Exp 3

OBJECTIVE
1. To observe the oxidation of cyclohexanol with PCC on a Silica Gel Substrate.

2. To determine the Infrared spectrum of cyclohexanone
INTRODUCTION
Pyridinium chlorochromate (PCC) is a yellow-orange salt with the formula
[C5H5NH]+ [CrO3Cl]−. It is the most used of these reagents, due to its availability,
stability and versatility. PCC is a milder version of chromic acid that oxidize alcohol
from primary alcohols to aldehydes and from secondary alcohols to ketones. It is no
strong enough to oxidize aldehydes to carboxylic acids. Besides, silica gel is an
amorphous substance and its chemical formula is mSiO2. nH2O
Oxidation reactions of alcohols greatly increase the synthetic usefulness of
these compounds. Only primary and secondary alcohols can be easily oxidized with
the former converted to aldehydes or carboxylic acids and the latter to the
corresponding ketones. The strength and selectivity of oxidizing agents varies
widely, the use of oxochromium (VI)-amine reagents is fundamental for several
organic oxidative transformations. Oxidation with PCC generally proceeds through a
simple, one step reaction:
EQUIPMENTS AND INSTRUMENTS

Pestle and mortar, Magnetic stirrer, Rotary evaporator, IR spectroscopy
MATERIALS
4-tert-butyl cyclohexanol (FW 156.27) 0.16 g (1.0 mmol)
Pyridinium chlorochromate (FW 215.56) 0.43 g (2.00 mmol)
Silica gel (230 – 400 mesh) 0.43 g (for synthesis)
Dichloromethane
Celite
Saturated NaCl
Anhydrous Na2SO4
Ethyl acetate
Petroleum ether
Silica gel (30 – 70 mesh) - for filtering
PROCEDURE
PCC and silica gel (230 – 400 mesh) were combined and grinded with a pestle and
mortar to form a light orange powder. This powder was added to a 25 mL round
bottomed flask along with 6 mL dichloromethane. While stirring, 4-tert-butyl
cyclohexanol was added. The solution was stirred for additional 30 – 40 minutes.
The reaction solution was tested every five minutes with TLC (develop in iodine).
After the reaction has completed, the reaction solution was diluted with 10 mL of
ether and the solution was filtered through the pipet containing a cotton plug, 1 cm
Celite, 3 cm silica gel. The filtrate was concentrated by blowing on it with N 2 until it is
a yellow oil. Then, the concentrated filtrate was diluted with 5 mL of ether and
transferred to a reaction tube. The filtrate was extracted with (2 X 25 mL) of water
and saturated NaCl solution. It was dried over anhydrous Na 2SO4 and the organic
layer was transferred to a tared 10 mL flask. The solvent allowed to evaporate
overnight.
The yield, melting point, NMR, and IR data of the product ware recorded.
RESULT AND OBSERVATON (PREDICTED)
Group Frequency (cm-1)

3
Sp C-H stretch 2935.36
-CHO stretch 2862.37
Ketone C=O stretch 1704.68
-CH3 bend 1449.41
C- stretch 1221.06
Table 1. Table of IR spectrum
Group Chemical shift (ppm)

Ketone 1.8 – 1.6
Secondary alkyl 1.3 – 1.2
Primary alkyl 1.2 – 1.0
Table 2. Table of H-NMR spectrum
Group Chemical shift (ppm)

Ketone C=O 210.07
R-CH2-R 41.13
R-CH3 26.48
R-CH3 24.37
Table 3. Table of Carbon NMR spectrum
Observation;
Celite was added to the bottom of the flask to avoid a nasty brown after the
experiment.
DISCUSSION
Oxidation reactions are incredibly important in the chemical an biochemical

sciences. This experiment is conducted to observe the oxidation of 4-tert-butyl
cyclohexanol with PCC on a silical gel substrate. In organic chemistry, oxidaton is
increasing the oxygen content o an molecule or decreasing its hydrogen content.
Generally, oxidation is the process of removing electrons from a substances. In this
experiment, oxidation of cyclohexanol with pyridinium chlorochromate (PCC)
resulted to produce cyclohexanone.
Cyclohexanol and cyclohexanone have different properties. Cyclohexanone

has lower solubility in water than cyclohexanol. This alows the product to be isolated
without distillation. In this experiment, the cyclohexanone formed was not very
soluble in water, so it separates and form a new layer. Cyclohexanol is a hydrogen
bond donor and a hydrogen bond acceptor while, cyclohexanone is not hydrogen
bond donor and very polar. Cyclohexanone has a density of 0.9478 g/mL which is
lower than the density of water ( 1.0 g/mL). This cause the new layer to be on the
surface of the water. If cyclohexanone had the density higher than water this new
layer will be on the bottom of the flask.
There is a present of ketone group based on the infrared spectrum analysis at

the frequency 1704.68 cm-1. Carbon NMR spectrum and proton NMR spectrum
analysis also show the present of ketone group at chemical shift 210.07 ppm and 1.7
ppm approximately. In IR spectrum, C=O functional group for ketone supposed to
have IR absorption at range of 1680-1750 cm -1 and the IR spectrum that was
obtaoined from this experiment is between the range. Aromatic hydrocarbons show
absorptions in the regions 1600-1585 cm -1 and 1500-1400 cm-1 due to carbon-carbon
stretching vibrations in the aromatic ring.
There are a few precaution should been take while conducting the
experiment. Firstly, cyclohexanol is an irritant. Avoid contact with skin, eyes and
cloth. Next, wear gloves while handling the chemical to avoid the chemical irritates
your hand and skin. Lastly, please wears a aproper attire before doing the
experiment to avoid any injury when conducting the experiment.
CONCLUSION
In conclusion, the objective of the experiment to observe and oxidize cyclohexanol to

cyclohexanone using PCC on silica gel subtrate was achieved. There is a present of
ketone group based on the infrared spectrum analysis at the frequency 1704.68 cm-
1
. Carbon NMR spectrum and proton NMR spectrum analysis also show the present
of ketone group at chemical shift 210.07 ppm and 1.7 ppm approximately.
QUESTIONS
1. Would the final product have been any different if you had used a stronger
oxidizing agent such as chromic acid?
- Yes. The final product produce is different when used a stronger oxidizing
agent.
What would your products have been if you had been oxidizing the following
compound with?
a) PCC
- Secondary alcohol converted to ketones, while primary alcohol converts
to aldehyde.
b) Chromic acid
- Secondary alcohol converted to ketones, primary alcohol
converts to carboxylic acids.
2. Given that PCC is only sparingly soluble in CH 2Cl2 while cyclohexanol is

miscible in CH2Cl2, suggest a reason for the importance of grinding the PCC
and silica gel to form a fine powder.
- The reason for the importance of grinding the PCC and silica gel to form a
fine powder are chromium byproduct deposits with pyridine as a sticky
black tar, which can complete workup. Addition of an inert adsorbent that
is silica gel to allows the sticky byproduct to absorb to the surface and
makes workup easier.
REFERENCES
Dave, Dave, & 23, krishna deo yadav O. (2010, January 8). Preparation & Reactions
of Aldehydes and Ketones, RHO & ROR'. Retrieved April 25, 2020, from
https://biochem.co/2010/01/preparation-reactions-of-aldehydes-and-ketones-rho-
ror/
Goloho Polymer (Changzhou) Co., ltd. (2018, July 1). Information On Chemical
Composition Of Silica Gel. Retrieved April 25, 2020, from http://www.goloho-
polymer.com/news/industry-news/information-on-chemical-composition-of-silica-
gel.html
Lexy, Moody, D., Ashenhurst, J., Eleanor, Wang, G., Yang, J., … Robertson, D.
(2020, February 21). Reagent Friday: PCC (Pyridinium Chlorochromate).
Retrieved April 25, 2020, from
https://www.masterorganicchemistry.com/2011/09/09/reagent-friday-pcc-
pyridinium-chlorochromate/
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OBJECTIVE

1. To observe the oxidation of cyclohexanol with PCC on a Silica Gel Substrate.

EQUIPMENTS AND INSTRUMENTS

Group Frequency (cm-1)

Group Chemical shift (ppm)

Group Chemical shift (ppm)

Oxidation reactions are incredibly important in the chemical an biochemical

Cyclohexanol and cyclohexanone have different properties. Cyclohexanone

There is a present of ketone group based on the infrared spectrum analysis at

In conclusion, the objective of the experiment to observe and oxidize cyclohexanol to

2. Given that PCC is only sparingly soluble in CH 2Cl2 while cyclohexanol is

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