Bakelite Reaction

Bakelite is a polymeric material based on the thermosetting phenol formaldehyde resin,

polyoxybenzylmethylenglycolanhydride formed by the condensation reaction of phenol
and formaldehyde.
• Phenol is treated with formaldehyde in the presence of alkali or acids, resulting in the
formation of Bakelite, a high molecular weight substance in which many phenol rings are
held together by –CH2- groups.
• It was developed in 1907–1909 by Dr. Leo Baekeland. It was the first plastic made from
synthetic components.

Mechanism of Bakelite reaction: The stages involved in the formation of the polymer
seem to be the followings:

• Phenol react with formaldehyde to form o- or p-hydroxymethylpheol.

• Hydroxymethylphenol then reacts with another molecule of phenol to form a compound in

which two rings are joined by a –CH2- link with the loss of water.
• This process then continue to yield a product of high molecular weight.
Since three positions in each phenol molecule are susceptible to attack, the final product
may contains many cross link-links and hence has a rigid three dimensional structure and
thus a space network polymer.
 OH OH OH
CH2OH
HCHO C6H5OH CH2 OH
H or OH

CH2
OH

H2C CH2 OH
HCHO
C6H5OH
CH2
CH2

HO CH2

CH2

Applications of Bakelite
• It is used for its electrically nonconductive and heat-resistant properties in radio and
telephone casings and electrical insulators.
• It is also used in such diverse products as kitchenware, jewelery, pipe stems, children's
toys and as a bonding adhesive in plywood.
 Wolff-Kishner Reduction
Wolff-Kishner reduction is a chemical reaction that fully reduces a ketone or aldehyde to
an alkane.
Reaction of an aldehyde or ketone with excess hydrazine generates a hydrazone derivative,
which on heating with base gives the corresponding hydrocarbon.

Mechanism of Wolff-Kishner Reduction:

The mechanism involves the formation of the hydrazone and successive deprotonations
eventually result in the evolution of nitrogen converting aldehyde and ketones to alkanes
The hydrazone is deprotonated to give a resonance stabilized intermediate

 The anion intermediate is protonated by the water and then deprotonated

The deprotonated intermediate then looses N2 gas to form a carbanion. 

The carbanion is protonated to give the reduction product
 Clemmensen reduction
Clemmensen reduction is a chemical reaction described as a reduction of ketones
or aldehydes to alkanes using zinc amalgam and hydrochloric acid.

The Clemmensen Reduction allows the deoxygenation of aldehydes or ketones, to

produce the corresponding hydrocarbon.
This reaction is named after Erik Christian Clemmensen, an American chemist.

Mechanism of Clemmensen reduction: The reductant is zinc metal dissolving in

HCl. As the metal dissolves, it gives up two electrons which would reduce the H+ in
the acid to H2 to reduce the C=O bond.
 Birch reduction

• Birch reduction is the organic reduction of aromatic rings with sodium /potassium /
lithium in liquid ammonia in the presence of an alcohol such as ethanol, isopropanol or
tert-butanol to form 1,4-cyclohexadienes.

• This reaction provides an alternative to catalytic hydrogenation of aromatic rings, which

is extremely difficult to perform on aromatics, due to the stability of the extended
conjugated system.

• The reaction was invented by the Australian chemist Arthur John Birch in 1944

ROH
Reaction mechanism of Birch reduction:
• First step: Birch reduction is a one-electron reduction of the aromatic ring to a
radical anion. Sodium is oxidized to the sodium ion Na+ and creates a redical
anion. The redical ion accepts a proton from alcohol to give the second intermediate,
a free radical.
• Second step: The free redical is reduced to a cabanion by another sodium atom.
This carbanion abstracts another proton from the alcohol to form the
cyclohexadiene.

• The function of alcohol is to supply protons

• In substituted aromatic compounds, electron donating groups such as alkyl or
alkoxyl decrease the rate of reaction, whereas electron withdrawing groups such
COOH or CONH2 groups increase the rate of reaction.
 Diels-Alder reaction
Diels-Alder reaction is an organic chemical reaction (specifically, a cycloaddition)
between a conjugated diene and a alkene or substituted alkene, commonly termed the
dienophile, to form a cyclohexene or substituted cyclohexene system.

The Diels-Alder reaction combines a diene (a molecule with two alternating double bonds)
and a dienophile (an alkene) to make rings and bicyclic compounds. The three double
bonds in the two starting materials are converted into two new single bonds and one new
double bond.

Diels-Alder reaction is favored when either the diene is substituted with electron donating
groups (like -OR, -NR2, etc) or when the dienophile is substituted with electron-withdrawing
groups (like -NO2, -CN, -COR, etc).
Friedel-Crafts reaction
Friedel-Crafts reactions are a set of reactions developed by Charles Friedel
and James Crafts in 1877. There are two main types of Friedel-Crafts reactions:
alkylation reactions and acylation reactions.

Friedel-Crafts alkylation
Friedel-Crafts alkylation involves the alkylation of an aromatic ring and an
alkyl halide using a strong Lewis acid catalyst.

Friedel-Crafts alkylation
Friedel-Crafts acylation is the acylation of aromatic rings with an acyl chloride
using a strong Lewis acid catalyst.
Friedel-Crafts acylation is also possible with acid anhydrids.
Mechanism of Friedel-Crafts alkylation

Step 1:
The alkyl halide reacts with the Lewis acid to
form a more electrophilic C, a carbocation

Step 2:
The  electrons of the aromatic C=C act as a
nucleophile, attacking the electrophilic C+.
This step destroys the aromaticity giving the
cyclohexadienyl cation intermediate.

Step 3:
Removal of the proton from C bearing the
alkyl- group reforms the C=C and the
aromatic system, generating HCl and
regenerating the active catalyst.
Mechanism of Friedel-Crafts acylation

Step 1:
The acyl halide reacts with the Lewis acid to
form a a more electrophilic C, an acylium ion

Step 2:
The  electrons of the aromatic C=C act as a
nucleophile, attacking the electrophilic C+. This
step destroys the aromaticity giving the
cyclohexadienyl cation intermediate.

Step 3:
Removal of the proton from C bearing the
acyl- group reforms the C=C and the
aromatic system, generating HCl and
regenerating the active catalyst.
 Limitations of Friedel-Crafts alkylation reactions
CH3

CH3Cl
AlCl3

A. The halide must be either an alkyl halide. Vinyl or aryl halides do not react.

B. Over alkylation can be a problem since the product is more reactive than the starting
material. The product is more nucleophilic than the reactant due to the electron donating
alkyl-chain. Therefore, another hydrogen is substituted with an alkyl-chain, which leads
to overalkylation of the molecule.

CH3 CH3 CH3

CH3
CH3Cl CH3Cl
AlCl3 AlCl3

CH3
C. Alkylation reactions are prone to carbocation rearrangements. The carbocation
(i.e. R+) formed by the "removal" of the halide by the Lewis acid catalyst. The reactive
carbocation is prone to rearrangement to a more stable carbocation which will then
undergo the alkylation reaction. It is therefore not possible to put a primary alkyl group
(other than methyl, ethyl) on the aromatic ring.

CH3CH2CH2 Cl AlCl3 CH3CH2CH2 CH3CHCH3

1º carbocation 2º carbocation
D. Deactivated benzenes are not reactive to Friedel-Crafts conditions, the benzene
needs to be as or more reactive than a mono-halobenzene. For example, metadirecting
groups make the ring to inactive for alkylation.

 Starting Material Relative rate* ortho meta para Comments

activated
25 63% 3% 34%
                             ortho / para director

deactivated
2.5 x 10-5 6% 91% 3%
                            meta director

E. Aryl rings substituted with OH, OR, NH2 etc do not facilitate the reaction since
the catalyst often complexes/co-ordinates with these basic groups. However, phenols
give the usual Friedel-craft alkylation reactions but the reaction is very poor for
amines.
OH NH2 OR
Advantages of Friedel-Crafts acylation over alkylation reactions
O

O R C

R C Cl
AlCl3

A. Friedel–Crafts acylation is the acylation of aromatic rings with an acyl chloride using a
strong Lewis acid catalyst. Friedel–Crafts acylation is also possible with acid anhydrides.

B. In Friedel–Crafts acylation, due to the electron-withdrawing effect of the carbonyl

group, the ketone product is always less reactive than the original molecule, so multiple
acylations do not occur.

C. Friedel–Crafts acylation is free from carbocation rearrangement. The acyl cation or

acylium ion (i.e. RCO+ ) formed by the "removal" of the halide by the Lewis acid catalyst.
The acylium ion is stabilised by resonance. This extra stability prevents the problems
associated with the rearrangement of simple carbocations.
O O

R C Cl AlCl3 R C
D. The reduction of acylation products can be used to give the equivalent of alkylation
but avoids the problems of rearrangement. Therefore, it is possible to put a primary alkyl
group (other than methyl, ethyl) on the aromatic ring using Friedel-Crafts acylation.
 Gabriel synthesis
• Gabriel synthesis is a chemical reaction that transforms primary alkyl halides into
primary amines using phthalimide that is the conversion of alkyl halides to primary
amines by treatment with potassium phthalimide followed by hydrolysis
• This reaction is named for the German chemist Siegmund Gabriel
• Reaction of phthalimide with KOH removes the N-H proton giving an imide ion, a
good nucleophile.
• Nucleophilic substitution by the imide ion on the alkyl halide generates an
intermediate, N-alkyl phthalimide.
• Hydrolysis of N-alkyl phthalimide liberates a primary alkyl amine.
Step 1:
An acid/base reaction. Deprotonation of the imide
N-H proton by the base, hydroxide. This proton is
more acidic than a simple amine due to the resonance
stabilisation by the two adjacent C=O groups.
This generates a strong nucleophile, the -ve N.

Step 2:
The N nucleophile attacks the electrophilic C of the
alkyl halide displacing the bromide and creating the
new C-N bond. This product can be compared to an
N-alkyl amide.

Step 3:
Hydrolysis creates the dicarboxylic acid and the
required amine.
 Gattermann-Koch reaction
• Gattermann-Koch reaction, named for the German chemists Ludwig Gattermann
and Julius Arnold Koch, refers to a reaction in which carbon monoxide and
hydrochloric acid are used in-situ with Friedel-Crafts catalyst, namely AlCl 3 to produce
a benzaldehyde-derivative from a benzene-derivative in one step.
• Benzaldehyde and many aromatic aldehydes are conveniently synthesized by this
reaction.
• Presence of traces of copper(I) chloride are also needed.
Mechanism of reaction
 Baeyer-Villiger oxidation
• Baeyer-Villiger oxidation is an organic reaction in which a ketone is oxidized to an ester
by treatment with peroxy acids or hydrogen peroxide. It is the oxidative cleavage of a
carbon-carbon bond adjacent to a carbonyl, which converts ketones to esters.
• Reagents typically used to carry out this rearrangement are meta-chloroperoxybenzoic
acid (mCPBA), peroxyacetic acid, peroxytrifluoroacetic acid or hydrogen peroxide and a
Lewis acid.
•Disodium hydrogen phosphate is added as a buffering agent to prevent transesterification.

• It is named after the German chemist Johann Friedrich Wilhelm Adolf von Baeyer and
the Swiss chemist Victor Villiger
Mechanisms of Baeyer-Villiger oxidation :
• The reaction mechanism of this oxidative cleavage involves first addition of the peroxy
acid to the carbonyl forming a tetrahedral intermediate.
• Next is a concerted* migration of one of the adjacent carbons to oxygen with loss of a
carboxylic acid.

*In chemistry, a concerted reaction is a chemical reaction in which all bond breaking
and bond making occurs in a single step.
 Eschweiler-Clarke reaction
• Eschweiler-Clarke reaction (also called the Eschweiler-Clarke methylation) is a
chemical reaction whereby a primary (or secondary) amine is methylated using excess
formic acid and formaldehyde.
• This reaction allows the preparation of secondary methylamines from primary amines and
tertiary methylamines from secondary amines via treatment with formaldehyde in the
presence of formic acid.
• It is a reductive amination reactions such as this one will not produce quaternary
ammonium salts, but instead will stop at the tertiary amine stage.
• It is named for the German chemist Wilhelm Eschweiler (1860-1936) and the British
chemist Hans Thacher Clarke(1887-1972).

The formate anion acts as hydride donor to reduce the imine or iminium salt, so that the
overall process is a reductive amination.
Mechanism of Eschweiler-Clarke reaction
• Methylation of the amine begins with imine formation with formaldehyde.
• Formic acid acts as a source of hydride and reduces the imine to a secondary amine.
• Formation of the tertiary amine is similar, but slower due to the difficulties
in iminium ion formation
• The driving force is the formation of the gas carbon dioxide.
Darzens reaction
• Darzens reaction / Darzens condensation / glycidic ester condensation is the
chemical reaction of a ketone or aldehyde with an α-haloester to form α,β-epoxy esters.
• Darzens Reaction is the condensation of a carbonyl compound with an α-halo ester in
the presence of a base to form an α,β-epoxy ester.
• α,β-Epoxy esters, also called glycidic esters, upon hydrolysis yield aldehydes or ketones
• This reactions was discovered by the organic chemist Auguste George Darzens
Mechanism of Darzens reaction:
• The reaction is base initiated, which leads to the generation of a stabilized carbanion or
ester enolate after deprotonation.
• Nucleophilic attack of a carbonyl group by the carbanion i.e. the α-halo ester adds to the
carbonyl compound follows.
• The unstable anion attacks intramolecularly via a SN2 mechanism, with chloride as a
leaving group. A new carbon-carbon bond is formed in the process.
• In this case EtO- should be used as a base to prevent ester hydrolysis.
Arndt-Eistert synthesis
Named for the German chemists Fritz Arndt and Bernd Eistert, Arndt-Eistert synthesis
is a series of chemical reactions designed to convert a carboxylic acid to a higher carboxylic
acid homologue (ie. contains one additional carbon atom). An acyl halide is reacted with
diazomethane resulting in the formation of a homologous carboxylic acid with one
additional carbon atom.
• Acid chlorides react with diazomethane to give diazoketones, then diazoketones will form
the desired acid homologue in the presence of a nucleophile (water) and a metal catalyst
(Ag2O)
•Arndt-Eistert synthesis uses thionyl chloride to convert the starting acid to an acid chloride

Mechanisms:
First step: The diazomethane carbon adds to the acid halide, to give an α-diazoketone.
Second step: Treatment with water or silver salt initiates a rearrangement with the R-group
migrating to produce an isocyanate, which readily hydrolyses to give a carboxylic acid.
If alcohols or amines are used
instead of water, esters and
amides are obtained, respectively.
Grignard reaction
The Grignard reaction (pronounced ) is an organometallic chemical reaction in
which alkyl- or aryl-magnesium halides (Grignard reagents) add to a carbonyl
group in an aldehyde or ketone. This reaction is an important tool for the formation
of carbon–carbon bonds.
Perkin reaction
The Perkin reaction is an organic reaction developed by William Henry Perkin
that can be used to make cinnamic acids i.e. α-β-unsaturated aromatic acid by
the aldol condensation of aromatic aldehydes and acid anhydrides in the
presence of an alkali salt of the acid.
Reimer–Tiemann reaction
The Reimer-Tiemann reaction is a chemical reaction used for the ortho-
formylation of phenols. The reaction was discovered by Karl Ludwig Reimer and
Ferdinand Tiemann. In the simplest case, the product is salicylaldehyde.
Kolbe–Schmitt reaction
The Kolbe–Schmitt reaction/Kolbe process (named after Adolph Wilhelm
Hermann Kolbe and Rudolf Schmitt) is a carboxylation chemical reaction that
proceeds by heating sodium phenolate (the sodium salt of phenol) with carbon
dioxide under pressure (100 atm, 125°C), then treating the product with sulfuric
acid. The final product is an aromatic hydroxy acid which is also known as
salicylic acid (the precursor to aspirin).