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Republic of the Philippines

ISABELA STATE UNIVERSITY
Jones, Isabela

COLLEGE OF CRIMINAL JUSTICE

EDUCATION
Second Semester, School Year 2021-2022

ORGANIC CHEMISTRY

I. TITLE OF THE MODULE

Chapter Four (4): ALKYNE

II. INTRODUCTION

Alkynes are hydrocarbons that contain carbon-carbon triple bonds. Many of the
reactions of alkynes are similar to the corresponding reactions of alkenes because both
involve πbonds between two carbon atoms. Like the π-bond of an alkene, the π-bonds of
an alkyne are also electron rich, and readily undergo addition reactions.

III. TABLE OF CONTENT

i. Unsaturated Hydrocarbons: Alkyne

ii. IUPAC Nomenclature of Alkynes
iii. Physical Properties of Alkynes
iv. Chemical Properties of Alkynes
v. Alkyne Synthesis
vi. Alkyne Preparation
vii. Additional Reactions of Alkynes
viii. Natural Occurring Alkynes

IV. LEARNING OUTCOME

At the end of this module, the students are expected to:

 Name alkynes using IUPAC (systematic) and selected common name nomenclature;
 Draw the structure of alkynes from IUPAC (systematic) and selected common names;
 Distinguish the difference of saturated and unsaturated hydrocarbons; and
 Distinguish reactions of alkenes and alkynes and their properties.

V. LEARNING CONTENT

i. UNSATURATED HYDROCARBONS: ALKYNE

Alkynes also called acetylenes represent the second class of unsaturated

hydrocarbons. An alkyne is an acyclic unsaturated hydrocarbon that contains one or more
carbon–carbon triple bonds. The alkyne functional group is, thus, a C≡C group. As the
family name alkyne indicates, the characteristic “ending” associated with a triple bond is -
yne.
The general formula for an alkyne with one triple bond is CnH2n+2. Thus the
simplest member of this type of alkyne has the formula C2H2, and the next member, with
n = 3, has the formula C3H4.
The presence of a carbon–carbon triple bond in a molecule always results in a linear
arrangement for the two atoms attached to the carbons of the triple bond. Thus, ethyne is a
linear molecule.
The simplest alkyne, ethyne (C2H2), is the most important alkyne from an
industrial standpoint. A colorless gas, it goes by the common name acetylene and is used
in oxy- acetylene torches, high-temperature torches used for cutting and welding material

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ii. IUPAC NOMENCLATURE OF ALKYNES

The rules for naming alkynes are identical to those used to name alkenes, except the
ending -yne is used instead of -ene.
 Find the longest carbon chain that includes both carbons of the triple bond.
 Number the longest chain starting at the end closest to the triple bond.
 After numbering the longest chain with the lowest number assigned to the
alkyne, label each of the substituents at its corresponding carbon. While writing
out the name of the molecule, arrange the substituents in alphabetical order.

4-chloro-6,6-diiodo-7-methyl-2-nonyne
 If there are more than one of the same substituent use the prefixes di, tri, and
tetra for two, three, and four substituents respectively.
 When there are two triple bonds in the molecule, find the longest carbon chain
including both the triple bonds. Number the longest chain starting at the end
closest to the triple bond that appears first. The suffix that would be used to
name this molecule would be –diyne. For example:

1,5-octadiyne
 Substituents containing a triple bond are called alkynyl.

4-bromo-1-chloro-1-ethynylcyclohexane
 A molecule that contains both double and triple bonds is called an alkenyne.
The chain can be numbered starting with the end closest to the functional
group that appears first. For example:

6-ethyl-3-methylnon-4-en-1-yne

iii. PHYSICAL PROPERTIES OF ALKYNES

 The physical properties of alkynes pretty much follow the same pattern of those
of alkanes and alkenes.
 Alkynes are unsaturated carbon that shares a triple bond at the carbon site
 All alkynes are odorless and colorless with the exception of ethylene, which has
a slight distinctive odor.
 The first three alkynes are gases, and the next eight are liquids. All alkynes
higher than these eleven are solids
 Alkynes are slightly polar in nature
 The boiling point and melting point of alkynes increases as their molecular
structure grows bigger. The boiling point increases with increase in their
molecular mass. Also, the boiling points of alkynes are slightly higher than those
of their corresponding alkenes, due to the one extra bond at the carbon site.

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iv. CHEMICAL PROPERTIES OF ALKYNES

The triple-bond functional group of alkynes behaves chemically quite

similarly to the double-bond functional group of alkenes. Thus there are many
parallels between alkene chemistry and alkyne chemistry. The same substances that
add to double bonds (H2, HCl, Cl2, and so on) also add to triple bonds. However,
two molecules of a specific reactant can add to a triple bond, as contrasted to the
addition of one molecule of reactant to a double bond. In triple-bond addition, the
first molecule converts the triple bond into a double bond, and the second molecule
then converts the double bond into a single bond. For example, propyne reacts with
H2 to form propene first and then to form propane.
Alkynes, like alkenes and alkanes, are flammable, that is, they readily
undergo combustion reactions.

v. ALKYNE SYNTHESIS

 CRACKING
- It is the process of breaking down heavier hydrocarbon molecule into a
lighter molecule through the introduction of heat and sometimes
catalysts.

vi. ALKYNE PREPARATION

The preparations of alkynes are very similar to those of the alkenes. The
main preparative reactions involve the elimination of groups or ions from
molecules, resulting in the formation of π bonds.
Dehydrohalogenation. The loss of a hydrogen atom and a halogen atom
from adjacent alkane carbon atoms leads to the formation of an alkene. The loss of
additional hydrogen and halogen atoms from the double‐bonded carbon atoms leads
to alkyne formation. The halogen atoms may be located on the same carbon
(a geminal dihalide) or on adjacent carbons (a vicinal dihalide).

Substitution. Larger alkynes can be generated by reacting an alkyl halide

with an acetylide ion, which is generated from a shorter alkyne.

Because acetylide ions are bases, elimination reactions can occur, leading
to the formation of an alkene from the alkyl halide. Because substitution and
elimination reactions proceed through the formation of a common intermediate,
these two types of reactions always occur simultaneously.

Ethyne (acetylene) preparation. Ethyne, which is commonly called

acetylene, is the simplest alkyne. Historically, it was prepared by reacting
calcium carbide with water.

Today, ethyne is normally prepared by the pyrolysis of methane. In this

procedure, a stream of methane gas is briefly heated to 1500°C in an airless
chamber. Air must be excluded from the reaction or oxidation (combustion) will
occur.

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vii. ADDITIONAL REACTIONS

The principal reaction of the alkynes is addition across the triple bond to form
alkanes. These addition reactions are analogous to those of the alkenes.
Hydrogenation. Alkynes undergo catalytic hydrogenation with the same catalysts
used in alkene hydrogenation: platinum, palladium, nickel, and rhodium.
Hydrogenation proceeds in a stepwise fashion, forming an alkene first, which
undergoes further hydrogenation to an alkane.

This reaction proceeds so smoothly that it is difficult, if not impossible, to stop the
reaction at the alkene stage, although by using palladium or nickel for the catalyst, the
reaction can be used to isolate some alkenes. Greater yields of alkenes are possible with
the use of poisoned catalysts. One such catalyst, the Lindlar catalyst, is composed of
finely divided palladium coated with quinoline and absorbed on calcium carbonate.
This treatment makes the palladium less receptive to hydrogen, so fewer hydrogen
atoms are available to react. When a catalyst is deactivated in such a manner, it is
referred to as being poisoned.
The mechanism of alkyne hydrogenation is identical to that of the alkenes. Because
the hydrogen is absorbed on the catalyst surface, it is supplied to the triple bond in a
syn manner.
Alkynes can also be hydrogenated with sodium in liquid ammonia at low
temperatures. This reaction is a chemical reduction rather than a catalytic reaction, so
the hydrogen atoms are not attached to a surface, and they may approach an alkene
from different directions, leading to the formation of trans alkenes.

Halogenation. The addition of halogens to an alkyne proceeds in the same manner

as halogen addition to alkenes. The halogen atoms add to an alkyne molecule in a
stepwise fashion, leading to the formation of the corresponding alkene, which
undergoes further reaction to a tetrahaloalkane.

Unlike most hydrogenation reactions, it is possible to stop this reaction at the alkene
stage by running it at temperatures slightly below 0°C.
Hydrohalogenation. Hydrogen halides react with alkynes in the same manner as
they do with alkenes.

Both steps in the above addition follow the Markovnikov rule. Thus, the addition
of hydrogen bromide to 1‐butyne gives 2‐bromo‐1‐butene as the major product of thefirst
step.

The reaction of 2‐bromo‐1‐butene in the second step gives 2,2‐dibromobutane asthe

major product.

Hydration. The addition of the elements of water across the triple bond of an
alkyne leads to the formation of aldehydes and ketones. Water addition to terminal
alkynes leads to the generation of aldehydes, while nonterminal alkynes and water
generate ketones.

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These products are produced by rearrangement of an unstable enol (vinyl alcohol)

intermediate. The term “enol” comes from the en in “alkene” and ol in “alcohol,”
reflecting that one of the carbon atoms in vinyl alcohol has both a double bond (alkene)
and an OH group (alcohol) attached to it. A vinyl group is

and a vinyl alcohol is

Water adds across the triple bond of an alkyne via a carbocation mechanism. Dilute
mineral acid and mercury(II) ions are needed for the reaction to occur.

Oxidation. Alkynes are oxidized by the same reagents that oxidize alkenes.
Disubstituted alkynes react with potassium permanganate to yield vicinal diketones or,
under more vigorous conditions, carboxylic acids.
Polymerization. Alkynes can be polymerized by both cationic and free‐radical
methods. The reactions and mechanisms are identical with those of the alkenes.

viii. NATURAL OCCURRING ALKYNES

Alkynes are organic or carbon-based compounds that contain a triple bond

between two carbon atoms. This triple bond ensures these compounds have different
structural and chemical properties from compounds with double-bonded carbons,
which are called alkenes, or alkanes that have single-bonded carbons only. Although
alkynes are uncommon in nature, one of them is important in industry and some
naturally occurring compounds do contain triple-bonded carbons.

Ethyne aka Acetylene

Ethyne is the simplest of the alkynes; its molecular formula is C2H2, and it consists
of two carbon atoms triple-bonded to each other with a hydrogen atom bonded to each
of the carbons. At room temperature it's a colorless gas. The short, electron-rich triple
bond has a high energy content and thus burning ethyne releases a lot of energy,
which makes it a popular fuel in welding torches and other similar applications. Most
welders refer to it by its common name, acetylene. In the early 20th century it was
also an important starting material for synthesis of industrial chemicals, although its
popularity waned as oil-based starting materials took its place.

Ethinyl Estradiol
Ethinyl Estradiol is a synthetic compound similar in structure to the naturally
occurring compound estradiol, which is an important estrogen hormone in the female
body. Like estradiol, it acts as an estrogen but it's extraordinarily potent and long
lasting -- and that's why it's administered as an active ingredient in oral
contraceptives. Introducing this compound into the body changes the body's hormone
balance so that the ovaries do not ovulate and the lining of the womb becomes thinner.

Poisonous Alkynes
Some organisms produce poisonous alkyne compounds to help them deal with
predators or prey. One example is ichthyothereol, a highly toxic alkyne found in the
leaves of a small herb named Ichthyothere terminalis in Brazil. Indians living in the
region once used this poison to kill fish. Another example is histrioconicotoxin, an
alkyne compound found in the skin of the poison arrow frog from the same region.
As the name suggests, its historical use was as a coating for arrowheads.

Medical Alkynes
A few compounds of medical interest aside from ethinyl estradiol also contain alkyne
units. One example is the compounds calicheamicin and esperamicin. Both are found
in nature and have similar structures. They are extremely toxic to cells and work by
breaking double-stranded DNA. Unfortunately, they are so toxic it's not possible to
use them untethered as cancer drugs because they're too good at killing healthy cells.

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Some researchers, however, have sought to attach calicheamicin to antibodies that

specifically target cancer cells so the poison will be delivered to the cancer cells only.
One such drug called gemtuzumab ozogamicin was approved by FDA for treatment
of acute myelogenous leukemia in 2000, but was withdrawn from the U.S. market in
2010.

VI. ASSESSMENTS

1. What is the general molecular formula for an alkyne in which two carbon–carbon triple
bonds are present?
2. What is the general molecular formula for a cycloalkyne in which one carbon–carbon
triple bond is present?
3. Assign an IUPAC name to each of the following unsaturated hydrocarbons.

4. Contrast alkynes and alkenes in terms of general physical properties.

5. Contrast alkynes and alkenes in terms of general chemical properties.
6. Draw skeletal structural formulas and give the IUPAC names for the three possible
alkyne isomers with the molecular formula C5H8.

VII. RESOURCES
 Sachkheim, George I. and Lehman Denis D. Chemistry for the Health Sciences. 8th
Edition. Prentice-Hall, Inc.
 Stoker, Stephen H. General, Organic, and Biological Chemistry. 5th Edition.
Brooks//Cole, Cenage Learning. 2010
 Holm, Johanna Forgotten Chemistry. Barron’s Educational Series, Inc. 2006
 Vollhardt, Peter, and Neil E. Schore. Organic Chemistry: Structure and Function. 5th
Edition. New York: W. H. Freeman & Company, 2007.
 https://sciencing.com/methanol-isopropyl-alcohol-same-thing-5652093.html

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