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Traya, Levie Grace M.

BS Chemistry 4

6 September 2014

ELIMINATION
(27 August 2014)
I.

INTRODUCTION

The dehydration of alcohol is an important elimination reaction that takes


place under acidic rather than basic condition. It involves an E1 mechanism. The
function of the acidic reagent is to convert the hydroxyl group to a better leaving
group by protonation: (1)

This elimination reaction is the reverse of acid-catalyzed hydration. Because


a carbocation or closely related species is the intermediate, the elimination step
would be expected to favor the more substituted alkene. The E1 mechanism also
explains the general trend in relative reactivity. Tertiary alcohols are the most
reactive, and reactivity decreases going to secondary and primary alcohol. Also
in accord with E1 mechanism is the fact that rearranged products are found in
cases where a carbocation intermediate would be expected to rearrange: (2)

For many alcohols, exchange of the hydroxyl group with solvent competes
with dehydration. This exchange indicates that the carbocation can undergo S N1
capture in competition with elimination. Under conditions where proton removal
is rate-determining, it would be expected that significant isotope effect would be
seen. This is, in fact, observed.
In connection to the facts stated this experiment aims to understand the
concept of elimination and synthesize an alkene from an alcohol and test it using
potassium permanganate test and bromine test.

II.

METHODOLOGY

Traya, Levie Grace M.


BS Chemistry 4

6 September 2014

A. Materials
Tert-butyl alcohol
Conc. H2SO4
CaCl2
Acetone
1% Aqueous
KMnO4
Carbon
tetrachloride
2% bromine

250-mL round-bottomed
flask
Pipet
Aspirator
Thermometer
Reflux condenser (Relfux
set-up)
Iron stand

Thermometer holder
Alcohol lamp
Separatory funnel
Glass dropper
Wire gauze

Iron ring

B. Procedure
In a 250-mL round-bottomed flask, a 14-mL of water and conc. H 2SO4
was added. The acid was then cooled to about 50

and a 12.6-mL of

t-butyl alcohol was slowly added to the solution. The solution was then
subjected to reflux where it was ensured that no steam should be produce
or there will be lesser percentage yield.
The solution was then cooled at room temperature and then
transferred to a separatory funnel where the aqueous acid layer was
carefully drawn. The hydrocarbon layer was then washed with water in
order to remove traces of acid.
Due to limited resources, the experiment was cut to this part and the
hydrocarbon was then immediately subjected to the potassium
permanganate test and bromine test to check for the presence of alkene.
Potassium permanganate test was done by adding 3 drops of the
alkene solution in a 1-mL acetone and with vigorous shaking the 1%
Aqueous KMnO4 was added. The test would be positive if within 1 minute
the purple color will fade and there will be a formation of insoluble brown
hydrated oxides of manganese.
Bromine test was carried out in a hood. It was done by adding 3 drops
of the alkene solution to a 1-mL bromide in carbon tetrachloride. The test
would be positive if there will be a loss in the brown color of the solution.

Traya, Levie Grace M.


BS Chemistry 4
III.

6 September 2014

DATA AND RESULTS


Table 1. Observation for potassium permanganate test
Before the test
Violet solution

After the test


Brown insoluble solution

Table2. Observation for bromine test


Before the test
Brown solution

IV.

After the test


Became a colorless solution

DISSCUSSION/ INTERPRETATION OF RESULTS

Many secondary and tertiary halides undergo E1 elimination in competition


with the SN1 reaction in neutral or acidic solutions. For this experiment, when
tert-butyl alcohol solvolyzes in sulfuric acid it produce diisobutylene by
elimination.
Alcohols and ethers rarely undergo substitution or elimination unless strong
acid is present. The acid is necessary to convert a relatively poor leaving group,
OH for this particular experiment, into a relatively good one, H 2O. Thus the
dehydration of alcohols to alkenes is an acid-catalyzed reaction requiring strong
acids. In this experiment, the starting material was an alcohol, tert-butyl alcohol,
was reacted to an acid, sulfuric acid, to produce diisobutylene. The mechanism
was shown as follows: (3)

Looking at the reaction, notice that water is a product of the dehydration


reaction. In the mechanism shown, the starting material was reacted with
sulfuric acid where the acid converted the poor leaving group OH into H 2O which

Traya, Levie Grace M.


BS Chemistry 4

6 September 2014

is a better leaving group. The leaving group then cleaves out producing the
carbocation where it was attacked by the base. The base removes a beta-proton,
leaving behind its bonding electrons to form the new double bond.
Due to shortage of reagents the procedure was cut after the hydrocarbon was
isolated. The hydrocarbon was subjected to two confirmatory tests namely
potassium permanganate test and bromine test.
For bromide test, the brown solution became colorless which indicates a
positive test affirming the presence of alkene. The Bromine test for the alkene
crude product was positive because bromine is electron deficient and alkenes
have pi electrons forming a double bond that are open for attack. The reaction is:
(4)

Due to their C=C double bonds which can be broken, alkenes react readily
with bromine to produce saturated dibromoalkanes. In the presence of Br 2 or BrBr (which is red/brown), the Br-Br bond attacks the double bond forming C-Br
new bonds. Thus the red/brown color disappears.
In the potassium test, the violet solution turned into a brown insoluble
solution. Below is the reaction equation of the said test: (5)

Under acidic conditions, the manganate(VII) ions were reduced to


manganese(II) ions. Under alkaline conditions, the manganate(VII) ions are first
reduced to green manganate(VI) ions and then further to dark brown solid
manganese(IV) oxide (manganese dioxide). The last reaction is also the one that
would obtained if the reaction was done under neutral conditions. And as seen in
the reaction, there are neither hydrogen ions nor hydroxide ions on the left-hand
side of the equation.

V.

CONCLUSION AND RECOMMENDATION

Traya, Levie Grace M.


BS Chemistry 4

6 September 2014

Just as there were two mechanisms for nucleophilic substitution, there are
two elimination mechanisms. For this experiment, it followed the E1 mechanism.
The E1 mechanism is nearly identical to the SN1 mechanism, differing only in the
course of reaction taken by the carbocation intermediate.

As shown by the following equations, a carbocation bearing beta-hydrogens


may function either as a Lewis acid (electrophile), as it does in the SN1 reaction,
or a Brnsted acid, as in the E1 reaction.
Thus, hydrolysis of tert-butyl alcohol in a mixed solvent of water and sulfuric
acid gives a product isobutylene and further reaction gives a product
diisobutylene at a rate independent of the water concentration. Diisobutylene
was produced because isobutylene is an unstable product and thus react
furthermore with the carbocation being created. The alcohol is the product of an
SN1 reaction and the alkene is the product of the E1 reaction. The characteristics
of these two reaction mechanisms are similar, as expected. They both show first
order kinetics; neither is much influenced by a change in the nucleophile/base;
and both are relatively non-stereospecific.
To summarize, when carbocation intermediates are formed one can expect
them to react further by one or more of the following modes:
1. The cation may bond to a nucleophile to give a substitution product.
2. The cation may transfer a beta-proton to a base, giving an alkene product.
3. The cation may rearrange to a more stable carbocation, and then react by
mode #1 or #2.
Since the SN1 and E1 reactions proceed via the same carbocation
intermediate, the product ratios are difficult to control and both substitution and
elimination usually take place.
The isolated crude product did contain alkene as shown in the results of the
two tests namely potassium permanganate test and bromine test. The
potassium permanganate test was positive due to the appearance of brown
insoluble solution which was due to the hydrated oxide manganese. And the
isolated crude product was positive which affirms the presence of hydrocarbons.

Traya, Levie Grace M.


BS Chemistry 4

VI.

6 September 2014

REFERENCES
Books:
Bruice, Paula Y. Organic Chemistry. 4th ed. Pearson Prentice Hall. 2004
Boyd, R. N. & Morrison, R.T. Organic Chemistry. 6th Ed. Prentice Hall.

1992
Carey, Francis A. Organic Chemistry. 4th ed. McGraw-Hill. 2000
Chang, Reymond. Chemistry. 10th ed. McGraw-Hill. 2010
McMury, John.Organic. Chemistry.8th ed. Brooks/Cole, Cengage Learning.
2012

Web:
E1 Reaction. ChemWiki. Retrieved on 3 August 2014, from
http://chemwiki.ucdavis.edu/Organic_Chemistry/Reactions/E1_Reaction
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http://www.mhhe.com/physsci/chemistry/carey/student/olc/graphics/carey0
4oc/ref/ch05eliminationreactions.html
EXPLAINING THE ELIMINATION REACTIONS PRODUCING ALKENES FROM
SIMPLE HALOGENOALKANES. ChemGuide. Retrieved on 4 September 2014,
from http://www.chemguide.co.uk/mechanisms/elim/elimtt.html
Introduction to Elimination Reactions. Master Organic Chemistry. Retrieved
on 3 September 2014, from
http://www.masterorganicchemistry.com/2011/10/10/introduction-toelimination-reactions/