Chem 216 S11 Notes - Dr.

Masato Koreeda
Topic: _Experiment 2_ page 1 of 3.

Date: May 10, 2011

Experiment 2. Oxidation of an Alcohol (see Eges: pp 515-519)

R

O-H

[ox]

C
R'
H

1o -alcohol: R = alkyl or aryl; R' = H

C O
H
R

C O
R'

2o -alcohol: R/R' = alkyl or aryl

aldehyde

C O ketone

R'

A number of chromium (VI)-based reagents have been developed for the oxidation of alcohols, e.g., Jones
reagent [CrO3/H2SO4/acetone/water]. The oxidation of a primary alcohol by the use of the Jones reagent results
in the formation of mostly a carboxylic acid.
Pyridinium chlorochromate (abbreviated as PCC; developed in 1975 by E. J. Corey) is one of the mildest and
yet highly versatile reagents used for the oxidation of alcohols. With this reagent, the oxidation of a primary
alcohol cleanly produces the corresponding aldehyde.
Mechanism of the PCC oxidation of an alcohol:

R
R'

more electrophilic than the

Cr in CrO3 because of Cl

O-H
C

O
Cr
Cl
O

H
O

R
C

R'

O
Cr O
O
Cl

N
H

-Cl

N
H

R
C O
R'
+

oxidation
step

R
R'

O Cr

O
C

B:

O
Cr O

R'

C
H

O
Cr O
O

N
H

Cl

still Cr+6

still Cr+6

B:

H
O

Cr+4
(chromium is reduced!)

extremely acidic!

often referred to as
"Chromate" ester

N
H

Cl

Due to the suspected toxicity of Cr(VI)-based reagents, a number of alternate reagents have been developed.
Oxidation of secondary alcohols can be efficiently achieved using much environmentally safer reagents such as a
5.25% (0.75M) sodium hypochlorite (NaOCl) solution available in the grocery store as household bleach.
Mechanism of the oxidation with bleach:
Na-OCl +H3O

OH

Na

Cl

H
O
H

+ H-O-Cl

H2O
H3O

oxidation
step

O
+

H
H2O

H2O

Cl
O

Cl
O

ketone

H
H

Cl
O

H
H2O

O H + Cl

H
H

O H

Chem 216 S11 Notes - Dr. Masato Koreeda

Topic: _Experiment 2_ page 2 of 3.

Date: May 10, 2011

Notes for experimental procedures:

1. The TLC spot of neither any of the alcohol we use nor the ketone product could be visible under the
254 nm UV lamp. Use the vanillin stain (this stain contains vanillin and conc. sulfuric acid in ethanol).
After developing the spots, evaporate off the solvent from the plate and strongly heat the plate on a
heater.
2. The ketone product is to be collected by the steam distillation.
3. The distillate obtained is to be extracted with ether.
4. Make the 2,4-DNP [2,4-dinitrophenylhydrazone] derivative of the ketone product and recrystallize
the 2,4-DNP derivative from methanol (obtain the mp data as well as IR).
O
N
O
H

R
C O

R'
ketone

N N
H H

O
N
O

H+

O
N
O

R
R'

2,4-Dinitrophenylhydrazine

O
N
O

N N
H

+ H2O

2,4-Dinitrophenylhydrazone

2,4-DNP derivative: usually highly crystalline

and sharp melting solids

Mechanism of the 2,4-DNP formation:

See Eges book (pp 575-576). Please note the mechanism for the formation of 2,4-DNP is essentially
identical with that described for the formation of oximes. Simply replace the OH in the oxime
formation with NHAr in the 2,4-DNP formation [Ar = 2,4-dinitrophenyl].
This N reacts with the ketone C=O!

The internal NH lone pair electron is delocalized throughout the

aromatic pi system and two nitrogroups by extensive resonance.

O
N
O
H
N N
H H

O
N
O

O
N
O
H
N N
H H

O
N
O
O
N
O

H
N N
H H

O
N
O

not basic, not nucleohpilic

O
O N
H
N N
H H

O
O N
O
N
O

H
N N
H H

O
N
O

Chem 216 S11 Notes - Dr. Masato Koreeda

Date: May 10, 2011

Topic: _Experiment 2_ page 3 of 3.

Steam distillation setup [see: textbook, pp 141-150 (distillation) and 153-155 (steam
distillation)].
Modified setup for this experiment:

Extraction procedure [see: textbook, pp 128-137 (extraction) and 137-140 (drying)]

The organic layer (i.e., ether in this case) used for extraction from an aqueous solution
contains about 2%! of water in it. Thus, this organic layer needs to be dried.
The organic layer is next washed with a roughly equal volume of brine (saturated
aqueous NaCl).
Brine is highly ionic, thus expelling non-ionic organic
compounds/solvents out of the aqueous layer (i.e., brine).
brine and water-immiscible organic solvents separate better drier organic layer
The brine washed organic layer still contains a trace amount of water. In order to
further remove water in the organic layer, an inorganic drying agent, for example,
anhydrous MgSO4, Na2SO4, or CaCl2, is used by taking advantage of the following
chemical reactions with water.
MgSO4 + 7 H2O MgSO47H2O
Na2SO4 + 10 H2O Na2SO410H2O
CaCl2 + 2 H2O (or 6 H2O) CaCl22H2O (or CaCl26H2O)
These are semi-transparent crystalline water-containing inorganic salts. Water
molecules are not simply adsorbed on the surface of these inorganics. These
water molecules are ligands and are part of their crystalline structures.
Remove the drying agent by gravity filtration and evaporate the organic solvent from
the filtrate.