Chapter 13

Organic Chemistry
NMR Spectroscopy John McMurry
Nuclear Magnetic Resonance (NMR)
Spectroscopy
Identify the carbon–hydrogen framework of an organic
compound
1
H NMR spectrum of
1-bromo-2,2-dimethylpropane
Certain nuclei such as 1H, 13C, 19F, and 31P have
allowed spin states of +1/2 and –1/2; this property allows
them to be studied by NMR
The spin state of a nucleus is affected by an applied
magnetic field

“-” “+”

“+”
“+”

“-”
“-”
An NMR Spectrometer

Radiofrequency held constant

The energy difference between the two spin states
depends on the strength of the magnetic field
 spin flip:
Nuclei are in resonance with
applied electromagnetic radiation
absorb E
-spin states -spin states
release E
Overpopulates
Higher E state

System “relaxes” when

rf pulse removed
E

Signals detected
by NMR
 An NMR Spectrometer

Magnetic field is varied

Radiofrequency held constant

 The Chemical Shift
The reference point of an NMR spectrum is defined by
the position of TMS (zero ppm) H3C

H3C Si CH3

H3C

The chemical shift is a measure of how far the signal is

from the reference signal
The common scale for chemical shifts =  (ppm)
distance downfield from TMS (Hz)
=
operating frequency of the spectrometer (MHz)
The electrons surrounding a nucleus affect the effective
magnetic field sensed by the nucleus
Beffective = Bapplied - Blocal
Electron withdrawal causes NMR signals to appear at
higher frequency (at larger  values)
Characteristic Values of
Chemical Shifts
 Chemically equivalent protons: protons in the
same chemical environment

Each set of chemically equivalent protons in a compound

gives rise to a signal in an 1H NMR spectrum of that
compound
The three methyl protons are chemically equivalent due
to rotation about the C–C bond

We see one signal for the methyl group in the 1H NMR

spectrum
Chemically equivalent protons: protons in the
same chemical environment
Chemically non-equivalent protons: protons in
the different chemical environment

H NO 2

H H H H

H H H H

H H
 Proton Equivalence
• Unrelated protons
• Homotopic protons
• Enantiotopic protons
• Diastereotopic Protons
 Proton Equivalence
• Unrelated protons
H2
H 3C C
replace either set of equivalent H with X C C X
H2 H2 H2
H 3C C
C CH3
H2 H2
H 3C C
H
C CH3

Constitutional Isomers

Red H and green H are unrelated

 Proton Equivalence
• Homotopic protons
H2
H3 C C
replace equivalent H with X C C X
H2 H2 H2
H3 C C
C CH 3
H2 H2 H2
X C C
C CH 3
H2

Named the same

The green H are homotopic to each other

Are the red H are homotopic to each other?
 Proton Equivalence
• Enantiotopic protons

replace red H with X

H2 H2
H3 C C H3 C C
C CH 3 C CH 3

H H
H X
H2
H 3C C
C CH3
p ro-R
H X
p ro-S
Enantiomers
 Proton Equivalence

• Diastereotopic Protons

H H OH
OH replace red H with X
H3 C C H3 C C
C CH 3 C CH 3

H H
H X
H OH

H3 C C
p ro-R
C CH3
p ro-S
H X

Diastereomers
Part II
 1
H NMR spectrum of
1-bromo-2,2-dimethylpropane

9.0

2.0
 Integration Line

The area under each signal is proportional to the number

of protons that give rise to that signal

The height of each integration step is proportional to the

area under a specific signal

The integration tells us the relative number of protons

that give rise to each signal, not absolute number
 1
H NMR spectrum of
1-bromo-2,2-dimethylpropane

9.0

2.0
 1,1-Dichloroethane

Splitting of the Signals

 Splitting of the Signals
• An 1H NMR signal is split into N + 1 peaks, where N is
the number of equivalent protons bonded to adjacent
carbons
1 equiv proton
H
Cl

H3 C Cl

Adjacent carbons
3 equiv protons
 Splitting of the Signals
• Coupled protons split each other’s signal N + 1

These protons are coupled

H
Cl

H 3C Cl

Why one proton splits signal of proton on

adjacent carbon?
Splitting of the Signals
H
Cl

H 3C Cl
 H
Cl

H 3C Cl
 H
Cl

H 3C Cl
The ways in which the magnetic fields of three protons
can be aligned
HH H HH H HH H HH H

H
Cl

H 3C Cl
The ways in which the magnetic fields of three protons
can be aligned
HH H HH H HH H HH H

H
Cl

H 3C Cl
The ways in which the magnetic fields of three protons
can be aligned
HH H HH H HH H HH H

H
Cl

H 3C Cl
 Coupling Constants
The coupling constant (J) is the distance between two
adjacent peaks of a split NMR signal in hertz

Jab = Jba

Coupled protons have the same coupling constant

Students: make a note of this correction!

Splitting is observed if the protons are separated by

three  bonds
 Splitting of the Signals
• An 1H NMR signal is split into N + 1 peaks, where N is
the number of equivalent protons bonded to adjacent
carbons

• Coupled protons split each other’s signal

• The number of peaks in a signal is called the multiplicity

of the signal

• The splitting of signals, caused by spin–spin coupling,

occurs when different kinds of protons are close to one
another
Example of 1H NMR Spectrum
Why this
difference?
 Diamagnetic Anisotropy
The  electrons are less tightly held by the nuclei than
are  electrons; they are more free to move in response
to a magnetic field

Causes unusual chemical shifts for hydrogen bonded to

carbons that form  bonds
Why this
difference?
Why this
difference?
 13
C NMR Spectroscopy

• The number of signals reflects the number of different

kinds of carbons in a compound

• The overall intensity of a 13C signal is about 6400 times

less than the intensity of an 1H signal

• The chemical shift ranges over 220 ppm

• The reference compound is TMS

Proton-Decoupled 13C NMR of
2-Butanol
DEPT 13C NMR distinguish among CH3, CH2, and CH
groups
More Examples of 1H NMR Spectra
The three vinylic protons are at relatively high frequency
because of diamagnetic anisotropy
The signals for the Hc, Hd, and He protons overlap
The signals for the Ha, Hb, and Hc protons do not overlap
End
When two different sets of protons split a signal, the
multiplicity of the signal is determined by using the N + 1
rule separately for each set of the hydrogens when the
coupling constants for the two sets are different

When the coupling constants are similar, the N + 1 rule

can be applied to both sets simultaneously
A Splitting Diagram for
a Quartet of Triplets
1
H NMR spectra of cyclohexane-d11 at various
temperatures

axial
equatorial
H

H
H

H
equatorial

axial
the rate of
chair–chair
conversion is
temperature
dependent
The trans coupling constant is greater than the cis
coupling constant
The Difference between a Quartet
and a Doublet of Doublets
A Splitting Diagram for
a Doublet of Doublets