Grignard

Reactions
Dr. M. Abbas Bhatti

Ph.D (Scholar-BZU), M.Phil (PU), B.Pharm (PU)

Pharmaceutical Chemistry
Islam College of Pharmacy, Sialkot.

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Learning objectives

Definition of Grignard reagent and its method

of preparation.
What are the physical and chemical properties
of grignard reagent.
Various reactions of grignard reagent and its
pharmaceutical significance.

Grignard reagents (RMgX)

Organomagnesium halides or alkyl magnesium
halides are called Grignard reagent.
General formula: R Mg X
R=alkyl/aryl group, X=Cl, Br or I
Examples: CH3MgI, CH3MgBr
Victor Grignard discovered them and
developed their use as synthetic reagents.
reagents

The Grignard reagents are highly reactive &

used in the synthesis of alkanes, alkenes,
alcohols, aldehydes, ketones & carboxylic
acids.
Preparation: They are prepared in the
laboratory by the action of alky halides on
magnesium metal in the presence of dry ether
(anhydrous, C2H5OC2H5).
ether
R X + Mg
R MgX

CH3 I + Mg

reflux
ether
reflux

CH3 MgI
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Grignard reagent is produced by dropping a

solution of alkyl halide in dry ether into the
reaction flask containing magnessium ribbon
suspended in dry ether.
ether
Diethyl ether plays two important roles:
a)- It provide medium for the reaction.
b)- It dissolve Grignard reagent through
solvolysis.
solvolysis
Tetrahydrofuran (THF) can also be used in
place of dry ether.
Order of reactivity. RI>RBr>RCl.
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Physical properties:
a)- Non volatile colorless solids.
b)- They are seldom isolated in the free state
because of their explosive nature.
nature Therefore,
always prepared & used in ether solution.
Chemical properties:
The C-Mg bond in GRs is covalent but highly
polar.
polar
The C atom is more electronegative than Mg
& electrons are drawn towards the C atom.
As a result, the C atom has a partial ve & Mg
has partial +ve charge.
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1)- Reaction with compounds containing

active H.

Compounds like water, alcohols, & amines

react with Grignard reagents to form alkanes.
alkanes
CH3MgI + HO H

Methylmegnesium
iodide

water

CH4 + MgI(OH)

Methane

CH3MgI + C2H5O H

CH4 + MgI(OC2H5)

CH3MgI + C2H5NH H

CH4 + MgI(NHC2H5)

Ethanol

Ethylamine

2)- Reaction with Alkyl Halides to form

higher alkanes or alkenes.
CH3MgBr + CH3 Br

CH3 CH3 + MgBr2

Ethane

3)- Reaction with Cyanogen chlride to form

alkyl nitrile.

CH3MgBr + ClCN

CH3CN + MgBr(Cl)
Methyl nitrile

4)- Reaction with Carbonyl compounds.

Grignard reagents react with carbonyl group of

aldehydes & ketones forming an addition
product,
product which on acid hydrolysis give
different types of alcohols.
alcohols
i)- Reaction with Formaldehyde (primary
alcohol synthesis).
From
RMgX

ii)- Reaction with Acetaldehyd to produce

secondary alcohol.
From
RMgX

iii)- Reaction with Ketones to produce tertiary

alcohol.
alcohol
From
RMgX

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5)- Reaction with Esters

i)- Reaction with Ethyl Formate to produce

aldehyde.
From
RMgX

ii)- Reaction with ethyl acetate to produce

ketones.
ketones

CH3

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6)- Reaction with Acid Chlorides to form ketones.

CH3

7)- Reaction with CO2 to produce carboxylic acid.

+ MgI(OH)

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8)- Reaction with Ethylene Oxide to form

primary alcohol.
CH3CH2CH2OH
1-Propanol
Primary
alcohol

9)- Reaction with Cyanides to produce

ketones.

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10)- Reaction with Sulphur to produce

corresponding alcohol.

11)- Reaction with inorganic halides to form

other organometalic compounds.

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References

A TEXT BOOK OF ORGANIC CHEMISTRY

BY M. YOUNAS.

Solvolysis: combining of solute and solvent: a chemical reaction in which a dissolved solute
and its solvent combine to form a new compound.

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