3022-beckers-chem-MS Spectroscophy (Teory) PDF

Teory of Mass Spectrometry
Taslim Ersam
The Mass Spectrum and Structural Analysis

I. Fragmentation – Chemistry of Ions
1. One bond σ-cleavages:
a cleavage of C
a. C-C
C
C C C C
+
b. cleavage
g of C-heteroatom
C Z C + Z
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1. One bond σ-cleavages:
c. α-cleavage of C-heteroatom
C C Z C + C Z
C C Z C C + Z
C C Z C + C Z
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IV. The Mass Spectrum and Structural Analysis
D
D. Fragmentation – Chemistry of Ions
2. Two bond σ-cleavages/rearrangements:
a. Elimination of a vicinal H and heteroatom:
C C Z C C + H Z
H
b. Retro-Diels-Alder
Full mechanism
+
Abbreviated:
+
3
15/09/2011
Fragmentation – Chemistry of Ions
2. Two bond σ-cleavages/rearrangements:
c. McLaffertyy Rearrangement
g
Full mechanism
H H
+
Abbreviated:
H H
+
3. Other types of fragmentation are less common, but in specific cases are
dominant processes
These include: fragmentations from rearrangement,
rearrangement migrations
migrations, and
fragmentation of fragments
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IV
4. When deducing any fragmentation scheme:
– The even-odd electron rule applies: “thermodynamics dictates that
even electron ions cannot cleave to a pair of odd electron
fragments”
– Mass losses of 14 are rare
– The order of carbocation/radical stability is

benzyl/3° > allyl/2° > 1° > methyl > H
* the loss of the longest carbon chain is preferred
– Fragment
g ion stabilityy is more important
p than fragment
g radical
stability
– Fragmentation mechanisms should be in accord with the even-odd

even odd
electron rule
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II. Fragmentation Patterns of Groups
A id
Aside: S
Some nomenclature
l t – rather
th than
th explicitly
li itl writing
iti outt single
i l bond
b d
cleavages each time:
CH2 + H2C
CH3
Fragment Neutral fragment
obs by MS
obs. inferred by its loss
– not observed
Is written as:
57
15/09/2011 6
III. Fragmentation Patterns of Groups
1. Alkanes
a) Very predictable – apply the lessons of the stability of carbocations
(or radicals) to predict or explain the observation of the fragments
b) Method of fragmentation is single bond cleavage in most cases
c) This is governed by Stevenson

Stevenson’ss Rule – the fragment with the
lowest ionization energy will take on the + charge – the other
fragment will still have an unpaired electron
E l iso
Example: i -butane
b t
+ CH3
+ CH3
15/09/2011 7
4. Fragmentation Patterns of Groups
1. Alkanes
g
Fragment Ions : n-alkanes
• For straight chain alkanes, a M+ is often observed
• Ions observed: clusters of peaks CnH2n+1 apart from the loss of

–CH3, -C2H5, -C3H7, etc.
• Fragments lost: ·CH3, ·C2H5, ·C3H7, etc.
• In longer
g chains – p
peaks at 43 and 57 are the most common
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1 Alkanes
1.
Example MS: n-alkanes – n-heptane
43
57
M+
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1. Alkanes
Fragment Ions : branched alkanes
• Where the possibility of forming 2°
2 and 3
3° carbocations is high,
the molecule is susceptible to fragmentation
• Whereas in straight chain alkanes

alkanes, a 1
1° carbocation is always
formed, its appearance is of lowered intensity with branched
structures
• M+ peaks become weak to non-existent as the size and

branching of the molecule increase
• Peaks at 43 and 57 are the most common as these are the iso-
propyl and tert-butyl cations
15/09/2011 10
1 Alkanes
1. Alk
Example MS: branched alkanes – 2,2-dimethylhexane
57 M+ 114
15/09/2011 11
Mass Spectrometry

5 Fragmentation Patterns of Groups
5.
1. Alkanes
Fragment Ions : cycloalkanes
• Molecular ions strong and commonly observed – cleavage of
the ring still gives same mass value
• A two-bond cleavage to form ethene (C2H4) is common – loss

ofH28
2C CH2
HC
C C R
+ H2C CH2
H H
C
H2
n
• Side chains are easilyy fragmented

g
15/09/2011 Prof Dr. Taslim Ersam 12

Mass Spectrometry

1 Alkanes
1.
Example MS: cycloalkanes – cyclohexane
M - 28 = 56
M+ 84

Mass Spectrometry
IV
E. Fragmentation Patterns of Groups
1. Alkanes
Example MS: cycloalkanes – trans-p-menthane
97
M+ 140

Mass Spectrometry
IV
2. Alkenes
a) The π-bond of an alkene can absorb substantial energy – molecular
ions are commonly observed
b) After ionization, double bonds can migrate readily – determination

of isomers is often not possible
c) Ions observed: clusters of peaks CnH2n-1 apart from -C3H5, -C4H7, -

C5H9 etc. at 41, 55, 69, etc.
d) Terminal alkenes readily form the allyl carbocation, m/z 41
H2
R C C CH2
H R + H2C C CH2
H

IV
2. Alkenes
Example MS: alkenes – cis- 2-pentene
55
M+ 70
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IV
E. Fragmentation Patterns of Groups Take home assignment:
2. Alkenes What is M-42 and m/z 42?
Example MS: alkenes –1-hexene
56
41
M+ 84
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Mass Spectrometry
IV
E. Fragmentation Patterns of Groups Take home assignment 2:
2. Alkenes What is m/z 42?
Example MS: alkenes –1-pentene
M+ 70
0

Mass Spectrometry
IV
Comparison: Alkanes vs. alkenes
Octane (75 eV)

M+ 114
m/z
/ 85,, 71,, 57,, 43 (base),
( ), 29
( eV))
Octene (75
M 112 (stronger @ 75eV than octane)
+
m/z 83, 69, 55, 41, 29

IV
2. Alkenes
Fragment Ions : cycloalkenes
• Molecular ions strong and commonly observed – cleavage of
g still gives
the ring g same mass value
• Retro-Diels-Alder is significant
observed loss of 28
• Side chains are easily fragmented
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IV
2. Alkenes
Example MS: cycloalkenes –1-methyl-1-cyclohexene
81
68
M+ 96
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3. Alkynes – Fragment Ions
a) The π-bond of an alkyne can also absorb substantial energy –
molecular ions are commonly observed
b) For terminal alkynes, the loss of terminal hydrogen is observed (M-

1) – this may occur at such intensity to be the base peak or
eliminate
e ate tthe
eppresence
ese ce o
of M+
c) Terminal alkynes form the propargyl cation, m/z 39 (lower intensity

than the allyl cation)
H2
R C C CH R H2C C CH
+
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Mass Spectrometry
IV
3. Alkynes
Example MS: alkynes – 1-pentyne
H 67
39
M+ 68

Mass Spectrometry
IV
3. Alkynes
Example MS: alkynes – 2-pentyne
53
M+ 68

Mass Spectrometry
IV
4. Aromatic Hydrocarbons – Fragment Ions
a) Very intense molecular ion peaks and little fragmentation of the
ring system are observed
75 eV e-
b) Where alkyl groups are attached to the ring,

ring a favorable mode of
cleavage is to lose a H-radical to form the C7H7+ ion (m/z 91)
c) This ion is believed to be the tropylium ion; formed from

rearrangement of the benzyl cation
CH3 CH2

Mass Spectrometry
IV
4. Aromatic Hydrocarbons – Fragment Ions
d) If a chain from the aromatic ring is sufficiently long, a McLafferty
rearrangement is possible
e) Substitution patterns for aromatic rings are able to be determined

by MS – with the exception of groups that have other ion chemistry

Mass Spectrometry
IV
4. Aromatic Hydrocarbons
Example MS: aromatic hydrocarbons – p-xylene
m/z
/ 91
CH3 CH3
H3C
M+ 106

Mass Spectrometry
IV
4. Aromatic Hydrocarbons
Example MS: aromatic hydrocarbons – n -butylbenzene
H H
+
92
M+ 134
91

Mass Spectrometry
IV
5. Alcohols– Fragment Ions
a) Additional modes of fragmentation will cause lower M+ than for the
corresponding alkanes
1° and 2° alcohols have a low M+, 3° mayy be absent
b) The largest alkyl group is usually lost; the mode of cleavage

typically is similar for all alcohols:
m/z
primary OH O H 31
+ H2C
secondaryy OH +
O H 45
tertiary
OH + O H 59

Mass Spectrometry
IV
c) Dehydration (M - 18) is a common mode of fragmentation –
importance increases with alkyl chain length (>4 carbons)
• ,
1,2-elimination – occurs from hot surface of ionization chamber
• 1,4-elimination – occurs from ionization
• both modes give M - 18, with the appearance and possible

subsequent fragmentation of the remaining alkene
d) For longer chain alcohols, a McLafferty type rearrangement can

produce water and ethylene (M - 18, M - 28)
H H
R H H R O
O
+

Mass Spectrometry
IV
e) Loss of H is not favored for alkanols (M – 1)
f) Cyclic alcohols fragment by similar pathways

• α-cleavage
H OH H OH H OH H OH
H H +
m/z 57
• dehydration
H OH
, + H2O
M - 18
Mass Spectrometry
IV
5. Alcohols
Example MS: alcohols – n -pentanol
H H
OH OH
+
42
-H2O
OH
70
31
M+ 88

Mass Spectrometry
IV
5. Alcohols
Example MS: alcohols – 2-pentanol
OH
45
M+ 88

Mass Spectrometry
IV
5. Alcohols
Example MS: alcohols – 2-methyl-2-pentanol
OH
59
OH
87
M+ 102

Mass Spectrometry
IV
5. Alcohols
Example MS: alcohols – cyclopentanol
H OH H OH
57
M+ 86

Mass Spectrometry
IV
6. Phenols– Fragment Ions
a) Do not fully combine observations for aromatic + alcohol; treat as a
unique group
b) For example, loss of H· is observed (M – 1) – charge can be

delocalized by ring – most important for rings with EDGs
c) Loss of CO (extrusion) is commonly observed (M – 28); Net loss of

the formyl radical (HCO·, M – 29) is also observed from this process
H
O O O
H
H
O
-CO
CO -H
H
C

Mass Spectrometry
IV
5. Example MS: phenols – phenol
-CO 66
-HCO 65
M+ 94

Mass Spectrometry
IV
An interesting combination of functionalities: benzyl alcohols
Upon ring expansion to tropylium ions, they become phenols!
M+ 108
H H
OH
“tropyliol” - CO
+
79 M – 1, 107
“tropyliol”
HO
+ H2
77

Mass Spectrometry
IV
7. Ethers– Fragment Ions
a) Slightly more intense M+ than for the corresponding alcohols or
alkanes
b) The largest alkyl group is usually lost to α-cleavage; the mode of

cleavage typically is similar to alcohols:
H2
R C O R R + H2C O R
c) Cleavage of the C-O bond to give carbocations is observed where

favorable
H
R C O R R CH + O R
R R

Mass Spectrometry
IV
7. Ethers– Fragment Ions
d) Rearrangement can occur of the following type, if α-carbon is
branched:
H
H
R C O C CH2 R C O +
H H R
R H
e) Aromatic ethers, similar to phenols can generate the C6H5O+ ion by

loss of the alkyl group rather than H; this can expel C≡O as in the
phenolic
h li degradation
d d ti
R
O O
R + C O + C5H5+

Mass Spectrometry
IV
7. Example MS: ethers – butyl methyl ether
45
M+ 88

Mass Spectrometry
IV
E. Fragmentation Patterns of Groups Take home – what is m/z 78?
7. Example MS: ethers – anisole
O
M+ 108
77
M-28 (-CH3, -CO)

65
O
93

Mass Spectrometry
IV
8. Aldehydes - Fragment Ions
a) Weak M+ for aliphatic, strong M+ for aromatic aldehydes
b) α cleavage is characteristic and often diagnostic for aldehydes –

α-cleavage
can occur on either side of the carbonyl
O
R H
R C O + H M 1 peak
M-1
O
R + H C O m/z 29
R H
c) β-cleavage
β cleavage is an additional mode of fragmentation
O
O
m/z R+
R
H
R + M - 41
H can be R-subs.
Mass Spectrometry
IV
8. Aldehydes - Fragment Ions
d) McLafferty rearrangement observed if γ-Hs present
R H R H
O O m/z 44
+
H
e)) Aromatic
A i aldehydes
ld h d – a-cleavages
l are more favorable,
f bl both
b h to lose
l
H· (M - O1) and HCO· (M – 29)
H C O + H
O m/z R+
O
H +
Remember:
H aromatic ring can
be subs.

Mass Spectrometry
IV
8. Example MS: aldehydes (aliphatic) – pentanal
m/z 44
H H
O O
O +
C H
H
29
M-1
85
M+ 86

Mass Spectrometry
IV
8. Example MS: aldehydes (aromatic) – m-tolualdehyde
O M-1
M 1
119 M+ 120
H
91

Mass Spectrometry
IV
9. Ketones - Fragment Ions
a) Strong M+ for aliphatic and aromatic ketones
b) α cleavage can occur on either side of the carbonyl – the larger

α-cleavage
alkyl group is lost more often
O M – 15, 29, 43…

R R1
R C O + R1 m/z 43, 58, 72, etc.
R1 is larger than R
c) β-cleavage is not as important of a fragmentation mode for

p
ketones compared to aldehydes
y – but sometimes observed
O
R O
R +
R1
R1

Mass Spectrometry
IV
d) McLafferty rearrangement observed if γ-H’s present – if both alkyl
chains are sufficiently long – both can be observed
R H R H
O O
+
R1 R1
e) Aromatic ketones – α-cleavages are favorable primarily to lose R·

(M – 15, 29…) to form the C6H5CO+ ion, which can lose C≡O
O
R C O + R
m/z 105
Remember:
R b
aromatic ring can
be subs.
+ C O
m/z 77
Mass Spectrometry
IV
f) cyclic ketones degrade in a similar fashion to cycloalkanes and
cycloalkanols:
O O O O
H H +
m/z 55
O O O
m/z 70
- CO
m/z 42
Mass Spectrometry
IV
9. Example MS: ketones (aliphatic) – 2-pentanone
43
H H
O O +
58
M+ 86
M 15
M-15

Mass Spectrometry
IV
9. Example MS: ketones (aromatic) – propiophenone
C O
m/z 105
m/z 77
M+ 134

Mass Spectrometry
IV
10. Esters - Fragment Ions
a) M+ weak in most cases, aromatic esters give a stronger peak
b) Most important α α-cleavage

cleavage reactions involve loss of the alkoxy
alkoxy-
radical to leave the acylium ion
O
R1 R C O + OR1
R O
c) The other α-cleavage (most common with methyl esters, m/z 59)
involves the loss of the alkyl group
O O
R1 R + C O R1
R O

Mass Spectrometry
IV
d) McLafferty occurs with sufficiently long esters
H H
O O
+
R1 R1
O O
e)) Ethyl
E h l and
d longer
l (alkoxy
( lk chain)
h i ) esters can undergo
d the
h McLafferty
M L ff
rearrangement
H H
O O
+
R O R O

Mass Spectrometry
IV
f) The most common fragmentation route is to lose the alkyl group by
α-cleavage, to form the C6H5CO+ ion (m/z 105)
O O
R C
O + R
Can lose CO to
give m/z 77

Mass Spectrometry
IV
g) One interesting fragmentation is shared by both benzyloxy esters
and aromatic esters that have an ortho-alkyl group
O
O O
benzyloxy ester OH
+ C
H CH2
ketene
fragmentation
O
O
R C
ortho-alkylbenzoate ester O
+ HO
R
H
C CH2
H2

Mass Spectrometry
IV
10. Example MS: esters (aliphatic) – ethyl butyrate
O
O
O
O
71
29
both McLafferty
O (take home exercise)
O
m/z 88
43
M+ 116

Mass Spectrometry
IV
10. Example MS: esters (aliphatic) – ethyl butyrate
O
O
O
O
71
29
both McLafferty
O (take home exercise)
O
m/z 88
43
M+ 116

Mass Spectrometry
IV
10. Example MS: esters (benzoic) – methyl ortho-toluate
119
O O
91 C
O O
CH2
O
m/z 118 M+ 150

Mass Spectrometry
IV
11. Carboxylic Acids - Fragment Ions
a) As with esters, M+ weak in most cases, aromatic acids give a
stronger peak
b) Most important α-cleavage reactions involve loss of the alkoxy-

radical to leave the acylium ion
O
H R C O + OH
R O
c) The other α-cleavage (less common) involves the loss of the alkyl
radical. Although less common, the m/z 45 peak is somewhat
diagnostic for acids.
O O
H R + C O H
R O

Mass Spectrometry
IV
d) McLafferty occurs with sufficiently long acids
H H
O O
+
H H
O O
m/z 60
e) aromatic acids degrade by a process similar to esters, loss of the

HO· gives the acylium ion which can lose C≡O:
O O
H C
O + H
+ further loss of
CO to
t m/z/ 77

Mass Spectrometry
IV
f) As with esters, those benzoic acids with an ortho-alkyl group will
lose water to give a ketene radical cation
O
O
H C
O
ortho-alkylbenzoic
alkylbenzoic acid + HO
H
H
C CH2
H2

Mass Spectrometry
IV
11. Example MS: carboxylic acids (aliphatic) – pentanoic acid
H
O OH
OH OH
m/z 60
M+ 102

Mass Spectrometry
IV
11. Example MS: carboxylic acids (aromatic) – p-toluic acid
OH
O M+ 136
OH
119
91

Mass Spectrometry
IV
Summary – Carbonyl Compounds
For carbonyl compounds – there are 4 common modes of fragmentation:
¾ A1 & A2 -- two α-cleavages
O
R G O C G2 + R
O
R C O + G
R G
¾ B -- β
β-cleavage
g
O O
R R +
G G
¾ C – McLafferty Rearrangement
R H R H
O O
+
G G

Mass Spectrometry
IV
Summary – Carbonyl Compounds
In tabular format:
m/z of ion observed
Aldehydes Ketones Esters Acids Amides
F
Fragmentation
t ti P th
Path G=H G=R G = OR’ G = OH G = NH2
A1 -R 29 43b 59b 45 44d
α-cleavage
A2 -G 43b 43b 43b 43b 43b
α-cleavage
B -G 43a 57b 73b 59a 58a
β-cleavage
C 44a 58b,c 74b,c 60a 59a
McLafferty
b = base, add other mass attached to this chain
a = base, if α-carbon branched, add appropriate mass
c = sufficiently
ffi i l long
l structures can undergo
d on either
i h side
id off C=O
C O
d = if N-substituted, add appropriate mass
Mass Spectrometry
IV
12. Amines - Fragment Ions
a) Follow nitrogen rule – odd M+, odd # of nitrogens; nonetheless, M+
weak in aliphatic amines
b) α-cleavage reactions are the most important fragmentations for

amines; for 1° n-aliphatic amines m/z 30 is diagnostic
C C
R N R + N
c) McLafferty not often observed with amines, even with sufficiently

long alkyl chains
d) Loss of ammonia (M – 17) is not typically observed

Mass Spectrometry
IV
12. Amines - Fragment Ions
e) Mass spectra of cyclic amines is complex and varies with ring size
f) Aromatic amines have intense M+
g) Loss of a hydrogen atom, followed by the expulsion of HCN is

typical
typ ca for
o aanilines
es
NH2 NH H H H
+ H + HCN + H
h) Pyridines have similar stability (strong M+, simple MS) to aromatics,

expulsion of HCN is similar to anilines

Mass Spectrometry
IV
12. Example MS: amines, 1° – pentylamine
NH2
30
M+ 87

Mass Spectrometry
IV
12. Example MS: amines, 2° – dipropylamine
H N
H
N
72
H
M+ 101

Mass Spectrometry
IV
12. Example MS: amines, 3° – tripropylamine
114
M+ 143

Mass Spectrometry
IV
13. Amides - Fragment Ions
a) Follow nitrogen rule – odd M+, odd # of nitrogens; observable M+
b) α cleavage reactions afford a specific fragment of m/z 44 for

α-cleavage
primary amides
O
C R +
R NH2 O C NH2
m/z 44
c) McLafferty observed where γ-hydrogens are present
H H
O O
+
NH2 NH2

Mass Spectrometry
IV
13. Example MS: amides – butyramide
O
C
NH2
44 H
O
NH2
59
M+ 87

Mass Spectrometry
IV
13. Example MS: amides (aromatic) – benzamide
O NH2
C
77
M+ 121
O NH2
C
105

Mass Spectrometry
IV
14. Nitriles - Fragment Ions
a) Follow nitrogen rule – odd M+, odd # of nitrogens; weak M+
b) Principle degradation is the loss of an H atom (M – 1) from α

H-atom α-
carbon:
H2
R C C N H + R C C N
H
c) Loss of HCN observed (M – 27)
d) McLafferty observed where γ-hydrogens are present
H H
N N
C +
C
H2C
m/z 41
e)) Aromatic nitriles
l give a strong M+ as the
h strongest peak,
k loss
l off
HCN is common (m/z 76) as opposed to loss of CN (m/z 77)
Mass Spectrometry
IV
14. Example MS: nitriles – propionitrile
M-1 54
- HC≡N
M+ 55

Mass Spectrometry
IV
14. Example MS: nitriles – valeronitrile (pentanenitrile)
N
C
H
N 43
C
H2C
m/z 41 N
54 C
M+ 83

Mass Spectrometry
IV
15. Nitro - Fragment Ions
a) Follow nitrogen rule – odd M+, odd # of nitrogens; M+ almost never
observed, unless aromatic
b) Principle degradation is loss of NO+ (m/z 30) and NO2+ (m/z 46)
O O
R N R + N
O O
m/z 46
O O
R N R N R O N O R O + N O
O O m/z 30

Mass Spectrometry
IV
15. Nitro - Fragment Ions
c) Aromatic nitro groups show these peaks as well as the fragments of
the loss of all or parts of the nitro group
NO2 O
+ NO + CO
m/z 93 m/z 65
NO2
+ NO2 C4H3 + HC CH
m/z 77 m/z 51

Mass Spectrometry
IV
15. Example MS: nitro – 1-nitropropane
NO2
43
NO+ 30 NO2+ 46 M+ 89

Mass Spectrometry
IV
15. Example MS: nitro (aromatic) – p-nitrotoluene
NO2
91 M+ 137
C5H5+
O
m/z 107

Mass Spectrometry
IV
16. Halogens - Fragment Ions
a) Halogenated compounds often give good M+
b) Fluoro and iodo

Fluoro- iodo-compounds
compounds do not have appreciable contribution
from isotopes
c) Chloro- and bromo-compounds

Chloro bromo compounds are unique in that they will show
strong M+2 peaks for the contribution of higher isotopes
d) For chlorinated compounds, the ratio of M+ to M+2 is about 3:1
e)) For brominated compounds,

p , the ratio of M+ to M+2 is 1:1
f) An appreciable M+4, 6, … peak is indicative of a combination of

these two halogens – use appropriate guide to discern number of
each
Mass Spectrometry
IV
g) Principle fragmentation mode is to lose halogen atom, leaving a
carbocation – the intensity of the peak will increase with cation
stability
R X R + X
h) Leaving group ability contributes to the loss of halogen most

strongly for -I and -Br less so for -Cl, and least for –F
i) LLoss off HX is
i the
th second
d mostt common moded off fragmentation
f t ti –
here the conjugate basicity of the halogen contributes (HF > HCl >
HBr > HI)
H H
R C C X R C CH2 + H X
H H H

Mass Spectrometry
IV
j) Less often, α-cleavage will occur:
H
R C X R + H2C X
H
k) For longer chain halides, the expulsion of a >δ carbon chain as the
radical is observed
R
X X
+ R
l) Aromatic halides give stronger M+, and typically lose the halogen
atom to form C6H5+

Mass Spectrometry
IV
16. Example MS: chlorine – 1-chloropropane
Cl
43
M+2
H2C Cl
m/z 49, 51 M+ 78

Mass Spectrometry
IV
16. Example MS: chlorine – p-chlorotoluene
Cl
91
M+ 126
6
M 2
M+2

Mass Spectrometry
IV
16. Example MS: bromine – 1-bromobutane
B
Br
57
M+2
M+ 136
H2C Br

Mass Spectrometry
IV
16. Example MS: bromine – p-bromotoluene
Br
91
M+2
M+ 170

Mass Spectrometry
IV
16. Example MS: multiple bromines – 3,4-dibromotoluene
B
Br M+2
Br Br
Br 169,
90 171 M+4
M+ 248

Mass Spectrometry
IV
16. Example MS: iodine – iodobenzene
M+ 204
77

Mass Spectrometry
IV
F. Approach to analyzing a mass spectrum
1. As with IR, get a general feel for the spectrum before you analyze
anything – is it simple, complex, groups of peaks, etc.
2. q
Squeeze everything
y g you
y can out of the M+ p peak that you
y can (once
( you
y
have confirmed it is the M+)
– Strong or Weak?
– Isotopes? M+1? M+2 M+2, 4,4 …
– Apply the Nitrogen rule
– Apply the Rule of Thirteen to generate possible formulas (you can
quickly
i kl dispose
di off possibilities
ibiliti based
b d on the
th absence
b off isotopic
i t i
peaks or the inference of the nitrogen rule)
– Use the HDI from the Rule of Thirteen to further reduce the
possibilities
ibiliti
– Is there an M-1 peak?

Mass Spectrometry
IV
F. Approach to analyzing a mass spectrum
3. Squeeze everything you can out of the base peak
– What ions could give this peak? (m/z 43 doesn’t help much)
– What was lost from M+ to give this peak?
initially only think of the most
– When considering the base peak initially,
common cleavages for each group
4
4. Look for the loss of small neutral molecules from M+
– H2C=CH2, HC≡CH, H2O, HOR, HCN, HX
5
5. Now consider
N id the
th possible
ibl diagnostic
di ti peaks
k on the
th spectrum
t (e.g.:
( 29,
29
30, 31, 45, 59, 77, 91, 105 etc.)
6. Lastly, once you have a hypothetical molecule that explains the data,
see if you can verify it by use of other less intense peaks on the
spectrum – not 100% necessary (or accurate) but if this step works it
can add
dd to the
h confidence
fd level
l l
Mass Spectrometry
End of material
Schedule:
Workshops: Friday Oct. 28th, Monday Oct. 31st, Wednesday Nov. 2nd (if needed).
Exam: Monday, November 7th (5 PM?); take home portion given out Friday,
November 4th, due Wednesday, November 9th.
NMR material will begin Friday November 4th.
We will have lecture on Monday, November 7th (NMR)!
What’ss left: Two NMR exams

What
– one in class, one take-home + Final are left 100, 100 and 125 pts.

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Teory of Mass Spectrometry

The Mass Spectrum and Structural Analysis

– Mass losses of 14 are rare

– The order of carbocation/radical stability is

– Fragmentation mechanisms should be in accord with the even-odd

b) Method of fragmentation is single bond cleavage in most cases

c) This is governed by Stevenson

• Ions observed: clusters of peaks CnH2n+1 apart from the loss of

• Fragments lost: ·CH3, ·C2H5, ·C3H7, etc.

• Whereas in straight chain alkanes

• M+ peaks become weak to non-existent as the size and

The Mass Spectrum and Structural Analysis

• A two-bond cleavage to form ethene (C2H4) is common – loss

• Side chains are easilyy fragmented

15/09/2011 Prof Dr. Taslim Ersam 12

The Mass Spectrum and Structural Analysis

15/09/2011 Prof Dr. Taslim Ersam 13

15/09/2011 Prof Dr. Taslim Ersam 14

b) After ionization, double bonds can migrate readily – determination

c) Ions observed: clusters of peaks CnH2n-1 apart from -C3H5, -C4H7, -

d) Terminal alkenes readily form the allyl carbocation, m/z 41

15/09/2011 Prof Dr. Taslim Ersam 15

15/09/2011 Prof Dr. Taslim Ersam 18

Octane (75 eV)

m/z 83, 69, 55, 41, 29

15/09/2011 Prof Dr. Taslim Ersam 19

• Side chains are easily fragmented

b) For terminal alkynes, the loss of terminal hydrogen is observed (M-

c) Terminal alkynes form the propargyl cation, m/z 39 (lower intensity

15/09/2011 Prof Dr. Taslim Ersam 23

15/09/2011 Prof Dr. Taslim Ersam 24

b) Where alkyl groups are attached to the ring,

c) This ion is believed to be the tropylium ion; formed from

15/09/2011 Prof Dr. Taslim Ersam 25

e) Substitution patterns for aromatic rings are able to be determined

15/09/2011 Prof Dr. Taslim Ersam 26

15/09/2011 Prof Dr. Taslim Ersam 27

15/09/2011 Prof Dr. Taslim Ersam 28

b) The largest alkyl group is usually lost; the mode of cleavage

15/09/2011 Prof Dr. Taslim Ersam 29

• 1,4-elimination – occurs from ionization

• both modes give M - 18, with the appearance and possible

d) For longer chain alcohols, a McLafferty type rearrangement can

15/09/2011 Prof Dr. Taslim Ersam 30

f) Cyclic alcohols fragment by similar pathways

15/09/2011 Prof Dr. Taslim Ersam 32

15/09/2011 Prof Dr. Taslim Ersam 33

15/09/2011 Prof Dr. Taslim Ersam 34

15/09/2011 Prof Dr. Taslim Ersam 35

b) For example, loss of H· is observed (M – 1) – charge can be

c) Loss of CO (extrusion) is commonly observed (M – 28); Net loss of

15/09/2011 Prof Dr. Taslim Ersam 36

15/09/2011 Prof Dr. Taslim Ersam 37

15/09/2011 Prof Dr. Taslim Ersam 38

b) The largest alkyl group is usually lost to α-cleavage; the mode of

c) Cleavage of the C-O bond to give carbocations is observed where

15/09/2011 Prof Dr. Taslim Ersam 39

e) Aromatic ethers, similar to phenols can generate the C6H5O+ ion by

15/09/2011 Prof Dr. Taslim Ersam 40

15/09/2011 Prof Dr. Taslim Ersam 41

M-28 (-CH3, -CO)

15/09/2011 Prof Dr. Taslim Ersam 42

b) α cleavage is characteristic and often diagnostic for aldehydes –