CM2127 – Organic Chemistry

Alkenes
Reaction mechanisms

1
 Objectives of this lecture

• Explain the structure of alkenes

• Be able to name alkenes.

2
 Saturated and
Unsaturated Hydrocarbons

CH3CH2CH2CH3 CH3CH=CHCH3
An alkane An alkene
A saturated hydrocarbon An unsaturated hydrocarbon
CH3CCCH3
An alkene
An unsaturated hydrocarbon

Saturated hydrocarbons have no double bonds.

Unsaturated hydrocarbons have one or more double/triple
bonds.
3
 Molecular Formula of Alkenes
Molecular formula of alkanes = CnH2n+2

Molecular formula of alkenes with 1 p bond = CnH2n

In general, number of H atoms = 2n + 2 – 2 for every π

bond

CH3CH2CH2CH3 CH3CH=CHCH3

C4H10 An alkane C4H8 An alkene

4
 Nomenclature of Alkenes
1) Replace “ane” of alkane with “ene.”
H2C=CH2 CH3CH=CH2
Ethene (ethylene) Propene (propylene)

2) The functional group gets the lowest possible number.

CH3CH2CH=CH2 CH3CH=CHCH3
1-butene 2-butene

CH3CH=CHCH2CH2CH3
2-hexene
5
 Nomenclature of Alkenes
Number in the direction so that the C=C functional
group gets the lowest number.

CH3 CH2CH3
| |
CH3CH=CHCHCH3 CH3C=CHCH2CH2CH3
4-methyl-2-pentene 3-methyl-3-heptene

6
 Nomenclature of Alkenes
Substituents are stated in alphabetical order.

CH3 CH2CH3
| | 6-ethyl-3-methyl-3-octene
CH3CH2C=CHCH2CHCH2CH3

Cl

5-bromo-4-chloro-1-heptene

Br
7
 Nomenclature of Alkenes

CH3CH2CH2C=CHCH2CHCH3 2,5-dimethyl-4-octene
| | Not
CH3 CH3 4,7-dimethyl-4-octane
(because 2 < 4)

CH3CHCH=CCH2CH3 2-bromo-4-methyl-3-hexene
| | Not
Br CH3 5-bromo-3-methyl-3-hexene
(because 2 < 3)

8
 Vinylic and Allylic Carbons

vinylic carbons

RCH2CH=CHCH2R

Allylic carbon Allylic carbon

• vinylic carbon: the sp2 carbon of an alkene.

• allylic carbon: a carbon adjacent to a vinylic carbon
9
 Double bonds have restricted rotation
- While C atoms can rotate around a C-C single bond,
they cannot rotate around a C=C double bond.
- Double bonds in alkenes restrict rotation.

http://philschatz.com/chemistry-book/contents/m51058.html
https://creativecommons.org/licenses/by/4.0/
10
Six Atoms around the double bond are in the
Same Plane

H3C CH3
C C
H3C CH3
The 6 C atoms are in the same plane.
11
 Stereoisomers : cis–trans Isomers

cis-1,2-dichloroethene trans-1,2-dichloroethene
Bp: 60.3°C Bp: 47.5°C

• Alkenes can form stereoisomers : cis / trans isomers

• cis: H atoms are on the same side of the double bond.
• trans: H atoms are on opposite sides of the double bond.

• cis and trans isomers have different physical properties.

12
https://en.wikipedia.org/wiki/Cis%E2%80%93trans_isomerism
 Stereoisomers : cis–trans Isomers

cis-2-pentene trans-2-pentene

https://en.wikipedia.org/wiki/Cis%E2%80%93trans_isomerism
13
 Stereoisomers : cis–trans Isomers
• We use the cis–trans notation when there are only two
different substituents on the double bond.
• If all 4 substituents on the double bond are different,
we use the E/Z notation.
• Z (German “zusammen”) means "together".
• E (German “entgegen”) means "opposed" (i.e.
opposite).
• Higher atomic numbers are given higher priority.
• Determine the priority of each substituent.
• If both the higher-priority substituents are on the
same side, the arrangement is Z; if on opposite sides,
the arrangement is E.
14
 Stereoisomers : cis–trans Isomers
Br Cl Br F

H F H Cl
(Z)-2-bromo-1-chloro-1- (E)-2-bromo-1-chloro-1-
fluoroethene fluoroethene

• ( )-2-butene • ( )-2-butene
• cis-2-butene • trans-2-butene 15
 Revision Quiz 3
Which set of answers is organized in order from highest
to lowest priority?

a. –CH2NH2 > –CN > –COOH > –NH2

b. –COOH > –CN > –CH2NH2 > –NH2

c. –NH2 > –CN > –CH2NH2 > –COOH

d. –NH2 > –COOH > –CN > –CH2NH2

e. –CN > –NH2 > –CH2NH2 > –COOH

16
 Revision Quiz 5
Which of the following structures is an E-isomer?

1 2

H CH2OH CH
(H3C) 3CH2
2HC CH2OH
a. 1

b. 2 H3CD CH2CO2H CH22CH

ClH (Cl)CH
2C 2 CH2OCH3

c. 3
3
d. 1 & 2
H3C CH2NH2
e. 1 & 3

17
Some alkenes do not have cis–trans
Isomers

Cl

CH3 CH2CH3

18
 Nomenclature of Cyclic Alkenes
For cyclic alkenes, a number is not needed to denote the
position of the C=C functional group; it is always
between C1 and C2.

CH2CH3

3-ethylcyclopentene 4,5-dimethylcyclohexene
 Nomenclature of Alkenes
Cl

Cl

1,6-dichlorocyclohexene 5-ethyl-1-methylcyclohexene
not not
2,3-dichlorocyclohexene 4-ethyl-2-methylcyclohexene
(because 1 < 2) (because 1 < 2)
 Revision Quiz 2

Which is the correct name for the following compound?

a. 1-methyl-2-chlorocylohex-2-ene Cl
b. 1-chloro-2-methylcylohex-2-ene
c. 2-methyl-3-chlorocyclohexene
d. 6-chloro-1-methylcylohexene
e. 3-chloro-2-methylcyclohexene

21
 Properties of alkenes
1) Physical properties
• Very similar to alkanes.
• Less dense than water.
• B.p. increases with increasing MW.
• Relatively non-polar and insoluble in water.

2) Chemical properties
• Alkanes are relatively inert.
• Alkenes undergo many reactions.
• Alkenes have electrons that they are willing to
share, and are reactive with electrophiles
(electron-loving species).
22
 Saturated and Unsaturated Fats

Saturated fats : no C=C bonds. https://en.wikipedia.org/wiki/Saturated_fat

Mono-unsaturated fats : one C=C bond.

Poly-unsaturated fats : more than 1 C=C bond. 23
Saturated and Unsaturated Fats
https://en.wikipedia.org/wiki/Saturated_fat

24
Trans Fat https://en.wikipedia.org/wiki/Trans_fat

25
 Summary

• Explain the structure of alkenes

• Be able to name alkenes.

26
CM2127 – Organic Chemistry

Alkenes
Reaction mechanisms

27
 Objectives of this lecture

• Be able to draw reaction mechanism using

curved arrows.

• Explain the factors that affect the rate and

progression of reactions.

• Explain the differences between reactive

intermediates and transition states.

28
 Reaction mechanisms
• We want to understand how organic reactions take
place i.e. how the products are formed from the
reactants.

• A reaction mechanism describes the events that occur

at the molecular level as reactants become products.

• Very often, the reaction takes place in more than one

step, and we want to know what are chemical
intermediates are formed before the products.

29
 Reactions of Organic Compounds

• Organic compounds can be divided into families.

• The family a compound belongs to depends on its

functional group.

• All members of a family react in similar ways.

30
 Each Family Can Be Put in One
of Four Groups

Groups Alkenes Alkyl halides Carbonyl Aromatics

Families Alkenes Alkyl halides
Aldehydes
in the Alkynes Alcohols Benzenes
Ketones
group Dienes Ethers
Typical
Addition
reactions Elimination Addition
Addition Elimination
of the Substitution Substitution
Substitution
group

31
 Electrophiles
An electrophile (Lewis acid) has
• a positive charge,
• a partial positive charge,
• or an incomplete octet.

+
H+ CH3CH2

32
 Nucleophiles
A nucleophile (Lewis base) has
• a negative charge
• or a lone pair.

OH- Cl- CH3NH2 H2 O

These are nucleophiles

because they all have a pair
of electrons to share.

33
 Revision Quiz 9
Which of the following can behave as a nucleophile?

CH3CH=CH2 (CH3)3N CH3-O- CH3CCH

1 2 3 4

a. 1
b. 2
c. 3
d. 4
e. All of these

34
A Nucleophile wants to react with an Electrophile

electrophile nucleophile

CH3CH=CHCH3 + H-Br  CH3CH-CH2CH3 + Br-

+
nucleophile electrophile carbocation

CH3CH-CHCH3
2-bromobutane | |
(alkyl halide) Br H

Your first organic reaction is a two-step reaction.

35
 Curved Arrows
• Curved arrows are used to show the mechanism of a
reaction.

• The curved arrow shows the movement of an electron

pair.

• The curved arrow does not show the movement of

atoms.

• The curved arrow begins with a covalent bond or a lone

pair of electrons and points toward a site of electron
deficiency.
36
 Curved Arrows
p bond has
s bond breaks broken

_ _
CH3CH=CHCH3 + H Br  CH3CH CHCH3 + Br-
+ |
A curved arrow
indicates where the H
electrons start from New s bond
and where they end up has formed

first step of the reaction

37
 Curved Arrows
The curved arrow shows where the electrons start from and
where they end up

CH3CH-CHCH3 + Br-  CH3CH-CHCH3

+ | | |

H Br H
New s bond

second step of the reaction

38
 How to Draw Curved Arrows
O H
incorrect
C
H3C CH3

O H
O

C C + H+
H3C CH3 correct
H3C CH3

O H
incorrect
C
H3C CH3 39
 How to Draw Curved Arrows

correct O O

H3C C Br H3C C + Br -

CH3 CH3

incorrect
O

H3C C Br

CH3 40
 How to Draw Curved Arrows

correct O O

C + HO- H3C C OCH3

H 3C OCH3
OH

O
+ HO-
C
H 3C OCH3
incorrect 41
 How to Draw Curved Arrows

correct
+
CH3CH=CHCH3 + H-Br  CH3CH-CHCH3 + Br-
|
H

CH3CH=CHCH3 + H-Br

incorrect 42
 Thermodynamics and Kinetics

Y Z

1) Thermodynamics answers the question how much

products are formed.
• Acid-base equilibrium
• Le Chatelier’s principle

2) Kinetics answers the question how fast the products

are formed.
• Electrophile, nucleophile
• Order of reaction
43
 A Reaction Coordinate Diagram
• A reaction coordinate diagram shows the energy
changes that take place in each step of a reaction.

• An energy barrier exists between the reactants and

the products.

• The difference in free energy between the reactants

and products is given by:

 free energy   free energy 

G       
 of products   of reactants 
44
 A Reaction Coordinate Diagram
A---B---C

A-B + C
Free energy
of products
A + B-C
Free energy of
reactants

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 Exergonic reaction
• In an exergonic reaction, the change in the free
energy is negative (i.e. there is a net release of free
energy).

G   0

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 Endergonic reaction
• In an endergonic reaction, the change in the free
energy is positive (i.e. there is a net absorption of
free energy).

G   0

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 The Equilibrium Constant
Thermodynamics

reactants products

[ products]
K eq 
[reactants ]

The equilibrium constant Keq gives the relative

concentration of reactants and products at equilibrium.
48
 The Equilibrium Constant and free energy

G    RT ln K eq

G  0  K eq  1 G  0  K eq  1
products favored reactants favored
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 Rate of a Reaction (kinetics)
The rate of a chemical reaction depends on :
 number of   fraction with   fraction with 
 Rate of       
    collisions per    sufficient    proper 
 reaction   unit time   energy   orientation 
     

• Increasing the concentration increases the rate.

• Increasing the temperature increases the rate.

• The rate can also be increased by a catalyst.

50
 The Rate of a Reaction

A  B
 C  D
• For a first order reaction:

Rate = k[A]

where k is the rate constant for the reaction

51
 The Rate of a Reaction

A  B
 C  D
• For a second order reaction:

Rate = k[A][B]

where k is the rate constant for the reaction

52
 The Arrhenius Equation
The rate constant is given by:

Ea

k  Ae RT

where
- A is Arrhenius constant. It pertains to the frequency
of collisions in the correct orientation.
- Ea is the activation energy
- T is absolute temperature.
- The exponential term refers to the fraction of
molecules with energy larger than Ea. 53
 A Reaction Coordinate Diagram
• The transition state (TS) lies at the top of the energy
hill.
• The transition state represents a species in which
bonds are being broken and/or bonds are being
formed.
• It is very unstable, has very short lifetime and cannot
be isolated.

Transition state
Bonds are partially broken
and partially formed 54
 A Reaction Coordinate Diagram
A---B---C

A-B + C
Free energy
of products
A + B-C
Free energy of
reactants

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 A Reaction Coordinate Diagram
• The height of the energy barrier above the level of the
reactants is called the free energy of activation DG.

DG = DH - TDS

DG = Ea - TDS
Ea

k  Ae RT

• Ea is related to the energy required to partially break

the bonds in the reactants to form the TS.
• The stronger the bonds, the larger the Ea, the smaller
the value of k and the reaction rate. 56
 Fast versus slow reactions

https://en.wikipedia.org/wiki/Transition_state_theory 57
 A 2-step reaction revisited

carbocation

CH3CH=CHCH3 + H-Br  CH3CH-CH2CH3 + Br-

+

CH3CH-CHCH3
2-bromobutane | |
(alkyl halide) Br H

58
 A 2-step reaction revisited – transition states

CH3CH=CHCH3 + H-Br Step 1

H
H3C C C CH3
H Partially formed bond
TS H

Br Partially broken bond

CH3CH-CH2CH3 + Br-
+
59
 A 2-step reaction revisited – transition states

CH3CH-CH2CH3 + Br- Step 2

+

H
H3C C CH2CH3
TS
Br

CH3CH-CHCH3
| |
Br H 60
Reaction Coordinate Diagram for a 2-step reaction

https://en.wikipedia.org/wiki/Solvent_effects
61
 Reactive intermediates and TS
• The carbocation formed after step 1 is a reactive
intermediate.

• A reactive intermediate is quite reactive and is usually

much higher in energy than the reactant or product.

• Reactive intermediates can be observed with special

instruments, but are usually too unstable to be isolated.

• Reactive intermediates are lower in energy than the

transition states.

62
 Rate-limiting step
• In chemical kinetics, the overall rate of a reaction is
often approximately determined by the slowest step,
known as the rate determining step (RDS) or rate-
limiting step.
• Given a reaction coordinate (energy diagram), the rate
determining step can be determined by taking the
largest Ea between any starting material or
intermediate on the diagram and any transition state
that comes after it. That transition state will then be the
rate-determining step of a given reaction.
• The transition state with highest absolute energy may
not necessarily correspond to the rate determining step.
63
Reaction Coordinate Diagram for a 2-step reaction

https://en.wikipedia.org/wiki/Solvent_effects
64
 Catalysts and enyzmes
• A catalyst provides a pathway for a reaction with a
lower energy barrier.

• A catalyst does not change the energy of the starting

point (the reactants) or the energy of the end point
(the products).

• A catalyst is not consumed in the reaction.

• Enzymes are biological catalysts (usually proteins).

65
 Catalysts and enyzmes

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 Revision Quiz 10
The rate of a chemical reaction depends on which of the
following?

a. the concentration of reactants

b. the temperature at which the reaction is carried out
c. the fraction of collisions that occur with the proper
orientation
d. the presence of a catalyst
e. all the above

67
 Revision Quiz 11
Which of the following statements about catalysts is false?

a. A catalyst decreases the activation energy of a

reaction.
b. A catalyst does not change the energy of the
reactants or products.
c. A catalyst increases the amount of product formed.
d. A catalyst increases the rate of a reaction.
e. A catalyst is not consumed in a reaction.

68
 Summary

• Be able to draw reaction mechanism using

curved arrows.

• Explain the factors that affect the rate and

progression of reactions.

• Explain the differences between reactive

intermediates and transition states.

69