Luminescent Lariat Aza-Crown Ether
Institute of Organic Chemistry, University of Regensburg, D-93040 Regensburg, Germany
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Author to whom correspondence should be addressed.
Molbank 2010, 2010(1), M662; https://doi.org/10.3390/M662
Submission received: 24 February 2010
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Accepted: 9 March 2010
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Published: 10 March 2010
Abstract
:Lariat ethers are interesting recognition motifs in supramolecular chemistry. The synthesis of a luminescent lariat ether with triglycol chain by azide–alkyne (Huisgen) cycloaddition is presented.
1. Introduction
Luminescent crown ether amino acids bind ammonium ions and signal the binding event by changes of their specific emission properties [1]. They are versatile building blocks for amino acid and peptide receptors [2,3,4]. Introduction of podand arms [5] may enhance the cation binding affinity of crown ethers [6]. The copper(I) catalyzed dipolar cycloaddition (Huisgen cycloaddition) is known to be a robust ligation method for a variety of differently substituted azides and alkynes [7,8,9]. We present the functionalization of a luminescent aza-crown ether with triglykol podand arm by this method. Such a compound is expected to have enhanced ammonium ion binding properties.
2. Synthesis
The lariat ether was prepared by Huisgen cycloaddition at the side chain of a propargyl-substituted crown ether (1) with 2-(2-(2-azidoethoxy)ethoxy)ethanol (2).
Scheme 1.
Synthesis of a lariat ether (3) by copper(I) mediated dipolar cycloaddition.
Conditions: MeOH, H2O, CuSO4 * 5 H2O, Na-ascorbate, N2, RT to reflux, 5h
3. Experimental
14-[2-(2-(2-(4-Methyl-1H-1,2,3-triazol-1-yl)ethoxy)ethoxy)ethanol]-6,7,9,10,13,14,15,16,18,19,21,22-dodecahydro-12H-5,8,11,17,20,23-hexaoxa-14-aza-benzocycloheneicosene-2,3-dicarboxylic acid dimethyl ester (3)
Compound 1 (102 mg, 0.2 mmol) and compound 2 (53 mg, 0.3 mmol) were dissolved in 1.0 mL of methanol. A solution of copper(II)sulphate pentahydrate (10 mg, 0.02 mmol) in 0.5 mL of water containing 16 mg sodium ascorbate (0.1 mmol) was added drop wise. After stirring for 1 h at room temperature, the reaction mixture was heated to reflux for 4 h in a nitrogen atmosphere (TLC control). After cooling to room temperature, 9.0 mL dichloromethane were added, the aqueous layer was separated off and the organic phase was washed with 3.0 mL of brine. After drying over MgSO4 the solvent was evaporated and the solid residue was purified by column chromatography with ethyl acetate/ethanol 3:1. The pure product is a yellow oil (132 mg, 0.192 mmol, 96 %).
MF: C31H48N4O13–FW: 684.75 g/mol; -IR (neat): ν (cm-1) = 3040 (w), 2970 (m), 2870 (m), 1720 (s), 1599 (m), 1519 (m), 1435 (m), 1351 (m), 1323 (m), 1287 (m), 1247 (m), 1198 (m), 1122 (s), 1052 (m), 978 (m), 961 (m), 923 (m), 889 (m), 748 (s), 665 (m); -MS (ESI-MS, CH2Cl2/MeOH + 10 mmol NH4OAc): e/z (%) = 685.3 (100 %, MH+); -HRMS (PI-LSIMS Glycerine): calc. for C31H49N4O13+: 685.3296, found: 685.3283; -1H-NMR (300 MHz, CDCl3): δ [ppm] = 2.87 (m, 4 H), 3.17 (bs, 1 H), 3.54 (t, 2 H, J = 4.1 Hz), 3.59 (m, 4 H), 3.61–3.78 (m, 14 H), 3.82–3.87 (m, 2 H), 3.86 (s, 6 H), 3.90 (m, 4 H), 3.96 (s, 2 H), 4.18 (m, 4 H), 4.48 (t, J = 4.95 Hz, 2 H), 7.17 (s, 2 H), 7.94 (s, 1 H); -13C-NMR (75 MHz, CDCl3): δ [ppm] = 49.9 (-, 1 C), 50.0 (-, 1 C), 52.6 (+, 2 C), 53.3 (-, 2 C), 61.5 (-, 1 C), 68.9 (-, 1 C), 69.2 (-, 1 C), 69.3 (-, 2 C), 69.5 (-, 2 C), 70.2 (-, 1 C), 70.3 (-, 1 C), 70.5 (-, 2 C), 71.1 (-, 2 C), 72.6 (-, 2 C), 113.5 (+, 2 C), 124.9 (+, 1 C), 125.4 (Cquat, 2 C), 140.3 (Cquat, 1 C), 150.4 (Cquat, 2 C), 167.8 (Cquat, 2 C); -UV (MeOH): λ (ε) = 268 (7600), 224 (31400);
Supplementary materials
Supplementary File 1Supplementary File 2Supplementary File 3Supplementary File 4Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (GRK 760) and the University of Regensburg for support of this work.
References and Notes
- Mandl, C.P.; König, B. Luminescent crown ether amino acids - selective binding to N-terminal lysine in peptides. J. Org. Chem. 2005, 70, 670–674. [Google Scholar] [CrossRef] [PubMed]
- Späth, A.; König, B. Modular synthesis of Di- and tripeptides of luminescent crown ether aminocarboxylic acids. Tetrahedron 2009, 65, 690–695. [Google Scholar] [CrossRef]
- Späth, A.; König, B. Ditopic crown ether–guanidinium ion receptors for the molecular recognition of amino acids and small peptides. Tetrahedron 2010, 66, 1859–1873. [Google Scholar] [CrossRef]
- Stadlbauer, S.; Riechers, A.; Späth, A.; König, B. Utilizing Reversible copper(II) peptide coordination in a sequence-selective luminescent receptor. Chem. Eur. J. 2008, 14, 2536–2541. [Google Scholar] [CrossRef] [PubMed]
- Gokel, G.W. Lariat ethers: From simple sidearms to supramolecular systems. Chem. Soc. Rev. 1992, 21, 39–47. [Google Scholar] [CrossRef]
- Gokel, G.W.; Arnold, K.A.; Delgado, M.; Echeverria, M.; Gatto, V.J.; Gustowski, D.A.; Hernandez, J.; Kaifer, A.; Miller, S.R.; Echegoyen, L. Lariat ethers: From cation complexation to supramolecular assemblies. Pure Appl. Chem. 1988, 60, 461–465. [Google Scholar] [CrossRef]
- Kolb, H.C.; Finn, M.G.; Sharpless, K.B. Click chemistry: Diverse chemical function from a few good reactions. Angew. Chem. Int. Ed. 2001, 40, 2004–2021. [Google Scholar] [CrossRef]
- Krivopalov, V.P.; Shkurko, O.P. 1,2,3-Triazole and its derivatives. Development of methods for the formation of the triazole ring. Russ. Chem. Rev. 2005, 74, 339–379. [Google Scholar] [CrossRef]
- Moses, J.E.; Moorhouse, A.D. The growing applications of click chemistry. Chem. Soc. Rev. 2007, 36, 1249–1262. [Google Scholar] [CrossRef] [PubMed]
- Canaria, C.A.; Smith, J.O.; Yu, C.J.; Fraser, S.E.; Lansford, R. New syntheses for 11-(mercaptoundecyl)triethylene glycol and mercaptododecyltriethyleneoxy biotin amide. Tetrahedron Lett. 2005, 46, 4813–4816. [Google Scholar] [CrossRef]
- The product can be easily prepared by a simplified procedure: Thoroughly dried triethylenglykol monotosylate (3.33 g, 10.0 mmol) is mixed with 10.0 mL of dry DMF. Sodium azide (0.78 g, 12.0 mmol) was added and the mixture was stirred over night at 40 °C under nitrogen. The solvent was evaporated and the residue was extracted with ethyl acetate (50 mL). After filtration over celite and subsequent washing of the filter cake with ethyl acetate, all volatiles were removed to give the product as pale yellow oil (1.71 g, 9.75 mmol, 89%).; 1H-NMR (300 MHz, CDCl3): δ [ppm] = 2.64 (bs, 1 H), 3.31 (t, J = 5.4 Hz, 2 H), 3.56 (t, J = 5.4 Hz, 2 H), 3.58 – 3.71 (m, 8 H); -13C-NMR (75 MHz, CDCl3): δ [ppm] = 50.6 (-, 1 C), 61.7 (-, 1 C), 70.1 (-, 1 C), 70.3 (-, 1 C), 70.7 (-, 1 C), 72.5 (-, 1 C); - IR (neat): ν (cm-1) = 3300 (bm), 2920 (m), 2871 (m), 2094 (s), 1520 (w), 1456 (m), 1347 (m), 1285 (s), 1118 (s), 1065 (s), 928 (m), 887 (m), 821 (m), 632 (m).
© 2010 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland. This article is an open-access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).
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Späth, A.; Rummel, E.-M.; König, B. Luminescent Lariat Aza-Crown Ether. Molbank 2010, 2010, M662. https://doi.org/10.3390/M662
AMA Style
Späth A, Rummel E-M, König B. Luminescent Lariat Aza-Crown Ether. Molbank. 2010; 2010(1):M662. https://doi.org/10.3390/M662
Chicago/Turabian StyleSpäth, Andreas, Eva-Maria Rummel, and Burkhard König. 2010. "Luminescent Lariat Aza-Crown Ether" Molbank 2010, no. 1: M662. https://doi.org/10.3390/M662
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