Donor-acceptor-substituted phenylacetylene macrocycles with threefold symmetry

Article abstract of DOI:10.1002/ejoc.200400603

A stepwise synthesis of the donor-acceptor-substituted macrocycle 5,21,37-tris(diethylamino)-13,29,45-trinitro[2.2.2.2.2.2]metacyclophane-1,9,17, 25,33,42-hexayne (1a) from 3,5-bis(3-iodo-5-nitrophenylethynyl)-N,N- diethylaniline (11) and 3,5-bis([3-dieth

Full text of DOI:10.1002/ejoc.200400603

FULL PAPER
Donor–Acceptor-Substituted Phenylacetylene Macrocycles with Threefold
Symmetry
Boris Traber,[a] Thomas Oeser,[a] and Rolf Gleiter*[a]
Dedicated to Professor Franz Effenberger on the occasion of his 75th birthday
Keywords: Donor-acceptor systems / Macrocycles / Cyclophanes / Alkynes / UV/Vis spectroscopy
A
stepwise synthesis of the donor–acceptor-substituted
diiodo-5-nitrobenzene (3) and 3,5-diethynyl-N,N-di(n-hexyl)
aniline (16) in 23% yield. X-ray investigations on 1b revealed
a planar π ring system with an inner diameter of 10 Å. De-
spite a high absorbance of 1b at 300 nm, no measurable NLO
activity was found.
macrocycle 5,21,37-tris(diethylamino)-13,29,45-trinitro[2.2.2-
.2.2.2]metacyclophane-1,9,17,25,33,42-hexayne (1a) from
3,5-bis(3-iodo-5-nitrophenylethynyl)-N,N-diethylaniline (11)
and 3,5-bis([3-diethylamino-5-ethynylphenyl]ethynyl)nitro-
benzene (12) failed, mostly due to the low solubility of 1a.
The synthesis of the 5,21,37-tris(N,N-di-n-hexylamino) con-
gener of 1a, 1b, was achieved in a one-pot reaction from 1,3-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
though the greatly extended π system of the unsubstituted
PAM has a very high absorbance in the short-wavelength
range of UV/Vis spectra.[32] The latter property is a neces-
sary requirement for good NLO activities (efficiency trans-
parency problem).[33]
Introduction
[2.2.2.2.2.2]Metacyclophane-1,9,17,25,33,41-hexaynes
have become an increasingly popular topic within the last
decade.[1–12] The conformationally rigid and shape-persist-
ent molecules of nanometer scale have attracted much inter-
est because of their potential in materials science, in host–
guest systems[13] and as theoretical subjects.[14,15] As in
other planar π systems, these combinations of carbon–car-
bon triple bonds and benzene units are useful building units
for such systems, thanks to the reduction in steric hindrance
and the rigidity of the building blocks. Furthermore there
are several available procedures allowing the connection of
a sp carbon to a sp2 carbon centre.[16–18] In addition, the
capability of the acetylene linkage to transmit electronic
perturbation within a conjugated system makes them useful
components in the construction of molecular wires,[19,20]
conjugated dendrimers[21,22] and optical systems.[23–25]
Interest in such macrocycles published in recent years has
predominantly been focused on self-association behaviour
based on weak interactions[26–29] involving liquid crystals[30]
and monolayer surfaces.[7] The large cavities of these phen-
ylacetylene macrocycles (PAMs) should allow the incorpo-
ration of metal salts. Moore et al. showed evidence of a
PAM doped with silver triflate without destruction of the
liquid-crystalline order.[31]
The structures of 1 and 2 each represent an extended
octopole, so their syntheses seemed to be a promising tar-
get. It is obvious that two-dimensional structures are supe-
rior to one-dimensional NLO chromophores in terms of the
βzzz values, as shown in our last paper.[23] It is therefore to
be expected that, after the introduction of the chromophore
groups, the absorbance maximum should not be shifted too
far bathochromically, because an absorption over 500 nm is
problematic. Another clear advantage of the PAM is the
rigidity of the π system. We showed that planarity of the π
system corresponds to an increase in βzzz values, so a planar
π system with only a limited degree of torsion is advan-
tageous.[23]
Another interesting question is the π stacking with the
aromatic units. Studies on other synthesized PAMs have
found that PAMs with electron-withdrawing groups have
stronger tendencies towards self-association then PAMs
with electron-donating groups.[34] The previous work relates
to ether and ester groups, so the introduction of other func-
tional groups as in 1 should be interesting as amino and
nitro groups should be able to form stronger intermolecular
interactions and make the π stacking easier. Studies on
these systems should improve understanding of π–π interac-
tions. Experiments with donor–acceptor-substituted PAMs
may be compared with already derived theoretical mod-
els.[14] PAMs are also interesting as possible candidates for
To the best of our knowledge, however, PAMs have not
been used for optical or nonlinear optical investigations, al-
[a] Organisch-Chemisches Institut der Universität Heidelberg
Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Fax: +49-6221-544205
E-mail: rolf.gleiter@urz.uni-heidelberg.de
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DOI: 10.1002/ejoc.200400603
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B. Traber, T. Oeser, R. Gleiter
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Scheme 3.
the formation of tubular structures in the solid state,[7] and
it would also be very desirable to insert some host molecules
and compare the differences in their NLO behaviour.
Synthesis
Our first approach involved a one-pot synthesis, the
starting materials being 3,5-bis(ethynyl)-N,N-diethylaniline
(7a) and 1,3-diiodo-5-nitrobenzene (8).[35] Compound 7a
was readily available from 3,5-diiodoaniline (3)[36] by the
sequence shown in Scheme 1.
Scheme 1.
An attempted one-pot synthesis[30] with 7a and 8 under
high-dilution conditions with use of Pd(PPh3)4/CuI and di-
ethylamine (Scheme 2) was unsuccessful, as we were unable
to detect any 1a in the mass spectrum of the raw material.
In a second procedure we applied a stepwise approach to
the preparation of 1a. As starting materials we used 7a,
3-iodo-5-nitroaniline (9),[37] 3-(diethylamino)-5-iodoaniline
(11) and 1-nitro-3,5-bis(trimethylsilylethynyl)benzene (13).
The last two species were readily available by the procedures
shown in Scheme 3.
Scheme 2.
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Donor–Acceptor-Substituted Phenylacetylene Macrocycles with Threefold Symmetry
FULL PAPER
Scheme 4.
In two parallel runs we utilized Pd catalysis (Scheme 4).
The Sonogashira coupling of 7a[16,37,38] and 9 afforded 14,
whilst from 11 and 13 we obtained 15 in 72% yield. The
free amino groups in 14 and 15 were converted to afford
the corresponding diiodo species 16 and 17, respectively, by
a Sandmeyer reaction.[39] In both cases the yields were
above 70% when the reaction was carried out at –15 to
–10 °C. The bisiodide 17 was transformed into 18 by coup-
ling with two equivalents of trimethylsilylacetylene under
Sonogashira conditions.[37,38,40] The removal of the TMS
groups to yield 19 was achieved with diluted KOH in
EtOH.
Now the stage was set for the final coupling reaction.
The two components 16 and 19 were added dropwise to a
Pd(PPh3)4/CuI catalyst solution in dry THF as solvent at
65 °C (Scheme 5). It was possible to detect 1a by mass spec-
trometry in the raw material, but because of its low solubil-
ity it was not possible to isolate and purify the desired pro-
duct.
Scheme 5.
To increase the solubility of the target molecule we
planned the introduction of two hexyl substituents at the
amino groups of 16 and 19. Before embarking in the syn- This produced N,N-di(n-hexyl)-3,5-iodoaniline, which was
thesis of the di(n-hexylamino)-substituted congeners of 16 subsequently ethynylated to produce 7b (see also Experi-
and 19 (see Scheme 5) we again explored a one-pot synthe- mental Part).
sis, arguing that our first effort (Scheme 2) might have also
The coupling reaction between 7b and 8 (Scheme 6) was
been in vain because of the low solubility of 1a. One com- carried out at different addition rates to the catalyst
ponent for our new product was 3,5-bis(ethynyl)-N,N-di(n- (Pd(PPh3)4/CuI) with triethylamine in benzene. We found
hexyl)aniline 7b, prepared analogously to 7a (Scheme 1) by that the highest yields of 1b were obtained with addition
dialkylation of 3,5-diiodoaniline (3) with 1-iodohexane.[41] rates of starting material to a 10 mol% catalyst solution of
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B. Traber, T. Oeser, R. Gleiter
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lysed coupling of 21 with 5 in diethylamine afforded 22,
which was converted into 23. To prepare 2 we slowly and
simultaneously added 8 and 23 to the catalyst in the pres-
ence of triethylamine in benzene solution (Scheme 8). Our
1
evidence for the formation of 2 is based on the H NMR
spectroscopic data and mass spectrometric (MS(FD) and
MALDI) data on a few milligrams recrystallized from diox-
ane.
Scheme 8.
Scheme 6.
5 mL·h–1. At higher concentrations of the catalyst (25
mol%) the amounts of byproducts were higher. From the
raw material we were able to isolate 1b by column
Structural and Optical Investigations
We were able to grow single crystals of 1b suitable for X-
chromatography in yields of up to 20%, although the yield ray investigations; the results are presented in Figure 1 and
was reduced if the reaction was scaled up. Figure 2. Crystals of 1b were obtained from a hexane/
Encouraged by the success in synthesizing 1b we went CH2Cl2 solution. The molecular structure of 1b shows the
on to prepare 2, in which the π system is enlarged by a anticipated planar π ring system with a diameter of 10.9 Å
phenylethynyl unit relative to 1. This system provides a (closest transannular distance between carbon centres) for
larger cavity than 1 and is therefore better suited for hosting the cavity. The nitro and amino groups, with the exception
other molecules. Scheme 7 summarizes our approach to the of the hexyl side chains, are oriented nearly coplanar to the
preparation of the starting materials.
adjacent phenyl rings.
Sonogashira coupling between 7b and 1-bromo-4-iodo-
A section of the unit cell shows a pairing of two rings in
benzene (20) produced 21 in good yields. Further Pd-cata- such a way that the amino group of one ring faces the nitro
Scheme 7.
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Donor–Acceptor-Substituted Phenylacetylene Macrocycles with Threefold Symmetry
FULL PAPER
ane is displayed in Figure 3. The spectrum shows an intense
absorption below 300 nm and a band of low intensity at
400 nm. The chromophore has an enormously high ab-
sorbance coefficient with complete transparencyin the vis-
ible region.
Figure 3. UV/Vis spectrum of 1b.
Figure 1.Molecular structure of 1b. Nitrogen atoms are dotted,
oxygen atoms are hatched.
The absorbance coefficient of 1b at λmax = 292 nm is ε
= 177600 l·mol–1·cm–1. Hyper Rayleigh experiments were
carried out, unfortunately without any measurable NLO
signal in spite of the high absorbance. To find out if this is
due to association of 1b in solution as found in the solid
state (c.f. Figure 2), we recorded the electronic absorption
spectrum of 1b in dichloromethane in concentrations be-
tween 2·10–5 and 8·10–5 mol·L–1 and found no derivation
from the Lambert–Beer law. We also found no shift of the
1
proton signals of 1b in the H NMR spectrum in the con-
centration range between 2·10–3 and 7·10–3 mol·L–1 in chlo-
roform. These observations led us to assume that the ab-
sence of any measurable NLO signals is due to the meta
connection of the donor and acceptor groups in 1b. The
resulting conjugation is apparently too weak to give rise to
distinct interactions resulting in a stronger charge-transfer
transition.
Conclusions
Our experiments have shown that the macrocyclic meta-
cyclophanes 1a and 1b can be synthesized either in a step-
wise fashion or in a one-pot reaction under high-dilution
conditions. A key step for both approaches was a Sonoga-
shira reaction between an alkyne unit and an iodobenzene
fragment. The resulting macrocyclic system possessed a
planar ring with a D3h symmetry. The rings are oriented in
a pairwise fashion in the solid state in such a way that the
dihexylamino groups of one ring face the nitro groups of
the other. The associated pairs are shifted towards each
other, so a tubular arrangement is prevented. Although 1b
shows a strong absorption band at 300 nm, no measurable
NLO signal could be detected, probably due to the weak
donor–acceptor coupling through the meta conjugation.
Figure 2. Packing arrangement of 1b. View of two PAMs. Hydrogen
atoms were omitted, nitrogen atoms are crossed, and oxygen atoms
are filled in.
group of the other and vice versa (Figure 2). However, no
occurrence of a tubular packing was detected, because the
pairs of rings are shifted with respect to one another, so an
ABCDABCD stacking results. The distances between the
nitrogen centres of the NO2 groups and those of the oppo-
site dihexylamino groups vary between 4.2 Å and 5.0 Å for
one pair. Probably the voluminous hexyl groups prevent a
closer contact. The ring systems are not completely planar,
but open a very flat cone. Within a pair of rings the centers
of the two cones point towards each other, so the intermo-
lecular distances to the ring planes are smaller at the inner
perimeter of the π system and larger at the outer perimeter
(3.7–4.6 Å distance between corresponding face-to-face car-
Experimental Section
General: Reactions were carried out in oven-dried (120 °C) glass-
bon atoms). The UV/Vis spectrum of 1b in dichlorometh- ware under argon and with magnetic stirring. Solvents: THF was
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B. Traber, T. Oeser, R. Gleiter
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dried by distillation over sodium, DMF (Acros) and diethylamine
(Merck) were purchased. Starting materials and chemicals were ob-
tained from commercial sources. The 1-iodohexane (Aldrich) and
1-bromo-4-iodobenzene (Aldrich) were used without further purifi-
cation. Trimethylsilylacetylene,[42] tetrakis(triphenylphosphane)pal-
ladium,[43] 3,5-diiodoaniline,[36] 1,3-diiodo-5-nitrobenzene[35] and 3-
iodo-5-nitroaniline[37] were synthesized by literature methods. For
reactions under inert gas, the Schlenk technique was used. Melting
points (Büchi B-540) are given uncorrected. NMR spectra:
and was used for analysis without further purification. 1H NMR
(300 MHz, CDCl3): δ = 1.14 (t, 3J = 7.0 Hz, 6 H), 3.06 (s, 2 H),
3.33 (q, 3J = 7.0 Hz, 4 H), 6.77 (d, 4J2,6–4 = 1.5 Hz, 2 H), 6.85 ppm
4
(t, J4–2,6 = 1.5 Hz, 1 H). 13C NMR (75.5 MHz, CDCl3): δ = 12.6,
44.7, 76.6, 84.1, 115.9, 122.6, 123.3, 148.0 ppm. IR (neat): ν = 3289,
˜
3082, 2971, 2101, 1799, 1583, 1444 cm–1. UV/Vis (CH2Cl2): λmax
[nm] (ε, L·m–1·cm–1) = 246 (25500), 286 (11300), 358 (3100). MS
(EI+, 70 eV): 197 (40) [M]+, 182 (100) [M – CH3]+, 154 (22).
C14H15N (197.28): calcd. C 85.24, H 7.66, N 7.10; found C 85.20,
300 MHz for 1H, 75 MHz for 13C. Microanalyses: Analytical Labo- H 7.95, N 7.11.
ratory, Universität Heidelberg.
N,N-Diethyl-3-iodo-5-nitroaniline (10): NaHCO3 (60 g, 714 mmol)
was added to a stirred solution of 3-iodo-5-nitroaniline (9, 35.1 g,
133 mmol) in diethyl sulfate (150 mL) and the mixture was stirred
at 120 °C overnight. Gas formation could be observed. The reac-
tion was interrupted when the suspension could not be stirred any
more. After the mixture had cooled to room temp., NH3 solution
was added and the mixture was stirred for a further hour. The
suspension was dissolved in Et2O and washed with half conc. brine
(100 mL). The organic phase was dried and the solvent was re-
moved in vacuo. The dark red oil was chromatographed (silica gel,
light petroleum ether/diethyl ether 9:1) to give 10 (10.5 g, 72.0%) as
an orange-red powder. M.p. 37 °C. 1H NMR (300 MHz, CDCl3): δ
N,N-Diethyl-3,5-diiodoaniline (4a): A mixture of 3,5-diiodoani-
line(3, 10.0 g, 29.0 mmol) and triethyl phosphate (5.3 g, 29.0 mmol)
was heated under argon for 2 h at 205 °C, during which the solution
darkened. After the mixture had cooled to room temp., NaOH
(3.9 g, 96.0 mmol) in water (30 mL) was added and the mixture was
stirred for further 2 hours. The aqueous phase was separated and
washed three times with diethyl ether. The combined organic phase
was washed with brine and dried, and the solvent was removed in
vacuo. Acetic anhydride (40 mL) and catalytic amounts of DMAP
(20 mg) were added to the crude product, and the mixture was
warmed briefly and then diluted with diethyl ether. After the mix-
ture had cooled to 0 °C, HCl (20%) was added, the phases were
separated, and the organic phase was washed with HCl. The acid
solution was neutralised with NaOH solution and washed with di-
ethyl ether. The organic phase was washed with brine and dried,
and the solvent was removed in vacuo. Column chromatography
(silica gel, light petroleum ether/dichloromethane 9:1) gave 4a
(4.9 g, 12.2 mmol, 42.0%) as a white, crystalline solid. M.p. 59.8–
3
3
= 1.19 (t, J = 7.1 Hz, 6 H), 3.38 (d, J = 7.1 Hz, 4 H), 7.01 (dd,
4
4
4
4J2–6 = 2.5, J4–6 = 1.4 Hz, 1 H), 7.21 (dd, J2–6 = 2.5, J2–4
=
1.6 Hz, 1 H), 7.45 ppm (dd, J4–2 = 1.6, J4–6 = 1.4 Hz, 1 H). 13C
4
4
NMR (75.5 MHz, CDCl3): δ = 12.5, 44.5, 95.9, 108.8, 116.4, 122.1,
149.3, 154.1 ppm. IR (KBr): ν = 3121, 2969, 2928, 2892, 1608,
˜
1553, 1526, 1495 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1)
= 254 (19100), 280 (11450), 328 (2920), 426 (1850). MS (EI+,
70 eV): 320 (35) [M]+; 306 (100) [M – CH3]+, 277 (13), 259 (12),
132 (14). C10H13IN2O2 (320.13): calcd. C 37.52, H 4.09, N 8.75, I
39.64; found C 37.53, H 4.15, N 8.68, I 39.58.
1
3
62.8 °C. H NMR (300 MHz, CD2Cl2): δ = 1.12 (t, J = 7.1 Hz, 6
H), 3.25 (q, 3J = 7.1 Hz, 4 H), 6.90 (s, 2 H), 7.25 ppm (s, 1 H).
13C NMR (75.5 MHz, CD2Cl2): δ = 12.3, 44.5, 95.7, 119.8, 131.7,
149.4 ppm. IR (KBr): ν = 3077, 2969, 2924, 2890, 2860, 1569, 1522,
˜
3-(Diethylamino)-5-iodoaniline (11): Tin(ii) chloride (95.3 g,
421.2 mmol) was added to a stirred solution of ethanol (143 mL)
and conc. HCl (95 mL). Afterwards, N,N-diethyl-3-iodo-5-nitro-
aniline (10, 28.9 g, 90.2 mmol) was added in small portions, the
reaction temperature being held at 35 °C. The system was stirred
overnight. NaOH was added until the pH of the solution was alka-
line, while the suspension was cooled with ice water. The suspen-
sion was extracted into Et2O and washed with conc. brine
(100 mL). The organic phase was dried and the solvent was re-
moved in vacuo. Column chromatography (silica gel, CH2Cl2) gave
11 (24.1 g, 83.0 mmol, 91.9%) as an orange oil. 1H NMR
(300 MHz, CDCl3): δ = 1.11 (t, 3J = 7.5 Hz, 6 H), 3.25 (d, 3J =
1486 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 238
(22100), 272 (17460), 320 (3140). MS (EI+, 70 eV): 401 (65) [M]+;
386 (100) [M – CH3]+, 357 (16), 231 (6).
N,N-Diethyl-3,5-bis(trimethylsilylethynyl)aniline (6a): A mixture of
N,N-diethyl-3,5-diiodoaniline (4a,5.2 g, 13.0 mmol), trimethylsi-
lylacetylene (5, 3.6 g, 35.2 mmol), Pd(PPh3)4 (680 mg, 0.7 mmol)
and CuI (220 mg, 1.2 mmol) in degassed Et2NH (40 mL) was
heated at reflux under argon for 2 h. The solvent was evaporated
in vacuo and the residue was dissolved in dichloromethane and
washed three times with water. The organic phase was dried and
the solvent was removed in vacuo. Column chromatography (silica
gel, light petroleum ether/dichloromethane 1:1) gave 6a (3.6 g,
10.5 mmol, 80.6%) as colourless crystals. M.p. 140 °C. ,1H NMR
4
4
7.5 Hz, 4 H), 5.89 (dd, J2–4 = 1.9, J2–6 = 2.3 Hz, 1 H), 6.35 (dd,
4
4
4
4J4–6 = 1.4, J2–4 = 1.9 Hz, 1 H), 6.42 ppm (dd, J4–6 = 1.4, J2–6
=
2.3 Hz, 1 H). 13C NMR (75.5 MHz, CDCl3): δ = 12.6, 44.2, 96.2,
97.6, 111.9, 112.0, 148.4, 149.7 ppm. MS (EI+, 70 eV): 290 (65)
[M]+, 275 (100) [M – CH3]+, 247 (8). C10H15IN2 (290.14): calcd. C
41.40, H 5.21, N 9.66, I 43.74; found C 41.28, H 5.24, N 9.62, I
43.74.
3
(300 MHz, CDCl3): δ = 0.21 (s, 18 H), 1.12 (t, J = 7.1 Hz, 6 H),
3.29 (q, 3J = 7.1 Hz, 4 H), 6.66 (d, 4J = 1.3 Hz, 2 H), 6.87 ppm (m,
4J = 1.3 Hz, 1 H). 13C NMR (75.5 MHz, CD2Cl2): , CDCl3): δ =
0.02, 12.5, 44.2, 93.1, 105.5, 115.3, 123.1, 123.8, 147.4 ppm. IR
(neat): ν = 3062, 2956, 2923, 2853, 1799, 1760, 1633, 1525 cm–1.
˜
UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 242 (22300), 286
(2350), 334 (118). MS (EI+, 70 eV): 240.9 (44) [M]+, 325.8 (100)
[M – CH3]+. C20H31NSi2 (341.64): calcd. C 70.31, H 9.15, N 4.10;
found C 70.11, H 9.20, N 4.25.
1,3-Bis(ethynyl)-5-nitrobenzene (13): A mixture of 1,3-diiodo-5-
nitrobenzene (34.4 g, 92.1 mmol), trimethylsilylacetylene (18.9 g,
192.8 mmol), Pd(PPh3)4 (1.2 g, 1.0 mmol) and CuI (0.4 g,
2.1 mmol) in degassed Et2NH (150 mL) was stirred at r.t overnight.
The reaction is slightly exothermic. The solvent was evaporated in
vacuo. Column chromatography (silica gel, light petroleum ether/
dichloromethane 1:2) gave 1,3-(bistrimethylsilylethynyl)-5-nitroben-
zene (12, 24.2 g, 76.8 mmol, 83.4%) as colourless crystals, which
were not purified for subsequent use.
N,N-Diethyl-3,5-bis(ethynyl)aniline (7a): KOH (1.3 g, 23.2 mmol) in
H2O (5 mL) was added to a solution of N,N-diethyl-3,5-bis(trime-
thylsilylethynyl)aniline (6a) (3.6 g, 10.5 mmol) in EtOH (71 mL)
and the mixture was heated at reflux for 15 min. The solvent was
removed and the residue was dissolved in Et2O. The organic layer
was washed with half conc. brine (100 mL) and dried. After evapo-
ration, 7a (2.1 g, 10.5 mmol, 100%) was obtained as an orange oil
KOH (10.3 g, 184.6 mmol) in H2O (10 mL) was added to a solution
of 12 (24.2 g, 76.8 mmol) in EtOH (100 mL) and the mixture was
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Donor–Acceptor-Substituted Phenylacetylene Macrocycles with Threefold Symmetry
FULL PAPER
stirred for 1 h. After the reaction was finished (TLC monitoring) were added. The mixture was poured into an ice–water solution
the solvent was removed and the residue was dissolved in Et2O. of potassium iodine (10 g, 60.3 mmol) with vigorous stirring. The
The organic layer was washed with brine (100 mL) and dried. After mixture was stirred overnight without cooling. The formed iodine
evaporation and recrystallisation from ethanol, 13 (10.0 g, was destroyed by addition of NaHSO3, and the solution was made
58.5 mmol, 76.1%) was obtained as colourless crystals. M.p. 113.5– alkaline (pH = 12) and extracted several times with dichlorometh-
115 °C. 1H NMR (300 MHz, CDCl3): δ = 3.23 (s, 2 H), 7.84 (d, ane. The combined organic phases were washed several times with
4
4J4–2,6 = 1.5 Hz, 1 H), 8.25 ppm (d, J2,6–4 = 1.5 Hz, 2 H). 13C water and dried. The solvent was removed in vacuo, the obtained
NMR (75.5 MHz, CDCl3): δ = 80.3, 80.7, 124.3, 126.8, 140.8, solid was washed several times with dichloromethane until the resi-
148.0 ppm. IR (KBr): ν = 3285, 3079, 2883, 2112, 1799, 1613, due was free of any side products, and the filtrate was chromato-
˜
1544 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 244 graphed (SiO2: CH2Cl2/light petroleum ether 1:9) The overall yield
(26200), 272 (4360), 328 (1340). MS (EI+, 70 eV): 171 (100) [M]+, of 16 was 3.5 g (5.1 mmol, 71.6%) as ochre-coloured crystals.
125 (41) [M – NO2]+, 99 (16) [M – NO2-(CH)2]+, 75 (21) [M – M.p.Ͼ200 °C (decomp.). ,1H NMR (300 MHz, DMSO -d6): δ =
3
3
4
NO2 – (CCH)2]+. C10H5NO2 (171.15): calcd. C 70.18, H 2.95, N 1.19 (t, J = 7.0 Hz, 6 H), 3.44 (q, J = 7.0 Hz, 4 H), 6.93 (d, J =
8.18; found C 69.97, H 3.03, N 8.16.
4
4
4
1.09 Hz,2 H), 7.01 (dd, J = 1.1, J = 1.4 Hz, 2 H), 8.29 (dd, J =
1.4, 4J = 1.6 Hz, 2 H), 8.35 (dd, 4J = 1.4, 4J = 1.6 Hz, 2 H),
3,5-Bis(3-amino-5-nitrophenylethynyl)-N,N-diethylaniline (14):
A
8.55 ppm (t, J = 1.91 Hz, 1 H). 13C NMR (75 MHz, [D6]DMSO):
4
mixture of N,N-diethyl-3,5-bis(ethynyl)aniline (7a, 2.0 g,
10.3 mmol), 3-iodo-5-nitroaniline (9, 5.7 g, 21.5 mmol), Pd(PPh3)4
(0.6 g, 0.6 mmol) and CuI (0.2 g, 1.1 mmol) in dry triethylamine
(50 mL) was heated at reflux under argon overnight. After the mix-
ture had cooled to room temp. the solvent was removed. The crude
product was pulverized, washed several times with water and
recrystallized from water/acetone. Several fractions with different
degree of purity were obtained, the overall yield of 14 was 3.7 g
(7.8 mmol, 75.9%) as an ochre-coloured powder. M.p. 223–227 °C.
δ = 12.7, 44.9, 85.8, 93.2, 94.2, 116.2, 122.6, 124.0, 126.3, 127.2,
132.6, 146.4, 148.8, 149.6 ppm. IR (KBr): ν = 3091, 2971, 2215,
˜
1623, 1582, 1530, 1446, 1347 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε,
L·m–1·cm–1) = 238 (49400), 276 (57300), 286 (55300), 302 (45410),
338 (9860), 376 (5900). MS (FAB+, NBA-Matrix): 691 [M]+, 692
[M + H]+, 676 [M – CH3]+
.
1,3-Bis[(3-diethylamino-5-iodophenyl)ethynyl]-5-nitrobenzene (17):
1,3-Bis(3-amino-5-nitrophenylethynyl)-5-nitrobenzene (15, 6 g,
12.1 mmol) was added to hydrochloric acid (20%, 96 mL), during
which an orange suspension was formed. NaNO2 (2.1 g,
30.3 mmol) was dissolved in water, and the solution was cooled and
added dropwise to the suspension at –20 °C. The solid dissolved
and a clear red, foaming solution was obtained. The solution was
stirred for 30 min at this temperature; afterwards some amounts of
urea were added. The mixture was poured into an ice–water solu-
tion of potassium iodide (10 g, 60.3 mmol) with vigorous stirring
and stirred overnight without cooling. The formed iodine was de-
stroyed by addition of NaHSO3, and the solution was made alka-
line (pH = 12) and extracted several times with dichloromethane.
The combined organic phases were washed several times with water
and dried, and the solvent was removed in vacuo. The obtained
crude product was washed several times with dichloromethane until
the residue was free of any side products to give 17 (9.2 g,
9.9 mmol, 81.8%) as ochre-coloured crystals. M.p. 224.6–225.5 °C.
1H NMR (300 MHz, CD2Cl2): δ = 1.17 (t, 3J = 7.1 Hz, 12 H), 3.34
3
1H NMR (300 MHz, DMSO -d6): δ = 1.09 (t, J = 7.0 Hz, 6 H),
3.34 (m, 4 H), 6.02 (br., 4 H), 6.85 (m, 2 H), 6.93 (m, 1 H), 7.07
(m, 2 H), 7.40 (m, 2 H), 7.42 ppm (m, 2 H). 13C NMR (75 MHz,
[D6]DMSO): δ = 12.2, 43.5, 87.3, 89.9, 107.6, 112.4, 114.6, 120.8,
121.4, 123.0, 123.7, 147.4, 148.9, 150.2 ppm. IR (KBr): ν = 3231,
˜
2971, 2215, 1625, 1582, 1529 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε,
L·m–1·cm–1) = 266 (49100), 282 (59440), 302 (35600), 356 (10480),
378 (9860). MS (FAB+, NBA-Matrix): 469 [M]+, 470 [M + H]+, 454
[M – CH3]+. C26H23N5O4 (469.49): calcd. C 66.51, H 4.94, N 14.92;
found C 66.21, H 4.95, N 14.57.
3,5-Bis(3-amino-(diethylamino)-phenylethynyl)nitrobenzene (15): A
mixture of 1,3-bis(ethynyl)-5-nitrobenzene (13, 6.6 g, 38.3 mmol),
diethylamino-3-iodo-5-nitroaniline (11, 22.2 g, 76.5 mmol),
Pd(PPh3)4 (1.2 g, 1.0 mmol) and CuI (0.4 g, 2.1 mmol) in dry tri-
ethylamine (100 mL) was heated at reflux under argon overnight.
After the mixture had cooled to room temp., the solvent was re-
moved. Column chromatography (SiO2, CH2Cl2/ethyl acetate 5:1)
yielded 15 (13.6 g, 27.5 mmol, 71.9%) as a yellow powder. M.p.
179.3–180.4 °C. 1H NMR (300 MHz, CD2Cl2): δ = 1.14 (t, 3J =
3
4
4
(q, J = 7.1 Hz, 8 H), 6.80 (dd, J = 2.5, J = 1.2 Hz, 2 H), 7.01
(dd, 4J = 1.5, 4J = 2.4 Hz, 2 H), 7.14 (t, 4J = 1.5 Hz, 2 H), 7.94 (t, 4J
= 1.5 Hz, 1 H), 8.29 ppm (d, 4J = 1.5 Hz, 2 H). 13C NMR(75 MHz,
CD2Cl2): δ = 12.5, 44.7, 86.3, 92.2, 92.2, 95.3, 114.3, 121.6, 124.4,
3
7.0 Hz, 12 H), 3.30 (q, J = 7.0 Hz, 8 H), 3.66 (br., 4 H), 6.00 (t,
4
4
4J = 2.1 Hz, 2 H), 6.19 (dd, J = 1.3, J = 1.8 Hz, 2 H), 6.30 (dd,
4J = 1.2, 4J = 2.3 Hz, 2 H), 7.90 (t, 4J = 1.5 Hz, 1 H), 8.22 ppm
(d, 4J = 1.5 Hz, 2 H). 13C NMR (75 MHz, CD2Cl2): δ = 12.8, 44.7,
84.8, 94.3, 99.9, 106.2, 106.5, 123.3, 125.5, 126.1, 139.9, 148.3,
125.7, 127.0, 140.0, 148.7, 148.9 ppm. IR (KBr): ν = 2970, 2929,
˜
2872, 2214, 2105, 1584, 1539, 1486, 1452 cm–1. UV/Vis (CH2Cl2):
λmax [nm] (ε, L·m–1·cm–1) = 234 (53400), 276 (68700), 288 (60800),
306 (44000), 356 (10900). MS (FAB+, NBA-Matrix): 717 [M]+, 718
[M + H]+, 702 [M – CH3]+ . C30H29I2N3O2 (717.38): calcd. C 50.23,
H 4.07, N 5.86, I 35.38; found C 50.35, H 4.17, N 5.85, I 35.60.
148.6 149.3 ppm. IR (KBr): ν = 2969, 2929, 2895, 2871, 2212, 1586,
˜
1533, 1490, 1449 cm–1.UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1)
= 240 (54700), 270 (62600), 310 (28800), 360 (8060), 376 (5760).
MS (FAB+, NBA-Matrix): 495 [M]+, 496 [M + H]+, 480
[M – CH3]+, 465 [M – CH3 – CH3]+. C30H33N5O2 (495.62): calcd.
C 72.70, H 6.71, N 14.13; found C 72.79, H 6.65, N 13.84.
1,3-Bis([3-diethylamino-5-(trimethylsilylethynyl)phenyl]ethynyl)-5-
nitrobenzene (18): A mixture of 17 (3.0 g, 4.1 mmol), trimethylsi-
lylacetylene (3.0 g, 31.0 mmol), Pd(PPh3)4 (0.9 g, 0.8 mmol) and
CuI (0.3 g, 1.6 mmol) in dry diethylamine (80 mL) was heated at
N,N-Diethyl-3,5-bis(3-iodo-5-nitrophenylethynyl)aniline (16): 3,5- reflux at 50 °C for 2 h. A further amount of trimethylsilylacetylene
Bis(3-amino-5-nitrophenylethynyl)-N,N-diethylaniline (14, 3.3 g, (1.45 g) was added and the mixture was heated for an additional 2
7.1 mmol) was added to hydrochloric acid (20%, 50 ml), during hours. After the mixture had cooled to room temp., the solvent was
which a yellow suspension was formed. NaNO2 (1.2 g, 4.4 mmol) removed. Column chromatography (SiO2, CH2Cl2/light petroleum
was dissolved in water, and the solution was cooled and added ether 6:4) yielded 18 (2.0 g, 3.0 mmol, 71.9%) as a yellow-brown
1
dropwise to the suspension at –20 °C. The solid dissolved and a powder. M.p. 152.3–153.3 °C. H NMR (300 MHz, CD2Cl2): δ =
3
3
clear orange solution was obtained. The solution was stirred for a 0.26 (s, 18 H), 1.18 (t, J = 7.1 Hz, 12 H), 3.36 (q, J = 7.1 Hz, 8
4
4
4
4
further hour at this temperature; afterwards some amounts of urea H), 6.77 (dd, J = 2.6, J = 1.3 Hz, 2 H), 6.81 (dd, J = 1.3, J =
Eur. J. Org. Chem. 2005, 1283–1292
www.eurjoc.org © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1289

B. Traber, T. Oeser, R. Gleiter
FULL PAPER
4
4
2.6 Hz, 2 H), 6.91 (t, J = 1.3 Hz, 2 H), 7.95 (t, J = 1.5 Hz, 1 H), Pd(PPh3)4 (783 mg, 0.7 mmol) and CuI (258 mg, 1.4 mmol) in de-
8.29 ppm (d, 4J = 1.5 Hz, 2 H). 13C NMR (75 MHz, CD2Cl2): δ = gassed Et2NH (60 mL) was heated at reflux under argon for 3 h.
0.01, 12.6, 44.7, 85.8, 93.1, 93.9, 105.5, 115.3, 115.9, 122.3, 123.2,
124.6, 125.8, 125.9, 140.0, 148.1, 148.7 ppm. MS (FAB+, NBA-Ma-
The solvent was evaporated in vacuo, and the residue was dissolved
in dichloromethane and washed three times with water. The organic
phase was dried and the solvent was removed in vacuo. Column
chromatography (silica gel, light petroleum ether/diethyl ether 99:1)
gave 6b (11.0 g, 79.1%) as a clear oil. 1H NMR (300 MHz,
trix): 656 [M]+, 657 [M + H]+, 642 [M
–
CH3 + H]+.
C40H47N3O2Si2 (657.99): calcd. C 73.01, H 7.20, N 6.39; found C
72.68, H 7.27, N 6.40.
3
CD2Cl2): δ = 0.23 (s, 18 H), 0.90 (t, J = 7.1 Hz, 6 H), 1.32 (s, 12
1,3-Bis[(3-diethylamino-5-ethynylphenyl)ethynyl]-5-nitrobenzene
(19): KOH (76 mg, 1.4 mmol) in H2O (5 mL) was added to a solu-
tion of 1,3-bis([3-diethylamino-5-(trimethylsilylethynyl)phenyl]eth-
ynyl)-5-nitrobenzene (18, 450 mg, 0.7 mmol) in EtOH (20 mL) and
the mixture was heated at reflux for 15 min. The reaction was mon-
itored by TLC. The mixture was diluted with water and extracted
with CH2Cl2. The organic layer was dried, the solvent was re-
moved, and 19 and 1-([3-diethylamino-5-(ethynyl)phenyl]-ethynyl)-
3-[(3-diethylamino-5-(trimethylsilylethynyl)phenyl)-ethynyl]-5-nitro-
benzene were separated and purified by column chromatography
(SiO2; CH2Cl2/light petroleum ether 1:1) to yield 19 (345 mg,
0.7 mmol, 98.3%) as orange crystals. M.p. 202.5–203.3 °C. 1H
NMR (300 MHz, CD2Cl2): δ = 1.18 (t, 3J = 7.1 Hz, 12 H), 3.10 (s,
3
4
H), 1.54 (m, 4 H), 3.23 (t, J = 7.7 Hz, 4 H), 6.85 (d, J = 1.1 Hz,
1 H), 6.77 ppm (t, 4J = 1.3 Hz, 2 H). 13C NMR (75.5 MHz,
CD2Cl2): δ = 0.0, 14.2, 23.1, 27.1, 27.3, 32.1, 51.1, 93.5, 105.7,
115.4, 122.6, 124.2, 148.4 ppm. IR (neat): ν = 2958, 2929, 2857,
˜
2153, 1580 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 242
(42800), 254 (35600), 292 (8140), 362 (3050). MS (EI+, 70 eV): 453
(30) [M]+, 382 (100) [M – C5H11]+, 312 (39) [M – C5H11
C5H10]+.
–
3,5-Bis(ethynyl)-N,N-dihexylaniline (7b): KOH (3.3 g, 57.9 mmol)
in H2O (5 mL) was added to a solution of 6b (11.0 g, 24.1 mmol)
in EtOH (150 mL) and the mixture was heated at reflux for 15 min.
The solvent was removed and the residue was dissolved in Et2O.
The organic layer was washed with half conc. brine (100 mL) and
dried. After evaporation, 7b (7.5 g, 100%) was obtained as an
orange oil and was used for analysis without further purification.
3
4
4
2 H), 3.37 (q, J = 7.1 Hz, 8 H), 6.81 (dd, J = 1.3, J = 2.6 Hz, 2
H), 6.84 (dd, 4J = 1.3, 4J = 2.6 Hz, 2 H), 6.93 (t, 4J = 1.3 Hz, 2
H), 7.97 (t, J = 1.5 Hz, 1 H), 8.29 ppm (d, J = 1.5 Hz, 2 H). 13C
NMR (75.5 MHz, CDCl3): δ = 12.6, 44.7, 76.8, 84.0, 85.9, 93.0,
115.5, 116.3, 122.3, 123.3, 123.5, 125.8, 125.9, 140.0, 148.1,
4
4
3
1H NMR (300 MHz, CDCl3): δ = 0.89 (t, J = 7.2 Hz, 6 H), 1.30
3
(s, 12 H), 1.50–1.54 (m, 4 H), 3.00 (s, 2 H), 3.21 (t, J = 7.2 Hz, 4
148.7 ppm. IR (neat): ν = 3290, 2970, 2929, 2214, 2106, 1579, 1535,
˜
H), 6.70 (s, 2 H), 6.88 ppm (s, 1 H). 13C NMR (75.5 MHz, CDCl3):
1483, 1445 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 246
δ = 14.0, 22.6, 26.7, 27.0, 31.6, 50.9, 78.3, 83.9, 115.7, 122.6, 122.8,
(69000), 288 (65400), 306 (46000), 352 (12400), 424 (3540). MS
147.8 ppm. IR (neat): ν = 3294, 2956, 2929, 2856, 2107, 1581, 1461,
˜
(FAB+, NBA-Matrix): 513 [M]+, 514 [M + H]+, 498 [M – CH3]+
;
1370, 1308 cm–1.UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 246
(26950), 288 (11800), 362 (2630). MS (EI+, 70 eV): 309 (24) [M]+,
238 (100) [M – C5H11]+, 168 (39, [M – C5H11 – C5H10]+, 154 [M –
C5H11 – C5H10 – CH2]+. C22H31N (309.49): calcd. C 85.38, H 10.10,
N 4.53; found C 85.26, H 10.13, N 4.76.
5,21,37-Tris(diethylamino)-13,29,45-trinitro-[2.2.2.2.2.2]-metacyclo-
phane-1,9,17,25,33,41-hexayne (1a): mixture of Pd(PPh3)4
A
(115 mg, 0.1 mmol) and CuI (38 mg, 0.2 mmol) was suspended in
dry THF (20 mL) under argon, and diisopropylamine (240 mg,
2.4 mmol) was added. Compounds 19 (513 mg, 1.0 mmol) and 16
(691 mg, 1.0 mmol), both dissolved in dry THF (200 mL), were
added dropwise by dropping funnel while the reaction mixture was
slowly heated to 68 °C. After the addition was complete, the reac-
tion was heated at reflux overnight. The solution was filtered off
and the solvent was removed. A yellow brown solid containing the
expected mass spectroscopic peak for 1a was obtained, but it was
not possible to separate the product from the byproducts.
Phenylacetylene Macrocycle 1b: A suspension of Pd(PPh3)4 (46 mg,
0.04 mmol) and copper(i) iodide (16 mg, 0.08 mmol) in triethyl-
amine (60 mL) was heated under argon to 75 °C, during which the
suspension turned dark. A mixture of 1,3-diiodo-5-nitrobenzene (8,
149 mg, 0.4 mmol) and 3,5-diethynyl-N,N-dihexylaniline (7b,
124 mg, 0.4 mmol), dissolved in benzene (50 mL) and triethylamine
(50 mL), was added to the catalyst suspension by syringe pump.
The rate of addition was 5 mL·h–1. After the completion of ad-
dition the reaction mixture was heated at 75 °C for 2 more hours,
and then cooled down to room temp. The solvent was removed in
vacuo. The crude product was purified by column chromatography
(silica gel, light petroleum/CH2Cl2) to yield 118 mg (23%) of 1b.
M.p.Ͼ250 °C (decomposition). The purity of the sample was moni-
tored by HPLC. 1H NMR(300 MHz, CDCl3): δ = 0.94 (t, 3J =
6.8 Hz, 18 H), 1.36 (s, 36 H), 1.50–1.60 (m, 12 H), 3.13 (t, 3J =
6.8 Hz, 12 H), 6.51 (d, 4J = 1.1 Hz, 6 H), 6.77 (t, 4J = 1.1 Hz, 3
N,N-Dihexyl-3,5-diiodoaniline (4b): 1-Iodohexane (19.9 mL,
93.9 mmol) and Na2CO3 (5.2 g, 49.0 mmol) were added to a solu-
tion of 3,5-diiodoaniline (3, 9.8 g, 28.5 mmol) in DMF (87 mL) and
the mixture was stirred at 125 °C for 20 h. Further 1-iodohexane
(10 mL, 67.4 mmol) was added to this solution and the mixture
was stirred at 125 °C for two more hours. After the mixture had
cooled to room temp. the solution was separated from the resulting
salts by filtration and the solvent was removed in vacuo. The resi-
due was dissolved in Et2O, washed with half conc. brine (100 mL)
and dried. The residue was chromatographed (silica gel, light petro-
leum ether/CH2Cl2 7: 3) to give 4b (10.5 g, 72.0%) as a clear oil.
4
4
H), 7.75 (t, J = 1.5 Hz, 3 H), 8.04 ppm (d, J = 1.5 Hz, 6 H). 13C
NMR (75 MHz, CD2Cl2): δ = 14.3, 23.1, 27.2, 27.3, 32.1, 51.1,
86.3, 93.0, 115.1, 122.4, 123.4, 125.3, 125.6, 140.0, 148.1,
3
1H NMR (250 MHz, CDCl3): δ = 0.90 (t, J = 7.1 Hz, 6 H), 1.30
148.2 ppm. IR (KBr): ν = 2954, 2928, 2856, 2218, 1610, 1581,
˜
3
4
(s, 12 H), 1.51 (m, 4 H), 3.16 (t, J = 7.1 Hz, 4 H), 6.85 (d, J =
1.4 Hz, 2 H), 7.23 ppm (t, 4J = 1.4 Hz, 1 H). 13C NMR (75.5 MHz,
CDCl3): δ = 14.0, 22.7, 26.8, 27.0, 31.7, 51.0, 95.7, 119.8, 131.7,
1536 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 274
(149500), 292 (177600), 308 (153000), 394 (15200). MS(FD+): m/z
= 1285 (100) [M]+, 1255 (22), 1201 (18), 1164 (13). C84H96N6O6
(1285.7) calcd. C 79.26, H 7.54, N 6.16, found C 79.20, H 7.73, N
6.04.
149.4 ppm. IR (neat): ν = 2955, 2928, 2856, 1729, 1573, 1526,
˜
1462 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 234
(109900), 272 (86600), 322 (15200). MS (EI+, 70 eV): 513 (42)
[M]+, 441 (100) [M – C5H11]+, 372 (57) [M – C5H11 – C5H10]+. HR-
EI+: calcd. C18H29NI2 513.0388, found 513.0389 (–0.1).
3,5-Bis(4-bromophenylethynyl)-N,N-dihexylaniline(21):
A mixture
of 3,5-diethynyl-N,N-dihexylaniline (16, 2.5 g, 8.1 mmol), 1-bromo-
4-iodobenzene (20, 5.5 g, 19.4 mmol), Pd(PPh3)4 (0.5 g, 0.4 mmol)
and CuI (20 mg, 0.1 mmol) in dry triethylamine was heated at re-
N,N-Dihexyl-3,5-bis(trimethylsilylethynyl)aniline (6b): A mixture of
4b (15.7 g, 30.5 mmol), trimethylsilylacetylene (7.2 g, 73.2 mmol),
1290
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 1283–1292

Donor–Acceptor-Substituted Phenylacetylene Macrocycles with Threefold Symmetry
FULL PAPER
flux under argon overnight. After the mixture had cooled to room
temp., the solvent was removed and the residue was dissolved in
CH2Cl2,. The organic phase was washed with water, dried and
evaporated in vacuo. Column chromatography (silica gel, light pe-
troleum/CH2Cl2 gradient) yielded 21 (3.3 g, 66.6%) as yellow, waxy
argon for 3 h. The solvent was evaporated in vacuo, and the residue
was dissolved in dichloromethane and washed three times with
water. The organic phase was dried and the solvent was removed
in vacuo. Column chromatography (silica gel, light petroleum ether/
diethyl ether 99:1) gave 22 (3.1 g, 88.7%) as a yellow, vitreous oil.
1H NMR (300 MHz, CD2Cl2): δ = 0.21 (s, 18 H), 0.87 (t, 3J =
crystals. M.p. 85 °C. 1H NMR (300 MHz, C2D2Cl4): δ = 0.87 (t,
3
3J = 7.0 Hz, 6 H), 1.30 (s, 12 H), 1.56–1.60 (m, 4 H), 3.24 (t, J = 6.9 Hz, 6 H), 1.30 (s, 12 H), 1.50–1.55 (s, 4 H), 3.24 (t, 3J = 6.9 Hz,
4
4
4
7.0 Hz, 4 H), 6.73 (d, 4J = 1.4 Hz, 2 H), 6.90 (t, J = 1.4 Hz, 1 H),
4 H), 6.73 (d, J = 1.2 Hz, 2 H), 6.89 (t, J = 1.2 Hz, 1 H), 7.44 (d,
3J = 8.6 Hz, 4 H), 7.49 ppm (d, 3J = 8.6 Hz, 4 H). 13C NMR
(75.5 MHz, CD2Cl2): δ = 0.1, 14.2, 23.1, 27.1, 27.4, 32.1, 51.3, 88.4,
7.38 (d, 3J = 9.1 Hz, 4 H), 7.48 ppm (d, 3J = 9.1 Hz, 4 H). 13C
NMR (75.5 MHz, C2D2Cl4): δ = 14.2, 23.1, 27.1, 27.4, 32.1, 51.3,
87.7, 91.2, 115.1, 121.6, 122.7, 124.1, 132.0, 133.4, 147.9, 92.0, 96.7, 104.8, 115.2, 121.7, 123.3, 123.8, 124.1, 131.8, 132.2,
148.5 ppm. IR (KBr): ν = 2950, 2930, 2867, 2852, 2211, 1895, 1576,
148.5 ppm. MS (EI+, 70 eV): 653 (88) [M]+, 582 (100) [M –
C5H11]+, 512 (26) [M – C5H11 – C5H10]+, 424 (5).
˜
1527 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 262
(44500), 274 (57400), 284 (63200), 290 (72200), 300 (58350), 308
(57400), 376 (5800). MS (EI+, 70 eV): 621 (21) [M]+ (81Br2), 619
(45) [M]+ (79Br81Br), 617 (22) [M]+ (79Br2), 550 (43) [M – C5H11]+
(81Br2), 548 (100) [M – C5H11]+ (79Br81Br), 546 (46) [M-C5H11]+
(79Br2), 480 (13) [M – C5H11 – C5H10]+ (81Br2), 478 (27) [M –
C5H11 – C5H10]+ (79Br81Br), 476 (14) [M – C5H11 – C5H10]+ (79Br2).
HR-EI+ calcd. for C34H37N81Br2 (621.1251), found 621.1238
(–1.3), calcd. for C34H37N79Br81Br (619.1272), found 619.1273
(+0.1) calcd. for C34H37N79Br2 (617.1309), found 617.1291 (–1.8).
3,5-Bis(4-ethynylphenylethynyl)-N,N-dihexylaniline (23): KOH
(0.6 g, 11.5 mmol) in H2O (5 mL) was added to a solution of 22
(3.1 g, 4.8 mmol) in EtOH (150 mL) and the mixture was heated at
reflux for 15 min. The solvent was removed and the residue was
dissolved in Et2O. The organic layer was washed with half conc.
brine (100 mL) and dried. After evaporation, 23 (2.4 g, 100%) was
obtained as a yellow solid, and was used for analysis without fur-
ther purification. M.p. 76 °C. 1H NMR (300 MHz, CDCl3): δ =
3
0.92 (t, J = 7.1 Hz, 6 H), 1.35 (s, 12 H), 1.50–1.60 (m, 4 H), 3.25
(s, 2 H), 3.29 (t, 3J = 7.1 Hz, 4 H), 6.79 (s, 2 H), 6.95 (s, 1 H),
7.49 ppm (t, 3J = 9.0 Hz, 8 H). 13C NMR (75.5 MHz, CDCl3): δ
= 14.2, 23.1, 27.1, 27.4, 32.1, 51.2, 79.2, 83.4, 88.2, 92.1, 115.2,
Table 1. Crystallographic data.
Compound
1b
121.7, 122.2, 124.1, 124.2, 131.9, 132.5, 148.5 ppm. IR (neat): ν =
˜
Empirical formula
Molecular mass [g·mol–1]
Crystal size (mm)
Crystal colour
Crystal shape
Space group
Crystal system
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C84H96N6O6
1285.67
0.35×0.25×0.07
yellow
irregular plate
P-1
triclinic
13.135(4)
16.688(4)
17.429(5)
89.897(6)
77.443(6)
73.787(6)
3574(2)
1.20
2
1380
100
–14/13
–18/18
–18/19
1.27–23.26
0.075
3295, 3265, 2954, 2954, 2927, 2856, 2209, 2104, 1911, 1633,
1581 cm–1. UV/Vis (CH2Cl2): λmax [nm] (ε, L·m–1·cm–1) = 270
(36400), 282 (47300), 290 (52700), 300 (64500), 308 (55400), 320
(53400), 384 (4550). MS (EI+, 70 eV): 509 (92) [M]+, 438 (100)
[M – C5H11]+, 368 (27) [M – C5H11 – C5H10]+. C34H39N (509.72)
calcd. C 89.54, H 7.71, N 2.75; found: C 89.25, H 8.00, N 2.74.
Evidence for Formation of Phenylacetylene Macrocycle 2: A suspen-
sion of Pd(PPh3)4 (46 mg, 0.04 mmol) and copper(i) iodide (16 mg,
0.08 mmol) in triethylamine (60 mL) was heated under argon to
75 °C, while the suspension turned dark. A mixture of 1,3-diiodo-
5-nitrobenzene (8, 0.4 mmol, 149 mg) and 23 (204 mg, 0.4 mmol),
dissolved in benzene (50 mL) and triethylamine (50 mL), was
added to the catalyst suspension by syringe pump. The rate of the
addition was 5 mL·h–1. After the completion of addition the reac-
tion mixture was heated at 75 °C for 2 more hours, and then cooled
down to room temp. The solvent was removed in vacuo. The crude
product was washed with CH2Cl2, and recrystallisation with diox-
ane yielded small amounts of a product consisting of six compo-
γ [°]
V [Å3]
Dcalcd. [Mg·m–3]
Z
F(000)
Temperature [K]
hmin/hmax
kmin/kmax
lmin/lmax
Θ range [°]
1
µ [mm–1]
nents (2). H NMR(300 MHz, C2D2Cl4): δ = 1.01 (s, 18 H), 1.45
(s, 12 H), 1.72 (s, 12 H), 3.29 (s, 12 H), 7.01 (s, 6 H), 7.20 (s, 3 H),
7.62 (s, 24 H), 8.03 (s, 3 H), 8.33 (s, 6 H). MS (FD+): m/z = 1884
[M]+, (MALDI): m/z = 1884 [M]+. There was also mass spectro-
scopic evidence of a second product consisting of four components
Tmin.
Tmax.
Rint
0.974
0.995
0.029
17800
10224
7362
963
0.001
0.066
0.177
1.01
0.51
Refl. collected
Refl. unique
Refl. observed [I Ͼ 2σ (I)]
Variables
(Δ/σ)max
R
(C88H80N4O4): MS(FAB+): m/z = 1256 [M]+, 1257 [M + H]+
.
X-ray Structural Analysis: Table 1 contains the crystallographic data
and details of the refinement procedure. The reflections were col-
lected with a Bruker SMART APEX-diffractometer (Mo-Kα-radia-
tion, graphite monochromator). Data collection and reduction were
Rw
S (Gof)
performed with the BRUKER SMART and SAINT software.[44]
A
(Δρ)max [e·Å–3]
(Δρ)min [e·Å–3]
semiempirical absorption correction was performed with SAD-
ABS.[44] The structure was solved by direct methods (SHELXTL[45]).
Structural parameters of the non-hydrogen atoms were refined aniso-
tropically by a full-matrix, least-squares technique (F2). The hydro-
gen atoms linked to aromatic rings were refined isotropically, all
other H atoms were calculated. Refinement was carried out with
SHELXTL.[45] Disorder was found in two of the n-hexyl groups:
–0.31
3,5-Bis([4-trimethylsilylethynylphenyl]ethynyl)-N,N-dihexylaniline
(22): A mixture of 21 (3.3 g, 5.4 mmol), trimethylsilylacetylene
(2.0 g, 20.4 mmol), Pd(PPh3)4 (270 mg, 0.2 mmol) and CuI (89 mg,
0.5 mmol) in degassed Et2NH (60 mL) was heated at reflux under
Eur. J. Org. Chem. 2005, 1283–1292
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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of charge from The Cambridge Crystallographic Data Centre via
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Received: August 26, 2004
1292
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Eur. J. Org. Chem. 2005, 1283–1292