Dehydration of an alcohol: cyclohexene from cyclohexanol

Objectives:
1. to produce cyclohexene through the acid catalyzed elimination of water from
cyclohexanol.
2. to understand mechanism involved in the reaction.
3. to learn the technique of distillation.
Introduction:
This experiment is regarding to produce cyclohexene through the acid catalyzed
elimination of water from cyclohexanol (dehydration) in which it is used to focus on
substitution and elimination in organic chemistry.
Substitution is that the nucleophile attacks carbon but elimination is the base attack
the hydrogen. To differentiate nucleophile from base is that strong hindered base is favour to
elimination while small, unhindered nucleophile is favour to substitution. Substitution
reactions always compete with elimination reactions. Therefore, this experiment is conducted
at relatively high temperatures and phosphoric acid is used as the catalyst, since HPO 4- is a
poor nucleophile. Also, both the cyclohexene and the water will be removed from the
reaction as they are formed to force the elimination reaction to completion.
Finally, even after all of the cyclohexene are collected, it is not pure because it
distilled as an azeotrope with water. Azeotropes are mixture of at least two different liquids.
Their mixture can either have a higher boiling point than either of the components or they can
have a lower boiling point. Azeotropes occur when fraction of the liquids cannot be altered by
distillation. Typically when dealing with mixtures, the more volatile component tends to
vaporize and is collected separately while the least volatile component remains in the
distillation container and ultimately, the result is two pure, separate solutions. One of the
components of our azeotrope is water throughout this experiment, since it is not very soluble
in cyclohexene, the distillation needed is only two stages. Moreover, the little amount of
water in the cyclohexene can be removed by the use of a chemical 'drying agent' such as
calcium chloride, sodium sulphate, magnesium sulphate to clump and remove the water by
forming hydrates to trap the water in their crystal structure. In this experiment, magnesium
sulphate is used to make sure there is completely does not have the content of water to avoid
inaccuracy (Neilan, 2010).
Results:

Weight of cyclohexanol: 10g

Weight of dry beaker: 40.96g
Weight of cyclohexanol + weight of dry beaker: 42.25g
Experimental of weight of cyclohexene: 42.25-40.96=1.29g
From the reaction, 1 mol of cyclohexanol produce 1 mol of cyclohexene.
Molecular mass of cyclohexanol is 100g mol-1
Mole of cyclohexanol = 10g / 100g mol-1 = 0.1 mol
So, 0.1 mol of cyclohexene produced too.
Molecular mass of cyclohexene is 82g mol-1
Mass of cyclohexene = 0.1 mol x 82g mol-1 = 8. 2g (theoretical mass)
But, experiment weight of cyclohexene is only 1.29g.
Percentage yield: (experimental yield / theoretical yield) x 100%
(1.29/8.2) x 100%= 15.73%
Questions:
1. Dehydration of cyclohexanol gives cyclohexene. Draw mechanism for the reaction.

2. What alkene(s) will be produced when each of the following alcohols is dehydrated?
a. t-butylalcohol b. 3-methylcyclohexanol
a.

3. The dehydration of 3, 3-dimethyl-2-butanol yields three different products. Write

equations to show how carbocation rearrangements explain two of the products.

Product yield is (CH3)3CCH=CH2 (3, 3 Dimethyl-1-butene). It is a normal

elimination product and the least from the amount. Rearrangement of carbocation:
Elimination step 2 (Tertiary carbocation): Product yield is 2, 3-dimethyl-2-butene. It
is the major product. Elimination step 3 (Tertiary carbocation): Product yield is 2, 3dimethyl-1-butene. It is the minor product.
Discussion:

Dehydration is an elimination of alcohol in which elimination involves the loss of a small

molecule (H-X) from adjacent carbon atoms, resulting in pi-bond formation. So, elimination
reactions are ideal to produce alkenes or alkynes by eliminating of a molecule of water
(Dr.Pahlavan, n. d.) These reactions occur through a process called heterolytic bond cleavage.
Heterolytic bond cleavage occurs when one atom leaves a compound with both electrons of
the original bond, resulting in the formation of ions. For example, elimination of H-X from an
organic molecule involves the loss of a proton (H+) and a leaving group (X-). The leaving
group departs with both electrons from the original C-X bond . The electrons in the adjacent
C-H bond form the new pi bond of the alkene, with the loss of the proton. Alcohol
dehydration (loss of water molecules) is an acid-catalyzed reaction that needs heat to proceed
by an elimination mechanism called E1. The key intermediate in the mechanism is a
cyclohexyl cation, which can undergo substitution as well as elimination (Solomons and
Fryhle, n. d.).
To prepare high yield of alkene, we have to suppress the substitution reaction. In this
experiment, the substitution reaction is suppressed by using of strong acids with anions that
are relatively poor nucleophiles together with a high reaction temperature, which favors
elimination. The anion of phosphoric acids in this experiment is a poor nucleophile, this
causes substitution reactions are not favoured (Chandran, 2012). Because the OH group is a
very poor leaving group, an alcohol is able to undergo dehydration only if its OH group is
converted into a better leaving group. One way to convert an OH group into a good group is
to protonate it. Thus, in the first step of dehydration reaction, protonation changes the very
poor leaving group OH into a good leaving group OH2+. The second step of the
dehydration reaction is loss of water from the oxonium ion forming a positively charged
secondary carbocation. This step of the mechanism is rate determining. The ease of alcohol
dehydration follows the trend from tertiary to primary. The final step, the base HPO 4 removes
a proton from the carbon adjacent to the positively charged carbon, forming an alkene and
regenerating the acid catalyst H2PO4 (Dr.Pahlavan, n. d. ).
For the first time distillation, the receiving flask containing cyclohexene, water and small
amount of the impurities. Two layers liquid are present in the receiving flask, one drop of
distilled water is added into flask in order to determine the location of aqueous layer. Since
the water droplet mix with the lower layer, so the upper layer is determined as cloudy
solution while the lower layer is aqueous layer. The upper cloudy layer is cyclohexene with
some impurities and water inside. The lower aqueous layer is removed and discarded. But,

that is not easy to remove all the water in the receiving flask. So, anhydrous magnesium
sulphate is being added. The anhydrous magnesium sulphate was added due to it is an
inorganic drying agent that binds and clumps strongly with water and thus removing all water
content from the solution and thus we were able to get an accurate reading of weight of
cyclohexene without the content of water interference (Chandran, 2012).In the second
distillation, the temperature of mixture drops to 83C and remains constant. This
phenomenon takes place because the cyclohexene with lowest boiling point will tends to be
distilled first before the higher one. The temperature remains unchanged because the heat is
being absorbed to break down the bond between cyclohexene molecules.
From the experiment, only 1.29g of cyclohexene was produced, which is 15.73 % from the
theoretical mass. This is because of a significant amount of product left and lost during
distillation. Since the connection of the distillation set has been closed fitly, thus we could see
some products that were left between the flask and column. As the reaction mixture is heated,
the lower boiling products (cyclohexene, boiling point is 83 oC, and water boiling point is 100
o

C) distill out and are collected in the receiving flask. Any unreacted cyclohexanol (the

starting material) and phosphoric acid (the catalyst) are left in the distilling flask because of
their high boiling points (161 oC and 213 oC, respectively). However, since a small amount of
phosphoric acid still appears in the receiving flask, the product is washed with aqueous
sodium carbonate to neutralize the acid. Cyclohexene is insoluble in water and thus is not lost
during the washing with aqueous sodium carbonate solution (Dr. Pahlavan, n. d.).
Some precaution steps that we have to be aware of are such as phosphoric acids are strong,
corrosive acids. If any acid is splashed on your skin or clothing, wash immediately with
copious amounts of water. Cyclohexene and toluene are not particularly dangerous but are
highly flammable. Both are quite painful if splashed in the eyes and must be removed by
extensive eye washing. Remaining cyclohexene should be disposed of in the fume-hood sink
because cyclohexene vapours are heavier than air, they will accumulate in the sink
(Behaviour modification, 2011).
Conclusions:
1.29g of cyclohexene was produced, which is 15.73% from the theoretical mass. The loss of
water from a cyclohexanol to give a cyclohexene needs a series of steps.
References:

1. J.

Neilan,

2010.

Dehydration

of

Alcohol.

[Online].

Available:

http://www2.volstate.edu/chem/2010/Labs/Cyclohexene.html [Accessed on 5 July

2015].
2. Dr.
Pahlavan,

n.

d.

Cyclohexene

Synthesis.

[Online].

Available:

http://swc2.hccs.edu/pahlavan/2423L9.pdf [Accessed on 5 July 2015].

3. T.W.G. Solomons and C. Fryhle, n. d. Organic Chemistry: Dehydration of Alcohols.
4. Behaviour modification, 2011. Dehydration of An Alcohol: Cyclohexene from
Cyclohexanol.

[Online].

Available:

http://1chemistry.blogspot.com/2011/05/dehydration-of-alcohol-cyclohexanoland.html [ Accessed on 5 July 2015].

5. Losshenee Chandran, 2012. Dehydration of An Alcohol. [Online]. Available:
http://loshechandran.blogspot.com/2012/11/title-dehydration-of-alcohol.html
[Accessed on 5 July 2015].