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Chemical shift - Inductive effects in alkanes -Anisotropy -Inductive effects in alkenes -δ values...
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Transcript of Chemical shift - Inductive effects in alkanes -Anisotropy -Inductive effects in alkenes -δ values...
Chemical shift
- Inductive effects in alkanes-Anisotropy-Inductive effects in alkenes-δ values for different groups-13C chemical shift in different groups-Solvents-Rotation
Inductive effects in alkanes
Inductive effect and chemical shift
δ-values: Hybridization effects
δ values: sp3 < sp2 < sp
Carbons with sp2 hybridization hold the electrons closer to the nucelus than do sp3 carbons. This leadsto less shielding of the attached protons. Thus vinyl hydrogens have higher chemical shifts than alifatic hydrogens
Acetylenic protons (sp-hybridized C) would be expected to have a higher chemical shift than vinyl protons.
This is not true due to magnetic anistropy
Magnetic anisotropy
A magnetic field with non-uniform density or non-sperical distribution
The presence of π-electrons in a magnetic field sets up a small, localcurrent and an anisotropic magnetic field in its close proximity
Applies only to atoms with sp2 and sp hybridization
Inductive effects i alkenes
Alkynes
Chemical shift overview
Alkaner: δ-values
Alkener: δ values
Benzene derivatives: δ values
13C-Carbonyl chemical shift
13C-cyclic compounds
13C-Arenes
Cyclic alkenes
N-H and O-H chemical shift
δ: very dependent on solvent and concentration
R-O-H: 0,5 < δ < 4,5
R-N-H: 1,0 < δ < 5,0
Carboxylic acids (usually dimeric): 10 < δ 12
Enols: 12 < 18
In deuterated protic solvents: N-H, O-H and S-H can rapidly exchangeD with solvent and the 1H-NMR signal disappears.
Solvents
Non polar solvents: Small effect on chemical shift
Polart + benzene : significant effect on chemical shift
Slow rotation