Basic theory of NMR spectroscopy

Nuclear magnetic resonance spectroscopy depends on the absorption of energy in the

radiofrequency region when the nucleus of an atom is excited from its lowest energy spin
state to the next higher one. Nuclear magnetic resonance spectroscopy gives us information
about the number and types of atoms in a molecule: for example, about hydrogens using 1H-
NMR spectroscopy, about carbons using 13C-NMR spectroscopy. It also gives us substantial
information about the connectivity of the atoms.
Magnetic property of nuclei: A nucleus with an odd number of protons and/or an odd
number of neutrons possesses a quantum mechanical property called nuclear spin.
Nuclear spin: The Nuclear Spin is different from the electron spin. The nuclear spin
represents the total angular momentum of the nucleus. It is represented by symbol, I. The
nucleus is composed of neutrons and protons and they have intrinsic angular momentum. The
total angular momentum of a nucleus is represented by the symbol-I and we call it
"nuclear spin".
For electrons in atoms we make a clear distinction between spin angular momentum and orbital
angular momentum, and then combine them to give the total angular momentum. But nuclei
often act as if they are a single entity with intrinsic angular momentum I.
A magnetic moment is associated with nuclear spin. The magnetic moment is much smaller
than that of the electron. For the combination of neutrons and protons into nuclei, the situation
becomes complicated. All nuclei with even atomic number and even mass number have
nuclear spin I=0.
Across the entire periodic table, nuclear spin values ranging from I = 0 to I = 8 in ½-unit
increments can be found. Protons and neutrons each have net spins of ½, but this derives
from the elementary quarks and gluons of which they are composed. As a result of this
complexity, no simple formula exists to predict I based on the number of protons and neutrons
within an atomic nucleus. Nevertheless, there are some general observations.
1) Even/Even: Nuclei containing even numbers of protons and neutrons have I = 0 and
therefore cannot undergo NMR. Examples include 4He,12C,16O and 32S. These nuclei are NMR-
inactive.
2) Odd/Odd: Nuclei with odd numbers of both protons and neutrons (even mass number and
odd atomic number) have spin quantum numbers that are positive integers. Examples
include14N (I=1),2H (deuterium, I=1), and10B (I=3).
3) All others: The remaining nuclei (odd/even and even/odd) all have spins that are half
integral. Examples include 1H (I=½), 17O (I=5/2), 19F (I=½), 23Na (I=3/2), and 31P (I=½).
Every element in the periodic table has at least one isotope with I > 0. For odd-atomic
number elements the isotope with highest natural abundance has I > 0. For even-atomic number
elements, the principal isotope will nearly always have I=0, but there will be one or more less
abundant isotopes that are NMR-active.

Page-1
Bas
sic theo
ory of NM
MR specttroscopy
Maass Atomic I Examplle
number number
1
Od
dd Odd Half in
nteger (1/2),1H3(1/2),7N15(1/2),
1H ( 19
9F (11/2),
31
1 P (1/2) etc.
15 e
13 17
Oddd Even Half in
nteger 6C (1 1/2), 8O (55/2) etc.
2 14 10
Eveen Odd Inteeger 1H (1), 7N (1),5B (3) etc.
12 16
Eveen Even Zerro 6C , 8O etc.
e
A spinning
s p
proton caan be view wed as a rotating sphere off charge, which geenerates a
maggnetic fielld along the
t axis of o rotationn. The maagnetic mooment of a spinningg proton iss
simiilar to the magnetic
m field
f produuced by a bar
b magnet.

Eachh nucleuss having I > 0, haave characcteristic magnetic

m m
moment. N
Number o possiblee
of
orieentations of
o a magneetic nucleu
us in preseence of a uniform
u m
magnetic fiield = (2I+
+1).

Pro oblem: Which of th

he followin R active: 1H
ng nuclei are NMR H, 2H, 12
C
C, 13
C, 15
N
N, 17
O, 18
O
O,
19
F, 31P, 37Cl?
Anss: For a nuucleus to bee NMR acttive it musst contain odd
o numbeer of protonn and/ or odd
o numberr
of neutron.
n If both
b the nu
umbers aree even, the nucleus iss NMR inaactive.
1
H: number off proton = 1(odd); nuumber of neeutron = 0;; NMR acttive
2
H: number off proton = 1(odd); nuumber of neeutron = 1((odd); NM
MR active
12
C: number of
o proton = 6(even); number
n of neutron = 6(even); NMR
N inactiive
13
C: number of
o proton = 6(even); number
n of neutron = 7(odd); NM
MR active
15
N:: number of
o proton = 7(odd); nuumber of neutron
n = 8(even);
8 NM
MR activee
17
O:: number of
o proton = 8(even); number
n of neutron = 9(odd); NM
MR activee

Page-22
Basic theory of NMR spectroscopy
18
O: number of proton = 8(even); number of neutron = 10(even); NMR inactive
19
F: number of proton = 9(odd); number of neutron = 10(even); NMR active
31
P: number of proton = 15(odd); number of neutron = 16(even); NMR active
37
Cl: number of proton = 17(odd); number of neutron = 20(even); NMR active
Problem: Which of the following is/are not NMR active: 12C, 2H, 19F? (CU 2004)

Problem: Comment on NMR-activity of the following nuclei: 14N, 2D. (KU 2011)

Problem: Which one is NMR active: 12C; 2H? (KU 2013)

Problem: Give example of two NMR active nuclei. (CU 2021 CBCS)

Problem: Explain why 12C is NMR inactive. (CU 2022 CBCS)

Precessional motion: When placed in a magnetic field, charged particles will precess about
the magnetic field. In NMR, the magnetic nucleus, exhibits precessional motion at a
characteristic frequency known as the Larmor Frequency. The Larmor frequency is specific
to each nucleus.
Atomic nuclei with odd atomic number/ mass number contain intrinsic spin. The nucleus will
spin along an axis (which is the direction of the angular momentum for the nucleus). The spin
angular momnetum of the nucleus is given the relation = γ I.
Where, μ is the magnetic moment and γ is a proportionality constant known as the
gyromagnetic ratio. This constant may be positive or negative, depending on if the nucleus
precesses clockwise or anticlockwise, respectively. The frequency of precession is known as
the Larmor frequency: ν0 = γB0
ν0 = Larmor frequency B0 = Strength of external magnetic field

Page-3
Bas
sic theo
ory of NM
MR specttroscopy

Effeect of extternal ma agnetic fiield on th he orienta ation of proton:

p A proton haas two spinn
statees with quuantum nu umbers of +1/2 and -1/2. In absence
a off any exteernal maggnetic field d
therre is no difference
d e in energgy betweeen these two t nuclear spins states. Hoowever, inn
pressence of ann external magnetic field,
f this degeneracyy is lost. Some nucclei are aliigned with h
the magnetic field and some are aligned aggainst it. Consequen
C ntly, they have
h differeent energyy.
In presence
p off an extern
nal magnettic field B0, the statee in whichh the magn netic mom ment of thee
nuccleus is aliggned with B0 is loweer in energgy than thee one in whhich it oppooses B0.

By convention, nuclei with

w spin designateed as +1/2 are aligned with th he applied
d magneticc
field
d and are in the low
wer energy state (orr α-state) and
a nucleii with spinn designatted as -1/22
are aligned against
a thee applied magneticc field and he higher energy state (or β-
d are in th
statee).

Page-44
Basic theory of NMR spectroscopy
Energy
‐spin state

Energy differnece =  E
h B
E = * * o
2
 ‐spin state h is Plank's constant
 is known as gyromagnetic
ratio, its value depends on
External magnetic field Bo the particular nucleus.
The value of ΔE depends on the strength of the external magnetic field.
E'
E


E E'
No external
magnetic field
E
E '

Increasing external magnetic field

When the lower energy state is more highly populated than the higher one absorption of
electromagnetic radiation is possible.
Very strong magnetic fields are required to achieve the separation necessary to give a detectable
signal. A magnetic field of 4.7 T, which is about 100,000 times stronger than earth’s
magnetic field, separates the two spin states of 1H by only 8 10-5 kJ mol-1 (1.9 10 -5 kcal
mol-1). In this connection it may be informed that the strength of earth’s magnetic field is 0.57
Gauss.
The resonance frequencies of most nuclei are sufficiently different that an NMR experiment is
sensitive only to a particular isotope of a single element. The frequency for 1H is 200 MHz
at 4.7 T, but that of 13C is 50.4 MHz.
Thus, when recording the NMR spectrum of an organic compound, we see signals only for 1H
or 13C, but not both; 1H and 13C NMR spectra are recorded in separate experiments .
At applied field strength of 7.05 T, the difference in energy between nuclear spin states for
1
H is approximately 0.120 J (0.0286 cal)/mol (corresponding to electromagnetic radiation
of 300 MHz). At 7.05 T, the energy difference in nuclear spin states for 13C nuclei is
approximately 0.030 J (0.00715 cal) mol-1 (corresponding to radiation of 75 MHz).
Energies for transitions between vibrational energy levels observed in infrared (IR)
spectroscopy are 8 to 63 kJ (2 to 15 kcal)/mol. Those between electronic energy levels in

Page-5
Basic theory of NMR spectroscopy
ultraviolet-visible spectroscopy are 167 to 585 kJ (40 to 140 kcal)/mol. Nuclear transitions
involve only small energies.

Page-6
Chemical shift
It is clear that 1H and 13C nuclei absorb at different frequency. What about different 1Hs and
different 13Cs present in a molecule? We might expect that all 1H (and 13C) nuclei should
absorb at the same frequency as the gyromagnetic ratio is same for all 1Hs (and all 13Cs).
Fortunately the situation is not so simple. Different types of 1Hs (and 13Cs) absorb at different
frequencies. Practically the magnetic field experienced by different 1H nuclei (and different
13
C nuclei) is different (i.e. not exactly equal to the applied magnetic field).
Reason for the difference: A key physical principle for NMR is that circulating electrons
induce a magnetic field. Organic molecules contain covalently bonded nuclei. Each nucleus is
surrounded by electrons (σ and π electrons), in a magnetic field these electrons set up a tiny
magnetic field.
When a nucleus surrounded by electrons is exposed to a magnetic field of strength B0,
these electrons move in such a way as to generate a small local magnetic field, Blocal, which
may oppose or reinforce B0. As a consequence, the total field strength near the hydrogen
nucleus is altered.
If induced field (Blocal) is aligned against the applied magnetic field, the Hs experience a
resultant lower magnetic field (compared to the applied magnetic field). Such Hs are said to
be shielded and the effect is known as shielding (or diamagnetic shielding).
When induced magnetic field reinforces the applied field, the Hs experience a resultant
higher magnetic field (compared to the applied magnetic field). Such Hs are said to be
deshielded and the effect is known as deshielding.
The more shielded is a H the higher applied magnetic field would be required to achieve
resonance and produce a signal. Shielding causes a shift of resonance frequency to higher
values of the applied field; this is termed as upfield shift.
Deshielding causes a shift of resonance frequency to lower values of the applied field; this
is termed as downfield shift.
The difference in resonance frequencies caused by differing amounts of shielding is called
chemical shift. This is where the real power of NMR lies. The chemical shifts of various
protons in a molecule can be different and are characteristic of particular structural features.
The differences in resonance frequencies among the various hydrogen nuclei within a
molecule is due to shielding-deshielding are generally very small.
Example: The difference between the resonance frequencies of hydrogens in chloromethane
(CH3Cl) compared with those in fluoromethane (CH3F) under an applied field of 7.05 T (i.e the
operating frequency is 300MHz) is only 360 Hz.
The difference in resonance frequencies between these two sets of hydrogens is very small
compared with the irradiating frequency. It is expressed in p.p.m. unit.
. . . .

Page-1
Chemical shift
Instead of measuring chemical shifts in absolute terms, it is customary to measure the
resonance frequencies of individual nuclei relative to the resonance frequency of nuclei in a
reference compound.
The reference compound now universally accepted for 1H-NMR and 13C-NMR spectroscopy is
tetramethylsilane (CH3)4Si or TMS, which is assigned a chemical shift of 0.00 ppm by
convention.
CH3

H3 C Si
CH3
H3 C
Tetra methyl silane (TMS)
Rather than actually referring to the strength of the magnetic field we usually refer to its
operating frequency. A 9.4 T NMR machine is referred to as a 400 MHz spectrometer. In
this strength field at 400 MHz the protons in the reference sample resonate (a 4.7 T NMR
machine is referred to as 200 MHz spectrometer; a 7.04 T NMR machine is referred to as 300
MHz spectrometer etc.).
Other nuclei, for example 13C would resonate at a different frequency, but the field strength is
quoted in terms of the proton operating frequency.
The chemical shift (δ): When a 300 MHz spectrometer is used, absorption of most Hs fall
within a range of 3000 Hz. Rather than recording the exact frequency we measure it
relative to a standard compound TMS. The signals for the Hs of 2,2-dimethyl-1-propanol
are reported as being located 266, 541, and 978 Hz higher from the Hs of TMS.
A problem with these numbers is that they vary with the strength of the applied magnetic
field. Because field strength and resonance frequency are directly proportional. To make it
easier the difference in frequency w.r.t TMS is divided by the frequency of the spectrometer.
This procedure yields a field-independent number, the chemical shift δ.
Definition of chemical shift (δ): The difference in absorption position of a particular proton
in a sample with respect to that of the proton of a reference compound (e.g. TMS) is expressed
by the term ‘Chemical shift’. The chemical shift δ (in p.p.m.) is defined as:
Position of signal (Hz) - Position of TMS peak (Hz)
 (p.p.m) =
Operating frequency of the spectrometer in MHz
Problem: The OH signal of benzyl alcohol appears at 144 Hz higher frequency than TMS
in a 60MHz spectrometer. How many δ-units does it correspond to?
Position of signal (Hz) - Position of TMS peak (Hz) 144 = 2.4
Ans:  (p.p.m) = =
Operating frequency of the spectrometer in MHz 60

NOTE: Chemical shift () value is independent of field strength.

Page-2
Chemical shift
Problem: The signal for >CH2 Hs of benzyl alcohol appears at δ = 4.6. Calculate the
difference in frequency (Hz) between this and the TMS signal in a 300 MHz NMR
machine and 400 MHz NMR machine.

Ans:  (p.p.m) = Position of signal (Hz) - Position of TMS peak (Hz) = 4.6
Operating frequency of the spectrometer in MHz
In 300 MHz machinePosition of signal (Hz) - Position of TMS peak (Hz) =4.6 X 300= 1380 Hz
In 400 MHz machinePosition of signal (Hz) - Position of TMS peak (Hz) =4.6 X 400= 1840 Hz
Problem: How many hertz does 1 p.p.m correspond to in an instrument recording proton
spectrum at 500 MHz?
Ans: Let the difference in frequency from TMS signal = ν Hz.

= 1,  = 500 Hz
500
Problem: Define chemical shift and explain the terms: (i) shielding (ii) deshielding (iii)
downfield shift (iv) upfield shift in NMR spectroscopy.
Ans: Definition of chemical shift (δ): The difference in absorption position of a particular
proton with respect to that of the proton of a reference compound (e.g. TMS) is expressed by
the term ‘Chemical shift’.
The chemical shift (δ in p.p.m.) is defined as:
Position of signal (Hz) - Position of TMS peak (Hz)
 (p.p.m) =
Operating frequency of the spectrometer in MHz
In presence of a strong external magnetic field, the magnetic field experienced by different 1H
nuclei (and different 13C nuclei) present in a molecule is different (i.e. not exactly equal to the
applied magnetic field). Organic molecules contain covalently bonded nuclei, and the electrons
in these bonds affect nuclear magnetic resonance absorptions. Each nucleus is surrounded by
electrons (σ and π electrons), in a magnetic field these electrons set up a tiny electric current.
This electric current generates a small local magnetic field, Blocal, which may oppose or
reinforce B0. As a consequence, the total field strength near the hydrogen nucleus is altered.
If induced field is aligned against the applied magnetic field, the Hs experience a resultant
lower magnetic field (compared to the applied magnetic field). Such Hs are said to be shielded
and the effect is known as shielding (or diamagnetic shielding).
When induced magnetic field reinforces the applied field, the Hs experience a resultant higher
magnetic field (compared to the applied magnetic field). Such Hs are said to be deshielded and
the effect is known as deshielding.
The more shielded is a H the higher applied magnetic field would be required to achieve
resonance and produce a signal. Shielding causes a shift of resonance frequency to higher
values of the applied field; this is termed as upfield shift.

Page-3
Chemical shift
Deshielding causes a shift of resonance frequency to lower values of the applied field; this is
termed as downfield shift.
The difference in resonance frequencies caused by differing amounts of shielding is called
chemical shift. This is where the real power of NMR lies. The chemical shifts of various
protons in a molecule can be different and are characteristic of particular structural features.
Problem: Why TMS is used as a reference compound in NMR spectroscopy?
Ans: There are several advantages of using TMS:

Problem: Which compound is used as internal standard for recording 1HNMR spectra of
water soluble compounds in D2O? (KU 2021 CBCS)
Problem: Find the δ-value of a signal if the observed shift of that signal from TMS is 162
Hz in 60 MHz instrument. (CU 2015, 2021)
Problem: Define chemical shift. (KU 2010)

Problem: Why the unit of chemical shift is dimensionless? (KU 2021 CBCS)
Hint: Chemical shift is ratio of two frequency terms.
Problem: Why TMS protons appear upfield in NMR? (KU 2021 CBCS)
Problem: Define chemical shift and explain the terms: (i) downfield and (ii) upfield shifts
as used in NMR spectroscopy. Explain why TMS is used as a reference compound. (CU
2004)

Page-4
Chemical shift
Problem: Explain the term 'deshielding' in 1H-NMR spectroscopy. (KU 2012)

Problem: Why TMS is used as reference compound for 1HNMR spectrum? (CU 2009,
2013, 2020, 2021 CBCS, 2022 CBCS)
International convention of representation of NMR-spectrum
(i) An NMR spectrum is always plotted with the reference (e.g. TMS) at the right hand side at
low frequency (δ = 0). Frequency (and δ value) increases on the left hand side and decreases on
the right hand side. Absorption due to most Hs in organic compounds occurs within a range
of 10 ppm of the operating frequency.
3000 2700 2400 2100 1800 1500 1200 900 600 300 0  Hz
10 9 8 7 6 5 4 3 2 1 0  ppm
NMR scale at 300 MHz

Higher frequency Lower frequency

Less shielding More shielding
Deshielded Shielded

6000 5400 4800 4200 3600 3000 2400 1800 1200 600 0  Hz
10 9 8 7 6 5 4 3 2 1 0  ppm
NMR scale at 600 MHz
(ii) If a signal is shifted toward the left on the spectrum (i.e. larger chemical shift), we say
that it is shifted downfield. A downfield shift corresponds to decreased shielding around a
nucleus, that is, deshielding. If a signal is shifted toward the right (i.e. smaller chemical shift),
we say that it is shifted upfield and corresponds to increased shielding around a nucleus.
Deshielded Hs are more exposed to the applied field than shielded protons. They absorb at
higher frequency.

Page-5
Chemical shift
Number of signals in 1H-NMR spectrum: chemically non equivalent hydrogens: The
number of signals in a 1HNMR spectrum indicates the number of different kinds of protons
(protons in different electronic environments).
Protons that belong to identical electronic environments are called chemically equivalent,
and they will produce only one signal. The following compounds contain only one type of
hydrogen. They show one signal for hydrogen.
O H
O H
H 3C CH3
H3 C C CH3 O
C C C CMe3
H3 C CH3 O 2N NO2 Me3C
H3 C CH3
CH3 CH3 H 3C CH3
H H
Protons that have different chemical shifts are said to be chemical-shift nonequivalent (or
chemically nonequivalent). A separate NMR signal is given for each chemically non-
equivalent proton in a substance. Two protons are chemically equivalent if they can be
interchanged via a symmetry operation: rotation or reflection.
Homotopic and enantiotopic protons are chemically equivalent. Diastereotopic and
constitutionally heterotopic protons are chemically non-equivalent.
CH3-CH2-CH3 Contains two sets of chemically non-equivalent Hs
CH3-CH2-O-CH3 Contains three sets of chemically non-equivalent Hs
O
Contains two sets of chemically non-equivalent Hs
H3CH2C CH2CH3
O
H2
H 3C C Contains two sets of chemically non-equivalent Hs
C CH3
H2
O
H
H CH3
Contains two sets of chemically non-equivalent Hs
H3 C H
H
O
H3C setstypes of chemically non-equivalent Hs
CH3
Ha Hb

Enantiotopic Hs; same chemical shift

Page-6
Chemical shift
OH
H
H 3C Total six sets of chemically non-equivalent Hs
CH3
Ha Hb

Diastereotopic Hs; different chemical shift

Problem: How can you distinguish the following compounds by 1H-NMR spectroscopy?

(i) Ortho nitro aniline and para nitro aniline (CU 2001) (ii) para dichloro benzene and
ortho dichloro benzene (CU 2006)
Cl O
Cl O
(iii) and (CU 2010) (iv) and (CU 2007)
Cl Cl O O

(v) H3CH2CC CH and H3CC CCH3 (CU 2011)

NH2
Ans: Ha NO2
(i) ortho nitro aniline contains 4-types of aromatic Hs. They
would appear as a multiplet.
Hb Hd
Hc
NH2
Ha Ha
para nitro aniline contains 2-types of aromatic Hs. Both of them would appear
as a distorted doublet.
Hb Hb
NO2
Cl
Ha Ha
(ii) para dichloro benzene contains 1-type of aromatic Hs.
Ha Ha
Cl
Cl
Ha Cl
ortho dichloro benzene contains 2-type of aromatic Hs. Both Ha and Hb would
appear as dd.
Hb Ha
Hb
Cl
Hb Ha meta dichloro benzene contains 3-type of aromatic Hs. Both H would appear as
a
dd. Hb and Hc would appear as a multiplet.
HC Cl
Hb

Page-7
Chemical shift
Ha O Ha
(iv) Contains one type of H which would appear as 4-H singlet.
Ha O Ha
Ha O Hc Contains three types of Hs. Ha would appear as 3-H doublet. Hb
Ha Hc would appear as 1-H quartet. H would appear as 4-H singlet.
Hc c
Ha Hb O Hc

(v) H3CH2CC CH This compound contains three types of Hs. Ha-would appear as a 3-H
triplet, Hb as 2-H quartet and Hc as 1-H singlet.
Ha Hb Hc

H3CC CCH3 This compound contains only one type of H. They appear as a 6-H singlet.

Ha

Page-8
Factors influencing chemical shifts
The chemical shift for a signal in a 1H-NMR spectrum can give valuable information about the
type of hydrogens giving rise to that signal. Hydrogens on methyl groups bonded to sp3-
hybridized carbons give signals near δ = 0.8 to 1.0. Hydrogens on methyl groups bonded
to a carbonyl carbon give signals near δ = 2.1 to 2.3 and hydrogens on a methyl group
bonded to oxygen give signals near δ = 3.7 to 3.9. The following factors influence the
chemical shift.
Electronegativity of the substituents and inductive effect: To a very rough
approximation, the shielding effect of hydrogen attached to a carbon would depend upon the
inductive effect of the other substituents attached to the carbon atom. Groups with +I effect
make the C-H σ-bond electron rich, whereas electron withdrawing groups attached to
carbon, make the C-H σ-bond electron deficient.
Example-1: CH3F CH3OCH3 (CH3)3N CH3CH3
 (ppm): 4.3 3.2 2.2 0.9
Example-2: CH3F CH3Cl CH3Br CH3I CH4
 (ppm): 4.3 3.1 2.7 2.2 1.0
Example-3: CH3Cl CH2Cl2 CHCl3
(ppm): 3.1 5.3 7.3

H H  = 1.6 ppm
H Cl
H H H  = 3.3 ppm
 = 0.9 ppm H
Problem: Arrange CH3F, CH3Cl and CH3Br in increasing order of chemical shift and
explain. (CU 2020)
Problem: Define the term 'chemical shift'. What differences in chemical shift values are
expected for the protons of CH3F, CH3Cl and CH3Br and why? (CU 2007)
Problem: Arrange the following halides with increasing chemical shifts (δ-values) of the
α-protons with explanation: CH3CH2CH2F, CH3CH2CH2Cl, CH3CH2CH2Br,
CH3CH2CH2I (CU 2009)
Van Der Walls deshielding: In a rigid molecule it is possible for a proton to occupy a
sterically hindered position. The electron clouds of the groups creating steric hindrance
tend to repel the electron cloud surrounding the proton. Consequently the proton would be
deshielded. Influence of this effect is small (< 1ppm).
Effect of circulating π-electrons: Anisotropic effect: Electrons in π-MOs circulate
more readily in the external magnetic field than those in sigma MOs because they are less
strongly held by the nuclei. The effects arising due to circulation of π-electrons are different
in different directions. This is known as anisotropic effect.

Page-1
Factors influencing chemical shifts
Depending on the exact geometry of the molecule, the magnetic field of these circulating
electrons at the hydrogen may be aligned with the external magnetic field (paramagnetic
effect), causing a downfield shift, or opposed to it (diamagnetic effect), causing an upfield
shift.
Alkenes: Vinylic Hs (Hs bonded to double bonded carbon) experience a paramagnetic
deshielding effect, as the induced field is aligned with the applied field at the regions
where the vinylic Hs are located. Consequently vinylic Hs are deshielded (the deshielding
cannot be explained by the larger electronegativity of the sp2 carbon alone).

On the other hands, the protons held below or above the plane of the π-bond, experience a
diamagnetic shielding effect (lines of force of the induced magnetic field are aligned against
the applied magnetic field in these areas).
 = 0.99 ppm  = 1.63 ppm
CH3 CH3
Example: CH2
= 1.01 ppm  = 5.15 ppm
H
CH3 CH3 CH3
= 1.17 H3C  = 1.23  = 0.72ppm
 = 1.27 H3C
ppm  = 0.85 ppm ppm H3 C
ppm

Pinane -pinene -pinene

Page-2
Fac
ctors inffluencing chemiical shiffts
Alky
kynes: Aceetylinic Hss are attachhed to sp-hhybridized carbon. Hoowever, they appear around δ =
1.5~~3.5 i.e accetylinic Hs
H are shieelded com mpared to vinylic Hss. The infl
fluence of π-electrons
π s
on the
t chemiccal shift of acetylinic hydrogen, can be exxplained byy consideriing the oriientation of
carbbon-carbonn triple bon
nd with resspect to thee applied fiield.

Duee to the linnear geom

metry of an n alkyne and
a the cylindrical nature
n of its
i π-electron cloudd,
the induced magnetic
m field
f is shiielding in the
t vicinitty of the acetylinic
a h
hydrogen. The locaal
maggnetic fieldd induced by the π-bbonds shiftts the signal of an accetylinic hydrogen
h u
upfield to a
smaaller δ-valuue.
Pro
oblem: Wh hy do aceetylinic protons resoonate at upfield
u reggion with respect too ethylenicc
protons though acetyliinic hydroogens are more aciddic than etthylenic hydrogens
h ? Explain
n.
(CU
U 2007)
Anss: Electronns in π-MO Os circulatte more reeadily in thhe externaal magnetic field thaan those inn
sigmma MOs because
b th
hey are lesss stronglyy held byy the nucleei. The efffects arisiing due too
circuulation off π-electronns are diff
fferent in different
d d
directions. This is known
k as anisotropic
a c
effeect.
Deppending onn the exacct geometrry of the molecule, the magnnetic field of these circulatingg
elecctrons at thhe hydrogen
n may be aligned
a witth the exterrnal magneetic field (pparamagneetic effect)),
caussing a dow wnfield sh
hift, or oppposed to it (diamaggnetic effe
fect), causiing an upfield shiftt.
Ethhylenic or Vinylic Hs H lie on th he paramaagnetic deeshielding region wh hile acetyllinic Hs liee
on the
t diamaggnetic shieelding reggion.

Page-33
Fac
ctors inffluencing chemiical shiffts
Carrbonyl compounds s: For carbbonyl grouups, the situuation is similar to thhat of C=C
C. Protonss
attaached to th
he carbonnyl carbon n are deshiielded and d appear at a high δ-vvalues. Su uch Hs aree
deshhielded duue to both paramaggnetic anisotropic efffect and electron
e w
withdrawin ng effect off
the oxygen. Hence
H they are even more
m deshiielded thann vinylic Hs.

O O
E
Example:
R
R H H O
Ald
dehyde pro
oton and proton off formate ester abso gh  -valu
orb at hig ue.
Pro
oblem: Exxplain why
y aldehyd
de protonss appear much
m wnfield in 1H-NMR spectrum
dow m.
(KU
U 2018)
Aroomatic co ompounds s: Benzenee protons are
a even more
m deshieelded than vinylic protons. It iss
duee to existence of rin ng currentt: a speciaal property of arom matic ringgs. The appplied fieldd
causses the π-eelectrons to
o circulate around thee ring, giviing rise to the
t ring cuurrent. Thhis inducedd
ringg current has a magnetic
m field assoociated wiith it thaat opposess the app plied field
d
(diaamagnetic)) in the middle
m of thhe ring buut reinforcces the applied field d (paramaagnetic) on n
the outside off the ring.

Thee aromaticc hydrogen ns lie in th he paramagnetic zoone. Thereefore theyy are deshiielded and
d
exhibit largerr chemicall shift. Lett us consideer the folloowing exam
mples.

Page-44
Fac
ctors inffluencing chemiical shiffts

Thee chemical shifts for the

t Hs of 1,6-methan
1 no-[10] annnulene are

Pro
oblem: Why
W aroma atic protonns are moore deshieelded thann ethyleniic protonss although
h
both
h the types are attacched to sp 2
n atoms. (C
p -hydridizzed carbon CU 2013 3)
Anss: The effeect for pressence of arromatic rinng and nonn aromatic C=C are conceptually similarr.
But aromatic ring
r contaiins continuuous cyclee of (4n +22)-π-electroons. So thee anisotroppic effect iss
morre pronounnced in casee of aromaatic compouunds.
Prooblem: Hoow can yo ou distingguish the following
f pairs by 1H-NMR spectrosccopy? Cis--
stilb
bene and trans
t stilbene

Page-55
Factors influencing chemical shifts
NMR spectroscopy has become the principle criteria to decide whether a molecule has aromatic
character or not. The method has been successfully applied to heterocyclic systems and
different annulenes.
 = 8.9  = 7.6
Example: H H H
H H H H
 = -1.8  = 0.0
H H H H HH H
H H
H H HH
H H H H H

H H H H
H H H
[18] annulene-aromatic [14] annulene-aromatic
Outer Hs apeear at  = 8.9 Outer Hs apeear at  = 7.6
inner Hs appear at  = -1.8 inner Hs appear at  = 0.0
Anti aromatic compounds also exhibit anisotropic effect. However, the effect is exactly
reverse of aromatic compounds. The inner Hs fall in the paramagnetic region (deshielded)
and the outer Hs fall in the diamagnetic region (shielded).
 = 5.35
H
Example: H H
H H  = 6.0  = 10.56
H H H H

H  = 8.0
H H H H
H H H H H H

H H
H H
H H
H
[12] annulene-anti aromatic, H
At below -170° C [16] annulene-anti aromatic,
Outer Hs apeear at = 6.0 At below -130 °C
inner Hs appear at = 8.0 Outer Hs apeear at  = 5.35
inner Hs appear at  = 10.56

Problem: Which hydrogen in CH3COOCH3 exhibits the more downfield signal relative to
Me4Si in the 1H-NMR spectrum? (KU 2016)
O These methyl protons are more deshielded due to strong -I effect of the
Ans:
CH3 oxygen atom. So these Hs appear more downfield compared to Me4Si.
H3C O

Problem: Arrange the following labeled hydrogens in order of increasing chemical shift
a b c
value in H-NMR: CH3CH2CHO(KU 2019)
1

a b O
Ans: CH3 CH2 C Order of chemical shift: (Hc) > (Hb) > (Ha)
Hc

Page-6
Approximate chemical shift values for different types of proton

Page-1
Approximate shifts in the position of benzene Hs (δ=7.27) caused by substituents
Substituent ortho meta para
-CH3/ -R
-0.15 -0.1 -0.1

-CH=CH2 +0.2 +0.2 +0.2

-COOH/ -COOR +0.8 +0.15 +0.2

-CN +0.3 +0.3 +0.3

-CONH2 +0.5 +0.2 +0.2

-COR +0.6 +0.3 +0.3

-SR +0.1 -0.1 -0.2

-NH2/ -NHR -0.8 -0.15 -0.4

-NMe2 -0.5 -0.2 -0.5

-I +0.3 -0.2 -0.1

-CHO +0.7 +0.2 +0.4

-Br 0 0 0

-NHCOR +0.4 -0.2 -0.3

-Cl 0 0 0

-NH3(+) +0.4 +0.2 +0.2

-OR -0.2 -0.2 -0.2

-OH -0.4 -0.4 -0.4

-OCOR +0.2 -0.1 -0.2

-NO2 +1.0 +0.3 +0.4

-SO3H/-SO2Cl,/-SO2NH2 +0.4 +0.1 +0.1

etc.
Problem: Predict the number of signals with their tentative chemical shifts in the 1H-
NMR spectrum of the following compounds.
O O
(A) O
(B) (C) H3CO NO2
O

Page-2
 O
Ans: CH3
(A) The compound contains two types of chemically non-identical Hs: H3C O
 ~ 3.6
The tentative chemical shifts ot these two types of Hs are:  ~ 1.9 O
CH3
H3C O
(B) The compound contains 5-types of chemically non-equivalent Hs:
Ha O Hd
He
Hb O
Hc
The tentative chemical shifts of these Hs are:
 ~7.8  ~4.1

Ha O Hd  ~1.3
He
Hb O
Hc
 ~7.5
 ~6.2
(i) β-Hs of α,β-unsaturated carbonyls are deshielded due to –R effect of the carbonyl group and
these Hs lie on the paramagnetic deshielding zone. Two β-Hs are diastereotopic and chemically
non-equivalent (Ha and Hb).
(ii) The α-H (Hc) is vinylic H.
(iii) Hd and He are methylene and methyl Hs respectively, of an ethyl ester. They appear at their
corresponding δ-values.
(C) 4-nitro anisole contains three types of chemically non-equivalent Hs:
CH2 Ha
O
Ha Ha

Hb Hb
NO2

CH2 Ha  ~3.7
The tentative chemical shifts of these Hs are: O
Hb Hb  ~7.0

 ~8.27
Hc Hc
NO2

Page-3
Taking benzene Hs (δ = 7.27) as reference, the Hs ortho to –NO2 group are deshielded (~1 ppm)
due to –I and –R effect of –NO2. The Hs ortho to –OMe are slightly shielded than benzene Hs
due to its +R effect.
Problem: The 1H-NMR spectrum of N,N-dimethyl formamide shows two signals for the
methyl Hs at room temperature. However, at elevated temperature only one signal is
found. Explain.
Ans: N,N-dimethyl formamide may be represented by the following canonical structures:
O O(-)
Me (+) Me

:
H N H N
Me Me
The C-N bond is partial double bond. Under room temperature rotation about C-N bond is
restricted. One methyl group is cis to the oxygen and the other is trans. They are
diastereotopic. So two signals are observed for these methyl groups.
O
O(-)  =2.88 ppm
CH3
:

H N (+)
CH3
H N
CH3  =2.97 ppm
CH3

At elevated temperature rotation about the C-N bond is very fast (faster than NMR time
scale). So we get one signal for the methyl groups. The 1H-NMR spectrum of the compound
recorded at ~130° C shows only one signal for the methyl Hs. At elevated temperature
rotation about the C-N bond is so rapid that both methyl groups experience the same time
average environment.
Problem: The 1H-NMR spectrum of chloroform dissolved in cyclohexane shows the peak
for CHCl3 at δ = 7.3. However, in benzene the peak appears at δ = 5.74. Explain.
Ans: Due to presence of a closed loop of π-electrons, benzene acts as a Lewis base.
Considerable charge transfer occurs from benzene to chloroform. As a result, the electron
density around the H in chloroform in increased and it is more shielded in benzene solvent as
compared to cyclohexane. The benzene ring current may have some contribution as well.
Problem: Give approximate chemical shift values for the underlined protons of the
following compound. (KU 2010)
Ha COOH

Ph Hb

Page-4
Problem: Predict the relative chemical shifts, multiplicities and relative intensities of the
1
HNMR spectrum of (CH3)2CHCOCH3. (CU 2016)

Problem: Arrange the indicated protons of the following compounds in order of

decreasing chemical shift value. (KU 2011)
CH3
H Ha

H Hb
NO2

Ans: Order of decreasing chemical shift is: δ(Hb) > δ(Ha) > δ(CH3)
Problem: Give approximate chemical shifts for the underlined protons. (KU 2010)
CH3 OCH3
(i) (ii) (iii) RCH2CHO (iv) RCOOCH3 (v) ROCOCH3

 
Ans:  
CH3 O  O O
OCH3
(i) C C C
(ii) (iii) RH2C H (iv) R OCH3 (v) RO CH3

Problem: Give appropriate chemical shift values for the methyl protons in the following
compounds. (KU 2013)
CH3 NHCOCH3 COCH3

CH2=CH-OCOCH3

 

CH3 NHCOCH3 
COCH3
Ans: CH2=CH-OCOCH3

Page-5
Problem: Give the approximate chemical shift values for the underlined protons in vinyl
acetate. Explain their coupling pattern. (KU 2012)
H H

H OCOCH3

Solvent used in NMR spectroscopy: The essential criteria for a substance to be used as
solvent is that it does not give signals for its own absorption. Moreover, it should dissolve at
least 10% of the substance under investigation. The compound should be chemically inert
and magnetically isotropic. Non-viscous samples give the sharpest peaks in NMR spectra.
Therefore NMR spectra of organic compounds are usually recorded in solution. If the sample is
non-viscous liquid, it may be used without any added solvent. The following solvents are
commonly used in NMR spectroscopy.
CCl4 Carbon tetrachloride
CS2 Carbon disulphide
CDCl3 Deuteriochloroform (chloroform-d)
C6D6 Hexadeuteriobenzene (benzene-d6)
D2O Deuterium oxide (heavy water)
(CD3)2SO Hexaduterio dimethyl sulphoxide
(DMSO-d6)
(CD3)2CO Hexaduterio acetone (acetone-d6)
(CCl3)2CO Hexachloroacetone

Page-6
Isotopic purity of the deuteriated solvent must be extremely high. Otherwise the peaks due
to the Hs in the solvent would cause ambiguity, e.g. The H of CHCl3 appears at δ=7.3 (very
close to aromatic region). However, this small peak in 99% pure CDCl3 does not cause
ambiguity. These solvents differ considerably regarding their polarity. NMR spectrum
recorded in solvents of different polarity are slightly different. H-bonding also affects
chemical shift positions. So always the solvent used during recording of the spectrum is
mentioned.
Problem: Can CHCl3 be used as a solvent in 1HNMR studies? (CU 2008)
Ans: The hydrogen of CHCl3 appears at δ = 7.3. This value falls within the range for the
chemical shifts of benzenoid Hs. So CHCl3 would interfere during recording 1HNMR spectra
for benzenoid hydrocarbons. So CHCl3 cannot be used as a solvent in 1HNMR spectroscopy.
Problem: Why duterated solvents are used for NMR studies?
Ans: When we have to record the NMR spectrum of any solid compound, the solid is dissolved
in suitable solvent in order to ensure homogeneous magnetic environment. The solvent should
be chemically inert and it must not contain any hydrogen. Deuterium does not resonate under
the conditions of 1H-NMR spectroscopy as the magnetic moment of hydrogen is almost
three times higher than deuterium.
Solvent shifts: Concentration; temperature and effect of hydrogen bonding: The
solvents used for NMR spectroscopy considerably differ in their polarity and magnetic
susceptibility. Consequently, NMR spectrum of a compound dissolved in one solvent may
differ from that dissolved in another. All NMR works are required to quote the solvent
used. However, the effect is generally small for Hs attached to carbon. But NH, SH and
particularly OH hydrogens have their NMR signals considerably moved on using solvents with
different polarity. Even when different concentrations are used in the same solvent, the
signals due to such Hs are shifted. This effect is generally associated with hydrogen bonding.
Hydrogen bonding involves transfer of the electron cloud from H to a nearby
electronegative atom. Consequently the H-atom experiences a net deshielding.

At low concentration of the sample, intermolecular H-bonding is ruptured. It is found that at

high concentration of the sample, such Hs appear at higher δ, compared to at low
concentration.
Increased temperature also reduces intermolecular H-bonding. Therefore position of the
signals of these Hs is temperature dependent as well. Intermolecular H-bond increases δ-
value. However δ-value is reduced on dilution and increasing temperature. Intramolecular H-
bonding is unchanged by dilution and signals for such Hs are virtually unaltered on
dilution. Systems, which are chelated by intramolecular H-bond, show the signal for the H-
atom involved in the intramolecular H-bond, at very high δ-value.

Page-7
Intramolecular H-bonding causes much downfield shift for a proton. NMR-spectral studies
are useful to distinguish between intermolecular H-bond and intramolecular H-bond. In case of
intramolecular H-bond there is no change in spectral pattern upon dilution.
Example: OH-proton of salicylate esters and enolic Hs.
OR
H
O O
O
H
O
Carboxylic acids are a special case of H-bonding because of their stable dimeric association,
which persists even at very dilute concentrations. The carboxyl H-atom of carboxylic acids
appear at high δ-values (>δ=10).
Problem: 1HNMR signal for O-H proton of ortho hydroxy acetophenone is shifted upfield
when temperature is increased. Explain. (CU 2020)
Ans: In ortho hydroxy acetophenone we have intramolecular H-bonding.
CH3
C
O

O H
Increased temperature also reduces intermolecular H-bonding. Therefore position of the signals
of O-H Hs is temperature dependent. Reduction in H-bonding caused shielding of the O-H
proton. So we observe upfield shift.
Problem: How would you verify that a particular proton in 1HNMR arises from the
following groups –OH, -SH, -NH2? (KU 2015)
Ans: All these Hs are involved in H-bonding. Formation of intermolecular H-bond causes
downfield shift for these Hs. When the solution is diluted, the H-bonds are ruptured and
the downfield shift is not observed anymore. This effect observed by changing concentration
of the sample is most pronounced for -OH, less for -NH2 and even lesser for -SH.

Page-8
Integration in 1H-NMR: counting of hydrogens: The NMR spectrum not only
distinguishes how many different types of protons a molecule has, but also reveals how many
of each type-H are contained within the molecule. The first characteristic of every signal is
the position of the signal or chemical shift. The second characteristic is integration, or the
area under each signal. This value indicates the number of protons giving rise to the signal.
In the NMR spectrum, the area under each peak is proportional to the number of Hs
generating that peak. The more hydrogens of one kind there are in a molecule, the more
intense is the corresponding signal.
After acquiring a spectrum, the computer calculates the area under each signal and then displays
this area as a numerical. The relative peak area is recorded i.e. the ratio between different
types of Hs is given. By measuring the area under a peak we can estimate the ratio of Hs.
Example-1: 1H-NMR spectrum of 3-pentanone

In order to convert these numbers into useful information, choose the smallest number (32.5 in
this case), and then divide all integration values by this number.
32.5/32.5 = 1; 48/32.5 = 1.476
These numbers provide the relative number, or ratio, of protons giving rise to each signal.
In order to arrive at whole numbers, we multiply all the numbers by 2. These values give a
ratio of 2:3, but again the values 2 and 3 are just relative numbers. They actually
represent 4 protons and 6 protons. This can be determined by inspecting the molecular
formula (C5H10O).

Page-1
Exa
ample-2: 1H-NMR spectrum
s of benzy
yl acetate
e

Pro
oblem: A compoun
nd with molecular
m formula C5H10O2 has the followingg 1H-NMR
R
specctrum.

Determine th
he numberr of Hs giving rise too each sign
nal. Identiffy the com
mpound.

Anss: 6.33/6.33=1; 19.4 4/6.33=3.006; 37.9/6.333=5.99 Round

R off: 1: 3: 6. Too determinne the exact
nummber of prootons givin
ng rise to eaach signal,, we look at
a the moleecular form
mula, which h indicatess
a tootal of ten (1+3+6) protons in the compoound.
Theerefore, thee numbers 1: 3: 6 are not only reelative valuues, but th
hey are alsso the exacct values.

Page-22
 O CH3
The probable structure is:
C CH
H 3C O CH3

Page-3
Spiin-spin coupling
c g: signal splitting
g
It iss quite com
mmon to sees a signaal for partticular hyd
drogen ap
ppear not as a a singleet, but as a
collection of peaks.
p Thee signal may
m be splitt into two peaks (a doublet),
d thhree peaks (a triplet)),
fourr peaks (a quartet),
q orr even morre.

Thee origin ofo signal splitting:: 1H-NMR R signal spllitting cann be undersstood by considering
c g
1
spinn-spin couppling betw
ween H nuclei,
n (ann interactiion in wh hich nucleear spins of nearbyy
atomms influen nce each other).
o A proton
p in the NMR R spectrom meter is su
ubjected too both thee
exteernal magnetic fieldd and the induced
i fieeld of the shielding electrons.. If there arre other Hss
nearrby, their small
s magn
netic fieldss also affecct the obserrved signalls.
To spin coup ple, the hydrogens
h must haave differeent chemiical shiftss, and theyy must bee
relattively closse togetherr because the effectt of the sm
mall magnetic field
ds of the hydrogens
h s
decrreases rap pidly with distance.
H H H H H H
C C C
Geminal Hs
V
Vicinal Hs
Alllylic Hs
Hyd drogens bonded
b to
o the samme carbon (called geminal
g hyydrogens) couple iff they aree
diasstereotopic and have differeent chemiical shifts. Hydrogeens bondedd to adjaccent atomss
(viccinal hydroogens) alsoo couple. Coupling between vicinal hyydrogens (vicinal coupling
c orr
threee bond couupling) is the
t most common
c tyype.
Couupling is not
n commonly observed betw ween hydrrogens thaat are fartther apartt than thiss
unleess a π-boond is inv
volved, in which caase a smaall couplin ng (knownn as allylicc coupling))
betw
ween hydrrogens sep parated byy three carrbons is soometimes observed.
o
A very
v imporrtant charracteristicc of spin–sspin splitting is that protons that havee the samee
chemmical shifft do not split eachh other’s signal.
s Leet us conssider the following
f molecularr
fraggment:

Page-11
Spin-spin coupling: signal splitting
Let us consider the following molecular fragment

The two-Hb influence the magnetic field experienced by Ha as:

The signal for Ha is split into a triplet with relative peak intensity 1:2:1.
Let us consider the following molecular fragment

The three Hb influence the signal for Ha as:

The signal for Ha is split into a quartet with relative peak intensity 1:3:3:1.

Number of lines in a multiplet: (n+1) rule: In many situations, the degree of signal
splitting can be predicted on the basis of the (n+1) rule. According to this rule, if a hydrogen
has n-nonequivalent hydrogens to it (but equivalent among themselves) on the same or
adjacent atom(s), its 1H-NMR signal is split into (n+1) peaks.

Page-2
Spin-spin coupling: signal splitting
For this H
n=3. The signal
splits into (3+1)=4 peaks
For these Hs
H Cl i.e a quartet
n=1. The signal
splits into (1+1)=2 peaks H3C
i.e a doublet Cl
Problem: Predict the number of signals, relative peak area and the splitting pattern of
each signal in the 1H-NMR spectrum of each molecule.
O O O
(i) (ii) (iii)

Triplet
Ans: (i) O Hc
Hc The compound contains three types of Hs marked as H ,H and H .
Ha a b c
Ha Hc
Ha Hb Hb

Quartet
Singlet
The carbon adjacent to Ha does not contain any H. Therefore Ha would appear as a singlet.
The carbon adjacent to Hb contains 3-Hs non-equivalent with Hb. Hence Hb would appear as a
quartet. Hc would appear as a triplet. Ratio of peak are for Ha,Hb and Hc is 3:2:3.

O
Triplet
Ha Ha
(ii) Ha Ha
Ralative peak area of Ha and Hb is 3:2.
Ha Ha
Hb Hb Hb
Hb
Quartet
O
Singlet Hc Doublet
Hc
(iii) Ha Hc
Hc
Relative peak area of Ha, Hb and Hc is 3:1:6.
Ha
Ha Hc
Hb Hc
Septet
NOTE: For the following structural fragment the signal for Ha is split by Hb as well as Hc.

Page-3
Spin-spin coupling: signal splitting
If we have n-number of non-equivalent Hs on one adjacent carbon and m-number of non-
equivalent Hs on another adjacent carbon, we get a signal split into total of (n+1) x (m+1)
number of lines.
Problem: Write with explanation the 1HNMR signals of the protons of: (i) CH3CH2Br and
(ii) CH3CHBr2 in terms of singlet/doublet/triplet/quartet. (CU 2006)
Ans: The nature of signal splitting can be predicted on the basis of the (n+1) rule. According to
this rule, if a hydrogen has n-nonequivalent hydrogens to it (but equivalent among
themselves) on the same or adjacent atom(s), its 1H-NMR signal is split into (n+1) peaks.
CH3-CHBr2
CH3-CH2-Br 1H-quartet
2H-quartet
3H-doublet
3H-triplet
Problem: Draw a clean 1HNMR spectrum of CH3CHBr2. Mention the multiplicities of
different signals. Explain the multiplicities on the basis of spin-spin coupling. (CU 2010)

Let us consider the following molecular fragment

The three Hb influence the signal for Ha as:

Page-4
Spin-spin coupling: signal splitting
The signal for Ha is split into a quartet with relative peak intensity 1:3:3:1.
Problem: Sketch the 1HNMR spectrum with integrations showing relative chemical shifts
of isomeric dibromo ethanes. (CU 2014)
Ans: 3H, doublet Br Br Br

H3C CH 1H, quartet H2 C CH2

Br 4H, singlet
1,1-dibromo ethane 1,2-dibromo ethane
Coupling constant (J): The distance between the centers of two lines in a multiplet is
usually constant and it is known as the coupling constant. A coupling constant (J) is the
separation between adjacent lines in a multiplet and is a quantitative measure of the
influence of adjacent nuclei.
The magnitude of a coupling constant is expressed in hertz (Hz); for Hs the coupling constant is
generally in the range 0 to 18 Hz. The values of J depend only on interactions with other
nuclei within a molecule, and so it is independent of the applied field strength.
Molecular fragment Jab (Hz)
Ha 10-18
C (Geminal coupling)
Hb
Ha Hb 0-12
C C (Vicinal coupling) Depends upon dihedral angle
Ha 1-4
C C
Hb
5-14 (generally 6-8)
C C (Cis coupling)
Ha Hb
Ha 11-19 (generally 14-16)
C C (Trans coupling)
Hb
2-10 (Generally 2-3)
C Hb
C C (allylic coupling)
Ha
Ha Hb 10-13
C C C C
Ha ortho coupling 7-10
X meta coupling 2-3
Hb para coupling 0-1

Page-5
Spin-spin coupling: signal splitting
Long range couplings
1-2 Hz

He
4
Jee
He
Hb 4
Ha Jac = 8 Hz
4
Jbc = 0.2 Hz

Hc
Ha 18 Hz
4
Jab
Hb

Now we need an understanding of the factors that influence the coupling constant. As the
coupling is transmitted through bonds, the number of bonds separating the atoms in an
important factor. In this connection it is worth mentioning that J does not depend on the
H

applied magnetic field. Coupling between geminal is symbolized as 2J H . Similarly,

coupling between vicinal Hs is symbolized as 3J H H .

Geminal coupling (2J): Coupling between geminal Hs occur when these Hs are diastereotopic.
Geminal coupling is strong with J~10-18 Hz.
Vicinal coupling (3J): Varies from 0-12 Hz , but in case of freely rotating carbon chains, it is
usually 8Hz.
Long range coupling (extending over more than three bonds i.e. 4J and higher): In alkane
systems this type of couplings are vanishingly small. But they can be observed in rigid
molecules.
Trans coupling and cis coupling in alkanes (3J): Trans coupling (usually 11-19 Hz) is
stronger than cis coupling (5-14 Hz). Typical values of trans coupling and cis coupling are 16
Hz and 8 Hz respectively.
Aromatic coupling: Depends on the position if the coupling Hs. 3Jortho = 7-10 Hz; 4Jmeta = 2-
3 Hz; 5J para = 0-1 Hz. In simple benzenoid compounds, the coupling constants are helpful to
identify the substitution pattern.
Other magnetic nuclei such as 13C, 19F, 14N etc. also couple with 1H.

Page-6
Spin-spin coupling: signal splitting
Factors influencing geminal coupling: Geminal coupling is somewhat rare and is
observed in case of diastereotopic Hs only. So the factors that influence geminal coupling
cannot be easily determined. One indirect method is to replace one diastereotopic H with D
R R
H D
R' H R' H
, then measuring JH-D and calculating JH-H following the equation JH-H
= 6.53 JH-D. Electronegativity of the substituents affects geminal coupling. But this effect is not
so straightforward.

Magnitude of Jgem also depends on bond angle. Highest magnitude is found in case of strain
free cyclohexanes and cyclopentanes. With increasing angle strain Jgem is reduced (8-14 Hz
for cyclobutanes and 4-9 Hz for cyclopropanes).
Factors influencing vicinal coupling: Electronegativity of the attached substituents alter
the value of vicinal coupling. In alkanes this value is ~ 8Hz and in haloalkanes 6-7 Hz. In case
of rigid molecules, the dihedral angle influences this value. When the Hs are anti periplanar or
syn periplanar, this value is maximum. The value decreases when the Hs are gauche. Karplus
formulated the following equation to calculate Jvic.
When ϕ is between 0° and 90°, Jvic = 8.5cos2ϕ-0.28
When ϕ is between 90° and 180°, Jvic = 9.5cos2ϕ-0.28.
A successful illustration of this rule is cyclohexane systems.

Ha

Hb Coupling constants for axial Hs 10-13 Hz and for equatorial Hs 2-

Hb 5 Hz

Ha

Page-7
Spin-spin coupling: signal splitting
"Leaning" of a multiplet: Often the peak height of a multiplet is distorted. For example, in a
doublet the intensity ratio of the peaks should be equal. But sometimes it is found not to be
equal. Same is the case with triplets and other multiplets. The multiplets do not appear to be
symmetrical. A multiplet often "leans" upward toward the protons that are causing the
splitting. The ethyl multiplets in ethyl benzene lean toward each other.

Problem: Explain the coupling patterns of the protons in the following compounds: (i)
Vinyl protons in trans cinnamic acid. (ii) The underlined protons in allyl chloride. (KU
2013)
H H H
H C C C Cl
H

Page-8
Spin-spin coupling: signal splitting

Page-9
Problems on 1H-NMR spectroscopy
Problem: How many kinds of non equivalent protons are there in C2H5CH=CH2? Label
them. (CU 2001)
This H-is chemically non-equivalent from the others.
Ans: H H

C C These Hs are diastereotopic. So they are chemically non-equivalent.

H3C CH2 H
These Hs are enantiotopic. So we get 1-signal
These Hs are homotopic so we get one signal
There are total five types chemically non-equivalent Hs.
Problem: Toluene is oxidized to benzaldehyde. What changes in 1HNMR spectral
features would you expect for the product with respect to that for starting compound?
(CU 2004, KU 2012)
Ans: When toluene is oxidized to benzaldehyde we have several change in the 1H-NMR
spectra. The most prominent change is as follows:

For toluene we get only one peak for five aromatic Hs. In benzaldehyde we get three signals for
aromatic Hs.
Problem: How can you show that the three methyl protons in ethanol are equivalent?
(KU 2016)
Ans: The three methyl Hs of ethanol show a single signal in the 1H-NMR spectrum. They are
chemically equivalent Hs. These are homotopic Hs. So they are chemically equivalent.
Problem: Determine which Hs are chemical shift equivalent and which are non-
equivalent in the following compounds: (KU 2016)
H
Br
H H H
H C H
Cl
Br Br

Page-1
Problems on 1H-NMR spectroscopy

Problem: Chemical shift equivalent protons do not show spin-spin coupling. Justify or
criticize. (KU 2020)
Ans: Spin-spin coupling is a result of the effect of the magnetic field developed by one
proton on the magnetic field experieced by another proton. For spin-spin coupling the Hs
must be chemical shift non-equivalent or their electronic environment must be different.
Only nearby non-equivalent Hs i.e. Hs belonging to different electronic environment undergo
spin-spin coupling.
Problem: How many signals will you expect in the 1HNMR spectrum of o-dinitro
benzene? Assign the signals and arrange them in the increasing order of their chemical
shifts. State the splitting pattern of the signals. How can you distinguish it from p-di-nitro
benzene from their 1HNMR spectrum? (CU 2003, 2015, 2019)

Problem: Sketch the 1HNMR spectrum with integrations showing relative chemical shifts
of m-dinitrobenzene. (CU 2013)

Page-2
Problems on 1H-NMR spectroscopy

Problem: An isomer of dinitro benzene shown three signals in its 1H-NMR spectrum.
Identify the compound. Compare relative δ-values of the protons. Give reasons. (CU
2021 CBCS)
Hint: Ha has highest δ-value. It is flanked by two -NO2 groups and hence it is most
deshielded. Hbs are ortho to one -NO2 group and meta to the other -NO2 group. So they
have the next higher δ-value. Hc is meta to both -NO2 group. So Hc has lower δ-value than
Ha/Hb.
Problem: State with labels the expected number of signals for meta dichloro benzene in
its 1HNMR spectrum. (CU 2005)

Page-3
Problems on 1H-NMR spectroscopy
Problem: Draw a rough sketch of the 1HNMR spectrum of nitrobenzene assigning the
protons in the diagram. Actual δ-values and meta-coupling may be ignored. (CU 2008)

Problem: Draw 1HNMR spectrum of p-chloro nitrobenzene. Explain the relative chemical
shifts and splitting pattern. (CU 2008)

Ha/Hb are chemically non-equivalent. Ha/Ha' and Hb/Hb' are magnetically non-equivalent.
Hb/Hb' are more deshielded compare to Ha/Ha'. So they appear at lower applied magnetic
field (higher δ-value).
Ha/Ha' appear as a doublet of doublet. The signal is split into a doublet by ortho Hb. The doublet
is split by meta Hb'. Similarly Hb/Hb' appear as doublet of doublet.

Problem: Give a sketch of 1H-NMR spectrum of CH3CH2Br showing approximate

chemical shifts and coupling constants of each type proton. (KU 2012)

Page-4
Problems on 1H-NMR spectroscopy
Problem: Sketch an approximate 1H-NMR spectrum of C6H5COOCH2CH3. (KU 2010)

Problem: Draw the approximate NMR spectrum of the following compound. (KU 2020)
Br
H C CHO
CH2CH3

Problem: Tertiary butyl fluoride shows a doublet in its 1H-NMR spectrum at δ = 1.5 with
J = 20 Hz. On adding SbF5 it shows only a singlet at δ = 4.6. Explain. (KU 2021 CBCS)

Page-5
Problems on 1H-NMR spectroscopy

Page-6
Acc cidental equivale ence: Sevveral monno substittuted arom matic com mpounds, containingg
subsstituents which
w do not
n have strong
s shiielding or deshieldiing effectss, produce nearly (orr
totally) unsplit signals fo
or the arom
matic Hs, although
a th
hey are noot chemicaally equivaalent. Thiss
is teermed as 'aaccidental equivalennce'.
Exaample-2: 1H-NMR spectrum
s of toluenee:

Exaample-3: 1H-NMR spectrum of ethyl benzene

b

The eth
hyl group iss recognized
d by the –CH
H3 triplet an
nd CH2 quartet

Exaample-4: 1H-NMR spectrum

s of cumenee:

The isop
propyl group is recogniized by the 6-H
6 doublett and 1-H seeptet

Page-11
Example-1: 1H-NMR spectrum of benzyl butanoate
H e Hd Hd O H b Hb
Hf Ha
O
Ha
Hc Hc Ha
Hg He
Hf

1H-NMR spectra of alcohols: Proton exchange: The hydroxyl proton of a primary

alcohol RCH2OH is vicinal to two protons, and its signal would be expected to be split into a
triplet. Under certain conditions signal splitting of alcohol protons is observed, but often it
is not found to be so. The 1H-NMR spectrum of benzyl alcohol shows the methylene Hs (δ =
4.7ppm)and hydroxyl protons (δ = 2.5 ppm)as singlets.

200 MHz 1H-NMR spectrum of benzyl alcohol

Page-2
The reason that splitting of the hydroxyl proton of an alcohol is not observed is that, it is
involved in rapid exchange reactions with other alcohol molecules. Transfer of a proton
from oxygen of one alcohol molecule to the oxygen of another is very fast and it effectively
decouples it from other protons in the molecule.

: :
H3O(+) (+) H R O
R OH H (+) H
R O R O + R O
H
H
This reaction is much faster than the NMR time scale and the –OH proton does not reside on a
particular oxygen for sufficiently long time, a large number of different hydrogens have been
bonded to the oxygen.
50% of these hydrogens have their magnetic fields oriented in one direction and 50% have
them oriented in the opposite direction, the average field is zero. Therefore, the peak due to
the methyl group is not split, nor is the peak due to the hydroxyl hydrogen.
Factors that slow down this exchange of OH protons, such as diluting the solution,
lowering the temperature, or increasing the steric factor around the OH group, can cause
the splitting.
The 1H-NMR spectrum of ethyl alcohol was recorded with two different samples, ordinary
grade ethanol (contained acidic impurities) and the other one was highly pure.

Spectrum of the ordinary grade ethanol showed that the –OH proton was not involved in
coupling with the methylene protons. The spectrum for the pure sample shows this coupling.

Page-3
Signnal for the methyl Hs
H appear as a a triplet due to couupling withh methylenne Hs. Siggnal for thee
methhylene Hs is split intto a quarteet by the methyl
m Hs. If
I the sam
mple is extrremely pu ure, proton n
exchhange doees not takee place and d each linee of the qu
uartet ate further sp
plit into a doublet.
d
Butt this secoond coupliing is abssent in th he spectrum of the ordinary grade saample. Thee
ordiinary gradee sample iss not ultrappure. Therre remainss some acid
dic impurrity. So rap
pid proton
n
exchhange reaction takees place.
Pro
oblem: Hoow many signals wouldw n the 1HNMR specttrum ethyyl alcohol??
you expect in
Corrrectly asssign the chemical
c s
shifts of the signalss with reaasoning. Predict
P the splittingg
patttern of thee signals. (CU
( 2000
0)
oblem: Drraw the 1HNMR
Pro H siggnals of CH
H3CH2OH H (ordinarry grade) showing
s th
he relativee
chem
mical shiffts, integra
ation and spin-spin
s c
coupling p
patterns. (
(CU 2005 5)
Temmperature dependenc
d ce of spin––spin splittting is obbserved meethanol. The
T singletts at 37°C
C
illusstrate the effect of fast
f proton n exchangee in alcohools.

Dep pendence e of the –OH sig gnal position of alcohols

a on diffeerent fac ctors: Thee
chem mical shiftt of the hyd
droxyl proton is variaable, with a range off δ = 0.5–55 ppm, dep
pending on n
the solvent, th he temperrature at which
w thee spectrum
m is record ded, and the
t concen ntration off
the solution.
Thee alcohol proton shiftts to lowerr field strenngth in moore concenntrated soluutions. These can bee
explained on the basis of interm molecular H-bondin ng. H-bond ding reduces electroon densityy
arou und the –OH proto ons and make
m them deshieldeed. Intermoolecular H-bond is disrupted
d inn
diluute conditioon in non-ppolar solveents.

000 MHz 1H--NMR speectrum of ethanol in

n CDCl3 (w
was alloweed to stand
d overnigh
ht in air)

Page-44
 3
M 1H-NM
300 MHz MR spectrrum of eth hanol in drry DMSO-d6
Thee different splitting patterns
p caan be undeerstood on the basis of proton exchange in CDCl3.
Thee shift in –OH
– signal position can be exp plained on
n the basiss of higherr polarity of DMSO.
1H-N
NMR spe
ectrum off 1,3-dica arbonyl co ompound ds: Tautom meric interrconversionns at room
m
tempperature arre slow en nough to obbserve signnals for booth the tauutomers. Let
L us conssider acetyyl
1
acettone. HNM MR spectrrum of thiis compou unds clearlly shows signals for both ketoo and enoll.
It inndicates thaat the rate of
o enolizattion is slow
wer than thhe NMR tim me scale.

Thee signal att δ= 5.50 is more intense

i han the siggnal at δ = 3.60. It
th I indicatees that thee
amoount of en nol is highher than keto.
k Alsoo the signaal for methhyl at δ = 2.05 (enool) is moree
intennse than thhe signal fo
or methyl at
a δ = 2.24 (keto). Soo δ = 2.05 must
m be frrom the en
nol.
Commparing thee area under the signnal for the two
t methyyl groups we
w can calculate relatiive amounnt
of keto
k and ennol. The ratio
r is fouund to bee 4:21. It indicates
i t
that the equilibrium
e m mixturee
contains 16%
% keto and d 84% enol.
Bothh the metthyl groups of the enol
e appeaar at δ = 2.05.It in
ndicates th
hat the sttructurallyy
equ
uivalent en
nols undergo intercoonversion faster than the NMR R time scaale.

Page-55
Chemical shift equivalence and magnetic equivalence: Two Hs are said to be
chemically equivalent if by virtue of the symmetry within the molecule their electronic
environment is indistinguishable. Such Hs exhibit the same chemical shift (δ-value).
Two protons are said to be magnetically equivalent if both of them couples with another
proton exactly the same way. Otherwise they are magnetically non-equivalent. Magnetic
equivalence means spin-coupling equivalence (same J-value). Let us consider the following
structure.
H H
The gemical Hs on C1 are chemically equivalent. The geminal Hs on C2 are
Y chemically equivalent. Let us consider the following conformation:
1 2
X Ha
H H Hb Y
1
2
X Ha'
Hb'
Dihedral angle between Ha and Hb is ~ 60o and between Ha' and Hb is ~ 180o.Value of Jvic
depends on dihedral angle. Ha undergoes geminal coupling with Hb but this geminal coupling
is different from the geminal coupling involving Ha' and Hb. In this conformation Ha' and Ha
are magnetically non-equivalent. Similarly Hb' and Hb are magnetically non-equivalent.
Magnetically equivalent Hs must be chemically equivalent but chemically equivalent Hs
may not be magnetically equivalent. For magnetically equivalent pair of Hs we use A2/B2 etc.
notations. For magnetically non equivalent Hs we use AA'/BB' such notations.
NO2 Cl
Ha Fa
Ha Ha' Ha Cl
C C
Hb Hb' Hb Ha' Ha' Fa'
Cl Hb'
Problem: Explain the terms 'chemical equivalence' and 'magnetic equivalence'. Comment
on the equivalence of the labeled protons in the following compounds. (KU 2013)
X H
H H H Y H F

X H H F
Y H

Problem: Define the terms 'chemical equivalence' and 'magnetic equivalence' used in
1
HNMR spectroscopy. Give example of a molecule containing chemically equivalent but
magnetically non equivalent proton with justification. (CU 2022 CBCS)
Problem: Comment on chemical and magnetic equivalence of the vinyl protons of trans
stilbene. (KU 2011)

Page-1
Ans: H Ph The vinylic Hs belong to identical electronic envireonment. So they are
chemically equivalent. There is not any other H to couple with. So they are
Ph
magnetically equivalent as well.
H
trans-stilbene
First order spin-spin coupling: Let us consider the following molecular fragment. Here the
methylene Hs (Hb) appear as a doublet with J ~ 7.0 Hz and the methyne H (Ha) appears as
triplet with J ~ 7.0 Hz.

C C Hb

Ha Hb

J-is independent of operating frequency. In case of an applied field 300 MHz, the  ranges
over usually 3600 Hz. J rarely ever exceeds 20 Hz (for 1H-1H coupling).
Problem: What do you understand by first order NMR-spectrum?

First-order splitting pattern: A multiplet is called a first order multiplet when the chemical
shift difference in Hertz between coupled protons is much larger than the J coupling constant
(/J >8). Simple first order multiplets have the following characteristics: (i) The number
of peaks in a multiplet is given by the (n+1) rules with the same value of coupling constant. (ii)
A simple first order multiplet is centrosymmetric.
Where Δν is the difference of chemical shift. In other word, the proton is only coupled to
other protons that are far away in chemical shift. The spectrum is called first-order
spectrum. Let us consider the following doublets.

High-order splitting pattern: High-order splitting pattern takes place when  J. If the
spectrum is recorded using an instrument with lower operating frequency,  is reduced but J is

Page-2
unaffected. When J is particularly large (~20 Hz),  and J become very close. It has been
illustrated in the following diagram.

Along with the requirements mentioned above, we need to consider the concept of magnetic
equivalence as well. Two chemical shift equivalent Hs are magnetically equivalent only when
they are symmetrically disposed with respect to each neighboring proton in the spin state.
Aromatic compounds often contain magnetically non equivalent Hs. Let us consider the
following compounds.

Page-3
 Cl Cl
Ha Ha' Ha Cl

Hb Hb' Hb Ha'
NO2 Hb'

Page-4
These aromatic Hs do not represent first order spin systems.

Page-5
Distinction type problems
Problem: How would you distinguish p-dichloro benzene and o-dichloro benzene by
comparison of their 1HNMR spectrum? (CU 2006, 2021 CBCS)

Problem: How many signals will you expect in the 1HNMR spectrum of o-dinitro
benzene? How can you distinguish it from p-dinitro benzene from their 1HNMR
spectrum? (CU 2002, 2003, 2015, 2019)
Similar to previous answer
Problem: How would you distinguish o-dichloro benzene and m-dichloro benzene by 1H-
NMR spectroscopy? (CU 2010)
Ans: 2H-dd
Cl Cl 1H-triplet
2H-dd Ha Cl Hb Ha
1H-triplet
Hb Ha 2H-dd Hc Cl
Hb Hb
ortho dichloro benzene meta dichloro benzene
Contains two types of aromatic H Contains three types of aromatic H
Problem: How would you distinguish p-dinitrobenzene and m-dinitrobenzene by 1H-
NMR spectroscopy. (KU 2010)
Hint: p-dinitro benzene contains one type of aromatic H, m-dinitrobenzene contains three types
of aromatic-H.
Problem: How would you distinguish the following pair by 1H-NMR? (KU 2019)
CH3
CH3
H3C CH3

Page-1
Distinction type problems
Problem: Indicate the differences in the 1HNMR spectra of the following. (CU 2007)
O O
and
O O

Problem: Distinguish CH3CH2Br and CH3CH2OH (ordinary grade) by 1HNMR. (CU

2008)
2H-quartet
Ans: CH3-CH2-Br
3H-quartet
The ordinary grade sample of CH3CH2OH contains acidic impurity. The -OH-proton undergoes
rapid exchange. So this proton does not undergo spin-spin coupling with adjacent methylene
Hs. CH3-CH2-OH 1H-singlet

2H-quartet
3H-triplet
The 1H-singlet for -OH group is observed in the spectrum of the alcohol.
Problem: How would you distinguish CH3CH2CHO and CH3COCH3 by 1H-NMR
spectroscopy. (KU 2009)

Page-2
Distinction type problems
Problem: How can you distinguish between o-fluoro phenol and p-fluoro phenol by 1H-
NMR spectroscopy? (CU 2017)

The ortho isomer contains intramolecular H-bonding. In the para isomer intermolecular H-
bonding is present. When diluted with non polar solvent such as CS2, the intermolecular H-bond
is diminished. The intramolecular H-bond in the ortho isomer is not affected by dilution. So the
-OH signal for the dilute sample of ortho isomer appears at higher δ-value.
Problem: How can you distinguish the following pair of compounds by 1H-NMR
spectroscopy? (KU 2010)
OCOCH3 COOCH3

Problem: Distinguish the following pair of compounds by 1H-NMR spectroscopy:

CH3CH2OCH2CH3 and CH3CH2CH2OCH3 (KU 2013)
(2H,multiplet) (2H,triplet)
Ans: (4H,quartet)
(3H, siglet)
(6H,triplet) (3H,triplet)
CH3CH2OCH2CH3 CH3CH2CH2OCH3

Contains two types of hydrogen. So we Contains four types of hydrogen. So we

get two signals in the 1H-NMR spectrum. get four signals in the 1H-NMR spectrum.
Problem: Distinguish the following pair of compounds by 1H-NMR spectroscopy. (KU
2014)
CH2OMe OMe OMe OMe
CH3 O
(i) and (ii) and (iii) and
O
CH3 CH3

Page-3
Distinction type problems
CH2OMe
Ans: (i)
H 3C OMe

Contains five aromatic Hs Contains four aromatic Hs of two different types.

that appear as 5H, multiplet Each aromatic H appears as a 2H, doublet
OMe
CH3
(ii) H3C OMe

Contains two types of aromatic Hs Contains four types of aromatic Hs

 ~ 7.5 (1H,dd)
 ~5.1 (1H,dd) H  ~6.0 (1H,dd)
 ~ 6.5 (1H,dd) H
H H
 ~5.3 (1H,dd) O
(iii) CH3 H H2C
CH2
H  ~ 1.1 (3H,t) CH3
O
 ~3.1 (2H,d)
 ~ 2.3 (2H,q)  ~ 2.0 (3H,s)
 ~ 7.8 (1H,dd)
Problem: How can you distinguish between the following pairs by 1H-NMR spectroscopy?
(CU 2011)
H3CH2CC CH and H3CC CCH3
3H, triplet
2H, quartet
1H,singlet
H3CH2CC CH H3CC CCH3
Ans: Contains 6-Hs of one type.
Contain three types of H.
Appears as 6H,singlet
GIves rise to three signals
Problem: How will you distinguish between p-xylene and mesitylene by PMR
spectroscopy? (KU 2017, 2019)
Ans: H H  ~ 7.1 (4H,S) H3C H  ~ 7.1 (3H,S)
H3C CH3 CH3
H
H H H3C H
para xylene mesitylene
 ~ 2.5 (6H,S)  ~ 2.5 (9H,S)
Relative peak area of aromatic Relative peak area of aromatic
and aliphatic Hs is 2:3 and aliphatic Hs is 1:3

Page-4
Distinction type problems
Problem: How would you identify the following three isomers (C4H8O2) with the help of
1
H-NMR spectroscopy? (KU 2018)
O O
O
C OCH3
C CH2CH3 C
H 3C CH2 H3CO CH2CH3
H3 C O

Problem: Acid catalyzed dehydration of 1-methyl cyclohexanol gives a mixture of two

alkenes. How would you distinguish between them using 1HNMR spectroscopy? (KU
2015, 2020)

These two compounds show different 1HNMR spectra.

Page-5
Identification type problems

Problem: Write down the structure of the compound C5H11Cl which shows two singlets in
its 1HNMR spectrum. (CU 2004, 2015)

The compound shows two singlets in the 1HNMR spectrum. When there are so many Hs but
signals appear as singlets, it may indicate tertiary butyl group.

Problem: A compound C4H6O2 shows a very strong IR band at 1720 cm-1 and only one
singlet in its 1HNMR spectrum. Identify the compound. (CU 2010, 2011)

Also there is only one type of hydrogen. The probable structure of the compound is:
O
C CH3
H 3C C
O
Problem: Compound A (C9H18O) gives only one peak in its 1H-NMR spectrum at δ 1.40.
Suggest a plausible structure of A. (KU 2010)

Page-1
Identification type problems
Problem: A compound with the molecular formula C2H2BrCl exhibits two doublets (J =
16Hz) in its PMR spectrum. Suggest the structure. (KU 2017)

Problem: Establish the structure of the compound with molecular formula C4H8O which
shows the following spectral data: IR: 1711 cm-1; 1H-NMR: δ 1.17 (3H,t); 2.72 (2H,q); 2.21
(3H,s). (KU 2017)

Problem: An organic compound C6H12O gives positive iodoform test. Its IR spectrum
shows strong signal at 1710 cm-1. 1H-NMR spectrum shows signals at: δ 2.1 (9H,singlet)
and δ (1.1 9H,s). Deduce the structure with proper justification. (CU 2022 CBCS)
Problem: An organic compound shows the following spectral data:
Mass: 130 (molecular weight)
IR: 3082-2860, 1825, 1755, 1455 cm-1
1
HNMR: δ 1.30 (triplet, J = 7Hz) and 2.20 (quartet, J = 7.1 Hz) of peak areas 3:2.
Establish the structure of the compound. (CU 2010)

The probable structure is:

O O
C C
H3CH2C O CH2CH3
Page-2
Identification type problems
Problem: A compound of molecular formula C6H12O shows a strong IR band at 1705 cm-1
and two singlet signals at δ = 2.1 and 1.2 in its 1HNMR spectrum. Establish the structure
of the compound. (CU 2011)
Problem: A compound having molecular formula C6 H12O shows in its 1H-NMR spectrum
two singlets at δ 1.1 (9H) and 2.1 (3H) both as singlets. Identify the compound. (CU
2018)
Problem: A compound having molecular formula C6H12O shows the following spectral
features: IR: 1715 cm-1 and 2900 cm-1; 1H-NMR: two singlets at δ 1.0 (9H) and 2.0 (3H).
Identify the compound. (CU 2021)

Problem: A compound having molecular formula C12H18 is characterized by 1H-NMR

spectrum which contains a single peak at δ 2.2 as a singlet. Identify the compound. (CU
2018)

Problem: An organic compound with the formula C9H12 shows the following spectral
data: UV (λmax): 268 nm εmax= 480;IR: Significant absorption at 3065-2091 cm-1; 1680 cm-1
and 1473 cm-1. 1H-NMR: δ 2.26 (9H,s); 6.79 (3H,s) Derive the structure of the compound
from the supplied data with explanation. (CU 2019)

Page-3
Identification type problems

Problem: An organic compound with molecular formula C8H6 shows the following
spectral data: IR: 3300, 3080, 1500, 1600 cm-1; 1H-NMR: δ 7.3 (s, 5H); 2.9 (s,1H).
Establish the structure of the compound. (KU 2018)

Problem: Which of the compounds below most closely matches the following 1H-NMR
data? Explain your answer. (CU 2018)
OCH3 CH3
H3C
H3CO CH3 OCH2CH3
CH3
δ-value No of protons Splitting
7.6 2H Doublet
7.3 2H Doublet
3.5 3H Singlet
2.2 3H Singlet

Ans: The compound contains 4-aromatic Hs, with 2Hs in each set. δ = 2.2 (3H,s) indicates
benzylic -CH3; δ = 3.5(3H,s) indicates-OCH3. Probably this is a para disubstituted compound.
The probable structure is:

Page-4
Identification type problems
= 7.3 (2H,d) Ha Hb = 7.6 (2H,d)

= 3.5 (3H,s) H3CO CH3 = 2.2 (3H,s)

Ha Hb

Problem: An organic compound having molecular formula C8H7NO3 shows a strong IR

band at 1690 cm-1 and three signals at δ = 8.5 (doublet), 7.9 (doublet), 2.5 (singlet) in its
1
HNMR spectrum. Establish the structure of the compound. (CU 2012)

DBE = 6 may indicate one benzene ring. IR band at 1690 cm-1 indicates unsaturated carbonyl.

Problem: A compound of the molecular formula C9H8O has the following spectral
features: UV: 284 nm (intense); 308 nm (weak) IR: 1690 cm-1 1H-NMR: δ 6.7 (1H,dd,J=16
and 8); 7.4 (5H,m); 7.45 (1H,d,J=16); 9.75 (1H,d,J=8). Deduce the structure of the
compound. (KU 2013)

Page-5
Identification type problems

Problem: A compound having molecular formula C6H10O shows 6-H singlet at 2.30 ppm,
1-H singlet at 6.09 ppm and 3H singlet at 2.27 ppm in the NMR spectrum. The compound
shows UV absorption at λmax 230 nm and 329 nm in hexane. Identify the structure of the
compound with proper assignment of the NMR signals. (CU 2014)

Problem: An organic compound C6H10O2 shows the following spectral data: UV: 210 nm
(ϵ = 11700); IR: 1620, 1695 cm-1; 1H-NMR: δ 6.45 (1H, s), 2.1 (6H, s), 1.9 (3H, s). Deduce
the structure of the compound. (KU 2014)

IR signal at 1620 cm-1 probably indicates C=C and 1695 cm-1 probably indicates unsaturated
carbonyl.

Page-6
Identification type problems

6.45 (1H,s)
2.1 (6H,s)
H3 C O
The probable structure is: C CH O C
H3 C 1.9 (3H,s)
CH3
Problem: A compound having molecular formula C9H8O2 shows 1H doublet at 7.8 ppm,
2H multiplet at 7.56 ppm, 3H multiplet at 7.42 ppm, 1H doublet at 6.45 ppm, and 1H brS
at 12.7 ppm. In IR it shows a peak at 1680 cm-1 and 2520-3070 cm-1 broad signal. Draw the
structure of the compound. (CU 2015)

1
HNMR signal at 12.7 ppm (1H, brS) probably indicates -COOH group; 7.56 (2H,m) and 7.42
(3H,m) probably indicates aromatic Hs. Therefore it must be monosubstituted benzene ring.
δ = 7.8 (1H,d) and 6.45 (1H,d) probably indicates vinylic Hs. The probable structure of the
compound is.

Problem: Assign the structure to each of the following compounds on the basis of 1H-
NMR data: Compound-I (C8H10): δ 1.2 (3H,t); 2.6 (2H, q); 7.2 (5H,s) Compound-II
(C10H14): δ 1.3 (9H,s); 7.2 (5H,s). (KU 2015)

Page-7
Identification type problems

Problem: Draw the structures of the compounds that meet the following descriptions in
1
H-NMR spectroscopy: (i) C2H6O (one singlet) (ii) C4H8O2 (one singlet, one triplet, one
quartet) (iii) C3H7Cl (one doublet, one septet). (KU 2015)

Problem: A compound having molecular formula C9H11Cl shows the following signals in
its 1H-NMR spectrum: 2.25 ppm (2H,m); 2.80 ppm (2H,t); 3.50 ppm (2H,t); 7.23ppm (5H,
brs). Deduce structure of the compound. (KU 2016)

Page-8
Identification type problems

Problem: Suggest the structure for a compound having molecular formula C8H7OCl
which shows a strong band at 1690 cm-1 in its IR spectrum. Its 1H-NMR spectrum shows
peaks at δ 7.4-7.9 (5H) and a singlet at δ 4.75 (2H). (KU 2016)

1
H-NMR signal at δ 7.4-7.9 (5H) probably indicates aromatic Hs. So it must be monosubstituted
aromatic ring. A 2H-singlet at δ 4.75 may indicate -CH2Cl.

Problem: An organic compound with molecular formula C10H12O2 gives positive iodoform
test. Its IR and 1HNMR data are given below; deduce the structure of the compound. IR:
3050, 2950, 1730 cm-1.1H-NMR: δ 1.3 (d, 6H), 5.2 (m, 1H), 7.2 (m, 3H), 8.0 (m, 2H). (CU
2017)

IR signal at 1730 cm-1 probably indicates ester. 1HNMR signal at δ = 1.3 (d, 6H), 5.2 (m, 1H)
probably indicates isopropyl group.
Page-9
Identification type problems
δ = 7.2 (m, 3H), 8.0 (m, 2H) probably indicates aromatic Hs. So there are 5-aromatic Hs. It
must be a monosubstituted benzene. The probable structure is:
 =5.2 (1H,m)
Ha
Hb O CH(CH3)2
C
O  = 1.3 (6H,d)
Hc Ha
 =7.2 (3H,m) Hb  = 8.0 (6H,m)

Alkaline hydrolysis of this compound would produce iso-propyl alcohol. Isopropyl alcohol
gives positive iodoform test.
Problem: A compound (C9H10O2) shows strong band at 1680 cm-1 in the IR-spectrum. 1H-
NMR shows signals in three distinct regions at δ 2.3 (3H,s); δ 3.6 (3H,s) and δ 6.4-7.5 (4H,
a pair of doublets J = 8 Hz). Assign the structure. (KU 2017)

Problem: An organic compound of the molecular formula C9H10O2 shows the following
spectral pattern: UV: λmax = 270 nm IR: 1680 cm-1. 1H-NMR: δ 7.6 (2H,d, J= 8 Hz); 6.9
(2H,d,J=8Hz); 3.9 (3H,s); 2.0 (3H,s). Identify the compound. (CU 2020)
Similar as the previous problem

Page-10
Identification type problems
Problem: A compound C8H8O gives the following spectra: IR: 3100, 1700(s), 1640, 1680
cm-1, 1H-NMR: δ 7.3-8.2 (complex multiplet), 2.5 (3H,s). Identify the compound with
proper justification. (CU 2018)

δ = 2.5 (3H,s) probably indicates ketomethyl group. δ 7.3-8.2 (complex multiplet) (for 8-
3=5Hs) probably indicates aromatic Hs. This compound must contain monosubstituted benzene
ring. The probable structure is:
H O
H C = 2.5 (3H,s)
CH3
= 7.3~8.2 (5H, complex multiplet)
H H
H
Problem: An organic compound with molecular mass 69 is transparent above 200 nm.
The absorption bands in IR spectrum are 2941 cm-1 (m); 2273 cm-1 (m) and 1460 cm-1 (m).
In 1H-NMR two signals are observed: one septet at 2.72 ppm and another doublet at 1.33
ppm. Deduce the structure of the compound. (KU 2019)
Ans: Transparent over 200 nm indicates that there is no conjugated double bonds. IR signal at
2273 cm-1 may indicate C N. In 1HNMR spectrum septet at 2.72 ppm and doublet at
1.33 ppm probably indicates isopropyl group. So the probable structure is:
=1.33 (6H,doublet)
H3C
=2.72 (1H,septet)
CH C N
H3C

Problem: A compound has molecular formula C10H13Cl. Assign its structure with the help
of the following proton NMR data: singlet 1.57 δ 6H; singlet 3.07 δ2H; singlet 7.27 δ 5H.
(KU 2019)

Page-11
Identification type problems
Probable structure of the compound is:

H H3C
H C CH3  = 1.57 (6H,s)
 = 7.27(5H,s) CH2Cl

H H
H
 = 3.07(2H,s)

Problem: A compound C7H8O shows 1HNMR signal at δ = 7.3 (5H), 4.4 (2H) and 3.7 (1H).
Identify the structure. (KU 2020)

Problem: A liquid with the molecular formula C6H7NO2 shows characteristic IR

absorption at 2240 cm-1 and 1730 cm-1 and 1HNMR peaks at δ = 2.7 (4H,s) and 3.8 (3H,s).
Assign the structure. (KU 2020)

There are four unsaturations/ combination of unsaturation and ring. IR signal at 1730 cm-1
probably indicates ester group and 2240 cm-1 probably indicates C Ngroup.
1
HNMR signal at δ = 2.7 (4H,s) probably indicates -CH2-CH2- moiety. δ = 3.8 (3H,s) probably
indicates -OCH3. The probable structure is:

Page-12
Identification type problems
Problem: An organic compound A, C6H12O2 on heating with Na/xylene produces another
compound B, C6H12O2 along with an alcohol C3H8O which does not give iodoform test.
Oxidation of compound B with BiO3/HOAc generates compound C, C6H10O2 which shows
one quartet and one triplet signal in 1HNMR spectrum and a characteristic IR band at
1730 cm-1. Treatment of compound C with excess C2H5MgBr followed by usual work up
gives compound D, C10H22O2 which shows one quartet (8H), one triplet (12H) and a broad
peak (2H) in 1HNMR spectrum and a broad IR band at 3350 cm-1. Heating compound D
with dil.H2SO4 (1:1) affords E (C10H20O) containing two types of ethyl groups and showing
an IR band at 1710 cm-1. Identify the compounds A to E and explain the reaction. (CU
2007)

Page-13
Identification type problems

Problem: Write the most probable structure of the compound with molecular formula
C4H8O with the following 1HNMR data. (KU 2021 CBCS)

Page-14
Identification type problems

Problem: Compound A shows only one singlet n its 1H-NMR spectrum at δ=2.17. When
treated with PhCHO on presence of ethanolic NaOH it forms B. IR spectrum of B displays
bands at: 3025, 1665, 1630, 1600, 763 and 753 cm-1. 1H-NMR spectrum of compound B
shows signals at: δ: 7.82 (2H, d, J = 18 Hz), 7.05 (2H,d, J = 18 Hz), 7.60 (10H, m). Identify
the structures of A and B. (KU 2021 CBCS)

Page-15