Chapter 14

Organic Chemistry
6th Edition
NMR Spectroscopy Paula Yurkanis Bruice

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 Nuclear Magnetic Resonance (NMR)
Spectroscopy

Identify the carbon–hydrogen framework of an organic

compound

Certain nuclei, such as 1H, 13C, 15N, 19F, and 31P, have
non-zero value for their spin quantum number; this
property allows them to be studied by NMR

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The spin state of a nucleus is affected by an applied
magnetic field:

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The energy difference between the spin states increases
with the strength of the applied magnetic field:

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 absorb DE
a-spin states b-spin states
release DE

Signals detected by NMR

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 An NMR Spectrometer

In pulsed Fourier transform (FT) spectrometers, the

magnetic field is held constant, and a radio frequency (rf)
pulse of short duration excites all the protons
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The electrons surrounding a nucleus decrease the
effective magnetic field sensed by the nucleus:
Beffective = Bo – Blocal

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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:

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

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

from the reference signal

The common scale for chemical shifts = d

distance downfield from TMS (Hz)
d=
operating frequency of the spectrometer (MHz)
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 1H
NMR spectrum of
1-bromo-2,2-dimethylpropane

The greater the chemical shift, the higher the frequency

The chemical shift is independent of the operating
frequency of the spectrometer 11
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Protons in electron-poor environments show signals at
high frequencies

Electron withdrawal causes NMR signals to appear at

higher frequency (at larger d values):

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Characteristic Values of
Chemical Shifts

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 Diamagnetic Anisotropy
The unusual chemical shifts associated with hydrogens
bonded to carbons that form p bonds:

The p electrons are freer to move than the s electrons in

response to a magnetic field
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The protons show signals at higher frequencies because
they sense a larger effective magnetic field:

benzene

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The alkene and aldehyde protons also show signals at
higher frequencies:

alkene aldehyde

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The alkyne proton shows a signal at a lower frequency
than it would if the p electrons did not induce a magnetic
field:

alkyne

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 1H
NMR spectrum of
1-bromo-2,2-dimethylpropane
The area under each signal is proportional to the number
of protons giving rise to the signal:

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 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 the absolute number
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 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
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It is not the number of protons giving rise to a signal that
determines the multiplicity of the signal

It is the number of protons bonded to the immediately

adjacent carbons that determines the multiplicity

a: a triplet
b: a quartet
c: a singlet
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Equivalent protons do not split each other’s signal:

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The ways in which the magnetic fields of three protons
can be aligned:

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Splitting is observed if the protons are separated by no
more than three s bonds:

Long-range coupling occurs over

psystems, such as benzene
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More Examples of 1H NMR Spectra
Triplet: two neighboring protons

Quintet: four neighboring protons

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 Doublet: one neighboring proton

Sextet: five
neighboring
protons

Septet: six neighboring protons

Triplets: two
neighboring protons
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The three vinylic protons are at relatively high frequency
because of diamagnetic anisotropy
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The signals for the Hc, Hd, and He protons overlap
because the electronic effect of an ethyl substituent is
similar to that of a hydrogen:

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The signals for the Ha, Hb, and Hc protons do not overlap
because of the strong electron-withdrawing property of
the nitro group:

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

Coupled protons have the same coupling constant 37

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 Summary
1. The number of chemical shifts d specify the number
of proton environments in the compound

2. The chemical shift d values specify the nature of

the chemical environment: alkyl, alkene, etc.

3. The integration values specify the relative

number of protons
4. The splitting specifies the number of neighboring
protons
5. The coupling constants specify the orientation of
the coupled protons
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A Splitting Diagram for
a Doublet of Doublets

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 Complex Splitting

JAC = JAB JAC > JAB

Triplet Doublet of doublets
Ha Ha

JAC JAC

JAB
JAB

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The trans coupling constant is greater than the cis
coupling constant:

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A Splitting Diagram for
a Quartet of Triplets

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Why is the signal for Ha a quintet rather than a
triplet of triplet?

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 The Difference between a Quartet
and a Doublet of Doublets

Methylene has three

neighbors, appears as a
quartet
Doublet Doublet 46
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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, as long as
the coupling constants for the two sets are different

When the coupling constants are similar, the multiplicity

of a signal can be determined by treating both sets of
adjacent hydrogens as though they were equivalent

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Replacing one of the enantiotopic hydrogens by a
deuterium or any other atom or group other than CH3 or
OH forms a chiral molecule:
prochiral
carbon

Ha is the pro-R-hydrogen, whereas Hb is the

pro-S-hydrogen; and they are chemically equivalent
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Diastereotopic hydrogens have different chemical shifts:

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Diastereotopic hydrogens are not chemically equivalent:

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The three methyl protons are chemically equivalent
because of rotation about the C—C bond:

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

spectrum
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1H 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
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 Protons Bonded to
Oxygen and Nitrogen
The greater the extent of the hydrogen bond, the
greater the chemical shift

These protons can undergo proton exchange

They always appear as broad signals
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pure ethanol

ethanol with acid

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A 60-MHz 1H
NMR spectrum

A 300-MHz 1H
NMR spectrum

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To observe well-defined splitting patterns, the difference
in the chemical shifts (in Hz) must be 10 times the
coupling constant values

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 13C 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.

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Proton-Decoupled 13C NMR of
2-Butanol

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Proton-Coupled 13C NMR of 2-Butanol

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The intensity of a signal is somewhat related to the
number of carbons giving rise to it
Carbons that are not attached to hydrogens give very
small signals

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DEPT 13C NMR distinguishes CH3, CH2, and CH
groups:

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The COSY spectrum identifies protons that are coupled:

Cross peaks indicate pairs of protons that are coupled

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COSY Spectrum of 1-Nitropropane

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The HETCOR spectrum of 2-methyl-3-pentanone
indicates coupling between protons and the carbon to
which they are attached:

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Unknown Identification Using Spectroscopy

Example 1: 13C-NMR of C5H9Br

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Example 1: 1H-NMR of C5H9Br

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Example 1: IR of C5H9Br

Answer:

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 Example 2: 13C-NMR of C6H10O4

33.4 24.1

174.4
Solvent:

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 Example 2: 1H-NMR of C6H10O4

2.21 1.50

11.97

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Example 2: IR of C6H10O4

Answer:

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