Chapter 8

Chapter 8
Alkyl Halides and Elimination
E2 reactions are generally run with strong, negatively charged bases like –OH and –OR.
Two
strong, sterically hindered nitrogen bases, called DBN and DBU, are also sometimes
used.
These sterically hindered bases are used for E2 elimination.

Amide Bases
Amide bases are also the strongest bases that used for E2 elimination. The typical base is
amide (–NH2), used as the sodium salt NaNH2 (sodium amide).
Weak Bases
Some bases are good nucleophiles, but weak bases and they favor substitution
over elimination. The examples included I–, Br–, HS–, –CN, and CH3COO–.
Water and Methanol
Water and methanol act as both weak nucleophile as well as weak base, so they
give a mixture of substitution and elimination products.
Chapter 9
Alcohols, ethers and epoxides
Crown Ethers
Some cyclic polyethers known as Crown ethers are compounds with two or more
ether linkages i.e., they contain cavities that can complex specific-sized cations. For
example, 18-crown-6 binds K+, whereas 12-crown-4 binds Li+.
 A crown ether–cation complex is called a host–guest complex. The crown ether

is the host and the cation is the guest.
• The ability of a host molecule to bind specifi c guests is called molecular

recognition.
For example, KCN is insoluble in nonpolar solvents alone, but with 18-crown-6,
it is soluble. When 18-crown-6 is added to the reaction of CH3CH2Br with KCN, for
example, the crown ether forms a tight complex with K+ that has nonpolar C – H bonds
on the outside, making the complex soluble in nonpolar solvents like benzene (C6H6) or
hexane. When the crown ether/K+ complex dissolves in the nonpolar solvent, it carries
the –CN along with it to maintain electrical neutrality. The result is a solution of tightly
complexed cation and relatively unsolvated anion (nucleophile). The anion, therefore, is
extremely nucleophilic because it is not hidden from the substrate by solvent
molecules.So, A rapid nucleophilic substitution reaction occurs in nonpolar solvents when
a crown ether is added.
Sodium hydride (NaH) base is used to extract a proton to form sodium alkoxides
that are used in substitution reactions.
Reagents for the Dehydration of Alcohols
Strong acids like Sulfuric acid (H2SO4) and p-toluenesulfonic acid (TsOH) can be
used to convert alcohols into alkene. Sometimes, the rearrangement of carbocation occurs
while dehydrating alcohols with acids.
Because some organic compounds decompose in the presence of strong acid,

other methods that avoid strong acid have been developed to convert alcohols to alkenes.
A common method uses phosphorus oxychloride (POCl3) and pyridine (an amine base) in
place of H2SO4 or TsOH. For example, the treatment of cyclohexanol with POCl 3 and
pyridine forms cyclohexene in good yield. No rearrangements occur during dehydration
with POCl3, suggesting that carbocations are not formed as intermediates in this reaction.
Reagents for the conversion of Alcohols to Alkyl halides
Alcohols undergo nucleophilic substitution reactions only if the OH group is

converted into a better leaving group before nucleophilic attack. Thus, substitution does
not occur when an alcohol is treated with X– because –OH is a poor leaving group , but
substitution does occur on treatment of an alcohol with HX because H 2O is now the
leaving group.
H2O is a good leaving group, similarly there is another good leaving group known as
tosylate group. Alcohols on reacting with p-toluenesulfonyl chloride (TsCl) in the
presence of pyridine to form alkyl tosylates. Tosyl group can be substituted with a
nucleophile.
Halogen acids (HX) can be used for the conversion of Alcohols into Alkyl halides. The
Halogen acids include HF, HCl, HBr, HI.
As Cl- is a poor nucleophile, a Lewis acid like ZnCl2 is also used. ZnCl2 complexes with
the O atom of the alcohol in a Lewis acid–base reaction, making an especially good
leaving group and facilitating the SN2 reaction.
SOCl2 and PBr3 are also used to convert alcohols into alkyl halides.
Reagents for conversion of Ethers into Alkyl halides
When ethers react with HBr or HI, both C – O bonds are cleaved, and two alkyl halides
are formed as products. HBr or HI serves as a strong acid that both protonates the O atom
of the ether and is the source of a good nucleophile (Br– or I–). Because both C – O
bonds in the ether are broken, two successive nucleophilic substitution reactions occur.
The SN1 or SN2 product depends upon the identity of the alkyl part connected to ether.
For example
Reactions of Epoxides
Although epoxides do not contain a good leaving group, they contain a strained three-
membered ring with two polar bonds. Nucleophilic attack opens the strained three-
membered ring, making it a favorable process even with the poor leaving group.
Common nucleophiles that open epoxide rings include –OH, –OR, –CN, –SR, and NH3.
With these strong nucleophiles, the reaction occurs via an SN2 mechanism.
HCl, HBr, and HI all open an epoxide ring by first protonating the oxygen atom of the
epoxide and then the negative part attacks the epoxide from backside and opens the ring.
H2O and ROH can, too, but acid must also be added. Regardless of the reaction, the
product has an OH group from the epoxide on one carbon and a new functional group
from the nucleophile on the adjacent carbon. For example,
Chapter 10
Reagents for the addition reaction of Alkene
Alkenes undergo electrophilic addition reaction with several reagents. Those reagents
along with the addition reaction are given below.
Alcohol is also added into alkenes in the presence of H2SO4 to form ethers.
An addition product of alkene, Bromohydrin, is also formed with N-bromosuccinimide

(abbreviated as NBS) in aqueous DMSO [CH3)2S=O]. NBS serves as a source of Br2,
which then goes on to form a bromohydrin.
Commercially available dialkylboranes having the general structure R 2BH are also used
for hydroboration. A common example is 9-borabicyclo[3.3.1]nonane (9-BBN). 9-BBN
undergoes hydroboration in the same manner as BH3.
Chapter 11
Alkynes
Alkynes are prepared by elimination reactions. A strong base removes two equivalents of
HX from a vicinal or geminal dihalide to yield an alkyne by two successive E2
eliminations. Na+-NH2 and K+-OC(CH3)3 are used for the preparation of alkynes from alkyl
halides.
Addition reactions of Alkynes
Like alkenes, alkynes undergo addition reactions because they contain weak Π bonds. Two
sequential reactions take place: addition of one equivalent of reagent forms an alkene, which then
adds a second equivalent of reagent to yield a product having four new bonds.
The reagents and the respective addition products of Alkynes are given below.
Reaction of Acetylide Anions
Terminal alkynes are readily converted to acetylide anions with strong bases such as
NaNH2 and NaH. These anions are strong nucleophiles, capable of reacting with
electrophiles such as alkyl halides and epoxides.
Reaction of Acetylides Anions with Alkyl Halides
Acetylide anions react with unhindered alkyl halides to yield products of nucleophilic
substitution.
Reaction of Acetylides Anions with Epoxides
Acetylide anions are strong nucleophiles that open epoxide rings by an SN2 mechanism.
This reaction also results in the formation of a new carbon–carbon bond. Backside attack
occurs at the less substituted end of the epoxide.

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Chapter 8

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Chapter 8

Alkyl Halides and Elimination

These sterically hindered bases are used for E2 elimination.

Water and Methanol

Alcohols, ethers and epoxides

 A crown ether–cation complex is called a host–guest complex. The crown ether

• The ability of a host molecule to bind specifi c guests is called molecular

Reagents for the Dehydration of Alcohols

Because some organic compounds decompose in the presence of strong acid,

Reagents for the conversion of Alcohols to Alkyl halides

Alcohols undergo nucleophilic substitution reactions only if the OH group is

Reagents for conversion of Ethers into Alkyl halides

Reagents for the addition reaction of Alkene

An addition product of alkene, Bromohydrin, is also formed with N-bromosuccinimide

Addition reactions of Alkynes

Reaction of Acetylides Anions with Alkyl Halides

Reaction of Acetylides Anions with Epoxides

occurs at the less substituted end of the epoxide.

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