Alkene & Alkyne PDF

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

CH2
CH2
H3C
Delocalized systems are more stable !!!
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).
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
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
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.
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
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.
Mechanism for E2
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.
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

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Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes:

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Cycloalkenes and their derivatives are named by adapting cycloalkane

Structure and Bonding in Alkenes

Chapter 4 Alkenes and Alkynes: Structure and Preparation

conjugated double bonds

Delocalized systems are more stable !!!

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Naming by the E-Z notational system

Chapter 4 Alkenes and Alkynes: Structure and Preparation

When the two groups of higher priority, each on

Chapter 4 Alkenes and Alkynes: Structure and Preparation

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

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes: Structure and Preparation

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

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Dehydrohalogenation of Alkyl Halides

The regioselectivity follows Zaitsev rules and overall the reaction is

E2- Reaction Mechanism

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes: Structure and Preparation

Chapter 4 Alkenes and Alkynes: Structure and Preparation

b) double dehydrohalogenation of vicinal alkyl dihalides

Important Diynes : tumor inhibitors:

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