Experiment 19.ppt

Experiment 19: OXIDATION OF 9-FLUORENOL Objectives: To synthesize a ketone from a secondary alcohol using household bleach. To monitor the reaction progress using TLC analysis. To purify product using simple extraction. To analyze the purity of the product using TLC and melting point analysis. To characterize reactants and products using IR analysis. Before coming to lab… Review these techniques: TLC analysis Acid-base Extraction Drying over MgSO4 Melting Point Analysis TYPICAL OXIDATION VS. GREEN OXIDATION Typical oxidation using chromium compound Greener oxidation using household bleach THE OXIDIZING AGENT NaOCl + CH3CO2H ? HOCl + CH3CO2Na Sodium acetic hypochlorous sodium Hypochlorite acid acid acetate Sodium hypochlorite is the main ingredient in bleach. It must first be converted to hypochlorous acid in order to oxidize the alcohol. HOCl is a source of a positive Cl, which has 2 fewer electrons than a chloride anion. Remember, oxidation is the loss of H or the addition of O. PROPOSED MECHANISM Although complex, the mechanism results in the exchange of a Cl+ with a H+ on oxygen, followed by subsequent elimination of HCl to form the ketone. 1. Bleach is reacted with acetic acid to produce hypochlorous acid. 2. Electropositive chlorine atom undergoes nucleophilic attack by oxygen of alcohol to form O-Cl bond… 3. Water abstracts a proton from the oxygen bearing the chlorine… 4. …followed by another attack on the proton of the carbon bearing the oxygen. 5. Both electrons from the C-H bond form the p bond of the carbonyl, and a chlorine atom is eliminated to form the neutral product ketone. 1 2 3 4 5 Reason for difference in Rf values The 9-fluorenol can DONATE hydrogen bonds to the silica gel on the TLC plate, resulting in a lower TLC Rf value! The 9-fluorenone can ACCEPT hydrogen bonds, but not donate to the silica gel on the TLC plate, resulting in a higher TLC Rf value! Reason for