Organic Chemistry 1

ORC601S
2025

Unit 6:
Alkynes

Based on
Janice G. Smith’s Organic Chemistry, 6th Edition, Chapter 11

Prepared by Tjaronda Karumendu

Namibia University of Science and Technology

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 Unit Preface
In this unit, we will we continue our focus on organic molecules with
electron-rich functional groups. Like alkenes, alkynes are nucleophiles
with easily broken π bonds, and as such, they undergo addition
reactions with electrophilic reagents.

In addition, alkynes undergo a reaction that has no analogy in alkene

chemistry. Because a C-H bond of an alkyne is more acidic it is readily
deprotonated with strong base. The resulting nucleophiles react with
electrophiles to form new carbon–carbon a bonds, so that complex
molecules can be prepared from simple starting materials.

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 Introduction to Alkynes
• 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 bonded directly to a carbon atom of the triple
bond.
✓ An internal alkyne has a carbon atom bonded to each carbon atom of
the triple bond.
• 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

➢ Both π bonds of a C–C triple bond are weaker than a C–C σ bond, making them much
more easily broken. As a result, alkynes undergo many addition reactions.
➢ Alkynes are more polarizable than alkenes because the electrons in their σ bonds are
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more loosely held.
 Nomenclature of Alkynes

• Alkynes are named in the same general way that are alkenes are named.
• In the IUPAC system, change the –ane ending of the parent alkane name to
the suffix –yne.
• Choose the longest continuous chain that contains both atoms of the triple
bond and number the chain to give the triple bond the lower number.
• Compounds with two triple bonds are called diynes, those with three are
called triynes and so forth.
• Compounds with both a double and a triple bond are named as enynes. The
chain is numbered to give the first site of unsaturation (either C=C or C≡C)
the lower number.
• The two carbon alkyl group derived from acetylene is called an ethynyl
group.
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 Nomenclature of Alkynes

Worked Examples

5-chloro-5,6-dimethyloct-3-yne

4-ethyl-7,7-dimethyldec-1-en-5-yne

3-isopropylocta-1,5-diyne

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 Properties of Alkynes
The physical properties of alkynes resemble those of
hydrocarbons having a similar shape and molecular weight.
✓ Alkynes have low melting points and boiling points.
✓ Melting points and boiling points increase as the number of carbons
increases.
✓ Alkynes are soluble in organic solvents and insoluble in water.
Some Interesting Alkynes

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 Preparation of Alkynes

• Alkynes are prepared by elimination reactions, as discussed in Unit 3-II.

• A strong base removes two equivalents of HX from a vicinal or
geminal dihalide to yield an alkyne by two successive E2 eliminations
✓ Because vicinal dihalides are
synthesized by adding halogens to
alkenes, an alkene can be converted to
an alkyne by the two-step process
illustrated below

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 Introduction to Alkyne Reactions
All reactions of alkynes occur because they contain easily broken π bonds
or, in the case of terminal alkynes, an acidic, sp hybridized C–H bond

Addition Reactions
• 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.

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 Introduction to Alkyne Reactions
All reactions of alkynes occur because they contain easily broken π bonds
or, in the case of terminal alkynes, an acidic, sp hybridized C–H bond
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.

Recall from Unit 1 that the acidity of a C–H bond increases as the percent s-character of C
increases. Thus, the following order of relative acidity results:

• 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
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 Introduction to Alkyne Reactions
All reactions of alkynes occur because they contain easily broken π bonds
or, in the case of terminal alkynes, an acidic, sp hybridized C–H bond
Terminal Alkynes: Reaction
as an Acid

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.

As shown above , −NH2 and H− are strong enough to

deprotonate a terminal alkyne, but −OH and −OR are not.
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 Addition of Hydrogen Halides

• 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.
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 Addition of Hydrogen Halides
• With two equivalents of HX, both H atoms bond to the same
carbon.
• With a terminal alkyne, both H atoms bond to the terminal
carbon; that is, the hydrohalogenation of alkynes follows
Markovnikov's rule.

• With only one equivalent of HX, the reaction stops with

formation of the vinyl halide

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 Electrophilic Addition of HX to an Alkyne Mechanism
The scrutiny

The vinyl carbocation formed in Step [1]

o Why is carbocation A, having a positive
is sp hybridized and therefore less stable
charge on a carbon that also has a Br atom,
than a 2° sp2 hybridized carbocation
more stable?
o Shouldn't the electronegative Br atom
✓ Electrophilic addition of HX to an alkyne
withdraw electron density from the positive
slower than electrophilic addition of HX
charge, and thus destabilize it?
to an alkene, even though alkynes are
more polarizable and have more loosely
held π electrons than alkenes.
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 Addition of Halogen
• Halogens, X2 (X = Cl or Br), add to alkynes in much the same
way they add to alkenes (Unit 5).
• Addition of one mole of X2 forms a trans dihalide, which can then
react with a second mole of X2 to yield a tetrahalide.

Food for Thought

Although alkenes are generally more reactive than alkynes toward
electrophiles, the reaction of Cl2 with but-2-yne can be stopped after one
equivalent of Cl2 has been added. Explain this observation.
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 Addition of Water
• Although the addition of H2O to an alkyne resembles the acid-
catalyzed addition of H2O to an alkene in some ways, an important
difference exists.
• 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.

✓ Because an enol contains both a C=C and a hydroxy group, the

name enol comes from alkene + alcohol.
✓ HgSO4 is often used in the hydration of internal alkynes as well,
because hydration can be carried out under milder reaction
conditions.
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 Addition of Water

• Internal alkynes undergo hydration with concentrated acid

• Terminal alkynes require the presence of an additional Hg2+
catalyst -usually HgSO4
- To both yield methyl ketones by Markovnikov addition of H2O.

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 Addition of Water
Tautomers
• Tautomers are constitutional isomers that differ in the location of a double bond and
a hydrogen atom. Two tautomers are in equilibrium with each other.

Tautomers differ in the position of a double bond

and a hydrogen atom
✓ An enol tautomer has an O–H group bonded to a C=C.
✓ A keto tautomer has a C=O and an additional C–H bond.
Equilibrium favors the keto form largely because a C=O is much stronger than a C=C.

• The process of converting one tautomer into another (Tautomerization), is catalyzed

by both acid and base.
• Under the strongly acidic conditions of hydration, tautomerization of the enol to the
keto form occurs rapidly by a two-step process: protonation, followed by
deprotonation as shown in Mechanism below

[1] -Protonation of the double bond forms a resonance-stabilized carbocation.

[2] -Loss of a proton, which can be drawn with either resonance structure,
forms the carbonyl group. Because acid is re-formed in this step,
tautomerization is acid-catalyzed. 17
 Addition of Water
Mechanism
Hydration of an internal alkyne with strong acid forms an enol by a mechanism
similar to that of the acid-catalyzed hydration of an alkene (Unit 5). Once formed,
the enol then tautomerizes to the more stable keto form by protonation followed
by deprotonation.
Mechanism illustrated by the hydration of but-2-yne with H2O and H2SO4
Part [1] Addition of H2O to form an enol

Part [2] Tautomerization

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

✓ Addition of borane forms an organoborane.

✓ Oxidation with basic H2O2 forms an enol.
➢ Tautomerization of the enol forms a carbonyl compound.
➢ The overall result is addition of H2O to a triple bond.

Hydroboration of a terminal alkyne

is generally carried out with a
dialkylborane (R2BH), which has
been prepared from BH3 (Unit 5 )

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 Comparing Hydration Products Using
the Two Different Methods

Hydration (H2O, H2SO4, and HgSO4) and hydroboration–oxidation

(BH3 or R2BH followed by H2O2, HO−) both add the elements of H2O
across a triple bond
✓ Addition of H2O using H2O, H2SO4, and HgSO4 forms methyl ketones
from terminal alkynes.
✓ Addition of H2O using an organoborane, then H2O2, HO− forms
aldehydes from terminal alkynes.

E.g.,

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 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.

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 Reaction of Acetylide Anions
Reaction of Acetylide Anions with Alkyl Halides
• Acetylide anions react with unhindered alkyl halides to yield products
of nucleophilic substitution.

✓ Because acetylide anions are strong nucleophiles, the mechanism of

nucleophilic substitution is SN2, and thus the reaction is fastest with CH3X
and 1° alkyl halides.
✓ Terminal alkynes (Reaction [1]) or internal alkynes (Reaction [2]) can be
prepared depending on the identity of the acetylide anion.

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 Reaction of Acetylide Anions
Reaction of Acetylide Anions with Epoxides

• Acetylide anions are strong nucleophiles that open epoxide rings by

an SN2 mechanism

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 Synthesis
The reactions of acetylide anions give us an opportunity to
examine organic synthesis more systematically.

➢ Performing a multistep synthesis can be difficult.

✓ Not only must you know the reactions for a
particular functional group, you must also put these
reactions in a logical order, a process that takes
much practice to master.

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 Synthesis
General Terminology and Conventions
• To plan a synthesis of more than one step, we use the process of
retrosynthetic analysis
• i.e., working backwards from the desired product to determine the
starting materials from which it is made (Unit 5 ).
• To write a synthesis working backwards from the product to the
starting material, an open arrow (⇒) is used to indicate that the
product is drawn on the left and the starting material on the right.

• The product of a synthesis is often called the target compound.

• In designing a synthesis, reactions are often divided into two
categories:
1. Reactions that form new carbon–carbon bonds.
2. Reactions that convert one functional group to another—that is,
functional group interconversions.
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 Synthesis
How To Develop a Retrosynthetic Analysis

Step [1] Compare the carbon skeletons of the starting material and product.
✓ If the product has more carbon–carbon σ bonds than the starting material,
the synthesis must form one or more C–C bonds. If not, only functional
group interconversion occurs.
✓ Match the carbons in the starting material with those in the product to see
where new C–C bonds must be added or where functional groups must be
changed.

Step [2] Concentrate on the functional groups in the starting material and
product and ask:
✓ What methods introduce the functional groups in the product?
✓ What kind of reactions does the starting material undergo? 26
 Synthesis
How To Develop a Retrosynthetic Analysis
Step [3] Work backwards from the product and forwards from the starting
material.
✓ Ask: What is the immediate precursor of the product?
✓ Compare each precursor to the starting material to determine if there is a
one-step reaction that converts one to the other. Continue this process until
the starting material is reached.
✓ Always generate simpler precursors when working backwards.
✓ Use fewer steps when multiple routes are possible.
✓ Keep in mind that you may need to evaluate several different precursors for
a given compound.
Step [4] Check the synthesis by writing it in the synthetic direction.
✓ To check a retrosynthetic analysis, write out the steps beginning with the
starting material, indicating all necessary reagents. 27
 Devising a Synthesis in practice
Problem
Devise a synthesis of the following compound from starting materials
having two or fewer carbons.

A carbon–carbon bond-forming reaction must be used to convert the two carbon starting
materials to the four-carbon product.
[1] Form the carbonyl group by hydration
of a triple bond.
[2] Form a new C–C bond using an
acetylide anion and a 1° alkyl halide.
[3] Prepare the acetylide anion from
acetylene by treatment with base.

The synthesis in the synthetic direction.

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END
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