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15 Feb 2012 4:30pm Experiment #15: Sodium Borohydride Reduction of a Ketone

Goal: To reduce a ketone (4-t-butylcyclohexanone) to an alcohol using sodium borohydride, and then to verify the correct product formation via IR spectrum analysis. Physical Properties of Reagents: Molecular Formula C10H18O NaBH4 C 2H 6O Structural Formula Molecular W eight 154.25 g/mol 37.83 g/mol 46.07 g/mol Boiling Point 113-116˚C 500˚C 78˚C

Reagent KETONE TO BE REDUCED: t -butylcyclohexanone MILD REDUCING AGENT: sodium borohydride (Density: 1.0740 g/mL) POLAR PROTIC SOLVENT: ethanol ACID TO DECOMPOSE EXCESS REDUCING AGENT: 3M hydrochloric acid (Density: 1.048 g/mL) DRYING AGENT: sodium Sulfate

Melting Point 47-50˚C 400˚C -114˚C


H+ –Cl

36.461 g/mol 142.04 g/mol (anhydrous) 322.20 g/mol (decahydrate) 84.93 g/mol

-18˚C 884˚C (anhydrous) 32.4˚C (decahydrate) -96.7˚C



1429˚C (anyhydrous)

ORGANIC EXTRACTING SOLVENT: dichloromethane PRODUCT: 4- t -butylcyclohexanol SALT TO MAKE IR SPECTRUM PELLET: potassium bromide Reactions: Overall reaction: R–(C=O)–R’ ketone




156.2682 g/mol




K+ –Br

119.002 g/mol



+ NaBH 4 + (4) R”–OH —acidify (4) R–(CH—OH)–R’ + sodium borohydride (4) 1º alcohols (4) 2º alcohols

B(OH) 3 boric acid

Reaction mechanism: Formation of the tetrasubstituted ALKOXY-BORON INTERMEDIATE: 1. The BORON ANION (sodium borohydride with a 4th group that gives it a negative charge) attacks the carbonyl carbon of the KETONE breaking the pi bond. [RESULT: NEUTRAL BORON (with empty porbital) + OXYGEN ANION (negatively charged)]

3 mL ethanol to same vial. 2. Added 0. 3. WATER or a 1ºALCOHOL is added under acidic conditions to displace (1) (R2CHO)4B– +Na + (4)R’–OH — acidify (4) R2 CHOH + B(OH)3 alkoxy group from the tetrasubstituted tetraalkoxyborate (4) 1º alcohols (4) 2º alcohols boric acid ALKOXY-BORATE INTERMEDIATE. [RESULT: (1) ALKOXY ANION + OXONIUM ION INTERMEDIATE] 2. [RESULT: A tetrasubstituted ALKOXY-BORATE INTERMEDIATE] Formation of four 2º ALCOHOLS and B(OH) 3 : 1. The ALKOXY ANION deprotonates the OXONIUM ION INTERMEDIATE. 4.Page 2 15 Feb 2012 4:30pm Experiment #15: Sodium Borohydride Reduction of a Ketone 2. [RESULT: A new BORON ANION] 3. FINAL RESULT: (4) 2º ALCOHOLS + B(OH)3 Specific reaction: equatorial attack SLOW 10% cis4-t-butylcyclohexanol axial attack FAST 90% trans4-t-butylcyclohexanol Procedures & Observations: Reduction of 4-t-butylcyclohexanone: 1. [RESULT: (1) 2º ALCOHOL + the ALKOXY-BORATE INTERMEDIATE (minus one oxygen anion group & plus one hydroxyl group)] 3. Stirred at room temperature for 15 minutes noting a small amount of white precipitate formation. The process repeats x 3 as each new BORON ANION attack the carbonyl carbon of the KETONE as it did in step 1. Added 0. Added 0. Process is repeated x 3 to replace all four alkoxy groups with hydroxyl groups. The OXYGEN ANION attacks NEUTRAL BORON (empty p orbital).083 grams (about 0. Stirred at room temperature using a stirring plate until solid dissolved. .6 NaBH4 solution in ethanol to the vial being sure to use the bottom slurry of the solution.52 moles) t-butylcyclohexanone to a 5 mL conical vial with spin vane. 5.

t -butylcyclohexanone: Theoretical yield: Experimental yield: Percent yield: • • 0. 2. Waited until foaming stopped to proceed. and hydroxyl group. Extraction of the product – 4-t-butylcyclohexanol: 1. Completion of evaporation was evident once the bubbles in the conical vial were no longer visible. Characterization & Results: Results Summary: W eight of 4. 2. 7. 5. The 5 mL conical vial was accidentally knocked over prior to the second extraction introducing experimental error.t -butylcyclohexanol 0. 3. 6. Placed the vial in an ice bath for better crystallization of the product and allowed it to dry for 15 minutes at room temperature.Page 3 15 Feb 2012 4:30pm Experiment #15: Sodium Borohydride Reduction of a Ketone Isolation of the product – 4-t-butylcyclohexanol: 1. Noted a small amount of foaming indicating H2 gas formation. 4. Prepared a 25mL Erlenmeyer flask with 1 mm of anyhydrous Na2SO4 (dehydrating agent) in the bottom. Added 10 more drops of 3M HCl to the vial followed by 1. water and 0. Decanted the organic layer (CH2Cl2solution) from the flask into this vial. Allowed the two layers in the 5 mL conical vial to settle before removing the first extract from the organic layer (top layer) with a filter-tipped Pasteur pipette and transferring it to the 25mL Erlenmeyer flask mentioned in step 2. alkyl functional group. Swirled the flask several times and then allowed the solution to stand while the subsequent extractions were performed on the mixture in the 5 mL conical vial. See attached IR spectrum for analysis.5 mL CH2Cl2 each time followed by removal of the organic layer as in step 3.5 mL CH2Cl2 (the extracting solvent) and stirred the mixture for 1 minute. Added 3 drops of 3M HCl to the vial to decompose any excess NaBH4.73% Analysis of IR : IR spectrum showed expected peaks for the cycloalkane ring.510 g 4.52 mmol [LIMITING REAGENT] 0. Allowed the vial to cool to room temperature and reweighed the vial. The remaining solution was extracted and the organic layer was transferred to the flask as before. Preweighed another 5 mL conical vial with a boiling chip.813 g 4. Characterization of the product – 4-t-butylcyclohexanol: 1.t -butylcyclohexanol 62. Made a KBr pellet from the product formed.0 mL D. Calculations: Molar Ratio:  1mole 4-t-butylcyclohexanone : 4 moles NaBH4 : 1 mole 4-t-butylcyclohexanol [ 1 : 0.I.t -butylcyclohexanone used: Millimoles of 4. Placed vial in a warm water bath (40˚C) under the fume hood allowing the CH2Cl2 solvent to evaporate.25 : 1 ] . Ran an IR spectrum analysis on the product. Extracted the aqueous layer two more times using 0. This process took approximately 15 minutes.083 g 0. 8.

2682 g 4-t-butylcyclohexanol / 1000 mmol = 0.butylcyclohexanol Percent yield: 0. that the largest amount of organic product will be extracted on the first extraction attempt.t. Post-Lab Questions: 1. however.773 g (3mL conical vial with boiling chip + product) – 23.t.butylcyclohexanol Experimental (actual) yield: 23. This yield does demonstrate.510 g (experimental yield) / 0. however.73% yield. The IR data confirmed that proper technique was used to produce a pure product of 4-t-butylcyclohexanol.510 g 4. Draw the products for the following reduction reactions: (a) (b) .813 g (theoretical yield) x 100% = 62. The mixture remaining in the vial was extracted x 2 per protocol.73% Conclusions: The experiment was completed per protocol with an introduction of experimental error after the first extraction when the conical vial was knocked over.52 mmol 4-t-butylcyclohexanone x [1/1 molar ratio] x 156. the loss of an unknown amount of organic material was probably the reason for an only 62.813 g 4.Page 4 15 Feb 2012 4:30pm Experiment #15: Sodium Borohydride Reduction of a Ketone Theoretical Yield: 0.263 g (3mL conical vial with boiling chip) = 0.

It is effective in reducing aldehydes and ketones to alcohols. ketones.Page 5 15 Feb 2012 4:30pm Experiment #15: Sodium Borohydride Reduction of a Ketone 2. LiAlH4 is a very strong reducing agent that must be handled carefully. esters. It is reactive towards aldehydes. It reacts slowly with water (neutral) and is stable in basic solutions. In what ways do these two reagents differ? NaBH4 is a mild reducing agent that is safer to handle and used in protic or aqueous solvents. epoxides. and nitro groups. It can be used in aprotic solvents and reacts violently with water and other hydroxylic solvents producing H2 gas. NaBH4 is a less powerful reducing agent compared to LiAlH4. . nitriles.

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