ALKYNES

Organic Chemistry

DITA FLORESYONA
OUTLINE

1. Introduction alkynes 6. Hydration of alkynes

2. Acidity of acetylene and terminal acetylenes 7. Halogenation of alkynes
3. Preparation of alkynes 8. Ozonolysis of alkynes
4. Reduction of alkynes 9. Alkylation of terminal alkynes
5. Hydrohalogenation of alkynes 10. Synthesis strategies
 1. INTRODUCTION TO ALKYNES

Structure and geometry of alkynes

Alkynes compounds contain C  C bond

The σ bond results from the overlap of sp-

hybridized orbitals, while each of the π
bonds results from overlapping p orbitals
The atomic orbitals used to form a triple bond. The σ bond is
formed from the overlap of two hybridized orbitals, while each
of the two π bonds is formed from overlapping p orbitals.
2. ACIDITY OF ACETYLENE AND TERMINAL ALKYNES

➢ Acetylene (pKa = 25) is significantly more acidic than ethane or ethylene.

➢ Acetylene is 19 orders of magnitude (10,000,000,000,000,000,000 times) more acidic than ethylene

The acidity of acetylene
The relative acidity of acetylene can be explained by exploring the stability of its conjugate base, called an acetylide ion.

The stability of an acetylide ion can be rationalized using hybridization theory

In an sp-hybridized orbital, the electron density is closer to the positively charged nucleus and is therefore more stable.
The acidity
of acetylene
The acidity of acetylene
Now let’s consider the equilibrium that is established when a strong base is used to deprotonate acetylene

Acid base reaction will always favour formation of the weaker acid and weaker base

In this case, the equilibrium favors formation of the acetylide ion, because it is more stable (a weaker base) than the
amide ion
The acidity of acetylene
Consider what happens when a hydroxide ion is used as the base

In this case, the equilibrium does not favor formation of the acetylide ion, because the acetylide ion is less stable (a
stronger base) than the hydroxide ion. Therefore, hydroxide is not sufficiently basic to produce a significant amount of
the acetylide ion.That is, hydroxide cannot be used to deprotonate acetylene.
The acidity of acetylene
Much like acetylene, terminal alkynes are also acidic and can be deprotonated with a suitable base:

The conjugate base of a terminal alkyne, called an alkynide ion, can only be formed with a sufficiently strong base.
Sodium hydroxide (NaOH) is not a suitable base for this purpose, but sodium amide (NaNH2) can be used.
Strong base in alkene
3. PREPARATION OF ALKYNES
Preparation of Alkynes
Preparation of Alkynes
The first elimination can be readily accomplished using many different bases, but the second elimination requires a
very strong base.

Sodium amide (NaNH2), dissolved in liquid ammonia (NH3), is a suitable base for achieving two successive elimination
reactions in a single reaction vessel. This method is used most frequently for the preparation of terminal alkynes,
because the strongly basic conditions favor production of an alkynide ion, which serves as a driving force for the
overall process:

In total, three equivalents of the amide ion are required: two equivalents for the two E2 reactions, and one equivalent
to deprotonate the terminal alkyne and form the alkynide ion.
Preparation of Alkynes
After the alkynide ion has formed and the reaction is complete, a proton source can be introduced into the reaction
vessel, thereby protonating the alkynide ion to regenerate the terminal alkyne:

Comparison of the pKa values indicates that water is a sufficient proton source. In summary, a terminal alkyne can be
prepared by treating a dihalide with excess (xs) sodium amide followed by water:
4. REDUCTION OF ALKYNES

a. Catalytic Hydrogenation

b. Dissolving Metal Reduction

a. Catalytic Hydrogenation

Alkynes undergo many of the same addition reactions as alkenes. For example, alkynes will undergo catalytic

hydrogenation just as alkenes do:

a. Catalytic Hydrogenation
b. Dissolving Metal Reduction
Alkynes can also be reduced to trans alkenes via an entirely different reaction called dissolving metal reduction:

The reagents employed are sodium metal (Na) in liquid ammonia (NH3). Ammonia has a very low boiling point (-33
°C), so use of these reagents requires low temperature. When dissolved in liquid ammonia, sodium atoms serve as
a source of electrons:
b. Dissolving Metal Reduction
b. Dissolving Metal Reduction
In the first step of the mechanism, a single electron is transferred to the alkyne,
generating an intermediate that is called a radical anion. It is an anion because of
the charge associated with the lone pair, and it is a radical because of the
unpaired electron:

The intermediate achieves a lower energy

state when the paired and unpaired electrons
are positioned as far apart as possible,
Arrows used in ionic mechanisms minimizing their repulsion.
(double barbed) and radical
mechanisms (single barbed).
5. HYDROHALOGENATION OF ALKYNES
Experimental Observations
Alkenes will react with HX via a Markovnikov addition, thereby installing a halogen at the more substituted position:

A similar Markovnikov addition is observed when alkynes are treated with HX:

When the starting alkyne is treated with excess HX, two successive addition reactions occur, producing a geminal
dihalide:
Experimental Observations
Two-step mechanism for HX addition to alkenes:

(1) protonation of the alkene to form the more stable carbocation intermediate
(2) nucleophilic attack:
Experimental Observations
A similar mechanism can be proposed for addition of HX to a triple bond:
(1) protonation to form a carbocation followed by
(2) nucleophilic attack:

This proposed mechanism invokes an intermediate vinylic carbocation (vinyl = a carbon atom bearing a double bond) and can
successfully explain the observed regioselectivity. Specifically, the reaction is expected to proceed via the more stable, secondary
vinylic carbocation, rather than via the less stable, primary vinylic carbocation:
Radical Addition of HBr
In the presence of peroxides, HBr undergoes an anti-Markovnikov addition across an alkene:

The Br is installed at the less substituted carbon, and the reaction is believed to proceed via a radical mechanism. A
similar reaction is observed for alkynes. When a terminal alkyne is treated with HBr in the presence of peroxides, an
anti Markovnikov addition is observed. The Br is installed at the terminal position, producing a mixture of E and Z
isomers:

Radical addition only occurs with HBr (not with HCl or HI)
Interconversion of Dihalides and Alkynes
The reactions discussed thus far enable the interconversion between dihalides and terminal alkynes:
6. HYDRATION OF ALKYNES
Acid-Catalyzed Hydration of Alkynes
Alkenes will undergo acid-catalyzed hydration when treated with aqueous acid (H3O+). The reaction proceeds via a

Markovnikov addition, thereby installing a hydroxyl group at the more substituted position:
Acid-Catalyzed Hydration of Alkynes
Alkynes are also observed to undergo acid-catalyzed hydration, but the reaction is slower than the corresponding
reaction with alkenes. The rate of alkyne hydration is markedly enhanced in the presence of mercuric sulfate
(HgSO4), which catalyzes the reaction:

The initial product of this reaction has a double bond (en) and an OH group (ol ) and is therefore called an enol. But
the enol cannot be isolated because it is rapidly converted into a ketone.
Acid-Catalyzed Hydration of Alkynes
Acid-Catalyzed Hydration of Alkynes
The π bond of the enol is first protonated, generating a resonance-stabilized intermediate, which is then

deprotonated to give the ketone. Notice that both steps of this mechanism are proton transfers. The result of this

process is the migration of a proton from one location to another, accompanied by a change in location of the π

bond:
Hydroboration-Oxydation of Alkynes
Alkenes will undergo hydroboration-oxidation.
The reaction proceeds via an anti-Markovnikov addition, thereby installing a hydroxyl group at the less substituted
position:

Alkynes are also observed to undergo a similar process:

The initial product of this reaction is an enol that cannot be isolated because it is rapidly converted into an aldehyde
via tautomerization
Hydroboration-Oxydation of Alkynes
Controlling the Regiochemistry of Alkyne Hydration
Two methods for the hydration of a terminal alkyne:
7. HALOGENATION OF ALKYNES

Alkenes will react with Br2 or Cl2 to produce a dihalide.

In much the same way, alkynes are also observed to undergo halogenation. The one major difference is that alkynes
have two π bonds rather than one and can, therefore, add two equivalents of the halogen to form a tetrahalide:
 8. OZONOLYSIS OF ALKYNES
When treated with ozone followed by water, alkynes undergo oxidative cleavage to produce carboxylic acids:

When a terminal alkyne undergoes oxidative cleavage, the terminal side is converted into carbon dioxide:
 9. ALKYLATION OF TERMINAL ALKYNES
A terminal alkyne can be deprotonated in the presence of a sufficiently strong base, such as sodium amide (NaNH2):

This reaction has powerful synthetic utility, because the resulting alkynide ion can function as a nucleophile when
treated with an alkyl halide:

This transformation proceeds via an SN2 reaction and provides a method to install an alkyl group on a terminal alkyne.
This process is called alkylation, and it is achieved in just two steps; for example:
Alkylation of Terminal Alkynes
Acetylene possesses two terminal protons (one on either side) and can therefore undergo alkylation twice:

Notice that two separate alkylations are required. One side of acetylene is first alkylated, and then, in a separate
process, the other side is alkylated. This repetition is required because NaNH2 and RX cannot be placed into the
reaction flask at the same time. Doing so would produce unwanted substitution and elimination products resulting
from the reactions between NaNH2 and RX. It might seem burdensome to require two separate alkylation processes,
but this requirement does provide additional synthetic utility. Specifically, it enables the installation of two different
alkyl groups; for example:
10. SYNTHESIS STRATEGIES
In particular, a triple bond can be converted into a double bond (either cis or trans), or into a single bond: