Aromatic compounds chemical shift

There has been no work published assessing the aromatic character of 1,2,3-thiadiazole. From the Huckel definition of aromaticity, (4n + 2) ir-electrons in a ring constitute an aromatic compound and by this criterion 1,2,3-thiadiazoles should be considered aromatic compounds. Chemical shifts for 1,2,3-thiadiazoles in both 13C and 1H NMR, which are related to the electronic environment, are in accord with an aromatic heterocyclic ring. 

The general absorption pattern of quaternary pavines strongly resembles that of the tertiary analogs with the exception of the expected downfield shifts for each of the protons. In particular, the bridgehead protons will move downfield by about 1-1.5 ppm (32,35). N,N-Dimethyl protons will be observed as a singlet between 8 3.3 and 3.7 (29,32,35). The set of empirical rules deduced for aromatic proton chemical shifts in a tertiary system has been shown to apply also to the quaternary system (29). A listing of aromatic proton chemical shifts of some quaternary pavine bases has been presented as a reference for future studies on similar compounds (29). 

The NMR spectra of thiazoles show the same behavior as those of aromatic compounds, but the chemical shifts also depend on the two heteroatoms. 

HETCOR (Section 13 19) A 2D NMR technique that correlates the H chemical shift of a proton to the chemical shift of the carbon to which it is attached HETCOR stands for heteronuclear chemical shift correlation Heteroatom (Section 1 7) An atom in an organic molecule that IS neither carbon nor hydrogen Heterocyclic compound (Section 3 15) Cyclic compound in which one or more of the atoms in the nng are elements other than carbon Heterocyclic compounds may or may not be aromatic... 

Azolinone derivatives and the corresponding thiones and imines are listed in Table 18 only substituted derivatives have been measured frequently. The chemical shifts of non-aromatic azole derivatives are given in Tables 19-21 relatively few data are available and these are generally for substituted derivatives rather than for the parent compounds. 

Aromatic character in isoxazoles has been studied from a number of viewpoints, and these studies indicate that although isoxazole may be formally considered an aromatic system, the disposition of the ring heteroatoms modifies this character to an appreciable extent. From a qualitative viewpoint, thermal stability and electrophilic attack at the 4-position may be considered consistent with an aromatic character. Furthermore, NMR chemical shifts of the ring protons are consistent with those of an aromatic compound. References related to these studies may be found in Section 4.16.2.3.4. 

The NMR chemical shifts of non-aromatic isothiazoles can be predicted with reasonable accuracy using standard substituent increments. A particular usefulness of NMR is its ability to distinguish between very similar compounds, and for this reason NMR finds application in pharmaceutical and other analyses. As an example CNMR allows ready distinction of the dlastereolsomers of dehydromethionine (14) and the possibility of detection of one dlastereolsomer in the presence of the other (79JOC2632). 

The stability of isothiazole derives from the fact that it has an aromatic delocalized ir-electron system. The NMR chemical shifts, which depend, inter alia, on ring currents, and the high stability of the molecular ions in mass spectrometry, are typical of aromatic compounds, and X-ray measurements confirm the partial double bond character of all the bonds of the ring. 

Z Arrangement was also ascribed to the isomer absorbing at higher field in the case of the ethyl compounds. CH and CH2 protons near the ring nitrogen are shielded by the aromatic ring in the Z compound. The protons at the ring carbon absorb at lower field (near 5.2 p.p.m.) in the Z compounds than in the E compounds (4.50-4.70 p.p.m.). The chemical shift of this proton may be used for E-Z discrimination in further substances. 

In contrast to H shifts, C shifts cannot in general be used to distinguish between aromatic and heteroaromatic compounds on the one hand and alkenes on the other (Table 2.2). Cyclopropane carbon atoms stand out, however, by showing particularly small shifts in both the C and the H NMR spectra. By analogy with their proton resonances, the C chemical shifts of k electron-deficient heteroaromatics (pyridine type) are larger than those of k electron-rieh heteroaromatic rings (pyrrole type). 

Substituent effects (substituent increments) tabulated in more detail in the literature demonstrate that C chemical shifts of individual carbon nuclei in alkenes and aromatic as well as heteroaromatic compounds can be predicted approximately by means of mesomeric effects (resonance effects). Thus, an electron donor substituent D [D = OC//j, SC//j, N(C//j)2] attached to a C=C double bond shields the (l-C atom and the -proton (+M effect, smaller shift), whereas the a-position is deshielded (larger shift) as a result of substituent electronegativity (-/ effect). 

In the chemical shift range for alkenes and aromatic and heteroaromatic compounds enol ether fragments (furan, pyrone, isoflavone, 195-200 Hz) ... 

One criterion of aromaticity is the ring current, which is indicated by a chemical shift difference between protons, in the plane of the conjugated system and those above or below the plane. The chemical shifts of two isomeric hydrocarbons are given below. In qualitative terms, which appears to be more aromatic (Because the chemical shift depends on the geometric relationship to the ring current, a quantitative calculation would be necessary to confirm the correctness of this qualitative impression.) Does Hiickel MO theory predict a difference in the aromaticity of these two compounds ... 

In studies aimed at understanding the influence of structure on the reactivity of diazonium ions, Diener and Zollinger (1986) found that the NMR chemical shifts of the aromatic or heteroaromatic parent compounds provided a novel probe. This method can be applied both to substituted benzenediazonium ions and to various heteroaromatic diazonium ions, and it also provides semiquantitative information on the relative reactivities of the l,3,4-triazole-2-diazonium ion (12.5) and its deprotonated zwitterion (12.6). 

The isomeric 1- and 2-fluoronaphthalenes have fluorine chemical shifts of -124 and -116 ppm, respectively. A full analysis of the proton and carbon spectra of 1-fluoronaphthalene is given in Scheme 3.56. NMR data for a number of other fluoropolycyclic aromatic compounds are available.7... 

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