Elimination reaction

The reaction rate, inuenced by both the alkyl halide

and the base (bimolecular), is second order.
Because E2 mechanism results in formation of a
pi bond, the two leaving groups (often a hydrogen and a halogen) need to be antiperiplanar. An
antiperiplanar transition state has staggered conformation with lower energy than a synperiplanar transition state which is in eclipsed conformation with
higher energy. The reaction mechanism involving
staggered conformation is more favorable for E2 reactions (unlike E1 reactions).

Elimination reaction of cyclohexanol to cyclohexene with sulfuric

acid and heat [1]

An elimination reaction is a type of organic reaction

in which two substituents are removed from a molecule
in either a one or two-step mechanism.[2] The one-step
mechanism is known as the E2 reaction, and the two-step
mechanism is known as the E1 reaction. The numbers
do not have to do with the number of steps in the mechanism, but rather the kinetics of the reaction, bimolecular
and unimolecular respectively.

E2 typically uses a strong base, it needs a chemical

strong enough to pull o a weakly acidic hydrogen.
In order for the pi bond to be created, the
hybridization of carbons need to be lowered from
sp3 to sp2 .

In most organic elimination reactions, at least one hydrogen is lost to form the double bond: the unsaturation of
the molecule increases. It is also possible that a molecule
undergoes reductive elimination, by which the valence of
an atom in the molecule decreases by two. An important
class of elimination reactions are those involving alkyl
halides, with good leaving groups, reacting with a Lewis
base to form an alkene. Elimination may be considered
the reverse of an addition reaction. When the substrate
is asymmetric, regioselectivity is determined by Zaitsevs
rule or through Hofmann elimination if the Carbon with
the most substituted Hydrogen is inaccessible.

The C-H bond is weakened in the rate determining

step and therefore a primary deuterium isotope effect much larger than 1 (commonly 2-6) is observed.
E2 competes with the SN2 reaction mechanism.

E2 mechanism

Scheme 1. E2 reaction mechanism

During the 1920s, Sir Christopher Ingold proposed a

model to explain a peculiar type of chemical reaction;
the E2 mechanism. E2 stands for bimolecular elimination. The reaction involves a one-step mechanism in
which carbon-hydrogen and carbon-halogen bonds break
to form a double bond. C=C Pi bond.

An example of this type of reaction in scheme 1 is the

reaction of isobutylbromide with potassium ethoxide in
ethanol. The reaction products are isobutylene, ethanol
and potassium bromide.

The specics of the reaction are as follows:

2 E1 mechanism

E1 is a model to explain a particular type of chemical

E2 is the rst step of elimination with a single
elimination reaction. E1 stands for unimolecular elimitransition state.
nation and has the following specicities.
Typically undergone by primary substituted alkyl
halides, but is possible with some secondary alkyl
halides.

It is a two-step process of elimination: ionization

and deprotonation.
1

5
Ionization: the carbon-halogen bond breaks to
give a carbocation intermediate.
Deprotonation of the carbocation.
E1 typically takes place with tertiary alkyl halides,
but is possible with some secondary alkyl halides.

REFERENCES

Highly substituted carbocations are more stable than

methyl or primary substituted cations. Such stability
gives time for the two-step E1 mechanism to occur.
If SN1 and E1 pathways are competing, the E1 pathway can be favored by increasing the heat.

The reaction rate is inuenced only by the concen- Specic features : 1 . Rearrangement possible 2 . Indetration of the alkyl halide because carbocation for- pendent of concentration and basicity of base
mation is the slowest step aka rate-determining step.
Therefore rst-order kinetics apply (unimolecular).
Reaction usually occurs in complete absence of base 3 E2 and E1 elimination nal notes
or presence of only a weak base (acidic conditions
and high temperature).
The reaction rate is inuenced by halogen's reactivity,
iodide and bromide being favored. Fluoride is not a good
E1 reactions are in competition with SN1 reactions
leaving group. There is a certain level of competition
because they share a common carbocationic interbetween elimination reaction and nucleophilic substimediate.
tution. More precisely, there are competitions between
A secondary deuterium isotope eect of slightly E2 and SN2 and also between E1 and SN1. Substitution generally predominates and elimination occurs only
larger than 1 (commonly 1 - 1.5) is observed.
during precise circumstances. Generally, elimination is
No antiperiplanar requirement. An example is the favored over substitution when
pyrolysis of a certain sulfonate ester of menthol:
steric hindrance increases
basicity increases
temperature increases
the steric bulk of the base increases (such as in
Potassium tert-butoxide)
E1 elimination Nash 2008, antiperiplanar relationship in blue

the nucleophile is poor

In one study [4] the kinetic isotope eect (KIE) was determined for the gas phase reaction of several alkyl halides
with the chlorate ion. In accordance with an E2 elimination the reaction with t-butyl chloride results in a KIE of
2.3. The methyl chloride reaction (only SN2 possible) on
Accompanied by carbocationic rearrangement reac- the other hand has a KIE of 0.85 consistent with a SN2 reaction because in this reaction type the C-H bonds tighten
tions
in the transition state. The KIEs for the ethyl (0.99) and
isopropyl (1.72) analogues suggest competition between
the two reaction modes.
Only reaction product A results from antiperiplanar elimination, the presence of product
B is an indication that an E1 mechanism is
occurring.[3]

4 See Also
Scheme 2. E1 reaction mechanism

E1cB-elimination reaction

An example in scheme 2 is the reaction of tertbutylbromide with potassium ethoxide in ethanol.

5 References

E1 eliminations happen with highly substituted alkyl

halides due to 2 main reasons.
Highly substituted alkyl halides are bulky, limiting
the room for the E2 one-step mechanism; therefore,
the two-step E1 mechanism is favored.

[1] Organic Syntheses I:185 http://orgsynth.org/orgsyn/pdfs/

CV1P0183.pdf
[2] March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York:
Wiley, ISBN 0-471-85472-7

[3] Nash, J. J.; Leininger, M. A.; Keyes, K. (April

2008). Pyrolysis of Aryl Sulfonate Esters in the
Absence of Solvent: E1 or E2?
A Puzzle for
the Organic Laboratory. Journal of Chemical Education 85 (4): 552. Bibcode:2008JChEd..85..552N.
doi:10.1021/ed085p552.
[4] Stephanie M. Villano, Shuji Kato, and Veronica M. Bierbaum (2006). Deuterium Kinetic Isotope Eects in GasPhase SN2 and E2 Reactions: Comparison of Experiment
and Theory. J. Am. Chem. Soc. 128 (3): 736737.
doi:10.1021/ja057491d. PMID 16417360.

6 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

Text and image sources, contributors, and licenses

6.1

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Elimination reaction Source: http://en.wikipedia.org/wiki/Elimination%20reaction?oldid=636465402 Contributors: Michael Hardy,

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LOL, Jfx319, V8rik, Bubbachuck, YurikBot, Person unknown, Esprit15d, GraemeL, Itub, SmackBot, Edgar181, Lovecz, MalafayaBot,
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Rmashhadi, ClueBot NG, Bibcode Bot, Gladissk, ChrisGualtieri, Physchem 13, Priyanka Sandhu, Monkbot, Owais Khursheed, Mtalley90,
Y-S.Ko and Anonymous: 77

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