NMR (Nuclear Magnetic Resonance Spectroscopy)

 useful to map the carbon-hydrogen

network of the molecule
Remember
Many atomic nuclei have a property
called spin-nuclei behaves
as if it is spinning

A spinning nuclei

Creates a tiny local

magnetic field
 1
H and 13C have spin and the nuclei act as a tiny magnet

The tiny magnetic field of the

1H and 13C can either orient
in the same direction or in
opposite

Most nuclei: align in the same

Without external direction as external magnetic field
magnetic field are
randomly oriented
Two energy states are created:
protons which align and protons
which don't align.
Energy states of the nuclei in a magnetic field (Two energy states)

 Have two energy states: The low energy state is when the spin orient in
the same direction while the nuclei with opposite orientation have high energy

 High energy spin state are small in population

 In the absence of magnetic field, the spin states have the same energy
 When light of the correct energy (ΔE= λν) is applied, the
nuclei jump from lower state to higher state and is said
the nuclei is in resonance-nuclear magnetic resonance

High H0 means high resonance frequency required

Magnetic field of NMR spectrometer vary in the range 1.4-21 T

For a given proton, different frequency by using different spectrometer

Complicated as different spectrometer gives different frequency for the same proton
NMR instrument comes with different Bo: some are small magnet and some are
big

 Splitting will be different

 Different frequency (Chemical shift) for same sample that was run with
different spectrometer
Different value for the same molecule!

P-methylbenzyl nitrile

141x06 =2.35 ppm

60,000,000

235x06 =2.35 ppm

100,000,000

 Both values are

independent of the applied
frequency

Chemical shift is the distance between the standard and the sample frequency, which is
dependent on the spectrometer
 P-methylbenzyl nitrile

141x06 =2.35 ppm

60,000,000

235x06 =2.35 ppm

100,000,000

 Both values are independent of the applied

frequency
 Nuclei are shielded to a different degree and hence the
resonance at different frequency because of the electrons
moving around the nuclei and the local magnetic field

Even for the same nuclei within the same nuclei B effective= B applied- B local

Proton NMR of CH3CH2OH

Effect of groups attached to the nuclei in question.

Electron donating groups: High electron density means (shielding effect)

Nuclei feels lower Bo which implies lower energy required for resonance and that
implies lower frequency of resonance and appear at low ppm.

Electron withdrawing groups means low electron density (deshielding effect)

Nuclei feel a higher magnetic field and hence bigger splitting of the spin states and
requiring higher energy (high frequency) and thus appear to higher ppm.
Resonance frequency increases
 Nuclei are shielded to a different degree and hence the
resonance at different frequency because of the electrons
moving around the nuclei and the local magnetic field
B effective= B applied- B local

More deshielded than the other CH3 due to the EW

effect of oxygen

Deshielded, Shielded
Downfield Upfield
1800 HZ with 400 MHZ 1400 HZ with 400 MHZ 1360 HZ with 400 MHZ 12800 HZ with 400 MHZ
spectrometer spectrometer spectrometer spectrometer
singlet

Split into 3 (triplet)

Split into 4 (quartet)
General region of proton resonance
Spin-spin splitting
Coupling constant (J)
Is a measure of the
interaction between two
protons (HZ)
Not
triplet
for Ha
 For C5H10O

DBE= 5+1-10/2
C= Number of Carbon atoms present ; H = Number of =1 means there is
Hydrogen atoms present; X= Number of Halogen atoms present one ring or one
(Cl, Br, I or F); double bond the
N= Number of Nitrogen atoms present; DBE = Double bond molecule
equivalent a.k.a Level of Unsaturation

DBE or double bond equivalent or level of unsaturation is the

number of unsaturations present in a organic molecule. The
term unsaturation mean a double bond or a ring system. For
instance , in benzene there are 3 double bonds and 1 ring which
gives us 4 DBE. Moreover a tripple bond can be regarded as
DBE=2. It must be noted that X is the total number of halogens, 3-pentanone
namely Cl, Br, F and I present in the structure. Presence of an
oxygen atom does not effect the DBE calculation.       
Predict structure
Predict spectra