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Oxidation has a somewhat different meaning in organic chemistry than you
have been used to in inorganic, where oxidation is defined as a process
involving loss of electrons, as in the conversion of Fe+2 to Fe+3. Oxidation of
organic compounds also normally involves electron transfer, but because the
valence of carbon usually remains at four, it is more useful to define
oxidation as either (a) loss of hydrogen atoms or (b) addition of oxygen or
other electronegative atoms. Thus, all of the following reactions are
classified as oxidations:









Oxidations of alcohols provides one of the most general methods for the
preparation of carbonyl compounds; oxidation of primary alcohols affords
aldehydes (or carboxylic acids, if oxidation is continued), while oxidation of
secondary alcohols affords ketones. Tertiary alcohols cannot be oxidized
without breaking carbon-carbon bonds.


Primary alcohol



Carboxylic Acid


The most common oxidizing agents for the conversion of alcohols to

aldehydes and ketones are chromium trioxide (CrO3) and its relatives,
chromate and dichromate ions (CrO4-2 and Cr2O7-2), as well as a series of

modified forms of CrO3, such as Collins reagent, in which CrO3 is complexed

with pyridine (Collins reagent is used in nonaqueous media, and is especially
useful for oxidizing primary alcohols to aldehydes without overoxidation to
the carboxylic acid). KMnO4 can also be used to oxidize alcohols.
An alternative oxidizing agent for the preparation of ketones, sodium
hypochlorite (NaOCl) in acetic acid, was introduced by Stevens, Chapman,
and Weller in 1980 (J. Org. Chem. 45, 2030). This reagent offers several
advantages: it is cheap (sodium hypochlorite is the reagent in Clorox and
"swimming pool chlorine"); it oxidizes secondary alcohols rapidly and in high
yield; and it avoids the problem of disposing of toxic wastes associated with
chromium and manganese reagents.
The example chosen to illustrate the oxidation of alcohols is the sodium
hypochlorite oxidation of isoborneol to camphor:






Camphor is a bridged bicyclic ketone widely distributed in nature, especially

in trees of the Far East. It is used as a plasticizer for the production of
celluloid film, for smokeless powders and explosives, as an insect repellent,
and for medicinal purposes (you will recognize the characteristics odor of
Vicks). Borneol, one of the stereoisomeric related alcohols, is found in
certain trees of Borneo, and isoborneol, used in today's experiment, is made
commercially from pinenes (the C10 hydrocarbons of turpentine).

Safety and Waste Disposal

1. Sodium hypochlorite (Clorox) is a strong oxidizing agent and bleach; be
careful to keep it off your skin and clothing. Wash spills with water.
2. Excess Clorox, as well as the filtrate from the collection of camphor, can
be poured down the drain if diluted well with water.

3. If you distill the methylene chloride at the end of the experiment, put the
distillate in the bottle labeled "RECOVERED METHYLENE CHLORIDE"

Dissolve 5 g of isoborneol in 15 mL of glacial acetic acid in a 125-mL
Erlenmeyer flask. Add 50 mL of Clorox by the milliliter over 5 minutes,
cooling the flask as necessary to keep the internal temperature in the range
15-25C. A white precipitate will separate out at this point. Allow the
mixture to stand at room temperature for 30 mins with swirling (every 3
mins). A positive KI-starch test should be obtained at this point (White KIstarch paper will turn blue-violet for positive test).
Add saturated NaHSO3 (Sodium bisulfite: Quenches excess oxidizing agent)
solution carefully until the yellow color of the reaction mixture disappears
and the KI-starch test is negative (White paper stays white). Pour the
mixture over 100 mL of brine (Saturated NaCl) and ice[take 100 ml brine
and add a fistful of ice], collect the solid by filtration on a Buchner funnel,
and wash it with saturated NaHCO3 (Sodium bicarbonate) solution until
foaming is no longer evident. Air-dry your solid for 15 minutes (use high
vacuum) by using the Buchner filtration system.
Weigh the dry product so that you can calculate the yield.
Wait until the product dries above; you will need to get all the material
needed for this step! Once the product dries, you will need to prepare the
2,4 Dinitrophenyl hydrazone derivative of camphor: Dissolve about 0.2 g of
your camphor in 5 mL of 95% ethanol, add 10 mL of the 2,4dinitrophenylhydrazine reagent solution, heat to boiling on a hot plate for 3
minutes (The solution will turn deep yellow or yellow-orange at this point.
Dont worry if some of you dont observe this. You will see crystals upon
cooling the flask on ice!), and allow the mixture to cool (1-2 min). Scratch
the bottom of the flask with a clean spatula and keep the flask on ice.
Crystallization (yellowish crystals) usually occurs within a few minutes. Filter
the yellow precipitate by suction filtration, wash with 2-3 mL of chilled
water, and allow drying to occur (high vacuum for 5 min).
Determine the melting point (reported mp 164 oC) of your 2,4-DNPHderivative of camphor from above.
Calculate the percent yield of your product (camphor).
Post-lab Questions: (Answer these in your notebook).

1. Write a balanced equation for the oxidation of isoborneol by NaOCl.

2. What do you actually observe in a "positive KI-starch test"? What does it
mean when it is mentioned at the end of the first paragraph in the
Experimental Procedure that the KI-Starch test is positive?
3. What is the purpose of adding NaHSO3 at the end of the oxidation? Write
a balanced equation for the reaction it undergoes.

1. Commercial Clorox contains about 6.5% NaOCl.
2. Preparation of 2,4-dinitrophenylhydrazine reagent:
Add 50 mL of concentrated sulfuric acid to 10 g of 2,4-dinitrophenylhydrazine
in a 500-mL Erlenmeyer flask and mix well. Add 75 mL of water dropwise
(CAREFUL! HEAT EVOLUTION), with stirring or swirling, until solution is
complete. To this warm solution add 250 mL of 95% ethanol. This scale
provides enough reagents for 35 students. The solution should be prepared
fresh each day.
3. For alternative oxidations of secondary alcohols with Clorox, see
Oxidation of cyclohexanol: N.M. Zuczek and P.S. Furth, in J.
Chem Educ. 58, 824 (1981).
Oxidation of cyclic and acyclic secondary alcohols: R.A.
Perkins and F. Chau, in J. Chem. Edu. 59, 981 (1982).
Oxidation of 9-fluorenol: C.S. Jones and K. Albizati, in J.
Chem. Educ. 71, A271 (1994).