Beruflich Dokumente
Kultur Dokumente
Chapter 14
Chapter 14
14-1
An analytical technique for measuring the massto-charge ratio (m/z) of ions in the gas phase.
Mass spectrometry is our most valuable analytical
tool for determining accurate molecular masses.
Also can give information about structure.
Proteins can now be sequenced by MS.
14-2
14-3
14-4
A Mass Spectrometer
Electron Ionization MS
The sample is injected into an ionization chamber,
the sample under high vacuum.
Here the sample is bombarded with a beam of highenergy electrons (70 eV).
H
H C H + eH
+
H
H C H
+ 2eH
Molecular ion
(a radical cation)
Molecular Ion
Molecular Ion
At times, however, we find it useful to depict the
radical cation at a certain position in order to
better understand its reactions.
CH3 CH2 OCH(CH3) 2
.
CH3 CH2 OCH(CH3 ) 2
Mass Spectrum
14-8
MS of dopamine
A partial MS of dopamine showing all peaks with
intensity equal to or greater than 0.5% of base
peak (Fig 14.2).
14-9
MS of Dopamine
The number of peaks in the MS spectrum of
dopamine is given here as a function of detector
sensitivity.
HO
HO
NH2
Peak Intensity
Number
Relative to of Peaks
Base Peak Recorded
>
>
>
>
5%
1%
0.5%
0.05%
8
31
45
120
14-10
A. Resolution
Resolution
C3H6O and C3H8O have nominal masses of 58 and
60, and can be distinguished by low-resolution
MS.
C3H8O and C2H4O2 both have nominal masses of
60.
Distinguish between them by high-resolution MS.
Molecular Nominal Precise
Formula
Mass
Mass
C3 H8 O
60
60.05754
C2 H4 O2
60.02112
60
14-13
Atomic
Mass
Element weight Isotope (amu)
hydrogen 1.0079 1H
1.00783
2
H
2.01410
carbon
12.011 1123C
12.0000
C
13.0034
14.0031
nitrogen 14.007 14N
15
N
15.0001
16
oxygen
15.999 O
15.9949
18
O
17.9992
sulfur
32.066 32S
31.9721
34
S
33.9679
chlorine 35.453 35Cl
34.9689
37
Cl
36.9659
bromine 79.904 79Br
78.9183
81
Br
80.9163
Relative
Abundance
100
0.016 M+1
100
1.11 M+1
100
0.38 M+1
100
0.20 M+2
100
4.40 M+2
100
M+2
32.5
100
M+2
98.0
14-14
Isotopes
Carbon, for example, in nature is 98.90% 12C and
1.10% 13C. 12C = M and 13C = M+1.
There are 1.11 atoms of carbon-13 in nature for
every 100 atoms of carbon-12.
100 = 1.11 atoms 13C per 100 atoms 12C
1.10 x
98.90
14-15
14-16
14-17
D. Fragmentation of M
Fragmentation of M
A-B
Molecular ion
(a radical cation)
A +
B+
Radical
Cation
A+ + B
Cation
Radical
14-20
Fragmentation of M
2
3
< 1 < 1 allylic < 2 allylic < 3 allylic
3 benzylic
1 benzylic 2 benzylic
14-21
14.3 Interpreting MS
A. Alkanes
Alkanes
MS of octane (Fig 14.5):
14-24
Alkanes
MS of 2,2,4-trimethylpentane (Fig 14.6):
14-25
Alkanes
MS of methylcyclopentane (Fig 14.7):
14-26
B. Alkenes
CH2 =CHCH2
+ CH2 CH3
14-27
Cyclohexenes
Cyclohexenes give a 1,3-diene and an alkene,
a process that is the reverse of a Diels-Alder
reaction (Section 24.3).
CH3
CH3
H3C
H3 C
CH2
CH2
Limonene
(m/z 136)
14-28
C. Alkynes
HC C=CH2
14-29
D. Alcohols
R C O H
R"
Molecular ion
(a radical cation)
R +
A radical
R'-C
O H
R'-C=O-H
R"
R"
A resonance-stabilized
oxonium ion
14-30
Alcohols
MS of 1-butanol (Fig 14.10):
14-31
-cleavage
m/z 128
Molecular ion
m/z 114
m/z 43
CH3
+
McLafferty
rearrangement
O
+
m/z 113
H
+
m/z 58
14-32
14-33
F. Carboxylic Acids
-cleavage
OH
O
OH
Molecular ion
m/z 88
m/z 45
Molecular ion
m/z 88
H
O=C-O-H
McLafferty
rearrangement
H
+
O
OH
m/z 60
14-34
Carboxylic Acids
MS of butanoic acid (Fig 14.12):
14-35
Esters
O
OCH3
-cleavage
+
+
m/z 71
O
+ +
Molecular ion
m/z 102
O
OCH3
Molecular ion
m/z 102
OCH3
OCH3
m/z 59
McLafferty
rearrangement
H
+
O
OCH3
m/z 74
14-36
Esters
MS of methyl butanoate (Fig 14.13):
14-37
G. Aromatic Hydrocarbons
Most show an intense molecular ion peak.
Most alkylbenzenes show a fragment ion of m/z 91
(Fig 14.14).
CH3
Toluene radical
cation
H
-H
H
+
H
H
H Tropylium cation
(m/z 91)
H
14-38
H. Amines
(Fig 14.15).
CH3
CH3
-cleavage
+
+
CH3 -CH-CH2 -CH2 -NH2
CH3 -CH-CH2
CH2 =NH2
m/z 30
14-39
Mass Spectrometry
End Chapter 14
14-40