Oxidation, by definition, is a reaction involved the loss of electrons (Chang, 2010).

However,
in Organic chemistry, oxidation is defined as the gain of oxygen atom or the loss of hydrogen
atoms. If we treat hydrogen as a proton, therefore, oxidation can be stated also as the process
of losing proton which contrast the previous premise wherein there is an electron loss when
oxidation reaction takes place.

A special type of oxidation will be used in this study, namely, Stevens-Chapman. The reaction
was names after Robert Stevens and Orville Chapman. This reaction focuses on the oxidization
of a secondary alcohol into a ketone using hypochlorite solution. On the other hand, the said
oxidant involved the principle of Green Chemistry. This field promotes the use of as much safer,
non-toxic and environmentally-friendly reagents in every chemical synthesis (USEPA, n.d.)

The general equation for this Steven-Chapmans oxidation is given below:

The hydroxyl of alcohol can be further oxidized into a carbonyl compound via the loss of hydrogen
attached to the oxygen atom of one specific alcohol. Alcohols oxidize in different ways based on
the number of alkyl or aryl group attached to the ipso carbon. Per McMurry (date), primary
alcohols can be oxidized to an aldehyde and can further oxidize into carboxylic acids if non-
selective oxidizing agents were used. On the other hand, ketone will be the product of a secondary
alcohol once it was oxidized. Phenol, an aromatic alcohol can be oxidized to quinone and
eventually to hydroquinone. A tertiary alcohol does not undergo oxidation sine pentavalent carbon
will be produced (Smith, date).

The summary of oxidation of different kinds of alcohol is then given below:

(equation)

The reaction of the alcohol to an hypochlorite solution is much faster since it can react
exothermally with alcohols in a just a matter of minutes. These reagents also prefer to oxidize
secondary alcohols rather than primary alcohol (Hudlicky,1990). Thus, its best fit to use
hypochlorite solution in oxidizing cyclohexanol, a secondary alcohol.

Cyclohexanol, once oxidized, is expected to become a cyclohexanone via two step mechanistic
process. The first step involves the formation of cyclohexanol hypochlorite through a direct
reaction of the alcohol with the generated hypochlorous acid. This synthesis will generate in-situ
the said acid through the reaction of calcium hypochlorite with acetic acid.

(Mechanism) formation of hypochlorous acid and alcohol hypochlorite

The next step involved the nucleophilic attack of water to deprotonate the substrate. This attack
will result in the pi bond formation of between the carbon and oxygen making the chloride leaves.
An equilibrium process will occur between the acetate ion and the formed hydronium ion for the
regeneration of

The synthesis can be summarized as a reduction-oxidation reaction through inspection of the

oxidation state of the chlorine atom. Initially, chlorine in the hypochlorous acid has an oxidation
state of +1. But as the reaction progress, it was converted to a monoatomic chloride ion with an
oxidation of -1. With that, since there is a gain of the electron, reduction process occurred while
the oxygen was oxidized.

Symmetric ether may be produced in the reaction of two equivalent of alcohol. In this case,
cyclohexanol. This may be done in the presence of an acid catalyst. This acid was used to form
an oxonium ion. The second equivalent alcohol will then attack the ipso carbon of the oxonium
making the water leaves. However, the synthesis does not permit the ether formation to proceed.
First, a strong acid must be used. Second, though sulfuric acid (a strong acid) is present in the
Jones’ reagent, the acid is diluted. The ether formation also requires a primary alcohol due to the
reaction’s SN2 approach (Klein, date).

The mechanism for this side-reaction is then given below:

(equation)

Another possible-reaction is the synthesis of ester via nucleophilic acyl substitution. Per McMurry,
this reaction of carboxylic acid to alcohol proceeds in the presence of an acid catalyst, preferably
HCl or H2SO4. This side-reaction was minimized in this synthesis since hypochlorous acid is a
weak acid. One way that also minimized this reaction is the elimination of acetic acid using sodium
bicarbonate.

The reaction of acetic acid with alcohol and with sodium bicarbonate are given below:

(equations)

Dehydration may also be a possible side-reaction in this synthesis. The hydroxyl group of
cyclohexanol may be lost resulting in the formation of cyclohexene. However, same limitations
apply in this reaction, there are no available strong acids in the mixture that may protonate the
cyclohexanol. Another prevention is the maintenance of mixture’s temperature between 40-50
centigrade. If the temperature was raised beyond, the said elimination reaction may also
compete. The mechanism for this reaction is then given below:

(equations)

Chlorine gas may be formed if the dropwise addition of hypochlorite solution is too fast. The
reaction is exothermic and it needs to be subjected in an ice bath. The use of acetic acid, a weak
acid, also limits this reaction. The mechanism for the formation of chlorine gas is given below:

(equations)

Another side-reaction in the presence of the acid catalyst is the carbonyl alpha-substitution. Per
McMurry, in the presence of an acid catalyst, cyclohexanol tautomerizes to form its enol form.
Once the enol tautomer form, the pi bond will act as a nucleophile to attack the chlorine in
hypochlorite solution. This reaction will result in the formation of 2-chlorocyclohexanone. It was
also minimized due to the use of a weak organic acid, an acetic acid. The mechanism of the
reaction is given below:
The synthesis also employs the use of simple distillation to separate the starting material to the
synthesized product. Second, the use of liquid-liquid extraction for the separation of ions to
cyclohexanol. And lastly, the employment of a drying agent to eliminate any traces of water in
the liquid product.

Test reagent will also be used like Jones’ reagent and warm dilute, neutral KMnO4. The former
will be employed to test the completeness of the reaction whether most of the alcohol is already
converted to a ketone or not. Both tests are an oxidation reaction and with that, both reagents
will only give a positive result to the starting material. The general reaction for this
characterization is given below:

Another test reagent that will use for the characterization of cyclohexanone is Brady’s reagent.
Cyclohexanone 2,4-dinitrophenylhydrazone is expected to form and its melting point will be
determined. If the melting point of the obtained crystals in this derivatization is precise and
accurate to the range of 159-160, the exercise, therefore, is successful in synthesizing
cyclohexanone

(BP determination and objective)