BACHELOR OF SCIENCE (HONS.

) CHEMISTRY WITH
MANAGEMENT
FACULTY OF APPLIED SCIENCES
CHM557
ORGANIC CHEMISTRY

EXPERIMENT 2
SODIUM BOROHYDRIDE REDUCTION OF
CYCLOHEXANONE

NAME STUDENT ID
MOHAMAD ALIF HAIQAL BIN ZUNRINA 2022971573
NOR FATIHAH BINTI JAAZIS 2022786211

DATE OF SUBMISSION: 27th JANUARY 2023

PREPARED FOR: DR. SHAARI DAUD
OBJECTIVE
1) To synthesize cyclohexanol from the reduction of cyclohexanone using sodium borohydride.
2) To characterize the reduction product using IR spectroscopy.

INTRODUCTION

In organic chemistry, a ketone is a compound with the structure RC(=O)R’, where R and R’
can be a variety of atoms and groups of atoms. It features a carbonyl group (C=O) bonded to
two other atoms. Carbonyl reduction is the organic reduction of any carbonyl group by
reducing agent. Ketone can be reduced to primary and secondary alcohols. (Peter et al.,2007)
The relatively weak reducer sodium borohydride is typically used for reducing ketones
because unlike lithium aluminium hydride, it tolerates many functional groups (nitro group,
nitrile, ester) and can be used with water or ethanol as solvents.(Berkessel, A., 2011)
Lithium aluminium hydride and other strong reducer such as diisobutylaluminium hydride, L-
selectride, diborane, diazene and aluminium hydride can also reduce ketones, but are
disfavoured because they are hazardous and reactive. However, these compounds are useful
for reducing carboxylic acids and ester to alcohols, since sodium borohydride is not powerful
to do so.(Peter et al., 2007)

Reduction of ketones:

Mechanism of reduction:
PROCEDURE

1) A 5ml of methanol followed by 2ml of cyclohexanone were placed in large test

tube. The mixture was cooled in the ice bath and added carefully to sodium
borohydride (200mg). A vigorous, bubbling reaction took place for several minutes

2) After the reaction ceased, removed the test tube from ice bath and allowed it to
cold at room temperature. Sodium hydroxide (5mL) was added to the solution to
decompose the borate ester, leaving a cloudy solution.

3) Water (4mL) was added, allowing the product to separate as a mostly clear upper
layer.
4) The layer was
4 removed by using Pasteur pipette and transfer it into a clean test
tube and then two successive methylene chloride (5mL each) additions were used to
extract the remaining product (in the bottom layer).

5) The recovered products were dried using anhydrous sodium sulphate and the
methylene chloride was subsequently boiled away using roto-evaporator.
During the boiling, methylene chloride vigorously formed bubbles and carried some
product away.

6) Reweight the flask and calculate the percentage yield of product.In further
experiments, temperature must be more carefully moderated, or a larger flask must
be used.

7) IR spectrum and gas chromatography were conducted with the product.

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) 1.502 g

c. IR data (in Table):

i. Cyclohexanone
ii. Product

Wavenumber (cm-1) Type of bond (group)

1750 C=O
2850-2950 C-H
3350 O-H
2900 C-H
1100 C-O

d. Appearance of the product : Clear/colorless solution

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.
CALCULATIONS/TASKS
1. Calculation of the theoretical yield of product.

2. Calculation of the percentage yield of product.

3. Mechanism for this reaction.

DISCUSSION

The data table of the infrared (IR) spectra and the compound 's IR
spectrum can be used to determine functional groups in a molecule. A
graphical map of the absorption and transmission of infrared light over a
number of wavelengths is the IR spectrum. An identification of the
functional groups present in a molecule is possible by comparing the IR
spectrum of a compound to the IR spectra data table, which is a table of
characteristic absorptions for functional groups. For example, if an IR
spectrum includes a wide O-H range between 3,550 and 3,200 cm -1, the
alcohol is probably included in the compound. If an IR spectrum includes
a C = O range between 1,780 and 1,630 cm-1 but not the corresponding C-
O range between 1,150 and 1,050 cm-1, therefore it is possible that the
compound does not contain an ester but a different form of carbonyl.

It is just as necessary to recognize what is not present as what is present

when evaluating a continuum. For instance, if a spectrum does not include
a range between 3,550 and 3,200 cm-1, no functional group from that range
is included in the compound, such as an O-H or N-H. Similarly, if a
spectrum does not contain a range of between 1,700 and 1,600 cm-1, there
is no carbonyl in the compound, which is the functional group present in
that area.

It is also important to remember not only the position of a stretch, but also
the form of the stretch when evaluating a spectrum. If there is a slight
stretch between 1,700 and 1,600 cm-1 in a continuum, this does not mean
that the stretch is due to the presence of carbonyl. Carbonyls offer very
strong stretches, so it is most probable that a short stretch in that area is not
due to the presence of a carbonyl, but rather to statistical noise or some
other factor.

It is also possible to analyze the IR spectrums of two compounds and

compare them to track the progress of a reaction. The reduction of
cyclohexanone (C6H10O) to cyclohexanol (C6H11OH) transforms a ketone
into an alcohol in this experiment. Ketone (C = O) and alcohol (O−H) are
the two major functional groups in this reaction.
 An IR cyclohexanone spectrum readout reveals an indicative sharp C = O
stretch of about 1,750 cm-1. There are also hybridized C-H stretches of
C(sp3)-H between 2,950 and 2,850 cm-1. Although other stretches are
present, these are the main stretches that define the cyclohexanone
functional groups.

The addition of an indicative wide O-H range around 3,350 cm-1 along
with a sharp C-O range around 1,100 cm -1 is shown by an IR spectrum
readout of cyclohexanol. Hybridized C-H stretches of C(sp3)-H at ~2,900
cm-1 are also present. Although other stretches are present, these are the
main stretches that can be used as cyclohexanol to recognize this
molecule.

CONCLUSION

In conclusion, the percentage yield of cyclohexanol is calculated to be 77.37%. The IR

spectrum showed a broad absorption peak around 3300-3500 cm -1 that belongs to a hydroxyl
O–H group, indicating that the compound is an alcohol and confirms that the reaction has
successfully converted cyclohexanone, a ketone, into cyclohexanol, an alcohol.
QUESTIONS

1. How do you confirm that the cyclohexanone has been reduced to

cyclohexanol using IR analysis?
The presence of a broad absorption peak around 3300-3500 cm-1 that indicates
an O–H group, and the absence of the C=O stretch around 1735-1750 cm-1 in the
IR spectrum.

2. What is the function of anhydrous sodium sulphate in the experiment?

Anhydrous sodium sulphate is used as a drying agent to remove any traces of
water in organic solutions.

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

Yes. This is because sodium borohydride is selective and can only reduce
carbonyls of ketones and aldehydes, but not carbonyls of carboxylic acids and
esters.
REFERENCES

1. Dr. Peter I. Dalko, Pavel Kočovský and Andrei V. Malkov,. (2007). Enantioselective
Organocatalysis: Reactions and Experimental Procedures, DOI:
10.1002/9783527610945.ch7

2. Prof. Dr. Albrecht Berkessel and Dr. Harald Gröger,. (2011) Asymmetric
Organocatalysis: From Biomimetic Concepts to Applications in Asymmetric
Synthesis, Chapter 11, Reduction of Carbonyl Compound (Print ISBN:
9783527305179 Online ISBN: 9783527604678 )

3. Siesler, H. W., Ozaki, Y., Kawata, S., & Heise, H. M. (Eds.). (2008). Near-infrared
spectroscopy: principles, instruments, applications. John Wiley & Sons
APPENDIX 1

C–H stretch
C=O stretch

O–H stretch C–H stretch

C–O stretch