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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 113-116C 500C 78C
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
HCl
H+ Cl
36.461 g/mol 142.04 g/mol (anhydrous) 322.20 g/mol (decahydrate) 84.93 g/mol
103C
Na2SO4
1429C (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
CH2Cl2
39.6C
C10H20O
156.2682 g/mol
60-69C
110-115C
KBr
K+ Br
119.002 g/mol
734C
1435C
+ NaBH 4 + (4) ROH acidify (4) R(CHOH)R + sodium borohydride (4) 1 alcohols (4) 2 alcohols
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)]
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2. The OXYGEN ANION attacks NEUTRAL BORON (empty p orbital). [RESULT: A new BORON ANION] 3. The process repeats x 3 as each new BORON ANION attack the carbonyl carbon of the KETONE as it did in step 1. [RESULT: A
tetrasubstituted ALKOXY-BORATE INTERMEDIATE]
Formation of four 2 ALCOHOLS and B(OH) 3 : 1. WATER or a 1ALCOHOL is added under acidic conditions to displace (1) (R2CHO)4B +Na + (4)ROH acidify (4) R2 CHOH + B(OH)3 alkoxy group from the tetrasubstituted tetraalkoxyborate (4) 1 alcohols (4) 2 alcohols boric acid ALKOXY-BORATE INTERMEDIATE. [RESULT: (1) ALKOXY ANION + OXONIUM ION INTERMEDIATE] 2. The ALKOXY ANION deprotonates the OXONIUM ION INTERMEDIATE. [RESULT: (1) 2 ALCOHOL + the ALKOXY-BORATE INTERMEDIATE (minus one oxygen anion group & plus one hydroxyl group)] 3. Process is repeated x 3 to replace all four alkoxy groups with hydroxyl groups. FINAL RESULT: (4) 2 ALCOHOLS + B(OH)3
Specific reaction:
10% cis4-t-butylcyclohexanol
90% trans4-t-butylcyclohexanol
Procedures & Observations: Reduction of 4-t-butylcyclohexanone: 1. Added 0.083 grams (about 0.52 moles) t-butylcyclohexanone to a 5 mL conical vial with spin vane. 2. Added 0.3 mL ethanol to same vial. 3. Stirred at room temperature using a stirring plate until solid dissolved. 4. Added 0.6 NaBH4 solution in ethanol to the vial being sure to use the bottom slurry of the solution. 5. Stirred at room temperature for 15 minutes noting a small amount of white precipitate formation.
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Isolation of the product 4-t-butylcyclohexanol: 1. Added 3 drops of 3M HCl to the vial to decompose any excess NaBH4. Noted a small amount of foaming indicating H2 gas formation. Waited until foaming stopped to proceed. Extraction of the product 4-t-butylcyclohexanol: 1. Added 10 more drops of 3M HCl to the vial followed by 1.0 mL D.I. water and 0.5 mL CH2Cl2 (the extracting solvent) and stirred the mixture for 1 minute. 2. Prepared a 25mL Erlenmeyer flask with 1 mm of anyhydrous Na2SO4 (dehydrating agent) in the bottom. 3. 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. 4. 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. 5. Extracted the aqueous layer two more times using 0.5 mL CH2Cl2 each time followed by removal of the organic layer as in step 3. The 5 mL conical vial was accidentally knocked over prior to the second extraction introducing experimental error. The remaining solution was extracted and the organic layer was transferred to the flask as before. 6. Preweighed another 5 mL conical vial with a boiling chip. Decanted the organic layer (CH2Cl2solution) from the flask into this vial. 7. Placed vial in a warm water bath (40C) under the fume hood allowing the CH2Cl2 solvent to evaporate. Completion of evaporation was evident once the bubbles in the conical vial were no longer visible. This process took approximately 15 minutes. 8. Allowed the vial to cool to room temperature and reweighed the vial. Placed the vial in an ice bath for better crystallization of the product and allowed it to dry for 15 minutes at room temperature. Characterization of the product 4-t-butylcyclohexanol: 1. Made a KBr pellet from the product formed. 2. Ran an IR spectrum analysis on the product.
Characterization & Results: Results Summary: W eight of 4- t -butylcyclohexanone used: Millimoles of 4- t -butylcyclohexanone: Theoretical yield: Experimental yield: Percent yield:
0.083 g 0.52 mmol [LIMITING REAGENT] 0.813 g 4- t -butylcyclohexanol 0.510 g 4- t -butylcyclohexanol 62.73%
Analysis of IR : IR spectrum showed expected peaks for the cycloalkane ring, alkyl functional group, and hydroxyl group. See attached IR spectrum for analysis. Calculations: Molar Ratio: 1mole 4-t-butylcyclohexanone : 4 moles NaBH4 : 1 mole 4-t-butylcyclohexanol [ 1 : 0.25 : 1 ]
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Theoretical Yield: 0.52 mmol 4-t-butylcyclohexanone x [1/1 molar ratio] x 156.2682 g 4-t-butylcyclohexanol / 1000 mmol = 0.813 g 4- t- butylcyclohexanol Experimental (actual) yield: 23.773 g
(3mL conical vial with boiling chip + product)
23.263 g
(3mL conical vial with boiling chip)
0.510 g 4- t- butylcyclohexanol
Percent yield: 0.510 g (experimental yield) / 0.813 g (theoretical yield) x 100% = 62.73%
Conclusions: The experiment was completed per protocol with an introduction of experimental error after the first extraction when the conical vial was knocked over. The mixture remaining in the vial was extracted x 2 per protocol; however, the loss of an unknown amount of organic material was probably the reason for an only 62.73% yield. This yield does demonstrate, however, that the largest amount of organic product will be extracted on the first extraction attempt. The IR data confirmed that proper technique was used to produce a pure product of 4-t-butylcyclohexanol. Post-Lab Questions: 1. Draw the products for the following reduction reactions: (a)
(b)
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2. NaBH4 is a less powerful reducing agent compared to LiAlH4. 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. It reacts slowly with water (neutral) and is stable in basic solutions. It is effective in reducing aldehydes and ketones to alcohols. LiAlH4 is a very strong reducing agent that must be handled carefully. It can be used in aprotic solvents and reacts violently with water and other hydroxylic solvents producing H2 gas. It is reactive towards aldehydes, ketones, esters, epoxides, nitriles, and nitro groups.