Nuclear Magnetic Resonance (NMR)

The term NMR deals with the change of the spin state of a nuclear magnetic moment of an
atom in a molecule when the nucleus absorbs electromagnetic radiation in a strong magnetic
field.

The motion involved in NMR is nuclear spin. Like electrons the nuclei of certain atoms are
considered to have spin. These nuclei behave as tiny bar magnet. One such nucleus is proton,
the nucleus of ordinary hydrogen. The hydrogen nucleus has a nuclear spin that also can

assume either of two values, designated by quantum numbers + (α) and - (β).

Let us represent hydrogen nuclei in a chemical sample with arrows indicating their
magnetic polarity (north-south). In absence of external magnetic field the nuclear magnetic
poles are oriented randomly. When an external magnetic field is applied, the magnetic poles

of nuclei with spin + (α) are oriented parallel to that magnetic field and those nuclei with

spin - (β) oriented anti parallel to that magnetic field. The + spin state has a lower

energy than - spin state. In addition the protons of two spin states remains in rapid
equilibrium. The spin equilibrium like a chemical equilibrium favours the state with lower
energy. The energy difference between two spin state is vary small. Out of million nuclei,
only about ten more nuclei remain in the lower energy than that of higher energy spin state at
25 oC.

- 1/2 - 1/2
Magnetic field Electromagnetic
∆E
radiation of
energy E0= ∆E
+ 1/2 + 1/2

Randomly oriented
nuclear magnets H0

The energy needed to flip the proton depends on the strength of external magnetic field since
∆E is proportional to H0 and also ∆E= E0 = hν where H0 is external magnetic field. Stronger
is the applied magnetic field greater is the difference between two spin state higher is the
frequency of the radiation needed to resonance.

In a relatively common NMR spectrometer, a magnetic field (H0) of 1.4 tesla is applied.
The energy required corresponds to electromagnetic radiation of 60 MHz.

The only nuclei that exhibit NMR phenomena are those for which the spin quantum
number I is greater than zero. The spin quantum number is associated to mass and atomic
number of the nuclei as shown below.

1 S. Debnath
Mass number Atomic number Spin quantum number

odd Odd or even
, , , ......

even even 0
even odd 1,2,3, ........

Proton (1H) is NMR active since the nucleus of proton (1H) has I = whereas 12C and 18O

have I = 0 and are therefore nonmagnetic i.e. NMR inactive. Other important magnetic nuclei
that have been studied extensively by NMR are 11B, 13C, 14N, 17O, 19F and 31P. 13C is the
second most used nuclei after 1H since all organic compounds contain H and C.

Under the influence of external magnetic field, a magnetic nucleus can take up different
orientations with respect to the field. The number of possible orientation is given by (2I+1).

Therefore the nuclei with spin (1H, 13
C, 19
F etc.) only two orientation are allowed.

Deuterium (2D) and 14N have I = 1 and so it can take up three orientations and hence spectra
becomes complex.

Theory of NMR spectroscopy: In an applied magnetic field, magnetic nuclei like proton
precess at a frequency ν, which is proportional to the strength of applied field. The exact
frequency is given by

ν=

Where H0 = strength of the applied external magnetic field experienced by the proton, γ =
gyromagnetic ratio, being the ratio between nuclear magnetic moment (µ) and the angular
momentum (I). This magnetic moment (µ) is a constant for a particular nucleus.

Thus energy is needed to flip the proton from its lower energy state to higher energy state.
This energy in NMR spectroscopy is supplied by electromagnetic radiation in the radio
frequency region. When this energy absorption occurs at the frequency that causes flip, the
nuclei are said to be in resonance with the electromagnetic radiation. This terminology is the
origin of ‘nuclear magnetic resonance’ and it has no relationship with the delocalisation of π
electrons.

The exact frequency of energy required for resonance depends on the strength of applied
external field and on the isotope being brought into resonance. For 1H 60 MHz frequency of
energy is required for resonance when the field strength is 1.4 tesla. Similarly 600 MHz
frequency of energy is required for resonance when the field strength is 14 tesla.

The NMR spectrometers are designed so that the radio frequency is kept constant (e.g. 60
MHz) and the magnetic field is varied. On tuning the magnetic field to the right strength, the
protons of a particular set in a molecule flip one state to other. In this process the radio
frequency is absorbed and by this flipping of protons a small electric current is generated in
the coil of wire surrounding the sample. After amplification this current display itself a signal
(i.e. peak) in the spectrum. Now, different set of protons remain in different magnetic

2 S. Debnath
environment (due to different electronic environment) causing different energy differences
between their spin orientations which ultimately lead to different peaks in the spectrum.

Chemical Shift: Electrons surrounding a nucleus, under the influence of a magnetic field
will circulate and in doing so they generate their own magnetic field. This is opposed to the
applied field at the nucleus as shown for a proton of a C-H bond in the following picture.

Because the nucleus experiences a weaker magnetic field than that applied externally, it is
said to be shielded. This type of shielding is called diamagnetic shielding. The externally
applied magnetic field H0 is uniform over the entire molecule and therefore it cannot make
different proton non-equivalent. However the magnetic field that is induced by the movement
of electrons over the molecule is not uniform and this situation makes the proton in the
molecule non-equivalent. Thus each nucleus in a different environment experiences a slightly
different local magnetic field due to the circulation of electrons in the neighbouring bonds.
Due to this induced field, the 1H nuclei in the molecule may be shielded or deshielded and
they experience an effective magnetic field that is either less or greater than the external
magnetic field (H0) since induced magnetic field either opposing or reinforcing H0. The
shielded nuclei will need the application of stronger external magnetic field to absorb energy
for spin flipping. The reverse is deshielding. If the induced magnetic field reinforces the
external magnetic field (H0), the strength of external magnetic field (H0) must be reduced for
absorption of energy to occur for spin flipping.

Effects which cause shift to lower field (downfield) are called deshielding whereas the
opposite effect i.e. upfield shift is termed as shielding. In short, a high electron density
shields the nucleus and causes resonance to occur at high field (low δ value) while a low
electron density causes resonance to occur at low field (high δ value).

The upfield and downfield absorption shift the position of NMR spectra arising from
shielding and deshielding by electrons are called chemical shift.

3 S. Debnath
Unit of chemical shift: the unit in which a chemical shift is most conveniently expressed is
parts per million (ppm) of the total applied magnetic field since shielding and deshielding
arise from induced magnetic field. The magnitude of chemical shift is proportional to the
strength of the applied magnetic field. Chemical shift is expressed as a fraction of applied
field i.e. the observed shift is divided by the particular radio frequency used. Thus the
chemical shift is a constant value and independent of the radio frequency and applied
magnetic field.

The standard reference compound which is universally accepted and used is

tetramethylsilane (TMS), (CH3)4Si. It is chosen because i) it is volatile (bp is 26.5oC)
compound and hence valuable samples can be recovered after NMR experiment. ii) it is inert
in most reagents and is soluble in most organic liquids. iii) since TMS has 12 equivalent
proton, a small amount of it is sufficient to get an intense peak. iv) Silicon is more
electropositive than carbon. That’s why the protons of TMS are highly shielded and comes at
very upfield. Most of the other protons in organic compounds comes downfield than that of
TMS protons. So, all the peaks of the sample come in the same direction in the spectra.

The most commonly used scale is δ. The position of TMS signal is taken as 0.00 ppm. Most
chemical shift has δ value between 0-10 ppm. Small δ value represents small downfield shift
whereas large δ value represents large downfield shift.

δ= 10 ppm

( )
= 10 ppm in 60 MHz instrument

( )
= ppm

Problem: Find δ value and observed shift from TMS in Hz of a signal in 100 MHz instrument
if the proton shows chemical shift 160 Hz in a 60 MHz instrument.
Answer. We know
!"#$%&' (!$)* $+ ,-
δ=
&..'$"/ 0$"'/ $+ 1,-

=

2
=

Now since δ value is independent of the external applied magnetic field, δ of the said proton
will remain same in 100 MHz instrument i.e. 8/3.
Now in 100 MHz instrument,
!"#$%&' (!$)* $+ ,-
δ=
&..'$"/ 0$"'/ $+ 1,-
2 3

= (let the chemical shift in Hz is x)
x = 267 Hz
Therefore in 100 MHz instrument the same proton will shift 267 Hz but the δ remains same at
8/3.

4 S. Debnath
NMR signals: NMR signals give us the following information
1) The number of NMR signals tells us how many different kinds of protons are there in
a molecule.
2) The position of signals tells us something about the electronic environment of each
kind of protons.
3) The intensity of the signals tells us how many protons of each kind are there.
4) The splitting of the signal into several peaks tells us the environment of the proton
with respect to each other.
Equivalent and non-equivalent protons: A set of protons with same environment are said
to be equivalent. The protons with different environment are termed as non-equivalent
protons. Equivalent protons in a given molecule absorb at the same applied field whereas
non-equivalent protons absorbs at different applied field and appears as different peaks.
Examples:
NO2
H H H H
1. 2.
All the protons are equivalent
H H H H
All the protons are equivalent NO2

b a
two types of protons, two CH2 protons are equivalent and
3. H3C CH2
three CH3 protons are equivalent. thus the molecule has
Cl two types of protons and hence it will give two signals.

b Ha b Six methyl protons assigned as b are equivalent. Thus

4. H3C C CH3 this molecule has two types of protons and hence it
gives two signals in NMR spectra.
Cl
b H c
H
a Three types of non-equivalent protons are there in this
5. H3C C C Cl molecule; a,b and c. Thus this molecule give three signals.

H H
b H c
H
6. a Four types of non-equivalentprotons are there in this
H3C C C Cl molecule; a,b, c and d. c and d are non-equivalent since
they are diastereotopic protons.Thus this molecule give
Cl H d four signals.

a
CH3
Two types of non-equivalent protons are there in this
H Hb
molecule; a and b. Thus this molecule give two signals.
7.
All nine protons of methyl groups are equivalent. similarly
H3C CH3 three aromatic protons are equivalent.
H
a Two types of non-equivalent protons are there in this
H3C b molecule; a and b. Thus this molecule give two signals.
8. H3C CH2Cl All nine protons of methyl groups are equivalent. Two
H3C methylene protons are equivalent.

5 S. Debnath
c
H Hd Five types of non-equivalentprotons are there in this
molecule; a,b, c, d and e. d and e are non-equivalent since
9. they are diastereotopic protons, cis and trans with respect to ethyl
H3C CH2 H e
a b group. Thus this molecule gives five signals.

Factors affecting the chemical shift:

1) Electronegativity of the attached atom:
The δ values of the protons of methyl halides are as follows.
H3C F H3C Cl H3C Br H3C I
δ 4.26 δ 3.0 δ 2.82 δ 2.16

The chemical shift of the methyl protons of methyl halides are directly proportional to the
electronegativity of the halogen atoms. The electronegativity of halogens increases from
Iodine to Fluorine i.e. F is the most effective element to withdraw (-I) the electron density
from methyl group. Therefore the proton of methyl fluoride is most deshielded than any other
protons in the series and thus their signal is found at most downfield. On the other hand
iodine is least electronegative in the series and hence the signal from methyl iodide protons is
found most upfield.
Similarly we get the following trend

H3C F H3C O H3C N H3C C

signal of protons move downfield

2) Anisotropic Effect:
Like σ electrons, π electrons are also circulated in the presence of external magnetic field to
generate an induced magnetic field. Generally the strength of the magnetic field generated by
π electrons is stronger than that of σ electrons. Thus the presence of π electrons can have a
pronounced effect on the chemical shift of the nearby protons. In case of benzene, alkene and
aldehyde the induced magnetic field generated by moving π electrons increase the external
magnetic field in the region of the protons. For these protons the direction of induced
magnetic field and external magnetic field are same. Thus the protons absorbs energy at
relatively downfield because less external field strength is now needed to bring them into
resonance.

6 S. Debnath
The aldehyde proton shifted downfield both by anisotropic effect and electron withdrawing
effect by carbonyl oxygen (C=O). Due to these combined effect aldehyde protons appear at
far downfield (δ 9-10 ppm).

However, the alkyne protons comes relatively higher field than alkene and hence gives
lower δ values. The alkyne molecule is linear. When external field is applied, the alkyne
group lies parallel to the applied magnetic field since the cylindrical sheath of π electrons are
induced to circulate around the axis as shown below. The induced magnetic field generated
by the movement of π electrons oriented in opposite direction of applied magnetic field

7 S. Debnath
around acetylenic proton. Thus relatively higher field is required to bring them into resonance
than that of alkene protons. That’s why acetylenic protons appears at upfield (lower δ value)
than that of ethylenic protons.

δ values of some common protons:

Protons in the conpoud δ values Protons in the conpoud δ values
(ppm) (ppm)
R CH3 0.9
CH2 2.2 - 3
R 1.2
CH2 R
R O
R 2.5
1.5 R CH
R C H
R O
9 -10
4.5 - 6
R H
H
O
6.5 - 8.5 CH3 3.77
H R O
O
2-3 R 2.5
H3C O
C H
O
1.8 H 10-13
R O
CH3

Certain large ring compounds obey Huckel’s rule i.e. they are planar, cyclic, (4n+2) π
electronic system and hence aromatic. These compounds have two types of protons, some are
shielded and other are deshielded. This type of shielding and deshielding by ring current is
found in some annulenes.

8 S. Debnath
H H
H H

H
H H H H
[18] annulene
H H H H
H

H H
H H

In [18] annulene, the 12 peripheral protons i.e. the protons which are outside of the ring are
strongly deshielded because the induced magnetic field and the external applied magnetic
field are in the same direction in this region. These 12 protons are equivalent and appear at
highly downfield showing δ value 8.9. The protons inside the ring are strongly shielded as the
induced magnetic field and applied magnetic field are in the opposite direction in this region.
These 6 protons are equivalent and appear at highly upfield showing δ value -1.8.

Cis stilbene and trans stilbene can be differentiated by NMR spectroscopy. In cis stilbene
the molecule can not be perfectly planar due to steric effect between two phenyl rings. On the
other hand the trans isomer is perfectly planar due to absence of any steric crowding. Thus
the anisotropic effect of phenyl rings on two vinylic protons is to some extend less in cis
isomer. Thus the δ value of two vinylic protons of cis isomer will be less than that of trans
isomer. In fact δ value of vinylic protons osf cis isomer is 6.49 whereas for trans isomer it is
6.99.
δ 6.49 δ 6.99

H H H

trans stilbene
Cis stilbene

Spin – Spin Coupling (Splitting of peaks): Because of spin-spin coupling, most NMR
spectra don’t show simple peaks rather groups of peaks that tend to cluster about a certain δ
value. Spin –spin coupling usually occurs between the non-equivalent protons in adjacent
atoms. In general if ‘n’ number of non-equivalent protons are affecting the peak of protons on
an adjacent atoms, the peak is split into (n+1) peaks.

Origin of spin –spin coupling: Let us take an example of adjacent carbon atoms carrying a
pair of secondary protons (Ha) and a tertiary proton (Hb) and consider first the absorption by
one of the secondary proton.
Hb Ha

Ha

9 S. Debnath
The magnetic field that proton Ha feels at a particular time is slight increased or decreased by
the spin of neighbouring Hb proton; increased if Hb at that time to be aligned with applied
field or decreased if Hb to be against the applied field. Thus for half of the molecules
absorption by Ha is shifted to slightly downfield and for other half of the molecules the
absorption is shifted slightly upfield. The signal is split into two peaks; a doublet with equal
peak intensity

Ha two magnetic orientation of Hb

signal from Ha in absence of Hb

magnetic moment of Hb split the

signal of Ha into two peaks of
equal intesity

Now the proton Hb is affected by the spin of neighbouring protons Ha but now there are two
equivalent protons whose alignment in the applied field may be four types and two of which
are equivalent at any instant. Proton Hb feels any one of the three fields and its signal is split
into three equally spaced peaks, a triplet with relative intensity 1:2:1.

Hb four magnetic orientation of Ha protons

signal from Hb in absence of Ha

magnetic moment of Ha split the

signal of Hb into three peaks of
intesity 1:2:1
From the above explanation we can say, protons peak split into (n+1) number of peaks if at
the adjacent atom it has ‘n’ number of equivalent protons. Thus a doublet (d) comes from one
adjacent proton, a triplet (t) comes from two adjacent equivalent protons, a quartet (q) comes
from three adjacent equivalent protons and so on. Singlet is indicated by (s). It may not
always be possible to relate the split peaks clearly and these peaks are termed as multiplet
(m).
Peak area relative ratio within the a split peak are doublet, 1:1, triplet, 1:2:1, quartet 1:3:3:1
and so on. This ratio can easily be obtained by Pascal’s triangle as shown below.

10 S. Debnath
Multiplicity Relative intensity of the peak

Singlet 1

Doublet 1 : 1

Triplet 1 : 2 : 1
Quartet 1 : 3 : 3 : 1
Quintet 1 : 4 : 6 : 4 : 1

Sextet 1 : 5 : 10 : 10 : 5 : 1

and so forth

Examples of splitting of peaks of few compounds:

Hb Ha
H H Cl C C Ha
Cl C C Cl Cl Ha
H H

δ (ppm) δ (ppm)

In 1,2 dichloroethane all the four protons are equivalent and hence we get a singlet at
δ 3.8. But in isomeric 1,1 dichloroethane the adjacent carbon atoms bear two different types
of protons. This compound gives two peaks; one at δ 2.01 and other at δ 5.8 with relative
intensities 3:1. The peak at δ 2.01 is due to methyl protons whereas peak at δ 5.8 is due to
methine proton. Proton assigned ‘b’ appears at highly downfield since it attached to a carbon
which bears two electronegative chlorine atoms. Three methyl protons (a) split the signal of
proton ‘b’ into a quartet (q). The intensity inside the quartet peaks is 1:3:3:1. Similarly proton
‘b’ split the proton ‘a’ into a doublet (d) with intensity of the doublet peaks is 1:1.

a
H3C this compound gives two peaks; one at around δ 1 and other
2. b
H3C CH2Br at around δ 3.4 with intensity ratio 9:2. this compound does
not show any splitting since it has no proton on adjacent
H3C atoms. This compound shows two singlet.

11 S. Debnath
a
H3C Absorption by six methyl protons Ha appear upfield and split into a
3. b
CH Br doublet by proton Hb. Absorption by Hb appear at downfield and split
into a septet by six equivalent protons Ha. Doublet and a sextet is the
H3C
characteristic of a isopropyl group.
b
H2
C It gives two peaks at δ 1.7 and other at δ 3.4 at intensity ration 3:2.
a
H3C Br protons 'b' appear at downfield since it is directly attached a carbon
4.
which bears electronegative bromine. Now protons Ha is split by Hb
into a triplet and similarly Hb is split by Ha into a quartet. the
intensity ration of triplet peaks is 1:2:1 and quartet peaks is 1:3:3:1.

Coupling Constant (J): The spacing between the peaks in a resonance multiplet is called
coupling constant between the two protons and is designated as J. The value of J varies with
the environment of the protons and their geometric relationship to each other. The code Jab
means the coupling constant for Ha split by Hb or for for Hb split by Ha. For a pair of coupled
protons the J value is same in each of the two multiplets. The J values are reported as Hertz
and not in δ. This is because the magnitude of coupling constant are not depended upon the
strength of the applied magnetic field and their value in Hertz (Hz) will be same regardless of
the operating frequency of the spectrometer.

Magnitude of some important coupling constant (J):

12 S. Debnath
Jab, Hz Structure Jab, Hz
Structure
Ha
Ha Hb 6-9
8 hz
(for freely rotating Hb
alkyl group)
Ha
1-3
Ha Hb 7-12
this type Hb
of couplings
are called
Hb Ha
13-18 long range
coupling
Ha 0-1

Hb

When two protons couple to each other, they cause splitting of each other’s peaks. The
spacing between the peaks is the same for both protons, and is referred to as the coupling
constant (J). This number is always given in hertz (Hz), and is determined by the following
formula:

J (Hz) = ∆ ppm X instrument frequency

∆ ppm is the difference in ppm of two peaks for a given proton. The instrument frequency is
determined by the strength of the magnet.
For example if the spacing between the peaks of a doublet is 0.05 ppm in 300 MHz
instrument then the coupling constant (J) will be (0.05 X 300) = 15 Hz.

Solvents used in NMR experiment: The common organic solvents with replacement of its
hydrogen by deuterium are generally used as NMR solvent. Most commonly used solvents
are:
D
O O D D
C S CD3OD D2O
CDCl3 D3C CD3
D3C CD3
D D
Chloroform-d Acetone-d6 DMSO-d6 D
Benzene-d6

For deuteriated solvents the isotopic purity should ideally be as high as possible. But since
greater isotopic purity means greater cost, most users compromise their ideals. A small peak
of CHCl3 at δ 7.26 in 99% CDCl3 will cause no difficulty unless an aromatic peak comes in
this δ value and accurate integrals for that proton is needed. Nowadays intentionally
isotopically impure solvent is used since most spectra are now calibrated against the residual
solvent peak. e.g. if δ7.26 is calibrated for CHCl3 in CDCl3 solvent, no TMS is needed.

Spectra of Ethanol: The protons on oxygen and nitrogen differs from the protons on
carbon and spin – spin coupling is not normally observed.

13 S. Debnath
The spectrum of commercially grade sample of ethanol (ethanol with acidic or basic
impurities) shows an upfield signal of three protons as triplet of CH3 group, a quartet signal
of two CH2 protons and a lower field signal for O-H proton as shown below.

This spectra clearly shows that the O-H proton is not involved in the coupling with CH2
protons. Thus CH3 protons appear as a triplet due to coupling with CH2 protons and CH2
protons appear as quartet due to coupling with CH3 protons.

In presence of acidic or basic impurities the protons attached to oxygen of ethanol exchange
rapidly i.e. a particular proton does not reside for a sufficient long time on particular oxygen
to be seen by the neighbouring protons for a nuclear coupling. i.e. no coupling between O-H
proton and CH2 proton is observed in impure ethanol.

acidic or basic
impurities
RA O HA + RB O HB RA O HB + RB O HA

O-H proton of a highly pure ethanol sample appear as a triplet since in pure ethanol this rapid
exchange of proton is largely diminished and hence the O-H proton undergoes coupling with
–CH2 protons. –CH2 protons split into a quartet by coupling with CH3 protons and each line
is further split into a doublet by –O-H protons show below.

14 S. Debnath
Chemically and magnetically equivalent protons:
The two protons are defined as being chemically equivalent if, by virtue of symmetry
within the molecule, their electronic environments are indistinguishable and therefore they
possess the same value of chemical shift.
Two protons are defined as being magnetically equivalent if each couples equally to a
third neighbouring proton, otherwise they are magnetically non-equivalent.
All para substituted derivatives (where two substituents are different) have chemically
equivalent but magnetically different protons.
X
Ha Ha'

Hb Hb'
Y
Here Ha and Ha’ are chemically equivalent since they are in same electronic environment
and hence have the same δ value. Similarly Hb and Hb’ are chemically same. But Ha and Ha’
are magnetically different since the coupling constant of Ha and Ha’ are not same with a third
proton Hb. Similarly Hb and Hb’ are also magnetically different. Due to this different coupling
constant, the spectra becomes complex.
Thus in short, chemical equivalence means simply means chemical shift equivalence,
and magnetic equivalence means coupling equivalence.

NMR spectra of benzene derivative: 1) Theoretically a monosubstituted benzene derivative

has three different protons.
X
Ha Ha

Hb Hb
Hc

In a monosubstituted benzene when the substituent is an alkyl group or some other group
with about same electronegativity having no strong shielding or deshielding, all the aromatic
protons have the same chemical shift and thus behave as equivalent and appears as a singlet.
These are called ‘accidental equivalence’. E.g. the NMR spectra of ethylbenzene

15 S. Debnath
Thus it is easy to understand the singlet nature of five aromatic protons around δ 7.2 in
ethylbenzene. The other protons give the expected chemical shift.

2) A single substituent that is either strongly shielding or deshielding (e.g –COCH3

group in acetophenone or nitro group in nitrobenzene) usually causes the ortho protons to
move lower or higher δ values with respect to the meta or para protons. We generally
observed a two protons complex multiplet and a three protons complex multiplet.

C B
H H

D H C
A
CH3

H H
C B

3) The para disubstituted benzene where two substituents are of different shielding
influences, can give rise to almost simple AB simplicity for the aromatic protons. The spectra
becomes sufficiently simple as to be interpretable by first order approximation. The aromatic
region may be regarded as pair of doublet with equal intensity having two protons in each
peak. e.g. p-chloronitrobenzene gives two doublet in the aromatic region. The protons ortho
to nitro group will be more deshielded due to higher electron withdrawing effect of nitro
group than that of chlorine. P-chloroaniline also gives this type of doulets

16 S. Debnath
4) Compounds with identical para substitutents, whatever their eletronegativity, give
single line spectra because of the molecular symmetry, all the four protons in the ring
are magnetically equivalent. E.g. p-dinitrirobenzene and p-dichlorobenzene give
singlet at δ 8.36 and δ 7.25 respectively.
5) For ortho disubstituted benzene, e.g o-dichlorobenzene the chemically equivalent
protons are not magnetically equivalent
Cl Cl

Ha' Ha

Hb' Hb
Ha and Ha’ are chemically equivalent but magnetically different. Similarly Hb and Hb’ are
chemically equivalent but magnetically different. Coupling constant of Ha and Ha’ will
not be same with a third proton Hb or Hb’. But considerable symmetry is present in the
molecule. In NMR spectra this molecule shows 24 lines though the lines are symmetrical
about the mid-point.

Cl Cl

Ha' Ha

Hb' Hb

17 S. Debnath
Some more examples of NMR spectra:

18 S. Debnath