Problems with structure elucidation

Since the late 1950s PMR spectroscopy has contributed immensely to many areas of the chemistry of alkaloids (7). With the advent of Fourier transform spectrometers CMR has rapidly approached the level of PMR in its application to problems of structural elucidation and stereochemistry. In the case of the alkaloids many classes of the isoquinoline family have been studied. These alkaloids are of particular interest not only because of their widespread occurrence in nature but also because of their pharmacological activity (2-5). Wenkert et al. (6) were the first to review progress in this area. More recently, Shamma and Hindenlang (7) have made an extensive compilation of chemical shift data on amines and alkaloids that includes many... 

In problems of structure elucidation an NMR spectrum may provide useful, even vital data, but it is seldon the sole piece of information available. A knowledge of the source of the compound or its method of synthesis is frequently the single most important fact. In addition, the interpretation of the NMR spectrum is carried out with concurrent knowledge of other physical properties, such as elemental analysis from combustion or mass spectral studies, the molecular weight, and the presence or absence of structural features, as indicated by infrared or ultraviolet spectra or by chemical tests. Obviously, the procedure used for analyzing the NMR spectrum is highly dependent on such ancillary knowledge. 

In Section 7-9a, we saw that the critical delay time A in the HMBC experiment is set to approximately 8 Hz, which is an average value of (2 7ch) with n usually equal to 2 or 3. Implicit in this relationship is the fact that the HMBC experiment cannot differentiate two-bond from three-bond (and occasionally greater) X-H couplings. This is an unfortunate shortcoming, especially with regard to problems involving structural elucidation (Chapter 8). 

The above examples are selected for purposes of illustration of the concepts and methods that have been applied to the problem of structure elucidation. There are other variations of structure generators and systems that merge them with spectrum interpretation. 

WebSpectra includes 75 problems All the problems display the and C spectra several with DEPT or COSY enhancements A number include IR spectra Organic Structure Elucidation contains 64 problems all with and C NMR IR and mass spectra The exercises in both WebSpectra and Organic Structure Elucidation are graded according to difficulty Give them a try... 

FIGURE 13 27 These two welcome screens open the door to almost 150 spectroscopy problems The screens are used with permission of Professors Craig A Merlic (WebSpectra) and Bradley D Smith (Organic Structure Elucidation) See the text for the respective URLs... 

First, the qualitative and quantitative variability of the amount of catechins and proanthocyanidins present in plant extracts used for different studies is probably the most significant. This might be due to the use of different procedures of extraction, quantification and structural elucidation. In most cases, even the lack of rigorous phytochemical characterization and quantification of active compoimd(s) constitutes a severe limitation on the rehabihty of the results. The lack of commercially available pure standards (particularly for some proanthocyanidins) represents an additional problem that has so far hampered the execution of rigorous SAR studies. This hmitation means that although a munber of in vitro or in vivo studies have been carried out by using more or less pure standards of catechins or with plant extracts containing both catechins and proanthocyanidins, only a handful of authors have... 

GC-AAS has found late acceptance because of the relatively low sensitivity of the flame graphite furnaces have also been proposed as detectors. The quartz tube atomiser (QTA) [186], in particular the version heated with a hydrogen-oxygen flame (QF), is particularly effective [187] and is used nowadays almost exclusively for GC-AAS. The major problem associated with coupling of GC with AAS is the limited volume of measurement solution that can be injected on to the column (about 100 xL). Virtually no GC-AAS applications have been reported. As for GC-plasma source techniques for element-selective detection, GC-ICP-MS and GC-MIP-AES dominate for organometallic analysis and are complementary to PDA, FTIR and MS analysis for structural elucidation of unknowns. Only a few industrial laboratories are active in this field for the purpose of polymer/additive analysis. GC-AES is generally the most helpful for the identification of additives on the basis of elemental detection, but applications are limited mainly to tin compounds as PVC stabilisers. 

Structure elucidation of semiochemicals by modern NMR-techniques (including HPLC/NMR) is often hampered by the very small amounts of available material and problems in the isolation of pure compounds from the complex mixtures they are embedded in. Thus, the combination of gas chromatography and mass spectrometry, GC/MS, is frequently the method of choice. Determination of the molecular mass of the target compound (by chemical ionisation) and its atomic composition (by high resolution mass spectrometry) as well as a careful use of MS-Ubraries (mass spectra of beetle pheromones and their fragmentation pattern have been described [27]) and gas chromatographic retention indices will certainly facihtate the identification procedure. In addition, the combination of gas chromatography with Fourier-transform infrared spec-... 

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