Reactions involving Grignard’s reagent:
Grignard’s reagent is one of the most basic yet important reagents in general organic
chemistry.
The Grignard reagent functions as a nucleophile, attacking the electrophilic carbon atom that is
present within the polar bond of a carbonyl group. Grignard reagents form via the reaction of an
alkyl or aryl halide with magnesium metal. The reaction proceeds through single electron transfer. In
the Grignard formation reaction, radicals may be converted into carbanions through a second
electron transfer.
R−X + Mg → R−X•− + Mg•+
R−X•− → R• + X−
R• + Mg•+ → RMg+
RMg+ + X− → RMgX
A limitation of Grignard reagents is that they do not readily react with alkyl halides via an SN2
mechanism. On the other hand, they readily participate in transmetalation organic reactions:
RMgX + AlX → AlR + MgX2
2. Wurtz reaction
The reaction consists of a halogen-metal exchange involving the radical species R• (in a similar
fashion to the formation of a Grignard reagent and then the carbon–carbon bond formation in a
nucleophilic substitution reaction.) One electron from the metal is transferred to the halogen to
produce a metal halide and an alkyl radical.
R–X + M → R• + M+X−
The alkyl radical then accepts an electron from another metal atom to form an alkyl anion and the
metal becomes cationic. This intermediate has been isolated in several cases.
R• + M → R−M+
The nucleophilic carbon of the alkyl anion then displaces the halide in an SN2 reaction, forming a new
carbon-carbon covalent bond.
R−M+ + R–X → R–R + M+X−
3. Corey-House synthesis
This reaction occurs in two steps. The alkyl halide is treated with lithium metal, and solvated in dry
ether, which converts the alkyl halide into an alkyl lithium compound, R-Li. The starting R-X can be
primary, secondary or tertiary alkyl halide:
R-X + 2Li → R-Li + Li-X
The second step requires the alkyl lithium compound to be treated with cuprous iodide (CuI). This
creates a lithium dialkyl cuprate compound.
2RLi + CuI → R2CuLi + LiI
The lithium dialkyl cuprate is then treated with the second alkyl halide, which couples to the
compound:
R2CuLi + R’-X → R-R’ + RCu + LiX
A very easy, yet important of all the organic reactions.
4. Esterification and de-esterification
Esterification is a reversible reaction. Esters undergo hydrolysis under acid and basic conditions.
Under basic conditions, hydroxide acts as a nucleophile, while an alkoxide is the leaving group. This
reaction, saponification, is the basis of soap making.
De-esterfication :
RCO2R′ + 2 H2 → RCH2OH + R′OH
5. Aldol condensation
One of the most important organic reactions, the first part of this reaction is an aldol reaction, the
second part a dehydration—an elimination reaction.
6. Cannizzaro reaction
The reaction involves a nucleophilic acyl substitution on an aldehyde, with the leaving group
concurrently attacking another aldehyde in the second step. First, hydroxide attacks a carbonyl. The
resulting tetrahedral intermediate then collapses, re-forming the carbonyl and transferring hydride
to attack another carbonyl. In the final step of the reaction, the acid and alkoxide ions formed
exchange a proton.
7. Hoffman bromamide synthesis
Another amongst very important organic reactions, the reaction of bromine with sodium hydroxide
forms sodium hypobromite, which transforms the primary amide into an intermediate isocyanate via
a formation of a nitrene.
8. Carbylamine reaction
The carbylamine reaction is a chemical test for detection of primary amines. In this reaction, the
analyte is heated with alcoholic potassium hydroxide and chloroform. If a primary amine is present,
the isocyanides (carbylamine) are formed which are foul smelling substances.
For example, the reaction with ethylamine:
The reaction with aniline:
The carbylamine test does not give a positive reaction with secondary and tertiary amines.
9. Reimer-Tiemann reaction
10. Birch reduction
The solution of metal in ammonia providlistes electrons which are taken up by the aromatic ring to
form the corresponding radical anion B in the first step of the reaction. This is followed by
protonation by the alcohol to form a cyclohexadienyl radical C. Next, a second electron is transferred
to the radical to form a cyclohexadienyl carbanion D. In the last step a second proton leads the
cyclohexadienyl carbanion to the unconjugated cyclohexadienyl product. These steps are outlined
below for the case of anisole.
The reaction is known to be third order – first order in aromatic, first order in the alkali metal, and
first order in the alcohol. This requires the rate-limiting step to be the conversion of radical anion B
to the cyclohexadienyl radical C.
A Bottom-Up Approach
A bottom-up approach will be to do the reverse of what I have just told you. You buy chemistry
NCERT books and one or two reference books and start mugging-up. What you have to mug-up is
below-
1. All named reactions and their mechanisms with their intermediary products (if any) and the final
products and by-products. Take note of reaction catalysts and atmospheric conditions required to
carry out the reactions.
2. Order of nucleophilicity, electrophilicity, steric hindrance, etc.
3. Polymers and their monomers. Reactions and processes involved in polymerization.
4. Various configurations of organic compounds like R-S, cis-trans, etc
5. Sugars.
6. Structure of DNA and RNA.
7. Carbon and its Compounds.
1. Sandmeyer Reaction
When a primary aromatic amine is treated with sodium nitrite in the presence of cold aqueous
mineral acid, a diazonium salt is formed. This freshly prepared diazonium salt is further mixed with
cuprous chloride or bromide which results in the replacement of diazonium group by –Cl or –Br. This
reaction for the synthesis of haloarenes from a diazonium salt is popularly known as Sandmeyer
reaction.
2. Gattermann Reaction
The Gattermann reaction, (also known as the Gattermann salicylaldehyde synthesis) is a chemical
reaction in which aromatic compounds are formylated by hydrogen cyanide in the presence of a
Friedel–Crafts catalyst (e.g. AlCl3). It is named for the German chemist Ludwig Gattermann and is
similar to the Friedel-Crafts reaction.
3. Balz-Schiemann Reaction
The conversion of aryl amines to aryl fluorides via diazotisation and subsequent thermal
decomposition of the derived tetrafluoroborates or hexafluorophosphates. The decomposition may
also be induced photochemically.
2. Gattermann Reaction
The Gattermann reaction, (also known as the Gattermann salicylaldehyde synthesis) is a chemical
reaction in which aromatic compounds are formylated by hydrogen cyanide in the presence of a
Friedel–Crafts catalyst (e.g. AlCl3). It is named for the German chemist Ludwig Gattermann and is
similar to the Friedel-Crafts reaction.
3. Balz-Schiemann Reaction
The conversion of aryl amines to aryl fluorides via diazotisation and subsequent thermal
decomposition of the derived tetrafluoroborates or hexafluorophosphates. The decomposition may
also be induced photochemically.
7. Fitting Reaction
In Fittig reaction, two aryl halides are coupled in presence of sodium metal in dry ether or
tetrahydrofuran to furnish biaryls.
8. Wurtz – Fittig Reaction
The Wurtz–Fittig reaction is the chemical reaction of aryl halides with alkyl halides and sodium metal
in the presence of dry ether to give substituted aromatic compounds.
9. Kolbe’s Reaction
10. Reimer- Tiemann Reaction
The Reimer–Tiemann reaction is a chemical reactionused for the ortho-formylation of phenols; with
the simplest example being the conversion of phenol to salicylaldehyde. The reaction was
discovered by Karl Reimer and Ferdinand Tiemann.
11. Rosenmund Reduction
The reaction is catalysed by palladium on barium sulfate, which is sometimes called the Rosenmund
catalyst. Barium sulfate has a low surface area which reduces the activity of the palladium,
preventing over-reduction. However, for certain reactive acyl chlorides the activity must be reduced
further, by the addition of a poison.
12. Gattermann – Koch Reaction
The Gattermann–Koch reaction, named after the German chemists Ludwig Gattermann and Julius
Arnold Koch, refers to a Friedel–Crafts acylation reaction in which carbon monoxide, hydrochloric
acid, and a Friedel–Crafts catalyst (e.g. AlCl3) are used to produce aromatic aldehydes from various
aromatic compounds, including derivatives of benzene and naphthalene:
13. Stephen Reaction or Stephen Reduction
14. Clemmensen Reduction
Clemmensen reduction is a chemical reaction described as a reduction of ketones (or aldehydes) to
alkanes using zinc amalgam and hydrochloric acid. This reaction is named after Erik
Christian Clemmensen, a Danish chemist.
This is very important for JEE Mains and Advanced Exam.
15. Wolff – Kishner Reduction
Never, I repeat, Never ever memorise Organic chemistry reactions if you want to score high in this
section of Chemistry on your JEE Main / Advanced exam. (Although some memorising can be
good, for instance you should try to remember the different Organic functional groups- Organic
Chemistry Functional Groups Cheatsheet)
I was spending so much time focusing on the why and how of chemical reactions, but could not co-
relate between the structures of the reagents and the resulting compounds.
This is when my mentor (AIR 359 - IIT JEE 2003) gave me the best piece of advice:
“When you are studying reactions in Organic Chemistry, ask yourself - what specific bonds are
formed, and what specific bonds are broken”
