ALKYNE

ORGANIC CHEMISTRY
CHEMISTRY DEPARTMENT
FST UIN SGD BANDUNG
 Chapter 9; Alkynes

I. Nomenclature
II. Physical Properties; Polarity, Acidity
III. Preparation of Alkynes
-SN2 with Acetylide Ion
-Elimination of Dihalides
IV. Reaction of Alkynes
- Acid/Base
- Addition (H2, HX, H2O, X2)
- Redox
 Chapter 9; Alkynes
Types of Alkynes

C C Internal Alkyne
CH3 CH3

H C C CH3 Terminal Alkyne

 Nomenclature

Acetylene and ethyne are both acceptable

IUPAC names for HC CH

1. Higher alkynes are named in much the same

way as alkenes except using an -yne suffix
instead of -ene.
HC CCH3 HC CCH2CH3
Propyne 1-Butyne
(CH3)3CC CCH3

4,4-Dimethyl-2-pentyne
 Nomenclature

2. Compounds with two or three triple bonds

are named as –diynes or –triynes (retain –a
of parent alkane)
3. If there is a double and triple bond in the
molecule; name as an -en yne rather than –
yn ene
 9.3
Physical Properties of Alkynes

The physical properties of alkynes are

similar to those of alkanes and alkenes.

9.4
Structure and Bonding in
Alkynes:
sp Hybridization
  Bonds in Acetylene

Each carbon is
connected to a
hydrogen by a
 bond. The two
carbons are connected
to each other by a
 bond and two  bonds.

Figure 9.2 (a)

  Bonds in Acetylene

One of the two , pi, bonds in acetylene is

above and below the two carbons; The second
bond is at right angles to the first
Figure 9.3 Electrostatic Potential in Acetylene

The region of highest The region of highest

negative charge lies negative charge
above and below the encircles the
molecular plane in molecule around its
ethylene. center in acetylene.
 9.5
Acidity of Acetylene
and Terminal Alkynes

H C C
 Acetylene

Acetylene is a weak acid, but not nearly

as weak as alkanes or alkenes.

Compound pKa
HF 3.2
H2O 15.7
HC CH 26
NH3 36
H2C CH2 45
CH4 60
 Carbon: Hybridization and Electronegativity

pKa = 60
C H H+ + –C : sp3

H
pKa = 45 : sp2
C C H+ + C C
–
pKa = 26
–
C C H H+ + C C : sp

Electrons in an orbital with more s character are closer to the

nucleus and more strongly held.
 9.6(1)
Preparation of Alkynes

1. Substitution Reactions Using the Acetylide

Ion
2. Elimination Reactions
1. Substitution Reactions Using the Acetylide Ion

Forming Internal Alkynes Using the Acetylide Ion

H—C C—H 1. Form Nucleophile by

removing acidic H from
terminal alkyne
R—C C—H
2. SN2 Substitution with

alkyl halide to form internal

R—C C—R alkyne
 Forming Internal Alkynes Using the Acetylide Ion

1. Form Nucleophile by removing acidic H from

terminal alkyne
NaNH2
HC CH HC CNa
NH3
2. SN2 Substitution with alkyl halide to form internal

alkyne

– SN2
H—C C: + R X H—C C—R + : X–
 Example: Alkylation of Acetylene

NaNH2
HC CH HC CNa
NH3

CH3CH2CH2CH2Br

HC C CH2CH2CH2CH3

(70-77%)
Example: Alkylation of a Terminal Alkyne

(CH3)2CHCH2C CH
NaNH2, NH3

(CH3)2CHCH2C CNa

CH3Br

(CH3)2CHCH2C C—CH3
(81%)
Example: Dialkylation of Acetylene

H—C C—H
1. NaNH2, NH3
2. CH3CH2Br

CH3CH2—C C—H
1. NaNH2, NH3
2. CH3Br

CH3CH2—C C—CH3

(81%)
 Limitation

Effective only with primary alkyl halides

Secondary and tertiary alkyl halides
undergo elimination
 Acetylide Ion as a Base
E2 predominates over SN2 when alkyl
halide is secondary or tertiary

–
H—C C: H C

C X
E2

H—C C —H + C C + : X–
 9.6(2)
Preparation of Alkynes

1. Substitution Reactions Using the Acetylide Ion

2. Elimination Reactions
 Preparation of Alkynes
by "Double Dehydrohalogenation"

H X H H

C C C C

H X X X

Geminal dihalide Vicinal dihalide

The most frequent applications are in preparation

of terminal alkynes.
Geminal dihalide  Alkyne

(CH3)3CCH2—CHCl2

1. 3NaNH2, NH3
2. H2O

(CH3)3CC CH
(56-60%)
 Geminal dihalide  Alkyne

(CH3)3CCH2—CHCl2
NaNH2, NH3 (slow)
(CH3)3CCH CHCl
NaNH2, NH3 (slow)
(CH3)3CC CH
H2O NaNH2, NH3 (fast)
(CH3)3CC CNa
Vicinal dihalide  Alkyne

CH3(CH2)7CH—CH2Br

Br

1. 3NaNH2, NH3
2. H2O

CH3(CH2)7C CH

(54%)