Nuclear Overhauser enhancement (NOE) allows determination of through-space relationships between protons or nuclei in close proximity. NOE experiments show slightly increased intensity for resonances of nuclei near the irradiated protons. This effect is also seen between different nuclei like protons and carbon-13. Integration of carbon-13 peaks may not be accurate due to variable NOE effects and relaxation times. NOE can help assign peaks by showing enhanced intensity for carbons near irradiated protons.
Nuclear Overhauser enhancement (NOE) allows determination of through-space relationships between protons or nuclei in close proximity. NOE experiments show slightly increased intensity for resonances of nuclei near the irradiated protons. This effect is also seen between different nuclei like protons and carbon-13. Integration of carbon-13 peaks may not be accurate due to variable NOE effects and relaxation times. NOE can help assign peaks by showing enhanced intensity for carbons near irradiated protons.
Nuclear Overhauser enhancement (NOE) allows determination of through-space relationships between protons or nuclei in close proximity. NOE experiments show slightly increased intensity for resonances of nuclei near the irradiated protons. This effect is also seen between different nuclei like protons and carbon-13. Integration of carbon-13 peaks may not be accurate due to variable NOE effects and relaxation times. NOE can help assign peaks by showing enhanced intensity for carbons near irradiated protons.
Nuclear Overhauser enhancement (NOE) allows determination of through-space relationships between protons or nuclei in close proximity. NOE experiments show slightly increased intensity for resonances of nuclei near the irradiated protons. This effect is also seen between different nuclei like protons and carbon-13. Integration of carbon-13 peaks may not be accurate due to variable NOE effects and relaxation times. NOE can help assign peaks by showing enhanced intensity for carbons near irradiated protons.
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Nuclear Over Hauser Enhancement (NOE)
Sometimes, no coupling constant is observed, which can give some valuable information about the stereochemistry/environment.
NOE is one method that allows us to find out the through space relation/which groups in a molecule are close to each other/proximity. (between non-equivalent protons/nuclei)
It is helpful in finding out the groups which are near in space to each other.
In NOE experiments, if protons are in proximity of the irradiated protons would appear as slightly more intense (only few percent) peak in the NMR spectrum. •When a proton-decoupled spectrum is obtained, the intensities of the carbon resonances are increased. This effect is known as the Nuclear Overhauser enhancement (NOE). The NOE is heteronuclear in this case (operating between two different atoms H and C). Hetronuclear effect operates between dissimilar atoms
This can be either positive or negative
•The NOE effect is quite general; it occurs when one of the two different types of atoms is irradiated while the NMR spectrum of the other type is determined. In the proton- decoupled experiment, the carbon-13 nuclei are observed at the same time that the hydrogen nuclei are irradiated.
Enhansement is positive if the proton is directly attached to the “C”
•Why does this type of experiment cause an enhancement in the observed signals? When the hydrogen nuclei are irradiated, the number of nuclei in the higher energy "spin-opposed" state is increased. The carbon atoms to which these protons are attached adjust their equilibrium distribution to increase the population of carbon atoms in the lower energy "spin-aligned" state due to the interaction of spin dipoles. This larger population of carbon atoms in the lower spin state results in a larger number of nuclei that can be detected, and therefore an increased signal.
•Not all carbon-13 signals will be enhanced to the same extent. Generally, the total NOE for a given carbon increases as the the number of attached protons increases .
CH3>CH2>CH>>C
• NOE effect can be used to verify peak assignments.
The NOE effect is distance dependent. The closer a hydrogen atom is to a particular carbon atom, the larger the enhancement for that carbon atoms signal. As an example, consider dimethyl formamide. Because of resonance, the two methyl groups attached to nitrogen are not equivalent (anti 31.1ppm, syn 36.2 ppm). Irradiation of the aldehyde hydrogen will cause an enhancement of the syn methyl group and verify the identity of that peak. Problems with integration in 13C – Spectra
Integration of carbon – 13 peaks will not always provide an accurate count of each type of carbon atom in the structure for two reasons:
a.) NOE is not the same for every carbon. When proton decoupling is used, the intensity of a carbon peak is NOE enhanced by hydrogens directly attached or found close by.
b.) Relaxation time is not the same for all carbons: One problem experienced in carbon-13 spectroscopy is that the carbon-13 nuclei have to "relax" back to the ground state before the next scan is taken. Highly substituted carbon nuclei (tertiary and quaternary carbon atoms) relax very slowly (on the order of several minutes). If the delay time between scans is too short, not all of these nuclei will relax, and therefore will not be detected. This problem can be overcome by setting quite a long delay time between scans. However, this procedure will usually make the acquisition of a carbon-13 spectrum take several hours. A compromise is usually made: the delay time is set to about 30 seconds (this will allow most nuclei to relax), and the spectroscopist understands that integration of the peaks will not be possible.
Some Sample Spectra – Equivalent Carbons
Equivalent 13C atoms appear at the same chemical shift value.
The proton-decoupled 13C NMR spectrum of 2,2-dimethylbutane The proton –decoupled 13C NMR of cyclohexanol Compound with Aromatic Rings :
Compound with carbon-carbon double bonds or aromatic rings give rise to chemical shift in the range from 100- 175
Monosubstituted benzene ring shows :
four peaks in the aromatic carbon area of a proton – decoupled 13 C spectrum since the ortho and meta are doubled by symmertry.
carbon with no protons attached, the ipso carbon, has a very weak peak due to a long relaxation time and a weak NOE.
Two larger peaks for the doubled ortho and meta carbonsand a medium sized peak for the para carbon. Depending on the mode of substitution , a symmetrically disubstituted benzene ring can show two, three, or four peaks in the proton-decoupled 13C spectrum. Most other polysubstitution patterns on benzene ring yield six different peaks in the proton decoupled 13C NMR , one for each carbon. However when identical substituents are present, watch the plane of symmetry that may reduce the number of peaks.
Carbon – 13 NMR Solvents – Heteronuclear coupling of carbon to Deuterium
•No peak for the deuterated solvent in 1H-NMR
•Deuterated solvents show in 13C NMR since they have carbon atoms. Chloroform-d CDCl3:
•Give 3- peak multiplet in 13C spectrum
•All three lines in the triplet have approximately same intensity (1:1:1)
•D spin value I = 1, Number of spin states = 2I + 1 = 3 (+1, 0, -1)
•The carbon atom could see the Deuterium in any of the three states with the same probability. Hence 3 lines with equal intensity .
•Multiplicity rule.Multiplicity = 2nI + 1 n = number of nuclei
I = spin of that type
Dimethyl Sulfoxide – d6 CD3 SOCD3
•Signal in 13C spectrum appears as septet
•Relative intensity of the seven lines 1:3:6:7:6:3:1
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 2: Gravitational and Inertial Control, #2
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 2: Gravitational and Inertial Control, #2
