Sodium borohydride reduction of 2-Methylcyclohexanone

Kella Ortega, Miguel Fernandez, Andrei Maghirang

Experiment performed July 15, 2013; final report submitted August 25, 2013

Abstract
A reduction reaction was done on a 2-methylcyclohexanone to form a 2-
methylcyclohexanol. The product made was a white liquid solution, despite the fact that 2-
methylcyclohexanol is supposed to be colorless. This was accountable to the error committed by
the group in regulating the temperature of one of the reactants. The group was unable to analyze
the product through the IR spectrum or the MS. This is due to the limited amount of product
produced and errors committed by the group with regards to handling the product. In addition,
the properties of the product (melting point, density, etc.) had not been tested.

Introduction
Reduction of sodium borohydride was discovered in 1943 by H. I. Schlesinger and H. C.
Brown. Brown devoted his entire scientific career to this reagent, making it and other hydrides
the most useful and versatile of reducing reagents. The principal application of sodium
borohydride is the production of sodium dithionite from sulfur dioxide; sodium dithionite is used
as a bleaching agent for wood pulp and in the dyeing industry. Sodium borohydride reduces
aldehydes and ketones to give the related alcohols. This reaction is used in the production of
various antibiotics including chloramphenicol, dihydrostreptomycin, and thiophenicol. Various
steroids and vitamin A are prepared using sodium borohydride in at least one step.
Reduction is a reaction that involves an increase in number of electrons in a molecule.
For example, metabolism, a chemical process that is responsible for the different processes that
keep organisms alive, is driven by Redox reactions. This reaction is usually accompanied by
another reaction called oxidation reaction. An oxidation reaction is characterized by a decrease in
number of electrons by another molecule. In these two reactions, the organic compound and the
reagent may be the reducing agent or the oxidizing agent, depending on the whole reaction. The
reducing agent is the compound that experiences oxidation while it reduces or it takes the proton
from the other compound. On the other hand, the oxidizing agent is the compound that
experiences reduction, while it oxidizes or gives the proton the other compound. In this
experiment, reduction is seen when the 2-methylcyclohexanone was reduced by the sodium
borohydride when it was added to the reaction6.
 Figure 1: Reaction; formation of 2-Methylcyclohexanol

Figure 1: Mechanism; formation of 2-Methylcyclohexanol

The starting material, 2-methylcyclohexanone, is liquid with a molecular weight of

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112.172 g/mol. Its boiling point is 165.1 degC. It has a density of .9240 g/cm and it can be

soluble in methanol, diethyl ether, and acetone. It is insoluble in cold water. The reactants used
were sodium borohydride and methanol. Sodium borohydride is solid with a molecular weight of

37.83 g/mol. At melting point, it decomposes. Its density is 1.3 g/cm3 and it would be easily

soluble in cold water1. Methanol is a liquid that has a molecular weight of 32.04 g/mol. Its
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boiling point is 64.5degC, while its melting point is 97.8 degC. Its density is 1.11 g/cm . It is

soluble in both cold and hot water3.

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 If done properly, the expected product of this experiment is 2-methylcyclohexanol. This
is usually used to form a mixture of cyclic alkenes which has become a standard experiment in
the organic chemistry and upper-level laboratory curricula at several colleges and universities.
Among other things, this compound illustrates the utility of Zaitsev's rule. Other than the aimed
product, 2-methylcyclohexanol, the by-products Na, BH 3 and OCH3 were also expected to be
made6.

Methodology
A combination of 1.25 mL of methanol and 300 mg of 2-methylcyclohexanone was
added in a reaction tube. The reaction tube was then cooled in an ice bath. While inside the ice
bath, 50 mg of sodium borohydride was added. However, the expected clarity of the solution
was not seen even after the reaction ended. This may be because the added sodium borohydride
was colder than room temperature, because one member of the group accidentally placed it in the
ice bath. After adding sodium borohydride, it was cooled for 10 minutes5.
The resulting reaction, borate ester, was then decomposed by adding 1.25 mL of M
sodium hydroxide solution. After adding the sodium hydroxide, since the solution was already
murky even before the sodium hydroxide was added, the experimenters were not able to witness
the expected change of becoming murky in the appearance of the solution. After letting the
solution settle, it was placed in a separatory funnel and 1 mL of water was added. The reaction
separated into layers. The upper layer was placed in a reaction tube, since the organic product is
theorized to have less density. Then it was extracted two times with the use of 0.5 mL
dichloromethane. The extracts where then dried with use of anhydrous sodium sulfate. The
solution was then transferred to a dry reaction tube which had a couple of boiling chips in it. It
was then boiled under the hood. It was boiled for only a short time so that most of the
dichloromethane and methanol would evaporate; leaving what was the expected product on the
reaction tube5.
The sample was too small to run be run on both IR and MS. So, the group decided to run
it through MS. However, in the end, the group was not able to get the results of the run since the
product was taken out of the machine and replaced with other solutions before the group was
able to see the results of the run5.

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 Also, the group was unable to retrieve data regarding most of the physical properties of
the product during the experiment because it was advised to not do so with the limited given to
complete the experiment. However, the experimenters were able to note that the color of the
product was white. According to theory, however, it is supposed to be clear or colorless. This
may still be due to the error committed earlier in the experiment. Other than its theoretical
appearance, its odor is said to be associated with menthol, while its boiling point is supposed to

g
be from 163 - 166 deg C. It is slightly soluble and its density is supposedly 0.930 cm3 . Its

g
C7 H 14 O
molecular formula is , and its molecular weight is 114.19 mol . 2

Results and Discussion

The experiments main objective is to experimentally show the process of reduction of 2-
methylcyclohexanone. In the mechanism of the reaction, the carbonyl carbon in the 2-
methylcyclohexanone would reduce the sodium borohydride by taking one of the hydrogen
atoms. The new bond in the carbonyl carbon would cause the double bond between the carbon
and oxygen atom to break, which in turn would make the oxygen atom negatively charged. The
negatively charged oxygen would then take a proton from ethyl alcohol, neutralizing the charge
in the oxygen atom and making 2-methycyclohexanol. Two products were formed because the
reagent had a stereocenter, which made it possible for the sodium borohydride to attack either
from the front or the back of the 2-methycyclohexanone.
In the experiment, 1.25 mL of methanol and 300 mg of 2-methylcyclohexanone were
combined in a reaction tube. After the reaction, the reaction tube was cooled in an ice bath. Then,
while it was still in the ice bath, 50 mg of sodium borohydride was added. Sodium borohydride
was added into the solution while the solution was in an ice bath in order to keep tominimize the
temperature. If the temperature was not properly controlled, a side reaction between sodium
borohydride and methanol would occur. However, an error was still committed in this procedure
since the sodium borohydride added was not in room temperature, but instead was accidentally
cooled by an ice bath before it was added to the solution. After this procedure, the solution was
set aside to cool for 10 minutes. The resulting reaction was borate ester. This solution was murky,

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despite the fact that it should not be. It is theorized that the murkiness of the solution is caused by
the error committed with regards to the temperature of sodium borohydride. This was then
decomposed through the addition of 1.25 mL of M sodium hydroxide solution. The expected
change in the solution's texture was not seen because the solution was already murky to begin
with. After which, it was transferred to a separatory funnel and 1 mL of water was added. This
caused the reaction to separate into 2 layers. The expected product was the top-most layer. This
is because organic substances usually have less density. This layer underwent extraction two
times with 0.5 mL of dichloromethane. Dichloromethane was used since it has a higher density
than water. Then, the solution was dried through the use of anhydrous sodium sulfate. It needed
to be dried because there was still water inside the solution; drying it was supposed to take out
the water in the solution. After drying the solution, it was transferred to a reaction tube which
contained boiling chips. Then, it was briefly boiled under the hood to evaporate most of the
substances that were not the expected product, 2 Methylcyclohexanol5.
There were many errors committed in this experiment. The first being that one member of
the group accidentally decreased the temperature of sodium borohydride. Next time, it would be
advisable to check the procedures before such things are done. In addition, the other members of
the group should be more vigilant in checking what the other members do in order to prevent
such other mishaps from occurring. The other error committed was leaving our product to run on
its own in the MS. The experimenters should have thoroughly been present as the product was
undergoing MS.
If the experiment was a success, the IR spectrum of the product would be similar to that
of the IR spectrum of a 2-methylcyclohexanol (Appendix 1). The peaks in 3351.73 and 2938.07
represent the presence of alcohol and alkyl groups, respectively. Also, it would have a peak alike
the one found in 1452.73, which represents the presence of benzene.

Conclusion and Recommendations

As the product had not been tested, the group finds it hard to scope the success of the
experiment conducted, especially since there were significant errors committed by the group as
they were conducting the experiment. So, the product may not truly be what was expected. It is
recommended that the researchers follow the procedures of the experiment thoroughly because
anything that was changed or done unnecessarily may have unwanted outcomes like a lessened

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yield or obtaining different reactions. To add to that, the group should always take note of the
yield they obtained after every experiment so they may have a point of comparison with the
theoretical value. Knowing the difference between the experimental and the theoretical yield
would help the group know if they efficiently conducted the experiment or not.

References

1 Material Safety Data Sheet. (n.d.). Science Lab. Retrieved August 24, 2013, from
http://www.sciencelab.com/msds.php?msdsId=9924969

2 Material Safety Data Sheet. (n.d.). Science Lab. Retrieved August 24, 2013, from
http://www.sciencelab.com/msds.php?msdsId=9923625

3 Material Safety Data Sheet. (n.d.). Science Lab. Retrieved August 24, 2013, from
http://www.sciencelab.com/msds.php?msdsId=9927227

4 Material Safety Data Sheet. (n.d.). Fisher Scientific. Retrieved August 24, 2013, from
http://fscimage.fishersci.com/msds/87070.htm

5 Williamson, K., Minard, R., Masters, K. (2007). Macroscale and microscale organic
experiments (5th ed.). Boston: Houghton Mifflin Company.

6 Zumdahl, S., & Zumdahl, S. (2012).Chemistry: An Atoms First Approach . Belmont:

Cengage Learning.

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Appendices

Appendix 1 IR spectrum of 2-Methylcyclohexanol