Lab Report: using sodium

hypochlorite to oxidize

cyclohexanol to cyclohexanone

under acidic conditions

Purpose:

The purpose of this experiment was to observe the reaction of sodium hypochlorite

as an oxidizing agent to synthesize a ketone from a secondary alcohol. This reaction

is very useful for chemists, because it is a synthetic process that allows for chemists

to synthesize ketones from alcohol reagents, which are often more available to the

chemist than ketones reagents in themselves. Ketones are also to undergo specific

reactions that only ketones and aldehydes undergo, such as the Wittig reaction. So,

the formation of these ketones may be a vital step in the synthesis of a final

product. This reaction also allowed us to get practice with many of the techniques

that we use every lab in organic synthesis, such as liquid-liquid extraction, and it

was also our first introduction to the process of salting out a product, wherein a

more soluble product is dissolved in order to make the less soluble product come

out of solution. This served to be extremely useful, because the cyclohexanone

product was dissolved in an aqueous solution, so in order to remove it from solution

it was necessary to reduce its solubility. Once this was done, a normal liquid-liquid

extraction could be carried out to separate the cyclohexanone product. This

experiment also allowed us to test our skills in using microscale apparatus, as well

as doing microscale distillations, which are fairly new and considerably different in

setup from a macroscale distillation. Since we were able to test all of these skills all

at once, this is a very useful experiment for chemists to test many synthetic skills at

once.

Procedure:

First, 150 mg of cyclohexanol was added to a 5 mL long necked round bottom flask,

along with 2.3 mL of a 6% sodium hypochlorite solution (bleach). Enough acetic acid

was added to make the solution have a pH of 6, which proved to require much more

than the 80 mg of acetic acid in the books procedure. A discussion on why this is

believed to be so can be found in the Discussion section. Once the solution read

as acidic, it was heated to 45 degrees Celsius to allow the reaction to begin. Once

45 degrees was reached, the solution was capped and shaken for three minutes

continuously, in order to ensure that all of the contents are thoroughly mixed. Once

this was done, the flask was places in 45 degree water for 15 minutes to allow the

reaction to progress completely.

Once fifteen minutes had elapsed, any remaining oxidizing agent had to be

destroyed. This was done by adding sodium bisulfite, a reducing agent, to the

solution. Two drops were added and shaken into solution, and then the solution was

tested on starch-iodide paper. This paper indicates the presence of an oxidizing

agent by making the colorless iodide ions in the paper be oxidized with starch to
form a blue-purple iodine-starch complex. The solution was tested and was found to

contain no oxidizing agent, so the next step was to destroy any remaining acid in

the solution. Thymol blue was added to the solution to act as an indicator, where it

is yellow in acidic-neutral conditions and blue in basic conditions. 6M NaOH solution

was added dropwise until a very faint blue color could be seen, indicating that all of

the acid had been destroyed.

Next, a distillation was set up and carried out to collect the cyclohexanone. This

distillation was actually a steam distillation, where the cyclohexanone was being

carried over in the steam that was boiling from the solution, since cyclohexanone is

slightly soluble in water. 1 mL of distillate was collected, and then the next

necessary step was to separate the cyclohexanone from the aqueous solution. This

was done by adding 100 mg of NaCl to the aqueous solution. NaCl is much more

soluble than cyclohexanone in water, so it will actually displace the cyclohexanone,

causing an organic layer of cyclohexanol to form. Now a standard liquid-liquid

extraction can be used in order to separate the product. 0.4 mL of anhydrous ether

was added into the reaction flask, and then a water drop test was carried out and

the etherous layer was extracted into another reaction tube. This was carried out

twice, and then the combined ether layers were dried using anhydrous sodium

sulfate, since ether absorbs water. Once this was done, the ether solution was

placed into a distillation setup and the ether was boiled off using a hot water bath.

The product was then weighed to come to a mass of 78 mg. A calculation of percent

yield can be found under the Data & Results tab

Data & Results

Calculation of yield:

Mechanism:

Discussion:
This lab was extremely useful for a multitude of reasons. Firstly, it allowed us to get

more experience with many of the techniques we use on a regular basis in organic

synthesis, such as liquid-liquid extractions and distillations. This is not specific to

this reaction, but one specific method to this reaction is the use of oxidizing and

reducing agents in reactions, and how to test for them. This is something that we

have not experienced yet in organic chemistry, so using the starch-iodide paper was

crucial to this reaction in order to allow us to determine that all of our reactants had

been used up. Had this not been done, we would have only known that the

reactants were not completely reacted is if we did chemical tests, or if we did a

spectroscopy of the product and saw impurities.

Using acid-base reactions was also a very crucial part of this reaction. If it werent

for the ability to do acid-base reactions and test for acids and bases, our final

product would almost certainly be contaminated with acetic acid from the first step

of the reaction, because the acetic acid is not consumed in the reaction. The

addition of 6M NaOH serves no other purpose to destroy the acetic acid. It also

produces sodium acetate, which can dissolve into solution and begin the salting out

process before the NaCl solution is added.

Liquid-liquid extractions were also a very crucial method in this synthesis. When

synthesizing a liquid product that is insoluble in another liquid in the reaction

mixture, it is very difficult to separate the layers by decanting, especially on such a

small scale as this. So, the best choice is to introduce more solvent to dissolve the

product, which can be more easily pipetted or decanted since the addition of the

solvent increases the volume of the desired layer to be extracted. If we were not

able to use liquid-liquid extractions, there would be a very great possibility of

contamination of the final product.

This reaction would have greatly benefitted from the use of IR spectroscopy, which

was planned to happen but time restricted the opportunity to carry out an IR

spectrum. If we had, there would have been two very defining characteristics to

look for to determine purity. First, since we are producing a ketone, we would expect

a very sharp spike at ~1710 cm-1, which indicates a carbonyl group. So, the

presence of this reading would indicate that the reaction has progressed enough to

produce the ketone product. Next, if not all of the alcohol has reacted, there would

be a very broad peak at ~3300 cm-1. The presence of this peak would be a negative

sign for our reaction, because it would indicate that not all of the reactions were

consumed in the reaction. I would have used this data to get feedback on whether

or not my reaction progressed fully, and then I would determine what I could do to

redo the experiment better.

This reaction is a characteristic oxidation reaction of alcohols. Specifically, only

primary and secondary alcohols can undergo this oxidation, as well as methanol.

This is because of a few reasons, the first being steric reasons. In tertiary alcohols,

there are three bulky alkyl groups which do not allow the hypochlorite ion room to

access the central carbon atom, in order to react with the alcohol. The second is

because in the mechanism, a proton is lost when the hypochlorite oxidation is

carried out, as can be seen in the mechanism. Since tertiary alcohols cannot lose a

proton, they do not undergo oxidation. Secondary alcohols always form ketones

when oxidized with any oxidizing agents, but primary alcohols are more complex.

When reacting with a strong oxidizing agent, such as sodium dichromate, primary

alcohols will be oxidized into carboxylic acids. But hypochlorite is known as a more

selective oxidizing agent, and it will only oxidize primary alcohols to aldehydes. This

is extremely useful in synthesis of aldehydes, since we are able to oxidize alcohols

which may be more common, rather than doing complicated organic synthetic steps

to synthesize an aldehyde, such as ozonolysis of alkenes.

If I were to redo this reaction, I would be sure to make the measurements extremely

accurate in order to ensure proper yield. I have a few hypotheses for the loss of

yield. One of which is the fact that the sodium hypochlorite used was scented

bleach, which the procedure advised against. There is a possibility that this could

have caused side reactions which could have destroyed reactants, but this could

only be confirmed if the whole lab got poor yield. Another hypothesis has to do with

the fact that in the first step with the addition of acetic acid, I had to add much

more acetic acid than was stated in the procedure in order to get the solution to be

acidic. I am not sure why this is, but my hypothesis is that the addition of more

acetic acid increased the volume and diluted the concentration of cyclohexanone.

But since I only collected the amount of distillate in the first distillation that was

recommended in the book for the optimal volume, I only isolated a small amount of

cyclohexanone. If I were to redo this reaction again, I would be sure to use only the

recommended amount of acetic acid, and if that was not sufficient to acidify the

solution, I would try to research further to figure out why this was happening and

correct it. Overall, even though the reaction didnt go perfectly, it was a very good

learning experience for me in order to learn how to analyze my reaction failures.