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Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes:


Structure and Preparation
Examples:
Isobutylene, -Pinene, Farnesene, Cicutoxin
H3C

CH3

H3 C
CH2
H
H3 C

H3C

H3C
CH2

CH3

CH3

CH3

OH

OH

CH3

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Nomenclature:
Replace the ane ending of the parent hydrocarbon with ene. The longest
continuous chain which includes the double bond forms the base name., and
the chain is numbered in such a way, so that the alkene carbons obtain the
lowest possible numbers.
CH3

CH3
H3C

H2C

but-1-ene

(2E)-pent-2-ene

H3C
CH3
(2E)-5-methylhex-2-ene

CH3

C-C double bonds outrank alkyl groups and halogens in determining the
main carbon chain. Hydroxyl groups, however, outrank the double bond.
OH
Br
1

3
4

6
4

CH3

5
2
1

H2 C
6-bromo-3-ethylhex-1-ene

H2 C
4-ethylhex-5-en-1-ol

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Cycloalkenes and their derivatives are named by adapting cycloalkane


terminology.
HO
H3C

CH3

1,3-dimethylcycloheptene

cyclohex-2-en-1-ol

cyclopentene

CH3

Cl

3-chloro-1-methylcyclohexene

Structure and Bonding in Alkenes


o

1.33 A

1.54 A

1.08 A

H
Alkene

C
121.7o

1.09 A

116.6

H
Alkane

C
H

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Hybridization at C: sp2
CC -bond
CC -bond
Isolated double bonds:
H2C

conjugated double bonds


CH2

CH2
H3C

Delocalized systems are more stable !!!

Chapter 4 Alkenes and Alkynes: Structure and Preparation

ISOMERISM IN ALKENES.
There are four possible Isomers of butene:
CH3
CH2
H3 C

CH2

H3 C
but-1-ene
2-methylprop-1-ene

CH3
H3 C

CH3

H3 C
(2E)-but-2-ene
trans

(2Z)-but-2-ene
cis

Naming by the E-Z notational system

Prioritize substituents:
1. Higher atomic number, higher priority (e.g., NH2
shows higher priority than CH3).
2. If the group has the same atomic number, go to the
next atom (e.g, CH2CH3 has higher priority than
CH3).

Chapter 4 Alkenes and Alkynes: Structure and Preparation

When the two groups of higher priority, each on


different carbon atoms of the double bond, are on the
same side of the molecule, the name of the molecule
is prefixed with (Z) (from the German zusammen,
together).
When the groups of higher priority are on opposite
sides of the molecule, the designation (E) (from the
German entgegen, across) is used.
Examples:
OH

high

high

Br

high

CH3

H
low
(1Z)-1-bromo-1-chloroprop-1-ene

CH3

Cl

Cl

low

low

Br

low
H3C

high
(3E)-4-bromo-4-chloro-3-isopropylbut-3-en-1-ol

CH3

high H C
3

low
OH

low

H
H3C

high

(3E)-3-(1-hydroxyethyl)pent-3-en-2-one

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Stabilities:
We distinguish mono- di- tri- tetrasubstituted alkenes. Generally, the higher
the substitution order the more stable the alkene.
CH3

CH3
H2C

H2C

H3C

CH3

H3C

CH3

CH3

CH3

H3C

H3C

CH3

H3C

Preparation of Alkenes
H

H
H

Alkene formation requires X and Y-substituents to be on adjacent carbons.


Principal methods would be deydration of alcohols (X=H, Y=OH),
dehydrohalogenation of alkylhalides (X=H, Y= Cl, Br, I)
Dehydration of alcohols
An acid catalyst is needed for the reaction to proceed.
H

H+
OH

H
H

alcohol
additional product would be water (dehydration)

alkene

Chapter 4 Alkenes and Alkynes: Structure and Preparation

other examples:
OH

CH3
H3C
OH

H3C

CH2
H3C

CH3

H3C

OH

H3 C

H3C

+
H3C

CH3

H3C

CH3

90%

CH3

H2C

10%

From the last example we see, that there is a preference to from the highest
substituted alkene. We call this behavior regioselective. The first to look into
this regioselectivity was Zaitsev, therefore the rule to determine the main
product is called Zaitsev rule.
HO

75%
H3C

CH3

H3C

CH3

H3C

25%

CH3

In case we have a chance to produce cis and trans products, than there is a
tendency to form the more stable trans product. This behavior is called
stereoselective.

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Mechanism:
H3C
H3C

OH

CH2

H2SO4
H3C

CH3

H3C

H
H3C

H3C

H
O

+
H

H3C

H
H3C

CH3

CH3

CH3
H
H3C
O

CH3

H3C

H
H3C

O
H

CH3
CH3

CH3

H+

O
H

H
H3C

H3C

+
CH2

O
H

For primary carbons, there is no carbocation intermediate. Two steps, bond


cleavage and bond formation, occur simultaneously
H
H

H
O

+
H

H2C
H
+

O
H

CH2
H
O

+
H

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Dehydrohalogenation of Alkyl Halides


Means elimination of a hydrogen and a halogen, which are bound to two
different carbon atoms.

The regioselectivity follows Zaitsev rules and overall the reaction is


regioselective, meaning the most stable alkene is formed in the elimination
process.

E2- Reaction Mechanism


In the E2 mechanism the two leaving groups have to be in an anti
configuration, which leads to a stereospecific reaction.

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Mechanism for E2

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Alkynes
Hydrocarbons with a triple bond are named alkynes general formula CnH2n-2.
Follow the hydrocarbon nomenclature end substitute ane with yne.
The carbons in a triple bond are sp-hybridized.

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Preparation:
a) double dehydrohalogenation of geminal alkyl dihalides
H3C

3 NaNH2 / NH3

H3C

Cl
CH
Cl

b) double dehydrohalogenation of vicinal alkyl dihalides


Br
H3C

3 NaNH2 / NH3

H3C

Br
CH

Important Diynes : tumor inhibitors:


Dynemicin A:

CH3
HO

OH

HN
O
O
H3C

OH

OH