Syntheses, spectroscopic properties and stereochemistry of bis-C-pivot macrocycles with two dialkyl phosphonate groups

Abstract

Bis-C-pivot macrocycles containing dimethyl ( 1a, 2a) or diethyl phosphonate ( 1b, 2b) groups have been prepared by adding dimethyl or diethyl phosphite to two –CH N bonds in corresponding dibenzo-bis-imino crown ethers ( 1 and 2). Bis-C-pivot macrocycles possess two equivalent stereogenic centres giving rise to diastereoisomers ( meso and racemate). The structures were characterized by elemental analysis, FTIR, MS, TGA, DSC and NMR measurements. 1H, 13C and 31P NMR assignments were made for the isolated meso form of compounds 2a and 2b and for the meso and racemic forms of compounds 1a and 1b by analysis of chemical shifts, signal intensities and splitting patterns and the DEPT and 2D HETCOR NMR techniques. Thermal analysis and 1H NMR showed that the crystallised form of compound 1a contained an equimolar amount of water of crystallisation.