Chapter 9

Nuclear Magnetic
Resonance and Mass
Spectrometry
Created by
Professor William Tam & Dr. Phillis
Chang
Ch. 9 - 1

1. Introduction

Classic methods for organic

structure determination:

Boiling point
Refractive index
Solubility tests
Functional group tests
Derivative preparation
Sodium fusion (to identify N, Cl, Br, I
& S)
Mixture melting point
Combustion analysis

Ch. 9 - 2

Classic methods for organic

structure determination.
These methods require
large quantities of sample
and are time consuming.

Ch. 9 - 3

Spectroscopic methods for organic

structure determination.
a) Mass Spectroscopy (MS)
Molecular Mass &
characteristic fragmentation
pattern
b) Infrared Spectroscopy (IR)
Characteristic functional
groups
c) Ultraviolet Spectroscopy (UV)
Characteristic chromophore
Ch. 9 - 4

Spectroscopic methods for

organic structure determination.
Combination of these
spectroscopic techniques
provides a rapid, accurate and
powerful tool for Identification
and Structure Elucidation of
organic compounds.
Effective in mg and microgram
quantities.
Ch. 9 - 5

General steps for structure

elucidation.
1. Elemental analysis
Empirical formula
e.g. C2H4O
2. Mass spectroscopy
Molecular weight
Molecular formula
e.g. C4H8O2, C6H12O3 etc.
Characteristic
fragmentation pattern for
Ch. 9 - 6

General steps for structure

elucidation.
3. From molecular formula
Double bond equivalent
(DBE)
4. Infrared spectroscopy (IR)
Identify some specific
functional groups
e.g. C=O, CO, OH, COOH,
NH2 etc.
Ch. 9 - 7

General steps for structure

elucidation.
5. UV
Sometimes useful especially
for conjugated systems.
e.g. dienes, aromatics,
enones

6. 1H, 13C NMR and other

advanced NMR techniques.
Ch. 9 - 8

Electromagnetic spectrum

cosmic
& -rays

X-rays

0.1nm

ultraviolet

200nm

X-Ray
Crystallography

visible

400nm

infrared

800nm
IR

UV

microwave

radiowave

50m

NMR

1 = 10-10m
1nm = 10-9m
1m = 10-6m

Ch. 9 - 9

2. Nuclear Magnetic Resonance

(NMR) Spectroscopy

A graph that shows the

characteristic energy absorption
frequencies and intensities for a
sample in a magnetic field is
called a nuclear magnetic
resonance (NMR) spectrum.
Ch. 9 - 10

Typical

H (Proton) NMR spectrum

Ch. 9 - 11

1.

The number of signals in the

spectrum tells us how many
different sets of protons there are
in the molecule.

2.

The position of the signals in the

spectrum along the x-axis tells us
about the magnetic environment
of each set of protons arising
largely from the electron density
in their environment.
Ch. 9 - 12

3.

The area under the signal tells us

about how many protons there
are in the set being measured.

4.

The multiplicity (or splitting

pattern) of each signal tells us
about the number of protons on
atoms adjacent to the one whose
signal is being measured.

Ch. 9 - 13

Typical 1H NMR spectrum

Chemical Shift ().
Integration (areas of peaks
no. of H).
Multiplicity (spin-spin splitting)
and coupling constant.
Ch. 9 - 14

Typical 1H NMR spectrum

Record as:

H NMR (300 MHz, CDCl3):

4.35 (2H, t, J = 7.2 Hz, Hc)

b
2.05 (2H, sextet, J = 7.2 Hz, H )
1.02 (3H, t, J = 7.2 Hz, Ha)
chemical
shift ()
in ppm

coupling
constant
no. of H
(integration) multiplicity in Hz

Ch. 9 - 15

2A. Chemical Shift

The position of a signal along the xaxis of an NMR spectrum is called its
chemical shift.
The chemical shift of each signal gives
information about the structural
environment of the nuclei producing
that signal.
Counting the number of signals in a 1H
NMR spectrum indicates, at a first
approximation, the number of distinct
proton environments in a molecule.

Ch. 9 - 16

H Chemical Shifts

Ch. 9 - 17

13

C Chemical Shifts

Ch. 9 - 18

Normal range of 1H NMR

"upfield" (more shielded)

"downfield" (deshielded)
15
(low field
strength)

ppm

0
(high field
strength)

Ch. 9 - 19

Reference compound:

Me
Me

Si Me

TMS = tetramethylsilane Me
as a reference standard (0
ppm).
Reasons for the choice of TMS:
Resonance position at higher
field than other organic
compounds.
Unreactive and stable, not
Ch. 9 - 20
toxic

NMR solvent
Normal NMR solvents should
not contain hydrogen.
Common solvents:

CDCl3

C6D6

CD3OD

CD3COCD3 (d6-acetone)
Ch. 9 - 21

The 300-MHz 1H NMR spectrum of

1,4-dimethylbenzene.
Peaks are in blue, integration in
black.

Ch. 9 - 22

2B. Integration of Signal Areas

Integral Step Heights
The area under each signal in a 1H
NMR spectrum is proportional to
the number of hydrogen atoms
producing that signal.
It is signal area (integration), not
signal height, that gives
information about the number of
hydrogen atoms.

Ch. 9 - 23

Ha
R

Ha

O
Hb

Hb
Hb

2H
Splitting of
protons on
adjacent
atoms.

3H

a
Ch. 9 - 24

2C. Coupling (Signal Splitting)

Coupling is caused by the
magnetic effect of nonequivalent
hydrogen atoms that are within 2
or 3 bonds of the hydrogens
producing the signal.
The n+1 rule
Rule of Multiplicity:
If a proton (or a set of
magnetically equivalent nuclei)
has n neighbors of

Ch. 9 - 25

Examples

(1)

Hb Ha

Hb

Ha: multiplicity = 3 + 1 = 4 (a quartet)

Cl

Hb Ha

(2) Ha Hb
Cl

Cl Hb

Hb: multiplicity = 2 + 1 = 3 (a triplet)

Ha: multiplicity = 2 + 1 = 3 (a triplet)

Cl

Hb: multiplicity = 1 + 1 = 2 (a doublet)

Ch. 9 - 26

Example

of splitting

Ch. 9 - 27

Examples

(3)

Hb Ha

Hb

C
Hb
Hb

Br

Ha: multiplicity = 6 + 1 = 7 (a septet)

Hb Hb: multiplicity = 1 + 1 = 2 (a doublet)

Hb

Note: All Hbs are chemically

and magnetically
equivalent.
Ch. 9 - 28

Pascals Triangle:
Used to predict relative
intensity of various peaks in
multiplet.
Given by the coefficient of
binomial expansion (a + b)n.
singlet (s)
1
doublet (d)
11
triplet (t)
121
quartet (q)
1331
quintet
14641
sextet
1 5 10 10 5 1

Ch. 9 - 29

Pascals Triangle
Ha Hb

For

Br

Br

Cl Cl

Ha Hb

For

Cl

Cl Br

Br

Due to
symmetry, Ha
and Hb are
identical
a singlet
Ha Hb
two doublets
Ch. 9 - 30

3. How to Interpret Proton NM

Spectra
1.

Count the number of signals to

determine how many distinct
proton environments are in the
molecule (neglecting, for the
time being, the possibility of
overlapping signals).

2.

Use chemical shift tables or

charts to correlate chemical

Ch. 9 - 31

3.

Determine the relative area of each

signal, as compared with the area of
other signals, as an indication of the
relative number of protons producing
the signal.

4.

Interpret the splitting pattern for

each signal to determine how many
hydrogen atoms are present on
carbon atoms adjacent to those
producing the signal and sketch
possible molecular fragments.

5.

Join the fragments to make a

Ch. 9 - 32

Example: 1H NMR (300 MHz) of

an unknown compound with
molecular formula C3H7Br.

Ch. 9 - 33

Three distinct signals at ~ 3.4,

1.8 and 1.1 ppm.
3.4 ppm: likely to be near an
electronegative group (Br).
Ch. 9 - 34

 (ppm):

3.4

1.8

1.1

Integral:

3
Ch. 9 - 35

 (ppm):

3.4

Multiplicity:triplet

1.8

1.1

sextet

triplet

2 H's on
5 H's on
2 H's on
adjacent C adjacent C adjacent C

Ch. 9 - 36

Complete structure:
most downfield
CH2
signal
Br

most upfield sign

CH3

CH2

2 H's from 2 H's from

integratio
integratio
n
n

3 H's from
integratio
n

Ch. 9 - 37

4. Nuclear Spin:
The Origin of the Signal
The magnetic
field
associated
with a
spinning
proton

The spinning
proton
resembles a
tiny bar
magnet

Ch. 9 - 38

Alignment of nuclei in presence

and absence of an applied
magnetic field:
random
with or against

Ch. 9 - 39

Difference in energy is proportional

to applied field strength.

Ch. 9 - 40

Spin quantum number (I)

H:

12

C,

I=
(two spin states: +
or -)
(similar for 13C, 19F, 31P)
16

O, 32S:I = 0
These nuclei do not give
an NMR spectrum

Ch. 9 - 41

5. Detecting the Signal: Fourier

Transform NMR Spectromete

Ch. 9 - 42

Ch. 9 - 43

6. Shielding & Deshielding of Proto

All protons do not absorb energy at
the same frequency in a given
external magnetic field.
Lower chemical shift values
correspond with lower frequency.
Higher chemical shift values
correspond with higher frequency.

"upfield" (more shielded)

"downfield" (deshielded)
15
(low field
strength)

ppm

0
(high field
strength) Ch. 9 - 44

Ch. 9 - 45

Deshielding by electronegative
groups
CH3X

X=

Electro4.0
negativity
4.2
(ppm)
6

OH

Cl

Br

3.5

3.1

2.8

2.5

2.1

3.4
0

3.0
5

2.6
8

2.1
6

0.2
3

Greater electronegativity
Deshielding of the proton
Larger
Ch. 9 - 46

Shielding and deshielding by

circulation of electrons:
If we were to consider only the
relative electronegativities of
carbon in its three hybridization
states, we might expect the
following order of protons
attached to each type of
carbon:
(higher
(lower
2
sp < sp <
frequency)
frequency)
3
sp

Ch. 9 - 47

 In fact, protons of terminal

alkynes absorb between 2.0
and 3.0, and the order is:
(higher
sp2 < sp <
frequency)
sp3

(lower
frequency)

Ch. 9 - 48

 This upfield shift (lower

frequency) of the absorption of
protons of terminal alkynes is a
result of shielding produced by
the circulating electrons of
the triple bond (anisotropy).
H

Shielded
( 2 3 ppm)

Ch. 9 - 49

 Aromatic system
Shielded region

Deshielded region

Ch. 9 - 50

 e.g.
Hd

Hc

Hb
Ha

(ppm)
a

H & H : 7.9 & 7.4 (deshielded)

H & H : 0.91 1.2 (shielded)
Ch. 9 - 51

 Alkenes

Anisotropic effect

Deshielded
( 4.5 7 ppm)

Ch. 9 - 52

 Aldehydes

R
H

Electronegativity effect + Anisotropy

effect
= 8.5 10 ppm (deshielded)
Ch. 9 - 53

7. The Chemical Shift

Me

Reference compound:
Me

Si Me

TMS = tetramethylsilane
Me
as a reference standard (0 ppm).
Reasons for the choice of TMS as
reference:
Resonance position at higher
field than other organic
compounds.
Unreactive and stable, not
toxic.

Ch. 9 - 54

7A. PPM and the Scale

The chemical shift of a proton,
when expressed in hertz (Hz), is
proportional to the strength of the
external magnetic field.
Since spectrometers with different
magnetic field strengths are
commonly used, it is desirable to
express chemical shifts in a form
that is independent of the
strength of the external field.

Ch. 9 - 55

Since chemical shifts are always very

small (typically 5000 Hz) compared with
the total field strength (commonly the
equivalent of 60, 300, or 600 million
hertz), it is convenient to express these
fractions in units of parts per million
(ppm).

This is the origin of the delta scale for

the expression of chemical shifts 6
(observed shift from TMS in hertz) x 10
=relative to TMS.

(operating frequency of the instrument in hertz)

Ch. 9 - 56

For example, the chemical shift for

benzene protons is 2181 Hz when the
instrument is operating at 300 MHz.
6
2181
Hz
x
10
Therefore
=
= 7.27 ppm
300 x 106 Hz

The chemical shift of benzene protons

6
436
Hz
x
10
in a 60
436ppm
Hz:
= MHz instrument is
= 7.27
60 x 106 Hz

Thus, the chemical shift expressed in

ppm is the same whether measured
with an instrument operating at 300
Ch. 9or
- 57

8. Chemical Shift Equivalent and

Nonequivalent Protons

Two or more protons that are in

identical environments have the
same chemical shift and,
therefore, give only one 1H NMR
signal.

Chemically equivalent protons

are chemical shift equivalent in
1
H NMR spectra.
Ch. 9 - 58

8A. Homotopic and Heterotopic Ato

If replacing the hydrogens by a

different atom gives the same
compound, the hydrogens are said
to be homotopic.

Homotopic hydrogens have

identical environments and will
have the same chemical shift.
They are said to be chemical
shift equivalent.
Ch. 9 - 59

Br H

same
compounds

Br

Br H

Ethane
H

Br

Br

same
compounds

Br

The six hydrogens of ethane are

homotopic and are, therefore, chemical
shift equivalent.
Ethane, consequently, gives only
Ch. 9 - 60

If replacing hydrogens by a
different atom gives different
compounds, the hydrogens are
said to be heterotopic.

Heterotopic atoms have different

chemical shifts and are not
chemical shift equivalent.

Ch. 9 - 61

same
Cl Br
compound H C C H
s
H H
these 3
H Br
H Br
Hs of the
H C C
CH3 group Cl C C H
H H
H H
are
homotopi
H Br
c
H C C H
the CH3
Cl H
H
H Br
group
gives only
H C C Cl
one 1H
H H
different
NMR
compounds
signal

These 2
Hs are
also
H
homotopi
c to each
other
H

Br

Cl

Ch. 9 - 62

Br

CH3CH2Br
two sets of hydrogens that are
heterotopic with respect to
each other.
two 1H NMR signals.
Ch. 9 - 63

Other examples:
H

(1)

CH3
C

CH3

H
(2)

2 1H NMR signals

CH3
H

4 1H NMR signals

CH3
Ch. 9 - 64

Other examples:
H

(3)

H
CH3

H3C
H

3 1H NMR signals

Ch. 9 - 65

(1)

Application to
spectroscopy
Examples
H3C

CH3

13

C NMR

C NMR signal

13

CH3
(2)

CH3

C NMR signals

13

Ch. 9 - 66

(3)
HO

(4)

OH

HO
OH

5 13C NMR
signals

4 13C NMR
signals
Ch. 9 - 67

8B. Enantiotopic and Diastereotopi

Hydrogen Atoms

If replacement of each of two

hydrogen atoms by the same
group yields compounds that are
enantiomers, the two hydrogen
atoms are said to be
enantiotopic.

Ch. 9 - 68

Enantiotopic hydrogen atoms

have the same chemical shift and
give only one 1H NMR signal:
H

enantiotopic
H
H3C

H3C

G
Br

enantiomer

Br
G
H3C

H
Br
Ch. 9 - 69

OH

H3C
Hb

Ha

OH

H3C
Hb

CH3

CH3

diastereotopic

OH

H3C
G

Ha

diastereomers

chirality
centre

CH3

Ch. 9 - 70

Br
Ha
Br

Hb
H

Hb
Ha

diastereotopic

Br

diastereomers

G
H
Ch. 9 - 71

9. Signal Splitting:
SpinSpin Coupling

Vicinal coupling is coupling

between hydrogen atoms on
adjacent carbons (vicinal
hydrogens), where separation
between the hydrogens is by three
b
bonds.
a
H
H
3

J or vicinal coupling
Ch. 9 - 72

9A. Vicinal Coupling

Vicinal coupling between
heterotopic protons generally
follows the n + 1 rule. Exceptions
to the n + 1 rule can occur when
diastereotopic hydrogens or
conformationally restricted
systems are involved.
Signal splitting is not
observed for protons that are
homotopic (chemical shift

Ch. 9 - 73

9B. Splitting Tree Diagrams and the

Origin of Signal Splitting

Splitting analysis for a doublet.

Hb Ha
C

Ch. 9 - 74

Splitting analysis for a triplet

Hb Ha
C

Hb
Hb Ha Hb
C

Ch. 9 - 75

Splitting analysis for a quartet

Hb Ha
Hb

Hb

Ch. 9 - 76

Pascals Triangle
Use to predict relative
intensity of various peaks in
multiplet.
Given by the coefficient of
binomial expansion (a + b)n.
singlet (s)
1
doublet (d)
11
triplet (t)
121
quartet (q)
1331
quintet
14641
sextet
1 5 10 10 5 1

Ch. 9 - 77

9C. Coupling Constants Recognizi

Splitting Patterns
Ha Hb
X

Hb

Ha Hb

Ch. 9 - 78

9E. Complicating Features

The 60 MHz 1H NMR spectrum of

ethyl chloroacetate.

Ch. 9 - 79

The 300 MHz 1H NMR spectrum of

ethyl chloroacetate.

Ch. 9 - 80

9F. Analysis of Complex Interaction

Ch. 9 - 81

The 300 MHz 1H NMR spectrum of

1-nitropropane.

Ch. 9 - 82

10.Proton NMR Spectra and Rat

Processes

Protons of alcohols (ROH) and amines

may appear over a wide range from 0.5
5.0 ppm.
Hydrogen-bonding is the reason for
range.
in conc. solution (H-bonded):
in highthis
dilution
(free OH):

O H

= ~0.5-1.0 ppm

O
H

O
H

proton more deshielded

Ch. 9 - 83

Why dont we see coupling with

the OH proton, e.g. CH2OH
(triplet?).
Because the acidic protons
are exchangeable about 105
protons per second
(residence time 10-5 sec), but
the NMR experiment requires
a time of 10-2 10-3 sec. to
take a spectrum, usually
we just see an average (thus,
OH protons are usually a Ch. 9 - 84

Trick:
Run the spectrum at lower
temperaturewhichslows the H
exchangeand coupling is
observed,
or
Run NMR in d6-DMSO where Hbonding with DMSOs oxygen
prevents Hs from exchanging
and we may be able to see the
coupling.
Ch. 9 - 85

Deuterium Exchange
To determine which signal in the
NMR spectrum is the OH proton,
shake the NMR sample with a
drop of D2O and whichever peak
disappears that is the OH peak
(note: a new peak of HOD
appears).
R

D2O

HOD
Ch. 9 - 86

Phenols
Phenol protons appear
downfield at 4-7 ppm.
They are more acidic - more
H+ character.
More dilute solutions - peak
appears upfield: towards 4
ppm.
OH

Ch. 9 - 87

Phenols
Intramolecular H-bonding
causes downfield shift.
12.1 ppm
O

H
O

Ch. 9 - 88

11.Carbon-13 NMR Spectroscop

11A. Interpretation of
Spectra

C NMR

13

Unlike 1H with natural abundance

~99.98%, only 1.1% of carbon,
namely 13C, is NMR active.

Ch. 9 - 89

11B.One Peak for Each Magneticall

Magnetical
Distinct Carbon Atom
13C NMR spectra have only
become commonplace more
recently with the introduction of
the Fourier Transform (FT)
technique, where averaging of
many scans is possible (note 13C
spectra are 6000 times weaker
than 1H spectra, thus require a lot
more scans for a good spectrum).
Ch. 9 - 90

Note for a 200 MHz NMR (field

strength 4.70 Tesla)
1H NMR Frequency = 200
MHz
13C NMR Frequency = 50
MHz

Ch. 9 - 91

Example:
2-Butanol

H
CH3

CH2

CH3

OH

Proton-coupled
13
C NMR spectrum

Ch. 9 - 92

Example:
2-Butanol

H
CH3

CH2

CH3

OH

Proton-decoupled
13
C NMR spectrum

Ch. 9 - 93

11C. 13C Chemical Shifts

Decreased electron density
around an atom deshields the
atom from the magnetic field and
causes its signal to occur further
downfield (higher ppm, to the
left) in the NMR spectrum.
Relatively higher electron density
around an atom shields the atom
from the magnetic field and
causes the signal to occur upfield

Ch. 9 - 94

Factors affecting chemical shift

i.

Diamagnetic shielding due to

bonding electrons.
ii. Paramagnetic shielding due to lowlying electronic excited state.
iii. Magnetic Anisotropy through
space due to the near-by group
(especially electrons).

In 1H NMR, (i) and (iii) most

significant; in 13C NMR, (ii) most
significant (since chemical shift
1

Ch. 9 - 95

Electronegative substituents
cause downfield shift.

Increase in relative atomic mass

of substituent causes upfield shift.

Electronegativity Atomic Mass

13

C NMR: CH3X

Cl

2.8

35.5

23.9 ppm

Br

2.7

79.9

9.0 ppm

2.2

126.9

-21.7 ppm
Ch. 9 - 96

Hybridization of carbon and

NMR:

13

sp2 > sp > sp3

e.g.
H2C

CH2

HC

CH

123.3 ppm 71.9 ppm

H3C

CH3

5.7 ppm

Ch. 9 - 97

Anisotropy effect and

13

C NMR:

Shows shifts similar to the

effect in 1H NMR.
e.g.
C

shows large
upfield shift
Ch. 9 - 98

Ch. 9 - 99

13

C NMR Chemical Shifts:

Ch. 9 - 100

13

C NMR spectrum:
Cl

(a)
CH2

(b)
CH

(c)
CH3

OH
1-Chloro-2-propanol

(b) (a)

(c)

Ch. 9 - 101

11D. Off-Resonance Decoupled Spectra

NMR spectrometers can differentiate among

carbon atoms on the basis of the number of
hydrogen atoms that are attached to each
carbon.
In an off-resonance decoupled 13C NMR
spectrum, each carbon signal is split into a
multiplet of peaks depending on how many
hydrogens are attached to that carbon. An n
+ 1 rule applies, where n is the number of
hydrogens on the carbon in question. A
carbon with no hydrogens produces a singlet
(n = 0), a carbon with one hydrogen produces
a doublet (two peaks), a carbon with two
hydrogens produces a triplet (three peaks),
Ch. 9 - 102

Off-resonance
decoupled 13C
NMR

9
2

7
6

4
5

Broadband proton-decoupled
NMR

13

Ch. 9 - 103

11E. DEPT

C Spectra

13

DEPT 13C NMR spectra indicate

how many hydrogen atoms are
bonded to each carbon, while also
providing the chemical shift
information contained in a
broadband proton-decoupled 13C
NMR spectrum. The carbon signals
in a DEPT spectrum are classified
as CH3, CH2, CH, or C accordingly.
Ch. 9 - 104

Cl

(a)
CH2

(b)
CH

(c)
CH3

(b)

(a)

(c)

OH
1-Chloro-2-propanol

Ch. 9 - 105

The broadband proton-decoupled

13
C NMR spectrum of methyl
methacrylate

Ch. 9 - 106

13.An Introduction to Mass

Spectrometry

Partial MS of octane (C8H18, M =

114)
14 (CH2)
29 (CH3CH2)

57

85
71

M+
114

Ch. 9 - 107

The M+ peak at 114 is referred to

as the parent peak or molecular
ion.
e
C8H18

70 eV

[C8H18] + 2 e(M+)

The largest or most abundant

peak is called the base peak and
is assigned an intensity of 100%,
other peaks are then fractions of
that e.g. 114(M+,40), 85(80),
71(60), 57(100) etc.
Ch. 9 - 108

Masses are usually rounded off to

whole numbers assuming:
H = 1, C = 12, N = 14, O = 16, F = 19
etc.
[C8H18]

fragmentation

(M , 114) -CH3CH2 (29)

+

-CH3CH2CH2 (29+14)
Molecular ion (parent peak)

[C6H13]

Daughter
ions

(85)
[C5H11]
(71)
Ch. 9 - 109

14.Formation of Ions: Electron

Impact Ionization
In the mass spectrometer, a molecule
in the gaseous phase under low
pressure is bombarded with a beam of
high-energy electrons (70 eV or ~
1600 kcal/mol).
This beam can dislodge an electron
from a molecule to give a radical
cation which is called the molecular
ion, M+ or more70accurately.
eV e

Ch. 9 - 110

This molecular ion has

considerable surplus energy so it
can fly apart or fragment to give
specific ions which may be
diagnostic for a particular
compound.
- m1

- m2

- m3

etc.

m = neutral fragment radical

Ch. 9 - 111

15.Depicting the Molecular Ion

CH3CH2 CH3

Radical cations from

ionization
of nonbonding on
electron
H3C

OH

H3C

CH3

H2C

CHCH2CH3

CH3
Methanol

Trimethylamine

1-Butene
Ch. 9 - 112

Ionization potentials of selected

molecules:
Compound
CH3(CH2)3NH2

Ionization
Potential (eV)
8.7

C6H6
(benzene)
C2H4

9.2
10.5

CH3OH

10.8

C2H6

11.5

CH

12.7

Ch. 9 - 113

16.Fragmentation
The reactions that take place in a mass
spectrometer are unimolecular, that is,
they do not involve collisions between
molecules or ions. This is true because
the pressure is kept so low (10-6 torr)
that reactions. involving bimolecular
collisions do not occur
2. We use single-barbed arrows to depict
mechanisms involving single electron
movements.
3. The relative ion abundances, as
1.

Ch. 9 - 114

16A. Fragmentation by Cleavage

Single Bond
When a molecular ion fragments, it
will yield a neutral radical (not
detected) and a carbocation
(detected) with an even number of
electrons.
The fragmentation will be dictated
to some extent by the fragmention
of the more stable carbocation:
ArCH

> CH =CHCH

o 9 - 115
Ch.
> 3o > 2o > 1
>

e.g.

CH

R+

+ CH3

+ +CH3

Site of ionization: n > >

nonbonding
Ch. 9 - 116

As the carbon skeleton becomes

more highly branched, the
intensity of the molecular ion peak
decreases.
+ CH3
a
Butane vs. isobutane:
a
(43)

70eV
e-

70eV
e

b+
M (58)

M+(58)

(29)

(43)

+ CH2CH3

+ CH3
Ch. 9 - 117

16B.Fragmentation of Longer Chai

and Branched Alkanes
Octane vs. isooctane:
(85) +
(71) +
(57) +

M (114)

(43) +
+
M+(114)

(57)
Ch. 9 - 118

16C. Fragmentation to Form

Resonance-Stabilized Cations
Alkenes
Important fragmentation of
terminal alkenes.
Allyl carbocation (m/e = 41)
R
R

+
(41)
Ch. 9 - 119

Carboncarbon bonds next to an

atom with an unshared electron
pair usually break readily because
the resulting carbocation is
resonance stabilized.
Ethers

Cleavage (to ether oxygen) CC

O
bonds
CH3

(m/e = 59)
Ch. 9 - 120

Alcohols
Most common fragmentation: loss of alkyl groups.
a

CH3 +

OH
(m/e = 59)

a OH b
M+(74)

OH

CH3CH2 +

OH

OH

(m/e = 45)
Ch. 9 - 121

Carboncarbon bonds next to

the carbonyl group of an
aldehyde or ketone break
readily because resonancestabilized ions called acylium
ions are produced via an cleavage.

Ch. 9 - 122

Aldehydes
M+ peak usually observed but
may be fairly weak.
Common fragmentation
pattern.
-cleavage
H + R C O

acylium ion

O
R

H
R

+ H C O
(m/e = 29)
Ch. 9 - 123

Ketones
-cleavage
O

a
b

(m/e = 71)

a
b

(m/e = 99)

Ch. 9 - 124

Alkyl-substituted benzenes ionize

by loss of a electron and
undergo loss of a hydrogen atom
or methyl group to yield the
relatively stable tropylium ion
(see Section 14.7C). This
fragmentation gives a prominent
peak (sometimes the base peak)
at m/z 91.
Ch. 9 - 125

Aromatic hydrocarbons
very intense M+ peaks
characteristic fragmentation
pattern (when an alkyl group
attached to the benzene ring): tropylium cation.
CH3

CH3 +

CH2 rearrangement

benzyl cation

tropylium cation
(m/e = 91)

Ch. 9 - 126

16D. Fragmentation by Cleavage

Two Bonds

Alcohols frequently show a

prominent peak at M - 18. This
corresponds to the loss of a
molecule of water.
May lose H2O by 1,2- or 1,4elimination.
Ch. 9 - 127

1,2-elimination:

OH

+
(M - 18)

1,4-elimination:
M

H2O

OH

(M - 18)

OH + CH3CH2

H2O
Ch. 9 - 128

Cycloalkenes show a
characteristic fragmentation
pattern which corresponds to a
reverse Diels-Alder reaction
retro Diels-Alder

e.g.
+
Ch. 9 - 129

Aromatic hydrocarbons
e.g.

H
McLafferty Rearrangement
CH2
H
H
(m/e = 92)

Ch. 9 - 130

Ketones
McLafferty rearrangement
H
OH

1st McL. Rearr.

OH

OH

(m/e = 86)

2nd McL. Rearr.

OH

(m/e = 58)

Ch. 9 - 131

McLafferty rearrangement:
OH

i
H

ii

2 radical

i
ii

OH

1 radical

OH

(m/e = 86)
observed

OH

(m/e = 114)
NOT observed

Ch. 9 - 132

Characteristic of McLafferty
rearrangement.
1. No alkyl migrations to C=O,
only H migrates.
H

Ch. 9 - 133

Characteristic of McLafferty
rearrangement.
2. 2o is preferred over 1o.
H
H
O
ii
i

OH
2 radical

not

OH
1 radical
Ch. 9 - 134

17. How To Determine Molecular

Formulas and Molecular Weights
Using Mass Spectrometry

17A. Isotopic Peaks & the Molecular Ion

Ch. 9 - 135

The presence of isotopes of

carbon, hydrogen, and nitrogen in
a compound gives rise to a small
M + 1 peak.
The presence of oxygen, sulfur,
chlorine, or bromine in a
compound gives rise to an M + 2
peak.
M + 1 Elements: C, H, N

M + 2 Elements: O, S, Br, Cl
Ch. 9 - 136

The M + 1 peak can be used to

determine the number of carbons
in a molecule.

The M + 2 peak can indicate

whether bromine or chlorine is
present.

The isotopic peaks, in general,

give us one method for
determining molecular formulas.
Ch. 9 - 137

Example
Consider 100 molecules of CH4
1

H
1

12

H1

H
1

H1

13

C12

H2

H1

H1
M + 1 = 17

M : 16

C12: 100
H1: 100

C13: 1.11
H2: 0.016
Ch. 9 - 138

H1
1

H1

H1

C12

H1

H1

C13

H1

1.11 molecules
contain a 13C
atom

H2

H1

H1

M : 16

C12

M + 1 = 17

4x0.016 = 0.064
molecules contain a 2H
atom

+
+

Intensity of M + 1 peak:
1.11+0.064=1.174% of the M
peak

Ch. 9 - 139

relative ion abundance

100

m/z

M +1
1.17
Ch. 9 - 140

17B.How To Determine the Molecul

Formula
m/z

Intensity
(% of M )

72

73.0/73 x 100 = 100

73

3.3/73 x 100 = 4.5

74

0.2/73 x 100 = 0.3

Ch. 9 - 141

Is M odd or even? According

to the nitrogen rule, if it is
even, then the compound
must contain an even number
of nitrogen atoms (zero is an
even number).
For our unknown, M is even.
The compound must have an
even number of nitrogen
atoms.
Ch. 9 - 142

The relative abundance of

the M +1 peak indicates
the number of carbon
atoms. Number of C atoms
= relative abundance of (M
+1)/1.1.
For our unknown

Number of C atoms =

4.5
1.1

~4
Ch. 9 - 143

The relative abundance of the M

+2 peak indicates the presence
(or absence) of S (4.4%), Cl (33%),
or Br (98%).
For our unknown M +2 = 0.3%;
thus, we can assume that S, Cl, and
Br are absent.

The molecular formula can now be

established by determining the
number of hydrogen atoms and
adding the appropriate number of
oxygen atoms, if necessary. Ch. 9 - 144

Since M is m/z 72
molecular weight = 72.
As determined using the relative
abundance of M +1 peak, number
of carbons present is 4.
Using the nitrogen rule, this
unknown must have an even
number of N. Since M.W. = 72,
and there are 4 C present, (12 x 4
= 48), adding 2 N will be greater
than the M.W. of the unknown.
Thus, this unknown contains zero

Ch. 9 - 145

For a molecule composed of C and

H only
H = 72 (4 x 12) = 24
but C4H24 is impossible

For a molecule composed of C, H

and O
H = 72 (4 x 12) 16 = 8
and thus our unknown has the
molecular formula C4H8O.
Ch. 9 - 146

17C. High-Resolution Mass Spectromet

Ch. 9 - 147

Example 1
O2, N2H4 and CH3OH all have M.W.
of 32 (by MS), but accurate masses
are different
O2 = 2(15.9949) = 31.9898

N2H4 = 2(14.0031) +
4(1.00783) = 32.0375

CH4O = 12.00000 + 4(1.00783)

+ 15.9949 = 32.0262

Ch. 9 - 148

Example 2
Both C3H8O and C2H4O2 have M.W.
of 60 (by MS), but accurate masses
are different

C3H8O = 60.05754

C2H4O2 = 60.02112

Ch. 9 - 149

18. Mass Spectrometer Instrument

Designs

Ch. 9 - 150

19. GC/MS Analysis

Ch. 9 - 151

 END OF CHAPTER 9

Ch. 9 - 152