Chapter 7:Alkynes

Alkynes
Electron (orbital) Potential Energy

3d 4p
4s
ENERGY LEVEL

3p
3s

2p
2s

1s
 1s 2s 2px 2py 2pz sp sp
Hybridized
Promoted

2s + 2px
Linear
Acetylene: Carbon
π bond

π
bond
Alkyne acidity: formation of acetylide
anions
Preparation of alkynes : Alkylation of
Acetylide anions with Methyl and 1o
Haloalkanes
nucleophilic
substitution
HC C Na
Na+Br-
Br
Limitations of Alkylation of Acetylide
anions
 Reactions only are efficient with 1o alkyl bromides and 1o alkyl
iodides
 Acetylides anion can behave as base as well as nucleophiles
 Reactions with 2o and 3o alkyl halides give dehydrohalogenation,
converting alkyl halide to alkene
Preparation of alkynes: Elimination
Reaction of Dihalides
Reaction of Alkynes: Addition of HX
Addition of Bromine and Chlorine
Addition of H-OH as in alkenes
 Mecury(II) catalyzes Markovnikov oriented addition.
 Hydroboration-oxidation give the non- Markovnikov.
 Catalytic reduction of an alkyne can be brought about at
or slightly above room temperature and with moderate
pressure of H2

Pd, Pt, or Ni H2 H2
H3C C C CH3 2H2 H3C C C CH3
3 atm
2-Butyne Butane

Twostages: formanalkene, thenformthealkane

 Anti addtion of two hydrogen atoms to the triple bond
MECHANISM FOR THE REDUCTION OF
ALKYNES WITH Na / NH3
 Step 1: Sodium transfers an electron
to the alkyne giving a radical anion.

 Step 2: The radical anion removes a

proton from the ammonia in an
acid / base reaction.

 Step 3: A second atom of sodium

transfers another electron to the
alkyne giving an anion.

 Step 4: The anion removes a proton

from the ammonia in an acid / base reaction.
An Introduction to Organic Synthesis
Target Molecule:
cis-3-Hexene

 Analysis:
 Retrosynthesis:

C C 2CH3CH2Br

cis-3-Hexene 3-Hexyne Acetylide Bromoethane

dianion
 Synthesis

1. NaNH2
HC CH 3. NaNH2
2. CH3CH2Br
Acetylene 4. CH3CH2Br
1-Butyne 3-Hexyne

5. H2
Lindlar catalyst

cis-3-Hexene
 O

Target Molecule:
2-Heptanone
 Analysis
An acid-catalyzed hydration
gives a mixture of 2-heptanone
and 3-heptanone

2-Heptanone

Acid-catalyzed
hydration gives
2-heptanone

HC C Br
 Synthesis: 2-Heptanone

O
1. NaNH2
3. H2O
HC CH
2.Br
H2SO4, HgSO4
Example
Answer: