NMR Studies of Agricultural Compounds. Applications of Achiral and Chiral Lanthanide Shift Reagents to the Herbicide,Diclofop Methyl

The 60 MHz H NMR spectra for the herbicide, diclofop methyl, 1, have been studied in CDCl₃ solution at 28±1° with the added achiral lanthanide shift reagent (LSR) tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium(III), Eu (FOD)₃, 2, and with the chiral LSRs, tris3-(heptafluoropropylhydroxymethylene)-(+)-camphorato]europium(III)₃, Eu(HFC)₃, 3, and tris3-(trifluoromethylhydroxymethylene)-(+)-camphorato]europium(III), Eu(FACAM)₃, 4. Both 2 and 3 produced substantial lanthanide-induced shifts (LIS) consistent with predominant LSR binding at the ester carbonyl. Much smaller LIS magnitudes were observed with 4. Modest enantiomeric shift differences (ΔΔδ) were elicited with 3 for the OCH₃ and the CCH₃ resonances of 1. The former signal appears to offer greatest potential for the direct determination of enantiomeric excess of samples of 1, with 3:1 molar ratios ca. 0.3–0.4 resulting in valley heights as low as 33% of the average peak heights of the OCH₃ signals of the two enantiomers.