Chem-805

Identification of organic and inorganic

compounds by spectroscopy

Mass Spectrometry
•fragmentation
NMR
Infrared
Index MS
 Fragmentation process
There are 3 type of fragmentations:
1) Cleavage of s bond
+.
---- C – C ---- ---- C + +
. C ----

At heteroatom
+.
---- C – Z ---- ---- C + +
. Z ----

a to heteroatom
+.
---- C - C – Z ---- C=Z + + ---- C .

+.
---- C - C – Z ---- Z+. + ---- C = C
 Fragmentation process
There are 3 type of fragmentations:
2) Cleavage of 2 s bond (rearrangements)
+.
---- HC – C – Z ---- ---- C=C + + HZ

Retro Diels-alder CH2

+ . +. CH2
+ CH2
CH2

McLafferty
H H
Z +. Z +. CH2

CH2
Z R Z R
 Fragmentation process
There are 3 type of fragmentations:
3) Cleavage of Complex rearrangements
 Fragmentation rules in MS
1. Intensity of M.+ is Larger for linear chain than
for branched compound
2. Intensity of M.+ decrease with Increasing M.W.
(fatty acid is an exception)
3. Cleavage is favored at branching
 reflecting the Increased stability of the ion
R
Stability order: CH3+ < R-CH2+ < R
R
CH+ < R C+
R
R’
R CH
R”
Loss of Largest Subst. Is most favored
Illustration of first 3 rules (large MW)
 Branched alkanes
H3C H3C H3C
CH3
H3C
CH3
H3C

MW=170

M.+ is absent with heavy branching

Fragmentation occur at branching: largest fragment loss
 Illustration of first 3 rules
(Linear alkane with Smaller MW)
Molecular ion is stronger than
in previous sample
 Illustration of first 3 rules
(Branched alkane with Smaller MW)
43 Molecular ion smaller than
linear alkane

Cleavage at branching is
favored
Rule 3 Alkanes

Cleavage Favored at branching

Loss of Largest substituent

Favored

Rule1: intensity of M.+

is smaller with branching
 Fragmentation rules in MS
4. Aromatic Rings, Double bond, Cyclic
structures stabilize M.+
5. Double bond favor Allylic Cleavage
 Resonance – Stabilized Cation

-R
.
+
H2C+ CH CH2 R H2C CH CH2

H2C CH CH+2
Aromatic ring has stable M.+
Cycloalkane ring has stable M.+
 Fragmentation rules in MS
6. a) Saturated Rings lose a Alkyl Chain
(case of branching)
R
+. +
-R.

b) Unsaturated Rings  Retro-Diels-Alder

CH2
+ . +. CH2
+ CH2
CH2
Retro Diels-alder
+. +.
 Fragmentation rules in MS
7. Aromatic Compounds Cleave in b
 Resonance Stabilized Tropylium
+
CH2 CH2
R
C
-R. CH
+
+
CH

Tropylium ion +

m/z 91
 Tropylium ion
+

+
 Fragmentation rules in MS
8. C-C Next to Heteroatom cleave leaving
the charge on the Heteroatom
+
x - [RCH2 ] H2C Y R
R CH2 CH2 Y R

+
H2C Y R

R2 R1 R1 R1
- [R2] C C
+
C
larger
+ O
O O
x
 Fragmentation rules in MS
9. Cleavage of small neutral molecules
(CO2, CO, olefins, H2O ….)
Result often from rearrangement

McLafferty
H
H H O

x
- CH2=CH2
x
x

O CH2 O CH2
C
C CH2 C CH2 Y CH2
Y CH2 Y CH2

Ion Stabilized
Y  H, R, OH, NR2
by resonance
 Alkenes
Most intense peaks are often:
m/z 41, 55, 69

Rule 4: Double Bond Stabilize M+

Rule 5: Double Bond favor

Allylic cleavage

-Et
CH2 + CH CH Et +CH
2 CH CH CH2 CH CH +
-29
Me Et Me Et Me Et
M+ = 112 m/z = 83
Alkenes
 Aromatic
compound
Alcohols
 Hydroxy compounds
R1
R1 R1 +
x
- R3  +
R2 C O H C O H C O H
R2 R2
R3 If R1=H m/z 45, 59, 73 …
Loss of largest group If R1=alkyl m/z 59, 73, 87 …

H H CHR
x CHR
CHR OH CHR OH
+ – (H2O)
+ +
CHR CHR CHR CHR
CHR CHR CHR CHR
CHR CHR
CHR CHR M – (H2O)

H
CHR OH
x
- H2O CHR
- CHR=CHR
CHR CHR CHR
CHR M – (H2O) – (C1=C2) Alkene
Phenol
Aromatic Ether Molecular ion is prominent

+
O x
O
R -CO
1) - R C5H5

m/z 93 m/z 65
Cleavage in b of aromatic ring
O O

2) - CH2=CH2 x

H
H
H
Rearrangement m/z 94
O
H
x

H
 B
Aliphatic Ether
Cleavage of C-C next ot Oxygen
Loss of biggest fragment

•+
CH3 —CH2 —O—CH2 —CH2 —CH2 —CH3 CH3 —CH2 —O+ =CH2

m/z 59 CH3 —CH2 —O —CH2+

 m/z 45
Ether B
Rearrangement m/z 73

1- Cleavage of C-C next to Oxygen H— CH3

CH3 —CH2—CH —O —CH2 —CH3 CH =O+ —CH2 Box rearr.

CH3 CH3
M·+ m/z 73 CH =O+ H

2- Cleavage of C-O bond: charge on alkyl CH3

m/z 45
Index MS MS-fragmentation-2