Nuclear Magnetic Resonance

Spectroscopy
Nuclear magnetic resonance (NMR) is a spectroscopic
method that is even more important to the organic
chemist than infrared spectroscopy. Many nuclei may
be studied by NMR techniques, but hydrogen and
carbon are most commonly available. Whereas infrared
(IR) spectroscopy reveals the types of functional groups
present in a molecule, NMR gives information about the
number of magnetically distinct atoms of the type
being studied.
When hydrogen nuclei (protons) are studied, for
instance, one can determine the number of each
of the distinct types of hydrogen nuclei as well as
obtain information regarding the nature of the
immediate environment of each type. Similar
information can be determined for the carbon nuclei.
The combination of IR and NMR data is often sufficient
to determine completely the structure of an unknown
molecule.
 1. Nuclear Spin State
Many atomic nuclei have a property called spin: the
nuclei behave as if they were spinning. In fact, any
atomic nucleus that possesses either odd mass, odd
atomic number, or both has a quantized spin
angular momentum and a magnetic moment ()
proportional to the spin. The more common nuclei
that possess spin include:
 Natural % Magnetic Magnetogyric
Isotope Spin (I)
Abundance Moment ()* Ratio ()

1H 99.9844 1/2 2.7927 26.753

2H 0.0156 1 0.8574 4,107

11B 81.17 3/2 2.6880 --

13C 1.108 1/2 0.7022 6,728

17O 0.037 5/2 -1.8930 -3,628

19F 100.0 1/2 2.6273 25,179

29Si 4.700 1/2 -0.5555 -5,319

31P 100.0 1/2 1.1305 10,840

* in units of nuclear magnetons =5.05078x10-27 JT-1

in units of 107rad T-1 sec-1
For each nucleus with spin, the number of allowed
spin states it may adopt is quantized and is
determined by its nuclear spin quantum number (I).
For each nucleus, the number I is a physical constant,
and there are 2I + 1 allowed spin states with integral
differences ranging from +I to I.
The individual spin states fit into the
sequence
+I, (I 1), . . . , (I + 1), I Equation 1
For instance, a proton (hydrogen nucleus) has the
spin quantum number I = 1/2 and has two allowed
Spin states (2(1/2)+1 )=2 for its nucleus + 1/2 and
1/2.
 Table 1:Spin Quantum Numbers of Some Common Nuclei
The most abundant isotopes of C and O do not have spin.

Element 1H 2H 12C 13C 14N 16O 17O 19F

Nuclear Spin
Quantum No 1/2 1 0 1/2 1 0 5/2
(I)

No. of Spin 2 3 0 2 3 0 6 2
States

Elements with either odd mass or odd atomic number

have the property of nuclear spin.
The number of spin states is 2I + 1,
here I is the spin quantum number.
Figure 1:NUCLEAR SPIN STATES - HYDROGEN NUCLEUS
The spin of the positively
m charged nucleus generates
a magnetic moment vector, m.

+ +

The two states

are equivalent
m in energy in the
absence of a
+ 1/2 - 1/2 magnetic or an
electric field.
TWO SPIN STATES
 2. Nuclear Magnetic Moments
Spin states are not of equivalent energy in an applied
magnetic field because the nucleus is a charged particle,
and any moving charge generates a magnetic field of its
own. Thus, the nucleus has a magnetic moment
generated by its charge and spin. A hydrogen nucleus
may have a clockwise (+ 1/2) or counterclockwise (1/2)
spin, and the nuclear magnetic moments () in the two
cases are pointed in opposite directions. In an applied
magnetic field, all protons have their magnetic moments
either aligned with the field or opposed to it. Figure 2
illustrates these two situations.
Figure 2:Nuclear Spin Energy Levels
N

-1/2

In a strong magnetic
unaligned
field (Bo) the two
spin states differ in
energy.

+1/2
aligned
Bo S
Hydrogen nuclei can adopt only one or the other of
these orientations with respect to the applied field. The
spin state +1/2 is of lower energy since it is aligned with
the field, while the spin state 1/2 is of higher energy
since it is opposed to the applied field. This should be
intuitively obvious to anyone who thinks a little about
the two situations depicted in Figure2, involving
magnets.
Figure 3
The aligned configuration of magnets is stable (low
energy). However, where the magnets are opposed
(not aligned), the center magnet is repelled out of
its current (high-energy) orientation if the central
magnet were placed on a pivot, it would
spontaneously spin around the pivot into alignment
(low energy). Hence, as an external magnetic field is
applied, the degenerate spin states split into two
states of unequal energy, as shown in Figure 3.
 3. Absorption of Energy
The nuclear magnetic resonance phenomenon occurs when
nuclei aligned with an applied field are induced to absorb
energy and change their spin orientation with respect to the
applied field. Figure 4 illustrates this process for a hydrogen
nucleus.
The energy absorption is a quantized process, and the energy
absorbed must equal the energy difference between the two
states involved.
E absorbed = (E -1/2 state E+ 1/2 state) = h Equation 2
In practice, this energy difference is a function of the strength
of the applied magnetic field B0 , as illustrated in Figure 5.
 Figure 4:Absorption of Energy
quantized
Opposed

-1/2 -1/2

DE

DE = hn
Radiofrequency

+1/2 +1/2
Applied
Field
Aligned
Bo
Figure 5 :Energy difference as a function of the strength
of the applied magnetic field
- 1/2

DE = kBo = hn
degenerate
at Bo = 0

+ 1/2

Bo
increasing magnetic field strength
 A SECOND EFFECT OF A STRONG MAGNETIC FIELD

WHEN A SPIN-ACTIVE HYDROGEN ATOM IS

PLACED IN A STRONG MAGNETIC FIELD

.. IT BEGINS TO PRECESS

OPERATION OF AN NMR SPECTROMETER DEPENDS

ON THIS RESULT
 N

Nuclei precess at
w frequency w when
placed in a strong
magnetic field.
RADIOFREQUENCY
40 - 600 MHz
The axis of rotation also rotates in a
circular manner about the external
hn magnetic field axis, like a spinning
top

If n = w then
energy will be
absorbed and
the spin will
invert. S
The magnitude of the energy-level separation
also depends on the particular nucleus involved.
Each nucleus (hydrogen, chlorine, and so on) has a
different ratio of magnetic moment to angular
momentum since each has different charge and
mass. This ratio, called the magnetogyric ratio, is
a constant for each nucleus and determines the
energy dependence on the magnetic field
 Resonance Frequencies of Selected Nuclei
Isotope Abundance Bo (Tesla) Frequency(MHz) g(radians/Tesla)
1H 99.98% 1.00 42.6 267.53
1.41 60.0
2.35 100.0
7.05 300.0

2H 0.0156% 1.00 6.5 41.1 4:1

7.05 45.8

13C 1.108% 1.00 10.7 67.28

2.35 25.0
7.05 75.0

19F 100.0% 1.00 40.0 251.7

 POPULATION AND SIGNAL STRENGTH
The strength of the NMR signal depends on the
Population Difference of the two spin states

Radiation
induces both
upward and
downward induced
resonance
emission
transitions.

For a net positive signal excess

there must be an excess population
of spins in the lower state.

Saturation = equal populations = no signal

The Nuclear magnetic Resonance Spectrometer
The continuous wave instrument
 4. The Chemical Shift & Shielding
Nuclear magnetic resonance has great utility because
not all protons in a molecule have resonance at the
same frequency. This variability is due to the fact that
the protons in a molecule are surrounded by electrons
and exist in slightly different electronic environments
from one another. The valence-shell electron densities
vary from one proton to another. The protons are
shielded by electrons surround them .
In an applied magnetic field , the valence-electrons
of the protons are caused to circulate. This circulation ,
called a local magnetic current, generates a counter
magnetic field which opposes the applied magnetic
field .Figure 6 illustrate this effect , which is called
diamagnetic shielding or diamagnetic anisotropy.
 Diamagnetic Anisotropy
shielding of the nucleus by valence electrons
Figure 6
Circulation of electrons around a nucleus can be as
being similar to flow of electric current in an electric
wire .From physics, we know that the flow of a current
in a wire induces a magnetic filed. In an atom, the local
diamagnetic current generates a secondary field which
has a direction opposite to the applied magnetic field.
As a result of diamagnetic anisotropy, each proton in a
molecule is shielded from the applied magnetic field to
an extent that depends on the electron density surrounding
it.
The greater the electron density around a
nucleus, the greater the induced counter field
that opposes the applied field. The counter field
that shields a nucleus diminishes the net applied
magnetic field that the nucleus experiences. As a
result, the nucleus precesses at a lower frequency.
This means that it also absorbs radiofrequency
radiation at this lower frequency.
Each proton in a molecule is in a slightly different
chemical environment and consequently has a slightly
different amount of electronic shielding, which results in a
slightly different resonance frequency.
These differences in resonance frequency are very small.
For instance, the difference between the resonance
frequencies of the protons in chloromethane and those in
fluoromethane is only 72 Hz when the applied field is 1.41
Tesla.
Since the radiation used to induce proton spin
transitions at that magnetic field strength is of a
frequency near 60 MHz, the difference between
chloromethane and fluoromethane represents a
change in frequency of only slightly more than one
part per million! It is very difficult to measure exact
frequencies to that precision; hence, no attempt is
made to measure the exact resonance frequency of
any proton.
Instead, a reference compound is placed in the solution
of the substance to be measured, and the resonance
frequency of each proton in the sample is measured
relative to the resonance frequency of the protons of the
reference substance. The standard reference substance
that is used universally is tetramethylsilane, (CH3)4Si,
also called TMS. This compound was chosen initially
because the protons of its methyl groups are more
shielded than those of most other known compounds.
At that time, no compounds that had better-
shielded hydrogens than TMS were known, and
it was assumed that TMS would be a good
reference substance since it would mark one end
of the range. Thus, when another compound is
measured, the resonances of its protons are
reported in terms of how far (in Hertz) they are
shifted from those of TMS.
The shift from TMS for a given proton depends on
the strength of the applied magnetic field. In an
applied field of 1.41 Tesla the resonance of a proton
is approximately 60 MHz, whereas in an applied
field of 2.35 Tesla (23,500 Gauss) the resonance
appears at approximately 100 MHz. The ratio of the
resonance frequencies is the same as the ratio of
the two field strengths:
Hence, for a given proton, the shift (in Hertz) from
TMS is 5/3 larger in the 100-MHz range (B0 = 2.35
Tesla) than in the 60-MHz range (B0 = 1.41 Tesla).
This can be confusing for workers trying to
compare data if they have spectrometers that differ
in the strength of the applied magnetic field.
The confusion is easily overcome if one defines a
new parameter that is independent of field
strengthfor instance, by dividing the shift in Hertz
of a given proton by the frequency in megahertz of
the spectrometer with which the shift value was
obtained. In this manner, a field-independent
measure called the chemical shift () is obtained
The chemical shift in units expresses the amount by
which a proton resonance is shifted from TMS, in parts
per million (ppm), of the spectrometers basic operating
frequency. Values of for a given proton are always the
same irrespective of whether the measurement was
made at 60 MHz(B0 = 1.41 Tesla) or at 100 MHz (B0 =
2.35 Tesla). For instance, at 60 MHz the shift of the
protons in CH3Br is 162 Hz from TMS, while at 100 MHz
the shift is 270 Hz. However, both of these correspond to
the same value of (2.70 ppm):
By agreement , most workers report chemical
shifts in delta () units , or parts per million
(ppm) , of the main spectrometer frequency. On
this scale , the resonance of the protons in TMS
comes at exactly 0.00 ppm(by definition)
Chemical Shift Scale
 6. Chemical Equivalence
- a brief overview -
All of the protons found in chemically identical
environments within a molecule are chemically
equivalent, and they often exhibit the same chemical
shift. Thus, all the protons in tetramethylsilane (TMS) or
all the protons in benzene, cyclopentane, or acetone
which are molecules that have protons that are
equivalent by symmetry considerationshave resonance
at a single value of (but a different value from that
of each of the other molecules in the same group).
Each such compound gives rise to a single
absorption peak in its NMR spectrum. The protons
are said to be chemically equivalent. On the other
hand, a molecule that has sets of protons that are
chemically distinct from one another may give rise
to a different absorption peak from each set, in
which case the sets of protons are chemically
nonequivalent. The following examples should help
to clarify these relationships:
Molecules giving rise to one NMR
absorption peak
Molecules giving rise to two NMR
absorption peak
Molecules giving rise to three NMR
absorption peak
 7. Integrals & Integration
The NMR spectrum not only distinguishes how
many different types of protons a molecule has, but
also reveals how many of each type are contained
within the molecule. In the NMR spectrum, the area
under each peak is proportional to the number of
hydrogens generating that peak. Hence, in
phenylacetone (see Fig. 6), the area ratio of the
three peaks is 5:2:3, the same as the ratio of
the numbers of the three types of hydrogens.
Figure 7
The NMR spectrometer has the capability to
electronically integrate the area under each
peak. It does this by tracing over each peak a
vertically rising line, called the integral, which
rises in height by an amount proportional to the
area under the peak. Figure 8
Figure 8
 8. Chemical Environment &
Chemical Shift
Not only do different types of protons have different
chemical shifts, but each also has a characteristic value
of chemical shift. Every type of proton has only a limited
range of values over which it gives resonance. Hence,
the numerical value (in units or ppm) of the chemical
shift for a proton gives a clue regarding the type of
proton originating the signal, just as an infrared
frequency gives a clue regarding the type of bond or
functional group.
For instance, notice that the aromatic protons of both
phenylacetone (Fig. 7) and benzyl acetate(Fig. 8) have
resonance near 7.3 ppm, and that both of the methyl
groups attached directly to a carbonyl have resonance
at about 2.1 ppm. Aromatic protons characteristically
have resonance near 7 to 8 ppm, whereas acetyl groups
(methyl groups of this type) have their resonance near
2 ppm.
Figure 9:NMR Correlation Chart
 APPROXIMATE CHEMICAL SHIFT RANGES (ppm) FOR SELECTED TYPES OF PROTONS

R-CH3 0.7 - 1.3 R-N-C-H 2.2 - 2.9 R-C=C-H

R-CH2-R 1.2 - 1.4 R-S-C-H 2.0 - 3.0 4.5 - 6.5
R3CH 1.4 - 1.7
I-C-H 2.0 - 4.0
H
R-C=C-C-H 1.6 - 2.6
Br-C-H 2.7 - 4.1
O 6.5 - 8.0
R-C-C-H 2.1 - 2.4 Cl-C-H 3.1 - 4.1 O
O RO-C-H 3.2 - 3.8 R-C-N-H
5.0 - 9.0
RO-C-C-H 2.1 - 2.5
HO-C-H 3.2 - 3.8 O
O
O R-C-H
HO-C-C-H 2.1 - 2.5 9.0 - 10.0
R-C-O-C-H 3.5 - 4.8
N C-C-H 2.1 - 3.0 O
O2N-C-H 4.1 - 4.3 R-C-O-H
R-C C-C-H 2.1 - 3.0
F-C-H 4.2 - 4.8 11.0 - 12.0

C-H 2.3 - 2.7 R-N-H 0.5 - 4.0 Ar-N-H 3.0 - 5.0 R-S-H

R-C C-H 1.7 - 2.7 R-O-H 0.5 - 5.0 Ar-O-H 4.0 - 7.0 1.0 - 4.0
 9. Local Diamagnetic Shielding
1. Electronegativity effect:
The trend of chemical shifts that is easiest to explain is
that involving electronegative elements substituted on
the same carbon to which the protons of interest are
attached. The chemical shift simply increases as the
electronegativity of the attached element increases.
Table3 illustrates this relationship for several
compounds of the type CH3X.
 DESHIELDING BY AN ELECTRONEGATIVE ELEMENT

d- d+ Chlorine deshields the proton,

Cl C H that is, it takes valence electron
d- d+ density away from carbon, which
electronegative in turn takes more density from
element hydrogen deshielding the proton.
NMR CHART

deshielded highly shielded

protons appear protons appear
at low field at high field

deshielding moves proton

resonance to lower field
Table 3:Electronegativity Dependence
of Chemical Shift
Dependence of the Chemical Shift of CH3X on the Element X

Compound CH3X CH3F CH3OH CH3Cl CH3Br CH3I CH4 (CH3)4Si

Element X F O Cl Br I H Si
Electronegativity of X 4.0 3.5 3.1 2.8 2.5 2.1 1.8
Chemical shift d 4.26 3.40 3.05 2.68 2.16 0.23 0

most TMS
deshielded deshielding increases with the
electronegativity of atom X
Multiple substituents have a stronger effect than
a single substituent. The influence of the
substituent drops off rapidly with distance, an
electronegative element having little effect on
protons that are more than three carbons
distant. Table 4 illustrates these effects for the
underlined protons.
 Table 4:Substitution Effects on Chemical Shift

most The effect

deshielded CHCl3 CH2Cl2 CH3Cl increases with
greater numbers
7.27 5.30 3.05 ppm
of electronegative
atoms.

most
deshielded -CH2-Br -CH2-CH2Br -CH2-CH2CH2Br
3.30 1.69 1.25 ppm

The effect decreases

with increasing distance.
Electronegative substituents attached to a carbon
atom, because of their electron-withdrawing effects,
reduce the valence electron density around the
protons attached to that carbon.
These electrons, it will be recalled, shield the proton
from the applied magnetic field. Figure 6 illustrates
this effect, called local diamagnetic shielding.
Electronegative substituents on carbon reduce the
local diamagnetic shielding in the vicinity of the
attached protons because they reduce the electron
density around those protons. Substituents that
have this type of effect are said to deshield the
proton. The greater the electronegativity of the
substituent, the more it deshields protons and hence
the greater is the chemical shift of those protons.
 Ring Current in Benzene

Circulating electrons

Deshielded
H H

Bo Secondary magnetic field

generated by circulating
electrons deshields aromatic
protons
Shielded regions are designated by a plus sign, and
deshielded regions by a negative sign.
 10. SPIN-SPIN SPLITTING
Often a group of hydrogens will appear as a multiplet
rather than as a single peak.
Multiplets are named as follows:

Singlet Quintet
Doublet Septet
Triplet Octet
Quartet Nonet

This happens because of interaction with neighboring

hydrogens and is called SPIN-SPIN SPLITTING.
 (n+1) RULE
Even in simple molecules, one finds that each type of
proton rarely gives a single resonance peak. For
instance, in 1,1,2-trichloroethane there are two
chemically distinct types of hydrogens:
On the basis of the information given thus far, one
would predict two resonance peaks in the NMR
spectrum of 1,1,2-trichloroethane, with an area ratio
(integral ratio) of 2:1.
In 2-nitropropane, the methine proton (on the carbon
bearing the nitro group) has a larger chemical shift than
the hydrogens of the two methyl groups.
Finally, note that the spinspin splitting gives a new type
of structural information. It reveals how many hydrogens
are adjacent to each type of hydrogen that is giving an
absorption peak or, as in these cases, an absorption
multiplet. For reference, some commonly encountered
spinspin splitting patterns are collected in Table 6.
In reality, the higher-resolution NMR spectrum of this
compound has five peaks: a group of three peaks (called a
triplet) at 5.77 ppm and a group of two peaks (called a
doublet) at 3.95 ppm. Figure 11 shows this spectrum.
The methine (CH) resonance (5.77 ppm) is said to be split
into a triplet, and the methylene resonance (3.95 ppm) is
split into a doublet. The area under the three triplet peaks
is 1, relative to an area of 2 under the two doublet peaks.
Figure 11
This phenomenon, called spinspin splitting, can be
explained empirically by the so-called n + 1 Rule.
Each type of proton senses the number of
equivalent protons (n) on the carbon atom(s) next
to the one to which it is bonded, and its resonance
peak is split into (n + 1) components.
Examine the case at hand, 1,1,2-trichloroethane,
utilizing the n + 1 Rule. First the lone methine
hydrogen is situated next to a carbon bearing two
methylene protons.
According to the rule, it has two equivalent
neighbors (n = 2) and is split into n + 1 = 3 peaks
(a triplet). The methylene protons are situated
next to a carbon bearing only one methine
hydrogen. According to the rule, these protons
have one neighbor (n = 1) and are split into
n + 1 = 2 peaks (a doublet).
Before proceeding to explain the origin of this
effect, let us examine two simpler cases predicted
by the n + 1 Rule. Figure 12 is the spectrum of
ethyl iodide (CH3CH2I). Notice that the methylene
protons are split into a quartet (four peaks), and the
methyl group is split into a triplet (three peaks).
This is explained as follows:
Figure 12
Consider 2-nitropropane, which has the spectrum
given in Figure 13.One neighbor gives a doublet .Six
equivalent neighbors give a septet
(n + 1 = 2) (area = 6) (n + 1 = 7) (area = 1)
Notice that in the case of 2-nitropropane there are
two adjacent carbons that bear hydrogens(two
carbons, each with three hydrogens), and that all six
hydrogens as a group split the methine hydrogen
into a septet.
Figure 13
 Also notice that the chemical shifts of the various
groups of protons make sense according to the
discussions in Sections 8 and 9. Thus, in 1,1,2-
trichloroethane, the methine hydrogen (on a carbon
bearing two Cl atoms) has a larger chemical shift than
the methylene protons (on a carbon bearing only one Cl
atom). In ethyl iodide, the hydrogens on the carbon-
bearing iodine have a larger chemical shift than those
of the methyl group.
Table 6
 EXCEPTIONS TO THE N+1 RULE
IMPORTANT !

1) Protons that are equivalent by symmetry

usually do not split one another

X CH CH Y X CH2 CH2 Y

no splitting if x=y no splitting if x=y

2) Protons in the same group

usually do not split one another
H H
C H or C
H H
3) The n+1 rule applies principally to protons in
aliphatic (saturated) chains or on saturated rings.
CH3
CH2CH2CH2CH2CH3 or H

YES YES

but does not apply (in the simple way shown here)
to protons on double bonds or on benzene rings.
H CH3 CH3

H H
NO NO
 THE ORIGIN OF
SPIN-SPIN SPLITTING

HOW IT HAPPENS
 THE CHEMICAL SHIFT OF PROTON HA IS
AFFECTED BY THE SPIN OF ITS NEIGHBORS
aligned with Bo opposed to Bo

50 % of +1/2 -1/2 50 % of
molecules molecules
H HA H HA
C C C C

Bo
downfield upfield
neighbor aligned neighbor opposed

At any given time about half of the molecules in solution will

have spin +1/2 and the other half will have spin -1/2.
 SPIN ARRANGEMENTS
one neighbor one neighbor
n+1 = 2 n+1 = 2
doublet doublet

H H H H
C C C C

The resonance positions (splitting) of a given hydrogen is

affected by the possible spins of its neighbor.
 SPIN ARRANGEMENTS
two neighbors one neighbor
n+1 = 3 n+1 = 2
triplet doublet

H H H H
C C C C
H H

methine spins
methylene spins
 SPIN ARRANGEMENTS
three neighbors two neighbors
n+1 = 4 n+1 = 3
quartet triplet

H H H H
C C H C C H
H H H H

methylene spins
methyl spins
 11. Pascals Triangle
We can easily verify that the intensity ratios of
multiplets derived from the n+1 rule follow the
entries in the mathematical mnemonic device called
Pascals Triangle (Figure 14 ).Each entry in the
triangle is the sum of the two entries above it and to
its immediate left & right .Notice that the intensities
of the outer peaks of a mutiplet such as a septet are
so small compared to the inner peaks that they are
often obscured in the baseline of spectrum. Figure
15.
 Figure 14
no. of neighbors relative intensities pattern example
0 1 singlet (s)

H H
1 1 1 doublet (d)
C C
H H
2 1 2 1 triplet (t) C C H
H H
3 1 3 3 1 quartet (q) C C H
H H H H

4 1 4 6 4 1 pentet C C C H

H H H H

5 1 5 10 10 5 1 sextet H C C C H
H H H H

6 1 6 15 20 15 6 1 septet H C C C H
H H
Figure 15
 12. The Coupling Constant
The distance between the peaks in a simple
multiplet is called the coupling constant J. The
coupling constant is a measure of how strongly a
nucleus is affected by the spin states of its neighbor.
The spacing between the multiplet peaks is
measured on the same scale as the chemical shift,
and the coupling constant is always expressed in
Hertz (Hz).
 J H H
C C H

J J H H
J J
J

The coupling constant is the distance J (measured in Hz)

between the peaks in a multiplet.

J is a measure of the amount of interaction between the

two sets of hydrogens creating the multiplet.
 FIELD COMPARISON
100 MHz 200 Hz

100 Hz
Coupling constants are
constant - they do not
7.5 Hz
change at different J = 7.5 Hz
field strengths

6 5 4 3 2 1
200 MHz
400 Hz
Separation
is larger 200 Hz

The shift is 7.5 Hz

J = 7.5 Hz
dependant
on the field

3 2 1 ppm
 NOTATION FOR COUPLING CONSTANTS
The most commonly encountered type of coupling is
between hydrogens on adjacent carbon atoms.

H H This is sometimes called vicinal coupling.

3J It is designated 3J since three bonds
C C intervene between the two hydrogens.

Another type of coupling that can also occur in special

cases is
2J or geminal coupling
H
( most often 2J = 0 )
C H
2J
Geminal coupling does not occur when
the two hydrogens are equivalent due to
rotations around the other two bonds.
 LONG RANGE COUPLINGS
Couplings larger than 2J or 3J also exist, but operate
only in special situations.

H C H
C C
4J, for instance, occurs mainly
when the hydrogens are forced
to adopt this W conformation
(as in bicyclic compounds).

Couplings larger than 3J (e.g., 4J, 5J, etc) are usually

called long-range coupling.
 SOME REPRESENTATIVE COUPLING CONSTANTS
H H
6 to 8 Hz three bond 3J
vicinal
C C
H
trans C C 11 to 18 Hz three bond 3J

H
H H 3J
cis
C C 6 to 15 Hz three bond
H
geminal C 0 to 5 Hz two bond 2J
H

Hax Hax,Hax = 8 to 14
Heq Hax,Heq = 0 to 7 three bond 3J

Heq Hax Heq,Heq = 0 to 5

 H
cis 6 to 12 Hz
three bond 3J
trans 4 to 8 Hz
H
H
C 4 to 10 Hz three bond 3J
C H

H 4J
four bond
C C 0 to 3 Hz
C H

H C C C 0 to 3 Hz four bond 4J

H
Couplings that occur at distances greater than three bonds are
called long-range couplings and they are usually small (<3 Hz)
and frequently nonexistent (0 Hz).
EXAMPLE SPECTRA
FOR DISCUSSION
1 Methyl Ethyl Ketone NMR 07

O
CH3 C CH2CH3
 2 Ethyl Acetate NMR 08

Compare the methylene shift to that of Methyl Ethyl Ketone (previous slide).

O
CH3 C O CH2CH3
3
a-Chloropropionic Acid NMR 04

O
CH3 CH C OH
Cl
4 t-Butyl Methyl Ketone NMR 03
(3,3-dimethyl-2-butanone)

O CH3
CH3 C C CH3
CH3
 5 1-Nitropropane NMR 05

+ O
CH3CH2CH2 N
O-
6 1,3-Dichloropropane NMR 17

Cl CH2CH2CH2 Cl
AROMATIC RINGS
 BENZENE RING HYDROGENS
Ring current causes protons attached to the
ring to appear in the range of 7 to 8 ppm.

An anisotropy diagram (next slide) shows

the origin of the effect.

Protons in a methyl or methylene group

attached to the ring appear in the range
of 2 to 2.5 ppm.
MONOSUBSTITUTED RINGS
 ALKYL-SUBSTITUTED RINGS
In monosubstituted rings with an alkyl substitutent
all ring hydrogens come at the same place in the NMR
spectrum.

R R = alkyl (only)

Apparently the ring current

equalizes the electron density
at all the carbons of the ring
and, therefore, at all of the
hydrogen atoms.
NMR Spectrum of Toluene

CH3
5

3
 THE EFFECT OF CARBONYL SUBSTITUENTS
When a carbonyl group is attached to the ring the
o- and p- protons are deshielded by the anisotropic
field of C=O

R R
O C C O
H H H H

Only the o- protons are in range for this effect.

The same effect is sometimes seen with C=C bonds.

Acetophenone (90 MHz)

CH3 3
O C
H H
Compare:

CH3

The ring protons in

toluene come at
about 7.2 ppm at
the red line.
2 3

deshielded
para -DISUBSTITUTED RINGS
 para-Disubstitution
1,4-Disubstituted benzene rings will show
a pair of doublets, when the two groups
on the ring are very different

an example:
1-iodo-4-methoxybenzene
 NMR Spectrum of
1-iodo-4-methoxybenzene

3
I OCH3

CHCl3 impurity
2 2
 NMR Spectrum of
1-bromo-4-ethoxybenzene

Br OCH2CH3 3
4

2
 THE p-DISUBSTITUTED PATTERN CHANGES AS THE
TWO GROUPS BECOME MORE AND MORE SIMILAR
All peaks move closer.
Outer peaks get smaller .. and finally disappear.
Inner peaks get taller. and finally merge.

X X X

X all H
Y X' equivalent

X=Y X ~ X X=X
same groups
 NMR Spectrum of
1-amino-4-ethoxybenzene

3
H2N OCH2CH3
4

2 2
 NMR Spectrum of p-Xylene
(1,4-dimethylbenzene)

CH3 CH3
4
 NMR Spectrum of
2-Chloropropanoic Acid
COOH O
CH3 CH C OH 3
1
Cl

1
~12 ppm

offset = 4.00 ppm

UNEQUAL COUPLING
TREE DIAGRAMS

SPLITTING DIAGRAMS
aka TREE DIAGRAMS
 WHERE DOES THE N+1 RULE WORK ?

The n+1 rule works only for protons in aliphatic chains

and rings, and then under special conditions.

There are two requirements for the n+1 rule to work:

1) All 3J values must be the same all along the chain.
2) There must be free rotation or inversion (rings) to
make all of the hydrogens on a single carbon be
nearly equivalent.
THE TYPICAL SITUATION WHERE THE n+1 RULE APPLIES

Hydrogens can
interchange their
H H H positions by
rotations about
C C C the C-C bonds.
H H H This makes all the
3J = 3J hydrogens on each
a b
of the carbon atoms
All the couplings equivalent.
along the chain
have the same J value.
WHAT HAPPENS WHEN THE J VALUES ARE NOT EQUAL ?

H H H
3J
a = 3J
b C C C
H H H
3J 3J
a b

In this situation each coupling must be considered

independently of the other.

A splitting tree is constructed

USE THESE VALUES

H H H
C C C
H H H
7 Hz 3 Hz
CONSTRUCTING A TREE DIAGRAM
SPLITTING FROM
HYDROGENS TO THE LEFT

H H H -CH2-CH2-CH2-
LEVEL ONE
C C C The largest J value
is usually used first.
H H H
3J Two neighbors gives
a= 7 a triplet.

The next splittings will

Each level of the be added to each leg of
splitting uses the the first splitting.
n+1 rule.
 WHEN BOTH 3J VALUES ARE THE SAME
The n+1 rule is followed ..
LEVEL ONE -CH -CH -CH -
2 2 2
Splitting from
INTENSITIES hydrogens on
the left n+1 = (4 + 1) = 5
1:2:1
1:2:1 LEVEL TWO
1:2:1 Splitting from
+ 1:2:1 hydrogens on
the right
1:4:6:4:1

Splittings .. because of overlapping legs.

overlap
You get the quintet predicted by
the n+1 rule.
WHEN THE n+1 RULE APPLIES WE CAN JUMP TO THE FINAL RESULT
NO TREE NEEDED
If there are more than two interacting groups,
the multiplicity of A as split by B and C is expressed by
(2nBIB + 1)(2nCIC + 1) etc..For example consider :
R-CH2-CH2-CH2-R
B A C
The expression becomes (2+1)(2+1) = 9, proton A
resonance will therefore be seen as a pattern with a
maximum of nine lines(three triplets).If however R & R are
identical then the B & C protons are chemically and
magnetically equivalent and give rise to five lines pattern A
protons.
 2-PHENYLPROPANAL

A case where there are unequal J values.

 a b d
CH3 CH CHO
J = 7 Hz

J = 2 Hz
 7 Hz 2 Hz Rather than the expected
quintet ..
CH3 CH CHO
the methine hydrogen
is split by two different
3J values.

3J
quartet
1 = 7 Hz by -CH3

3J = 2 Hz doublet
2
ANALYSIS by -CHO
OF METHINE
HYDROGENS
SPLITTING

quartet of doublets
PURE ETHANOL
ETHANOL 400 MHz

Old sample
Rapid exchange catalyzed
by impurities

hydrogen on OH
is decoupled
HO-CH2-CH3

triplet

broad
quartet singlet
expansion expansion

doublet of triplet
quartets

ETHANOL
Ultrapure sample (new)
Slow or no exchange

400 MHz
triplet
 J=7
J=5 J=7
J=5

triplet quartet of doublets triplet

VINYL ACETATE

ALKENE HYDROGENS
 COUPLING CONSTANTS
PROTONS ON C=C DOUBLE BONDS
3J-cis = 8-10 Hz H H

3J-trans = 16-18 Hz H

H
protons on the same carbon
2J-geminal = 0-2 Hz H

For protons on saturated aliphatic chains 3J ~ 8 Hz

NMR Spectrum of Vinyl Acetate

60 MHz
O
CH3 C
O CH CH2
 Analysis of Vinyl Acetate
O 3J-trans > 3J-cis > 2J-gem
C H3 C
HC O HB HB HA
C C
HC HA
3J
3J 3J AC
BC BC cis
trans trans

3J 2J 2J
AC AB AB
cis gem gem
2,4-DINITROANISOLE

BENZENE HYDROGENS
 2,4-DINITROANISOLE

400 MHz

9.0 8.0 7.0

2,4-DINITROANISOLE

8.72 ppm 8.43 ppm 7.25

END
 To determine a structure from a 'H
NMR spectrum, we usually need the
molecular formula. Analysis of the
spectrum involves:
A. Look at the integration, and from the molecular
formula see how many hydrogen atoms are represented
by each group of signals.
B. Look for any signals which disappear on a D20 shake.
C. See how many carbon atoms are involved in the
groups of hydrogen atoms. Then look at the molecular
formula to see how many carbon atoms are left over, and
which other atoms the molecule contains.
.
D. Look at the chemical shifts. This should identify
alkenes, alkynes and aromatic groups, and show
which atoms are moved downfield by neighbouring
electronegative substituents.
E. Look at the splittings of the peaks, and hence
determine how many hydrogen atoms are on the
carbon next to that carrying the hydrogen atom(s)
that you are studying.
F. Assemble the atoms into a molecule. With short
carbon chains, it will be obvious how the carbon
atoms fit together, but for longer chains, work from
a 'chain ending group' (i.e. a group with only one
unused linkage), such as CH3, CH20H, CH2Br, =CH2,
phenyl, etc. If you have more than two of these
groups, the molecule must be branched.