TOPIC 20

ORGANIC
CHEMISTRY
20.1
TYPES OF ORGANIC REACTIONS

ESSENTIAL IDEA
Key organic reaction types include nucleophilic
substitution, electrophilic addition, electrophilic substitution
and redox reactions. Reaction mechanisms vary and help in
understanding the different types of reactions taking place.
NATURE OF SCIENCE (3.1)

Looking for trends and discrepancies by understanding different types

of organic reactions and their mechanisms, it is possible to synthesize
new compounds with novel properties which can then be used in
several applications. Organic reaction types fall into a number of
different categories.
NATURE OF SCIENCE (4.1 and 4.5)

Collaboration and ethical implications scientists have collaborated to

work on investigating the synthesis of new pathways and have
considered the ethical and environmental implications of adopting
green chemistry.

INTERNATIONALMINDEDNESS
What role does green and
sustainable chemistry, in
relation to organic chemistry,
play in a global context?

ORGANIC REACTIONS
Organic reactions are broadly organized
according to what happens (type of
reaction) and how it happens (the
mechanism of the reaction).
Many organic mechanisms describe the
reactants according to electrophilic and
nucleophilic behavior.

 Nucleophiles are reactants that are

electron rich so they are very attracted to
electron deficient atoms.
Nucleophiles have a lone pair of electrons
and may also carry a negative charge.
They act as Lewis bases.
H2O, OH-, NH3, CN Electrophiles are electron deficient and
accept electron pairs from a nucleophile.
They act as Lewis acids: H+, Br+ and NO2+.

GUIDANCE
Be able to differentiate between
homolytic and heterolytic
fission.

GUIDANCE
Know the difference between
curly arrows and fish-hooks in
reaction mechanisms.

 The curly arrow represents the motion of an

electron pair, with the tail showing where the
electrons come from and the full arrow showing
where they are going.
The fishhook notation (half arrow on curve)
shows movement of one electron.
Heterolytic fission both electrons go to one
product and two oppositely charged ions are
produced
Homolytic fission the shared pair of electrons
are split evenly between the 2 atoms
Leaving group the halogen that becomes
detached in the reaction.

GUIDANCE

www.chemistry.about.com

GUIDANCE
Typical conditions and reagents
of all reactions should be known
such as catalysts, reducing
agents, reflux, etc. Specific
temperatures need not be
specified.

UNDERSTANDING/KEY
IDEA 20.1.A

SN1 represents a nucleophilic

unimolecular substitution reaction
and SN2 represents a nucleophilic
bimolecular substitution reaction.
SN1 involves a carbocation
intermediate. SN2 involves a
concerted reaction with a transition
state.

UNDERSTANDING/KEY
IDEA 20.1.B
For tertiary halogenoalkanes, the
predominant mechanism is SN1 and
for primary halogenoalkanes, it is
SN2. Both mechanisms occur for
secondary halogenoalkanes.
Nucleophilic Substitution Reactions

APPLICATION/SKILLS
Be able to deduce the
mechanism of the nucleophilic
substitution reactions of
halogenoalkanes with aqueous
sodium hydroxide in terms of
SN1 and SN2 mechanisms.
Nucleophilic Substitution Reactions

NUCLEOPHILIC
SUBSTITUTION
REACTIONS

The polarity in halogenoalkanes is due to the fact that

the halogen atom is more electronegative than carbon
and therefore it exerts a stronger pull on the shared
electrons in the carbon-halogen bond.
The halogen gains a partial negative charge and the
carbon gains a partial positive charge and is said to be
electron deficient.
This electron deficient carbon defines much of the
reactivity of the halogenoalkanes.
Nucleophiles are reactants that are electron rich so
they are very attracted to electron deficient atoms.
Nucleophiles have a lone pair of electrons and may
also carry a negative charge: H2O, OH-, NH3, CN-

 The nucleophiles are attracted to the electron deficient

carbon in the halogenoalkane which leads to a reaction
where substitution of the halogen occurs.
This reaction is called Substitution Nucleophilic and
has the shorthand notation of SN.
During this reaction, the carbon-halogen bond breaks and the
halogen is released as a halide ion.
When both of the shared electrons go to one product, it is
known as heterolytic fission.
The halogen that becomes detached is sometimes referred to
as the leaving group.

C2H5Br + OH-

C2H5OH + Br-

PRIMARY
HALOGENOALKANES S N2
MECHANISM
Primary halogenoalkanes have at least two
hydrogens attached to the carbon of the carbonhalogen bond.
Because the hydrogen atoms are so small, the
carbon is pretty open to an attack from the
nucleophile.
The rate of this one-step mechanism is dependent
upon the concentration of both the
halogenoalkane and the hydroxide ion, it is known
as a bimolecular reaction.
This mechanism is fully described as SN2:
substitution nucleophilic bimolecular.
CH3Cl + OH- CH3OH + Cl-

www.iversion.cm.utexas.edu

This is a one-step concerted reaction

with an unstable transition state.
Note the nucleophile attacks the
electrophilic carbon atom on the opposite
side of the leaving group which causes
an inversion in the arrangement of the
atoms around the carbon atom. (Like an
umbrella blowing inside out)

 The SN2 reaction is stereospecific

because the three-dimensional
arrangement of the reactants determines
the three-dimensional configuration of
the products.
This happens because bond formation
comes before bond cleavage in the
transition state and the stereochemistry
is not lost.

TERTIARY
HALOGENOALKANES:
S N1 MECHANISM
Tertiary halogenoalkanes have three
alkyl groups attached to the carbon of the
carbon-halogen bond.
These bulky alkyl groups make it difficult
for an incoming group to attack the
carbon atom causing steric hindrance.

GUIDANCE
Be able to make reference to
heterolytic fission in SN1
reactions.
Nucleophilic Substitution Reactions

 The first step of the reaction is ionizing the halide ion

heterolytically leaving the carbon with a temporary
positive charge called carbocation.
The second step is the attack of the carbon atom by
the nucleophile leading to the formation of the new
bond.
Because the rate-determining step is determined only
by the concentration of the halogenoalkane, it is
described as unimolecular.
The reaction mechanism is fully described as SN1:
substitution nucleophilic unimolecular.

 You should be able to write rate equations for

the rate-determining step in both reaction
mechanisms using your knowledge of kinetics.

UNDERSTANDING/KEY
IDEA 20.1.C

The rate determining step (slow

step) in an SN1 reaction depends
only on the concentration of the
halogenoalkane, rate =
k[halogenoalkane]. For SN2, rate =
k[halogenoalkane][nucleophile]. SN2
is stereospecific with an inversion
of configuration at the carbon.

UNDERSTANDING/KEY
IDEA 20.1.D
SN2 reactions are best conducted
using aprotic, polar solvents and
SN1 reactions are best conducted
using protic, polar solvents.
Nucleophilic Substitution Reactions

APPLICATION/SKILLS
Be able to outline the difference
between protic and aprotic
solvents.
Nucleophilic Substitution Reactions

S N2 prefers polar,
aprotic solvents

Aprotic solvents are those which are not

able to form hydrogen bonds as they do
not contain OH or NH bonds.
They may have strong dipoles.
They solvate the metal ion rather than the
nucleophile.
The unsolvated bare nucleophile has a
higher energy state and increases the rate of
reaction.
Examples are propanone, ethanenitrile and
ethyl ethanoate.

S N1 prefers polar, protic

solvents
Protic solvents are those which are able
to form hydrogen bonds and they do
contain OH or NH bonds.
They stabilize the carbocation intermediate.
They do this by solvation involving ion-dipole
interactions.
Examples are water, alcohols and carboxylic
acids.

APPLICATION/SKILLS
Be able to explain why hydroxide is
a better nucleophile than water.
Nucleophilic Substitution Reactions

HYDROXIDE A BETTER
NUCLEOPHILE
Nucleophiles are reactants that are
electron rich so they are very
attracted to electron deficient atoms.
Nucleophiles have a lone pair of
electrons and may also carry a
negative charge: H2O, OH-, NH3, CN The hydroxide ion is a stronger
nucleophile than water because it
carries a negative charge.

APPLICATION/SKILLS
Be able to explain how the rate
depends on the identity of the
halogen (ie the leaving group),
whether the halogenoalkane is
primary, secondary or tertiary
and the choice of solvent.
Nucleophilic Substitution Reactions

IDENTITY OF THE
HALOGEN
The identity of the halogen influences the rate of
the nucleophilic substitution.
There are however two opposing factors.
1. The polarity of the carbon-halogen bond
Electronegativity decreases down Group 7
The carbon-halogen bond becomes progressively less
electron deficient so it is less vulnerable to nucleophilic
attack.
We would expect fluoroalkane to be the most reactive
and iodoalkane to be the least.

HOWEVER.

 2. Strength of the carbon-halogen bond

Bond energy data shows that the carbon-halogen
bond decreases in strength from fluorine to
iodine.
Since nucleophilic substitution involves the
breaking of this bond, one would expect that the
iodoalkane to be the most reactive and
fluoroalkane to be the least reactive.
Reaction rate data indicates that the carbonhalogen bond strength dominates the outcome.
Iodoalkanes>bromoalkanes>chloroalkanes>fluoroalkanes

RATE OF REACTION
The rate of nucleophilic substitution
reactions in halogenoalkanes depends
on the class of the halogenoalkane.
It is fastest with tertiary halogenoalkanes
with the SN1 mechanism and slowest with
primary halogenoalkanes with the SN2
mechanism.

UNDERSTANDING/KEY
IDEA 20.1.E
An electrophile is an electrondeficient species that can accept
electron pairs from a nucleophile.
Electrophiles are Lewis acids
(electron pair acceptors).
Electrophilic Addition Reactions

APPLICATION/SKILLS
Be able to deduce the
mechanism of the electrophilic
addition reactions of alkenes
with halogens/interhalogens and
hydrogen halides.
(Interhalogens are compounds made up of two
or more halogens.)

Electrophilic Addition Reactions

ELECTROPHILIC
ADDITION REACTIONS
Alkenes are unsaturated molecules and
readily undergo addition reactions.
An addition reaction occurs when two
reactants combine to form a single
product.
This type of reaction is characteristic in
compounds containing double or triple
bonds (unsaturated compounds).

 The carbon atoms of a double bond are

sp2 hybridized and have a trigonal planar
shape with bond angles of 120 degrees.
This is a fairly open structure making it
relatively easy for groups to attack.

The bond is composed of a sigma bond

and a pi bond which has an area of
electron density above and below the
plane of the bond axis.

 Because the electrons in the pi bond are

less closely associated with the nuclei, it
is a weaker bond than the sigma bond
and so breaks more easily during the
addition reactions.
Because the pi bond is and area of
electron density, it is very attractive to
electrophiles (species that are electron
deficient).

 Reactions between electron deficient

reagents and alkenes are known as
electrophilic addition reactions.
There are four types of these
mechanisms that we will study.

Alkenes + halogens
Alkenes + hydrogen halides
Alkenes + interhalogens
Unsymmetrical alkenes + hydrogen halides

ALKENES + HALOGENS
(Ethene + bromine)
When ethene gas is bubbled through
bromine, the brown color disappears as it
forms 1,2-dibromoethane.

http://www.bbc.co.uk/staticarchive

Remember that the color change shows

presence of unsaturation.

 The mechanism is as follows:

Bromine, a non-polar molecule, becomes polarized
as it approaches the electron rich area of the
alkene.
The electron rich area repels the electrons on the
bromine molecule causing an area of positive
charge and an area of negative charge.

 The bromine atom nearest the alkenes double

bond gains a partial positive charge and acts
as the electrophile.
The bromine molecule splits heterolytically
forming Br+ and Br- and the initial attack on the
ethene in which the pi bond breaks is carried
out by Br+.
This first step is slow forming an unstable
positive carbocation intermediate.

 This carbocation then reacts rapidly with

the negative bromide ion forming the
product.

 If you mix this reaction with the presence

of chlorine ions, the carbocation readily
reacts with either the Cl- or Br- ions.
However, no dichloro compound is ever
formed confirming that the initial attack is
from the Br+ ion.

ALKENES + HYDROGEN HALIDES

(Ethene + hydrogen bromide)
The reaction occurs by a similar reaction
as alkenes + halogens.
HBr is a polar molecule that undergoes
heterolytic fission to form H+ and Br-.
The electrophile, H+, attacks the alkenes
double bond.
The unstable positive carbocation
intermediate then reacts readily with the
Br- to form the addition product.

 A piece of evidence that supports this

mechanism is that the reaction if favored by a
polar solvent that facilitates the production of
ions from heterolytic fission.
HI > HBr > HCl

ALKENES + INTERHALOGENS

(Ethene + BrCl)

An interhalogen is a compound made up

of two halogens.
Chlorine is more electronegative than
bromine so BrCl is polarized so that Br
has a partial positive charge and is the
electrophile and Cl has the partial
negative charge and will react with the
carbocation.
Draw the reaction mechanism.

UNDERSTANDING/KEY
IDEA 20.1.F
Markovnikovs rule can be applied to
predict the major product in electrophilic
addition reactions of unsymmetrical
alkenes with hydrogen halides and
interhalogens. The formation of the
major product can be explained in terms
of the relative stability of possible
carbocations in the reaction mechanism.

Electrophilic Addition Reactions

UNSYMMETRIC
ADDITION

(Propene + hydrogen bromide)

When unsymmetric alkenes react, there

are two different products that can form
resulting from the two possible pathways
that come from the two possible
carbocations that can form.
The difference comes from whether the
attacking electrophile bonds to carbon 1
in the double bond or carbon 2.
The answer comes from which pathway
will give the most stable carbocation.

MARKOVNIKOVS RULE
The electrophile will attack the carbon
that is already bonded to the greater
number of hydrogens.
Or it can be stated that the electrophile
will bond to the carbon with the smaller
number of carbons attached.
The negative species will go to the
carbon with the most carbons attached.

SAMPLE PROBLEM
Write the names and structures for the
two possible products of the addition of
the interhalogen BrCl to propene.
Which is likely to be the major product?
Explain.

Solution

UNDERSTANDING/KEY
IDEA 20.1.G
Benzene is the simplest aromatic
hydrocarbon compound (or arene) and
has a delocalized structure of bonds
around its ring. Each carbon to carbon
bond has a bond order of 1.5. Benzene is
susceptible to attack by electrophiles.

Electrophilic Substitution Reactions

ELECTROPHILIC
SUBSTITUTION
REACTIONS
(BENZENE)
Benzene is highly unsaturated due to its three
double bonds, but it does not behave like
alkenes.
The benzene ring favors substitution reactions
over addition reactions.
Benzene is very attractive to electrophiles
because of its high electron density.
The delocalized cloud of pi electrons seeks
electron-deficient species and forms a new bond
when a hydrogen is lost.

 The mechanism of electrophilic

substitution follows a similar pathway
with different electrophiles.
The reaction has a high activation energy
and proceeds slowly.

 The E+ is the electrophile.

The first step is slow with a high activation
energy.
The incomplete circle in the center shows a loss
of symmetry with the positive charge distributed
over the bulk of the molecule.
Loss of H+ from the intermediate leads to
substitution.

APPLICATION/SKILLS
Be able to deduce the mechanism of
the nitration (electrophilic
substitution) reaction of benzene
(using a mixture of concentrated
nitric acid and sulfuric acid).
Electrophilic Substitution Reactions

NITRATION OF BENZENE
The nitration of benzene is the
substitution of an H by NO2 to form
nitrobenzene, C6H5NO2.
The overall reaction is
Conc H SO
C6H6 + HNO3 50 C C6H5NO2 + H2O
2

The electrophile is the nitronium ion, NO2+.

This ion is generated by using a nitrating
mixture which is mixture of concentrated nitric
and sulfuric acid at 50C.

 The sulfuric acid protonates the nitric

acid which then loses a molecule of
water to produce NO2+.

 NO2+ is a strong electrophile and reacts with the

pi electrons of the benzene ring to form the
carbocation intermediate.
Loss of a proton from this leads to reformation of
the arene ring in the product nitrobenzene which
appears as a yellow oil.
The H+ released reacts with the base HSO4- to
reform sulfuric acid.

UNDERSTANDING/KEY
IDEA 20.1.H
Carboxylic acids can be reduced to
primary alcohols (via the aldehyde).
Ketones can be reduced to secondary
alcohols. Typical reducing agents are
lithium aluminium hydride (used to
reduce carboxylic acids) and sodium
borohydride.
Reduction Reactions

APPLICATION/SKILLS
Be able to write reduction reactions
of carbonyl containing compounds:
aldehydes and ketones to primary
and secondary alcohols and
carboxylic acids to aldehydes, using
suitable reducing agents.
Reduction Reactions

REDUCTION OF
CARBONYL COMPOUNDS

We have already seen that primary alcohols can

be oxidized to aldehydes then to carboxylic acids
and that secondary alcohols can be oxidized to
ketones.
We can reverse these reactions using a suitable
reducing agent.
Sodium borohydride, NaBH4 in aqueous or
alcoholic solution
Lithium aluminum hydride, LiAlH4, in
anhydrous conditions, such as dry ether
followed by aqueous acid.

 Both reducing agents produce the hydride

ion, H-, which acts as a nucleophile on the
electron deficient carbonyl carbon.
[+H] represents reduction just as [+O]
represents oxidation.
NaBH4 is the safer reagent but is not
reactive enough to reduce carboxylic acids
so LiAlH4 must be used in this case.

Reduction of a Ketone

Reduction of a
Carboxylic Acid

APPLICATION/SKILLS
Be able to convert nitrobenzene to
phenylamine via a two-stage
reaction.
Reduction Reactions

REDUCTION OF
NITROBENZENE
Nitrobenzene (C6H5NO2) can be
converted to phenylamine,
C6H5NH2 in a two step reduction
process.

Step 1
C6H5NO2 is reacted with a mixture of tin and
concentrated HCl.
The reaction mixture is heated under reflux in a
boiling water bath.
The product C6H5NH3+, phenylammonium ions, is
protonated because of the acidic conditions.

Step 2
C6H5NH3+ is reacted with sodium
hydroxide to remove H+ and form the
product phenylamine, C6H5NH2.

SUMMARY OF
REACTION
MECHANISMS

Citations
International Baccalaureate Organization. Chemistry Guide, First
assessment 2016. Updated 2015.
Brown, Catrin, and Mike Ford. Higher Level Chemistry. 2nd ed.
N.p.: Pearson Baccalaureate, 2014. Print.
Most of the information found in this power point comes directly
from this textbook. Photos and graphs are copied directly from the
text.
The power point has been made to directly complement the Higher
Level Chemistry textbook by Catrin and Brown and is used for
direct instructional purposes only.