SEMESTER 20214

OCTOBER 2021 – FEBRUARY 2022

EXPERIMENT 2:
SODIUM BOROHYDRIDE REDUCTION OF
CYCLOHEXANONE

NAME : SITI NUR AFIQAH BINTI MAHAZAN

STUDENT ID : 2020897786
GROUP : AS2533A1
DATE : 5TH NOVEMBER 2021

Objective (1M)

Introduction (2M)

Procedure in flowchart (2M)

Calculation (5M)

Discussion (3M)

Conclusion (1M)

Questions (4M)

References (1M)

Appendix 1 (1M)

TOTAL (20M)
OBJECTIVES

1. To synthesize cyclohexanol from the reduction of cyclohexanone using sodium

borohydride.
2. To characterize the reduction product using IR spectroscopy.

INTRODUCTION

Many functional groups, including aldehydes, ketones, amides, and others, rely on the
carbonyl group. The carbonyl carbon atom is sp2 hybridised, so the carbonyl carbon and the
three atoms attached to it are in the same plane. The bond angles between the three attached
atoms are approximately 120°, as expected for a trigonal planar structure. The carbonyl group
is a polar group. As a result, aldehydes and ketones have higher boiling points than
hydrocarbons of the same molecular weight. However, because aldehydes and ketones cannot
form strong hydrogen bonds between their molecules, they have a lower boiling point than
the corresponding alcohols.

The inorganic compound sodium borohydride, also known as sodium tetrahydroborate, has
the formula, NaBH4 . This white solid, which is usually found as a powder, is a versatile
reducing agent that has a wide range of applications in chemistry, both in the laboratory and
on a larger scale. A large amount is used in the bleaching of wood pulp. In the absence of a
base, the compound is insoluble in ether and soluble in glyme solvents, methanol, and water.

Sodium borohydride works well as a reducing agent. Although it is not as strong as lithium
aluminium hydride (LiAlH4 ), it is very effective at converting aldehydes and ketones to
alcohols. It will not reduce esters, carboxylic acids, or amides on its own (although it will
reduce acyl chlorides to alcohols). It is also used to replace mercury (Hg) with H in the
second step of the oxymercuration reaction.

Organic molecule reduction usually results in an increase in hydrogen content or a decrease

in oxygen content. In this experiment, ketones were converted to alcohol. The reducing
agents for ketones to alcohols are lithium aluminium hydride (LiAlH4 ) and sodium
borohydride (NaBH4 ). LiAlH4 is a strong reducing agent. It can reduce esters, acids,
aldehydes, and ketones, whereas NaBH4 can only reduce aldehydes and ketones. Because
LiAlH4 reacts violently in water, the experiments cannot be performed in water or alcohol
solutions, whereas NaBH4 experiments can be performed in both water and alcohol solutions.
In this experiment, NaBH4 is used as a reducing agent, and the expected product is
cyclohexanol, which is formed from cyclohexanone. The following is a chemical equation for
cyclohexanone reduction:
APPARATUS

Large test tube

Measuring cylinder (5 mL, 10 mL)
Beaker (250 mL)
Stainless steel spatula
Pasteur pipette
Separatory funnel (250 mL)
Retort stand
Ring clamp
Bosshead for retort stand
Test tube rack
Conical flask (100 mL or 250 mL)
Filter paper
Bottle sample
Aluminium foil
Rotary evaporator
IR Spectrometer

CHEMICALS

Methanol
Cyclohexanone
Ice
Sodium borohydride (NaBH4 )
3 M sodium hydroxide (NaOH) solution
Distilled water
Dichloromethane (CH2 Cl2 )
Anhydrous sodium sulphate (Na2 SO4 )
PROCEDURE
RESULTS AND OBSERVATIONS

Results:

a. Volume of cyclohexanone: 2 mL
b. Weight of product:
Weight of empty sample bottle (g) 43.9982 g

Weight of sample bottle + product (g) 45.5002 g

Weight of product (cyclohexanol) (g) 1.5020

c. IR data (in Table):

i. Cyclohexanone
Wave number (𝐜𝐦−𝟏 ) Type of bond (group)

1,680 − 1,750 cm−1 C=O

2,850 − 2,950 cm−1 C−H

ii. Product
Wave number (𝐜𝐦−𝟏 ) Type of bond (group)

1,000 − 1,250 cm−1 C−O

2,800 − 3,000 cm−1 C−H

3,200 − 3,550 cm−1 O−H

d. Appearance of the product: Colourless liquid formed

Observations:

1. The solution of methanol and cyclohexanone react vigorously when added with
sodium borohydride.
2. The solution turned to pale yellow in colour after the reaction.
3. Two layers of solutions were observed after the addition of borate ester: a clear
solution at the upper layer and cloudy solution at the bottom layer.
4. The solution formed emulsion when been extracted.
5. Full reaction mechanism of cyclohexanone being reduced by sodium borohydride can
be observed here: https://www.youtube.com/watch?v=gMWEC8AIJyc
Calculations/Task:

Theoretical yield Molar mass of cyclohexanone = 98.15 g mol−1

of the product
Mass
Density =
Volume

Mass of cyclohexanone used = Density × Volume

= 0.9478 g/ml × 2 mL

= 1.8956 g

Mass
Moles of cyclohexanone used =
Molar mass
1.8956 g
=
98.15 g mol−1

= 0.0193 mol

From stoichiometry,

1 mole of cyclohexanone ≡ 1 mole of cyclohexanol

0.0193 mol of cyclohexanone ≡ 0.0193 mol of cyclohexanol

Molar mass of cyclohexanol = 100.158 g mol−1

Theoretical yield of cyclohexanol = Moles × Molar mass

= 0.0193 mol × 100.158 g mol−1

= 1.933 g

Percentage yield of Actual yield

Percent yield = × 100%
the product Theoretical yield

1.5020 g
= × 100%
1.933 g

= 77.70%
 Mechanism for this
reaction

DISCUSSION

In this experiment, ketone is reduced into alcohol using sodium borohydride, NaBH4 as the
reducing agent. In this case, cyclohexanone will be converted to cyclohexanol. The reduction
process mechanism is considered in this experiment as the sodium borohydride will be
broken down into NaBH3 + and H − . The H − will act as a nucleophile, attacking the carbonyl
group and breaking up the double bond. Because O− is unstable, protonation of oxygen will
occur by adding H3 O+ to produce an alcohol.

Sodium borohydride, NaBH4 , is commonly used to convert ketone and aldehyde to alcohol as
it is a mild reducing agent. Methanol was used as a solvent during the experiment because it
can determine whether the NaBH4 used was active in the reduction process. Because a
vigorous reaction occurred during the addition of NaBH4 to methanol solution, it is safe to
conclude that NaBH4 is active. With the addition of distilled water, a 3M NaOH solution was
added to decompose the borate ester. During the separation process, two layers can be seen: a
clear upper layer and a yellowish cloudy bottom layer. The clear upper layer should be the
product. The extracting solvent used was dichloromethane, and the extraction process was
repeated twice to ensure that all cyclohexanol was extracted. The extracted cyclohexanol will
then be combined and dried to remove the water using anhydrous sodium sulphate. Finally, a
rotary evaporator will be used to evaporate the product. After the experiment was completed,
the product will be tested to see if alcohol was produced by using IR spectroscopy.

The mechanism of the reaction of sodium borohydride with aldehydes and ketones were
divided into two steps. In the first step, H − was separated from the BH4 − and was added to
the carbonyl carbon. This forms the C − H bond and breaks the C − O bond, resulting in a
new lone pair on the oxygen, which makes the oxygen negatively charged; these negatively
charged oxygens were alkoxides because they were deprotonated alcohols. To produce
alcohol, a proton from water (or an acid such as NH4 Cl) was added to the alkoxide in the
second step. This was done at the end of the reaction. The mechanism for the reduction of
cyclohexanone to cyclohexanol using sodium borohydride was shown below:
 2,850 − 2,950 cm−1
C − H stretch

1,680 − 1,750 cm−1

C = O stretch
Cyclohexanone's IR spectroscopy will be performed to determine whether it is a true ketone.
The infrared spectrum of cyclohexanone is shown above. Based on the IR spectrum, the
presence of carbonyl group (C = O stretch) of ketone can be determined at peak 1,680 −
1,750 cm−1 and peak 2,850 − 2,950 cm−1 which represent the C − H stretch. While there are
other stretches present, these are the key stretches that identify the functional groups of
cyclohexanone. Following that, the colourless sample will be run through IR spectroscopy to
determine whether the product is cyclohexanol. Additionally, the loss of the broad O − H
stretches at ~3,300 cm−1 can be used to identify this molecule as cyclohexanone and not
cyclohexanol. The IR spectrum produced is shown below:

2,800 − 3,000 cm−1

C − H stretch

3,200 − 3,550 cm−1

O − H stretch
1,000 − 1,250 cm−1
C − O stretch
Based on the IR spectroscopy, the colourless product can be proven to be an alcohol based on
the peak shown. The alcohol functional group has a broad U-shaped peak at 3,200 −
3,550 cm−1 , a C − H stretch at 2,800 − 3,000 cm−1, and a C − O stretch at 1,000 −
1,250 cm−1 . While there are other stretches present, these are the key stretches that can be
used to identify this molecule as cyclohexanol. According to the results, the cyclohexanol
obtained was 77.70%. It is possible that an error occurred during the experiment, resulting in
the loss of the product, and thus a 100% yield of the product cannot be obtained. There could
be a chemical spill or parallax error during the experiment.

CONCLUSION

The percentage yield of the product (cyclohexanol) is 77.70%. The IR spectrum showed a
broad absorption peak at 3,200 – 3,550 cm−1 belonged to a hydroxyl group, confirming this
experiment has successfully reduced a ketone to an alcohol.

QUESTIONS

1. How do you confirm that the cyclohexanone has been reduced to cyclohexanol using
IR analysis? (1M)

To confirm that the cyclohexanone has been reduced to cyclohexanol using IR

analysis is the result obtained from the IR analysis shown broad wavelength peak
between 3,200 cm−1 – 3,550 cm−1 due to the presence of a characteristic O-H bond
to represent the OH functional group.

2. What is the function of anhydrous sodium sulphate in the experiment? (1M)

The function of anhydrous sodium sulphate in the experiment is to act as the drying
agent to absorb all the access water moisture in the cyclohexanol solution due to its
affinity for water. During extraction with base/acid and water, some of the water is
trapped in the ether layer

3. If you have the following compound, can you reduce the ketone using sodium
borohydride without affecting the ester functional group? Explain your answer. (2M)

As sodium borohydride is a mild reducing agent, it can be used to reduce ketone to

alcohol. The ester functional group could neither be reduced nor oxidised by sodium
borohydride. As a result, after the reaction, it remains unchanged. The C = O bond
will be broken down to form the C − OH bond. Only ketone, aldehyde, and acyl
chloride can be converted to alcohol using sodium borohydride.
REFERENCES

Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory Techniques 3rd Edition
(2011). page 610-614.

Kayser, M. M., Eliev, S., & Eisenstein, O. (1983). Reduction of ketones by sodium
borohydride in the absence of protic solvents. Inter versus intramolecular mechanism.
Tetrahedron Letters, 24(10), 1015–1018. https://doi.org/10.1016/s0040-
4039(00)81590-7

Welker, M. (n.d.). Organic Chemistry II. 19.3. Reductions using NaBH4, LiAlH4 | Organic
Chemistry II. Retrieved November 4, 2021, from
https://courses.lumenlearning.com/suny-potsdam-organicchemistry2/chapter/19-3-
reductions-using-nabh4-lialh4/.

APPENDIX 1

IR spectrum of Cyclohexanone:

2,850 − 2,950 cm−1

C − H stretch

1,680 − 1,750 cm−1

C = O stretch
IR spectrum of Cyclohexanol:

2,800 − 3,000 cm−1

C − H stretch

3,200 − 3,550 cm−1

O − H stretch
1,000 − 1,250 cm−1
C − O stretch