Mass Spectrometry Interpretation

Interpretation of Mass Spectra

 Select a candidate peak for the molecular ion

(M+)
Examine spectrum for peak clusters of
characteristic isotopic patterns
Test (M+) peak candidate by searching for other
peaks correspond to reasonable losses
Look for characteristic low-mass fragment ions
Compare spectrum to reference spectra
 Fragmentação
• Governada pela estabilidade do íon produzido
• consideração
regra do octeto
deslocalização por ressonância
polarizabilidade e hiperconjugação
eletronegatividade
• Regra de Stevenson:
Para quebra de uma ligações simples, o fragmento com o
potencial de ionização mais baixo fica com a carga
(em outras palavras, forma-se o íon mais estável)
 Fragmentation process
There are 3 type of fragmentations:
1) Cleavage of s bond
+.
---- C – C ---- ---- C + +
. C ----

At heteroatom
+.
---- C – Z ---- ---- C + +
. Z ----

a to heteroatom
+.
---- C - C – Z ---- C=Z + + ---- C .

+.
---- C - C – Z ---- Z+. + ---- C = C
 Fragmentation process
2) Cleavage of 2 s bond (rearrangements)

+.
---- HC – C – Z ---- ---- C=C + + HZ

CH2
+ . +. CH2
Retro Diels-alder + CH2
CH2

H H
McLafferty Z +. Z +. CH2

CH2
Z R Z R

3) Cleavage of Complex rearrangements

 Regras Gerais de
Fragmentação
Quebra de Uma Ligação (Quebras-a)

Quebra de Duas Ligações

• Eliminação de H-X
• retro Diels-Alder
• Rearranjo de McLafferty
 FRAGMENTATION PATTERNS

ALKANES
The mass spectra of simple hydrocarbons have peaks at m/z values corresponding to
the ions produced by breaking C-C bonds. Peaks can occur at ...

m/z 15 29 43 57 71 85 etc.
CH3+ C2H5+ C3H7+ C4H9+ C5H11+ C6H13+

• the stability of the carbocation formed affects its abundance

• the more stable the cation the higher the peak

• the more alkyl groups attached to the carbocation the more stable it is

most stable tertiary 3° > secondary 2° > primary 1° least stable

alkyl groups are electron releasing and stabilise the cation
 Alkane Fragmentation
• Long chains give homologous series of m/z = 14
units
• Long chains rarely lose methyl radical
• Straight chain alkanes give primary carbocation
• branched alkanes have small or absent M+
• enhanced fragmentation at branch points

Cycloalkanes
• loss of side chain
• loss of ethylene fragments
octane
 29 43 57 71 85
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3

m/z = 114

linear alkane pattern

sequential peaks 14 mass units apart

isooctane
 CH3 CH3
CH3 C CH2 CH CH3
CH3
m/z = 114

CH3 CH3 CH3 CH3

CH3 C CH2 CH CH3 CH3 C CH2 CH CH3
CH3 CH3
m/z = 57 m/z = 99

branched alkane - formation of most stable carbocation

 Alkene Fragmentation
• Fairly prominent M+
• fragment ions of CnH2n+ and CnH2n-1+
• terminal alkenes lose allyl cation if possible

Cycloalkenes
• prominent molecular ion
• retro Diels-Alder cleavage
 1-butene & 2-butene
mass spectra are identical - not a good method for alkene isomers
• Cycloalkenes –1-methyl-1-cyclohexene

81

68
M+● 96
 e-
CH 3

+ CH3

2 e-

m/z = 81

CH 2

+
CH 2

m/z = 68
Retro Diels-alder
+. +.
 Alkyne Fragmentation
• Molecular ion readily visible
• terminal alkynes readily lose hydrogen atom
• terminal alkynes lose propargyl cation if
possible
Proposta de Fragmentação Proposta de Fragmentação
Alternativa
 Aromatic Hydrocarbon
Fragmentation

• Molecular ion usually strong

• alkylbenzenes cleave at benzylic carbon
tropylium ion formation

• McLafferty rearrangement of aromatics

need g-hydrogens
benzene
 ei
+ e

C6 H 6 m/z = 78

closed shell
open shell
(paired electrons)
(odd electron ion)
toluene
 CH3

-H
+

m/z = 92 m/z = 91
C7H7
tropylium ion
 FORMAÇÃO DO ÍON TROPÍLIO
H2 CH2
C
R

H
R
H

CH2 [1,2] H-

C7H7
m/z= 91
n-propylbenzene
 CH3
CH2
CH2

- CH2CH3
++

m/z = 120 m/z = 91

C7 H 7
tropylium ion

H CH2
+ - CH2CH2 H
+
H

m/z = 92
isopropylbenzene
 CH3
CH CH3 CH CH3

- CH3
+

m/z = 120 m/z = 105

o-xylene
m-xylene
 Halide Fragmentation
• Loss of halogen atom
• Elimination of HX
• alpha-cleavage
• 1,4-rearrangement
chloroethane
 CH3 CH2 Cl CH3 CH2 Cl
m/z 64

CH3 CH2 Cl CH3 CH2 Cl

(loss m/z 49 m/z 29 (loss of 35)
of 15)
bromoethane
bromohexane
 CH3 CH2 CH2 CH2 CH2 CH2 Br

m/z = 164

- Br
Br
+
CH3 CH2 CH2 CH2 CH2 CH2
85
- CH2CH3
+
Br

135
 Alcohol Fragmentation
• Molecular ion strength depends on substitution
primary alcohol weak M+
secondary alcohol VERY weak M+
tertiary alcohol M+ usually absent

• Dehydration fragmentation
thermal vs. 1,4-dehydration of M+
• Loss of alkyl group
largest R group lost as radical
 Hydroxy compounds
R1
R1 R1 +
x
- R3  +
R2 C O H C O H C O H
R2 R2
R3 If R1=H m/z 45, 59, 73 …
Loss of largest group If R1=alkyl m/z 59, 73, 87 …

H H CHR
x CHR
CHR OH CHR OH
+ – (H2O)
+ +
CHR CHR CHR CHR
CHR CHR CHR CHR
CHR CHR
CHR CHR M – (H2O)

H
CHR OH
x
- H2O CHR
- CHR=CHR
CHR CHR CHR
CHR M – (H2O) – (C1=C2) Alkene
1-butanol
 - CH3CH2CH2 +
CH3 CH2 CH2 CH2 OH CH2 OH
a-cleavage 31
74

- H 2O

+
C4H9
56
2-butanol
 - CH3CH2 +
CH3 CH2 CH OH CH OH
CH3 a-cleavage CH3
74
59
- H 2O - CH3 +
CH3 CH2 CH OH
+ a-cleavage
C4H9 45

56
t-butanol
benzyl alcohol
 +
OH O
CH2 -H CH2 - CH O
2
+

108 107 77
O
H H
H H
- CO
+ H
+

79
o-cresol
ethylamine
 - CH3 +
CH3 CH2 NH2 CH2 NH2
 a
45 30

a - cleavage
diethylamine
 - CH3 +
CH3 CH2 NH CH2 NH
 a
CH2 CH2
CH3 CH3

73 58
a - cleavage
- C2 H 4

+ +
H NH H NH
30
triethylamine
 Carbonyl Compounds
Dominant fragmentation pathways:
a-cleavage
-cleavage
McLafferty rearrangement
 FRAGMENTATION PATTERNS

ALDEHYDES AND KETONES

Cleavage of bonds next to the carbonyl group (C=O) is a characteristic fragmentation
of aldehydes and ketones. A common fragment is carbon monoxide (CO) but as it is
a molecule and thus uncharged it will not produce a peak of its own. However, it will
produce an m/z drop of 28 somewhere in the spectrum.

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group

the more stable the acylium ion RCO+, the more abundant it will be and
the more abundant the species the taller its peak in the mass spectrum
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+

O
C4H9 C+ CH3• Breaking the bond between the methyl
group and the carbonyl group
m/z = 85 produces two possible ions,
depending on how the bond breaks.
O
Two peaks at m/z values 15 and 85 will
C4H9 C• CH3+ appear in the mass spectrum.
m/z = 15
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+

O
Breaking the bond between the butyl
group and the carbonyl group CH3 C+ C4H9•
produces two further ions, depending m/z = 43
on how the bond breaks.

Two peaks at m/z values 43 and 57 will O

appear in the mass spectrum.
CH3 C• C4H9+
m/z = 57
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
Example; MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+

O O
C4H9 C+ CH3• CH3 C+ C4H9•
m/z = 85 m/z = 43

O O
C4H9 C• CH3+ CH3 C• C4H9+
m/z = 15 m/z = 57

A further peak occurs at m/z = 72 (100-28) due to loss of CO

 Rearranjo de McLafferty

H
H H O

x
- CH2=CH2

x
x

O CH2 O CH2
C
C CH2 Y CH2
C CH2
Y CH2 Y CH2

Ion Stabilized
Y  H, R, OH, NR2
by resonance
2-butanone
 a-cleavage

O O
- CH2 CH3
CH3 C CH2 CH3 CH3 C+

72 43
- CH3 O
+C CH2 CH3
57

favor loss of larger radical

2-octanone
 43
O
CH 3 C CH 2CH 2CH 2CH 2CH 2CH 3

113

128

H H
O O
C C
CH 3 CH 3
58

McLafferty Rearrangement
butyraldehyde
butyric acid
p-anisic acid
methyl butyrate
 59
O O
- CO
- CH 3O +
CH 2CH 2CH 3
CH 3 O C CH 2CH 2CH 3 + C CH 2CH 2CH 3
71 43
71
M+ 102

H H
O O
C C
CH 3O CH 3O
74

McLafferty Rearrangement
methyl benzoate