Reactions

of
Alkynes

Organic Chemistry. 4th Edition.Paula Yurkanis Bruice

Irene Lee. Case Western Reserve University. Cleveland, OH ©2004, Prentice Hall
Alkynes are hydrocarbons that contain a carbon–carbon
triple bond
General formula: CnH2n–2 (acyclic); CnH2n–4 (cyclic)
 Nomenclature
In common nomenclature, alkynes are named as
substituted acetylenes
A substituent receives the lowest number if there is no
functional group suffix,

Cl Br
3-bromo-2-chloro-4-octyne
CH3CHCHC CCH2CH2CH3 not 6-bromo-7-chloro-4-octyne
because 2 < 6
1 2 3 4 5 6 7 8

or if the same number for the functional group suffix is

obtained in both directions

CH3 1-bromo-5-methyl-3-hexyne
CH3CHC CCH2CH2Br not 6-bromo-2-methyl-3-hexyne
because 1 < 2
6 5 4 3 2 1
 The Structure of Alkynes

A triple bond is composed of a  bond and two  bonds

Addition Reactions of Alkynes
Sequential Addition of HCl
An alkyne is less reactive than an alkene
Relative Stabilities of Carbocations
 1. Addition of Hydrogen Halides

In the presence of 1 mole equivalent of HBr

H Br H
CH3CH2C CH CH3CH2C CH CH3CH2C CH

Br-

H
CH3CH2C CH CH3CH2CH CH

The secondary vinylic cation

is more stable
In the presence of excess HBr,
a carbocation is formed by adding the electrophile to the
sp2 carbon bonded to the greater number of hydrogen
Br Br
HBr
CH3CH2C CH2 CH3CH2CCH3
Br

Br Br
CH3CH2C CH3 CH3CH2C CH3
A secondary vinylic cation is about as stable as a primary
cation,
therefore a pi-complex may be the actual reaction
intermediate

- Cl

+ H
HC CH

Many (but not all) alkyne addition reactions are

stereoselective
2. Addition of HBr in the presence of peroxide
peroxide
CH3CH2C CH + HBr CH3CH2CH CHBr
3. Addition of Halogens to Alkynes

Cl Cl Cl
Cl2 Cl2
CH3CH2C CCH3 CH3CH2C CCH3 CH3CH2C CCH3
CH2Cl2 CH2Cl2
Cl Cl Cl

Br Br Br
Br2 Br2
CH3C CH CH3C CH CH3C CCH3
CH2Cl2 CH2Cl2
Br Br Br
 4. Addition of Water

O tautomerization OH
RCH2 C R RCH C R
keto tautomer enol tautomer
Examples of Water Addition
Hg2+ is added to increase the rate of water addition to
terminal alkynes
Hydroboration–Oxidation of Internal
Alkynes
 Hydroboration–Oxidation of Terminal
Alkynes

CH3 CH3
CH3 CH3
CH3CH CH B H
CH3CH2C CH + CH3CH CH BH 2
2
C C
H CH2CH3

CH2CH3 O
-
HO , H2O2 H
C C CH3CH2CH2CH
H 2O HO H
Formation of Ketone versus Aldehyde
5. Addition of Hydrogen
Formation of Cis Alkene
Conversion of Internal Alkynes to Trans
Alkenes
Reason for trans addition:
Acidity of a Hydrogen Bonded to an sp
Hybridized Carbon

HC CH H2C CH2 CH3CH3

pKa = 25 pKa = 44 pKa = 50
 Electronegativities versus Acid
Strengths

relative base strength

CH3CH2- > H2C CH- > H2N- > HC C- > HO- > F-

strongest weakest
base base
The stronger the acid, the weaker its conjugate base

top 252
Synthesis Using Acetylide Ions:
Formation of C–C Bond
 Designing a Synthesis

Example 1

O
?
CH3CH2C CH CH3CH2CCH2CH2CH3
Example 2
Example 3
Commercial Use of Ethyne