Organic Chemistry: Proton Nuclear Magnetic Resonance Spectros

Organic Chemistry
300876
Module 3
Proton Nuclear Magnetic Resonance Spectroscopy
1
Module 3 - Proton NMR spectroscopy
16.1 Intro to NMR Spectroscopy
What is spectroscopy?
Nuclear Magnetic Resonance (NMR) spectroscopy may be the most
powerful method of gaining structural information about organic
compounds.
It is also of immense value in medical diagnosis, where it is known as
Magnetic Resonance Imaging (MRI), why different names?
NMR involves an interaction between electromagnetic radiation (light)
and the nucleus of an atom.
– Typically we will focus on C and H nuclei. WHY?
– The structure (connectivity) of a molecule affects how the
radiation interacts with each nucleus in the molecule.
16-2
Protons and neutrons in a nucleus behave as if they are spinning.
If the total number of neutrons and protons is an ODD number, the
atoms will have net nuclear spin.
Examples: 1H, 13C, 15N, 19F, and, 31P.
A nucleus with an odd number of protons and/or an odd number of
neutrons possesses a quantum mechanical property called nuclear
spin.
A spinning proton can be viewed as a rotating sphere of charge, which
generates a magnetic field, called a magnetic moment.
16-3
It depends on isotopes.
The nucleus of a 12C atom has an even number of protons and an even
number of neutrons and therefore does not possess this property.
In contrast, the nucleus of 13C has an odd number of neutrons and
therefore exhibits spin.
However our study of NMR spectroscopy will begin with 1H NMR
spectroscopy.
We saw in module 2 (Chapter 15) how a dipole moment creates an
electric field.
What does a magnetic moment create?
16-4
The magnetic moment exists perpendicular to the axis of nuclear spin
15-5
If the normally disordered magnetic moments of atoms are exposed to
an external magnetic field (B0), their magnetic moments will align with
the field, or against the field:
15-6
 spin state = aligned with B0, higher energy spin state
 spin state = opposing B0, lower energy spin state
15-7
When an atom with an α spin state is exposed to radio waves with just
the right energy (DE), the photons are absorbed and spin flips to the β
spin state.
The stronger the magnetic field, the greater the energy gap
15-8
B0 causes electrons to circulate, inducing an opposing magnetic field
(diamagnetism)
Nuclei then experience less B0, and are said to be shielded, requiring
less energy to spin flip
Nuclei surrounded by less electron density are said to be deshielded
15-9
The amount of radio wave energy necessary for the α → β energy
transition depends on the electronic environment for the atom
When the α spins are flipped to β spins, energy is absorbed, and the
atoms are said to be in resonance
The use of the term, “resonance” here is totally different from when
we are talking about electrons in molecular orbitals
The amount of energy required for each 1H to spin flip tells us about
it’s electronic environment, and thus the structure of the compound.
15-10
15.2 Acquiring a 1H NMR Spectrum
NMR requires a strong magnetic field (B0) and radio wave energy
The strength of the magnetic field affects the energy gap
15-11
16-12
Solvents are used such as chloroform-d. WHY?
If the solvent itself has
protons, the spectrum will be
overwhelmed with signals
from the solvent, rendering it
unreadable.
As a result, solvents without
protons must be used.
Although there are several
solvents that lack protons,
such as CCl4, these solvents do
not dissolve all compounds.
In practice, deuterated
solvents are generally used.
16-13
Solvents are used such as chloroform-d. WHY?
16-14
16.3 Characteristics of a 1H NMR Spectrum
NMR spectra contain a lot of structural information and in some cases
the structure of a compound can be determined using only NMR
spectroscopy.
Number of signals.
Signal location – shift.
Signal area – integration.
Signal shape – splitting pattern.
16-15
16.4 Number of Signals
As mentioned protons with different electronic environments will give
different signals.
Protons that are homotopic will have perfectly overlapping signals.
Protons are homotopic if the molecule has an axis of rotational
symmetry that allows one proton to be rotated onto the other without
changing the molecule.
Such protons are chemically equivalent.
16-16
16-17
Identify the number of signals expected in the 1H NMR spectrum of
the following compounds:
16-18
spectroscopy.
Number of signals.
16-19
16.5 Chemical Shifts
Early NMRs analyzed samples at a constant energy over a range of
magnetic field strengths from low field strength = downfield to high
field strength = upfield.
Shielded protons required a stronger external magnetic field to be
excited at the same energy as deshielded protons. WHY?
16-20
16-21
Alkane protons generally give signals around 1-2 ppm.
Protons can be shifted downfield when nearby electronegative atoms
cause deshielding. HOW?
16-22
15.5 Chemical Shift – Anisotropic Effects
When the electrons in a pi system are subjected to an external
magnetic field, they circulate and produce a magnetic field, causing
diamagnetic anisotropy
15-23
15.5 Chemical Shift
Diamagnetic anisotropy means that different regions of localized space
has different magnetic strengths
Regions outside
the ring have
increased magnetic
field
15-24
15.5 Chemical Shift
The result of the diamagnetic anisotropy effect is similar to deshielding
for aromatic protons. More magnetic field means more energy
required to spin-flip the proton(s)
Aromatic protons appear in the neighborhood of 7 ppm.
15-25
15.5 Chemical Shift
The result of the diamagnetic anisotropy effect is similar to shielding
for protons on the inside of the pi system
protons outside the ring: appear at 8 ppm

Protons inside the ring: appear at -1 ppm.
15-26
16.5 Chemical Shifts – π-Bonds
16-27
16.5 Chemical Shifts – π-Bonds
16-28
16-29
16-30
spectroscopy.
Number of signals.
16-31
16.6 Integration
The integration or area under the peak quantifies the relative number
of protons giving rise to a signal.
A computer will calculate the area of each peak representing that area
with a step-curve.
•The curve height represents the integration
16-32
16.6 Integration
16-33
16.6 Integration
A compound with molecular formula C5H10O2 has the following 1H
NMR spectrum:
Determine the number of protons giving rise to each signal.
16-34
16.6 Integration
STEP 1 Compare the relative integration values and choose the lowest
number.
STEP 2 Divide all the integration values by the number from step 1,
which gives the ratio of protons.
STEP 3 Identify the number of protons in the compound (from the
molecular formula) and then adjust the relative integration values so
that the sum total equals the number of protons in the compound.
16-35
16.6 Integration
The spectrum exhibits three signals.
Begin by comparing the relative integration values: 6.33, 19.4, and
37.9. Divide each of these three numbers by the smallest number
(6.33):
16-36
16.6 Integration
This gives a ratio of 1 : 3 : 6, but these are just relative numbers. To
determine the exact number of protons giving rise to each signal, look
at the molecular formula, which indicates a total of 10 protons in the
compound.
Therefore, the numbers 1 : 3 : 6 are not only relative values, but they
are also the exact values. Exact integration values can be illustrated in
the following way:
16-37
spectroscopy.
Number of signals.
16-38
16.7 Multiplicity
When a signal is observed in the 1H NMR, often it is split into multiple
peaks.
Multiplicity or a splitting patterns results.
16-39
16.7 Multiplicity
16-40
16.7 Multiplicity
Multiplicity results from magnetic affects that protons have on each
other.
Consider protons Ha and Hb
We already saw that protons align with or against the external

magnetic field.
Hb will be aligned with the magnetic field in some molecules. Other
molecules in the sample will have Hb aligned against the magnetic
field.
Some Hb atoms have a slight shielding affect on Ha and others have a
slight deshielding affect.
16-41
16.7 Multiplicity
The resulting multiplicity or splitting pattern for Ha is a doublet.
A doublet generally results when a proton is split by only one other

proton on an adjacent carbon.
16-42
16.7 Multiplicity
Consider an example where there are two protons on the adjacent
carbon.
There are three possible affects the Hb protons have on Ha
16-43
16.7 Multiplicity
Ha appears as a triplet.
WHY?
The three peaks in the triplet have an integration ratio of 1:2:1.
WHY?
16-44
16.7 Multiplicity
Consider a scenario where Ha has three equivalent Hb atoms splitting it.
16-45
16.7 Multiplicity
Ha appears as a quartet
What should the integration ratios be for
the 4 peaks of the quartet?
16-46
16.7 Multiplicity
16-47
16.7 Multiplicity
Sometimes recognizable splitting patterns will stand out in a spectrum.
An isolated ethyl group gives a triplet and a quartet, Note the
integrations.
The triplet and quartet must have the same coupling constant if they
are splitting each other.
16-48
16.7 Multiplicity
A peak with an integration equal to 9 suggests the presence of a tert-

butyl group.
An isolated isopropyl group gives a doublet and a septet, Note the
integrations.
16-49
16.7 Multiplicity
Splitting is not observed for some protons. Consider ethanol.
The protons bonded to carbon split each other, but the hydroxyl
proton is not split.
16-50
15.7 Multiplicity
The hydroxyl proton and other labile or exchangeable protons undergo
rapid exchange with trace amounts of acid. Show a reasonable
mechanism
Such exchange blurs the shielding/deshielding affect of the

neighboring protons giving a singlet that is often broadened
15-51
Summary of Key Points
16-52
Mid semester exam 2016
Compound A isolated from a mixture was suspected to be having the
chemical structure as shown below. Spectroscopic analysis was carried
out to confirm the identity of the compound ()
(a) Write down the IUPAC name for compound A.

(b) Predict the expected 1H NMR spectrum of this compound. For each
signal expected indicate:
- its structural origin (label each distinct hydrogen environment on
the structure above with the letters a, b, c, etc.),
- approximate chemical shift range predicted from the table on page
5, the number of hydrogens in each environment, and the
multiplicity of each signal for each signal.
Final exam 2015
Deduce the structure of the compound, which gave rise to the following
spectra.
Molecular formula of unknown compound: C7H14O (final exam 2015)

Solving a structure-based problem with IR and NMR
55

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Aromatic protons appear in the neighborhood of 7 ppm.

protons outside the ring: appear at 8 ppm

•The curve height represents the integration

Determine the number of protons giving rise to each signal.

Consider protons Ha and Hb

We already saw that protons align with or against the external

A doublet generally results when a proton is split by only one other

A peak with an integration equal to 9 suggests the presence of a tert-

Such exchange blurs the shielding/deshielding affect of the

(a) Write down the IUPAC name for compound A.

Module 3 - Proton NMR spectroscopy

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