Dr.

Dr.Nisreen
NisreenAlhaj
Alhaj
 Goals for Chapter 7
Sections : 3-13 and 18

1 Draw and name alkenes and cycloalkenes.

2 Given a molecular formula, calculate the number of pi bonds and rings.

3 Explain how the stability of alkenes depends on their structures.

4 Write equations to show how alkenes can be synthesized by eliminations from alkyl
halides and alcohols.

5 Predict the products of substitution and elimination reactions, and explain what
factors favor each type of reaction.

6 Identify the differences between unimolecular and bimolecular eliminations and

explain what factors determine the order of the reaction.

7 Given a set of reaction conditions, identify the possible mechanisms, and predict which
mechanism(s) and product(s) are most likely.
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 7-3 Elements of Unsaturation
• Alkenes are hydrocarbons with carbon–carbon double bonds ( unsaturated)

• Alkenes are also called olefins, meaning “oil-forming gas.”

• The functional group of alkenes is the carbon–carbon double bond, which gives this group its reactivity.

trigonal planar 120°

The pi bond in ethylene

• sp2 hybrid orbitals have more s character than the

sp3 hybrid orbitals.
• Pi overlap brings carbon atoms closer, shortening the C—C bond
from 1.54 Å in alkanes down to 1.33 Å in alkenes.

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 7-3 Elements of Unsaturation
• Saturated : cannot react with any more hydrogen.

• Unsaturation is a structural element that decreases the number of hydrogens in the molecule by two.

• Each element of unsaturation corresponds to two fewer hydrogen atoms than in the “saturated” formula

• Double bonds and rings are elements of unsaturation.

Elements of Unsaturation,
Degree of Unsaturation,
Unsaturation Number, and
Index of Hydrogen Deficiency
are all equivalent terms

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 7-3 Elements of Unsaturation
7-3A Elements of Unsaturation in Hydrocarbons

Calculate the maximum number of hydrogen atoms from the, and see how many are missing.
The number saturated formula, CnH(2n + 2) of elements of unsaturation is simply half the number of missing
hydrogens
If you prefer to use a formula,
elements of unsaturation =
C = number of carbons, H = number of hydrogens
This calculation cannot distinguish between unsaturations from multiple bonds and those from rings.

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 7-3 Elements of Unsaturation
7-3B Elements of Unsaturation with
Heteroatoms
Heteroatoms (hetero, “different”) are any atoms other than carbon and hydrogen

Halogens:
Halogens simply substitute for hydrogen atoms in the molecular formula
• The formula C2H6 is saturated, so the formula C2H4F2 is also saturated.

• C4H8 has one element, of unsaturation, and C4H5Br3 also has one element of unsaturation.
In calculating the number of elements of unsaturation, simply count halogen atoms as hydrogen atoms

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 7-3 Elements of Unsaturation

Oxygen
An oxygen atom can be added to the chain (or added to a C¬H bond to make a C¬OH group) without
changing the number of hydrogen atoms or carbon atoms.
In calculating the number of elements of unsaturation, ignore the number of oxygen atoms

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 7-3 Elements of Unsaturation

Nitrogen:
A nitrogen atom can take the place of a carbon atom in the chain, but nitrogen is trivalent.
A nitrogen atom has only one additional hydrogen atom, compared with two hydrogens for each additional
carbon atom.
In computing the elements of unsaturation, count nitrogen as half a carbon atom.

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 7-3 Elements of Unsaturation

CnH(2n + 2)

In figuring elements of unsaturation:

• Count halogens as hydrogens.
• Ignore oxygen.
• Count nitrogen as half a carbon.

n=4.5 C4.5 H(11) 11-7=4

4/2=2

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 7-3 Elements of Unsaturation

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 7-4 Nomenclature of Alkenes
• Find the longest continuous carbon chain that includes the double-bonded carbons.
• Ending -ane changes to -ene.
• Number the chain so that the double bond has the lowest possible number.
• In a ring, the double bond is assumed to be between carbon 1 and carbon 2.

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 7-4 Nomenclature of Alkenes
A compound with two double bonds is a diene. A triene has three double bonds, and a tetraene has four.
Numbers are used to specify the locations of the double bonds.

Rings:
• 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.

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 7-4 Nomenclature of Alkenes
Alkenes as Substituents
we name the group containing the double bond as a substituent called an alkenyl group
Common alkenyl substituents are the vinyl, allyl, methylene, and phenyl groups

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 7-4 Nomenclature of Alkenes

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 7-5 Nomenclature of Cis-Trans Isomers
7-5A Cis-Trans Nomenclature

• cis-trans isomerism, also called geometric isomerism

• A double bond that gives rise to cis-trans stereoisomerism is called stereogenic

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 7-5 Nomenclature of Cis-Trans Isomers
7-5B E-Z Nomenclature

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).

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 7-5 Nomenclature of Cis-Trans Isomers

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 7-5 Nomenclature of Cis-Trans Isomers

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 7-6 Commercial Importance of Alkenes
Ethylene is the largest-volume industrial
organic chemical.
Most of the ethylene produced each year is
polymerized to make polyethylene.
Much of the rest is used to produce a
variety of useful two-carbon compounds.

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 7-6 Commercial Importance of Alkenes

Uses of propylene:
Most propylene is polymerized to make polypropylene.
It is also used to make several important three-carbon compounds

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 7-6 Commercial Importance of Alkenes
A polymer (Greek, poly, “many,” and meros, “parts”)
is a large molecule made up of many monomer
(Greek, mono, “one”) molecules.

An alkene monomer can polymerize by a chain

reaction where additional alkene molecules add to the
end of the growing polymer chain. Because these
polymers result from addition of many individual
alkene units, they are called addition polymers

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 7-7 Physical Properties of Alkenes
7-7A Boiling Points and Densities

• Most physical properties of alkenes are similar to those of the corresponding alkanes.
For example, the boiling points of but-1-ene, cis-but-2-ene, trans-but-2-ene, and n-butane are all close to 0 °C.
• The boiling points of alkenes increase smoothly with molecular weight.
• As with alkanes, increased branching leads to greater volatility and lower boiling points.
• Also like the alkanes, alkenes have densities around 0.6 or 0.7 g>cm3.

7-7B Polarity

• Cis alkenes have a greater dipole moment than

trans alkenes, so they will be slightly polar.
• The boiling point of cis alkenes will be higher
than the trans alkenes.
• alkenes are relatively nonpolar. They are
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 7-7 Physical Properties of Alkenes

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 7-8 Stability of Alkenes
• we need to know how the stability of an alkene depends on its structure
• We can compare stabilities by converting different compounds to a common product and comparing
the amounts of heat given off.
• One possibility would be to measure heats of combustion from converting alkenes to CO 2 and H2O, or
easier to measure Heats of Hydrogenation

7-8A Heats of Hydrogenation

The more stable compound , the lower its heat of hydrogenation

trans-But-2-ene is more stable by

Dr. Nisreen Alhaj 125.9 kJ/mol - 114.6 kJ.mol = 11.3 kJ/mol (2.7 kcal/mol) 24
 7-8 Stability of Alkenes

More substituted double bonds are usually more stable with the lower heat of
Dr.hydrogenation
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 7-8 Stability of Alkenes
7-8B Substitution Effects

The most stable double bonds are those with the most alkyl groups
attached ( more substituents)

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 7-8 Stability of Alkenes

The alkyl substituents are separated

farther in trans isomers than they are in
cis isomers
• Alkyl groups are mildly electron-donating, and they contribute
electron density to the pi bond. In addition, bulky substituents
such as alkyl groups are best situated as far apart as possible.
• In an alkane, they are separated by the tetrahedral bond angle,
about 109.5°.
• A double bond increases this separation to about 120°.
• In general, alkyl groups are separated best by the most
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highly substituted double bond (less steric effect)
 7-8 Stability of Alkenes

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 7-8 Stability of Alkenes
7-8D Stability of 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.
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 7-8 Stability of Alkenes

• 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.

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 7-8 Stability of Alkenes

7-8E Bredt’s Rule

unstable arrangement

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 7-8 Stability of Alkenes

Bredt’s rule violation (not

stable stable)

stable stable

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 7-8 Stability of Alkenes
7-8F Enhanced Stability of Conjugated Double Bonds

• Double bonds can interact with each other if they are separated by just one single bond. Such interacting
double bonds are said to be conjugated.
• Double bonds with two or more single bonds separating them have little interaction and are called isolated
double bonds

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 7-8 Stability of Alkenes

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7-9 Formation of Alkenes by Dehydrohalogenation of Alkyl
Preparation of alkenes: Halides
• E2 dehydrohalogenation (–HX)
• E1 dehydrohalogenation (–HX)
• Dehalogenation of vicinal dibromides (–X2)
• Dehydration of alcohols (–H2O)

Dehydrohalogenation of Alkyl Halides

• An elimination involves the loss of two atoms or groups from the substrate, usually with formation of
a new pi bond.
• Elimination of a proton and a halide ion is called dehydrohalogenation, and the product is an alkene.

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7-9 Formation of Alkenes by Dehydrohalogenation of Alkyl
Halides

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 7-10C Rearrangements in E1 Reactions

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7-11 Positional Orientation of Elimination: Zaitsev’s Rule
Zaitsev’s Rule
If more than one elimination product is possible, the most-substituted alkene is the
major product (most stable).

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 7-10B Orbitals and Energetics of the E1 Reaction
In the second step of the E1 mechanism, the carbon atom next to the C+ must rehybridize to sp2 as
the base attacks the proton and electrons flow into the new pi bond.

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 7-10 Unimolecular Elimination: The E1 Reaction
7-10A Competition between the E1 and SN1 Reactions

• The E1 elimination almost always competes with the SN1 substitution.

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

a solvolysis (solvo for “solvent,” lysis for

“cleavage”) because the solvent reacts with
the substrate

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 7-10C Rearrangements in E1 Reactions

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 7-10C Rearrangements in E1 Reactions

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 7-12 Bimolecular Elimination: The E2 Reaction
• E2 for Elimination, bimolecular.
• a strong base should present.
• This is a concerted reaction: The proton is abstracted, the double bond forms, and the leaving group
leaves, all in one step
• No substitution product is observed, however. The SN2 mechanism is blocked because the tertiary
alkyl halide is too hindered.

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 7-12 Bimolecular Elimination: The E2 Reaction

This reactivity order reflects the

greater stability of highly
Mixtures of Products in the E2 substituted double bonds

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 7-12 Bimolecular Elimination: The E2 Reaction

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7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation

Use of a Bulky Base:

1) If the substrate in an E2 elimination is prone to substitution, we can minimize the amount of

substitution by using a bulky base.
2) Bulky bases can accomplish dehydrohalogenations that do not follow the Zaitsev rule. They form the
Hofmann product.

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 7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation
Formation of the Hofmann Product

• Steric hindrance often prevents a bulky base from abstracting the proton that leads to the most highly
substituted alkene.
• In these cases, it abstracts a less hindered proton, often the one that leads to formation of the least
substituted product, called the Hofmann product.

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7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation

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 7-18 Alkene Synthesis by Dehydration of Alcohols

A common laboratory synthesis of alkenes involves the elimination of the elements of water
from alcohols under acidic conditions.
This reaction is called dehydration, which literally means “removal of water.”

• Use concentrated H2SO4 or H3PO4 as catalysts and remove low-boiling alkene as it forms
( by distillation) to shift the equilibrium and increase the yield of the reaction.
• E1 mechanism
• Rearrangements are common.
• The reaction obeys Zaitsev’s rule.
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 7-18 Alkene Synthesis by Dehydration of Alcohols
KEY MECHANISM

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 7-18 Alkene Synthesis by Dehydration of Alcohols

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 7-18 Alkene Synthesis by Dehydration of Alcohols

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