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Alkenes: Structure and Synthesis

Introduction to Alkenes
Alkenes are hydrocarbons characterized by carbon–carbon double bonds.
They're also known as olefins, which means "oil-forming gas."
The carbon–carbon double bond is the functional group that dictates the reactivity of
alkenes.

The image
showcases three distinct alkenes: ethylene (a simple alkene), α-pinene (a cyclic alkene), and
cis-tricos-9-ene (a long-chain alkene), which illustrates the variety of structures that alkenes
can have.

A carbon–carbon double bond comprises a stable sigma bond and a reactive pi bond.
The pi bond is more reactive than the sigma bond.
The reactions of alkenes are characterized by the reactivity of their double bonds.

Sigma Bonds of Ethylene

Sigma bonds around the double-bonded carbon are sp2 hybridized.
Bond angles are approximately 120°.
The molecular geometry is trigonal planar.
Unhybridized p orbitals overlap to form the pi bond.

Bond Lengths and Angles

sp2 hybrid orbitals have more s character than sp3 hybrid orbitals.
Pi overlap reduces the C—C bond length from 1.54 Å in alkanes to 1.33 Å in alkenes.

Pi Bonding in Ethylene

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The pi bond in ethylene forms through the overlap of unhybridized p orbitals of the sp2
hybridized carbon atoms.
Each carbon has one unpaired electron in the p orbital.
This overlap requires the two ends of the molecule to be coplanar.

Cis-Trans Interconversion
Cis and trans isomers cannot be interconverted.
Rotation around the carbon–carbon bond is restricted due to the pi bond (264 kJ/mole).
Six atoms, including the double-bonded carbons and their four substituents, must
remain in the same plane, which is the origin of cis-trans isomerism.

Structure of Alkenes
Double bonds restrict rotation; breaking the π bond is necessary for rotation about a double
bond.

Elements of Unsaturation
Unsaturation is a structural element that reduces the number of hydrogens in a
molecule by two.
It is also referred to as the index of hydrogen deficiency.
Double bonds and rings are elements of unsaturation.

General molecular formula for a hydrocarbon = C nH2n+2 (minus 2 hydrogens for

every π bond or ring).

Degree of unsaturation = the total numbers of π bonds and rings.

Calculating Unsaturation
To calculate unsaturation:

1. Determine the number of hydrogens the carbons would have if the compound were
saturated (C H
n 2n+2
).
2. Subtract the actual number of hydrogens.
3. Divide by 2.

Example: Calculate the unsaturations for a compound with the formula C 5

H8 .

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1. Saturated compound with five carbons: (2×5) + 2 = 12

2. Subtract from the actual number of hydrogen atoms and divide by 2: 12–8

2
= 2

unsaturations.

The compound has two unsaturations, which can be two double bonds, two rings, or one
double bond and one ring.

This image illustrates examples of compounds with one degree of unsaturation. The diagrams
show a hexagon, a pentagon with a protruding line, a zigzagging line, and a triangular
structure.

Heteroatoms in Unsaturation Calculations

Heteroatom Effect on Calculation Example

Calculate the unsaturations for C H

4 7
Br . Saturated:
Replace hydrogen atoms;
Halogens (2×4) + 2 = 10. Unsaturation:
10–(7+1)
= 1
count halides as hydrogens. 2

unsaturation.
Does not change the C:H
Oxygen N/A
ratio; ignore oxygen.
Calculate the unsaturations for C H N . Saturated:
Trivalent; acts like half a
6 7

Nitrogen (2×6) + 2 + 1 = 15. Unsaturation:

15–7
= 4
carbon. Add N atoms. 2

unsaturations.

Solved Problem Example

Draw at least four compounds of formula C 4
H6N OCl .

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Count nitrogen as carbon, ignore oxygen, and count chlorine as a hydrogen, making the
formula equivalent to C H .
4.5 7

The saturated formula for 4.5 carbon atoms is C H , so C H N OCl has two elements
4.5 11 4 6

of unsaturation.
These could be two double bonds, two rings, one triple bond, or a ring and a double
bond.

Here is an image showcasing five compounds of formula C 4H6N OCl . Each compound has two
degrees of unsaturation.

IUPAC Nomenclature
Find the longest continuous carbon chain that includes the double-bonded carbons.
Change the ending -ane to -ene.
Number the chain to give the double bond the lowest possible number.
In a ring, the double bond is assumed to be between carbon 1 and carbon 2.

This image shows a variety of hydrocarbons with both their old and new IUPAC names.

Ring Nomenclature
In a ring, the double bond is assumed to be between carbon 1 and carbon 2.

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Multiple Double Bonds

diene = a compound with two double bonds
triene = three double bonds
tetraene = four double bonds
Give the double bonds the lowest numbers possible.
Use di-, tri-, or tetra- before the ending -ene to specify how many double bonds are
present.

Alkyl Groups and Double Bonds

Each alkyl group attached to the main chain is listed with a number to indicate its
location.
The double bond is given preference in numbering.

Alkenes as Substituents
When a double bond is not part of the main chain, the group containing the double bond is
named as a substituent called an alkenyl group.

Common Names
Most alkenes are conveniently named by the IUPAC system, but common names are
sometimes used for the simplest compounds.

Antifungal Drugs

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The image provides a detailed view of the complex molecular structure of Amphotericin B,
highlighting its polyene nature and various functional groups.

Cis-Trans Isomers
Also called geometric isomerism.
If similar groups are on the same side of the double bond, the alkene is cis.
If similar groups are on opposite sides of the double bond, the alkene is trans.
Not all alkenes show cis-trans isomerism.

Cyclic Compounds
Trans cycloalkenes are not stable unless the ring has at least eight carbons.
All cycloalkenes are assumed to be cis unless otherwise specifically named trans.

E-Z Nomenclature

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Use the Cahn–Ingold–Prelog rules to assign priorities to groups attached to each carbon
in the double bond.
If high-priority groups are on the same side, the name is Z (for zusammen).
If high-priority groups are on opposite sides, the name is E (for entgegen).

Example
Assign priority to the substituents according to their atomic number (1 is highest
priority).
If the highest priority groups are on opposite sides, the isomer is E.
If the highest priority groups are on the same side, the isomer is Z.

This image
clearly shows the difference between Z and E isomers based on the position of high-priority
groups (Br and Cl) around the double bond.

Cyclic Stereoisomers
Double bonds outside the ring can show stereoisomerism.

Stereochemistry in Dienes
If there is more than one double bond in the molecule, the stereochemistry of all the double
bonds should be specified.

Cahn-Ingold-Prelog Rules for Ranking Priorities

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1. Rule 1: Higher atomic number gets higher priority (Br > Cl > S > P > O > N > C > H).

The greater the atomic number of the atom bonded to the sp carbon, the higher
2

the priority of the substituent.

2. Rule 2: If atomic numbers are the same, compare at the next connection point at the
same distance until something has a higher atomic number.

If the two atoms attached to an sp carbon are the same (there is a tie), then
2

consider the atomic numbers of the atoms that are attached to the “tied” atoms.

3. Rule 3: Multiple Bonds.

If an atom is doubly bonded to another atom, the priority system treats it as if it

were singly bonded to two of those atoms. If an atom is triply bonded to another
atom, the priority system treats it as if it were singly bonded to three of those
atoms.

This image depicts a carbon atom double bonded to an oxygen atom. Rule 3 states that this is
equivalent to the carbon singly bonded to two oxygen atoms.

4. Rule 4: Isotopes.

If two isotopes (atoms with the same atomic number, but different mass numbers)
are being compared, the mass number is used to determine the relative priorities.
The atom with the greater mass number has the higher priority.

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This image shows an example of Z and E isomers when deuterium is present. The Z isomer
has D and CH on the same side, while the E isomer has them on opposite sides.
3

E/Z will always work even when cis/trans fails.

E,Z will work but may not agree with cis, trans

Multiple Double Bonds

If the compound contains more than one double bond, then each one is analyzed and declared
to be E or Z.

Physical Properties of Alkenes

Low boiling points that increase with mass.
Branched alkenes have lower boiling points.
Less dense than water.
Slightly polar. Pi bonds are polarizable, leading to instantaneous dipole–dipole
interactions. Alkyl groups are electron-donating toward the pi bond, potentially creating
a small dipole moment.

Polarity and Dipole Moments of Alkenes

Cis alkenes have a greater dipole moment than trans alkenes and are slightly polar.

The boiling point of cis alkenes will be higher than trans alkenes.

The effect of bond polarity is even more apparent in the 1,2-dichloroethenes, with their
strongly polar carbon–chlorine bonds. The cis isomer has a large dipole moment (2.4 D),
giving it a boiling point 12 degrees higher than the trans isomer, with zero dipole
moment.

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Stability of Alkenes: Heat of Hydrogenation

Combustion and hydrogenation of an alkene can provide valuable data regarding the
stability of the double bond.
The more substituted the double bond, the lower its heat of hydrogenation.
More substituted double bonds are usually more stable.
Compare heats of hydrogenation only for compounds that give the same alkane.
Most alkenes with similar substitution patterns give similar heats of hydrogenation.

The heat of hydrogenation is a measure of the energy content of the pi bond and is
used to compare the stabilities of different alkenes as long as they hydrogenate to
give alkanes of similar energies.

Zaitsev’s Rule
Alkenes with more highly substituted double bonds are usually more stable because the alkyl
groups attached to the double-bonded carbons stabilize the alkene.

Energy Differences in cis-trans Isomers

Trans isomers are generally more stable than the corresponding cis isomers because the alkyl
substituents are separated farther in trans isomers than they are in cis isomers.

Cycloalkenes
A ring makes a major difference only if there is ring strain, either because of a small ring
or because of a trans double bond.
Rings that are five-membered or larger can easily accommodate double bonds, and
these cycloalkenes react much like straight-chain alkenes.

Cyclopropene
Cyclopropene has bond angles of about 60°, compressing the bond angles of the
carbon–carbon double bond to half their usual value of 120°.
The double bond in cyclopropene is highly strained.

Stability of Cycloalkene

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Cis isomer is more stable than trans in small cycloalkenes.

Small rings have additional ring strain.
It must have at least eight carbons to form a stable trans double bond.
For cyclodecene (and larger), the trans double bond is almost as stable as the cis.

Bredt’s Rule
A bridged, bicyclic compound cannot have a double bond at a bridgehead position unless one
of the rings contains at least eight carbon atoms.

Solved Problem Example

Which of the following alkenes are stable?

Compound (a) is stable because the double bond is in a ten-membered ring.

Compound (b) violates Bredt’s rule and is not stable.
Compound (c) (norbornene) is stable because the double bond is not at a bridgehead
carbon.
Compound (d) is stable because there is an eight-membered ring to accommodate the
trans double bond.

Alkene Synthesis Overview

E2 dehydrohalogenation (–HX)
E1 dehydrohalogenation (–HX)
Dehalogenation of vicinal dibromides (–X2 )
Dehydration of alcohols (–H2O)

Elimination Reactions
Elimination reactions produce double bonds.
Also called dehydrohalogenation (–HX)

E1 Reaction

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Unimolecular elimination.

Two groups are lost: a hydrogen and the halide.

The nucleophile acts as a base.

The E1 and SN1 reactions have the same conditions, so a mixture of products will be
obtained.

Step 1: Ionization to form a carbocation

Step 2: Solvent abstracts a proton to form an alkene.

The rate-limiting step involves ionization of the alkyl halide. Because the step is
unimolecular (involves only one molecule), the rate equation is first-order.

E1 rate = k [RX]
r

The rate depends only on the concentration of the alkyl halide and not on the strength or
concentration of the base.
The weak base (often the solvent) takes part in the fast second step of the reaction.
E1 dehydrohalogenations usually take place in a good ionizing solvent (such as an
alcohol or water); the substrate is usually a tertiary alkyl halide.

Competition between the E1 and SN1 Reactions

Whenever a carbocation is formed, it can undergo either substitution or elimination, and
mixtures of products often result.

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This
image breaks down the SN1 and E1 reaction pathways from a single starting material with
MeOH. It highlights how MeOH can act as both a nucleophile (SN1) and a base (E1).

Rearrangements in E1 Reactions
1. Ionization to form a carbocation (slow).

This image shows the first step of a rearrangement reaction in E1 reactions. Note the
carbocation intermediate.

2. A hydride shift forms a more stable carbocation.

3. The weakly basic solvent removes either adjacent proton (fast).

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This image shows the second step of a rearrangement reaction in E1 reactions. Note that there
are two different possible products.

Solved Problem Example

When the following compound is heated in methanol, several different products are formed.
Propose mechanisms to account for the four products shown.

With no strong base and a good ionizing solvent, we would expect a first-order reaction. But
this is a primary alkyl halide, so ionization is difficult unless it rearranges.

From these rearranged intermediates, either loss of a proton (E1) or attack by the solvent
(SN1) gives the observed products. Note that the actual reaction may give more than just
these products, but the other products are not required for the problem.

Positional Orientation of Elimination: Zaitsev’s Rule

If more than one elimination product is possible, the most-substituted alkene is the major
product (most stable).

In this image, the major product is the more substituted alkene, with three alkyl substituents.

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Solved Problem Example

When 3-iodo-2,2-dimethylbutane is treated with silver nitrate in ethanol, three elimination
products are formed. Give their structures, and predict which ones are formed in larger
amounts.

Silver nitrate forces ionization of the alkyl iodide to give solid silver iodide and a cation. This
secondary carbocation can lose a proton to give an unrearranged alkene (A), or it can
rearrange to a more stable tertiary cation.

The tertiary cation can lose a proton in either of two positions. One of the products (B) is a
tetrasubstituted alkene, and the other (C) is disubstituted. Product B predominates over
product C.

Bimolecular Elimination: The E2 Reaction

The E2 reaction is an elimination, bimolecular reaction that requires a strong base. It's a
concerted reaction, meaning:

The proton is abstracted, the double bond forms, and the leaving group leaves, all
in one step.

E2 Mechanism

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Key characteristics of the E2 mechanism:

Order of reactivity for alkyl halides: 3° > 2° > 1°

Occurs in a single step where a strong base abstracts a proton on a carbon next to the
leaving group, causing the leaving group to depart and form an alkene.
A mixture of products may form, but the Zaitsev product generally predominates.

Example of E2 Elimination

Bulky Bases in E2 Eliminations: Hofmann

Orientation

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When a substrate in an E2 elimination is prone to substitution, using a bulky base can

minimize substitution.
Bulky bases can cause dehydrohalogenations that do not follow Zaitsev's rule, leading
to the Hofmann product.

For bromocyclohexane, a secondary alkyl halide, elimination (E2) is favored over substitution
(SN2) by using a bulky base such as diisopropylamine. Diisopropylamine is too bulky to be a
good nucleophile, so it acts as a strong base to abstract a proton.

Zaitsev and Hofmann Products

E2 Stereochemistry
The halide and the proton to be abstracted must be anti-coplanar (θ = 180º) to each
other for the elimination to occur.
The orbitals of the hydrogen atom and the halide must be aligned to form a pi bond in
the transition state.
The anti-coplanar arrangement minimizes steric hindrance between the base and the
leaving group.

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Molecules rigidly held in eclipsed conformations with a hydrogen atom and leaving group in a
syn-coplanar arrangement may undergo E2 elimination by a concerted syn-coplanar
mechanism, but anti-coplanar eliminations are more common.

Most E2 reactions go through an anti-coplanar transition state, and this geometry is most
apparent when viewing the reaction with the alkyl halide in a Newman projection.

Stereospecific E2 Reactions
Like the SN2 reaction, the E2 is stereospecific.

Different stereoisomers of the reactant yield different stereoisomers of the product,

typically due to the anti-coplanar transition state requirement.

The anti-coplanar elimination of different diastereomers leads to different stereoisomers of the

product.

Solved Problem: Stereospecificity

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Problem: Show that the dehalogenation of 2,3-dibromobutane by iodide ion is stereospecific

by showing that the two diastereomers of the starting material give different diastereomers of
the product.

Solution: Rotating meso-2,3-dibromobutane into a conformation where the bromine atoms

are anti and coplanar yields trans-2-butene. Similarly, either enantiomer of the (±)
diastereomer yields cis-2-butene.

E2 Reactions on Cyclohexanes

In a cyclohexane chair conformation:

All carbon–carbon bonds are staggered.

Any two adjacent carbon atoms have axial bonds in an anti-coplanar conformation,
ideally oriented for the E2 reaction.
On any two adjacent carbon atoms, one has its axial bond pointing up, and the other has
its axial bond pointing down; these two bonds are trans to each other, referred to as
trans-diaxial.

An anti-coplanar conformation (180°) can only be achieved when both the hydrogen and the
halogen occupy axial positions. The chair must flip to the conformation with the axial halide
for the elimination to take place.

Solved Problem: E2 on Cyclohexanes

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Problem: Explain why the following deuterated 1-bromo-2-methylcyclohexane undergoes

dehydrohalogenation by the E2 mechanism, to give only the indicated product, and why two
other alkenes are not observed.

Solution: In an E2 elimination, the hydrogen atom and the leaving group must have a trans-
diaxial relationship. In this compound, only one hydrogen atom—the deuterium—is trans to
the bromine atom. When the bromine atom is axial, the adjacent deuterium is also axial,
providing a trans-diaxial arrangement.

Another Example of E2 on Cyclohexanes

Comparison of E1 and E2 Elimination Mechanisms

Characteristic E1 E2

Base Effect Weak base or no base Requires strong base

Solvent Effect Polar protic solvents favor Not significantly affected by solvent
Substrate Effect Favors 3° > 2° > 1° Favors 3° > 2° > 1°
Kinetics First order Second order
Orientation Zaitsev's rule usually applies Zaitsev's or Hofmann product
Stereochemistry Not stereospecific Stereospecific
Rearrangements Common Not common

Substitution or Elimination?

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The strength of the nucleophile determines the order: strong nucleophiles or bases
promote bimolecular reactions.
Primary halides usually undergo SN2.
Tertiary halides undergo a mixture of SN1, E1, or E2. SN2 is not possible.
High temperatures favor elimination.
Bulky bases favor elimination.

Secondary Alkyl Halides

Secondary alkyl halides are more challenging to predict:
Strong nucleophiles promote SN2/E2.
Weak nucleophiles promote SN1/E1.
Strong nucleophiles with limited basicity favor SN2 (e.g., Bromide and Iodide).

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This image depicts a diagram illustrating the reactivity of alkyl halides in organic chemistry,
specifically their behavior under different nucleophilic substitution and elimination conditions.
The diagram is divided into three sections, each representing a primary (1°), secondary (2°),
and tertiary (3°) alkyl halide, with their respective chemical structures and reactivity pathways.
For each type of alkyl halide, the diagram shows the possible reactions with strong and weak
nucleophiles/bases, including SN2, SN1, E1, and E2 reactions, and notes the reaction
conditions and outcomes. The diagram provides a clear visual representation of how the
structure of an alkyl halide influences its reactivity in various organic reactions. Overall, the
diagram effectively summarizes key concepts in organic chemistry regarding alkyl halide
reactivity.

Solved Problems: Predicting Mechanisms and Products

The image depicts an organic chemistry reaction pathway, specifically illustrating the
formation of products from a given reactant through carbocation intermediates. The reaction
starts with a bromoalkane, which undergoes a departure of the bromide ion to form a
carbocation. This carbocation then leads to two types of products: those resulting from E1
elimination reactions, yielding two alkenes labeled as major and minor, and a substitution
product (SN1) forming an ether. The reaction pathway is presented in a clear and structured
manner, highlighting the possible outcomes of the reaction.

The image depicts a diagram of organic chemistry reactions, specifically illustrating the E2
and SN2 products of an alkyl halide reaction. The diagram shows two E2 products, with the
major product being CH3–CH=CH–CH2CH2CH3 and the minor product being CH2=CH–
CH2CH2CH2CH3. Below these products, an SN2 product is displayed: CH3–CH–
CH2CH2CH2CH3 with an OCH3 group attached to the second carbon. The diagram is
presented in a simple black text format on a white background, providing a clear visual
representation of the reaction outcomes. Overall, the image effectively communicates the
results of these organic chemistry reactions.

Dehydration of Alcohols
This image depicts a chemical reaction, specifically the dehydration of an alcohol to form an
alkene. The reaction involves the conversion of an alcohol on the left, with the molecular
formula showing a carbon-carbon bond, a carbon-hydrogen bond, and a carbon-hydroxyl
bond, into an alkene on the right, with a carbon-carbon double bond, in the presence of an
acidic catalyst and heat. The reaction is reversible, as indicated by the double-headed arrow.
Water (H2O) is produced as a byproduct of the reaction. Overall, the image illustrates a
fundamental reaction in organic chemistry.

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Use concentrated H2SO4 or H3PO4 and remove low-boiling alkene as it forms to shift
the equilibrium and increase the yield of the reaction.
Follows an E1 mechanism
Rearrangements are common.
Obeys Zaitsev’s rule.

Dehydration Mechanism: E1
Step 1: Protonation of the hydroxyl group (fast equilibrium).

The image depicts a chemical reaction involving the transfer of a proton, also known as a
hydrogen ion. The reaction shows an alcohol, specifically ethanol (CH3CH2OH), reacting with
sulfuric acid (H2SO4) to form a protonated alcohol and a hydrogen sulfate ion (HSO4-). The
reaction is represented by a curved arrow indicating the movement of electrons, and a straight
arrow indicating the direction of the reaction. The reactants and products are shown in their
structural formulas, with the atoms and bonds clearly labeled. Overall, the image illustrates
an acid-base reaction in which the sulfuric acid acts as an acid and donates a proton to the
alcohol.

Step 2: Ionization to a carbocation (slow; rate-limiting).

Step 3: Deprotonation to give the alkene (fast).

The image depicts an organic chemistry reaction mechanism, specifically the process of a
carbocation intermediate reacting with water to form an alkene. The reaction involves a
positively charged carbon atom (carbocation) on the left side, which is attacked by a water
molecule (H2O) to form a new bond. A hydrogen atom from an adjacent carbon migrates to
the positively charged carbon, forming an alkene (C=C) on the right side of the image. The
reaction also produces a hydronium ion (H3O+). The image effectively illustrates the acid-
catalyzed elimination reaction.

Solved Problem: Dehydration of t-butyl alcohol

Problem: Propose a mechanism for the sulfuric acid-catalyzed dehydration of t-butyl alcohol.

Solution:

1. Protonation of the hydroxyl group, converting it to a good leaving group.

2. Ionization of the protonated alcohol to give a carbocation.
3. Abstraction of a proton completes the mechanism.

Catalytic Cracking and Dehydrogenation of Alkanes

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Catalytic Cracking of Alkanes

A long-chain alkane is heated with a catalyst to produce an alkene and a shorter alkane. This
process results in complex mixtures.

Dehydrogenation of Alkanes
The image depicts a chemical reaction, specifically the dehydrogenation of an alkane to form
an alkene. The reactant is an alkane with a single bond between two carbon atoms, which are
also bonded to hydrogen atoms. When heated in the presence of a catalyst, the alkane loses a
molecule of hydrogen gas (H2) and forms a double bond between the two carbon atoms,
resulting in the formation of an alkene. This reaction is a type of elimination reaction, where
the loss of a small molecule (in this case, H2) leads to the formation of a new bond. The image
effectively illustrates this process through simple and clear structural formulas.

Dehydrogenation is the removal of H2 from a molecule, forming an alkene, which is

the reverse of hydrogenation.

This reaction has an unfavorable enthalpy change but a favorable entropy change.

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