ORGANIC

CHEMISTRY
ASSIGNMENT
UNIT - III
PREPARATION OF BENZIL FROM BENZYL
ALDEHYDE :
 Benzil is the organic compound with the formula (C6H5CO)2.
 It’s IUPAC name is 1,2 – diphenylethane – 1,2 – dione.

USES:
It is mainly used as a photo initiator in polymer chemistry.
PREPARATION OF BENZIL FROM BENZOIN
:
Here alcohol group of benzoin is oxidized to ketone group forming
benzoin in the presence of concentrated nitric acid.
Nitration of aromatic ring is not possible here because of
absence of sulphuric acid in the whole process.


MECHANISM OF BENZIL FROM BENZOIN:

 PREPARATION OF FURYL FROM FURFURYL:
Furyl can be synthesized from furfural through the formation of furoin by
condensation reaction in the presence of alcoholic KOH. Furoin on oxidation to
produce furyl.
STRUCTURE:

USES:
It is used in cosmetics.
It is mainly used as drug clinically.
 PREPARATION OF VANILLIN FROM
CATECHOL THROUGH GUAIACOL :
•Vanillin (4-hydroxy-3-
methoxybenzaldehyde) is a
synthetic compound .
•It is phenolic aldehyde.
•Its functional groups include
aldehyde,hydroxyl and ether.
 Catechol is treated with dimethyl sulphate in presence of NaOH to
form guaiacol then it's treated with glyoxalic acid in presence of NaOH
followed by treatment of HCl to form vanillylmandelic acid and then
it's treated with bismuth product in presence of acetic acid in dimethyl
sulfoxide ( DMSO) solvent to form vanillin.

NaOH

Catechol Guaiacol Vanillylmandeic acid (VMA) Vanillin

 USES:
It is used extensively as a flavoring agent in many foods like
chocolate, ice cream, and baked goods.
• It is also used for its pleasant scent in perfumes and is a
flavoring agent in beverages.
•A large amount of vanillin (about 40% of all synthesized) is used
as a pharmaceutical intermediate as well.
 GRAMINE (MANNICH REACTION) :

• Gramine (also called donaxine) is a

naturally occurring indole alkaloid
present in several plant species. It is an
aminoalkylindole that is indole carrying
a dimethylaminomethyl substituent at
position 3.
PREPARATION OF GRAMINE FROM
INDOLE:
Indole undergoes Mannich reaction with formaldehyde and
dimethylamine to give 3-dimethylaminomethylindole [Gramine].
USES :
• It has a role as a
 plant metabolite
 a serotonergic antagonist
 an antiviral agent
 an antibacterial agent.
• Gramine may play a defensive role in these plants,
since it is toxic to many organisms.
SALOL

Phenyl Salicylate (C13H10O3)

USES:-
Salol used in sunscreens
Used in manufacture of polymers,waxes,polishes etc.
 PREPARATION:-

1 )
step

Phenol reacts with sodium hydroxide to give sodium phenoxide.

C6H5ONa then heated with CO2 to give salicylic acid.

This is known as Kolbe Schmitt reaction.

2 )
step

 Salicylic acid reacts with phenol in presence of

phosphorus oxychloride to give salol.
N-ACETYL 5-BROMO INDOLINE

C10H10BrNO

USES:-
 Used as intermediate in pharmaceutical industry
 PREPARATION:-
1step)

Indole undergoes hydrogenation to produce Indoline.

Indoline then undergoes acetylation to produce N-Acetyl

Indoline.
2step)

• N-Acetyl Indoline undergoes bromination to produce N-

Acetyl 5-Bromo Indoline
 ALANINE-
STRUCTURE

USES :
• Alanine is an amino acid that is used to make proteins.
• It is used to break down tryptophan and vitamin B6.
• It is a source of energy for muscles and the central nervous system.
• It strengthens the immune system
 PREPARATION OF ALANINE FROM
PROPIONIC ACID:
• Using Hell- Volhard- Zelinsky Bromination, the creation of racemic alanine
can be formed from propanoic acid.
• Hell- Volhard- Zelinsky Bromination allows for an addition of a functional
group at the carbon 2 of propanoic acid.
• Through this reaction, a nucleophile can displace the bromine that is formed
on carbon number two.
• In using a nucleophile such as ammonia, the amino acid Alanine can
therefore be formed.
 HETEROAUXIN

Indole-3-acetic acid is a monocarboxylic acid

that is acetic acid in which one of the
methyl hydrogens has been replaced
by a 1H-indol-3-yl group.

It is a growth promoting hormone

found naturally in plants.

Molecular formula: C10H9NO2

PREPARATION OF HETEROAUXIN FROM INDOLE
It is also prepared by treating indole with glycolic acid in the presence of
base at 250°C.

USES:

• IAA is often used along the Vitamin B,C.

• It is often used in horticulture to promote adventitious root growth.
• They are used commercially to create root stem cuttings and to
promote uniform fruit and flowering growth.
 CHLORAMPHENICOL
[CHLOROMYCETIN]
• Chloramphenicol is wide spectrum antibiotic
[bacteriostatic] .

• It is optically active compound and is

levorotatory.
• It was first Isolated from Streptomyces Venezuela in the year 1947.

• The synthesis of chloramphenicol is carried out by two methods :

BALTZ SYNTHESIS:
[Benzaldehyde and Nitro ethanol as the initial reactants].

LONG’S SYNTHESIS:
[p-nitroacetophenone as initial reactant]
BALTZ
SYNTHESIS:
LONG’S
SYNTHESIS :
 CHLORAMPHENICOL :
• It is used as an eye ointment to treat conjunctivitis
and sometimes as ear drops.

• It is also used to cure meningitis ,typhoid , rickettsial

infection etc.

SIDE EFFECTS:
• It causes Aplastic anemia which is a rare disease.
• Grey baby syndrome is caused in babies.
 ACYLOIN CONDENSATION
• The bimolecular reductive coupling of carboxylic esters by reaction with metallic sodium in an inert solvent
under reflux gives an α-hydroxyketone, which is known as an acyloin.

• The intramolecular version of this reaction has been used extensively to close rings of different sizes, e.g.
paracyclophanes or catenanes.

• If the reaction is carried out in the presence of a proton donor, such as alcohol, simple reduction of the ester
to the alcohol takes place (Bouveault-Blanc Reduction).
MECHANISM OF ACYLOIN CONDENSATION:
 BAEYER VILLIGER
OXIDATION
The Baeyer–Villiger oxidation is an organic reaction that forms an ester
from a ketone or a lactone from a cyclic ketone, using peroxyacids or
peroxides as the oxidant

GENERAL
REACTION
REACTION MECHANISM

• In the first step of the reaction mechanism, the peroxyacid protonates the
oxygen of the carbonyl group.
• This makes the carbonyl group more susceptible to be attacked by the
peroxyacid.
• Next, the peroxyacid attacks the carbon of the carbonyl group forming what is
known as the Criegee intermediate.
• Through a concerted mechanism, one of the substituents on the ketone
migrates to the oxygen of the peroxide group while a carboxylic acid leaves.
• This migration step is thought to be the rate determining step. Finally,
deprotonation of the oxocarbenium ion produces the ester.
Stereochemistry
The migration does not change the stereochemistry of the group that transfers, i.e.: it is stereo
retentive.

Reagents
• Although many different peroxyacids are used for the Baeyer–Villiger oxidation, some of the
more common oxidants include meta-chloro perbenzoic acid (mCPBA) and trifluoroperacetic
acid (TFPAA).
• The general trend is that higher reactivity is correlated with lower pKa (i.e.: stronger acidity)
of the corresponding carboxylic acid (or alcohol in the case of the peroxides).
• Therefore, the reactivity trend shows TFPAA > 4-nitroperbenzoic acid > mCPBA and
performic acid > peracetic acid > hydrogen peroxide > tert-butyl hydro peroxide.[4] The
peroxides are much less reactive than the peroxyacids.
 GABRIEL’S PTHALIMIDE
SYNTHESIS
The Gabriel synthesis is a chemical reaction that transforms
primary alkyl halides into primary amines. Traditionally, the
reaction uses potassium phthalimide. The name of the
reaction comes from the German chemist Siegmund Gabriel.
GENERAL REACTION
 MECHANISM
STEP 1:
When potassium hydroxide is introduced to the phthalimide. The
hydroxide ion deprotonates the imide. The resulting proton is more
acidic than any simple amine, generating a strong nucleophile – the
imide ion.
 STEP 2:
The nucleophilic imide ion attacks the electrophilic carbon of the alkyl
halide. The nitrogen atom subsequently replaces the halogen in the
alkyl halide and bonds with the carbon itself. This results in the
formation of an N-Alkyl Phthalimide.
 STEP 3
The hydroxide ion attacks the carbon atom bonded to the nitrogen
atom, cleaving the N-Alkyl phthalimide. The cation in the base attaches
itself to the oxygen atom as well. It is important to note that the
nitrogen atom attached to the R group bonds with the hydrogens
ejected from the hydroxide ion when the oxygen atom replaces it in the
phthalimide.
 BARTOLI INDOLE
REACTION
The Bartoli indole synthesis is the
chemical reaction of ortho-substituted
nitroarenes and nitrosoarenes with vinyl
Grignard reagents to form substituted
indoles.
GENERAL REACTION
REACTION
MECHANISM
DONE BY
• Vaneshree K (2019303052)
• Vasanthan V (2019303054)
• Vigneshwaran K (2019303055)
• Abdul Bazith K (2019303501)
• Anuja M (2019303504)
• Ashwin S (2019303508)
• Athithakandan J (2019303509)
• Dhaksha Aniesh (2019303513)
• Diwakar R (2019303515)
• Krishnakaanth S R (2019303524)
• Krishnan Shankar (2019303525)