3-2 MS

Mass Spectrometry: Fragmentation
Remember ! ! ! ! !
e
*
e M M FRAGMENTS
propane
ionization
H H H H H H H H H
Mass Spectrum
H C C C H H C C C H H C C C H 100
29
H H H H H H H H H
80
relative intensity
m/z = 15 m/z = 44 m/z = 29 28
(molecular ion) 60
H H H H H
40
H C C C H C C C 44
43
H H H H H H 20 15
m/z = 43 m/z = 28 0
0 10 20 30 40 50
m/z
Initial Loss of Electron !
non-bonding orbital > π-orbital > σ-orbital
from a non-bonding orbital
-e O
O O
from a π orbital
O -e O O
-e
from a σ orbital
-e
Localization of Charge can Inform Fragmentation
-e
or
A B C
vs +
O O O
REMEMBER: ONLY POSITIVELY CHARGED FRAGMENTS OBSERVED BY MS

Basic Fragmentation Processes
homolytic cleavage
CH3 CH2 O R CH3 + H2C O R
heterolytic cleavage
CH3 CH2 CH2 Br CH3 CH2 CH2 + Br
CH3 CH2 CH2 CH3 + H2C CH2

One Bond Cleavage !
R CH3 R + CH3
O O
R +
R R' R'
X R + X
R R' R'
R, R' = H, alkyl, aryl

X = halogen, OR, SR, NR , etc.
Two Bond Cleavage !
H OH
R C C R' + H OH
R R'
C C + C C
R R
R, R' = H, alkyl, aryl

Rearrangements !
McLafferty
R H R H
X X
+
Y Y
X, Y = C, N, O
retro Diels-Alder
R' R'
+
R R
Mass Spectrometry
Basic Fragmentation Processes!
Electron Count & Fragmentation
even + R
odd # electrons
odd + N
even + N
even # electrons
odd + R rare
NOTE: an even electron species will not fragment to give two radicals!
(Here, N = neutral)
Factors that Impact Fragmentation
• Energetic factors
- relative bond strengths (BDE)
bond: C–Cl C–Br C–I
BDE: 81 68 51 kcal mol-1
- stability of the resulting cations or radical ions
H R R R
H C < H C < R C < R C < < < O
H H H R
least most
stable stable
- stability of the resulting radicals or neutrals

radical stability as above
• Kinetic factors
- availability of a favorable cyclic transition state
Stevenson’s Rule
• The most probable fragmentation is the one that leaves the positive charge on the
fragment with the lowest ionization energy
- fragmentation processes that lead to the formation of more stable
ions are favored over processes that lead to less stable ions
• Cleavages that lead to formation of more stable carbocations are favored

- cation stability is more important than radical stability
• When loss of more than one radical is possible, the largest alkyl radical will be lost
preferentially
+ CH2CH3
+ CH2CH3
Mass Spectrometry
Ease of Fragmentation
less fragmentation aromatics higher relative

abundance of M+
alkenes
unbranched hydrocarbons
ketones
amines
esters
ethers
carboxylic acids
branched hydrocarbons lower relative
more fragmentation alcohols abundance of M+
Alkanes ! ! ! ! !
Straight Chain Alkanes

• Molecular ion peak usually present but weak
• Clusters of fragments appear spaced by 14 amu (corresponds to loss of CH2)
• The largest peak in each cluster corresponds to an alkyl radical cation, CnH2n+1
• A peak for M-CH3 is often weak or absent
• The intensity of lower m/z fragments is greater in large molecules; relative
intensities decrease smoothly up to M-C2H5
Branched Alkanes
• Smaller molecular ion peak; may be absent
• More fragmentation at highly branched positions
Cycloalkanes
• Relatively large molecular ion peak
• Significant peak at M-28 (often the base peak) due to loss of ethylene
• M-15: from rearrangement
Mass Spectrometry: Fragmentation CH3 CH2 CH2 CH2 CH2 CH3
MW = 86
hexane
57
M-29
43
M-43
29
M-57 M (86)
71
M-15
base peak
Mass Spectrometry: Fragmentation CH3 CH2 CH2 CH2 CH2 CH3
MW = 86
hexane
m/z = 71
m/z = 57
C4H9 C2H5 C5H11 CH3
b CH3 CH2 CH2 CH2 CH2 CH3 a
C4H9 C2H5 c b a C5H11 CH3

m/z = 29 m/z = 15
c
C3H7 C3H7
m/z = 43
secondary fragmentation
-H -H
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH CH2
m/z = 42
(etc.)
Mass Spectrometry: Fragmentation CH3
CH3 CH CH2 CH2 CH3
Branched Alkanes
MW = 86
2-methylpentane
43
M-43
71
M-15
larger M-15
57
29
M-29
M-57
M (86)
smaller M+
base peak
CH3 CH CH2 CH2 CH3
Branched Alkanes
MW = 86
2-methylpentane
CH3 CH3
m/z = 15 m/z = 71
C5H11 CH3
C3H7
CH3
m/z = 43 c a
CH3 CH2 CH2 CH2 CH3
d c b a CH3
C3H7
m/z = 15
m/z = 43
b
C4H9 C2H5
m/z = 57 m/z = 29
CH3 CH2 CH CH2 CH3
Branched Alkanes MW = 86
3-methylpentane
57
M-29
29
M-57
43
M-43
71
M (86)
M-15
base peak
CH3 CH2 CH CH2 CH3
Branched Alkanes MW = 86
3-methylpentane
fragmentation pattern
m/z = 29
m/z = 57
m/z = 15 b
m/z = 71
CH3
c
CH3 CH2 CH CH2 CH3
where does m/z = 43 come from?
a
m/z = 15 m/z = 43
m/z = 71 d
cationic
rearrangement
CH3
Mass Spectrometry: Fragmentation CH3 C CH2 CH3
CH3
Branched Alkanes
MW = 86
2,2-dimethylbutane
43 57
M-43 M-29
71
M-15
larger M-15
29
M-57
M+ absent
base peak
Practice Problem
C10H22 (MW = 142)
match to spectrum
C
Cycloalkanes
MW = 84
cyclohexane
even m/z
56
M-28 loss of H2C=CH2
M (84)
41
M-43
strong M+
69
M-15
base peak
Cycloalkanes
ring fragmentation
[C4H8] + H2C=CH2
≡
[C5H9] + CH3
Cycloalkanes
ring fragmentation
[C4H8] + H2C=CH2
≡
[C5H9] + CH3
loss of ethylene
+ H2C CH2
loss of CH3 radical
H H
H H
H + CH3
H
or rearrangement
products
Cycloalkanes
MW = 84
methylcyclopentane
56
M-28
loss of H2C=CH2
41
M-43
69
M-15
loss of side chain
M (84)
Cycloalkanes MW = 112
ethylcyclohexane
loss of H2C=CH2
55
83-28
83
M-29
loss of side chain
M (112)
Alkenes ! ! ! ! !
Acyclic Alkenes
• Relatively strong M+ ion
• Clusters of fragments appear spaced by 14 amu (corresponds to loss of CH2)
• Strong peak from fragmentation to form a resonance stabilized allylic cation
(m/z = 41 in terminal double bonds,)
• Difficult to identify position of alkene since the double bond migrates easily
Cyclic Alkenes
• Molecular ions strong and commonly observed – cleavage of the ring still
gives same mass value
• Double bonds favor allylic cleavage to give the resonance stabilized allylic
carbocation
• Cyclohexenes can undergo retro-Diels-Alder reactions; may be significant
• Side chains are easily fragmented
Alkenes MW = 70
1- pentene
42 loss of
M-28 H2C CH2
55
M-15
41
M-29 M (70)
Alkenes MW = 70
cis-2-pentene
55
M-15
42 loss of
M-28 H2C CH2 M (70)
MW = 70
Alkenes
trans-2-pentene
55
M-15
42 loss of
M-28 H2C CH2 M (70)
Alkenes
fragmentation processes
• McLafferty rearrangement
H H
• allylic α-cleavage
R R +
R' R'
≡
R
R'
CH3 +
M-15
Alkenes
comparison: alkanes vs. alkenes
Octane (75 eV)

M+ 114
m/z 85, 71, 57, 43 (base), 29
Octene (75 eV)

M+ 112 (stronger @ 75eV than octane)
m/z 83, 69, 55, 41 (base), 29
Cyclic Alkenes MW = 82
cyclohexene
loss of
H2C CH2 67
54 M-15
M-28
M (82)
Cyclic Alkenes
limonene MW = 138
68
M-70
M (138)
base peak
Alkynes ! ! ! ! !
Alkynes
• Relatively strong M+ ion
• Strong M-1 peak is observed in terminal alkynes
• Strong peak from fragmentation to give resonance stabilized propargyl
cation (m/z = 39 in terminal alkynes)
H
Alkynes MW = 68
1-pentyne
67
M-1
39
M-29
53
M-15
M (68)
base peak
Alkynes
MW = 68
2-pentyne
M (68)
53
M-15
Aromatic Hydrocarbons
• Strong M+ ion
• Strong M-1  tropylium ion
• Substituted benzenes can undergo McLafferty rearrangement
(substitutent = propyl or larger)
MW = 78
benzene
M (78)
toluene MW = 92
91
M-1
M (92)
m/z = 39 m/z = 65
base peak
formation of tropylium ions
R
CH2 CH2
-R ≡
benzyl tropylium
cation ion
m/z = 91
further fragmentation
H H
+ +
H H
m/z = 65 m/z = 39
CH2CH3
ethylbenzene MW = 106
91
M-15
M (106)
39 65
m/z 65-26 m/z 91-26
MW = 134
butylbenzene
91
H R
M-43
92
M-42
+ McLafferty
H
R
H
m/z = 92 M (134)
CH3
o-xylene MW = 106
91
M-15
CH3
105 M (106)
M-1
tropylium formation
CH3 CH3 CH2

CH3 - CH3 H
m/z = 91
- H
CH2
CH3 ≡
CH3
m/z = 105
xylenes
CH3
CH3
CH3
CH3
Alcohols ! ! ! ! !
Acyclic Alcohols
• Weak M+ peak; may be absent
• Dehydration (M-18), sometimes with loss of CH2=CH2
• α-Cleavage of an alkyl radical (1° alcohols show m/z = 31)
Largest substituent lost first
• Loss of H radical adjacent to OH (M-1) may occur; usually minor
Cyclic Alcohols
• M+ weak
• Dehydration by complex mechanism
• α-cleavage of ring, with subsequent fragmentation to give protonated acrolein
Benzyl Alcohols
• Strong M+ peak
• formation of tropyliol ions; then fragmentation to C6H5+
Alcohols
dehydration processes
H H3C
1,2-elimination H3C O Δ O
+
H H
H e- H3C
H3C
H OH R R'
1,4-elimination + O
H H
R n R' n
δ-H abstraction R H H R H H R
O O + O
H H
rearrangement R H H R
O + + O
H H
Alcohols
α-cleavage
m/z
H O
primary OH + H 31
H
OH + H O
secondary H 45
CH3
H3C O
OH H
tertiary + 59
CH3
OH
Acyclic Alcohols
MW = 88
1-pentanol
m/z = 42
loss of H2O and
H2C=CH2
m/z = 55
H O
H loss of H2O and CH3
H
m/z = 31 70
M-18
M (88)
base peak
Mass Spectrometry: Fragmentation OH
Acyclic Alcohols
MW = 88
2-pentanol
H O
H
CH3
m/z = 45
CH3CH2CH2 O
H
H
m/z = 55
loss of H2O and CH3
73 M (88)
M-15
base peak
Acyclic Alcohols
MW = 88
2-methyl-2-butanol
H3C O
H
CH3
CH3CH2CH2 O
H
m/z = 59
CH3
73
M-15
m/z = 55
Cyclic Alcohols
cyclohexanol MW = 100
H m/z = 57
O
α-cleavage and
H fragmentation
82
M-18
OH
99
M-1
M (100)
OH OH OH OH
H H H
+
m/z = 57
Benzyl Alcohols
MW = 108
benzyl alcohol
M (108)
m/z = 79
fragmentation of
tropyliol ion
OH
m/z = 77
107
M-1
Benzyl Alcohols
fragmentation of tropyliol
OH H H
H
-H -C O - H2
OH
m/z = 107 H m/z = 77

m/z = 79
dehydration
OH O
+
H H H
OH
Benzyl Alcohols CH3
α-methylbenzyl alcohol MW = 122
104
M-18
m/z
= 107
M (122)
m/z = 77
Phenols ! ! ! ! !
Phenols
• Strong M+ peak
• May show strong [M-1]
• Loss of C≡O (M-28) and net loss of formyl radical (M-29)
Thiols
• M+ more intense than that of corresponding alcohol
• Show significant M+2 peak
• Fragmentation patterns similar to alcohols
• May lose hydrogen sulfide (M-34)
Phenols
phenol m/z = 94
M (94)
strong M+
65
M-29 66
loss of HC=O M-28 loss of C O
93
M-1
CH3
Phenols
m/z = 108
o-cresol
M (108)
107
M-1
79
M-29 80
M-28
Phenols
Loss of C≡O and H-C=O radical (net)
H
O O O
H
H
O -C O - H O
≡ M-
H
M-28 M-29
SH
Thiols
2-propanethiol MW = 76
M (76)
strong M+
61
M-15
42
M-34 78
M+2

3-2 MS

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Mass Spectrometry: Fragmentation

non-bonding orbital > π-orbital > σ-orbital

from a non-bonding orbital

REMEMBER: ONLY POSITIVELY CHARGED FRAGMENTS OBSERVED BY MS

CH3 CH2 O R CH3 + H2C O R

CH3 CH2 CH2 Br CH3 CH2 CH2 + Br

CH3 CH2 CH2 CH3 + H2C CH2

R, R' = H, alkyl, aryl

R, R' = H, alkyl, aryl

Electron Count & Fragmentation

Factors that Impact Fragmentation

- stability of the resulting cations or radical ions

- stability of the resulting radicals or neutrals

• Cleavages that lead to formation of more stable carbocations are favored

less fragmentation aromatics higher relative

Straight Chain Alkanes

C4H9 C2H5 C5H11 CH3

b CH3 CH2 CH2 CH2 CH2 CH3 a

C4H9 C2H5 c b a C5H11 CH3

C10H22 (MW = 142)

loss of CH3 radical

comparison: alkanes vs. alkenes

Octane (75 eV)

Octene (75 eV)

formation of tropylium ions

CH3 CH3 CH2

m/z = 107 H m/z = 77

α-methylbenzyl alcohol MW = 122

Loss of C≡O and H-C=O radical (net)

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