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. 2020 Oct 23;10(64):39033-39036.
doi: 10.1039/d0ra07677e. eCollection 2020 Oct 21.

Circular linkage of intramolecular multi-hydrogen bonding frameworks through nucleophilic substitutions of β-dicarbonyls onto cyanuric chloride and subsequent tautomerisation

Ayano Awatani  1 , Masaaki Suzuki  1
Affiliations

Circular linkage of intramolecular multi-hydrogen bonding frameworks through nucleophilic substitutions of β-dicarbonyls onto cyanuric chloride and subsequent tautomerisation

Ayano Awatani et al. RSC Adv. .

Abstract

Nucleophilic substitution reactions of cyanuric chloride with a series of β-dicarbonyls give triply β-dicarbonyl-embedded 1,3,5-triazines. Their subsequent but spontaneous tautomeric transformation leads to circularly linked, intramolecular, multi-hydrogen bonding networks. Their structural elucidation by X-ray crystallography showed elongated double bonds and shortened single bonds. This is likely due to a resonance hybrid formed via tautomerisation and simultaneous proton transfer.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Chart 1
Chart 1. Selected examples demonstrating intramolecular proton transfers: (a) 1,8-dihydroxy-2-naphthaldehyde (DHNA) and its excited-state double proton transfer (ESDPT), (b) triquinolonobenzene, and (c) tautomerism of 2,4,6-tris(β-monocarbonyl)-1,3,5-triazine (TMCT).
Chart 2
Chart 2. Concept of this work: (i) nucleophilic substitution, (ii) tautomerism, and (iii) resonance.
Scheme 1
Scheme 1. Nucleophilic substitution reactions of β-dicarbonyls onto cyanuric acid with diisopropylethylamine in toluene at room temperature.
Fig. 1
Fig. 1. X-ray crystal structures of (a) 3a and (b) 4c. Thermal ellipsoids are set at 50% probability levels.
Scheme 2
Scheme 2. Nucleophilic substitution of β-dicarbonyls (2b–d) onto cyanuric acid with sodium hydride in toluene under reflux.
Fig. 2
Fig. 2. UV-visible absorption spectra of the synthesised products in dichloromethane.
See this image and copyright information in PMC

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