John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 13
Structure Determination:
Nuclear Magnetic
Resonance Spectroscopy

© 2016 Cengage Learning. All Rights Reserved.

Learning Objectives
(13.1)
 Nuclear magnetic resonance spectroscopy
(13.2)
 The nature of NMR absorptions
(13.3)
 The chemical shift
(13.4)
 Chemical shifts in 1H NMR spectroscopy

© 2016 Cengage Learning. All Rights Reserved.

Learning Objectives
(13.5)
 Integration of 1H NMR absorptions: Proton
counting
(13.6)
 Spin–spin splitting in 1H NMR spectra
(13.7)
 1H NMR spectroscopy and proton equivalence
(13.8)
 More complex spin–spin splitting patterns

© 2016 Cengage Learning. All Rights Reserved.

Learning Objectives
(13.9)
 Uses of 1H NMR spectroscopy
(13.10)
 13C NMR spectroscopy: Signal averaging and
FT–NMR
(13.11)
 Characteristics of 13C NMR spectroscopy
(13.12)
 DEPT 13C NMR spectroscopy

© 2016 Cengage Learning. All Rights Reserved.

Learning Objectives
(13.13)
 Uses of 13C NMR spectroscopy

© 2016 Cengage Learning. All Rights Reserved.

Nuclear Magnetic Resonance
Spectroscopy
 Nuclei are positively charged and interact with
an external magnetic field denoted by B0
 Magnetic rotation of nuclei is random in the
absence of a magnetic field
 In the presence of a strong magnet, nuclei adopt
specific orientations

© 2016 Cengage Learning. All Rights Reserved.

Nuclear Magnetic Resonance
Spectroscopy
 When exposed to a certain frequency of
electromagnetic radiation, oriented nuclei
absorb energy and causes a spinflip from a
state of lower energy to higher energy
 Nuclear magnetic resonance - Nuclei are in
resonance with applied radiation
 Frequency that causes resonance depends on:
 Strength of external magnetic field
 Identity of the nucleus
 Electronic environment of the nucleus

© 2016 Cengage Learning. All Rights Reserved.

Nuclear Magnetic Resonance
Spectroscopy
 Larmor equation
 Relation between
 Resonance frequency of a nucleus
 Magnetic field and the magnetogyric ratio of the
nucleus  γ 
ν =   B0
 2π 

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Calculate the amount of energy required to spin-
flip a proton in a spectrometer operating at 300
MHz
 Analyze if the increase of spectrometer frequency
from 200 MHz to 300 MHz increases or
decreases the amount of energy necessary for
resonance

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:
8
c 3.0 × 10 m / s
λ= = ; ν = 300 MHz = 3.0 ×108 Hz
ν ν
8
c 3.0 × 10 m / s
λ= = = 1.0 m
ν 3.0 × 10 Hz
8

1.20× 10-4 kJ / mol

E= = 1.20 ×10-4 kJ / mol
1.0
 Increasing the spectrometer frequency from 200
MHz to 300 MHz increases the amount of energy
needed for resonance
© 2016 Cengage Learning. All Rights Reserved.
The Nature of NMR Absorptions
 Absorption frequencies differ across 1H and 13C

molecules
 Shielding: Opposing magnetic field produced
by electrons surrounding nuclei to counteract
the effects of an external magnetic field
 Effect on the nucleus is lesser than the applied
magnetic field
 Beffective = Bapplied – Blocal
 Individual variances in the electronic environment
of nuclei leads to different shielding intensities

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.3 - NMR Spectrum of
1H and 13C

© 2016 Cengage Learning. All Rights Reserved.

Working of an NMR
Spectrometer
 Organic sample dissolved in a suitable solvent is
placed in a thin glass tube between the poles of
a magnet
 1H and 13C nuclei respond to the magnetic field
by aligning themselves to one of the two
possible orientations followed by rf irradiation
 Constant and varied strength of the applied field
causes each nucleus to resonate at a slightly
varied field strength
 Absorption of rf energy is monitored by a
sensitive detector that displays signals as a
peak © 2016 Cengage Learning. All Rights Reserved.
Figure 13.4 - Operation of a
Basic NMR Spectrometer

© 2016 Cengage Learning. All Rights Reserved.

NMR Spectrometer
 Time taken by IR spectroscopy is about 10–13 s
 Time taken by NMR spectroscopy is about 10–3
s
 Provides a blurring effect that is used in the
measurement of rates and activation energies of
vary fast processes

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Explain why 2-chloropropene shows signals for
three kinds of protons in its 1H NMR spectrum
 Solution:

 2-Chloropropene has three kinds of protons

 Protons b and c differ because one is cis to the
chlorine and the other is trans

© 2016 Cengage Learning. All Rights Reserved.

The Chemical Shift
 The left segment of the chart is the downfield
 Nuclei absorbing on the downfield have less
shielding as they require a lower field for
resistance
 The right segment is the upfield
 Nuclei absorbing on the upfield have more
shielding as they require a higher field strength
for resistance

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.5 - The NMR Chart

© 2016 Cengage Learning. All Rights Reserved.

The Chemical Shift
 Chemical shift is the position on the chart at
which a nucleus absorbs
 The delta (δ) scale is used in calibration of the
NMR chart
1 δ = 1 part-per-million of the spectrometer
operating frequency
Observed chemical shift (number of Hz away from TMS)
δ=
Spectrometer frequency in MHz
 The delta scale is used as the units of
measurement can be used to compare values
across other instruments
© 2016 Cengage Learning. All Rights Reserved.
Worked Example
 The 1H NMR peak of CHCl3 was recorded on a
spectrometer operating at 200 MHz providing
the value of 1454 Hz
 Convert 1454 Hz into δ units
 Solution:
Observed chemical shift (number of Hz away from TMS)
δ=
Spectrometer frequency in MHz

1454Hz
δ= = 7.27 δ for CHCl3
200MHz

© 2016 Cengage Learning. All Rights Reserved.

Chemical Shifts in 1H NMR
Spectroscopy
 Chemical shifts are due to the varied
electromagnetic fields produced by electrons
surrounding nuclei
 Protons bonded to saturated, sp3-hybridized
carbons absorb at higher fields
 Protons bonded to sp2-hybridized carbons
absorb at lower fields
 Protons bonded to electronegative atoms
absorb at lower fields

© 2016 Cengage Learning. All Rights Reserved.

Table 13.2 - Regions of the 1H
NMR Spectrum

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 CH2Cl2 has a single 1H NMR peak
 Determine the location of absorption
 Solution:
 For CH2Cl2 , δ = 5.30
 The location of absorption are the protons
adjacent to the two halogens

© 2016 Cengage Learning. All Rights Reserved.

Integration of 1H NMR
Absorptions: Proton Counting

 In the figure, the peak caused by (CH3)3C–

protons is larger than the peak caused by –OCH
protons
 Integration of the area under the peak can be
used to quantify the different kinds of protons in
a molecule
© 2016 Cengage Learning. All Rights Reserved.
Worked Example
 Mention the number of peaks in the 1H NMR
spectrum of 1,4-dimethyl-benzene (para-xylene
or p-xylene)
 Mention the ratio of peak areas possible on
integration of the spectrum

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:
 There are two absorptions in the 1H NMR
spectrum of p-xylene
 The four ring protons absorb at 7.05 δ and the six
methyl-groups absorb at 2.23 δ
 The peak ratio of methyl protons:ring protons is
3:2

© 2016 Cengage Learning. All Rights Reserved.

Worked Example

© 2016 Cengage Learning. All Rights Reserved.

Spin-Spin Splitting in 1H NMR
Spectra
 Multiplet: Absorption of a proton that splits into
multiple peaks
 The phenomenon is called spin-spin splitting
 Caused by coupling of neighboring spins

© 2016 Cengage Learning. All Rights Reserved.

Spin-Spin Splitting in 1H NMR
Spectra
 Alignment of –CH2Br proton spins with the
applied field can result in:
 Slightly larger total effective field and slight
reduction in the applied field to achieve resonance
 There is no effect if one of the –CH2Br proton
spins aligns with the applied field and the other
aligns against it
 Alignment of –CH2Br proton spins against the
applied field results in:
 Smaller effective field and an increased applied
field to achieve resonance
© 2016 Cengage Learning. All Rights Reserved.
Figure 13.8 - The Origin of Spin-Spin
Splitting in Bromoethane

© 2016 Cengage Learning. All Rights Reserved.

Spin-Spin Splitting in 1H NMR
Spectra
 n + 1 rule: Protons that exhibit n + 1 peaks in
the NMR spectrum possess
 n = number of equivalent neighboring protons
 Coupling constant is the distance between
peaks in a multiplet

© 2016 Cengage Learning. All Rights Reserved.

Spin-Spin Splitting in 1H NMR
Spectra
 It is possible to identify multiplets in a complex
NMR that are related
 Multiplets that have the same coupling constant
can be related
 Multiplet-causing protons are situated adjacent to
each other in the molecule

© 2016 Cengage Learning. All Rights Reserved.

Rules of Spin-Spin Splitting
 Chemically equivalent protons do not show spin-
spin splitting
 The signal of a proton with n equivalent
neighboring protons is split into a multiplet of n +
1 peaks with a coupling constant
 Two groups of photons coupled together have
the same coupling constant, J

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 The integrated 1H NMR spectrum of a
compound of formula C4H10O is shown below
 Propose a structure

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:
 The molecular formula (C4H10O) indicates that
the compound has no multiple bonds or rings
 The 1H NMR spectrum shows two signals,
corresponding to two types of hydrogens in the
ratio 1.50:1.00, or 3:2
 Since the unknown contains 10 hydrogens, four
protons are of one type and six are of the other
type
 The upfield signal at 1.22 δ is due to saturated
primary protons

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 The downfield signal at 3.49 δ is due to protons
on carbon adjacent to an electronegative atom -
in this case, oxygen
 The signal at 1.23 δ is a triplet, indicating two
neighboring protons
 The signal at 3.49 δ is a quartet, indicating three
neighboring protons
 This splitting pattern is characteristic of an ethyl
group
 The compound is diethyl ether,
CH3CH2OCH2CH3

© 2016 Cengage Learning. All Rights Reserved.

1H NMR Spectroscopy and
Proton Equivalence
 Proton NMR is much more sensitive than 13C

and the active nucleus (1H) is nearly 100 % of

the natural abundance
 Shows how many kinds of nonequivalent
hydrogens are in a compound
 Theoretical equivalence can be predicted by
comparing structures formed by replacing each
H with X gives the same or different outcome
 Equivalent H’s have the same signal while
nonequivalent are different
 There are degrees of nonequivalence
© 2016 Cengage Learning. All Rights Reserved.
1H NMR Spectroscopy and
Proton Equivalence
 One use of 1H NMR is to ascertain the number
of electronically non-equivalent hydrogens
present in a molecule
 In relatively small molecules, a brief look at the
structure can help determine the kinds of
protons present and the number of possible
NMR absorptions
 Equivalence or nonequivalence of two protons
can be determined by comparison of structures
formed if each hydrogen were replaced by an X
group

© 2016 Cengage Learning. All Rights Reserved.

1H NMR Spectroscopy and
Proton Equivalence
 Possibilities
 If the protons are chemically unrelated and non-
equivalent, the products formed by substitution
would be different constitutional isomers

© 2016 Cengage Learning. All Rights Reserved.

1H NMR Spectroscopy and
Proton Equivalence
 If the protons are chemically identical, the same
product would be formed despite the substitution

© 2016 Cengage Learning. All Rights Reserved.

1H NMR Spectroscopy and
Proton Equivalence
 If the hydrogens are homotopic but not identical,
substitution will form a new chirality center
 Hydrogens that lead to formation of enantiomers
upon substitution with X are called enantiotopic

© 2016 Cengage Learning. All Rights Reserved.

1H NMR Spectroscopy and
Proton Equivalence
 If the hydrogens are neither homotopic nor
enantiotopic, substitution of a hydrogen at C3 would
form a second chirality center

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 How many absorptions will (S)-malate, an
intermediate in carbohydrate metabolism have
in its 1H NMR spectrum? Explain

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:

 Because (S)-malate already has a chirality

center(starred), the two protons next to it are
diastereotopic and absorb at different values
 The 1H NMR spectrum of (S)-malate has four
absorptions

© 2016 Cengage Learning. All Rights Reserved.

More Complex Spin-Spin
Splitting Patterns
 Some hydrogens in a molecule possess
accidentally overlapping signals
 In the spectrum of toluene (methylbenzene), the
five aromatic ring protons produce a complex,
overlapping pattern though they are not
equivalent

© 2016 Cengage Learning. All Rights Reserved.

More Complex Spin-Spin
Splitting Patterns
 Splitting of a signal by two or more
nonequivalent kinds of protons causes a
complication in 1H NMR spectroscopy

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.14 - Tree Diagram for the C2
proton of trans-cinnamaldehyde

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 3-Bromo-1-phenyl-1-propene shows a complex
NMR spectrum in which the vinylic proton at C2
is couples with both the C1 vinylic proton (J = 16
Hz) and the C3 methylene protons (J = 8 Hz)
 Draw a tree diageam for the C2 proton signal and
account for the fact that a live-line multiplet is
observed

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:

 C2 proton couples with vinylic proton (J = 16) Hz

 C2 proton’s signal is split into a doublet
 C2 proton also couples with the two C3 protons
(J = 8 Hz)
 Each leg of the C2 proton doublet is split into a triplet
to produce a total of six lines
© 2016 Cengage Learning. All Rights Reserved.
Worked Example

© 2016 Cengage Learning. All Rights Reserved.

Uses of 1H NMR Spectroscopy
 The technique is used to identify likely products
in the laboratory quickly and easily
 NMR can help prove that hydroboration-oxidation
of alkenes occurs with non-Markovnikov
regiochemistry to yield the less highly substituted
alcohol

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.15 - 1H NMR Spectra of
Cyclohexylmethanol

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Mention how 1H NMR is used to determine the
regiochemistry of electrophilic addition to
alkenes
 Determine whether addition of HCl to 1-
methylcyclohexene yields 1-chloro-1-
nethylcyclohexane or 1-chloro-2-
methylcyclohexane

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:

 Referring to 1H NMR methyl group absorption

 The unslpit methyl group in the left appears as a
doublet in the product on the right
 Bonding of a proton to a carbon that is also bonded
to an electronegative atom causes a downfield
absorption in the 2.5–4.0 region
 1H NMR spectrum of the product would confirm
the product to be 1-chloro-1-methylcyclohexane

© 2016 Cengage Learning. All Rights Reserved.

13CNMR Spectroscopy: Signal
Averaging and FT–NMR
 Carbon-13 is the only naturally occurring carbon
isotope that possesses a nuclear spin, but its
natural abundance is 1.1%
 Signal averaging and Fourier-transform NMR
(FT–NMR) help in detecting carbon 13
 Due to the excess random electronic
background noise present in 13C NMR, an
average is taken from hundreds or thousands of
individual NMR spectra

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.16 - Carbon-13 NMR
Spectra of 1-Pentanol

© 2016 Cengage Learning. All Rights Reserved.

13CNMR Spectroscopy: Signal
Averaging and FT–NMR
 Spin-spin splitting is observed only in 1H NMR
 The low natural abundance of 13C nucleus is the
reason that coupling with adjacent carbons is
highly unlikely
 Due to the broadband decoupling method used
to record 13C spectra, hydrogen coupling is not
seen

© 2016 Cengage Learning. All Rights Reserved.

Characteristics of 13C NMR
Spectroscopy
 13C
NMR provides a count of the different
carbon atoms in a molecule
 13C resonances are 0 to 220 ppm downfield
from TMS

© 2016 Cengage Learning. All Rights Reserved.

Characteristics of 13C NMR
Spectroscopy
 General factors that determine chemical shifts
 The electronegativity of nearby atoms
 The diamagnetic anisotropy of pi systems
 The absorption of sp3-hybridized carbons and sp2
carbons

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.18 - Carbon-13 Spectra of 2-
butanone and para-bromoacetophenone

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Classify the resonances in the
spectrum of 13C

methyl propanoate, CH3CH2CO2CH3

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:
 Methyl propanoate has four unique carbons that
individually absorb in specific regions of the 13C
spectrum

© 2016 Cengage Learning. All Rights Reserved.

DEPT 13C NMR Spectroscopy
 DEPT-NMR (distortionless enhancement by
polarization transfer)
 Stages of a DEPT experiment
 Run a broadband-decoupled spectrum
 Run a DEPT-90
 Run a DEPT-135
 The DEPT experiment manipulates the nuclear
spins of carbon nuclei

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.20 – DEPT-NMR Spectra
for 6-methyl-5-hepten-2-ol

© 2016 Cengage Learning. All Rights Reserved.

Uses of 13C NMR Spectroscopy
 Helps in determining molecular structures
 Provides a count of non-equivalent carbons
 Provides information on the electronic
environment of each carbon and the number of
attached protons
 Provides answers on molecule structure that IR
spectrometry or mass spectrometry cannot
provide

© 2016 Cengage Learning. All Rights Reserved.

Figure 13.21 - 13C NMR Spectrum of
1-methylcyclohexane

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Propose a structure for an aromatic
hydrocarbon, C11H16, that has the following 13C
NMR spectral data:
 Broadband decoupled: 29.5, 31.8, 50.2, 125.5,
127.5, 130.3, 139.8 δ
 DEPT-90: 125.5, 127.5, 130.3 δ
 DEPT-135: positive peaks at 29.5, 125.5, 127.5,
130.3 δ; negative peak at 50.2 δ

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 Solution:
 Calculate the degree of unsaturation of the
unknown compound
 C11H16 has 4 degrees of unsaturation
 Look for elements of symmetry
 7 peaks appearing in the 13C NMR spectrum indicate
a plane of symmetry (4 Carbons are similar)
 According to the DEPT-90 spectrum, 3 of the
kinds of carbons in the aromatic ring are CH
carbons

© 2016 Cengage Learning. All Rights Reserved.

Worked Example
 The unknown structure is a monosubstituted
benzene ring with a substituent containing CH2
and CH3 carbons

© 2016 Cengage Learning. All Rights Reserved.

Summary
 Nuclear magnetic resonance spectroscopy or
NMR is the most important spectroscopic
technique used in the determination of molecular
structure
 Magnetic nuclei such as 1H and 13C spin-flip
from a lower energy state to a higher energy
state when they absorb radiofrequency waves
 Each 1H or 13C nucleus possesses a unique
electromagnetic field that causes it to resonate
at different values of the applied field causing
peaks whose exact position is termed a chemical
shift
© 2016 Cengage Learning. All Rights Reserved.
Summary
 Delta (δ) is the unit of calibration in NMR charts
 Tetramethylsilane (TMS) is a reference point on
the NMR chart
 TMS absorption that occurs at the right-hand
(upfield) side of the chart is assigned a value of
0δ
 Fourier-transform NMR (FT–NMR)
spectrometers are used to obtain 13C spectra
using broadband decoupling of proton spins

© 2016 Cengage Learning. All Rights Reserved.

Summary
 Electronic integration of the area under each
absorption peak in 1H NMR spectra is used to
determine the number of hydrogens that cause
each peak
 Neighboring nuclear spins can couple to cause
the spin-spin splitting of NMR peaks into
multiplets
 The NMR signal of a hydrogen neighbored by n
equivalent adjacent hydrogens splits into n + 1
peaks (the n + 1 rule) with coupling constant J

© 2016 Cengage Learning. All Rights Reserved.