Recap

Chemical shifts are reported on the scale

= ( o) x 106
o
= o+ (o/106)
o is the resonance frequency of the standard
> 0 deshielded w.r.to TMS protons
< 0 shielded w.r.to TMS protons
TMS has +ve value
and taken as reference.
Compared to that
majority of the protons
have -ve value and
therefore would
resonate at higher
frequencies that lead to
downfield chemical
shift.
 Summary of Recap
Actual field experienced by a proton Bloc= Badd
+ B = (1- ) B
TMS has +ve value and taken as reference
(=0). Compared to that in majority of the cases
protons have -ve value and therefore would
resonate at higher frequencies that lead to
downfield chemical shift with respect to TMS.
Protons attached with electronegative
elements come at higher . In other words, more
dehielding results in more chemical shift.
The decreases with the distance of
electronegative atoms
Homotopic hydrogens have same chemical shift
 Equivalent (Homotopic) Hydrogens

Equivalent hydrogens: Hydrogens that

have the same chemical environment.
A molecule with 1 set of equivalent
hydrogens gives 1 NMR signal.

O H3 C CH3
CH3 CCH3 ClCH2 CH2 Cl C C
H3 C CH3
Propanone 1,2-Dichloro- Cyclopentane 2,3-Dimethyl-
(Acetone) ethane 2-butene
 Equivalent Hydrogens
A molecule with 2 or more sets of
equivalent hydrogens gives a different
NMR signal for each set.
Cl Cl CH3
CH3 CHCl O C C
H H
1,1-Dichloro- Cyclopent- (Z)-1-Chloro- Cyclohexene
ethane anone propene (3 signals)
(2 signals) (2 signals) (3 signals)
 Chemical Equivalence
How many signals in 1H NMR spectrum?
CH3

1 3 5 4
2

O
O O
O

4
6
 1
H NMR CHEMICAL SHIFT RANGES

Proton IR resonance NMR resonance

environment frequency (cm-1) frequency ()
Alkane, -CCH ~ 2900 3000 0 1.5
Alkene, -C=CH ~ 3000 3100 4.5 6.5
Alkyne, -CCH ~ 3100 3300 1.5 3

Note the variation in the trend for NMR. Reason?

Diamagnetic anisotropy
DUE TO THE PRESENCE OF BONDS
Anisotropic in Greek means different in different directions

The presence of a nearby bond or system greatly affects the

chemical shift.

Benzene rings have the

greatest effect.

valence electrons
shield the nucleus
from the full effect
of the applied field
Aromatic Protons, = 7- 8
shield
ed

deshield
ed
ANISOTROPIC FIELD IN AN ALKENE
The double bond is oriented perpendicular to the
external field with electrons likewise circulating 4.5-6.5
at right angles
protons are
Deshielded deshielded

fields add
H H shifted
downfield

C=C
H H
secondary
magnetic
(anisotropic)
Bo field lines
 ANISOTROPIC FIELD IN AN ALKYNE
For alkynes the most effective orientation is the external field in
parallel with electrons circulation around the triple bond

1.5 3.5

secondary
magnetic
Shielded hydrogens
(anisotropic)
fields subtract are shielded
field
Aldehyde Proton, 9-10

Electronegative
oxygen atom
 The fine structure
The splitting of the groups of resonances into
individual lines is called fine structure.
Relative areas of signals are proportional to the
number of H giving rise to each signal,
(n+1) Rule
 Signal Splitting: Spin-Spin Coupling
The signal from a given proton will be split by the
effect of magnetic fields associated with protons on
adjacent carbons
Characteristic peak patterns result from signal splitting
that are related to the number of protons on adjacent
carbons
Signal splitting is not observed between homotopic or
enantiotopic protons
 Signal Splitting: Spin-Spin Coupling
The effect of signal splitting is greatest between atoms
separated by 3 or fewer bonds
Signal splitting occurs only when two sets of protons
have different chemical shifts (i.e., are not chemical
shift equivalent)

Two singlet
signals
 Signal Splitting: Spin-Spin Coupling

Each magnetic nucleus contributes to the local

magnetic field of other nuclei.
Spin-spin coupling constant J (Hz) is
independent of the applied magnetic field.

Consider, AB where A and B are spin nuclei

 THE CHEMICAL SHIFT OF PROTON HA IS
AFFECTED BY THE SPIN OF ITS NEIGHBOURS
aligned with Bo opposed to Bo
50 % of +1/2 -1/2 50 % of
molecules molecules
H HA H HA
C C C C

Bo
downfield upfield
neighbour aligned neighbour opposed
At any given time about half of the molecules in solution will
have spin +1/2 and the other half will have spin -1/2.
 SPIN ARRANGEMENTS
One neighbour One neighbour
n+1 = 2 n+1 = 2
doublet doublet

H H H H
C C C C

The resonance positions (splitting) of a given hydrogen is

affected by the possible spins of its neighbour.