9-Fluorenone: NaOCl Oxidation of 9-Fluorenol REACTION

H OH O

9-Fluorenol

9-Fluorenone

DISCUSSION This experiment illustrates the oxidation of a 2 alcohol to a ketone. In the past, chromium-based oxidants were commonly used to accomplish this type of oxidation in the research laboratory. Chromium based oxidations produce toxic waste, and the reagents themselves are known to be carcinogenic. The experiment we are going to perform uses a modification of a procedure originally developed by the late Bob Stevens of UCLA to use a mixture of household bleach acidified with acetic acid. This alternative method for the oxidation of 9-fluorenone employs inexpensive, easy to handle, and environmentally safe reagents (Clorox, a dilute solution of sodium hypochlorite and acetic acid). Sodium hypochlorite solutions (1.8-2.0M) sold as liquid bleach are often described as having 11.5-12.5% available chlorine. The term available chlorine compares the oxidizing capacity of the solution relative to that of the same weight of chlorine, Cl2. Sodium hypochlorite solutions are used extensively in swimming pool sanitation and as a bleach in the pulp and textile industries. A less-concentrated product (5% available chlorine) is used in laundries and as household bleach. Consumption statistics for 1982 indicate that 210 10 3 tons of sodium hypochlorite were consumed in the United States alone. World consumption of sodium hypochlorite for household use is estimated to be 426 10 3 metric tons annually in 2005. The reaction described in this experiment illustrates the use of household liquid bleach (5.25% available chlorine) as an oxidizing agent in the organic laboratory. Sodium hypochlorite is prepared commercially by passing chlorine gas through a solution of aqueous sodium hydroxide:
Cl2 + NaOH NaOCl + HOAc NaOCl + NaCl HOCl + NaOAc

In the presence of acetic acid the hypochlorite anion is converted to unstable hypochlorous acid. The actual oxidizing agent in the present experiment is the chloronium ion (Cl +), which can exchange with the hydroxyl of fluorenol producing a short-lived hypchlorite ester. A elimination reaction results in the formation of fluorenone with the concomitant formation of chloride. The 9-Fluorenol acts as a reducing agent giving up two electrons to form 9-Fluorenone while the Cl+ accepts two electrons and is reduced to Cl.

H OH NaOCl, HOAc acetone, water B: HO-Cl (Cl+) H O Cl

O + NaCl

The progress of the reaction is followed using TLC. EXPERIMENTAL PROCEDURE Estimated time to complete the experiment: 3h. Compound 9-Fluorenol Acetone Acetic acid, glacial Sodium hypochlorite(5.25 %) MW 182.23 58.08 60.05 74.44 Amount 2.5 g 50 mL 6 mL ~40 mL mmol 13.7 104.8 28.2 mp(C) 154 16.7 bp(C) 56.5 118

Reagents and Equipment Weigh and add 2.5g (13.7 mmol) of 9-fluorenol to a 250mL round bottom flask containing a magnetic stir bar. Add 50mL of acetone and sample the resulting solution (2-4L) for TLC analysis. Add 6mL of glacial acetic acid and then attach the flask to an air condenser. CAUTION: Dispense the glacial acetic acid in the hood by use of an automatic delivery pipet. This acid burns skin! Add an ice-bath to cool the round bottom flask to 0C. From the top of the air condenser, use pipet to slowly add, with gentle stirring, 20mL of aqueous sodium hypochlorite solution (5.25% commercial bleach). Reaction Conditions Gently stir the reaction mixture in the ice-bath. After a period of 5 min, sample the solution (24L) for TLC analysis. Sample the reaction solution by inserting a 9-in. Pasteur pipette down the air condenser to obtain a drop of solution by capillary action. If starting material is present as shown by TLC analysis, add an additional 20mL of the hypochlorite solution as before. Stir for 5 min and sample again. Continue this process until TLC analysis shows that the 9-fluorenol has been completely consumed. Approximately 40mL of hypochlorite solution should be sufficient, if the reagent is fresh. SUGGESTED TLC CONDITIONS. Use Eastman Kodak Fluorescent silica gel sheets (1.0cm x 6cm). Elute the plates with 30% acetone/70% hexane solvent, and visualize the spots by UV light. Rf values are 0.56 for 9-fluorenol and 0.80 for 9-fluorenone.

Isolation of Product Transfer the reaction solution to a separation funnel. Separate the organic layer and extract the aqueous layer with two 50mL portions of hexane. Combine the hexane extracts (upper layer) with the separated organic layer. Wash the combined organic layer with one 50mL of 5% sodium bicarbonate solution followed by one 50mL portion of saturated sodium chloride solution. Dry the organic solution by addition of anhydrous sodium sulfate. Pour the solution, not the salt, into a round bottom flask. Remove the solvent under reduced pressure. Purification and Characterization Obtain the weight of the crude product and calculate the percent yield. Recrystallize the 9-fluorenone from hexane (~1.0mL of hexane/50 mg of ketone) using Erlenmeyer flask. Determine the melting point of this purified material and compare your data to those reported in the literature. Calculate the percent recovery on recrystallization. 9-Fluorenone has a characteristic UV spectrum. The following data were obtained at a concentration of 8.66 x 10-6 M: max248nm(max = 5.27 x 104, methanol) max255nm(max = 7.83 x 104, methanol) max290nm(max = 3.93 x 103, methanol)