Introduction to NMR Spectroscopy

Nuclear magnetic resonance spectroscopy is a powerful analytical technique

used to characterize organic molecules by identifying carbon-hydrogen
frameworks within molecules.

Two common types of NMR spectroscopy are used to characterize organic

structure: 1H NMR is used to determine the type and number of H atoms in a
molecule; 13C NMR is used to determine the type of carbon atoms in the
molecule.

The source of energy in NMR is radio waves which have long wavelengths,
and thus low energy and frequency.

When low-energy radio waves interact with a molecule, they can change the
nuclear spins of some elements, including 1H and 13C.
 Introduction to NMR Spectroscopy
When a charged particle such as a proton spins on its axis, it creates a magnetic field.
Thus, the nucleus can be considered to be a tiny bar magnet.

Normally, these tiny bar magnets are randomly oriented in space. However, in the
presence of a magnetic field B0, they are oriented with or against this applied field. More
nuclei are oriented with the applied field because this arrangement is lower in energy.

The energy difference between these two states is very small (<0.1 cal).
• In a magnetic field, there are now two energy states for a proton: a
lower energy state with the nucleus aligned in the same direction as Bo,
and a higher energy state in which the nucleus aligned against Bo.

• When an external energy source (hν) that matches the energy

difference (ΔE) between these two states is applied, energy is
absorbed, causing the nucleus to “spin flip” from one orientation to
another.

• The energy difference between these two nuclear spin states

corresponds to the low frequency RF region of the electromagnetic
spectrum.
• Thus, two variables characterize NMR: an applied magnetic field Bo, the
strength of which is measured in tesla (T), and the frequency (ν) of
radiation used for resonance, measured in hertz (Hz), or megahertz
(MHz)—(1 MHz = 106 Hz).
• The frequency needed for resonance and the applied magnetic field
strength are proportionally related:

• NMR spectrometers are referred to as 300 MHz instruments, 500 MHz

instruments, and so forth, depending on the frequency of the RF radiation
used for resonance.
• These spectrometers use very powerful magnets to create a small but
measurable energy difference between two possible spin states.
 NUCLEAR SPIN
The nuclei of some atoms have a property called “SPIN”.

These nuclei behave as if

they were spinning.

This is like the spin property

of an electron, which can have
two spins: +1/2 and -1/2 .

Each spin-active nucleus has a number of spins defined by

its spin quantum number, I.

The spin quantum numbers of some common nuclei follow …..

Although interest is increasing in other nuclei, particulary C-13, the hydrogen nucleus (proton) is studied
most frequently, and we will discuss it first.
 Spin Quantum Numbers of Some Common Nuclei
The most abundant isotopes of C and O do not have spin.

Element 1H 2H 12C 13C 14N 16O 17O 19F

Nuclear Spin
Quantum No 1/2 1 0 1/2 1 0 5/2 1/2
(I)
No. of Spin 2 3 0 2 3 0 6 2
States

Elements with either odd mass or odd atomic number

have the property of nuclear “spin”.

The number of spin states is 2I + 1,

where I is the spin quantum number.
NUCLEAR SPIN STATES - HYDROGEN NUCLEUS
The spin of the positively
m charged nucleus generates
a magnetic moment vector, m.

+ +

The two states are equivalent in

m energy in the absence of a
magnetic or an electric field and
+ 1/2 - 1/2 randomly oriented.

TWO SPIN STATES

 Nuclear Spin Energy Levels
N

-1/2

In a strong magnetic
unaligned
field (Bo) the two
spin states differ in
energy.

+1/2

aligned
Bo S
(a) In the absence of an external magnetic
field, the nuclear spins of the
protons are randomly oriented.
(b) In the presence of an external magnetic
field B0, the nuclear spins are oriented so
that the resulting nuclear magnetic
moments are aligned either parallel or
antiparallel to B0. The lower energy
orientation is the one parallel to B0, and
more nuclei have this orientation.
 THE ENERGY SEPARATION DEPENDS ON Bo
Higher the external magnetic field strength, larger the separation of two spin states.
 Absorption of Energy
quantized
Opposed

-1/2 -1/2

DE

DE = hn
Radiofrequency

+1/2 +1/2
Applied
Field
Aligned
Bo
 The Larmor Equation
DE = kBo = hn can be transformed into

gyromagnetic
ratio g
frequency of g
the incoming
n = Bo
radiation that
will cause a
transition
2p
strength of the
g is a constant which is different for magnetic field
each atomic nucleus (H, C, N, etc)
1. Calculate the magnetic fields that correspond to proton resonance frequencies
of 60 MHz and 300 MHz.
A SECOND EFFECT OF A STRONG MAGNETIC FIELD

WHEN A SPIN-ACTIVE HYDROGEN ATOM IS PLACED IN A STRONG

MAGNETIC FIELD IT BEGINS TO PRECESS

OPERATION OF AN NMR SPECTROMETER DEPENDS ON THIS RESULT

 N

w Nuclei precess at
frequency w when
RADIOFREQUENCY
placed in a strong
40 - 600 MHz magnetic field.

hn
NUCLEAR
If n = w, the MAGNETIC
nucleus and rf are RESONANCE
said to be in
resonance,energy will NMR
be absorbed and the S
spin will invert.
• If rf energy having a frequency (ν) matching the Larmor frequency (ω) is introduced at a right
angle to the external field (e.g. along the x-axis), the precessing nucleus will absorb energy and
the magnetic moment will flip to its I = _1/2 state, the nucleus and rf are said to be in resonance;
hence the term nuclear magnetic resonance. This excitation is shown in the following diagram.
Note that frequencies in radians per second may be converted to Hz (cps) by dividing by 2π. ν =
ω / 2π
• The energy difference between nuclear spin states is small compared with the average kinetic energy
of room temperature samples, and the +1/2 and _1/2 states are nearly equally populated.

• Indeed, in a field of 2.34 T the excess population of the lower energy state is only six nuclei per million.
Although this is a very small difference , when we consider the number of atoms in a practical sample
(remember the size of Avogadro's number), the numerical excess in the lower energy state is sufficient
for selective and sensitive spectroscopic measurements.
Resonance Frequencies of Selected Nuclei
Isotope Abundance Bo (Tesla =10,000gauss) Frequency(MHz) g(radians/Tesla)

1H 99.98% 1.00 42.6 267.53

1.41 60.0
2.35 100.0
7.05 300.0

2H 0.0156% 1.00 6.5 41.1 4:1

45.8

13C 1.108% 1.00 10.7 67.28

2.35 25.0
7.05 75.0

19F 100.0%1.00 40.0 251.7

POPULATION AND SIGNAL STRENGTH
The strength of the NMR signal depends on the Population
Difference of the two spin states

Radiation
induces both
upward and
downward resonance
induced
emission
transitions.

For a net positive signal excess

there must be an excess population
of spins in the lower state.

Saturation = equal populations = no signal

 Relaxation- Return to Equilibrium
 Spin-lattice relaxation (longitudinal) (along the axis of the
external magnetic field)
converts the excess energy into translational, rotational, and vibrational energy of the
surrounding atoms and molecules (the lattice) and returning to the lower state.
 Spin-spin relaxation (transverse) (perpendicular to the external
magnetic field)
transfers the excess energy to other magnetic nuclei in the sample.
In this mechanism there is no net change in the populations of the energy states, but the average lifetime of
a nucleus in the excited state will decrease. This can result in line-broadening.
1. Why do we see peaks? When the excited nuclei in the beta orientation start to relax back down to
the alpha orientation, a fluctuating magnetic field is created. This fluctuating field generates a current in a
receiver coil that is around the sample. The current is electronically converted into a peak. It is the
relaxation that actually gives the peak not the excitation.
• The sample is dissolved in a suitable solvent and placed in a thin glass
tube.The tube is placed between the poles of a powerful magnet.

• In the CW instrument, the frequency of the Electromagnetic radiation in the

radio region is held constant and the strength of the magnetic field is slowly
varied.

• When the magnetic field strength is such that the difference between the
energy states of the hydrogen nucleus matches the energy of the radiation,
the hydrogen absorbs the energy of the radiation and is said to be in
resonance.

• It takes several minutes to scan the entire spectrum.

1H NMR—The Spectrum
• An NMR spectrum is a plot of the intensity of a peak against its
chemical shift, measured in parts per million (ppm).
Fortunately, different types of protons precess at
different rates in the same magnetic field.

N Bo = 1.41 Tesla

EXAMPLE: 59.999995 MHz

59.999700 MHz
O
CH2 C CH3

hn
To cause absorption
60 MHz 59.999820 MHz of the incoming 60 MHz
the magnetic field strength,
Bo , must be increased to
S a different value for each
type of proton.
Differences are very small,
in the parts per million range.
IN THE CLASSICAL NMR EXPERIMENT THE INSTRUMENT
SCANS FROM “LOW FIELD” TO “HIGH FIELD”

LOW HIGH
FIELD FIELD
NMR CHART

DOWNFIELD UPFIELD
scan
NMR Spectrum of Phenylacetone

O
CH2 C CH3

NOTICE THAT EACH DIFFERENT TYPE OF PROTON COMES

AT A DIFFERENT PLACE - YOU CAN TELL HOW MANY
DIFFERENT TYPES OF HYDROGEN THERE ARE
MODERN INSTRUMENTATION

PULSED FOURIER TRANSFORM

TECHNOLOGY

FT-NMR
requires a computer
 PULSED EXCITATION
N

n2
n1
O
BROADBAND
RF PULSE CH2 C CH3
contains a range
of frequencies n3
(n1 ..... nn)

S
All types of hydrogen are excited
simultaneously with the single RF pulse.
FREE INDUCTION DECAY
( relaxation )

n1

O
CH2 C CH3 n2

n3

n1, n2, n3 have different half lifes

COMPOSITE FID

“time domain“ spectrum

n1 + n2 + n3 + ......
time
 FOURIER TRANSFORM
A mathematical technique that resolves a complex
FID signal into the individual frequencies that add
together to make it. ( Details not given here. )

converted to DOMAINS ARE

TIME DOMAIN FREQUENCY DOMAIN MATHEMATICAL
FID NMR SPECTRUM TERMS

FT-NMR
computer
COMPLEX
SIGNAL n1 + n2 + n3 + ......
Fourier
Transform

individual
a mixture of frequencies
frequencies
decaying (with time)
converted to a spectrum
The Composite FID is Transformed into
a classical NMR Spectrum :

O
CH2 C CH3

“frequency domain” spectrum

 COMPARISON OF
CW AND FT TECHNIQUES
CONTINUOUS WAVE (CW) METHOD
THE OLDER, CLASSICAL METHOD

The magnetic field is “scanned” from a low field

strength to a higher field strength while a constant
beam of radiofrequency (continuous wave) is
supplied at a fixed frequency (say 100 MHz).

Using this method, it requires several minutes to plot

an NMR spectrum.

SLOW, HIGH NOISE LEVEL

PULSED FOURIER TRANSFORM
(FT) METHOD FAST
THE NEWER COMPUTER-BASED METHOD LOW NOISE

Most protons relax (decay) from their excited states

very quickly (within a second).

The excitation pulse, the data collection (FID), and

the computer-driven Fourier Transform (FT) take
only a few seconds.

The pulse and data collection cycles may be repeated

every few seconds.

Many repetitions can be performed in a

very short time, leading to improved signal …..
IMPROVED SIGNAL-TO-NOISE RATIO
By adding the signals from many pulses together, the
signal strength may be increased above the noise level.

signal enhanced
noise signal

1st pulse

2nd pulse
add many
pulses

noise is random
nth pulse etc. and cancels out
 DIAMAGNETIC ANISOTROPY

Diamagnetism is theSHIELDING
pro BY VALENCE ELECTRONS
[Diamgnetism is the property of an object which causes it to create a magnetic field in opposition of an externally applied magnetic field.
The word "anisotropic" means "non-uniform". So magnetic anisotropy means that there is a "non-uniform magnetic field". ]

In realty, nuclei are surrounded by electrons which also generate small local
magnetic fields (Bloc) as they circulate. These local magnetic fields can either
oppose or augment the external magnetic field. If the field created by the
electron oppose the external field, nuclei ‘experience’ an effective field which is
smaller than the external field and it is said to be SHIELDED. If the field created
by the electron augments the external field, nuclei ‘experience’ an effective field
which is larger than the external field. It is said to be DESHIELDED.
i.e. Beff = Bo - Bloc
This can be represented as Beff = Bo( 1 - σ )
 Diamagnetic Anisotropy
The applied field
induces circulation
of the valence
electrons - this
generates a valence electrons
magnetic field shield the nucleus
that opposes the
applied field.
from the full effect
of the applied field

magnetic field
lines

Bo applied B induced
(opposes Bo)
fields subtract at nucleus
PROTONS DIFFER IN THEIR SHIELDING
All different types of protons in a molecule
have a different amounts of shielding.

They all respond differently to the applied magnetic

field and appear at different places in the spectrum.

This is why an NMR spectrum contains useful information

(different types of protons appear in predictable places).

SPECTRUM
DOWNFIELD UPFIELD
Less shielded protons Highly shielded
appear here. protons appear here.
It takes a higher field
to cause resonance.
CHEMICAL SHIFT
PEAKS ARE MEASURED RELATIVE TO TMS
Rather than measure the exact resonance position of a
peak, we measure how far downfield it is shifted from TMS.

CH3 reference compound

tetramethylsilane
CH3 Si CH3 “TMS”
CH3
Highly shielded
protons appear
way upfield.

TMS Chemists originally

shift in Hz thought no other
compound would
downfield
come at a higher
n 0 field than TMS.
REMEMBER FROM OUR EARLIER DISCUSSION

Stronger magnetic fields (Bo) cause

field
strength the instrument to operate at higher
frequency frequencies (n).

g
hn = B
2p o
NMR Field 1H Operating
Strength Frequency
constants
1.41 T 60 Mhz
2.35 T 100 MHz
n = ( K) Bo 7.05 T 300 MHz
HIGHER FREQUENCIES GIVE LARGER SHIFTS

The shift observed for a given proton

in Hz also depends on the frequency
of the instrument used.
Higher frequencies
= larger shifts in Hz.

TMS
shift in Hz
downfield
n 0
 THE CHEMICAL SHIFT
The shifts from TMS in Hz are bigger in higher field
instruments (300 MHz, 500 MHz) than they are in the
lower field instruments (100 MHz, 60 MHz).
We can adjust the shift to a field-independent value,
the “chemical shift” in the following way:
parts per
million

chemical shift in Hz
shift
= d = = ppm
spectrometer frequency in MHz

This division gives a number independent

of the instrument used.

A particular proton in a given molecule will always come

at the same chemical shift (constant value).
HERZ EQUIVALENCE OF 1 PPM
What does a ppm represent?

1H Operating Hz Equivalent 1 part per million

Frequency of 1 ppm of n MHz is n Hz
1
n MHz ( ) = n Hz
60 Mhz 60 Hz 10 6

100 MHz 100 Hz

300 MHz 300 Hz

7 6 5 4 3 2 1 0 ppm

Each ppm unit represents either a 1 ppm change in

Bo (magnetic field strength, Tesla) or a 1 ppm change
in the precessional frequency (MHz).
2. A 300-MHz spectrometer records a proton that absorbs at a frequency
2130 Hz downfield from TMS.
(a) Determine its chemical shift, and express this shift as a magnetic field difference.
(b) Predict this proton's chemical shift at 60 MHz. In a 60-MHz spectrometer, how far downfield
(in gauss and in hertz) from TMS would this proton absorb?

3. In a 300-MHz spectrometer, the protons in iodomethane absorb at a position 650 Hz

downfield from TMS.
(a) What is the chemical shift of these protons?
(b) Determine the difference in the magnetic field required for resonance of the
iodomethane protons compared with the TMS protons.
(c) What is the chemical shift of the iodomethane protons in a 60-MHz spectrometer?
(d) How many hertz downfield from TMS would they absorb at 60 MHz?
 YOU DO NOT NEED TO MEMORIZE THE
PREVIOUS CHART

IT IS USUALLY SUFFICIENT TO KNOW WHAT TYPES

OF HYDROGENS COME IN SELECTED AREAS OF
THE NMR CHART

C-H where C is
CH on C
acid aldehyde benzene alkene attached to an aliphatic
next to
COOH CHO CH =C-H electronega- pi bonds C-H
tive atom
X=C-C-H
X-C-H
12 10 9 7 6 4 3 2 0

MOST SPECTRA CAN BE INTERPRETED WITH

A KNOWLEDGE OF WHAT IS SHOWN HERE
DESHIELDING AND ANISOTROPY
Three major factors account for the resonance
positions (on the ppm scale) of most protons.

1. Deshielding by electronegative elements.

2. Anisotropic fields usually due to pi-bonded

electrons in the molecule.
3. Deshielding due to hydrogen bonding.

We will discuss these factors in the sections that

follow.
 DESHIELDING BY
ELECTRONEGATIVE ELEMENTS
 DESHIELDING BY AN ELECTRONEGATIVE ELEMENT

d- d+ Chlorine “deshields” the proton,

Cl C H that is, it takes valence electron
density away from carbon, which
d- d+ in turn takes more density from
electronegative hydrogen deshielding the proton.
element

NMR CHART

“deshielded“ highly shielded

protons appear protons appear
at low field at high field

deshielding moves proton

resonance to lower field
The electrons in a σ-bond shield the nuclei from the magnetic field. So, if there is more electron density around a proton, it sees a slightly lower magnetic
field, less electron density means it sees a higher magnetic field.
Electronegativity Dependence
of Chemical Shift
Dependence of the Chemical Shift of CH3X on the Element X

Compound CH3X CH3F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si

Element X F O Cl Br I H Si
Electronegativity of X 4.0 3.5 3.1 2.8 2.5 2.1 1.8
Chemical shift d 4.26 3.40 3.05 2.68 2.16 0.23 0

most TMS
deshielded
deshielding increases with the
electronegativity of atom X
 Substitution Effects on
Chemical Shift
most The effect
deshielded increases with
CHCl3 CH2Cl2 CH3Cl
greater numbers
7.27 5.30 3.05 ppm of electronegative
atoms.

most
deshielded -CH2-Br -CH2-CH2Br -CH2-CH2CH2Br
3.30 1.69 1.25 ppm

The effect decreases

with incresing distance.
 ANISOTROPIC FIELDS
DUE TO THE PRESENCE OF PI BONDS

The presence of a nearby pi bond or pi system

greatly affects the chemical shift.

Benzene rings have the greatest effect.

 Ring Current in Benzene

Circulating p electrons

Deshielded
H H fields add together

Bo Secondary magnetic field

generated by circulating p
electrons deshields aromatic
protons
ANISOTROPIC FIELD IN AN ALKENE

protons are
deshielded

H H
Deshielded
shifted
fields add downfield

C=C
H H
secondary
magnetic
(anisotropic)
field lines
Bo
ANISOTROPIC FIELD FOR AN ALKYNE

H
C
C
H secondary
magnetic
(anisotropic)
Shielded hydrogens field
Bo
are shielded
fields subtract
HYDROGEN BONDING
HYDROGEN BONDING DESHIELDS PROTONS

The chemical shift depends

R on how much hydrogen bonding
is taking place.
O H H
Alcohols vary in chemical shift
O H O R from 0.5 ppm (free OH) to about
5.0 ppm (lots of H bonding).
R

Hydrogen bonding lengthens the

O-H bond and reduces the valence
electron density around the proton
- it is deshielded and shifted
downfield in the NMR spectrum.
SOME MORE EXTREME EXAMPLES

O H O Carboxylic acids have strong

R C C R hydrogen bonding - they
form dimers.
O H O

With carboxylic acids the O-H

absorptions are found between
10 and 12 ppm very far downfield.
H3C O
O
H
In methyl salicylate, which has strong
O internal hydrogen bonding, the NMR
absortion for O-H is at about 14 ppm,
way, way downfield.

Notice that a 6-membered ring is formed.

4. Using theTable , predict the chemical shifts of the protons i n the following compounds.

[(a) The methyl group in acetic acid is next to a carbonyl group; table predicts a chemical shift of about δ2.1 . (The
experimental value is δ 2.10). The acid proton ( - COOH) should absorb between δ 1 0 and δ 1 2. (The experimental
value is δ 1 l .4, variable.)
(b) Protons a are on the carbon atom bearing the chlorine, and they absorb between δ 3 and δ 4 (experimental: δ 3.7).
Protons b are one carbon removed, and they are predicted to absorb about δ l .7, like the β protons in I -bromobutane
(experimental: δ l.8). The methyl protons c will be nearly unaffected, absorbing around δ 0.9 ppm (experimental: δ l .0).
(c) Methyl protons a are expected to absorb around δ 0.9 (experimental: δ 1 .0). The vinyl protons b and c are expected
to absorb between δ 5 and δ 6 (experimental δ 5.8 for b and δ 4.9 for c).]

(b) The three types of aromatic hydrogens in toluene appear in a relatively small space around δ 7.2. The signal is complex
because all the peaks from the three types of hydrogens overlap.
1H NMR—Number of Signals
• The number of NMR signals equals the number of different types
of protons in a compound.
• Protons in different environments give different NMR signals.
• Equivalent protons give the same NMR signal.

• To determine equivalent protons in cycloalkanes and alkenes,

always draw all bonds to hydrogen.
1H NMR—Number of Signals

The number of 1H NMR signals of some representative organic compounds

1H NMR—Number of Signals
• In comparing two H atoms on a ring or double bond, two
protons are equivalent only if they are cis (or trans) to
the same groups.
1H NMR—Number of Signals

• Proton equivalency in cycloalkanes can be determined

similarly.
1H NMR—Enantiotopic and Diastereotopic Protons.
1H NMR—Enantiotopic and Diastereotopic Protons.
SPIN-SPIN SPLITTING
 SPIN-SPIN SPLITTING
Often a group of hydrogens will appear as a multiplet
rather than as a single peak.

Multiplets are named as follows:

Singlet Quintet
Doublet Septet
Triplet Octet
Quartet Nonet

This happens because of interaction with neighboring

hydrogens and is called SPIN-SPIN SPLITTING.
 1,1,2-Trichloroethane
The two kinds of hydrogens do not appear as single peaks,
rather there is a “triplet” and a “doublet”.

integral = 2

Cl H
H C C Cl
integral = 1 Cl H

triplet doublet The subpeaks are due to

spin-spin splitting and are
predicted by the n+1 rule.
n + 1 RULE
 1,1,2-Trichloroethane

integral = 2

Cl H
H C C Cl
integral = 1 Cl H

Where do these multiplets come from ?

….. interaction with neighbors
this hydrogen’s peak these hydrogens are MULTIPLETS
is split by its two neighbors split by their single
neighbor

singlet
doublet
H H H H
triplet
C C C C quartet
H H quintet
sextet
two neighbors
n+1 = 3 one neighbor septet
triplet n+1 = 2
doublet
EXCEPTIONS TO THE N+1 RULE
IMPORTANT !

1) Protons that are equivalent by symmetry

usually do not split one another

X CH CH Y X CH2 CH2 Y

no splitting if x=y no splitting if x=y

2) Protons in the same group

usually do not split one another
H H
more
C H or C detail
H H later
 EXCEPTIONS TO THE N+1 RULE
3) The n+1 rule applies principally to protons in
aliphatic (saturated) chains or on saturated rings.

CH3
CH2CH2CH2CH2CH3 or H

YES YES

but does not apply (in the simple way shown here)
to protons on double bonds or on benzene rings.

H CH3 CH3

H H
NO NO
SOME COMMON PATTERNS
SOME COMMON SPLITTING PATTERNS

X CH CH Y CH3 CH
(x=y)

CH2 CH CH3 CH2

CH3
X CH2 CH2 Y
CH
(x=y) CH3
LEANING OF MULTIPLETS

In general, a multiplet "leans"

upward toward the signal of the
protons responsible for the splitting.
In the ethyl signal the quartet at
lower field leans toward the triplet
at a higher field, and vice versa.
SOME EXAMPLE SPECTRA
WITH SPLITTING
NMR Spectrum of Bromoethane

Br CH2CH3
NMR Spectrum of 2-Nitropropane

H
CH3 C CH3
N +
O O-

in higher multiplets the outer peaks

1:6:15:20:16:6:1
are often nearly lost in the baseline
 NMR Spectrum of Acetaldehyde

O
CH3 C
H

offset = 2.0 ppm

 INTENSITIES OF
MULTIPLET PEAKS
PASCAL’S TRIANGLE
 PASCAL’S TRIANGLE
Intensities of
multiplet peaks
1 singlet

The interior
entries are 1 1 doublet
the sums of
the two 1 2 1 triplet

1 3 3 1
numbers
immediately
quartet
above.
1 4 6 4 1 quintet

Coefficients of (1+x)n
expansion 1 5 10 10 5 1 sextet

Where n = no. of
neighbouring 1 6 15 20 15 6 1 septet

1 7 21 35 35 21 7 1
Equivalent atoms
octet
 THE ORIGIN OF
SPIN-SPIN SPLITTING

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

Bo
downfield upfield
neighbor aligned neighbor opposed

At any given time about half of the molecules in solution will

have spin +1/2 and the other half will have spin -1/2.
 SPIN ARRANGEMENTS
one neighbor one neighbor
n+1 = 2 n+1 = 2
doublet doublet

H H H H
C C C C

yellow spins
blue spins

The resonance positions (splitting) of a given hydrogen is

affected by the possible spins of its neighbor.
 SPIN ARRANGEMENTS
two neighbors one neighbor
n+1 = 3 n+1 = 2
triplet doublet

H H H H
C C C C
H H

methine spins
methylene spins
 SPIN ARRANGEMENTS
three neighbors two neighbors
n+1 = 4 n+1 = 3
quartet triplet

H H H H
C C H C C H
H H H H

methylene spins
methyl spins
THE COUPLING CONSTANT
 THE COUPLING CONSTANT
H H
J
C C H

J J H H

J J
J

The coupling constant is the distance J (measured in Hz)

between the peaks in a multiplet.

J is a measure of the amount of interaction between the

two sets of hydrogens creating the multiplet.
 FIELD COMPARISON
100 MHz 200 Hz

100 Hz
Coupling constants are
constant - they do not
7.5 Hz
change at different J = 7.5 Hz
field strengths

6 5 4 3 2 1
200 MHz
400 Hz
Separation
is larger 200 Hz

The separationJ = 7.5 Hz 7.5 Hz

is dependant
on the field

3 2 1 ppm
100 MHz 200 Hz

100 Hz
J=
7.5 Hz
J = 7.5 Hz

6 5 4 3 2 1
200 MHz Separation 400 Hz
is larger
Note the compression of 200 Hz
multiplets in the 200 MHz
spectrum when it is J = 7.5 Hz
plotted on the same scale
as the 100 MHz spectrum
instead of on a chart which
is twice as wide.
6 5 4 3 2 1 ppm
 50 MHz
J = 7.5 Hz
Why buy a higher
field instrument?

3 2 1
Spectra are
simplified! 100 MHz
J = 7.5 Hz

Overlapping
multiplets are
separated. 3 2 1

200 MHz
Second-order J = 7.5 Hz
effects are
minimized.

3 2 1
NOTATION FOR COUPLING CONSTANTS
The most commonly encountered type of coupling is
between hydrogens on adjacent carbon atoms.

H H This is sometimes called vicinal coupling.

3J It is designated 3J since three bonds
C C intervene between the two hydrogens.

Another type of coupling that can also occur in special

cases is
2J or geminal coupling
H
( most often 2J = 0 )
C H
2J
Geminal coupling does not occur when
the two hydrogens are equivalent due to
rotations around the other two bonds.
 LONG RANGE COUPLINGS
Couplings larger than 2J or 3J also exist, but operate
only in special situations.

H C H
C C
4J , for instance, occurs mainly
when the hydrogens are forced
to adopt this “W” conformation
(as in bicyclic compounds).

Couplings larger than 3J (e.g., 4J, 5J, etc) are usually

called “long-range coupling.”
SOME REPRESENTATIVE COUPLING CONSTANTS
H H
vicinal 6 to 8 Hz three bond 3J
C C
H
trans C C 11 to 18 Hz three bond 3J

H
H H
cis C C 6 to 12 Hz three bond 3J

H
geminal C 0 to 3 Hz two bond 2J
H

Hax Hax,Hax = 8 to 14
Heq Hax,Heq = 0 to 7 three bond 3J

Heq Hax Heq,Heq = 0 to 5

 H
Ha
cis 6 to 12 Hz ortho, 7- 10

three bond 3J Hb meta, 2- 3

para, 0- 1
trans 4 to 8 Hz
H
H
C 4 to 10 Hz three bond 3J
C H
H
C C 0 to 3 Hz four bond 4J

C H

H C C C 0 to 3 Hz four bond 4J

H
Couplings that occur at distances greater than three bonds are
called long-range couplings and they are usually small (<3 Hz)
and frequently nonexistent (0 Hz).
INTEGRATION
NMR Spectrum of Phenylacetone

O
CH2 C CH3

RECALL Each different type of proton comes at a different place .

from last You can tell how many different types of hydrogen
time there are in the molecule.
 INTEGRATION OF A PEAK
Not only does each different type of hydrogen give a
distinct peak in the NMR spectrum, but we can also tell
the relative numbers of each type of hydrogen by a
process called integration.

Integration = determination of the area

under a peak

The area under a peak is proportional

to the number of hydrogens that
generate the peak.
 Benzyl Acetate
The integral line rises an amount proportional to the number of H in each peak

METHOD 1
integral line

integral
line

simplest ratio
55 : 22 : 33 = 5:2:3 of the heights
 Benzyl Acetate (FT-NMR)
Actually : 5 2 3

58.117 / 11.3 21.215 / 11.3 33.929 / 11.3

= 5.14 = 1.90 = 3.00

O
CH2 O C CH3

METHOD 2
digital assume CH3
33.929 / 3 = 11.3
integration

Integrals are
good to about
10% accuracy.

Modern instruments report the integral as a number.

 TYPES OF INFORMATION
FROM THE NMR SPECTRUM
1. Each different type of hydrogen gives a peak
or group of peaks (multiplet).
2. The chemical shift (d, in ppm) gives a clue as
to the type of hydrogen generating the peak
(alkane, alkene, benzene, aldehyde, etc.)
3. Spin-spin splitting gives the number of hydrogens
on adjacent carbons.
4. The integral gives the relative numbers of each
type of hydrogen.
5. The coupling constant J also gives information
about the arrangement of the atoms involved.
 1,2-dibromoethane
3.80
Br
Br
3.80

4 3 2 1 0
PPM
HYDROXYL AND AMINO
PROTONS
Hydroxyl and Amino Protons
Hydroxyl and amino protons can appear
almost anywhere in the spectrum (H-bonding).

These absorptions are usually broader than

other proton peaks and can often be identified
because of this fact.

Carboxylic acid protons generally appear far

downfield near 11 to 12 ppm.
SPIN-SPIN DECOUPLING BY EXCHANGE
In alcohols coupling between the O-H hydrogen and
those on adjacent carbon atoms is usually not seen.
This is due to rapid exchange of
C O OH hydrogens between the various
alcohol molecules in the solution.

H H In ultra pure alcohols, however,

coupling will sometimes be seen.

R-O-Ha + R’-O-Hb R-O-Hb + R’-O-Ha

The exchange happens so quickly that the C-H group

sees many different hydrogens on the O-H during the
time the spectrum is being determined (average spin = 0)
Any exchangeable hydrogens are quickly replaced by deuterium
atoms, which are invisible in the proton NMR spectrum.

When a second NMR spectrum is recorded (after shaking with D2O),

the signals from any exchangeable protons are either absent or
much less intense.
ETHANOL 400 MHz

Old sample
Rapid exchange catalyzed
by impurities

hydrogen on OH
is decoupled

HO-CH2-CH3

triplet

broad
quartet singlet
expansion expansion

doublet of triplet
quartets

ETHANOL HO-CH2-CH3
Ultra pure sample (new)
Slow or no exchange

400 MHz
triplet
 J=7
J=5 J=7
J=5

triplet quartet of doublets triplet

 NMR Spectrum of
2-Chloropropanoic Acid
COOH O

1 CH3 CH C OH 3
Cl

~12 ppm
1

offset = 4.00 ppm

AROMATIC RINGS
BENZENE RING HYDROGENS

Ring current causes protons attached to the

ring to appear in the range of 7 to 8 ppm.

An anisotropy diagram (next slide) shows

the origin of the effect.

Protons in a methyl or methylene group

attached to the ring appear in the range
of 2 to 2.5 ppm.
 Ring Current in Benzene

Circulating p electrons

Deshielded
H H

Bo Secondary magnetic field

generated by circulating p
electrons deshields aromatic
protons
 7.26

7.26 7.26

Benzene
7.26 7.26

7.26

8 7 6 5 4 3 2 1 0
PPM
ALKYL-SUBSTITUTED RINGS
In monosubstituted rings with an alkyl substitutent
all ring hydrogens come at the same place in the NMR
spectrum.

R
R = alkyl (only)

Apparently the ring current

equalizes the electron density
at all the carbons of the ring
and, therefore, at all of the
hydrogen atoms.
NMR Spectrum of Toluene

CH3
5
3
Proton NMR spectrum of o-xylene. There are three types of protons in o-xylene, but only two absorptions are
seen in the spectrum. The aromatic protons Hb and Hc are accidentally equivalent, producing a broadened peak
at δ7.1 .
In some cases, there may be fewer signals in the NMR spectrum than there are
different types of protons in the molecule. For example, the above figure shows the
structure and spectrum of o-xylene.There are three different types of protons,
labeled ‘a’ for the two equivalent methyl groups, ‘b’ for the protons adjacent to the
methyl groups, and ‘c’ for the protons two carbons removed. The spectrum shows
only two distinct signals, however.
The upfield signal at δ 2.3 corresponds to the six methyl protons, Ha. The absorption
at δ 7.2 corresponds to all four of the aromatic protons, Hb and Hc. Although the two
types of aromatic protons are different, the methyl groups do not strongly influence
the electron density of the ring or the amount of shielding felt by any of the
substituents on the ring. The aromatic protons produce two signals, but these
signals happen to occur at nearly the same chemical shift. Protons that are not
chemically equivalent but happen to absorb at the same chemical shift are said to
be accidentally equivalent.
SUBSTITUENTS WITH UNSHARED PAIRS
Electronegative elements with unshared pairs shield
the o- and p- ring positions, separating the hydrogens
into two groups.
.. unshared pair
X
Electron-donating groups
shield the o-, p- positions due to
resonance (see below).

.. ..
X = OH, ..
.. OR, :O R
+
:O R
+
:O R
+
:O R
.. ..
NH2, NR2, :- -
:
..
-O(CO)CH
.. 3 .. -
ester
Anisole (400 MHz)

O CH3
Compare:

CH3

The ring protons in

toluene come at
about 7.2 ppm at
the red line.

2 3

shielded
THE EFFECT OF CARBONYL SUBSTITUENTS
When a carbonyl group is attached to the ring the
o- and p- protons are deshielded by the anisotropic
field of C=O

R R
O C C O
H H H H

Only the o- protons are in range for this effect.

The same effect is sometimes seen with C=C bonds.

Acetophenone (90 MHz)

CH3 3
O C
H H Compare:

CH3

The ring protons in

toluene come at
about 7.2 ppm at
the red line.

2 3

deshielded
 7.81 7.45
O

Benzaldehyde 9.87
7.54

7.81 7.45

10 8 6 4 2 0
PPM
 8.19 7.52
-O

Nitrobenzene N+ 7.65

O
8.19 7.52

9 8 7 6 5 4 3 2 1 0
PPM
Spectrum for Styrene
H
a
C C
H
c
Splitting Tree
Hb
 a c
H H
C C
Hb Complex Splitting

• Signals may be split by adjacent

protons, different from each other, with
different coupling constants.
• Example: Ha of styrene which is split by
an adjacent H trans to it (J = 17 Hz) and
an adjacent H cis to it (J = 11 Hz).
 para-Disubstitution
1,4-Disubstituted benzene rings will show
a pair of doublets, when the two groups
on the ring are very different

an example:
1-iodo-4-methoxybenzene
 NMR Spectrum of
1-iodo-4-methoxybenzene

I OCH3

CHCl3 impurity

2 2
 NMR Spectrum of
1-bromo-4-ethoxybenzene

Br OCH2CH3
3
4

2
THE p-DISUBSTITUTED PATTERN CHANGES AS THE
TWO GROUPS BECOME MORE AND MORE SIMILAR
All peaks move closer.
Outer peaks get smaller …………………..… and finally disappear.
Inner peaks get taller…………………………. and finally merge.

X X X

X all H
Y X' equivalent

X=Y X ~ X’ X=X
same groups
 NMR Spectrum of
1-amino-4-ethoxybenzene

3
H2N OCH2CH3
4

2 2
NMR Spectrum of p-Xylene
(1,4-dimethylbenzene)

6
CH3 CH3

4
 2,4-DINITROANISOLE

400 MHz

9.0 8.0 7.0

2,4-DINITROANISOLE

8.72 ppm 8.43 ppm 7.25 ppm

 Cl
o-chloronitrobenzene
7.53
-O

N+ 7.59

O
8.13 7.40

9 8 7 6 5 4 3 2 1 0
PPM
 Cl
m-chloronitrobenzene 8.20
-O

N+ 7.66

O
8.07 7.46

9 8 7 6 5 4 3 2 1 0
PPM
 8.13 7.53
-O

N+ Cl
p-chloronitrobenzene
O
8.13 7.53

9 8 7 6 5 4 3 2 1 0
PPM
 Cl
7.21

o-dichlorobenzene
Cl 7.08

7.21 7.08

8 7 6 5 4 3 2 1 0
 7.28
Cl Cl
m-dichlorobenzene
7.15 7.15

7.14

8 7 6 5 4 3 2 1 0
PPM
 7.21 7.21

p-dichlorobenzene Cl Cl

7.21 7.21

8 7 6 5 4 3 2 1 0
PPM
 O 7.78
-O N+ 8.58 8.58 8.45 8.45
-O O-
8.45
-O
-
O O- N+ N+
N+ 7.91 N+ N+
9.12 O O
O 8.45 8.45
8.45 7.91
O O
m-dinitrobenzene p-dinitrobenzene
o-dinitrobenzene
Antiaromatic systems
Antiaromatic systems are paratropic. That is, they are able to sustain a paramagnetic
ring current, which lead to shielding of outer ring protons and deshielding of inner protons (opposite
to that of aromatic compounds which show diamagnetic effect). Examples presented below
demonstrate the behavior of magnetic nuclei situated in an antiaromatic environment.
At -170oC, inner protons of [12]-annulene comes at ~8 ppm and outer protons comes at
~6 ppm which is characteristic of antiaromaticity. Above -150oC, all protons are magnetically
equivalent showing conformational flexibility. Above -50oC, it rearranges to a bicyclic system as
shown below.
SPECTROSCOPY IS A POWERFUL TOOL

Generally, with only three pieces of data

1) empirical formula (or % composition)

2) infrared spectrum

3) NMR spectrum

a chemist can often figure out the complete

structure of an unknown molecule.
EACH TECHNIQUE YIELDS VALUABLE DATA

FORMULA

Gives the relative numbers of C and H

and other atoms

INFRARED SPECTRUM

Reveals the types of bonds that are present.

NMR SPECTRUM

Reveals the enviroment of each hydrogen

and the relative numbers of each type.
Questions
1. What happens when a magnetic nucleus is placed in a magnetic field?
2. Why is the 1H-nucleus able to absorb radio waves?
3. Why do protons in different chemical environments absorb at different radio
frequencies?
4. What is the reference molecule that is used to calibrate spectra?
5. How many peaks would there be in the low-resolution nmr spectrum of
methanol? What about
ethanol? What about propan-1-ol?
6. How can we deduce from an nmr spectrum how many protons there are in
each chemical
environment?
7. Why does a neighbouring proton cause the peak in an nmr spectrum to split
into two?
8. What is the origin of the n+1 rule for identifying how many protons are
adjacent to a particular proton?
Prob 1:For each of the compounds A through F indicate the number of structurally-distinct groups of carbon atoms, and
also the number of distinct groups of equivalent hydrogens. Enter a number from 1 to 9 in each answer box.
Prob.2: For each of the compounds A through D indicate the number of structurally-distinct groups of carbon atoms, and
also the number of distinct groups of constitutionally equivalent hydrogens. Stereochemically distinct hydrogens should
not be reported. Enter a number from 1 to 9 in each answer box.
Prob 3:What splitting pattern in the 1H nmr spectrum would you expect for the hydrogen atom(s) colored red in the
compounds shown below?
Your choices are: s singlet d doublet t triplet q quartet m multiplet. Enter the appropriate letter in the answer box
to the right of each formula.
Prob 4: Which of the following compounds would be expected to show spin-spin splitting in their H NMR spectra?
1

(Check the appropriate button).

 Prob 5.The following 1H nmr spectrum of a C10H12O compound was obtained on a 90 MHz spectrometer.
2

A series of questions are presented below the spectrum. To answer each question enter a number or letter in the
designated answer box.
1. Ignoring the TMS signal at δ = 0,
7. You should now be able to assign a structure to this how many discrete groups of proton
C10H12O compound. signals are present in this spectrum?
2. What is the multiplicity ( s, d,
t, q ) of the highest field signal
from this sample?

3. The sample has a singlet at δ =

3.8 ppm. In units of Hertz (Hz)
how far is this signal from the
TMS signal?

5. From multiplet line separations

(Js), which of the other signals is
coupled to the quartet at δ = 2.9 ppm?
4. What structural feature is suggested by the singlet at δ = 3.8 ppm? δ = 1.2 ppm, δ = 3.8 ppm, δ = 6.9
CH3–C=O B –CH2– C –O–H D –O–CH3 E C–CH3 C=C–H ppm, δ = 7.9 ppm
6. Using the integrated trace and the formula of the sample, assign a whole number ratio to the sample signals as
follows: 7.9 ppm; 6.9 ppm; 3.8 ppm; 2.9 ppm; 1.2 ppm signal.
7. Select the structure most likely to give the spectrum from the following structures A through G.