Tafline Grace Borromeo Sia 29C

Dehydration of Cyclohexanol 5 November 2019

I. Data and Results [10.0 pts]

Table 1. Gravimetric data for the dehydration of cyclohexanol

Appearance Clear colorless liquid

Odour Sharp, unpleasant

Mass of cyclohexanol 8.17 g

Mass of product 2.94 g

Theoretical yield 5.35 g

% yield 55.0%

Table 2. Qualitative test results for the dehydration of cyclohexanol

Test Result Indication

Baeyer test Positive Presence of unsaturation

Chromic acid test Negative Absence of cyclohexanol

Figure 1. FT-IR spectrum of synthesized product. IR analysis of the final product showed
peaks at 3022, 2926, and 1651 cm-1, which were due to Csp2-H, Csp3-H, and C=C stretching
frequencies respectively; also, a broad peak at 3100-3500 cm-1 indicated the presence of an
O-H bond.

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Figure 2. Comparison of FT-IR spectrum of synthesized product with literature IR spectra of
cyclohexene and cyclohexanol [1, 2]. From top to bottom: cyclohexanol, cyclohexene,
product. The product had strong aliphatic C-H stretching peaks in the 2850-3000 cm-1 region.
It also had an alkenyl =C-H stretching peak from 3010-3095 cm-1 and a C=C stretching peak
at around 1620-1680 cm-1.

II. Discussion [20.0 pts]

Owing to the reactivity of the carbon-carbon double bond, alkenes can be used to
synthesize a wide variety of organic compounds and common polymers. There are two main
ways to prepare alkenes in the laboratory. One is the E2 dehydrohalogenation of alkyl halides
with the use of a strong and bulky base. Another is the E1 dehydration of an alcohol with the
use of an acid catalyst [1].
An acid-catalysed dehydration of an alcohol operates through the E1 mechanism.
First, the hydroxyl group is protonated by the acid to yield alkyloxonium. Second, the C-O
bond is cleaved, thus allowing the alkyloxonium to depart as H2O to give a carbocation
intermediate. The β carbon is then deprotonated by water and a π bond between the α and β
carbons is formed. Without an acid, the leaving group would have to be the strongly basic
HO− ion, which is a very poor leaving group that is very unlikely to depart from the molecule.
In such a case, an E1 reaction would not proceed to a significant extent [3, 4]. An example of
this is the acid-catalysed dehydration of 2-methylcyclohexanol, which gives rise to a mixture
of 1-methylcyclohexene and 3-methylcyclohexene. Following Zaitev’s rule, the major
product would be 1-methylcyclohexene [1, 6] <AtQ#6>.
In contrast to this, the dehydrohalogenation of alkyl halides operates through the E2
mechanism. The deprotonation of the β carbon and the departure of the halide (a good leaving
group) occurs in a concerted one-step reaction. The base is consumed because
dehydrohalogenation is a bimolecular reaction in which both the base and the alkyl halide
react. In dehydration reactions, acids function as catalysts because the reaction is
unimolecular (first-order) in the rate-determining step. The first step involves the addition of
H+ from the acid to the substrate while the last step involves the loss of H+ from the substrate
to the acid [3] <AtQ#4>.

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 In this experiment, cyclohexene was synthesized through the acid-catalysed
dehydration of cyclohexanol. Phosphoric acid was used as the reagent for dehydration
because it acts both as an acidic catalyst and as a dehydrating agent [3]. A
carefully-controlled continuous distillation of the reaction mixture was performed to shift the
equilibrium position towards the formation of cyclohexene as product. Probable side products
such as dicyclohexyl ether, which may have co-distilled with the first distillate, were removed
by performing a second distillation. The purity and the identity of the product were then
assessed using chemical tests and FTIR spectroscopy.
For the identity of the product, a positive result for Baeyer’s test indicated that the
product was an unsaturated hydrocarbon (Table 2). Even though the IR spectrum of the
product indicated the presence of an O-H bond (Figure 1), the sample most likely did not
contain cyclohexanol. Not only did it test negative in the chromic acid test (Table 2), but the
reaction mixture was kept at a temperature range of 85-95°C as a measure to prevent the
distillation of too much unreacted cyclohexanol <AtQ#3>. The observed Csp2-H, Csp3-H, and
C=C stretches were consistent with the desired product and the cyclohexene spectrum
reported in literature, and the O-H stretch in the IR spectrum of the product did not match that
of cyclohexanol (Figure 2) <AtQ#5>. These indicated the successful conversion of
cyclohexanol to cyclohexene <AtQ#2A>.
The dehydration reaction of cyclohexanol had a 55.0% yield (Table 1), which was
lower than the expected 80% yield [6]. This may have been due to significant product loss in
liquid transfer. Also, since the distilling flask was, for safety purposes, not distilled to
dryness, a modest amount of unreacted cyclohexanol may have been left in it instead of being
dehydrated to cyclohexene. The moderately high yield, however, may have been due to the
presence of a small amount of water as evinced by the unexpected peak in the 3100-3500
cm-1 region of the product’s FT-IR spectrum (Figure 1). This may have been caused due to
insufficient drying with sodium sulphate. However, as the product most likely did not contain
cyclohexanol, the distillation must have been carried out quickly enough to prevent the
reverse reaction (that of the hydration of cyclohexene to cyclohexanol) from happening in the
presence of distilled water and cyclohexene, which would have decreased the purity of the
product <AtQ#2B>.
Despite all these, the experiment was a success because its objectives were fulfilled.
The synthesized product was a colorless liquid with a sharp, unpleasant smell, which
according to its FT-IR spectrum was most probably cyclohexene with a small amount of
water as a contaminant (Figures 1 and 2). The percent yield for the experiment was
reasonably high, seeing as a 100% yield is not expected of an equilibrium reaction like the
dehydration reaction of cyclohexanol <AtQ#1>. The dehydration reaction proceeded as
expected, but the purification and the IR analysis steps had minor discrepancies that may
have been caused by insufficient use of dehydrating agents. In future experiments, it is
recommended that a fractional distillation setup be employed in the second distillation instead
of the simple distillation setup used in this experiment. Fractionally distilling the second
batch of distillate would ensure a more efficient purification of cyclohexene from water and
other high-boiling impurities.

III. Sample calculations [3.0 pts]

Theoretical yield [stoichiometric]= (8.17g cyclohexanol)*(1mol/100.2g)*(1 mol
cyclohexene/1 mol cyclohexanol)*(82.1g/mol cyclohexene) = 6.69 g
Theoretical yield from literature [6]: 80%
Theoretical yield: 0.8*6.69g = 5.35g

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% yield = (2.94 g/5.35 g) * 100% = 55.0%

References [2.0 pts]

[1] National Institute of Standards and Technology. NIST Chemistry Webbook [Internet].
Gaithersburg [Maryland]: U.S. Department of Commerce; [cited 2019 November 4].
Available from: https://webbook.nist.gov/
[2] Palardonio S. FT-IR spectra of cyclohexene and cyclohexanol [unpublished course notes].
Ateneo de Manila University; notes provided at lecture given 2019 October 5.
[3] Wade, LG. Organic Chemistry. 8th ed. USA: Prentice Hall; 2012.
[4] Rummel SA, Beiswenger KM. Chemistry 213: Introductory Organic Chemistry
Laboratory 2015-2016. USA: Hayden-McNeil; 2016.
[5] Most CF. Experimental Organic Chemistry. USA: Wiley & Sons; 1988.
[6] Solomon, TWG, Fryhle, CB, Snyder SA. Organic Chemistry. 11th ed. USA: Wiley &
Sons; 2014.