Carbon-13 signal

Section 13 17 Carbon signals normally appear as singlets but several techniques are available that allow one to distinguish among the various kinds of car bons shown... 

A nitrogen atom at X results in a variable downfield shift of the a carbons, depending in its extent on what else is attached to the nitrogen. In piperidine (45 X = NH) the a carbon signal is shifted by about 20 p.p.m., to ca. S 47.7, while in A-methylpiperidine (45 X = Me) it appears at S 56.7. Quaternization at nitrogen produces further effects similar to replacement of NH by A-alkyl, but simple protonation has only a small effect. A-Acylpiperidines show two distinct a carbon atoms, because of restricted rotation about the amide bond. The chemical shift separation is about 6 p.p.m., and the mean shift is close to that of the unsubstituted amine (45 X=NH). The nitroso compound (45 X = N—NO) is similar, but the shift separation of the two a carbons is somewhat greater (ca. 12 p.p.m.). The (3 and y carbon atoms of piperidines. A- acylpiperidines and piperidinium salts are all upfield of the cyclohexane resonance, by 0-7 p.p.m. 

The C NMR spectrum displays five instead of ten carbon signals as expected from the empirical formula C107//0O4. To conclude, two identical halves C5//5O2 build up the molecular structure. 

All carbon signals and resolved couplings can be assigned C-6 is more deshielded (8c = 150.0) than C-7 (8c = 146.5) due to electron withdrawal of the carboxy carbonyl group in para position. 

The C NMR spectrum of the metabolite shows 16 signals instead of 8 as expected from the elemental composition determined by high-resolution mass spectrometry. Moreover, aromaticity of the 2,6-xylenol is obviously lost after metabolism because two ketonic carbonyl carbon atoms (5c = 203.1 and 214.4) and four instead of twelve carbon signals are observed in the shift range of trigonal carbon nuclei (5c = 133.1, 135.4, 135.6 and 139.4) in the C NMR spectra. To conclude, metabolism involves oxidation of the benzenoid ring. 

In the //broadband decoupled C NMR spectrum, 15 carbon signals can be identified, in agreement with the molecular formula which indicates a sesquiterpene. The DEPT experiments show that the compound contains four quaternary C atoms, three CH units, seven CH units and a CH3... 

All cyclic compounds of types 83-88 have been characterized by their diagnostically simple and C-NMR spectra. Some general regularities can be observed, namely, a small but steady upfield shift in the C-NMR spectra of the carbon signals of the polyacetylenic macrocycle with increasing ring sizes. 

One disadvantage of the APT experiment is that it does not readily allow us to disdnguish between carbon signals with the same phases, i.e., between CH3 and CH carbons or between CH2 and quaternary carbons, although the chemical shifts may provide some discriminatory information. The signal strengths also provide some useful information, since CH3 carbons tend to be more intense than CH carbons, and the CH2 carbons are usually more intense than quaternary carbons due to the greater nuclear Overhauser enhancements on account of the attached protons. 

The broad-band decoupled C-NMR spectrum of ethyl acrylate shows five carbon resonances the DEPT (6 = 135°) spectrum displays only four signals i.e., only the protonated carbons appear, since the quaternary carbonyl carbon signal does not appear in the DEPT spectrum. The CH and CH3 carbons appear with positive amplitudes, and the CHj carbons appear with negative amplitudes. The DEPT (6 = 90°) spectrum displays only the methine carbons. It is therefore possible to distinguish between CH3 carbons from CH carbons. Since the broadband decoupled C spectrum contains all carbons (including quaternary carbons), whereas the DEPT spectra do not show the quaternary carbons, it is possible to differentiate between quaternary carbons from CH, CHj, and CH3 carbons by examining the additional peaks in the broad-band spectrum versus DEPT spectra. The chemical shifts assigned to the various carbons are presented around the structure. 

The selective heteronuclear /-resolved experiment (Bax, 1984) is used to determine heteronuclear long-range coupling constants via a selecdve n pulse that causes splitting of all carbon signals coupled to that proton. 

We have so far looked at the NOE only in a homonuclear manner, but of course there is also a heteronuclear NOE. Theory tells us that when we are dealing with C-H fragments in small molecules, the decoupling of the proton leads to an increase in the carbon signal intensity by up to almost 200% So signals of protonated carbons should be stronger than those of non-proton-ated carbons. 

Because of the NOE and differences in relaxation rates, the intensity differences for carbon signals in a broad-band decoupled spectrum are extremely large, so that quantitative information is not available. 

The integration of the various carbon signals now gives intensity values which are sufficiently accurate for most purposes. 

The theory behind both of these experiments, and in particular the DEPT experiment, is rather complicated, so that we refer you to NMR textbooks for details. The important feature of both is that the carbon signals appear to have been simply broad-band decoupled, but that according to the multiplicity they appear either in positive (normal) phase or in negative phase, according to their multiplicity. 

Organic compounds almost always contain carbon and hydrogen, so that the C,H correlation is a key experiment in every structural determination. This experiment tells us which carbon signal corresponds to which proton signal, and the result for model compound 1 is shown in Fig. 27. 

Note that, apart from the solvent signal, two aromatic carbon signals (at 125 and 147 ppm) show no correlation because they are quaternary (i.e. not bonded to protons). 

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