Organic Chemistry: Richard F. Daley and Sally J. Daley

Richard F. Daley and Sally J.
Daley
www.ochem4free.com
Organic
Chemistry Chapter 10
Nuclear Magnetic Resonance
10.1 Theory of Nuclear Magnetic Resonance 475

10.2 Shielding 478
10.3 Chemical Shift and Molecular Structure 480
10.4 Interpreting Proton NMR Spectra 484
10.5 Spin-Spin Splitting 491
10.6 Integration Signals in an NMR Spectrum 501
10.7 Analyzing an NMR Spectrum 503
Sidebar – Magnetic Resonance Imaging 511
10.8 Strategy for Solving Spectral Problems 513
Key Ideas from Chapter 10 519
Organic Chemistry - Ch 10 474 Daley & Daley
Copyright 1996-2005 by Richard F. Daley & Sally J. Daley

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www.ochem4free.com 5 July 2005

Chapter 10
Nuclear Magnetic Resonance

Chapter Outline
10.1 Theory of Nuclear Magnetic Resonance
The physical principles behind nuclear magnetic resonance
10.2 Shielding
How nearby atoms in a molecule change the observed
location for the resonance signal in an NMR spectrum
10.3 Chemical Shift and Molecular Structure
Correlating the chemical shift of a proton with molecular
structure
10.4 Interpreting Proton NMR Spectra
Correlating an NMR spectrum with the structure of the
original molecule
10.5 Spin-Spin Splitting
Interaction of a proton at resonance with protons on
adjacent carbons not at resonance
10.6 Integration of Signals in an NMR Spectrum
Determining the relative numbers of protons for each signal
in an NMR spectrum
10.7 Analyzing an NMR Spectrum
Techniques for analyzing an NMR spectrum
10.8 Spectroscopic Analysis of Unknown
Organic Compounds
Combining IR, NMR, and MS to deduce the structure of a
unknown compound

Objectives
✔ Understand the molecular basis for nuclear magnetic resonance

spectroscopy
✔ Know how the molecular features of a molecule affect the position
of resonance for a particular proton in an NMR
✔ Be able to sketch the expected NMR for simple molecules
✔ Use spin-spin splitting along with integration to further learn
about the structure of a molecule
✔ Be able to combine the information from an IR, NMR, and MS to
postulate a reasonable structure for an unknown compound
The quick harvest of applied science is the usable

process, the medicine, the machine. The shy fruit
of pure science is Understanding.
- Lincoln Barnett
C hapter 10 continues the study of molecular spectroscopy

techniques by investigating nuclear magnetic resonance
(NMR). NMR provides information about the nuclei of the atoms in a
molecule.
Nuclear magnetic resonance spectroscopy is a powerful tool
that chemists use to help determine the structure of molecules. The
environment of the nuclei in a molecule affects the appearance and
position of the signals in the NMR spectrum. A number of nuclei give
rise to NMR spectra. These include 1H, 13C, 15N, 19F, and 31P.
Because organic compounds contain carbon and hydrogen, organic
chemists use both proton (1H) and carbon (13C) magnetic resonance.
Most frequently, they use proton NMR, although carbon NMR is
becoming much more widely used. Assume NMR means proton
magnetic resonance, unless otherwise stated.
Chapter 9 covered IR spectroscopy and mass spectrometry. IR
spectroscopy provides information about the bonds in a compound and
is particularly useful for the identification of functional groups.
Combining IR, NMR, and MS along with chemical analysis provides
sufficient information to routinely identify most unknown compounds.
The goal of Chapter 9 and this chapter is to provide you with the tools

needed to identify the structure of unknown compounds based on

these three spectral types.
10.1 Theory of Nuclear Magnetic Resonance

A nucleus with an odd atomic number and/or an odd mass
Nuclear spin is the number has a nuclear spin. It is the transition between nuclear spin
sum of the spin states that the NMR spectrometer detects. Such a nucleus behaves as
quantum numbers of if it were spinning on an axis. For a proton the nuclear spin, based on
the particles in the the spin quantum number, has one of two possible values: +1/2 or –
nucleus. 1
1/2 . Under ordinary circumstances, both spin states have the same
energy level.
The simplest example of an atom with a nuclear spin is a
hydrogen atom that contains a single proton in its nucleus. Visualize a
proton as a spinning sphere with a positive charge. Because the
spinning movement of a charged particle generates a magnetic field
(called H), a proton behaves similarly to a small bar magnet. See
The magnetic moment Figure 10.1. Chemists call this magnetic field the magnetic moment
of a nucleus is the of the nucleus.
magnetic field
generated by the
nuclear spin.
N
H + H H S
H
Spinning proton Bar magnet
Figure 10.1. A spinning proton generates a magnetic field called its magnetic
moment. The magnetic field (H) of a proton resembles the magnetic field of a small
bar magnet.
If you place a small magnet in the magnetic field of a larger

magnet, the small magnet immediately aligns itself with the magnetic
field of the larger magnet. This alignment is either parallel with or
antiparallel to the field of the larger magnet. The external magnetic
field of the larger magnet is called Ho. When you place a nucleus with
a magnetic moment in an external magnetic field, as with the small
1
There are a variety of possible nuclear spins: 0, ±1/2, ±1, ±3/2, etc. Any non-zero spin
states all give rise to magnetic resonance spectra. In this text, we consider only the ±1/2
spin states which includes 1H, 13C, 15N, 19F, 31P, and some other elements.

magnet, the two spin states of the nucleus align themselves with the
applied magnetic field. The +1/2 spin state aligns itself parallel to the
applied field, and the –1/2 spin state aligns antiparallel with the
applied field. Chemists often call the +1/2 spin state the α-spin state
and the –1/2 the β-spin state. Because the β-spin state aligns itself
against the applied magnetic field, it is the higher energy state. See
Figure 10.2. Typically, nearly equal amounts of both spin states are in
the magnetic field.
H
+ H0 +
H
- sp in state - sp in sta te
Figure 10.2. The nuclear spin states of a proton in the presence of an external
magnetic field, H0. The magnetic field of the spin state on the left is the lower energy
α-spin state. The one on the right is the higher energy β-spin state.
As stated earlier, in the absence of an external magnetic field

the energy levels of the two spin states are the same. If you apply an
external magnetic field, the energy levels change so that one energy
level is greater than the other. The difference in energy between the
two spin states is directly proportional to the strength of the applied
magnetic field. Still, this energy difference is quite small even in very
powerful magnetic fields. For example, with a magnetic field strength
of 25,000 gauss, the energy difference is only about 10–5 kcal/mole.
This energy difference is around the energy of photons in the
radiofrequency region of the electromagnetic spectrum.
When photons of proper energy strike nuclei aligned with the
external magnetic field of the NMR spectrometer, then the nuclei
A nucleus undergoes
spin flip when going
“flip” to the other alignment. This flip, called a spin flip, between the
from parallel to two spin states requires just the right combinations of magnetic field
antiparallel to the and electromagnetic radiation. A nucleus is then in resonance as it
external magnetic field. flips in time with the applied radiofrequency. The NMR spectrometer
detects and records this absorption of energy.
A typical student instrument has a magnetic field of 14,092
A nucleus in resonance
is spin flipping in time gauss and a radiofrequency of 6 x 107 Hz or 60 MHz. In research
with the applied laboratories, spectrometers commonly operate at the higher
radiofrequency field. radiofrequencies of 200 MHz, 300 MHz, and 500 MHz. There are two
types of NMR spectrometers. One type has a stable magnetic field and

a variable radiofrequency. The other type has a stable radiofrequency

and a variable magnetic field. When using a 60 MHz instrument to
look at most organic molecules, the total range for the radiofrequency
is about 750 Hz, or about 0.18 gauss for the magnetic field. Figure
10.3 is a schematic diagram of an NMR instrument.
M ag net p ol es
Sam pl e
Ho Rad i of r eq uency
r ecei ver Pl o t t er o ut pu t
Radi o f r equ ency

t r an s m i t t er
Figure 10.3. Schematic diagram of an NMR spectrometer.
Because chemists commonly use NMR spectrometers of various

magnetic field strengths, they adopted a machine independent method
to measure chemical shift. This method measures chemical shift as
parts per million (ppm) of the applied field. Each measurement
produces the same value for a given proton whether the applied field
is the 14,092 gauss of the 60 MHz instrument or 46,972 gauss of the
200 MHz instrument. A chemical shift of one ppm is equal to 60 Hz, or
1.4 x 10–2 gauss, for a 60 MHz NMR and 200 Hz, or 4.7 x 10–2 gauss
for a 200 MHz NMR. Figure 10.4 shows the separation of peaks with
increasing magnetic field.
H0

Figure 10.4. The energy difference between the α and β states increases with
increasing applied magnetic field strength. This is known as the Zeeman effect.
Most student NMR instruments have a fixed radiofrequency

and a variable magnetic field. The machine plots the spectrum on a
special paper designed to read the chemical shift in Hz and ppm. The
number of Hz in one ppm depends on the radiofrequency of the
instrument. The chemical shift value in ppm stays the same if the
radiofrequency was varied, or if the magnetic field was varied.
10.2 Shielding
Section 10.1 briefly examined the spin flip, or resonance, of an
isolated proton if that proton were placed within an NMR
spectrometer’s magnetic field. A proton is an isolated hydrogen
nucleus, but the protons in actual organic molecules are not isolated
at all. They are a part of a molecule. An organic molecule is made up
of carbon atoms, heteroatoms, the electrons associated with the bonds
of the atoms, and the nonbonding electrons present on some
heteroatoms. The arrangement of these four molecule parts affects the
resonance of the proton being considered. The proton’s electrons and
the electrons in the adjacently bonded atoms surround the proton and
A proton is shielded partially shield it from an externally applied magnetic field. The
when electrons from shielding is a result of a small magnetic field generated by the
adjacent atoms cause movement of the electrons within the applied magnetic field. This
resonance to occur at internally generated, or induced, magnetic field always opposes the
higher field strength
externally applied magnetic field, so chemists say the protons in the
than it otherwise
would. molecules are shielded from the applied magnetic field. See Figure
10.5.
Ha Hb Ha Hb
C C C C
(a) (b)
Figure 10.5. The magnetic field of non-equivalent adjacent protons affects the
position of resonance. (a) The magnetic field of proton Ha shields proton Hb. (b) The
magnetic field of proton Ha deshields proton Hb.
Because of the shielding, the effective magnetic field reaching

the proton from an externally applied magnetic field is less than the
amount that would reach the proton if it was not shielded. Thus, a

shielded proton requires a greater amount of applied magnetic energy

for resonance to occur. In a 60 MHz spectrometer, an unshielded
proton absorbs at 14,092 gauss. For a proton shielded by 0.5 gauss,
the magnetic field at the proton then becomes 14,091.5 gauss. You
must increase the applied field to 14,092.5 gauss to bring this proton
into resonance. See Figure 10.6.
Sh ie ld in g
+ + +
H0
H 0 = 14,092 H 0 = 14 , 09 2 H 0 = 14,092.5
Figure 10.6. A “bare,” or isolated, proton is in resonance in a 14,092 gauss field at 60

MHz (left). A proton shielded by 0.5 gauss does not resonate at 14,092 gauss (center),
but it does at 14,092.5 gauss (right).
A proton, as well as the nuclei of all kinds of atoms that

resonate, requires a specific amount of applied magnetic energy to
spin flip. Each proton that is surrounded by a different set of atoms
within a molecule has a different amount of shielding. The differences
in shielding are due to different magnetic environments in the
molecule. The factors that affect the magnetic environment include
nonbonding electrons, the electronegativity of adjacent atoms, and
electron circulation. Thus, the resonance of each of these protons
occurs at a different combination of magnetic field and radiofrequency.
For example, consider the protons in methanol. The electronegative
oxygen withdraws electron density from its proton, giving it less
shielding than the methyl protons. Therefore, the hydroxyl protons
absorb at a lower magnetic field than the methyl protons.
H Less shielded
C OH
H
More shielded
H
The number of absorptions in an NMR spectrum tells how

many different types of hydrogens a molecule contains. The amount of
shielding for each NMR signal also allows the chemist to deduce the
structural features of the molecule in the region of each of the protons.

This information from an NMR spectrum is particularly valuable

when determining the carbon skeleton of a molecule.
10.3 Chemical Shift and Molecular Structure

Chemical shift is the Shielding produces the variations in the positions of the
measure of the amount absorption peaks in an NMR spectrum. These variations result in
of shielding possessed
by a proton as a result
changes in the chemical shift of the protons. Because the induced
of the induced magnetic fields of protons are small in relation to the applied
magnetic fields from magnetic field, an absolute measurement scale is impractical to use.
the electrons belonging Instead, the amount of shielding, or chemical shift, is measured
to the surrounding relative to a standard substance. There are two possible types of
atoms.
standards substances: external where the substance is measured
separately from the sample and internal where the substance is added
to the sample. Tetramethylsilane, (CH3)4Si, abbreviated as TMS, is
used as the internal standard substance. In TMS, the silicon shields
the methyl protons more than almost any other organic compound.
TMS does not react with the compound under study and, when the
spectrum is completed, the TMS evaporates easily. All the hydrogens
in TMS are equivalent so it gives only one peak. The position of TMS
on an NMR spectrum is always assigned a value of zero.
CH 3
H3C Si CH 3
CH 3
Tetramethylsilane (TMS)
Most student NMR spectrometers operate at 60 MHz, so this

book uses only spectra recorded at 60 MHz, unless labeled otherwise.
Figure 10.7, an NMR spectrum of methanol, shows two signals for the
methanol and one signal for the TMS. The TMS signal occurs at 0.0
Downfield is lower ppm. The methyl protons absorb at 203 Hz (0.048 gauss) downfield
applied magnetic field. from the TMS signal. This absorption is called downfield because the
magnetic field required for resonance to occur in methyl protons is
lower than for the TMS protons. The methyl protons absorb upfield
Upfield is higher
applied magnetic field. from the hydroxyl proton because methyl resonance requires a higher
magnetic field than does a hydroxyl resonance. The hydroxyl protons
absorb 285 Hz (0.067 gauss) downfield from TMS. The chemical shifts
are 3.4 ppm for the methyl protons and 4.8 ppm for the hydroxyl
proton.

HO CH 3
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
Figure 10.7. A 60 MHz NMR spectrum of 10% methanol in CDCl3. The methyl
protons absorb at 3.4 ppm and the hydroxyl proton at 4.8 ppm.
Within a molecule, an electronegative substituent affects the

resonance of nearby protons by pulling the electrons toward itself and
decreasing the amount of shielding felt by the protons. Chemists call
this electronegative pull deshielding. Deshielding influences protons
Deshielding moves the
on the carbon adjacent to the electronegative functional group and, to
resonance of the
affected protons a much smaller extent, the second carbon. Figure 10.7 shows the
downfield from where deshielding effects of the electronegative oxygen atom on both the
resonance occurs when methyl and the hydroxyl groups. The chemical shift of a methyl group
the molecule does not in a hydrocarbon is 0.9 ppm, so the oxygen has deshielded the methyl
contain an
hydrogens in methanol by 2.5 ppm.
electronegative
substituent. Other electronegative atoms besides oxygen produce similar
deshielding effects. Chlorine, for example, causes a chemical shift of
3.1 ppm for the methyl protons in methyl chloride. This shift is
reasonable because chlorine has a slightly lower electronegativity
than oxygen so it exerts a smaller deshielding affect. Table 10.1 lists
the chemical shifts of various methyl substituted electronegative
groups showing the correlation of electronegativity with the chemical
shift that results from deshielding.
Compound Electronegativity Chemical Shift (in

CH3—X of X ppm) for the CH3
(CH3)3N 3.1 2.2
(CH3)2O 3.5 3.3
CH3F 4.1 4.3
CH3Cl 2.8 3.1
CH3Br 2.7 2.7
CH3I 2.2 2.2

CH3CH3 2.5 0.9

CH3H 2.2 0.2
Table 10.1. Variation of chemical shift of a methyl group with electronegativity of the
heteroatom X.
When a carbon contains more than one electronegative

substituent, the deshielding effects are almost additive. Each
additional electronegative atom causes a similar, though slightly
smaller, deshielding effect. The chemical shift data for the various
chlorinated derivatives of methane shows this additive effect.
CH3Cl CH2Cl2 CHCl3

3.1 ppm 5.3 ppm 7.3 ppm
Vinyl and aryl compounds provide much less shielding for their
protons than do alkanes. Peaks appear at 7.2 ppm for benzene
protons, 5.3 ppm for ethene protons, and 0.9 ppm for ethane.
H
H H H H
H H
C C H C C H
H H
H H H H
H
Benzene Ethene Ethane
7.2 ppm 5.3 ppm 0.9 ppm
The magnetic field internally induced by π electrons is strong

enough to deshield vinyl and aryl protons. The circulation of the
electrons in the π bonds causes the internal magnetic field. The three
conjugated bonds of benzene interact to produce a ring of current and
an even stronger induced magnetic field than does a compound with
only one double bond. At the center of the ring, the induced field
opposes the external field; however, outside the ring, the induced field
Anisotropic shielding
caused by the reinforces the applied field. The deshielding of the protons is caused
nonuniform magnetic by anisotropic shielding. Figure 10.8 shows this effect in benzene.
field in the vicinity of a
π bond.

H H
H H
H H
H0
Figure 10.8. The induced magnetic field of the π electrons in benzene reinforces the
applied field where the protons are located. This is an example of anisotropy in
benzene.
Because the π bonds of alkenes and arenes deshield their

protons, you might expect an even larger amount of deshielding in
alkynes because a triple bond has two π bonds. However, just the
opposite occurs. Acetylenic protons absorb around 2.5 ppm compared
to 5 - 6 ppm for alkenes and 7 - 8 ppm for arenes. With alkynes the
two π bonds form a cylinder of electron density around the C—C σ
bond. The axis of the induced magnetic field is aligned parallel to the
C—C σ bond of the triple bond, placing the adjacent protons in a
region where the induced field opposes the external field. This is
another effect of the anisotropy of the magnetic fields around a π bond.
As a result, the protons are shielded, as shown in Figure 10.9.
C
H0
H
Figure 10.9. The acetylenic triple bond aligns itself with the external magnetic field.
As the electrons circulate, they create an induced magnetic field. The protons lie along
the axis of the induced magnetic field within the area where the induced magnetic
field opposes the external magnetic field.
10.4 Interpreting Proton NMR Spectra

An NMR spectrum provides four types of information: 1) the
position (energy) of the signals, 2) the number of signals present, 3)

the intensity of the signals, and 4) the multiplicity (splitting) of the

signals. You must use all four of these types of information to
interpret NMR spectra. This section covers the position and number of
signals. The next two sections cover the signal intensity and splitting.
Protons with different chemical shifts are magnetically and
chemically nonequivalent. Each nonequivalent proton produces a
separate NMR signal. For example, the NMR spectrum in Figure
10.10 shows the protons in the two methyl groups in methyl acetate.
Although each of the three protons in each methyl group has the same
magnetic environment, the two methyl groups have different
environments. Therefore, each set of protons experiences a different
induced magnetic field, and each set resonates at a different applied
magnetic field. The difference shows up in their signals: one appears
at 3.7 ppm and the other at 2.1 ppm.
2.1 ppm
O 3.7 ppm
CH3 C O CH3
Methyl acetate
The methyl group attached to oxygen is more deshielded, so it appears

further downfield from TMS at 3.7 ppm.
O
CH3COCH3
1 0 9 8 7 6 5 4 3 2 1 0 ppm ( )
6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0 H z
Figure 10.10. The NMR spectrum of methyl acetate (CH3COOCH3).

The environment of a proton determines its chemical shift.

Each atom in the molecule contributes a characteristic amount of
shielding to the total amount of shielding a particular proton
experiences. The amount of shielding that a particular atom
contributes is relatively constant for any molecule containing that
atom.
Figure 10.11 shows the general regions of a typical NMR
spectrum where certain types of protons resonate. The OH and NH
bonds tend to vary widely over a range of the spectrum based on their
concentration. Higher concentrations tend to produce more
deshielding because of hydrogen bonding. The proton on a carbonyl
group of aldehydes is subject to the same conditions as those on a
double bond as well as the electron-withdrawing effect of the oxygen.
Their signals appear around 9.5 ppm. Signals for acid protons on a
carboxylic acid appear above 10 ppm.
COOH (12.5 - 11 ppm)

RCHO
ArH
ArOH
C C H
ArNH2
C CH
ROH
RNH2
Alkyl Groups
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
Figure 10.11. Regions where different types of protons resonate in the NMR.
Alkyl groups show a wide range of positions because they are

affected by the functional groups adjacent to them. For example,
consider the effect of a chlorine atom on the protons bonded to the
same carbon as the chlorine. A methyl group in a hydrocarbon appears
at 0.9 ppm, but in methyl chloride it appears at 3.2 ppm. The
difference between the two is 2.3 ppm.
CH3CH3 CH3Cl
0.9 ppm 3.2 ppm

A methylene group appears at 1.3 ppm in a hydrocarbon and at 3.6

ppm in ethyl chloride. The difference is again 2.3 ppm.
CH3CH2CH3 CH3CH2Cl
1.3 ppm 3.6 ppm
A methine group appears at 1.6 ppm in a hydrocarbon and at 3.9 ppm

in 2-chloropropane. Again the difference is 2.3 ppm.
CH3 CH3
CH3CHCH3 CH3CHCl
1.6 ppm 3.9 ppm
The change in resonance position of 2.3 ppm is the characteristic

amount of shielding of a chlorine atom. Chemists call this constant
The shielding constant amount of shielding the α shielding constant. Table 10.2 lists the
is a measure of how base values of the CH, CH2, and CH3 groups.
much a group affects
the resonance position
of adjacent protons.
Group Base value
CH 1.6
CH2 1.3
CH3 0.9
Table 10.2. Base values for the CH, CH2, and CH3 groups.
The shielding effects of an atom primarily affect the protons

bonded to the same carbon as itself. However, atoms with larger
shielding constants also shield the protons on adjacent carbons. This
shielding is much smaller because the protons are farther away. For
example, the methyl group in ethyl chloride appears at 1.5 ppm,
CH3CH2CH3 CH3CH2Cl
0.9 ppm 1.5 ppm
which is only 0.6 ppm downfield from a methyl group in a hydrocarbon

(0.9 ppm). Thus, the shielding constant for chlorine in adjacent bonds
is 0.6 ppm and is called the β shielding constant. Table 10.3 lists both
the α and the β shielding constants for a variety of functional groups.
Functional Group α Shielding β Shielding

Constant Constant

Functional Group α Shielding β Shielding

Constant Constant
C C 0.7 0.1
C C 0.8 0.2
Ph 1.3 0.3
F 3.3 0.7
Cl 2.3 0.6
Br 1.8 0.9
I 1.3 0.9
OX (X = H, R) 2.4 0.3
OX (X = Ph, C O) 2.9 0.4
C O 1.2 0.4
SX (X = H, R) 1.1 0.4
C N 1.2 0.3
NX2 (X = H, R) 1.4 0.2
NO2 3.2 0.7
Table 10.3. A table of α and β shielding constants for a variety of functional groups.
Use the data in Table 10.2 and 10.3 either to predict the
position or to confirm the identification of the signals in an NMR
spectrum. These numbers do have a limitation: they do not cover all
the possible arrangements of atoms in a molecule. Although the
numbers are usually within 0.2 ppm for the α shielding constants,
they can be as much as 0.6 or 0.7 ppm in error. This is especially true
when two or more shielding groups affect the position of a proton. The
larger the number of functional groups, the larger the potential error.
Calculating proton positions is helpful when identifying an
unknown. For example, by using the numbers in Tables 10.2 and
10.3, you can calculate predicted positions of the protons in methyl
acetate CH3COOCH3. Here is the calculation of the position for the
CH3 group adjacent to a carbonyl group.
0.9 for the CH3
1.2 α constant for carbonyl
2.1 ppm
This number agrees with the observed position of 2.1 ppm as shown in
the spectrum in Figure 10.10. The other CH3, which is attached to an
sp3 hybrid oxygen, has the following calculated position.
0.9 for the CH3

2.9 α constant for COO group
3.8 ppm
This number agrees very well with the observed 3.7 ppm.

The following example of 3,3-dimethyl-2-butanone shows the

effects of β shielding.
CH3
H3C
C CH3
C
H3C
O
Again, using the information in Tables 10.2 and 10.3, calculate the
position of the CH3 adjacent to the carbonyl.
0.9 base position of methyl groups

1.2 α constant for carbonyl groups
2.1 ppm.
The other three CH3 groups are magnetically equivalent and are β to
the carbonyl. The β shielding constant for the carbonyl group is 0.4
ppm, so the predicted positions of these methyl groups is 1.3 ppm:
0.9 base position of methyl groups

0.4 constant for β carbonyl groups
1.3 ppm
The signals in the spectrum appear at 2.2 and 1.3 ppm, respectively,
as shown in Figure 10.12.
(CH 3 )3 CCCH 3
1 0 9 8 7 6 5 4 3 2 1 0
ppm ( )
6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0 H z
Figure 10.12. The NMR spectrum of 3,3-dimethyl-2-butanone.

Exercise 10.1
Predict the number of NMR signals and their locations for each of the
following compounds.
a) 1-Propanol b) 1,4-Dichlorobutane
c) Ethyl propanoate d) 2,2-Dibromobutane
e) Hexane f) Toluene (methylbenzene)
g) 2,3-Dimethyl-2-butene h) N-Methylethanamine
Sample solution
b) 1,4-Dichlorobutane is symmetrical between C2 and C3, so it

has only two resonance signals.
ClCH2CH2CH2CH2Cl
The position of the resonances of the protons on the carbons bearing

the chlorine atoms is 1.3 + 2.3 ppm = 3.6 ppm. The protons on the
adjacent carbons experience only the β shielding and so the resonance
is 1.3 + 0.6 ppm = 1.9 ppm. The positions of resonance in the actual
spectrum are 3.6 and 2.0 ppm respectively.
The shielding constants apply only to protons bonded to sp3

hybrid carbons. Although substituent groups also affect vinyl and
aromatic protons, they do so to a much smaller extent due to the
strong deshielding of the π electrons.
Protons bonded to a double bond usually appear between 4.6
and 6 ppm—typically about 5.3 ppm. Electron-donating groups shield
those protons in an amount proportional to the electron density of the
group. Typically, this amount is in the range of 0.3 to 0.5 ppm.
Conversely, an electron-withdrawing group deshields those protons in
an amount proportional to the strength of the electron-withdrawing
power of the group. Typically, this deshielding is in the range of 0.3 to
1.5 ppm. Chapter 14 covers this topic in greater length.
Arenes also show the same type of effects toward donating or
withdrawing groups on the ring, as do alkenes. These effects are due
to conjugation, so the substituent affects only those protons bonded
ortho or para to itself. Chapter 16 covers this topic in greater length.
The shielding or deshielding of the ortho and para protons
relative to the meta protons usually allows you to infer the general
class of the substituent. Meta protons appear at, or near, 7.3 ppm. An
electron-withdrawing group deshields the ortho or para protons, but
an electron-donating group shields the ortho or para protons. This
effect changes the position of the ortho or para signals by 0.2 to 1.0
ppm. For example, the ortho and para protons of benzoic acid appear

at 8.2 ppm, and those of phenol appear at 6.8 ppm. The meta protons
appear at 7.5 and 7.2 ppm respectively.
O
OH
OH
H H H H
8.2 ppm 8.2 ppm 6.8 ppm 6.8 ppm
H H
7.5 ppm 7.2 ppm
Exercise 10.2
Predict the number of resonance signals and their locations for each of
the following compounds. Only approximate locations for vinyl and
aryl protons are possible.
a) 2-Butene b) Methyl benzoate

c) Nitrobenzene d) Phenyl butanoate
e) 1-Phenyl-1-propene f) 1-Butene
Sample solution
c) Nitrobenzene has two absorptions in the NMR. The nitro

group is an electron-withdrawing substituent, so one signal is near 8
ppm and the other at 7.2 ppm.
10.5 Spin-Spin Splitting

The NMR spectra of methanol, methyl acetate, and 3,3-
dimethyl-2-butanone, which you examined earlier, all have one single
sharp absorption signal for each type of proton. It turns out, however,
that protons giving a single absorption signal are the exception rather
A singlet is an NMR than the rule. Usually, instead of a singlet, each signal appears as a
absorption signal with
only one absorption.
collection of absorption signals called peaks. A single absorption
signal can be split into two peaks (a doublet), three peaks (a triplet),
A peak is one or more four peaks (a quartet), etc. Chemists call the splitting of NMR signals
absorptions making up spin-spin splitting.
the signal for a proton
in an NMR spectrum.
Thus, a signal for a proton with three adjacent protons splits
into a quartet. For example, look at the spectrum of 1,1-
A doublet (2), triplet dichloroethane (Figure 10.13). The spectrum has three peaks: the
(3), quartet (4), etc. TMS peak at 0.0 ppm, the CH peak at 5.9 ppm, and the CH3 peak at
describes a resonance 2.1 ppm. The CH is adjacent to the three hydrogens of the —CH3
signal split into a
collection of peaks.
group, so its signal splits into a quartet. The —CH3 group is adjacent
Spin-spin splitting is
the process that splits
an NMR signal into www.ochem4free.com 5 July 2005
multiple peaks.
to the single hydrogen of the —CHCl2 group, so its signal splits into a
doublet.
Cl2HC CH3
1 0 9 8 7 6 5 4 3 2 1 0 ppm ( )
6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0 H z
Figure 10.13. The NMR spectrum of 1,1-dichloroethane. Spin-spin splitting produces

a quartet for the methine proton and a doublet for the methyl group.
The magnetic fields of adjacent protons cause spin-spin

splitting. For example, all three protons in the methyl group of 1,1-
dichloroethane are equivalent and all have the same chemical shift;
thus, you would expect them to produce one peak. However, because of
Vicinal protons are the magnetic moment of the vicinal proton in the —CHCl2 group,
protons attached to
adjacent carbons.
their signal splits into two lines.
You have now studied three types of magnetic fields that
influence protons. They are the external magnetic field, the induced
fields of any shielding substituents, and the magnetic fields of
adjacent protons. Thus, each type of proton in a molecule resonates at
a different location in the NMR spectrum.
Return to Figure 10.13 and assume that the spectrometer is
scanning the region of the spectrum where methyl protons appear.
Recall from Section 10.1 that when an external magnetic field is
applied to a compound, the protons align themselves with that applied
magnetic field with approximately half of the protons aligning
themselves parallel to the applied magnetic field and the other half
aligning themselves antiparallel to the applied magnetic field. Thus,
in approximately half of the 1,1-dichloroethane molecules, the methyl
protons are under the influence of the methine protons with their
magnetic moment parallel to the applied field, and the other half are
under the influence of the methine protons with their magnetic
moment antiparallel to the applied field.

When the magnetic moment of the methine proton is aligned

parallel to the applied magnetic field it exerts a slightly stronger total
magnetic field over the methyl protons. Thus, it effectively deshields
the methyl protons, absorbing radio frequency energy at a lower
external magnetic field. When the magnetic moment of the methine
proton is aligned antiparallel to the external magnetic field it shields
the methyl protons. They absorb radio frequency energy at a higher
external field. Figure 10.14 shows the effects of an applied magnetic
field.
Chemical Shift
of H b
Cl H b Cl H b
Cl Hb Cl Hb
Hb Hb
Reinforces Opposes
Field Field
H 0 Vector
Increas ing H 0
Figure 10.14. When the vicinal proton is aligned with the applied magnetic field, it
deshields Hb; when aligned against the field, it shields Hb.
Spin-spin splitting is a reciprocal property in that the protons

on two vicinal carbons split each other. You observed this in 1,1-
dichloroethane. The methyl protons split the signal for the methine
proton into a quartet, and the methine proton splits the signal for the
methyl protons into a doublet. Figure 10.15 shows the possible spin
states of the methyl protons.
Ho vector
Increasing Ho
Figure 10.15. There are eight possible combinations of nuclear spins for the three
methyl protons in 1,1-dichloroethane. These represent four different magnetic field

strengths with a ratio of 1:3:3:1. The arrow pointing up is parallel to the applied field
and the arrow pointing down is antiparallel.
The arrangement of the magnetic moments of the three

hydrogens of the methyl group, as shown in Figure 10.15, produces
four signals in a ratio of 1:3:3:1. At one extreme of the arrangement,
the three protons align themselves parallel to the external magnetic
field. At the other extreme, they align themselves antiparallel to the
external field. Between the two extremes there are two groups of
three. In the first group of three, two protons align themselves parallel
with the external field, and the other aligns itself antiparallel to the
external magnetic field. In the second group of three, one proton aligns
itself parallel to the external magnetic field, and the other two align
themselves antiparallel to the external magnetic field. This
arrangement produces a quartet in the NMR similar to Figure 10.16.
Chemical shift of
the methine group
Figure 10.16. These eight combinations, as shown in Figure 10.15, cause the splitting
of the signal of the —CHCl2 group into a quartet. The areas of the peaks are in a
1:3:3:1 ratio seen in Figure 10.15.
This analysis of spin-spin splitting patterns extends to more

complicated systems than the above example. Here is a simple rule
that allows you to predict spin-spin splitting patterns. The number of
peaks into which the signal for a particular proton splits equals the
number of vicinal protons plus one. Table 10.4 gives the relative areas
of these multiplets. These relative areas are determined by an
A multiplet is a NMR
signal that is split into analysis like that shown in Figure 10.15. The table of relative areas is
multiple peaks by spin- known as Pascal’s triangle.
spin splitting.
Number of equivalent Number of peaks in the Intensities of the lines in
protons causing splitting multiplet the multiplet
0 1 (singlet) 1

Number of equivalent Number of peaks in the Intensities of the lines in

protons causing splitting multiplet the multiplet
1 2 (doublet) 1 1
2 3 (triplet) 1 2 1
3 4 (quartet) 1 3 3 1
4 5 (quintet) 1 4 6 4 1
5 6 (sextet) 1 5 10 10 5 1
6 7 (septet) 1 6 15 20 15 6 1
Table 10.4. Splitting patterns and relative peak intensities of common multiplets.
CH3CH2Br
1 0 9 8 7 6 5 4 3 2 1 0 ppm ( )
6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0 H z
Figure 10.17. The NMR spectrum of bromoethane shows the spin-spin splitting
pattern produced by a typical ethyl group.
The triplet and quartet in the spectrum of bromoethane (Figure

10.17) are not symmetrical. Signal dissymmetry commonly occurs in
NMR spectra and helps to determine which protons are splitting each
other. In general, the stronger signals are on the side of the multiplet
closest to the signal responsible for the splitting. Canting, the term
Canting is signal used to describe signal dissymmetry, is more pronounced when the
dissymmetry due to the
proximity of two two signals are closer together. The ethyl group pattern, as shown in
signals that are Figure 10.18, is an example of this phenomenon. Canting also occurs
splitting each other. in the spectrum of 1,1-dichloroethane.
The spectrum of 1,1-
dichloroethane is in
figure 10.13, page 000.

Figure 10.18. The peaks in a multiplet often “point” toward the absorption of the
protons that cause the splitting. The two signals in the ethyl splitting pattern from
bromoethane point toward each other.
An important characteristic of spin-spin splitting is that

protons having the same magnetic environment do not split each
other. For example, benzene gives only one single peak in the NMR
spectrum, even though there are several possible sets of vicinal
protons. It gives only one peak because all the protons are equivalent
to each other, and they all have the same chemical shift.
Exercise 10.3
Sketch the appearance of the NMR spectra of the following

compounds. Show how many signals you would expect to find, the
location of these signals, and how many peaks each signal splits into.
a) 1,2-Dichloroethane b) 1,1,2-Trichloroethane
c) Diisopropyl ether d) p-Diethoxybenzene
e) Ethyl acetate f) C6H5CH(CH3)2
Sample solution
a) All the protons in 1,2-dichloroethane are chemically

equivalent and thus have the same chemical shift. Because chemically
equivalent protons do not split each other, the spectrum should show a
singlet at the following calculated position.
1.3 ppm for base

2.3 ppm for α Cl
0.6 ppm for β Cl
4.2 ppm

Magnetic coupling is The range of magnetic coupling is usually limited to protons

the interaction of on adjacent carbons. Protons separated by more than three bonds
protons on adjacent
atoms that results in
seldom produce spin-spin splitting because protons transmit their
spin-spin splitting. splitting information through the electrons in the bonds between the
nuclei rather than through space. Geminal protons are normally
Geminal protons are equivalent, thus they do not usually split one another. In cases where
protons on the same
carbon.
they are not equivalent, splitting, called geminal splitting, occurs.
Sets of magnetically coupled protons have a characteristic
Geminal splitting is spacing between adjacent pairs of peaks in a multiplet. This spacing,
spin-spin splitting called the coupling constant, is represented by the symbol J. The
between geminal
coupling constant has the same value, in Hz, for any magnetic field
protons that are not
equivalent. strength. The coupling constant for 1,1-dichloroethane is
approximately 7 Hz. Thus, the interval between the two peaks of the
The coupling constant methyl doublet is approximately 7 Hz, as is the distance between any
is the characteristic adjacent pair of peaks in the methine quartet. Table 10.5 lists some
interval between typical coupling constants.
adjacent peaks in a
multiplet. Molecular Approximate Molecular Fragment Approximate
Fragment coupling constant, J. coupling constant, J.
The NMR spectrum of H
1,1-dichloroethane is
in Figure 10.13, page C C 7 Hz C 12 Hz
000. H H H
(In rigid systems)
H
C C 10 Hz C C 2 Hz
H H H
H H H
C C 15 Hz 2 Hz
H
C H H C H
C C 6 Hz C C 2 Hz
H
O
C H
C C 3 Hz C C 1.5 Hz
H H
H
H
C C C H 2 Hz
8 Hz
H
H

Table 10.5. Typical values of proton coupling constants. Included in this table are
some 2J and 4J coupling constants (right column) as well. See below for a discussion
of the right column constants.
Spin-spin splitting occurs in all cases when the protons on

adjacent carbon atoms have different magnetic environments. An
exception to this is where conformational changes take place faster
than the time frame for measuring an NMR spectrum. For example,
cyclohexane has two sets of protons—axial and equatorial. Each of
these sets of hydrogens is in a different magnetic environment.
H H
H H
H H
H H
H H
H H
Equatorial hydrogens Axial hydrogens
of cyclohexane of cyclohexane
Ring flips in As you may recall, these two sets of hydrogens are exchanged via a
cyclohexane is ring flip. This ring flip occurs at a higher rate than the time frame for
introduced in Section
3.6, page 000.
measurement on an NMR spectrometer. Thus, cyclohexane gives rise
to a single peak in the NMR spectrum. To observe separate signals for
the axial and equatorial hydrogens, the rate of ring flip must be
slowed by cooling the sample or the time frame for measurement of
the NMR must be shortened by increasing the magnetic field and
radio frequency of the instrument.
However, in most cases where the protons readily exchange
with the protons on another atom, splitting does not occur. Protons on
atoms that hydrogen bond, particularly oxygen or nitrogen, usually
are not split even though there is a proton on an adjacent atom. They
aren’t split because protons involved with hydrogen bonding are
constantly being exchanged and thus are not in the same magnetic
environment long enough to be split by any adjacent protons. This
hydrogen bonding exchange significantly broadens many, but not all,
such peaks in the NMR. Figure 10.19 shows the NMR spectrum of 2-
propanol. The signal at 3.1 ppm is the —OH peak that illustrates this
signal broadening.

CH3CHCH3
OH
1 0 9 8 7 6 5 4 3 2 1 0 ppm ( )
6 0 0 5 0 0 4 0 0 3 0 0 2 0 0 1 0 0 0 H z
Figure 10.19. The NMR spectrum of 2-propanol showing signal broadening at 3.1
ppm due to proton exchange of the —OH protons.
Exercise 10.4
Draw the NMR spectra you would expect for each of the following
compounds.
a) 4-Methylmethoxybenzene b) 2-Methylbenzoic acid

c) 1-Bromo-2-methylpropane d) 2-Butanone
e) trans-3,3-Dimethyl-1-phenyl-1-butene f) Chloromethyl ethyl ether
Sample solution
d) 2-Butanone is a ketone with ethyl and methyl groups on

either side of the carbonyl group. The position of the methyl group (a
singlet) is 0.9 + 1.2 ppm = 2.1 ppm. The ethyl group has the CH2 at 1.3
+ 1.2 = 2.5 ppm and the CH3 at 0.9 + 0.4 ppm = 1.3 ppm. The signal
for the CH2 of the ethyl group splits into a quartet and the signal for
the CH3 of the ethyl group splits into a triplet. The coupling constant
for the ethyl group is about 7 Hz.
Spin-spin splitting becomes more complicated when two or

more magnetically non-equivalent protons split one proton. In most of
these cases, the n + 1 rule for predicting splitting patterns fails.
Consider Figure 10.20, which shows a single proton being split by two
adjacent magnetically non-equivalent protons. In Figure 10.20 (a), one
proton has a coupling constant of 8 Hz and the other a coupling

constant of 6 Hz. Note that while there are two adjacent protons, the
signal in the NMR has four lines—a pair of doublets. The n + 1 rule
predicts that there would be three lines from the two adjacent protons.
Because the coupling constants are different, a pair of doublets is
produced instead. Figure 10.20 (b) shows the effect of having J1 = 8 Hz
and J2 = 11 Hz. It shows a pair of overlapping doublets.
J1 = 8 Hz J1 = 8 Hz
J2 = 6 Hz J2 = 6 Hz
J2 = 11 Hz
J2 = 11 Hz
(a) (b)
Figure 10.20. An analysis of the splitting pattern for a single proton (a) where J1 = 8
Hz and J2 = 6 Hz and (b) where J1 = 8 Hz and J2 = 11 Hz.
Exercise 10.5
An important, but complex, splitting pattern is that of the vinyl group

(CH2=CH–). This common pattern is one you should learn to
recognize. Using the values Jgeminal = 2 Hz, Jcis = 10 Hz, and Jtrans =
15 Hz as well as the chemical shifts shown below, draw the splitting
patterns for each of the three protons on the vinyl group. Please take
care in drawing this splitting pattern to scale.
5.6 ppm
H
4.6 ppm
H
R
H
4.9 ppm
The right hand column in Table 10.5 shows the coupling

constants between hydrogens that are not vicinal. These couplings
include two geminal couplings as well as several couplings where the

protons are on more distant carbons. The geminal couplings are both
for rigid molecules which change conformations more slowly than the
time frame for the NMR spectrum, if at all. More distant couplings
generally have π bonds between the protons that split each other.
10.6 Integration of Signals in an NMR Spectrum

The area under an NMR signal, not its height, is proportional
to the number of hydrogens giving rise to that signal. For example,
Figure 10.20 shows that the spectrum of 3,3-dimethyl-2-butanone has
two singlets. One of these singlets comes from a single methyl group;
the other comes from three methyls of the tert-butyl group. The area
under the single methyl group signal is one third of the area that is
under the signal for the three methyl groups. Therefore, the ratio of
the number of hydrogens is 1:3.
An integrator is a An NMR spectrometer has an integrator that computes the
device that computes areas under the signals. By using the trace produced by the
the areas under the
signals in an NMR
integrator, chemists determine the relative numbers of hydrogens
spectrum. represented by each signal in the spectrum. In Figure 10.20, note that
the integration does not show that 3,3-dimethyl-2-butanone has three
methyl hydrogens and nine hydrogens on the tert-butyl group. It
simply indicates that there are three times as many hydrogens
represented by the peak at 1.3 ppm as by the peak at 2.2 ppm.
O
( CH 3 ) 3 CCCH 3
4.5 units
1.5 units
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
Figure 10.20. Integrated NMR spectrum of 3,3-dimethyl-2-butanone. As it passes

over a signal, the integrator (upper trace) rises by an amount that is proportional to
the area under the signal.

Exercise 10.6
Match the following compounds with the spectra shown below. Assign
the signals in the spectra to the specific protons they represent in the
molecular structure.
4-Nitrotoluene 2-Methyl-3-butyn-2-ol 2-Chloropropane

3-Ethylphenol 1,3-Dibromopropane Oxacyclobutane
a)
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
b)
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz

c)
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
Sample solution
b) 4-Nitrotoluene. The doublet at 8 ppm arises from the protons

adjacent (ortho) to the nitro group on the ring. The doublet at 7.2 ppm
arises from the protons adjacent to the methyl group. The peak at 2.4
ppm arises from the methyl group protons.
2.4 ppm
CH3
H H 7.2 ppm
H H 8.0 ppm
NO2
4-Nitrotoluene
10.7 Analyzing an NMR Spectrum

When beginning the interpretation of an NMR spectrum, it's
easy to get bogged down in the minor details. Before looking at spin-
spin splitting, or canting, or the details of calculating the positions of
peaks, make some tentative identifications of the types of molecular
features present. The following rules may help you do this:

1. Any broadened singlet is an —OH or —NH group. If the peak

is deshielded above 10 ppm, the compound is almost certainly a
carboxylic acid. The absence of a broadened peak is not
evidence for the absence of an —OH or —NH proton.
Sometimes a peak is so broadened that is does not appear
above the baseline of the spectrum. Adding a drop of D2O to the
NMR sample will make the —OH and many —NH bonds
disappear through proton exchange.
2. An absorption between 9 and 10 ppm is an aldehyde.
3. Absorptions near 7 ppm suggest the presence of an aromatic
ring. When the signal is closer to 8 ppm, the ring has an
electron-withdrawing group (e.g., NO2 or CHO) bonded to it.
When the signal is closer to 6.5 ppm, the ring has an electron-
donating group (e.g., —OH or —NH2) bonded to it.
4. Absorptions in the 5 to 6 ppm range are most likely vinyl
protons. Use coupling constants to differentiate between the cis
and trans isomers.
5. Peaks in the 3 to 4 ppm range indicate protons bonded to a
carbon that also bears an oxygen or a halogen.
6. A sharp singlet, or a peak with coupling constants of about 2
Hz, at 2.5 ppm suggests a terminal alkyne.
7. Signals at 2 to 2.5 ppm are protons on a carbon adjacent to an
sp2 hybridized carbon, a carbon bonded with double bonds, or a
carbonyl.
8. Signals below 2 ppm usually indicate sp3 hybridized
hydrocarbon sections of the molecule.
As you use these rules, keep in mind that they probably will
not completely solve a spectrum, but they will usually get you started
in the right direction. Their goal is to give you a simple method to
eliminate some types of structural features and to include others.
Figure 10.11 is found Figure 10.11, which delineates the regions where different types of
on page 000.
protons resonate in the NMR, graphically illustrates many of these
rules.

10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
Figure 10.21. The NMR spectrum for the first NMR spectrum analyzed in this
section.
Consider the NMR spectrum in Figure 10.21. It has four

signals, indicating that the molecule contains four types of protons:
two singlets at 7.2 and 2.3 ppm, a multiplet at 2.7 ppm, and a doublet
at 1.3 ppm. Use the above rules to tentatively identify the types of
molecular features present in the molecule. The peak at 7.2 ppm
indicates an aromatic ring (Rule 3). The signals at 2.7 and 2.3 ppm
indicate that there are two carbons bonded to the aromatic ring (Rule
7). The signal at 1.3 ppm simply indicates some hydrocarbon section of
the molecule (Rule 8).
Next, determine the integration ratios for the number of
hydrogens present. They are 4:1:3:6. Not having a molecular formula,
you don't know for sure how many hydrogens there are. To begin with,
use the total of the integrals as the number of hydrogens present.
That number is 14. Because 14 is an even number, it might be that 14
is the number of hydrogens in the molecule.
Now, look at the details of the signals. The peak at 7.2 ppm
indicates an aromatic ring that does not contain any electron-donating
or electron-withdrawing groups. Because the integral for this signal
indicates 4 protons, the ring must have two substituents. In addition,
the substitutions must be symmetrical or nearly symmetrical because
the signal is a sharp singlet. A sharp singlet is typical of many para
substituents and of some ortho substituents, as long as the two are
similar. Usually, a pair of meta substituents has a more complex
aromatic region than either an ortho or para substituted molecule.

or
The septet at 2.7 ppm and the doublet at 1.3 ppm with an
integration ratio of 1:6 is typical of an isopropyl group. You should
An example of the learn to recognize this pattern and the ethyl pattern, which is a
NMR of an ethyl group quartet and a triplet. Both patterns are common in organic molecules.
is in Figure 10.17, page The signal position of 2.7 ppm is typical of a CH group on an aromatic
000. ring (1.6 ppm for the position of a methine, CH, group + 1.3 ppm for
the shielding constant of the aromatic ring). The doublet at 1.3 ppm is
typical for a methyl group β to an aromatic ring (0.9 ppm for the
position of a methyl group + 0.3 ppm for the beta shielding constant of
the aromatic ring). You can now add the following substituent.
CH(CH3)2
The remaining signal is a singlet at 2.3 ppm that integrates for

3 hydrogens. This signal indicates a methyl group attached to the ring
(0.9 + 1.3 ppm). Thus, the structure is either ortho- or para-
isopropylmethylbenzene. The effects of the substituents on the ring
protons is more symmetrical for the para than for the ortho
substitution pattern.
CH(CH3)2 CH(CH3)2
or
CH3 H3C
It is probably the para isomer, as the para isomer is more likely to

have a singlet for the ring protons than the ortho isomer.
H CH3 1.3 ppm

H CH
CH3
H3C H 2.7 ppm

H
2.3 ppm 7.2 ppm

Deciding between these two isomers based only on the NMR

spectrum would be difficult. However, if you ran an IR spectrum of the
compound, you could immediately tell that the NMR spectrum is of
the para isomer. The ortho isomer has an IR absorption at 730 to 690
cm–1, while the para isomer has an absorption at 830 to 780 cm–1.
Figure 10.22 shows another NMR spectrum for guided
analysis. Because it has three signals, the molecule it represents
contains three types of protons. The signal at 3.4 ppm indicates the
presence of a carbon bearing either an oxygen or a halogen. The
signals at 1.6 ppm and 0.9 ppm are for sp3 hydrocarbon sections of the
molecule.
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
Figure 10.22. The NMR spectrum for the second NMR spectrum analyzed in this
section.
The integration ratios are 2:2:3. That adds up to seven, which

is an odd number of hydrogens. Because the total is an odd number,
the molecule must have either a substituent that does not appear in
the NMR, an ether or halogen, or the actual number of hydrogens is a
multiple of the integration values. As you continue with the analysis,
work from both assumptions.
The signal at 3.4 ppm, which integrates for two protons, must
be a CH2 group attached to either a halogen or an oxygen. Because the
predicted position for a chlorine (1.3 + 2.3 ppm) or an oxygen (1.3 + 2.4
ppm) are so close, include both as a possibility. If the substituent is an
oxygen, the group is an ether because the spectrum does not show an
—OH proton signal. From this information, you know that the
molecule is either an alkyl chloride (—CH2Cl) or a symmetrical ether
(—CH2OCH2—). Because the peak at 3.4 ppm is a triplet, it must also

represent a proton group adjacent to two hydrogens, probably another

—CH2— group.
The signal at 1.6 ppm, which is split into a sextet and
integrates for 2 protons, appears to be a CH2 group adjacent to five
protons. Because chlorine has a larger β shielding constant (0.6 ppm)
than does an —OR group (0.3 ppm), the position of the signal is closer
to that of a hydrogen β to an ether (1.3 + 0.3 ppm) than that of a
hydrogen β to a chlorine (1.3 + 0.6 ppm). Thus, the molecule is more
likely a dialkyl ether, but it needs some confirmation. Below are the
fragments identified to this point.
—CH2CH2OCH2CH2— or —CH2CH2Cl
The final signal is a triplet at 0.9 ppm that integrates for three
protons. In order to be consistent with the analysis of the sextet
signal, this fragment must be a CH3 group adjacent to a CH2 group.
Adding this to the fragments above, the spectrum is likely one of
dipropyl ether, but may possibly be 1-chloropropane. There is not
enough proof to know for sure.
CH3CH2CH2OCH2CH2CH3 or CH3CH2CH2Cl
The spectrum is of dipropyl ether. Running an infrared

spectrum would immediately show a strong peak around 1050 cm–1
for the C—O bond of the ether.
Exercise 10.7
Make structural generalizations about the types of protons in each of

the spectra shown below. If possible, determine the actual structures
that gave rise to the spectra.
a)

10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
b)
+10 ppm
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
c)

10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
Sample solution
c) The complex pattern of peaks between 4.7 and 6.1 ppm is

typical of the three signals of a terminal vinyl group. This is another
pattern that you should, along with the ethyl and isopropyl groups,
recognize instantly. The integral values from left to right are
1:1:1:1:1:3. The signal at 1.1 ppm is a methyl group adjacent to a
single proton and, because the signal at 4.1 has five peaks, it is a CH
group adjacent to four protons. The proton at 2.5 ppm is a single
proton not magnetically coupled to the other protons in the molecule.
Adjacent protons do not usually split a typical alcohol —OH group.
Thus, this molecule has the following fragments:
CH2=CH—, —CH—CH3, —OH
Exercise 10.8
The molecular formulas for the three compounds are: C4H8O2,

C8H8O2, and C4H8O. What are the structures for the three
compounds?
Sample solution
c) This molecular formula confirms the fragments proposed in

Exercise 10.7 above. You can assemble these three fragments in only
one way.

OH
The molecule is 3-buten-2-ol.
Sidebar–Magnetic Resonance Imaging

Physicians have used NMR since the early 1980s to obtain
images of tissues from living beings. This technique, known as
magnetic resonance imaging (MRI), involves placing an individual in a
magnetic field and irradiating that person with pulses of radio
frequency. The radio frequency pulses excite the protons and as the
protons relax, they emit a signal called a free-induction decay signal.
A computer, using Fourier transform techniques, then processes this
signal into an image. Figure 10.23 is an image of a normal human
brain using MRI. This image is essentially a map of the density of
protons contained in the water and lipid molecules in the brain.
Figure 10.23. Image of a normal human brain obtained by the technique of magnetic
resonance imaging.

Two important factors in the formation of the image are the

presence of proton containing molecules and the mobility of the
molecules. The most important factor is the presence of protons in the
molecules in the head. Bones have few proton-containing substances
and thus do not show up in the image. The instrument plots the
The relaxation time is various types of tissues using the relaxation times of the substances
the time that an excited in these tissues. During relaxation the excited nucleus returns to a
nucleus returns to its
ground state. lower energy state. The relaxation times depend on the mobility of the
molecules. Physicians use this plot to differentiate between healthy
and diseased tissues.
Relaxation occurs by several different processes. One is spin-
lattice relaxation. With spin-lattice relaxation the energy of one
nucleus dissipates to nuclei in adjacent molecules. The time required
for a nucleus to lose energy by spin-lattice relaxation is called T1. In
another process for relaxation the excited nucleus transfers its energy
to a single adjacent atom. Chemists call this process spin-spin
relaxation. The time required for a nucleus to lose its energy in this
manner is called T2.
The amount of intermolecular contact is the main factor in
determining the values of T1 and T2. For pure water the values of T1
and T2 are both about 3 seconds. For water in biochemical systems,
the times are shorter ranging from .5 to 2 seconds. The more mobile
the molecule, the less intermolecular contact there is between
molecules, thus, the relaxation times become longer. In a biochemical
system because water is mixed with a number of other components,
individual water molecules are less mobile and thus have more
efficient relaxation times. For larger molecules, the values of T1 and
T2 are shorter, because they undergo relaxation more efficiently.
With many molecules, and that includes water in biochemical
systems, the values of T1 and T2 are different. A change in the
environment also affects those values of T1 and T2. With tumors,
lesions, or scar tissue the relaxation times of the proton containing
molecules are different from the relaxation times in surrounding
tissues. If, for example, the interval between radio frequency pulses is
short compared to T1, the second pulse arrives before the nuclei have
relaxed from the first pulse. Thus, there is no energy absorption and
no signal is obtained from that tissue. Some regions have a large T1,
whereas, others have a large T2. The computer assembling the image
uses different timings and different orientations of the radio frequency
pulses to obtain a detailed map of the different relaxation values. This
imaging allows a physician to get a detailed picture of soft tissues
without the damaging effects of x-rays or the need to inject contrast-
enhancing agents. Figure 10.24 shows an MRI image of the brain of a
patient with <************>.
<<<<<<<<<<<<Need Image>>>>>>>>>>>>>

Figure 10.24. MRI image of a brain of a patient with <**********>.
Compare Figure 10.24 with Figure 10.23. You can see that
Figure 10.24 has a region corresponding to the <*********>. The
water molecules in this region have a shorter/longer relaxation time
and thus appear darker/brighter than the surrounding healthy
tissues.
10.10 Strategy for Solving Spectral Problems

Before you can use IR, NMR, and MS to accurately determine
the structure of an unknown organic compound, you must work from a
strategy, and you must understand the strengths and weaknesses of
each type of spectroscopy. Until you gain an intuitive grasp of
spectroscopy, simply scanning the three types of spectra looking for
the obvious likely leads to failure. Table 10.6 summarizes the
information provided by each spectroscopic technique. Use this table
only as an approximate guide because the details of the information
provided by each technique depend on the compound you are
analyzing.
IR NMR MS
Functional Groups E H S
Alkyl Groups S E H
Heteroatoms S S E
Molecular Weight N N E
Molecular Formula N S E
Notes: E - Essential, H - Helpful, S - Sometimes, N - Never.
Table 10.6. Utility of the various spectral types in determining molecular features.
Here are some suggestions for using IR, NMR, and MS spectra
to determine the structure of an unknown organic compound. Take a
sheet of paper, divide it into three columns and label the columns IR,
NMR, and MS. In the appropriate column keep notes about the
molecular features that you see in each spectrum. As you work,
propose molecular structures and test them. Work carefully and you
will successfully identify the compound. When considering the spectra,
keep in mind the types of information available in each type of
spectra. Refer to Table 10.6 if you need help. Use the following
guidelines to assist your search for molecular features from each type
of spectroscopy.
IR Use the IR spectrum to help identify the functional groups

present in the molecule. Then combine the IR spectrum with
the MS to confirm the presence of any nitrogen-containing

functional groups. If there is an —OH group present, suspect

that the molecular weight of the tentative molecular ion is low
by 18 because of loss of water.
NMR Use the NMR spectrum to confirm the structures of the alkyl
groups and to suggest the locations of the functional groups,
heteroatoms, alkenes, or aromatic rings. Do this by considering
the effect of the particular group on the chemical shifts of
nearby protons.
MS Look for the molecular ion and determine its molecular weight.
This is the molecular weight of the molecule you are
identifying. Remember, however, that the molecular ion may
not be visible. Also, when the molecular ion is small, the M+2
peak may be too small to be visible. If the molecular weight is
odd, nitrogen is present. A particularly large M+2 peak
indicates the presence of S, Cl, or Br. A peak at 127 or a mass
loss of 127 usually indicates iodine.
After you finish with this preliminary examination of the three

types of spectra, decide on a tentative molecular formula and propose
a few tentative structures. Then consider each structure, accounting
for all its features in the spectra. Ask yourself the following questions.
1) Does the structure account for the major stretching frequencies of
the IR? 2) Does it account for the chemical shift and any spin-spin
splitting of each proton in the NMR? 3) Does the structure have the
same molecular weight as that obtained by the MS?
Figure 10.31 contains a set of spectra illustrating the above
procedure. This set of spectra includes the IR, NMR, and MS of a
single pure compound.
T 100
r
a
n
s
m
i
t
t
a
n
c
e
(%) 0
4000 3000 2500 2000 1500 1300 1100 1000 900 800 700 650
Wavenumber (cm–1)

10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
100
I
80
n
t
60
e
n
s 40
i
t 20
y
0
20 40 60 80 100 120 140 160 180
m/z
Figure 10.31. IR, NMR, and MS of a single pure compound.
The IR spectrum in Figure 10.31 clearly shows an OH group at

3300 cm–1. In addition, it shows some type of sp2 C—H bonds with
weak peaks in the 3100 to 3000 cm–1 range. The peak at 1050 cm–1
confirms that the alcohol is an aliphatic alcohol.
The integration in the NMR is 5:2:1:2. The signal at 7.2 ppm in
the NMR confirms the presence of sp2 C—H bonds on an aromatic
ring. Because this signal integrates for five protons, the ring is
monosubstituted. The IR peaks at 740 and 690 cm–1 confirm the
monosubstitution.
The MS indicates the molecular ion has a mass of 122 with a
base peak at 91. This information, along with that gathered from the
IR and NMR, makes it possible to deduce the molecular formula.

122 Molecular weight

–77 Phenyl group
–17 OH group
28 Unaccounted mass
Assuming that only carbon and hydrogen remain, a mass of 28 gives a

formula of C2H4. Thus, the molecular formula is C6H5 + OH + C2H4 =
C8H10O.
Putting together all this information makes it possible to
propose the following two structures. Both fit the data accumulated to
date. Each molecule contains an alcohol and a monosubstituted
aromatic ring with a two carbon chain.
OH
OH
1-Phenylethanol 2-Phenylethanol
Going back to the spectra to confirm the proposed structures, the first
molecule does not fit in with the integration of the NMR. The alkyl
groups have a 2:2 ratio in the NMR, but 1-phenylethanol has a 1:3
ratio. The second molecule does fit. Therefore, the molecule is 2-
phenylethanol.
Exercise 10.9
Below are IR, NMR, and MS spectra for two different compounds.
Following the above example, make a list of the structural
characteristics for each of the compounds that you find in the
individual spectrum. Then combine this structural information and
propose a compound that fits the data. Finally, verify that the
structure you proposed accounts for the major features of all three
spectra.

Compound 1
T 1 0 0
r
a
n
s
m
i
t
t
a
n
c
e
0
( % )
4000 3000 2500 2000 1500 1300 1100 1000 900 800 700 650
Wavenumber (cm–1)
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
100
I
80
n
t
60
e
n
s 40
i
t 20
y
0
20 40 60 80 100 120 140 160 180
m/z

Compound 2
100
0
4000 3000 2500 2000 1500 1300 1100 1000 900 800 700 650
-1
Wavenumber (cm )
10 9 8 7 6 5 4 3 2 1 0 ppm ( )
600 500 400 300 200 100 0 Hz
100
I
80
n
t
60
e
n
s 40
i
t 20
y
0
20 40 60 80 100 120 140 160 180
m/z
Sample solution
Aside from saturated alkyl groups, the IR of compound 2 shows little

above 1500 cm–1. The strong peak at 1100 cm–1 suggests an ether. The
positions of the peaks in the NMR indicate protons adjacent to an

electronegative atom. These peaks are consistent with the presence of

an ether group. The molecular weight of the molecule from the MS is
90. To calculate the molecular formula, subtract the oxygen (90 - 16) to
get 74. Assuming the remaining portion of the molecule is carbons and
hydrogens, this gives possible formulas of C5H14 or C6H2. Neither of
these formulas is even close to the molecular formula of a alkane. The
formula of C4H10 fits the formula of an alkane and the NMR
integration. If compound 2 is an ether, the integration ratio of 2:3
suggests that the molecule is symmetrical and the actual ratio is 4:6.
The weight of C4H10 is 58. Remaining is 74 - 58 = 16, the weight of
another oxygen. Thus, the formula is C4H10O2. The following
structure is the only four carbon symmetrical diether.
CH3OCH2CH2OCH3
Key Ideas from Chapter 10

❏ Hydrogen nuclei exist in two energy states when placed in a
magnetic field. In the lower energy state, the magnetic
moments of the nuclei align parallel to the external field. In the
higher energy state, they align antiparallel to the external
magnetic field.
❏ While aligned, the lower energy state nuclei absorb

radiofrequency energy and go to the higher energy state.
Chemists call this change resonance. The record of the exact
energies required for resonance is a nuclear magnetic
resonance spectrum.
❏ An NMR spectrum gives four types of information: 1) the

number of sets of nonequivalent hydrogens, 2) the relative
numbers of each type of hydrogen, 3) the chemical environment
for each type of hydrogen, and 4) data about other nearby
hydrogens through spin-spin splitting.
❏ Determining the structure of an unknown organic molecule

using only one of the spectroscopic techniques is difficult; using
a combination of IR, NMR, and MS with the proper strategy
makes it relatively easy.

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Richard F. Daley and Sally J.

Nuclear Magnetic Resonance

10.1 Theory of Nuclear Magnetic Resonance 475

Copyright 1996-2005 by Richard F. Daley & Sally J. Daley

No part of this publication may be reproduced, stored in a retrieval system, or

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Nuclear Magnetic Resonance

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✔ Understand the molecular basis for nuclear magnetic resonance

The quick harvest of applied science is the usable

C hapter 10 continues the study of molecular spectroscopy

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needed to identify the structure of unknown compounds based on

10.1 Theory of Nuclear Magnetic Resonance

Spinning proton Bar magnet

If you place a small magnet in the magnetic field of a larger

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As stated earlier, in the absence of an external magnetic field

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a variable radiofrequency. The other type has a stable radiofrequency

Radi o f r equ ency

Figure 10.3. Schematic diagram of an NMR spectrometer.

Because chemists commonly use NMR spectrometers of various

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Most student NMR instruments have a fixed radiofrequency

Because of the shielding, the effective magnetic field reaching

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shielded proton requires a greater amount of applied magnetic energy

Figure 10.6. A “bare,” or isolated, proton is in resonance in a 14,092 gauss field at 60

A proton, as well as the nuclei of all kinds of atoms that

The number of absorptions in an NMR spectrum tells how

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This information from an NMR spectrum is particularly valuable

10.3 Chemical Shift and Molecular Structure

Most student NMR spectrometers operate at 60 MHz, so this

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600 500 400 300 200 100 0 Hz

Within a molecule, an electronegative substituent affects the

Compound Electronegativity Chemical Shift (in

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CH3CH3 2.5 0.9

When a carbon contains more than one electronegative

CH3Cl CH2Cl2 CHCl3

The magnetic field internally induced by π electrons is strong

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Because the π bonds of alkenes and arenes deshield their

10.4 Interpreting Proton NMR Spectra

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the intensity of the signals, and 4) the multiplicity (splitting) of the

The methyl group attached to oxygen is more deshielded, so it appears

Figure 10.10. The NMR spectrum of methyl acetate (CH3COOCH3).

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The environment of a proton determines its chemical shift.

COOH (12.5 - 11 ppm)

600 500 400 300 200 100 0 Hz

Alkyl groups show a wide range of positions because they are

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A methylene group appears at 1.3 ppm in a hydrocarbon and at 3.6

1.3 ppm 3.6 ppm

A methine group appears at 1.6 ppm in a hydrocarbon and at 3.9 ppm

1.6 ppm 3.9 ppm

The change in resonance position of 2.3 ppm is the characteristic