STUDENT’S COPY

UNIT 8: ALKYNES

Objectives:

When the students have completed this lesson, the students should be able to:
 Learn the characteristic features of alkynes
 Know the physical properties of alkynes
 Learn the preparation of alkynes
 Learn addition reactions of alkynes – addition of hydrogen halides, addition
of halogen, addition of water, and hydroboration-oxidation

Unit 8 Alkynes 283 Arranged by: Janet A. Dungog

INTRODUCTION
Alkynes are compounds that contain a carbon–carbon triple bond.
Like alkenes, alkynes are nucleophiles with easily broken π bonds, and as such, they undergo
ADDITION REACTIONS with electrophilic reagents.
A C– H bond of an alkyne is more acidic than a C – H bond in an alkene or an alkane.
As such, alkynes are readily deprotonated with strong base. The resulting nucleophiles react with
electrophiles to form new carbon–carbon σ bonds, so that complex molecules can be prepared
from simple starting materials.
Characteristic Features
1. Alkynes contain a carbon–carbon triple bond.
A terminal alkyne has the triple bond at the end of the carbon chain, so that a hydrogen atom is
directly bonded to a carbon atom of the triple bond.
An internal alkyne has a carbon atom bonded to each carbon atom of the triple bond.

2. An alkyne has the general molecular formula CnH2n – 2, giving it four fewer hydrogens than the
maximum number possible.
Because every degree of unsaturation removes two hydrogens, a triple bond introduces TWO
DEGREES OF UNSATURATION.
3. Each carbon of a triple bond is sp hybridized and linear, and all bond angles are 180°.

Unit 8 Alkynes 284 Arranged by: Janet A. Dungog

4. The triple bond of an alkyne consists of one σ bond and two π bonds.

6. Like trans cycloalkenes, cycloalkynes with small rings are unstable.

The carbon chain must be long enough to connect the two ends of the triple bond without
introducing too much strain.
Cyclooctyne is the smallest isolated cycloalkyne, though it decomposes upon standing at room
temperature after a short time.

Unit 8 Alkynes 285 Arranged by: Janet A. Dungog

Exercise
1. Santalbic acid, a fatty acid isolated from the seeds of the sandalwood tree, is an unusual fatty acid
that contains a carbon–carbon triple bond. What orbitals are used to form each of the three
indicated single bonds in santalbic acid? Rank these σ bonds in order of increasing bond strength.

PHYSICAL PROPERTIES OF ALKYNES

The physical properties of alkynes resemble those of hydrocarbons having a similar shape and
molecular weight.
1. Alkynes have low melting points and boiling points.
2. Melting points and boiling points increase as the number of carbons increases.
3. Alkynes are soluble in organic solvents and insoluble in water.
Physical Properties of Some Low-Molecular-Weight Alkynes
-------------------------------------------------------------------------------------------------------------

Exercise
Explain why an alkyne often has a slightly higher boiling point than an alkene of similar molecular
weight. For example, the bp of 1-pentyne is 39 °C, and the bp of 1-pentene is 30 °C.

Unit 8 Alkynes 286 Arranged by: Janet A. Dungog

PREPARATION OF ALKYNES
Alkynes are prepared by elimination reactions.
1. A strong base removes two equivalents of HX from a vicinal or geminal dihalide to yield an alkyne
by two successive E2 eliminations.

2. Because vicinal dihalides are synthesized by adding halogens to alkenes, an alkene can be
converted to an alkyne by the two-step process.

Sample Problem
Convert alkene A into alkyne B by a stepwise method.

Solution
A two-step method is needed:
Step 1 Addition of X2 forms a vicinal dihalide.
Step 2 Elimination of two equivalents of HX forms two π bonds.

• This two-step process introduces one degree of unsaturation: an alkene with one π bond is
converted to an alkyne with two π bonds.
Exercise
Convert each compound to hex-1-yne, HCCCH2CH2CH2CH3.
a. Br2CH(CH2)4CH3
b. CH=CCl(CH2)3CH3
c. CH2=CH(CH2)3CH3

Unit 8 Alkynes 287 Arranged by: Janet A. Dungog

INTRODUCTION TO ALKYNE REACTIONS
All reactions of alkynes occur because they contain easily broken  bonds or, in the case of terminal
alkynes, an acidic, sp hybridized C – H bond.
Like alkenes, alkynes undergo addition reactions because they contain weak  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.

Alkynes are electron rich, as shown in the electrostatic potential map of acetylene. Alkynes react
with electrophiles.
The two π bonds form a cylinder of electron density between the two sp hybridized carbon atoms,
and this exposed electron density makes a triple bond nucleophilic.
Four addition reactions are discussed here with 1-butyne as the starting material.

Unit 8 Alkynes 288 Arranged by: Janet A. Dungog

TERMINAL ALKYNES—REACTION AS AN ACID
Because sp hybridized C – H bonds are more acidic than sp2 and sp3 hybridized C – H bonds, terminal
alkynes are readily deprotonated with strong base in a Brønsted–Lowry acid–base reaction.
The resulting anion is called an acetylide anion.

What bases can be used for this reaction?

Because an acid–base equilibrium favors the weaker acid and base, only bases having conjugate acids
with pKa values higher than the terminal alkyne—that is, pKa values > 25—are strong enough to
form a significant concentration of acetylide anion.
As shown in the table below, –NH2 and H– are strong enough to deprotonate a terminal alkyne, but –
OH and –OR are not.
A Comparison of Bases for Alkyne Deprotonation

Why is this reaction useful?

The acetylide anions formed by deprotonating terminal alkynes are strong nucleophiles that can react
with a variety of electrophiles.

Unit 8 Alkynes 289 Arranged by: Janet A. Dungog

HYDROHALOGENATION - Addition of Hydrogen Halides (HX)
Alkynes undergo hydrohalogenation, the addition of hydrogen halides, HX (X = Cl, Br, I).

 Two equivalents of HX are usually used: addition of one mole forms a vinyl halide, which then
reacts with a second mole of HX to form a geminal dihalide.
 Addition of HX to an alkyne is another example of electrophilic addition, because the
electrophilic (H) end of the reagent is attracted to the electron-rich triple bond.

Unit 8 Alkynes 290 Arranged by: Janet A. Dungog

Exercise
Draw the organic products formed when each alkyne is treated with two equivalents of HBr.

HALOGENATION - Addition of Halogen

Halogens, X2 (X = Cl or Br), add to alkynes in much the same way they add to alkenes.

 Addition of one mole of X2 forms a trans dihalide, which can then react with a second mole of
X2 to yield a tetrahalide.

Exercise
Draw the products formed when CH3CH2CCCH2CH3 is treated with each reagent:
a. Br2 (2 equiv)
b. Cl2 (1 equiv)

Unit 8 Alkynes 291 Arranged by: Janet A. Dungog

HYDRATION - Addition of Water
In the presence of strong acid or Hg2+ catalyst, the elements of H2O add to the triple bond, but the
initial addition product, an ENOL, is unstable and rearranges to a product containing a carbonyl
group—that is, a C=O.

Internal alkynes undergo hydration with concentrated acid, whereas terminal alkynes require the
presence of an additional Hg2+ catalyst—usually HgSO4—to yield methyl ketones by Markovnikov
addition of H2O.

Unit 8 Alkynes 292 Arranged by: Janet A. Dungog

HYDROBORATION - OXIDATION
Hydroboration–oxidation is a two-step reaction sequence that converts an alkyne to a carbonyl
compound.

1. Hydroboration–oxidation of an internal alkyne forms a ketone.

2. Hydroboration of a terminal alkyne adds BH2 to the LESS substituted, terminal carbon.

3. Hydration (H2O, H2SO4, and HgSO4) and hydroboration–oxidation (BH3 followed by H2O2, HO–) both
add the elements of H2O across a triple bond.

Sample Problem below shows that different constitutional isomers are formed from terminal alkynes
in these two reactions despite their similarities.

Unit 8 Alkynes 293 Arranged by: Janet A. Dungog

Sample Problem
Draw the product formed when CH3CH2CCH is treated with each of the following sets of reagents: (a)
H2O, H2SO4, HgSO4; (b) BH3, followed by H2O2, HO–.
Solution
(a) With H2O + H2SO4 + HgSO4, electrophilic addition of H and OH places the H atom on the less
substituted carbon of the alkyne to form a ketone after tautomerization. (b) In contrast, addition of
BH3 places the BH2 group on the less substituted terminal carbon of the alkyne. Oxidation and
tautomerization yield an aldehyde.

Exercise
Draw the products formed when the following alkynes are treated with each set of reagents: [1] H2O,
H2SO4, HgSO4; or [2] BH3 followed by H2O2, –OH.

Unit 8 Alkynes 294 Arranged by: Janet A. Dungog

Reaction Map for Alkynes

Unit 8 Alkynes 295 Arranged by: Janet A. Dungog