CHEM 232 NMR Primer

D. Wardrop, UIC
Introduction

Molecules are inconveniently small – too small to be observed and studied directly. One therefore needs a spy,
capable of relaying information on the structures, motions, and chemical properties of molecules without
significantly modifying those properties, and versatile enough to report on a wide range of molecules in a number
of situations. The spies that are involved in NMR spectroscopy are atomic nuclei, and the attribute that make
them so successful at espionage is their magnetism. The diagram below summarizes the formation of a nuclear
magnetic resonance signal.
NMR Tube
with Sample

E 2 (β)

ΔE = hυ
B0

E 1 (α)
Compound in Energy Level Resonance
the Magnetic Diagran Signal
Field B 0

THE FORMATION OF AN N.M.R. SIGNAL

The nuclei of many element atoms behave as though they are spinning on an axis i.e. they have spin in
the same way electrons do. Since they are spinning and positively charged, nuclei behave as tiny bar
magnets. In other words, these nuclei have magnetic moments. When no external magnetic field is
present these magnetic moments are oriented in random fashion. However, when the nuclei are placed
in a magnetic field, their magnetic moments can to adopt one of a small number of allowed orientations
of different energy. In the case of 1H (protons), 13C and 19F, the nuclei can either align with the field
(α−spin state) or against the field (β−spin state), as summarized below.

Applied hυ
Magnetic
Field
α β

Absorption of light of proper frequency

changes the magnetic nuclear spin state

In an applied magnetic field, a magnetic moment instinctively tends to align with the field in the same
way that a compass needle will always point to magnetic north and not south. As a result, a magnet
moment which is aligned against a magnetic field is in a higher energy state than one aligned with the
field. For 1H, 13C and 19F nuclei the β−spin state (comparable to a compass needle pointing south)
corresponds to a higher energy state than the α−spin state (compass needle pointing north).
Key Point

If the system is irradiated with electromagnetic radiation of the proper frequency or wavelength, a
nucleus with α−spin can absorb a quantum of light (hυ) and be converted to the higher energy β−spin
state. This process is called “flipping the spin”. Not surprisingly the energy difference (ΔE) between the
α and β spin states depends on the strength of interaction between the nucleus and the applied
magnetic field and this is illustrated in the following graph.

β−spin state

ΔE
E

α−spin state

B
The energy difference ΔE between α− and β−spin
states is a function of the magnetic field at the nucleus

This energy difference between the two spin states is given by the relationship below in which B is the
magnetic field strength at the nucleus and γ is the magnetogyric ratio of the nucleus. From this simple
equation we can easily see that the energy difference between the α- and β−states in a magnetic field is
proportional to the strength of the magnetic field. The greater the strength of the external magnetic
field the bigger the energy difference between spin states. When there is no external field (B = 0), the
two spin states have the same energy. Remember that frequency is directly proportional to energy
(from E = hυ), i.e. higher frequency = higher energy.

γB
ν=
2Π
We can now measure the energy difference between the two spins, ΔE by applying electromagnetic
radiation of frequency υ, which causes nuclei to “flip the spin” from the lower energy level to the upper
one (E = hυ!). This energy gap corresponds to radiation of wavelength 1-100 meters or 1010 Hz which
is in the radiowave section of the spectrum. This means that only tiny amounts of energy are involved
in “flipping the spin” – about 0.015 cal per mole (remember this is calories not kilocalories!).

Applied hυ
Magnetic
Field
α β

Absorption of light of proper frequency

changes the magnetic nuclear spin state

Because the energy gap between the two orientation is so small there is actually only a small excess of
nuclei in the α−spin state but there are enough to observe the absorption of energy by the hydrogen
atoms within molecules.

In Summary

If we can assemble an instrument which can deliver radiowaves of the right energy and detect the
absorption of the tiny amounts of energy involved we should be able to find the signal (or resonance)
from hydrogen atoms in a molecule. In other words – our spy can now relay to us that the molecule
being studied contains hydrogen atoms (or 13C atoms). However, this is not really very useful in
structural determination - what we really want to know is:

• The types of hydrogen atoms present in the molecule

• The number of hydrogen atoms present in the molecule

• How these protons are related to one another

How does an Nuclear Magnetic Resonance Spectrometer Work?

In order to obtain an nuclear magnetic resonance spectrum, a sample of the molecule being studied is
dissolved in an NMR inactive solvent (usually CDCl3) and the resulting solution placed in a glass sample
tube. This tube is placed between the poles of a super conducting magnet and the sample irradiated
with radio waves of constant frequency (constant energy) while the applied magnetic field (B0) of the
magnet is varied continuously from low to high field. As the applied magnetic field increases in strength,
the energy gap between the α and β-spin states of the protons in the molecule also increases, as
illustrated below. At a certain point, the applied magnetic field will be just the right strength to cause
the energy gap between the two spin states (ΔE) for the proton to match the energy (and frequency) of
the radio waves. It is at this stage that the proton absorbs the radio wave, the proton spin states are
flipped and an absorbance (or resonance) is recorded.

β-Spin State

ΔEspin states matches

Energy
energy (hν) of the
radio wave

Proton Energy Levels α-Spin State

At this applied field strength the

energy gap between the spin states
matches the energy of the radio
frequency signal (hυ ) and the
proton absorbs energy. As a result,
Absorbed NMR Spectrum a resonance is observed in the 1 H
Energy of Proton NMR spectrum as shown below.

Increasing Magnetic Field (B0)

These diagrams illustrate a) the relationship between the applied

magnetic field and the energy gap between α and β− spin states, and
b) the position of an 1 H NMR resonance signal in the spectrum.

If all protons in a molecule had exactly the same environment then 1H NMR spectra would consist of
only one absorption signal which would not be very useful! However, up until this point we have only
been considering isolated protons (H+) when in reality protons in a molecule are imbedded within
clouds of electrons, i.e. orbitals. When an external magnetic field (B0) is applied to a molecule these
electrons circulate and create a local induced magnetic field (Binduced) which opposes (subtracts from) the
applied magnetic field (B0). As a result, the protons within molecules are shielded from the applied
magnetic field and what the protons actually “sense” through the surrounding electrons is an effective
magnetic field (Beffective). The result of this is that the greater the electron density of the environment in
which a certain proton is located, the more that proton will be shielded from the applied magnetic field
and the greater the applied field will have to be to overcome the effect of the local induced magnetic
field.
If we irradiate a proton which has no nearby electrons, i.e. a “naked” proton (H+), with radio waves of
exactly 180 MHz frequency, the magnetic field required to flip the spin states (α to β) is 42,276 gauss
(gauss are just another unit of magnetic strength). However, in a molecule since the nucleus is shielded
by electrons, the applied field must be somewhat higher than 42,276 gauss in order for the effective field
at the nucleus to be 42,276 gauss.

circulating electron

proton
orbital

Binduced
Beffective = Bapplied - Binduced

Beffective
Bapplied

An applied magnetic field induces the electrons in a molecule to circulate within their
orbitals. This motion generates an extra magnetic field B induced at the nucleus which
opposes the applied field B applied . As a result, the effective field at the proton is
slightly less than the applied field.

NMR vs. Infrared Spectroscopy

During the NMR experiment we supply radiation (in the form of radio waves) of constant energy and
change the energy levels of the proton spin states to match; this is different from infrared spectroscopy
where we change the energy of the radiation to match set vibrational energy levels.

Key Point

Since individual protons within a molecule are often in different electronic environments we observe
separate signals due to each set of chemically non-equivalent protons. Where these signals appear in
the NMR spectrum depends on strength of the effective magnetic field which each proton experiences,
this in turn depends on the electronic environment surrounding the proton. Let’s examine a simple 1H
NMR spectrum to illustrate this point.

these hydrogens require a lower these hydrogens require a higher

applied magnetic field to applied magnetic field to
"experience" the magnetic field that "experience" the magnetic field that
corresponds to the energy of the corresponds to the energy of the
radio waves radio waves
Absorption of Radiation

Deshielded Nuclei Shielded Nuclei

Low Magnetic Field High Magnetic Field

"DOWNFIELD "UPFIELD"
1-Bromo-2,2-dimethylpropane

The 1H NMR spectrum of 1-bromo-2,2-dimethylpropane (1) has two signals because the 1-bromo-2,2-
dimethylpropane has two different kinds of protons, methyl and methylene which are in different
electronic environments. The methylene protons (b) are in a less electron-dense environment than the
methyl protons (a) because they are closer to the electron withdrawing bromine atom (electronegativity
= 3.0). As a result, the methylene protons are less shielded from the applied magnetic field in fact they
are deshielded and accordingly the signal for these protons occurs at a lower applied magnetic field
(Bapplied) than the signal for the more shielded methyl protons.

a b
a CH3 b
CH3 C CH2Br
CH3 reference peak
1 a
Peak area ratio: (a:b) = 9:2

8 7 6 5 4 3 2 1 0
ppm
Deshielded Shielded
Protons Protons

Key Points
• The right-hand side of an NMR spectrum is the high magnetic field side,
where protons with less electron-dense environments show a signal
(more shielded protons).

• The left-hand side is the low magnetic field side, where protons with less
electron-dense environments show a signal (less shielded or deshielded
protons).
Chemical Shift

q. Why do we use the ppm scale and not B0 for the nmr spectrum?

a. Since it is difficult to measure the exact applied magnetic field at which each absorbance occurs, a
small amount of a reference compound is added to the NMR sample tube and measurements are then
made with respect to the NMR signal of the reference compound. The reference compound most
commonly used by organic chemists is tetramethylsilane (TMS). The protons in tetramethylsilane are
in a more electron-dense environment than most protons encountered in organic molecules because
silicon is less electronegative than carbon. Consequently, the signal for the methyl protons of TMS is
farther upfield than most signals: upfield is towards the right in an NMR spectrum; downfield is
towards the left. The location of signals in an NMR spectrum are therefore defined according to how
far they are shifted from the reference signal.

CH3
CH3 Si CH3
CH3

Tetramethylsilane (TMS)

The position in an NMR spectrum where the signals occurs is called the chemical shift, because the
signal has been shifted upfield or downfield depending on the environments in which the proton
resides:

• upfield for protons with electron-dense environments

• downfield for protons with less electron-dense environment.

What about the PPM Scale?

The most common scale for chemical shift is the δ (delta) scale. The TMS signal is used to define the
zero position on the δ scale. The 1H NMR spectrum for 1-bromo-2,2-dimethylpropane (1) shows that
the chemical shift of the methyl protons is δ 1.05 and the chemical shift of the methylene protons is δ
3.28. The chemical shift indicates how far a signal is from the TMS signal. It is determined by measuring
the distance from the TMS peak (in Hertz) and dividing the operating frequency of the instrument by (in
megahertz). The chemical shift is reported in ppm (parts per million), e.g. “the chemical shift for proton
A was δ 1.05 ppm…”. Most chemical shifts are between 0 and 12 ppm.

Distance downfield from TMS (Hz)

δ = Chemical Shift (ppm) =
Operating frequency of the spectrometer (Hz)

Important Point

The chemical shift of the methyl protons of 1-bromo-2,2-dimethylpropane (1) occurs at 63 Hz in a 60-
MHz instrument and at 378 Hz in a 360-MHz instrument. Both, however, occur at δ 1.05 (63/60 = 1.05;
378/360 = 1.05) ppm.

Bottom Line: chemical shift does not change with operating frequency of the instrument.
What Factors Effect the Chemical Shift of a Proton?

As discussed in class, there a four major factors which conspire to effect the chemical shift of a proton
signal. These guidelines also apply to 13C NMR spectroscopy.

1. Electronegativity of Groups or Atoms Attached Either Directly or Indirectly to the Proton

As the electron withdrawing power of X increases, the electron density surrounding the proton in each
case shown below will decrease as X is pulls electron density towards itself. Accordingly, the protons
will be deshielded and their signals will occur at higher chemical shift (downfield). The electron
withdrawing power of an atom can be gauged by its electronegativity, the larger the value the more that
atom will pull electron density towards itself and the more the nearby proton will be deshielded.

δ+ δ−
H C X δ− or H X C
δ+

For example, if we compare the chemical shifts of the methylene protons immediately adjacent to the
halogen atom in each of the alkyl halides below. The position of the methylene signal depends on the
electronegativity of the halogen: the signal for the protons adjacent to fluorine (electronegativity = 4.0)
is farthest downfield while the signal for the iodoalkane methylene protons is farthest upfield (iodine’s
electronegativity = 2.7).
CH3 CH2CH2CH2 CH2F CH3 CH2CH2CH2 CH2Cl

δ 4.50 δ 3.50

CH3 CH2CH2CH2 CH2Br CH3 CH2CH2CH2 CH2I

δ 3.40 δ 3.20
Armed with this knowledge, we can now explain why methyl protons (δ 0.80-1.00 ppm for most simple
alkanes) often appear at lower chemical shift than methylene protons (δ 1.20-1.50 ppm for most simple
alkanes). If we consider the atoms attached to the carbon bearing the protons we see that while in the
case of the methyl group only one carbon atom is attached to the carbon bearing the protons, the
methylene group has two carbon atoms attached to the carbon atom bearing the protons. When we
compare the electronegativity of carbon (2.5) to hydrogen (2.2) we can see that carbon is slightly more
electronegative that hydrogen and as a result the addition of more carbon atoms to the carbon atom
carrying a proton will tend to deshield that proton. Be careful! As the diagram below shows, this effect
is not all that large and it is possible for methyl protons to appear at higher chemical shift than
methylene protons particularly if the methyl group is attached to an electronegative atom such as
oxygen; as is the case with a methyl ester.
H H H H
C C
C H C C

δ 0.80 - 1.00 ppm δ 1.20 - 1.50 ppm

2. Hybridization of the Atom Carrying the Proton

In general, protons which are attached to sp3-hydridized carbon atoms have signals at lower chemical
shift (shielded) than protons attached to an sp2-hydridized carbon. Why? Carbons atoms which are sp2-
hybridized tend to be more electron-withdrawing than sp3-hybridized carbon atoms and as a result
deshield protons which are attached to them. What about protons attached to sp-hydridized carbons?
This is a special case: see Magnetic Anisotropy.

Downfield C Upfield
(Deshielded) C (Shielded)
H H
C-sp2 C-sp3

3. Magnetic Anisotropy

This effect occurs with functional groups containing π electrons; alkenes, aromatic rings and alkynes. In
the presence of the applied magnetic field, the π electrons in these groups circulate and induce a large
induced magnetic field (Binduced). This field is anisotropic (“different in different directions”) and
depending on where a proton is positioned within this field it can be deshielded and therefore have high
chemical shifts (in this class are protons attached to alkenes (~5-6 ppm) and aromatic rings (~7-8 ppm),
or be shielded, as in the case of protons directly attached to triple bonds, and have lower chemical shifts
(alkynic protons appear at ~2.5ppm despite being attached to an sp-hydridized carbon).

Aromatic Alkenes Carbonyl Groups

Rings
+ +
+ Alkynes (Triple Bonds)
- -
H - - - - O
H H
+

H H
-
+
+ +

This diagram illustrates the anisotropic fields associated with common

functional groups: The (+) symbol indicates that a proton in this region
will be sheilded while the (-) symbol indicates that a proton in this
region will be desheilded.

4. Hydrogen Bonding

Protons which are hydrogen-bonded tend to have high, or very chemical shifts (up to 15.00 ppm).
Coupling And Peak Splitting

When we compare the 1H NMR spectrum of chloroacetone (1) with that of propanoyl chloride (2) we
notice not only a difference in the position of the resonance signals but also a difference in the
multiplicity of the signals, i.e. the signals are split. In the case of chloroacetone, singlets are observed for
both the methyl and methylene protons while with propanoyl chloride the methylene and methyl
protons give rise to a signal split into four lines (a quartet) and a signal split into three lines (a triplet),
respectively.

-CH3

ClCH2-

O
TMS reference peak
ClCH2 CH3
1

8 7 6 5 4 3 2 1 0
ppm
-CH3
O
-CH2-
CH3 CH2 Cl
2
8 7 6 5 4 3 2 1 0
ppm

The cause of this signal splitting is spin-spin coupling. Spin-spin coupling is also observed in 1,1-
dichloroethane (3) where the signal due to the three equivalent methyl protons is split into a doublet
(two lines) and the signal due to the more deshielded methine proton is split into a quartet (four lines).

H Cl
H H
H Cl
3

(δ 2.30, d, 3H) (δ 4.20, q, 1H)

The N+1 Rule

The splitting of signals in NMR spectroscopy is described by the N + 1 rule, where N is the number of
equivalent protons bonded to an adjacent atom. For example, the carbon adjacent to the methyl group
in 1,1-dichloroethane (3) is bonded to one proton, so the signal caused by the methyl protons is split
into a doublet (N+1 = 1+1 = 2). The methine proton, on the other hand, is adjacent to three equivalent
methyl protons and as a result its signal is split into a quartet (N+1 = 3+1 = 4). Since the methine and
methyl protons split each other’s signals, the two sets of protons are called coupled protons.

Cl
H
CH3 Cl
3

8 7 6 5 4 3 2 1 0

ppm

Important Point

Remember that it is not the number of protons giving rise to a signal that determines the splitting
pattern of that signal; rather, it is the number of protons bonded to the adjacent atom that determines
the splitting. We can see this important point if we reexamine the spectrum of propanoyl chloride (2).
The signal for the methyl protons is split into a triplet (N+1 = 2+1 = 3) because the adjacent carbon is
bonded to two hydrogens. The signal for the methylene protons, on the other hand, is a quartet
because the adjacent carbon is bonded to three equivalent hydrogens (N+1 = 3+1 = 4).

H O
(δ 1.20, t, 3H) H
2
H Cl
H H

(δ 2.90, q, 2H)

What Causes the Splitting of NMR Signals?

The splitting of signals is caused by spin-spin coupling which is brought about by a magnetic interaction
between individual protons. This effect is transmitted by the bonds through which the protons are
indirectly connected. In order to illustrate this effect let us consider the splitting of the signal from the
methyl protons in 1,1-dichloroethane (3). Since the splitting of a proton NMR signal is effected by the
number of adjacent protons in order to understand the splitting of the methyl signal we must consider
the spin states of the adjacent methine proton. We know that when a nucleus (spin = 1/2) is placed in a
magnetic field, the magnetic moment of that nucleus either aligns with (α-spin state) or against (β-spin
state) the applied magnetic field. These individual magnetic moments alter the effective magnetic field
(Bffective) which the adjacent methyl protons “feel” and as a result, the orientation of the methine
proton’s magnetic moment can effect the chemical shift of the methyl protons. The diagram below
demonstrates the two possible methine proton spin states in 1,1-dichloroethane and the orientation of
the proton’s magnetic moment in each case.
 In an applied field (B0 ) the magnetic moment of
H H the methine proton in 1,1-Dichloroethane can
Cl Cl align itself in one of two ways. As a result, the
Cl CH3 Cl CH3 methyl protons experience two slightly different
magnetic field strengths and therefore the signal
for the methyl protons will be split into two lines,
Bo A (α) B (β) a doublet. Remember! we are thinking about
the signal from the methyl protons.

Case A
If the magnetic moment of the methine proton is lined up with the applied field (B0), the magnetic
moment of the methine proton will be added to B0 and as a result a slightly lower applied field will be
required to induce to methyl protons to produce a signal (flip their spin): the signal for the methyl
protons will appear at higher chemical shift. In other words, in case A the orientation of the methine
proton’s magnetic moment is slightly deshielding the methyl protons.
Case B
If the magnetic moment of the methine proton is lined up against the applied magnetic field, the
magnetic moment of the methine proton will be subtracted from the applied magnetic field (Bapplied)
and a slightly high applied field will be required to flip the spin of the methyl protons: the signal for the
methyl protons will appear at lower chemical shift, i.e. upfield. In other words, in case B the orientation
of the methine proton’s magnetic moment is slightly shielding the methyl protons.

chemical shift of the signal

for the methyl protons if
there were no protons on
the adjacent carbon

H
H Cl
Cl H
H Cl
Cl H
H H
H
A B
the magentic moment of the magentic moment of
the methine H is lined the methine H is lined
up with the applied field up against the applied
so a lower magnetic field so a higher
field is required for the magnetic field is
methyl protons to come required for the methyl
into resonance protons to come into
resonance

3 2 1
Increasing Strength of Applied Magnetic Field

Since in a sample of 1,1-dichloroethane, at any given time, 50% of the molecules will have a methine
proton in the α−spin state (Case A) while the remaining 50% of the molecules will have a methine
proton in the β−spin state (Case B) the methyl protons actually sense two different effective magnetic
fields and the methyl signal is split into two peaks, one corresponding to the lower applied magnetic field
(Case A) and the other one corresponds to the higher applied field (Case B). Since there are an equal
number of molecules in situation A and B the two peaks will have approximately the same area (1:1).
The way in which the signal for the methyl protons is split by the methine proton is illustrated in the
diagram below. Note that without the presence of the methine proton the three methyl protons would
appear as a singlet in the 1H NMR spectrum.
If we now consider the splitting of the methine proton in 1,1-dichloroethane (3) we can see that the
number of different applied magnetic field strengths this proton can experience and therefore the
splitting pattern observed will be affected by the way in which the magnetic moments of the adjacent
methyl protons can be aligned (this is illustrated in the diagram below). The three magnetic moments
can all line up with the applied field (A); two can line up with the field and one against it (B); one can line
up with it and two against (C); or all three can line up against it (D). Since the methine proton is
capable of sensing four slightly different magnetic fields, depending on the orientation of the each of the
three magnetic moments belonging to the methyl protons, the signal for the methine proton is split into
four different lines, i.e. a quartet which has the relative peak area ratio of 1:3:3:1.

Chemical Shift of the

methine proton if there
were no protons on the
adjacent carbon

q H Cl
H
Cl
H
H
3

A B C D

Increasing Strength of Applied Magnetic Field

Important Point - The number of peaks in an NMR signal is called the multiplicity of the signal.

The relative peak intensities of a multiplet can be determined by figuring out how many ways the
adjacent proton magnetic moments can be aligned. Alternatively the relative intensities can be obtained
using Pascal’s triangle which is draw in the table below.

Number of equivalent Multiplicity of Relative peak

protons causing the the signal intensities
splitting
0 Singlet 1
1 Doublet 1:1
2 Triplet 1:2:1
3 Quartet 1:3:3:1
4 Quintet 1:4:6:4:1
5 Sextet 1:5:10:10:5:1
6 Septet 1:6:15:20:15:6:1
How Close Do Protons Have To Be To Couple Each Other?

Protons do not normally split each others NMR signals if they are separated by more than three sigma
(σ) bonds, e.g. the different protons in chloroacetone (1) are separated by four σ bonds, do not couple
one another and, as a result, appear as singlets. If, however, protons are separated by four bonds and
one of those bonds is a double or triple (π) bond, a small coupling is observable. This type of four bond
coupling is called long-range coupling.
Ha Hb Ha Hb Ha Hb
C C C C C C C C

Ha and Hb will split Ha and Hb will not Ha and Hb will split

each others signals split each other each other because
because they are because they are they are separated by
separated by 3 σ separated by 4 σ 4 bonds: 3 σ + 1 π
bonds bonds. There may
be a small coupling.

What Is The Coupling Constant?

The distance (in Hertz) between two adjacent peaks of a split NMR signal is called the coupling constant
(denoted by J). If we again consider 1,1-dichloroethane (3) the coupling constant for Ha being split by Hb
is denoted by Jab. We have seen that because the methine proton and the methyl proton of 1,1-
dichloroethane (3) split each other’s signals, they are called coupled protons. The signals of coupled
protons have the same coupling constant; in other words, Jab = Jba
Jab

Jab = Jba

Jba
Jba
The Ha and H b protons of
1,1-dichloroethane are coupled
protons, so their signals have the
a b same coupling constant, Jab =
CH3CHCl2 Jba.

Increasing Strength of Applied Magnetic Field

Important Point
Remember that it is not the number of protons giving rise to a signal that determines the splitting
pattern of that signal; rather, it is the number of protons bonded to the adjacent atom that determines
the splitting.
What Else Does the Magnitude of the Coupling Constant Tell Us?

Remember that it is not the number of protons giving rise to a signal that determines the splitting
pattern of that signal; rather, it is the number of protons bonded to the adjacent atom that determines
the splitting

Coupling constants can be very useful in determining the geometry of double bonds as well as dihedral
angles. Coupling constants can be used to distinguish between the 1H NMR spectra of cis and trans
olefin isomers because the coupling constant of trans-protons is significantly greater than the coupling
constant of cis-protons. The reason for this is because the dihedral angle between the two C-H bonds
in the H-C-C-H unit; the coupling constant is greatest when the angle between the two C-H bonds is
180° (trans), smaller when it is 0° (cis) and in the case of alkanes, near zero when cloase to 90°. The
dependence of coupling constant on dihedral angle is called the Karplus relationship.
Hb Ha Hb Ha

Jba = 14 Hz Jab = 14 Hz Jba = 9 Hz Jab = 9 Hz

Hb CO2H Hb Ha

Cl Ha Cl CO2H

trans-3-chloropropenoic acid cis-3-chloropropenoic acid

The observed doublets for the Ha and Hb protons in the 1 H NMR of

trans-3-chloropropenoic acid and cis-3-chloropropenoic acid. The coupling
constant for trans protons (14 Hz) is greater than the coupling constant for
cis protons (9 Hz)

What Happens When A Signal Is Split By More Than One Set Of Protons?

This situation is very common in most organic molecules. The splitting pattern you might expect to
observe when a signal is split by more than one set of protons can be best understood by using a
splitting or tree diagram. In a splitting diagram, the NMR peaks are shown as vertical lines and the effect
of each of the splittings is shown one at a time. For example, a tree diagram is shown below for the
splitting of the signal due to the Hc proton in 1,1,2-trichloro-3-methylbutane (4). This signal is split into
a doublet of doublets by the Hb and Hd protons (use the N+1 rule here to make sure you understand
this point).
 chemical shift of the signal
A Splitting for the Hc proton if there
Diagram or were no spin-spin coupling
"Tree" Diagram
Jcb splitting by the Hb proton

splitting by the Hd proton

Jcd

c
H Cl
a CH3 Cl
bH Hd
CH3 Cl
1,1,2-Trichloro-3-methylbutane

Increasing Strength of Applied Magnetic Field

Proton Hc is close enough (3 bonds away) to two other non-equivalent

protons, Hb and Hd to undergo spin coupling. The six methyl protons
are five sigma bonds away and do not couple with H c

You should notice that the relative intensity of this doublet of doublet, i.e. (1:1:1:1) is different from that
caused by a quartet (1:3:3:1). This can be important since the outcome of your analysis will be
dramatically altered if you mistake a doublet of doublet for a quartet. For example, the presence of a
doublet of doublet in an NMR spectrum indicates that the proton causing this signal is adjacent to two
different non-equivalent protons while the presence of a quartet indicates that the proton causing the
signal is adjacent to three equivalent protons (in most cases, the presence of a quartet indicates that
there is a methyl group nearby).

Ha
Hc C
C Hb

or
Ha
Ha C Hb
Hc
C C C
CH3
only
quartet doublet of doublets
relative intensities: 1:3:3:1 relative intensities: 1:1:1:1

Another point to note is that while the individual peaks within a quartet are equally spaced (all the same
coupling constant) the peaks in a doublet of doublet do not necessarily have to be since there are two
different coupling constants which are independent of one another. (Do you know which lines you
would have to measure between in each of the above splitting patterns to extract the coupling
constant(s)?).