Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry.

Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.

E1 and SN1 Reactions

Unimolecular reactions E1 and S N1 are characterized by the slow, rate-determining
dissociation of a leaving group to form a carbocation:

- X-

X HH

carbocation

Figure 1. Dissociation of a Leaving Group Forms a Carbocation.

The formation of carbocation involves only the substrate to which the leaving group is
attached. The rate of the reaction depends only on the concentration of the substrate;
hence, the reaction is called unimolecular.

The rate-determining step in unimolecular reactions is the spontaneous dissociation of the

leaving group to form a carbocation. Anything that stabilizes the carbocation intermediate
increases the rate of a unimolecular reaction. The order of stability of alkyl carbocations
proceeds as follows:
H
H H H
HH > H >
H H

tertiary secondary allylic benzylic primary

Figure 2. Stability of Carbocations.

Hence, tertiary alkyl halides/alcohols are the fastest to react while primary alkyl
halides/alcohols do not react through this mechanism.

The leaving group is also involved in the rate-determining step so good leaving groups
increase the rate of the reaction. Conjugate bases of strong acids, such as halides, are
excellent leaving groups. On the other hand, the solvent stabilizes the positively-charged
carbocation intermediate. Polar molecules such as water orient themselves around the
carbocation in such a way that electron-rich domains face the positively-charged
carbocation, thereby stabilizing it. It is for this reason that polar solvents are used in
unimolecular reactions.

After the formation of a carbocation, competition arises between substitution and

elimination. Substitution occurs when a nucleophile attacks the carbocation while
elimination occurs when a base attacks the proton on the adjacent carbon atom of a
carbocation.

Second Edition Draft For use only within the Ateneo de Manila University.
Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry. Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.
Unimolecular Elimination Reaction (E1)
Elimination occurs when a base attacks the proton on the adjacent carbon atom of a
carbocation to form an alkene.

H - HB
B
HH
alkene

Figure 3. Loss of a Proton Forms an Alkene.

E1 reactions are favored with the use of non-nucleophilic bases. These are conjugate bases
of weak acids that are basic enough to attack a proton on an adjacent carbon; however,
they are weakly nucleophilic that they wont attack the carbocation itself. Heating
promotes the reaction to proceed through an E1 mechanism.

Dehydration of Alcohols
Alkenes are formed by the acid-catalyzed dehydration of secondary or tertiary alcohols
through an E1 mechanism. The OH group of alcohols is a bad leaving group because the
resulting hydroxide ion is a strong base. For dehydration to occur, the OH group is
protonated to form a substituted hydronium ion (H3O+, but one of the protons is replaced
with an alkyl group). The OH group will then be OH2+, which leaves as water, a weak
base.

H - B- H
B H

OH OH2
alcohol hydronium ion

H - H2O H

OH2 HH

carbocation

H - HB
B
HH
alkene

Figure 4. Mechanism of E1 Dehydration of Alcohols.

The reaction, however, is an equilibrium reaction. The alkene produced can be protonated
with an acid to form a carbocation, which can be attacked by water to form an alcohol. In
order to get a good yield, the resulting alkene must be removed as soon as it is formed to
prevent it from reverting back to an alcohol. This can done through distillation as alkenes
have lower boiling points than alcohols or water.

Second Edition Draft For use only within the Ateneo de Manila University.
Guidote AM, del Rosario DR, Abuzo AL. Experiencing Organic Chemistry. Quezon City:
Office of Research and Publications, Ateneo de Manila University; 2005.
Unimolecular Nucleophilic Substitution Reaction (SN1)
Substitution occurs when a nucleophile attacks the carbocation.

Nu Nu
alkene

Figure 5. Nucleophilic Attack Forms a Substitution Product.

SN1 reactions are favored with the use of weakly basic nucleophiles. These are conjugate
bases of strong acids, such as halides or water that have electron-rich domains but weakly
basic that they will attack the carbocation and not its neighboring protons.

Substitution of Alcohols
Alkyl halides are formed by the acid-catalyzed substitution of secondary or tertiary alcohols
through an SN1 mechanism. Similar to E1 dehydration of alcohols, an acid is used to convert
the OH group to a better leaving group before substitution can occur. Tertiary alcohols are
the fastest to react while secondary alcohols react more slowly. Shaking tert-butanol (2-
methylpropan-2-ol) with concentrated hydrochloric acid readily produces tert-butyl
chloride (2-chloro-2-methylpropane). However, reactions of secondary alcohols are carried
out at higher temperatures using a zinc chloride catalyst dissolved in concentrated
hydrochloric acid. Zinc chloride complexes with the oxygen atom of the OH group to
weaken the CO bond.

References:
Boyd RN, Morrison RT. Organic Chemistry. 5th ed. USA: Allyn and Bacon; 1987.

McMurry J. Organic Chemistry. 5th ed. USA: Brooks/Cole; 2000.

Most CF. Experimental Organic Chemistry. USA: Wiley & Sons; 1988.

Solomons TW. Organic Chemistry. 6th ed. USA: Wiley & Sons; 1996.

Second Edition Draft For use only within the Ateneo de Manila University.