TABLE 11.1 Common biotransformations and the corresponding elemental composition and
m
/z
changes.
Metabolic reaction
Description
Molecular formulachange
m
/z
change
R–CH
C 2
H 6
! 5
R–H
Debenzylation
–C
H 7
6
90.0468
R
79
Br
!
R
H
Reductive debromination
–Br + H
77.9104
R–CF
! 3
R–H
Trifluoromethyl loss
–CF
+H 3
67.9874
2R
35
Cl
!
2R
H
2
reductive dechlorination
–Cl
+H 2
2
67.9222
R
79
Br
!
R
OH
Oxidative debromination
–Br + OH
61.9156
R–C(CH
) 3
! 3
R–H
Tert
–butyl dealkylation
–C
H 4
8
56.0624
R–ONO
! 2
R–OH
Hydrolysis of nitrate ester
–NO
+H 2
44.9851
R–COOH
!
R–H
Decarboxylation
–CO
2
43.9898
R–CH(CH
) 3
! 2
R–H
Isopropyl dealkylation
–C
H 3
6
42.0468
R–CH
COCH 2
CH 2
CH 2
3
!
R–COOH
Propyl ketone to acid
–C
H 4
+O 8
40.0675
R–C(CH
) 3
! 3
R–OH
Tert
-butyl to alcohol
–C
H 4
+O 8
40.0675
2R–F
!
2R–H
2
reductive defluorination
–F
+H 2
2
35.9811
R
35
Cl
!
R
H
Reductive dechlorination
–Cl + H
33.9611
R–CH
OH 2
!
R–H
Hydroxymethylene loss
–CH
O 2
30.0106
R–NO
! 2
R–NH
2
Nitro reduction
–O
+H 2
2
29.9742
R–CH
OCH 2
CH 2
CH 2
! 3
R–COOH
Propyl ether to acid
–C
H 3
+O 8
28.0675
R–C
H 2
! 5
R–H
Deethylation
–C
H 2
4
28.0312
R–CO–R
0!
R–R
0
Decarboxylation
–CO
27.9949
R–CH
COCH 2
CH 2
! 3
R–COOH
Ethyl ketone to acid
–C
H 3
+O 6
26.0519
R–CH(CH
) 3
! 2
R–OH
Isopropyl to alcohol
–C
H 3
+O 6
26.0519
R–CH
–CH 2
OH 2
!
R–CH = CH
2
Alcohols dehydration
–H
O 2
18.0105
R–CH = N–OH
!
R–CN
Dehydration of oximes
–H
O 2
18.0105
R–F
!
R–H
Reductive defluorination
–F + H
17.9906
R
35
Cl
!
R
OH
Oxidative dechlorination
–Cl + OH
17.9662
RR
0 S=O
!
R–S–R
0
Sulfoxide to thioether
–O
15.9949
R–NHNHR
0 C=S
!
R–NHNHR
0 C = O
Thioureas to ureas
–S + O
15.9772
(continued
)
331