Synthesis of new cryptands starting from trans (diprotected and disubstituted) 1,4,7,10-tetraazacyclododecane

Article abstract of DOI:10.1081/SCC-120015394

New cryptands are synthesised by aminolysis between 1,7- di(ethylacetate)-4,10-di(tosyl)-1,4,7,10-tetraazacyclododecane and various diamines.

Full text of DOI:10.1081/SCC-120015394

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SYNTHESIS OF NEW CRYPTANDS STARTING FROM
TRANS (DIPROTECTED AND DISUBSTITUTED) 1,4,7,10-
TETRAAZACYCLODODECANE
H. Mouaziz a , V. Montembault a , J.-C. Soutif a & J.-C. Brosse a
a LCOM–Chimie des Polymères , UCO2M , Université du Maine , UMR CNRS n°6011, Avenue O.
Messiaen, Le Mans cedex 9, 72085, France
Published online: 23 Aug 2006.
To cite this article: H. Mouaziz , V. Montembault , J.-C. Soutif & J.-C. Brosse (2002) SYNTHESIS OF NEW CRYPTANDS
STARTING FROM TRANS (DIPROTECTED AND DISUBSTITUTED) 1,4,7,10-TETRAAZACYCLODODECANE, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:24, 3763-3766, DOI: 10.1081/
SCC-120015394
To link to this article: http://dx.doi.org/10.1081/SCC-120015394
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 24, pp. 3763–3766, 2002
SYNTHESIS OF NEW CRYPTANDS
STARTING FROM TRANS (DIPROTECTED
AND DISUBSTITUTED) 1,4,7,10-
TETRAAZACYCLODODECANE
H. Mouaziz, V. Montembault, J.-C. Soutif,
and J.-C. Brosse
LCOM–Chimie des Polymeres, UCO2M, UMR CNRS
nꢀ6011, Universite du Maine, Avenue O. Messiaen,
72085 Le Mans cedex 9 - France
ABSTRACT
New cryptands are synthesised by aminolysis between 1,7-
di(ethylacetate)-4,10-di(tosyl)-1,4,7,10-tetraazacyclododecane
and various diamines.
The design and synthesis of new cross-bridged ligands containing a
1,4,7,10-tetraazacyclododecane backbone is of growing interest justified by
their remarkable complexing properties with transition elements and heavy
metal ions.[1–3] Only a few reports of cryptands based on 1,4,7,10-tetra-
azacyclododecane (cyclen) have appeared.[4–8] In search of new compounds
for applications in magnetic resonance imaging, in purification of water or
in molecular recognition, we developed a strategy which can be applied to
the preparation of many other cryptands.
The synthesis of the aimed cryptands involves the use of a trans (dipro-
tected and disubstituted) 1,4,7,10-tetraazacyclododecane. First of all,
3763
DOI: 10.1081/SCC-120015394
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3764
MOUAZIZ ET AL.
Scheme 1.
Table 1.
Compound
Yield (%)
2
3
4
x ¼ 2
x ¼ 6
x ¼ 12
29
8
4
selective ‘‘trans’’ protection of cyclen has been carried out by reaction of
cyclen with p-toluenesulfonylchloride in pyridine leading exclusively to the
1,7-isomer with agood yield. [9] Then, difunctionalization has been realized by
reaction between 1,7-di(tosyl)-1,4,7,10-tetraazacyclododecane with ethyl
bromoacetate in presence of sodium carbonate in acetonitrile. The mixture
was refluxed during a few hours and then solvent was evaporated. 1,7-di(ethy-
lacetate)-4,10-di(tosyl)-1,4,7,10-tetraazacyclododecane 1 was isolated and
purified by liquid chromatography (CH3OH/H2O, 80/20) with 63% yield.
This strategy has previously been described for the synthesis of the diester
derivative of dioxocyclen.[10] Our route to synthesis of the cryptands is shown
in Sch. 1 and yields are reported in Table 1. It proceeds from 1 and various
diamines (ethylenediamine, hexamethylenediamine and dodecanediamine) in
methanol at T ¼ 100ꢀC. A control of the cryptands formation carried out by
1H NMR spectroscopy in deuterated methanol has shown the necessity of a
reaction time of seven days to obtain a complete conversion whatever the
diamine used. After evaporation of the solvent, the resulting cryptands were
analysed by liquid chromatography (CH3CN/H2O, 70/30) coupled mass
spectrometry (APCI). The analyses showed up formation of linear and
macrocyclic oligomers. Among them the cryptands 2, 3, a nd4 were isolated
in 29, 8 and 4% yields respectively after chromatography.

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SYNTHESIS OF NEW CRYPTANDS
3765
The introduction of a bridge containing two amide functions
allow further functionalization. Moreover, deprotection of tosyl groups
could permit a double difunctionalization. On the other hand, different
bridges containing other functional groups could be linked to the
trans(diprotected and difunctionalized) 1,4,7,10-tetraazacyclododecane
using this strategy.
EXPERIMENTAL
1
1: m/z ¼ 653 (Mþ); H NMR (400.13 MHz, CDCl3) ꢀ: 1.27 (6H, t, J
7 Hz, CH3(Et)), 2.42 (6H, s, CH3(Ts)), 3 (8H, t, J 4.7 Hz, CH2N), 3.22 (8H,
t, J 4.7 Hz, CH2NTs), 3.43 (4H, s, CH2COOEt), 4.14 (4H, q, J 7 Hz,
CH2(Et)), 7.28 (4H, d, J 8 Hz, CH ar.), 7.64 (4H, d, J 8 Hz, CH ar.).
1
2: m/z ¼ 624 (Mþ); H NMR (400.13 MHz, CDCl3) ꢀ: [7.29 (1H, d, J
8.4 Hz); 7.35 (3H, d, J 8.4 Hz); 7.64 (4H, d, J 8.4 Hz), CH ar.]; [2.41 (1H, s);
2.46 (5H, s), CH3(Ts)]; [3.08–3.21 (m), CH2NTs]; [2.80–3.02 (m), CH2N];
[3.28 (2H, s); 3.43 (2H, s), CH2CONH]; [3.55 (4H, s), CH2NHCO].
1
3: m/z ¼ 680 (Mþ); H NMR (400.13 MHz, CDCl3) ꢀ: [7.30 (2H, d, J
8 Hz); 7.33 (2H, d, J 8 Hz); 7.63–7.66 (m), CH ar.]; [2.42 (5H, s); 2.44 (1H, s),
CH3(Ts)]; [3.14 (4H, m); 3.20 (4H, m), CH2NTs]; [3.04 (8H, m),
CH2N]; [3.25–3.31 (8H, m), CH2CONH, CH2NHCO]; [1.58 (4H, m),
CH2CH2NHCO]; [1.37–1.44 (4H, m), CH2CH2CH2NHCO].
1
4: m/z ¼ 764 (Mþ); H NMR (400.13 MHz, CDCl3) ꢀ: [7.30 (4H, d, J
8 Hz); 7.61 (4H, d, J 8 Hz), CH ar.]; [2.34 (6H, s), CH3(Ts)]; [2.7, 2.76, 2.9
(8H, m), CH2N]; [3.1–3.3 (16H, m), CH2NTs, CH2CONH, CH2NHCO];
[1.19–1.39 (20H, m), (CH2)10CH2NHCO].
N. B. The obtained results in mass spectrometry show higher values
than those expected, because of deuterium exchange between deuterated
methanol and cryptands during aminolysis reaction.
REFERENCES
1. Poon, C.K.; Che, C.M. Inorg. Chem. 1981, 20, 1640.
2. Parker, D. Chem. Soc. Rev. 1990, 19, 271.
3. Izatt, R.M.; Pawlak, K.; Bradshaw, J.S. Chem. Rev. 1995, 95, 2529.
4. Bencini, A.; Bianchi, A.; Borselli, A.; Ciampolini, M.; Garcia-Espana,
E.; Dapporto, P.; Micheloni, M.; Paoli, P.; Ramirez, J.; Valtancoli, B.
Inorg. Chem. 1989, 28, 4279.
5. Ciampolini, M.; Nardi, N.; Valtancoli, B. Coord. Chem. Rev. 1992,
120, 223.

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3766
MOUAZIZ ET AL.
6. Bencini, A.; Bianchi, A.; Bazzicalupi, C.; Ciampolini, M.; Fusi, V.;
Micheloni, M.; Nardi, N.; Paoli, P.; Valtancoli, B. Supramolecular
Chem. 1994, 3, 141.
7. Jacques, V.; Mesbani, M.; Boskovic, V.; Desreux, J.F. Synthesis 1995,
1019.
8. Brandes, S.; Denat, F.; Lacour, S.; Rabiet, F.; Barbette, F.; Pullumbi,
P.; Guilard, R. Eur. J. Org. Chem. 1998, 2349.
9. Dumont, A.; Jacques, V.; Qixiu, P.; Desreux, J.F. Tetrahedron Lett.
1994, 22, 3707.
10. Montembault, V.; Mouaziz, H.; Blondeau, V.; Touchard, R.; Soutif,
J.-C.; Brosse, J.-C. Synth. Commun. 1999, 29(23), 4279.
Received in the Netherlands November 26, 2001