Linear and macrocyclic molecular thread, ribbon and belt assemblies of nanometric scale

Article abstract of DOI:10.1055/s-1999-3385

The hitherto longest molecular thread-belt assemblies 8, 29, 32 and 43 based on benzene-connected [3.3]metacyclophane units were prepared by means of a repetitive synthetic method. The preparation of difunctionalized [3.3]metacyclophane units (14, 22, 26) succeeded in good yields by an iteration sequence including the cyclization to the cyclophane skeleton and the derivatization of the ester groups. The covalent linkage of the [3.3]metacyclophane belt parts to the thread part leads to higher product yields compared to cyclophane belts only. The final intermolecular macrocyclizations are done by reaction of diamide, dithiol or dibromide functionalized belt fragments to obtain a minimum of single bridged benzene units in the macrocyclic thread-belt assemblies ('pseudobelts').

Full text of DOI:10.1055/s-1999-3385

PAPER
295
Linear and Macrocyclic Molecular Thread, Ribbon and Belt Assemblies
of Nanometric Scale
Holger Schwierz, Fritz Všgtle*
KekulŽ-Institut fŸr Organische Chemie und Biochemie der UniversitŠt Bonn, Gerhard-Domagk-Str. 1, D-53121 Bonn (Germany)
Fax: +49(228)735662; E-mail: voegtle@uni-bonn.de
Received 23 June 1998
One possible strategy for the synthesis of molecular belts
starts with the formation of molecular ribbons based on
[3.3]metacyclophane units, which can then be macrocyclized
making use of four functional groups. For that we developed
a repetitve synthetic strategy7. Following this we prepared
structure-perfect molecular ribbons like 6 with up to nine
benzene units8 and molecular belts like 7 containing five ben-
zene units9 (Figure 2). Mass spectrometry revealed molecu-
lar belts with up to 30 benzene units9, but their separation met
with difficulties. As a consequence it seems that avoiding oli-
gomeric macrocycles by structure directed synthesis of every
single belt is the better choice presently.
Abstract: The hitherto longest molecular thread-belt assemblies 8,
29, 32 and 43 based on benzene-connected [3.3]metacyclophane
units were prepared by means of a repetitive synthetic method. The
preparation of difunctionalized [3.3]metacyclophane units (14, 22,
26) succeeded in good yields by an iteration sequence including the
cyclization to the cyclophane skeleton and the derivatization of the
ester groups. The covalent linkage of the [3.3]metacyclophane belt
parts to the thread part leads to higher product yields compared to
cyclophane belts only. The final intermolecular macrocyclizations
are done by reaction of diamide, dithiol or dibromide functionalized
belt fragments to obtain a minimum of single bridged benzene units
in the macrocyclic thread-belt assemblies (ÒpseudobeltsÓ).
Keywords: Cyclophanes, macrocycles, molecular ribbons, nano-
structures, repetitive synthesis
Introduction
In supramolecular chemistry1 and especially in
nanochemistry2 macrocyclic and concave hydrocarbons
play an important role. Nanometric scale molecules are
fascinating due to their often appealing architecture, high
symmetry and host-guest interactions. Efforts on the way
to [0]n-paraphenylenes3 1 have been reported. Concrete
belt shaped hydrocarbons like 2 and 5 had been postulated
more than ten years ago4. At present several research
groups are working on the synthesis of belt shaped mole-
cules and particularly belt shaped hydrocarbons5 like 3
and 4, yet no genuine cyclic polyacene has been prepared6
so far (Figure 1).
Figure 2 Longest known tetrafunctionalized molecular ribbon 6
and molecular belt 7
A problem on the way to longer molecular belts was the
final macrocyclization step with low yields due to the high
number of covalent bonds which have to be formed9,10
.
The new strategy described here bases on the following
consideration: The substitution of one or more
[3.3]metacyclophane11 bridges by single bridges of the
same character should result in higher flexibility and sol-
ubility of the macrocycle. Two times covalently linking of
difunctionalized belt fragments (that can include
[3.3]metacyclophane units) should also lead to higher
yields of the macrocycle as the formation of cyclization
by-products is prevented. Furthermore, the preparation of
the belt precursors is then carried out more easily and in
good yields. According to space filling models the mixed
thread-belt macrocycles still look very similar to molecu-
lar belts and like those we described earlier9 (cf. Figure 3).
The waist of the molecular belt is hardly seen by looking
on space filling models. Yet with increasing number of
single-bridged benzene units the ribbon structure is ham-
pered. In the following we report on the preparation of the
first examples of such tied molecular pseudo-belts based
on [3.3]metacyclophane units including the longest yet
synthesized and fully characterized molecular Òpseudo-
Figure 1 Belt-shaped synthetic targets 1Ð5
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H. Schwierz, F. Všgtle
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Figure 3 New molecular pseudo-belt 8 containing six benzene units
beltaneÓ12 8 containing six benzene rings connected in the
Scheme 2
38-membered macrocycle (Figure 3).
termolecular cyclization of dibromide 11 and 1,2,4,5-
tetrakis[N-(4-tolylsulfonyl)aminomethyl]benzene9 18 we
obtained the meta/meta-cyclophane 19b in 10% yield and
meta/para-cyclophane 20 in 21Ð24% yield (Scheme 3).
Separation of the isomeric mixture is possible by extrac-
tion of 20 in ethyl acetate (residue: 19).
Results and Discussion
The synthesis of the monofunctionalized diamide 13 fol-
lows similar steps as the synthesis of the corresponding
difunctionalized diamide 2,4-bis[N-(4-tolylsulfonyl)ami-
nomethyl]-1,5-bis(ethoxycarbonyl)benzene formerly pre-
pared in 14% yield7,8,13, but as anticipated (see
introduction) the total yield is more than twice as high (13:
35%, Scheme 1).
Scheme 3
The cyclophanes 22Ð24 and 26Ð28 containing four and
five benzene units respectively are the first examples in
the series of difunctionalized molecular ribbons where the
repetition sequence is used twice. The cyclophane tetra-
bromides 2113 and 257Ð9 are obtained after one complete
repetitive reaction sequence of intermolecular cyclization,
reduction and bromination in the synthesis sequence of
tetrafunctionalized molecular ribbons. The difunctional-
ized [3.3][3.3][3.3]cyclophane 22 is prepared in 40%
yield from diamide 13a and cyclophane tetrabromide 21
(Scheme 4). The yields for the derivatization reactions to
Scheme 1
The intermolecular cyclization of dibromide 11 and
diamide 13 to the 6,15-difunctionalized metacyclophane
skeleton 14 with terminal ester groups succeeded under
high-dilution conditions14 in 60Ð61% yield. The cycliza-
tion of dibromide 11 with TosNHNa15 afforded the cyclo-
phane unit in one step only, but in lower yields. In
connection with the formation of the 12-membered
[3.3]metacyclophane ring system the derivatization of the
terminal ester group lead to the corresponding alcohol 15,
bromide 16 and thiol 17 (Scheme 2).
The synthesis of [3.3]metacyclophane ribbons including
three to five benzene units was succeeded using the
known procedures adapted from the synthesis of the tet-
rafunctionalized molecular ribbons (cf. 6). By double in-
Scheme 4
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Molecular Thread, Ribbon and Belt Assemblies of Nanometric Scale
297
dialcohol 23 and dibromide 24 of this cyclophane are as
high as in the [3.3]cyclophane system 14.
[3.3][3.3][3.3][3.3]Cyclophane 26 with a sequence of five
benzene units is formed by the reaction of tetrabromide 25
and diamide 13a (Scheme 5). The solubility of this cyclo-
phane diester is low and only after derivatization to the cor-
responding dibromide 28 a characterization was possible.
Scheme 7
There is only little difference in the belt shape as one com-
pares the space filling-models of pseudobeltanes 29 and
32 and completely cyclophane bridged beltanes 309,13 and
33 generated from tetrafunctionalized molecular ribbons
(Figure 4). Single bridges in parts of the belt are seeming-
ly only of low influence for the gross appearence.
Scheme 5
In the final macrocyclizations generating pseudobeltanes
(cf. 8, 29, 32, 38, 40, 41 and 43) always a difunctionalized
cyclophane bromide (16 and 24) is used as one of the cy-
clization compounds reacting intramolecularly with
TsNHNa (Scheme 7) or intermolecularly with a dithiol
(Scheme 6) or diamide (Schemes 9, 10 and 12), both of
which can include cyclophane units.
Pseudobeltane 29 containing four benzene units can be
prepared under high-dilution conditions in 28% yield
from the cyclophane dibromide 16 and the cyclophane
dithiol 17. A comparison to 3% macrocyclization yield
using tetrafunctionalized cyclophane units13 to generate
beltane 309,10,13 demonstrates the advantage of this new
approach (Scheme 6).
Scheme 6
Intramolecular cyclization of dibromide 16 and dibromide
24 using TsNHNa leads to pseudobeltanes 3116 and 32
containing two and four benzene units (Scheme 7).
Figure 4 Space filling models of pseudobeltanes 29, 32 in compar-
ison to beltanes 30, 33
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The smallest intermolecular possibility for macrocycliza-
tion to benzene based pseudobeltanes is the cyclization
with the p-xylene-bis(tosylamide) 37. The yield of this
amide is even 10% higher than the yield of the known du-
rene based tetraamide 189 to generate tetrafunctionalized
molecular ribbons and genuine belts9,13,17 derived from
these (Scheme 8).
Scheme 8
Scheme 10
In contrast to published procedures the following final
macrocyclization was not carried out under high-dilution
conditions by simultaneous and dropwise addition of the
cyclization components to a suspension of potassium car-
bonate in DMF. In this case the cyclophane dibromide 16
is added dropwise to a suspension of the diamide 37 and
caesium carbonate in DMF18. The idea was to build up an
intermediate spaced diamide to favour a 2:2-cyclization
product. Three products were isolated (Scheme 9): The
1:1-cyclization product 38, a pseudobeltane containing
three benzene units (12%), the cyclophane-spaced open
diamide 39 (0.5%), and the 2:2-cyclization product 8, a
pseudobeltane containing six benzene units (15%). This
pseudobeltane 8 is the biggest yet synthesized tied molec-
ular belt by the synthetic strategy described.
A molecular belt 43 with a size of five benzene units we
prepared with a new thread-like bistosylamide precursor
42 containing three benzene units. This precursor 42 can
be synthesized in only four steps (Scheme 11).
Scheme 11
In the cyclophane series the tosylamide function could
only be prepared in low yields following repetitive se-
quences of steps that failed in the preparation of longer
molecular ribbons and belts9,13,19. In this former strategy
we carried out one cyclization step to form the cyclophane
skeleton and a sequence of reactions to refunctionalize the
terminal functional groups. An advantage of the synthesis
of the thread-like bis(tosylamide) 42 is that the skeleton
and the tosylamide function is obtained in only one step
adding the dibromide 35 dropwise to a suspension of the
diamide 37 and caesium carbonate in DMF. Formation of
cyclic side ([3.3]-and [3.3.3.3]paracyclophane) products
was observed (MS, vide infra). Additionally it was not
necessary to use the less soluble and less stable dithiol
compounds in the final cyclization. The preparation of the
Scheme 9
Under analogous conditions the amide 13b and bromide
16 were macrocylized to yield the pseudobeltanes 40 and
41 containing three and six benzene units with exocyclic
ester groups (Scheme 10). The 2:2-cyclization product 41,
a pseudobeltane containing six benzene units, could not
be isolated, but detected by mass spectrometry (MALDI
and FAB).
Scheme 12
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Molecular Thread, Ribbon and Belt Assemblies of Nanometric Scale
299
MALDI-TOF spectra were recorded on a Micromass Tof spec E
spectrometer using 2,5-dihydroxybenzoic acid (DHB) as a matrix.
The 1H and 13C NMR spectra were recorded on a Bruker AM 250
[250 MHz (1H), 62.9 MHz (13C)] or a Bruker AM 400 [400 MHz
(1H), 100.6 MHz (13C)] spectrometer at r.t. (20¡C) in commercial
deuterated solvents (internal reference was the residual undeuterat-
ed solvent: CHCl3, d = 7.27; DMSO-d6, d = 2.5; DMF-d6, d = 2.74,
2.91, 8.05; CD2Cl2, d = 5.31). The following abbrevations were
used to indicate NMR-multiplicities and IR-intensities: s (singlet),
d (doublet), t (triplet), q (quartet), m (multiplet), br (broad); vs (very
strong), s (strong), m (medium), w (weak).
molecular belt 43 with a size of five benzene units was
successful in 32% macrocyclization yield (Scheme 12)
using this new toslyamide 42 compared to 9% for a four-
fold covalent linkage using tetrafunctionalized cyclo-
phane precursors9. The 2:2-cyclization product, a
pseudobeltane containing ten benzene units, could not be
found.
In all reactions leading to large ring molecules like 8 and
26, side products, especially higher cyclic oligomers,
were formed and detected by MALDI-MS in the crude
product, but the isolation was not successful. Formation of
catenanes and polycondensed networks was not observed.
1,4-Bis[N-acetyl-N-(4-tolylsulfonyl)aminomethyl]benzene (36)
A suspension of K2CO3 (82.93 g, 0.60 mol), 1,4-bis(bromometh-
yl)benzene (35;23 31.68 g, 0.12 mol) and N-acetyl-4-tolylsulfona-
mide (TsNHAc; 63.96 g, 0.60 mol) in anhyd DMF (500 mL) was
stirred for 48 h under argon atmosphere. The solvent was evaporat-
ed, and the remaining residue treated with CHCl3 (500 mL). The un-
dissolved components were removed by filtration, and the filtrate
was washed twice with H2O, dried (Na2SO4), filtered, and concen-
trated to give a colourless substance, which was recrystallized from
acetone to yield colourless crystals; Rf 0.79 (CHCl3/acetone, 20:1);
52.02 g (82%); mp 194¡C.
Conclusions
The synthetic strategy presented here demonstrates a
route to tied molecular pseudobeltanes based on difunc-
tionalized [3.3]cyclophane units. All procedures are car-
ried out in good yields compared to the preparation of
tetrafunctionalized ribbons and belts. The synthesis of
spaced bis(tosylamides) is a key step to obtain longer cy-
clizable molecules in less steps and in good total and mac-
rocyclization yields. Due to the higher flexibility of these
corded up belts further reactions should be possible. The
detosylation20 of the connecting bridges, the nitrosation of
the resulting free secondary amine, the extrusion of N2O21
and subsequent reduction will lead to belt shaped hydro-
carbons based on [2.2]metacyclophane units.
FAB-MS (NBA): m/z = 567.1 [M + K]+, 529.1 [M + H]+.
1H NMR (250 MHz, DMSO-d6): d = 2.21 (s, 6 H, Ac-CH3), 2.38 (s,
6 H, Ts-CH3), 5.06 (s, 4 H, NCH2), 7.36 (s, 4 H, Ar-H), 7.45 (d, 3J
= 8 Hz, 4 H, Ts-H), 7.68 (d, 3J = 8 Hz, 4 H Ts-H).
13C NMR (62.9 MHz, DMSO-d6): d = 21.1 (Ts-CH3), 24.3 (Ac-
CH3), 49.2 (NCH2), 126.6 (CH), 127.7 (CH), 129.8 (CH), 136.1
(Cq), 139.2 (Cq), 144.8 (Cq), 170.8 (CO).
¥
Anal. C26H26N2O6S2 0.5 H2O: calcd. C 58.08, H 5.44, N 5.21; found
C 57.85, H 5.48, N 5.18.
Pseudobelts of the types described above are of interest as
host molecules having cavities of the size of cyclodex-
trins. Substituting benzene units by biphenyl or terphenyl
building blocks should lead to longer molecular pseudo-
beltanes, and, after cyclization, to larger cavities inside.
1,4-Bis[(4-tolylsulfonylamino)methyl)]benzene (37)
A suspension of 36 (21.15 g, 40 mmol) and K2CO3 (49.76 g,
0.36 mol) in a mixture of EtOH (1 L) and H2O (50 mL) was refluxed
for 7 h. The solvent was evaporated, and the remaining residue
treated with H2O (250 mL) to dissolve the inorganic salts. The un-
Such variations should make it possible to produce con- dissolved product was obtained by filtration; evaporation and re-
crystallization from acetone; Rf 0.75 (CHCl3/MeOH, 20:1); 14.40 g
(81%); mp 221¡C.
MALDI-TOF (DHB): m/z = 483.7 [M + K]+.
FAB-MS (NBA): m/z = 483.1 [M + K]+, 445.1 [M + H]+.
1H NMR (250 MHz, DMSO-d6): d = 2.38 (s, 6 H, Ts-CH3), 4.04 (s,
4 H, NCH2), 7.06 (s, 4 H, Ar-H), 7.36 (d, 3J = 8 Hz, 4 H, Ts-H), 7.70
(d, 3J = 8 Hz, 4 H, Ts-H).
cave macrocyclic host molecules that fulfill the size re-
quirement for a given guest. The aim will be to tune
structure-property relationships ending up with new mate-
rial properties22, e.g. periodically arranged molecular
tubes filled with known guests, e.g. from the cyclodex-
trins or chemoselective sensing.
13C NMR (62.9 MHz, DMSO-d6): d = 22.1 (Ts-CH3), 45.9 (NCH2),
126.6 (CH), 127.5 (CH), 129.6 (CH), 136.7 (Cq), 137.8 (Cq), 142.6
(Cq).
Chemicals were purchased from Merck, Fluka and Aldrich and
were used as received. DMF, CH2Cl2, and CHCl3 were destilled and
dried over 4 • molecular sieve before use. THF was distilled from
LiAlH4 [indicator: Ph3CH (red)]. Yields refer to chromatographi-
cally and spectroscopically homogeneous materials. All reactions
were monitored by TLC carried out on aluminum sheets precoated
with silica gel 60 F254 (Merck 1.05554). The sheets were visualized
by UV light (l = 254 nm). Column chromatography was carried out
on silica gel 60 (Merck 15101). Melting points were determined on
a Kofler microscope heater (Reichert, Wien) and are not corrected.
Microanalyses were performed by the Microanalytical Department
at the ÒKekulŽ-Institut fŸr Organische Chemie und Biochemie der
UniversitŠt BonnÓ. IR spectra were recorded on a FT-IR-spectro-
meter (Perkin-Elmer Model 1600). GC/MS spectra were recorded
on HP 5890 Serie II gas chromatograph and HP 5898 A (EI-MS)
mass spectrometer from Hewlett Packard. Fast-atom bombardment
(FAB-MS) mass spectra were obtained using a Kratos Concept 1 H
spectrometer. The matrix used was m-nitrobenzyl alcohol (NBA).
¥
Anal. C22H22N2O4S2 C2H5OH: calcd. C 59.00, H 5.76, N 5.73, S
13.12; found C 59.20, H 5.34, N 6.07, S 13.13.
1,4-Bis[(N-(4-tolylsulfonyl)aminomethyl)benzyl-N-(4-tolyl-
sulfonyl)aminomethyl]benzene (42)
The dibromide 35 (0.79 g, 3.00 mmol) was dissolved in anhyd DMF
(50 mL). This solution was added dropwise over 6 h to a suspension
of Cs2CO3 (5.91 g, 18.00 mmol) and diamide 37 (8.00 g,
18.00 mmol) in anhyd DMF (250 mL) under argon atmosphere. The
suspension was then stirred for further 72 h. The solvent was evap-
orated, and the remaining residue treated with CHCl3 (300 mL). The
undissolved inorganic salts were removed by filtration, the filtrate
was washed with H2O, dried (Na2SO4) and concentrated to give a
colourless substance, which was purified by column chromatogra-
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H. Schwierz, F. Všgtle
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phy (silica gel, CHCl3/MeOH, 20:1); Rf 0.32 (CHCl3/MeOH, 20:1);
0.62 g (21%); mp 96¡C.
3,5-Bis[(4-tolylsulfonylamino)methyl]benzoic Acid Alkyl Esters
13a, b
A suspension of 12 (5 mmol, 3.85 12a/3.92 g 12b) and catalyst
(0.5 g, 10%-Pd on carbon) in CHCl3 (100 mL) was stirred at r.t. for
6 h under an H2 atmosphere (4 bar). The suspension was filtered
through Celite and the filtrate was evaporated to give a colourless
oil, which was purified by column chromatography (silica gel,
CHCl3/acetone, 10:1).
MALDI-TOF (DHB): m/z = 1013.7 [M + Na]+.
FAB-MS (NBA): m/z = 991.2 [M]+, 835.3 [M Ð Ts]+, 679.4 [M Ð 2
Ts]+.
1H NMR (250 MHz, DMSO-d6): d = 2.35 (s, 6 H, Ts-CH3), 2.41 (s,
6 H, Ts-CH3), 3.86 (d, 3J = 6 Hz, 4 H, NCH2), 4.06 (s, 4 H, NCH2),
4.16 (s, 4 H, NCH2), 6.88 (s, 4 H, Ar-H), 6.90 (d, 3J = 8 Hz, 4 H, Ar-
H), 7.07 (d, 3J = 8 Hz, 4 H, Ar-H), 7.34 (d, 3J = 8 Hz, 4 H, Ar-H),
7.42 (d, 3J = 8 Hz, 4 H, Ar-H), 7.65 (d, 3J = 8 Hz, 4 H, Ar-H), 7.73
(d, 3J = 8 Hz, 4 H, Ar-H), 8.02 (t, 3J = 6 Hz, 2 H, NH).
Methyl ester 13a
Rf 0.14 (CHCl3/acetone, 20:1); 2.11 g (80%); mp 180¡C.
FAB-MS (NBA): m/z = 525.1 [M + Na]+, 503.1 [M]+, 347.1 [M Ð Ts]+.
13C NMR (62.9 MHz, DMSO-d6): d = 20.9 (Ts-CH3), 21.0 (Ts-
CH3), 45.7 (NCH2), 50.3 (NCH2), 50.4 (NCH2), 126.5 (CH), 127.0
(CH), 127.4 (CH), 128.1 (CH), 128.2 (CH), 129.6 (CH), 129.9
(CH), 135.0 (Cq), 135.3 (Cq), 136.7 (Cq), 136.9 (Cq), 137.8 (Cq),
142.6 (Cq), 143.3 (Cq).
1H NMR (250 MHz, CDCl3): d = 2.39 (s, 6 H, Ts-CH3), 3.87 (s, 3
H, OCH3), 4.05 (br, 4 H, NCH2), 7.24 (t, 4J = 2 Hz, 1 H, Ar-H), 7.31
(d, 3J = 8 Hz, 4 H, Ts-H), 7.56 (d, 3J = 8 Hz, 4 H, Ts-H), 7.65 (d, 4J
= 2 Hz, 2 H, Ar-H).
13C NMR (62.9 MHz, CDCl3): d = 21.1 (Ts-CH3), 46.1 (NCH2),
52.0 (OCH3), 126.8 (CH), 127.8 (Cq), 129.5 (CH), 130.2 (Cq),
131.7 (CH), 136.8 (Cq), 137.7 (CH), 143.3 (Cq), 166.7 (CO).
3,5-Bis[N-benzyloxycarbonyl-N-(4-tolylsulfonyl)aminometh-
yl)]benzoic Acid Alkyl Esters 12a,b
¥
Anal. C24H26N2O6S2 2 H2O: calcd. C 53.51, H 5.61, N 5.20; found
A suspension of K2CO3 (14.00 g, 0.10 mol), 3,5-bis(bromometh-
yl)benzoic acid alkyl ester (11;24 25 mmol, 8.05 g 11a/8.40 g 11b)
and N-(4-tolylsulfonyl)benzylcarbamate (TsNHZ; 16.79 g, 55 mmol)
in anhyd DMF (500 mL) was stirred for 72 h under argon atmo-
sphere. The solvent was evaporated, and the remaining residue
treated with CHCl3 (300 mL). The undissolved components were
removed by filtration, and the filtrate was washed twice with brine
and twice with H2O, dried (Na2SO4), filtered, and concentrated to
give a crude oil, which was recrystallized from MeOH to yield
colourless crystals.
C 53.17, H 5.11, N 5.17.
Ethyl ester 13b
Rf 0.18 (CHCl3/acetone, 20:1); 2.02 g (79%); mp 151¡C.
FAB-MS (NBA): m/z = 539.1 [M + Na]+, 517.1 [M]+, 361.1 [M Ð Ts]+.
1H NMR (250 MHz, CDCl3): d = 1.35 (t, 3J = 7 Hz, 3 H, CH3CH2O),
2.40 (s, 6 H, Ts-CH3), 4.06 (d, 3J = 6 Hz, 4 H, NCH2), 4.30 (q, 3J =
7 Hz, 2 H, OCH2), 5.18 (t, 3J = 6 Hz, 2 H, NH) , 7.27 (d, 3J = 8 Hz,
4 H, Ts-H), 7.31 (t, 4J = 2 Hz, 1 H, Ar-H), 7.70 (d, 3J = 8 Hz, 4 H,
Ts-H), 7.72 (d, 4J = 2 Hz, 2 H, Ar-H).
13C NMR (62.9 MHz, CDCl3): d = 14.4 (CH3CH2O), 21.6 (Ts-
CH3), 46.7 (NCH2), 61.4 (OCH2), 127.2 (CH), 128.4 (Cq), 129.9
(CH), 131.2 (Cq), 131.7 (CH), 136.7 (Cq), 137.5 (CH), 143.8 (Cq),
165.9 (CO).
Methyl Ester 12a
Rf 0.64 (CHCl3/acetone, 20:1); 13.50 g (70%); mp 128¡C.
FAB-MS (NBA): m/z = 771.1 [M + H]+, 739.2 [M Ð OCH3]+, 605.1
[M Ð OCH3 Ð Z]+.
1H NMR (250 MHz, CDCl3): d = 2.38 (s, 6 H, Ts-CH3), 3.88 (s, 3 H,
OCH3), 5.04 (s, 4 H, NCH2), 5.09 (s, 4 H, OCH2Ph), 7.14Ð7.32 (m,
10 H, Ar-H), 7.11 (d, 3J = 8 Hz, 4 H, Ts-H), 7.55 (d, 3J = 8 Hz, 4 H,
Ts-H), 7.61 (t, 4J = 2 Hz, 1 H, Ar-H), 7.97 (d, 4J = 2 Hz, 2 H, Ar-H).
13C NMR (62.9 MHz, CDCl3): d = 21.6 (Ts-CH3), 46.1 (NCH2),
52.2 (OCH3), 69.2 (OCH2Ph), 128.5 (CH), 128.6 (CH), 128.8 (CH),
129.3 (CH), 130.9 (Cq), 132.3 (CH), 134.3 (Cq), 136.0 (Cq), 137.8
(Cq), 144.6 (Cq), 152.2 (CO), 166.3 (CO).
Anal. C25H28N2O6S2: calcd. C 58.12, H 5.46, N 5.42, S 12.41; found
C 58.07, H 5.49, N 5.40, S 12.15.
6,15-Bis(alkoxycarbonyl)-2,11-bis(4-tolylsulfonyl)-2,11-di-
aza[3.3]metacyclophanes 14a, b
The diamide (4 mmol, 2.01 g 13a/2.07 g 13b) and the dibromide
(4 mmol, 1.29 g 11a/1.34 g 11b) were each dissolved in anhyd
DMF (50 mL). These solutions were added dropwise and simulta-
neously over 23 h to a suspension of K2CO3 (5.03 g, 40 mmol) in
anhyd DMF (350 mL) under argon atmosphere. The mixture was
stirred at 20¡C for further 72 h. The solvent was evaporated, and the
remaining residue treated with CHCl3 (200 mL).The undissolved
inorganic salts were removed by filtration, the filtrate was washed
with water, dried (Na2SO4), concentrated and purified by recrystal-
lization from EtOAc to yield a colourless solid.
Anal. C40H38N2O10S2: calcd. C 62.32, H 4.97, N 3.63; found C
62.17, H 4.90, N 3.59.
Ethyl Ester 12b
Rf 0.68 (CHCl3/acetone, 20:1); 15.70 g (80%); mp 119¡C.
FAB-MS (NBA): m/z = 786.0 [M + H]+, 739.2 [M Ð OC2H5]+, 605.1
[M Ð OC2H5 Ð Z]+.
6,15-Bis(methoxycarbonyl)-2,11-bis(4-tolylsulfonyl)-2,11-di-
aza[3.3]metacyclophane 14a
Rf 0.47 (CH2Cl2/acetone, 20:1); 1.61 g (61%); mp 184¡C.
1H NMR (250 MHz, CDCl3): d = 1.44 (t, 3J = 7 Hz, 3 H, CH3CH2O),
2.39 (s, 6 H, Ts-CH3), 4.34 (q, 3J = 7 Hz, 2 H, OCH2), 5.04 (s, 4 H,
NCH2), 5.07 (s, 4 H, OCH2Ph), 7.10Ð7.34 (m, 10 H, Ar-H), 7.11 (d,
3J = 8 Hz, 4 H, Ts-H), 7.58 (d, 3J = 8 Hz, 4 H, Ts-H), 7.60 (t, 4J = 2
Hz, 1 H, Ar-H), 7.98 (d, 4J = 2 Hz, 2 H, Ar-H).
FAB-MS (NBA): m/z = 663.1 [M]+, 631.1 [M Ð OCH3]+, 507.1 [M
Ð Ts]+.
1H NMR (250 MHz, CDCl3): d = 2.49 (s, 6 H; Ts-CH3), 3.80 (s, 6
H; OCH3), 4.05 (br, 8 H; NCH2), 7.40 (s, 4 H; Ar-H), 7.42 (d, 3J =
8 Hz, 4 H; Ts-H), 7.65 (s, 2 H; Ar-H), 7.80 (d, 3J = 8 Hz, 4 H; Ts-H).
13C NMR (62.9 MHz, CDCl3): d = 21.7 (Ts-CH3), 52.1 (OCH3),
54.5 (NCH2), 127.2 (CH), 129.2 (Cq), 130.3 (CH), 130.4 (Cq),
135.8 (Cq), 136.0 (CH), 137.2 (Cq), 144.1 (CH), 166.1 (CO).
13C NMR (62.9 MHz, CDCl3): d = 14.4 (CH3CH2O), 21.7 (Ts-
CH3), 49.5 (NCH2), 61.2 (OCH2), 69.3 (OCH2Ph), 128.6 (CH),
128.7 (CH), 128.8 (CH), 129.3 (CH), 131.3 (Cq), 132.3 (CH), 134.5
(Cq), 136.1 (Cq), 137.8 (Cq), 144.7 (Cq), 152.4 (CO), 166.0 (CO).
Anal. C41H40N2O10S2: calcd. C 62.74, H 5.14, N 3.57, S 8.17; found
C 62.47, H 5.15, N 3.46, S 8.12.
Anal. C34H34N2O8S2¥0.5 CHCl3: calcd. C 56.52, H 4.74, N 3.87;
found C 55.91, H 4.70, N 3.66.
Synthesis 1999, No. 2, 295–305 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Molecular Thread, Ribbon and Belt Assemblies of Nanometric Scale
301
6,15-Bis(ethoxycarbonyl)-2,11-bis(4-tolylsulfonyl)-2,11-diaza-
[3.3]metacyclophane 14b
FAB-MS (NBA): m/z = 650.0 [M + Na]+, 637.1 [M]+, 603.0 [M Ð
H2S]+, 567.9 [M Ð 2 H2S]+, 481.8 [M Ð Ts]+.
Rf 0.52 (CH2Cl2/acetone, 20:1); 1.74 g (60%).
FAB-MS (NBA): m/z = 691.1 [M]+, 645.1 [M Ð OCH2CH3]+, 535.1
6,24-Bis(alkoxycarbonyl)-2,11,20,29-tetrakis(4-tolylsulfonyl)-
2,11,20,29-hexaaza[3.3](1,3)(1,2)[3.3](4,5)(1,3)benzeno 3
phane (19a, 19b) and 6,24-Bis(methoxycarbonyl)-2,11,20,29-
tetrakis(4-tolylsulfonyl)-2,11,20,29-hexaaza[3.3](1,3)(1,3)[3.3]-
(4,6)(1,3)benzeno-(3)-phane (20a)
[M Ð Ts]+.
1H NMR (250 MHz, CDCl3): d = 1.31 (t, 3J = 7 Hz, 6 H; CH3CH2O),
2.49 (s, 6 H; Ts-CH3), 4.24 (q, 3J = 7 Hz, 4 H; OCH2), 4.36 (br, 8 H;
NCH2), 7.37 (s, 4 H; Ar-H), 7.40 (d, 3J = 8 Hz, 4 H; Ts-H), 7.50 (s,
2 H; Ar-H), 7.82 (d, 3J = 8 Hz, 4 H; Ts-H).
13C NMR (62.9 MHz, CDCl3): d = 14.3 (CH3CH2O), 21.7 (Ts-CH3),
54.4 (NCH2), 61.0 (OCH2), 127.3 (CH), 129.0 (Cq), 130.3 (CH), 130.6
(Cq), 135.9 (Cq), 136.0 (CH), 137.0 (Cq), 144.1 (CH), 165.6 (CO).
The tetraamide 189 (3 mmol, 2.43 g) and the dibromide (6 mmol,
1.93 g 11a/2.02 g 11b) were each dissolved in anhyd DMF (50 mL).
These solutions were added dropwise and simultaneously over 8 h
to a suspension of K2CO3 (3.00 g, 22 mmol) in anhyd DMF
(500 mL) under argon atmosphere. The mixture was stirred for fur-
ther 18 h. The solvent was evaporated, and the remaining residue
treated with CHCl3 (300 mL). The undissolved inorganic salts were
removed by filtration, the filtrate was washed with H2O, dried
(Na2SO4) and concentrated. The mixture was purified by recrystal-
lization from acetone. The meta/para-isomers (19a/19b) were ob-
tained by extraction with CHCl3. The residue was the meta/meta-
isomer (20a). The ethyl ester 20b could not be isolated.
6,15-Bis(hydroxymethyl)-2,11-bis(4-tolylsulfonyl)-2,11-di-
aza[3.3]metacyclophane (15)
A suspension of 14 (3 mmol, 1.99 g 14a/2.07 g 14b) and LiBH4
(1.00 g, 46 mmol) in anhyd THF (200 mL) was refluxed for 24 h un-
der argon atmosphere. The cooled mixture was evaporated in vac-
uo. H2O (50 mL) was added to the remaining residue and the
suspension was stirred for 30 min at r.t. to dissolve the inorganic
salts. The alcohol remained undissolved and was filtered, washed
with H2O, and dried. The compound was used in the next step with-
out further purification; 1.51 g (80%); mp 248¡C.
meta/para-6,24-Bis(methoxycarbonyl)-2,11,20,29-tetrakis(4-tol-
ylsulfonyl)-2,11,20,29-hexaaza[3.3](1,3)(1,2)[3.3](4,5)(1,3)-ben-
zeno 3 phane (19a)
0.84 g (24%); mp >280¡C.
FAB-MS (NBA): m/z = 607.1 [M]+, 451.1 [M Ð Ts]+.
FAB-MS (NBA): m/z = 1169.1 [M + K]+, 1153.1 [M + Na]+, 1131.3
1H NMR (250 MHz, DMSO-d6): d = 2.47 (s, 6 H; Ts-CH3), 4.21 (d,
3J = 7 Hz, 4 H; OCH2), 4.24 (br, 8 H; NCH2), 5.08 (t, 3J = 7 Hz, 2
H; OH), 6.70 (s, 4 H; Ar-H), 7.10 (s, 2 H, Ar-H), 7.49 (d, 3J = 8 Hz,
4 H; Ts-H), 7.84 (d, 3J = 8 Hz, 4 H; Ts-H).
13C NMR (62.9 MHz, DMSO-d6): d = 21.1 (Ts-CH3), 54.0 (NCH2),
62.6 (OCH2), 125.9 (Cq), 126.9 (CH), 130.2 (CH), 131.5 (Cq),
135.2 (CH), 136.2 (CH), 141.9 (Cq), 143.4 (Cq).
[M + H]+, 1013.2 [M Ð Ts]+.
IR (KBr): n = 2962 (s), 1718 (vs), 1598 (s), 1434 (m), 1339 (s), 1261
(s), 1218 (s), 1161 (s), 1090 (vs), 1010 (s), 888 (m), 803 (m), 663 cmÐ
1 (s).
1H NMR (250 MHz, CDCl3): d = 2.50 (s, 12 H; Ts-CH3), 3.62 (d,
2J = 14 Hz, 4 H; NCH2), 3.68 (d, 2J = 14 Hz, 4 H; NCH2), 3.80 (d,
2J = 14 Hz, 4 H; NCH2), 3.97 (s, 6 H; OCH3), 4.39 (d, 2J = 14 Hz, 4
H; NCH2), 5.48 (s, 2 H; Ar-H), 6.15 (s, 2H; Ar-H), 7.41 (d, 3J = 8
Hz, 8 H; Ts-H), 7.74 (d, 3J = 8 Hz, 8 H; Ts-H), 7.80 (s, 4 H; Ar-H).
6,15-Bis(bromomethyl)-2,11-bis(4-tolylsulfonyl)-2,11-dia-
za[3.3]-metacyclophane (16)
A suspension of alcohol 15 (2.42 g, 4 mmol) and PBr3 (19.36 mL,
0.20 mol) in anhyd CHCl3 (250 mL) was refluxed for 48 h under ar-
gon atmosphere. The cooled mixture was poured into ice-water
(200 mL)and stirred for 1 h. The organic layer was separated,
washed with concd NaHCO3 solution (3 × 100 mL), dried (Na2SO4),
filtered, and evaporated to yield a colourless substance, which was
purified by column chromatography (silica gel, CHCl3/acetone,
50:1); Rf 0.62 (CHCl3/acetone, 50:1); 2.40 g (82%); mp 239¡C.
MALDI-TOF (DHB): m/z = 754.9 [M + Na]+, 732.9 [M]+.
FAB-MS (NBA): m/z = 757.2 [M + Na]+, 733.0 [M]+, 577.0 [M Ð Ts]+.
1H NMR (250 MHz, CDCl3): d = 2.48 (s, 6 H; Ts-CH3), 4.22 (s, 4
H; BrCH2), 4.28 (br, 8 H; NCH2), 6.80 (s, 4 H; Ar-H), 7.16 (s, 2 H;
Ar-H), 7.48 (d, 3J = 8 Hz, 4 H; Ts-H), 7.78 (d, 3J = 8 Hz, 4 H; Ts-H).
13C NMR (62.9 MHz, CDCl3): d = 21.7 (Ts-CH3), 33.5 (BrCH2),
54.7 (NCH2), 127.2 (CH), 128.8 (CH), 130.3 (CH), 131.0 (Cq),
133.4 (Cq), 136.0 (CH), 137.5 (Cq), 144.0 (Cq).
meta/meta-6,24-Bis(methoxycarbonyl)-2,11,20,29-tetrakis(4-
tolylsulfonyl)-2,11,20,29-hexaaza[3.3](1,3)(1,3)[3.3](4,6)(1,3)-
benzeno 3 phane (20a)
0.33 g (10%); mp >280¡C.
FAB-MS (NBA): m/z = 1169.1 [M + K]+, 1153.1 [M + Na]+, 1131.3
[M + H]+, 1013.2 [M Ð Ts]+.
1H NMR (250 MHz, CDCl3): d = 2.48 (s, 12 H; Ts-CH3), 3.7Ð4.7
(br, 22 H; NCH2 and OCH3), 7.17 (s, 2 H; Ar-H), 7.33 (s, 2 H; Ar-
H), 7.40 (d, 3J = 8 Hz, 8 H; Ts-H), 7.71 (s, 4 H; Ar-H), 7.76 (d, 3J =
8 Hz, 8 H; Ts-H).
meta/para-6,24-Bis(ethoxycarbonyl)-2,11,20,29-tetrakis(4-tolyl-
sulfonyl)-2,11,20,29-hexaaza[3.3](1,3)(1,2)[3.3](4,5)(1,3)ben-
zeno(3)phane (19b)
0.68 g (21%); mp >280¡C.
FAB-MS (NBA): m/z = 1197.3 [M + K]+, 1181.3 [M + Na]+, 1159.3
[M + H]+, 1113.3 [M Ð OCH2CH3]+, 1003.3 [M Ð Ts]+, 849.3 [M Ð
2 Ts]+.
¥
Anal. C32H32Br2N2O4S2 2 H2O: calcd. C 50.01, H 4.72, N 3.64, S
8.34; found C 50.38, H 4.31, N 3.51, S 8.13.
IR (KBr): n = 2969 (m), 1723 (vs), 1679 (m), 1592 (m), 1432 (m),
1342 (s), 1260 (s), 1213 (s), 1161 (s), 1090 (vs), 1010 (s), 880 (m),
809 (m), 666 cmÐ1 (s).
1H NMR (250 MHz, CDCl3): d = 1.44 (t, 3J = 7 Hz, 6 H; CH3CH2O),
2.48 (s, 12 H; Ts-CH3), 3.63 (d, 2J = 14 Hz, 4 H; NCH2), 3.76 (d, 2J
= 14 Hz, 4 H; NCH2), 3.81 (d, 2J = 14 Hz, 4 H; NCH2), 4.39 (d, 2J
= 14 Hz, 4 H; NCH2), 4.40 (q, 3J = 7 Hz, 4 H; OCH2), 5.48 (s, 2 H;
Ar-H), 6.16 (s, 2 H; Ar-H), 7.40 (d, 3J = 8 Hz, 8 H; Ts-H), 7.75 (d,
3J = 8 Hz, 8 H; Ts-H), 7.79 (s, 4 H; Ar-H).
6,15-Bis(thiomethyl)-2,11-bis(4-tolylsulfonyl)-2,11-diaza[3.3]-
metacyclophane (17)
A solution of the dibromide 16 (147 mg, 0.2 mmol) and thiourea
(31 mg, 0.2 mmol) in DMSO (10 mL) was stirred for 24 h under ar-
gon atmosphere. Aq 10% NaOH solution (10 mL) was added drop-
wise during a few minutes at 0¡C and the mixture was further
stirred 1 h. With half concentrated HCl a colourless substance pre-
cipitated at pH 1. The thio compound 17 remained undissolved, was
filtered and used without further purification; Rf 0.19 (CHCl3/ace-
tone, 20:1); 89 mg (70%).
Synthesis 1999, No. 2, 295–305 ISSN 0039-7881 © Thieme Stuttgart · New York

302
H. Schwierz, F. Všgtle
PAPER
13C NMR (62.9 MHz, CDCl3): d = 14.4 (CH3CH2O), 21.6 (Ts-
CH3), 50.3 (NCH2), 52.2 (NCH2), 61.3 (OCH2), 127.5 (CH), 128.7
(Cq), 130.2 (CH), 131.2 (Cq), 132.4 (CH), 133.2 (CH), 134.4 (Cq),
135.1 (Cq), 137.2 (Cq), 144.0 (CH), 165.9 (CO).
FAB-MS (NBA): m/z = 1669.2 [M + H]+, 1589.3 [M Ð Br]+, 1513.2
[M Ð Ts]+, 1359.2 [M Ð 2 Ts]+.
1H NMR (250 MHz, CDCl3): d = 2.46 (s, 12 H; Ts-CH3), 2.48 (s, 6
H; Ts-CH3), 4.04 (s, 4 H; CH2Br), 4.25Ð5.30 (br, 24 H; ArCH2),
6.31 (s, 2 H; Ar-H), 6.50 (s, 2 H; Ar-H), 6.59 (s, 4 H; Ar-H), 6.88
(s, 2 H; Ar-H), 7.37 (d, 3J = 8 Hz, 8 H; Ts-H), 7.45 (d, 3J = 8 Hz, 4
H; Ts-H), 7.79 (d, 3J = 8 Hz, 12 H; Ts-H).
13C NMR (62.9 MHz, DMF-d7): d = 21.3 (Ts-CH3), 21.4 (Ts-CH3),
29.4 (CH2Br), 61.5Ð55.5 (NCH2), 128.1 (CH), 128.6 (CH), 129.0
(CH), 130.7 (CH), 130.8 (CH), 131.7 (Cq), 132.6 (Cq),134.4 (CH),
134.7 (CH), 136.0 (Cq), 136.5 (Cq), 137.1 (Cq), 138.1 (Cq), 138.5
(Cq), 144.4 (Cq), 144.6 (Cq).
6,36-Bis(methoxycarbonyl)-2,11,20,29,32,41-hexakis(4-tolyl-
sulfonyl)-2,11,20,29,32,41-hexaaza[3.3](1,3)(1,3)[3.3](4,6)-
(1,3)[3.3)-(4,6)(1,3)benzeno 4 phane (22)
The diamide 13a (2.00 mmol, 1.01 g) and the tetrabromide 21
(1.00 mmol, 1.01 g) were each dissolved in anhyd DMF (50 mL).
These solutions were added dropwise and simultaneously over 83 h
to a suspension of K2CO3 (3.00 g, 22 mmol) in anhyd DMF (500 mL)
under argon atmosphere. The mixture was stirred for further 72 h.
The solvent was evaporated, and the remaining residue treated with
CHCl3 (100 mL). The undissolved inorganic salts were removed by
filtration, the filtrate was washed with H2O, dried (Na2SO4), concen-
trated and purified by (silica gel, CHCl3/acetone, 15:1) to yield a
colourless substance; Rf 0.47 (CHCl3/acetone, 15:1); 0.60 g (40%);
mp 252¡C.
6,48-Bis(methoxycarbonyl)-2,11,20,29,32,41,44,53-octakis(4-
tolylsulfonyl)-2,11,20,29,32,41,-44,53-octaaza[3.3](1,3)(1,3)-
[3.3](4,6)(1,3)[3.3)(4,6)(1,3)[3.3)(4,6)(1,3)benzeno 5 phane (26)
The diamide 13a (1.00 mmol, 0.51 g) and the tetrabromide 25
(0.5 mmol, 0.67 g) were each dissolved in anhyd DMF (50 mL).
These solutions were added dropwise and simultaneously over 83 h
to a suspension of K2CO3 (4.18 g, 30 mmol) in anhyd DMF
(200 mL) under argon atmosphere. The mixture was stirred for fur-
ther 48 h. The solvent was evaporated, and the remaining residue
treated with CHCl3 (100 mL). The undissolved inorganic salts were
removed by filtration, the filtrate was washed with H2O, dried
(Na2SO4), concentrated and purified by (silica gel, CHCl3/acetone,
15:1) to yield a colourless solid; Rf 0.44 (CHCl3/acetone, 15:1);
0.33 g (32%); mp >280¡C.
FAB-MS (NBA): m/z = 1622.2 [M + Na]+, 1600.3 [M + H]+, 1568.2
[M Ð OCH3]+, 1443.2 [M Ð Ts]+, 1289.2 [M Ð 2 Ts]+.
1H NMR (250 MHz, CDCl3): d = 2.46 (s, 6 H; Ts-CH3), 2.49 (s, 12
H; Ts-CH3), 3.74 (s, 6 H; OCH3), 4.00Ð5.50 (br, 24 H; ArCH2), 6.45
(s, 2 H; Ar-H), 6.79 (s, 2 H; Ar-H), 7.34 (s, 2 H; Ar-H), 7.55 (d, 3J
= 8 Hz, 8 H; Ts-H), 7.82 (d, 3J = 8 Hz, 4 H; Ts-H), 7.91 (d, 3J = 8 Hz,
4 H; Ts-H), 7.98 (d, 3J = 8 Hz, 8 H; Ts-H), 8.38 (s, 4 H; Ar-H).
13C NMR (62.9 MHz, CDCl3): d = 21.3 (Ts-CH3), 21.4 (Ts-CH3),
52.2 (OCH3), 61.4 (NCH2), 128.1 (CH), 128.6 (CH), 130.1
(Cq),130.3 (Cq), 130.7 (CH), 130.8 (CH), 131.8 (Cq), 133.2 (Cq),
136.7 (Cq), 136.9 (Cq), 137.2 (Cq), 144.4 (Cq), 166.3 (CO).
FAB-MS (NBA): m/z = 2105.4 [M + K]+, 2068.5 [M + H]+, 1913.5
[M Ð Ts]+, 1757.5 [M Ð 2 Ts]+.
6,48-Bis(hydroxymethyl)-2,11,20,29,32,41,44,53-octakis(4-
tolylsulfonyl)-2,11,20,29,32,41,44,53-octaaza[3.3](1,3)(1,3)-
[3.3](4,6)-(1,3)[3.3)(4,6)(1,3)[3.3)(4,6)(1,3)benzeno 5 phane (27)
A suspension of 26 (0.18 g, 0.09 mmol) and LiBH4 (0.20 g, 9 mmol)
in anhyd THF (150 mL) was refluxed for 18 h under argon atmo-
sphere. The cooled mixture was evaporated in vacuo. H2O (100 mL)
was added to the remaining residue and the suspension was stirred
for 30 min at r.t. to dissolve the inorganic salts. The alcohol re-
mained undissolved and was filtered, washed with H2O, and dried.
The compound was used without further purification; 0.17 g (95%);
mp >280¡C.
Anal. C82H82N6O16S6¥1.5 CHCl3: calcd. C 55.36, H 4.65, N 4.72;
found C 55.73, H 4.70, N 4.48.
6,36-Bis(hydroxymethyl)-2,11,20,29,32,41-hexakis(4-tolylsulfo-
nyl)-2,11,20,29,32,41-hexaaza[3.3](1,3)(1,3)[3.3](4,6)(1,3)[3.3)-
(4,6)(1,3)benzeno 4 phane (23)
A suspension of 22 (0.48 g, 0.3 mmol) and LiBH4 (0.50 g, 23 mmol)
in anhyd THF (200 mL) was refluxed for 24 h under argon atmo-
sphere. The cooled mixture was evaporated in vacuo. H2O (50 mL)
was added to the remaining residue and the suspension was stirred
for 30 min at r.t. to dissolve the inorganic salts. The alcohol re-
mained undissolved and was filtered, washed with H2O, and dried.
The compound was used in the next step without further purifica-
tion; 0.35 g (75%).
6,48-Bis(bromomethyl)-2,11,20,29,32,41,44,53-octakis(4-tolyl-
sulfonyl)-2,11,20,29,32,41,44,53-octaaza[3.3](1,3)(1,3)[3.3]-
(4,6)-(1,3)[3.3)(4,6)(1,3)[3.3)(4,6)(1,3) benzeno 5 phane (28)
A suspension of alcohol 27 (0.17 g, 0.09 mmol) and PBr3 (5.00 mL,
52 mmol) in anhyd CHCl3 (100 mL) was refluxed for 96 h under ar-
gon atmosphere. The cooled mixture was poured into ice-water and
stirred for 1 h. The organic layer was separated, washed three times
with concd NaHCO3 solution, dried (Na2SO4), filtered, and evapo-
rated to yield a colourless solid, which was purified by column
chromatography (silica gel, CHCl3/acetone, 15:1); Rf 0.63 (CHCl3/
acetone, 15:1); 65 mg (35%); mp >280¡C.
FAB-MS (NBA): m/z = 1549.3 [M + Li]+, 1543.3 [M + H]+, 1387.3
[M Ð Ts]+, 1233.3 [M Ð 2 Ts]+.
1H NMR (250 MHz, CDCl3): d = 2.47 (s, 12 H; Ts-CH3), 2.49 (s, 6
H; Ts-CH3), 4.19 (s, 4 H; OCH2), 4.25Ð5.30 (br, 24 H; ArCH2), 6.33
(br, 2 H; Ar-H), 6.42 (br, 2 H; Ar-H), 6.82 (br, 2 H; Ar-H), 6.91 (br,
4 H; Ar-H), 7.38 (d, 3J = 8 Hz, 8 H; Ts-H), 7.45 (d, 3J = 8 Hz, 4 H;
Ts-H), 7.76 (d, 3J = 8 Hz, 4 H; Ts-H), 7.79 (d, 3J = 8 Hz, 8 H; Ts-H).
FAB-MS (NBA): m/z = 2139.1 [M + H]+, 1983.1 [M Ð Ts]+.
6,36-Bis(bromomethyl)-2,11,20,29,32,41-hexakis(4-tolylsulfo-
nyl)-2,11,20,29,32,41-hexaaza[3.3](1,3)(1,3)[3.3](4,6)(1,3)[3.3)-
(4,6)(1,3)benzeno 4 phane (24)
1H NMR (250 MHz, CD2Cl2): d = 2.49 (s, 24 H; Ts-CH3), 3.00Ð
5.30 (br, 36 H; ArCH2), 6.24 (s, 2 H; Ar-H), 6.41 (s, 2 H; Ar-H),
6.60 (s, 4 H; Ar-H). 6.84 (s, 2 H; Ar-H), 6.91 (s, 2 H; Ar-H), 7.43
(d, 3J = 8 Hz, 16 H; Ts-H), 7.79 (d, 3J = 8 Hz, 16 H; Ts-H).
A suspension of the alcohol 23 (0.3 g, 0.2 mmol) and PBr3
(9.72 mL, 0.10 mol) in anhyd CHCl3 (200 mL) was refluxed for 72
h under argon atmosphere. The cooled mixture was poured into ice-
water (100 mL) and stirred for 1 h. The organic layer was separated,
washed with concd NaHCO3 solution (3 × 100 mL), dried
(Na2SO4), filtered, and evaporated to yield a colourless substance,
which was purified by column chromatography (silica gel, CHCl3/
acetone, 15:1); Rf 0.64 (CHCl3/acetone, 15:1); 0.25 g (77%); mp
186¡C.
2,11,20-Tris(4-tolylsulfonyl)-2,11,20-triaza[3.3.3](1,3,5)ben-
zeno 2 phane (31)
The dibromide 17 (140 mg, 0.19 mmol) was dissolved in anhyd
DMF (50 mL). This solution was added dropwise over 1 h to a sus-
pension of Cs2CO3 (1.63 g, 5.00 mmol) and TsNHNa (0.45 g,
1.00 mmol) in anhyd DMF (100 mL) under argon atmosphere at
Synthesis 1999, No. 2, 295–305 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Molecular Thread, Ribbon and Belt Assemblies of Nanometric Scale
303
90¡C. The mixture was further stirred for 24 h. The solvent was
evaporated, and the remaining residue treated with CHCl3
(150 mL). The undissolved inorganic salts were removed by filtra-
tion, the filtrate was washed with H2O, dried (Na2SO4) and concen-
trated. The product was purified by recrystallization from dioxane;
Rf 0.52 (CHCl3/acetone 20:1); 98 mg (70%); mp >280¡C.
1H NMR (250 MHz, CDCl3): d = 2.44 (s, 6 H; Ts-CH3), 2.48 (s, 6
H; Ts-CH3), 3.76 (s, 4 H; NCH2), 3.00Ð5.20 (br, 8 H; NCH2), 6.81
(s, 4 H; Ar-H), 7.25 (s, 2 H; Ar-H), 7.26 (s, 4 H; Ar-H), 7.34 (d, 3J
= 8 Hz, 4 H; Ts-H), 7.40 (d, 3J = 8 Hz, 4 H; Ts-H), 7.68 (d, 3J = 8 Hz,
4 H; Ts-H), 7.78 (d, 3J = 8 Hz, 4 H; Ts-H).
13C NMR (62.9 MHz, CDCl3): d = 21.6 (Ts-CH3), 22.4 (Ts-CH3),
54.5 (NCH2), 55.0 (NCH2), 126.9 (Cq), 128.0 (CH), 129.9 (CH),
130.1 (CH), 130.2 (CH), 133.4 (Cq), 133.9 (Cq), 134.7 (Cq), 143.6
(Cq), 144.0 (CH).
FAB-MS (NBA): m/z = 742.1 [M + H]+, 587.1 [M Ð Ts]+.
IR (KBr): n = 3030.3 (m), 2960.5 (w), 2910.8 (w), 2855.0
(m),1460.0 (m), 1335.1 (s), 1160.8 (vs), 1095.4 (s), 922.3 (m),
811.1 (m), 777.6 (m), 667.1 cmÐ1 (s).
1H NMR (250 MHz, CDCl3): d = 2.49 (s, 9 H; Ts-CH3), 4.08Ð4.66
(br, 12 H; NCH2), 6.92 (s, 6 H; Ar-H), 7.40 (d, 3J = 8 Hz, 6 H; Ts-
H) , 7.77 (d, 3J = 8 Hz, 6 H; Ts-H).
Anal. C54H54N4O8S4¥H2O: calcd. C 62.77, H 5.46, N 5.42, S 12.41;
found C 62.79, H 5.48, N 5.01, S 12.30.
2,11,20,29,32,41,44,53-Octakis(4-tolylsulfonyl)-2,11,20,29,32,-
41,44,53-octaaza[3.3](1,3)(1,3)[3.3](1,3)(1,3)[3](5,5)[3](5.5)[3]-
(1,4)[3](1,4)benzeno 6 phane (8)
Rf 0.45 (CHCl3/acetone, 50:1); 92 mg (15%); mp > 300¡C.
MALDI-TOF (DHB): m/z = 2052.3 [M + Na]+ .
2,11,20,29,32,41,44-Heptakis(4-tolylsulfonyl)-2,11,20,29,32,41,
44-heptaaza[3.3](1,3) (1,3)[3.3](4,6)(1,3)[3.3)(4,6)(1,3)[3](5,5)-
benzeno 4 phane (32)
The dibromide 24 (250 mg, 0.15 mmol) was dissolved in anhyd
DMF (50 mL). This solution was added dropwise over 2 h to a sus-
pension of Cs2CO3 (4.90 g,15 mmol) and TsNHNa (1.34 g, 3 mmol)
in anhyd DMF (200 mL) under argon atmosphere at 90¡C. The mix-
ture was further stirred for 72 h. The solvent was evaporated, and
the remaining residue treated with CHCl3 (150 mL). The undis-
solved inorganic salts were removed by filtration, the filtrate was
washed with H2O, dried (Na2SO4) and concentrated. The product
was isolated by column chromatography (silica gel, CHCl3/acetone,
15:1); Rf 0.48 (CHCl3/acetone, 15:1); 55 mg (22%); mp >280¡C.
FAB-MS (NBA): m/z = 2030.6 [M]+, 1875.5 [M Ð Ts]+, 1719.5 [M
Ð 2 Ts]+, 1563.4 [M Ð 3 Ts]+, 1407.4 [M Ð 4 Ts]+.
IR (KBr): n = 2923.9 (s), 2861.0 (m), 1597.1 (s), 1437.4 (s), 1331.9
(vs), 1159.4 (vs), 1087.0 (vs), 915.3 (m), 812.6 (s), 761.0 (s),
662.2 cmÐ1 (s).
1H NMR (250 MHz, CDCl3): d = 2.36 (s, 12 H; Ts-CH3), 2.52 (s,
12 H; Ts-CH3), 3.76 (d, 2J = 12 Hz, 8 H; NCH2), 3.20Ð5.80 (br, 16
H; NCH2), 6.54 (s, 4 H; Ar-H), 6.85 (s, 8 H; Ar-H), 7.25 (d, 3J = 8
Hz, 8 H; Ts-H), 7.31 (s, 8 H; Ar-H), 7.42 (d, 3J = 8 Hz, 8 H; Ts-H),
7.57 (d, 3J = 8 Hz, 8 H; Ts-H), 7.80 (d, 3J = 8 Hz, 8 H; Ts-H).
13C NMR (62.9 MHz, CDCl3): d = 21.6 (Ts-CH3), 21.8 (Ts-CH3),
48.2 (NCH2), 48.5 (NCH2), 127.2 (CH), 127.3 (CH), 129.5 (Cq),
129.9 (CH), 130.4 (CH), 134.7 (CH), 135.7 (Cq), 138.5 (Cq), 143.4
(Cq), 143.9 (Cq).
FAB-MS (NBA): m/z = 1679.2 [M + H]+, 1522.2 [M Ð Ts]+, 1368.2
[M Ð 2 Ts]+.
1H NMR (400 MHz, CD2Cl2): d = 2.34 (s, 3 H; Ts-CH3), 2.40 (s, 6
H; Ts-CH3), 2.43 (s, 12 H; Ts-CH3), 3.50Ð5.00 (br, 28 H; NCH2),
6.69 (s, 4 H; Ar-H), 6.99 (s, 2 H; Ar-H), 7.04 (s, 2 H; Ar-H), 7.05
(s, 2 H; Ar-H), 7.42Ð7.44 (br, 14 H; Ts-H), 7.63Ð7.75 (br, 14 H; Ts-
H).
Anal. C108H108N8O16S8¥2 H2O: calcd. C 62.77, H 5.46, N 5.42, S
12.41; found C 62.77, H 5.37, N 5.31, S 12.38.
13C NMR (62.9 MHz, CDCl3): d = 21.4 (Ts-CH3), 21.6 (Ts-CH3),
51.4Ð55.4 (NCH2), 126.7.1 (Cq), 127.5 (CH), 127.7 (CH), 128.3
(CH), 129.6 (CH), 130.4 (CH), 132.7 (Cq), 133.2 (Cq), 134.7 (CH),
135.4 (Cq), 136.2 (Cq), 136.8 (Cq), 144.3 (Cq), 144.4 (Cq).
6,15-Bis[(N-(4-tolylsulfonyl)aminomethyl)benzyl-N-(4-tolyl-
sulfonyl)aminomethyl]-2,11-diaza[3.3]metacyclophane (39)
Rf 0.39 (CHCl3/acetone, 10:1); 2 mg (0.5%).
MALDI-TOF (DHB): m/z = 1481.6 [M + Na]+.
Anal. C87H87N7O17S7: calcd. C 62.23, H 5.22, N 5.84; found C
62.07, H 5.15, N 5.69.
2,11,32,41-Tetrakis(4-tolylsulfonyl)-20,29-dithia-2,11,32,41-
tetraaza[3.3](1,3)(1,3)[3.3](1,3) (1,3)[3](5,5)[3](5,5)benzeno 4
phane (29)
Pseudobeltanes 38, 8 and Cyclophane Spaced Diamide (39)
The dibromide 16 (440 mg, 0.6 mmol) was dissolved in anhyd DMF
(250 mL). This solution was added dropwise over 6 h to a suspen-
sion of Cs2CO3 (4.90 g, 15 mmol) and diamide 37 (267 mg,
0.6 mmol) in anhyd DMF (350 mL) under argon atmosphere. The
mixture was further stirred for 110 h. The solvent was evaporated,
and the remaining residue treated with CHCl3 (200 mL). The undis-
solved inorganic salts were removed by filtration, the filtrate was
washed with H2O, dried (Na2SO4) and concentrated. All three prod-
ucts were isolated by column chromatography (1. filter column: sil-
ica gel, CHCl3/acetone, 10:1; 2. column: silica gel, CHCl3/acetone,
50:1).
The dithiol 17 (64 mg, 0.1 mmol) and the dibromide 16 (73 mg,
0.1 mmol) were each dissolved in anhyd DMF (50 mL). This solu-
tions were added dropwise and simultaneously over 83 h to a sus-
pension of Cs2CO3 (1.63 g, 5.00 mmol) in anhyd DMF (500 mL)
under argon atmosphere. The mixture was stirred for further 72 h.
The solvent was evaporated, and the remaining residue treated with
CHCl3 (250 mL). The undissolved inorganic salts were removed by
filtration, the filtrate was washed with H2O, dried (Na2SO4), con-
centrated and purified by column chromatography (silica gel,
CHCl3/MeOH, 30:1) to give a colourless oil; Rf 0.35 (CHCl3/
MeOH, 20:1); 34 mg (28%); mp 197¡C.
MALDI-TOF (DHB): m/z = 1341.0 [M + Cs]+, 1293.2 [M + Na +
2,11,20,29-Tetrakis(4-tolylsulfonyl)-2,11,20,29-tetra-
aza[3.3](1,3)-(1,3)[3](5,5)[3](1,4) benzeno 3 phane (38)
Rf 0.53 (CHCl3/acetone, 50:1); 73 mg (12%); mp 205¡C.
MALDI-TOF (DHB): m/z = 1037.3 [M + Na]+.
K]+, 1249.4 [M + K]+, 1232.4 [M + Na]+.
FAB-MS (NBA): m/z = 1210.5 [M + H]+, 900.4 [M Ð 2 Ts]+.
IR (KBr): n = 2922.0 (m), 1700.0 (m), 1598.1 (m), 1445.5 (m),
1334.8 (s), 1157.2 (vs), 1093.2 (s), 914.9 (m), 880.4 (s), 814.5 (m),
771.7 (m), 664.5 cmÐ1 (s).
1H NMR (400 MHz, CDCl3): d = 2.46 (s, 12 H; Ts-CH3), 2.72 (br,
8 H; SCH2), 4.30 (br, 16 H; NCH2), 6.79 (s, 8 H; Ar-H), 7.38 (s, 4
FAB-MS (NBA): m/z = 1015.3 [M]+, 859.3 [M Ð Ts]+.
IR (KBr): n = 2922.3 (m), 2856.3 (m), 1597.8 (m), 1438.0 (m),
1336.3 (s), 1158.3 (vs), 1091.4 (vs), 915.3 (m), 814.1 (m), 757.6 (s),
657.1 cmÐ1 (s).
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304
H. Schwierz, F. Všgtle
PAPER
H; Ar-H), 7.39 (d, 3J = 8 Hz, 8 H; Ts-H), 7.77 (d, 3J = 8 Hz, 8 H;
MALDI-TOF (DHB): m/z = 1600.6 [M + K]+, 1583.6 [M + Na]+.
Ts-H).
FAB-MS (NBA): m/z = 1561.4 [M + H]+, 1405.5 [M Ð Ts]+, 1251.5
Anal. C64H64N4O8S6¥CHCl3: calcd. C 58.75, H 4.93, N 4.22; found
C 58.28, H 5.19, N 4.61.
[M Ð 2 Ts]+, 1095.3 [M Ð 3 Ts]+, 844.2 [M Ð 4 Ts]+.
IR (KBr): n = 2919.8 (s), 1597.3 (m), 1444.3 (m), 1335.7 (vs),
1156.6 (vs), 1091.2 (vs), 908.7 (s), 814.0 (s), 767.2 (s), 656.8 cmÐ1
(s).
Pseudobeltanes 40 and 41
The dibromide 16 (150 mg, 0.2 mmol) was dissolved in anhyd
DMF (100 mL). This solution was added dropwise over 18 h to a
suspension of Cs2CO3 (1.67 g, 5.00 mmol) and diamide 13b (104
mg, 0.2 mmol) in anhyd DMF (150 mL) under argon atmosphere.
The mixture was further stirred for 72 h. The solvent was evaporat-
ed, and the remaining residue treated with CHCl3 (200 mL). The un-
dissolved inorganic salts were removed by filtration, the filtrate was
washed with H2O, dried (Na2SO4) and concentrated. Product 40 was
isolated by column chromatography (silica gel, CHCl3/acetone,
50:1) to yield a colourless oil.
1H NMR (250 MHz, CDCl3): d = 2.37 (s, 6 H; Ts-CH3), 2.42 (s, 6
H; Ts-CH3), 2.47 (s, 6 H; Ts-CH3), 3.65 (s, 4 H; NCH2), 3.82 (s, 4
H; NCH2), 4.00 (s, 8 H; NCH2), 4.00Ð4.70 (br, 8 H; NCH2), 6.62 (s,
2 H; Ar-H), 6.64 (d, 3J = 8 Hz, 4 H; Ar-H), 6.70 (s, 4 H; Ar-H), 6.86
(d, 3J = 8 Hz, 4 H; Ar-H), 7.26 (d, 3J = 8 Hz, 4 H; Ar-H), 7.28 (s, 4
H; Ar-H), 7.30 (d, 3J = 8 Hz, 4 H; Ar-H), 7.42 (d, 3J = 8 Hz, 4 H;
Ar-H), 7.56 (d, 3J = 8 Hz, 4 H; Ar-H), 7.71 (d, 3J = 8 Hz, 4 H; Ar-
H), 7.79 (d, 3J = 8 Hz, 4 H; Ar-H).
13C NMR (62.9 MHz, CDCl3): d = 21.4 (Ts-CH3), 21.5 (Ts-CH3),
21.6 (Ts-CH3), 49.4 (NCH2), 49.6 (NCH2), 51.2 (NCH2), 54.7
(NCH2), 126.9 (CH), 127.1 (CH), 127.2 (CH), 128.9 (CH), 129.1
(CH), 129.2 (CH), 129.7 (CH), 129.8 (CH), 130.2 (CH), 132.5 (Cq),
134.0 (Cq), 134.8 (CH), 135.4 (CH), 135.7 (Cq), 136.0 (Cq), 136.2
(Cq), 136.4 (Cq) 136.5 (Cq), 137.8 (Cq), 143.4 (Cq), 143.5 (Cq),
143.8 (Cq).
6-Ethoxycarbonyl-2,11,20,29-Tetrakis(4-tolylsulfonyl)-
2,11,20,29-tetraaza[3.3](1,3)(1,3)[3](5,5)[3](1,3)ben-
zeno 3 phane (40)
Rf 0.33 (CHCl3/acetone, 50:1); 99 mg (46%).
MALDI-TOF (DHB): m/z = 1219.6 [M + Cs]+, 1205.6 [M + Cs Ð
CH3]+, 1111.7 [M + Na]+,1065.6 [M Ð CH3]+.
Anal. C84H84N6O12S6¥2.5 CH2Cl2: calcd. C 58.56, H 5.06, N 4.74, S
10.84; found C 58.91, H 5.08, N 4.76, S 10.84.
FAB-MS (NBA): m/z = 1219.2 [M + Cs]+, 1205.8 [M + Cs Ð CH3]+,
1087.2 [M]+,1065.1 [M Ð CH3]+,1041.2 [M Ð OCH2CH3]+, 931.2
[M Ð Ts]+, 755.2 [M Ð 2 Ts]+.
1H NMR (250 MHz, CDCl3): d = 1.29 (t, 3J = 7 Hz, 3 H,
CH3CH2O), 2.42 (s, 6 H; Ts-CH3), 2.46 (s, 6 H; Ts-CH3), 3.69 (s, 4
H; NCH2), 3.98 (br, 8 H; NCH2), 4.22 (q, 3J = 7 Hz, 2 H, CH2O),
6.50 (br, 4 H; Ar-H), 6.61 (br, 2 H; Ar-H), 7.22 (d, 3J = 8 Hz, 4 H;
Ts-H), 7.37 (d, 3J = 8 Hz, 4 H; Ts-H), 7.65 (d, 3J = 8 Hz, 4 H; Ts-
H), 7.78 (d, 3J = 8 Hz, 4 H; Ts-H), 7.82 (s, 2 H; Ar-H), 7.90 (s, 1 H;
Ar-H).
13C NMR (62.9 MHz, CDCl3): d = 14.4 (CH3CH2O), 21.6 (Ts-
CH3), 49.9 (NCH2), 54.9 (NCH2), 61.2 (OCH2), 125.1 (Cq), 126.9
(CH), 127.4 (CH), 129.9 (CH), 130.1 (CH), 130.5 (Cq), 131.6 (Cq),
132.0 (Cq), 134.9 (Cq), 136.2 (Cq), 135.3 (CH), 135.7 (CH), 134.7
(Cq), 143.6 (Cq), 143.7 (CH), 143.8 (CH), 166.1 (CO).
Acknowledgement
This work was supported by the Deutsche Forschungsgemein-
schaft (project no. Vo 145/45-2).
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(1,3)-(1,3)[3](5,5)[3](5.5)[3](1,3)[3] (1,3)benzeno 6 phane (41)
Rf 0.30 (CHCl3/acetone, 50:1).
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CH3]+, 2174.2 [M]+. FAB-MS (NBA): m/z = 2306.2 [M + Cs]+,
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5.00 mmol) in anhyd DMF (400 mL) under argon atmosphere. The
mixture was further stirred for 72 h. The solvent was evaporated, and
the remaining residue treated with CH2Cl2 (200 mL). The undis-
solved inorganic salts were removed by filtration, the filtrate was
washed with H2O, dried (Na2SO4), concentrated and purified by col-
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less substance; Rf 0.57 (CHCl3/EtOH, 30:1); 152 mg (32%); mp
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(12) (a) Whereas a ÒbeltaneÓ is composed of building blocks,
which are connected by two bridges each, we define the term
ÒpseudobeltaneÓ as a macrocycle with belt or tube shape, the
framework of which is missing bridges or is narrowed in at
least one position. For the first definition of the term ÒbelteneÓ
see ref. [6h].
(21) Nitrosation and N2O-extrusion:
(a) Overberger, C. G.; Lombardino, J. G.; Hiskey, R. G. J. Am.
Chem. Soc. 1958, 80, 3009.
(b) Overberger, C. G.; Marullo, N. P. J. Am. Chem. Soc. 1961,
83, 1378.
(c) Takemura, H.; Shinmyozu, T.; Inazu, T. Tetrahedron Lett.
b) Older nomenclature: Benzeno<n>phane; n = number of
building blocks. For the meaning of < > see: cyclophane no-
menclature: Hohner G.; Všgtle, F. Chem. Ber. 1977, 110,
3052.
1988, 29, 1031.
(d) Introductory work: Ohren, S. diploma thesis, UniversitŠt
Bonn, 1994.
(22) (a) Desiraju, G. R. Angew. Chem. 1995, 107, 2541; Angew.
Chem. Intl. Ed. Engl. 1995, 34, 2328.
(c) Space filling models were calculated (without Ts-groups)
by MM2-algorithm using CSC Chem 3Dª 4.0.
(13) Schršder, A.; Karbach, D.; GŸther, R.; Všgtle, F. Chem. Ber.
1992, 125, 1881.
(14) Review: Knops, P.; Sendhoff, N.; Mekelburger, H.-B.;
Všgtle, F. Top. Curr. Chem. 1991, 161, 1.
(15) Takemura, H.; Suenaga, M.; Sakai, K.; Kawachi, H.; Shin-
myozu, T.; Miyahara, Y.; Inazu, T. J. Inclusion Phenom.
1984, 2, 207.
(b) Desiraju, G. R. Crystal Engineering, The Design of Orga-
nic Solids; Elsevier Verlag: Amsterdam, 1989.
(23) Preparation of 1,4-bis(bromomethyl)benzene:
(a) Offermann, W; Všgtle, F. Synthesis 1977, 272.
(b) Werner, W. J. Org. Chem. 1952, 17, 523.
(24) Preparation of 3,5-bis(bromomethyl)benzoic acid alkyl esters
11a, b: see Refs. 16b and 23a.
(16) (a) Neumann, P.; Všgtle, F. J. Chem. Soc., Chem. Commun.
1970, 1464.
Synthesis 1999, No. 2, 295–305 ISSN 0039-7881 © Thieme Stuttgart · New York