CHAPTER 6

Alkenes and
Alkynes
• Alkenes are unsaturated hydrocarbons that
contain one or more carbon-carbon double
bonds. H H H H H
H C C CH3 H C C C CH2

• Molecular formula of alkenes with one

double bond is CnH2n and the name ends
with "-ene".
example: 3 carbons is propene
5 carbons is pentene
7 carbons is heptene
• The different between alkanes and alkenes is they
have the same number of carbon atoms but differs
in the number of hydrogen atoms.
Structural formula
H H
H H
C C
H C C H
H H
H H
ethane ethene

Molecular formula
C2H6 C2H4
• Example: Propane would become a
propene with molecular formula C3H6.

CH3CH CH2

H H H

H C C C H

H
 Naming Alkenes
• Find the longest continuous carbon chain
containing the double bond.

• Start numbering from the end closest to the

double bond.

• Name the parents compound and indicates

the position of the double bond.
• Indicate the position of the substituent and
list in alphabetical order when writing the
name.
Example:
6 5 4 3 2 1
CH3CH2CH2CH CHCH3
Start numbering
Parent name The name is 2-hexene
Position of the = NOT 4-hexene OR 3-hexene
• Halogens group are treated equally like
alkyl groups.

Cl
CH3CHCH2CH CHCH3

5-chloro-2-hexene
 Naming Alkenes with More than One
Double Bond

• Alkenes with two double bonds are called

dienes, three are trienes and four are
tetraenes.

• Name the following alkene.

H2C C CH CH2
CH3
 1 2 3 4
H2C C CH CH2
CH3

• Start numbering from the blue carbon to

give the substituent, methyl group the
lowest position number.

The name is 2-methyl-1,3-butadiene

 Naming Cycloalkenes
• There is no chain end for cycloalkenes to
start the numbering. Therefore, the carbon
atom in the double bond is assigned as C1
and C2. If substituent is exists, the ring is
numbered clockwise or counterclockwise to
give the first substituent the lowest position
number.
Example 1: Choose the correct name for the
following compound.

CH3CH2

A) 1-ethylcyclopentene
B) 2-ethylcyclopentene
C=C is assigned as C1 and C2, therefore the
numbering system for A and B are correct.
But, since the ethyl group is attached to the C
double bond, the priority (C1) is goes to the
substituent.

2 1

1
2
CH3CH 2 CH3CH2
1-ethylcyclopentene 2-ethylcyclopentene
A B
1) Which one shows the correct numbering system?
2) Name the compound.
1 2
6 2 3 1

3
4 6
H3C 5
4 CH3 H3C 5 CH3
A B
The name5 of the compound 3
4 2
is 3,5-dimethylcyclohexene
6 4

1
H3C 1 3
CH3 H3C 5
6 CH3
2

C D
Example 3:

CH3
5 6
1
4 CH3
3 2

1,6-dimethylcyclohexene
 Geometric Isomers (Cis- and Trans-)
Cis- Trans-
• Two substituents • Two substituents
that are on the that are on the
same side of the opposite side of the
double bond. double bond.

H H CH3 H
C C C C
CH3 CH3 H CH3
cis-2-butene trans-2-butene
 E-Z System of Nomenclature
• For the following compounds, there is no
obvious way in which the cis-trans system
can be applied because there are four
different substituents attached on the two
vinylic carbon.
• To name the compound by using E-Z
System of Nomenclature, first, determine
the priorities of the two substituents
bonded to the sp2 carbons and then the
priorities of the substituents bonded to
the other sp2 carbon.

Z = together
E = opposite
• At C1, the two atoms attached to the double
bond are Br and I. I is higher priority than Br
(higher atomic number, I = 53, Br = 35).
• At C2, the atoms are Cl and F, with Cl being
higher priority (atomic number, Cl = 17, F =
9).
• The higher priority group is "down" at C1 and
"down" at C2. The two priority groups are
both on the same side of the double bond
("down"), they are zusammen = together.
Therefore, this is the (Z) isomer.
• Exercise: Name the following compounds
by using the E-Z System of Nomenclature.

a) Br Cl
C C
H CH 3

CH 3
b) ClH 2C CH 2CH3
C C
Cl CH 2OH
 Synthesis of Alkenes
• Preparation of alkenes is carried out by
elimination reactions.
a) dehydration of alcohols
Remove H-OH

b) dehydrohalogenation of haloalkanes
Remove HX
c) debromination of alkyl halides
 Zaitsev’s Rule
• According to Zaitsev’s Rule, the major product is
obtained when a proton is removed from the
carbon that is bonded to the least hydrogen.
H CH3
CH3C C CH3
H CH3
2-methylbut-2-ene
CH3C C CH3 CH3CH2OH (more stable)

H Br H CH3
2-bromo-2-methylbutane + CH3C C CH2
H
2-methylbut-1-ene
(less stable)
• Dehydration is carried out by the treatment
of an alcohol with a strong acid; example,
warmed aqueous sulfuric acid in
tetrahyfrofuran (THF) solvent.

CH3
CH3
OH H2SO4/H2O
+ H2O
THF/50oC
 A Mechanism for Dehydration of Secondary Alcohols: An E1
Reaction

H H
OH rapid and O
H O H reversible O H
CH3CHCH2CH3 + CH3CHCH2CH3 +
H H
1. Proton transfer from H3O+ to the OH
group to form oxonium ion. this step
convert OH-, a poor leaving group into H2O,
a better leaving group.

H H
O
slow
CH3CHCH2CH3 CH3CHCH2CH3 + H2O

2. C-O bond breaks, gives a secondary carbocation and H2O.

 H H
H
O H rapid H O H
CH3C CHCH3 +
CH3C CHCH3 +
H H
3. Proton transfer from the carbon adjacent
to the C+ to H2O. The sigma electron of a C-
H bond become the pi electrons of the C=C.
A Mechanism for Dehydration of Primary Alcohols:
An E2 Reaction
H
rapid and H H
CH3C O H + H O H reversible H
CH3C O H + O
H H H
H
+
1. Proton transfer from H3O to the OH
group to form oxonium ion.

H H H H H
slow
H O + H C C O H H O H + C C
H H H H H H

2. Simultaneous proton transfer to

+ O H
solvent and loss of H2O gives the alkene.
H
 Dehydrohalogenation of Alkyl Halides
• It is normally occurs by reaction of an alkyl
halide with a strong base, such as sodium
ethoxide or KOH in ethanol solution. It
involves the loss of a hydrogen and a halide
from an alkyl halide (RX). 

Na+ heat
Cl + O -
+ OH
ethyl chloride sodium ethoxide ethene ethanol

+ NaCl
 • Alkyl halide treated with strong base such
as potassium hydroxide in ethanol
solution.

H H
Br
KOH + KBr + H2O
CH3CH2OH
H
H H
cyclohexene
bromocyclohexane
 Debromination of Vicinal Dibromides
compound that have halogens on adjacent carbons

• Vicinal dibromides can be converted to

alkenes by reduction with iodide ion or zinc in
acetic acid.

Na+ I- Br H
H3C H
CH3C CCH3 acetone NaBr + IBr
C C
H Br H CH3

Br H
H3C H
CH3C CCH3 Zn/CH COOH C C + ZnBr2
3
H Br H CH3
 Addition Reactions of Alkenes
• Alkenes undergo an addition reaction for
conversion of unsaturated compound to
saturated. C=C behave as nucleophiles and
donate a pair of electrons from their electron
rich C=C bond to an electrophile.

• Only one product is produced at the end of

the reaction.
Mechanism:
Br-
H-Br
H3C H H3C H
C C C C H
H3C H H3C H
carbocation
A H atom is attacked by pi electron
intermediate
from the nucleophilic double bond,
forming a new C-H bond anf
leaves the other C as carbocation.
Two electrons from H-Br bond
move onto bromine to form
bromide ion.

Bromide ion donates an electron

Br H
pair to the positively charged H3C C C H
carbon atom to form C-Br bond and
forming neutral addition product.
H3C H
 Markovnikov’s Rule
Look at the different between Example A and Example B:

H H H H
H H
H-Cl H
H3C C C H H3C C C H + H3C C C
H H
primary carbocation secondary carbocation

H H H H
H3C C C H H3C C C H
H Cl Cl H
product NOT formed product formed
 CH3 H CH3H CH3H
H-Cl
H3C C C H H3C C C H + H3C C C H
H H
primary carbocation tertiary carbocation

CH3H CH3H
H3C C C H H3C C C H
H Cl Cl H
product NOT formed product formed

Conclusion: Tertiary carbocation is more stable

than secondary or primary carbocation.
 Carbocation Stability
• Tertiary carbocation is more stable and react
the fastest compared to secondary and
primary carbocations. Following is the order
stability of four types of alkyl carbocations:
 Hydrogenation Reaction

• Hydrogenation is the addition of H2 to an

alkene.

• Platinum and palladium are the most

common catalyst for alkene hydrogenation.
Palladium used on an inert material such as
charcoal (Pd/C) while platinum used as
platinum dioxide, PtO2.
Addition of Water by Oxymercuration
• Hydration is the addition of water in the
presence of a strong acid such as sulfuric
acid, H2SO4 or phosphoric acid, H3PO4 to an
alkene to form an alcohol.

• There is NO reaction takes place when only

H2O is added to an alkene because the –O-H
bonds of water are too strong.
***Mechanism of the acid-catalysed hydration of an alkene to produce an
alcohol: H O

H3C H H
H H O H H3C
C C + C C H
H3C H H H3C H
1. A H atom on the H3O+ is attacked
2. The nucleophile H2O donates an
by pi electrons from nucleophilic
electron pair to the C+, forming a C-O
double bond, forming a new C-H
bond and leaving +ve charge on oxygen
bond. The other C leaves with a +ve
in the protonated alcohol addition product.
charge and two electrons from H-O
bond move onto oxygen, giving
neutral water.

O H
H O H
H H
H
H O + H3C C C H H O
H H
H H3C H
H3C C C
3. H2O acts as a base to remove H+, H
regenerating H3O+ and produce alcohol. H3C
• Oxymercuration is the treatment of alkene with
mercury(II) acetate, [Hg(O2CCH3)2 or abbreviated
as Hg(OAc)2 in aqueous tetrahydrofuran (THF)
solvent to produce intermediate organomercury
compound. Organomercury compound is then
treated with sodium borohydrate NaBH4 (also
known as demercuration) to produce alcohol. This
reaction obey the Markovnikov’s Rule.

CH3 CH3
1. Hg(OAc)2, H2O/THF OH
2. NaBH4
Mechanism of the Oxymercuration:
CH3 CH3
Hg(OAc)2
HgOAc
1-methyl cyclopentene
H
mercurinium ion

H2O/THF

CH3 CH3
OH NaBH4 OH
H HgOAc
H H
organomercury
compound
 Addition of Water by Hydroboration
• Hydroboration is also the addition of water to
alkene; but the product is opposite of the
Markovnikov’s Rule (anti-Markovnikov’s).
H3C H BH3 H BH2
C C THF solvent H3C C C H
H3C CH2CH3 H3C CH2CH3
2-methylpent-2-ene organoborane
intermediate

H OH
H3C C C H H2O2/OH-
H3C CH2CH3
2-methylpentan-3-ol
 Hydrohalogenation Reaction

• Addition of hydrogen halides (HX) to an

alkene to form alkyl halide.

• X is any halogens group such as fluorine,

chlorine, bromine or iodine
 Hydrohalogenation Reaction
(unsymmetrical alkenes-Markovnikov’s Rule)
CH3
CHCH3 HBr/CCl4
CH3C
2-methyl-2-butene

CH3 CH3
CH3C CHCH3 + CH3C CHCH3
H Br Br H
2-bromo-3-methylbutane 2-bromo-2-methylbutane
minor major
 Anti Markovnikov’s Addition
• It is an addition of hydrogen bromide (HBr)
to alkenes in the presence of peroxide
(ROOR’).

• Contradictory with Markovnikov’s Rule,

hydrogen is attached to the carbon with
fewer hydrogen atoms.
 Example 1: This reaction only occurs if HBr is
used with peroxide. It is not occur with HF, HI
or HCl.

CH3CH CH 2 HBr/ROOR'
propene
CH3CH CH 2
H Br
1-bromopropane
Example 2:
CH3
CH3C CHCH3 HBr/ROOR'
2-methyl-2-butene

CH3 CH3
CH3C CHCH3 + CH3C CHCH3
H Br Br H
2-bromo-3-methylbutane 2-bromo-2-methylbutane
major minor
Addition of X2 to Produce Vicinal Dihalide
• The addition of bromine or chlorine in an inert
solvent like dichloromethane or carbon
tetrachloride to an alkene will produce a vicinal
dihalide. The solvents will dissolve both reactants
but does not participate in the reaction.

• Only Cl2 and Br2 are useful for halogenation

reaction because the addition of I2 is too slow and
unstable at room temperature. The addition of F2
is too explosive.
Example:

Cl Cl
H H
Cl2
C C H C C H
H H H H
ethene
1,2-dichloroethane
 Halogenation of Cycloalkenes
• Only the trans- stereoisomer of the dihalide
addition product is formed when
halogenation reaction is carried out on a
cycloalkene. One bromine atom come from
the top face and one from the bottom face
of the double bond.
H Br
Br2/CH2Cl2

H H Br H
 The Production of Halohydrin from Alkene
• If water is used as solvent, the major product
of the reaction will be a vicinal halohydrin. A
halohydrin is an organic molecule that
contains both a halogen and an –OH group.

• For unsymmetrical alkenes, a compound with

halogen atom bonded to carbon atom with
greater number of hydrogen atom. Water
molecule always attack the carbon atom with
more alkyl substituents.
 The Formation of Vicinal Halohydrin

CH3
Cl2/H2O
CH3C CHCH3
2-methyl-2-butene

CH3 CH3
CH3 C CHCH3 + CH3C CHCH3
OH Cl Cl Cl
2-methyl-3-chloro-2-butanol 2,3-dichloro-2-methylbutane
(a chlorohydrin as a major product)
 Oxidation of Alkenes: Epoxidation and
Hydroxylation
• Alkenes are oxidized to give epoxides on treatment
with a peroxyacid (RCO3H), usually meta-
chloroperoxybenzoic acid (mCPBA). An epoxide is
called oxirane. It is a cyclic ether with an oxygen
atom in a three-membered ring.
O
Cl OH
O H O
O Cl
3-chlorobenzoperoxoic acid
H + OH
cyclopentene CH2Cl2 solvent
1,2-epoxy cyclopentane 3-chlorobenzoic acid
• Peroxyacids transfer an oxygen atom to the
alkene with syn stereochemistry – both C-O
bonds form on the same face of the double bond
– through a one-step mechanism without
intermediates. The O atom farthest from the
carbonyl group is the one transferred.

O H
H C
C O
C O +
O O R C C
C O R
peroxyacid
epoxide acid
alkene
 • Another method for the synthesis of epoxides is
through the use of halohydrins. When
halohydrin is treated with base, HX is
eliminated and an epoxide is produced.

H H
H OH
Cl2/H2O NaOH O
H H H2O
cyclohexene Cl Cl
trans-1,2-chloro 1,2-epoxycyclohexane
cyclohexanol + H2O + NaCl
• Epoxides undergo an acid-catalyzed ring-
opening reaction with water (a hydrolysis) to
produce diol or glycol. The two-step alkene
epoxidation/hydrolysis is hydroxylation.
Example conversion of alkene to glycol or
diol.
• Hydroxylation can be carried out directly without
going through the intermediate epoxide by
treating alkene with osmium tetroxide, OsO4. This
cyclic osmate is then cleaved using aqueous
sodium bisulfite, NaHSO3.

CH3 CH3 CH3

OsO4 O O NaHSO3 OH
pyridine Os
H2O
CH3 O O OH
1,2-dimethyl CH3 CH3
cyclopentene a cyclic osmate cis-1,2-dimethyl
intermediate cyclopentane-1,2-diol
 Oxidation of Alkenes: Cleavage to
Carbonyl Compounds
O
O3 O O
C C O O
CH2Cl2, low temp. C C
C C O
1. Ozone (O3) adds rapidly an azonide
to alkene to produce a a molozonide
cyclic intermediate
molozonide and rearranges 2. Ozonide is immediately
to form an ozonide. treated with a reducing agent
such as zinc metal in acetic
acid to produce carbonyl
compounds.

Zn
C O + O C
CH3COOH/H2O
Example:

CH3
CH3
1. O3
C + O + O C
2. Zn, H3O
CH3
CH3
cyclohexanone propan-2-one
isopropylidenecyclohexane

CH3 CH3
1. O3
H2C CCH2CH3 + H2C O + O CCH2CH3
2. Zn, H3O
2-methylbut-1-ene
• Another method to produce carbonyl compound
is by oxidation of alkene with KMnO4 in neutral or
acidic solution. If hydrogens are present on the
double bond, carboxylic acids are produced; if
two hydrogens are present on one carbon, CO2 is
formed.
O

KMnO4/H3O+ OH + CO2

3-methylbutene 2-methylpropanoic acid

 Uses of Alkanes/Alkenes

Methane/propane - A solvent in
Natural gas for Lubricating oil paint thinner
heating and cooking
Paraffin wax

Petroleum jelly Fuel/diesel

Alkynes
 Introduction to Alkynes
• Alkynes are hydrocarbons that contain
carbon-carbon triple bonds as a functional
group.
H C C H
• Molecular formula of alkynes with one double
bond is CnH2n-2 and the name ends with "-yne".
example: 3 carbons is propyne
5 carbons is pentyne
7 carbons is heptyne
 Naming of Alkynes
The rules:
• Choose the longest continuous carbon chain
that contain the triple bond.

• Number the carbon chain to give the triple

bond the lowest position.

• In the IUPAC system, change the “-ane”

ending of alkane to the suffix “-yne”.
Example 1:

7 8
CH2CH3
6 5 4 3 2 1
CH3CHCH C C CH2CH3
Br
5-bromo-6-methyl-3-octyne
 Example 2:

6 7
CH2CH3
1 2 3 4 5
CH3 C C CH2C CH3

CH3
5,5-dimethyl-2-heptyne
• Compounds that contain both double and
triple bonds are called “enynes”.

• When both double and triple bonds are at

equal distant from each end of the chain,
starts numbering from the end nearer to
the double bond.

CH3CH CHCH2 C C CH3

2-hepten-5-yne
• Numbering of an enyne chain starts from
the end nearer to the multiple bonds
whether double or triple.

HC C CH2CH2CH2CH2C CHCH3
CH3

7-methyl-7-nonen-1-yne
 Synthesis of Alkynes: Elimination
Reactions of Dihalides
• 1,2-dihaloalkanes (a vicinal dihalide) treated with
excess strong base such as KOH or sodium amide,
NaNH2results in elimination of HX and formation
of alkyne.

Br
2 KOH
ethanol
Br

1,2-dibromo-1,2-diphenylethane
diphenylacetylene
• Vicinal or geminal dihalides can also undergo
consecutive dehydrohalogenation reactions to
yield the alkyne.
Br H
R C C H
H Br Br H
vicinal dihalide
NaNH2
R C C H + NaBr + NH3
Br H alkenyl halide

R C C H
NaNH2
Br H
geminal dihalide R C C H + NaBr + NH3
Reactions of
Alkynes
 Addition of Hydrogen Halides
• Addition of one equivalent of HX to alkyne
will produce alkene, and addition of excess
HX produce a dihalide product. The
reaction follows Markonikov’s rule.

Br H Br H
HBr H3CC CH HBr
H3CC CH excess H3CC C
prop-1-yne 2-bromoprop-1-ene
Br H
2,2-dibromopropane
Mechanism: H Br-
H-Br
H C C CH2CH3 H C C CH2CH3
Addition of H+ from HBr
form a carbocation Nucleophilic attack by Br-
(Markovnikov’s rule). forms a vinyl bromide.

H Br H Br
H C C CH2CH3 H C C CH2CH3
H
Br- H-Br

H Br
H C C CH2CH3
H Br
 Addition of Halogens
• Addition of one mole X2 to alkyne forms a
trans dihalide and the reaction with second
mole of X2 produce tetrahalide.

X X X
X2/CCl4 X2/CCl4
C C C C C C
X X X
trans-dihalide
tetrahalide
 Cl
CH3CH2C CCH3 Cl2/CH2Cl2 H3CH2CC CCH3
Cl
Cl Cl
Cl2/CH2Cl2
H3CH2CC CCH3
Cl Cl
 Addition of Water/Hydration
• Alkynes don’t react directly with aqueous acid but
undergo hydration in the presence of mercury (II)
sulfate as a Lewis acid catalyst.
H C C CH3
H2O/H+
H C C CH3 H OH
HgSO4 less stable enol

H O
H C C CH3
H
methyl ketone
• The hydration of alkyne forms enol as an
intermediate which can rearranges to a ketone.
The individual keto and enol forms are said to be
tautomers. H
O H
O rapid
C C C C

enol tautomer keto tautomer

(less favored) (more favored)

• Enol is a compound which hydroxyl group is a

substituent on a carbon-carbon double bond. The
name comes from alkene + alcohol. Actually is
“eneol”
• The process of conversion enol to a carbonyl
compound is called keto-enol isomerism or
keto-enol tautomerism.

C C C C
O H O

An enol tautomer has A keto tautomer has a

an O-H group bonded C=O and an additional
to a C=C. C-H bond.
 Mechanism for Hydration of an Alkyne

Step 1: The alkyne uses a pair of electrons to

attack the electrophile mercury(II) ion, formed
a mercury-containing vinylic carbocation
internmediates.

Hg2+SO42-
H
CH3 C C H + 2-
CH3 C C Hg SO4
 • Nucleophilic attack of water on the
carbocation forms a C-O bond and
produced a protonated mercury containing
enol.

H H2O
H2O H
R C C H O H
Hg+SO42- C C
R Hg+SO42-
• Abstraction of H+ from the protonated enol by
water gives an organomercury compound.
Then, replacement of Hg2+ by H+ occurs to give
a neutral enol. The enol undergoes
tautomerization to give a ketone product.
H O H
+ H3O+ H O H
C C
+ H3O+ C C + H2O
R Hg SO42-
R H

O H
C C H
R H
• A mixture of both possible ketones results
when unsymmetrically substituted internal
alkyne is hydrated. Only a methyl ketone is
formed with a terminal alkyne.

An internal alkyne
O O
H3O+
R C C R' R C CH2R' + R C CH2R'
HgSO4
mixture
A terminal alkyne
+
O
H3O
R C C H R C CH3
HgSO4
 Hydroboration-Oxidation of Alkynes

• The addition of borane to alkyne results in

the formation of vinylic borane and can be
oxidize to enol by H2O2.

• Tautomerization of enol gives either an

aldehyde or ketone depends on the
structure of alkyne.
• Hydroboration-oxidation of an internal alkyne
gives a ketone

BH3 H BR2 H2O2

3 R C C R' C C
THF H2O, NaOH
An internal R R'
alkyne tetrahydrofuran
solvent a vinylic borane
H OH
C C
H O R an enol
R'

R C C R'
a ketone
• Hydroboration-oxidation of a terminal alkyne gives
an aldehyde.

H BR2 H O
BH3 H2O2
R C C H R C C H R C C H
A terminal H2O
alkyne H BR2 pH 8 H
an aldehyde

Unhindered terminal alkyne undergoes two

additions, giving a doubly hydroborated
intermediate. Oxidation with peroxide at pH 8
replaces both boron atoms by oxygen and
generates the aldehyde.
 Summary: Reaction of Terminal Alkyne to
Produce Aldehyde and Methyl Ketone
R C C H
A terminal alkyne

H2O/H2SO4 1. BH3/THF
/HgSO4 2. H2O2

O H O
R C CH3 R C C H
a methyl ketone H
an aldehyde
 Hydrogenation/Reduction of Alkyne
• The addition of hydrogen in the presence of
metal catalyst reduced alkynes to alkanes. During
the conversion, alkenes produce as intermediate.
H2/catalyst
H C C H H C C H
H H
H2/catalyst

H H
H C C H
H H
• Complete reduction to alkane occurs when
palladium on carbon (Pd/C) is used as
catalyst, and the reaction can be stopped at
the alkene if the Lindlar catalyst is used. The
cis- alkene produce from this reaction.
H3C CH3
H2
H3C C C CH3 C C
Lindlar catalyst
H H

H2 Pd/C catalyst

H H
H3C C C CH3
H H
• The conversion of alkyne to alkene can also
be done by using sodium or lithium metal
as a reducing agent in liquid ammonia as
solvent. The trans- alkene will be produced
rather than cis- alkene.

CH3
Li/NH3 H
H3C C C CH3 C C
H3C H
 Oxidative Cleavage of Alkynes
• Alkyne is less reactive compared to alkene.
The alkynes can be cleaved by powerful
oxidizing agents such as ozone or KMnO4.

O O
KMnO4 or O3
R C C R' R C OH + R C OH
An internal alkyne

O
KMnO4 or O3
R C C H R C OH + O C O
A terminal alkyne
 Alkyne Acidity: Formation of Acetylinide
Anions
• Terminal alkynes are weakly acidic. When a
terminal alkyne is treated with a strong base
such as sodium amide, Na –NH2, the terminal
hydrogen is removed and acetylide anion is
formed.

-
NH2Na+
R C C H R C C Na+ + NH3
A terminal alkyne acetylide anion
 Alkylation of Acetylide Anions
• The negative charge and unshared electron pair
on carbon make an acetylide anion strongly
nucleophilic. Therefore, acetylide anion can
react with an alkyl halide to substitute for the
halogen and produce a new alkyl product.

R C C Na+ + H C Br R C C CH3 + NaBr

H
• Any terminal alkyne can be converted into
its corresponding anion and then alkylated
by treatment with an alkyl halide to produce
an internal alkyne.

H3C C C H NaNH2/NH3 H3C C C Na+ + NH3

CH3CH2Br
NaBr + H3C C C CH2CH3
(alkylation)
• The alkylation reaction is limited to use of primary
alkyl bromide and alkyl iodide because acetylide
ions are sufficiently strong bases to cause
dehydrohalogenation instead of substitution when
they react with secondary and tertiary alkyl
halides.
H3C C C Na+
Br

C CCH3 + H3C C C H + NaBr

NOT FORMED