-coupled system 16 was extended further by a palla-
dium-catalyzed coupling with 2 equiv. of terminal alkyne
29 (Scheme 5). Standard coupling conditions were used
except that the reaction temperature was increased to 808
to aid in the oxidative addition of the hindered tri¯ate.
Under these conditions the two-unit oligomer 30 could be
produced in a reasonable yield of 44% after puri®cation on
normal phase silica. Solubility problems were encountered
with 30, nevertheless, the reactions outlined in Schemes 1
and 5 highlighted the regioselective coupling of iodoaryl
tri¯ates with terminal alkynes and indicated that further
coupling of the hindered tri¯ate was possible.
The formation of the mono-strapped thiacyclophane 35 was
accomplished by the addition of 3 equiv. of Na2S´Al2O3
Scheme 6.

8338
G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
Scheme 7.
Scheme 8.
(2.5 mmol/g)9 to 24 in dichloromethane/ethanol (20.2 mM,
5:1 v/v) as outlined in Scheme 7. After stirring at room
temperature for 1 h the crude product was puri®ed on
alumina to afford 35 in 85%. The 1H NMR spectrum showed
a characteristic up®eld shift in the singlet methylene protons
for 35 (d 3.43) compared to 24 (d 4.31). Variable tempera-
ture 1H NMR spectra for 35 obtained at 58 intervals between
258 and 2558 in CDCl3 showed no splitting, or even broad-
ening, of the benzylic methylene protons as the temperature
was lowered.
Molecular modeling (semi-empirical method using Spartan)
indicated that for 35 and 36 the effect of the strapping arm of
the cyclophane would be to introduce strain resulting in
rotation about the aryl±alkyne bonds. For 37 a signi®cant
degree of strain to the cyclophane structure would result in a
bending of the anthracene±alkyne±aryl bond. The three
atom strapping arm, ±CH2SCH2, was shown to be too
short to allow the formation of a strain free cyclophane.
The single crystal X-ray structure of 35 showed that the two
aromatic rings were not parallel to one-another, but that one
was approximately parallel to the anthracene and the other
was approximately perpendicular.13 This conformation was
probably due to intermolecular p±p stacking between
adjacent molecules in the crystal lattice. The distance
between one of the aryl rings of the cyclophane and the
anthracene ring of an adjacent molecule in the crystal lattice
Formation of azacyclophane 36 was possible by the addition
of 1.5 equiv. of TosNHNa to 24 in DMF under nitrogen with
heating. The reaction was complete in 1 h and an extractive
workup followed by chromatography on normal silica
yielded 36 in a quantitative yield. The azacyclophane 36
was observed to decompose in solution over several hours
in the sunlight, over several days in the dark and in the solid
state over several weeks. No identi®able decomposition
products could be isolated and characterized.
Ê
was 3.5 A, typical for intermolecular p±p stacking inter-
actions.14
The ultra-violet and ¯uorescence spectra of cyclophanes
have been studied in detail, as these compounds possess
interesting transannular interactions between the cyclophane
rings.15 These interactions arise when the linker-arms are
The bis-strapped thiacyclophane 37 was prepared in very
low yield from the reaction of 25 with Na2S´Al2O3 (Scheme
8). The H NMR spectrum for 37 showed the benzylic
1
methylene protons as an AB quartet (Jˆ15.0 Hz) which
suggested that the structure was more rigid than the
mono-strapped compounds 35 and 36.
Figure 1. The UV±Vis spectra of 13 and 30.
Figure 2. Ultra-violet spectra of 17 and 18.

G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
8339
equipped with a Reichart microscope. Electron impact (EI)
and fast atom bombardment (FAB) mass spectra were
recorded at 70 eV on a Vacuum Generators ZAB 2HF
mass spectrometer. Liquid secondary ionization mass spec-
trometry (LSIMS) and accurate mass spectra were
performed by the University of Tasmania mass spectro-
metric service. Infrared spectra were recorded on an ATI
Mattson Genesis FTIR as nujol mulls between sodium
chloride plates. Elemental analyses were performed at the
University of Otago, New Zealand. The UV±Vis spectra
were recorded as dilute solutions (,1025 M) in HPLC
grade THF. Thin layer chromatography (tlc) was carried
out using Merck Silica gel (Kieselgel) 60F254 on aluminum
backed plates. Solvents were puri®ed and dried using
standard laboratory procedures. All organic extracts were
dried over anhydrous magnesium sulphate. All solvents
for palladium catalyzed coupling reactions were degassed
by the freeze±pump±thaw method and kept under an atmos-
phere of nitrogen. All reactions involving anhydrous
solvents were also kept under an atmosphere of nitrogen.
Figure 3. Fluorescence spectra of 17 and 18.
short, typically two or three methylene units long, thereby
introducing deformations to the aromatic rings and so
reducing the ®ne structure observed. All the anthracene
containing compounds showed a broad series of absorptions
centered around 390 nm resulting from p±pp transitions to
low excited states (primary band) for the anthracene portion
of the molecule, and a quite sharp peak centered about
265 nm resulting from higher energy p±pp transitions
(secondary band) for the aryl alkyne portion of the
molecule.16 In general, the primary band contained more
vibrational ®ne structure than the secondary.
The following compounds were all prepared by literature
procedures: 1,8-diethynylanthracene 1,6 methyl 3-iodo-
benzoate 4,5 dimethyl-5-bromoisophthalate 5,5 2,6-bis-
(morpholinomethyl)-4-iodophenol 6,5 dimethyl 5-iodo-2-
{[(tri¯uoromethyl)sulphonyl]oxy}isophthalate 8,5 1,8-
diiodo-10-methoxyanthracene 19,10 3-(hydroxymethyl)-
ethynylbenzene 20,17 3,5-bis(hydroxymethyl)ethynylben-
zene 21,18 and Na2S´Al2O3 (2.5 mmol/g)9.
3,5-Bis[(t-butyldimethyl)silyloxymethyl]bromobenzene
6. Prepared according to the general procedure outlined in
Ref. 19 from 1,3-bis(hydroxymethyl)-5-bromobenzene and
2.2 equiv. of both tert-butyldimethylsilyl chloride and
imidazole. The reaction mixture was stirred at 508C for
4 h, and puri®ed by ¯ash chromatography [hexane/dichloro-
methane 5/1 (v/v), Rf 0.33] to give 6 as a colourless oil
(93%); Anal. Calcd for C20H37O2BrSi2: C, 53.91; H, 8.37,
Found: C, 54.28; H, 8.52; dH (300 MHz) 0.07 (12H, s,
ArCH2OSi(CH3)2tBu), 0.92 (18H, ArCH2OSi(CH3)2C(CH3)3),
4.67 (4H, s, ArCH2OR), 7.18 (1H, br s, ArH), 7.31 (2H, br s,
ArH); dC (75.47 MHz) 25.4, 18.3, 25.8, 64.2 (ArCH2OR),
122.1, 122.3, 127.5, 143.7; m/z (EI) 446 (M1, 81Br, 14%),
444 (M1, 79Br, 12%), 389 (8), 387(8).
A small bathochromic shift was observed for the primary
band between 13 (lmax 424 nm) and 30 (lmax 428 nm) but a
signi®cant bathochromic shift for the secondary band was
observed between 13 (l 285 nm) and 30 (lmax 324 nm), as
expected for an extension in the aryl alkyne portion of the
molecule, (Fig. 1).
The ultra-violet and ¯uorescence spectra for the mono-
strapped cyclophane 18 and its immediate precursor 17
were very similar as shown in Figs. 2 and 3, respectively.
The only difference was to be seen in the ¯uorescence
spectrum (Fig. 3), where more vibrational structure was
observed in the spectrum of the cyclophane 18 compared
to that of the precursor 17, although the Stokes shift in both
compounds was small.
1,8-Di[2-(4-methylphenyl)-1-ethynyl]anthracene 9.
A
solution containing 4-iodotoluene (0.043 g, 0.195 mmol),
Pd(PPh3)4 (0.010 g, 0.00929 mmol), 1 (0.021 g, 0.0929
mmol) and CuI (0.004 g, 0.0186 mmol) in a degassed
solvent system of piperidine (0.5 mL)/acetonitrile (2 mL)
was stirred for 0.5 h at room temperature. An extractive
workup with dichloromethane (25 mL) gave an orange
solid. Puri®cation by squat column chromatography
[dichloromethane, Rf 0.38] followed by recrystallization
from ethanol gave the title compound as a ®ne golden
needles (0.034 g, 92%); mp 170.5±172.08C; Anal. Calcd
for C32H22O: C, 94.55; H, 5.46, Found: C, 94.63; H, 5.41;
dH (200 MHz) 2.38 (6H, s, ArCH3), 6.99 (4H, d, Jˆ7.8 Hz,
ArH), 7.44±7.51 (6H, m, ArH), 7.79 (2H, d, Jˆ6.2 Hz,
AnthrylH), 8.01 (2H, d, Jˆ8.4 Hz, AnthrylH), 8.47 (1H, s,
AnthrylH), 9.63 (1H, s, AnthrylH); dC (75.47 MHz) 21.6,
87.0 (CuC), 95.1 (CuC), 120.2, 121.7, 124.2, 125.2,
127.4, 128.7, 129.1, 130.3, 131.4, 131.5, 131.7, 138.2; m/z
In conclusion, we have developed an approach to novel,
extended orthogonal p-systems and shown that mono-
strapped cyclophanes containing an orthogonal anthracene
could be readily prepared using standard palladium-
catalyzed coupling and intramolecular nucleophilic sub-
stitution.
Experimental
1H NMR spectra were recorded at 600 MHz on a Varian
Nova or at 300 MHz on a Varian Gemini NMR spectro-
meter or at 200 MHz on a Varian Gemini spectrometer
using a dual 5 mm 13C/1H probe. All spectra were recorded
as dilute solutions in CDCl3. Melting points were deter-
mined on a Ko¯er hot-stage micro-melting point apparatus

8340
G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
(FAB) 407 ((M1H)1, 56%), 406 (M1, 100); nmax (cm21
)
1,8-Di{2-[3,5-di(methoxycarbonyl)phenyl]-1-ethynyl}-
anthracene 13. solution containing (0.068 g,
0.0251 mmol), Pd(PPh3)4 (0.014 g, 0.0121 mmol),
2203 (CuC); UV±Vis (nm) 257 (97 000), 264 (141 000),
285 (38 000), 308 (11 000), 323 (12 000), 355 (7 000), 375
(14 000), 395 (23 000), 418 (22 000); Fluorescence (nm)
386, 407, 429, 453, 480.
A
5
1
(0.027 g, 0.114 mmol), DBU (0.20 mL, 1.34 mmol) and
CuI (0.005 g, 0.0263 mmol) in degassed DMSO (5 mL)
was stirred at 508C for 40 min. An extractive workup with
chloroform (30 mL) gave a yellow/orange solid. Puri®-
cation by squat column chromatography [dichloro-
methane/ethyl acetate 5/1 (v/v), Rf ,0.50] yielded the title
compound as a yellow solid (73 mg, 100%); mp 254.0±
258.0 8C; Exact Mass Calcd for C38H26O8: 610.1628,
Found: 610.1583; dH (300 MHz) 3.83 (12H, s, ArCO2CH3),
7.51 (2H, dd, Jˆ6.9, 8.4 Hz, AnthrylH), 7.83 (2H, d,
Jˆ6.9 Hz, AnthrylH), 8.06 (2H, d, Jˆ8.4 Hz, AnthrylH),
8.30 (4H, d, Jˆ1.8 Hz, ArH), 8.49 (2H, t, Jˆ1.8 Hz,
ArH), 8.50 (1H, s, AnthrylH), 9.57 (1H, s, AnthrylH); dC
(75.47 MHz) (15 signals only) 52.3, 89.4 (CuC), 93.1
(CuC), 120.7, 123.9, 124.2, 125.2, 127.6, 129.5, 129.9,
130.8, 131.4, 131.5, 136.3, 165.1 (CvO); m/z (LSIMS)
611 ((M1H)1, 69%), 610 (M1, 100), 579 (39); nmax
(cm21) 2208 (CuC), 1723 (CvO); UV±Vis (nm) 244 (53
000), 265 (116 000), 285 (40 000), 357 (7 000), 376 (13
000), 396 (20 000), 419 (18 000); Fluorescence (nm) 386,
407, 431, 456, 484.
1,8-Di{2-[4-(dimethylthexyl)silyloxyphenyl]-1-ethynyl}-
anthracene 11. The procedure was analogous to that for 9
except for the use of 4-iodophenol in place of 4-iodotoluene,
and the reaction mixture was stirred for 1 h. After the
extractive workup, the crude material was redissolved into
dry THF (3 mL) along with dimethythexylsilyl chloride
(0.10 mL, 0.508 mmol) and imidazole (0.040 g, 0.588
mmol). The resulting solution was re¯uxed for 4.5 h. The
reaction mixture was cooled to room temperature, diluted
with ether (10 mL) and washed with water (10 mL). The
aqueous layer was re-extracted with ether (10 mL), the
organic layers combined, dried and the solvent removed.
Puri®cation by ¯ash chromatography [hexane/dichloro-
methane 5/1 (v/v), Rf 0.25] gave the title compound as a
yellow oil that solidi®ed on standing (0.016 g, 52%); mp
124.0±128.0 8C; Exact Mass Calcd for C46H55O2Si2:
695.3742, Found: 695.3757; dH (300 MHz) 0.26 (6H, s,
ArOSi(CH3)2R), 0.96 (6H, d, Jˆ6.8 Hz, (CH3)2CHR), 0.97
(6H, s overlap with 0.96, (CH3)2CHC(CH3)2SiR), 1.75 (1H,
septet, Jˆ6.8 Hz), 6.74 (4H, AA0 portion of AA0XX0, ArH),
7.46 (2H, dd, Jˆ6.9, 8.4 Hz, AnthrylH), 7.54 (4H, XX0
portion of AA0XX0, ArH), 7.78 (2H, d, Jˆ6.9 Hz,
AnthrylH), 7.99 (2H, d, Jˆ8.4 Hz, AnthrylH), 8.46 (1H, s,
AnthrylH), 9.62 (1H, s, AnthrylH); dC (75.47 MHz) 22.3,
18.6, 20.1, 25.1, 34.0, 86.6 (CuC), 95.0 (CuC), 116.1,
120.3, 121.9, 124.2, 125.1, 127.3, 128.5, 130.2, 131.3,
131.5, 133.2, 156.0; m/z (LSIMS) 695 ((M1H)1, 100%),
694 (M1, 99); UV±Vis (nm) 258 (77 000), 266 (99 000),
287 (38 000), 314 (18 000), 357 (7 000), 377 (11 000), 397
(17 000), 420 (17 000); Fluorescence (nm) 387, 408, 432,
457, 485.
1,8-Di{2-[3,5-bis([tert-butyldimethyl]siloxymethyl)phenyl]-
1-ethynyl}anthracene 14. A solution containing 6 (0.134 g,
0.301 mmol), Pd(PPh3)4 (0.031 g, 0.0265 mmol),
(0.030 g, 0.133 mmol), triethylamine (0.10 mL,
1
1.38 mmol) and CuI (0.002 g, 0.0105 mmol) in degassed
acetonitrile (3 mL) was stirred at 508C for 1.5 h. An extrac-
tive workup with ether (20 mL) gave an orange oil. Puri®-
cation by ¯ash chromatography on reverse phase silica
[acetonitrile/dichloromethane 2/1 (v/v), Rf 0.20] yielded
the title compound as a yellow oil (20 mg, 16%); Exact
Mass Calcd for C58H82O4Si4: 954.5290, Found: 954.5284;
dH (200 MHz) 0.07 (6H, s, Si(CH3)2), 0.92 (9H, s,
SiC(CH3)3), 4.47 (8H, s, ArCH2OR), 7.37 (6H, br s, ArH),
7.48 (2H, dd, Jˆ7, 8.4 Hz, AnthrylH), 7.82 (2H, d, Jˆ7 Hz,
AnthrylH), 8.02 (2H, d, Jˆ8.4 Hz, AnthrylH), 8.47 (1H, s,
AnthrylH), 9.67 (1H, s, AnthrylH); dC (75.47 MHz) 25.6,
18.3, 25.9, 64.3 (ArCH2OR), 87.3 (CuC), 95.6 (CuC),
121.7, 122.8, 124.0, 124.3, 125.3, 127.4, 127.9, 128.5,
130.6, 131.5, 131.6, 141.8; m/z (LSIMS) 955 ((M1H)1,
100%), 954 (M1, 98%), 897 (24), 823 (31).
1,8-Di{2-[3-(methoxycarbonyl)phenyl]-1-ethynyl}anthra-
cene 12. A solution containing methyl 3-iodobenzoate
(0.331 g, 1.27 mmol), Pd(PPh3)4 (0.066 g, 0.06 mmol), 1
(0.130 g, 0.58 mmol) and CuI (0.011 g, 0.06 mmol) in a
degassed solvent system of triethylamine (2 mL)/benzene
(5 mL) was stirred at 508C for 5 h. An extractive workup
with THF (50 mL) gave an orange oil. Puri®cation by squat
column chromatography [dichloromethane, Rf 0.32] yielded
the title compound as a yellow solid (281 mg, 99%). A small
quantity was recrystallized from a THF/methanol mixture to
give ®ne golden needles; mp 188.0±191.5 8C; Anal. Calcd
for C34H22O4: C, 82.58; H, 4.48, Found: C, 82.62; H, 4.42;
dH (300 MHz) 3.85 (6H, s, ArCO2CH3), 7.16 (2H, t, Jˆ
7.8 Hz, ArH), 7.50 (2H, dd, Jˆ7.2, 8.7 Hz, AnthrylH),
7.67 (2H, dt, Jˆ7.8, 1.8 Hz, ArH), 7.83 (2H, dd, Jˆ7.2,
1.2 Hz, AnthrylH), 7.96 (2H, dt, Jˆ7.8, 1.8 Hz, ArH),
8.04 (2H, d, Jˆ8.7 Hz, AnthrylH), 8.26 (2H, t, Jˆ1.8 Hz,
ArH), 8.49 (1H, s, AnthrylH), 9.58 (1H, s, AnthrylH); dC
(75.47 MHz) (only 17 signals observed) 52.1, 88.6 (CuC),
93.9 (CuC), 121.2, 123.8, 124.0, 125.3, 127.7, 128.5, 129.3
(br), 130.6, 130.8, 131.5, 131.6, 132.8, 135.9; m/z (EI) 494
(M1, 100%), 463 (3); nmax (cm21) 1737 (CvO); UV±Vis
(nm) 265 (109 000), 283 (29 000), 356 (4 000), 375 (9 000),
395 (16 000), 417 (16 000); Fluorescence (nm) 385, 407,
429, 453, 481.
1,8-Di{2-[4-(dimethylthexyl)siloxy-3,5-(methoxycarbonyl)-
phenyl]-1-ethynyl}anthracene 15. The procedure was
analogous to that for 14 using 1 and 7, and the reaction
mixture was stirred at 508C for 0.5 h. Instead of an extrac-
tive workup, the reaction mixture was ®ltered through a
short squat column of silica, and the residue was washed
with a 1:1 dichloromethane:ethyl acetate solution. The
®ltrate was concentrated in vacuo and further puri®cation
by ¯ash chromatography on reverse phase silica [acetone/
methanol (v/v), Rf 0.42] gave the title compound as a yellow
solid (60%). A small quantity was reprecipitated from
i-PrOH as a ®ne yellow powder; mp 190.0±196.08C;
Exact Mass Calcd for C54H63O10Si2: 927.3961, Found:
927.3886; dH (300 MHz) 0.00 (6H, s, Si(CH3)2), 0.96 (6H,
d, Jˆ6.6 Hz, SiC(CH3)2CH(CH3)2), 1.03 (6H, s, SiC(CH3)2),
1.76 (1H, septet, Jˆ6.6 Hz, SiC(CH3)2CH(CH3)2), 3.77
(12H, s, ArCO2CH3), 7.49 (2H, dd, Jˆ6.9, 8.4 Hz,

G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
8341
AnthrylH), 7.80 (2H, dd, Jˆ0.9, 6.9 Hz, AnthrylH), 8.03
(2H, d, Jˆ8.4 Hz, AnthrylH), 8.10 (4H, s, ArH), 8.49 (1H,
s, AnthrylH), 9.57 (1H, s, AnthrylH); dC (75.47 MHz) 22.9,
18.3, 19.9, 25.1, 33.6, 52.0, 88.4 (CuC), 93.1 (CuC),
116.4, 121.2, 123.9, 125.3, 126.3, 127.6, 129.1, 130.8,
131.2, 137.9, 153.8, 165.9 (CvO); m/z (EI) 418 (M1,
44%), 331 (98); nmax (cm21) 1735 (CvO); UV±Vis (nm)
243 (44 000), 265 (12 000), 285 (40 000), 379 (13 000), 400
(21 000), 423 (20 000); Fluorescence (nm) 389, 409, 432,
456, 486.
Jˆ7.5 Hz, ArH), 7.36 (2H, dd, Jˆ1.8, 7.5 Hz, ArH), 7.49
(2H, dd, Jˆ6.9, 8.4 Hz, AnthrylH), 7.60 (2H, t, Jˆ1.8 Hz,
ArH), 7.82 (2H, dd, Jˆ1.2, 6.9 Hz, AnthrylH), 8.04 (2H, d,
Jˆ8.4 Hz, AnthrylH), 8.49 (1H, s, AnthrylH), 9.58 (1H, s,
AnthrylH); dC (50.28 MHz) 32.6 (ArCH2Br), 88.3 (CuC),
94.2 (CuC), 121.3, 123.9, 124.0, 125.3, 127.6, 129.0,
129.1, 129.2, 130.8, 131.5, 131.6, 131.8, 132.0, 138.2; m/z
(EI) 566 (M1, 81Br81Br, 61%), 564 (M1, 81Br79Br, 100%),
562 (M1, 79Br79Br, 48%), 404 (27); UV±Vis (nm) 235 (43
000), 264 (127 000), 285 (38 000), 322 (11 000), 356 (8
000), 375 (13 000), 395 (20 000), 418 (19 000); Fluor-
escence (nm) 386, 406, 432, 451, 477.
1,8-Di{2-[3,5-di(methoxycarbonyl)-4-{[(tri¯uoromethyl)-
sulphonyl]oxy}phenyl]-1-ethynyl}anthracene 16.
A
solution containing 8 (0.128 g, 0.272 mmol), Pd(PPh3)4
(0.016 g, 0.0138 mmol), 1 (0.030 g, 0.132 mmol), triethyl-
amine (0.40 mL, 2.86 mmol) and CuI (0.002 g,
0.0100 mmol) in degassed DMF (2 mL) was stirred at
508C for 9 h. An extractive workup with ether (40 mL)
gave a yellow oil. Puri®cation by ¯ash chromatography on
reverse phase silica [acetonitrile, Rf 0.38] yielded the title
compound as a yellow solid (81 mg, 68%); mp 87.0±89.0
8C; Exact Mass Calcd for C40H24O14S2F6: 906.0545, Found:
906.0539; dH (300 MHz) 3.90 (12H, s, ArCO2CH3), 7.53
(2H, dd, Jˆ7.2, 8.4 Hz, AnthrylH), 7.86 (2H, dd, Jˆ7.2,
0.9 Hz, AnthrylH), 8.09 (2H, d, Jˆ8.4 Hz, AnthrylH),
8.32 (4H, s, ArH), 8.52 (1H, s, AnthrylH), 9.42 (1H, s,
AnthrylH); dC (75.47 MHz) 53.0 (ArCO2CH3), 91.3
(CuC), 91.7 (CuC), 118.6 (q, Jˆ324.5 Hz, ArOSO2CF3),
120.0, 123.2, 125.0, 125.2, 126.4, 128.0, 130.1, 131.1,
131.4, 131.9, 138.4, 145.3, 163.3 (CvO); m/z (LSIMS)
906 (M1, 100%), 875 (19); nmax (cm21) 1734 (CvO).
6-Thia-1(1,8)-anthacena-4,8(1,3)-dibenzacyclodeca-2,9-
diynaphane 18. To a solution of 17 (0.010 g, 0.0177 mmol)
in a solvent mixture of dichloromethane (5 mL) and ethanol
(1 mL), was added Na2S´Al2O3 (0.030 g, 0.0750 mmol) and
the resulting suspension stirred at room temperature for 3 h.
The reaction mixture was ®ltered and the solvent removed
in vacuo. Puri®cation by gravity column chromatography on
reverse phase silica [acetonitrile/dichloromethane 4/1 (v/v),
Rf 0.44] gave the title compound as a yellow solid (0.004 g,
50%); mp 230.0±233.08C; Exact Mass Calcd for C32H20S:
436.1303, Found: 436.1299; dH (300 MHz) 3.45 (4H, s,
ArCH2SCH2Ar), 7.44±7.62 (8H, m, ArH), 7.86 (2H, dd,
Jˆ1.8, 6.9 Hz, AnthrylH), 8.03 (2H, d, Jˆ8.4 Hz,
AnthrylH), 8.49 (1H, s, AnthrylH), 9.59 (1H, s, AnthrylH);
dC (75.47 MHz) (only 16 signals observed) 33.1, 87.8
(CuC), 94.6 (CuC), 121.4, 122.9, 123.9, 125.2, 127.7,
129.1, 129.4, 129.5, 130.7, 131.3, 131.6, 132.6, 138.7; m/z
(EI) 436 (M1, 100%); nmax (cm21) no signi®cant absorption;
UV±Vis (nm) 235 (24 000), 266 (80 000), 287 (35 000), 313
(10 000), 339 (6 000), 360 (5 000), 378 (9 000), 399 (15
000), 422 (14 000); Fluorescence (nm) 289, 410, 430, 456,
484.
1,8-Di{2-[3-(bromomethyl)phenyl]-1-ethynyl}anthracene
17. A solution of 12 (0.085 g, 0.172 mmol) in dry THF
(10 mL) was added dropwise with stirring to a cooled
suspension of LiAlH4 (0.020 g, 0.526 mmol) in dry THF
(3 mL) at 08C. The resulting suspension was allowed to
warm to room temperature over 3 h with further stirring.
The reaction mixture was quenched with `wet' ether and
then added to 1% HCl (10 mL). The organic layer was
separated, and the aqueous layer re-extracted with ether
(2£10 mL). The organic layers were combined, dried and
the solvent removed. Puri®cation by ¯ash chromatography
on reverse phase silica [acetonitrile/acetone 9/1 (v/v), Rf
0.41] gave 1,8-di{2-[3-(hydroxymethyl)phenyl]-1-ethynyl}-
anthracene as a yellow solid (0.050 g, 81%); The compound
was not characterized, but converted directly to 17. A solu-
tion of dppe (0.032 g, 0.0795 mmol) in dry dichloromethane
(2 mL) was cooled to 08C before 0.2 M bromine in dichloro-
methane (0.80 mL, 0.159 mmol) was added over 10 mins
with stirring. 1,8-di{2-[3-(hydroxymethyl)phenyl]-1-ethy-
nyl}anthracene (0.029 g, 0.0662 mmol) in dry dichloro-
methane (3 mL) was then added and the reaction mixture
allowed to warm to room temperature over 45 min. The
reaction mixture was then diluted with dichloromethane
(20 mL) and washed with sat. Na2S2O3 (20 mL). The
aqueous layer was re-extracted with dichloromethane
(20 mL), the organic layers combined, dried and the solvent
removed. Puri®cation by ¯ash chromatography [hexane/
dichloromethane 2/1 (v/v), Rf 0.48] gave the title compound
as a yellow solid (29 mg, 78%); mp 129.0±131.58C; Exact
Mass Calcd for C32H2079Br2: 561.9933, Found: 561.9910;
dH (300 MHz) 4.31 (4H, s, ArCH2Br), 7.12 (2H, t,
1,8-Di{2-[3-(hydroxymethyl)phenyl]-1-ethynyl}-10-meth-
oxyanthracene 22. A solution containing 19 (0.100 g,
0.217 mmol), Pd(PPh3)4 (0.025 g, 0.0217 mmol), 20
(0.060 g, 0.456 mmol) and CuI (0.004 g, 0.0217 mmol) in
a degassed solvent system of piperidine (1 mL)/DMF
(1 mL) was stirred at 408C for 2 h. An extractive workup
with ether (20 mL) gave an orange oil. Puri®cation by squat
column chromatography [ethyl acetate/dichloromethane 2/1
(v/v), Rf 0.40] yielded the title compound as a yellow solid
(0.102 g, 100%). A small quantity was reprecipitated from a
dichloromethane/hexane mixture to give a ¯uffy yellow
powder; mp 91.5±93.0 8C; Exact Mass Calcd for
C33H24O3: 468.1725, Found: 468.1713; dH (200 MHz)
4.13 (3H, s, ArOCH3), 4.33 (4H, s, ArCH2OH), 7.17 (2H,
t, Jˆ8 Hz, ArH), 7.25±7.49 (8H, m, ArH), 7.75 (2H, dd, Jˆ
7.0, 1.0 Hz, AnthrylH), 8.27 (2H, d, Jˆ6.8 Hz, AnthrylH),
9.37 (1H, s, AnthrylH); dC (50.28 MHz) 63.6, 64.3, 87.8
(CuC), 94.5 (CuC), 119.8, 121.7, 123.0, 123.4, 124.5,
125.0, 127.0, 128.6, 130.1, 130.8, 130.9, 132.0, 141.3,
153.3; m/z (LSIMS) 468 (M1, 100%); nmax (cm21) no
signi®cant absorption; UV±Vis (nm) 268 (118 000), 284
(36 000), 307 (15 000), 327 (12 000), 366 (6 000), 386
(11 000), 407 (18 000), 431 (17 000); Fluorescence (nm)
381, 396, 420, 447, 470, 497.
1,8-Di{2-[3,5-bis(hydroxymethyl)phenyl]-1-ethynyl}-10-
methoxyanthracene 23. A solution containing 19 (0.100 g,

8342
G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
0.217 mmol), Pd(PPh3)4 (0.025 g, 0.0217 mmol), 21
(0.072 g, 0.446 mmol) and CuI (0.004 g, 0.0210 mmol) in
a degassed solvent system of piperidine (1 mL)/DMF
(2 mL) were stirred together at 508C for 3 h. An extractive
workup with ether (30 mL) gave a yellow solid. Puri®cation
by ¯ash chromatography [ethylacetate/methanol 9/1 (v/v),
Rf 0.49] yielded the title compound as a yellow solid
(0.114 g, 100%); mp 174.0±177.0 8C; Exact Mass Calcd
for C35H28O5: 528.1936, Found: 528.1942; dH (300 MHz,
CDCl3/d6-DMSO) 3.94 (3H, s, ArOCH3), 4.18 (8H, d,
Jˆ5.7 Hz, ArCH2OH), 7.19 (4H, br s, ArH), 7.30 (2H, dd,
Jˆ8.4, 6.6 Hz, AnthrylH), 7.56 (2H, d, Jˆ6.6 Hz,
AnthrylH), 7.77 (2H, br s, ArH), 8.08 (2H, d, Jˆ8.4 Hz,
AnthrylH), 9.15 (1H, s, AnthrylH); dC (75.47 MHz,
CDCl3/d6-DMSO) 62.6, 62.8, 86.3 (CuC), 94.7 (CuC),
118.6, 120.8, 121.7, 122.2, 123.5, 124.3, 124.8, 127.7,
130.1, 131.0, 141.7, 152.5; m/z (EI) 528 (M1, 100%);
nmax (cm21) (®lm) 2203 (CuC); UV±Vis (nm) 268 (59
000), 286 (27 000), 309 (14 000), 366 (4 000), 386 (6
000), 408 (9 000), 433 (8 000); Fluorescence (nm) 398,
422, 445, 468, 502.
(within M1 and (M1H)1 cluster) (M1, 100%); UV±Vis
(nm) 238 (55 000), 268 (122 000), 290 (32 000), 313 (11
000), 328 (10 000), 367 (6 000), 388 (12 000), 409 (20 000),
433 (18 000); Fluorescence (nm) 381, 396, 422, 450, 471,
505.
1,8-Di{2-[2-(4-[2-{3-(hydroxymethyl)phenyl}-1-ethynyl]-
3-(hydroxymethyl)phenyl)-1-ethynyl]-1-ethynyl}-10-
methoxyanthracene 27. A solution of 19 (0.050 g,
0.108 mmol), Pd(PPh3)4 (0.013 g, 0.0113 mmol), 26
(0.058 g, 0.221 mmol) and CuI (0.002 g, 0.0105 mmol) in
a degassed solvent system of piperidine (0.5 mL)/DMF
(2 mL) was stirred at 408C for 1 h. An extractive workup
with a 3:1 ether/THF mixture (20 mL) gave a yellow solid.
Puri®cation by squat column chromatography [ethyl
acetate, Rf 0.40] yielded the title compound as a yellow
solid. The compound was not characterized but converted
directly to the tetra-bromomethyl compound 30.
1,8-Di{2-[2-(4-[2-{3-(bromomethyl)phenyl}-1-ethynyl]-3-
(bromomethyl)phenyl)-1-ethynyl]-1-ethynyl}-10-methoxy-
anthracene 28. A solution of dppe (0.130 g, 0.326 mmol) in
dry THF (10 mL) was cooled to 08C before 0.2 M bromine
in chloroform (2.72 mL, 0.543 mmol) was added over
10 min with stirring. Crude 27 dissolved in dry THF
(6 mL) was then added and the reaction mixture allowed
to warm to room temperature over 1 h. The reaction mixture
was then diluted with chloroform (20 mL) and washed with
sat. Na2S2O3 (20 mL). The aqueous layer was re-extracted
with chloroform (20 mL), the organic layers combined,
dried and the solvent removed. Puri®cation by ¯ash chro-
matography [hexane/dichloromethane 1/1 (v/v), Rf 0.45]
gave the title compound as a yellow solid (0.093 g, 89% 2
steps); mp 180.0±183.08C; Exact Mass Calcd for
C51H32O79Br4: 975.9189, Found: 975.9147; dH (300 MHz)
4.19 (3H, s, ArOCH3), 4.37 (4H, s, ArCH2Br), 4.55 (4H, s,
ArCH2Br), 7.18 (2H, t, Jˆ8.1 Hz, ArH), 7.31±7.56 (10H,
m, ArH), 7.64 (2H, d, Jˆ1.5 Hz, ArH), 7.82 (2H, dd, Jˆ0.9,
6.9 Hz, AnthrylH), 8.35 (2H, d, Jˆ9 Hz, AnthrylH), 9.37
(1H, s, AnthrylH); dC (75.47 MHz) 31.2, 32.6, 63.8, 86.7
(CuC), 90.1 (CuC), 94.3 (CuC), 96.5 (CuC), 119.7,
121.3, 123.0, 123.3, 123.6, 123.7, 124.5, 125.0, 128.9,
129.4, 120.9, 131.5, 131.6, 131.9, 132.1, 132.6, 132.7,
138.1, 139.6, 153.5; m/z (LSIMS) 980 (within M1 isotope
cluster) (M1, 100%); UV±Vis (nm) 245 (60 000), 267
(96 000), 319 (71 000), 391 (19 000), 414 (27 000), 438
(25 000); Fluorescence (nm) 397, 430, 457, 480.
1,8-Di{2-[3-(bromomethyl)phenyl]-1-ethynyl}-10-meth-
oxyanthracene 24. A solution of 22 (0.050 g, 0.107 mmol)
in dry THF (5 mL) was cooled to 2208C before PPh3
(0.059 g, 0.214 mmol) and NBS (0.040 g, 0.224 mmol)
were added. The reaction mixture was then allowed to
warm to room temperature over 2 h with stirring. The reac-
tion was quenched by addition to sat. NaHCO3 (20 mL),
followed by extraction with ether (2x20 mL). The organic
layers were combined, dried and the solvent removed. Puri-
®cation by ¯ash chromatography [hexane/dichloromethane
2/1 (v/v), Rf 0.30] gave the title compound as a yellow solid
(0.035 g, 56%); mp 135.0±137.0 8C; Exact Mass Calcd for
C33H22O79Br2: 592.0038, Found: 592.0016; dH (200 MHz)
4.18 (3H, s, ArOCH3), 4.31 (4H, s, ArCH2Br), 7.14 (2H, t,
Jˆ7.6 Hz, ArH), 7.34±7.38 (2H, m, ArH), 7.45±7.59 (4H,
m, ArH), 7.81 (2H, dd, Jˆ1 and 6.8 Hz, AnthrylH), 8.34
(2H, dt, Jˆ1, 7.8 Hz, AnthrylH), 9.40 (1H, s, AnthrylH); dC
(50.28 MHz) 32.6, 63.7, 88.3 (CuC), 94.4 (CuC), 119.8,
121.6, 123.4, 123.9, 124.6, 125.1, 129.0, 129.1, 130.9,
131.8, 132.0, 132.1, 138.2, 153.5; m/z (LSIMS) 596 (M1,
81Br81Br, 58%), 594 (M1, 81Br79Br, 100%), 592 (M1,
79Br79Br, 44%); UV±Vis (nm) 268 (141 000), 287 (32
000), 312 (12 000), 327 (12 000), 366 (7 000), 386 (14
000), 408 (22 000), 432 (21 000); Fluorescence (nm) 381,
396, 420, 447, 470, 497.
1,8-Di{2-[3,5-bis(bromomethyl)phenyl]-1-ethynyl}-10-
methoxyanthracene 25. The procedure was analogous to
that for 24 using 23, and allowing the reaction mixture to
warm to room temperature over 1.5 h. Puri®cation by ¯ash
chromatography [hexane/dichloromethane 3/2 (v/v), Rf
0.38] gave the title compound as a yellow solid (64%);
mp 182.5±186.5 8C; Exact Mass Calcd for C35H24O79Br4:
775.8563, Found: 775.8587; dH (300 MHz) 4.18 (3H, s,
ArOCH3), 4.21 (8H, s, ArCH2Br), 7.38 (2H, t, Jˆ1.5 Hz,
ArH), 7.48 (4H, d, Jˆ1.5 Hz, ArH), 7.52 (2H, dd overlap
with 7.48, Jˆ6.9, 8.7 Hz, AnthrylH), 7.82 (2H, d, Jˆ6.9 Hz,
AnthrylH), 8.35 (2H, d, Jˆ8.7 Hz, AnthrylH), 9.37 (1H, s,
AnthrylH); dC (50.28 MHz) 32.0, 63.7, 88.9 (CuC), 93.8
(CuC), 119.6, 121.3, 123.5, 124.4, 124.5, 125.0, 129.7,
131.0, 131.9, 132.0, 138.9, 153.5; m/z (LSIMS) 780
Dimethyl 5-ethynylisophthalate 29. A solution of
dimethyl 5-(trimethylsilylethynyl)isophthalate20 (0.200 g,
0.690 mmol) in methanol (10 mL) was stirred with potas-
sium carbonate (0.010 g, 0.0725 mmol) at room tempera-
ture for 2 h. The suspension was ®lter and the solvent
removed in vacuo to give a fawn solid. The crude product
was sublimed at 1208C/0.02 mmHg to give the title
compound as a colourless solid (0.130 g, 87%); mp
130.0±131.08C with rapid heating; Anal. Calcd for
C12H10O4: C, 66.05; H, 4.62, Found: C, 65.96; H, 4.60; dH
(200 MHz) 3.18 (1H, s, ArCuCH), 3.96 (6H, s,
ArCO2CH3), 8.32 (2H, d, Jˆ1.8 Hz, ArH), 8.65 (1H, t,
Jˆ1.8 Hz, ArH); dC (50.28 MHz) 52.5 (ArCO2CH3), 79.1
(CuC), 81.5 (CuC), 123.2, 130.7, 131.0, 137.0, 165.5
(CvO); m/z (EI) 218 (M1, 63%), 187 (100), 159 (18),

G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
8343
144 (19); nmax (cm21) 3249 (C±H of ArCuC±H), 2104
(CuC), 1727 (CvO).
OAc), 7.46 (2H, dd, Jˆ7.2 and 8.7 Hz, AnthrylH), 7.65
(4H, s), 7.80 (2H, d, Jˆ7.2 Hz, AnthrylH), 7.98 (2H, d,
Jˆ8.7 Hz, AnthrylH), 8.41 (1H, s), 9.54 (1H, s); dC
(75.47 MHz) 20.2 (CH3OR), 20.4 (CH3OR), 60.6
(ArCH2OAc), 88.6 (CuC), 93.6 (CuC), 121.1, 121.7,
123.9, 125.2, 127.6, 129.3, 130.0, 130.8, 131.4, 131.5,
133.0, 147.4 (ArOAc), 168.6(CvO), 170.3 (CvO) m/z
(EI) 782 (M1, 24%); nmax (cm21) 1764, 1747, 1731
(CvO); UV±Vis (nm) 266 (109 000), 274 (37 000), 286
(48 000), 358 (7 000), 377 (12 000), 399 (19 000), 420 (18
000); Fluorescence (nm) 387, 410, 429, 454, 484.
1,8-Di{2-[2-(4-[2-{3,5-di(methoxycarbonyl)phenyl}-1-
ethynyl]-3,5-di(methoxycarbonyl)phenyl)-1-ethynyl]-1-
ethynyl}anthracene 30. A solution containing 16 (0.069 g,
0.0762 mmol), Pd(PPh3)4 (0.018 g, 0.0156 mmol), 29
(0.035 g,
0.161 mmol),
triethylamine
(0.11 mL,
0.791 mmol) and CuI (0.003 g, 0.0158 mmol) in degassed
DMF (3 mL) was stirred at 808C for 7 h. An extractive
workup with dichloromethane (40 mL) gave a yellow
solid. Puri®cation by ¯ash chromatography [dichloro-
methane/ethylacetate 9/1 (v/v), Rf 0.37] yielded the title
compound as a yellow solid (0.035 g, 44%); mp 294.0±
296.0 8C; Exact Mass Calcd for C62H43O16: 1043.2553,
Found: 1043.2511; dH (300 MHz) 3.94 (12H, s,
ArCO2CH3), 3.95 (12H, s, ArCO2CH3), 7.54 (2H, dd, Jˆ
7.2, 8.7 Hz, AnthrylH), 7.84 (2H, d, Jˆ7.2 Hz, AnthrylH),
8.09 (2H, d, Jˆ8.7, AnthrylH), 8.18 (8H, m, ArH), 8.44 (2H,
t, Jˆ1.8 Hz, ArH), 8.53 (1H, s, AnthrylH), 9.58 (1H, s,
AnthrylH); dC (75.47 MHz) 52.4 (ArCO2CH3), 52.6
(ArCO2CH3), 87.6 (CuC), 91.4 (CuC), 93.3 (CuC),
99.4 (CuC), 120.7, 121.6, 123.0, 123.9, 124.3, 125.3,
127.7, 129.8, 130.3, 130.7, 130.8, 131.4, 131.5, 134.7,
135.8, 136.5, 165.2 (CvO), 165.4 (CvO); m/z (LSIMS)
1043 ((M1H)1, 100%); nmax (cm21) (CH2Cl2 solution)
1730 (broad CvO); UV±Vis (nm) 250 (74 000), 260 (75
000), 324 (65 000), 386 (20 000), 406 (27 000), 428 (23
000); Fluorescence (nm) 395, 445, 469.
12,52-Dihydroxy-13,53-bis(hydroxymethyl)-3-oxa-8(1,8)-
anthracena-1,5(1,5)-dibenzacyclodeca-6,9-diynaphane
34. A solution of 33 (0.050 g, 0.0639 mmol) in THF (3 mL)
and 2 M H2SO4 (1 mL) was re¯uxed for 48 h. The reaction
mixture was diluted with ether (10 mL) and washed with
water (20 mL). The aqueous layer was then extracted with
ether (3£10 mL) and the organic layers combined, dried and
the solvent removed. Puri®cation by squat column chroma-
tography [ethyl acetate, Rf 0.56] gave the title compound as
a yellow solid (0.019 g, 56%); mp .307.08C with decom-
position; Exact Mass Calcd for C34H24O5: 512.1624, Found:
512.1597; dH (600 MHz, d6-acetone) 4.88 (4H, s), 5.07 (4H,
s), 7.65 (2H, d, Jˆ1.8 Hz, ArH), 7.72 (2H, dd, Jˆ7.2,
8.4 Hz, AnthrylH), 7.93 (2H, d, Jˆ1.8 Hz, ArH), 8.03
(2H, d, Jˆ7.2 Hz, AnthrylH), 8.28 (2H, d, Jˆ8.4 Hz,
AnthrylH). 8.84 (1H, s, AnthrylH), 9.61 (1H, s, AnthrylH);
dC (75.47 MHz) 62.6, 65.75, 86.4 (CuC), 95.7 (CuC),
114.4, 122.3, 123.8, 125.1, 125.9, 127.7, 128.7, 129.3,
131.2, 131.6, 131.7, 132.3, 133.1, 155.8; m/z (LSIMS) 512
(M1, 30%), 495 (7); UV±Vis (nm) 235 (34 000), 259 (61
000), 268 (66 000), 290 (34 000), 361 (6 000), 382 (9 000),
403 (13 000), 427 (12 000); Fluorescence (nm) 446, 467,
490.
1,8-Di{2-[3,5-bis(morpholinomethyl)-4-hydroxyphenyl]-
1-ethynyl}anthracene 32. A solution of 315 (1.22 g,
2.92 mmol), Pd(PPh3)4 (0.16 g, 0.29 mmol), 1 (0.32 g,
1.39 mmol) and CuI (26 mg, 0.29 mmol) in degassed piperi-
dine (15 mL) was stirred at room temperature for 1 h. An
extractive workup with dichloromethane (200 mL) gave an
orange oil. Puri®cation by ¯ash chromatography on silica
gel [acetone, Rf 0.43] yielded the title compound as a light
orange oil (1.07 g, 95%); Exact Mass Calcd for
C50H55N4O6: 807.4123, Found: 807.4246; dH (300 MHz)
2.46 (16H, t, Jˆ4.2 Hz), 3.39 (8H, s, ArCH2R), 3.71
(16H, t, Jˆ4.2 Hz), 7.34 (4H, s, ArH), 7.45 (2H, dd, Jˆ
6.9 and 8.4 Hz, AnthrylH), 7.77 (2H, d, Jˆ6.9 Hz,
AnthrylH), 7.97 (2H, d, Jˆ8.4 Hz, AnthrylH), 8.44 (1H, s,
AnthrylH), 9.62 (1H, s, AnthrylH); dC (75.47 MHz) 53.1,
58.7, 66.7 (ArCH2R), 86.3 (CuC), 95.2 (CuC), 113.6,
121.9, 122.6, 124.2, 125.2, 127.3, 128.5, 130.0, 131.3,
131.6, 132.6, 156.7 (ArOH); m/z (FAB) 807 ((M1H)1,
5%), 806 (7); nmax (cm21) 2192 (CuC).
110-Methoxy-6-thia-1(1,8)-anthracena-4,8(1,3)-dibenza-
cyclodeca-2,9-diynaphane 35. To
a suspension of
Na2S´Al2O3 (0.060 g, 0.152 mmol) in ethanol (3 mL) was
added 24 (0.030 g, 0.0505 mmol) in CH2Cl2 (5 mL) via a
syringe pump over 2.5 h. After addition was complete, the
reaction mixture was allowed to stir for 0.5 h before an extra
quantity of Na2S´Al2O3 (0.030 g, 0.0760 mmol) was added
and the suspension stirred for a further 1 h. The reaction
mixture was ®ltered and the solvent removed in vacuo.
Puri®cation by ¯ash chromatography on alumina [hexane/
ethyl acetate 20/1 (v/v), Rf 0.50] gave the title compound as
a yellow solid (85%). A small sample was recrystallized
from an ethyl acetate/hexane mixture as small orange
prisms; mp 236.0±238.58C; Exact Mass Calcd for
C33H22OS: 466.1391, Found: 466.1386; d (300 MHz) 3.43
(4H, s, ArCH2SCH2Ar), 4.16 (3H, s, ArOCH3), 7.42±7.59
(10H, m, ArH), 7.84 (2H, d, Jˆ6.9 Hz, AnthrylH), 8.31 (2H,
d, Jˆ8.7 Hz, AnthrylH), 9.39 (1H, s, AnthrylH); dC
(75.47 MHz) 32.9, 63.6, 87.9 (CuC), 94.8 (CuC), 119.7,
121.8, 122.9, 123.2, 124.6, 125.0, 129.4, 129.5, 130.8,
131.5, 131.9, 132.7, 138.7, 153.5; m/z (EI) 466 (M1,
98%), 451 (100); nmax (cm21) no signi®cant absorption;
UV±Vis (nm) 269 (11 000), 289 (40 000), 343 (7 000),
369 (7 000), 390 (13 000), 411 (21 000), 436 (21 000);
Fluorescence (nm) 380, 398, 423, 449, 473, 503.
1,8-Di{2-[3,5-bis(acetoxymethyl)-4-acetoxyphenyl]-1-
ethynyl}anthracene 33.
A solution of 32 (1.12 g,
1.39 mmol) in acetic anhydride (20 mL) and acetic acid
(0.5 mL) was re¯uxed for 17 h. The reaction mixture was
concentrated in vacuo and taken up into dichloromethane
(100 mL), washed with sat. Na2CO3 (2x50 mL) and water
(50 mL). The solvent was dried and removed to give an
orange oil. Puri®cation by ¯ash chromatography on silica
gel [dichloromethane/ethyl acetate 5/1 (v/v), Rf 0.36] gave
the title compound as an orange solid (0.37 g, 34%); mp
52.5±55.08C; Exact Mass Calcd for C40H38O12: 782.2363,
Found: 782.2378; dH (300 MHz) 2.04 (12H, s, ArCH2O-
COCH3), 2.36 (6H, s, ArOCOCH3), 4.83 (8H, s, ArCH2-
110-Methoxy-61-(4-methylphenyl)sulphonyl-6-aza-1(1,8)-

8344
G. T. Crisp, P. D. Turner / Tetrahedron 56 (2000) 8335±8344
2. Seel, C.; Vogtle, F. Angew. Chem., Int. Ed. Engl. 1992, 31,
528±549.
anthracena-4,8(1,3)-dibenzacyclodeca-2,9-diynaphane
36. To a solution of 24 (0.022 g, 0.0370 mmol) in dry DMF
(3 mL) was added TosNHNa (0.011 g, 0.0555 mmol) and
the resulting solution stirred at 508C for 1 h. The reaction
mixture was added to water (20 mL) and extracted with
ether (20 mL). The organic layers were combined, dried
and the solvent removed. Puri®cation by ¯ash chroma-
tography on silica [hexane/dichloromethane 1/1 (v/v), Rf
0.30] gave the title compound as a yellow solid (0.022 g,
100%); mp 155.0±160.08C; Exact Mass Calcd for
C40H29O3NS: 603.1885, Found: 603.1927; dH (200 MHz)
2.48 (3H, s, ArCH3), 4.17 (3H, s, ArOCH3), 4.24 (4H, s,
ArCH2R), 7.18 (2H, dt, Jˆ1.5, 7.8 Hz, ArH), 7.29±7.39
(4H, m, ArH), 7.48±7.58 (6H, m, ArH), 7.82±7.84 (4H,
m, ArH), 8.32 (2H, dt, Jˆ1.2, 8.7 Hz, AnthrylH), 9.34
(1H, s, AnthrylH); dC (105.87 MHz) (22 signals only)
21.6, 49.3, 63.7, 88.0 (CuC), 94.4 (CuC), 119.6, 121.6,
123.1, 123.2, 124.5, 124.9, 127.3, 129.2, 129.8, 131.2,
131.5, 131.9, 132.6, 135.8, 137.9, 143.6, 153.4; m/z
(LSIMS) 604 ((M1H)1 and isotopes of M1, 73%), 603
(M1, 100).
3. Bazan, G. C.; Oldham Jr., W. J.; Lachicotte, R. J.; Tretiak, S.;
Chernyak, V.; Mukamel, S. J. Am. Chem. Soc. 1998, 120, 9188±
9204.
4. Reiser, O.; Konig, B.; Meerholz, K.; Heinze, J.; Wellauer, T.;
Gerson, F.; Frim, R.; Rabinovitz, M.; de Meijere, A. J. Am. Chem.
Soc. 1993, 115, 3511±3518.
5. Crisp, G. T.; Turner, P. Tetrahedron 2000, 56, 407±415.
6. Vogtle, F.; Koch, H.; Rissanen, K. Chem. Ber. 1992, 125,
2129±2135.
7. Tsuji, J. Palladium Reagents and Catalysts; Wiley: Surrey,
1995.
8. Schmidt, S. P.; Brooks, D. W. Tetrahedron Lett. 1987, 28, 767±
770.
9. Bodwell, G. J.; Houghton, T. J.; Koury, H. E.; Yarlagadda, B.
Synlett 1995, 751±752.
10. Lovell, J. M.; Joule, J. A. Synth. Commun. 1997, 27, 1209±
1215.
11. Nicolaou, K. C.; Veale, C. A.; Webber, S. E.; Katerinopoulos,
H. J. Am. Chem. Soc. 1985, 107, 7515±7518.
12. Kunesh, N.; Miet, C. Tetrahedron Lett. 1987, 28, 3569±3572.
13. Crisp, G. T.; Turner, P. D.; Tiekink, E. R. T. Z. Kristallogr.
NCS 2000, 215, 77±78.
4(1,8)-Anthracena-1,7(1,3,5)-dibenza-9,12-dithiabicyclo-
[5.3.3]trideca-2,5-diynaphane 37. The procedure was
analogous to that for 35 using 25, and puri®cation by ¯ash
chromatography on silica [chloroform/hexane 3/5 (v/v), Rf
0.48] gave the title compound as a yellow solid (trace
,1 mg); Exact Mass Calcd for C35H24OS2: 524.1269,
Found: 524.1263; dH (300 MHz, CDCl3/d6-DMSO) 3.83
(4H, A portion of AB, Jˆ15 Hz, ArCHAHBSR), 3.87 (4H,
B portion of AB, Jˆ15.0 Hz, ArCHAHBSR), 4.18 (3H, s,
ArOCH3), 7.10 (2H, br s, ArH), 7.35 (4H, br s, ArH), 7.50
(2H, dd, Jˆ6.9, 9.0 Hz, AnthrylH), 7.66 (2H, d, Jˆ6.9 Hz,
AnthrylH), 8.31 (2H, d, Jˆ9.0 Hz, AnthrylH), 9.29 (1H, s,
AnthrylH); m/z (EI) 524 (M1, 100%).
14. Hunter, C. A.; Saunders, J. K. M. J. Am. Chem. Soc. 1990, 112,
5525±5534.
15. Diederich, F. Cyclophanes; The Royal Society of Chemistry:
Cambridge, 1991.
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