Deuterium nuclear magnetic resonance spectra

The nuclear magnetic resonance spectrum of sodium valproate as shown in Figure 3 was obtained on a Varian Associates T-60 NMR Spectrometer in deuterium oxide containing tetramethylsilane as the internal standard. The spectral peak assignments (2) are presented in Table I. 

Primary amines may be readily distinguished from secondary and tertiary analogues by the presence of two absorption bands in the infrared spectrum between 3320 and 3500 cm-1 (symmetric and antisymmetric NH str.). Secondary amines exhibit a single absorption band at about 3350 cm-1 (NH str.). In both cases deformation modes for the NH bond appear at about 1600 cm-1. There is no satisfactory absorption to allow a definitive characterisation in the case of tertiary amines. In the nuclear magnetic resonance spectrum of primary and secondary amines, the nitrogen-bound hydrogens are recognisable by their replaceability on the addition of deuterium oxide. 

At pH 4.4, 5-thio-D-xylopyranose (215) shows a slow mutarotation, namely, [a]p +202 - +178° (half-time, 10 hours). At pH 6.6, however, the half-time is only about 10 minutes. The direction of the rotation shows that 215 crystallizes in the a-D form. The nuclear magnetic resonance spectrum of 215 in deuterium oxide shows the presence of the H-1 proton of both anomers. The diaxial coupling of 8.2 Hz for the H-1 proton at the higher field (t 5.25) corresponds to the )8-D anomer in the CJ(d) conformation of the molecule having a sulfur-containing ring. 

Fig. 1.— Nuclear Magnetic Resonance Spectrum at 60 me. of nii-oZZo-Quercitol in Deuterium Oxide.

Pig. 3.—Nuclear Magnetic Resonance Spectrum at 60 and 100 mo. of meia-Cyclo-hexanetetrol, m.p. 180°, in Deuterium Oxide. 

The C-NMR spectrum ofindinavir sulfate, shown in Figure 13, was obtained using a Bruker Instruments model AMX-400 nuclear magnetic resonance spectrometer operating at a frequency of 100.55 MHz as an approximate 4.16 % w/v solution in deuterium oxide. The 67.4 ppm resonance of dioxane was used as an external reference standard. Peak assignments are found in Table 8, and make use of the numbered structural formula given previously [11]. 

In addition to detecting the heavy water content, we also utilized the deuterium NMR technique to study moisture/epoxy interactions. Figure 33 shows the 4.65 ppm nuclear magnetic resonance of isotopically tumbling heavy water molecules. Figure 34 shows the NMR spectrum of deuterium oxide as the moisture analog resides in an... 

As we shall see, each of these two terms, one for each nucleus, describes a second-rank scalar interaction between the electric field gradient at each nucleus and the nuclear quadrupole moment. De Santis, Lurio, Miller and Freund [44] included two other terms which involve the nuclear spins. One is the direct dipolar coupling of the 14N nuclear magnetic moments, an interaction which we discussed earlier in connection with the magnetic resonance spectrum of D2 its matrix elements were given in equation (8.33). The other is the nuclear spin-rotation interaction, also discussed in connection with H2 and its deuterium isotopes. It is represented by the term... 

Some of the important differences in the nuclear magnetic resonance spectra of the /3-n-furanose form in various solvents are shown in Table I. As expected, the chemical shifts are somewhat altered on changing the solvent however, new bands appear with pyridine. In methyl sulfoxide, the mutarotation is very slow, and only one form is seen soon after dissolution. In anhydrous pyridine, the mutarotation is a little faster, so that, in a few minutes, the a- and /S-n-furanose forms are present in equal amounts. With the addition of deuterium oxide, equilibrium between the three forms is rapidly reached. This last spectrum is essentially the same as that of the crude product mentioned earlier. The small values for Jz 4 indicate that all three forms are in fixed conformations and are, therefore, not acyclic. The spectrum of the a-D-pyranose form is closely related to that of (24). The two furanose forms show, overall, a similar spectrum, except that the proton at C-1 of the )3-d anomer shows a relatively large coupling, J = 3.25, of unknown origin. The spectra of many five-membered heterocyclic compounds are anomalous, and not yet fuUy understood. 

The assignment of these isomers was confirmed by nuclear magnetic resonance spectroscopy on a Perkin-Elmer 60 Mc./sec. NMR spectrometer, after removal of -OH by exchange with deuterium oxide. The spectrum of the cw-alcohol showed a single broad peak, while that of the trans-alcohol showed two peaks they thus resembled the spectra of the corresponding hydrocarbons (8). 

Nuclear magnetic resonance analysis with double and triple resonance was used to elucidate the structure as 3, 4 -dideoxykanamycin B 2"-adenylate. The spectrum of the inactivated 3, 4 -dideoxykanamycin B in deuterium oxide at pH 8.0, with tetramethylsilane as the external reference standard (8 =0), showed signals at 8 8.63 and 8.85 attributable to the adenine-ring protons, and at 8 6.53, 5.28, 4.98, 4.83 and 4.6 (H-2) the latter were assigned to the D-ribose-ring protons by successive doubleresonance experiments, and by comparison with disodium 5 -adenylate in deuterium oxide. Therefore, these observations confirmed the presence of one molecular proportion of 5 -adenylic acid in the molecule. Irradiation at 8 5.45 (7 3.6, H-1") caused the complex signal at 8 4.3 (H-2")... 

Phosphorous nuclear magnetic resonance ( P-NMR) No isotope labeling is required for P-NMR spectroscopy. The chemical shielding anisotropy, Aa, in P-NMR is comparable to the deuterium quadrupole splitting in H-NMR and can be determined from the edges of the spectrum. 

Figure 5.20 Nuclear magnetic resonance (NMR) spectrum deuterium oxide at 50°C. Reproduced with kind permission (...

When we studied the radio-frequency spectrum of D2 we hit another surprise [5]. The separation of the spectral lines in D2 were greater than in H2 even though the nuclear spin-spin interaction and the nuclear spin molecular rotation interaction should be much less. We found a similar anomaly for HD. We finally interpreted this as due the deuterium nucleus having a quadrupole moment (being ellipsoidal in shape) which gave rise to a spin dependent electrical interaction. The existence of the quadrupole moment, in turn, implied the existence of a new elementary particle force called a tensor force. In this way, magnetic resonance made a fundamental contribution to particle physics. 

---