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Fragmentation of Amines in EI-MS

Primary:
R1H2C

R3

H2C

R2

R2

R3

+ R1

-cleavage

Secondary:
H2C

H2C

R3

H2C

R2

R2

H2C

R2

[R3 - H]
onium reaction

[R2 - H]

liberation of neutral molecules (alkenes)


from iminium ion involves H-rearrangement
(R must be C2 or longer)

Aliphatic Amines

Examples of Aromatic Amines (Aniline Derivatives)

Fragmentation of Aliphatic Ethers in EI-MS


Primary:

+.
O

Ar

C2H5

Ar

-cleavage

C2H5
CH3

+.
O

Ar

C2H5

CH3

C-O cleavage

Ar

CH3

+.
O

+.

Ar

C2H5

Ar

elimination of neutral fragment


(H-rearrangement)

H
CH3

CH3

Secondary:
R

CH2

R(-H) +

O=CH2
H

onium reaction

Fragmentation of Aryl Ethers in EI-MS


C-O bond cleavage
+.

CH3

- CH3

- CO

H-rearrangement and loss of neutral molecule


+.
O

CH3

+ H2CO

C5H5+

Examples of Aromatic
Ether Cleavages

Fragmentation of Alcohols and Phenols in EI-MS

R2

R1

R2

+.

+.

R3

+ . OH

+ R1

-cleavage

R3

+O

OH

CH2

-C2H5

H-rearrangement

Examples of Aliphatic Alcohols

Examples of Aromatic Alcohols (Phenols)

Fragmentation of Halides in EI-MS

Examples of aromatic halides

Fragmentation of Ketones and Aldehydes in EI-MS


O

-CO

-CO
+CH3

-cleavages to an acylium ion and subsequent loss of CO

H
O

H-rearrangement (McLafferty rearrangement)

Notable features of the McLafferty rearrangement

Related fragmentation reactions occur in other C+X systems.

Secondary hydrogen atoms in the -position are more readily abstracted


than are primary.

Methyl groups do not rearrange when substituted for hydrogen; the


reaction does not occur in compounds that lack -hydrogens.

An analogous process occurs in even-electron ions.

If both alkyl groups can undergo the McLafferty rearrangement, the more
abundant product is due to reaction from the larger group. Also, the
product of two successive alkene eliminations usually appears as an
abundant ion.

Fragmentation of Carboxylic Acids in EI-MS


Molecular ions are of moderate abundance and the most typical fragmentation pathways
are the McLafferty rearrangement as well as C-C-bond cleavage some distance from the
functional group. Aromatic acids, in contrast, yield benzoyl ions by HO. loss.

Fragmentation of Esters in EI-MS


Molecular ions of esters are of moderate abundance and fragment by routes characteristic
of both ethers and ketones. Fragmentation at the ether oxygen gives acylium ions (RCO+)
that subsequently undergo CO loss.

Fragmentation of Amides in EI-MS


The molecular ions are usually of high intensity since the C-N bond resists cleavage
except in N-arylamides, where the cleavage is accompanied by H-rearrangement.
Amides undergo -cleavage, McLafferty rearrangement and other rearrangements
depending on the number and length of the aliphatic rests. Typical fragment ions are OCNH2+, R-C(=O)NH2, and CH3C(=O)NRR.

Fragmentation of Hydrocarbons in EI-MS


Aliphatic hydrocarbons display characteristic ions in CnH2n+1 series separated by
14 Da (successive methylene loss).
Aromatic hydrocarbons show few abundant fragments such as C7H7+ at 91 m/z.

Example of an aliphatic ketone

Example of an aromatic ketone

Example of an aliphatic aldehyde

Example of an aliphatic ester