Chemical Sensors and Microinstrumentation

The ¹H NMR spectra of racemic (erythro) methoxamine free base, 1, 1-(1-aminoethyl)-2,5-dimethoxybenzenemethanol, have been studied at or near ambient temperatures in CDCl₃ or CD₃CN with the added chiral lanthanide shift reagent (LSR), tris[3-(heptafluoropropylhydroxymethylene)-(+)-camphorato] europium (III), 2. Spectrometers operating at 60, 200 and 300 MHz were employed; some COSY spectra were acquired to support assignments. Enantiomeric shift differences (Δ Δ Δ) were observed for several nuclei of 1 with added 2 in either CDCl₃ or CD₃CN and an “anomalous” (upfield) shift was seen for the NCH signal. A high degree of signal broadening was seen for runs with either solvent, and surprising similarity was found for the slopes in plots of chemical shift versus [2]/[1] molar ratios for the different nuclei of 1 whether the hydrogen bond donor solvent (CDCl₃) or the hydrogen bond acceptor solvent (CD₃CN) was used. Together with the anomalous shift noted above, these results are interpreted as consistent with strong bidentate chelation of 2 by 1.