MASS SPECTROMETRY

Organic chemists use mass spectroscopy in two

principle ways:
a)To measure relative molecular mass
(molecular weights) with very high accuracy;
from these can be deduced exact molecular
formulae.
b)To detect within a molecule the places at
which it prefers to fragment; from this can be
deduced the presence of recognizable grouping
within the molecule.
Basic Principles
In the mass spectrometer, organic molecules are
bombarded with electrons and converted to highly
energetic positively charged ions (molecular ions, or
parent ions), which can break up into smaller ions
(fragment ions, or daughter ions); the loss of an
electron from a molecule leads to a radical cation, and
we can represent this process as M M+ . The
molecular ion M + commonly decomposes to a pair of
fragments, which may be either a radical plus an ion,
or a small molecule plus a radical cation. Thus:
+
M+ m1 +
+ m or m + m2
1 2 1
The Mass Spectrum

The mass spectrum is shown as plot of ion

abundance versum m/z ratio. The most
abundant ion formed in the ionization
chamber gives rise to the tallest peak in the
spectrum. This peak is called the base peak.
The relative abundance of all of the other
peaks in the spectrum are reported as
percentages of the abundance of the base
peak.
Isotope abundance

Besides looking for the molecular

ion (M+) peak, one also attempts to
locate the M + 1 and M + 2 peaks.
The relative abundances of these
M + 1 and M + 2 peaks can be used
to determine the molecular formula
of the substance being studied.
Nitrogen Rule
This rule states that if a compound has even
number of nitrogen atoms (or no nitrogen
atoms), its molecular ion will appear at an
even mass value. On the other hand, a
molecule with an odd number of nitrogen
atoms will form a molecular ion with an odd
mass.
Linear alkanes
The most common fragmentation mechanism
encountered with the linear alkanes is simple
cleavage of a C C single bond to produce a
carbocation and an alkyl radical. This can be
represented as
[CH3CH3]+ CH3+ + CH3
The carbocation formed will follow the order
of abundance CH3+ < RCH2+< R2C+ < R3C+.
In general, linear alkanes will show
significant intensity for the
molecular ion peak. As the amount
of branching increases, the intensity
of the molecular ion peak will
decrease, and when the molecule
has significant branching the
molecular ion may be undetectable.
Branched alkanes
The spectrum of a branched alkanes is
significantly different from that of the
corresponding linear alkanes. Fragmentation
at the branching points in the molecule
allows the formation of secondary or tertiary
carbocations, which are much more stable
than primary carbocations. This enhanced
stability results in greater intensity for these
lines in the mass spectrum.
Alkenes

In general, the presence of a double

bond will increase the abundance of the
molecular ion for compounds with low
molecular weights.
Alkenes tend to undergo allylic
cleavage as shown in the following
example.
Alkynes
Aromatic hydrocarbons
- In general, the presence of a benzene ring
increases the abundance of the molecular ion
peaks compared with the saturated analogs.
- In toluene we see the base peak at m/z 91. this is
due to the tropylium ion.
- The tropylium ion is known to be very stable and
is formed in preference to the C6H5CH2+
isomer. The tropylium ion is resonance
stabilized, with seven resonance structures.
Alcohols

- Alcohols do generally show an intense

molecular ion peak except for very low
molecular weight members.
- Ionization generally occurs by removal of an
electron from the oxygen atom, following
the trend n > > . The spectra o alcohols
are characterized by a-cleavage reactions.
- The base peak in 2-butanol is at m/z 45,
which is due to the loss of C2H5 from the
molecular ion.
2-Butanol (C4H10O)
2-Methyl-2-prpanol (C4H10O)
2-Butanol
2-Methyl-2-prpanol
5-Methylhexanal (C7H14O)
Benzaldehyde (C7H6O)
2-Pentanone (C5H10O)
6-Methyl-3-heptanone (C8H16O)
Hexanoic acid (C6H12O2)
4-Methylbenzoic acid (C8H8O2)
- Alcohols do not generally show an intense molecular
ion peak except for very low molecular weight
members (methanol and ethanol).
- Isomeric alcohols can be distinguished by their mass
spectra. The spectra of 2-butanol and 2-methyl-2-
propanol. Both have a line at m/z 59 which is due to
loss of CH3 from the molecular ion.
- While this line is moderately intense in 2-butanol, it is
the base peak in 2-methyl-2-propanol. The base peak in
2-butanol is at m/z 45, which is due to the loss of C2H5
from the molecular. Ion (Stevensons rule). These
fragmentations are shown.
- The spectra of aromatic alcohols
show the most intense molecular ion
lines of all alcohols. In benzyl
alcohol we see the molecular ion
line at m/z 108.
- The spectrum of 2-phenylethanol
shows m/z 120, m/z 91 (base peak)
is the tropylium.
- Finally, considerthe fragmentation reactions for 2-
methylbenzyl alcohol. This is an example of the
ortho effect.
- Aldehydes and ketones usually exhibit a molecular
ion, the -cleavage mechanism is generally more
important for ketones than for aldehydes.
- Aldehydes, loss of hydrogen from the carbonyl
carbon will be important when the acylium ion
(RCO+) can be stabilized (by an aromatic ring, for
example).
- In ketones, -cleavage can produce either of two
acylium ions or two alkyl ions.
- The more abundant acylium ion is formed by loss
of the larger a;kyl radical.
Alkanes
- The most common fragmentation mechanism
encountered with the linear alkanes is simple
cleavage of a CC single bond to produce a
carbocation and an alkyl radical. This can be
represented as the carbocation formed will follow
the order of abundance CH3+ < RCH2+ < R2CH+ <
R3C+. A secondary mechanism involves the loss of
an olefin molecule
+ +
RCH2CH2CH2 RCH2 + CH2= CH2

resulting in a new ion 28 mass unit smaller.

- In general, linear alkanes will show significant
intensity for the molecular ion peak. As the
amount of branching increases, the intensity of the
molecular ion peak will decrease, and when the
molecular has significant branching the molecular
ion may be undetectable.
Branched alkanes

- Fragmentation at the branching

points in the molecule allows the
formation of secondary or tertiary
carbocations, (2-methylpentane)
compared with Example 4
(hexane).
Alkenes
- In general, the presence of a double bond
will increase the abundance of the molecular
ion for compounds with low molecular
weights.
- The normal ionization site in an alkene is the
double bond, as opposed to ionization at any
CC bond in the alkanes.
- Alkenes tend to undergo allylic cleavage as
shown in the following example: In propene
the peak at m/z 27 is consistent with simple
cleavage.
Aromatic Hydrocarbon, Toluene
Alcohols
- Alcohols do not generally show an intense molecular
ion peak except for very low molecular weight
members (methanol and ethanol).
- Isomeric alcohols can be distinguished by their mass
spectra. The spectra of 2-butanol and 2-methyl-2-
propanol. Both have a line at m/z 59 which is due to
loss of CH3 from the molecular ion.
- While this line is moderately intense in 2-butanol, it is
the base peak in 2-methyl-2-propanol. The base peak in
2-butanol is at m/z 45, which is due to the loss of C2H5
from the molecular. Ion (Stevensons rule). These
fragmentations are shown.
2-Methyl-2-prpanol (C4H10O)
2-Butanol
2-Methyl-2-prpanol
Aromatic Alcohols
- The spectra of aromatic alcohols show the most
intense molecular ion lines of all alcohols. In benzyl
alcohol we see the molecular ion line at m/z 108.
Aldehydes and ketones
- Aldehydes and ketones usually exhibit a molecular
ion, the -cleavage mechanism is generally more
important for ketones than for aldehydes.
- Aldehydes, loss of hydrogen from the carbonyl
carbon will be important when the acylium ion
(RCO+) can be stabilized (by an aromatic ring, for
example).
- In ketones, -cleavage can produce either of two
acylium ions or two alkyl ions.
- The more abundant acylium ion is formed by loss
of the larger a;kyl radical.
5-Methylhexanal (C7H14O)
Benzaldehyde (C7H6O)
2-Pentanone (C5H10O)
6-Methyl-3-heptanone (C8H16O)
Esters and Acids
- For the esters, we can write three general
structures. Ordinary -cleavage would be
expected to produce six fragment ions.
- These expected fragment ions would be R+,
RCO+, RCO2+,R'+, R'O+ and R'OCO+.
- The molecular ion in methyl butanoate is very weak
but detectable. The line at m/z 87 corresponds to
C3H7CO2+.
- There is a very intense McLafferty peak at m/z 74,
while m/z 71 corresponds to C3H7CO+. The base peak
at m/z 43 is consistent with loss of CO from m/z 71.
the line at m/z 59 represents CH3OCO+.
- When the aromatic ring is part of the alcohol,
rearrangements can occur to eliminate a ketene
molecule.
- Aryl esters such as phenyl ethanoate can also
rearrange through a six-member ring transition
state, eliminating a ketene molecule and
producing a characteristic peak at m/z 94.
Butanoic acid
Benzoic acid
Hexanoic acid (C6H12O2)
4-Methylbenzoic acid (C8H8O2)
Amines
- Compounds containing a single nitrogen
atom, or an odd number of nitrogen atoms,
will have molecular ions occurring at odd
masses.
- The molecular ions of aliphatic amines are usually
observable, although weak.
- The -cleavage mechanism is very important
in understanding the spectra of aliphatic
amines.
[RCH2NH2] R + CH2=N+H2
+

m/z = 30
-Peaks due to ring formation reaction
producing a series of even-electron
fragments at m/z 58, 72, 86, 100 and
114.
NH2 CH2N+H2
RCH2 R +
(CH2)n (CH2)n
- The spectrum of 2-
butanamine shows a base
peak at m/z 44 (loss of the
ethyl group) and less intense
peak at m/z 58 corresponding
to loss of the methyl group.
2-Butanamine
3,3-Dimethyl-2-butanamine
- Aromatic amines, exhibit a molecular
ion peak that we have observed in other
aromatic compounds. Similar losses of
HCN from the molecular ion and from
(M-H) account for the lines at m/z 66
and 65 in the spectrum of aniline N-
Methylaniline produces a spectrum
which is almost indistinguishable from
that of 2-methylaniline.
Aniline
Amides
- The mass spectra of amides usually show an
observable molecular ion peak. The fragmentation
patterns of amides are quite similar to those of the
corresponding esters and acids.
- The presence of a strong fragment ion peak at m/e
= 44 is usually indicative of a primary amide. This
peak arises from -cleavage of the following sort:
-McLafferty rearrangements become
possible, for primary amides, the
McLafferty rearrangement gives rise to a
fragment ion peak at m/e = 59
-In the spectrum of butananamide
we see a weak molecular ion at
m/z 87.
-We also see lines at m/z 72
(cleavage between the - and -
carbons), m/z 59 (the McLafferty
rearrangement peak), and m/z 44
(loss of the alkyl group).
CH3CH2CH2CONH2
Butnamide
- The spectrum of benzamide
exhibits the molecular ion at m/z
121.
- Other peaks include m/z 105 (loss
of NH2), m/z 77 (loss of CO from
m/z 105) and m/z 51 (loss of
C2H2 from m/z 77).
Nitriles
-Aliphatic nitriles usually undergo
fragmentation so readily that the
molecular ion peak is too weak to be
observed. However, most nitriles form a
peak due to the loss of one hydrogen
atom, forming an ion of the type R
CH=C=N+.
-When the alkyl group attached to the
nitrile functional group is a propyl group
or some longer hydrocarbon group,
the most intense peak in the mass
spectrum results from a McLafferty
rearrangement:
-The strongest peak in the mass spectrum
of an aromatic nitrile is the molecular
ion peak. Loss of cyanide occurs, giving,
in the case of benzonitrile, the C6H5+
ion at m/e = 77. more important
fragmentation involves loss of the
elements of hydrogen cyanide.
- In benzonitrile, this gives rise to a peak
at m/e = 76.
Nitro Compounds
-The molecular ion peak for an aliphatic
nitro compound is seldom observed.
-The mass spectra of nitro compounds may
show a moderate peak at m/e = 30,
corresponding to the NO+ ion, and a
weaker peak at m/e = 46, corresponding to
the NO2+ ion. These peaks may be
observed in the mass. The intense peak at
m/e = 43 is due to the C3H7+ ion.
- Aromatic nitro compounds show an intense
molecular ion peak. The characteristic NO+ (m/e =
30) and NO2+ (m/e = 46) peaks may be found in the
mass spectrum.