Nuclear magnetic resonance reactions

R343 D. A. Foley, M. T. Zell, B. L. Marquez and A. Kaerner, Nuclear Magnetic Resonance Reaction-Monitoring as a Process Analytical Technique , Pharm. 

Ward H R and Lawler R G 1967 Nuclear magnetic resonance emission and enhanced absorption In rapid organometalllc reactions J. Am. Chem. Soc. 89 5518-19... 

McConnell H M 1958 Reaction rates by nuclear magnetic resonance J. Chem. Phys. 28 430-1... 

Analytical methods iaclude thin-layer chromatography (69), gas chromatography (70), and specific methods for determining amine oxides ia detergeats (71) and foods (72). Nuclear magnetic resonance (73—75) and mass spectrometry (76) have also been used. A frequentiy used procedure for iadustrial amine oxides (77) iavolves titratioa with hydrochloric acid before and after conversion of the amine to the quaternary ammonium salt by reaction with methyl iodide. A simple, rapid quaHty control procedure has been developed for the deterrniaation of amine oxide and unreacted tertiary amine (78). 

Physical Chemical Characterization. Thiamine, its derivatives, and its degradation products have been fully characterized by spectroscopic methods (9,10). The ultraviolet spectmm of thiamine shows pH-dependent maxima (11). H, and nuclear magnetic resonance spectra show protonation occurs at the 1-nitrogen, and not the 4-amino position (12—14). The H spectmm in D2O shows no resonance for the thiazole 2-hydrogen, as this is acidic and readily exchanged via formation of the thiazole yUd (13) an important intermediate in the biochemical functions of thiamine. Recent work has revised the piC values for the two ionization reactions to 4.8 and 18 respectively (9,10,15). The mass spectmm of thiamine hydrochloride shows no molecular ion under standard electron impact ionization conditions, but fast atom bombardment and chemical ionization allow observation of both an intense peak for the patent cation and its major fragmentation ion, the pyrimidinylmethyl cation (16). 

The principal methods for deterrnination of the deuterium content of hydrogen and water are based upon measurements of density, mass, or infrared spectra. Other methods are based on proton magnetic resonance techniques (77,78), F nuclear magnetic resonance (79), interferometry (80), osmometry (81), nuclear reaction (82), combustion (83), and falling drop methods (84). 

The presence of iminium salts can be detected by chemical means or by spectroscopic methods. The chemical means of detecting iminium salts are reactions with nucleophiles and are the subject of this review. The spectroscopic methods are more useful for rapid identification because with the large number of model compounds available now the spectroscopic methods are fast and reliable. The two methods that are used primarily are infrared and nuclear magnetic resonance spectroscopy. Some attempts have been made to determine the presence of iminium salts by ultraviolet spectroscopy, but these are not definitive as yet (14,25). 

A mixture of 24 g of 1,3-dimethyladamantane and BO ml of bromine was refluxed for 6 hours. The reaction product mixture was cooled, taken up in about 200 ml of chloroform, and poured onto ice. The excess bromine was removed by adding sodium hydrosulfite. The chloroform layer was separated from the aqueous layer, dried, concentrated in vacuo, and distilled at reduced pressure to yield 30.5 g of product having a boiling point of about 11B°C at 5-6 mm np = 1.5169-1.51B2. The product was identified by nuclear magnetic resonance (NMR) and elemental analyses as 1-bromo-3,5-dimethyladamantane. 

Some preliminary laboratory work is in order, if the information is not otherwise known. First, we ask what the time scale of the reaction is surely our approach will be different if the reaction reaches completion in 10 ms, 10 s, 10 min, or 10 h. Then, one must consider what quantitative analytical techniques can be used to monitor it progress. Sometimes individual samples, either withdrawn aliquots or individual ampoules, are taken. More often a nondestructive analysis is performed, the progress of the reaction being monitored continuously or intermittently by a technique such as ultraviolet-visible spectrophotometry or nuclear magnetic resonance. The fact that both reactants and products might contribute to the instrument reading will not prove to be a problem, as explained in the next chapter. 

The formation of compound (1) has been established under well-defined laboratory conditions in such reaction mixtures [15,26-35]. Comparison of nuclear magnetic resonance (NMR) spectra of model compounds prepared by Bakker and Cerfontain [29] with those of the reaction mixture has also clearly shown the presence of (1). p-Sultones (1) have also been identified in commercial scale equipment under less well-defined conditions [21-24]. 

Nagayama et al. [36] studied a-sulfonation using nuclear magnetic resonance (NMR). They reported the presence of two intermediates. The first intermediate is the adduct of S03 to the carbonyl oxygen formed at low temperatures. In contrast to the mechanism of Stein et al., they did not propose a rearrangement of this intermediate but a second addition of S03 to the activated a-hydrogen to give the second intermediate. The reaction of the intermediate with sodium hydroxide can lead to the disodium salt if the neutralization is immediate or to the sodium a-sulfo fatty acid ester if the neutralization is delayed. 

It is particularly important to study process phenomena under dynamic (rather than static) conditions. Most current analytical techniques are designed to determine the initial and final states of a material or process. Instmments must be designed for the analysis of materials processing in real time, so that the cmcial chemical reactions in materials synthesis and processing can be monitored as they occur. Recent advances in nuclear magnetic resonance and laser probes indicate valuable lines of development for new techniques and comparable instmmentation for the study of interfaces, complex hquids, microstmctures, and hierarchical assemblies of materials. Instmmentation needs for the study of microstmctured materials are discussed in Chapter 9. 

The majority of trichloroethylene present on soil surfaces will volatilize to the atmosphere or leach into the subsurface. Once trichloroethylene leaches into the soil, it appears not to become chemically transformed or undergo covalent bonding with soil components. When trichloroethylene was absorbed onto kaolinite and bentonite, the nuclear magnetic resonance (NMR) spectra showed no evidence of chemical reactions (Jurkiewicz and Maciel 1995). Because trichloroethylene is a dense nonaqueous phase liquid, it can move through the imsaturated zone into the saturated zone where it can displace soil pore water (Wershaw et al. 1994). 

Exchange reactions can be sometimes investigated by the techniques of polari-metry, nuclear magnetic resonance and electron spin resonance. The optical activity method requires polarimetric measurements on the rate of racemization in mixtures of d-X (or /-X) and /-Y (or d-Y). 

---