I.

Introduction

Opposite of the industrial process of creating an alcohol through hydration of an alkene, an

alkene may be formed through the subsequent dehydration of an alcohol, which follows a
reversible three-step process that have equilibria shifted to the right to force the reaction into
completion by fractional distillation (see Figure 8.1.).

FIGURE 8.1. Three-step dehydration of a primary alcohol.

Treating an alcohol with a strong acid, such as phosphoric acid in this exercise, causes the
elements of water to be removed by dehydration (Hunt 2014), and the results in an alkene. The
dehydration process is classified as E1, for "elimination, unimolecular" due to its rate-
determining step (second step), and the rate of this step as well as that of the overall reaction is
dependent upon the relative ease of the carbocation intermediate, and so the ease of
dehydration follows: 3 > 2 > 1. An E1 reaction generally involves the deprotonation of a hydrogen
nearby (usually a carbon away), with the carbocation resulting in the formation of an alkene
product, where a Lewis base is required in order to complete the reaction (Balasubramanian
2015).

Fractional distillation will be used in order to force the reversible reactions into completion. It is
different from simple distillation only in the setup, wherein it separates a mixture into different
parts or fractions through a column fitted above the mixture and several condensers; where the
column is cool at the top and heated at the bottom (BBC 2014). Substances with high boiling
points condense at the bottom of the column, while substances with low boiling points
condense at the top, and similarly with distillation, fractional distillation works through the
different substances having varying boiling points.

For comparison of the starting material and product, the chemical tests from Exercise 5,
combustion, reaction with bromine, and Baeyer's test will be done on cyclohexanol, along with
the Jones test or Jones oxidation, which uses a solution of chronic acid in sulfuric acid to test for
aldehydes and primary or secondary alcohols; a positive result is marked by the formation of a
green color within fifteen seconds upon addition of the reagent (Doe 2017), with the reaction
following in Equation 8.1.

[EQN 8.1.]

In this exercise, cyclohexene will be prepared from cyclohexanol through the process of
dehydration, and the mechanism for this reaction can be seen in Figure 8.3., beginning with the
formation of a carbocation.

FIGURE 8.2. Reaction mechanism for cyclohexene.

Other than cyclohexene, there are also possible side reactions to this process, such as the
carbocation reacting with cyclohexanol to yield dicyclohexyl ether (see Equation 8.2.), which can
be removed by a second distillation of the product of the first distillate.

[EQN 8.2.]

Another possible side reaction is the polymerization of cyclohexene (see Equation 8..), which can
be prevented or minimized by removing it during fractional distillation, as the boiling point of an
alkene is generally lower than that of an alcohol, as alcohols can form hydrogen bonds with each
other and increase their boiling point (Clark 2000).

[EQN 8.3.]

VI. Discussion

Upon heating with acid catalysts, alcohols typically undergo 1,2-elimination reactions to
generate an alkene and water, and this reaction is known as "dehydration" due to the removal of
a water molecule (Hunt and Spinney 2006). In this exercise, cyclohexanol underwent an E1
reaction with the use of sulfuric acid. An E1 reaction (unimolecular elimination reaction) involves
the deprotonation of a nearby hydrogen, with the carbocation resulting in the formation of an
alkene product, where a Lewis base is required in order to complete the reaction
(Balasubramanian 2015); this follows a reversible three-step process (see Figure 8.1.) that was
forced to completion in this exercise through use of fractional distillation.

Fractional distillation is used to separate the reaction mixture into different parts using the
fractionating column, thus enabling quick removal of products from the reaction mixture; this is
possible due to the presence of the fractionating column, whose purpose is to increase the
distance that the vapor must travel to reach the condenser, and the presence of the glass pegs
within the columb increases the surface area the vapor must come into contact with as it
transports to the condenser, thus causing the higher-boiling liquid to condense back to a liquid
and return to the boiling flask (Brubaker 2017). Thus, cyclohexene can be easily removed from
cyclohexanol during distillation due to its lower boiling point.

In this exercise, a mixture of sulfuric acid (193 degC) and cyclohexanol (161 degC) underwent
fractional distillation, this was done only for a certain amount of time and the temperature was
monitored to prevent mixture of other substances (such as excess cyclohexanol or sulfuric acid)
with the distillate, which could cause later difficulties in liquid-liquid extraction. The receivers
were ice-cooled in order to condense any produced vapors that were not liquefied in the
condenser, as any vapors escaping to the air may cause losses and later on, a negative yield.

During liquid-liquid extraction, the distillate was mixed with saturated sodium chloride (NaCl),
where the lower aqueous layer was removed along with any excess water as a pre-drying step,
and then the produced organic layer was made basic through saturated sodium carbonate
(Na2CO3), in order to neutralize any traces of sulfuric acid. Afterwards, the organic layer was
then dried first with anhydrous sodium sulfate and then with anhydrous calcium chloride.

The obtained liquid through decantating was distilled again, however the distillation
temperature range did not increase beyond 73 degC when the distillate was collected (see Table
8.1.), however this reading may be due to incorrect positioning of the thermometer within the
distillation flask, as the stopper was too loose and the thermometer was inclined within the
tubing. The literature value for the boiling point of cyclohexene is 82.8 deg C, which is at least
ten degrees higher than the observed value. The collected distillate amounted to 2.3 mL,
resulting in a percentage yield of 15.8 (see Table 8.1.).

In order to compare cyclohexanol with the obtained distilled product, simple chemical tests were
performed, namely combustion, Baeyer's test, reaction with bromine, and Jones' test.

In the combustion test, aromatic compound exhibit a large amount of suit, followed by moderate
sootiness in alkenes and very light sootiness in alkanes; this is due to the amount of soot
produced relating to the degress of unsaturation, where in the greater the amount of carbon
divided by hydrogen, the greater the amount of soot produce because of the unreacted carbon
produced from the incomplete combustion. Following this, cyclohexanol exhibited almost no
soot in comparison to the product (presumably cyclohexene), according to Table 8.2.1. (see
Equations 8.4. and 8.5.).

[EQN 8.4.]
[EQN 8.5.]

In the reaction with bromine test, light-catalyzed bromination is tested, and the product,
following the reaction with cyclohexene, showed decolorization (see Table 8.2.1.), which
determines that the bromine has reacted to become part of the molecule (see Equation 8.6.),
whie cyclohexanol did not exhibit any decolorizaion.

[EQN 8.6.]

In Baeyer's test, cold, dilute, neutral potassium permanganate (KMnO4) is used to determine the
presence of double or triple bonds, through the breaking of the pi bond to form a vicinal diol,
and producing the dark brown precipitate of manganese dioxide as an indicator for a positive
result (see Equation 8.7.). Following this, the product reacted as cyclohexene would (see Table
8.2.2.) and produced a dark brown precipitate, while cyclohexanol did not react with KMnO4
due to the absence of a double or triple bond.

[8.7.]

If cold, dilute, acidic KMnO4 were used instead of cold, dilute, neutral KMnO4 (Baeyer's
reagent), then the mangante ions woud be reduced to manganese ions, and there would be no
formation of manganese oxide to indicate that the reaction had occured or not, therefore giving
off a false negative result (Clark 2003), though the pi bond in the alkene or cycloalkene would
still have broken to create a vicinal diol (see Equation 8.8.). However, the use of acidified KMnO4
is rare in organic chemistry due to its tendency to break carbon-carbon bonds (Clark 2003).

[EQN 8.8.]

Finally, in Jones' test, also known as Jones Oxidation, chromic trioxide in diluted sulfuric acid,
which forms chromic acid in situ, reacts with primary and secondary alcohols to form a blue-
green color (due to theformation of Cr3+ by disproportionations and single electron transfer), by
conversion of secondary alcohols to ketones and of most primary alcohols to carboxylic acids;
the oxidation of primary allylic and benzylic alcohols gives aldehydes (Organic Chemistry Portal
2017). While cyclohexanol reacted positively, it was seen that the product also reacted positively
(see Table 8.2.2.), however this may be due to the presence of water that may have been added
incidentally during the simple distillation, causing an addition of an alcohol or oxygen group that
may have caused a positive Jones test.

[8.9.]
If dehydration were to be performed on a cyclohexanol with a substituent, Zaitsev's Rule predicts
that the major product ofa an elimination reaction is the more substituted alkene, due to the
transition state leading to the more substituted alkene being lower in energy and proceeding at
a higher rate (Ashenhurst 2012). Therefore, the result of the dehydration of trans-2-
methylcyclohexanol will thermodynamically prefer the formation of 1-methylcyclohexene due to
its lower enthalpy of formation, followed by 3-methylcyclohexene (see Equation 8.10.); however,
if the reaction is carried over a greater period of time, a larger fraction of methylenecyclohexane
will be produced, due to the greater stability of the tertiary carbocation making the final reaction
step thermodynamically reversible (Moores 2017).

[EQN 8.10.]

VII. References

A. Books

HUNT I., SPINNEY R. 2006. Organic Chemistry. 5th Edition. New York, USA: McGraw-Hill
Education. Chapter 5.

MOHRIG J.R., HAMMOND C.N., SCHATZ P.F. 2010. Techniques in Organic Chemistry. 3rd Edition.
New York, USA: W.H. Freeman and Company.

B. Web Sources

ASHENHURST J. 2012. Elimination Reactions (2): Zaitsev’s Rule. Retrieved November 1, 2017,
from: https://www.masterorganicchemistry.com/2012/08/31/elimination-reactions-2-zaitsevs-
rule/

BALASUBRAMANIAN S. 2015. E1 Reactions. Retrieved November 1, 2017, from:

https://chem.libretexts.org/Core/Organic_Chemistry/Reactions/Elimination_Reactions/E1_Reac
tions

BBC. 2014. Fractional distillation. Retrieved November 1, 2017, from:

http://www.bbc.co.uk/schools/gcsebitesize/science/aqa_pre_2011/rocks/fuelsrev3.shtml
BRUBAKER J. 2017. How Does Fractional Distillation Work? Retrieved November 1, 2017, from:
https://sciencing.com/fractional-distillation-work-6310159.html

CLARK, J. 2000. Intermolecular Bonding - Hydrogen Bonds. Retrieved November 1, 2017, from:
https://www.chemguide.co.uk/atoms/bonding/hbond.html

CLARK J. 2003. Alkenes and potassium permanganate (VII). Retrieved November 12, 2017, from:
https://www.chemguide.co.uk/organicprops/alkenes/kmno4.html

LANCASHIRE R.J. 2002. Experiment 10: Preparation of cyclohexene from cyclohexanol. Retrieved
November 1, 2017, from: http://wwwchem.uwimona.edu.jm/lab_manuals/c10expt8.html

MOORES B.W. 2017. Dehydration of 2-Methylcyclohexanol. Retrieved November 12, 2017, from:
http://www.thecatalyst.org/experiments/Moores/Moores.html

ORGANIC CHEMISTRY PORTAL. 2017. Jones Oxidation. Retrieved November 12, 2017, from:
http://www.organic-chemistry.org/namedreactions/jones-oxidation.shtm