Structure characteristic proton chemical shifts

The characteristics of the water pool of reverse micelles has been explored by H, 23Na, 13C, 3IP-NMR spectroscopy. Since the initial association process in RMs is not totally understood, and because of the low CMC, aggregation studies from NMR are rather scarce. Direct determination of a CMC in the diethyl hexyl phosphate /water/benzene system (at Wo = 3.5) was possible because the chemical shift of 31P in phosphate groups is very sensitive to hydration effects. The structure and state of water in RMs and particularly at low water content has received considerable attention. The proton chemical shifts have been explored in AOT/water/heptane, methanol, chloroform, isooctane and cyclohexanone. The water behavior in small reverse micelles is close to that of the corresponding bulk ionic solution. Until now, the effect of a solute on micellar structure was not well... 

Analyzing an NMR spectrum m terms of a unique molecular structure begins with the mfor matron contained m Table 13 1 By knowing the chemical shifts characteristic of various proton environments the presence of a particular structural unit m an unknown compound may be inferred An NMR spectrum also provides other useful information including... 

NMR of solids usually give broad featureless absorptions due to the dipolar interactions which, at least in the case of protons, are orders of magnitude larger than the characteristic chemical shifts and spin-spin couplings used for structure elucidation... 

Deplancheine (7) was isolated first from the stem and bark of Alstonia deplanchei van Heurck and Muell. Arg. by Husson et al. (14). The structure of this novel type of alkaloid has been established from spectral evidence the trans annellation of rings C and D is supported by the presence of characteristic Bohlmann bands in the IR spectrum and also by the chemical shift of the C-3 proton below 3.7 ppm. The ethylidene side chain was also indicated by the H-NMR spectrum [8 1.52 (3H, d, J =6 Hz), 5.30 (1H, q, J = 6 Hz)] and its E configuration was confirmed by regio- and stereospecific total synthesis (14). 10-Methoxydeplancheine (8) has been found in the leaves of Alstonia lanceolifera... 

Fig. 14. Typical signals of triglycerides in a proton spectrum, (a) Structure of a triglyceride with three different fatty acids (one saturated, two unsaturated). Different positions of protons in the molecule are indicated, resulting in different chemical shifts in the spectrum, (b) Characteristic signal pattern of triglycerides (or fatty acids) in a spectrum from yellow fatty bone marrow of the tibia, containing triglycerides in the adipocytes with more than 90% volume fraction. The spectrum was recorded with TE = 50 ms by a PRESS sequence.

The contributions of the first three types are practically local in character they are close in value for two protons with similar structural environment, such as the ethylenic- and aromatic-type protons. It is only the last term in Eq. (35) that defines the values of the chemical shifts characteristic of aromatic or antiaromatic compounds. 

By trapping PX at liquid nitrogen temperature and transferring it to THF at —80° C, the nmr spectmm could be observed (9). It consists of two sharp peaks of equal area at chemical shifts of 5.10 and 6.49 ppm downfield from tetramethylsilane (TMS). The fact that any sharp peaks are observed at all attests to the absence of any significant concentration of unpaired electron spins, such as those that would be contributed by the biradical (11). Furthermore, the chemical shift of the ring protons, 6.49 ppm, is well upheld from the typical aromatic range and more characteristic of an olefinic proton. Thus the olefin structure (1) for PX is also supported by nmr. 

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