Experiment 19:

OXIDATION OF 9-FLUORENOL
OH
HOCl
O
Objectives:
To synthesize a ketone from a secondary
alcohol using household bleach.

To monitor the reaction progress using TLC
analysis.

To purify product using simple extraction.

To analyze the purity of the product using
TLC and melting point analysis.

To characterize reactants and products
using IR analysis.


Before coming to lab
Review these techniques:

TLC analysis

Acid-base Extraction

Drying over MgSO
4

Melting Point Analysis
TYPICAL OXIDATION VS.
GREEN OXIDATION
OH
Na
2
Cr
2
O
7
H
2
O, CH
3
CO
2
H, heat
O
OH O
NaOCl, CH
3
CO
2
H
acetone
Typical oxidation using chromium compound
Greener oxidation using household bleach
THE OXIDIZING AGENT
NaOCl + CH
3
CO
2
H HOCl + CH
3
CO
2
Na
Sodium acetic hypochlorous sodium
Hypochlorite acid acid acetate
Sodium hypochlorite is the main ingredient in bleach.

It must first be converted to hypochlorous acid in
order to oxidize the alcohol.
HOCl is a source of a positive Cl, which has 2 fewer
electrons than a chloride anion.
Remember, oxidation is the loss of H or the addition
of O.
PROPOSED MECHANISM
HOCl
H
3
O
+
O
H Cl
H
+
OH
H
O H
Cl
H
- H
2
O
O
H H
O H
Cl
O
H H
O
+ H
3
O
+
+ Cl
-
- H
3
O
+
- H
3
O
+
Although complex, the
mechanism results in the
exchange of a Cl
+
with a H
+

on oxygen, followed by
subsequent elimination of
HCl to form the ketone.
1. Bleach is
reacted with
acetic acid to
produce
hypochlorous
acid. 2. Electropositive chlorine atom
undergoes nucleophilic attack by
oxygen of alcohol to form O-Cl
bond
3. Water
abstracts a
proton from
the oxygen
bearing the
chlorine
4. followed
by another
attack on the
proton of the
carbon
bearing the
oxygen.
5. Both electrons from the C-H
bond form the p bond of the
carbonyl, and a chlorine atom is
eliminated to form the neutral
product ketone.
1
2 3
4
5
OH
HOCl
O
Reason for difference in Rf values
The 9-fluorenol can DONATE
hydrogen bonds to the silica gel
on the TLC plate, resulting in a
lower TLC Rf value!
1 3 2
x x x
The 9-fluorenone can
ACCEPT hydrogen
bonds, but not donate
to the silica gel on the
TLC plate, resulting in
a higher TLC Rf value!
Reason for difference in color
OH
HOCl
O
The more conjugated a compound is, the higher the wavelength of
light it absorbs.

The visible region of the spectrum is the 400-700 nm wavelength
range.

If a compound absorbs light close to 400 nm, it will appear as a
yellow color.
More
conjugated
Less
conjugated
EXPERIMENTAL PROCEDURE
(SYNTHESIS)
Add Fluorenol to 50 mL flask with stir
bar.
Add acetone and stir of until dissolved.
Add acetic acid and bleach while
stirring. Place a small cork in top of
flask to reduce decomposition of bleach.
Stir 10 minutes.
Perform TLC experiment to check for
completion.
If oxidation is incomplete, add more acetic acid
and bleach, react for 10 additional minutes and
repeat TLC experiment.
If oxidation is complete, proceed to purification
steps.
1 3 2
x x x
Complete
reaction!!!
PROD
STD
YOUR
RXN
RCT
STD
EXPERIMENTAL PROCEDURE
(PURIFICATION)
Transfer liquid to separatory funnel.

Extract product into diethyl ether 2X.

Wash organic layer with 5% NaHCO
3

and Saturated NaCl.

Transfer organic layer to clean flask.

Dry over MgSO
4
.

Transfer liquid to preweighed 150 mL
beaker w/3 boiling chips.


125
mL
150
mL
EXPERIMENTAL PROCEDURE
(PURIFICATION)
Prepare a tap water bath using your
400mL beaker.
Place the water bath on a hotplate and
heat the water on a setting of 3 (NO
HIGHER) until just above room temp.
Remove water bath from hotplate.
Slowly place the 150mL beaker
containing diethyl ether into the water
bath to evaporate the liquid solvent.
If the solution boils too rapidly, remove
it immediately until it ceases to boil!


150
mL
400 mL
EXPERIMENTAL PROCEDURE
(PRODUCT ANALYSIS)
Place LABELED 150mL beaker in
oven for 10 minutes to dry.
Reweigh.
Repeat if %yield is greater than
100%!
Reweigh to obtain final product
mass and calculate % yield.
Perform melting point analysis.

YOUR
NAME
HERE
Table 19.1

Theoretical yield (g)
Calculate based on 9-fluorenol ONLY! Bleach is used
in excess!

Actual yield (g)
(Beaker + product weight) (empty beaker weight)


% yield
(Actual yield/theoretical yield) X 100


Melting Range (
o
C)
Compare to lit value of 81-85
o
C.

Product Appearance
Physical state and color of product
Table 19.2


Atom Economy (%)
Should be calculated based on 9-Fluorenol and
hypochlorous acid (HOCl), NOT bleach (NaOCl)
Review Experiment 13 for calculation.

Cost per Synthesis ($)
Remember to calculate COST PER SYNTHESIS
using 9-Fluorenol, bleach, acetic acid and acetone.
Cost of stock bottles on p. 167!

Cost per gram ($/g)
COST PER SYNTHESIS/ACTUAL YIELD
Table 19.3



Compound

TLC R
f
values

Standards

Sample


9-fluorenone
R
f
values are UNITLESS!

R
f
values are 2 decimal places ONLY!

If more than one TLC experiment is
performed, record data from final TLC plate!


9-fluorenol
IR Spectroscopy
OH O
9-fluorenone
9-fluorenol
Remember to
concentrate on
the types of
bonds that
indicate the
CONVERSION
from reactant
to product!
3196
1031
3041
1716
3060
Table 19.4
Functional Group Base Values
(cm
-1
)
9-fluorenol 9-fluorenone

OH stretch
3200-3400

C-O stretch
1000-1200

C=O stretch
1705-1725
sp
2
CH stretch 3000-3100
SAFETY CONCERNS
DIETHYL ETHER IS
EXTREMELY FLAMMABLE!
NEVER place diethyl ether
directly on a hotplate!

Acetic acid is corrosive!
WASTE MANAGEMENT
LIQUID WASTE container: any/all liquid waste
from extraction and TLC experiment.

SOLID WASTE container: any/all solid waste
from synthesis and purification.

BROKEN GLASS box: Place used TLC and melting
point capillaries.


CLEANING
Clean all glassware with soap, water,
and brush if necessary.

Rinse all glassware with wash acetone
before returning to lab drawer.

DO NOT return any glassware to lab
drawer dirty or wet.