1. Experiment 20: REDUCTION OF 9-FLUORENONE

2. Objectives: • To synthesize a secondary alcohol from a ketone using a sodium borohydride reduction. • To purify and isolate the product using recrystallization. • To analyzethe purity of the product using TLC, HPLC and melting point analysis. • To characterize the reactants and products using NMR spectroscopy.

3. Before coming to lab… • Review these techniques: • Fractional distillation • Vacuum filtration • GC Analysis

4. REDUCTION USING NaBH4 • NaBH4 (sodium borohydride) is a versatile and useful reducing agent in organic chemistry. • A reducing agent causes a reaction (a reduction) in which the product has more bonds from carbon to hydrogen (or fewer bonds to oxygen)

5. MECHANISM NaBH4 transfers a hydride ion to the carbonyl carbon. The oxygen anion eventually removes a proton from water.

6. EXPERIMENTAL PROCEDURE(Synthesis) • Weigh 9-fluorenone into 50 mL flask with stir bar. • Dissolve in ethanol. • Add NaBH4 slowly. Stir 20 minutes. • Add deionized water. • Add 0.1 M HCl dropwise until pH = 7.

7. EXPERIMENTAL PROCEDURE(Purification) • Suction filter. • RINSE SOLID WITH 10 ML COLD WATER! • Prepare TLC and HPLC samples. • Place product in warm oven for 10 minutes on a preweighed watch glass. • Obtain final product yield, calculate % yield. • Proceed to PRODUCT ANALYSIS.

8. EXPERIMENTAL PROCEDURE(Product Analysis) • TLC analysis • Identify components present in product solution and determine purity. • HPLC analysis • Identify components present in product solution and determine purity. • MP analysis • Compare to literature value of melting point to determine purity. • NMR analysis • Characterize reactant and product using spectra on page 169.

9. Table 20.1

10. Table 20.2

11. Tables 20.3 and 20.4

12. NMR Spectroscopy9-fluorenone Aromatic protons Aromatic carbons NMR solvent 194d

13. NMR Spectroscopy9-fluorenol Aromatic protons 5.54d TMS 1.75d Aromatic carbons NMR solvent 75d

14. SAFETY CONCERNS • All compounds used in today’s experiment are FLAMMABLE • and TOXIC! Use extreme caution when in use!

15. WASTE MANAGEMENT • Place aqueous filtrate from suction filtration in container labeled “AQUEOUS WASTE (Ketones)”. • Place TLC solvent in container labeled “ORGANIC WASTE (Ketones)”. • Place MgSO4, filter papers, and used TLC plates in yellow “SOLID WASTE” can. • Place used TLC and melting point capillaries in BROKEN GLASS CONTAINER. • Place product in container labeled “9-FLUORENOL (Student Prep).

16. CLEANING • Clean all glassware with soap, water, and a brush if necessary. • Rinse all glassware with wash acetone before returning it to the lab drawer! • DO NOT return glassware to lab drawer dirty or wet!