Chem Factsheet

April 2002 www.curriculumpress.co.uk Number 34

Organic Chemistry 5: Compounds Containing Nitrogen
To succeed in this topic you need to:- Nitriles
• Have a good knowledge and understanding of the organic
chemistry covered so far (Factsheets 15, 16, 17, 27 31, 32 and 33); Functional group: C N:, which is also written as CN
• Be confident in using organic nomenclature and structural
formulae.
The lone pair on the electronegative nitrogen atom makes the nitrile group
After working through this Factsheet you will:- a strong nucleophile.
• Know the functional groups of amines, amides, nitriles and amino
acids; Nitriles can be prepared by reacting a haloalkane with KCN in aqueous
• Have been given the required reaction types conditions and ethanol (which increases the length of the carbon chain by one) - see
equations of the nitrogen containing compounds for the A2 Factsheet 16.
exams.
Reactions of the nitriles.
Amines 1. Hydrolysis of nitriles.
.. Nitriles can be hydrolysed by refluxing them with aqueous hydrochloric
Functional group: C−NH2 acid or aqueous sodium hydroxide.

(a) Hydrolysis with acid.

Like alcohols, amines can be primary, secondary or tertiary:
H R2 R2 The carboxylic acid is formed (via the amide as an intermediate).
R1 C NH 2 R1 C NH 2 R 1 C NH 2 CH3CH2CN + HCl + 2H2O heat
CH3CH2COOH + NH4Cl

H H R3 Reaction type: hydrolysis

primary secondary tertiary Conditions: acidic, heat under reflux
The lone pair of electrons on the nitrogen atom makes the amine group
both basic (an acceptor of protons, H+) and a nucleophile (a donator of (b) Hydrolysis with alkali.
electrons).
The carboxylic acid salt is formed (again via the amide intermediate).
Reactions of the amines. heat
CH3CH2CN + NaOH + H2O CH3CH2COO-Na+ + NH3
1. Reaction of primary amines with aqueous hydrogen ions (acids). Reaction type: hydrolysis
Amines are basic, so react with acids to form salts. Conditions: alkaline, heat under reflux
CH3CH2NH2 + HCl CH3CH2NH3+Cl−
2. Reduction of nitriles
Reaction type: addition
Conditions: acidic, aqueous Nitriles are reduced to amines by LiAlH4 dissolved in dry ether - a
Mechanism: nucleophilic powerful reducing agent.
LiAlH4
C2H5CN + 4[H] C2H5CH2NH2
2. Reaction of primary amines with acid chlorides.
Primary amines react quickly with acid chlorides to form substituted Reaction type: reduction
amides. Conditions: dry ether, followed by addition of dilute acid.
O O
C2H5NH2 + CH3C CH3C + HCl
Cl NHC 2H 5
Recation type: substitution
Conditions: aqueous, room temperature
Mechanism: nucleophilic

3. Formation of polyamides. H H O O H H
The above reaction between primary amines and acid chlorides can be ○ ○
N (CH2)6 N C (CH2) 4 C N (CH2)6 N ○ ○

used to form polymers if monomers are used with 2 amine groups and 2 H H Cl Cl H H
acid chloride groups present. O O

For example, the formation of nylon−6,6 − so called because both N (CH2)6 N C (CH2)4 C N (CH2)6 N
monomers contain 6 carbon atoms. H H H H
With HCl molecules being eliminated, this is a form of “elimination
polymerisation”.

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Organic chemistry 5: compounds containing nitrogen Chem Factsheet
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Amino acids Amides

Functional group: Amino acids contain both -NH2 and - COOH O

Functional group: R C
groups (usually bonded to the same carbon atom).
H O NH 2
e.g. glycine
N C C
The amides are carboxylic acid derivatives.
NH 2 OH
They are formed by reacting ammonia with acyl chloride - see Factsheet 32.

Reactions of the amides

Exam Hint - Glycine is not a chiral molecule, but many amino acids 1. Dehydration of amides using phophorus (V) oxide.
are. Chirality will often figure in questions about amino acids, so
ensure that you understand this form of isomerism - see Factsheet 27. Amides are dehydrated to nitriles on heating with P4O10.
O
P4O10
CH3C CH3CN + H2O
Amino acids react as both acids and bases. NH 2
They are water soluble ionic solids because the molecules ethanenitrile
ethanamide
have ionic interactions.
Reaction type: dehydration (elimination)
Conditions: warm and distil off ethanenitrile
They form zwitterions, ions having both positive and negative charges
on them. CH3 O 2. Hoffmann degradation reaction with bromine and aqueous alkali.
CH3 O
(e.g.) N C C N C C Amides react with bromine in a solution of sodium hydroxide to give
- amines.
OH NH O
NH 2 3 O
+
CH3C + Br2 + NaOH → CH3NH2 + CO2 + 2NaBr + H2O
A "Zwitterion"
NH 2
Reactions of amino acids Conditions: Add liquid bromine to amide at room temperature, then
These reactions show that amino acids are amphoteric. add concentrated sodium hydroxide solution and warm.
The amine is then distilled off.
1. Reaction of amino acids with acids.
Note: The length of the carbon chain is decreased by one as CO2 is given off.
NH2CH3CHCOOH + H+ → NH3+CH3CHCOOH

2. Reaction of amino acids with bases.

NH2CH3CHCOOH + OH− → NH2CH3CHCOO− + H2O

The amphoteric nature of amino acids goes some way towards explaining Answers
why these compounds are commonly used in buffer solutions. 1. The lone pair of electrons on the nitrogen atom allows the group to
accept protons (H+), hence it is basic, and also to donate electrons to
Questions form dative covalent bonds with electron deficient species (hence a
1. The amine functional group is both basic and a nucleophile. Explain nucleophile).
why. 2.
2. Draw structural formulae for the following: (a) (b) (c)
(a) Propanamine. H H H H H H O H H
(b) Propanamide. H C C C N
H C C C N H C C C
(c) Propanenitrile.
H NH 2
H H H H H H H
3. (a) Draw the structure of NH2CH3CHCOOH, indicating the position
of the chiral centre.
3. (a) CH3
(b) Use equations to illustrate the amphoteric nature of
NH2CH3CHCOOH. NH 2 C* COOH * = chiral centre

4. The question refers to the following reaction scheme: H

step 1 step 2
(b) As a base:
CH3CONH2 CH3CN CH3CH2NH2 NH2CH3CHCOOH + H+ → NH3+CH3CHCOOH
step 3
CH3NH2 As an acid:
Give the reaction equations and conditions for: NH2CH3CHCOOH + OH− → NH2CH3CHCOO− + H2O
(a) Step 1.
4. (a) CH3CONH2 → CH3CN + H2O
(b) Step 2.
Conditions: P4O10, warm, and distil off ethanenitrile.
(c) Step 3
(b) CH3CN + 4[H] → CH3CH2NH2
Acknowledgements: This Factsheet was researched and written by Sam Goodman and Kieron Conditions: LiAlH4 in dry ether, followed by addition of dilute acid.
Heath. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF.
ChemistryFactsheets may be copied free of charge by teaching staff or students, provided
(c) CH3CONH2 + Br2 + 2NaOH → CH3NH2 + CO2 + 2NaBr + H2O
that their school is a registered subscriber. No part of these Factsheets may be reproduced,
stored in a retrieval system, or transmitted, in any other form or by any other means, without Conditions: Add Br2 at room temperature, then add
the prior permission of the publisher. ISSN 1351-5136 concentrated sodium hydroxide solution and warm.
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