Information contained in an NMR

spectrum includes:

1. number of signals
Interpreting 1 H (Proton) NMR
2. their intensity (as measured by area
Spectra
under peak)
3. splitting pattern (multiplicity)

NMR N CCH
CCH2OCH
OCH3
Number of Signals
OCH
OCH3

protons that have different chemical shifts

NCCH
NCCH2 O
are chemically nonequivalent
exist in different molecular environment

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ
(δ, ppm)
ppm)

Chemically equivalent protons Chemically equivalent protons

are in identical environments
have same chemical shift
replacement test: replacement by some
arbitrary "test group" generates same compound
Replacing protons at C-1 and C-3 gives same
compound (1-chloropropane)
C-1 and C-3 protons are chemically
equivalent and have the same chemical shift
ClC
ClCH2 CH2C H3 CH3CH2 CH2Cl

H3 CCH2 CH3 H3 CCH2 CH3

chemically equivalent chemically equivalent

 Chemical Shift: Chemically equivalent protons
Each set of chemically equivalent protons in a compound
gives rise to a signal in an 1H NMR spectrum of that
compound

1HNMR spectrum of
Question 1-bromo-2,2-dimethylpropane

• How many chemically non-equivalent

kinds of protons are there in 2,2-
dimethylbutane?
• A) 2
• B) 3
• C) 4
• D) 5
 Diastereotopic protons
Question
replacement by some arbitrary test group
• How many proton signals would you generates diastereomers
expect to find in the 1H-NMR spectrum
of 2-chloropentane? diastereotopic protons can have different
chemical shifts
• A) 2
• B) 3 Br H δ 5.3 ppm

• C) 4 C C
• D) 5
H3 C H δ 5.5 ppm
• E) More than 5

Enantiotopic
Enantiotopic protons protons
H
H
are in mirror-image environments C CH2OH
replacement by some arbitrary test group
generates enantiomers H3 C

enantiotopic protons have the same

chemical shift H Cl
Cl H
C CH2OH C CH2OH
R S
H3 C H3 C

Question
• How many proton signals would you
Spin-Spin Splitting
expect to possibly find in the 1H-NMR
in
spectrum of 2-chloropentane? NMR Spectroscopy
• A) 6
• B) 7 not all peaks are singlets
• C) 8 signals can be split by coupling of
• D) 9 nuclear spins
• E) More than 9
 NMR Cl2CH CH3
Two-bond and three-bond coupling

H
4 lines; 2 lines;
quartet doublet C C H C C H
H
protons separated by protons separated by
CH3 two bonds three bonds
CH
(geminal relationship) (vicinal relationship)

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ
(δ, ppm)
ppm)

Two-bond and three-bond coupling

H
C C H C C H
H

in order to observe splitting, protons cannot

have same chemical shift

coupling constant (2J or 3 J) is independent

of field strength

NMR Cl2CH CH3 Why do the methyl protons of

1,1-dichloroethane appear as a doublet?

4 lines; 2 lines; Cl H
quartet doublet signal for methyl
H C C H protons is split into
a doublet
Cl H

CH CH3
To explain the splitting of the protons at C-2,
we first focus on the two possible spin
coupled protons are vicinal (three-bond coupling) orientations of the proton at C-1
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
CH splits CH 3 into a doublet
Chemical
CH3 splits CH into a quartet shift (δ
(δ , ppm)
ppm )
 Why do the methyl protons of Why do the methyl protons of
1,1-dichloroethane appear as a doublet? 1,1-dichloroethane appear as a doublet?

Cl H Cl H
signal for methyl signal for methyl
H C C H protons is split into H C C H protons is split into
a doublet a doublet
Cl H Cl H

There are two orientations of the nuclear spin The protons at C-2 "feel" the effect of both the
for the proton at C-1. One orientation shields applied magnetic field and the local field
the protons at C-2; the other deshields the C- resulting from the spin of the C-1 proton.
2 protons.

Why do the methyl protons of

1,1-dichloroethane appear as a doublet?

Cl H
"true" chemical
H C C H shift of methyl
protons (no coupling)
Cl H
this line corresponds this line corresponds
to molecules in which to molecules in which
the nuclear spin of the nuclear spin of
the proton at C-1 the proton at C-1
reinforces opposes
the applied field the applied field

Why does the methine proton of

1,1-dichloroethane appear as a quartet?

Cl H
signal for methine
proton is split into H C C H
a quartet
Cl H

The proton at C-1 "feels" the effect of the

applied magnetic field and the local fields
resulting from the spin states of the three
methyl protons. The possible combinations
are shown on the next slide.
 Why does the methine proton of
1,1-dichloroethane appear as a quartet? The splitting rule for 1H NMR

Cl H There are eight combinations of

For simple cases, the multiplicity of a signal
nuclear spins for the three methyl
for a particular proton is equal to the number
H C C H protons.
of equivalent vicinal protons + 1.
These 8 combinations split the
Cl H signal into a 1:3:3:1 quartet.

Table 1H NMR Splitting

Splitting Patterns of Common Multiplets
Number of equivalent Appearance Intensities of lines
protons to which H of multiplet in multiplet
is coupled

1 Doublet 1:1
2 Triplet 1:2:1
3 Quartet 1:3:3:1
4 Pentet 1:4:6:4:1
5 Sextet 1:5:10:10:5:1
6 Septet 1:6:15:20:15:6:1

Question
• What is the multiplicity (spin-spin Splitting Patterns:
splitting) of the protons of 1,2- The Ethyl Group
dichloroethane?
• A) one singlet CH3CH2 X is characterized by a triplet-quartet
• B) two singlets pattern (quartet at lower field than the triplet)
• C) one doublet
• D) one triplet
 NMR BrCH
BrCH 2 CH3

4 lines; 3 lines;
quartet triplet Splitting Patterns:
The Isopropyl Group
CH3

(CH3 )2CHX is characterized by a doublet-

CH2 septet pattern (septet at lower field than the
doublet)

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ
(δ, ppm)
ppm)

NMR BrCH
BrCH (CH
(CH3)2
Question
2 lines;
7 lines; doublet • Which isomer of C4H9Br has only one
septet peak in its 1H-NMR spectrum having the
CH3
chemical shift δ 1.8?
• A) 1-bromobutane
CH • B) 2-bromobutane
• C) 1-bromo-2-methylpropane
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
• D) 2-bromo-2-methylpropane
Chemical shift (δ
(δ, ppm)
ppm)

Question

Splitting Patterns:
Pairs of Doublets

Splitting patterns are not always symmetrical,

Which compound is the most reasonable for the NMR spectrum above? but lean in one direction or the other when
A) Ethyl pentanoate “coupled”
coupled”.
B) Propyl isobutyrate
C) Butyl propanoate
D) Isopropyl butyrate
E) Isopentyl acetate
 Pairs of Doublets Pairs of Doublets

H C C H H C C H

Consider coupling between two vicinal
protons.
If the protons have different chemical shifts,
each will split the signal of the other into a
doublet.
Let Δν be the difference in chemical shift in Hz
between the two hydrogens.
hydrogens.
Let J be the coupling constant between them
in Hz.

The Difference between a Quartet A Splitting Diagram for

and a Doublet of Doublets a Doublet of Doublets

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

 AX H C C H
A trans coupling constant is greater than a cis
coupling constant

J J
Δν

When Δ ν is much larger than J the signal for

each proton is a doublet, the doublet is
symmetrical, and the spin system is called
AX.

AM H C C H AB H C C H

J J
J J

Δν Δν

As Δν/J decreases the signal for each proton When Δ ν and J are similar, the spin system is
remains a doublet, but becomes skewed. The called AB. Skewing is quite pronounced. It is
outer lines decrease while the inner lines increase, easy to mistake an AB system of two doublets
causing the doublets to "lean" toward each other. for a quartet.

To observe well-defined splitting patterns, the difference

in the chemical shifts (in Hz) must be 10 times the
A2 H C C H
coupling constant values

When Δ ν = 0, the two protons have the same

chemical shift and don't split each other. A
single line is observed. The two doublets
have collapsed to a singlet.
 NMR H H

skewed doublets
Question
Cl OCH
OCH3
• Which isomer of formula C4H6Cl4 has
H H two signals at δ 3.9 (doublet, 4H) and δ
4.6 (triplet, 2H) in its 1H-NMR spectrum?

OCH
OCH3 • A) B)

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 • C) D)
Chemical shift (δ
(δ, ppm)
ppm)

A Splitting Diagram for

a Quartet of Triplets

Complex Splitting Patterns

Multiplets of multiplets
MESS-plets

m-Nitrostyrene H
m-Nitrostyrene

H
H
H
O2 N
H
The signal for
H the proton
O2 N
16 Hz shown in red
Consider the proton shown in red.
red.
appears as a
It is unequally coupled to the protons shown doublet of
in blue and white.
white. doublets.
Jcis = 12 Hz; Jtrans = 16 Hz 12 Hz 12 Hz
 Figure

H
doublet doublet
H
H
O2 N
doublet of doublets

O— H H C O H

1H NMR Spectra of Alcohols & The chemical shift for O—

O—H is variable (δ
(δ 0.5-
Amines 5 ppm)
ppm) and depends on temperature and
concentration.
What about H bonded to O and N? Splitting of the O—
O—H proton is sometimes
observed, but often is not.
not. It usually appears
as a broad peak.
peak.
Adding D2 O converts O—
O—H to O—
O—D. The
O—H peak disappears.

Protons Bonded to
Oxygen and Nitrogen Question
Which of the following statements is false?
The greater the extent of the hydrogen bond, the greater • A) Splitting of the hydroxyl proton of
the chemical shift an alcohol is not usually observed.
• B) Alcohol protons shift to lower fields
in more concentrated solutions.
• C) Addition of D2 O to alcohol will result
in an increased intensity of the hydroxyl
proton signal.
• D) The chemical shift of the hydroxyl
These protons can undergo proton exchange proton depends on solvent, temperature, and
with deuterium. concentration of the solution.
They appear as broad signals.
 The three methyl protons are chemically equivalent due
to rotation about the C–C bond

NMR and Conformations

One signal is observed for the methyl group.

1H NMR spectra of cyclohexane-d11 at various NMR is "slow"

temperatures

Most conformational changes occur faster

axial than NMR can detect them.
equatorial
H
An NMR spectrum is the weighted average of
H
H the conformations.

equatorial
H
For example: Cyclohexane gives a single
peak for its H atoms in NMR. Half of the time
axial
the rate of a single proton is axial and half of the time it is
chair–chair equatorial. The observed chemical shift is
conversion is half way between the axial chemical shift and
temperature the equatorial chemical shift.
dependent

The signals for the Ha , Hb, and Hc protons do not overlap

The signals for the Hc, Hd, and He protons overlap