Organic Chemistry, 7th Edition

L. G. Wade, Jr.

Chapter 13
Nuclear Magnetic
Resonance Spectroscopy

Copyright © 2010 Pearson Education, Inc.

 Introduction
• NMR is the most powerful tool available for
organic structure determination.
• It is used to study a wide variety of nuclei:
 1H
 13C
 15N
 19F
 31P

Chapter 13 2
 Nuclear Spin
• A nucleus with an odd atomic number or
an odd mass number has a nuclear spin.
• The spinning charged nucleus generates
a magnetic field.

Chapter 13 3
 External Magnetic Field

• An external magnetic field (B0) applies a force to a small bar

magnet, twisting the bar magnet to align it with the external field.
• The arrangement of the bar magnet aligned with the field is lower
in energy than the arrangement aligned against the field.

Chapter 13 4
 Alpha-spin State and Beta-spin
State.

• The lower energy state with the proton aligned with

the field is called the alpha-spin state.
• The higher energy state with the proton aligned
against the external magnetic field is called the beta-
spin state.
Chapter 13 5
Proton Magnetic Moments

Chapter 13 6
 Two Energy States
• A nucleus is in resonance
when it is irradiated with
radio-frequency photons
having energy equal to the
energy difference between
the spin states.
• Under these conditions, a
proton in the alpha-spin
state can absorb a photon
and flip to the beta-spin
state.
Chapter 13 7
 E and Magnet Strength
• Energy difference is directly proportional
to the magnetic field strength.
E = h =  h B0
2
• Gyromagnetic ratio, , is a constant for
each nucleus (26,753 s-1gauss-1 for H).
• In a 14,092 gauss field, a 60 MHz photon
is required to flip a proton.
• Low energy, radio frequency.
Chapter 13 8
 Magnetic Shielding
• If all protons absorbed the same amount
of energy in a given magnetic field, not
much information could be obtained.
• But protons are surrounded by electrons
that shield them from the external field.
• Circulating electrons create an induced
magnetic field that opposes the external
magnetic field.

Chapter 13 9
 Shielded Protons

• A naked proton will absorb at 70,459 gauss.

• A shielded proton will not absorb at 70, 459 gauss so
the magnetic field must be increased slightly to
achieve resonance.
Chapter 13 10
 Protons in a Molecule

• Protons in different chemical environments are shielded by

different amounts.
• The hydroxyl proton is not shielded as much as the methyl
protons so the hydroxyl proton absorbs at a lower field than the
methyl protons.
• We say that the proton is deshielded somewhat by the presence
of the electronegative oxygen atom.

Chapter 13 11
 NMR Signals
• The number of signals shows how many
different kinds of protons are present.
• The location of the signals shows how
shielded or deshielded the proton is.
• The intensity of the signal shows the
number of protons of that type.
• Signal splitting shows the number of
protons on adjacent atoms.
Chapter 13 12
The NMR Spectrometer

Chapter 13 13
NMR Instrument

Chapter 13 14
 The NMR Graph

downfield upfield

• The more shielded methyl protons appear toward the

right of the spectrum (higher field); the less shielded
hydroxyl proton appears toward the left (lower field).
Chapter 13 15
 CH3
H3C Si CH3 Tetramethylsilane
CH3

• TMS is added to the sample as an

internal standard.
• Since silicon is less electronegative
than carbon, TMS protons are highly
shielded.
• The TMS signal is defined as zero.
• Organic protons absorb downfield (to
the left) of the TMS signal.
Chapter 13 16
 Chemical Shift
• Measured in parts per million.
• Ratio of shift downfield from TMS (Hz)
to total spectrometer frequency (Hz).
• The chemical shift has the same value
regardless of the machines (same value
for 60, 100, or 300 MHz machine).
• Called the delta scale.

Chapter 13 17
Delta Scale

Chapter 13 18
 Solved Problem 1
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
Solution
downfield (in gauss and in hertz) from TMS would this proton
absorb?
We substitute into the equation

Chapter 13 19
Location of Signals

• More electronegative
atoms deshield more and
give larger shift values.
• Effect decreases with
distance.
• Additional electronegative
atoms cause increase in
chemical shift.

Chapter 13 20
Typical Values

Chapter 13 21
 Magnetic Fields in Aromatic
Rings
• The induced magnetic
field of the circulating
aromatic electrons
opposes the applied
magnetic field along the
axis of the ring.
• Protons in the region
where the induced field
reinforces the applied
field are deshielded and
will appear at lower
fields in the spectrum
between 7–8.

Chapter 13 22
 Magnetic Field of Alkenes

• The pi electrons of the double bond generate a magnetic field

that opposes the applied magnetic field in the middle of the
molecule but reinforces the applied field on the outside where
the vinylic protons are located.
• This reinforcement will deshield the vinylic protons making them
shift downfield in the spectrum to the range of 5–6.
Chapter 13 23
 Magnetic Fields of Alkynes
• When the terminal triple
bond is aligned with the
magnetic field, the cylinder
of electrons circulates to
create an induced magnetic
field.
• The acetylenic proton lies
along the axis of this field,
which opposed the external
field.
• The acetylenic protons are
shielded and will be found at
2.5 (higher than vinylic
protons).

Chapter 13 24
Deshielding of the Aldehyde Proton

• Like a vinyl proton, the aldehyde proton is deshielded

by the circulation of electrons in the pi bond.
• It is also deshielded by the electron-withdrawing
effect of the carbonyl (C═O) group, giving a
resonance between 9–10.
Chapter 13 25
 O—H and N—H Signals
• The chemical shift of the acidic protons
depends on concentration.
• Hydrogen bonding in concentrated
solutions deshield the protons, so signal
is around 3.5 for N—H and 4.5 for
O—H.
• Proton exchanges between the molecules
broaden the peak.
Chapter 13 26
 Carboxylic Acid Proton

• Because of the high polarity of the carboxylic

acid O—H bond, the signal for the acidic
proton will be at shifts greater than 10.
Chapter 13 27
 Number of Signals

• Methyl tert-butyl ether has two types of protons,

giving two NMR signals.
• Chemically equivalent hydrogens have the same
chemical shift. All the methyl groups of the tert-butyl
group are equivalent and they produce only one
signal.
Chapter 13 28
 tert-Butyl Acetoacetate

• The spectrum of tert-butyl acetoacetate has only

three signals. The most shielded protons are the
methyl groups of the tert-butyl. The most deshielded
signal is the methylene (CH2) because it is in
between two carbonyl groups.
Chapter 13 29
 Solved Problem 2
Using Table 13.3, predict the chemical shifts of the protons in the
following compounds.

Solution

Chapter 13 30
Equivalent Hydrogens
 Equivalent hydrogens: have the same chemical
environment
• a molecule with 1 set of equivalent hydrogens gives 1
NMR signal
O H3 C CH3
CH3 CCH3 ClCH2 CH2 Cl C C
H3 C CH3
Propanone 1,2-Dichloro-Cyclopentane 2,3-Dimethyl-
(Acetone) ethane 2-butene

13-31
Equivalent Hydrogens
• a molecule with 2 or more sets of equivalent
hydrogens gives a different NMR signal for each set
Cl Cl CH3
CH3CHCl O C C
H H
1,1-Dichloro- Cyclopent- (Z)-1-Chloro- Cyclohexene
ethane anone propene (3 signals)
(2 signals) (2 signals) (3 signals)

13-32
 Intensity of Signals: Integration

• The area under each peak is proportional to the

number of hydrogens that contribute to that signal.
• The integration will have a trace for the tert-butyl
hydrogens that is 3 times as large as the trace for the
methyl hydrogens. The relative area for methyl and
tert-butyl hydrogens is 1:3.
Chapter 13 33
 Spin-Spin Splitting
• Nonequivalent protons on adjacent carbons
have magnetic fields that may align with or
oppose the external field.
• This magnetic coupling causes the proton
to absorb slightly downfield when the
external field is reinforced and slightly
upfield when the external field is opposed.
• All possibilities exist, so signal is split.
Chapter 13 34
 1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.

Chapter 13 35
Doublet: One Adjacent Proton
• Hb can feel the alignment
of the adjacent proton
Ha.
• When Ha is aligned with
the magnetic field, Hb will
be deshielded.
• When Ha is aligned
against with the
magnetic field, Hb will be
shielded.
• The signal is split in two
and it is called a doublet.
Chapter 13 36
Triplet: Two Adjacent Protons
• When both Hb are aligned with
the magnetic field, Ha will be
deshielded. (shift downfield)
• When both Hb are aligned
against the magnetic field, Ha
will be shielded. (shift upfield)
• It is more likely that one Hb will
be aligned with the field and
the other Hb against the field.
The signal will be at its normal
position.
• The signal is split in three and
it is called a triplet.

Chapter 13 37
 The N + 1 Rule
If a signal is split by N equivalent protons,
it is split into N + 1 peaks.

Chapter 13 38
 Splitting analysis for a quartet

Hb Ha
Hb C C
Hb

Ch. 9 - 3
 Spin-spin Splitting Distance
• Equivalent protons do not split each other.
• Protons bonded to the same carbon will
split each other if they are nonequivalent.
• Protons on adjacent carbons normally will
split each other.
• Protons separated by four or more bonds
will not split each other.

Chapter 13 40
 Long-Range Coupling

• When the hydrogen atoms are four bonds or

more apart, spin-–spin splitting is not
normally observed. When it actually does
occur it is called “long-range coupling.”
Chapter 13 41
 Splitting for Ethyl Groups

• The hydrogens on the CH3 are affected by the two neighboring

hydrogens on the adjacent CH2 group. According to the N+1
rule, the CH3 signal will be split into (2+1) = 3. This is a triplet.
• The hydrogens on the CH2 group are affected by the three
hydrogens on the adjacent CH3 groups. The N+1 rule for the
CH2 signal will be split into (3+1) = 4. This is called a quartet.
Chapter 13 42
 Splitting for Isopropyl Groups

• The hydrogen on the CH has 6 adjacent hydrogens. According

to the N+1 rule, the CH signal will be split into (6+1) = 7. This is
called a septet.
• The two CH3b are equivalent so they give the same signal. They
have one adjacent hydrogen (CH) so their signal will be: N+1,
1+1 = 2 (doublet).

Chapter 13 43
 Solved Problem 3
Propose a structure for the compound of molecular formula C4H10O whose
proton NMR spectrum follows.

Solution

Chapter 13 44
 Solved Problem 3 (Continued)
Solution (Continued)

Chapter 13 45
 Coupling Constants
• The coupling constant is the distance
between the peaks of a multiplet (in Hz).
• Coupling constants are independent of
strength of the external field.
• Multiplets with the same coupling
constants may come from adjacent groups
of protons that split each other.

Chapter 13 46
Values for Coupling Constants

Chapter 13 47
 Proton NMR for para-
Nitrotoluene

• para-Nitrotoluene has two pairs of equivalent aromatic

protons a and b. Since the coupling constant for ortho
hydrogens is approximately 8 Hz, the peaks of the
signal will be separated by around 8 Hz.
Chapter 13 48
 Vinylic Coupling Constants

• There are 2 vinylic protons in 4,4-dimethylcyclohex-2-

ene-1-one and they are cis. The coupling constant
for cis coupling is approximately 10 Hz so the peaks
should be separated by that amount.
Chapter 13 49
 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 Hb trans to it (J = 17 Hz)
and an adjacent Hc cis to it (J = 11 Hz).

Chapter 13 50
H
a
H
c Splitting Tree
C C
Hb

Chapter 13 51
H-NMR Spectrum of Styrene
1

Chapter 13 52
Stereochemical equivalence

Chapter 13 53
 Stereochemical Nonequivalence
• If the replacement of each of the protons of a —CH2
group with an imaginary “Z” gives stereoisomers,
then the protons are non-equivalent and will split
each other.

Chapter 13 54
Diastereotopic Vinylic Protons

• Replacing the cis hydrogen gives the cis diastereomer, and

replacing the trans hydrogen makes the trans diastereomer.
• Because the two imaginary products are diastereomers, these
protons are called diastereotopic protons.
• Diastereotopic hydrogens are capable of splitting each other.

Chapter 13 55
 Diastereotopic Protons

• The two protons on the —CH2Cl group are

diastereotopic; their imaginary replacements give
diastereomers.
• Diastereotopic protons are usually vicinal to
stereocenters (chiral carbons).
Chapter 13 56
 Proton NMR Spectrum of 1,2-
dichloropropane

• Proton NMR spectrum of 1,2-dichloropropane shows

distinct absorptions for the methylene protons on C1.
• These hydrogen atoms are diastereotopic and are
chemically non-equivalent.
Chapter 13 57
 Time Dependence
• Molecules are tumbling relative to the
magnetic field, so NMR is an averaged
spectrum of all the orientations.
• Axial and equatorial protons on
cyclohexane interconvert so rapidly that
they give a single signal.
• Proton transfers for OH and NH may occur
so quickly that the proton is not split by
adjacent protons in the molecule.
Chapter 13 58
pure
Hydroxyl
Proton
• Ultrapure samples
of ethanol show
splitting.
impure
• Ethanol with a small
amount of acidic or
basic impurities will
not show splitting.

Chapter 13 59
 N—H Proton

• The acidic proton on the nitrogen has a moderate

rate of exchange.
• Peak may be broad.
Chapter 13 60
Identifying the O—H or N—H Peak
• Chemical shift will depend on concentration
and solvent.
• To verify that a particular peak is due to O—H
or N—H, shake the sample with D2O too
exchange the H for a D. The deuterium is
invisible in the proton NMR so the original
signal for the OH will disappear.

R—O—H + D—O—D R—O—D + D—O—H

R—NH2 + 2 D—O—D R—ND2 + 2D—O—H

Chapter 13 61
 Typical 1H NMR spectrum

1
Record as: H NMR (300 MHz, CDCl3):

 4.35 (2H, t, J = 7.2 Hz, H c)

b
2.05 (2H, sextet, J = 7.2 Hz, H )
1.02 (3H, t, J = 7.2 Hz, H a)
chemical coupling
shift () constant
no. of H
in ppm
(integration) multiplicity in Hz

Ch. 9 - 6
 The 300-MHz 1H NMR spectrum of
1,4-dimethylbenzene

Ch. 9 - 6
 Carbon-13 NMR
• Carbon-12 (12C) has no magnetic spin.
• Carbon-13 (13C) has a magnetic spin, but is
only 1% of the carbon in a sample.
• The gyromagnetic ratio of 13C is one-fourth
of that of 1H.
• For carbon a technique called Fourier
transform spectroscopy is used.
Chapter 13 64
 Fourier Transform NMR
• Radio-frequency pulse given.
• Nuclei absorb energy and precess (spin)
like little tops.
• A complex signal is produced, then decays as
the nuclei lose energy.
• Free induction decay (FID) is converted to
spectrum.

Chapter 13 65
 Carbon Chemical Shifts

• Table of approximate chemical shifts values for 13C-

NMR. Most of these values for a carbon atom are
about 15–20 times the chemical shift of a proton if it
were bonded to the carbon atom.

Chapter 13 66
Combined C and H Spectra
13 1

Chapter 13 67
Differences Between 1H and
13
C Technique
• Resonance frequency is about one-
fourth that of hydrogen, 15.1 MHz
instead of 60 MHz.
• Peak areas are not proportional to
number of carbons.
• Carbon atoms with more hydrogens
absorb more strongly.
Chapter 13 68
 Spin-Spin Splitting
• It is unlikely that a 13C would be
adjacent to another 13C, so splitting by
carbon is negligible.
• 13C will magnetically couple with
attached protons and adjacent protons.
• These complex splitting patterns are
difficult to interpret.

Chapter 13 69
 Proton Spin Decoupling
• To simplify the spectrum, protons are
continuously irradiated with “noise,” so they
are rapidly flipping.
• The carbon nuclei see an average of all the
possible proton spin states.
• Thus, each different kind of carbon gives a
single, unsplit peak because carbon-
hydrogen splitting was eliminated.

Chapter 13 70
H and13C-NMR of 1,2,2-
1

Trichloropropane

Chapter 13 71
 Off-Resonance Decoupling

• C nuclei are split only by the protons attached

13

directly to them.
• The N + 1 rule applies: a carbon with N number of
protons gives a signal with N + 1 peaks.
Chapter 13 72
 Interpreting 13C NMR
• The number of different signals indicates
the number of different kinds of carbon.
• The location (chemical shift) indicates the
type of functional group.
• The peak area indicates the numbers of
carbons (if integrated).
• The splitting pattern of off-resonance
decoupled spectrum indicates the number
of protons attached to the carbon.
Chapter 13 73
Two C NMR Spectra
13

Chapter 13 74
 Magnetic Resonance Imaging
(MRI)
• Nuclear Magnetic Resonance Imaging is a
noninvasive diagnostic tool.
• “Nuclear” is omitted because of public’s
fear that it would be radioactive.
• Computer puts together “slices” to get 3-D
images.
• Tumors are readily detected.
Chapter 13 75
MRI Scan of a Human Brain
• MRI scan of a
human brain
showing a
metastatic tumor in
one hemisphere.

Chapter 13 76
MRI Image of the Pelvic Region

Chapter 13 77