ONE-STEP AND 2-STEP METAL-ION TEMPLATED SYNTHESES OF THE CRYPTANDS

New cryptands [3.2.1], [4.2.1] and [4.2.2] were prepared in good yield s by treating the appropriate diazacrown with the ditosylate esters of triethylene, tetraethylene or pentaethylene glycol as required. Treat ment of 4,10-diaza-15-crown-5 with alpha,alpha'-dibromo-m-xylene gave a mixture of the cryptand (1:1 cyclization) and the tricyclic bisdiaza -15-crown-5 connected by two m-xylylene units (2:2 cyclization) when K 2CO3 was used as the base. When Li2CO3 was used, the same reaction gav e only the 1:1 cyclization. An H-1 NMR spectrum of the m-xylylene-cont aining cryptand exhibited a peak at delta 8.85 which suggests that the proton on benzene position 2 is close to the diaza-15-crown-5 cavity. The X-ray crystal structure of that compound showed that to be the ca se. A metal ion template effect was also observed in the preparation o f [3.3.3] from 3,6,9-trioxa-1,11-diiodoundecane and its diamine analog . Only [3.3.3] was observed with K2CO3. When Cs2CO3 was used, mainly a bis(aza-12-crown-4) was isolated. When the diiodide was changed to th e corresponding ditosylate, both [3.3.3] and the bis(aza-12-crown-4) w ere isolated.