Imaan Hussain

Bence Zakota and Christian Ward

George Pappas

Borohydride reduction of 2-Methylcyclohexanone

Introduction

In contrast to the organic oxidation reaction - involving the addition of a bond between

carbon and oxygen an organic reduction reaction is characterized with a loss of a bond between

carbon and oxygen. In order to lose a bond for a reduction reaction, one would use a reducing

agent that would add a hydride to the reactant. A nucleophile is a compound that has excess

electron density, further allowing it to donate a hydrogen. With that said, the more desirable

reducing agent would be one that is also considered a good nucleophile. A nucleophilic addition

would further donate a hydride to the reactant, and further reduce the amount of bonds between

carbon and oxygen. Similar to the organic oxidation reaction, a reduction reaction is very

dependent on its reducing agent. Considering the strength of the reducing agent, will further

determine the number of bonds between carbon and oxygen. For instance, a strong nucleophilic

reducing agent as well as a strong base, like Lithium Aluminum Hydride, is capable of reducing

a carboxylic acid to a primary alcohol. Sodium Borohydride another nucleophilic reducing

agent is considered to be weaker. When an experiment is performed using NaBH4 to transform

a carboxylic acid to a primary alcohol, it concludes with no reaction due to the strength of the

reducing agent.

In this particular experiment, Sodium Borohydride is used to reduce a ketone - 2-

Methylcyclohexanone to an alcohol 2-Methylcyclohexanol. Due to the chirality of the ketone

in the reactant, the experiment will result with two products cis and trans products. In

conclusion, the two products will be further analyzed to determine which is a kinetic product and

which is a thermodynamic product.

Figure 1: Mechanism of Synthesis of 2-Methylcyclohexanol

Figure 2: Side reactions

Experimental Section
Added 1.5ml
Cool mixture Took a TLC (using
methanol and 0.299g Placed it in iodine
in ice bath in 1ml Ethyl Acetate
2- chamber (Found
small beaker and 4ml Hexane)
Methylcyclohexanone Rf for ketone)
of this mixture
into 5ml vial

Let mixture stand

Prepared separatory Took another in room
funnel with the help of TLC and found Added .053g Sodium
temperature for 10 Borohydride to
small iron ring and Rf value min (took out of
vertical rod mixture, while it was
ice bath) in ice bath
Rinsed vial with 2 Added 2 pipets of Shook the funnel and let it
Poured solution pipets of tap water and two settle. Drained bottom
into separatory dichloromethane full pipets of 3M layer to previously
funnel and added it to the sodium hydroxide weighed 25 ml flask.
Added
anhydrous funnel solution to funnel
sodium sulfate to
dry organic layer
Removed CH2Cl Washed aqueous layer
using filter pipetAdded
and 1ml Swirled, filtered Evaporated with dichloromethane
put it into pre- dichloromethane drying agent, and solvent with (let it settle and then
weighed small filter
to flask with joined vacuum and drained organic layer
flask drying agent dichloromethane aspirator until into
Repeated flask
oil last
layers formed step

Reweighed
product and
found % yield

Table of Chemicals
Obtained IR and
HNMR spectrum.

Chart 1: Chemicals used in Lab

Methanol CH30H
 MM: 32.04g/mol

MP: -97.6C

BP: 64.7C
Iodine I2

MM: 253.81g/mol

MP: 113.7C

BP: 184.4C
Dichloromethane CH2Cl2

MM: 84.93g/mol

MP: -96.7C

BP: 39.6C
Hexane C6H14

MM: 86.18g/mol

MP: -95.35

BP: 68.73C
Ethyl Acetate C4H8O2

MM: 88.11g/mol

MP: -83.6C

BP: 77.1C
Sodium Sulfate Na2SO4

MM: 142.04g/mol

MP: 884C

BP: 1429C
2-Methylcyclohexanone C7H12O

MM: 112.17g/mol

MP: -14C
 BP: 162.1C
Sodium Borohydride NaBH4

MM: 37.83g/mol

MP: 400C

BP: 500C
Sodium Hydroxide NaOH

MM: 39.997g/mol

MP: 318C

BP: 1388C

Results

Chart 2:

Appearance of Product Clear, oil-like, translucent

Mass of Product 0.319g
Percent Yield 100%
Rf of Ketone 0.575 cm
Rf of Product 0 cm

Calculation for percent yield:

Weight of empty flask: 118.657g

Weight of flask and product: 118.976g

Mass of product: 118.976g 118.657g = 0.319g

0.053g NaBH4 x 1 mol NaBH4 = 0.0014 mol NaBH4

37.83g NaBH4

0.299g 2-Methylcyclohexanone x 1 mol 2-Methylcyclohexanone = 0.0027 mol

112.17g 2-Methycyclohexanone

0.0014 mol NaBH4 x 2 mol 2-Methylcyclohexanol x 114.19g 2-Methylcyclohexanol = 0.319g

1 mol NaBH4 1 mol 2-Methcyclohexanol

% Yield: (0.319g 2-Methylcyclohexanol) x 100 = 100%

(0.319g 2-Methylcyclohexanol)

Calculation for Rf values:

Solvent front used: 4 cm

Rf Ketone: 2.3cm = 0.575 cm

4cm

Rf product: 0cm = 0 cm
4cm

Figure 3: IR Spectrum of 2-Methylcyclohexanol

Figure 4: IR Spectrum of 2-Methylcyclohexanone
Figure 5: HNMR Results
Discussion

The experiment concluded with 2-Methylcyclohexanol as the final product. A significant

characteristic of the product was that it was a translucent oil. The product resulted with a weight

of 0.319g which is the weight the experiment began with. This further led to the percent yield to

be 100%. Most likely there were possible errors that occurred, further causing the percent yield

to be exactly 100%. Possible errors include not evaporating all of the solvent, or not separating

the aqueous layer from the organic layer accurately. Incomplete drying of the organic layer could

have acted as another error that could have caused the percent yield to be as high as it concluded

to be.

Performing a TLC of the reaction helped determine whether or not the reaction was

complete. With the beginning Rf value standing at 0.575 cm and the final Rf value at 0 cm, the

experiment was successfully reduced and concluded. In more detail, analyzing the difference in

the location of the spot on the TLC plate aided in indicating whether the reaction was complete

or not. With that said, as the spot decreased from its original position to the base line, it was

known that the reaction was complete.

While TLC aided in clarifying if the reaction was complete or not, the IR spectrum acted

as an indication to whether or not the desired product was obtained at the end of the experiment.

In this experiment a ketone was simply reduced to a secondary alcohol. The IR spectrum in

Figure 4 for 2-Methylcyclohexanone depicted a sharp peak near 1710 cm-1 implying that a

carbonyl possibly a ketone is present. Sharp peaks slightly up-field from 3000 cm-1 indicated

that hydrocarbons are in this compound as well. In contrast, the IR spectrum in Figure 3 for 2-

Methylcyclohexanol magnifies that an alcohol is produced. The large, round peak near 3400

cm-1 clarifies that there is an alcohol present. The sharp peaks between 2700 cm-1 and 2900 cm-1
illustrate hydrocarbon bonds. Overall, the IR spectrum of the final product obtained, revealed

that the desired product was attained as it included the same characteristics in that of the

molecular structure of the desired product.

HNMR would have additionally aided in identifying the product. This spectrum goes

more into detail as it shows the difference between the two isomeric products attained from this

reduction reaction. HNMR makes it possible to figure out how many hydrogens are present and

where they are located by analyzing the given peaks. Considering that the objective is to

differentiate between the two isomers, HNMR would indicate which is the cis compound and

which is the trans by looking closer into the characteristics of the hydrogens. Overall, HNMR

aids in looking for the number of signals, position of each signal, splitting patterns, and the

integral to further help in differentiating between two similar compounds. In this particular

scenario, the cis compound would most likely show a greater coupling value than the trans

compound further differentiating the two products.

Conclusion

As stated previously, in order for a reduction reaction to succeed, the starting compound

must lose a bond between the carbon atom and oxygen atom. In this particular experiment, 2-

Methylcyclohexanone reduced to 2-Methylcyclohexanol, indicating that a bond between an

oxygen and a carbon was lost. This further reflects the theory stated above.

Reduction reactions can be found outside of the laboratory as well. In recovering metals,

sodium borohydride is used to reduce metal ions back into their free metal state. This further aids

in removing metals from a large amount of water, like a stream.

 The experiment successfully transformed a ketone into a secondary alcohol using a

reducing agent NaBH4. Although there might have been errors that conflicted with a proper

product, the overall lab accomplished the organic reduction reaction.

Reference

"NMR Spectroscopy and Stereochemistry." NMR Spectroscopy and Stereochemistry.

Web. 14 Feb. 2017.

Weldegirma, Solomon. Experimental Organic Chemistry. Tampa, Fl, Department of

Chemistry, 2016. Print.

"Definitions of Oxidation and Reduction (redox)." Definitions of Oxidation and

Reduction (redox). Web. 14 Feb. 2017.

"Industry Applications." Montgomery Chemicals - Producers of Sodium Borohydride and

Other Chemical Reducing Agents. Web. 14 Feb. 2017.