Chem Factsheet

April 2003 Number 52

Reactions of Functional Groups - A Summary

To succeed in this topic you need to: Be able to recall and write out the functional groups represented in this Factsheet; Have a thorough knowledge of the organic reactions and their conditions (described in the Organic Chemistry Factsheets to date 27, 31, 32, 33, 34 and 39); Recognise the summarised versions of the equations in this Factsheet and be able to write them out in full under exam conditions. After working through this Factsheet you will: Have revised the organic chemistry reactions that candidates are required to learn for AS and A2 Chemistry modules. Have a reference paper as you start to work through questions on organic pathways and synthesis. This Factsheet is designed to be used as a revision aid as candidates set about the sometimes daunting task of learning all of the organic reactions required by the A2 Chemistry course. These spider diagrams represent the reactions in a summarised version, in a visual fashion that suits many learners. They should be used in conjunction with Factsheets 27, 31, 32, 33, 34 and 39, which show the reactions in a more detailed format. A good way of using this Factsheet to revise effectively would be as follows: 1. Pick a group to revise (e.g. alkanes). 2. Pick a member of that group at random (e.g. propane). 3. Use the spider diagram to help you write out balanced chemical reactions, with conditions, for the organic chemical you have chosen. (e.g.) Propane and oxygen (combustion) C3H8 + 5O2
heat

Reactions of alkenes CO2 + H2O Alkane

H2 electrophilic heat, addition Ni catalyst O2 heat halogen

Di-halogenoalkane
electrophilic addition

Alkenes

Diol

alkaline KMnO4(aq)

hydrogen halide

Halogenoalkane
electrophilic addition

oxidation electrophilic addition

Reactions of alcohols bromo-alkane nucleophilic substitution chloro-alkane nucleophilic substitution

NaBr(s) + H2SO 4(conc.) to make HBr

iodo-alkane nucleophilic substitution

dry PCl5

P(s) + I2(s) to make PI 3

halogenation

3CO2 + 4H2O dehydration

Alcohol oxidation primary alcohols

Propane and chlorine (free radical substitution) C3H8 + Cl2

uv light

C3H7Cl + HCl

conc. H2SO4

In an exam, candidates are required to apply their knowledge of organic reactions to a wide variety of compounds, so the more of these you do, the better! Reactions of alkanes

heat to 170 o C

secondary alcohols
Cr2O72(aq) H+(aq)

Cr2O72(aq)

H+(aq)

alkene

Carbon Dioxide + Water

combustion

O2 heat

halogen

aldehyde Halogeno alkane

free radical substitution further oxidation Cr2O72(aq) H+(aq)

ketone

Alkanes
UV Light

carboxylic acid

Reactions of Functional Groups - A Summary

Fig. 3 Halogenoalkane reactions
Nitrile
nucleophilic substitution KCN in water/ethanol heat under reflux NH3 in ethanol NaOH(aq)

Chem Factsheet
Ester Reactions

Alcohol
nucleophilic substitution

Carboxylic acid + Alcohol

H 2O

H 2O

Ester
acid conditions alkaline conditions

Carboxylic acid + Alcohol

heat under reflux

Halogenoalkane
KOH in ethanol heat under reflux

heat

Acyl Chloride Reactions Carboxylic acid

nucleophilic substitution H 2O alcohol

Amines
nucleophilic substitution

Alkene
nucleophilic elimination

Ester
nucleophilic substitution

Grignard Reagents Preparation

Mg turnings

Halogenoalkane
Dry ether solvent Boil under reflux

Grignard Reagent "R-MgHal"

addition primary amine

Acyl Chloride
NH3

Reactions Primary Alcohol

nucleophilic addition / hydrolysis

N-substituted Amide
nucleophilic substitution

Amide
nucleophilic substitution

Alkane
nucleophilic substitution

methanal, CH2=O(g) then use + H2O(l) dilute acid for hydrolysis H 2O H+(aq)

Secondary Alcohol
nucleophilic addition / hydrolysis

Reactions of Aldehydes Primary Alcohol

reduction

Grignard Reagent "R-MgHal"

CO2 (g) + H2O(l) H+(aq) ketone + H2O(l)

aldehyde (not methanal) + H2O(l)

Hydroxy-nitrile compound
nucleophilic addition trace of KOH

Primary Alcohol
reduction LiAlH4 in ether Fehlings solution warm

H+(aq)

HCN

NaBH4 in ethanol

Carboxylic Acid
nucleophilic addition / hydrolysis

Tertiary Alcohol
nucleophilic addition / hydrolysis

Aldehydes
2,4-DNP in ethanol H2SO4 silver nitrate in ammonia warm solution

Carboxylic Acid Reactions Polyester Ester

nucleophilic substitution alcohol boil under reflux conc. H2SO4 Na2CO3 or NaHCO 3 nucleophilic substitution / polymerisation

2,4-DNP Derivative
nucleophilic addition then elimination

Positive Fehlings Test

redox

Positive Silver Mirror Test

redox

Alcohol
Diacid + H+(aq) Diol reduction LiAlH4 then H+(aq) LiAlH4 in dry ether PCl5

Carboxylic Acid
aqueous

dry

Sodium Salt + CO2 + H2O

neutralisation

Acyl Chloride
nucleophilic substitution

Reactions of Functional Groups - A Summary

Reactions of Aldehydes Secondary Alcohol
reduction

Chem Factsheet
Reactions of Amino Acids
acid alkali

Salt Secondary Alcohol

reduction LiAlH4 in ether neutralisation

Amino Acids

Salt
neutralisation

Hydroxy-nitrile compound
nucleophilic addition trace of KOH

HCN

NaBH4 in ethanol

Reactions of Phenol 2,4,6tribromophenol

electrophilic substitution OH (aq) Br 2(aq)
-

Ketones
2,4-DNP in H2SO4

Phenate ion
neutralisation

2,4-DNP Derivative
nucleophilic addition then elimination

Phenol
acyl chloride, in NaOH(aq)

Reactions of Amines Substituted Amides

nucleophilic substitution

Ester
nucleophilic substitution

Salts
nucleophilic addition / neutralisation acid

Reactions of Benzene Bromobenzene

acyl chloride

electrophilic substitution Br2 Fe cat. dry

Amines
primary amines + acyl chlorides if monomers contain 2 amine groups and 2 acyl chloride groups 50o C conc H2SO4

Benzene
Fe cat. dry HNO3 Br2

Polyamides
nucleophilic substitution polymerisation

Nitrobenzene
electrophilic substitution

Alkylbenzene
electrophilic substitution in alkali heat under reflux

Reactions of Nitrites Carboxylic acid salt

hydrolysis alkali heat under reflux acid heat under reflux LiAlH4 in ether

Nitriles

Carboxylic acid
hydrolysis

Sn, conc. HCL, NaOH

KMnO 4

Phenylamine
reduction HNO2 + HCl

Benzocarboxylic acid
oxidation

Amine
reduction

Reactions of Amides

Benzenediazonium ions
Br2(l) + NaOH(aq) warm

Nitrile
dehydration

P4 O10 warm

Amides

Amine + CO2
hydrolysis

Acknowledgements: This Factsheet was researched and written by Kieron 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 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 the prior permission of the publisher. ISSN 1351-5136