Lanthanide Shift Reagents. Paper 22 The Influence of Mixed Silver/Praseodymium Shift Reagents on the Proton NMR Spectra of Heteroaromatics

Previous work in these laboratories¹ and elsewhere^2,3 has pointed to the value of a mixture of lanthanide fod chelates with silver fod^1,2 or with silver trifluoroacetate³ in simplifying the ¹H NMR spectra of aryl substrates which do not possess the conventional (O or N) donor groups (fod = 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octane dionate).     

NMR Studies of Drugs. Applications of Lanthanide Shift Reagents to Afloqualone,an Axially Chiral Quinazolinone.

The skeletal muscle relaxant, aflogualone, 1, has been studied by ¹H NMR in CDC1₃ at 60 and 300 MHz in the presence of added chiral [Eu(HFC)₃] or achiral [Eu(FOD)₃] lanthanide shift reagents (LSR). With Eu(HFC)₃, significant enantiomeric shift differences, ΔΔδ, can be induced for most of the nuclei of 1, with near-baseline resolution obtainable for the H-5 signals of each enantiomer, indicating excellent analytical potential for direct determination of enantiomeric excess of samples of 1. Observation of ΔΔδ directly confirms hindered rotation about the bond between N (3) and the 2-methylphenyl group, i.e., the N (sp²) - C(sp²) bond, leading to axial chirality in 1 with slow rotation on the NMR timescale. Assignments are supported by 2D COSY spectra at 300 MHz. Relative lanthanide-induced shift magnitudes for the protons of 1 are compared.     

The Muonic Hydrogen Lamb Shift Experiment at PSI

A measurement of the 2S Lamb shift in muonic hydrogen (μ⁻p) is being prepared at the Paul Scherrer Institute (PSI). The goal of the experiment is to measure the energy difference ΔE(2⁵ P _3/2−2³ S _1/2) by laser spectroscopy (λ≈6μm) to a precision of 30 ppm and to deduce the root mean square (rms) proton charge radius with 10⁻³ relative accuracy, 20 times more precise than presently known. An important prerequisite to this experiment is the availability of long-lived μp_2S -atoms. A 2S-lifetime of ∼1 μs – sufficiently long to perform the laser experiment – at H₂ gas pressures of 1–2 hPa was deduced from recent measurements of the collisional 2S-quenching rate. A new low-energy negative muon beam yields an order of magnitude more muon stops in a small low-density gas volume than a conventional cloud muon beam. A stack of ultra-thin carbon foils is the key element of a fast detector for keV-muons. The development of a 2 keV X-ray detector and a 3-stage laser system providing 0.5 mJ laser pulses at 6 μm is on the way. This revised version was published online in August 2006 with corrections to the Cover Date.     

Lanthanide Shift Reagents. Paper 18. Equilibrium Binding Constants for Europium Shift Reagent with Nitrogen Heterocycles

Paper 16 in this series^{1, 2, 3} was concerned with the equilibrium binding constants (K) of the shift reagent Europium tris (2, 2, 6, 6-tetramethylheptane-3, 5-dionate), Eu(thd)₃, with primary, secondary and tertiary amines. One nitrogen heterocycle, pyridine, and two of its derivatives (see Table) were included. In the present paper we describe the binding constants for a further 9 nitrogen containing heterocycles and relate these to basicity and steric effects.     

Lanthanide Shift Reagents. Paper 21. Interaction of Arenes with Silver/Lanthanide Shift Reagent and Comparison with Chromium Tricarbonyl Complexes

Lanthanide shift reagents can bring about dramatic simplifications of highly complex NMR spectra^1,2. The applicability of the commonest of these (the thd and fod chelates of Eu, Pr and Yb) has been restricted to those molecules possessing a suitable N, O or S donor atom, although they may turn up in unusual guises, e.g. in quaternary ammonium compounds³.     

Three-Dimensional C Shift/H–N Coupling/N Shift Solid-State NMR Correlation Spectroscopy

Triple-resonance experiments capable of correlating directly bonded and proximate carbon and nitrogen backbone sites of uniformly ¹³C- and ¹⁵N-labeled peptides in stationary oriented samples are described. The pulse sequences integrate cross-polarization from ¹H to ¹³C and from ¹³C to ¹⁵N with flip-flop (phase and frequency switched) Lee–Goldburg irradiation for both ¹³C homonuclear decoupling and ¹H–¹⁵N spin exchange at the magic angle. Because heteronuclear decoupling is applied throughout, the three-dimensional pulse sequence yields ¹³C shift/¹H–¹⁵N coupling/¹⁵N shift correlation spectra with single-line resonances in all three frequency dimensions. Not only do the three-dimensional spectra correlate ¹³C and ¹⁵N resonances, they are well resolved due to the three independent frequency dimensions, and they can provide up to four orientationally dependent frequencies as input for structure determination. These experiments have the potential to make sequential backbone resonance assignments in uniformly ¹³C- and ¹⁵N-labeled proteins.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Meparfynol, 3-Methyl-L-Pentyn-3-Ol. Apparent Anomalous Results with a Binuclear Shift Reagent

The 60 MHz ¹H NMR spectra of racemic meparfynol, 1, have been studied in CDCl₃ solution at 28° with the achiral shift reagentt tris(6,6,7,7,8,8,8-hepta-fluoro-2,2-dimethyl-3,5-octanedionato) europium (III), 2, and the chiral reagent, tris[3-(heptafluoropropyl-hydroxymethylene)-d-camphorat01 europium(III), 3. With 3, observable enantiomeric shift differences for the 3-methyl should make possible direct optical purity determinations. Additions of increments of (6,6,7,7,8,8,8-heptafluoro-2,2-dimenthyl-3,5-octane-dionato)silver(I) 4, to a CDCl₃ solution of 1 and 3 resulted in changes in Δδ magnitudes and in some line intensities that are discussed in terms of interactions with the ethynyl and hydroxyl groups.     

Knight Shift of 90Nb, 93mMo, 96Tc,and 101mRh in Nb Using Brute-Force NMRON

Brute-force nuclear magnetic resonance on oriented nuclei (BF-NMRON) of ⁹⁰Nb, ^93mMo, ⁹⁶Tc, and ^101mRh was carried out in a new host metal, Nb. The resonance center frequencies at an external field of 11.922(6) T were obtained as ν(⁹⁰NbNb) = 56.572(9) MHz, ν(^93mMoNb) = 85.76(3) MHz, ν(⁹⁶TcNb) = 66.997(11) MHz, and ν(^101mRh Nb) = 111.010(19) MHz. A systematic analysis of the Knight shift of 4d elements in extremely dilute alloy systems is briefly discussed. This revised version was published online in September 2006 with corrections to the Cover Date.     

Line Shift Investigations for Different Isotopomers of Carbon Monoxide

Line shift coefficients for five lines of five different isotopomers in the fundamental band of CO in the spectral region near 2058 cm⁻¹were measured using a three channel lead salt diode laser spectrometer. The study includes the linesP(3) of¹³C¹⁷O,R(3) of¹³C¹⁸O,P(9) of¹²C¹⁸O,P(10) of¹³C¹⁶O, andP(21) of¹²C¹⁶O, and covers collisions with N₂, O₂, H₂, D₂, He, Ne, Ar, Kr, and Xe. Line shifts of the isotopomers¹³C¹⁶O,¹²C¹⁸O,¹³C¹⁸O, and¹³C¹⁷O were determined for the first time. Within the experimental uncertainty no significant dependence of the shift effect on the isotopomer was found. TheR-branch line under study shows a smaller line shift coefficient than aP-branch line with a similar rotational quantum number. With increasing mass of the noble gas perturber the absolute size of the shift coefficient increases. Moreover self- and nitrogen-broadening coefficients for the isotopomer lines were determined. Compared to previous measurements no significant deviations between different isotopomers were observed.     

NMR Studies of Drugs. Applications of Achiral and Chiral Wthanide Shift Reagents to Bupropion

Abstract

The ¹H NMR spectra of racemic samples of the antidepressant drug, bupropion, 1, have been studied in CDCl₃ solution at 60 and 200 MHz with the achiral lanthanide shift reagent (LSR), tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium (III), 2, and the chiral reagent, tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 3. Both LSR produced substantial lanthanide induced shifts consistent with ¹H assignments, but the bound complexes of 1 with 2 versus 3 may not be isostructural. With 3, substantial enantiomeric shift differences were observed for the t-butyl, CH ₃CH, NCH, and the aryl H-2 and H-6 signals, which should permit potential direct determination of enantiomeric excess.     

Hydroxyl Substituent Chemical Shift (SCS) Effects in Alcohols: The 17O NMR of Diols

The ¹⁷O NMR spectra for a series of saturated diols were investigated. From these studies both hydroxyl induced substituent chemical shift (SCS) effects of hydroxyl oxygen ¹⁷O NMR chemical shifts were determined. In addition, linear correlations between the ¹⁷O chemical shift of the hydroxyl oxygen (ROH) and the ¹³C chemical shift for the methyl group in the corresponding hydrocarbon (RCH₃) were obtained.

     

NMR Studies of Drugs. Methaqualone. Approaches to Rigorous 1H and 13C Assignments with Applications of Achiral and Chiral Shift Reagents

The ¹H and ¹³C NMR spectra of methaqualone, 1, have been extensively studied using one and two-dimensional techniques. These 300 MHz ¹H and 75 MHz ¹³C studies have allowed rigorous assignments to be made for the methyl groups and the quinazolinone nucleus. The 60 MHz ¹H spectra for 1 in CDCl₃ have been examined with     

Effect of Shift Reagents on Infrared Spectra

Abstract

Introduction

We have shown previously¹ that when Eu(fod)₃?d₂₇ shift reagent is added to the erythro and threo esters of 2,3-diphenyl-3-hydroxypropanoic acid, the vicinal coupling constants, J₂₃, vary in a manner which indicates bidentate coordination.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Ethchlorvynol. Novel Behavior of a Terminal Alkyne with Ag(I) - Lanthanide Binuclear Shift Reagent

The 60 MHz ¹H NMR spectra of racemic ethchlorvynol, 1, have been studied at 28° in CDCl₃ solution with the achiral reagent tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium(III).     

Binuclear NMR Shift Reagents. An Apparent Anomalous Effect with Vinclozolin

The 60 MHz ¹H NMR spectra of racemic vinclozolin, 1, have been studied at 28° in CDC1₃ solution with the chiral reagent tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 2, by incremental additions of (6,6,7,7,8,8,8-heptafluoro-2,2-di-methyl-3,5-octanedionato)silver(I), 3. Although the solution of 1 with 2 displayed substantial downfield lanthanide-induced shifts, Δδ, and enantiomeric shift differences, ΔΔδ, for selected nuclei, relative to the spectrum of unshifted 1, additions of 3 to the solution of 1 and 2 were unexpectedly found to dramatically reduce the magnitudes of both Δδ and ΔΔδ.     

Lanthanide Shift Reagents XIII the Influence of Phenyl, 1-Adamantyl and Tert-Butyl Substituents on Equilibrium Constants

We have recently extended our Infrared studies of the binding of anilines with lanthanide shift reagents¹ to an NMR examination of hindered phenyl-carbinols² and a series of aldehydes and ketones related to benzaldehyde and acetophenone³.     

Shift and broadening of hadronic resonances formed in nuclear interactions

The mass shift and broadening of the isobar Δ(1232) formed in the reaction ¹²C(p, n)Δ ^{++ 11}B*, are explained by taking into account the elastic and inelastic rescattering of the isobar decay products by the residual nuclear system. The computational results for the mass decrease and broadening of the peak are in good agreement with the experimental data. Predictions are given for a process of the same type on the deuteron, pd→nnΔ⁺⁺. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 3, 171–176 (10 August 1998)     

NMR Studies of Agricultural Products. Applications of Achiral and Chiral Lanthanide Shift Reagents to the Fungicide,Triadimefon.

Abstract

The 60 MHz ¹H NMR spectra of the systemic agricultural fungicide, triadimefon, 1, have been studied in CDCl₃ at 28±1° (as the racemic free base) 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, for spectral simplification, and with the chiral LSR, tris [3-(heptafluoropropylhydroxymethylene)-(+) -camphorato)europium(III), Eu(HFC)₃, 3, to induce enantiomeric shift differences (ΔΔδ) for several nuclei. Significant ΔΔδ values were seen for the two protons of the heterocyclic ring, the OCH methine, and aryl H-2′, 6′ of the chlorophenoxy ring. For each of these nuclei exhibiting ΔΔδ with added 3, the ΔΔδ magnitudes reached maximum values with 3: 1 molar ratios ca. 0. 18–0. 29, and decreased with higher levels of 3. To confirm analytical utility of 3 for % e. e. determinations of 1, a nonracemic (“spiked”) sample of racemic 1, with added R-(?) triadimefon, was examined with 3. At low 3: 1 ratios, both triazole H-3 and H-5, as well as the OCH and aryl H-2′, 6′ protons of (?)-1 showed a downfield sense of magnetic nonequivalence with (+) -3. With 3: 1 ratios ca. 0. 8, triazole proton H-3 reversed its sense of magnetic noneguivalence. The H-3 and H-5 signals were useful for % e. e determinations at this higher 3: 1 ratio.     

Lanthanide Shift Reagents XIV Equilibrium Binding Constants for Europium Shift Reagent with Alkyl and Aryl Esters

Methods have been developed for measuring the equilibrium binding constants (K) for lanthanide shift reagents with donor substrates. Although Infrared Spectroscopy proved useful¹ for determining the binding of substituted anilines to the tris-tetramethylheptanedionate of Ytterbium, it was found that NMR was more sensitive and applicable to a wider range of substrates than simple alcohols and amines^2,3. The NMR procedure of progressive     

A Reinvestigatton of the 13C-NMR Chemical Shift Assignments of Fluoranthene

Disparities in the protonated carbon NMR chemical shift assignments of the polynuclear aromatic molecule, fluoranthene, have been noted. Using two-dimensional ¹³C- ¹³C double quantum coherence, the ¹³C-NMR chemical shift assignments were reinvestigated and a set of unequivocal assignments obtained.