Anda di halaman 1dari 1

5

Aldehydes & Ketones Preparation


Chem 35

I. Alcohol Oxidation Summary (Jones 16.14a) II. Alkene Ozonolysis (Jones 10.5a,b)

NH + ClCrO 3 what is ozone? a blue gas at 25 C (room temperature) with a pungent odor that
H 2CrO 4
(2 equivalents) condenses to a dark blue explosive liquid
O OH (PCC) O
Me Me Me a highly reactive chemical oxidant
OH H
a carboxylic acid 1 alcohol an aldehyde O O+ O+
O3 O O O O O O
remember:
OOO angle ~ 117 ozone is a neutral molecule formal charges must sum to zero

O3 reacts rapidly to oxidize alkenes even at 78 C (110 F)


H 2CrO 4 PCC
Me Me Me Me Me Me O3 will oxidatively cleave C=C double bonds
O OH O

a ketone 2 alcohol a ketone the basic transformation:

O+
O O H H
O O oxidative conversion of alkenes to aldehydes or ketones
Me Me
Me Me Me
cannot oxidize to a carbonyl: an aldehyde
Me Me
OH
the mechanism:
3 alcohol rotate
O+ O Me Me
O O O
O O O O+ O H O H
Oxidation with sodium hypochlorite (bleach):
H H H H H O+ O
O Me O
Cl Me Me Me Me Me Me Me H
OH O O O
+ NaO Cl + + + H 2O an ozonide
R R HO Me R R O Me
H conversion of the alkene to the ozonide is a net 4 electron
Na reduction of O 3 and a net 4 electron oxidation of the alkene

ozonide must be reduced by 2 electrons in order to form 2 equiv of aldehyde


mechanism?

Me 2S = dimethylsulfide = a mild 2 electron reducing agent


O O
+ + Me Me Me
R R HO Me Na Cl H
O Me 2S O H O H H H
O O O
Me Me O Me O
O O Me Me
Key to all alcohol oxidations we will see: H H H
Me 2S+ O Me 2S+ O
Me 2S

R O [L.G.] R O + [L.G.]

H the overall process:

B L.G. = leaving group Me O3 Me 2S O H


+ Me
analogous to an E2 elimination O

a ketone