2.
27 OXIDATION WITH Se0 2
ic ac id or ac et ic an hy dr id e at I 0O - l 4Q°C,
a. SeO2 in acet
is es ac tiv e m et hy l an d ac tiv e m et hy le ne gr ou p to
oxid
y, e.g.,
aldehyde and ketone, respectivel
0 0
Se 02/MeCOOH )
•
I.
oup
() Active methylene (C Hi ) gr
0
A / Ph Se 02 /MeCOOH Ph
.. Ph,,,,,,..,....II._,,
> Ph
.-
u. .· ..
0 (Active (-C H2 ) group) 0
Se 02/MeCOOH
. ·> O H C -C H O
Active methyl group
SeOilMeCOOH ~ Me ~ CHO
(Active (]'1e) group)
C O O. Et . <CjOOEt
/ . Se 02/MeCOOH
,
V '
'
' . >O=
• \.. 'cooEt • , • COOEt
DEM (Active (-CH.i) group) Diethylmesooxalate
~ I I ri fn r~ m. Ha rya I I CA •- -
...., , 0
~~
vi. Me • II •••
Se02/MeCOOH II
M e~ M e
0 (Active (-M e) group) II
Butanone .
D1ace 0
tyl (Minor)
(Active (-C H2) group)
+
M e~ C li o
II
0
(Ethylglyoxat)
( Major)
vii. 0A~_,.-. .
l~
Se02/Me CO OH
)
9 ® 'C H O
a-Picoline
a-Picolinic aldehyde
0
C..)Se02 /Me CO OH II
\ viii. Ph /·· ~p h -- = -- -~ > Ph/"-...Ph
[t
Diphenyl methane
Benzophenone
b. seo2 in. gla cia l ace tic aci d is
als o use d for allylic
hydroxylation in a chain, e.g
.,
i.
• ••-- ..\ ~: ; allylic
.••--..\
> i
+Me
•. Se02 M ~ Me
Me ~ - •~--e· Me CO OH
> e
2° allylic )
~
. 0H
(2~ allylie is mc:,re reactive
... than 1° allylic)
- . OH
M:,· seai M ~ ~
_E l', \· ~ MeCOOH) e ......
allylic
'-M e 1
.. .. t
.
-,IICOholic solut_ion: In cyc
loalkenes ~the
at.a-position to the double bon
d is
~ substituted on the dou
ble
oyp at ~-position to the
ble bond is hydroxylatetl1. I
OH
R
Red~ and ()xldatlon Reaciions of Organic Compounds 2.31
:used for dehydrogenation at elevated
2.28 FJNTON'S REAGENT
.
SeOi i. Amixture ofFeSO4 or acetate and 8i02, known as Fenton 's
A.-Hf Ph -CHO •
reagent, has been.used to oxidise organic compounds.
COOH •• e
.,
[ Fel++ H-O-O -H ---+Fe3++ OH+OH
COOH I
•
Succinic acid ii. Aro~C bydr~bo ns are hydroxylated with Fenton's
0 0 reagent. The OH
radical absorbs a hydrogen from the site
, e
IM 6 1'2 4 6 of attack and oxidises the substrate.
1~ SeOi> M t ~ M e
aMe s II fl e II
0 0
._.2,5-dione Hex-3-en-2,5-dione •
H6+
H)(CO OEt ,
EtOOC
Diethyl fumarate
H
lJ.
.:, .
HOI>&
+Fe 3+ --+
e. 2, catalyses the trans hydroxylation of
11D01mids, e.g., iii. Coul~ng: The OH radical may abstract a hydrogen
from the susceptible position of the substrate producing
Mli-hydro~ylation) l radicalswhich couple. The susceptible reactive positions are
supposed to be the a-positions to the phenyl, ether, cyano,
"' .. COOH · COOH carboxyl, ester groups, etc.
.. ,•
HtOH _H~+H. -_ I'
! •
OCH3 O-CH2
H ~H+OH
iCOOH • . COOH
·. d •
. . I
«ncemic-tartaric acid -
I
I
•
,. ,l . 2[~fr- ' f½O, +Fl' )
,, . ·' ...
2 @
J
•• • -✓'
COOH i:r
• !~~Qi ,:
H",.· ~ ..
iI
l
10 (CH;},COOH 1
"!"'-"1.&.:r.
<
.. • ...
I
,,
/
':.,, ,I
~ ,tOH 0
:.,
.•. 1. ·/·
.., .
~- ";
iv.
A COOH•
Me '
H202 + Fe2+
> Me/'-...C OOH
II
·::.
.· I i • r
i
I
•
• Laytic acid Pyruvic acid
. .
::·.,· .. <:".'_
;.
,~,,:; ..-;-:.,
.
~ (
:---,s,::r.r
us acetic acid medium, 2 CHO
v. H202 + Fe ;
OJiSe03). The reaction
[O~
I
OH CHO
id on the enol form of ~
Glyoxal
hich eliminates "20 and Glycoi.
: -:a·)-~.'.., .
. (1/.••· ., - ;.~ .-- ·- • ..-
t,I ,.,.
'0
~
. , COOH
. ·.' .:...i=-.. --H20 _. vi. H+OH . H2C>i+Fo2+• HOOC )(OH
HO COOH
.·.•·o ~'oH l H+OH
COOH
,. Dihydroxy fumaric
0 . Tartaric acid acid
. . I
Dihy<!roxy fumaric acid forms a complex with Fe3+ ions.
~'iw.:: . H : ()~i ~ H- This complex has a violet colour in alkaline medium. This
is used as a test for tartaric acid•
• Selenate ester . , .: . 1.
