Alkene Chemistry Properties and Formation

Structure and Preparation of
Alkenes: Elimination Reactions

Alkene Nomenclature
First identify the longest continuous chain that includes

the double bond.
Replace the -ane ending of the corresponding unbranched
alkane with -ene.
Number the chain in the direction that gives the lowest
number to the first carbon of the alkene.
Alkene Nomenclature
Alkenes take precedence over

alkyl- and halo-substituents
when numbering the carbons.
The longest contiguous carbon chain including the alkene

takes precedence over a longer chain that does not
include the alkene.
Alkene Nomenclature
Hydroxyl groups outrank alkenes and the compound is

numbered so that the carbon with the –OH attached gets
the lowest number. The suffix is –enol and the locant for
the alkene precedes the –en and the locant for the –OH
precedes the –ol.
Practice Question
Name the alkene below according to the

IUPAC system.
A) 2-bromo-5-heptane
B) 6-bromo-2-heptene
C) 2-bromo-5-heptene
D) 5-bromo-2-heptene
E) 6-bromo-6-methyl-2-hexene
Common Names
Some common names are acceptable.

Naming Cycloalkenes
Change corresponding cycloalkane name suffix from –ane

to -ene. No substituents: no locant. With alkyl and halo
substituents number the alkene carbons 1 and 2 so that the
substituent has the lowest number.
Structure and Bonding in Alkenes
sp2 Hybridized Carbons
Alkene carbons are sp2 hybridized and alkenes are

planar (a).
The alkene has one -bond and one -bond (c) formed by
overlap of the p orbitals (b).
The electrostatic potential map shows the high electron
density shown as red above (and below) the C-C bond (d).
Bond Strength
The C=C double bond is stronger and shorter than a single

bond.
The  bond is weaker than a  bond.
Isomers of C4H8
The four isomers are:
1-Butene is a constitutional isomer of the other three.

Cis- and trans-2-butene are stereoisomers: same
connectivity but a different arrangement in space.
Practice Question
Which alkene can have cis/trans

stereoisomers?
A) B)
C) D)
Cis and Trans Isomers
Rotation about double bonds is restricted so

interconversion or rotation about a double bond
is not possible.
E-Z Nomenclature
Some alkenes are too complex to name using cis or trans.
For these alkenes the E-Z system is used.
The two atoms directly connected to each alkene are

compared. The atom with higher atomic number has
higher priority. The position of the high priority groups
are compared. If they are on the same side the compound
is (Z) – otherwise it is (E).
E-Z Nomenclature
This system is the Cahn-Ingold-Prelog (CIP) system.
When two atoms directly attached to the same carbon of

the double bond are identical, compare the atoms attached
to these two on the basis of their atomic numbers.
Precedence is determined at the first point of difference:
Compare the atoms connected to the two carbons on the

right and ethyl [⎯ C(C,H,H)] outranks methyl [⎯ C(H,H,H)]
E-Z Nomenclature
Compare the atoms directly connected to the two carbons

on the right and ⎯ CH(CH3)2 [⎯ C(C,C,H)] outranks
⎯ CH2CH2OH [⎯ C(C,H,H)].
The oxygen is NOT considered because the first point of

difference was reached with the first carbon. The O is
on the second carbon.
E-Z Nomenclature
Compare the atoms directly connected to the two carbons

on the right one by one, never as a group. Because oxygen
has a higher atomic number than carbon, ⎯ CH2OH
[⎯ C(O,H,H)] outranks ⎯ C(CH3)3 [⎯ C(C,C,C)].
The oxygen IS the first point of difference.

E-Z Nomenclature
A multiply bonded atom is considered as two bonds to that

atom. The group ⎯ CH = O [⎯ C(O,O,H)] outranks
⎯ CH2OH [⎯ C(O,H,H)]
Stability of Alkenes
The heat of combustion of alkenes can be used to
determine relative stabilities. Alkenes with the lowest
heat of combustion are most stable.
The most important factors governing alkene stability are:
1. Degree of substitution of C=C (an electronic effect);
2. van der Waals strain in the cis stereoisomer (a steric
effect)
3. Chain branching increases stability.
Highly substituted double bonds are more stable than

isomers with less substituted double bonds.
Trans alkenes are more stable than the cis stereoisomers.

The general trend is: more substituted alkenes are more

stable than less substituted alkenes.
tetrasubstituted trisubstituted disubstituted disubstituted monosubstituted
trans cis
Trans alkenes are more stable than the cis stereoisomers.

Steric strain between the methyl groups in the cis isomer.
With larger groups the effect is more pronounced.

Cycloalkenes
Cyclopropene has the most strained of the cycloalkenes
because the sp2 hybridized carbon prefers a bond angle
of 120o. Cyclobutene has less ring strain and the other
larger rings have negligible ring strain.
cyclopropene cyclohexene
Cyclooctene
Cyclooctene can exist as either a cis or trans isomer. Smaller
cycloalkenes can only have an alkene with a cis conformation .
Cyclododecene
Cis and trans-cyclododecene are almost equal in
stability.
trans-Cyclododecene cis-Cyclododecene
When there are more than 12 carbons in the ring, trans-

cycloalkenes are more stable than cis.
Preparation of Alkenes:
Elimination Reactions
The elimination of two substituents from adjacent

carbons ( and ) forms alkenes.
The process is -elimination.

Dehydration of Alcohols
The elimination where X=OH and Y=H is dehydration.
Catalyzed by strong acids.
Regioselectivity in Alcohol Dehydration:
The Zaitsev Rule
Selective reaction: when one product is preferentially formed.
Regioselective reactions proceed preferentially in one
direction.
Dehydration of 2-methyl-2-butanol is regioselective forming

the more substituted alkene.
Zaitsevs Rule
Zaitsevs rule states that the alkene formed in greatest
amount is the one that corresponds to removal of the
hydrogen from the β carbon having the fewest
hydrogens.
Alternatively it is stated that β elimination reactions of

alcohols yield the most highly substituted alkene as the
major product.
Stereoselectivity in Alcohol Dehydration
A stereoselective reaction yields one stereoisomer in

preference to another.
Dehydration normally favors the more stable trans
stereoisomer.
Practice Question
What is the major product of the dehydration

of 2-methylcyclohexanol?
A) 1-methylcyclohexene
B) 2-methylcyclohexene
C) 3-methylcyclohexene
D) cyclohexene
E) 2-methylcyclohexane
Dehydrohalogenation of Alkyl Halides
E2 Dehydrohalogenation
Dehydrohalogenation is loss of a H and halogen from an alkyl halide. This is a -
elimination reaction. A strong base like sodium ethoxide (NaOCH2CH3) is needed.
General equation:
The rate is dependent on the concentration of the base

and the alkyl halide so it is termed an E2 reaction.
Dehydrohalogenation
For primary alcohols a strong but more hindered base is

preferred.
Selectivity of Dehydrohalogenation
Dehydrohalogenation follows the Zaitsev rule. The more

substituted alkene is preferentially formed.
The reaction is also stereoselective preferentially forming

the more stable trans stereoisomer.
Formation of cycloalkenes
Dehydrohalogenation of cycloalkyl halides leads to

cycloalkenes. Cis cyloalkenes are formed if the ring has
10 or fewer C atoms. Larger ring sizes give a mixture of
cis and trans
The Leaving Group
The halide anion that leaves the alkyl halide is known as

the leaving group.
The choice of halogen affects the rate constant for this
reaction in the order below. The C-I bond is weakest
and iodide is the best leaving group. Fluoride is not a
good leaving group.
The Leaving Group
The halide anion that leaves the alkyl halide is known as

the leaving group.
The choice of halogen affects the rate constant for this
reaction in the order below. The C-I bond is weakest
and iodide is the best leaving group. Fluoride is not a
good leaving group.
The E1 Mechanism of
Dehydrohalogenation of Alkyl Halides
The E2 elimination is a concerted reaction. In contrast

the E1 reaction has a step by step mechanism. The
reaction equation “looks” similar.
The E1 Dehydrohalogenation
Step 1. Ionization.
The first step is the slow ionization of the alkyl halide.

Since a carbocation is formed this will not happen with a
primary alkyl halide. This is the slow rate determining step.
It is unimolecular so the reaction is termed E1.
The E1 Dehydrohalogenation
Step 2. Deprotonation (of a primary H).
Step 2’. Deprotonation (of a secondary H).
The second step is similar to step 3 in the E1 dehydration

of alcohols.
E1 vs E2
The E1 elimination generally only occurs with a tertiary
alkyl halide with a weak base (not charged). The rate of
an E1 reaction is given by:

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Structure and Preparation of

Alkenes: Elimination Reactions

First identify the longest continuous chain that includes

Alkenes take precedence over

The longest contiguous carbon chain including the alkene

Hydroxyl groups outrank alkenes and the compound is

Name the alkene below according to the

Some common names are acceptable.

Change corresponding cycloalkane name suffix from –ane

sp2 Hybridized Carbons

Alkene carbons are sp2 hybridized and alkenes are

The C=C double bond is stronger and shorter than a single

1-Butene is a constitutional isomer of the other three.

Which alkene can have cis/trans

Rotation about double bonds is restricted so

The two atoms directly connected to each alkene are

When two atoms directly attached to the same carbon of

Compare the atoms connected to the two carbons on the

Compare the atoms directly connected to the two carbons

The oxygen is NOT considered because the first point of

Compare the atoms directly connected to the two carbons

The oxygen IS the first point of difference.

A multiply bonded atom is considered as two bonds to that

Highly substituted double bonds are more stable than

Trans alkenes are more stable than the cis stereoisomers.

The general trend is: more substituted alkenes are more

tetrasubstituted trisubstituted disubstituted disubstituted monosubstituted

Trans alkenes are more stable than the cis stereoisomers.

With larger groups the effect is more pronounced.

When there are more than 12 carbons in the ring, trans-

The elimination of two substituents from adjacent

The process is -elimination.

Dehydration of 2-methyl-2-butanol is regioselective forming

Alternatively it is stated that β elimination reactions of

A stereoselective reaction yields one stereoisomer in

What is the major product of the dehydration

The rate is dependent on the concentration of the base

For primary alcohols a strong but more hindered base is

Dehydrohalogenation follows the Zaitsev rule. The more

The reaction is also stereoselective preferentially forming

Dehydrohalogenation of cycloalkyl halides leads to

The halide anion that leaves the alkyl halide is known as

The halide anion that leaves the alkyl halide is known as

The E2 elimination is a concerted reaction. In contrast

The first step is the slow ionization of the alkyl halide.

Step 2’. Deprotonation (of a secondary H).

The second step is similar to step 3 in the E1 dehydration

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