Organic Chemistry

Lecture 5-6: Alkene, Alkyne

and
Aromatics

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 Unsaturated Hydrocarbons

Mom’s trick: put the fruit in rice

container to ripen faster
Why?

Ethylene: gas of ripening fruit

Oleic acid, the major fatty acid in olive

oil, is a monounsaturated fatty acid.

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 Hydrocarbons

propene 1-butene 1-pentene

Name with “-ene” at the end 3

 Alkene and Alkyne Nomenclature

• Count the number of carbon atoms in the longest continuous carbon

chain containing the double bond (alkenes) or triple bond (alkynes).
Name the alkane with the same number of carbon atoms. This is the
parent compound.
• Replace the -ane ending of the alkane with the -ene ending for an
alkene or the -yne ending for an alkyne. For example:

• Number the parent chain to give the double or triple bond the lowest
number. For example:

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 Alkene and Alkyne Nomenclature

• Determine the name and carbon number of each group bonded to the parent
alkene or alkyne, and place the name and number in front of the name of the
parent compound.
• Remember that with alkenes and alkynes the double or triple bond takes
precedence over a halogen or alkyl group, as shown in the following
examples:

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 Alkene and Alkyne Nomenclature

• Alkenes having more than one double bond are called alkadienes (two double
bonds) or alkatrienes (three double bonds). Determine which double bond is
nearest one end of the chain. Number the carbon chain by using the number of
the first carbon of each double bond, using the lowest numbers. Use the
appropriate suffix (-diene or -triene), as seen in these examples:

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 Alkene and Alkyne Nomenclature

• If after numbering to give the functional group (alkene) the lowest number,
there is still more than one possibility for numbering substituents, number to
give the lowest substituent numbers.

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Practice

8
 Practice

3 1 3-methyl-3-buten-1-ol
2
4 (or 3-methyl-but-3-en-1-ol)

Hydroxyl groups take precedence over the double bond when the chain is numbered.

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 Isomers

Natural olive oil

V-shaped flexible
molecule

H on the same side

trans fat

Rigid linear molecule

Presence in synthetic fat
Unhealthy
H on opposite sides

• Skill to master: determine cis/trans, Z/E (review lecture 4) 10

 Chemical Reactions

The key reaction of the double bond is the addition reaction. This involves the
addition of two atoms or groups of atoms to a double bond.

The major alkene addition reactions are:

1. Hydrogenation—the addition of a hydrogen atom (H2)
2. Halogenation—the addition of a halogen atom (Br2 or Cl2)
3. Hydrohalogenation—the addition of a hydrogen halide molecule (HBr or HCl)
4. Hydration—the addition of a water molecule (H2O)

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 1. Hydrogenation: Addition of H2

• Margarine: partial hydrogenation of vegetable oils.

• While natural oils contain only cis fatty acids, the
hydrogenation reaction produces trans-fatty acids.
• What are the health risks associated with trans-
fats?

Beef fat, pork fat: solid at room T (saturated fat)

Olive oil, peanut oil (plant oil) : liquid at room T (unsaturated fat)
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 2. Halogenation: Addition of X2
Halogenation proceeds readily and does not require a catalyst:

Alkynes also react with the halogens bromine or chlorine.

Two molecules of halogen add to the triple bond to produce a tetrahaloalkane:

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 2. Halogenation: Addition of X2

The bromination reaction can be used to show the presence of double or

triple bonds in an organic compound

With
Absence of alkene/alkyne
alkene/alkyne

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 3. Hydrohalogenation: Addition of HX

• A hydrogen halide (HBr, HCl, or HI) added to an alkene

Markovnikov’s rule

“the rich get richer”

the carbon with the greater
number of hydrogens gets
the new one

• For unsymmetrical alkene:

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 3. Hydrohalogenation: Addition of HX

• But with a trace amount of ROOR (alkyl peroxide):

Practice: Draw the expected major product for each of the following reactions
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 3. Hydrohalogenation: Addition of HX

Markovnikov
Addition
Mechanism:

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• Stereochemistry of hydrohalogenation

HCl

(Racemic mixture)
 3. Hydrohalogenation: Addition of HX

• A similar Markovnikov addition is observed with alkynes :

“the rich keep getting richer”

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 4. Hydration: Addition of H2O
Requires trace of strong acid (H+) as catalyst.

Markovnikov’s rule

“the rich still get richer”

Stereochemistry?

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 4. Hydration: Addition of H2O
When a new chiral center is generated, a racemic mixture of enantiomers is
expected

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 4. Hydration: Addition of H2O

• Hydration of alkyne:

Markovnikov’s rule
Enol
“the rich still get richer”

Rapidly undergo
tautomerization

Ketone

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 Alkyne and Its Molecular Rigidity

Flexibility and rigidity in drug design

Parkinson’s disease : neurodegenerative disorder

marked by a decreased dopamine in the brain

MAO B MAO A
(Increase dopamine) (Significant chest pain, nausea…)

2 enzyme with similar structure but totally

different activity

Rigidity from the aromatic and triple bond

-> the molecule effectively bind to MAO B but not avoid
MAO A

Balance of flexibility and rigidity

Alkyne functionality is used to tailor rigidity of drug
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 Polymer Production

3 pathways:
• radical polymerization,
• anionic polymerization
• cationic polymerization

Packaging, insulation, food…

Conductive polymer

Used in LED (mobile phone, TV, traffic light…)

Nobel prize (2000) 23
 Polymer Production

A mixed blessing

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Waste in Vietnam (esp. PLASTIC)

Nam Dinh

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Nguyen Viet Hung

Hung Lekima
Waste in Vietnam (esp. PLASTIC)

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Binh Thuan
 Waste in Vietnam (esp. PLASTIC)

Quang Binh

Ho Chi Minh City

and many more ….

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Waste in Vietnam (esp. PLASTIC)

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 Aromatic Molecules
• Monosubstituted aromatics

• Common names accepted by IUPAC

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 Aromatic Molecules
• Disubstituted aromatics

• Polysubstituted Derivatives of Benzene

1. Identify and name the parent.
2. Identify and name the substituents.
3. Assign a locant to each substituent.
4. Arrange the substituents alphabetically. 30
 Aromatic Molecules
• Polysubstituted Derivatives of Benzene

5-bromo-2-chlorophenol

2,4,6-Trinitrotoluene

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 Stability of Benzene
• Unusual Stability

Stabilization energy
associated with
aromaticity

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 Stability of Benzene
• Unusual Stability

Compound A is an aromatic compound with the molecular formula C8H8. When

treated with excess Br2, compound A is converted into compound B, with the
molecular formula C8H8Br2.
Identify the structures of compounds A and B.

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 Stability of Benzene
• Source of Stability

A closed-shell electron configuration -> Stable 34

 Stability of Benzene
• Cyclic with conjugated 𝜋 bonds

But they are not stable!

• Hucker’s rule:

For aromatic compound: Number of 𝜋 electrons has to be 4n+2

2, 6, 10, 14, 18…

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 Chemical Properties

Electrophilic Aromatic Substitution

H is replaced by an electrophilic group and the aromatic ring is preserved

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 Chemical Properties

Electrophilic Aromatic Substitution

Mechanism

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 Chemical Properties

1. Halogenation
FeBr3
or

2. Sulfonation

(mixture of
H2SO4 and SO3)

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 Mechanisms

1. Halogenation

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 Mechanisms

2. Sulfonation

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 Chemical Properties

3. Nitration

4. Friedel–Crafts Alkylation

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 Mechanisms

3. Nitration

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 Mechanisms

4. Friedel–Crafts Alkylation

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 Chemical Properties

5. Friedel–Crafts Acylation

Substitutions on the aromatic ring will have effects on the electrophilic

substitution reaction

How?

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 Chemical Properties

Activating group

Toluene faster than

benzene 25X times

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 Chemical Properties

Activating group R is activating group and o-p director

Tertiary carbocation -> stable

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 Chemical Properties

Activating group

Anisole faster than

toluene 400X times

Induction Net: e donating

Resonance
(e withdrawing) (e donating)
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 Chemical Properties

Activating group -OR is e donating, activator and o-p director

Extra resonance
-> stable

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 Chemical Properties

Deactivating group

Nitrobenzene less
reactive than benzene
100,000X times

Both induction + resonance: e withdrawing

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 Chemical Properties

Deactivating group -NO2 is e withdrawing, deactivator and m director

(+) charge next to N+ -> unstable 50

 Chemical Properties

Exception of Halogen

Nitration of halogenated benzene is slower than benzene

Induction
(e withdrawing) Net: e withdrawing

Resonance
(e donating)

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 Chemical Properties

Exception of Halogen -X is e withdrawing, deactivator but o-p director

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Determining the Directing Effects of a Substituent

Alkyl groups are weak activators, because they donate electron density by the relatively weak
effect of hyperconjugation 5

3
Determining the Directing Effects of a Substituent

Many of the halogens (Cl, Br, or I) are weak deactivators (due to delicate balance between
induction and resonance)

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