Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks

.
El ABC + e- ABC + + 2e-

. .
ABC + AB+ + C
Fragmentation . .
ABC + A+ + BC

. .
Rearrangement ABC + AC + + B

• Nº of electrons and charges must be preserved!

• Homolytic vs heterolytic cleavage

• Radical cation vs cation (e- counting, nitrogen rule)

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks

Probability of cleavage is related to bond strength and stability of fragments

• Only single bonds are cleaved

• Order of radical/carbocation loss: 3º > 2º > 1º > methyl > hydrogen

loss of longest is preferred

• Fragmentation increases with: molecular weigth

branching

• Fragmentation decreases in: aromatic, olefins, cyclic compounds

• Several consecutive fragmentations can occur, specially if they lead to

highly stable radical/ion

• If loss of a stable neutral molecule is possible, it will do so (rearrangement)

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks: common types of fragmentation

i) Cleavage at branch points:

57

100

85

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks: common types of fragmentation

ii) β-cleavage: chain cleavage tends to occur β to heteroatoms, double bonds and
aromatic rings

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks: common types of fragmentation

iii) Cleavage α to carbonyl groups:

iv) Cleavage α to heteroatoms:

v) Retro Diels-Alder: vi) McLafferty rearrangement:

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks: long vs short alkyl chains

Base peak
57 Fragment Ions: n-alkanes
CH3-(CH2)12-CH3

43 • For straight chain alkanes, a M+ is often

71 observed although with low intensity.

85
• Fragmentation pattern: .clusters of peaks. In
each cluster: CnH2n+1 with CnH2n and
CnH2n-1
29
99 198 • Fragments lost: ·CH3 (-15), ·C2H5 (-29), ·C3H7
113 127 141 155 169
(-43), etc.

57 • In longer chains – peaks at 43 (C3H7+) and 57

CH3-(CH2)4-CH3
43 (C4H9+) are the most common

29

71 86

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks: linear vs branched alkanes

Smooth curve of decreasing intensities broken by preferred fragmentation at each branch

43
43 C3H7+
57

29 71

71 86
86

43 57
C3H7+ C4H9+

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA Fragment peaks: cyclic vs non cyclic alkanes

[M-C3H6].+ (56) • Relatively intense molecular peak ion (CnH2n)

[C4H7]+ (55)
• [M-C2H4].+ generally intense (even mass /radical cation)
[M-C4H8]. + (42) [M-C2H4]+. (70) • Even masses observed (14 mass units apart) and
[C3H5]+ (41)
[M]+. (98) also CnH2n-1 and CnH2n-2
• Most intense : C3 and C4
[M-CH3]+ (83)

[M-C4H8]+ (43)
CH3-(CH2)5-CH3
C3

[M-C3H6]+ (57)
[M-C2H5]+ (71)
[M]+ (100)
Loss of Me
Must involve rearrangements of H

(even mass /radical cation) 8

rearrangement
Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Propose a structure for a molecule compatible with the following spectrum.
The molecular peak is at m/z = 72. Explain the fragmentation processes for m/z = 57, 43 and 29

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Propose a structure for a molecule compatible with the following spectrum.
The molecular peak is at m/z = 98. Explain the fragmentation processes for m/z = 70, 55 and 42

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS OF MASS SPECTRA

Propose a structure for a molecule compatible with the following spectrum.
The molecular peak is at m/z = 100. Explain the fragmentation processes for m/z = 82 and 57

11

Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS
9 OF MASS SPECTRA
Propose a structure for a molecule compatible with the following spectrum.
The molecular peak is at m/z = 134. Explain the fragmentation processes for m/z = 91

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Copyright by Nuria Romero & Ona Illa INTRODUCTION TO MS

ANALYSIS
10/11 OF MASS SPECTRA
Propose a structure for a molecule compatible with the following spectrum.
The molecular peak is at m/z = 126 (m+2 = 127). Explain the fragmentation processes for m/z = 91

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