CHAPTER 9: ALKYNES

9.1 Introduction to Alkynes

*** Structure and Geometry of Alkynes

Reactive due to the triple bond present – concentrated

electron density. 9.2 Nomenclature of Alkynes

1. Identify and name the parent.

When naming the parent, the suffix “yne” is used to

indicate the presence of a C≡C bond:

- in a linear geometry
The parent of an alkyne is the longest chain that includes
- difficult to be in a ring because of ring strain. the C≡C bond:

- Has the shortest bond length because it has the

highest s character (note that s orbital is the are closer
than p orbitals to the positively charged nucleus)

- has a 50% s characteristic (1/2) 2. Identify and name the substituents.

The carbon atoms in acetylene utilize sp-hybridized
orbitals to form bonds with the hydrogen atoms, and a
high degree of s-character gives rise to shorter C−H
bonds.
- there is an attractive overlap of three pairs of bonding
electrons in between the carbon atoms
3. Number the parent chain and assign a locant to each
substituent.
When numbering the parent chain of an alkyne, the triple
bond should receive the lowest number possible, despite
the presence of alkyl substituents:

4. Assemble the substituents alphabetically

*** Alkynes in Industry and Nature

e.g., Acetylene Some common names with alkyl groups included:

- a colorless gas used to produce high temperature
flames.

- a precursor for the preparation of higher alkynes.

Alkynes can be classified according to the alkyl Recall that the equilibrium of an acid-base reaction will
group/s attached to it: always favor formation of the weaker acid and weaker
base.
1. Terminal - Monosubstituted acetylenes

2. Internal - disubstituted acetylenes

acetylide ion is stabler and weaker than amide ion.

If a weaker base is used as a starting reagent:

9.3 Acidity of Acetylene and Terminal Alkynes

Acetylene like other terminal alkynes:

Product formation will not be favored because

acetylide ion is stronger that OH.

The low pKa value of acetylene implies that it is a * hydroxide cannot be used to deprotonate acetylene.
strong acid.
Much like acetylene, terminal alkynes are also acidic and
REASONS: can be deprotonated with a suitable base:

* Based on its conjugate base, acetylide ion:

alkynide ion can only be formed with a sufficiently strong

base as shown above.
The negative charge is considered to be associated with
a lone pair that occupies an sp-hybridized orbital
according to the hybridization theory.

Since sp orbitals have the highest s characteristic, it is

closer to the nucleus which makes it stable.

A stable conjugate base implies a strong acid –

justifies the pKa of acetylene and other terminal
alkynes.
three bases on the bottom left of the chart all have the
negative charge on an oxygen atom, which is not strong
enough to deprotonate a terminal alkyne
- O is quite electronegative compared to N−, H−, or C−.
9.4 Preparation of Alkynes
alkynes can be prepared from alkyl dihalides:
transformation is accomplished via two successive
elimination (E2) reactions:
geminal dihalide - both halogens are connected to the
same carbon atom.
vicinal dihalides - the two halogens are connected to
adjacent carbon atoms.
The first elimination can be readily accomplished using
many different bases.
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.
Favorable reaction since NaNH2 is a strong base
reagent.
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.
Regenerating the alkyne, a proton source is
introduced to the alkynide ion.
Favorable since the conjugate acid is weaker than the
reagent acid.
Generally, a terminal alkyne can be prepared by treating
a dihalide with excess (xs) sodium amide followed by
water:
9.5 Reduction of Alkynes
*** Catalytic Hydrogenation
Two equivalents of molecular hydrogen are needed to
convert the Alkyne into an alkane.
Conversion of Alkyne into ALKENE ONLY is
possible if the alkene product is prohibited from
FURTHER hydrogenation.
- Poisoned catalyst is used.
There are many poisoned catalysts. One common
example is Lindlar’s catalyst, which is a Pd catalyst
prepared with CaCO3 and traces of PbO2.

A poisoned catalyst is used to convert alkynes into cis Trans product is preferred because of the steric
alkenes. interaction between possible intermediates:

A syn addition process as well.

Order: e−, H+, e−, H+.

*** Catalytic Hydrogenation vs. Dissolving Metal

Reduction

*** Dissolving Metal Reduction

Allows conversion of alkynes into TRANS alkene.

9.6 Hydrohalogenation of Alkynes

Reagents: Na in a liquid ammonia. use of these
reagents requires low temperature because NH3 has a *** Experimental Observations
low boiling point (-33C).
Similar to markovnikov addition in alkenes, the X- is
When dissolved in liquid ammonia, sodium atoms serve as added to the more substituted region in alkynes.
a source of electrons:

The alkyne proceeds to the Dissolving Metal Reduction.

A geminal dihalide is produced when an alkyne is
Dissolving Metal Reduction Mechanism treated with an excess HX.

*** A Mechanism for Hydrohalogenation

A radical anion is formed in the second step.

It is an anion because of the charge associated with the

lone pair, and it is a radical because of the unpaired
electron
Can be used as a reference on the flow of the reaction
but not exactly the mechanism because it invokes a
secondary vinylic intermediate.
Even though the X is most of the time preferable in a
secondary vinylic intermediate because of its stability
compared to the primary, it has exceptions.
* studies in the gas phase indicate that vinylic
carbocations are not particularly stable
* vinylic carbocations are believed to be similar in energy
to regular primary carbocations.
The mechanism is observed to be termolecular:
Rate = k [alkyne] [HX]2
Still exhibits some partial carbocationic character which
explains the regioselectivity.
The vinylic carbocation probably does play some limited
role.
*** Radical Addition of HBr
When a terminal alkyne is treated with HBr in the
presence of peroxides, an anti-Markovnikov addition is
observed.
Mixture of E and Z are observed.
Radical addition only occurs with HBr (not with HCl or HI).
*** Interconversion of Dihalides and Alkynes
9.7 Hydration of Alkynes
*** Acid-Catalyzed Hydration of Alkynes
Alkynes also undergo Acid-catalyzed hydration but
slower than alkenes – when alkyne is protonated, the
vinylic carbocation intermediate is higher in energy
than on alkenes.
Mercuric sulfate (HgSO4) is used as a catalyst to
enhance the rate of reaction.
The mercuric ion (Hg2+) activates the alkyne toward
nucleophilic attack, via the initial formation of a
mercurinium ion.
The mercurinium ion is attacked by a water then
deprotonation happens:
Under acidic conditions, the proton (H+) then replaces
Hg2+ in the product.
Enol product is formed:
called an enol because it has a double bond (en) and an
OH group (ol).
However, enol rapidly converts into ketone (under acidic
conditions:
*** Acid-Catalyzed Tautomerization Mechanism Acid-catalyzed hydration of unsymmetrical internal
alkynes yields a mixture of ketones:
- conversion of an enol into ketone:

lack of regiochemical control renders this process

significantly less useful.

*** Hydroboration-Oxidation of Alkynes

Since both steps are proton transfer, it results to an anti-Markovnikov addition – installs Oh at the less
migration of a proton (in a sense). This is substituted position.
accompanied by a change in location of the π bond.

The initial product of this reaction is an enol that cannot

The enol and ketone are said to be tautomers, which are
constitutional isomers that rapidly interconvert via the
migration of a proton.
- keto-enol tautomerization.
be isolated because it is rapidly converted into an
aldehyde via tautomerization.
- since base is used, it undergoes a base-catalyzed
mechanism.

** Tautomers and Resonance structures are not the *** Base-Catalyzed Tautomerization Mechanism
same!

Resonance Structures Tautomers

- are representations
- not in equilibrium.
- not constitutional (same
comp).
- constitutional isomers
that exist in equilibrium
with one another. - opposite of acid catalyzed conditions.
- different comp. Deprotonation of the enol leads to a resonance-stabilized
anion called an enolate ion, which is then protonated to
generate the aldehyde.

Once the equilibrium has been reached, the

concentrations of ketone and enol can be measured.
Hydroboration-oxidation of alkynes are similar to alkenes
Keto-enol tautomerization is an equilibrium process that with some difference:
is catalyzed by even trace amounts of acid (or base) –
a dialkyl borane (R2BH) is employed instead of BH3 to
susceptible to proceed reaction if trace amount/s is
prevent second addition since there are 2 pi bonds in an
present.
alkyne.
the enol initially produced by alkyne hydration will
immediately tautomerize to form a ketone.

- therefore the product of alkyne hydration is a ketone.

The product is an aldehyde, not a ketone
*** Controlling the Regiochemistry of Alkyne Hydration for example:

This process is only efficient with methyl or primary alkyl

halides.

When secondary or tertiary alkyl halides are used, the

alkynide ion functions primarily as a base, and elimination
products are obtained.

If the alkyne have 2 terminal protons, it can undergo

9.8 Halogenation of Alkynes
alkylation twice.
- similar to alkene halogenation

two equivalents of the halogen to form a tetrahalide is

possible because alkynes have 2 pi bonds. Alkylation process is done twice because NaNH2 and
RX cannot be placed into the reaction flask at the same
- production of dihalide is also possible (anti addition) time – produces an unwanted elimination and
– E stereoisomer is a major product. substitution products.

In addition, two different alkyl groups can be added:

9.9 Ozonolysis of Alkynes

When treated with ozone followed by water, alkynes 9.11 Synthesis Strategies
undergo oxidative cleavage to produce carboxylic acids:

When a terminal alkyne undergoes oxidative cleavage,

the terminal side is converted into carbon dioxide

9.10 Alkylation of Terminal Alkynes

alkynide ion can function as a nucleophile when treated

with an alkyl halide:

alkylation – the mechanism observed above and proceeds

via SN2 pathway.