Nuclear magnetic resonance aromatic compounds

The tautomerism of 2- and 3-aminothiophenes was mentioned by Hartough in his review of thiophenes/ but the first definite evidence became available in 1961 when Hoffman and Gronowitz showed conclusively by nuclear magnetic resonance spectroscopy that these compounds both exist in the amino form. In agreement with this finding, 3-aminothiophene generally behaves as an aromatic amine. ... 

Selifonov SA, PJ Chapman, SB Akkerman, JE Gurst, JM Bortiatynski, MA Nanny, PG Hatcher (1998) Use of nuclear magnetic resonance to assess fossil fuel biodegradation fate of [l- C]acenaphthene in creosote polycyclic aromatic compound mixtures degraded by bacteria. Appl Environ Microbiol 64 1447-1453. 

Proton nuclear magnetic resonance (NMR) chemical shifts of 1,2,3-thiadiazoles give another indication of the aromatic character of these compounds. Compiled in Table 4 are a number of examples of proton chemical shifts for ring-substituted 1,2,3-thiadiazoles. 

Since the product slowly darkens on exposure to air, it should be stored under nitrogen in a refrigerator. The compound solidifies on cooling m.p. 16.0-16.5°. Nuclear magnetic resonance spectrum (neat, tetramethylsilane internal standard) singlets at d 7.00 (aromatic protons), 3.93 (CH2), and 2.24 p.p.m. (NH). 

The nuclear magnetic resonance spectrum of aromatic compounds commonly contain the following features ... 

The spectroscopic properties of meso-ionic compounds have been discussed in detail elsewhere and the reviewers do not feel that it would be useful to include a comprehensive account here. Ultraviolet, infrared, and nuclear magnetic resonance spectra of meso-ionic heterocycles provide general support for the conjugative interaction that would be expected for aromatic heterocycles, " but detailed interpretation of their spectra is not justifiable. Mass spectrometry has been shown to be particularly useful for distinguishing between pairs of meso-ionic isomers... 

The structures of vanicosides A (1) and B (2) and hydropiperoside (3) were established primarily by one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy techniques and fast atom bombardment (FAB) mass spectrometry (MS).22 The presence of two different types of phenylpropanoid esters in 1 and 2 was established first through the proton (4H) NMR spectra which showed resonances for two different aromatic substitution patterns in the spectrum of each compound. Integration of the aromatic region defined these as three symmetrically substituted phenyl rings, due to three p-coumaryl moieties, and one 1,3,4-trisubstituted phenyl ring, due to a feruloyl ester. The presence of a sucrose backbone was established by two series of coupled protons between 3.2 and 5.7 ppm in the HNMR spectra, particularly the characteristic C-l (anomeric) and C-3 proton doublets... 

To return to the problem of the general invisibility or atoms, how does the chemist follow the course of a reaction ir the molecules cannot be imaged One way is to use spectroscopy. Thus the conversion or methanol, first to dimethyl ether, then to the higher aliphatic and aromatic compounds Round in gasoline, can be followed by nuclear magnetic resonance (NMR) spectroscopy (Fig. 1.6). As the reaction proceeds, the concentration or the methanol (as measured by the intensity or the NMR peak at <550 ppm) steadily decreases. The first product, dimethyl ether ( 60 ppm), increases at first and then decreases as the aliphatic and aromatic products eventually predominate. 

The organopolysilanes are those compounds containing at least one silicon-silicon bond and one silicon-carbon linkage. This review is mainly concerned with the chemistry of aliphatic derivatives of polysilanes. Consideration of aromatic organopolysilanes is excluded from this review except as far as they are used as intermediates for synthesis and their properties correlate with the aliphatic silicon-silicon compounds, because the aromatic organopolysilanes have recently been well reviewed elsewhere (31,51, 73, 76a, 212). Physical properties of the polysilanes also are excluded from consideration except for spectral properties of ultraviolet absorption and nuclear magnetic resonance, since they are well summarized in earlier excellent reviews and texts (8, 34, 35, 51,131,132). 

Solvent effects on nuclear magnetic resonance (NMR) spectra have been studied extensively, and they are described mainly in terms of the observed chemical shifts, 8, corrected for the solvent bulk magnetic susceptibility (Table 3.5). The shifts depend on the nucleus studied and the compound of which it is a constituent, and some nuclei/compounds show particularly large shifts. These can then be employed as probes for certain properties of the solvents. Examples are the chemical shifts of 31P in triethylphosphine oxide, the 13C shifts in the 2-or 3-positions, relative to the 4-position in pyridine N-oxide, and the 13C shifts in N-dimethyl or N-diethyl-benzamide, for the carbonyl carbon relative to those in positions 2 (or 6), 3 (or 5) and 4 in the aromatic ring (Chapter 4) (Marcus 1993). These shifts are particularly sensitive to the hydrogen bond donation abilities a (Lewis acidity) of the solvents. In all cases there is, again, a trade off between non-specific dipole-dipole and dipole-induced dipole effects and those ascribable to specific electron pair donation of the solvent to the solute or vice versa to form solvates. 

Figure 15.16. H Relaxation of 1-naphthol protons with increasing humic acid concentration at pH 7. All protons are observed to relax at a similar rate, suggesting a nonselective interaction between the protons of 1-naphthol and humic acid. Reprinted from Simpson, M. I, Simpson, A. J., and Hatcher, R G. (2004). Noncovalent interactions between aromatic compounds and dissolved humic acid examined by nuclear magnetic resonance spectroscopy. Environ. Toxi. Chem. 23, 355-362, with permission from the Society of Environmental Toxicology and Chemistry.

Simpson, M. J., Simpson, A. J., and Hatcher, E G. (2004c). Noncovalent interactions between aromatic compounds and dissolved humic acid examined by nuclear magnetic resonance spectroscopy. Environ. Toxicol. Chem. 23, 355-362. 

Schmidt, Brown and D. Williams [40] examined the nuclear magnetic resonance of 14N in three aromatic nitro compounds nitrobenzene, nitrobenzoic acid, di-nitrobenzoyl chloride. 

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