Nuclear magnetic spectra

One end of the lactone ring must be at position 1. This is apparent from the nuclear magnetic spectra of gibberellic acid and its derivatives (30). 

This interaction leads to hyperfine splittings in atomic and molecular spectra. One particular term for this interaction is the Fermi contact term, which dominates chemical shifts in nuclear magnetic spectra and splittings in electron paramagnetic spectra ... 

Table 3. Proton Nuclear Magnetic Spectra of Jnvenile Hormone III...

The proton nuclear magnetic spectra were recorded on a General Electric QE-3(X) Superconducting FTNMR spectrometer operating at 300 MHz. This NMR spectrometer is equipped with a 70.5 KG NB-Ti superconducting magnet, a magnet bore of 44 mm and a dual H/ C 5-mm probe. 

Lastly, Gill found that the ring proton frequency in the nuclear magnetic spectrum of aminothiadiazole is shifted upheld by -1-0.53t versus the unsubstituted compound. The NH3+ group in 98, however. 

The, 3C nuclear magnetic spectrum assignment for JH III is listed in Table 4 (Appendix I) [28]. 

Figure Bl.13.6. The basic elements of a NOESY spectrum. (Reproduced by penuission of Wiley from Williamson M P 1996 Encyclopedia of Nuclear Magnetic Resonance ed D M Grant and R K Harris (Chichester Wiley) pp 3262-71).

No molecule is completely rigid and fixed. Molecules vibrate, parts of a molecule may rotate internally, weak bonds break and re-fonn. Nuclear magnetic resonance spectroscopy (NMR) is particularly well suited to observe an important class of these motions and rearrangements. An example is tire restricted rotation about bonds, which can cause dramatic effects in the NMR spectrum (figure B2.4.1). 

Whatever the derivative considered, the nuclear magnetic resonance spectra of thiazoles are remarkably simple and apparently univoque. The first proton NMR spectrum of thiazole was described by Bak et al. (171). It was followed by a series of works establishing a systematic description... 

Nuclear magnetic resonance measurements have led to the conclu-sion that 2-pyridones have about 35% of the aromaticity of benzene and that the formally related l,2-dihydro-2-methylenepy-ridine is not aromatic. A substantial contribution by such resonance is indicated by the electronic spectrum of 2-quinolone, which is... 

Other methods of identification include the customary preparation of derivatives, comparisons with authentic substances whenever possible, and periodate oxidation. Lately, the application of nuclear magnetic resonance spectroscopy has provided an elegant approach to the elucidation of structures and stereochemistry of various deoxy sugars (18). Microcell techniques can provide a spectrum on 5-6 mg. of sample. The practicing chemist is frequently confronted with the problem of having on hand a few milligrams of a product whose structure is unknown. It is especially in such instances that a full appreciation of the functions of mass spectrometry can be developed. 

Infrared, ultraviolet, and nuclear magnetic resonance spectroscopies differ from mass spectrometry in that they are nondestructive and involve the interaction of molecules with electromagnetic energy rather than with an ionizing source. Before beginning a study of these techniques, however, let s briefly review the nature of radiant energy and the electromagnetic spectrum. 

C Nuclear magnetic resonance spectrum, acetaldehyde, 732 acetophenone, 732 anisole, 672 benzaldehyde, 732 benzoic acid, 771 p-bromoacetophenone, 449 2-butanone, 449, 732 crotonic acid. 771 cyclohexanol, 634 cyclohexanone, 732 ethyl benzoate, 477 methyl acetate, 443 methyl propanoate, 450 methyl propyl ether, 672... 

Nuclear magnetic resonance spectrum, acetaldehyde, 731 anethole, 683 bromoethane, 460... 

Mathematical models are the link between what is observed experimentally and what is thought to occur at the molecular level. In physical sciences, such as chemistry, there is a direct correspondence between the experimental observation and the molecular world (i.e., a nuclear magnetic resonance spectrum directly reflects the interaction of hydrogen atoms on a molecule). In pharmacology the observations are much more indirect, leaving a much wider gap between the physical chemistry involved in drug-receptor interaction and what the cell does in response to those interactions (through the cellular veil ). Hence, models become uniquely important. 

Vervoort, J., et al. (1986). Identification of the true carbon-13 nuclear magnetic resonance spectrum of the stable intermediate II in bacterial luciferase. Biochemistry 25 8062-8067. 

Abscisin II is a plant hormone which accelerates (in interaction with other factors) the abscission of young fruit of cotton. It can accelerate leaf senescence and abscission, inhibit flowering, and induce dormancy. It has no activity as an auxin or a gibberellin but counteracts the action of these hormones. Abscisin II was isolated from the acid fraction of an acetone extract by chromatographic procedures guided by an abscission bioassay. Its structure was determined from elemental analysis, mass spectrum, and infrared, ultraviolet, and nuclear magnetic resonance spectra. Comparisons of these with relevant spectra of isophorone and sorbic acid derivatives confirmed that abscisin II is 3-methyl-5-(1-hydroxy-4-oxo-2, 6, 6-trimethyl-2-cyclohexen-l-yl)-c s, trans-2, 4-pen-tadienoic acid. This carbon skeleton is shown to be unique among the known sesquiterpenes. 

The small amount of available crystalline abscisin II limited this investigation to the measurement and interpretation of elemental analysis, mass spectrum, and infrared, ultraviolet, and nuclear magnetic resonance (NMR) spectra (11). 

Figure 1. Nuclear magnetic resonance spectrum of abscisin II in CDCh...

Spectra. The UV spectra in w, acid, and base are given in Ref 5. The proton nuclear magnetic resonance spectrum shows a sharp singlet at 3.90ppm from te tram ethyl silane (Ref 15)... 

Solid state materials have been studied by nuclear magnetic resonance methods over 30 years. In 1953 Wilson and Pake ) carried out a line shape analysis of a partially crystalline polymer. They noted a spectrum consisting of superimposed broad and narrow lines which they ascribed to rigid crystalline and amorphous material respectively. More recently several books and large articles have reviewed the tremendous developments in this field, particularly including those of McBrierty and Douglas 2) and the Faraday Symposium (1978)3) —on which this introduction is largely based. 

Fig. 5. Solid-state i C nuclear magnetic resonance spectrum of corn cob xylan.

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