Tutorial 3

Mass Spectrometry

Fragmentation patterns II

Instrumental analysis II
Spring semester 2019
1
Objectives
By the end of this session, the student
should
be able to:

Describe Principles of fragmentation in

different organic classes.

Interpret mass spectrum and the major

peaks.

Compare between spectra of different

structural isomers.
2
 Fragmentation of ethers
1- Homolytic cleavage Loss of neutral
fragment, this is a
very special
example
H2 -R
R C O R H2C O R

H H H H H
- CH3
H3C C O C CH3 H3C C O C CH3 CH3CHO
H3C C

CH3 CH3 CH3 CH3

m/z 102 m/z 87 m/z 43

2- Heterolytic cleavage

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Fragmentation of Aldehyde
Homoloytic

acyl moiety

propene

4
Fragmentation of ketones
Similar to fragmentation patterns of aldehydes.
Homolytic cleavage and McLafferty re-arrangement are the most common
fragmentation patterns.

propene

5
Acids and Esters:
Homolytic fission
(like in ketones)

6
Amides

* Fragmentation is very similar to corresponding esters and acids

(homolytic cleavage ), m/z = 44 is very indicative of primary amides.

* Once the carbon chain in the acyl moiety of an amide becomes

long enough to permit the transfer of a hydrogen attached to the γ
position, McLafferty rearrangements become possible.

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McLafferty type fragmentation in ethyl esters

Exercise 6: Comment on the mass spectra of the methyl butyrate

ester

Molecular
ion peak
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Exercise 7: Predict the major fragmentation pattern of Butyric acid.

McLafferty type fragmentation

9
Exercise 8: Predict the major fragmentation pattern of the following
primary amide.

* For this primary amide, the McLafferty rearrangement gives

rise to a fragment ion peak at m/z = 59.

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Exercise 9 (self study)
The mass spectra of 1-methoxybutane, 2-methoxybutane, and 2-
methoxy-2-methylpropane are shown below. Match the compounds
with the spectra.

2-methoxy-2-
methylpropane 2-methoxybutane

88
88

1-methoxybutane

88

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12
 Fragmentation of aromatic hydrocarbons

Benzene gives very intense molecular ion peak and rarely fragments.

Alkyl benzene usually fragments through benzylic or less commonly

phenyl cleavage.

Loss of neutral
Benzylic cleavage fragment
CH3 CH2

-H - C2H2

m/z 91 m/z 65
m/z 92 Cyclopentadinyl cation
H2 Tropylium cation
C
- CH2-CH3
H2C CH3

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m/z 120
 Phenyl cleavage
Loss of neutral
fragment

CH3

-CH3 - C2H2

m/z=77 m/z=51
Phenyl cation, C6H5+ CyclobutadieneC4H4+

The pairs of ions, m/z =91/65 , m/z = 77/51,

are typical of mono-substituted alkyl aromatics.
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 Assignment 1 (5%)
Show the structure of all fragments (in blue) in the below spectrum of
di-sec-butyl ether

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Due date : your next tutorial

 QUIZ 1
Announcement
Quiz 1 takes place on Monday 18-2-2019 @3:15 to 3:45
(it includes lectures 1,2 and 3 + tutorial 1&2).

Types of Question: Match, complete, T/F, short essay

For exact location , see next slide.

NO MAKE UP QUIZ IS OFFERED AT THE END OF THE

SEMESTER ; IF YOU HAVE EITHER A CONFLICT OR AN
EMERGENY CASE , SEND ME AN EMAIL TO COMPENSATE
THE QUIZ AT THE SAME WEEK.
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Quiz location

H3 1-4
H4 5-8
H5 9-12
C7.01 13-16
C7.02 17-20

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