Synthesis and characterization of [3,3]- and [3,4]-perinophane

Article abstract of DOI:10.1016/S0040-4039(01)00528-7

Synthesis of [3,3]- and [3,4]-perinophanes is described via a novel route which will permit the synthesis of both symmetrical and unsymmetrical perinophanes and related cyclophane structures.

Full text of DOI:10.1016/S0040-4039(01)00528-7

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 42 (2001) 3559–3562
Synthesis and characterization of [3,3]- and [3,4]-perinophane†
Erwin Buncel,a,* Nabil L. Mailloux,a R. Stephen Brown,a Peter M. Kazmaierb and Julian Dustc
aDepartment of Chemistry, Queen’s University, Kingston, Ontario, Canada K7L 3N6
bXerox Research Center of Canada, Mississauga, Ontario, Canada L5K 2L1
cDepartment of Chemistry and Environmental Science, Sir Wilfred Grenfell College, Corner Brook,
Newfoundland, Canada A2H 6P9
Received 21 March 2001; accepted 28 March 2001
Abstract—Synthesis of [3,3]- and [3,4]-perinophanes is described via a novel route which will permit the synthesis of both
symmetrical and unsymmetrical perinophanes and related cyclophane structures. © 2001 Elsevier Science Ltd. All rights reserved.
Since Cram’s pioneering studies of cyclophanes,1 interest
in these molecules has continued unabated.2 On the one
hand the studies have been concerned with classical
motifs such as structural-strain effects on reactivity,
transannular effects, and calculational work aimed at
providing a theoretical basis for the wealth of chemistry
exhibited by these molecules. More recently, however,
other motifs are being explored which take advantage of
the proximity between sub-units offered by the
cyclophane structure, a feature that is also present in
supramolecular assemblies.3a,c This complementarity
with supramolecular chemistry has undoubtedly con-
tributed heavily to the burgeoning activity recently
witnessed in cyclophane chemistry.
inclusion phenomena involving neutral molecules such as
nitrobenzene, we were interested in perinophanes with
shorter bridges, both symmetrical and unsymmetrical, so
as to modulate their electronic properties. The overall
aim was to examine the resulting perinophanes as possi-
ble novel organic photoreceptor devices.
We report herein the first synthesis of an unsymmetrically
bridged perinophane. The present approach, involving
the sequential bridging of perinone chromophores,
should permit ready preparation of a range of novel
unsymmetrical cyclophanes.
Our general route to perinophanes features two steps, as
shown in Scheme 1. Starting with 1,4,5,8-naphthalene-
tetracarboxylic acid dianhydride (NTDA, 1),4 reaction
with 4 equivalents of base yielded the potassium tetra-
carboxylate which was converted into the monoanhy-
dride on acidification to pH 6.5 with 3 equivalents of
H3PO4. The monoanhydride was condensed under
reflux with the first diamine, H2N(CH2)nNH2 in this
case, to give 1,3-bis(1,8-naphthalene-tetracarboxylic-
monoimide-4,5-monohydrido)-alkane 2 in 85% yield
after heating with acetic anhydride. In the second step,5
reaction of the precursor 2 with the second diamine under
conditions of high dilution in DMF at 100°C, in the
presence of 1,4-diaza[2.2.2]bicyclooctane (DABCO) as
proton transfer catalyst, gave the desired perinophanes
3 and 4 in 2–3% yield, with polymeric material being
formed as the major product. The high yield of 2 that
was precursor to 3 and 4 combined with the low yield
of the perinophanes suggests that polymerization is more
facile than the clipping together of 2 even under high
dilution conditions.
We wish to report the synthesis of two new perinophanes,
extended cyclophane structures, and a general route
leading to both symmetrical and unsymmetrical
perinophanes. The first perinophane to be synthesized
and characterized was the [8,8]-perinophane, 5, which
was designed by Lehn and co-workers in 1987 as a
cyclobisintercaland receptor.3b Their method of prepara-
tion followed the classical technique of joining two
aromatic residues, at two junctions, via a bifunctional
coupling reagent under high dilution conditions (Scheme
1). While Lehn’s system (a supramolecular intercalate
displaying face-to-face complementarity),3b was designed
specifically to ensure a large cavity so as to observe
Keywords: cyclophanes; perinophanes; unsymmetrical; synthesis.
* Corresponding author. Tel.: +1.613.533.2653; fax: +1.613.533.6669;
e-mail: buncele@chem.queensu.ca
†
This paper is in memory of Professor Ray Lemieux, a great organic
chemist.
0040-4039/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(01)00528-7

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E. Buncel et al. / Tetrahedron Letters 42 (2001) 3559–3562
Scheme 1. Strategy in synthesis of perinophanes: (a) Lehn’s route (3b); (b) this work.

E. Buncel et al. / Tetrahedron Letters 42 (2001) 3559–3562
3561
Structural
identification
of
the
synthesized
D. J. Angew. Chem., Int. Ed. Engl. 1995, 34, 1862; (j)
Vidal-Ferran, A.; Clyde-Watson, Z.; Bampos, N.;
Sanders, J. K. M. J. Org. Chem. 1997, 62, 240; (k)
Nakamura, Y.; Tsuihiji, T.; Mita, T.; Minowa, T.;
Tobita, S.; Shizuka, H.; Nishimura, J. J. Am. Chem. Soc.
1996, 118, 1006; (l) Schneider, H.-J.; Ru¨diger, V.; Cuber,
V. J. Org. Chem. 1995, 60, 996; (m) Nakamura, Y.; Mita,
T.; Nishimura, J. Tetrahedron Lett. 1996, 37, 3877.
3. (a) Lehn, J.-M. Supramolecular Chemistry—Concepts and
Perspectives; VCH Publishers: Weinheim, 1995; (b)
Jazwinski, J.; Blacker, A. J.; Lehn, J.-M.; Cesario, M.;
Guilhem, J.; Pascard, C. Tetrahedron Lett. 1987, 28,
6057; (c) Beer, P. D.; Gale, P. A.; Smith, D. K.
Supramolecular Chemistry; Oxford University Press,
1999.
4. Synthesis of 1,4,5,8-tetracarboxylic-naphthalene-1,8-anhy-
dro-4,5-imidoalkanes (2)—NTDA (Aldrich, 10 g) was
added to a solution of KOH (13 g) in 2 L water with
stirring and the resulting brown solution was acidified
with phosphoric acid to pH 6.2–6.4. The 1,n-
diaminoalkane (0.5 equiv.) was added which caused the
pH to rise to 7.2 but this was adjusted to 6.2–6.4 with
further addition of phosphoric acid. The yellow solution
was then heated and maintained at reflux for 24 h when
a cloudy solution resulted. After cooling to ambient
temperature the solution was filtered and the filtrate
treated with acetic acid until the pH was brought to 5.0,
perinophanes followed a variety of techniques (FT-IR,
NMR, high resolution MS). High resolution MS was
possible using the EI method at high temperatures
which gave the molecular mass parent ions at 613 and
627 m/z, respectively, within +3 ppm of the theoretical
values.5 The observed 1H NMR upfield shift of the
aromatic protons by 0.8–1 ppm in the formation of 3
and 4 from the shift found for the comparable peak in
2 is characteristic of small cyclophane structures and
can be attributed to the close mutual proximity of the
shielding cones of the joined p-systems.6
We anticipate that the general method we have outlined
will be applicable to the synthesis of a variety of
cyclophane structures, such as perylenophanes, with
novel electronic properties. The first synthesis of
unsymmetrical perinophanes is significant because
unsymmetrical cyclophanes provide a unique opportu-
nity for systematically changing the chromophore ori-
entation. This is important since pigment orientation in
the solid state is responsible for crystallochromy,7 that
is color changes associated with different forms of
crystal packing and for their electronic properties.8
Further work will refine the synthetic procedure to
improve the yield and minimize polymeric side prod-
ucts. Also, other cyclophanes with architecturally inter-
esting structures will be investigated. The ring strain
that is expected to be present in such short-bridged
molecules as 3 and 4 will be probed by means of a full
range of spectroscopic and theoretical methods.9 The
study of host–guest interactions of the perinophanes,
and comparisons with other hosts, would be of further
interest.10
whereupon
a yellowish precipitate formed and was
filtered and subsequently dried under vacuum to yield the
free tetracarboxylic-acid. The latter was triturated with
boiling acetic anhydride (200 ml) which after cooling,
filtration and drying under vacuum yielded 9.5 g (85%) of
2 (n=3), mp 356.5–358°C.
2 (n=3): 1H NMR (200.1 MHz) CDCl3–TFA-d: l 9.30
(s, 8H, H5,6) 4.88 (t, J=5.9 Hz, 4H, H2), 2.74 (m, 2H,
H1). 13C NMR (50.3 MHz) JMOD CDCl3–TFA-d: l
165.3 (4%, C3) 160.5 (4%, C10), 133.9 (3%, C6), 132.2 (3%, C7),
129.3 (4%, C5), 127.5 (4%, C4), 122.7 (4%, C8), 122.1 (4%, C9),
40.0 (2%, C2), 27.5 (2%, C1). FT-IR (cm−1): 1781, 1744 (CꢀO
carbonyl stretch sym, anti-sym of anhydride), 1707, 1671
(CꢀO carbonyl stretch sym, anti-sym of imide). Calcd for
C31H14N2O10: C, 64.81; H, 2.45; N, 4.87. Found: C,
64.29; H, 2.66; N, 5.23. MS (CI): M+ 574.1; calcd: 574.43.
5. Preparation and characterization of perinophanes 3 and
4—The intermediate 2 (2 mmol) in 100 ml of N-methyl
pyrrolidinone (NMP) and an equivalent solution of
(1,m)-diaminoalkane (m=3, 4) were injected by means of
an automated syringe pump into a solution of DABCO
(10 g) in anhydrous DMF (1 L) contained in a Morton
flask over 48 h while heating to 100°C and stirring. After
a further 6 h reaction time, the solution was allowed to
cool to rt and then left standing for 48 h before concen-
trating to 100 ml. The reddish reaction mixture was
poured into aq HCl (1 L, 5% v/v) and the dark precipi-
tate was filtered, freeze-dried and Soxhlet extracted for 3
days with 250 ml of CHCl3. The red extract was concen-
trated to 20 ml, loaded onto a silica gel column and
eluted with ethyl acetate–methylene chloride (20:80 v/v).
Compounds 3 and 4 were obtained as yellowish solids in
2.0 and 2.7% yield, respectively, mp darken at 385°C.
Acknowledgements
Funding of this research by the Natural Sciences and
Engineering Research Council of Canada via a research
grant (E.B.) is gratefully acknowledged.
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3562
E. Buncel et al. / Tetrahedron Letters 42 (2001) 3559–3562
MHz) JMOD CDCl3–TFA-d: l 164.4 (4%, C3), 131.5 (3%,
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1
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