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A Green Method for Synthesis of Cyclohexanone: Oxidation of Cyclohexanol using

Sodium Hypochlorite
Oxidation-reduction reactions form an extremely diverse group, and they proceed by a variety of
mechanisms. Oxidation is defines as a loss of electrons or an increase in oxidation number, while in a
reduction electrons are gained and oxidation number is decreased.
Primary alcohol can readily be oxidized to aldehydes and carboxylic acids. The oxidation of aldehydes to
carboxylic acids in aqueous solutions is easier than oxidation of primary alcohols to aldehydes. It is difficult
to stop the oxidation of a primary alcohol at the aldehyde stage unless specialized agents are used. Primary
alcohols can be oxidized to carboxylic acids by chromic acid (H
2
CrO
4
) and potassium permanganate
(KMnO
4
). The reaction with KMnO
4
is usually carried out in basic aqueous solution, from which MnO
2

precipitates as the oxidation is complete. The aldehyde is formed as an intermediate, but it is unstable under
the reaction conditions and cannot be isolated. There is a color change that accompanies the reaction - the
purple solution (KMnO
4
) changes to a brown precipitate (MnO
2
). Many of the oxidizing agents in organic
chemistry are based on Cr. All forms of Cr(VI) are powerful oxidizing agents. Chromic acid is a commonly
used oxidant and is prepared by dissolving chromium(VI) oxide (CrO
3
) or sodium dichromate (Na
2
Cr
2
O
7
) in
a mixture of sulfuric acid and water, a mixture known as Jones reagent. In non-aqueous solutions, oxidation
by Cr(VI) does not go to completion and under these conditions, primary alcohols may be oxidized to
aldehydes without forming carboxylic acid. The most common agents for this partial oxidation are: PCC, or
pyridinium chlorochromate (formed by dissolving CrO
3
and HCl and then treated with pyridine).
Primary alcohols are also oxidized by atmospheric oxygen to aldehydes and carboxylic acids. This reaction is
very slow and it is catalyzed by enzymes (Acetobacter). This is how wine turns to vinegar!!!
Secondary alcohols are oxidized to ketones - and that's it. The reaction stops at the ketone stage because
further oxidation reaction requires the braking of carbon-carbon bond.

Scheme 1. Oxidation of Alcohols
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Tertiary alcohols, because they bear no -hydrogen, do not easily undergo oxidation. There aren't oxidized
by acidified sodium or potassium dichromate(VI) solution, there is no reaction at all. In order to oxidize,
there must be at least one C - H bond in the functional group.
Chromium-based oxidations are reliable and well established, but the toxicity associated with chromium salts
meant that they are generally considered the second choice. Chromium compounds have been shown to be
carcinogenic, they must be disposed of carefully, and they cannot biodegrade.
One experiment, found in virtually all organic chemistry laboratory programs, is the oxidation of an alcohol
with chromium(VI). Chromic acid has been used in introductory chemistry labs since the 1940's. Probably
the most popular experiment is the oxidation of cyclohexanol to cyclohexanone, using sodium dichromate in
an acidic medium. Waste disposal, safety, and cost considerations associated with the Cr(VI) oxidation
procedures provided the motivation to find some alternative oxidizing agents.
In 1980 Stevens, Chapman, and Weller reported in the Journal of Organic Chemistry

(Stevens, R.V.,
Chapman, K.T., Weller, H.N. J. Org. Chem., 1980, 45, 2030-2032) that "swimming pool chlorine" (calcium
hypochlorite) as the oxidizing agent is a convenient and inexpensive method of preparing ketones in good
yields from secondary alcohols. Jerry Mohrig was teaching an introductory organic chemistry laboratory
course at Carleton College at that time and decided to use the experimental procedure from the Journal of
Organic Chemistry. The adapted procedure using swimming pool chlorine to oxidize cyclohexanol to
cyclohexanone encountered several problems. First, the large amount of solvent and the ether used in
multiple extractions made the experiment too expensive, and second, storage of swimming pool chlorine
causes its concentration to decrease by about 20% per month. It was found that household bleach functions
even better that swimming pool chlorine as the oxidant for cyclohexanol (Mohrig, J.R., Mahaffy, P.G.,
Nienhuis, D.M., Linck, C.F., Van Zoeren, C. Fox, B.G. J. Chem. Edu. 1985, 62, 519-521). Yields were
comparable to slightly better and atmospheric Cl
2
concentrations were diminished considerably. Bleach is
inexpensive and has low toxicity if it is handling with care, and it reduces to products that are nontoxic as
well. There is no need for the large amount of acetic acid; 0.5 mL AcOH/g alcohol is sufficient.
In this experiment you will use household bleach in the presence of acetic acid as the oxidizing agent. The
reaction is oxidation of cyclohexanol to cycohexanone.

Scheme 2. Oxidation of Cyclohexanol to Cycohexanone
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Most bleach is an aqueous solution of sodium hypochlorite (NaOCl) prepared by adding Cl
2
to aqueous
sodium hydrohide solution:
Cl
2
+

2NaOH

NaOCl + NaCl + H
2
Eq. 1
When NaOCl is added to acetic acid, the following acid-base reaction produces hypochlorite (HOCl):
NaOCl + CH
3
COOH HOCl + CH
3
COO
-
Na
+
Eq. 2
In acid solution, HOCl is in equilibrium with Cl
2
:
HOCl + HCl Cl
2
+ H
2
O Eq. 3
Chlorine gas is toxic, but when household bleach is used to oxidize alcohols, Cl
2
is present in very low and
safe concentrations in the atmosphere if the reaction is performed in the fume hood.
Both Cl
2
and hypochlorous acid are sources of positive chlorine, which has two fewer electrons than does
chlorine anion. A key step in reactions of positive chlorine reagents is the transfer of Cl
+
to the substrate. It is
reasonable to expect that the first step in the oxidation of cyclohexanol is exchange of Cl
+
with the hydroxyl
proton. Subsequent E2 elimination of HCl from the resulting alkyl hypochorite forms the ketone,
cyclohexanone. If HOCl is not present, the first step cannot take place and the overall oxidation is very slow.
In the first reaction, Cl
+
is transferred to the substrate, and in the second reaction, Cl
-
is lost. The change is a
reduction by two electrons. Cyclohexanol provides the two electrons as it is oxidized to cyclohexanone.

Scheme 3. Mechanism of Hypochlorite Oxidation of Cyclohexanol
Oxidation of cyclohexanol to cyclohexanone using sodium hypochlorite is an example of green chemistry. In
this reaction water is used as a reaction medium and household bleach as the oxidizing agent. The by-
products of the reaction, water and sodium chloride, are nonhazardous wastes. Any excess acetic acid
remaining in the aqueous solution is neutralized with sodium hydroxide to form acetate ion, also a
nonhazardous waste that can be washed down the sink. Cyclohexanone has been separated from the two
phase reaction mixture by extraction with an organic solvent such as DCM. Steam distillation is a green
alternative for separating the cyclohexanone. The compromises are a lower yield (50-60%) instead of the 70-
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80% when extraction was used, as well as higher energy costs, versus no organic solvent waste that would
require disposal.
The new catch phrases green chemistry and green engineering are really about reaction optimization
with respect to materials and energy usage, waste reduction from all sources, and overall cost minimization.
Also included are minimization of toxicity and hazards and maximization of safety practices. When these
terms are applied to the performances of individual chemical reactions, chemical processes, and chemical
synthesis plans they really deal with the same issues. All of these ideas are implemented routinely by process
chemists and chemical engineers in the chemical industry who operate under a code of good laboratory
practice (GLP).
Green chemistry is the design of chemical products and processes that reduce or eliminate the use and
generation of hazardous substances. Green chemistry is also known as sustainable chemistry. The Twelve
Principles of Green Chemistry, originally published by Anastas, P. T.; Warner, J. C. Green Chemistry:
Theory and Practice, Oxford University Press: New York, 1998, p.30; provide a road map for chemists to
implement green chemistry. For more information on the 12 Principles of Green Chemistry, you can visit:
http://www.acs.org/content/acs/en/greenchemistry/about/principles/12-principles-of-green-chemistry.html
and to learn more about the basics of green chemistry visit: http://www2.epa.gov/green-chemistry
Purpose of the Experiment
Synthesize cyclohexanone by oxidation of cyclohexanol using an environmentally friendly reaction.
Learning Objectives
Perform an oxidation reaction; functional group modification
Procedure. To a 500 mL Erlenmeyer flask adds cyclohexanol (16 mL) and glacial acetic acid (7 mL). In a
hood, pour sodium hypochlorite solution (bleach, 100.6 mL of 6%) into a 125 mL dropping (separatory)
funnel. Prepare an ice-water bath for cooling the flask if the reaction becomes too warm. Introduce a
thermometer and slowly add to the reaction flask with swirling approximately one-fourth of the bleach
solution. Add the rest of the sodium hypochlorite solution over a period of 15 min. Adjust the rate of addition
so that the temperature remains between 40C and 45C during the addition. Cool the reaction flask briefly
with the ice-water bath if the temperature exceeds 45C; however, allowing the temperature of reaction
mixture to fall below 40C for any period of time slow down the reaction and may results in a lowered yield.
When the addition of sodium hypochlorite solution is complete, pour another 100.6 mL of bleach into the
separatory funnel and add this portion of bleach to the reaction flask over a period of 15 min, monitoring the
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temperature (between 40C and 45C). After the sodium hypochlorite addition is complete, continue stirring
the reaction mixture for 20 min.
Test the reaction mixture for excess of hypochlorite by placing a drop of the reaction solution on a piece of
wet starch-iodine indicator paper. The appearance of a blue-black color from the formation of the triiodide-
starch complex on the indicator paper signifies the presence of excess hypochlorite.
Eq. 4
Add 2 mL of saturated sodium bisulfite solution to the reaction flask and swirl the flask to mix the contents
thoroughly. Again test the reaction mixture with starch-iodine paper. If necessary, continue adding bisulfite
solution and testing with starch-iodine paper until excess oxidant is removed.
Eq. 5
Work-up. Add thymol blue indicator solution (2 mL) to the mixture and add 6M sodium hydroxide solution
over 3 min until the indicator changes to blue (30 40 mL will be needed). Swirl the flask during the
addition of NaOH.
You will separate the organic product from the reaction mixture by steam distillation. Transfer the reaction
mixture to a 500 mL RBF, add 2 or 3 boiling stones to it, and set up the apparatus for steam distillation.
Collect 70 80 mL of distillate consisting mainly of product and water. Add 10 g of solid NaCl to the
distillate to decrease the solubility of cyclohexanone in the aqueous phase. Stir the mixture until most of the
NaCl dissolves. Decant the liquid from undissolved NaCl into a separatory funnel. Allow the phases to
separate, and remove the lower aqueous layer. Pour the upper organic layer into a clean 50 mL Erlenmeyer
flask and dry it with anhydrous calcium chloride for 15 min. Decant the product into a tared small
Erlenmeyer flask. Determine the weight of your product and calculate the percent yield.
Analysis of the product. Obtain and analyze the IR spectrum of your product. Does your spectrum show
evidence of cyclohexanone? What band indicates that you have the desired product?
Cleaning up
Adjust the pH of the solution remaining in the reaction flask to 7 with dilute hydrochloric acid before
washing the solution down the sink.
Place the calcium chloride drying agent in the waste container labeled calcium chloride waste.

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Safety Notes
Read the MSDS!
Glacial acetic acid is a dehydrating agent and an irritant, and it causes burns. Do not get it on your skin,
clothing or in your eyes. Transfer this material in the hood only.
Chlorine gas is a respiratory and eye irritant. Some chlorine gas is produced when bleach is added to acetic
acid. Therefore, carry out this process in the hood and/or with an apparatus connected to a vacuum line.
Bleach (Sodium hypochlorite solution) emits chlorine gas. From the label of a bottle of bleach: "Causes
substantial but temporary eye injury. Do not get in eyes or in clothing. Harmful if swallowed. May irritate
skin. Wash thoroughly with soap and water after handling." Also, keep chlorine bleach in stoppered
containers so that the lab does not fill up with chlorine gas.
6M NaOH solutions are corrosive and cause burns. Avoid contacts with skin, eyes, and clothing.
Cyclohexanol is an irritant. Avoid contact with skin, eyes, and clothing.
Cyclohexene is flammable. It has an unpleasant smell. Cyclohexene can also form peroxides over time if
exposed to oxygen in air and light over an extended period.
Use personal protective gloves.