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Identification of Organic and Inorganic Compounds by Spectros
Identification of Organic and Inorganic Compounds by Spectros
Identification of Organic and Inorganic Compounds by Spectros
Mass Spectrometry
fragmentation
NMR Infrared
Index MS
Fragmentation process
There are 3 type of fragmentations:
1) Cleavage of s bond
---- C C ---At heteroatom
+. +.
---- C + ---- C +
. C ----
. Z ----
+.
+.
C=Z +
+
+
---- C .
---- C = C
Z+.
Fragmentation process
There are 3 type of fragmentations:
+.
---- C=C + +
CH2
HZ
CH2
+.
+
CH2
CH2
McLafferty
H Z
+.
R
H Z
+.
R
CH2 CH2
Fragmentation process
There are 3 type of fragmentations:
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 Stability order: CH3+ < R-CH2+
R R CH+ < R C+ < R R R
CH
Branched alkanes
H3C H3C H3C H3C H3C CH3 CH3
MW=170
M.+ is absent with heavy branching Fragmentation occur at branching: largest fragment loss
Rule 3
Fragmentation rules in MS
4. Aromatic Rings, Double bond, Cyclic structures stabilize M.+ 5. Double bond favor Allylic Cleavage Resonance Stabilized Cation
.
H2C
CH
CH2
-R
H2C
CH
CH2
H2C
CH
CH+ 2
Fragmentation rules in MS
6. a) Saturated Rings lose a Alkyl Chain (case of branching)
R
+.
-R.
CH2
+.
+
CH2 CH2
CH2
Retro Diels-alder
+.
+.
Fragmentation rules in MS
7. Aromatic Compounds Cleave in b Resonance Stabilized Tropylium
R C CH CH2
CH2
-R.
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
CH2
CH2
- [RCH2
H2C
H2C
R2 C
R1
- [R2]
larger
R1 C
+
R1 C
+
Fragmentation rules in MS
9. Cleavage of small neutral molecules (CO2, CO, olefins, H2O .) Result often from rearrangement
McLafferty
H
x x
O C Y
- CH2=CH2
Y
O C
CH2
Y H, R, OH, NR2
Alkenes
Most intense peaks are often: m/z 41, 55, 69
CH2 + CH Me
CH Et
Et
-Et -29
+CH
CH Me
CH Et
CH2
CH
Me
CH + Et
M+ = 112
m/z = 83
Alkenes
Aromatic compound
Alcohols
Hydroxy compounds
R1
x
R2
C R3
- R3
R1 R2
R1 H R2
OH CHR
(H2O)
CHR CHR
+
CHR
CHR CHR CHR
CHR CHR
CHR
OH CHR
CHR CHR
Phenol
Aromatic Ether
O
x
1)
- R
-CO m/z 93
O
C5H5 m/z 65
2)
H
- CH2=CH2
Rearrangement
m/z 94
O H
x
Aliphatic Ether
Cleavage of C-C next ot Oxygen Loss of biggest fragment
m/z 59
Ether Rearrangement
m/z 45 B m/z 73
Box rearr.
CH =O+ H
CH3
m/z 73
m/z 45
Index
MS
MS-fragmentation-2