U n i t 9 : Re a c t i o n s o f a l ky n e s

Introduction
- Contain triple bond
- General formula CnH2n-2
- Elements of unsaturation for each triple
bond: 2
- Most reactions resemble reactions of
alkenes
- Acetylene

- H-C≡C-H

- Simplest alkyne
- Can be synthesized from coal or
natural gas
- Used in welding torches
- ~56 kcal energy per mole
- Nomenclature
- Change -ane to -yne
- Start numbering parent chain closest
to triple bond
- All other functional groups except
ethers and halides have higher
priority than alkynes
- Alkyne priority is equal to alkenes
- Common names
- Named as substituted acetylene

- Ex. CH3-C≡CH =

methylacetylene

- Ex. CH3-CHCH3-CH2-C≡C-

CHCH3-CH3 =
isobutylisopropylacetylene
-
- Properties
- Nonpolar
- Insoluble in water

Alkynes Page 1
 - Soluble in most organic solvent
- BP similar to alkanes of same size
- Less dense than water
- Up to 4 carbons = gas at room
temperature
- Structure
- Bond lengths
- Triple bonds shower than
double or single bonds because
of the 2 pi overlapping orbitals
- C-C: ~1.5Å
- C=C: ~1.3Å

- C≡C: ~1.2Å

- C-H: ~1.1Å
- Linear molecule
- Each carbon has
- 2 sp hybridized orbitals
- 2 p unhybridized orbitals
- Each sp orbital is bonded to:
- Sp orbital of the other carbon
- 1s orbital of hydrogen
- Each p orbital overlaps with the other
p orbital to form each of the 2 extra
bonds

Acetylide ions
- Acidity
Compound S character pKA
Alkane 25% ~50
Alkene 33% ~45
Ammonia ~35
Alkyne 50% ~25
Water ~15
Carboxylic ~5
acid
Sulfuric acid ~0

Alkynes Page 2
 - S orbital keeps electrons close to
nucleus
- Good bases wants to donate e -
- The more s character something has,
the worse a base is it (the better an
acid it is)
- Formation
- H(+) can be removed from a terminal
alkyne using sodium amide, NaNH 2
- Stronger base than water must
be used
- Acetylide: v. strong nucleophile
- Can easily do substitution and
addition reactions
- Reagents
- Sodium amine
- Terminal alkyne
- Mechanism
- Step 1: :NH2 abstracts proton
from alkyne, e - from bond kick
off onto C

- Results in H-C≡C:(-)

- Use as nucleophile
- SN2 reaction
- Add acetylide to r -X
- r = CH3, 1°, 2°
- Very important reaction
- Lengthens the alkyne chain
- Reagents
- Acetylide ion (and counterion)
- Mechanism
- Step 1: X on r -X leaves; C (-)
attacks r
- Results in internal alkyne
- Use as strong base
- If SN2 is not possible, then E2 occurs

Alkynes Page 3
 - Reagents
- Acetylide ion (and counterion)
- Mechanism
- Step 1: Acetylide abstracts a
proton (e- form double bond) as
X leaves with e- from bond
- Reforms terminal alkyne

Synthesis of Alkynes
- By elimination reactions
- Review of alkene synthesis
- Alkyl halide (1 halogen) -
strong base-> alkene
- Synthesis of alkyne requires alkane
with 2 halogens
- Vicinal or geminal dihalide -
strong base-> alkyne
- Reagents
- 2 mol eq. NaNH2 @ 150°C and
water or
- KOH @ 200°C
- Mechanism
- Step 1: Base abstracts a proton;
C-H e- form double bond; X
leaves
- Step 2: Base abstracts another
proton; C-H e- form triple
bond; x leaves
- If molten KOH (at 200°C) is used, an
internal alkyne forms
- If NaNH2 and water (at 150°C) is
used, a terminal alkyne forms
- Terminal alkyne reacts with
:NH2 to form acetylide, which
can react further as a
nucleophile

Alkynes Page 4
Addition Reactions
- Similar to addition of alkenes
- Second and third bonds are reactive
- Mostly exothermic
- Addition of 1 or 2 molecules
- Hydrogenation
- Catalytic hydrogenation
- Reagents
- 2 mol eq. H2
- Pt, Pd, Ni catalyst
- Mechanism
- Step 1: Alkyne and H2
adsorbed onto metal and
alkyne is hydrogenated
- Alkyne is completely reduced
- Alkene intermediate cannot be
isolated
- Lindlar’s Catalyst
- Poisoned Pd
- Quinoline, Pd/BaSO4,
CH3OH
- Results in partial reduction
- Results in cis alkene
- Addition of 2 H in syn
orientation
- Reagents
- Lindlar’s catalyst
- 1 mol eq. H2
- Mechanism
- Step 1: Alkyne and H2
adsorbed onto metal and
alkyne is hydrogenate
- Sodium metal and Ammonia
- Results in trans alkene
- Addition of 2 H in anti
orientation
- Reagents

Alkynes Page 5
 - Na metal
- NH3 (l)
- Mechanism
- Step 0.5: Na0 reacts with
NH3 to form Na(+1) and
NH3 + 1e-
- Deep blue color in
solution
- Step 1: 1 e- attacks one
carbon of triple bond; pi
bond of triple bond
kicked off onto other
carbon
- Forms radical anion
and lone pair
opposite from each
other
- Step 2: Lone pair is
protonated (using NH 3)
- Step 3: 1 more e- is
added to radical anion,
forming a lone pair
- Step 4: Lone pair is
protonated (using NH 3),
resulting in a trans
alkene
- Halogenation
- Addition of 1 mol of halogen
- Results in cis and trans alkenes
- Addition is syn or anti
- Forms vinyl dihalides
- Dihalide products tend to react
further
- Reagents
- 1 mol eq. X2
- Mechanism

Alkynes Page 6
 - Step 1: X2 breaks apart
forming X(-) and X(+)
- Step 2: X(+) is attacked
by pi bond while X (-) -

attacks other carbon of

triple bond
- Addition of 2 mol of halogen
- Results in tetrahalide
- Reagents
- 2 mol eq. of X 2
- Mechanism
- Step 1: X2 breaks apart
forming X(-) and X(+)
- Step 2: X(+) is attacked
by pi bond while X (-) -

attacks other carbon of

triple bond
- Step 3: Step 1 repeats
- Step 4: Step 2 repeats
- Hydrohalogenation
- Addition of 1 mol of hydrogen
halide
- Forms a vinyl halide
- Markovnikov
- Mechanism
- Step 1: X leaves H-X
- Step 2: Pi bond attacks
proton while X attacks
the other carbon
- Addition of 2 mol of hydrogen
halide
- Forms a geminal halide
- Markovnikov
- Mechanism
- Step 1: X leaves H-X

Alkynes Page 7
 - Step 2: Pi bond attacks
proton while X attacks
the other carbon
- Step 3: Step 1 repeats
- Step 4: Step 2 repeats
- Addition of Hydrogen Bromide with
Peroxides
- Addition of hydrogen bromide
to a terminal alkyne
- Free radical addition
- Forms alkene
- Br adds to less substituted
carbon
- H adds to more substituted
carbon
- Anti-markovnikov
- Product is mixture of cis and
trans isomers
- Reagents
- HBr
- ROOR
- Mechanism
- Step 1: Peroxide bond
breaks homolytically
- Step 2: H abstracted from
HBr to form Br radical
- Radical e- or O-r
and radical e- from
H combine (r-O-H),
Br radical forms
- Step 3: Br radical adds to
triple bond, forming more
stable radical
- 1 e- from pi bond
combines with
radical e- from Br

Alkynes Page 8
 - Other e- from pi
bond kicks off onto
C to form carbon
radical
- Step 4: Hydrogen
abstracted from HBr
- Radical e- from
carbon radical
combined with
hydrogen radical e-
- Hydration
- Mercuric ion and Acid-catalyzed
tautomerism
- Similar to oxymercuration -
demercuration of alkenes
- Catalyzed by mercuric ion
- Addition produces an enol
which then tautomerizes to
more stable ketone or aldehyde
- Enol: compound
containing hydroxyl
directly connected to
C=C double bond (vinyl
alcohol)
- Tautomers:
constitutional isomers
that rapidly interconvert
through the migration of
a proton
- HO-Cr=CH-H becomes
O=Cr-CH3
- Keto: Ketone or aldehyde
- Keto-enol
tautomerization: the
equilibrium that is
established between an
enol and a ketone in

Alkynes Page 9
 either acid- or base-
catalyzed conditions
- Markovnikov
- Reagents
- HgSO4 in H2SO4
- Water
- Mechanism
- Step 1: pi bond on
terminal alkyne picks up
Hg(2+), which adds to less
substituted carbon
- Results in more
stable carbocation
(vinyl cation)
- Step 2: Water acts as
nucleophile, attacks
carbocation
- Step 3: water is
deprotonated by water
- Step 4: proton from
H3O(+) is attacked by
other pi bond, forming
carbocation again
- Step 4.5: lone pair on
hydroxyl moves to create
C=O double bond
- Step 5: Mercury leaves
and e- from C-Hg bond
and forms C=C double
bond; pi bond on C=O
kicks back off onto O
- Step 6: Enol
tautomeri zes into a more
stable ketone
- Keto-enol tautomerism
- Enols are not stable

Alkynes Page 10
 - HO-Cr=CR2= <-> O=C-
CHr2
- Isomerize to aldehyde or
ketone (keto)
- Mechanism (acid-
catalyzed tautomerism)
- Step 1: Protonation
of double bond
(not hydroxy
group)
(markovnikov)
- Step 2: Lone pair
on O forms double
bond with C
(resonance)
- Step 3: Hydroxyl
deprotonated by
water
- Hydroboration-oxidation and base -
catalyzed tautomerism
- Anti-Markovnikov addition
- For alkenes, we used BH3
- Here, we use BH(Sia)2
- Sia: amyl group (C5H11)
- Use of this reagent
instead of BH3 prevents
further addition across
the alkene
- Reagents
- BH(sia)2
- H2O2
- NaOH
- Mechanism
- Step 1: pi bond attacks B
while H(-) attacks other
carbon

Alkynes Page 11
 - Step 2: H2O2/NaOH
causes B(sia)2 to be
replaced by OH
- Step 3: Enol rapidly
tautomerizes in base into
the more stable aldehyde
- Base-catalyzed tautomerism
- Mechanism
- Step 1: Hydroxyl
group deprotonated
by hydroxide base,
forming enolate
- Enolate:
resonance-
stabilized
conjugate
base of
ketone,
aldehyde, or
ester
- Step 2: Lone pair
on O moves to form
C=O double bond
while C=C double
bond kicks off onto
other C
- Step 3: Lone pair
on C picks up
proton from water

Oxidation and oxidative cleavage

- Oxidation With Permanganate
- With internal alkyne, Results in
diketone (2 ketones)
- r-C(=O)-C(=O)-r
- With terminal alkyne, results in keto -
acid (ketone/carboxylic acid)

Alkynes Page 12
 - r-C(=O)-C(=O)-OH
- Reagents
- Cold KMnO4
- Water
- Oxidative Cleavage with permanganate
- Essentially breaks triple bond in half
- Splits into single and double
bond, each capped by O
- To create Carboxylic acid (single
bond with O -> single bond with OH),
add water in a second step
- Oxidative cleavage with internal
alkyne results in 2 carboxylic acids
- Oxidative cleavage with terminal
alkyne results in 1 carboxylic acid
and 1 carbonic aci d
- Carbonic acid dissociates
further to CO2 and water
- Reagents
- Cold KMnO4
- NaOH
- Heat
- (water if carboxylic acid
desired)
- Oxidation of carbon:
- Alkane < alkene < alkyne <
alcohol < aldehyde < carboxylic
acid < carbon dioxide
- Oxidative cleavage with ozone
- With alkenes, yields aldehydes and
ketones
- With alkynes, yields carboxylic acids
- Does not react further to create
CO2
- Oxidation of alkynes can be used to
determine the position of the triple
bond in an unknown alkyne

Alkynes Page 13
 - Reagents
- O3
- Water

Alkynes Page 14