Organic

( Chemistry
Nomenclature The ring in the middle shows that
the double bonds are alternating,
When naming organic compounds we
not fixed to any place. This
need to be careful of the precedence of the
structure was suggested because
functional groups. The importance of
when an X-ray analysis of
functional group is as follows (most
benzene was done, it showed that
important to least): the length of carbon to carbon
bond was neither that of a single

T
Functional groups Structure or a double bond but something in
O between,
"
COOH (Carboxylic acids) R C O H
- -

Nitriles C N

O
Aldehydes ↑

R C H
O ↑
Ketones R C R

Alcohols R C O H
The p-orbitals above and below the six
carbon atoms help in creating this
Amines R NH2
delocalised structure

Alkenes C C Since every carbon atom is sp 2

-
hybridised, the shape of benzene is
hexagonal planar.
Structure of Benzene Benzene has
Benzene’s molecular formula is C6H6 but 6 C-C sp hybridised bonds
has alternating double bonds in its · 6 C-H sp22 hybridised bonds
structure. The structure suggested by
Kekule was: This alternating double bond phenomenon is
known as conjugation, which makes benzene
more stable than it would be if it was a single
static structure, and it’s property of having
multiple structures, ultimately being defined as a
hybrid of these is known as resonance.
 Reactions of Benzene
Electrophilic Substitution in Benzene

Br2 HBr
AlBr3 / FeBr3
Catalyst Br

Cl2 HCl
AlCl3/ FeCl 3
Catalyst Cl

Conc. HNO3
+ conc. H2SO4 NO2
catalyst T=55

Electrophilic Substitution Mechanism

Chlorination or Bromination,

Step 1

Br

8+ 8- Fe Br
Br Br
Br
Since the charge density in benzene This is the catalyst that
Is very weak due to the alternating double increases the polarisation in the
bonds, unlike alkenes, it is unable to bromine molecule. You can also
polarise the bromine molecule to the extent use AlBr3
which would allow for electrophilic
substitution. Therefore, to increase the
polarisation of the bromine molecule we
have to use a catalyst.
 Step 2

-1

f
I
Br
H
. Br Fe Br
Br
Br
The H atom breaks the bond
The Fe-Br bond breaks and now the
and forms HBr by using
catalyst returns to its original
the bromine atom from the
state.
FeBr4-

Br
HBr
Br Fe Br

Br

C6 H6 Br2 C6H5Br HBr

Nitration
Nitronium
Conc. HNO 3 + conc. H2SO4 Electrophile

HNO3 2H2SO4 H3O+ 2HSO4- NO2+

Step 1

NO2+
 Step 2

fi H
HSO4-
-

NO2

The H atom breaks the bond

and forms sulfuric acid,
reforming the catalyst.

H2SO4
NO2

C6 H6 HNO3 C6H5NO2
H2SO4was a catalyst

2-4 (6) Directing Groups

Why do arenes prefer electrophilic

substitution reactions rather than
Arenes Benzene + Alkyl chain addition?
For example, This is mainly because of the
delocalisation of electrons in arenes.
1. Breaking the delocalisation of
CH2 CH3 CH3 electrons requires a lot of
energy. If benzene (or any
other arene) undergoes addition
CH3
reactions, that would
permanently break the
ethyl benzene 1,3-dimethyl benzene delocalisation, and the
energetics would be against this
happening.
2. Because of the delocalisation in
benzene ring, arenes are
relatively stable. They don’t
undergo addition reactions
because it would require
breaking that bond and losing
that stability.
 What are 2-4 directing groups?

H H

4
88 2
Since alkyl chains have an electron donating
effect , this creates two region with unequal

·
C C
electron density.

H C C CH2 CH2 CH3 ⑳ The blue region has a high electron density

W because the donating effect of the alkyl chain

repels the already present electrons in the
Alkyl chain benzene ring to the extreme left side of the
C C molecule.

⑳ The red region has a high electron density

H H
because of the electron donating
... effect of the
6 alkyl chain.

Now, only carbon atoms on positions 2, 4 and 6 Therefore, now whenever an electrophilic
have high electron density. We call them “directing substitution reaction needs to take place, the
groups” because they “direct” or guide where on the electrophile will be more strongly attracted to the
benzene ring electrophilic substitution reactions will carbon atoms at positions 2, 4 and 6.
predominantly occur.

Note: We don’t call them 2-4(6) but instead we only call them 2-4
directing groups. This is because position 6 and 2 are the same
positions.

1
⑳ Electrophilic Substitution of Arenes
2-bromo methyl benzene 4-bromo methyl benzene
You should treat chlorobenzenes
the same way
-
Br Br
Br2 HBr
AlBr3 / FeBr3
CH3 Catalyst CH3 CH3
2-chloro methyl benzene 4-chloro methyl benzene
Cl Cl

Cl2 HCl
CH3 AlCl3/ FeCl 3
CH3 CH3
Catalyst
2-methyl nitrobenzene 4-methyl nitrobenzene
NO2 NO2

CH3 Conc. HNO3 CH3

CH3
+ conc. H2SO4
Note: NO2 has more importance than
catalyst T=55 methyl group
What are phenols and phenylamines and why phenols
are not considered as a subclass of alcohols?

OH NH2
When a benzene ring has a hydroxy When a benzene ring has an
group attached to it, we call such amine group or an amino
structures phenols. Even though, it substituent attached to it,
has an OH group, it is still not we call such structures
considered as an alcohol phenylamines.
Just like the alkyl chain, the OH and the amine group create an electron imbalance in
the benzene ring in the highlighted regions because of their electron-donating
effect; However,this time the effect is larger because of the lone pairs on the
oxygen and nitrogen atom. Even though phenols may contain the hydroxy group,
they are not classified as alcohols. This is because of the following reasons:

Attachment to a carbon atom Acidity

Alcohols: The -OH group is attached Alcohols: Generally less acidic because
to a sp3 hybridized carbon atom the -OH is connected to an alkyl group,
which is not part of an aromatic which is electron-donating,
ring. strengthening the OH bond.
Phenols: The -OH group is attached Phenols: More acidic compared to
to a sp2 hybridized carbon atom alcohols because the -OH is connected
which is part of an aromatic ring to an aromatic ring, which can stabilize
(usually a benzene ring). the negative charge that results from
losing a proton through resonance.
Reactivity Physical Properties

Alcohols: They generally react with Alcohols: Their physical properties

acids, bases, and other agents in are greatly influenced by the
ways defined by the properties of nature of the alkyl group attached
the alkyl group. to the hydroxyl group.
Phenols: Phenols tend to engage in Phenols: The presence of the
reactions that are characteristic of aromatic ring significantly affects
aromatic compounds, including the physical properties of phenols,
electrophilic aromatic substitution including boiling point, melting point,
reactions, which aren’t typically and solubility.
observed with alcohols.
Why do alkyl groups make alcohols less acidic, and even if they are electron-donating
shouldn’t it become easier to lose the H+ ion since there would be repulsion between
the electrons?
When considering acidity, we need to look at the stability of the conjugate base
that’s formed after deprotonation. In the case of alcohols, an alkoxide ion is
formed as a conjugate base. Since alkyl groups are electron-donating they
destabilise this negative ion by increasing its negative charge. Essentially, the more
stable the conjugate ion is after deprotonation, the more acidic is the molecule.
Phenols, on the other hand, are more acidic because their resonance structure
greatly helps in stabilising the conjugate base formed after deprotonation. The
resonance structure spreads the negative charge over a larger volume which
stabilises the phenoxide ion. Alkyl groups do not exhibit resonance so they cannot
do the same.
 What is resonance and hyperconjugation?

Resonance
Whenever a molecule has For example, look at a phenol.
alternating double bonds in its The oxygen has lone pairs which
structure it might be depicted as will delocalise into the benzene
having 2 or more Lewis structures. ring, effectively spreading the
In chemistry, we use a hydrid charge over a larger area and
OH

·
structure for these types of stabilising the molecule while
molecules which is the average of also making some positions on
its different Lewis structures. This the benzene ring more suitable
phenomenon is known as for electrophilic substitution
resonance. It doesn’t simple imply reactions.
alternating double bonds but it is a
tool to describe the electron Delocalisation doesn’t mean that the lone pair leaves its
delocalisation using multiple Lewis original atom, it just means that when the original atom is
structures. connected to something that already exhibits resonance,
the lone pairs won’t remain in the same place but these
Whenever we say that an atom or electrons would shared over several atoms, including
a substituent group stabilises due those of the resonance structure, creating a system
to the “resonance effect” it purely where the electron density is spread over more than two
implies that the atom or group in atoms.
question delocalises its lone pair
into the resonance structure which
helps spread the electron density
over a larger volume which
consequently stabilises the
resonance structure.

Hyperconjugation ·

Hyperconjugation is the stabilising interaction that Some differences between

results from the interaction of the electrons in a σ- resonance and hyperconjugation
bond (usually C-H or C-C) with an adjacent empty or
partially filled p-orbital or a π-orbital to give an σ bonds are involved in the
extended molecular orbital that increases the stability electron delocalization, not π
of the system. bonds or lone pairs.
In hyperconjugation, we’re discussing a partial overlap of It is sometimes referred to as
orbitals, where the electrons in a σ bond (typically C-H or C- “σ-conjugation” as it involves
C) are able to interact with an adjacent p-orbital or a π the interaction between σ bonds
system. This overlap is not to the extent that it breaks the σ and an adjacent p-orbital or π-
bond entirely; rather, it allows for a slight delocalization of system.
the electron density from the σ bond into the adjacent It involves the overlap of filled σ
system. This interaction helps in spreading the electron orbitals with unfilled or partially
density over a larger volume, which contributes to the filled orbitals (like p-orbitals) to
stabilization of the molecule or ion. delocalize electron density and
stabilize the system.

Both of these effects will stabilise the benzene ring but it is

important to note that the effect of hyperconjugation or its
contribution to the stability of benzene is weaker compared to
resonance
 ..
OH NH2
Large electron-donating effect Large electron-donating effect

Both of them have a larger electron donating effect than alkyl chains because both of
them have lone pairs. These lone pairs can conjugate with the system of the
benzene ring, allowing electron density to be delocalised in the ring. Both the oxygen
and nitrogen atoms might have there electron withdrawing effects too (due to
induction) but the resonance effect is stronger and dominates any electron
withdrawing effect they might have. This is why the net effect is that these groups
are more electron donating than the alkyl chain.
The main point is that phenols and phenyl amines have greater electron density at the ortho (2) and
para (4) positions which result in them forming different products than the previous reactions.

2
Electrophilic Substitution of Phenols and Phenylamines
2,4,6-tribromophenol
Br Br
3Br2 No catalyst 3HBr (White precipitate formed)
(aq) needed
OH OH
Used as a test
Br for phenols. Will
decolourise
bromine and
produce a white
precipitate.
2-nitrophenol 4-nitrophenol
NO2 NO2

OH Dilute. HNO3 OH OH
No catalyst needed
Note: OH has more importance than nitro group

2,4,6-trinitrophenol
Conc. HNO3 Phenylamines will
and conc NO2 NO2
sulfuric acid as undergo same reactions
catalyst as these, just replace
the hydroxyl group with
OH the amine group.
Yellow crystalline solid NO2
&

3(-5) Directing groups =°

=\°
=
- =
i
↳

H H
What are 3(-5) directing groups?
88 3(-5) directing groups are those groups
that are electron-withdrawing due to

·
C C
certain reasons. They withdraw electrons
from the benzene ring which decreases
H C C NO2 electron density in position 2 and 4
(opposite of before). Consequently, the
electron density at position 3 is higher than
it was before. However, since these groups
C C are electron withdrawing, the attraction
that electrophiles feel towards position 3 is
still lower because the electron density of
H H the benzene ring has been decreased.

The groups that are electron donating (which direct electron density to 2-4 positions)
and groups that are electron withdrawing (which direct electron density to position 3)
are given in the data booklet.
Br

In these reactions, the conditions

Br2 are going to be extreme since the
(aq) electron density is lower. The
conditions used are not a part of
NO2 NO2 syllabus but you should just know
that if any electrophilic
substitution was to occur the
electrophile would be attached to
Conc HNO3 the 3 position

NO2 NO2

Alkylation
(Attaching an alkyl chain to benzene)

Cl H3C
H3C C CH2 CH2 CH3 C CH2 CH2 CH3
AlCl3
H catalyst H
HCl
We just need to react benzene with a halogenoalkane
to create an arene
 Acylation
(Reacting benzene with an acyl chloride)
Acyl chlorides follow the general formula RCOCl
O
R C An acyl chloride
Cl

Mechanism of this reaction Explanation of the mechanism

When benzene reacts with an acyl

chloride, the carbon atom attached
O St
to the chlorine and oxygen atom has
C CH2 CH3 a very high partial positive charge
Cl because both oxygen and chlorine
have high electronegativity. As a
result, it is attracted to the
electrons in the benzene ring and
behaves as an electrophile. When the
electrons attack the partial positive
O charge, they will repel the electrons
S C CH2 CH3
H
in chlorine, causing chlorine to break
off and become the chloride ion.
This ion will form HCl with an
Cl-
. hydrogen atom which later breaks
off from benzene.
The same mechanism can be applied
O to alkylation and AlCl3 catalyst is also
needed for this reaction
C CH2 CH3 HCl
Both acylation and alkylation require
heating under reflux
This also works if the acyl chloride is attached to
the benzene ring. It will form a cyclic compound

Hydrolysis of chlorine related compounds

Benzene with a chlorine Halogenoalkanes Acyl chlorides

atom
Cl O
Cl H3C C CH2 CH2 CH3 C CH2 CH3
H Cl
NaOH (aq) and Vigorous reaction even
heat with reflux with cold water. White
fumes of HCl formed

No hydrolysis Very strong

hydrolysis
 Why doesn’t benzene with a chlorine ...
atom undergo hydrolysis?
Chlorobenzenes do not undergo hydrolysis reactions
↳

u
Cl
.

because of the resonance effect of the benzene

ring. The chlorine atom is an electron donating
group and the pi electrons from the benzene ring
delocalise over the chlorine atom. The resonance
stabilisation makes the chlorine atom stronger and
less polar, making it less susceptible to hydrolysis.
In simpler words, the electrons of chlorine atom in
benzene overlap with the pi electron cloud of benzene
which strengthens the C-Cl bond. Therefore this high
charge density electron cloud repels hydroxide ions/
nucleophiles.
8-
Why do acyl chloride undergo
strong hydrolysis?
O St Acyl chloride undergo strong hydrolysis
because the the carbon atom that’s partially
C CH2 CH3
3-
positive is attached to 2 highly electronegative
atoms (oxygen and chlorine) which make it
Cl highly positive. As a result, it attracts
nucleophiles and water more strongly. And C-
Cl bond is weakened.
Hydrolysis of acyl chlorides
O O
CH3 CH2 C H2O CH3 CH2 C HCl
Cl Vigorous reaction even OH
with cold water,
although slower White fumes of
HCl formed
The mechanism for this reaction (Addition/Elimination mechanism)
Step 1 8- Step 2 - ...
Step 3
O O-
O
St

CH3 CH2 C S-
CH3 CH2 C CH3 CH2 C
Cl H O
+
Cl H O
+

....

O H H
H H -

O
L

Cl
Final products: CH3 CH2 C HCl
OH
-) #
All organic acids are weak acids (partially ionise, produce fewer H+ ion.)

O
CH3 CH2 OH H2O OH CH3 CH2 C
Water OH
Alcohol
Phenol Carboxylic acid

↑
WEAKEST ACID STRONGER ACID

O
CH3 CH2 OH OH CH3 CH2 C
Alcohol OH
REACTANTS Carboxylic acid
Phenol
O
Reactive Na CH3 CH2 ONa H2 CH3 CH2 C
Metal ONa H2 H2
Redox Reaction ONa

Strong O
base NaOH NO REACTION ONa H2O CH3 CH2 C H2O
Acid-Base reaction ONa

O
Weak CH3 CH2 C H2O
Base Na2CO3 NO REACTION NO REACTION ONa
Acid-Base reaction CO2

Weak O
Base NH3 NO REACTION NO REACTION CH3 CH2 C
Acid-Base reaction ONH4+
ite -
=
(-
Alcohols
Alcohols are the weakest of the weak acids. It
ionises even less than water. The reason for this
is that alcohols have an alkyl chain. An alkyl chain
is an electron donating group and we know that
CH3 CH2 OH
the more stable a conjugate is after Electrons move
deprotonation, the more acidic is the compound. towards O
Since the conjugate ion formed after
deprotonation of alcohol already has a negative
charge on the oxygen atom, the alkyl chain
makes this more negative (and hence more
unstable) since it is electron-donating. CH3 CH2 O- H+
Another explanation is that since the oxygen is u Strongly
now highly negative, it will be very difficult for Electron donating attracted
the hydrogen atom to break the bond. Even if due to high
the hydrogen atom breaks the bond and negative
becomes an ion, it is strongly attracted to the charge on O
alkoxide ion which has a high charge density in
the oxygen atom
Phenols
Phenols are stronger acids than alcohols because Less attraction
of the benzene ring. After deprotonation, the
lone pairs on the oxygen atom delocalise over
the benzene ring pi electron cloud, effectively O- H+
spreading the negative charge over a larger
volume (Less attraction for H+ ion). This makes
the phenoxide ion relatively more stable and a Lesser
weaker conjugate base. Since the conjugate Relatively weaker charge
formed is more stable than the alkoxide ion conjugate base density
(conjugate of alcohol), phenols will dissociate
more than alcohols.
Comparison of acid strength within phenols
Phenols with an alkyl chain are less acidic than
just a phenol without any alkyl chains. This is
again due to the electron-donating nature of
alkyl groups. The alkyl group on a phenol CH3 CH2 CH2 O- H+
donates electrons and consequently causes -
higher charge density. This makes the phenol ELECTRON
with an alkyl chain more unstable compared to DONATING
just a phenol.
Higher charge
If a group other than an alkyl chain was attached to a phenol, density (more
and it had an electron withdrawing effect, then that unstable)
compound would be more acidic than a phenol because it
reduces the charge density which makes the conjugate ion
more stable and hence it will be more acidic
=) e
↑
Why are carboxylic acids relatively the
strongest acids? O
In carboxylic acids, the highly electronegative
CH3 CH2 C
O- H+
oxygen atom in the C=O bond has a strong
electron-withdrawing effect. This reduces the
charge density of the RCOO- ion which
consequently makes it more stable. There is a
lesser attraction for the H+ ion, leading to more
dissociation. O
It is important noting that since alkyl chains
also have their electron donating effects, the CH3 CH2 CH2 CH2 C -
more alkyl chains connected to the acid, the
less acidic will be the carboxylic acid. However
since the inductive effect decreases with
u O
distance and is most significant in the first 3 Larger electron
carbon atoms, the difference in acidity donating effect
between propanoic acid and some other Higher charge density,
carboxylic acid with more than 3 carbon atoms more unstable, more
in its alkyl chain is likely to be very small. attraction for H+
Therefore the more longer the alkyl chain is in
a carboxylic acid, the weaker the acid is.

Cl substituted carboxylic acids

Carboxylic acids with Cl atoms are more acidic G-
O
than normal carboxylic acids because Cl has a
high electronegativity and has an electron Cl CH2 CH2 C
withdrawing effect. This reduces the charge
density of the carboxylate ion and makes it O-
more stable, thus increasing the acidity of the Electron Lesser
compound. withdrawing charge
effect density
The more chlorine atoms there are in a
carboxylic acid, the more acidic is the compound
because of the greater electron withdrawing
effect of not one but multiple Cl atoms.
The position of the Cl atom is also important
when comparing 2 compounds for their acidity.
Cl O
The Cl atom that is closest to the OH bond in
carboxylic acid will have higher electron CH3 CH C
withdrawing effect than the Cl atom that is
placed further away. Therefore the closer the
O-
Cl atom the more acidic is the compound. More acidic than the above
compound because Cl is closer to
the OH bond. It will have a
greater electron withdrawing
effect and will stabilise the
conjugate ion more
 ...
e

<
E
- E &

(ALL ARE WEAK)

Nitrogen bases
Accepts H+ ions
O
N H H N H CH3 CH2 N H
CH3 C N CH3
H H H H
Amides Phenylamine Ammonia Ethylamine

↑
NOT BASIC STRONGLY BASIC
Amides are not basic mainly because the
lone pair is not available to accept an H+
ion. The lone pair on the nitrogen atom is O Has a strong electron
withdrawing effect
delocalised into the carbonyl group -

through resonance. They are capable of

resonance because the lone pair of CH3 C N CH3
electrons on the nitrogen atom forms a
double bond with the carbon atom of the
carbonyl group which pushes the pi
H
electrons to the oxygen atom and causes
it to gain a negative charge. Since Resonance
nitrogen gives both the electrons for the - contributing
double bond it gains a positive charge. O structure
The actual structure of a resonance is +
something in between where the lone pair of
electrons of the nitrogen atom is shared
CH3 C N CH3
between the nitrogen and the oxygen atom.
Therefore, no lone pairs for the H+ ion and H
hence it’s not basic.
Phenylamines on the other hand are more
basic than amides. This is because the lone
pair of electrons in phenylamines is
delocalised over the benzene ring through -

resonance. They are still more basic than N H

amides because the delocalisation in
phenylamines is not as dominant as in amides
and the carbonyl group in amides also is a
H
strong electron withdrawing group which
also contributes to amide being less basic.
ou

Amines are very strong bases. This is

because they have alkyl chains attached to
the amine group. The alkyl chains are
CH3 CH2 N H
electron donating and so they increase the
charge density on the nitrogen atom which
makes it more attractive to H+ ions.
H
 - =

Hydrogenation of Benzene Reduction of nitrobenzene

Sn + conc. HCl, and

H2(g) Ni/Pt
NO2 heat under reflux NH2
followed by NaOH

·
catalyst EVERY ALKYL CHAIN (aq) Phenylamine
REGARDLESS OF
POSITION AND SIZE
WILL BECOME A COOH Reduction of amides
GROUP Amides are not basic. It
Oxidation of Arenes O H
obtained 2 hydrogen atoms
not because it accepted H+
ions but it was attacked by
CH3 C N CH3 LiAlH CH3 C N CH3 a hydride ion (H-) which
4 acted as a nucleophile.
H H H Therefore, the basicity of
CH2 CH3 COOH an amide does not relate to
Primary amides get reduced to primary amines its ability of being reduced.
Reflux with These are 2 different things
alkaline KMnO4 Reduction of nitriles
then acidify HOOC
CH3 with dilute H
sulfuric acid
R C N R C N H
H2(g) Ni catalyst
T=150 degrees H H
Only 2 carboxylic acids are oxidised Alkylamine
(Most carboxylic acids are resistant to oxidation)
1. Methanoic acid 2. Ethanedioic acid
HCOOH CO2 H2O
1.KMnO4 / H+and heat HOOCCOOH CO2 H2O
(reflux) +
1.KMnO4/ H and heat
2.K2Cr2 O7and heat (reflux)
3.Fehlings solution
and heat
4.Tollens reagent

Revise all oxidation and reduction reactions of AS level

 All alcohols can be oxidised except tertiary alcohols. Primary alcohols are oxidised to
carboxylic acids and secondary alcohols are oxidised to ketones
O (Use potassium dichromate (VI) or
CH3 CH2 OH 2[O] CH3 C H O potassium manganate (VII) acidified
2 and heat under reflux)
Primary alcohol OH
O Same regents but heat under
CH3 CH2 OH [O] CH3 C H H2O distillation
Primary alcohol

OH O
CH3 CH CH3 [O] CH3 C CH3 H2O Same regents, heat under reflux
Secondary alcohol

If we want aldehydes instead of carboxylic acids from primary alcohols we have to heat and
distill instead of heat under reflux. This is because aldehydes have a low boiling points and
heating it under reflux causes it to be further oxidised. This is because reflux prevents volatile
liquids from escaping the reaction mixture, so when aldehyde (which is highly volatile) tries to
leave the reaction mixture, it is forced back which causes it to oxidise further.

Aldehydes condense here

but are forced back into
Aldehydes condense here and escape the same flask, causing
into another flask further oxidation

Heat under distillation diagram Heat under reflux diagram

Potassium dichromate (VI) and potassium manganate

(VII) are both used to as a test to check for alcohols. Color changes
Potassium dichromate turns from orange to green, of potassium
whereas potassium manganate (VII) turns from dichromate
purple to colourless.
 Reduction of aldehydes, carboxylic acids and ketones

LiAlH4(lithium tetrahydridoaluminate) can reduce both aldehydes and carboxylic acids

as it is a strong reducing agent. It reacts violently with water that’s why the reaction
is carried out in a solution of dry ether. NaBH4 (sodium tetrahydridoborate) is a
weaker reducing agent so it cannot reduce the carboxylic acid but it can reduce both
aldehydes and ketones. To summarise,
Aldehydes Ketones Carboxylic acids
LiAlH4 LiAlH4 LiAlH4
NaBH4 NaBH4
H2 in the H2 in the
presence of presence of
Ni Ni
O
CH3 C 4[H] CH3 CH2 OH H2O
OH Primary alcohol

O
CH3 C H 2[H] CH3 CH2 OH H2O
Primary alcohol

O OH
CH3 C CH3 2[H] CH3 CH CH3 H2O
Secondary alcohol
Ketones cannot be oxidised because there is no hydrogen atom connected to the carbon
atom that’s double bonded to the oxygen atom. The hydrogen atom is important for
the reaction for oxidation to start
-
#( M

Synthesis of the diazonium ion

Nitrobenzene Phenylamine
Electrophilic
Substitution
Conc. HNO3 Sn + conc.
+ conc. H2SO4
catalyst T=55 NO2 HCl and heat
followed by NH2
NaOH (aq)
NaNO2+ HCl (HNO2 )
T< 10 degrees

- +
OH N2 Cl N N
Hydrolysis in the
HCl presence of water
T> 10 degrees Diazonium ion, very
unstable and is an
electrophile
Azo Dye formation
The diazonium ion acts as an electrophile and attacks an activated benzene (benzene
with OH or amine or electron donating group)

N+ N OH The N triple bond N group always goes to

the benzene ring that is inactive. This is
important for figuring out what the
reactants were when the product (an Azo
T<10 dye) is given.
degrees
NaOH (aq)

This is a coloured compound. Azo dyes with

different structures have different colours.
N N OH The one on the left is an orange coloured dye
w called Yellow Solvent 7.
Azo group Azo dyes can also be used as indicators
X

The diazonium ion will attach to the positions which are electron rich. In
this case 2,4 and 6. 6 is always considered if nothing is attached there
already but if something is attached at 6, then the diazonium ion will
attach itself at 2 or 4. The type of reaction is electrophilic substitution
 I
-

)
FORMATION OF ACYL CHLORIDES

O O 3CH3COOH PCl3 3CH3 COCl H3 PO3

R C OH PCl3 + heat R C Cl CH3COOH PCl5 CH3COCl POCl3 HCl
PCl5 CH3COOH SOCl2 CH3COCl SO2 HCl
7
SOCl2

Balanced equations
Heat only required with phosphorous (III) chloride. This is a
type of nucleophilic substitution reaction

FORMATION OF ESTERS
Conc. H2SO4 + reflux (Condensation reaction)

Carboxylic acid + alcohol Ester + Water

Dilute H2SO4 / NaOH and

reflux (Acid or alkaline hydrolysis)
O O
CH3 CH2 OH CH3 CH2 C CH3 CH2 C
OH O CH2 CH3 H2O
Ethanol Propanoic acid Ethylpropanoate Water
Fast and vigorous reaction,
Acylchlorides + Alcohols Esters + HCl no conditions needed
Reagent: NaOH (aq), room temperature
O O The chloride atom from
R1 C Cl HO R2 R1 C O R2 HCl the acyl chloride and the
hydrogen atom from the
alcohol join together and
for, HCl
This type of reaction is a condensation reaction
 Esters form cyclic structures

An easy way to make esters is to remove the hydrogen atom from the alcohol and the
OH group from the carboxylic acid and then join the 2 compounds. It is also important
to note that some aliphatic compounds containing both the hydroxy and acid groups
can react with themselves in solution to form a cyclic structure which contains an ester
linkage. For example, O

OH OH O O
HO HO
O O
O
An easy way to make such types of cyclic structures is to first count the number of
carbon atoms in your reactant and then multiply it by 2, which in this case gives us 4.
Add 2 to this number because of the ester linkages that would be formed. This gives
us the total number of corners in our skeletal structure. In the above compound the
number is 6, and this tells us we need to draw a hexagon since a hexagon has 6 corners

Alkaline hydrolysis of esters produces soaps.

O O
R1 C O R2 NaOH (aq) R1 C ONa R2 OH

Phenols do not forms esters with carboxylic acids. However, they can form esters
with acyl chlorides.

O O
R1 C Cl HO R1 C O HCl

The lone pair on the oxygen atom pairs

with the pi electron cloud of benzene.This

M
spreads the charge over a a larger area REASON WHY PHENOLS
and reduces the charge density in the DO NOT FORM ESTERS
oxygen atom. This makes the lone pair of WITH CARBOXYLIC
electrons in the oxygen atom less available ACIDS
for a nucleophilic attack on the carbonyl
carbon of the carboxylic acid.

Acyl chlorides form amides with phenylamines

O H O
St

R1 C Cl H Noo
R1 C N HCl
H
 Reaction with ammonia
Acyl chlorides react with ammonia to form primary amides
O O
R1 C Cl NH3 R1 C NH2 HCl
Room temp
If we use excess ammonia, the HCl formed will react with the excess ammonia to form
ammonium chloride

Mechanism
Every reaction of acyl chlorides follows to same mechanism. Only the nucleophiles changes.

O
S +
The lone pair from the nucleophiles will attack
R1 C Cl Nu H the partial positive carbon atom, and the
o o

electron in the pi bond between carbon and

oxygen are repelled to the oxygen atom.
"

:
O:
R1 C Cl The oxygen atom reforms the double bond,
Nu+ causing the chlorine atom to break away
H
O
R1 C The chloride ion attacks the hydrogen atom.
The hydrogen atom leaves its electron behind
Nu+ with the nucleophiles which makes it neutral
H ·
·

L
↳

Cl and forms hydrogen chloride.

 Primary and secondary amines react with acyl chlorides to form amides
O H O

·
R1 C Cl H N CH2 CH3 R1 C N CH2 CH3 HCl
Primary amine H
O CH3 O
R1 C Cl H N CH2 CH3 R1 C N CH2 CH3 HCl
Secondary amine CH3
Tertiary amines do not undergo this reaction because there is no hydrogen atom which
can react with the chlorine atom of the acyl chloride to form HCl.

Acid/ Alkaline hydrolysis of amides

O O H+
Acidic hydrolysis
R1 C N CH2 CH3 R1 C OH H N CH2 CH3
H H

O O
Alkaline hydrolysis R C -
R1 C N CH2 CH3 1 O Na+ H N CH2 CH3
H H

D
--
-
--
--
--
#

Amino acids are the monomer units that make up a protein (a polymer)

For example
H O
H N C C Alanine
H O H CH OH
H N C C 3
H R OH
H O
H N C C Valine
Only this group
changes which results H CH OH
in different amino
acids. CH3 CH3
We don’t need to memorise their names or anything. The exam just asks us to make
polymers from these amino acids.

Primary Structure/ Simple polypeptide

Amino acids undergo condensation polymerisation, which means they make a polymer
and produce water molecules. The hydrogen from the N-H bond and the OH from the
carboxylic group leave and form water. The remaining structures join up and make a
polymer
H O H O H O H O
H N C C H N C C H N C C H N C C
H CH OH H CH OH H CH OH H CH OH
3 3
CH3 CH3 CH3 CH3

The polymer that forms,

H O H O H O H O
H N C C N C C N C C N C C
H CH
3
H CH H CH
3
H CH OH
CH3 CH3 CH3 CH3

Amino acids as zwitterions

H O H H O
An amino acid has both a basic group H N+ C C -
and an acidic group. There is an H N C C
internal transfer of a hydrogen ion H R OH H R O
from the -COOH group to the -NH2
group to leave an ion with both a A zwitterion
negative charge and a positive charge.
This is called a zwitterion.
Zwitterions exist even when amino acids are in the solid state. If we add amino acid
to water, the solution would also contain this ion. Zwitterions can act as buffers
because they can accept a proton and also donate a proton.
If you add an alkali to a solution containing zwitterions,
NH3+ NH2
-
R CH COO- OH R CH COO- H2O
No longer a zwitterion
Similarly, if you were to add an acid,
NH3+ NH3+
No longer a zwitterion
R CH COO- H+ R CH COOH

What is the isoelectronic point?

Suppose we start with the ion that we just produced and we add an alkali to it. The
more acidic group from COOH or NH3+ is going to donate a proton. Since COOH is more
acidic, it’s going to lose a proton and we end up with the zwitterion.

NH3+ NH3+
-
R CH COOH OH R CH COO- H2O
The pH when you’ve added enough alkali and we obtain the zwitterion is called the
isoelectronic point. An important thing to note here is that the isoelectronic point will
not at pH 7 rather it will be at around pH 6. The isoelectronic point varies from amino
acid to amino acid so it is not fixed.

The reason why the isoelectronic point is at 6 is

because when we add the amino acid to water,
the zwitterion acts both as an acid and a base.
However the equilibrium position for the acid lies
further to the right which causes more negative
ions to be produced. To balance this negativity
we have to add hydrogen ions, and the balance
typically occurs at around pH 6.

-
Condensation Polymerisation
Condensation polymerisation is a type of polymerisation that eliminates a simple molecule
like water and the remaining structure joins up to make a polymer.
There are 2 example of this in the syllabus: polyesters and polyamides.

1. POLYESTERS A dioc acid A diol

When a dioc acid (compound with 2
carboxylic acid groups) reacts with a O O
diol, a polyester is formed. We can also OH OH
use diacylchloride instead of the dioc C C OH OH
acid.
A diacylchloride
O O
Cl C C Cl
 O O O O
OH OH OH OH
C C OH OH C C OH OH
An ester linkage
O O O O
OH O O
C C O C C OH 3H2O
The reaction with diacylchloride would be the same but instead of water, hydrogen
chloride would be eliminated.
Another way of producing polyesters is by using O
hydroxycarboxylic acids. These contain both an OH HO CH2 CH2 C
group and a COOH group at its ends. OH
3-hydroxypropanoic acid
O O O
HO CH2 CH2 C HO CH2 CH2 C HO CH2 CH2 C
OH OH OH
O O O
O CH2 CH2 C O CH2 CH2 C O CH2 CH2 C 2H 2O

2. POLYAMIDES
When a diacylchloride reacts with a diamine, A diamine
it forms a polyamide. We can also use dioc
acids but it can often result in an acid-base
reaction. Therefore, diacylchlorides are H N N H
preferred instead.
H H
O O O O
OH OH
C C OH H N N H C C OH H N N H
H H H H
O O O O
OH
C C N N C C N N H 3H2O
H H H H
An amide linkage

Some examples of polyamide and polyesters

Polyamide: Kevlar, Nylon and natural proteins
Polyesters: Terylene (fabric, clothing) and
natural polyesters (fats)

You can also form a polyamide by one An amino carboxylic acid

monomer which is called an amino carboxylic O
acid. It contains an amine group and a COOH H N C
group. OH
H
O O O O
H N C H N C H N C H N C
OH OH OH OH
H H H H
O O O O
N C N C N C N C 3H2O
H H H H

Addition Polymerisation
In this there is no molecule eliminated. The monomers are alkenes, which just join up
together after their double bond breaks

H H This will react with itself to form a polymer. The double bonds will
C C break. This doesn’t mean that a polymer made from addition will
never have double bonds. It can if the monomer has more than 1
CH3 H double bond.
 H H H H H H H H
C C C C C C C C
CH3 H CH3 H CH3 H CH3 H
A polymer can also be expressed using its monomer unit.
Polymer (repeat unit)n
Therefore, the above polymer can be expressed
as,
H H
C C Don’t forget the continuation bonds
CH3 H n
Condensation Addition
A small molecule like
water, methanol or HCl is No by-products
eliminated

Very polar linkages Linkage is non polar carbon

chain

Reactive and hydrolyses quickly Stable and unreactive

Many polymers can be degraded by exposure of UV light and this leads to discolouring
and breaking of the polymer chains which causes the material to break down. An
example of this is LDPE (low density polyethene)
One example of a conducting polymer is poly(ethyne)

Ethyne undergoes addition polymerisation to form

This has alternating double bonds. The pi bonds of

carbon overlap sideways to form a delocalised chain
of electrons which enables this to conduct electricity
=
(
What is optical isomerism?
Optical isomer are those isomers which have a chiral centre and form non-superimposable
mirror images. Substances which show optical isomerism exist as two isomers known as
enantiomers. Optical isomers can only exist if it contains a chiral carbon atom.
What is a chiral carbon atom?
When a compound has no plane of symmetry, it is
known as chiral. The carbon atom which causes H O This is a chiral
carbon atom
this lack of symmetry is called a chiral carbon
atom. A chiral carbon atom is always attached CH3 C C
to 4 different groups. It cannot have the same OH
groups because then the plane of symmetry OH
would exist.
Enantiomers can rotate plane polarised light. The enantiomer which rotates plane
polarised light clockwise is known as the (+) form while the one the rotates it
anticlockwise is known as the (-) form. If the solutions are equally concentrated, the
rotation caused by the 2 enantiomers is the same but in different directions.

Biological activity of an isomer -I -I

Enantiomers also differ in terms of their
biological activity. Every chiral centre
has two possible arrangement of bonds
around it. A different arrangement of (E **
⑳ (E

I
E I
bonds leads to a different shape of a
molecule and a different shape means it T
won’t necessarily bind itself to the
active site of the enzyme. Therefore, --
X
while one isomer can have required -
- -
⑳ ·

I1/
=I

/
/ /
#
=-

effects (as a medicine) the other isomer -I -

won’t have the same effect due to its

different shape and hence inability to
bind itself to the enzyme.
Enantiomer is able to Enantiomer not able to
bind to the active site bind, so there is no effect
When optically active substances are made in the lab, they often occur as a 50/50
mixture of the two enantiomers. This is known as a racemic mixture or racemate. It
has no effect on plane polarised light. Since one isomer is not biologically effective,
there is always a need to produce one isomer only. Other reasons for producing one
isomer are:
·
The patient can be given smaller doses if all the drug is active.
It is cheaper in the long-run, because it is a waste of money and
· materials producing a drug half of which is of no use.
It lowers the chances of undesirable side-effects
due to the other isomers.
 How to produce one enantiomer?
One way to obtain a single enantiomer is through the use of chiral catalysts. These
catalysts can promote the formation of one enantiomer over the other in a reaction, a
process known as asymmetric synthesis. The chiral catalyst, by its very nature, creates
an environment where one enantiomer is favored, leading to a product that’s
predominantly one optical isomer.
This increases efficiency as we don’t need to separate the useless enantiomer, less waste
disposal and its more economically viable to produce and purify just one enantiomer.

I
#/( ·
I
·

Why are halogenoalkanes more reactive than a halobenzene?

·

This is because of the following reasons

Bond polarity and strength: The lone pairs of the halogen in
halobenzene is delocalised into the benzene ring which makes the C-X
bond less polar and hence more unreactive. The C-X bond in
halobenzene is also stronger than in halogenoalkanes because it is sp2
hybridized. sp2 hydbrizided bonds are stronger because they have a
greater s-orbital overlap.
Delocalised electrons of benzene: The delocalised electrons of benzene
above and below the ring repel and nucleophiles from approaching and
starting a mechanism. Therefore, halogenoalkanes can undergo
nucleophilic substitution but halobenzenes can’t. This is why halobenzene
usually undergo addition-elimination reaction or nucleophilic substitution
reactions in harsh conditions.
Reaction with primary amines
Halogenoalkanes react with primary amines in ethanol, heated in a sealed tube to produce
secondary amines. For example
H H
CH3 CH2 Cl H N CH2 CH3
oo
CH3 CH2 N CH2 CH3
oo HCl
The mechanism for this reaction,
St

H H+
CH3 CH2 Cl CH3 CH2 N CH2 CH3
H N CH2 CH3
oo

H
-
Cl
 ---
1. All tests used to distinguish between phenols and alcohols.
2. Tests between phenylamines and alkylamines.
3. Use of chlorine and HF for monochlorination.
4. More reactions of phenylamines.

There are some tests that are used to differentiate between alcohols and phenols.
Ester formation: Phenols cannot forms esters with carboxylic acid whereas alcohols
can. You can use this for distinguishing between the 2 compounds. The observation with
an alcohol would be that it gives a fruity smell.
Precipitate formation: phenols can give a white precipitate when reacted with aqueous
bromine or chlorine, whereas alcohols cannot. (See here)
Complex ion formation: phenols can react with FeCl3 to give a purple solution while an
alcohol has no change. This is because phenols are acidic and can donate a proton after
which they form a complex with the iron ion.
Reaction with NaOH: Phenols react with NaOH and dissolve whereas alcohols show no
change.
Universal Indicator: You can use a universal indicator to distinguish between them.
Phenols are more acidic than alcohols so they will show an orange/yellow color whereas
alcohols will stay green.
Using diazonium ion: Phenols form coloured dyes when reacted with the diazonium ion
whereas alcohols don’t. Phenols will give an orange/red color while an alcohol won’t
show any change.
Oxidation of alcohol: An alcohol can be oxidised by using potassium dichromate or
potassium manganate. It will turn dichromate from orange to green and manganate from
purple to colourless. A phenol will show no change. However, this test won’t be valid for
tertiary alcohols since they don’t get oxidised.
Formation of Halogenoalkanes: Alcohols can react with multiple reagents to form
halogenoalkanes and they release HCl. So alcohols will give white fumes whereas there will
be no change with a phenol.

These are the tests that can be used to distinguish between phenols and phenylamines
Complex ion formation: Phenols give a violet/purple color when added to FeCl3 whereas
phenylamines do not. This is again due to the acidic nature of phenols
Universal Indicator: You can use a universal indicator to distinguish between them.
Phenols are acidic so they will show an orange/yellow color whereas phenylamines will
be blue. (memorise one color only)
Adding Na metal: This will show fizzing with phenols but no reaction with phenylamines.
Reaction with NaOH: Phenols react with NaOH and dissolve whereas phenylamines
show no change.
Add acid: phenylamines are bases so they will dissolve and alcohol will not.
Add HNO2 : if we add nitrous acid to phenyl amines at room temperature, then the
phenylamine forms the diazonium salt which further decomposes to produce phenols and
nitrogen gas. No reaction with phenols. If temperature is below 10 degrees, adding nitrous
acid followed by an alkaline solution of phenol would produce a coloured dye (Azo dye)
ALKANES AND ALKENES
Combustion of Alkane
> Products: carbon dioxide/CO and water
> Reagents and conditions: excess oxygen for complete combustion, limited for
incomplete
> Type of reaction: Combustion reaction
Halogenation of Alkane
> Products: halogenoalkanes
> Reagents and conditions: gaseous chlorine or bromine and ultraviolet light
> Type of reaction: Free-radical substitution.
Hydrogenation of Alkene
> Products: Alkanes
> Reagents and conditions: hydrogen and nickel catalyst, T=150
> Type of reaction: Electrophilic addition.
Hydration of alkene
> Products: Alcohols
> Reagents and conditions: steam and phosphoric acid catalyst, 330C and 60 atm
> Type of reaction: Electrophilic addition
Hydrohalogenation of alkene
> Products: halogenoalkanes
> Reagents and conditions: gaseous hydrogen halides at room temperature
> Type of reaction: Electrophilic addition
Halogenation of alkenes
> Products: halogenoalkanes (dibromide or dichloride)
> Reagents and conditions: aqueous halogens in tetrachloromethane solvent at room
temperature
> Type of reaction: Electrophilic addition
Oxidation of alkenes
> Products: diols
> Reagents and conditions: cold and dilute KMnO4 acidified, room temperature
> Type of reaction: oxidation/redox
Breaking double bond of alkenes
> Products: CO2 and H2O/carboxylic acids/ ketones
> Reagents and conditions: hot and concentrated KMnO4 acidified
> Type of reaction: oxidation
Polymerisation
> Products: polymer
> Reagents and conditions: T= 60C, a few atm pressure and Ziegler-Natta catalyst
(for HDPE) and T=200C and 2000 atm with a small amount of oxygen for LDPE
> Type of reaction: Addition polymerisation
HALOGENOALKANES
Reaction with NaOH (aq)
> Products: Alcohol + NaX
> Reagents and conditions: NaOH (aq) + heat under reflux
> Type of reaction/mechanism: nucleophilic substitution
Reaction with ethanolic NaOH
> Products: Alkene + NaX + water
> Reagents and conditions: NaOH in ethanol and heat under reflux
> Type of reaction: Elimination t
Reaction with primary amines
> Products: secondary amines + HX
> Reagents and conditions: ethanol as solvent and heat under pressure
> Type of reaction/mechanism: nucleophilic substitution
Reaction with ammonia
> Products: primary amines and ammonium salt (equilibrium)
> Reagents and conditions: excess ammonia in ethanol, heat under pressure
> Type of reaction/medhanism: nucleophilic substitution
Reaction with cyanide ions
> Products: nitriles and potassium halide
> Reagents and conditions: KCN in ethanol, heat under reflux
> Type of reaction/mechanism: nucleophilic substitution
 CARBONYL
Reduction
> Products: primary alcohols/ secondary alcohols
> Reagents and conditions: LiALH4 in dry ether or NaBH4 in aqueous alcoholic solution or
H2+ Ni around 150 degrees
> Type of reaction: Reduction
Oxidation
> Products: Aldehydes turn into carboxylic acids, ketones don’t get oxidised (except
phenylethanone)
> Reagents and conditions: acidified K2 Cr2 O7 or KMnO4
> Type of reaction: Oxidation
Formation of hydroxynitriles
> Products: hydroxynitriles
> Reagents and conditions: NaCN or KCN and sulfuric acid, room temperature
> Type of reaction/mechanism: nucleophilic addition
Reaction with 2,4-DNPH
> Products: water and an organic compound
> Reagents and conditions: 2,4-DNPH must be in methanol and sulfuric acid
> Type of reaction: condensation
> Obervations:orange-yellow precipitate
Reaction with Tollens reagent and fehlings reagent Aldehydes get oxidised to
carboxylate ion and shows silver mirror and red precipitate respectively.
ALCOHOLS
Combustion > same as alkanes
Dehydration
> Products: alkenes and water
> Reagents and conditions: excess concentrated sulfuric acid or aluminium (III) oxide,
heat at 170C
> Type of reaction: Dehydration
Reaction with sodium metal
> Products: Alkoxides and hydrogen gas
> Reagents and conditions: sodium metal, room temperature
> Type of reaction: Redox
Formation of halogenoalkanes
> Products: halogenoalkanes, by-products depend on reagent used
> Reagents and conditions: HX at room temperature or PCl3 and heat or PCl5 or thionyl
chloride (SOCl2)
> Type of reaction/mechanism: nucleophilic substitution
Oxidation
> Products: Primary alcohol - Aldehydes and carboxylic acids, secondary alcohols -
Ketones, Tertiary alcohols - no oxidation
> Reagents and conditions: acidified K2 Cr2 O7 or KMnO4 ,heat under reflux (heat under
distillation if you want to produce aldehydes from primary alcohols)
> Type of reaction: Oxidation
Esterification
> Products: Esters
> Reagents and conditions: heat under reflux with concentrated sulfuric acid as catalyst
> Type of reaction: esterification/condensation
CARBOXYLIC ACIDS
Reaction with bases
> Products: carboxylate salt and water
> Reagents and conditions: NaOH (aq)
> Type of reaction: acid-base
Reaction with sodium metal > same as alcohols
Formation of acyl chlorides
>Products: acyl chloride and by products depend on reagent used
> Reagents and conditions: PCl 3 or PCl 5 or SOCl2 (only heat with PCl3)
> Type of reaction/mechanism: nucleophilic substitution
Reaction with carbonates and hydrogencarbonates
> Products: carboxylate salt and water and carbon dioxide
> Reagents and conditions: carbonates and hydrogencarbonates
> Type of reaction: acid-base
Reduction to primary alcohols Carboxylic acids also
> Products: primary alcohol react with amine to
> Reagents and conditions: LiAlH4 in dry ether make amide. No
> Type of reaction: reduction special conditions
Esterification > same as alcohols needed
Oxidation of ethane dioc acid
> Products: carbon dioxide and water
> Reagents and conditions: acidified KMnO4 and heat under reflux
> Type of reaction/ mechanism: Oxidation
Oxidation of Methanoic acid
> Products: carbon dioxide and water
> Reagents and conditions: acidified KMnO4 /K2Cr2 O7 and heat under reflux or
Tollens reagent or Fehlings reagent and heat
> Type of reaction/ mechanism: Oxidation
ACYL CHLORIDES
Formation of Esters
> Products: ester and HCl gas
> Reagents and conditions: alcohols or phenol. With phenol we need to add NaOH and
heat
> Type of reaction: nucleophilic addition-elimination / condensation
Reaction with ammonia
> Products: primary amides
> Reagents and conditions: room temperature
> Type of reaction/mechanism: nucleophilic substitution
Reaction with primary and secondary amines or phenylamines
-
- _

> Products: secondary amides (if primary amine reacted) and tertiary amide (if
secondary amine reacted)
> Reagents and conditions: room temperature
> Type of reaction/mechanism: nucleophilic substitution IMPORTANT:
3

Acylation will
BENZENE occur with
phenylamines
Reaction of methylbenzene with halogens only if the
> Products: 2/4-(X)methylbenzene and HX catalyst AlCl3
> Reagents and conditions: X2 and AlX3 or FeX3 catalyst where X=Cl, Br is present and
> Type of reaction/mechanism: Electrophilic substitution heating under
Reaction of methylbenzene with nitric acid reflux.
> Products: 2/4-methylnitrobenzene
> Reagents and conditions: HNO3 and H2 SO4 , both concentrated and T=55 degrees
> Type of reaction/mechanism: Electrophilic substitution
Reaction of benzene with halogens and with nitric acid > same as above
Reaction of phenols/phenylamines with halogens
-

> Products: 2,4,6-tri(X)phenol and HX

> Reagents and conditions: X2 (aq) and no catalyst needed where X=Cl, Br
> Type of reaction/mechanism: Electrophilic substitution
Reaction of phenols/phenylamines with HNO3
> Products: mono-nitrated product (if dilute nitric acid at room temperature ) and a
trinitro product (if concentrated nitric acid used)
> Reagents and conditions: dilute or concentrated HNO3
> Type of reaction/ mechanism: Electrophilic substitution
Reaction of nitrobenzene with nitric acid
> Products: 1,3- dinitrobenzene
> Reagents and conditions: HNO3 and H2SO4 , both concentrated
> Type of reaction/ mechanism: Electrophilic substitution
Reaction of nitrobenzene with halogens
> Products: 3-(X)nitrobenzene and HX
> Reagents and conditions: X2 and AlX3 or FeX3 and more forcing conditions (X=Cl,Br)
> Type of reaction/ mechanism: Electrophilic substitution
Alkylation
> Products: an alkylbenzene (anhydrous)
> Reagents and conditions: a halogenoalkane and AlCl3 catalyst
> Type of reaction/ mechanism: Electrophilic substitution
Acylation
> Products: aromatic ketone (anhydrous)
> Reagents and conditions: an acyl chloride and AlCl3 catalyst
> Type of reaction/ mechanism: Electrophilic substitution
Hydrogenation of Benzene Reaction of
> Products: cyclohexane phenols with
> Reagents and conditions: H2 (g) and Ni catalyst temperature around 150 C Na is a type of
> Type of reaction/ mechanism: Reduction/Addition redox reaction
Oxidation of Arenes
> Products: benzoic acid (all alkyl groups replaced by COOH)
> Reagents and conditions: heated under reflux with hot alkaline KMnO4 then
acidified with dilute sulfuric acid
> Type of reaction/ mechanism: Oxidation
Reduction of nitrobenzene
> Products: phenylamine
> Reagents and conditions: Sn + concentrated HCl and heat under reflux, followed
by NaOH (aq) You can also use nitrous
> Type of reaction/ mechanism: Reduction
Formation of benzene diazonium chloride from phenylamine - acid (HNO2) and HCl

> Products: benzene diazonium chloride

> Reagents and conditions: react phenylamine with NaNO2 and HCl, temperature ↳
should be less than 10 degrees Note that esters do not hydrolyse in the
> Type of reaction/ mechanism: - temperature range for this reaction
(important if an ester group is attached
Decomposition of benzene diazonium chloride to a phenylamine)
> Products: phenol + N2 + HCl
> Reagents and conditions: hydrolysis in the presence of water, T>10 degrees
> Type of reaction/ mechanism: nucleophilic substitution
Reaction of benzene diazonium chloride with an alkaline phenol
> Products: an Azo dye and HCl
> Reagents and conditions: phenol dissolved in NaOH (aq), and T<10 degrees
> Type of reaction/ mechanism: Azo coupling reaction or electrophilic substitution
HYDROLYSIS REACTIONS
Acidic hydrolysis of esters
> Products: carboxylic acid and alcohol
> Reagents and conditions: HCl (aq) and heat under reflux
> Type of reaction/ mechanism: nucleophilic substitution
Alkaline hydrolysis of esters
> Products: carboxylate salt and alcohol
> Reagents and conditions: NaOH (aq) and heat under reflux
> Type of reaction/ mechanism: nucleophilic substitution
Acidic hydrolysis of amides
> Products: carboxylic acid and salt of primary amine (R-NH3+)
> Reagents and conditions: HCl (aq) and heat under reflux
> Type of reaction/ mechanism: nucleophilic substitution
Alkaline hydrolysis of amides
> Products: carboxylate salt and primary amine
> Reagents and conditions: NaOH (aq) and heat under reflux
> Type of reaction/ mechanism: nucleophilic substitution
Decomposition of benzene diazonium chloride
> Products: phenol + N2 + HCl
> Reagents and conditions: hydrolysis in the presence of water, T>10 degrees
> Type of reaction/ mechanism: nucleophilic substitution
Hydrolysis of acyl chlorides
> Products: carboxylic acids and HCl Reaction
> Reagents and conditions: water and room temperature > Products:
> Type of reaction/ mechanism: addition/elimination > Reagents and conditions:
Hydrolysis of nitriles > Type of reaction/ mechani
> Products: carboxylic acid and ammonium ion
> Reagents and conditions: heat under reflux with dilute hydrochloric acid
> Type of reaction/ mechanism: hydrolysis
 MISC REACTIONS
Reduction of amides
> Products: amines (primary amides produce primary amines, secondary amides produce
secondary amines)
> Reagents and conditions: LiAlH4
> Type of reaction/ mechanism: reduction
Reduction of nitriles
> Products: amines
> Reagents and conditions: Hydrogen gas and nickel as catalyst at T=150, OR
LiAlH4
> Type of reaction/ mechanism: Reduction

Reduction Reactions
LiAlH4 NaBH4 H2 and Ni/Pt
carboxylic acids Aldehydes Alkenes
Aldehydes Ketones Benzene ring
Ketones Aldehydes
Amides Ketones
Nitriles Nitriles

Oxidation Reactions
Alkenes: either hot and concentrated or cold and diluted potassium manganate
(acidified in both conditions)
Alcohols: acidified potassium manganate or dichromate and heat under reflux.
Aldehydes: acidified potassium manganate or dichromate and heat under reflux
Arenes: hot alkaline potassium manganate, then acidified with dilute sulfuric acid.

Halogenation Reactions
Benzene/arenes: Cl2 (g) with AlCl3 catalyst at room temperature
Phenols/phenylamines: Cl2 (g) at room temperature
Halogenation of alkenes: Br2 (aq) > a dibromide and an alcohol with a
halogen, Br2 in CCl4> 2 bromines substitute
Hydrohalogenation of alkenes: HX at room temperature
Alkanes: Cl2(g)/Br2 (g) with uv light
Alcohols: HX/PCl3 and heat/PCl5/SOCl2
Carboxylic acid: same as above but HX cannot be used