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Mass Spectrometry
Mass Spectrometry
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M E IN
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How to predict the
the chemical
structures from
fragment ions ?
2
Signals of Isotopic Elements
Isotope Natural Isotope Relative Isotope Natural
abundance abundance abundance
(%) (%) (%)
12
C 100 13
C 1.11
H
1
100 H
2
0.016
16
O 100 17
O 0.04 O
18
0.20
14
N 100 15
N 0.38
35
Cl 100 37
Cl 32.7
79
Br 100 81
Br 98
3
Unit-Molecular Ion and Isotopic Peaks
% (M+1) 1.1 x no. of C atoms + 0.36 x no. of N atoms
e.g., C7H7NO
Molecular weight = 7x12C + 7x1H + 1x14N = 1x16O = 121
% (M + 1) ≈ 8
% (M + 2) ≈ 0.5
4
Molecular Ion (m/z) = 121
e.g., C7H7NO
Molecular weight = 7x12C + 7x1H + 1x14N = 1x16O = 121
% (M + 1) ≈ 8
% (M + 2) ≈ 0.5 5
Nature of Carbon Signals (M+1)
9
High Resolution Mass Spectrometry
10
11
Mass Fragmentation by EI
13
Very stable ions
14
Mass Fragmentation Process
15
Fragmentation of Hydrocarbon Compounds
e.g., (1) n-pentane
16
e.g., Fragmentation of n-pentane
17
+ -H + -H
CH3CH2CH2 [CH3CHCH2] CH2CH=CH2
m/z = 43 m/z = 42 m/z = 41
18
Fragmentation of Hydrocarbon Compounds
e.g., (2) 2-methylbutane
19
2-methylbutane is more likely than n-pentane to
form more stable the sec-carbocation.
20
Fragmentation of Functional Groups
e.g., n-propylbromide
21
Fragmentation of n-propylbromide
79 81
CH3CH2CH2 Br + CH3CH2CH2 81Br
79
CH3CH2CH2 Br + CH3CH2CH2 Br
79 81
CH3CH2CH2 + Br + Br
m/z= 43
22
e.g., iso-propylchloride
23
e.g., Fragmentation of iso-propylchloride
24
Fragmentation of Ester Compounds
e.g., Ethylbenzoate
25
e.g., Ethylbenzoate
26
Fragmentation of Ether Compounds
R– Ọ+ – R’
27
Fragmentation of Ether Compounds
e.g., sec-butyl isopropyl ether
28
Fragmentation of stable ion peak (Base peak)
29
Homolytical Cleavage at α position
C - C bond is cleaved homolytically at α C
- Stable cation with shared by C and O atom
- Most stable radical (at alkyl group)
30
Please Quiz!
1-methoxybutane, CH3-CH2-CH2-CH2-OCH3 (OR) 2-methoxybutane, CH3-
CH(OCH3)CH2-CH3 (OR) 12-methoxy-2-methylpropane, (CH3)3C-OCH3
QUIZ!
1-methoxybutane, CH3-CH2-CH2-CH2-OCH3 (OR) 22-methoxybutane, CH3-
CH(OCH3)CH2-CH3 (OR) 2-methoxy-2-methylpropane, (CH3)3C-OCH3
QUIZ!
1-methoxybutane, 3CH3-CH2-CH2-CH2-OCH3 (OR) 2-methoxybutane, CH3-
CH(OCH3)CH2-CH3 (OR) 2-methoxy-2-methylpropane, (CH3)3C-OCH3
QUIZ!
1-methoxybutane, CH3-CH2-CH2-CH2-OCH3
Fragmentation patterns
C - O Cleavage
CH3-CH2-CH2-CH2 + O-CH3
m/z= 57
CH3-CH2-CH2-CH2-O-CH3
m/z = 88
CH3-CH2-CH2-CH2-O + CH3
m/z=15
C - C Cleavage
C - O Cleavage
CH3-CH2-CH-CH3 + O - CH3
CH3 m/z= 57
CH3-CH2-CH- O - CH3 CH3
CH3 - CH2 - CH- O + CH3
m/z = 88 m/z=15
C - C Cleavage
CH3 - CH = O - CH3 + CH2- CH3
CH3
m/z = 59
CH3-CH2-CH- O - CH3
CH3 - CH2 - CH = O - CH3 + CH3
m/z = 88 m/z = 73
QUIZ!
2-methoxy-2-methylpropane, (CH3)3C-OCH3
C - O Cleavage CH3
CH3 - C + O - CH3
CH3
CH3
CH3 - C - O - CH3 m/z= 57
CH3
CH3
C - C Cleavage
CH3
C - O Cleavage CH3
CH3 - C + O - CH3
CH3
CH3
CH3 - C - O - CH3 m/z= 57
CH3
CH3
C - C Cleavage
CH3
C - O Cleavage
CH3-CH2-CH-CH3 + O - CH3
CH3 m/z= 57
CH3-CH2-CH- O - CH3 CH3
CH3 - CH2 - CH- O + CH3
m/z = 88 m/z=15
C - C Cleavage
CH3 - CH = O - CH3 + CH2- CH3
CH3
m/z = 59
CH3-CH2-CH- O - CH3
CH3 - CH2 - CH = O - CH3 + CH3
m/z = 88 m/z = 73
QUIZ!
1-methoxybutane, CH3-CH2-CH2-CH2-OCH3
C - O Cleavage
CH3-CH2-CH2-CH2 + O-CH3
m/z= 57
CH3-CH2-CH2-CH2-O-CH3
m/z = 88
CH3-CH2-CH2-CH2-O + CH3
m/z=15
C - C Cleavage
40
α- cleavage of –OH group
41
Important fragmentation occurs in alcohols.
H OH
42
The fragmentations of alkyl halides, ethers, and
alcohols
44
Homolytically cleavage at the C - C bond
adjacent to the C = O bond
45
McLafferty rearrangement
47
e.g., 1,3-diphenylpropanone
48
Fragmentation of Ether or Alcohol Compounds
49
e.g., t-butyl ethyl ether
50
How could their mass spectra distinguish the following compounds?
O
(2) CH3 - C - CH2 - CH2 - CH3
53
54