Structure of Alkenes

• Alkenes (and alkynes) are unsaturated hydrocarbons

• Alkenes have one or more double bonds
• The two bonds in a double bond are different:
- one bond is a sigma () bond; these are cylindrical
in shape and are very strong
- the other is a pi (π) bond; these involve sideways
overlap of p-orbitals and are weaker than  bonds
• Alkenes are flat and have a trigonal planar shape
around each of the two C’s in a double bond
 Addition Reactions of Alkenes and Alkynes
• Addition (combination) reactions have the form
A + B  AB
• For alkenes the general reaction has the form
R2C=CR2 + A-B  R2AC-CBR2
(where R = any alkyl group or H)
• Addition reactions are the most common types of
reactions for alkenes and alkynes
• The π bonds are easily broken, and that pair of
electrons can form a new  bond
• The reactions are favorable because the products (all
 bonds) are more stable than the reactants
 Hydrogenation of Alkenes and Alkynes
• H2 can be added to alkenes or alkynes to form alkanes
• Usually a metal catalyst (Pt, Pd or Ni) is used to speed up the
reaction (the reaction generally doesn’t work without a catalyst)
• Because these reactions take place on a surface, hydrogenation
of substituted cycloalkenes produces cis products.
Examples:
H H

H 2C CH2 + H2 H H

H H

H H

HC CH + 2H2 H H

H H

H
CH3 + H2 CH3

CH3 H CH3
 Addition of H2 - Reduction
• Virtually all alkenes add H2 in the
presence of a transition metal
catalyst, commonly Pd, Pt, or Ni
H3 C H
Pd
C C + H2 CH3 CH2 CH2 CH3
25°C, 3 atm
H CH3 Butane
trans-2-Butene

Pd
+ H2
25°C, 3 atm
Cyclohexene Cyclohexane
 Hydrohalogenation of Alkenes
• Hydrogen halides (HCl, HBr or HI) can add to alkenes to form
haloalkanes
• When a hydrogen halide adds to a substituted alkene, the halide
goes to the more substituted C (Markovnikov’s rule)
Examples:
H H H Br

C C + HBr H C C H

H H H H

H H H Cl

C C + HCl H C C H

H CH3 H CH3

CH3
CH3

+ HI I

H H
H
 Addition of HX
– reaction is regioselective
– Markovnikov’s rule: H adds to the less
substituted carbon and X to the more
substituted carbon

Cl H H Cl
CH3 CH=CH2 + HCl CH3 CH-CH2 CH3 CH-CH2
Propene 2-Chloropropane 1-Chloropropane
(not formed)
 Mechanism of hydrohalogenation
• Hydrohalogenation takes place in two steps
• In the first step, H+ is transferred from HBr to the alkene to
form a carbocation and bromide ion
• Second, Br- reacts with the carbocation to form a bromoalkane
Example:

H H H H
C C + H Br H C C + Br
H CH3 H CH3

H H H Br

H C C + Br H C C H

H CH3 H CH3
 Addition of Water to Alkenes
• In the presence of a strong acid catalyst (HCl, H2SO4 etc.)
alkenes react with H2O to form alcohols
• Recall that acids form H3O+ in water; it is the H3O+ that reacts
with the alkene
• Hydration reactions follow Markovnikov’s rule
Examples:
H H Acid H OH
Cat.
C C + H 2O H C C H

H H H H

H CH3 Acid H OH
Cat.
C C + H 2O H C C CH3

H H H H

CH3
CH3 Acid
Cat. OH
+ H 2O
H
H
H
 Mechanism of Acid-Catalyzed Alkene Hydration
• First, the alkene reacts with H3O+ to form a carbocation
• Next an H2O quickly reacts with the carbocation to form a protonated alcohol
• In the last step the proton is removed by an H2O to form an alcohol

H CH3 H H CH3
O
C C + H O H C C + H H
H H H H H

H CH3 H O H
O
H C C + H H
H C C CH3

H H H H

H O H H O H H
O
H C C CH3 + H H
H C C CH3 + H O
H H H H H
 Halogenation of Alkenes and Alkynes
• Halogens (Cl2 or Br2) can add to alkenes or alkynes to form
haloalkanes
• Alkenes form dihaloalkanes; alkynes form tetrahaloalkanes
• Reaction with cycloalkenes produces a trans product
Examples:

H H Br H

C C + Br2 H C C H

H H H Br

Br

+ Br2

Br

Br Br
H C C CH3 + 2Br2 H C C CH3

Br Br
 Addition of Cl2 and Br2
• Addition takes place readily at room temperature
– reaction is generally carried out using pure reagents, or mixing
them in a nonreactive organic solvent
Br Br
CH3 CH=CHCH3 + Br2 CH3 CH-CHCH3
CH2 Cl2
2-Butene 2,3-Dibromobutane
Br
+ Br2
CH2 Cl2
Br
Cyclohexene 1,2-Dibromocyclohexane

– addition of Br2 is a useful qualitative test for the presence of a

carbon-carbon double bond
 Mechanism of Bromonation of Ethene
• First, a Br+ is transferred from Br2 to the alkene to form a
bromonium ion and a bromide ion
• Next, the bromide ion reacts with the bromonium ion to form
the product

H H Br
H H
C C + Br Br C C + Br

H H H H

Br Br H
H H
C C + Br H C C H
H H H Br
 Polymers
• A polymer is a long chain of repeating subunits called
monomers
- examples of natural polymers: DNA, protein, starch
- example of synthetic polymers: polyethylene
• Many synthetic polymers are made from alkenes,
although other functional groups are also used
• The monomers are added to the chain through a series
of addition reactions
• Polymerization reactions usually require high
temperature and pressure and are often radical
reactions carried out with a catalyst
 Polymerization
• From the perspective of the organic
chemical industry, the single most important
reaction of alkenes is polymerization
– polymer: Greek: poly, many and meros, part
– monomer: Greek: mono, single and meros, part

nCH2 =CH2 initiator

CH2 CH2 n
(polymerization)
Ethylene Polyethylene
 Polymerization
– show the structure of a polymer by placing parentheses
around the repeating monomer unit
– place a subscript, n, outside the parentheses to indicate that
this unit repeats n times
– the structure of a polymer chain can be reproduced by
repeating the enclosed structure in both directions
– following a section of polypropene (polypropylene)
monomer units shown in red

n
CH3 CH3 CH3 CH3 CH3
CH2 CH-CH2 CH-CH2 CH-CH2 CH CH2 CH
n
Part of an extended polymer chain The repeating unit
 Polyethylene
• Low-density polyethylene (LDPE)
– a highly branched polymer; polymer chains do not pack well and
London dispersion forces between them are weak
– softens and melts above 115°C
– approximately 65% used for the production of films for packaging
and for trash bags
• High-density polyethylene (HDPE)
– only minimal chain branching; chains pack well and London
dispersion forces between then are strong
– has higher melting point than LDPE and is stronger
– can be blow molded to squeezable jugs and bottles
 Aromatic Compounds
• Aromatic compound: a hydrocarbon that contains
one or more benzene-like rings
– arene: a term used to describe aromatic compounds
– Ar-: a symbol for an aromatic group derived by removing
an -H from an arene
– Kekulé structure for benzene (1872)

H
H C H
C C
C C
H C H
H
A Kekulé structure A Kekulé structure
showing all atoms as a line-angle formula
 Conjugated Alkenes and Aromatic Compounds
• Recall that a double bond consists of one  bond and one 
bond; a  bond is formed by sideways overlap of two p
orbitals (one electron comes from each orbital)
• A conjugated alkene has alternating double and single bonds
• The p orbitals overlap in a conjugated system (the  electrons
are “delocalized” throughout the system), making conjugated
alkenes more stable than non-conjugated alkenes
• An aromatic hydrocarbon consists of alternating double and
single bonds in a flat ring system
• Benzene (C6H6) is the most common aromatic hydrocarbon
• In benzene all the double bonds are conjugated, and so the 
electrons can circulate around the ring, making benzene more
stable than 1,3,5-hexatriene (the p orbitals on the end of a
chain can not overlap)
1,3,5-hexatriene
 Resonance Structures
• There are two ways to write the structure of benzene
• These are called “resonance structures”
• However, neither of these represents the true structure of
benzene since benzene has only one structure, with all C-C
bonds being equivalent
• The true structure is a hybrid of the the two resonance
structures; this can be represented by drawing the  bonds as a
circle
• We use the individual resonance structures when we write
reaction mechanisms involving benzene to show more clearly
the bond formation and bond breaking in the reaction
 Benzene
Delocalized electrons are not confined
between two adjacent bonding atoms, but
actually extend over three or more atoms.
 Naming Monosubstituted Benzene Compounds
• Benzene compounds with a single substituent are named by
writing the substituent name followed by benzene
• Many of these compounds also have common names that are
accepted by IUPAC (you should know those listed here)
CH3 OH NH2 OCH3

Toluene Phenol Analine Anisole

(methylbenzene) (hydroxybenzene) (aminobenzene) (methoxybenzene)

O H O OH
C C

Benzaldehyde Benzoic Acid Styrene

(benzenecarbaldehyde (benzenecarboxylic acid) (phenylethene)
 Naming Multisubstituted Benzene Compounds
• When there are 2 or more substituents, they are numbered to
give the lowest numbers (alphabetical if same both ways)
• Disubsituted benzenes are also named by the common prefixes
ortho, meta and para
Examples:
Br CH3

Cl

Br

meta-dibromobenzene ortho-chlorotoluene
(1,3-dibromobenzene) (1-chloro-2-methylbenzene)

OH NH2

Br

para-ethylphenol 4-bromo-2-fluoroanaline
(1-hydroxy-4-ethylbenzene) (1-amino-4-bromo-2-fluorobenzene)
 Nomenclature
• For three or more substituents:
– if one of the substituents imparts a special name, name the
molecule as a derivative of that parent
– if none of the substituents imparts a special name, number
the substituents to give the smallest set of numbers, and
list them in alphabetical order before the ending "benzene"

CH3 OH NO2
1
2 NO2 Br 6
1
2 Br 4
3

2
3 5 3
4 4
1
Br
Cl Br CH2 CH3
4-Chloro-2- 2,4,6-Tribromophenol 2-Bromo-1-ethyl-4-
nitrotoluene nitrobenzene
 Nomenclature
– phenyl group (C6H5- or Ph-): the substituent
group derived by loss of an H from benzene

4 2
3 1
C6 H5
Phenyl group 1-Phenylcyclohexene 4-Phenyl-1-butene
 PAHs
• Polynuclear aromatic hydrocarbon (PAH)
– a hydrocarbon that contain two or more
benzene rings, with each pair of rings sharing
two adjacent carbon atoms

Naphthalene Anthracene Phenanthrene Benzo[a]pyrene

 Physical Properties of Aromatic Compounds
• Because aromatic compounds (like benzene) are flat, they
stack well, and so have higher melting and boiling points than
corresponding alkanes and alkenes (similar to cycloalkanes)
• Substituted aromatic compounds can have higher or lower
melting and boiling points than benzene
- para-xylene has a higher m.p. than benzene
- ortho and meta-xylene have lower m.p.’s than benzene
• Aromatic compounds are more dense than other hydrocarbons,
but less dense than water (halogenated aromatics can be more
dense than water, as can haloalkanes)
• Aromatic compounds are insoluble in water, and are
commonly used as solvents for organic reactions
• Aromatic compounds are also flammable, and many are
carcinogenic
 Chemical Reactivity of Aromatic Compounds
• Aromatic compounds do not undergo addition reactions because
they would lose their special stability (aromaticity)
• Instead, they undergo substitution reactions, which allow them
to retain their aromaticity
• We will study three types of substitution reactions of benzene:
halogenation, nitration and sulfonation
Addition:
Br

+ Br 2
Br

Aromatic Loses aromaticity

Substitution:
Br
FeBr3
+ Br 2 + HBr

Aromatic Retains Aromaticity

 Halogenation of Benzene and Toluene
• Br2 or Cl2 can react with benzene, using a catalyst, to form
bromobenzene or chlorobenzene
• Only the monohalogenation product is produced
• When Br2 or Cl2 reacts with toluene, a mixture of isomers
is produced
- Ortho and para isomers are the major products, and meta
isomer is the minor product
Examples:

Cl
FeCl3
+ Cl 2 + H Cl

CH3
CH3 CH3 CH3

Br
FeBr3
+ Br2 + +
Br
+ H Br Br
(Minor)
 Mechanism of Bromonation of Benzene
• First, a Br+ is transferred from Br2 to benzene, forming a
carbocation and a chloride ion
• Next, the chloride ion removes an H+ from the carbocation
to form chlorobenzene and HBr

Br
H
FeBr3
+ Br Br + Br

Br
H Br

+ Br + H Br
 Nitration and Sulfonation of Benzene
• Nitric acid can react with benzene, using sulfuric acid as a
catalyst, to form nitrobenzene plus water
• First H2SO4 donates a proton to HNO3, which then
decomposes to form H2O and NO2+ (the reactive species)
• Sulfur trioxide plus sulfuric acid (fuming sulfuric acid) can
react with benzene to produce benzenesulfonic acid
• First H2SO4 donates a proton to SO3 to produce HSO3+ (the
reactive species)
NO2
H2SO4
+ HNO3 + H 2O

SO3 H
H2SO4
+ SO3