ADDITION REACTIONS OF ALKYNES

ADDITION REACTIONS OF ALKYNES

C C two pi bonds

A carbon-carbon triple bond is like two carbon-carbon

double bonds.

C C C C
C C
Most double bond reagents will react twice.
ALKYNES ARE LESS REACTIVE THAN ALKENES

(sp2) bonds are longer

C C weaker
less s character

(sp)
bonds are shorter
C C stronger
more s character

SSS Shorter - Stronger - more S character

RULE
SIMPLE ADDITIONS

DO IT TWICE !
 ADDITION OF HCl TO AN ALKYNE

HCl H3C H
H 3C C C H C C
fir st mole Cl H

HCl
second mole

Cl H
Follows the Markovnikoff
Rule in both additions. H3C C C H
Cl H

Also HBr and HI …..

ADDITION OF BROMINE TO AN ALKYNE

Br2 H 3C Br
anti
H 3C C C H C C addition
first mole Br H

-
Br2
Br sec ond mole

H3C C C H
+
Br Br
Br
H 3C C C H
Br Br

Both additions proceed through

a bridged intermediate and both
additions are stereospecific anti.
Also Cl2 and I2
 ENOL-KETO TAUTOMERISM

HYDRATION OF ALKYNES

SOMETHING DIFFERENT

When you add water to a triple bond, it doesn’t

add twice - rather only once, usually giving a
ketone as the product.
 ADDITION OF WATER
ALKYNES ARE LESS REACTIVE THAN ALKENES

dilute
H 2 SO4 +
H3C C CH H3C C CH
H2 O
+ H
H O H
reaction is slow
H
Water doesn’t add under the usual conditions (dil. H2SO4).
A stronger electrophile than H3O+ is required …….
……. HgSO4 is added.
MERCURY IS LIKE A “BIG PROTON”
Hg2+ is a stronger electrophile than H+

H3C C CH H3C C CH

slower H+ faster Hg2+

Hg2+ is not only a stronger Lewis acid, it is large

and it forms a bridged ion.

So we use a mixture of H2SO4, H2O and HgSO4 as our

reagents.
( HgSO4 = mercuric sulfate )
ADDITION OF WATER TO AN ALKYNE
O H
H 2 SO4 / HgSO4 H
H3C C CH H3C C CH
H2 O
2 bridged ion,
Hg +
Hg +2 stronger anti opening
electrophile

O H
OH H
+ H
H 3C C CH O H

H H3C C CH exchanges
+
Hg for a proton
unstable
enol
O
Follows the
H3C C CH3 Markovnikoff
ketone Rule
ENOLS ARE UNSTABLE (USUALLY)
discussed
later
ol
O H ENOLS :
( have -OH attached to a double bond)
Think of this combination as unstable.
C C
ene
OH
NOTE :
Phenols are not “enols” and they are
very stable (benzene resonance).
ENOL - KETO TAUTOMERISM
 TAUTOMERISM
ENOL KETO TAUTOMERS :
O H O
species in
H3C C CH 2 H3C C CH2 equilibrium
that differ in
H
unstable enol the position
of a proton or
other group.

Most enols are not favored, To interconvert tautomers,

a proton is transferred
enol E from oxygen to carbon.
N
E Mechanism, next
R slide…..
G
Bond Energies:
keto Y C=O 179 C=C 146
O-H 111 C-H 106
they rapidly change to keto.
CONVERSION OF AN ENOL TO A KETONE
( catalyzed by small amounts of acid )
ENOL
H H
O O H +O
H3C C CH2 H3C C CH2 H3C C CH2
+
+ H H
H O H
H
H H
+
O H H O H
H
+O O
H3C C CH2 H3C C CH2
H H
KETONE
OVERALL RESULT (NOT A STEPWISE MECHANISM)

ENOL
H H
+
:O-H H-O-H
..
..
O H O
H3C C CH 2 H3C C CH2
H
H
+
H-O-H
..
KETO
HYDROGENATION OF ALKYNES
 HYDROGENATION OF ALKYNES
Alkynes react twice with hydrogen when a metal
catalyst is present. The alkene is formed first, and
then the alkane.

H2 CH 3 CH3
CH 3 C C CH3 C C
Pd syn addition
H H
cis H2 /Pd

CH3CH2CH2CH3

Since alkenes are more reactive than alkynes, it is

difficult to stop the reaction after the first addition.
 MECHANISM OF CATALYTIC
HYDROGENATION
REVIEW R R
R R
H H
R R
ALKENE PICKS UP
R TWO HYDROGENS
R
.. .H. syn addition
.H H .H
.H H . .H
.H .H metal catalyst with
adsorbed hydrogen
atoms
 LINDLAR

Converting an alkyne to a cis alkene.

 LINDLAR CATALYST
There is a special deactivated catalyst, Lindlar, that
allows the hydrogenation of an alkyne to stop at the
alkene, after the addition of only one mole of hydrogen.

Lindlar is a palladium catalyst, where the palladium is

precipitated onto particles of barium sulfate from a
solution which has quinoline present.

Lindlar = Pd / BaSO4 / quinoline N

..
quinoline

The quinoline is thought to “poison”, or reduce the

activity, of the catalyst. Many sulfur and nitrogen-
containing compounds act as poisons.
With Lindlar catalyst, only one mole of hydrogen will
add to an alkyne. As with other catalysts, hydrogen-
ations with Lindlar are syn stereospecific additions.

H2 CH 3 CH 3
CH 3 C C CH 3 C C
Lindlar syn addition
catalyst H H
cis

H2
CH 3 C C CH 3 CH 3CH 2CH 2CH 3
Pd
(without Lindlar)
 POISONING MECHANISM IS UNKNOWN
A POSSIBLE HYPOTHESIS IS GIVEN HERE
Quinoline binds to sites on the catalyst.
Linear alkynes can approach and pick up hydrogens.
Planar alkenes are blocked.

bound quinoline alkyne fits

alkene blocked
QUINOLINE
QUINOLINE
QUINOLINE
R-C C-R R R
QUINOLINE QUINOLINE C=C QUINOLINE
R R
QUINOLINE

surface of QUINOLINE
QUINOLINE
Lindlar catalyst

( probably over-simplified )
 MAKING A trans -ALKENE

Can you also convert an alkyne to a trans -alkene?

YES …...
SODIUM METAL IN LIQUID AMMONIA
This is a different type of reaction
(not a catalytic hydrogenation)
and it converts an alkyne to a trans alkene.

CH3 H
Na
CH3 C C CH3 C C
NH3 (liq) anti addition
H CH3
- 60 oC trans

Just keep in mind that it is possible to make trans alkenes as well as

cis alkenes, however, a different reaction is used.
 CONTROLLING THE OUTCOME
Chemists are always trying to either discover or
design pairs of reactions that allow one to control
the outcome of a change
…. especially regioselectivity or stereochemistry.

Consider:

HBr (peroxide free) versus

HBr (peroxides
Markovnikoff Anti-Markovnikoff

and now

alkyne to cis alkene alkyne to trans alkene

versus
(catalytic hydrogenation) (sodium/ liquid ammonia)
 SYNTHESIS
If the organic chemist didn’t have methods giving
different results, it would be difficult to do synthesis.

The task of a synthetic chemist is to make molecules

where each atom is arranged in the correct place
and with the correct stereochemistry.

There are 256 stereoisomers of cholesterol!

To synthesize (construct) a molecule of cholesterol

in the lab, the chemist would have to arrange the atoms
in the correct order with the correct types of bonds and
control the outcome at all eight stereocenters or the
molecule would not be cholesterol.