Alkenes and Alkynes

Pt 1 : Review of structure and preparation

Dr. I.R. Hunt

Department of Chemistry, University of Calgary
SA 144G
irhunt@ucalgary.ca
What should you be able to do?
1. Terminology
2. Understand various methods for preparing alkenes and alkynes
3. Understand the reactions of alkenes and alkynes with a wide
variety of reagents including selectivity issues
4. Application of these reactions to the synthesis of larger molecules

Skills required:
alkene / alkyne structure and bonding
hybridisation
alkene / alkyne nomenclature
stability of reaction intermediates
stereochemistry : 3D-structural representations etc.

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Review of Alkenes
1. Nomenclature : -ene

2. Structure and bonding :

C(sp2) C(sp2)
C (p) C (p)
Shape =

3. Isomerism : cis or trans, E or Z

cis-2-butene trans-2-butene

(Z)-2-butene (E)-2-butene
(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary
Alkene stability
Heats of combustion / formation / hydrogenation measure
alkene stability

1-butene E-2-butene Z-2-butene

heat of combustion / kcal/mol

-30.3 -27.6 -28.6

Stability factors:

(1) (2) >

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary
Review of Alkynes

1. Nomenclature : -yne

R C C R' R C C H

2. Structure and bonding :

C(sp) C(sp)
2 x C (p) C (p)

Shape =

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Preparations of Alkenes (review)

Via

• Dehydration of alcohol

• Dehydrohalogenation of alkyl halides

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Dehydration of Alcohols
OH
H+ / heat
H2O
H
Dehydration

Typical reagents

Mechanism:
Zaitsev’s rule ?

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

 H2SO4
CH3CH2-OH + H2O
160oC

OH H2SO4
+ H2O
140oC

CH3 H2SO4
CH3 C OH + H2O
CH3 heat

alcohol alkene + water

DEHYDRATION

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Dehydrohalogenation of alkyl halides
X
B- / heat
HX
H
X = Cl, Br, I

Common reagents = “strong bases”

NaOCH3 / CH3OH
KOH or NaOH / CH3CH2OH
KOt-Bu / t-BuOH or DMSO

Mechanism:
Zaitsev’s rule ?
(1) (2)
(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary
 Cl NaOEt
100%
EtOH
55oC

KOC(CH3)3
CH3(CH2)15CH2CH2Cl CH3(CH2)15CH=CH2
DMSO
25 oC 86%

This reagent combination is good for elimination of

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Preparations of Alkynes
1. Dehydrohalogenation of alkyl dihalides

H X NaNH2 NaNH2 X X
C C C C C C
H X H H
geminal dihalide 2H X
or or
1,2-dihalide

Consecutive 1,2-eliminations of either 1,1- or 1,2-dihalides

gives alkynes

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

1. Dehydrohalogenation of alkyl dihalides

H X R X
R C C R
H X H R
anti
NaNH2
or R C C R
and H X

H X
X X R R
R C C R
H H H X
syn

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Mechanism
Dehydrohalogenation of alkyl dihalides (E2)
.. _
H2N :
NH3
H X R X
R C C R R C C R
H X anti H R
_
X
_
X
R X
R C C R
H R anti
.. _ NH3
H2N :

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Preparations of Alkynes
2. Dehydrohalogenation of vinyl halides

R X R R NaNH2
or R C C R H X
H R H X
anti syn

E2 elimination (strong base, H-C-C-LG = coplanar)

Mechanism : see previous example

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary

Preparations of Alkynes
3. Alkylation of terminal alkynes

1. NaNH2
R C C H R C C R'
2. R' X

terminal alkyne
H C CCH3 (pKa = )

sodium amide Na+ - NH

(base, pKa = ) 2

-C CCH3
CH3CH2 Br Br

reaction (strong nucleophile) : best for

(c) Dr I.R. Hunt, Dept of Chemistry, University of Calgary