Nuclear Magnetic

Resonance (NMR)
Spectroscopy

2001

NMR Spectroscopy is THE most powerful tool in determining

the structure of organic compounds.
Only requires a small amount (mg or less) of sample and the
sample can be recovered.
Can be used in conjunction with other means of identification,
but often this is the only tool necessary.
All nuclei carry charge due to the
positively charged protons located there.
Sometimes this charge spins and generates a
magnetic dipole along the axis of spin
A wide variety of nuclei can be observed: 1H, 13C, 15N, 19F, and
and 13C are the most common.

31P. 1H

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When a small magnet is placed in the magnet field of a larger,

stronger magnet, it will tend to align itself with the field of the
larger magnet - lower energy.

The same effect is seen

when a proton is placed in
an external magnetic field,
Ho.
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In the absence of Ho, the

magnetic moments are
random. When the field is
applied, they tend to align
with ( spin-lower energy) or
against ( spin-higher energy)
the external field.
When a proton in the state is
irradiated with the proper
frequency, , it can go to the
higher energy state or vice
versa. At that frequency, they
are in resonance.
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If all protons were equal, then NMR would be useless, but they
are not all equal. That is, the frequency needed to achieve
resonance varies depending on the protons environment.
Magnetic shielding in protons
When the electrons
surrounding a proton
encounter Ho, an
induced field is set
up opposite to Ho.
Heffective=Hexternal - Hshielding

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A naked proton absorbs at 14,092 gauss, at 60 MHz

But all protons have some amount of electron density
surrounding them, so they are somewhat shielded from the
effect of Ho.
The more the proton is shielded the stronger the external
magnetic field must be in order to bring the proton into
resonance.

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Consider methanol, CH3OH

The three equivalent protons on the carbon are more shielded
than the hydroxyl proton. Consequently, their signal appears
more upfield relative to the hydroxyl proton, which appears
downfield.

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Four pieces of information obtained from a spectrum

Amount of shielding - provides information about the
environment and electronic structure of the proton. The
chemical shift will indicate the amount of shielding.
Number of signals - indicates the number of unique
protons or sets of protons.
Signal intensity - Actually, the area under each signal
provides the relative number of protons making up each
signal.
Splitting - Provides information about the number of
neighboring protons.

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Shielding and Chemical Shift

The variations in shielding of the nucleus by the electrons result
in variations of the signal locations - called chemical shifts.
Chemical shift - the difference between the resonance frequency of
the proton being observed and that of tetramethylsilane (TMS)
(CH3)4Si

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Characteristic Values of Chemical Shifts

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Deshielding in compounds containing bonds

Aromatic rings

Alkenes and alkynes

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Protons on nitrogen (-N-H) and oxygen (-O-H)

Hydrogen bonding and proton exchange with the solvent cause
these protons to be shielded and deshielded to varying degrees.
Therefore, they may or may not show up.
The Number of Signals

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Signal Intesity or Area Under the Peaks

Proportional to the number of hydrogens contributing to that signal.
Consider tert-butyl methyl ether: ?How many unique sets of
protons are present?

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Br Br
b
Br C C H
Consider 1,1,2-tribromoethane
a b
H H
?How many unique sets of protons are present?
Spin-Spin Splitting

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Explain splitting patterns

The doublet of the Hb protons at ~4.1 ppm
The adjacent proton
can have a spin
with or against the
field, reinforcing or
opposing Ho.

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The triplet of the Ha proton at ~5.7 ppm

Again, the
adjacent protons
can spin with or
against Ho.

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The N+1 Rule

Number of
equivalent
neighboring
protons

0
1
2
3
4
5
6

Area
ratios

Multiplicity

1(singlet)
2(doublet)
3(triplet)
4(quartet)
5(pentet)
6(sextet)
7(septet)

1
1 1
1 2 1
1 3 3 1
1 4 6 4 1
1 5 10 10 5 1
1 6 15 20 15 6 1

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O
CH3 CH2 CH2 C CH2 CH2 CH3

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O
CH3 CH2 CH2 C O CH2 CH3

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Coupling constants
If the adjacent protons are equivalent, they will have identical
coupling constants and you may simply consider the total number
of adjacent protons.
If the adjacent protons are not equivalent, they will have
different coupling constants and give rise to complex splitting
patterns.

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Ha

Complex splitting

C C

Hc
Hb

styrene

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Ha

C C

Hc
Hb

styrene

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Ha

C C

Hc
Hb

styrene

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Typical coupling constants

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Splitting in p-ethoxybenzyl alcohol

HO

CH2

CH2 CH3

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General regions of various chemical shifts

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Problem Solving (see pp. 582-584)

If the molecular formula is known, determine the elements
of unsaturation = C - ((H+X-N)/2) + 1
Matching the integrations with protons in the formula give
the numbers of proton represented by the individual peaks,
as well as possible symmetry.
Any broadened singlets might be due to -OH or -NH
protons. Signals downfield from 10 ppm might be acids.
Learn to recognize ethyl and isopropyl groups.

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PROBLEM 13-21, p. 582

Propose a chemical structure consistent with the following

NMR spectra and molecular formulas.

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Determine the elements of unsaturation.

10
4 +1 = 0
2

Therefore the oxygens must be part

of either an alcohol or an ether.
The doublet at 1.1 represents 3H and must be a
CH3 next to a CH group.

CH3

The peaks centered at 1.6 integrating to 2H

appear to be an uneven quartet, which signifies a
CH2 between two sets of non-equivalent protons.

H
C

CH2

The broad 2H singlet at 3.3 has the earmark of

OH protons, so apparently the compound is a
diol.

OH

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The 3H multiplet centered around

3.8 is very complex; while the
splitting is hard to interpret, the
chemical shift suggests that these 3
hydrogens are on carbons bonded to
oxygen.
H

CH3

CH2

2H

H
CH3

OH

CH3

C CH2OH

C CH2CH2OH
OH

CH2OH

The structure on the left does not fit the NMR; it would show a
4H doublet about d3.8. The multiplet at d3.8 are the overlapping
signals of the methylene and methine protons.
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Another example

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