Chem-805

Identification of organic and inorganic compounds by spectroscopy

Mass Spectrometry
Fragmentation-2

NMR Infrared
Index MS MS-fragmentation-1

Aromatic Ketones

Aromatic Ketones 105 77

Aromatic Ketone with Chlorine

Aliphatic Ketones Longer Alkyl chain : McLafferty Rearrangement

H O C R CH R1 CH CH R2
x

R3

-R3-CH=CHR2
R

O C

O C CH R1 R

CH R1

Major peak

If R is a longer chain : the ion can rearrange again

O C H2C H2C CH2 CH H
H H
+

H
O
+

O R1 C H2C

R1
H2C

C CH

CH

R1

Aliphatic Ketones

H O O CH3
+

H CH2

H3C

H3C

CH2

CH3

m/z 58

H O O CH3
+

H CH2

H3C

H3C

CH2

CH3

m/z 58

43

113

Aldehydes
Straight Chain : M 18 (H2O loss) M 28 => Loss of CH2=CH2 M 43 => Loss of CH2=CH-O Long Chain : Hydrocarbon Pattern m/z 29, 43, 57, 71 . Aromatic : Large M .+ Large (M 1)

[-CO ]+

Aromatic Aldehyde
Large (M 1)

Aldehydes

Aldehydes

Long Chain Aldehyde

Acid McLafferty rearrangement (often Base peak) (stronger for a branch)

H O C HO CH R1 CH CH R2
x

R3

O C HO

H O CH HO R1 C CH R1
+

m/z 60, 74, 88

Aso cleavage next to C=O

Charge on Oxygen Charge on Alkyl

29

43

57

71

CH3CH2CH2CH2CH2COH
87 73 59

O
45

57 O H3C CH2 C OH 29 45

O C HO

H CH2 CH2 CH2 HO OH C CH2 m/z 60 + CH2 CH2

Aromatic Acid
M+ is large
(M 17) loss of OH (M 45) loss of COOH With ortho substituant rearrangement
O
x

O C

O C

Z H Y

- ZH
Y
Y

Z OH, OR, NH Y CH2, O, NH Easy loss of Neutral Molecule (H2O, R-OH, NH3)

135
O OH

O CH3

Ortho-Aromatic Acid
- H2O
120
O C OH H O

B
- COOH, H

92

138
M +

para-Aromatic Acid
121
O C OH

- OH

138

M +

HO

Ester

Ester

m/z 74

M-31

McLafferty
H O
x

H O+

OR

OR

CH2

OR

CH2

Also cleavage next to C=O

R

O C

m/z 74
OR

M OR (if R=Me, M-31)

Aliphatic Ester

Aromatic Ester

Aromatic Ether Molecular ion is prominent 1) Cleavage in b of aromatic ring

O
O+
+

- R

- CO

C5H5+ m/z 65

m/z 93 2) Rearrangement
O

O H
+

- CH2=CH2
+

H H

m/z 94

Primary Amines

Secondary Amines

M+. Odd, Cleavage next to heteroatom Fragmentation even

Tertiary Amine

M+. Odd, Cleavage next to heteroatom Fragmentation even

Aromatic Amines

Nitro

Nitrile

Nitrile

McLafferty:

Sulfide

Sulfoxyde

Isotope peaks in Halogen compounds

Chlorine compound

Bromine compound

Iodine compound

Halogen in alkyl chain

Cleavage at C-X produce: . [M-X]+

Weak [M]+ For linear chain

CH3 H Cl CH3

- HCl
H2C CH3

CH3

CH2
m/z 56

Halogen in alkyl chain

Straight chain longer than C6 Have the following mechanism

Weak [M]+ For linear chain

Halogens

Chloro, Bromo alkyl

Dichloromethane

Dibromomethane

Index

MS

MS-fragmentation-1

MS-Organometallic