NMR Spectroscopy

• NMR: (Nuclear Magnetic Resonance)

spectroscopy involves the interaction of
electromagnetic radiation with matter.
• Any atom whose nucleus contains an odd
number of protons or odd number of
neutrons behaves like a tiny bar magnet.
– Common nuclei that display this behavior
include 1H, 13C, 15N, 31P and 19F.
• Nuclei which contain an even number of
protons and neutrons are non-magnetic
and are not NMR active.
0
 NMR: Important Concepts
• NMR Signal/peak
• Chemical Shift δ and TMS
Shielding.
Deshielding.
Diamagnetic anisotropy – ring current.
• Integration ratio and count of proton number
• Splitting patterns and n+1 Rule.
– Signal multiplicity
– Non n+1 Rule
• Coupling constant, J value.

0
 Basic Principle of NMR
• Basic principle: Nuclear Spin and Radio Frequency
absorption.
• Several magnetic nuclei possess a nuclear spin.
• Nuclei of interest to Org. Chemists: 1H and 13C.
• Nuclei spin is a quantum phenomenon, but can be
understood as a classical magnetic moment.

0
0
0
 Production of NMR Signal
In a non-magnetic environment: spins are
randomly oriented in any direction. See
page 117
In an external applied magnetic field two
possibilities:
Nuclear spin can align with external applied field – a
lower energy state.
Nuclear spin can oppose the external applied filed – a
high energy state.
Outcome: separation into higher energy and
lower energy nuclei – absorption of energy.
0
The NMR Experiment

0
 The NMR Signal/Absorption

∆E is direct proportional to field strength, B

experienced by the nuclei. Give rise to
absorption/peak/signal 0
0
Spectrometer
 The NMR Signal

Radiation with appropriate radio frequency lead to

absorption excitation of nuclei from lower to higher
energy. The energy change is picked up and
processed into an absorption signal. 0
 Effective Magnetic Field
• Effective magnetic field is the actual field felt by
the spinning nuclei.
– Will differ between atoms in different environments.
• Determines the chemical shift of the signal.

0
 Shielding/Deshielding of Nuclei
• Removal of a thick electron cloud coat around
the nucleus exposes the nucleus to the
magnetic field – need weak effective field.
– Nucleus is unprotected (deshielded by electron
withdrawing group, EWG). See page 122
• Addition of a thick electron cloud coat around
the nucleus hides the nucleus from magnetic
field – need stronger effective field.
– Nucleus is protected (shielded by electron
donating group, EDG).

0
 Chemical Shift
• NMR spectrum is a plot of frequency against
intensity of the signal/peak.

• The chemical shift of a signal/peak in an NMR is its

displacement in the spectrum from a reference point
(TMS).

• The shift of the signal/peak in the spectrum tells

something about the electronic environment in the
vicinity of the atom(s) that give rise to that
signal/peak.

• Tells you what groups/atoms are connected to the

group/atom causing the signal.
0
 The Chemical Shift cont’.
• The local magnetic field experienced by the nuclei
is dominated by B but will also be influenced by
electrons in the molecule and nearby nuclear spins.

• ∆E will be different for each chemical environment.

• The disposition of the signal/absorption/peak from a

set reference point in a spectrum is the Chemical
Shift. See page 123
• Represented as δ (delta) in ppm from a reference
TMS signal at δ = 0. TMS is the standard, but can
use others e.g. in 13C NMR CHCl3 at 77ppm.
0
 Factors Affecting Chemical Shift
• Deshielding of Nuclei: Removal of a thick electron
cloud coat around the nucleus exposes the nucleus
to the magnetic field – need weak effective field.
Nucleus is unprotected (deshielded by EWG).

• Shielding: Addition of a thick electron cloud coat

around the nucleus hides the nucleus from magnetic
field – need stronger effective field. Nucleus is
protected (shielded by EDG).

• Diamagnetic anisotropy/Ring current: adjacent π

electron clouds influences the chemical shift.
0
An Example: EtOAc spectrum

0
Some NMR terms
0
0
0
0
0
0
0
0
0
0
0
0
 Spin-Spin Coupling (Splitting)
(a) If a CH3, CH2, or CH group is situated adjacent to
a carbon atom to which are attached n equivalent
protons, the resonance due to that group will be
split into n +1 peaks. e.g., in the case of
CH3CH2OH, the CH3 peak is a triplet centered at δ
1.2 and the CH2 peak is a quartet centered at δ 3.7.

0
CH3 will create 8 different local H magnetic fields which will be felt by CH2
protons. 2 sets of 3 fields are equivalent resulting in 1:3:3:1 signal splitting
ratio.
CH2 will create 4 different local H magnetic fields which will be felt by CH3
protons. 2 of 4 fields are equivalent resulting in 1:2:1 signal splitting ratio.
0
0
Pascal Triangle

0
n+1 Splitting Patterns

0
n+1 Splitting Patterns cont’.

0
 Non-n+1 Splitting Patterns

• Results from two groups of Hs (Ha and Hc) with different

J values coupling with the same group of Hs (Hb). 0
Non-n+1 Splitting Patterns

0
0
0
0
0
 Overlapping Signals

• The signal centered at δ 2.5 is an overlap of a

quartet (2.49) and pentet (2.52). Expanding the
region of the spectrum with resolve the signals. 0
 COUPLING CONSTANT J
• The distance between split lines of a signal
expressed in Hz.
• Common Proton-Proton couplings:
– Germinal: attached to same carbon.
– Vicinal: attached to adjacent carbons.
– Aromatic: attached at ortho, meta or para.
– Allylic: attached to β-carbon.
• Influenced by several factors:
– Number of bonds involved.
– Electronegativity of substituents.
– Dihedral angle, especially in rigid systems.
• Denoted by xJ where x is number of bonds between
coupling protons.
0
 Dihedral Angle

The larger the dihedral angle the larger the Coupling

constant J. Read about Karplus Equation 0
 Dihedral Angle vs J value

Dihedral Angle Calculated J Observed J

Axial-axial Hs 9 8-14(usually 8-10)

Axial-equatorial 1.8 1-7(usually 2-3)

Equatorial- 1.8 1-7(usually 2-3)

equatorial

0
0
0
 Splitting by H groups with Different J
values

• The signal at d 4.87 appears as doublet of triplets. Reason:

J trans is larger than J allylic, the doublet from trans each
split into 2 triplets. 0
 More than 3 Bonds Coupling
• In compounds containing aromatic rings,
double bonds, and triple bonds and in
saturated rigid systems, protons more than
three bonds away are also coupled.
• This type of coupling is referred to as long-
range coupling.
• Long range coupling leads to complicated
splitting patterns.

0
 Splitting Patterns in Aromatic Hs

• Spin-spin splitting of aromatic protons often

leads to a very complex splitting pattern.
• In the case of p-disubstituted aromatic
compounds, however, the expected pair of
doublets often shows up very clearly in the
region δ 7 to 8, and is very characteristic.
• A J1,4 coupling is observed for m-protons –
the W coupling in rigid systems.

0
Coupling: J1,2;J1,3; J1,4; J1,5

0
 Ortho coupling

• The largest coupling occurs when two protons are

ortho to each other (three bonds).
• The coupling constant between ortho protons is
generally around 8Hz. 0
 Meta coupling

• The long-range coupling constant between protons

that are meta to one another is around 2Hz.
0
 Long Range Coupling

• Benzylic protons are also coupled to protons on the

ring with a coupling constant of 0.5 to 1.0 Hz.
• The splitting is generally not resolved but leads to
peak broadening, particularly with methyls.
0
 Signal Sizes: Integration

• In 1H spectra, the signal size relates to the number of

contributing protons
• Spectrometers provide relative signal sizes, historically as
an integration trace
0
• Signal size is related to # of equivalent H's in proton spectra
 Integration cont’.
• The area of a peak is proportional to the
number of protons under that peak.
• Integration of a spectrum enables the relative
numbers of protons under different peaks to
be established.
• Measure the heights, add up all the heights,
divide by the number of Hs from formula to
get Hs per unit height.
• The number of units equals the Hs due to that
signal.
0
 Summary
From each 1H NMR signal you should be
able to obtain four pieces of information:
1. Chemical shift: the environment of the
proton-containing group.
2. The integration: the relative number of
protons in the proton-containing group.
3. The splitting pattern: the number of
protons on adjacent carbon atom/atoms.
4. The J values: the groups which the signal
is coupling with.

0
Example Spectrum 1

0
Example Spectrum 2

0
Example Spectrum 3

0
Example Spectrum 4

0
• The 2 spectra belong to isomeric compounds with
formulae C10H12O2. Determine the structure of
each isomer.
0
0
Assigning Chemical Shifts

0
 Exercise
1. Propose a structural formula of a
compound with the following 1H NMR
data: C5H10O2: δ 1.2 (d, 6H), 2.0 (s, 3H)
and 5.0 (septet, 1H)

0
STRUCTURAL INFORMATION FROM 1H
NMR
Each group of hydrogen gives a peak or group
of peaks – multiplets.
The δ value gives a clue as to the type of
hydrogen generating the peak sp; sp2; sp3 and
their environment
The spin-spin splitting gives the # of H on
adjacent carbons.
Integral gives the # of Hs for each peak.
Overall 1H NMR how the different atoms are
connected in the molecule: structure.
0
 Approach in Solving a Structure
Determine empirical formula and use it to determine
molecular formula (MS data give MM).
IHD Must be determined: multiple bonds/rings etc.
IHD = 4 - most likely aromatic.
Use IR to get idea about what functional groups are
there/not there.
1H NMR data to determine groups of Hs and their
connectivity (coupling when connected).
13C NMR: different carbon environments – functional
groups.
Get fragmented information together and suggest
possible structure.
Compare structure with spectra: does it make sense?
0
 Carbon Nuclear Magnetic Resonance
(13C-NMR) Spectroscopy
• NMR Spectroscopy is not limited to the study of
protons. Any element with a nuclear spin (13C,
17O, 19F, 31P and many others) will give rise to an
NMR signal.
• Carbon-13 has a nuclear spin (I = ½) and is about
1.1% of all naturally occurring carbon.
• 13C-NMR is a useful technique since carbon is the
element central to organic chemistry.
• 13C-NMR plays an important role in determining the
structure of unknown organic molecules and the
study of organic reactions and processes.
0
0
 13C-NMR
• The idea and theory behind 13C-NMR is the
same as with 1H-NMR, just a different
nucleus.
• The13C-NMR spectrum of an organic
compound provides information concerning:
– the # of different types of carbon atoms present
in the molecule.
– the electronic environment of the different types
of carbons.
– the number of H "neighbors" a carbon has
(splitting).
0
 13C-NMR: Differences with 1H-NMR

• The major differences that you will notice in

13C-NMR in comparison to 1H-NMR spectra
include:
• No integration of carbon spectra.
• Wide range (0-220 ppm) of resonances for
common carbon atoms (typical range for
protons 1-10 ppm).

0
 Chemical Shift
Generally, carbons attached to electron withdrawing
groups tend to resonate at higher frequencies (more
downfield (to the left) from TMS.
The position of where a particular carbon atom
resonates relative to TMS is called its chemical shift.
Since carbon atoms resonate over a wide range,
learning some common chemical shifts will provide
you with a tremendous advantage at solving
structural problems using NMR.
For example carbonyl carbons resonate furthest
downfield (typically160-210 ppm), aromatic carbons
(115-145 ppm) and saturated aliphatic carbons(5-40
ppm). 0
USEFUL 13C CHEMICAL SHIFTS
Carbon Structure δ, ppm
Primary R-CH3 0-40
Secondary R2-CH2 10-50
Tertiary R3-CH 15-50
Alcohol C-OH 50-90
Ether C-O-C 50-90
Alkene -C=C- 100-170
Aromatic C6H6 100-170
Aldehydes -CHO 182-215
Ketones -C(=O)- 182-215

0
0
CORRELATION CHART

0
Predicting 13C-NMR

0
 Number of Different Carbons

• 4-Methyl-2-pentanone contains 6 carbons and

some of them are different from each other.
0
Number of Different Carbons

0
 Splitting
• Carbons couple with the hydrogen atoms that are directly
attached to them. See page 130 and example, page 159…
• Thus, a methyl group (-CH3) appears as a quartet in the
13C-NMR spectra.
A methylene group with two attached hydrogens appears as
a triplet, a methine group (-CH) appears as a doublet, and
a quaternary carbon, with no hydrogens attached, appears
as a singlet.
• Carbon-13 will also couple with another directly bonded
carbon-13 atom, but the odds of this are very low (.01%) in
naturally occurring samples and this generally is not seen.
With this coupling to bound hydrogens, a 13C-NMR spectra
can appear as a real jungle of lines.

0
To improve the spectra allowing easy counting
of the number of carbons, the protons are
often "decoupled" from the carbons by
irradiating them at a frequency that excites
them and interrupts their normal coupling.
In the absence of coupling from the
protons, the carbon resonances all appear
as singlets and such a spectrum is said to
be "Proton Decoupled".

0
• Proton decoupled 13C-NMR is probably the most
widely used technique because it clarifies the 13C-
NMR spectrum making it easier to determine the
number of carbon atoms.
• Note: Be aware that the proton coupled
experiment does exist and can provide useful
information on how many hydrogen atoms are
bound to a particular carbon – in decoupled
spectrum letters, s, d, t and q indicate 0, 1, 2
and 3 Hs attached to carbons. See page 159-
189

0
1. Give the structures of these two C4H8O
isomers with the following NMR data:
1.a. 21 δ, CH3; 55 δ, CH3; 81 δ, CH2; 161 δ,
C.
1.b. 8 δ, CH3; 29 δ, CH3; 37 δ, CH2; 209 δ, C.

0
0
0
2. Give the structures of these three C4H8O
isomers with the following NMR data:
2.a. 14 δ, CH3; 16 δ, CH2; 46 δ, CH2; 203 δ,
CH.
2.b. 10 δ, CH3; 26 δ, CH2; 47 δ, CH2; 53 δ,
CH.
2.c. 15 δ, CH3; 64 δ, CH2; 86 δ, CH2; 152 δ,
CH.

0
0
0
0