ORGANIC CHEMISTRY

CHM032 ORGANIC CHEMISTRY FOR TEACHERS

FELIPA GISELA dL. TENIDO

Department of Chemistry
College of Science and Mathematics
FGdLTenido Department of Chemistry , College of Science and Mathematics 2
 CHAPTER 3
Alkenes and Alkynes:
The Nature of
Organic Reactions

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 3

The pink color of flamingo feathers is caused by the
presence in the bird’s diet of -carotene, a polyalkene.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 4
 Alkenes

sometimes called olefins

hydrocarbons that contain a carbon–carbon double bond, C = C
occur abundantly in nature
e.g. ethylene – plant hormone that induces ripening in fruits
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 5
 Alkenes

 – pinene - a major component of turpentine

Turpentine oil is made from the resin of certain pine trees.
It is used as medicine.
Turpentine oil is applied to the skin for joint pain, muscle pain, nerve pain, and
toothaches.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 6

 Alkenes

• β – carotene - an orange pigment in some fruits and

vegetables
• precursor of vitamin A
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 7
 Alkynes
hydrocarbons that contain a carbon–carbon triple bond,
C ≡C

The simplest acyclic alkynes with only one triple

bond and no other functional groups form a
homologous series with the general chemical formula
CnH2n−2.
Alkynes are traditionally known as acetylenes,
although the name acetylene also refer specifically
to C2H2, ethyne
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 8
 Alkynes
Hybridization due to triple bonds allows the
uniqueness of alkyne structure.

Hybridization : sp

This triple bond contributes to the nonpolar

bonding strength, linear, and the acidity of
alkynes.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 9
Properties of Alkenes and Alkynes

Their physical properties are similar to those

of alkanes with the same carbon skeletons.
They are nonpolar compounds.
The only attractive forces between their
molecules are very weak London dispersion
forces (Van der Waal’s forces).

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 10

Properties of Alkenes and Alkynes

Alkenes and alkynes that are liquid

at room temperature have
densities less than 1.0 g/mL (they
float on water).

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 11

Properties of Alkenes and Alkynes

Soluble in nonpolar solvents

(kerosene, hexane, CHCl3, CCl4)
Insoluble in water
Low boiling point and melting point

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 12

3.2 Electronic Structure of Alkenes

C atoms in a double bond have three equivalent sp2

hybrid orbitals at angles of 120° to one another
the fourth C orbital is an unhybridized p orbital
perpendicular to the sp2 plane
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 13
 3.2 Electronic Structure of Alkenes

 sigma (σ) bond is formed by head-on overlap of sp2

orbitals
 pi (π) bond is formed by sideways overlap of p orbitals
 The doubly bonded carbons and the four attached atoms
lie in a plane, with bond angles of approximately 120°.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 14
 3.2 Electronic Structure of Alkenes

restricted rotation
The π bond must break momentarily for rotation
around a carbon–carbon double bond to take place,
requiring a large amount of energy.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 15
3.2 Electronic Structure of Alkenes

The energy barrier to rotation around a double bond must be at

least as great as the strength of the π bond itself, an estimated
350 kJ/mol (84 kcal/mol).

rotation barrier for a single bond is only about 12 kJ/mol

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 16
3.3 Cis – Trans Isomers of Alkenes
cis and trans isomers of but-2-ene

The cis isomer has the two methyl groups on the same
side of the double bond, and the trans isomer has the
methyl groups on opposite sides.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 17
3.3 Cis – Trans Isomers of Alkenes
cis and trans isomers of but-2-ene

Because bond rotation can not occur, the two but-2-enes

can not spontaneously interconvert and are different
chemical compounds.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 18
3.3 Cis – Trans Isomers of Alkenes

Cis alkenes are less stable than their trans isomers

due to steric (spatial) interference (steric strain)
between the large substituents on the same side of
the double bond.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 19

3.3 Cis – Trans Isomers of Alkenes

Cis–trans isomerism is not limited to

disubstituted alkenes.
It occurs whenever each double-bond
carbon is attached to two different groups.
If one of the double-bond carbons is
attached to two identical groups cis–trans
isomerism is not possible.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 20
3.3 Cis – Trans Isomers of Alkenes

cis–trans isomers are possible only when both carbons are

bonded to two different groups

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 21

 practice exercise

Draw the cis and trans isomers of 5-chloropent-2-ene.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 22

 practice exercise
Draw the cis and trans isomers of 5-chloropent-2-ene.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 23

3.3 Cis – Trans Isomers of Alkenes
• Neither compound is clearly
“cis” or “trans”
– Substituents on C1 are
different than those on C2
– We need to define
“similarity” in a precise way to
distinguish the two
stereoisomers
• Cis, trans nomenclature only
works for disubstituted double
bonds
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 24
3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)

Assign a priority to the substituents

on each carbon of the double bond
E (German: entgegen, opposite)
- higher priority groups are on
opposite sides of the double bond
Z (German: zusammen, together)
- higher priority groups are on the
same side of the double bond

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 25

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)

RULE 1
Considering the double-bond carbons separately, look
at the atoms directly attached to each carbon and
rank them according to atomic number.
The atom with the higher atomic number has the
higher ranking, and the atom with the lower atomic
number (usually hydrogen) has the lower ranking.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 26

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)

example

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 27

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)
RULE 2
If a decision can not be reached by ranking the first
atoms in the substituents, look at the second, third,
or fourth atoms away from the double-bond carbons
until the first difference is found.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 28

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 29

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)
RULE 3
Multiple-bonded atoms are equivalent to the same
number of single-bonded atoms.
example
an aldehyde substituent ( - CH = O), which has a
carbon atom doubly bonded to one oxygen, is equivalent
to a substituent having a carbon atom singly bonded to
two oxygens
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 30
3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 31

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 32

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 33

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)
Name the following compounds:

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 34

3 .4 Sequence Rules : The E,Z Designation
(Cahn – Ingold Prelog)
Name the following compounds:

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 35

practice exercise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 36

practice exercise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 37

3.5 Kinds of Organic Reactions

addition reactions
• occur when two reactants add
together to form a single new
product with no atoms “left
over”

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 38

 3.5 Kinds of Organic Reactions
addition reactions
example
the reaction of fumarate with water to yield malate a
step in the citric acid cycle of food metabolism

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 39

 3.5 Kinds of Organic Reactions
addition reactions
example
the reaction of an alkene with HCl to yield an alkyl
chloride

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 40

3.5 Kinds of Organic Reactions

elimination reactions
• the opposite of addition reactions
• occur when a single organic
reactant splits into two products,
often with the formation of a
small molecule such as H2O or HCl
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 41
3.5 Kinds of Organic Reactions
elimination reactions
example
the acid-catalyzed reaction of an alcohol to yield
water and an alkene

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 42

3.5 Kinds of Organic Reactions

substitution reactions
• occur when two reactants
exchange parts to give two new
products

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 43

 3.5 Kinds of Organic Reactions
substitution reactions
example
the reaction of an alkane with Cl2 in the presence of
ultraviolet light to yield an alkyl chloride

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 44

3.5 Kinds of Organic Reactions

rearrangement reactions
• occur when a single organic
reactant undergoes a
reorganization of bonds and atoms
to yield a single isomeric product

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 45

3.5 Kinds of Organic Reactions
rearrangement reactions
example
the conversion of but-1-ene into trans-but-2-ene by
treatment with an acid catalyst

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 46

3.6 How Reactions Occur : Mechanisms

Mechanism
• an overall description of how a reaction
occurs
• describes what takes place at each stage of
a chemical transformation
• which bonds are broken and in what order
• which bonds are formed and in what order
• what are the relative rates of the steps
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 47
3.6 How Reactions Occur : Mechanisms
Mechanism : example

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 48

3.6 How Reactions Occur : Mechanisms
Mechanism : example

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 49

3.6 How Reactions Occur : Mechanisms

all chemical reactions involve

bond-breaking in the reactant molecules
bond-making in the product molecules
the electrons in those bonds must move
about and reorganize

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 50

3.6 How Reactions Occur : Mechanisms

two possible ways of bond breaking

a) symmetrical (homolytic) – one electron
remains with each of the product fragment
b) unsymmetrical (heterolytic) - both electrons
remain with one product fragment, leaving the
other fragment with a vacant orbital

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 51

3.6 How Reactions Occur : Mechanisms
bond breaking

homolytic cleavage

heterolytic cleavage
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 52
3.6 How Reactions Occur : Mechanisms

two possible ways of bond formation

a) symmetrical – one electron is donated
to the new bond by each reactant
b) unsymmetrical – both bonding electrons
are donated by one reactant

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 53

 3.6 How Reactions Occur : Mechanisms
bond formation

Note : the movement of one electron in the symmetrical process

is indicated using a half-headed, or “fishhook,” arrow
while the movement of two electrons in an unsymmetrical process
is indicated using a full-headed curved arrow

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 54

3.6 How Reactions Occur : Mechanisms

A process that involves symmetrical bond breaking

and bond formation is called a radical reaction.

radical or free radical

neutral chemical species
contains an odd number of electrons
has a single, unpaired electron in one of its
orbitals

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 55

3.6 How Reactions Occur : Mechanisms

A process that involves unsymmetrical bond breaking

and bond formation is called a polar reaction.

Polar reactions
involve species that have an even number of electrons
and thus have only electron pairs in their orbitals

Polar processes are the more common reaction type in

organic and biological chemistry.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 56

3.6 How Reactions Occur : Mechanisms
Effects of bond polarity in chemical reactions
greater e- density
(e-rich site)

greater e- density
(e-rich site)

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 57

3.6 How Reactions Occur : Mechanisms
Effects of bond polarity in chemical reactions

electron-rich sites in one molecule react with electron-

poor sites in another molecule or within the same
molecule
bonds are made when an electron-rich atom shares a
pair of electrons with an electron-poor atom
bonds are broken when one atom leaves with both
electrons from the former bond

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 58

3.6 How Reactions Occur : Mechanisms
Effects of bond polarity in chemical reactions

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 59

3.6 How Reactions Occur : Mechanisms
Nucleophiles and Electrophiles

Nucleophile
 a substance that is “nucleus loving” and thus
attracted to a positive charge
 has a negatively polarized, electron-rich atom
 can form a bond by donating an electron pair to a
positively polarized, electron-poor atom
 can be either neutral or negatively charged and
usually have lone-pairs of electrons

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 60

3.6 How Reactions Occur : Mechanisms
Nucleophiles and Electrophiles

Nucleophiles

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 61

3.6 How Reactions Occur : Mechanisms
Nucleophiles and Electrophiles
Strong Nucleophiles
usually anions with a full negative charge
recognizable by the presence of sodium, lithium or
potassium ions
examples : NaOCH3, LiCH3, NaOH or KOH,
NaCN or KCN, NaNH2, NaNHR,
NaNR2, NaI, KI, NaN3
Neutral Nucleophiles
examples : H2O, ROH, H2S, RSH
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 62
3.6 How Reactions Occur : Mechanisms
Nucleophiles and Electrophiles

Electrophile
• is “electron-loving”
• has a positively polarized, electron-poor atom
and can form a bond by accepting a pair of
electrons from a nucleophile
• can be either neutral or positively charged
• examples: acids (H+ donors), alkyl halides,
carbonyl compounds
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 63
3.6 How Reactions Occur : Mechanisms
Nucleophiles and Electrophiles
Electrophile

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 64

practice exercise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 65

practice exercise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 66

practice exercise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 67

practice exercise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 68

practice exercise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 69

3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 70

3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

electrophilic addition reaction

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 71
3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

ethylene : H2C = CH2

carbon–carbon double bond results from orbital overlap of
two sp2-hybridized carbon atoms
the  part of the double bond results from sp2–sp2 overlap
the  part of the double bond results from p–p overlap

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 72

3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

the valence electrons in alkanes are relatively inaccessible

because they are tied up in strong, nonpolar C - C and C - H
 bonds between nuclei
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 73
3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

the  electrons in alkenes are accessible to external

reagents because they are located above and below
the plane of the double bond rather than between the nuclei
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 74
3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

an alkene  bond is much weaker than an alkane 

bond
an alkene is more reactive
C = C bonds behave as nucleophiles in much of their
chemistry
alkenes typically react by donating an electron pair
from the double bond to form a new bond with an
electron-poor, electrophilic partner
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 75
3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

hydrogen chloride : H  Cl
as a strong acid, HCl is a powerful proton (H+) donor
a good electrophile
the reaction of HCl with ethylene is therefore a typical
electrophile–nucleophile combination as in all polar reactions
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 76
3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

The mechanism of
the electrophilic
addition of HCl to
ethylene.
The reaction takes
place in two steps
and involves an
intermediate
carbocation.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 77

3.7 The Mechanism of an Organic Reaction :
Addition of HCl to Ethylene

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 78

 practice exercise
What product would you expect from reaction of HCl with cyclohexene?

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 79

 practice exercise
What product would you expect from reaction of HCl with cyclohexene?

Strategy
HCl adds to the double-bond functional group in
cyclohexene in exactly the same way it adds to
ethylene, yielding an addition product.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 80
 practice exercise
What product would you expect from reaction of HCl with cyclohexene?

Solution

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 81

 3.8 Describing a Reaction :
Transition States and Intermediates
for a reaction to take place
reactant molecules must collide
reorganization of atoms and bonds occur

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 82

 3.8 Describing a Reaction :
Transition States and Intermediates
addition reaction of HCl and ethylene

H2C = CH2 and H ― Cl approach each other

the C = C  bond and the H ― Cl bond break
new C ― H bond forms in the first step
new C ― Cl bond forms in the second step
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 83
 3.8 Describing a Reaction :
Transition States and Intermediates

To depict graphically the energy changes that

occur during a reaction, chemists use energy
diagrams.
The vertical axis of the diagram represents
the total energy of all reactants, and the
horizontal axis, called the reaction coordinate,
represents the progress of the reaction from
beginning to end.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 84
 3.8 Describing a Reaction :
Transition States and Intermediates

as H2C = CH2 and HCl

molecules crowd
together

their electron clouds

repel each other

causing the energy

level to rise

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 85

 3.8 Describing a Reaction :
Transition States and Intermediates

if the collision has

occurred with
sufficient force and
proper orientation
the reactants continue
to approach each other
despite the repulsion
until the new C – H bond
starts to form and the
H – Cl bond starts to
break

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 86

 3.8 Describing a Reaction :
Transition States and Intermediates

at some point,
a structure of
maximum energy
is reached

a structure called
the transition
state

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 87

 3.8 Describing a Reaction :
Transition States and Intermediates

the transition
state represents
the highest-energy
structure involved
in the step of the
reaction
can not be isolated
or directly
observed
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 88
 3.8 Describing a Reaction :
Transition States and Intermediates

the transition state

is a kind of activated
complex of the two
reactants

the C = C  bond is
partially broken

the new C – H bond is

partially formed

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 89

 3.8 Describing a Reaction :
Transition States and Intermediates

Eact is the energy

difference
between the
reactants and the
transition state

Eact is a measure
of how rapidly the
reaction occurs
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 90
 3.8 Describing a Reaction :
Transition States and Intermediates

large Eact results

in a slow reaction
because few of
the reacting
molecules collide
with enough
energy to reach
the transition
state
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 91
 3.8 Describing a Reaction :
Transition States and Intermediates

small Eact results in

a rapid reaction

almost all reacting

molecules are
energetic enough
to climb to the
transition state

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 92

 3.8 Describing a Reaction :
Transition States and Intermediates

Eact of most organic reactions is in the range of 40 to

125 kJ/mol or 10 to 30 kcal/mol

reactions with activation energies less than 80

kJ/mol take place at or below room temperature

reactions with higher activation energies often

require heating to give the molecules enough energy
to climb the activation barrier
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 93
 3.8 Describing a Reaction :
Transition States and Intermediates

once the high-energy

transition state has
been reached
energy is released as
the new C – H bond
forms fully
curve turns downward
until it reaches a
minimum

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 94

 3.8 Describing a Reaction :
Transition States and Intermediates

the minimum energy is

the energy level of
the carbocation

the carbocation
formed transiently
during the course of
the multistep reaction

reaction intermediate

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 95

 3.8 Describing a Reaction :
Transition States and Intermediates

carbocation
intermediate formed
in the first step

immediately reacts
with Cl– in a second
step

to give the final

product chloroethane

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 96

 3.8 Describing a Reaction :
Transition States and Intermediates

the second step has its

own Eact2 and transition
state

an activated complex
between the electrophilic
carbocation intermediate
and nucleophilic Cl– anion

new C – Cl bond is
partially formed

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 97

 3.8 Describing a Reaction :
Transition States and Intermediates

curve turns
downward as
the C – Cl bond
forms fully to
give the final
addition
product
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 98
 3.8 Describing a Reaction :
Transition States and Intermediates

each individual step in

the reaction has its
own energy change
represented by the
difference in levels
between reactant and
intermediate (step 1)
intermediate and
product (step 2)

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 99

 3.8 Describing a Reaction :
Transition States and Intermediates

the energy
difference
between initial
reactants and final
products is the
overall energy
change for the
reaction, Erxn

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 100
 3.8 Describing a Reaction :
Transition States and Intermediates

if the energy level of the product is lower than that of the

reactants
Eproduct < Ereactant
Erxn = Eproduct - Ereactant = ( ― )

energy is released
exothermic reaction
favorable reaction

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 101
 3.8 Describing a Reaction :
Transition States and Intermediates

if the energy level of the product is higher than that of the

reactants
Eproduct > Ereactant
Erxn = Eproduct - Ereactant = ( + )

energy is absorbed
endothermic reaction
unfavorable reaction

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 102
 3.8 Describing a Reaction :
Transition States and Intermediates

Eproduct < Ereactant

Erxn = ( ― )
exothermic reaction
two - step reaction
slower step
rate-determining step
step 1

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 103
 3.8 Describing a Reaction :
Transition States and Intermediates
A sketch of an energy diagram for a one-step reaction that is fast
and releases a large amount of energy.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 104
3.8 Describing a Reaction : Catalysis

catalyst
substance that increases the rate of a
chemical transformation by providing an
alternative mechanism
pathway with lower activation energy for
the reaction

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 105
3.8 Describing a Reaction : Catalysis

catalyst

takes part in the reaction, but is

regenerated at some point

undergoes no net change

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 106
3.8 Describing a Reaction : Catalysis

in the absence of palladium, an alkene undergoes no reaction with H2

gas even at high temperature
in the presence of palladium, reaction occurs rapidly at room
temperature
hydrogenation reaction
process used industrially to convert liquid vegetable oil to
solid cooking fats
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 107
3.8 Describing a Reaction : Catalysis

Enzymes are large, structurally complex catalysts

provide reaction mechanisms that proceed through a series
of small steps rather than through one or two large steps
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 108
 Summary and Keywords
All chemical reactions, whether in the
laboratory or in living organisms, follow the
same “rules.”
To understand both organic and biological
chemistry, it is necessary to know not just
what occurs but also why and how chemical
reactions take place.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 109
 Summary and Keywords
Alkenes are hydrocarbons that contain a
carbon–carbon double bond, C = C.
Alkynes are hydrocarbons that contain a
carbon–carbon triple bond, C Ξ C.
Because they contain fewer hydrogens than
related alkanes, alkenes are often referred to
as unsaturated.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 110
 Summary and Keywords
A double bond consists of two parts:
a σ bond formed by head-on overlap of
two sp2 hybrid orbitals and
a π bond formed by sideways overlap of
two p orbitals
Because rotation around the double bond is not
possible, substituted alkenes can exist as
cis–trans isomers.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 111
 Summary and Keywords

cis isomer have both substituents

on the same side of the double
bond
trans isomer have substituents on
opposite sides

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 112
 Summary and Keywords
The trans isomer is more favored than
the cis isomer.
Cis alkenes are less stable than their
trans isomers because of steric (spatial)
interference between the large
substituents on the same side of the
double bond.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 113
 Summary and Keywords

Cis–trans isomerism is not limited to

disubstituted alkenes.
It occurs whenever each double-
bond carbon is attached to two
different groups.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 114
 Summary and Keywords
The geometry of a double bond can be
described by the E, Z system as either
E (entgegen) or Z (zusammen)
by application of a series of sequence rules
that rank the substituent groups on the
double-bond carbons.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 115
 Summary and Keywords
Organic chemical reactions can be organized
either by what kinds of reactions occur or
by how reactions occur.
There are four broad types of organic
reactions:
additions, eliminations, substitutions, and
rearrangements.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 116
 Summary and Keywords
A full description of how a reaction occurs is
called its mechanism.

There are two kinds of organic mechanisms:

polar and radical.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 117
 Summary and Keywords
Polar reactions, the most common kind, involve
even-electron species and occur when an electron
rich reagent, or nucleophile, donates an electron
pair to an electron-poor reagent, or electrophile, in
forming a new bond.
Radical reactions involve odd-electron species and
occur when each reactant donates one electron in
forming a new bond.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 118
 Summary and Keywords
all chemical reactions involve
bond-breaking in the reactant molecules
bond-making in the product molecules

the electrons in those bonds must move

about and reorganize

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 119
 Summary and Keywords
A reaction can be described pictorially by using an
energy diagram, which follows the course of the
reaction from reactant to product.

Every reaction proceeds through a transition

state, which represents the highest-energy point
reached and is a kind of activated complex
between reactants.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 120
 Summary and Keywords
The amount of energy needed by reactants
to reach the transition state is the
activation energy, Eact .

The larger the activation energy, the

slower the reaction.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 121
 Summary and Keywords
A catalyst can sometimes be used to
increase the rate of a reaction by
providing an alternative mechanistic
pathway.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 122
 Summary and Keywords
Many reactions take place in more than one
step and involve the formation of an
intermediate.
An intermediate is a species that is formed
during the course of a multistep reaction
and that lies in an energy minimum between
two transition states.
FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 123
 Summary and Keywords

Intermediates are more

stable than transition states
but are often too reactive to
be isolated.

FOC McMurry 7th ed Brooks/Cole 2011 FGdLTenido Department of Chemistry , CSM 124
Thank You