Alkenes

Alkenes are hydrocarbons with carbon–carbon double bonds. Alkenes are sometimes
called olefins, a term derived from olefiant gas, meaning “oil-forming gas”. This term
originated with early experimentalists who noticed the oily appearance of alkene
derivatives. Alkenes are among the most important industrial compounds and many
alkenes are also found in plants and animals. Ethylene is the largest-volume industrial
organic compound, used to make polyethylene and a variety of other industrial and
consumer chemicals.

The nomenclature of alkenes

The double bond is the functional group of an alkene. Therefore, the systematic (IUPAC)
name of an alkene is obtained by replacing the “ane” ending of the corresponding
alkane with “ene”. For example, a two-carbon alkene is called ethene, and a three-
carbon alkene is called propene.

1. When the chain contains more than three carbon atoms, the longest continuous
chain containing the carbon–carbon double bond is numbered in the direction
that gives the functional group suffix the lowest possible number. Cycloalkenes
are assumed to have the double bond between carbons 1 and 2.

Instead of placing the numbers before the root name (1-butene), in 1993 the IUPAC
recommended placing them immediately before the part of the name they locate (but-
1-ene). The new placement is helpful for clarifying the names of compounds containing
multiple functional groups. 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.

old IUPAC names: 1-pentene 1,3-butadiene

new IUPAC names: pent-1-ene buta-1,3-diene

old IUPAC names: 1,3,5-heptatriene 1,3,5,7-cyclooctatetraene

new IUPAC names: hepta-1,3,5-triene cycloocta-1,3,5,7-tetraene

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Abdullah-Al-Faysal, Lecturer, DOP, EWU
Notice that 1,6-dichlorocyclohexene is not called 2,3-dichlorocyclohexene because the
former has the lowest substituent number (1), even though it does not have the lowest
sum of substituent numbers (1 + 6 = 7 versus 2 + 3 = 5).

2. If the second functional group suffix has a higher priority than the alkene suffix,
number the chain in the direction that assigns the lower number to the
functional group with the higher-priority suffix.

Alkenes as Substituents: Alkenes named as substituents are called alkenyl groups.

Common alkenyl substituents are the vinyl, allyl and methylene groups. The sp 2 carbons
of an alkene are called vinylic carbons. A sp 3 carbon that is adjacent to a vinylic carbon is
called an allylic carbon.

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Cis-Trans Isomers: The stereoisomers of an alkene are named using a cis or trans prefix
(in italics).

 cis isomer: if two similar groups bonded to the carbons of the double bond are
on the same side of the bond.

 trans isomer: if the similar groups bonded to the carbons of the double bond are
on the opposite sides of the bond.

If either carbon of the double bond holds two identical groups, the molecule cannot
have cis and trans forms.

The structure of alkenes

Each carbon hybridizes three atomic orbitals: an s orbital and two p orbitals to form
three sp2 hybrid orbitals. Three sp2 hybrid orbitals lie in a plane, oriented 120° from each
other. The unhybridized p orbital is perpendicular to this plane.

Each C-H bond in ethylene is a sigma (σ) bond and results from the overlap of a sp2
orbital from carbon and s orbital from hydrogen. One of the C-C bond results from the
overlap of a sp2 orbital of one carbon with a sp2 orbital of the other carbon; this is a
sigma (σ) bond. The second carbon–carbon bond results from side-to-side overlap of the
two unhybridized p orbitals and forms a pi (π) bond.

For maximum overlap to occur, these p orbitals must be parallel, which requires that the
two carbon atoms be oriented with all their bonds in a single plane. Half of the pi-
bonding orbital is above the sigma bond, and the other half is below the sigma bond.
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Bond length

The bond in ethylene (1.33 Å) is much shorter than the bond (1.54 Å) in ethane, because

 The sigma bond of ethylene is formed from sp2 orbitals (with more s character)
 There are two bonds drawing the atoms together

Because of the sp2 orbital, the bond length in ethylene (1.08 Å) is slightly shorter than
the bond in ethane (1.09 Å).

The elements of unsaturation and Molecular formulas

Alkenes are said to be unsaturated because they are capable of adding hydrogen in the
presence of a catalyst. The product, an alkane, is called saturated because it cannot
react with any more hydrogen. The presence of a pi bond of an alkene (or an alkyne) or
the ring of a cyclic compound decreases the number of hydrogen atoms in a molecular
formula. The total number of pi bonds and rings is called the compound’s elements of
unsaturation. Each elements of unsaturation corresponds to two fewer hydrogen atoms
than in the “saturated” formula.

The general molecular formula for an acyclic alkene is CnH2n and for a cyclic alkene must
be CnH2n-2.

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How molecules react? (“nucleophiles react with electrophiles”)

Any reactions can be explained by a very simple rule: Electron-deficient atoms or

molecules are attracted to electron-rich atoms or molecules.

An electron-deficient atom or molecule is called an electrophile. Literally, “electrophile”

means “electron loving” which has either a positive charge or an incomplete octet that
can accept electrons. An electrophile looks for a pair of electrons.

An electron-rich atom or molecule is called a nucleophile. Nucleophiles and

electrophiles attract each other, because nucleophiles have electrons to share and
electrophiles are seeking electrons.

Reactivity of the Carbon–Carbon Double Bond

 Sigma bonds are more stable than pi bonds. The most common reactions of
double bonds are transforming the pi bond into a sigma bond. For example,
catalytic hydrogenation of alkene is exothermic, showing that the product is
more stable than the reactants.

 Pi bond of an alkene consists of a cloud of electrons above and below the σ

bond. As a result, an alkene is an electron-rich molecule (nucleophile). For these
reasons, we can predict that an alkene will react with an electrophile and, in the
process, the π bond will break.

Electrophilic addition to Alkenes

The first step is a relatively slow addition of an electrophile to the alkene (a

nucleophile). A carbocation intermediate (an electrophile) is formed, which then reacts
rapidly with a nucleophile to form a stable addition product. Notice that each step
involves the reaction of an electrophile with a nucleophile. The overall reaction is the
addition of an electrophile to one of the sp 2 carbons of the alkene and the addition of a
nucleophile to the other sp2 carbon.
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Carbocation stability

Carbocations are classified based on the carbon that carries the positive charge:

Positive charge on a carbon signifies an empty p orbital. In the ethyl cation, the orbital
of an adjacent C-H σ bond can overlap the empty p orbital. This movement of electrons
from a σ bond orbital toward the vacant p orbital decreases the charge on the sp 2
carbon and causes a partial positive charge to develop on the σ bonded two atoms (H &
C). With three atoms sharing the positive charge, the carbocation is stabilized because a
charged species is more stable if its charge is dispersed over more than one atom. In
contrast, the positive charge in the methyl cation is concentrated solely on one atom.

Delocalization of electrons by the overlap of a σ bond orbital with an empty orbital on

an adjacent carbon is called hyperconjugation.

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Table: Types of Additions to Alkenes

1.

Addition of Hydrogen Halides:

2.

Hydration (the addition of water):

Hydroboration-Oxidation:

3.

Hydrogenation:

4.
Addition of alcohol:

5.

Dihydroxylation:

6.

Halogenation:

Halohydrin formation:

Nucleophiles other than H2O:

7.
Ozonolysis/Oxidative cleavage:

8.

Epoxidation:
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  Syn addition: When two substituents add to the same side of a double bond.
 Anti addition: When two substituents add to opposite sides of a double bond.
 Geminal: identical functional groups bonded to the same carbon atom. 
 Vicinal: identical functional groups bonded to adjacent carbons.

The addition of a hydrogen halide to an alkene

If the electrophilic reagent that adds to an alkene is a hydrogen halide (HF, HCl, HBr, or
HI), the product of the reaction will be an alkyl halide.

Because the alkenes in the preceding reactions have the same substituents on both sp 2
carbons, it is easy to predict the product of the reaction: the electrophile (H +) adds to
either one of the sp2 carbons and the nucleophile (X -) adds to the other sp2 carbon. It
does not matter which sp2 carbon the electrophile adds to because the same product
will be obtained in either case.

Orientation of Addition: Markovnikov’s Rule

In the following reaction, the proton can add to C-1 to form a secondary carbocation or
it can add to C-2 to form a primary carbocation. Because the secondary carbocation is
more stable, it is formed more rapidly. As a result, the only product is 2-chloropropane.

A Russian chemist, Vladimir Markovnikov, first showed the orientation of addition of

HBr to alkenes in 1869. Markovnikov stated:

‘The electrophile adds to the sp2 carbon bonded to the most hydrogens.’

The rule is simply a quick way to determine the major product of an electrophilic
addition reaction.

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A carbocation will rearrange if it can form a more stable carbocation

In the following reaction, 2-bromo-3-methylbutane is the product according to

Markovnikov’s rule. But this is a minor product. 2-Bromo-2-methylbutane is an
“unexpected” product, and yet it is the major product of the reaction.

The unexpected product results from a rearrangement of the carbocation intermediate.

Carbocations rearrange only if they become more stable as a result of the
rearrangement.

In the reaction, a secondary carbocation is formed initially. However, the carbocation

has a hydrogen that can shift with its pair of electrons to the adjacent positively charged
carbon, creating a more stable tertiary carbocation. If a hydrogen shifts with its pair of
electrons, the rearrangement is called a hydride (H:-) shift.

Not all carbocations rearrange. If a rearrangement does not lead to a more stable
carbocation, then it typically does not occur.

9 PHRM103: Organic Pharmacy I

Abdullah-Al-Faysal, Lecturer, DOP, EWU
Free-Radical Addition of HBr: Anti-Markovnikov Addition
In 1933, Kharasch and Mayo found that some additions of HBr (but not HCl or HI) to
alkenes gave products that were opposite to those expected from Markovnikov’s rule.
These anti-Markovnikov reactions were most likely when the reagents or solvents came
from old supplies that had accumulated peroxides from exposure to the air. Peroxides
give rise to free radicals that initiate the addition, causing it to occur by a radical
mechanism.

i. Chain initiation: The oxygen–oxygen bond in peroxides is rather weak, so it can

break to give two alkoxy radicals. These free radicals extract a hydrogen atom
from a hydrogen bromide molecule to produce bromine radicals.

ii. Chain propagation: When the bromine radical joins to the propene, a secondary
radical is formed. This is more stable than the primary radical which would be
formed if it attached to the other carbon atom.

That radical reacts with another HBr molecule to produce 1-bromopropane and another
bromine radical to continue the process.

[*Both of the propagation steps are moderately exothermic for HBr, whereas one of
steps is strongly endothermic for HCl and HI]

iii. Chain termination: In termination step, two free radicals hit each other and
produce a neutral molecule.

In both cases (with and without peroxides), the electrophile adds to the less substituted
end of the double bond to give the more stable intermediate. In the ionic reaction, the
electrophile is H+ and in the peroxide-catalyzed reaction, Br· is the electrophile.

10 PHRM103: Organic Pharmacy I

Abdullah-Al-Faysal, Lecturer, DOP, EWU
The addition of borane to an alkene
H. C. Brown, of Purdue University, discovered that diborane (B 2H6) adds to alkenes with
anti-Markovnikov orientation to form alkylboranes, which can be oxidized to give anti-
Markovnikov alcohols. This discovery led to the development of a large field of borane
chemistry, for which Brown received the Nobel Prize in Chemistry in 1979.

BH3 is the electrophile that adds to the alkene and the nucleophile is an H - bonded to
boron. When the addition reaction is over, an aqueous solution of sodium hydroxide
and hydrogen peroxide is added to the reaction mixture to produce an alcohol.

Catalytic Hydrogenation of Alkenes

Hydrogen (H2) adds to the double bond of an alkene, in the presence of a metal catalyst,
to form an alkane. The most common metal catalyst is palladium.

One face of the alkene pi bond binds to the catalyst, which has hydrogen adsorbed on
its surface. Hydrogen inserts into the pi bond, and the product is freed from the catalyst.
Because the two hydrogen atoms add from a solid surface, they add with syn
stereochemistry.

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Addition of Halogens to Alkenes
A halogen molecule is electrophilic, which adds to alkenes to form vicinal dihalides.

The pi electrons of an alkene attack the halogen molecule, expelling bromide ion. A
bromonium ion results, containing a three-membered ring with a positive charge on the
bromine atom.

The three-membered ring has considerable ring strain. Attack by a nucleophile, such as a
bromide ion, opens the bromonium ion to give a stable product.

The relative stabilities of alkenes

 The stability of an alkene increases as the number of alkyl substituents bonded

to its sp2 carbons increases.

 In a cis isomer, their electron clouds can interfere with each other, causing steric
strain in the molecule. Steric strain makes a compound less stable. In a trans
isomer, their electron clouds cannot interact, so there is no destabilizing steric
strain.

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Electrophilic addition reactions are regioselective

A reaction in which two or more constitutional isomers could be obtained as products,

but one of them predominates, is called a regioselective reaction.

For example, the addition of HCl to 2-methylpropene (where the two possible
carbocations are tertiary and primary) is more highly regioselective than the addition of
HCl to 2-methyl-2-butene (where the two possible carbocations are tertiary and
secondary), because the two carbocations formed in the latter reaction are closer in
stability. In a completely regioselective reaction, only one of the possible products is
formed.

Stereoselective and stereospecific reactions

 Stereochemistry: field of chemistry that deals with the structures of molecules in

three dimensions.
 Stereoselective reaction: preferential formation of a stereoisomer.

 Stereospecific reaction: if the reactant can exist as stereoisomers and each

stereoisomer of the reactant forms a different stereoisomer or a different set of
stereoisomers of the product.

All stereospecific reactions are also stereoselective; however, not all stereoselective
reactions are stereospecific.

13 PHRM103: Organic Pharmacy I

Abdullah-Al-Faysal, Lecturer, DOP, EWU
Polymerization of Alkenes
A polymer is a large molecule composed of many smaller repeating units (the
monomers) bonded together. Alkenes serve as monomers for some of the most
common polymers, such as polyethylene, polypropylene, polystyrene, polyvinyl
chloride, and many others. Alkenes polymerize to give addition polymers resulting from
repeated addition reactions across their double bonds. There is generally a reactive
intermediate (cation, anion, or radical) at the growing end of the chain.

Free-Radical Polymerization: Many alkenes undergo free-radical polymerization when

they are heated with radical initiators. For example, styrene polymerizes to polystyrene
when it is heated to 100 °C with a peroxide initiator.

Alkene Synthesis

The reactions of alkenes involve the addition of atoms (or groups of atoms) to the two
sp2 carbons of the double bond. Reactions that synthesize alkenes are exactly the
opposite; they involve the elimination of atoms (or groups of atoms) from two adjacent
sp3 carbons.

14 PHRM103: Organic Pharmacy I

Abdullah-Al-Faysal, Lecturer, DOP, EWU