Synthesis
of 6-Chloro-N,N,N',N'-tetrakis-pyridin-2-ylmethyl-[1,3,5]triazine-2,4-diamine
Daniel Vomasta, Manfred Zabel and Burkhard König *
Institute of Organic Chemistry, University of Regensburg, D-93040 Regensburg, Germany.
* Author to whom correspondence should be addressed. E-mail:
[email protected]
Received: 2 August
2007 / Accepted: 6 September 2007 / Published: 7 September 2007
Keywords: dipicolylamine,
2,4,6-tris-chloro-triazine, phosphate binding
Transition metal complexes
of pyridine-containing ligands are widely used in catalysis
[1],
supramolecular self-assembly
[2], and anion recognition
[3]. Binuclear
Zn
2+-2,2’-dipicolylamine
(dpa) complexes are particular useful for the binding of phosphorylated
peptides in aqueous solution under physiological pH with high affinity and selectivity
[4-9]. Similar ligands based on
2,2’-bipyridylamine (bpa) and 2,4,6-tris-chloro-triazine, have been used to
form coordination networks with copper(II) ions. In these compounds the bpa
moiety is attached directly to the heteroaromatic core. Combination of
2,4,6-tris-chloro-triazine with dpa moieties leads to a new hybrid compound
B,
which should be used in phosphate binding studies. We describe the versatile
short synthesis of the dpa compound
B starting from
2,4,6-tris-chloro-triazine
A.
2,4,6-Tris-chloro-triazine
(
A, 3 g, 16.3 mmol) was dissolved in 120 mL of acetone and
di-(pyridylmethyl) amine (dpa; 6.49 g, 32.6 mmol) and K
2CO
3
(9 g, 65.2 mmol) were added subsequently. The reaction mixture was refluxed for
24 h and the insoluble parts were filtered off. The mixed was poured onto
crushed ice and stirred for 15 min at room temp., water was added and the
mixture stirred for an additional 15 min. The product was obtained by
filtration as a pale yellow solid (2.9 g, 35%).
Melting point: > 200°C
1H-NMR (300 MHz, CDCl
3):
δ = 4.82 (s, 4 H, CH
2), 5.03 (s, 4 H, CH
2), 6.90 (d,
3J
= 8.0 Hz, 2 H), 7.04 (t,
3J = 5.8 Hz, 2 H), 7.16 (t,
3J =
5.6 Hz, 2 H), 7.31 (d,
3J = 8.0 Hz, 2 H), 7.38 (t,
3J =
7.7 Hz, 2 H), 7.64 (t,
3J = 7.7 Hz, 2 H), 8.41 (d,
3J =
4.1 Hz, 2 H), 8.51 (d,
3J = 4.9, 2 H).
13C-NMR (75 MHz, CDCl
3):
δ = 51.9 (-, 2 C), 52.1 (-, 2 C), 121.3-122.5 (+, 8 C), 136.7 (+, 2 C), 136. 7
(+, 2 C), 149.2 (+, 2 C), 149.3 (+, 2 C), 157.2 (C
quat, 2 C), 157.2
(C
quat, 2 C), 165.7 (C
quat, 2 C), 169.9 (C
quat,
1 C).
ES-MS (DCM/MeOH + 10 mmol/l NH
4Ac):
m/z (%) = 510.3 (100) [MH
+].
Elemental analysis: Calc. C
63.59, H 4.74, N 24.72 found C 63.27, H 4.72, N 24.58; IR (KBr) n (cm
-1) = 2927 (w), 2529
(w), 1707 (s), 1571 (s), 1491 (m), 1433 (w), 1410 (w), 1354 (w), 1319 (w), 1237
(w), 1169 (w), 1084 (w), 1048 (w), 972 (w), 947 (w), 889 (w), 863 (w), 804 (w),
756 (m), 683 (w), 617 (w), 554 (w), 458 (w).
Figure 1. 1H-NMR spectrum of compound B
Figure 2. X-ray structure of B. Suitable
crystals were obtained by recrystallization from DCM/MeOH 5:1.
Conclusion
A new dpa compound
B
was prepared in a one step synthesis. The compound can be prepared from
commercially available compounds and is accessible by a simple reaction. Surprisingly,
in first attempts this compound did not form spontaneously complexes with Zn
2+
salts at conditions described for other dpa ligands
[4-9].
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2007 by MDPI (http://www.mdpi.org/).
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