Chemistry Reference
In-Depth Information
CO
2
CH
3
HN
N
CH
3
+
A
-
A
-
= MnO
4
-
, ClCrO
3
-
Fig.
8
.25
Oxidations with chromates
and permanganates on polypyrazole.
O
H
N
H
ketones
O
n
aldehydes
secondary alcohols
O
Cl
primary allylic and
benzylic alcohols
N
N
Cl
Fig.
8
.26
Oxidations with N-
halogenated nylons.
O
n
NH
2
NH
2
NH
2
NH
2
n
NH
Br
NH
Br
NH
Br
NH
Br
n
benzoin
benzhydrol
benzyl alcohol
1-phenyl ethanol
menthol
borneol
aldehydes or ketones
Fig.
8
.27
Oxidation with poly(
N
-
bromoacrylamide).
The bromination of polyacrylamide with hypo-
bromite [94] similarly gives a poly(
N
-bromoacry-
lamide), which is convenient for obtaining aldehydes
and ketones (Fig. 8.27).
The Swern oxidation of primary and secondary
alcohols with dimethylsulfoxide (DMSO) also is per-
formed with polystyrene-grafted methylsulfoxides
[95] in the presence of 1,3-dicyclohexylcarbodiimide
(DCCI) or trifluoroacetic anhydride as electrophilic
co-reactants (Fig. 8.28a). The grafting of sulfoxide
units is peformed better with the readily available 6-
(methylsulfinyl)hexanoic acid and the oxidation is
run with oxalyl chloride [96]; borneol is oxidised
quantitatively to camphor (Fig. 8.28b). The reduced
6-(methylthio)hexanoic acid can be reoxidised with
sodium metaperiodate. These are good examples of
