limonene

Chapter 3: Alkenes and Alkynes

© R. Spinney 2013
• Alkenes and alkynes are two families of organic molecules that contain
multiple bonds.
• They are unsaturated hydrocarbons. They contain fewer hydrogens per
carbon than alkanes
• Alkenes are compounds that contain a carbon−carbon double bond.

• Alkenes have the general formula .

Alkynes are compounds that contain a carbon−carbon triple bond.

• Alkynes have the general formula .

• Alkanes can be obtained from alkenes or alkynes by adding 1 or 2
moles of hydrogen.
 Exercise

Answers

a. Alkene
b. Sat’d HC or alkane
c. Alkyne
d. Alkene
• Alkadienes, or dienes, contain two C-C double bonds that can be cumulated
(next to each other), conjugated (separated by one C-C single bond), or
nonconjugated (separated by more than one C-C single bond).
• There are also trienes, tetraenes, and even polyenes (compounds with many
double bonds, from the Greek poly, many).
• Polyenes are responsible for the color of carrots (β-carotene, p. 76) and
tomatoes (lycopene, p. 68).
• Compounds with more than one triple bond, or with double and triple bonds,
are also known.
• each carbon atom of a double bond is connected to only three other atoms
(trigonal)
• two carbon atoms of a double bond and the four atoms that are attached to
them lie in a single plane (planar)
• rotation around double bonds is restricted
• carbon–carbon double bonds are shorter than carbon–carbon single bonds.
• sp2-Hybridized orbitals are one part s and two parts p in character and are
directed toward the three vertices of an equilateral triangle
• the angle between two sp2 orbitals is 120°
• Three valence electrons are placed in the three sp2 orbitals.
• The fourth valence electron is placed in the remaining 2p orbital, whose axis is
perpendicular to the plane formed by the three sp2 hybrid orbitals
Formation of Double Bond
• sigma () - bond is formed from the end-on overlap of two orbitals.
• pi () - bond is formed by lateral overlap of p orbitals on adjacent atoms.
• There is restricted rotation around the C atoms of a double bond.

• Configurational stereoisomers
• can be separated from one another by distillation, taking advantage of the
difference in their boiling points.
When the two groups on one end of the double bond are identical (for
example, both H or both ), no cis and trans isomers are possible.
• Geometric isomers of alkenes can be interconverted if sufficient energy is
supplied to break the pi bond and allow rotation about the remaining, somewhat
stronger, sigma bond
• The required energy may take the form of light or heat.
• This conversion does not occur under normal laboratory conditions.
Substitution  common for alkanes

Addition  common for alkenes

• addition of a reagent to the carbons of the double bond to give a product with a
C-C single bond.
• pi bond of the alkene is broken, and the sigma bond of the reagent is also broken
• Two new sigma bonds are formed
• we break a pi and a sigma bond, and we make two sigma bonds
• sigma bonds are usually stronger than pi bonds, the net reaction is favorable.
 two-step polar process

• halogen is dissolved in some inert solvent such as tri- or tetrachloromethane, and then is added
dropwise to the alkene
• nearly instantaneous, even at room temperature or below
• No light or heat is required, as in the case of substitution reactions.
• Bromine Test – test for unsaturation
• Bromine solutions in tetrachloromethane - are dark reddish-brown
• As the bromine solution is added to the unsaturated compound, the bromine color disappears.
• Saturated compound - will not react with bromine under these conditions, and the color of the
bromine solution will persist.
• acid catalyst is present because water molecule is not acidic enough to
provide protons to start the reaction
• water adds as H-OH, and the products are alcohols
• The hydrogen ion (or proton) adds to one carbon of the double bond, and the
remainder of the acid becomes connected to the other carbon.
• Acids that add in this way are the hydrogen halides (H-F, H-Cl, H-Br, H-I) and
sulfuric acid (H-OSO3H).
 • Regiospecific - gives only one of the two
possible regioisomers
Regioisomers • Regioselective - produce mainly one
regioisomer.

Regioisomers
 • only one product is observed
• Regiospecific - only product
is 2-propanol

• Vladimir Markovnikov
• formulated the following rule more
than 100 years ago
• When an unsymmetric reagent adds
to an unsymmetric alkene, the
electropositive part of the reagent
bonds to the carbon of the double
bond that has the greater number of
hydrogen atoms attached to it.
• same number of attached hydrogens (one)
• application of Markovnikov’s rule is ambiguous
• Both products are formed and the reaction is not regiospecific.
Electrophiles - electron-poor reactants; they seek electrons.
 often cations or otherwise electron-deficient species.
Nucleophiles - electron-rich reactants; they form bonds by donating electrons to
electrophiles.
• pi electrons - are involved in additions to alkenes
• double bond - act as a supplier of pi electrons to an electron-seeking reagent
Attacking electrophile

Nucleophile ( pi e-) Very reactive!!!

Electrophilic Addition Reaction

• the formation of the

• carbocation—is the
slower of the two
steps.
• combination with the
nucleophile is
extremely rapid.
 Carbocations are classified as
primary, secondary, and tertiary
when one, two, and three R
groups, respectively, are attached
to the positively charged carbon
atom.

 more stable when the positive

charge can be spread out, or
delocalized, over several atoms
in the ion, instead of being
concentrated on a single
carbon atom.
Markovnikov’s Rule: The
electrophilic addition of an
unsymmetric reagent to an
unsymmetric double bond
proceeds in such a way as to
involve the most stable
carbocation.
EXERCISE
(1)Under what conditions
is a reaction likely to
proceed?
(2)How rapidly will a
reaction occur?
equilibrium constant, Keq - indicates the direction that is favored for a reaction.
Keq > 1 - left to right, forward reaction or formation of products
 products are lower in energy (more stable) than the reactants.
 heat is given off (exothermic, ΔH = -)
Keq < 1 - right to left, backward reaction or re-formation of reactants
products are higher in energy than reactants
heat must be added (endothermic, ΔH = +)
Enthalpy, H – heat energy
ΔH – change in enthalpy
 • equilibrium constant for a reaction tells us whether or not products are more
stable than reactants
• equilibrium constant does not tell us anything about the rate of a reaction

reaction energy diagram - shows the changes in energy that occur in the course of a
reaction
transition state - is a structure with maximum energy for a particular reaction step.
Activation energy, Ea - is the difference in energy between reactants and the
transition state and determines the reaction rate.
In order to react:
• molecules must collide with each other with enough energy
• with the right orientation so that the breaking and making of bonds can occur
• the higher the energy barrier, the slower the reaction.
 endothermic

higher the energy barrier,

the slower the reaction.

exothermic
Increasing temperature or using a
catalyst increases reaction rates.
Hydroboration is the addition of to an alkene.

• discovered by Professor Herbert C. Brown (1912–2004).

• useful in synthesis that Brown’s work earned him a Nobel Prize in 1979.
• we will describe a two-step alcohol synthesis from alkenes

• all bond-breaking and bond-

making occur in one step
 • treated with some
other reagent to
obtain the desired
final product

• it provides a route to alcohols that

cannot be obtained by the acid-
catalyzed hydration of alkenes
Hydrogenation - addition of hydrogen to alkenes in the presence of a catalyst
• catalyst - finely divided metal, such as nickel, platinum, or palladium which
adsorb hydrogen gas on their surfaces and activate the hydrogen–hydrogen
bond
• H adds to same face of the double bond  cis

• Catalytic hydrogenation of double

bonds is used commercially to
convert vegetable oils to margarine
and other cooking fats
 • proton adds according to
Markovnikov’s Rule.

• resulting carbocation can be

stabilized by resonance

• positive charge is delocalized

over carbon-2 and carbon-4.
• carbocation reacts with
bromide ion (the nucleophile)
either at carbon-2 to give the
product of 1,2-addition or at
carbon-4 to give the product
of 1,4-addition.
allylic cation –
carbocation with a
carbon–carbon
double bond that
is adjacent to the
positively charged
carbon atom
Diels–Alder reaction - the cycloaddition reaction of a conjugated diene and a dienophile to
give a cyclic product in which three bonds are converted to two bonds and a new bond.
• Discovered by Otto Diels and Kurt Alder
• useful for making cyclic compounds
• 1950 Nobel Prize in chemistry for its discoverers
• Similar with hydroboration  reaction is concerted
• All bond-breaking and bond-making occur at the same time
• gives excellent yields at moderate temperatures if the dienophile has electron-withdrawing
groups
*Electron-withdrawing groups - are groups of atoms that attract the electrons of the bond,
making the alkene electron poor and therefore more electrophilic toward the diene.
dienes

dienophiles
O O
CN CO2CH3 CN
O
CO2CH3
O
 Cycloadditions: the Diels-Alder Reaction
The stereochemistry of the reactants is preserved in the product, i.e. a cis-dienophile give cis
substituents in the product, a trans-dienophile give trans substituents in the product, i.e.

CO2CH3
CO2CH3

CO2CH3 CO2CH3

CO2CH3
CO2CH3

CO2CH3 CO2CH3
• Polymer - large molecule containing a repeating unit derived from small molecules
called monomers.
• The process of polymer formation is called polymerization.
• Polyethylene - a material that is produced on a very large scale (more than 150 billion
pounds worldwide annually)
• catalyst for polymerization is an organic peroxide.
• degree of chain branching and other features of the
polymer structure can often be controlled by the choice of
catalyst and reaction conditions.
• purple color of the permanganate ion is replaced by the brown
precipitate of manganese dioxide
• can be used as a chemical test to distinguish alkenes from alkanes
• Alkenes react rapidly and quantitatively with ozone, O3.
• Ozone is produced naturally in lightning storms, but in the laboratory, ozone is generated by passing oxygen
over a high-voltage electric discharge.
• The resulting gas stream is then bubbled at low temperature into a solution of the alkene in an inert
solvent, such as dichloromethane.
• The first product, a molozonide, is formed by cycloaddition of the oxygen at each end of the ozone
molecule to the carbon–carbon double bond.
• This product then rearranges rapidly to an ozonideexplosive – usually treated directly with a reducing
agent, commonly zinc and aqueous acid, to give carbonyl compounds as the isolated products.
Ozonolysis can be used to locate the position of a double bond.
EXIT EXERCISE
• directly attached to only two
other atoms
• bond angle = 180°
• Linear
• bond distance = 1.21 Å
• shorter than that of most
double (1.34 Å) or single
(1.54 Å) bonds
• no cis–trans isomerism is
possible for alkynes
• sp-Hybrid orbitals are half s and
half p in character.
• The angle between two sp
orbitals is 180°.
• extend in opposite directions
from the carbon atom
• One valence electron - in each
sp-hybrid orbital
• two valence electrons – in two
different p orbitals that are
perpendicular to each other
and perpendicular to the hybrid
sp orbitals.
• many addition
reactions described
for alkenes also
occur
• slower

* ordinary nickel or platinum catalyst, alkynes are hydrogenated all the way to alkanes
 Lindlar’s catalyst limits addition of hydrogen to an alkyne to 1 mole and produces a
cis alkene.

 Unsymmetric triple bonds and unsymmetric reagents Markovnikov’s Rule

• Addition of water to alkynes requires not only an acid catalyst but mercuric ion
• Mercuric ion - forms a complex with the triple bond and activates it for addition
• Similar to that of alkenes  the initial product— vinyl alcohol or enol—rearranges to a
carbonyl compound
• hydrogen atom on a triply bonded carbon is weakly acidic
• can be removed by a very strong base

• As the hybridization at carbon becomes more s-like

and less p-like, the acidity of the attached hydrogen
increases.
• s orbitals are closer to the nucleus than are p
orbitals
• the bonding electrons are closest to the carbon
nucleus in the C-H bond, making it easiest for a base
to remove that type of proton