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Mesomolecules. Polyaza-Polyoxa Macropolycyclic Systems

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[4] H . Diirr and B. Ruyr, Liebigs Ann. Chem. /973, 214.
[5] H . Diirr and B. Ruye, Angew. Chem. 84, 215 (1972); Angew. Chem.
internat. Edit. 1 1 , 225 (1972); and earlier papers.
[6] R. Bosrhi, A. Dreiding, and E. Hrithronnvr, J. Amer. Chem. SOC.
92, 123 ( 1970).
[7] M. F. Srmmrlhack, J . S. Foos, and S. Katz, J. Amer. Chem. SOC.
94, 8637 (1972).
[8] W A. Bernetf, J. Chem. Educ. 44, 17 (1967).
Mesomolecules.
Polyaza-Polyoxa Macropolycyclic S y s t e m s [ * * ]
By Jean-Marie Lehn, Jacques Simon,and Joseph Wagner“]
The chemistry of molecular systems presents quite a clear
dichotomic separation into the micromolecules of organic
chemistry (M.W. < 500) and the macromolecules of
polymer chemistry and biochemistry (M.W. > 5000).
Although these definitions of size are arbitrary, it nevertheless appears that comparatively very few organic chemical
studies have been directed towards the design, the synthesis,
and the properties of molecules of intermediate size, i.e.
mesomolecules (not considering systems akin to natural
products like porphyrins, corrins, peptides, rtc.).
Such systems may present a multitude of new properties
compared to “small” molecules, by the mere token of
their size and the resulting palette of possible structural
variations, while also being challenging synthetic targets.
A number of macrocyclic[’], macrobicyclic[2-41, and macr o t r i c y c I i ~ ’ ~molecules
.~~
have been synthesized recently.
Many of them may act as ligands for the formation of
selective inclusion complexes[’.
- 8l
(“cryptates”)[’]
with various metal cations; natural macrocyclic peptides
and depsipeptides also form cation complexe~[~l;
macrocyclic polysugars, the cyclodextrins, are able to form molecular inclusion complexes[‘01.The common feature of these
systems, which are still of relatively small size, is the presence of a molecular cavity which confers upon them their
specific properties.
We preseyt here the synthesis of several macrotricyclic
and macrotetracyclic molecules. The intramolecular cavity
of these systems is appreciably larger than in the previously
reported cation ligands[” 3 . 4 . 6 1 ; thus, in addition to new
conformational and cation complexation properties, they
might be able to complex molecules, i.e. to function as
specific molecular receptors[ I41.
Monoprotection of the macrocyclic diamine ( 1 )[3a1 using
benzyl chloroformate in benzene (diamine: chloroformate= 1 : 1 ) gives compound (2) (viscous oil) in 50% yield[’’].
Condensation of (2) with the diacyl dichlorides ( 3 a ) ,
( 3 b ) [ ” l , and ( 3 c ) (m.p. 9 2 T ) affords respectively the
diamides (4a), ( 4 b ) , and ( 4 c ) , which are then converted
into ( j n ) , (Sb),and (Sc) with hydrogen bromidein acetic
acid (48%). Products ( 4 ) and (5) have not yet been
obtained in a crystalline form; the yields are about 90%
for the two steps.
The next step is performed under high dilution conditions
following a procedure very similar to the one used for
the synthesis of the previously described macrobicyclic
systernd31. Condensation of ( 5 0 ) . (.Sb). and ( 5 r ) with
the dichlorides ( 3 a ) , ( 3 b ) , and 1 3 ~ respectively
)
(in benzene and in the presence of thrcc equivalents of triethyl334,6
-
[*I
[“*I
578
Prof. J . . Lehn, J. Simon, and Dr. .I.
Wagner
lnstitut de Chimie, Universiti Louis Pasteur
I . rue Blaise Pascal, 67 Strasbourg (France)
ERA 265 du C.N.R.S.
Molecular Receptors, Part I .
(91, 2 = co
( l o } , Z = CH,
(a). Y = CH,;
(b), Y = 0; (c). Y = N T o s
amine) affords the macrotricyclic tetracarboxamides (6 a )
(m.p. 185-186°C; yield 75%), ( 6 b ) (m.p. 1 8 5 T ; yield
70%), and 6 c ) (m.p. 223°C; yield 55%). These tetraamides
(6) are reduced by diborane in tetrahydrof~ran[’~1
(reflux
for about 10 hours). Hydrolysis of the resulting products
with 6 N HCI (reflux for about 10 h) followed by passage
[ I ] C . J. Prdrrsen and H . K . Frensdorff, Angew. hem. 84, 16 (1972):
Angew. Chem. internat. Edit. 11, 16 (1972).
[2] H. E. Simmons and (’. H . Park, J. Amer. Chem. SOC.90, 2428 (1968).
[3] a) B. Dietrich, J . M . Lrhn, and J . P. Sauoagr, Tetrahedron Lett.
1969, 2885; b) Chem. Commun. 1970, 1055.
[4] J. M. Lrhn and F. Monracon, Tetrahedron Lett. 1972, 4557.
[S] H. E . Simon, C. H . Park, R . T U y d a , and M. F. Habibi, Trans.
N. Y. Acad. Sci. 32, 11, 521 (1970).
[6] J . Chrnry, J. M . Lrhn. J . P. Saucugr, and M . E . Strrbbs, J. C.
S . Chem. Commun. 1972, 1100.
[7] B Dirtrich, J . M . Lrhn, and J . P. Soucagr. Tetrahedron Lett. 1969,
2889.
[8] J. M Lehn, Struct. Bonding, in press.
[9] W E. Morfand W Simon, Helv. Chim. Acta 54, 2683 (1971).
[ 101 F. Cranirr. Einschlussverbindungen. Springer Verlag, Heidelberg
1954: F. Cramrr, W Sarnyer, and H.-Ch. Spatz, J. Amer. Chem. SOC.
NY, 14 (19671.
[ 1 I] R. Ansdtiitz and F. Birmaux, Liebigs. Ann. Chem. 273, 64 ( 1 890).
[ 121 The yield is almost quantitative when recovered ( I ) and diprotected
derivative (which may be hydrolyzed back to ( 1 ) ) are taken into account.
[I31 H. C. B r o w and P. Hrini, J. Amer. Chem. SOC.86, 3566 (1964).
[I41 J. M . Lrhn, J . Simon, and J . Wagiwr, Angew. Chem. 85, 622
(1973): Angew. Chem. internat. Edit. 12. 579 (19731.
Angrw. Chum. interifat. Edit.
1 Vol. 12 (1973) N o .
7
of the aqueous solutions over a quaternary ammonium
resin column in its hydroxide form affords the macrotricyclic tetraamines ( 7 a ) (m.p. 4 5 4 ° C ; yield 90%), ( 7 b )
(m.p. 64 C;-yield 90%),and ( 7 c ) (m.p. 152-C;yield 90%).
Removal of the tosyl groups of ( 7 c ) by treatment with
sodium in liquid ammonia/ethylamine ( I : I ) gives (8) (m.p.
92-94 C: yield 70%). The hexaamine ( 8 ) is then condensed under high dilution conditions with dodecanedioyl
dichloride to give the macrotetracyclic diamide (9) (viscous
oil ;40%). Reduction with diborane followed by acid hydrolysis and passage over a basic resin column, following
the procedure used above for the ( 6 ) + ( 7 ) conversion,
leads to the macrotetracyclic diamine (10) (viscous oil;
yield 95 Yo).
The analytical and spectral ('H-NMR, mass) data for all
compounds were in agreement with the proposed structures
( l ) - ( l O ) . The 13C-NMR spectra of ( 6 b ) and ( 6 c ) are
also in agreement with these structures. The tri- and tetracyclic substances (6)-( 10) are all soluble in water except
( 6 ~and
) ( 7 a ) (slightly soluble), as well as in most organic
sol vents.
Received: May 15, 1973 [Z 838 a IF]
German version: Angew. Chem. 85. 621 (1973)
Molecular and Cation Complexes of
Macrotricyclic and
Macrotetracyclic Ligands[**l
By Jean-Murie Lehn, Jucques Simon, and
~ o s e p hWagner[*]
The molecular recognition process involved in the association of two or more chemical species to form a complex
is controlled by the chemical information stored in the
ligandf '1. The control of spherical recognition of alkali
cations['' by synthetic macrocyclic['], macrobicyclic~31,and
macrotri~yclic[~]
ligands forming inclusion complexes has
been the subject of a number of recent studies.
Beyond the spherical substrate (alkali cations), the next
step resides in the design of synthetic ligands for organic
molecules, i. e. of synthetic molecular receptors. In addition
to being selective, such complexes might also in principle
display highly specific functions. For instance, they may
act as protoenzymes or induce the transport of molecules
through various "membrane" type barriers.
Substances capable of functioning as receptors for molecules should contain a molecular cavity so as to be able
to form inclusion complexes. Up to now one kind of
compound, the macrocyclic polysugars, cyclodextrin~[~],
has been shown to form well defined inclusion complexes
with various molecular substrated- 'I. Occlusion of solvent molecules by macrocyclic molecules has also been
reported18!
We present here a report on the complexation properties
displayed by the macrotricyclic and macrotetracyclic molecules[']. Three types of complexes have been observed
and we now describe the nature and the qualitative properties of these species.
First, the formation of merd cation coniplexes has been
observed as in the case of the previously described substance ( 4 ) l 4 ] A
. chloroform solution of ( 2 a ) turns yellow
when solid sodium, potassium, or cesium picrate is added,
__ .
[*] Prof. J. M. Lehn, J. Simon, and Dr. J . Wagner
[**I
lnstitut de Chimie, Uni\.ersit& Louis Pasteur
I , rue Blaisc Pascal, 67 Strasbourg (France)
ERA 265 du C.N.R.S.
Mofecular Receptors, Part 2.-Pdrt I : ref. [9]
Angrw. Chmi. internat. Ed!!. j Vol. 12 ( IY73) 1 N o . 7
(3)
(4)
owing to the dissolution of the salt by complexation of
the cation. It is probable that complexes of both 1 : 1 and
3: 1 cation/ligand stoichiometries may be obtained. A complex [ ( Z a ) , 2NaI] has been isolated and characterized.
The formation of 1: 1 and 2: I complexes with several
alkali cations has been detected for compounds ( 2 u ) and
( 2 h ) using cation selective electrodes. In analogy with
the results obtained for compound ( 4 ), these cation complexes may be formulated as 1 :1 and 2 :1 inclusion complexes of the 131-cryptate typeL4].
Second, iipophilic cation//ipophilic anion association occurs
when salts containing a complexable cation and a lipophilic
anion are used. The fluorescence of the fluorescent probe
6-p-toluidinonaphthalene-2-sulfonate
(TNS) is known to
increase markedly when the anion complexes with a lipophilic substrater'". "1. In the present case, complexation
of an alkali cation in aqueous solution by the ligand ( 2 a )
gives a lipophilic cation. The TNS anion may then associate
with the cation complex, forming a lipophilic cation/lipophilic anion pair. Such an association should lead to a
strong increase in TNS fluorescence. This is indeed observed for ligand ( 2 a ) with the TNS potassium salt, but no
special effect is found for the other alkali cations (Fig.
I). Thus, K' probably forms a quite stable complex with
( 2 a ) and the resulting [(Za),K + ] species associates with
the anion forming a neutral pair {[(Za),K'], T N S - ) .
400
w
n
500
Fig. 1 Fluorescence spectra of the TNS- anion a) N(C,H,)f T N S - .
N(C,H,)f T N S - + (2a) + Lil :
N(C,H,); T N S + (20) ;
N(C,H,)f T N S - + ( 2 a ) + C s l ; c) N(C,H,):
T N S - + ( 2 a ) + N a I : d)
N(C,H,): + ( 2 a ) + R b l ; e) N(C,H,): +12a) + K 1 (scale reduced
by a factor of 10 for e). Solvent: water; concentrations:
mol/l.
N(C,H,); T N S - :
mol/l. ( 2 a ) : !O-' mol/l; salt:
b)
579
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polyaza, polyoxo, macropolycyclic, system, mesomolecules
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