One-Pot Synthesis of 1,4,7,10,13,16,21,24-Octaazabicyclo[8.8.8]hexacosane - The Peraza Analogue of [2.2.2]Cryptand

Abstract

The peraza analogue of polyether cryptand [2.2.2], 1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane, has been synthesized in 70% yield via a two-step one-pot procedure by the condensation of tris(2-aminoethyl)amine (tren) with glyoxal in isopropanol at -78 °C followed by reduction of the intermediate with Na/liquid NH₃. This preparation is significantly faster, simpler, and higher yielding than the previously reported two-step procedure, with its lengthy isolation process and 45% overall yield.

Key words

macropolycyclic - polyamine - complexant - imines - sodium

References

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  The new material, which also is the first Na⁺ electride, is the formal adduct of Na⁰ and 1,4,7,10,13,16,21,24-octaazapentacy-clo[8.8.8.2 [4] [7] .2 [13] [16] .2 [21] [24] ]dotriacontane, a peraza ligand synthesized from compound 1. A publication is in preparation describing synthesis, structural details, and ab initio calculations for this new ligand.

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1

IUPAC name of 1: 1,4,7,10,13,16,21,24-octaaza­-bicyclo[8.8.8]hexacosane.

2

Organic-based alkalides and electrides are crystalline salts in which the cation is encapsulated by one or more saturated complexants (e.g. cryptands, crown ethers, or aza-crowns); the negative partner is an alkali metal anion (Na^- to Cs^-) or a trapped electron.

34

An anonymous reviewer has kindly offered the following suggestion: ‘As source of glyoxal for the Schiff-base condensation, some workers use the trimeric solid, which is depolymerized by reflux for 15 mins or so in the intended alcohol: perhaps the new synthesis of 2 could be extended to include this route to the starting dialdehyde, which might indeed present less hazard than the 40% aqueous solution which is described.’ Though we have not tested this suggestion, it appears sensible and we include it here for completeness.