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Synthesis 2006(5): 759-761  
DOI: 10.1055/s-2006-926335
SHORTPAPER
© Georg Thieme Verlag Stuttgart · New York

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

Mikhail Yurievich Redko*, Rui Huang, James Louis Dye, James Edward Jackson*
Department of Chemistry, Michigan State University, East Lansing, MI 48824-1322, USA
Fax: +1(517)3531793; e-Mail: redko@msu.edu; e-Mail: jackson@cem.msu.edu;
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Publication History

Received 3 August 2005
Publication Date:
07 February 2006 (online)

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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

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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.