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Entry point into new trimeric and tetrameric imide-based macrocyclic esters derived from isophthaloyl dichloride and methyl 6-aminonicotinate

Mocilac, Pavle and Gallagher, John F. (2013) Entry point into new trimeric and tetrameric imide-based macrocyclic esters derived from isophthaloyl dichloride and methyl 6-aminonicotinate. Acta Crystallographica Section B: Structural Science, 69 (1). pp. 62-69. ISSN 1600-5740

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Abstract

The one-step reaction of isophthaloyl dichloride with the 2-aminopyridine derivative (methyl 6-aminonicotinate) yields (i) a trimer-based macrocycle (EsIO)3 and (ii) a tetramer-based macrocycle (EsIO)4 in modest isolated synthetic yields (total of 25%), together with (iii) longer open-chain oligomers. The macrocyclisation relies on the semi-flexible imide hinge formed by reaction of the 2-amino(pyridine) functional group with two acyl chloride functional groups. The determining factors in macrocycle synthesis are (a) imide formation using the heteroaromatic ortho-N functionality; (b) the inherent ability of the imide to twist by 85-115 degrees from planarity (as measured by the CO...CO imide torsion angles and from computational calculations), thereby providing a hinge for macrocyclic ring closure or potentially (non)helical assembly in oligomer/polymer formation and (c) the conformational flexibility of the isophthaloyl group with meta-related carbonyl groups to twist and adopt either syn- or anti-conformations, although the syn-conformation is observed structurally for all isophthaloyl groups in both (EsIO)3 and (EsIO)4 macrocycles.

Item Type:Article (Published)
Refereed:Yes
Additional Information:Electronic Supplementary available at the following website http://journals.iucr.org/b/issues/2013/01/00/issconts.html. The idea to synthesise imide-based macrocycles stems from the original paper by Evans & Gale (2004) and our structural systematic studies of benzamides and carboxamides (Cryst. Eng. Comm. 2010, 2011) and Acta Crystallographica Section B68, 2012 together with some earlier research studies. Evans, L.S. & Gale, P.A. (2004). Chem. Commun. 1286–1287. Mocilac, P. (2012). PhD thesis. DCU, Ireland. Mocilac, P., Tallon, M., Lough, A.J. & Gallagher, J.F. (2010). CrystEngComm, 12, 3080–3090. Mocilac, P., Donnelly, K. & Gallagher, J.F. (2012). Acta Cryst. B68, 189–203.
Uncontrolled Keywords:macrocyclization; macrocycle synthesis
Subjects:Physical Sciences > Organic chemistry
Physical Sciences > Chemistry
Physical Sciences > Crystallography
DCU Faculties and Centres:DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences
Publisher:Wiley-Blackwell (International Union of Crystallography)
Official URL:http://journals.iucr.org/b/issues/2013/01/00/issconts.html
Copyright Information:© 2013 IUCR
Use License:This item is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 3.0 License. View License
Funders:Dublin City University for research support., Programme for Research in Third Level Institutions (PRTLI) Cycle 4, European Regional Development, European Union Structural Funds Programme 2007–2013
ID Code:17741
Deposited On:22 Jan 2013 11:53 by John Gallagher. Last Modified 22 Jan 2013 11:53

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