Experiment 4: Borohydride Reduction of 2Methylcyclohexanone

Pratik B. Patel
Lab partners:
John Parks
Ryan Sweeny
TA: Aleksandra Karolak
2/12/15

Introduction/Background
Reduction reactions in organic chemistry are typically defined as the removal of oxygen
atoms or the addition of hydrogen atoms from the organic substrate molecule of interest.1 More
accurately the term reduction refers to the addition of electrons the substrate while its counterpart
oxidation refers to the loss of electrons.1 This being said, oxygen is an electronegative atom and
has tendency to pull electrons towards it leaving the substrate with less electrons (oxidation)
while, hydrogen on the other hand has a tendency to share electrons more evenly with its
bounded carbon atoms effectively providing its substrate electrons (reduction).
Conditions for reduction reactions include easily de-potonated weak acidic with the
solvents being typically weakly acidic organic molecules such as methanol or ethanol.2 The
solvents chosen should have some tendency to give of protons so that reduction can be ensured.
The reducing agents used in this experiment are sodium borohydride (NaBH4).1, 2 Another
famous reducing agent in organic synthesis is Lithium aluminum hydride which also is a strong
reducing agent with similar reductive potential as the sodium borohydride.1, 2
The mechanism for the following reaction done in this experiment (the reduction of
2-methylcyclohexanone) is shown below in Figure 1. Figure 2 shows a possible side reaction in
this experiment.

Figure 1: (next page)

H
H

OH

O
O

OH

Figure 1: This figure shows the primary reaction of interest in this experiment the reduction of 2methylcyclohexanone to 2-methylcyclohexanol with borohydride.

Figure 2:

Na

Na

Figure 2: This figure shows a possible side reaction that could occur while trying to reduce 2-methylcyclohexanone.
This is the formation of a borate salt which would impede the rest of the reaction from occurring.

Experimental Section
1.5mL of MeOH and 0.3g of 2-methylcyclohexanone were added to a conical vial and cooled on ice.
This mixture had been Thin Layer chromatographed (TLC) in a 2:8 mixture of ethanol and hexane.
Once the mixture sufficiently cool 50mg of sodium borohydride was added to the conical vial and the
reaction was left to stay on ice.

Once the reaction had settled down another TLC was taken of the product. The sample was then
transferred to a separator funnel and 2 pipettes of dichloromethane and 3 pipettes of 3M sodium
hydroxide were added to the funnel and this mixture was shaken.

The layers in the funnel were allowed to separate and the bottom layer containing the organic product
was drained into a 25mL Erlenmeyer flask. Anhydrous sodium sulfate was added to this extract. Then
the liquid product was rinsed into a vacuum flask with dichloromethane and evaporated with vacuum
filtration.

The final obtained product was then weighed and had its percent yield calculated as well as its IR
spectrum was obtained.

Table of Chemicals
Name

Melting point (C)

Boiling Point (C)

Methanol

-98

65.4

Molecular Weight
(g/mol)
32.04

2-methylcyclohexanone

-14

163

112.17

2-methylcyclohexanol

-38

173

114.2

Sodium borohydride

7300

500

37.83

Table of chemicals: This table shows main reagent and the desired product utilized and observed in this experiment
along with their boiling and melting points and their molecular weight. (From ChemicalBook MSDS Product Index
2008) 3

Results
Table 1:
Physical properties of laboratory obtained
2-methylcyclohexanol
Color
Mass obtained
Percent Yield

Value or Description
Clear and transparent like water
0.21 g
68.9 %

Table 1: This table shows some of the physical properties that were observed and tested for the liquid product 2methylcyclohexanol at the end of this reduction reaction. Some properties that are listed are color, mass and
percentage yield.

Calculation of Percentage yield

The stiochometry of the reaction done in this experiment is:
4 ( S )+1 NaB H 4 4 ( P)
(Here S stands for 2-methylcyclohexanone and P stands for 2-methylcyclohexanol.)
H 41 mol NaB H 4
4 mol P
37.83 g NaB H 4
114.2 g P
1mol NaB H 4
0.05 g NaB
=0.604 g P
1 mol P

S1 mol S
4 mol P
112.17 g S
114.2 g P
4 mol S
0.3 g
=0.305 g P (theoretical yeild )
1mol g S

0.21 g P( actual yeild)

=68.9 ( percent ye ild )
0.305 g P(theoretical Yeild)

Calculation of Rf for2-methylcyclohexanone and 2-methylcyclohexanol

Rf ( 2methylcyclohexanone )=

Rf ( 2methylcycloh exanol )=

4.4 cm
=0.7857
5.6 cm

4.5 cm
=0.6429
7.0 cm

Discussion
2-methylcyclohexanol is a liquid at room temperature because of very low melting point

of -38 degrees Celsius. It is s clear colorless liquid with the same transparency as water. The
mass of this product obtained in this lab was 0.21 g and its percentage yield based on the amount
of reagents used was about 70%.
The IR spectrum of 2-methylcyclohexanol has a characteristic alcohol peak between
3500 to 3200 cm-1. The original substrate 2-methylcyclohexanone has a common peak around
1710 to indicate the carbonyl in its ketone functional group. This method of using the IR o
determine if the reaction is complete is useful because it allows for simple detection of the
desired chemical transformation in reactions that involve changing or modifying a functional
group into another.
Proton Nuclear Magnetic Resonance (HNMR) could potentially be used to determine
which isomer of 2-methylcyclohexanol is present based on the proton shift values. For instance
the major product in this reaction is the trans- 2-methylcyclohexanol. This trans product has a
shift value of 3.1 ppm. The cis product has a chemical shift value of 3.8 ppm. Both of these shift
values refers to the proton added by borohydride such as that shown in the mechanism in Figure
1.

Conclusion
This experiment ties in with the theory of reduction and the use of TLC and IR to verify
that the reaction had taken place. This reaction was a reduction reaction that reduced the ketone
functional group of 2-methylcyclohexanone to a ketone found in 2-methylcyclohexanol. The
purpose of the TLC was to monitor the reactions progress until it had completed so that it could
be verified that all of the 2-methylcyclohexanone had been reduced to 2-methylcyclohexanol.
The IR spectrum was used to verify also if the sample was pure.
Reduction is a process used in many chemical synthesis pathways to create an array of
diverse products. One such reduction done in by Carlos R. Carreras and colleagues involved the
transformation of 2-substituted butenolide to (E)-2-((4R,5R)-5-((benzyloxy)methyl)-2,2-dimethyl-

1,3-dioxolan-4-yl)but-2-ene-1,4-diol by the reducing agent DIBAL-H (or Disobutylamine). 4 The

researchers also used IR and proton NMR to verify if their reaction had taken place just as done in
this lab and the researchers additionally used Carbon-13 NMR to characterize the product. 4

This experiment had to some extent successfully accomplished what I had set out to do
because the 2-methylcyclohexanol obtained was of a very pure as indicated by the IR spectrum.
The TLC also showed satisfactory results in that the 2-methylcyclohexanone blot was completely
transferred into the 2-methylcyclohexanol blot on all two TLCs that were ran.

References
1. Wade, L. (2013). Organic Chemistry (8th ed.). Glenview, IL: Pearson Education, Inc.
2. Weldegirma, S. (2014). Experimental Organic Chemistry Laboratory Manual: CHM
2210L and CHM 2211L. Tampa: University of South Florida .
3. ChemicalBook. (2008). ChemicalBook Product Index. Retrieved from
ChemicalBook.com: http://www.chemicalbook.com/ProductIndex_EN.aspx
4. Carreras, C. R., Garca, C. E., Martn, V. S., Tonn, C. E., Daz, D. D., & Ceal, J. P.
(2010). (E)-2-((4R,5R)-5-((Benzyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)but-2ene-1,4-diol. Molbank, 1-4.