CHAPTER 7

ALKYNES

Nomenclature
IUPAC: use the infix -ynyn to show the
presence of a carbon-carbon triple bond.

Common names: prefix the substituents on

the triple bond to the word acetylene.
(Acetylene is an IUPAC accepted name for
ethyne.)
IUPAC name:
Common name:

2-Butyne
1-Buten-3-yne
Dimethylacetylene Vinylacetylene

Cycloalkynes
Cyclooctyne is the smallest cycloalkyne
isolated. (unstable; 155bond angle)
Cyclononyne has high degree angle strain.
It is stable at room temp.
The C-C-C bond angle about the triple bond is
approximately 160 (rather than the optimal
angle of 180), indicating high angle strain.

Cyclononyne

Physical Properties
Similar to alkanes and alkenes of
comparable molecular weight and carbon
skeleton.

Acidity
The pKa of acetylene and terminal alkynes is
approximately 25, which makes them
stronger acids than ammonia (pka 38) but
weaker acids than alcohols (pka ~16)
(Section 4.3).
H bonded to triple bonded C acidic enough to be
removed only by very strong base
Terminal alkynes react with sodium amide to
form alkyne anions.

Acidity
Terminal alkynes can also be converted to alkyne
anions by reaction with sodium hydride or lithium
diisopropylamide (LDA).

Because water is a stronger acid than terminal

alkynes, hydroxide ion is not a strong enough
base to convert a terminal alkyne to an alkyne
anion.

Alkylation of Alkyne Anions

Alkyne anions are both strong bases and
good nucleophiles.
They participate in nucleophilic substitution
reactions with alkyl halides to form new C-C
bonds to alkyl groups; they undergo
alkylation.
alkylation
Because alkyne anions are also strong bases,
alkylation is practical only with methyl and 1
halides

With 2 & 3 halides, elimination is the major

reaction.

Alkylation of Alkyne Anions

Alkylation of alkyne anions is the most
convenient method for the synthesis of terminal
alkynes.

Alkylation can be repeated and a terminal alkyne

in turn converted to an internal alkyne.

Alkylation of Alkyne Anions

What is the product of the following alkylation?
1) NaNH2, NH3

CH3CH2CH2CH2CCH

2) CH3CH2CH2CH2Br

Alkylation of Alkyne Anions

Using NaNH2, show the starting alkyne and alkyl
halide needed to make
A)

CH3CH2CH2CCCH3

B)
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Preparation of Alkynes from

Alkenes

Treatment of a vicinal dibromoalkane with

two moles of base, most commonly sodium
amide, results in two successive
dehydrohalogenation reactions (removal of
H and X from adjacent carbons) and
formation of an alkyne.

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Alkylation of Alkyne Anions

Draw the intermediate and the major product of
the following:

Cl2
DCM

NaNH2, NH3

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Preparation from Alkenes

For a terminal alkene to a terminal alkyne, 3
moles of base are required.

A side product of this synthetic scheme may be

an allene,
allene a compound containing adjacent
carbon-carbon double bonds, C=C=C.

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Allene
Allene: A compound containing a C=C=C
group
the simplest allene is 1,2-propadiene, commonly
named allene

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Allenes
Most allenes are less stable than their isomeric
alkynes, and are generally only minor products in
alkyne-forming dehydrohalogenation reactions.

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Addition of X2 (electrophilic
addition)

Alkynes add one mole of bromine to give a

dibromoalkene.
Addition shows anti stereoselectivity.
Addition of chlorine similar, but less
stereoselective.

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Addition of X2
Addition of bromine to an alkyne follows much
the same mechanism as that for the bromination
of an alkene, namely formation of a bridged
bromonium ion intermediate, which is then
attacked by bromide ion from the face opposite
that occupied by the positively charged bromine
atom.
Addition of a second mole bromine gives
tetrabromoalkane.

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Addition of X2
What is the major product of the following?

A)

CH2Cl2

CH3CH2CCH + Br2

CH2Cl2

B)

CH3CH2CH2CCH + 2 Cl2

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Electrophilic Addition of HX
Alkynes undergo regioselective (follows
Markovnikovs rule) addition of either 1 or 2
moles of HX, depending on the ratios in
which the alkyne and halogen acid are
mixed.

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Electrophilic Addition of HX
Step 1: Make a new bond between a nucleophile
(a bond) and an electrophileadd a proton.

Step 2: Make a new bond between a nucleophile

and an electrophile.

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Electrophilic Addition of HX
In the addition of the second mole of HX,
Step 1 is reaction of the electron pair of the
remaining pi bond with HBr to form a
carbocation.
Of the two possible carbocations, the resonancestabilized 2carbocation is favored.

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Addition of HX
What is the major product of the following?

A)

B)

+ HBr

CH3CH2CH2CH2CCH + HBr

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Hydroboration
Addition of borane to an internal alkyne
gives a trialkenylborane.
Addition is syn stereoselective.

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Hydroboration
To prevent dihydroboration with terminal alkynes,
it is necessary to use a sterically hindered
dialkylborane, such as (sia)2BH.

Treatment of a terminal alkyne with (sia)2BH

results in stereoselective and regioselective
hydroboration.

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Hydroboration
Treating an alkenylborane with H 2O2 in
aqueous NaOH gives an enol.

Enol: A compound containing an -OH group on one

carbon of a carbon-carbon double bond.
An enol is in equilibrium with a keto form by
migration of a hydrogen from oxygen to carbon
and migration of the double bond from C=C to
C=O.
Keto forms generally predominate at equilibrium.
Keto and enol forms are tautomers and their
interconversion is called tautomerism.
tautomerism

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Hydroboration/Oxidation; hydration
Hydroboration/oxidation of an internal alkyne
gives a ketone.

Hydroboration/oxidation of a terminal alkyne

gives an aldehyde.

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Hydroboration/oxidation
What alkyne and reagents would give the
following?

A)

B)

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Addition of H2O: hydration

In the presence of concentrated sulfuric acid
and Hg(II) salts, alkynes undergo addition of
water.

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Addition of H2O: hydration

Step 1: Make a new bond between a
nucleophile ( bond) and an electrophile.

Step 2: Make a new bond between a

nucleophile and an electrophile. (attack of
water opens ring)

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Addition of H2O: hydration

Step 3: Take a proton away. Proton transfer to
solvent gives an organomercury enol.

Step 4: Keto-enol tautomerism of the enol

gives the keto form.

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Addition of H2O: hydration

Step 5: Add a proton. Proton transfer to the
carbonyl oxygen gives an oxonium ion.

Steps 6 and 7: Break a bond to give stable

molecules or ions followed by keto-enol
tautomerism.

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Acid catalyzed hydration

What is the major product of the following?

A) CH3CH2CH2CCCH2CH2CH3

B) (CH3)2CHCH2CCCH2CH2CH3

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Reduction
Treatment of an alkyne with H2 in the
presence of a transition metal catalyst, most
commonly Pd, Pt, or Ni, converts the alkyne
to an alkane.

With the Lindlar catalyst, the reduction

stops at
syn-stereoselective addition of
one mole of H2.

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Hydroboration - Protonolysis
Syn-stereoselective addition of borane to an
internal alkyne gives a trialkenylborane.

Treatment of a trialkenylborane with acetic acid

results in stereoselective replacement of B by H.

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Dissolving Metal Reduction

Reduction of an alkyne with Na or Li in liquid
ammonia converts an alkyne to an alkene
with anti stereoselectivity.

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Dissolving Metal Reduction

Step 1: A one-electron reduction of the alkyne
gives a radical anion intermediate.

Step 2: Add a proton. The alkenyl radical anion (a

very strong base) abstracts a proton from
ammonia (a very weak acid).

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Dissolving Metal Reduction

Step 3: A second one-electron reduction gives an
alkenyl anion.
This step establishes the configuration of the
alkene
A trans alkenyl anion is more stable than its cis
isomer.

Step 4: Add a proton. A second acid-base

reaction gives the trans alkene.

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Organic Synthesis
A successful synthesis must
provide the desired product in maximum yield.
have the maximum control of stereochemistry
and regiochemistry.
do minimum damage to the environment (it must
be a green synthesis).

Our strategy will be to work backwards from

the target molecule.

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Organic Synthesis
We analyze a target molecule in the
following ways:
The carbon skeleton: how can we put it
together? Our only method to date for forming a
new C-C bond is the alkylation of alkyne anions
with 1 haloalkanes.
The functional groups: what are they, how can
they be used in forming the carbon-skeleton of
the target molecule, and will they be changed by
the reaction conditions to give the functional
groups of the target molecule?

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Organic Synthesis
We use a method called a retrosynthesis
and an open arrow to symbolize a step in a
retrosynthesis.
target
starting
molecule

materials

Retrosynthesis: A process of reasoning

backwards from a target molecule to a set
of suitable starting materials.

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Organic Synthesis
Target molecule: 2-heptanone; starting with
acetylene and haloalkanes.

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Organic Synthesis
Starting materials are acetylene and 1bromopentane.

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