Optical Purity Determination, Conformer Populations, and 1H NMR Spectral Simplification with Lanthanide Shift Reagents. Part VII: 3,4-Methylenedioxyamphetamine (MDA)

1985 ◽  
Vol 39 (4) ◽  
pp. 604-610 ◽  
Author(s):  
John Avolio ◽  
Robert Rothchild
1984 ◽  
Vol 38 (5) ◽  
pp. 734-737 ◽  
Author(s):  
John Avolio ◽  
Robert Rothchild

The 60 MHz 1H NMR spectra of racemic ethotoin, a, have been studied with the achiral shift reagent tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimeth-yl-3,5-octanedionato) europium (III), b, and the chiral tris[3-(rrifluoromethylhydroxymethylene)- d-camphorato] europium (III), c Appreciable values of the enantiomeric shift difference, ΔΔδ, were observed for the NH, CH3, CH, and ortho aryl protons in CDCl3 solutions at 28°C with the use of samples about 045 molal in a Optical purity assays should be feasible with the use of the NH or CH3 absorptions that display ΔΔδ of 224 and 70 Hz, respectively, at a c:a molar ratio of about 03, with the former resonance being optimal With a c:a ratio between 04–05, the methine proton can be used, with ΔΔδ 11 – 13 Hz Results are interpreted in terms of major coordination of the europium at the C-2 oxygen


1986 ◽  
Vol 40 (6) ◽  
pp. 743-745 ◽  
Author(s):  
Alexander Hatzis ◽  
Robert Rothchild

The 60 MHz 1H NMR spectra of racemic vinclozolin, 1, have been studied at 28° in CDCI3 solution with the achiral reagent tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium(III), 2, and the chiral reagents tris[3-(trifluoromethylhydroxymethylene)- d-camphorato] europium(III), 3, and tris[3-(heptafluoropropylhydroxymethylene)- d-camphorato]europium(III), 4. Reagent 3 produced only small lanthanide-induced shifts and no observable enantiomeric shift differences, ΔΔδ, with 3:1 molar ratios as high as 1.40. In contrast, chiral reagent 4 produced substantial ΔΔδ for the proton, Hβ, at C-2 of the ethenyl group syn to the oxazolidinedione ring and smaller ΔΔδ for the anti proton, Hβ, at the above carbon and for the CH3. With a 4:1 molar ratio of 0.581, ΔΔδ of 7.0 Hz was seen for Hβ. A 4:1 ratio of about 0.41 should be optimum for optical purity determinations; as little as 5% of the minor enantiomer should be detectable.


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