DETERMINACIÓN DE ESTRUCTURAS ORGÁNICAS

(ORGANIC SPECTROSCOPY)

NMR
Nuclear Magnetic Resonance

Hermenegildo García Gómez

Departamento de Química
Instituto de Tecnología Química
Universidad Politécnica de Valencia
46022 Valencia

E-mail: hgarcia@qim.upv.es
Telephone: +34 96 387 7807 or ext. 78572/73441
Fax: + 34 96 387 7809
1H, 13C, 15N, 19F, 31P
One Level is more populated than the other
Therefore a Resulting Net Magnetization
will be Macroscopically Observable
CW Continous Wave
The Exact Resonance Frequency Varies with the
Chemical and Electronical Environment of the Nucleus –
This is Called the Chemical Shift δ (measured in ppm)
The Chemical Shift is Measured Relative to a Reference or
‘Standard’ ppm ‘parts per million’ δ=(ω-ωref)/ωref * 106
The most common standard for 1H and 13C NMR is

TMS Tetramethylsilan

CH3
CH3 – Si - CH3
CH3
 1H NMR is ‘quantitative’
The intensity is measured as the integral below the
resonance signal. The intensities are proportional to the
number of protons, that contribute to the signal.
Each Particular Arrangement of Nuclei has a Characteristic
Coupling Pattern n Neighbors – (n+1) Lines

A–B

B–A –B

C–B–A
 example

CH2 CH3

No spin-spin coupling is observed if:

1. protons are separated by four or more single bonds, i.e.,
2. H-C-C-C-H
3. protons are equivalent, i.e.,within a CH3 or CH2 group
Pick the molecule that gives rise to the following 1H NMR spectrum!
Assign the Signals to the Correct Hydrogens
(almost) pure
α D Glucose

~50% - 50%
α/β D Glucose
FT NMR
‘Pulse Echo’ NMR
‘Broadband Excitation’
Record ‘Transient
Response’
FID Free Induction Decay

Extract Frequencies by
Fourier Transform to get
NMR Spectrum
More Complex Experiments
Measurement of Relaxation Times (‘Lifetimes’)
Inversion Recovery
?
?
13C NMR Spectroscopy
Sensitivity low: only 1.1% natural abundance
Complicated 1H coupling pattern,
no couplings between 13Cs (due to low abundance)
S/N can be improved by 1H ‘broadband decoupling’ and FT averaging
3J coupling constants contain
HH

Geometrical Information on Torsion Angles

‘Karplus Relation’
Two Dimensional NMR Spectroscopy
A Signal as a function of two times becomes after 2D FT
Spectrum as a function of two frequencies
Usually presented as ‘contour plot’

COSY Correlated SpectroscopY

Cyclosporin A
HN Hα Hβ CH3γ/δ etc
‘complex’ spectra can be resolved using
2dimensional NMR methods