Chem Factsheet

April 2002 www.curriculumpress.co.uk Number 31

Organic Chemistry 2: Halogeno-compounds and Grignard Reagents
To succeed in this topic you need to:- Reactions of Grignard reagents
• Have a good understanding of AS-level Organic Chemistry The Grignard reagent is very reactive.
(Factsheets 15, 16, 17 and 27);
H
• Be confident in using organic nomenclature and structural
formulae. δ− δ+
CH 3 C Mg I
After working through this Factsheet you will:-
• Have reviewed the chemistry of the halogeno-compounds covered H
so far;
They contain a δ- carbon, which gives rise to the extremely reactive R−
• Know how Grignard reagents are formed;
species i.e. in the above example,
• Know how Grignard reagents are used in a variety of organic
preparations. H
Halogeno-alkanes
CH 3 C−
Fig 1 below summarises the reactions of the halogeno-alkanes.

Fig. 1 Halogenoalkane reactions H

The R− species is a strong nucleophile, which is capable of attacking δ+

nitrile alcohol
carbons in other molecules - hence carbon chain lengths can be increased.
nucleophilic KCN in nucleophilic
substitution water/ethanol NaOH(aq) substitution 1. Reaction with water to form alkanes
heat under
heat under reflux R−MgI + H2O → R−H + Mg(OH)I
reflux
Halogenoalkane Reaction type: Substitution.
NH3 in KOH in Mechanism: Nucleophilic.
ethanol ethanol
heat heat under This reaction shows why Grignard reagents must be prepared in dry
amine reflux alkene conditions.
nucleophilic nucleophilic
substitution elimination 2. Reaction with methanal to form primary alcohol.
Methanal gas is passed into the solution of the Grignard, and the mixture
is then hydrolysed with dilute hydrochloric acid.
R−MgI + CH2=O→ R−CH2−O−MgI (Nucleophilic addition)
Grignard Reagents
The main focus of this Factsheet is on the formation and use of a commonly Then:
examined set of reagents derived from the halogenoalkanes - Grignard R−CH2−O−MgI + H2O → R−CH2−OH + Mg(OH)I (Hydrolysis)
reagents. Reaction conditions: In dry ether, followed by addition of dilute acid for
Preparation of Grignard Reagents hydrolysis.
Grignard reagents are prepared by refluxing alkyl or aryl bromide or iodide
compounds, dissolved in dry ether, with small magnesium turnings. 3. Reaction with other aldehydes to form secondary alcohols.
R−Br + Mg → R−MgBr R R
'Grignard reagent' H 2O
R−MgI + R'CHO → CH−O−MgI CH−OH + Mg(OH)I
The Grignard reagent cannot be isolated - it must remain in etheral solution R' R'
for further reaction.
Reaction conditions: In dry ether, followed by addition of dilute acid for
Example of Grignard reagent preparation: hydrolysis.

C2H5I + Mg → C2H5MgI For example:

C 2H 5
Reaction type: Addition C2H5MgI + CH3CHO → CH−O−MgI
Conditions: Dry ether solvent
Reflux CH3
H 2O
Trace of iodine as catalyst
C 2H 5
C−OH + Mg(OH)I
CH3
Butan-2-ol

1
Halogeno-compounds and Grigand Reagents Chem Factsheet
www.curriculumpress.co.uk

Answers.
4. Reaction with ketones to form tertiary alcohols. H Br H
1. (a)
R1 R1
R1 H C C C H
H 2O
R−MgI + C=O → R−C−O−MgI R−C−OH + Mg(OH)I
R2 H H H
R2 R2
(b) H H Cl Cl
Reaction conditions: In dry ether, followed by addition of dilute acid for H C C C C H
hydrolysis.
H H H H
For example:
C2H5 H
C2H5 (c)
CH3MgI + C=O CH3−C−O−MgI H C H
H H H Br Cl
C3H 7
C 3H 7
H C C C C C C H

H 2O H H H H Br H
2. Because they contain a very unstable δ- carbon atom, an extremely
strong nucleophile.
C2H5

CH3−C−OH + Mg(OH)I 3. CH3I should be dissolved in dry ether

Magnesium turnings added
C 3H 7 Iodine catalyst
Heat under reflux

5. Reactions of Grignard with carbon dioxide to form carboxylic acid. 4. (a) CH3CH2CH2I + Mg → CH3CH2CH2MgI
Carbon dioxide is bubbled through (or solid CO2, ‘dry ice‘, is added to) Conditions: Reflux in ether
an etheral solution of a Grignard reagent. Iodine catalyst
H 2O
R−MgI + CO2 → R−C−O−MgI R−C−OH + Mg(OH)I (b) CH3CH2CH2MgI + CO2 + H2O → CH3CH2CH2COOH + Mg(OH)I
O O Conditions: Addition of CO2 in dry ether, then dilute acid for
hydrolysis
Reaction conditions: In dry ether, followed by addition of dilute acid for
hydrolysis. 5. (a) CH3CH2Br + Mg → CH3CH2MgBr
Conditions: Reflux in ether
Iodine catalyst
Questions
1. Write the structural formulae of the following compounds: (b) CH3CH2CH2MgI + CH3CHO + H2O → CH3CH2CHOHCH3 + Mg(OH)Br
Conditions: Dissolved in dry ether, then dilute acid for
(a) 2-bromopropane
hydrolysis.
(b) 1,2-dichlorobutane

(c) 2,2-dibromo-1-chloro-3-methylhexane

2. Explain why Grignard reagents are very reactive.

3. Explain clearly how the Grignard reagent CH3MgI would be formed

from CH3I.

4. This question relates to the following reaction scheme:

step 1 step 2
CH3CH2CH2I CH3CH2CH2MgI CH3CH2CH2COOH

Give the reaction equations and conditions for:

(a) Step 1.
(b) Step 2.

5. This question relates to the following reaction scheme:

Acknowledgements: This Factsheet was researched and written by Sam
step 1 step 2
CH3CH2Br CH3CH2MgBr CH3CH2CHOHCH3 Goodman and Kieron Heath. Curriculum Press, Unit 305B, The Big Peg, 120
Vyse Street, Birmingham, B18 6NF. ChemistryFactsheets may be copied free
Give the reaction equations and conditions for: of charge by teaching staff or students, provided that their school is a registered
subscriber. No part of these Factsheets may be reproduced, stored in a retrieval
(a) Step 1. system, or transmitted, in any other form or by any other means, without the
(b) Step 2. prior permission of the publisher. ISSN 1351-5136