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More Functional Groups

lilil'lllN24724

@ Inner London Education Authority 1984

First published 1984by John Murray (Publishers) Ltd50 Albemarle Street~ London W1X 4BD

All rights reserved.Unauthorised duplicationcontravenes applicable laws

Printed in Great Britain byMartin's of Berwick

British Library Cataloguing in Publication Data

II. Series0161.2

Independent Learning Project for AdvancedMore functional groups. - (ILPACj unit1. ScienceI. Title500

ISBN 0 7195 4047 X

ii

Chemistry03)

CONTENTS

PREFACEAcknowledgementsKey to activity symbols and hazard symbols

INTRODUCTIONPre-knowledge

CARBONYL COMPOUNDS: ALDEHYDES AND KETONESNamesl structural formulae and shapesChemical properties of aldehydes and ketonesExperiment 1 - reactions of aldehydes and ketonesReactions of aldehydes and ketones - similaritiesThe mechanism of addition to carbonyl compoundsThe mechanism of condensation reactionsIdentifying carbonyl compoundsReactions of carbonyl compounds - differencesOxidation of aldehydesReaction of carbonyl compounds with alkaliTriiodomethane reactionDistinguishing testsExperiment 2 - identifying an unknown carbonyl compoundMethods of preparationSummary of reactions and preparationsSynthetic pathwaysUses of carbonyl compounds

CARBOXYLIC ACIDSNames and structural formulaeChemical properties of carboxylic acidsExperiment 3 - chemical properties of carboxylic acidsReactions of carboxylic acidsDistinguishing testsAcidityMethods of preparationSummary of reactions and preparationsSynthetic pathwaysUses of carboxylic acidoSalts of carboxylic acidsExperiment 4 - identifying salts of carboxylic acids

vvi

vii

11

223479

101111111213141720222325

27272828313233353738394041

CARBOXYLIC ACID DERIVATIVES 44Names and structural formulae 44Chemical properties of carboxylic acid derivatives 46Nucleophilic substitution of acid derivatives 46Experiment 5 - chemical properties of ethanoyl chloride 46Mechanism for nucleophilic substitution of carboxylic acid derivatives 50Reduction of carboxylic acid derivatives 51Other reactions of amides 52Comparing acyl halides and alkyl halides 53Comparing amides and amines 53Basicity 54Distinguishing tests 55Methods of preparation 55Experiment 6 - preparing an ester 57Summary of reactions and preparations 60Synthetic pathways 61

iii

ISOMERISMOptical isomerismOptical propertiesSynthesis of optically active compoundsSeparation of optical isomersSummary of isomerismDistinguishing isomers

END-Of-UNIT PRACTICAL TESTA suggestion for revisionEND-Of-UNIT CHECKLISTEND-Of-UNIT TEST

ANSWERS TO EXERCISES

iv

62636567686972

73757577

83

PREFACE

This volume is one of twenty Units produced by ILPAC, the Independent LearningProject for Advanced Chemistry, written for students preparing for the AdvancedLevel examinations of the G.C.E. The Project has been sponsored by the InnerLondon Education Authority and the materials have been extensively tested inLondon schools and colleges. In its present revised form, however, it isintended for a wider audience; the syllabuses of all the major ExaminationBoards have been taken into account and questions set by these boards have beenincluded.

Although ILPAC was initially conceived as a way of overcoming some of thedifficulties presented by uneconomically small sixth forms, it has frequentlybeen adopted because its approach to learning has certain advantages over moretraditional teaching methods. Students assume a greater responsibility fortheir own learning and can work, to some extent, at their own pacel whileteachers can devote more time to guiding individual students and to managingresources.

By providing personal guidance, and detailed solutions to the many exercises,supported by the optional use of video-cassettes, the Project allows studentsto study A-level chemistry with less teacher-contact time than a conventionalcourse demands. The extent to which this is possible must be determinedlocally; potentially hazardous practical work mustl of coursel be supervised.Nevertheless, flexibility in time-tabling makes ILPAC an attractive propo-sition in situations where classes are small or suitably-qualified teachersare scarce.

In addition, ILPAC can provide at least a partial solution to other problems.Students with only limited access to laboratories, for example, those studyingat evening classes, can concentrate upon ILPAC practical work in the laboratory,in the confidence that related theory can be systematically studied elsewhere.Teachers of A-level chemistry who are inexperiencedl or whose main disciplineis another science, will find ILPAC very supportive. The materials can be usedeffectively where upper and lower sixth form classes are timetabled together.ILPAC can provide 'remedial' material for students in higher education.Schools operating sixth form consortia can benefit from the cohesion that ILPACcan provide in a fragmented situation. The project can be adapted for use inparts of the world where there is a severe shortage of qualified chemistryteachers. And so on.

A more detailed introduction to ILPAC, with specific advice both to studentsand to teachers, is included in the first volume only. Details of the ProjectTeam and Trial Schools appear inside the back cover.

LONDON 1983

v

ACKNOWLEDGEMENTSThanks are due to the following examination boards for permission to reproducequestions from past A-level papers:

Joint Matriculation Board;Teacher-marked Exercises p.26(1980), p.72(1980)

Southern Universities Joint Board;Exercise 22(1977)

University of Cambridge Local Examinations Syndicate;Exercises 21(1974), 36(1979)

University of London Entrance and School Examinations Council;Exercises 20CL1978), 27CL1979), 28CN1976), 41CL1975), 43(1980)Experiment 4CL1982)End-of-Unit Test 1CL1976), 2 to 5CL1981l, 6CL1975), 7CL1976). 8CL1978),

9(L1979), 10(L1981), 14(L1979), 17(N1980), 19(L1978)Practical Test CL1978 and 1982)

Welsh Joint Education Committee;Exercises 49(1976), 55(1976)End-of-Unit Test 11(1978)

Where answers to these questions are includedJ they are provided by ILPACand not by the examination boards.

Questions from papers of other examining boards appear in other Units.

Photographs are included by permission as follows:Photographs of students, and those on pages 25, 39 and 50 - Tony Langham

SYMBOLS USED IN ILPAC UNITS

&, Reading

~Exercise

\\\;l Test

'A' Level question

'A' Level part question

'A' Level questionSpecial paper

Worked example

Teacher-marked exercise

Revealing exercises

~ Discussion

~ Computer programme

~ Experiment

II oIl Video programme

[J:2U Film loop

Model-making

INTERNATIONAL HAZARD SYMBOLS

~Harmful

~Toxic Radioactive

[6J Flammable II Explosive

~

~~I Corrosive Oxidisingl~ J,t--.

vii

INTRODUCTIONThis Unit is the third of four on organic chemistry. In it you conclude yoursurvey of functional groups by studying a variety of organic compoundsJ allof which contain the carbonyl group >C==o. (The fourth Unit deals with someof the special features of large molecules.) As beforeJ we have not splitthe Unit into levels of difficulty because this would cut across the morenatural divisions.

We begin by looking at the carbonyl group as a functional group on its ownJin compounds known as aldehydes and ketones. We then study carboxylic acidsJwhich have a carbonyl group and hydroxyl group attached to the same carbonatom. As you will seeJ these groups affect each other to such an extent thatthe combination -CooH is always regarded as a separate functional group inits own right. Following thisJ we look ata number of derivatives ofcarboxylic acidsJ namely acyl halidesJ amidesJ esters and acyl anhydrides.

FinallYJ we bring together the different forms of isomerism you have met sofar and introduce you to another form of isomerism called optical isomerism.

There are seven experiments in this UnitJ including an end-of-Unit practicalTest (in addition to the usual written test).

There are two ILPAC video-programmes designed to accompany this Unit. Theyare not essentialJ but you should try to see them at the appropriate timesif they are available.

Organic techniques 2

PRE-KNOWLEDGE

Identifying unknown substances

We assume that you have successfully completed Units 01 and 02 beforestarting this Unit and we do not specify any other requirements as pre-knowledge. AccordinglYJ there is no pre-test.

1

CARBONYL COMPOUNDS: ALDEHYDES AND KETONESIn this section, you study aldehydes and Ketones. Each of these classes ofcompound contains the carbonyl group ~C==O. In aldehydes, the carbonylgroup is linKed to a hydrogen atom (to two hydrogen atoms in the simplestmember of the series, methanal) whereas in Ketones, the carbonyl group islinKed to two hydrocarbon groups,e.g. o

IICH3-C-Hethanal(an aldehyde)

propanone(a Ketone)

Objectives. When you have finished this section, you should be able to:

(1) write the structural formulae and names of aldehydes and Ketones;(2) describe the shapes of some simple aldehydes and Ketones

Names~ structural formulae and shapesRead the introductory chapter or section on carbonyl compounds in your WC=>ItextbooK, noting particularly their systematic names. You should thenbe able to -do the first three exercises.

Write condensed structural formulae for:Exercise 1(a) butanal~(b) butanone,(cJ phenylethanone,(Answers on page 83 )

(d) 3-methylbutanal,(e) pentan-3-one.

Exercise 2 Name the following compounds(aJ CH3CH2COCH2CH2CH3 (d)(b) CH3CH2CHO (e)(c) C6HsCH2COCH3(Answers on page 83

C6 HsCOCH2CH3(CH3 ) 3CCHO

Exercise 3 ( a )

( b)

Write the structural formula of an aldehyde which is ~an isomer of the Ketone CH3COCH31 and give its name.Why is CH3CH2COCH3 referred to as butanone and not ~~as butan-2-one?

(Answers on page 83 )

You now use models to describe the shapes of aldehydes and Ketones.

2

Ask for a model-making kit and make models of molecules of propanone, ACH3COCH3, and ethanal, CH3CHO. With the models in front of you,attempt the next exercise.

( a )Exercise 4 What is the overall shape of the ethanal and propa- ~none molecules, treating the CH3 groups as singleatoms? ~~

(b) Sketch the propanone and ethanal molecules to showthis shape and the approximate bond angles.

(Answers on page 83

You now investigate some of the chemical properties of aldehydes and ketones.

Chemical properties of aldehydes and ketonesObjectives. When you have finished this section, you should be able to:

(3) compare the reactions of aldehydes and ketones.

In the next exercise you look at the nature of the carbonyl group in order topredict what type of reaction you might expect of aldehydes and ketones.

Exercise 5 The double bond in the carbonyl group, C==O, consists of ~a o-bond and a n-bond, so what type of reaction would youexpect aldehydes and ketones to undergo? ~~(Answer on page 83 )

The reactions of the carbonyl group, C==O, like the reactions of the C==Cbond, are essentially addition reactions of the type:

"C=O +- HA -+/

Superficially, addition to a C==O bond resembles addition to a C==C bond," /C-== C + HA -+

/ "I I-C-C-I IH A

but there are distinct differences due to the polarity of the c=o bonds, asyou show in the next exercise.

( b)

( a )Exerci se 6 Use electronegativity tables to predict the polarity ~of the c=o bond.What type of reagent might attack the carbon atom of ~~the carbonyl group?

(c) What type of reagent might attack the oxygen atom of thecarbonyl group?

(Answers on page 83)

3

We might, therefore, expect aldehydes and ketones to be susceptible to attackboth by nucleophiles at the carbon atom and by electrophiles at the oxygen.However, electrophilic attack on the oxygen atom is rare and you will not beexamined on it. So, for the majority of reactions of the carbonyl group, weare concerned with nucleophilic addition to the C==O bond.

8+ 8-'" c==o/'-nucleophile

Contrast this with electrophilic addition to the c==c bond in alkenes, whichyou studied in Unit 01 (Hydrocarbons), where the electrophile is attracted tothe 'IT-bond.

'" /C==C/ \ ~

electrophile

Consequently, reagents that add to the C==O bond are usually different tmfrom those that add to the C=C bond. Wi th this in mind, you shouldnow attempt the next experiment where you carry out some reactions of 1aldehydes and ketones. The reactions you will perform not onlyinvolve nucleophilic addition to the carbonyl group but reactions ofthe alkyl group(s) adjacent to the carbonyl group and oxidation reactions aswell.

EXPERIMENT 1Reactions of aldehydes and ketones

AimThe purpose of this experiment is to comparesome reactions of ethanal and propanone.

IntroductionWe have chosen ethanal and propanone as relatively safe examples of aldehydesand ketones to illustrate their reactions in simple test-tube experiments.

CH3'" c==o/

Hethanal

CH3'" C==O/CH3

propanone

4

The reactions or properties to be investigated are as follows:A Addition C Reaction with alkaliB Condensation D Oxidation

(Addition - elimination) E Triiodomethane (i'odoform) reactionYou have already used Fehling's solution and Tollen's reagent (ammoniacalsilver nitrate) in Unit 02 to test for an aldehyde as an oxidation productof a primary alcohol. Check that you understand the reactions in these tests.

Requirementssafety spectacles and gloves6 test-tubes:~~~~:l ~y~~:~~~~~P~i te_ S~lutiO~ ~aturated,_ NaHSO~ _ _ _ _ _ _ _ . Wpropanone. CH3COCH3-- - -- - ----- - - -- - --- - ---IXI L!J2,4-dinitrophenylhydrazine solution, C6H3(N02)2NHNH2sodium hydroxide solution, 2 M NaOH - - - - - - - - - - - - - - - - -I ~

Bunsen burner, tripod, gauze and bench mat - ~_beaker, 250 cm3potassium dichromate(VI) solution, 0.1 M K2Cr207sulphuric acid, dilute, 1 M H2S04Fehling's solutions, 1 and 2 --------------------- d:4silver nitrate solution, 0.05 M AgN03 - - - - - - - -- - - - - -'-'- - ~_ammonia solution. 2 M NH3iodine solution, 10% (in KI(aq))

Hazard warningEthanal and propanone are irritants to eyes. skin and lungsand are highly flammable. Therefore you MUST:PERFORM THE EXPERIMENT IN A FUME CUPBOARDKEEP THE BOTTLES WELL AWAY FROM FLAMESKEEP THE STOPPERS ON THE BOTTLES AS MUCH AS POSSIBLEWEAR SAFETY SPECTACLES AND GLOVES

Tollens' reagent becomes explosive on evaporation.Therefore you MUST:WASH AWAY RESIDUES IMMEDIATELY AFTER USE

ProcedureA. Addition reaction with sodium hydrogensulphite

1. Pour about 2 cm3 of saturated sodium hydrogensulphite solution intoa test-tube. Point the tUbe away from you and add, drop by drop, asimilar volume of ethanal.

2. Shake the tube gently and cool under a stream of cold water. Noteyour observations in a copy of Results Table 1.

3. Repeat steps 1 and 2 using propanone instead of ethanal.

B. Condensation reaction with 2,4-dinitrophenylhydrazine1. Put 1-2 drops of ethanal in a test-tube and add about 2 cm3 of

2,4-dinitrophenylhydrazine solution. Note your observations.2. Repeat for propanone.

5

C. Reaction with alkali

1. Into a test-tube, pour about 3 cm3 of sodium hydroxide solution and10 drops of ethanal.

2. Shake the tube gently and warm in a beaker of hot water for 5-10minutes. Note your observations and comment on the smell of I~' Ithe product. f'J

3. Repeat for propanone.D. Oxidation reactions

(a) With acidified potassium dichromate(VI)1. Into a test-tube, put 5 drops of ethanal, 2 drops of potassium

dichromate(VI) solution and 10 drops of dilute sUlphuric acid.Note2.

3.

(b)

1 •

2.

3.

(c)

1 •

2.

Shake the tube gently and warm in a beaker of hot water.your observations.Repeat for propanone.

With Fehling's solutionInto a test-tube, put about 1 cm3 of Fehling's solution 1 and thenadd Fehling's solution 2 dropwise until the precipitate justdissolves.Add about seven drops of ethanal. Shake the tube gently and I A Iplace in a beaker of boiling water for five to ten minutes -until no further colour change occurs. Note your observations. --Repeat for propanone.

With Tollens· reagentPut about 1 cm3 of 0.05 M AgN03 into a very clean test-tube and addthree or four drops of sodium hydroxide solution.Drop-by-drop, add ammonia solution until the precipitate of silveroxide nearly dissolves (do not try to get rid of all the littleblack specks of silver oxide] .

3. Add one or two drops of ethanal, shake the tube gently andplace in a beaker of warm water. Note your observations andimmediately rinse out the test-tube.

4. Repeat with propanone.E. Triiodomethane reaction

1. Into a test-tube, place five drops of ethanal followed by 1 cm3

of iodine solution, cork and shake.2. Drop-by-drop, add sodium hydroxide solution until the colour of

iodine just disappears (about 2 cm3) and a straw-colouredsolution remains. Note your observations.

3. Repeat with propanone.

6

Results Table 1

Observations

Test Ethanal Propanone

A. Addition reaction withsodium hydrogensulphite

B. Condensation reaction with2,4-dinitrophenylhydrazine

C. Reaction with alkali

D. Oxidation reactions:(a) acidified dichromate(VI)(b) Fehling's solution(c) Tollens' reagent

E. Triiodomethane reaction

(Specimen results on page 83 )

Questions1. Which tests serve to distinguish between ethanal and propanone?2. Which reaction do you think resulted in the production of a polymer?3. Which reagent could be used as a general test for a carbonyl compound?(Answers on page 83 )

The last experiment shows that although there are similarities in thereactions of aldehydes and ketones, there are also some distinct differences.We consider the similarities first.

Reactions of aldehydes and ketones - similaritiesObjective. When you have finished this section you should be able to:

(4) write equations for the reactions of aldehydes and Ketones whichillustrate their similarities.

Read about the addition reactions and condensation reactions ofaldehydes and Ketones in your textbooK(S). LooK for details of theproducts of addition reactions with sodium hydrogensulphite, hydrogencyanide, and hydrogen, and of the condensation reactions withhydroxylamine~ hydrazine, and substituted hydrazines. Note thatcondensation reactions are sometimes referred to as 'addition-elimination' reactions. You can see why when we consider mechanismsFor the next exercise, you need not mention mechanisms.

7

later.

(a)Exercise 7 Complete the equations in a copy of Table 1, which ~lists the similar reactions of aldehydes and ketones,and name the products. Ethanal and propanone are ~~taken as typical examples.

(b) Why do you think condensation reactions are so named?(An swers on page 84)

Table 1 Reactions common to aldehydes and most ketones

1. ADDITION REACTIONS

(HCN produced in situ fromKCN and acid.)

CH3CHO + NaHS03 -+

CH3COCH3 + NaHS03 -+

(b ) Addition of hydrogen cyanideCH3CHO + HCN -+

CH3COCH3 + HCN -+

(a) Addition of sodium hydrogensulphite*(Full systematic names of

products not required.)

(c) Addition of hydrogen (reduction)CH3CHO + H2 -+

CH3COCH3 + H2 -+

(There are at least threedifferent reducing agents.)

2. CONDENSATION REACTIONS(a) Condensation with hydroxylamine

CH3CHO + NH20H -+

CH3COCH3 + NH20H -+

(b) Condensation with hydrazineCH3CHO + NH2NH2 -+

CH3COCH3 + NH2NH2 -+

(c) Condensation with 2,4-dinitrophenylhydrazineNHNH2cQr N02

*Ketones with the carbonyl group attached to the benzene ring do not formhydrogensulphite addition products. The presence of the bulky benzene ringprevents the hydrogensulphite ion attacking the molecule.

We now consider the mechanisms of some of the reactions in the last exercise;starting with the mechanism of addition.

8

The mechanism of addition to carbonyl compoundsObjective. When you have finished this section you should be able to:

(5) describe the mechanism of nucleophilic addition in carbonyl compounds.

Essentially. nucleophilic addition in aldehydes and ketones takes place intwo stages: the nucleophile adds to the electron-deficient carbon atom ofthe carbonyl group, and the resulting negatively-charged oxygen then takesup a proton. This is illustrated for nucleophilic addition to a carbonylgroup in Fig. 1, where :Z-represents the nucleophile.

Fig.1.

I e-(-0Iz

I-(-OH

IZ

The product thus contains two funcfional groups, one of which is always - OH.The proton usually comes from the solvent but, in some cases, it may come fromthe attached nucleophile itself, in which case the final product is ionic.With this in mind, attempt the next exercise.

Exercise 8 Using Fig. 1 as a guide, write mechanisms for the reactions~between propanone, CH3COCH3~ and the following nucleo-philes in aqueous solution. ~~(a ) CN - (from HCN).(b) H- (from LiAIH4 or NaBH4)·

(c) S03H- (from NaHS03). (Hint: the nucleophile S03H- is acidicand will readily transfer a proton.)


In the next exercise, you compare the mechanisms of addition to the c==o andC==C bonds. Before attempting it, you may wish to refresh your memory on themechanism of addition in alkenes from Unit 01 (Hydrocarbons).

Exercise 9 The compounds hex-1-ene, CH3CH2CH2CH2CH=CH2' andpentan-2-one, CH3CH2CH2COCH3• are very similar as regardsshape and relative molecular mass.(a) Give one reagent which will form an addition product

with hex-1-ene but not with pentan-2-one, and writean equation for the reaction.

(b) Give one reagent which will form an addition productwith pentan-2-one but not with hex-1-ene, and writean equation for the reaction.

(c) Give the mechanisms involved in (a) and (b).(d) Explain briefly why reagents which form addition products with

carbonyl compounds will not, in general, form addition productswith alkenes.


9

Now we consider the mechanism of some condensation reactions in carbonylcompounds.

The mechanism of condensation reactionsObjective. When you have finished this section you should be able to:

(6) describe the mechanism of condensation reactions of carbonyl compounds.

In these reactions, the first step is nucleophilic addition. This is followedby the elimination of a small molecule, usually water. The condensationreactions we consider involve substituted ammonia compounds which have thegeneral formula :NHzY. Fig. 2 illustrates the mechanism in general terms.

",-cS+ cS- I eC==O-. - C-0 .,-.

/(U Ie):NH2Y Y-N-H

IH

Fig. 2.

I I-C-O-H -. -C +

I ~'- II:N-H :N,~ Y

O-HI

H

For simplicity, the overall reaction can be represented as follows:

You will find this useful in deciding the structure of the product, but itgives no clue as to the mechanism.

In the next exercise you write mechanisms for condensation reactions with somesubstituted ammonia compounds: hydroxylamine, hydrazine and phenylhydraZine.

Exercise 10 Using Fig. 2 as a guideJ write mechanisms for thereactions between propanone and(a) hydroxylamine, NHzOH,(b) hydrazine, NHzNHz,(c] phenylhydraZine, C6HsNHNHz.(Answers on page 85 )

You now find out how we can make use of the reaction between carbonylcompounds and 2,4-dinitrophenylhydrazine for identification purposes.

10

Identifying carbonyl compounds~bjective. When you have finished this section you should be able to:

(7J describe how the reaction with 2,4-dinitrophenylhydrazine is used toidentify carbonyl compounds.

Using your textbook, find out how 2;4-dinitrophenylhydrazine is used c=>to characterise carbonyl compounds. You should then be able to do ~Ithe next exercise. ~

(a JExercise 11 What properties of the 214-dinitrophenylhydrazine ~derivatives of carbonyl compounds make themsuitable for identification purposes? ~~

(bJ Due to careless labelling, a confusion arose in alaboratory store between pentan-2-one and pentan-3-one,each of which boil at 102 0[. Describe carefully how youwould use 2,4-dinitrophenylhydrazine to distinguishbetween them.


Later in this Unit, you can identify an unknown carbonyl compound bypreparing for yourself a derivative using 2,4-dinitroph8nylhydrazine.

We now consider the reactions which distinguish aldehydes and ketones - asseen in Experiment 1.

Reactions of carbonyl compounds - differencesObjectives. When you have finished this section you should be able to:

(8) compare and contrast the reactions of aldehydes and ketones withoxidizing agents and with alkalis;

(9) recognise the structural grouping that a carbonyl compound must havein order to undergo the triiodomethane (iodoformJ reaction.

Oxidation of aldehydesAldehydes, unlike ketones, can be oxidized by mild oxidizing ~agents, as yousaw in Experiment 1. We now take a closer look at these reactions.

Look up the oxidation of aldehydes by acidified potassium or sodium c=>dichromate(VI), Tollens' reagent and Fehling's solution in your ~textbook and attempt the exercise which follows. ~

11

Exercise 12 (al Complete and balance the following equations for ~the oxidation reactions of aldehydes with Tollens'reagent and Fehling's solution. Describe what you ~~would observe during the reactions.

(i) CH3CHO + H20 + Ag+ ~(ii) CH3CH2CHO + OH-+ Cu2+ ~

(b) Combine the following two half-equations into an equationwhich shows the oxidation of butanal using acidifiedsodium or potassium dichromate(VI). Describe what youwould observe during the reaction.CH3(CH2)2CHO + H20 ~ CH3(CH2)2C02H + 2H+ + 2e-Cr2072- + 6e- + 14H+ ~ 2Cr3+ + 7H20


The reason why aldehydes are so readily oxidized but ketones are not is thepresence of a hydrogen atom attached to the carbonyl group. This hydrogenis activated by the carbonyl group and is readily oxidized to -OH.

Another difference between aldehydes and ketones is in their reactions withalkali, which we now consider.

Reaction of carbonyl compounds with alkaliAs you will recall from Experiment 1, ethanal reacts with alkali to form aresin whereas propanone does not.

Read about the reaction of aldehydes and ketones with dilute alkali,such as sodium carbonate, and concentrated alkali. You may findthem under the headings aldol addition, aldol condensation,Cannizzaro·s reaction. You should then be able to do the nextexercise.

oCO

and /)

~

Exercise 13 Give equation(s) for the reactions of (a) ethanal,(b) propanone with

(i) dilute aqueous alkali (e.g. Na2C03),(ii) concentrated alkali.

(c) Certain other aldehydes and ketones undergo similarreactions. What structural feature do they all havein common?


The last exercise illustrates the fact ~hat aldehydes generally polymerizemore readily than ketones; your textbook(s) probably quote other examples,e.g. the variety of polymers of methanal which can be obtained underdifferent conditions. We suggest that you need not learn the details ofthese but you should study another possible reaction with alkali, known asCannizzaro·s reaction.

12

Aldehydes (and a few ketones) which do ~ot have the structural feature>CHC==O cannot undergo aldol addition and condensation reactions. Instead,

Ithey disproportionate (self-oxidize and self-reduce) when treated withconcentrated alkali, yielding an alcohol and a salt of a carboxylic acid. Inthe next exercise, you consider an example of this type of reaction, whichis known as Cannizzaro's reaction.

Exercise 14 Methanal reacts with alkali to form methanol andmethanoate ions.(a) Write the equation for this reaction.(bJ Calculate the oxidation number of carbon in each compound.(c) Explain why your answer to (bJ confirms that methanal has

undergone disproportionation.(Answers on page 86 J

As you will recall from Experiment 1, both ethanal and propanone react withiodine and alkali to form triiodomethane, but this is not a typical reactionof all carbonyl compounds, as we show in the next section.

Triiodomethane reactionRead about the reaction of carbonyl compounds with iodine and alkali ~(sometimes with iodide and chlorate(IJ ions). You may find it under ~the heading triiodomethane or iodoform reaction. You should then be ~able to do the next two exercises.

Exercise 15 Write the names and formulae of the products formedwhen iodine solution, followed by aqueous sodiumhydroxide, is added to:(a) ethanal, CH3CHO,(Answers on page 86 )

(b) propanone, CH3COCH3

Exercise 16 Table 2 shows the effect of adding iodine and sodiumhydroxide solution to a number of carbonyl compounds.Table 2 Triiodomethane test

--.----- -

Name Formula Observation

Ethanal CH3CHO Yellow precipitate.Propanal CH3CH2CHO No change.Propanone CH3COCH3 Yellow precipitate.Pentan-3-one CH3 CH2 COCH2 CH3 No change.Phenylethanone C6HsCOCH3 Yellow precipitate.

What structural grouping must be present before a carbonylcompound gives a positive triiodomethane reaction?(Answer on page 86 )

13

You will recall from Unit 02 (Some Functional Groups) that alcohols with thestructural unit CH3CHOH also give a positive triiodomethane reaction. In thenext exercise you explain why this should be so.

Exercise 17 Write a reaction sequence (showing intermediates) which ~explains why compounds represented as CH3CH(OH)R andCH3COR both give positive triiodomethane reactions. ~~(Hint: iodine in alkali acts as a strong oxidizing agent.)(Answer on page 86 )

In the next section, you use your knOWledge of the reactions of differenttypes of carbonyl compound to describe some distinguishing tests which givereadily-observable results.

Distinguishing testsObjective. When you have finished this section you should be able to:

(10) describe simple chemical tests which you could use to distinguishcarbonyl compounds.

Exercise 18 Complete a copy of Table 3, which compares the reactions~of some carbonyl compounds.(Answers on page 86 ) ~~

Table 3 DistingUishing tests for carbonyl compounds

Observations on testing with:

Sodium IodineCarbonyl hydrogen- Tollens' Fehling's and Concacompound sulphite reagent solution alkali alkali

Met hanal ReactionHCHO - no ppt.

Ethanal ReactionCH3CHO - no ppt.

Benzaldehyde Ag mirror No redC6H;;CHO slowly ppt.

PropanoneCH3 COCH3

Phenylethanone NoC6H;;COCH3 reaction

In the exercises which follow; you use some of these tests to distinguishbetween some carbonyl compounds.

14

Exercise 19 De$cribe one simple reaction to distinguish between themembers of each of the following pairs of compounds:(a) CH3CHO and C6H5CHO,(bJ CH3COCH3 and C6H5COCH3,

(cJ aqueous solutions of CH3CHO and HCHO,(d) CH3CH2CHO and CH3CH2COCH3.

State what is observed for each compound in each pair.(Answers on page 87 )

The following is a list of carbonyl compounds. each ofwhich is indicated by a capital letter.

Exercise 20

A CH3CHOB CH3COCH3

C C2H5COC2H5

o C6H5CHO(a) Give the names and structural formulae of TWO ketones which

are isomeric with C.(b) Give the names and structural formulae of TWO aldehydes

which are isomeric with E.(c) Give ONE chemical test in each case to distinguish between

(i) A and B, (ii) Band C.(d) (i) Write an equation for the reaction of 0 with sodium

hydroxide.(iiJ How would you isolate benzoic acid from the mixture?

(iii) This reaction may be described as disproportionation.Explain the meaning of this term as applied to thisreaction.


The first part of the next two exercises involves determining the molecularformula of a compound from mass percentage composition data and relativemolecular mass. You have already performed this type of calculation inUnit 02 (Some Functional Groups) in the section on structure determination,so this part of the question will be revision.

( b)

( a )Exercise 21 Give full structural formulae for the three 0carbonyl-containing compounds having the composition A(by mass) C = 66.7%; H = 11.1%; 0 = 22.2% and arelative molecular mass of 72.What would you observe when each of these three compoundsis treated separately with the following reagents:

(iJ aqueous 2,4-dinitrophenylhydrazine,(ii) iodine in aqueous alkali,

(iiiJ a solution of silver oxide in aqueous ammonia?Account for your observations.


15

In the next exerciseJ you determine the amount of oxygen by difference. Youhave already performed this type of calculation in Unit 02.

Exercise 22 The organic compound XJ which contains carbonJ hydrogenand oxygen onlYJ was found to have a relative molecularmass of about 85. When 0.43 g of X is burnt in excessoxygenJ 1.10 g of carbon dioxide and 0.45 g of water areformed.(H = 1J C = 12J 0 = 16)(aJ What is the empirical formula of X?(b) What is the molecular formula of X?(c) Write an equation for the complete combustion of X.(dJ X undergoes a condensation reaction with hydroxylamine and

also with 2J4-dinitrophenylhydrazine. Write the structuralformulae of FIVE possible non-cyclic compounds which X couldbe and give the systematic names for each of the fiveformulae.

(eJ What is meant by a condensation reaction?(f) Write an equation for the reaction of ONE of the five

possible compounds for X with hydroxylamine.(gJ Look closely at the five structures you have written for X.

(iJ Which will give a yellow precipitate on warming witha mixture of iodine and alkali?

(ii) Which will reduce diamminesilver(IJ ions?(Answers on page 88 )

In the next experimentJ you identify an unknown carbonyl compoundJ tillfirstly by using Tollen's and/or Fehling's solution to find out ifit is an aldehyde or ketone andJ secondlYJ by preparing a crystalline J1derivative to identify the particular aldehyde or ketone.

Objectives. By the end of this practical section you should be able to:

(11 ) explain the steps involved in preparing a solid derivative ofa compound;

(12) explain the steps involved in purifying a compound by recrystallization;(13) explain the procedure for measuring the melting-point of a substance.

The ILPAC video-programme 'Organic Techniques 21 shows you how toprepare a derivativeJ how to purify it by recrystallization andfiltration and how to identify it by determining its melting-point.You should watch this before you do the experiment if possible.

If the videotape is not available, read about these techniques in asuitable book and/or ask your teacher to demonstrate them. It isbest to read about them before you perform this experiment.

16

stirrer (see Fig. 4)

EXPERIMENT 2Identifying an unknown carbonyl compound

AimThe purpose of this experiment is to classifya carbonyl compound by a simple test andto identify it by the preparation of aderivative.

IntroductionYou are provided with a compound known to be an aldehyde or ketone from agiven list. In the first part of the experiment~ you identify the compound aseither an aldehyde or ketone using Tollen's and Fehling's tests. In thesecond part~ you prepare a derivative of the compound with 2~4-dinitrophenyl-hydrazine. Finally~ you determine the melting point of the derivative inorder to name the particular aldehyde or ketone.

RequirementsA. safety spectacles and protective gloves

2 test-tubesteat pipettesilver nitrate solution~ 0.05 M AgN03

sodium hydroxide solution 2 M NaOH- - - - - - - - - - - - - - - - ~ammonia solution ~ 2 M NH3 ~ r -- ~ ••Fehling's solutions 1 and 2 ---~-------'-------' I A Iunknown carbonyl compound~ x- - --- - - - - -- - - ---- --beaker~ 250 cm3 --

Bunsen burner~ tripod~ gauze and bench mat

B. ~:~~:~~l~O~H~~~ ~o~ ~oilin~ tube) --- _ -- -- _ -- -- _1"'12~4-dinitrophenylhydrazine solution ~glass stirring rodsulphuric acid~ dilute~ 1 M H2S04

retort stand~ boss and clampapparatus for suction filtration (see Fig. 3)spatulabea ker ~ 150 cm3

:~~:~~~at~o~~5~~m~~e~ker -------- 1 .•. 1

ice f'Jfilter paper

C. melting-point tubes (at least 2)watch-glassrubber ring or bandthermometer~ 0-360 °C~ long stemboiling tube, fitted with cork anddibutyl phthalate

17

WASH AWAY THE SOLUTION IMMEDIATELY AFTER USE.Tollens· reagent becomes explosive on evaporation. Therefore you MUST:

KEEP STOPPERS ON BOTTLES OF FLAMMABLE LIQUIDS AS MUCH AS POSSIBLE.KEEP FLAMMABLE LIQUIDS AWAY FROM FLAMES.WEAR SAFETY SPECTACLES.

Hazard warningAldehydes, ketones and alcohols are flammable. Therefore you MUST:

ProcedureA. Identification of the carbonyl compound as an aldehyde or ketone.

Carry out Tollens· and Fehling's tests on samples of the unknown compound.Try to remember the procedures before checking (Experiment 1, page 6).Classify the compound as an aldehyde or a ketone.

B. Preparation of a crystalline derivative.1. Into a 100 cm3 beaker (or boiling tube) put 0.5 cm3 (10 drops) of the

unknown compound. (If the substance is solid dissolve 0~5 g in aminimum amount of methanol.) Add 5 cm3 of the 2,4-dinitrophenyl-hydrazine solution and stir.

2. If precipitation does not occur, carefully add 1 cm3 of dilutesulphuric acid.

3. Using the suction filtrationapparatus in Fig. 3, filterthe precipitate.

4. Stop suction, either by liftingthe funnel or by disconnectingthe tubing, and soak the preci-pitate in about 1 cm3 of methanol.(If you turn off the tap, you mayget a 'suck-back· of water.)

5. Resume suction and dry the crystalsby drawing air through them for afew minutes.

---- Buchner funnel(or Hirsch funnel)

clamp

Fig. 3. Suction filtration

6. Recrystallize the solid using the following procedure.(a) Transfer the crystals to a 150 cm3 beaker standing on a steam

bath (or in a 250 cm3 beaker of hot water).(b) Dissolve the crystals in the minimum amount of hot ethanol.(c) When the crystals have dissolved, cool the solution in an ice-

water mixture until crystals reappear.(d) Filter the crystals as before. If necessary, rinse the beaker

with the filtrate (not extra solvent) to complete the transfer.Finally. wash the crystals with a few drops of cold ethanol.

(e) Press the crystals thoroughly between two wads of filter paper toremove excess solvent. Then put the crystals on another drypiece of filter paper placed alongside a Bunsen burner and gauze,turning the crystals over occasionally until they appear dry .

•

18

C. Determination of the melting point of the derivative.1. Take a melting-point tube and push the open end through a pile of the

derivative on a watch-glass, until a few crystals have entered thetube.

2. Tap the closed end of the tube vertically against a hard surface, orrub with the milled edge of a coin, to make the solid fall to thebottom.

3. Repeat the filling and tapping procedure until a total length ofbetween 0.5 - 1 cm is compacted at the bottom of the tube. Prepareanother tube in this way.

4. Attach one of the prepared melting-point tubes to the thermometer, asshown in Fig. 4.

stirrer

dibutyl phthalate

+HEATFig. 4. Melting-point determination

5. Half-fill the boiling-tube with dibutyl phthalate and position thethermometer with attached tube and the stirrer through the bung. asshown in Fig. 4.

6. Position the apparatus over a micro-burner (or low Bunsen flame) andgauze and gently heat the apparatus, stirring the dibutyl phthalateall the time by moving the stirrer up and down.

7. Keep an eye on the crystals and note the temperature as soon as signsof melting are seen (usually seen as a contraction of the solidfollowed by a damp appearance). This first reading gives only arough melting-point but is a gUide for the second determination.

B. Remove the burner and the old tube containing derivative. Allow thetemperature to drop about 10°C before positioning a fresh melting-point tube containing another portion of the derivative.

9. Repeat the above procedure in order to obtain a more accurate valueof the melting-point. Raise the temperature very slowly (about2 °c rise per minute) until the crystals melt (take the formation ofa visible meniscus as a sign of melting).

10. Compare the melting-point of your crystals with the values given in thetable which follows and identify the unknown compound.

11. Check with your teacher or the technician whether you have identifiedX correctly.

19

Table 3 Melting-points of some 2~4-dinitrophenylhydrazones

Melting point ofBoiling 2~4-dinitrophenyl-

Name Formula point/oC hydrazone/oC

Aldehydesmethanal HCHO -21 167ethanal CH3CHO 21 164 ~ 146 (2 forms)propanal CH3CHo2CHO 48 156butanal CH3CHo2CHo2CHO 75 1232-methylpropanal (CH3)o2CHCHO 64 187benzaldehyde C6HsCHO 178 237

Ketonespropanone CH3COCH3 56 128butanone CH3 CHo2COCH3 80 115pentan-2-one CH3 CHo2CHo2COCH3 102 141pentan-3-one CH3CH2COCHo2CH3 102 156hexan-2-one CH3CHo2CH2CH2COCH3 128 1074-methylpentan-2-one (CH3 )2 CHCH2 COCH3 117 95

cyclohexanone 00 156 162

Questions1. What factors decide the choice of solvent in the recrystallization

procedure?2. How were soluble impurities removed from the derivative?3. In the recrystallization procedure~ why were the crystals dissolved in

only the minimum amount of ethanol?4. If your sample had contained insoluble impurities~ such as pieces of

filter paper~ cork~ etc.~ suggest how these might have been removed.5. Why is it not satisfactory to identify aldehydes and ketones by measuring

their boiling points?(Answers on page 89)

We now consider the various methods of preparing aldehydes and ketones.

Methods. of preparationObjective. When you have finished this section you should be able to:

(14) write equations for the preparations of aldehydes and ketones givingspecific reaction conditions.

20

Read about the methods of preparing aldehydes and ketones in your 0textbook(sJ. Also look for the industrial preparations of methanal, ~ethanal and propanone since these compounds have many commercial uses. ~This will enable you to do the next exercise.

Exercise 23 Complete the equations in a copy of Table 4, which ~summarises the more important methods of preparingaldehydes and ketones. State any special reaction ~~conditions and name the organic reactants and products.Table 4 Methods for preparing aldehydes and ketones.

General methods

A. Oxidation of alcohols:1 • To aldehyde e.g. C2H5OH -+

2. To ketone e.g. CH3CHOHCH3 -+

B. Hydrolysis of gem*-dihalides1 . To aldehyde e.g. C6H5CHClz -+

2. To ketone e.g. CH3CC12CH3 -+

C. Thermal decomposition of calcium salts of carboxylic acids,

1 • To aldehyde e.g. (CH3C02 )2Ca + (HCOZ)2Ca -+

2. To ketone e.g. (CH3COZ) 2Ca -+

D. Friedel-Crafts reaction to aromatic ketonese.g.

© + CH3COCI -+

Industrial methods

A. MethanalCH30H + ~02 -+

B. Ethanal - Wacker processCH2==CH2 + ~Oz -+

c. Propanone - Wacker processCH3CH==CHz + ~Oz ~

D. Propanone - cumene processCH3CH=CH2 + C6H6 + Oz ~ (overall equation)

*gem is from the Latin gemini (meaning twins); thus agem-dihalide has two halogen atoms on the same carbon atom.(Answ'ers on page 88 )

You now summarise the reactions and preparations of aldehydes and ketones.

21

Summary of reactions and preparations of aldehydes and ketonesExercise 24 Complete copies of Figs. 5 and 6, which summarise the ~

reactions and preparations of aldehydes and ketones.Ethanal and propanone are taken as examples of each. ~~Where a particular reaction is not typical of the wholeclass, we have inserted an asterisk. In these casesl youshould include an explanatory note.(Answers on page 89 J

CH3CH==NNHC6H3(N02)2

ethanal 2,4-dinitro-phenyl hydrazone

CH3CH=NNH2

__ ethanal hydrazone

CH3C02H + Agethanoic acid

and silver

\Fehling'ssolution

\

CH3CH(OH)CN2-hydroxy-

prop,oeoitrile !.~ \ I.N,OHI.ql

CH3CH(OH)CH2CHO3-hydroxybutanal

CH3 CH2 OH ~ NaOH(aq)cone

ethanol warm

calcium ethanoate and '-.........calcium methanoate '-.........

Fig. 5. Summary of preparations and properties of ethanal

CCH3l2C(OHlS03-NaT

sodium 2-hydroxy-2-propanBsulphonatB

\

CH3CHCOHlCH3

propan-2-o1

/CCH3l2CCOHlCH2COCH3

4-hydroxy-S-mBthyl-pBntan-2-onB

IHCN

KCN,H+(aq)

CHh

triiodomBthanB

LiAfH4 ------

ethoxyethane

propanonB oximB

Fig. 6. Summary of preparations and properties of propanone

22

In the next exercise, you write some synthetic pathways which include thereactions and preparations of aldehydes and ketones. They may also includereactions of other functional groups you have studied.

Synthetic pathwaysExercise 25 Benzaldehyde, C6H5CHO, is in demand for perfumes,

flavouring essences and dyes. The main source is coaltar, where methylbenzene, C6H5CHs, is extracted from thebenzole fraction. Suggest a synthetic pathway for convertingthe methyl benzene into benzaldehyde.

(Answer on page 89 )

Exercise 26 Show how you could bring about the following conversions 0in no more than three stages. Indicate reagents,conditions and intermediate products.(a)

( b)

CH3CHO -+

CH3CH==CH2C2H50C2H5

-+ (CH3 )2CO( c) (CH3)2CHBr

(Answers on page 90

The following diagram shows the molecular formulae of anumber of related compounds.

-------~

E

r P/I2

C3HBOA

~CSH60

B

NaH2 + 0 -4-----

Exercise 27

(a) (i) Give the names and structural formulae of THREEcompounds of molecular formula C3HaO.

(ii) Which ONE of these compounds corresponds to compoundA in the diagram? Give your reasons.

( b)

( c)

What reagent( s) would be needed to(i) prepare compound B from compound A,

(ii) convert compound B into compound C?(i) Identify the compounds 0 and E.

(ii ) Give the name and formula of the organic product ofthe reaction between compounds 0 and E.

(d) In an experiment~ a student obtained 39 g of solid CHI3 from10 g of A. What was his percentage yield?


23

In the next exercise, a mass spectrum and infra-red absorption spectrum areincluded to assist you in identifying two organic compounds.

This question is about the identification of two organicsubstances~ A and B. Substance A contains carbon~

its mass spectrum is shown

605020 30 40mass/charge ratio

10o

20

80

100

~ 60'iiicQ)

,~ 40

hydrogen and oxygen only andin Fig. 7.It melts at 178 K and boilsat 329 K, gives a crys-talline derivative with2,4-dinitrophenylhydrazine,but does not reduceFehling's solution.

Exercise 28

Fig. 7. Mass spectrum of substance A

Substance B was prepared directly from A by reduction and itsinfra-red absorption spectrum is shown in Fig. 8.

wavelength/l0-6m7 8 9 10 11 12 131415166

~ - ...., - r' 1'\

" I \ I r\

\ ! \ f I \

\ A I/ .11 1\ I

V VIf A

11\)

10

o

5100

90

80c~ 70Qj-e- 60Q)

g 50co:::

"E 40<IlC~ 30

20

Characteristicwavelength(s)

Group 110-6 m

C=C 6.1

@ 6.3, 6.7

CH3 6.8-7.0, 7.3

CHO 5.8

CHOH 9.0

CH20H 9.5

Fig. 8. Infra-red absorption by substance B

(a) What is the relative molecular mass of A?(b) Write down the probable formulae of the two main fragments

of A produced in the mass spectrometer.(c) What can be deduced from the facts that A reacts with

2;4-dinitrophenylhydrazine but not with Fehling's solution?(d) Give the name of A and its formula.(e) By interpreting the infra-red absorption spectrum, what

groups in B can be identified?(f) Give the name of B and its formula.(Answers on page 90 )

24

It should be clear from your study of this section that carbonyl compoundsare reactiv~ materials, and consequently they have many commercial uses.

Uses of carbonyl compoundsObjective. When you have finished this section you should be able to:

(15) describe some of the uses of carbonyl compounds.

Read about the uses of carbonyl compounds in your textbook(s). Inparticular, look for the uses of methanal, ethanal and propanone inthe manufacture of useful materials. Don't worry too much about thedetails of manufacturing procedures; you are not likely to beexamined in them. In any case, we deal with polymers in more detailin Unit 04 (Big Molecules).

Now attempt the next exercise.

olit

Exercise 29 The photographs below illustrate some uses of carbonyl ~compounds. Match each photograph with one of thecompounds methanal, ethanal, benzaldehyde and propanone. ~~(Answers on page 90 )

A B c

o

25

E

To consolidate your understanding of the ch8mistry of carbonylcompounds you should now attempt the following Teacher-marked Exercisewhich is a question taken from a past A-level examination.

Teacher-markedExercise

Discuss the chemistry of phenylethanone~ C6HsCOCH3,by considering the following:(aJ a method of synthesis,(b) addition and addition-elimination reactions of the

carbonyl group,(c) a method of preparing benzenecarboxylic (benzoic) acid

from phenylethanone.

You have now completed a study of aldehydes and ketones. We suggest that yourevise what you have learned~ particUlarly Figs. 5 and 6 on page 22, beforeyou start the next section~ which deals with carboxylic acids.

26

CARBOXYLIC ACIDSCarboxylic acids contain the carboxyl group, C02H, which itself contains acarbonyl group and a hydroxyl group; hence the name. The carboxyl group canbe attached to an aliphatic or aromatic system as shown.

,.-:0CH3-C""

"OHethanoic acid

@-<oOH

benzoic acid

Objective. When you have finished this section you should be able to:

(16) write the structural formulae and names of carboxylic acids.

Names and structural formulaeRead the introductory chapter or section on carboxylic acids in your c=>textbookCs) and look for the systematic names of carboxylic acids. ~IYou should then be able to do the next two exercises. ~

Exercise 30 Write the condensed structural formulae of:(a) benzene-1,2-dicarboxylic acid,(b) butanoic acid,(c) 2-hydroxypropanoic acid (lactic ~cid),(d) 2-hydroxybenzoic acid (salicylic acid),(e) 3-methylpentanoic acid,(f) ethanedioic acid (oxalic acid).(Answers on page 90 )

Name the following compounds.( d )

Exercise 31(a) CH3CH2C02H(b) C6H5CH2C02H(c) CH3CH(CH3)CH2C02H


JQJ C02H

H02C

(e) C02H(CH2)3C02H

As we have shown above, the carboxyl group consists of two reactive groupswhich you have already stUdied. In the next section, you find out the extentto which carboxylic acids behave like carbonyl compounds and like hydroxylcompounds.

You will find it helpful to revise the reactions of carbonyl compounds andhydroxyl compounds in order to make comparisons with carboxylic acids.

27

Chemical properties of carboxylic acidsObjectives. When you have finished this section you should be able to:

(17) describe some simple chemical tests which characterise carboxylicacids;

(18) compare the reactions of carboxylic acids with alcohols and carbonylcompounds.

In the next exercise you make a prediction about the reactions you mightexpect of carboxylic acids based on your knowledge of alcohols and carbonylcompounds. Following that is an experiment to test your predictions.

Exercise 32 Predict what you might expect to observe when each ofthe following is added to a compound containing a> C=O group and an -OH group:(a) sodium,(b) sodium hydrogencarbonate solution,(c) phosphorus pentachloride,(d) 2,4-dinitrophenylhydrazine,(e) iodine followed by sodium hydroxide solution,(f) neutral iron(III) chloride solution,(g) universal indicator solution.(Answers on page 90 )

In the next experiment, you test your predictions from Exercise 32 .

EXPERIMENT 3Chemical properties of carboxylic acids

AimThe purpose of this experiment is to see ifcarboxylic acids show the typical reactionsboth of alcohols and of carbonyl compounds.

Introduction

.

You will be carrying out some test-tube reactions on ethanoic acid. Ethanoicacid melts at 17 o[ and therefore freezes in cold weather. Because solidethanoic acid looks like ice, it is often described as 'glacial'. Thereactions to be investigated are:

28

A pH of aqueous solution.B Reaction with sodium hydrogencarbonate solution.C Reaction with sodium.D Reaction with phosphorus pentachloride.E Reaction with 2~4-dinitrophenylhydrazine.F Triiodomethane (iodoform) reaction.G Action of iron(III) chloride.

Requirementssafety spectacles and gloves5 test-tubes in rackwash-bottle of distilled water I ~. Iethanoic acid, glacial, CH3C02H---------------- e .dsodium hydrogencarbonate solution~ saturated~ NaHC03 ~ __ ~

limewater~ Ca(OH)2(aq)forceps ~sodium~ Na (1 mm cube under oill- - - - - - - - - - - - - - - -- - - )(filter paperswood splint I~lphosphorus pentachloride~ PCls- - - - - - - - - - - - - - - - - - - - ftspatulaammonia solution ~ 2 M NH3

2~4-dinitrophenylhydrazine solutioniodine solutionl 10% 12 in KI(aq) ~sodium hydroxide solution~ 2M NaOH -----------------J.4sodium ethanoate (acetate)~ CH3C02Nairon(III) chloride solution~ 0.1 M FeC13

Hazard warningGlacial ethanoic acid is flammable and corrosive.Sodium and phosphorus pentachloride are extremely reactivel

especially with water. Therefore you MUST:WEAR SAFETY SPECTACLES AND GLOVESKEEP STOPPERS ON BOTTLES AS MUCH AS POSSIBLEKEEP BOTTLES OF FLAMMABLE LIQUIDS AWAY FROM FLAMESKEEP SODIUM AND PHOSPHORUS PENTACHLORIDE AWAY FROM WATER AND MOIST AIRProcedureA. pH of aqueous solution1. Into a test-tube~ pour about 2 cm3 of distilled water and one drop of

universal indicator solution. Shake gently.2. Add a few drops of glacial ethanoic acid~ shake gently and note your

observations in a copy of Results Table ~.B. Reaction with sodium hydrogencarbonate solutionInto a test-tube~ add about 1 cm3 of sodium hydrogencarbonate solutionfollowed by a few drops of glacial ethanoic acid. Shake gently and test anygas produced.

29

C. Reaction with sodium (WORK AT A FUME CUPBOARD, WITH YOUR TEACHER PRESENT)1. Pour about 2 cm3 of glacial ethanoic acid into a dry test-tube in a rack

standing in a fume cupboard.2. Using forceps, pick up a 1 mm cube of sodium and blot it free of oil on

some filter paper.3. Drop the clean piece of sodium into the glacial ethanoic acid.

Test any gas evolved and note your observations. 00 not washaway the mixture until you are sure that the sodium has reactedcompletely. If some sodium remains unreacted, add a little moreglacial ethanoic acid; on no account add water.

D. Reaction with phosphorus pentachloride1. Pour about 1 cm3 of glacial ethanoic acid into a dry test-tube in a rack

standing in a fume cupboard.2. A little at a time, carefully add a spatula measure of phosphorus

pentachloride. Bring the wet stopper of an ammonia bottle closeto the mouth of the tube and note your observations.

E. Reaction with 2,4-dinitrophenylhydrazineInto a test-tube, pour about 2 cm3 of 2,4-dinitrophenylhydrazine solutionand about 5 drops of glacial ethanoic acid. Shake gently and note yourobservations.

F. Triiodomethane Ciodoform) reactionInto a test-tube, place ten drops of iodine solution, and five drops ofglacial ethanoic acid, followed by sodium hydroxide solution addeddropwise until the colour of iodine disappears and a straw-colouredsolution remains. Shake the tUbe gently and note your observations.

G. Reaction with neutral ironCIIIJ chloride solutionInto a test-tube, place about 2 cm3 of sodium ethanoate solution (thisavoids having to neutralize the solution) and a few drops of iron(III)chloride solution. Shake gently and then heat the solution. Note yourobservations.

Results Table 3 Reactions of ethanoic acid

Reaction Observations

A. pH of aqueou s solution

B. Reaction with sodiumhydrogencarbonate solution ~

C. Reaction with sodium

D. Reaction with phosphoruspentachloride

E. Reaction with2,4-dinitrophenylhydrazine

F. Triiodomethane reaction

G. Action of ironCIII) chloride

(Specimen results on page 91 J

30

(two stages)

Qu estions1. Were the predictions you made in Exercise 32 verified by experiment?2. Does ethanoic acid more closely resemble hydroxy or carbonyl compounds

in its reactions? Explain.3. Which test indicates that ethanoic acid is a stronger acid than phenol?4. Explain the fact that ethanoic acid is very soluble in water~ whereas

benzoic acid~ C6H5C02H~ a solid~ is only slightly soluble in water.(Answers on page 91 )

The last experiment shows that~ although carboxylic acids have some propertiestypical of hydroxy compounds~ they have virtually nothing in common withaldehydes or ketones. We can deduce, therefore, that the close proximity ofthe hydroxyl and carbonyl groups causes a considerable interaction betweenthe two. This is why the -C02H group is treated as a separate functionalgroup with its own characteristic reactions.

Reactions of carboxylic acidsObjective. When you have finished this section~ you should be able to:(19) write equations for the reactions of carboxylic acids, giving

specific reaction conditions.

Read about the reactions of carboxylic acids in your textbook(s). ~Look for equations for the reactions you saw in the last experiment ~and for further reactions mentioned in the next exercise. Also, note ~how methanoic acid differs from other carboxylic acids in its reactionswith oxidiZing agents and with sulphuric acid.

Exercise 33 Complete the following equations for the reactions ofcarboxylic acids. naming the products and statingnecessary conditions.(a) CH3C02H + NaOH(aq) ~(b) C6H5C02H + NaOH (soda lime) ~(c) CH3CH2C02H + Na2C03 ~(d) CH3C02H + (NH4)2C03 ~(e) C6H5C02H + PC15 ~

(f) *CH3C02H + C12(g) CH3CH2C02H ~ (reduction)(h) CH3CH2C02H + CH30H ~( i) HC02H ~ (Reaction with H2S04)


*This reaction is not performed by methanoic acid, HC02H; nor by aromaticcarboxylic acids, which undergo electrophilic substitution by chlorine in thebenzene ring. For instance, benzoic acid. in the presence of a halogencarrier, gives predominantly 3-chlorobenzoic acid.

31

The reactions illustrated in the last exercise, apart from the reaction withchlorine and the dehydration of methanoic acid. are typical reactions of allcarboxylic acids. The red colour which is produced when aliphatic (alkyl)carboxylic acids react with neutral iron(III) chloride, however, serves todistinguish them from aromatic acids, which give a buff precipitate.

The simplest carboxylic acid, methanoic acid, HC02H, shows some anomalousbehaviour, as you have seen. Its structure suggests that it might have someof the properties of aldehydes as well as acids, and 'it does indeed reduceFehling's solution and Tollens'reag,ent. Note, however, that it does notundergo condensation reactions which are typical of aldehydes and ketones.

You now make a comparative summary of some of the reactions of carboxylicacids, hydroxy compounds and carbonyl compounds which give observable changesand can be used as distinguishing tests.


(20) describe simple chemical tests which you would use to distinguishbetween carboxylic acids, hydroxy compounds and carbonyl compounds.

Exercise 34 Complete a copy of Table 5, which compares the reactions ~of some carboxylic acids, hydroxy and carbonyl compounds.(Answer on page 92 ~~

Table 5 A comparative summary

Observation when tested with various reagents

Neutral Sodium 2,4-dinitro-iron(III) hydrogen- phenyl- Tollens'

Compound chloride carbonate hydrazine reagent

Methanoic acidHC02H

Ethanoic acidCH3C02H

Benzoic acidC6H5C02H

EthanolC2H5OH

PhenolC6H5OH

EthanalCH3CHO

32

In the two exercises which follow, you use these tests to distinguish betweencarboxylic acids, hydroxyl and carbonyl compounds.

(a) ©CHO ©C02H (c ) HC02Hand (d J CH3C02H

(bJ ©C02Hand ©OH


Describe one simple reaction to distinguish betweenmembers of each of the following pairs of compownds.

and CH3CHO

Exercise 35

Exercise 36 The compounds ethanol, phenol, ethanoicacid contain the hydroxyl group, -OH.(a ) (i) Which two of these compounds

hydrogencarbonate?

acid and benzoic ~

react with sodium ~

(ii) Write a balanced equation for the reaction involvingone of them.

(b) (i) Which one of the four compounds reacts with aqueoussodium hydroxide but does not react with sodiumhydrogencarbonate?

(ii) Write a balanced equation for this reaction.(c) (i) Which one of these compounds reacts with sodium metal

but does not react with sodium hydrogencarbonate orwith sodium hydroxide?

(ii) Write a balanced equation for this reaction.(Answers on page 92 )

We now take a close look at the structure of the carboxyl group in order toexplain the acidity of carboxylic acids.

Acidity


(21) account for the acidity of carboxylic acids.

The most important property of carboxylic acids is that they are weak acids.You will recall from Unit 02 (Some Functional Groups) in the section on phenolthat there are two principal factors which govern acidity. The acidity of acompound containing a hydroxy 1 group X - OH is increased firstly if X iselectron withdrawing and, secondly. if the anion XO- is stabilized bydistributing its charge over two or more atoms.

In the next exercise, you consider these factors along with some physicalevidence about the structure of the carboxylate ion, RC02-, in order toexplain the acidity of carboxylic acids.

33

Exercise 37 The carboxylate ion is conventionally represented as:/.0

CH C/3 "0-

However, electron diffraction measurements have shown the ion tobe symmetrical, and the distance of each oxygen atom from thecarbon atom is intermediate between the normal lengths ofc--o and C==O bonds.(a) What does this evidence suggest about the conventional way

of representing the carboxylate ion?(b) Suggest a better representation of the carboxylate ion.(c) Using an orbital diagram, show how your answer to part (b)

is possible. (Hint: see the orbital diagram of benzenefrom Unit S4 (Bonding and Structure).)

(d) Considering the two factors which govern acidity, togetherwith the diagrams of the carboxylate ion from parts (b)and (cJ, explain why ethanoic acid is a stronger acid thanethanol.


As well as delocalization in the carboxylate ion, RC02-, there must also beconsiderable delocalization in carboxylic acid molecules, RC02H, as shown inFig. 9.

Fig. 9. Delocalization in a carboxylic acid

This delocalization helps to explain why carboxylic acids undergo hardly anyof the reactions we associate with the carboxyl group.

You have seen how the acidity of the hydroxyl group is very much enhanced bythe carbonyl group next to it. An extension of this concept is that acidstrength is affected by electron-attracting or electron-withdrawingsubstituents in the alkyl or aryl group next to the carboxyl group. This isillustrated in the next exercise.

34

Exercise 38 Table 6 lists the values of the dissociation constants Of~some carboxylic acids and substituted carboxylic acids.Study them and attempt the questions which follow. ~~Table 6

Name Formula Ka/mol dm-3

Benzoic acid C6H5C02H 6.3 x 10-5

Methanoic acid HC02H 1 .6 x 10-4

Ethanoic acid CH3C02H 1 .7 x 10-5

Propanoic acid CH3CH2C02H 1.3 x 10-5

Chloroethanoic acid CH2ClC02H 1 .3 x 10-3

Oichloroethanoic acid CHC12C02H 5.0 x 10-2

Trichloroethanoic acid CC13C02H 2.3 x 10-1

2-chlorobutanoic acid CH3CH2CHClC02H 1 .4 x 10-3

3-chlorobutanoic acid CH3CHClCH2C02H 8.7 x 10-5

4-chlorobutanoic acid CH2ClCH2CH2C02H 3.0 x 10-5

(a) Explain the trend in the acid strength of ethanoic1

chloroethanoic1 dichloroethanoic and trichloroethanoic acids.(b) Arrange the following acids in order of decreasing acid

strengthl and explain the reasons for your suggested order.ClCH2C02H1 BrCH2C02H1 ICH2C02H1 FCH2C02H1 CH3C02H

(c) Explain the trend in the acid strength of 2-chlorobutanoic1

3-chlorobutanoic and 4-chlorobutanoic acids.(d) Explain the trend in the acid strength of methanoic1 ethanoic

and propanoic acids.(e) Explain why benzoic acid is a stronger acid than ethanoic

acid.(Answers on page 93 )

We now consider the various methods of preparing carboxylic acids.

Methods of preparation


(22) write equations for reactions in which carboxylic acids are producedl

giving specific reaction conditions.

Read about the methods of preparing carboxylic acids and hydroxy-carboxylic acids. Also1 look for the most recent industrialpreparations of methanoic1 ethanoic1 benzoic and ethanedioic (oxalic)acids - these have some commercial uses. This will enable you to dothe next exercise.

35

oW

Exercise 39 Complete the equations in a copy of Table 7, which ~summarises the reactions in which carboxylic acids areproduced. Name the reactants and products and state the ~~necessary conditions.Table 7

General methods of preparing carboxylic acids

A. Oxidation1_ primary alcohols" e.g. CH3CH2OH -+

}2 . aldehydes" CH3CHO write electronice.g. -+ 'half-equations'.3 . alkyl benzenes" e.g. C6H5CH3 -+

B. Hydrolysis1 • nitriles" e.g. CH3CH2CN + H2O + H+ -+

2 . amides" e.g. CH3CONH2 + H20 + H+ -+

3 • acyl halides" e.g. CH3COCI + H2O -+

4 .anhydrides" e.g. (CH3CO)20 + H2O -+

5 • esters" e.g. CH3CH2C02CH3 + H2O -+

Preparation of hydroxycarboxylic acids

Cyanohydrin reaction e.g. CH3CHO + HCN -+ (two stages)CH3COCH3 + HCN -+ (two stages)

Industrial methods

1• Methanoic acid NaOH + CO -+

2. Ethanoic acid Alkane mixture (equations-+ not required)from petroleum

3. Benzoic acid C6H5CH3 -+

4. Ethanedioic acid HC02Na -+ (two stages)

(Answers on page 93 1

You now summarise the reactions and preparations of carboxylic acids.

36

Summary of reactions and preparationsExercise 40 Complete a copy of Fig. 10 to summarise the preparations

and reactions of carboxylic acids.(Answer on page 94 )

---___ heat

CH3 CO2 -Na +

sodium ethanoate

~ CH3COClethanoyl chloride

/

\

IC2HsOH

conc. H2S04

/

\CH3CH20Hethanol

ethanenitrile

CH3COClethanoyl chloride _

~CC13C02H

trichloroethanoic acid

Fig. 10. Summary of preparations and properties of ethanoic acid

In the next section you devise some synthetic pathways which include thereactions and preparations of carboxylic acids; they also include reactionsof other functional groups you have studied.

37

Synthetic pathwaysThe following scheme outlines three different pathwaysby which compound C may be prepared.

Exercise 41

(i)----~ C2H4(OH)2

B

(ii) C02H~ IC02H

C

C02C2H5

(iii) I~ C02C2H5

(iv)~CN

ICN(a) Name the compounds A, Band C.(b) Write the equations and state the necessary conditions for

the reactions shown at (i), (ii) and (iii).(c) (i) Indicate possible intermediate compound(s)

which might be found at stage (iv).(ii) Suggest possible conditions for stage (iv), when

cyanogen (NC--CN) is converted to compound C.(d) In a quantitative check on the reaction (ii), it was found

that 45 g of the crystalline product C, (C02H)2"2H20, wasobtained from 30 g of B. What was the percentage yield?


Exercise 42 Show how you would bring about the following conversionsin no more than three stages.(a) C3H7C02H -+ C3H7CN(b) C6H5NH2 -+ C6H5C02H(c ) CH3CHO -+ CH3CH(OH)C02H(d) CH3(CH2)3I -+ CH3(CH2)3C02H(e J CH3(CH2)3C02H -+ CH3(CH2)4I

Exercise 43

(Answers on page 94

A liquid X contains by mass 31.5% of carbon, 5.3% ofhydrogen and 63.2% of oxygen. Its solution in waterliberates carbon dioxide from sodium carbonate and fromthe resulting solution a substance of formula C2H303Nacan be obtained. With phosphorus pentachloride, X giveshydrogen chloride and a compound of molecular formula C2H20C12.State and explain the information which may be obtained fromeach of these facts. Give the molecular formula of X anddevise a synthesis of it from ethene (ethylene).(Answers on page 95 )

We now consider some of the uses of carboxylic acids.

38

Uses of carboxylic acidsObjectives. When you have finished this section you should be able to:

(23) describe some of the uses of carboxylic acids.

Read about the uses of ca~boxylic acids in your textbook. Inparticular~ look for applications in the manufacture of syntheticflavourings~ nylon~ food preservatives~ vinegar and Terylene. Wesuggest that you do not learn the details of the procedures~ but gainsufficient background knowledge to do the next exercise. Furtherstudy of nylon and Terylene is included in Unit 04 (Big Molecules).

Exercise 44 Ethanoic acid~ hexanedioic (adipic) acid~ benzoic acid~ ~and benzene-1~4-dicarboxylic (terephthalic) acid are .used in the manufacture of the useful materials shown in ~\\the photographs below. Match each carboxylic acid withone or more photographs.


A

c

B

o

Finally in this section~ we deal with the salts of carboxylic acids. Theyshow some interesting differences when heated or treated with variousreagents and are frequently given as unknown compounds for identificationin practical examinations. However~ for some syllabuses~ this section isrelatively unimportant; ask your teacher whether you should study it.

39

Salts of carboxylic acidsCarboxylic acids react with inorganic bases to form ionic salts, e.g.

CH3C02H + NaOH ~ CH3C02-Na+ + H20sodium ethanoate

Different salts may react differently on heating or when treated with variousreagents. Observable changes can be used as distinguishing tests.


(24) perform specified tests on a given salt of a carboxylic acid andfrom your obervations make inferences about its identity.

Find out from a book of organic analysis tables how the testsmentioned in the next exercise enable you to distinguish betweensalts of different carboxylic acids.

Exercise 45 The following tests and observations were made on ~compounds A to D, which are sodium salts of carboxylicacids. Identify each in turn as a methanoate (formate), ~~ethanoate (acetate), ethanedioate (oxalate), benzoate,or 2-hydroxybenzoate (salicylate). Write equationswhere possible.(a) A was warmed in a test-tube with concentrated sulphuric acid.

Effervescence was seen and the gas turned limewater cloudy.When a lighted splint was held at the mouth of the tube, thegas burned quietly with a blue flame.

(b) B was mixed with soda-lime (NaOH/Ca(OHJ2, solid) and heatedin a test-tube. A strong 'carbolic' smell was noted.Drops of condensate at the mouth of the tUbe were slightlyacidic.

(c) C was heated in a test-tube and produced a gas which'popped' with a lighted splint. On stronger heating, thegas evolved did not 'pop' but burned quietly with a blueflame.

(d) Neutral iron(III) chloride was added to a solution of D.A buff precipitate was seen.

(e) E was warmed with concentrated sulphuric acid. A pungentvinegary smell was noted and a few drops of liquid condensedon the upper part of the tube.


40

Most of the tests for salts also apply to the corresponding carboxylic acids,and these reactions too may appear in practical examinations. Of course, youcan distinguish a salt from its parent acid by its ionic nature and its lackof acidic behaviour.

You can now identify some salts of carboxylic acids for yourself. In [ffithe experiment which follows, which is taken from an A-level practicalexamination, you perform specified tests on given 'unknown' substances, J1note your observations and make inferences. Since you will investigatethe metal ion as well as the anion, you may wish to refer to bothorganic and inorganic analysis tables.

If it is available, you may find it helpful to watch the second part It 00

11

of the ILPAC video-programme 'Identifying unknown substances'.

EXPERIMENT 4Identifying salts of carboxylic acids

AimThe purpose of this experiment is to give youpractice in 'observation and deduction'exercises, with particular reference tothe salts of carboxylic acids.

Requirementssafety spectaclesprotective gloves6 test-tubes, 2 with corkstest-tube holder and rackspatulaunknown salts, I and Jwash-bottle of distilled water ~sodium hydroxide solution, 2 M NaOH------------------ l~J:1--sulphuric acid, dilute, 1 M HzSO~Bunsen burner and bench mat .wood splintlitmus papers or pH paperslimewater, Ca(OH)z(aq)test-tube and bung fitted with right-angled delivery tube2,4-dinitrophenylhydrazine solution, C6H3(NOz)zNHNHz ~sulphuric acid, concentrated, H2S04------------------~~teat-pipette

41

Hazard warningSodium hydroxide solution is corrosive.Concentrated sulphuric acid is corrosive and reacts violentlywith water. Therefore you MUST:WEAR SAFETY SPECTACLES AND GLOVESIf contact with skin does occur, wash immediately with plenty ofcold water.Dispose of residues containing concentrated sulphuric acid by cooling firstand then pouring into plenty of cold, running water.

You are provided with two salts, I and J, which are composed of thesame elements. Carry out the following tests and record yourobservations and inferences in (a larger copy of) the table. Thenanswer the question which follows the table.

(Note that the question does not say anything about carboxylic acids - wehave made it easier for you!)---

Results Table 4

Test

(a) Dissolve some of I in the mlnlmum quantityof distilled water and use portions of thesolution for the following tests.

(i) To 1-2 cm3 of the solution of I addaqueous sodium hydroxide until inexcess.

(ii) To 1-2 cm3 of the solution of I addan equal volume of dilute sulphuricacid~ shake the tube, and allow thesolution to stand.

(b) Add a little dilute sulphuric acid to somesolid I and heat the mixture.

(c) Heat a little solid I in a Pyrex test-tube.

Observations Inferences

(d) Using the apparatusshown, heat a littleof I in a test-tubeand pass the vapourevolved into 2,4-dinitrophenylhydrazinereagent.

I:...•.~.:,:."

(e) Heat a little solid J in a Pyrex test-tube.

(f) To a little solid J add a little concen-trated sulphuric acid (CARE!) and warmgently.

Comment on the identify of I and J.


42

To consolidate your knowledge of the chemistry of carboxylic acidsyou should attempt the following Teacher-marked Exercise.


In the light of your knowledge of the chemicalreactions of carboxylic acids. discuss the truth ofthe following statement: 'The reactions of thecarboxyl group are typical of those of the carbonyland hydroxyl groups that it containsl•

Illustrate your answer with suitable reactions.

You have now completed a study of carboxylic acids. We suggest that youspend some time revising what you have learned, particularly Fig. 10 on page37, before you go on.

In the next section of this Unit we deal with acyl halides, amides, acylanhydrides and esters, all of which are grouped together as carboxylic acidderivatives.

43

CARBOXYLIC ACID DERIVATIVESIn this section, you study carboxylic acid derivatives. You may regard them ascompounds in which the hydroxyl group of a carboxylic acid has been replacedby another functional group. Four different classes of compounds which fallinto this category are illustrated below.

/-0 /-0 /.0 /.0R-C:I' R-C/ R-C/ R -C/'," "OR' -'0X NH2

an acyl halide amide ester R-C/an an ~ 0(X a halogen; R = alkyl or aryl group. ) an acyl anhydride

You have already met many examples of carboxylic acid derivatives in variousparts of your course. Here we consider them together because they have somecommon properties. Before we look at these we clarify the naming system.

Names and structural formulaeObjective. When you have finished this section you should be able to:

(25) write the structural formulae and names of carboxylic acid derivatives.

Acyl halides have names which are based on the acids from which they arederived. The suffix 'oic acid' is dropped and '-oyl halide' is added.

e.g.~o

CH C~ or CH3CoCl3 " Cl

ethanoyl chloride

Amides also have names which are based on the acids from which they arederived. The ending '-oic acid' is dropped and '-amide' added.

e.g./-0CHsC:I'"NH 2

ethanamide

oroIQ\- c,t/

~ 'NH2

benzamide

Acyl anhydrides are named as derivatives of the parent acid (or acids) byreplacing the word 'acid' with 'anhydride'.e.g.

Estsrs are narn8U iJ::j LJli,ylor aryl derivatives of the parent carboxylic acid.The ending -ic is dropped and -ate is added.

e.g.

44

To help you name the esters correctly, we give you a Worked Example.

Worked Example. Name the esters CH3C02CH2CH2CH3 and CH30COCH2CH2CH3 I ~ ISolution1. Identify the c==o group and the two atoms (one C, one 0) to which it is

attached.2. Draw a line through the formula to separate the CO2 group, with its

attached C atom, from the rest of the molecule.CHsCO~CH2CH2CHs CH~OCOCH2CH2CHs

If you are in doubt, draw the structural formula.

3.

/,0CH C/

s " IOCH2CH2CHsName the portion without

CHsCO 2\CH2CH2CHspropyl

I/,0

CHsO-C:CH2CH2 CH3

the CO2 group as an alkyl radical.CHs\OCOCH2CH2CHs

methyl4. Name the portion with the CO2 group as a carboxylate radical.

CHsCO~CH2CH2CHs CH~OCOCH2CH2CHsethanoate butanoate

5. Combine the two names from steps 3 and 4.CHSC021CH2CH2CHs CHs\OCOCH2CH2CHspropyl ethanoate methyl butanoate

You can reverse the process to write the formula from a given name.

In the next exercisel you write names and formulae for some esters and otherderivatives of carboxylic acids.

Exercise 46 (a) Name the following substances.

~(i) HC02CH2CHs (iv) CHsCOCCH2CHs

II II(ii) C2HsCOCl o 0(iii) C2HsCONH2 (v) C6HsC02CH2CHs

(b) Write formulae for the following substances.(i) propyl ethanoate

(ii) butanamide(Answers on page 95 )

(iii) benzoic ethanoic anhydride(iv) phenyl benzoate

Carboxylic acid derivatives have many reactions in common, as you see in thenext section.

45

Chemical properties of carboxylic acid derivativesObjectives. When you have finished this section you should be able to:

(26) write equations for the reactions of carboxylic acid derivatives withnucleophilic reagents;

(27) describe the mechanism for the reaction between carboxylic acidderivatives and nucleophiles;

(28) write equations for the reduction of carboxylic acid derivatives.

A feature common to all carboxylic acid derivatives is the attachment of anelectron-withdrawing group~ y~ next to the carbon atom.

0+R-C -y

110-o

(y is -Hal~ -OCOR'~ -OR' or NH2)

This makes the derivatives more susceptible than their parent carboxylic acidto nucleophilic attack at the carbonyl carbon atom.

We now consider the reactions between carboxylic acid derivatives andnucleophilic reagents.

Nucleophilic substitution of acid derivativesWe can represent the reactions between carboxylic acid derivatives andnucleophilic reagents by the general equation shown in Fig. 11.

R-C-Y + HZ ---.IIo

R-C-Z + HYIIo

(HZ = nucleophilic reagent)

Fig.11. tIDIn the next experiment you illustrate the reactions of carboxylic acid ~derivatives~ taking ethanoyl chloride as an example. Jl

EXPERIMENT 5Chemical properties of ethanoyl chloride

AimThe purpose of this experiment is to illus-trate the chemistry of carboxylic acidderivatives by investigating the reactionsof ethanoyl chloride with some nucleophilicreagents.

46

IntroductionYou or your teacher will be carrying out the following reactions of ethanoylchloride - a typical acyl halide.A. Reaction with water.B. Reaction with ethanol.

C. Reaction with ammonia.D. Reaction with phenylamine.

Since some of the reactions are violent, your teacher may decide to demon-strate this experiment. If you do it yourself, you must take great CARE!

Requirementssafety spectaclesprotective gloves4 beakersl 100 cm3wash-bottle of distilled water4 teat-pipettesethanoyl chloride, CH.COCl---- -----------------!VIammonia solution, dilute, 2 M NH3 ~glass roduniversal indicator paperiron(III) chloride solution, 0.1 M FeCl3test-tube ~sodium carbonate solution, 1 M Na2C03 ,- JI.~ethanol, C2H50H I

~:~~i:m~~~~t~:~:N~:~ent~ate~,-'~. 88~ ~H. = = = = = == = ====I_I~IHazard warningEthanoyl chloride gives off a vapour which burns the skin, eyes andrespiratory tract. Some of its reactions are violent.Phenylamine is very poisonous if inhaled, swallowed or absorbedthrough the skin.Concentrated aqueous ammonia burns the skin and the vapour irritatesthe eyes. Therefore you MUST:WEAR SAFETY SPECTACLES AND GLOVES.KEEP STOPPERS ON THE BOTTLES AS MUCH AS POSSIBLE.PERFORM THE EXPERIMENT IN A FUME CUPBOARD PROTECTED BY A SAFETY GLASS.

ProcedureA.1 .

2.

3.

4.

5.

Reaction with waterPour about 5 cm3 of distilled water into a small beaker placed in thefume cupboard with the front pulled down as far as is practicable.Wearing safety spectacles, add a few drops of ethanoyl chloride to IVIthe water. Bring the moist stopper of a bottle of ammonia ~solution near to the top of the beaker and note your observations.Neutralize the solution in the beaker by adding dilute aqueous ammoniadropwise until a drop of the solution from a glass rod gives a neutralcolour to universal indicator.In a test-tube, neutralize about 1 cm3 of iron(III) chloride solution byadding sodium carbonate solution dropwise until a faint precipitate justremains on shaking.Add a few drops of the neutral iron(III) chloride to the neutral solutionprepared in step 3 and note your observations in a copy of Results Table 5.

47

B. Reaction with ethanol'1. Repeat steps 1 and 2 of Experiment A using ethanol instead of

water in the beaker.2. Add sodium carbonate solution until there is no further effervescence and

note the smell of the product.C. Reaction with ammonia

Repeat steps 1 and 2 of Experiment A using concentrated aqueousammonia instead of water in the beaker. Take special care whenyou add the ethanoyl chloride a drop at a time. Note yourobservations.

D. Reaction with phenyl amine1. Pour five drops of phenylamine in a small beaker placed in

the fume cupboard with the front pulled down as far as ispracticable.

2. Wearing safety spectacles, add a few drops of ethanoyl chloride tothe phenylamine. Note your observations.

Results Table 5

Reaction Observations

A. Reaction with waterProduct tested with ammoniaProduct tested with iron(III) chloride

B. Reaction with ethanolProduct tested with ammoniaSmell of product

C. Reaction with ammonia solution

D. Reaction with phenylamine


Questions1. Using the general equation for the nucleophilic substitution reactions of

carboxylic acid derivatives in Fig. 11, together with your observationsfrom the experiment~ write equations for the reactions of ethanoylchloride and the following nucleophilic reagents. Name the products.

(c) Ammonia, NH3

(bJ Ethanol~ C,H50H (d) Phenylamine, C6H5NH,2. Explain the order of reactivity of the four nucleophiles towards ethanoyl

chloride. This will be easier to answer after the next section.(Answers on page 96 )

In the next exercise you write similar equations for the other carboxylicacid derivatives·.

48

Exercise 47 Using Fig. 11 as a guideJ complete the equations in a ~copy of Table 8J which lists some reactions of carboxylicacid derivatives with nucleophilic reagents. Name the ~~reactants and products.Table 8 Reactions of carboxylic acid derivatives with

nucleophiles

A. With water

1 . Acyl halides e.g. C2H5COCI + H2O -+

2. Acyl anhydrides e.g. (CH3COJ20 + H2O -+

3. Esters e.g. C2H5C02CH3 + H2O -+

4. Amides e.g. CH3CONH2 + H2O -+

B. With alcohols and phenols

1 . Acyl halides e.g. C2H5COCI + C2H5OH -+

2. Acyl anhydrides e.g. CH3C02COCH3 + C6H5OH -+

No reaction with esters or amides

C. With ammonia

1 • Acyl halides e.g. C2H5COCI + NH3 -+

2. Acyl anhydrides e.g. C2H5C02COC2H5 + NH3 -+

3. Esters e.g. CH3C02C2H5 + NH3 -+

No reaction with amides

D. With amines1 • Acyl halides e.g. C2H5COCI + CH3NH2 -+

2. Acyl anhydrides e.g. (CH3COJ20 + C3H7NH2 -+

3. Esters e.g. CH3C02C2H5 + C2H5NH2 -+

No reaction with amides


Note that the hydrolysis of an ester or an amide by aqueous alkali yields asalt rather than the carboxylic acid obtained by acid hydrolysis. HoweverJ

these salts are readily converted to the carboxylic acid by the addition ofmineral acid.

CH3C02C2H5 + OH- -+ CH3C02- + H20CH3CONH2 + OH- -+ CH3C02- + NH3

The fact that amides produce ammonia on warming with alkali serves todistinguish them from amines.

49

Judging by the number of reactions listed in Table 8, it would appear thatacyl halides and acyl anhydrides are more reactive than esters, with amidesbeing the least reactive towards nucleophilic reagents.

In practice, it is found that acyl halides react far more vigorously than acylanhydrides, so the order of reactivity of the carboxylic acid derivativestowards nucleophilic reagents is:

acyl halide > acyl anhydride > ester > amideThis corresponds to the known electron-attracting power of the substituentgroups:

- Ha 1 > - CO 2R > - OR > - NH 2

rnYC02H~ ~ + CH3C02H

OCOCH32-carboxyphenylethanoate(aspirinJ

+ CH3CoCCH3II IIo 0

ethanoicanhydride

&COZH

~oH2-hydroxybenzoicacid

Many of the reactions of carboxylic acid derivatives are important in synthesis.As you can see, the reactions of acyl halides and acyl anhydrides are similarin that they both replace a hydrogen atom with an acyl group, RCO- , andconsequently both are described as acylating agents. Since acyl anhydridesare not so violently reactive as acyl halides, they are sometimes preferredto them for making amides and esters. One important application of this is inthe manufacture of 2~carboxyphenyl ethanoate (aspirinJ.

We now consider the mechanism for the reaction between carboxylic acidderivatives and nucleophilic reagents. Your particular syllabus may notrequire you to know the details of the mechanisms of these reactions. Yourteacher will be able to tell you whether you can skip this section.

Mechanism for nucleophilic substitution of carboxylicacid derivatives

Before attempting the next exercise you should refresh your memoryof the mechanism of addition-elimination reactions of carbonylcompounds (discussed earlier in this UnitJ and the mechanism ofnucleophilic substitution reactions of alkyl halides (Unit 02:Some Functional GroupsJ.

oqJ

The two-stage reaction sequence shown below shows the reaction between anucleophile, HZ:, and a general carboxylic acid derivative, CH3COY. Study itand attempt the exercise which follows.

HZ:~

Fig. 12.

CH318+ 8-C ==0 -.I "'--J

Y

CH3IZ-C==O + HY

50

(b)

(a)Exercise 48 Using Fig. 12 as a guide6 write a sequence for the ~reaction between ethanoyl chloride and water.Classify each stage of the sequence you have just ~~written.

(c) How does the mechanism of these reactions compare with themechanisms for:

(i) addition-elimination (condensation) reactions ofcarbonyl compounds6

(ii) substitution reactions in alkyl halides?(Answers on page 97 )

Another example of this mechanism is the hydrolysis of esters6 which is thereverse of the esterification reaction you studied in Unit 02 (SomeFunctional Groups).

You may wish to refresh your memory on this before attempting the nextexercise.

Exercise 49 On hydrolysis of the ester6 a bond could be broken ateither (1) and (2) in the following diagram:

(1) (2)I I

R-CO-1-O-1-R II II I

Suggest a method by which, using an isotope of oxygen, you couldfollow the point at which bond-breaking occurs.(Answer on page 98 )

We have seen how carboxylic acid derivatives show similarities in theirreactions with nucleophilic reagents. Another similarity is in theirreactions with reducing agents.

Reduction of carboxylic acid derivativesAs with the parent carboxylic acids6 reduction of the derivatives can bebrought about with suitable reducing agents.

Read about the reactions of acyl halides, amides, esters and acyl c=2anhydrides with reducing agents in your textbook. You should then be ~able to do the next exercise. ~

51

Complete the equations in a copy of Table 9. Name theorganic reactants which can perform all the reductions.

Exercise 50

Table 9 Reduction of carboxylic acid derivatives

1 • Acyl halides e.g. CH3COCI + H2 ~

2. Acyl anhydrides e.g. (CH3CO) 20 + H2 ~

3. Este'rs e.g. CH3CH2C02CH3 + H2 ~

4. Amides e.g. CH3CONH2 + H2 ~


Amides undergo two other reactions which are important in organic synthesis.These are the Hofmann degradation reaction and dehydration.

Other reactions of ami desObjective. When you have finished this section you should be able to:

(29) write equations for the Hofmann degradation reaction of amides and thedehydration of amides.

Read about the reaction of amides with bromine in the presence ofalkali (Hofmann degradation) and find out why this reaction is ofparticular importance in organic synthesis. Also find out theconditions which are necessary for dehydrating amides to nitriles.You should then be able to do Exercises 51 and 52.

Exercise 51 (a) Complete the following equation for a Hofmann

~

degradation reaction.CH3CHaCONHa + Bra + 40H- ~

(b) Why is this reaction of particular importance in organicsynthesis?


You will have the opportunity of using this reaction in synthetic pathwayslater in this section.

Exercise 52 Write an equation to show how ethanamide may be dehYdra-~ted to ethanenitrile. State the necessary conditions.(Answer 0 n page 98 ) ~\\\

You have already studied the reactions of alkyl halides in Unit 02 (SomeFunctional Groups). By comparing their reactions with those of acyl halidesyou will see how the presence of a carbonyl group has a profound effect onthe properties of the latter.

52

Comparing acyl halides and alkyl halidesObjective. When you have finished this section you should be able to:

(30) compare the reactivity of acyl halides and alkyl halides and relate thedifferences to their structure.

oCO

Before you attempt the next exercise, refresh your memory on thereactions of alkyl halides from Unit 02 (Some Functional Groups) andthe reactions of acyl halides from Experiment 5 earlier in this Unit.Note the ways in which primary alkyl halides and acyl halides differin their reactions with nucleophilic reagents such as water and ammonia.

Exercise 53 (a) Does ethanoyl chloride, CH3COCl~ react more or less ~vigorously than chloroethane, C2H5Cl~ in itsreactions with the nucleophilic reagents water and ~~ammonia?

(b) How does the charge on the carbon atom in the -COCI group,compare with the charge on the carbon atom in the - CCIgroup?

(c) Use your answers from parts (a) and (b) to explnin thedifference in reactivity between acyl halides and alkylhalides.


We now consider the effect of the carbonyl group on the reactivity of the-NH2group. We do this by comparing the properties of amides and amines.

Comparing ami des and aminesObjectives. When you have finished this section you should be able to:

(31) describe how the presence of the carbonyl group modifies the propertiesof the adjacent - NH2 group.

(32) explain why amides are weaker bases than amines.

If you compare the reactions of amides with the reactions of amines 0you studied in Unit 02 (Some Functional Groups) you will see that theyhave very little in common. The amino group of the amide must there- ~fore undergo considerable interaction with the carbonyl group. This ~,is further illustrated by the fact that amides are much weaker basesthan amines~ being neutral to litmus and only forming unstable saltswith strong acids.

In the next section, you consider how the presence of the carbonyl group inamides has the effect of reducing their basic strength relative to amines.

53

Basicity

You will recall from your study of amines that their basicity is determinedby the availability of the lone pair of electrons on the nitrogen atom andby the relative stability of the aminel RNH21 and its conjugate acidl RNH3+.

Basic properties are lessened if the amine is relatively more stable than itsconjugate acid.

In the next exercise you consider these factorsl together with an orbitaldiagram of the -CONH2 groupl in order to explain why amides are weaker basesthan amines.

Exercise 54 It is believed thatl in amidesl the lone pair of electron~on the nitrogen atom interacts with the n-orbitals of thecarbonyl bondl giving an extended delocalized system. ~~Fig. 13 shows how the individual p-orbitals interact togive the extended delocalized system.

Fig. 13. Delocalization in an amide

In what way does this orbital diagram help to explain why amidesare weaker bases than amines?(Answer on page 98 )

Comparing the base strength of aliphatic aminesJ aromatic amines and amidesis a popular examination question - as the following exercise illustrates.The question includes some revision of your earlier work on amines in Unit 02.

Exercise 55 (a) Arrange the following in order of increasing basestrength (i.e. the least basic first): ammonialphenylamine (aniline)1 butylamine and ethanamide.

(b) Explain the difference in basicity between:(i) butylamine and phenylaminel

(ii) butylamine and ethanamidel(iii) ethanamide and phenylamine.


Distinguishing testsl as you know1 often appear in A-level questions. Younow describe some simple chemical tests which would enable you to distinguishbetween carboxylic acid derivatives and compounds containing similar groups.

54

oUJ


(33) describe some simple chemical tests to distingUish between carboxylicacid derivatives and compounds containing similar groups.

Use your textbook, if necessary, to find out how the reaction withsodium hydroxide serves to distinguish between amides, amines andammonium salts. Also find out how the reaction with water serves todistingUish between acyl halides and alkyl halides, and how differentesters may be distinguished by means of hydrolysis. This should enable youto do the next exercise.

Exercise 56 Describe how you would distingUish by chemical meansbetween:(a) ammonium ethanoate, CH3C02-NH4+; ethanamide,

CH3CONH2; and ethylammonium chloride, C2HsNH3+Cl-;(b) chlorobenzene, C6H5Cl; 1-chlorobutane, C4H9Cl; and

ethanoyl chloride, CH3COCl;( c)

( d)

and

and

(Answers on page 99

We now consider the various methods of preparing carboxylic acid derivatives.You have met most of these reactions already as reactions of other functionalgroups.

Methods of preparationObjective. When you have finished this section you should be able to:

(34) write equations for the preparation of carboxylic acid derivatives,giving specific reaction conditions.

Look up methods of preparing acyl halides (acid halides), amides, 0esters and acyl anhydrides in your textbook. This will enable you to ~,do the next exercise. ~

55

( a)Exercise 57 Complete the equations in a larger copy of Table 10'~which summarises the reactions in which carboxylicacid derivatives are produced. Name the reactants ~~and products and state any special reaction conditions.

Table 10 Formation of derivatives of carboxylic acids

A. Acyl halides

1 . From carboxylic acids e.g. CH3C02H + ? -+

(3 different reagents)

B. Amides

1 . From ammonium salts e.g. C2HsC02-NH4+ -+

2. From acyl halides e.g. C3H7COCl + ? -+

3. From esters e.g. CH3C02C2Hs + ? -+

4. From anhydrides e.g. (CH3CO)20 + ? -+

C. Esters

1 . From carboxylic acidsand hydroxy compounds e.g. CH3C02H + C2HsOH -+

2. From acyl halidesand hydroxy compounds e.g. C2HsCOCl + C6HsOH -+

3. From anhydridesand hydroxy compounds e.g. (CH3CO)20 + C2Hs OH -+

4. From silver salts andhalogenoalkanes e.g. C3H7C02Ag + C2Hs I -+

D. Anhydrides

1 . From acyl halides and e.g. CH3C02-Na+ + C2HsCOCl -+

sodium salts

(b) In the preparation of acyl halides from carboxylic acids,why is sulphur dichloride oxide (thionyl chloride) oftenused in preference to other reagents? (Hint: look at thenature of the inorganic products.)

(Answers on page 100)

In the next experiment you prepare the ester phenyl benzoate. As we tillhave already discussed in Unit 02 (Some Functional Groups), phenolsdiffer from alcohols in the ease with which they form esters. It is 1not possible to prepare phenyl benzoate directly from phenol andbenzoic acid; instead you prepare it from phenol and benzoyl chloride.

The ILPAC video-programme 'Organic Techniques 2', shows you the [c:Jprocesses of recrystallization, filtration and melting-point ~determination. If you are not already familiar with these techniques 00

you should either view this video-tape or ask your teacher for ademonstration.

56

EXPERIMENT 6Preparing an ester

AimThe purpose of this experiment is to preparea sample of phenyl benzoate, purify it byrecrystallization, and measure its meltingpoint.

IntroductionYou prepare phenyl benzoate by shaking phenol with benzoyl chloride inalkaline solution.

C6HsCOCl + C6HsOH ~ C6HsC02C6Hs + HClThe product appears as a solid and you purify it by filtering, dissolving inhot ethanol, and cooling to recrystallize the ester.

RequirementsA. safety spectacles and protective gloves

weighing bottlespatula , .~,phenol, C6HsOH------------- ~_access to balance, sensitivity ± 0.01 gconical flask, 250 cm3, with tight-fitting rubber bungmeasuring cylinder, 100 cm3

'.:---1:,4,£sodium hydroxide solution, 2 M NaOH- - - - - - - - - - - - __measuring cylinder, 10 cm3

benzoyl chloride, C6HsCOCl-------------------1 ~suction filtration apparatus as in Fig. 14 - ~~wash-bottle of distilled water

B. boiling tubeethanol, C2HsOHglass rodwater-bath or 250 cm3 beakerBunsen burner, tripod, gauze and bench matthermometer, 0-100 °cicesuction filtration apparatus as in Fig. 14filter papersspecimen bottleaccess to balance, Qensitivity ± 0.01 g

C. mel ting-point tUbes, (at least 2)watch-glassrubber ring or bandthermometer, 0-100 °c, long stemboiling-tube fitted with cork and stirrer (see Fig. 4, page 17)dibutyl phthalateretort stand, boss and clamp

57

Hazard warningBenzoyl chloride is lachrymatory (produces tears), is irritating tothe skin and can cause burns.Phenol vapour is harmful to the eyes, lungs~ and skin. Solid andsolution are corrosive and poisonous by skin absorption.Therefore you MUST:WORK AT A FUME CUPBOARDWEAR SAFETY GLASSES AND PROTECTIVE GLOVES.

ProcedureA. Preparation of phenyl benzoate'i. Transfer about 5.0 g of phenol into a weighing bottle and weigh

it to the nearest 0.01 g.2. Into a conical flask pour 90 cm3 of 2 M sodium hydroxide and the

bulk of the phenol from the weighing bottle.3. Reweigh the weighing bottle, with any remaining phenol~ to the nearest

0.01 g.4. In a fume cupboard pour 9 cm3 of benzoyl chloride into the conical

flask.5. Insert the bung securely and shake the bottle for 15 minutes,

carefully releasing the pressure every few minutes as the flaskgets warm.

6. Cool the flask under cold, running tap-water.7. Filter the crude product using a suction filtration apparatus (Fig. 14).

Use a spatula to break up the lumps of ester on the filter paper, beingcareful not to puncture the filter paper.

Fig. 14 .. Suction filtration

--- Buchner funnel(or Hirsch funnel)

clamp

8. Pour more water over the crude ester to destroy any remaining benzoylchloride.

B. Recrystallization1. Transfer the crystals to a boiling tube and just cover them with ethanol.2. Place the beaker in a water-bath or beaker of hot water., kept at about

60°C and stir with a glass rod.3. If some solid ester is still visible, add j,ust enough ethanol to dissolve

it completely after stirring.

58

4. In order to allow the separation of the ester as a solid rather than anoily liquid (phenyl benzoate has a low melting-point) add more ethanolto double the volume of solution.

5. Cool the solution in an ice-water mixture until crystals appear.6. Filter the crystals through the suction apparatusJ using a clean Buchner

funnel and filter paper. To avoid losing any solidJ break the vacuum anduse the filtrate to rinse the boiling tube into the funnel.

7. Using suction againJ rinse the crystals with about 1 cm3 of cold ethanoland drain thoroughly.

8. Press the crystals between two wads of filter paper to remove excesssolvent. Then put the crystals on another dry piece of filter paperplaced alongside a Bunsen burner and gauze~ turning the crystals overoccasionally until they appear dry. Don't let them get too hot or theywill melt!

9. Weigh the dry crystals in a pre-weighed specimen bottle and record themass of your sample of phenyl benzoate.

C. Determination of melting-pointFollow the procedure which is described in Experiment 2 (page 19) and recordthe melting-point of your sample of phenyl benzoate.

Results Table 6

Mass of weighing bottle + phenol gMass of weighing bottle after emptying gMass of phenol gMass of specimen bottle gMass of specimen bottle + phenyl benzoate gMass of phenyl benzoate gMelting-point of phenyl benzoate °c

(Specimen results on page 100)

Questions1. Calculate the maximum mass of phenyl benzoate that could be formed from

the mass of phenol you usedJ assuming complete conversion according tothe equation.

2. Calculate the percentage yield of phenyl benzoate using the expression:

Mass obtainedTheoretical maximum mass x 100 = % yield

3. The melting-point of pure phenyl benzoate is 69°C. What can you sayabout the purity of your sample?

(Answer on page 100)

You now summarise the reactions and preparations of carboxylic acid derivatives.Because of the very close relationship between the derivatives of a parentcarboxylic acidJ the reactions are best shown on a single chart.

59

Summary of reactions and preparationsExercise 53 Complete a copy of Fig. 15, which summarises the ~

reactions and preparations of carboxylic acid derivatives.(Answers on page 101 ) ~\\\

For otherreactionssee Fig. 10.

1HeatNasalt with

soda-lime

propanone

/ /Electrolysisof aqueous

solutionethanoic

~ anhydride

LiAIH4ethoxyethane

~

CH3NH2

methylamine

Fig. 15.

ethanol

Summary of interconversions of carboxylic acid derivatives

In the next exercise you write some synthetic pathways which include thereactions and preparations of carboxylic acid derivatives. Two of thepathways involve the removal of a carbon atom from a compound, so you willhave practice in using the Hofmann degradation reaction.

60

Synthetic pathwaysExercise 59

Exercise 60

Suggest synthetic pathways suitable for bringing aboutthe following conversions. State the reaction conditionsfor each step and indicate the intermediate products.(a) C3H7C02H -+ C3 H7NH2(b) CH3CHO -+ CH3CONH2(c) CH3CONH2 -+ CH3C02CH2CH3

(d) C6HsC02H -+ C6HsC02C2Hs(e) CH3C02H -+ C2HsC02H(f) C3H7OH -+ C2HsOH(Answers on page 101 )

Devise a reaction scheme for the preparation ofN-phenylbenzamide~ C6HsCONHC6Hs~ from benzene andmethylbenzene. No other organic compound is availablebut you may use whatever inorganic reagents you wish.For each step in the synthesis you should give the names of thereagents~ the conditions of reaction and the structures ofintermediate compounds. Balanced equations will not beexpected.(Answers on page 101 )

Carboxylic acid derivatives have a variety of uses which you may care c=>to read about. Esters~ for instance~ are widely used as solvents ~Ifor paints and varnishes and synthetic flavourings. Acyl anhydrides ~such as cis-butenedioic (maleic) anhydride~ when reacted with poly-functional alcohols such as ethan-1~2-diol~ form polyesters. Youstudy polyesters as well as polyamides in Unit 04 (Big Molecules).

You have now completed a study of the major functional groups in organicchemistry. In the remaining sections of this Unit you extend and summarisethe knowledge of isomerism you have gained during this study.

61

ISOMERISMIsomerism occurs when there are two or more compounds (called isomers) withthe same molecular formula but different arrangements of their atoms.Isomers have some different physical and chemical properties, but thedifferences may be great or small depending on the type of isomerism.

You have already met some of the different forms of structural isomerismand one of the forms of stereoisomerism - called geometrical isomerism - inearlier organic Units. We now bring them together under one heading andintroduce you to the other form of stereoisomerism - called optical isomerism.Fig. 16 shows how the two main classes of isomerism are sub-divided.

opticalisomerism

Istereoisomerism

Igeometrica 1

isomerism

ISOMERISM

I

metamerism

Ifunctional

groupisomerism

Istructural isomerism

Iposition

isomerismchain

isomerism

Fig. 16.

Metamerism is liKe position isomerism in that the same functional groupappears in different positions. However, metamers have more than one carbonsKeleton. For example~ the esters ethyl methanoate, HC02C2Hs, and methylethanoate, CH3C02CH31 are metamers. Another pair of metamers comprises theethers methoxypropane, CH30C3H7• and ethoxyethane, C2HsOC2Hs.

Isomers are usually stable distinct structures but occasionally two isomersare readily converted into each other and exist in dynamic equilibrium. Suchisomerism is called tautomerism and is most often a special type of functionalgroup isomerism. For example, ethyl 3-oxobutanoate, a Ketone, is alwaysmixed with a small proportion of a tautomer Known as an enol because itcontains a carbon-carbon double bond and a hydroxy group:

The most important type of isomerism we have not discussed before is opticalisomerism, which is the subject of the next section.

62

Optical isomerismObjectives. When you have completed this section you should be able to:

(35) recognise optical isomers by their structural formulae;(36) explain the meanings of the terms, asymmetric, enantiomer and

chiral molecules.

Read about optical isomerism in your textbook(s). For the timebeing, concentrate on the structural features of optical isomersrather than their opt~cal properties. Find out why asymmetricmolecules exist in two forms called enantiomers. Also, find out themeaning of the term 'chiral molecule'. The model-making exercisewhich follows should aid your understanding.

Ask for a model-making kit and a mirror. Maketwo identical models of a molecule in which acarbon atom is attached tetrahedrally to fourdifferent groups (four diff~rently colouredballs would be suitable). Make sure the modelsare identical by superimposing one on the other.Now take any two of the substituent groups (orcoloured balls) in one of the models and exchangethem. Are the two models still identical, i.e.can you still superimpose them? Look at one ofthe models in a mirror and at the other directly.What do you see? Can you remove the mirror andreplacB the image with the other model?Repeat the exercise above using only threedifferently coloured balls, i.e. two of the foursubstituent groups are the same.With the models in front of you, attempt the next exercise.

Exercise 61 With the aid of diagrams, answer the following qUestions.~(aJ Is structure A identical with its mirror image?

(Can you superimpose the two structures?) ~~

A a B a

I Ib ------l"', b

C,b --------J "'d

c c

(b) Is structure B identical with its mirror image?(Can you superimpose the two structures?)

(c) Which of the structures A and B has a plane of symmetrywhich divides the molecule into two identical halves?

(d) Which structures represent optical isomers (enantiomers)?(Answers on page 102 )

63

You can see from the last exercise that the existence of optical isomers is aresult of the asymmetry (lack of symmetry) of the molecules. The two formsare not identical - they cannot be superimposed one on another.

The relationship between optical isomers is rather like the relation betweena right and left-hand glove. A left-hand glove does not possess a plane ofsymmetry. and its mirror image is not another left-hand glove but a ri8ht-hand glove. The two gloves are not identical, for they are not superimposable.If we were to lay one on top of the other, the thumbs would be on oppositesides.

mirror object mirror image

Fig 17. Enantiomers (non-superimposable mirror images) Fig. 18. Object and mirror image are not identical

Molecules, gloves or any other object lacking a plane of symmetry are saidto possess chirality, which means 'handedness' (Greek: cheir, the hand).Any chiral object will exist in two forms.

The next exercise tests your understanding of asymmetry.

Exercise 62 Explain briefly whybut compound 0 does

HI

CH - C -COOH:3 IOHC

(Answer on page 102 )

compound C exhibits optical activity~not.

H ~I

CH -C-COOH3 I

COOHo

The most common examples of optical isomers contain an asymmetric carbon atom,i.e. a carbon atom linked to four different atoms or groups as in your modelsand in compound C (Exercise 62). However, asymmetry can arise in other ways,as you see in the next exercise. Furthermore, if there are two asymmetriccarbon atoms in a moleculel the whole structure mayor may n~be asymmetric.

Exercise 63 Which of the following compounds have optical isomers?(a ) CH3CHOHCH2CH3 (e) H02 C, C02H, /

(b) CH3CHOHCH3H__ C-C"--H

I ,(c ) CH3CH(OH)C02H HO OH

(d) CH3CH==CH2 (f) H02 C, CO2 HH--'C-C/~OH

Hoi ~H(Answers on page 102)

64

Optical isomerism is not limited to carbon compounds, nor to tetrahedralstructures. We discuss some examples of inorganic isomerism in Unit 15(Transition Elements). For the moment, however, we consider only organiccompounds.

The form of 2,3-dihydroxybutanedioic acid (tartaric acid) shown inExercise 63(e) has two asymmetric carbon atoms but, nevertheless, has nooptical isomers; this is because it has a plane of symmetry which divides itinto identical halves. Such compounds are named using the prefix meso;structure (e) in Exercise 63 is meso-2,3-dihydroxybutanedioic acid (meso-tartaric acid). Other prefixes, which we explain in the next section, may beused to distinguish between pairs of optical isomers, such as structure (f)and its mirror image.

The fact that optical isomers are structurally very similar means that theyhave very similar properties. These include identical melting- and boiling-points, solubilities, refractive indices and chemical properties. This maylead you to wonder how we can distinguish between two enantiomers. Theanswer to this question also explains why we call this type of isomerism'optical isomerism'.

Optical propertiesObjectives. When you have finished this section you should be able to:

(37) explain how two optical isomers can be distinguished by their effecton polarized light;

(38) explain the meaning of the term racemic* form (racemate).

Read about the effect of enantiomers on polarized light in your 0textbook. Look for a simple diagram and description of the apparatus illwhich is used for measuring optical activity. Also find out themeanings of the terms dextrorotatory, laevorotatory and racemicform (racemic mixture, racemate). This should help you to do thenext exercise.

*Racemic is pronounced 'rass-ee-mick', with the emphasis on the middlesyllable.

65

Exercise 64 Fig. 19 shows a simple representation of the apparatusused to distinguish between enantiomers. Copy it andlabel the parts as you answer the questions.

~ II B ~~ --- --O---~-- -- - -- -- ---- --~- --0----Fig. 19.

(a) Name the apparatus shown in Fig. 19.(b) In what way does the source of light shown as D differ

from ordinary light?(c) Identify A and C and describe their function.(d) Where is the compound placed in order to tests its optical

activity?(e) When no cell is in the apparatus, the light can pass

through A only if the polarizing axis is parallel to thatof C. What happens when A is rotated so that its axis isat right angles to that of C, i.e. when A and CareIcrossedl?

(f1 In an experiment I a student placed a solution of anoptically active compound, X, in the cell between crossedprisms. She found that the sample altered the plane ofpolarization so that A had to be rotated clockwise in orderto obtain minimum brightness again. What had the studentfound out about the optical activity of X?

(g) The experiment was repeated using compound Y, the enantiomerof X used in the previous experiment. What would thestudent have to do in order to obtain minimum brightnessthis time? What term is used to describe compound Y?

(h) Describe what would happen if the experiment were againrepeated, this time using an equimolar mixture of the twoenantiomers X and Y. What term is used to describe thismixture?

(Answer on page102

The names of dextrorotatory and laevorotatory isomers are distinguished bymeans of the prefixes (+) and (-) respectively. The racemic form, whichconsists of an equimolar mixture of the two, is optically inactive and isgiven the prefix (±). (Older texts may use the prefixes d, land dl.)

Note that you cannot telll by inspection of the structural formulae, whichenantiomer is (+) and which is (-). For this reason, structural formulaeare sometimes labelled' with other prefixes, such as D and L, which refer tofeatures of the structure and not to optical rotation. At A-level, you needonly concern yourself with the-prefixes (+) and (-).

66

Synthesis of optically active compounds

dI

a--C~/ J c

b

b, c

~ a--c/

1Either 'bl

can besubstituted

bI

a--C~, c

b

dI

a--C~/ , c

b

~ ba- '/C

Group 'd I can - Capproach fro~ Ieither direction d

The laboratory synthesis of an optically active compound from inactive rawmaterials almost always produces a racemic mixture. The step in thesynthesis which introduces asymmetry can be either addition or substitution.Fig. 20 shows how these processes can occur in two equally likely ways togive a racemic mixture.

Fig. 20.

Use this idea in the next exercise.

CH3CH2C02H/C12

ICH3CHC1C02H/hydrolysis

ICH3CH(OH)C02H2-hydroxypropanoic acid

(lactic acid)

CH3CHO'\

HCN

"CH3CH(OH)CN\hydrolysis

'\

The compound 2-hydroxypropanoic acid (lactic acid) maybe formed in two ways as shown in the followingreaction scheme.

Exercise 65

(a) 2-hydroxypropanoic acid can exist as two optically activeisomers. Draw their structural formulae.

(b) When using either of the pathways suggested, a racemicmixture will be formed. Explain this term, and thereasons for this assertion.


Whereas racemic mixtures are usually produced in laboratory synthesis, inliving systems a preponderance of either (+) or (-) forms of naturally-occurring compounds is the norm. This is due to the highly specific actionsof enzymes throughout the synthesis. The next exercise illustrates the point.

67

Exercise 66 In a thriller mystery by Dorothyl L. Sayers and Robert ~Eustace entitled 'The Documents in the Case', a man whois supposedly an expert on edible fungi is at first ~~assumed to have accidentally died from eating poisonousmushrooms. Examination of the contents of his stomach shows thepresence of muscarine (an alkaloid found in certain poisonousfungi). Analysis of this compound shows it to be opticallyinactive. In what way might this evidence cause you to alteryour opinion as to the circumstances of this man's death?(Answer on page 103 )

We now consider the methods of separating enantiomers from a racemic mixture.

Separation of optical isomersObjective. When you have finished this section you should be able to:

(39) describe a chemical method for the resolution of a racemic mixtureinto its enantiomers.

Read about the methods of resolving (separating) a racemic mixture c=>into its enantiomers, especially chemical methods of resolution. You ~Ishould then be able to do the next exercise. ..~

To help you understand the chemical method of separating a racemic form intoenantiomers, we use an analogy.

Suppose we have a mixture of right-handed and left-handed spirals~ as inFig. 21. This is analogous to a racemic mixture.

Fig. 21.

Now we attach to each spiral a second spiral which is, say, left-handed(Fig. 22). The two types of combined spiral are no longer mirror images ofeach other, and can easily be separated.

Fig. 22.

68

There are many chemical analogies for the linking together of spirals asdescribed above. In general, if (+)A and (-)A represent two enantiomerspresent in a racemic form and (-)6 represents a single optically active formof another compound that will combine in some way with A, then the process ofresolution may be achieved. You show this in the next exercise.

Exercise 67 (a) Complete the following equation which shows thereaction between the racemic form of an acid (AJand an optically-active base (6).

(±JA +

acid(racemic

formJ

2(-)6 ~base

(laevorotatoryform)

(bJ What further steps must be taken to obtain the separateacid enantiomers (+)A and (-JA?


Now that you have studied several different types of isomerism, you shouldsummarise what you have learned.

Summary of isomerismObjective. When you have completed this section you should be able to:

(40) describe the different types of isomerism which occur in carboncompounds.

Use your textbook(s) and notes as necessary to help you to complete 0Fig. 23 in the follOWing exercise. You should be able to define the ~Ivarious types of isomerism, giving examples and indicating how ~isomers generally differ in physical and chemical properties.

69

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70

Exercise 68 (a) Complete the upper part of a copy of Fig. 23 byinserting the following sentences in theappropriate boxes.Isomers have molecules with no plane of symmetry.The structures are non-superimposable mirror images.Isomers have different structural formulae, i.e.corresponding atoms form different bonds.Isomers have different carbon sKeletons.Isomers have the same functional group but it is attachedto two or more different carbon sKeletons.Isomers have the same structural formulae, i.e.corresponding atoms form the same bonds.Isomers have different functional groups.Isomers (of any type) are in equilibrium with each other.Isomers are compounds with the same molecular formula butdifferent arrangements of their atoms.Isomers have the same carbon sKeleton but with a functionalgroup (or groups) at different positions.Isomers have atoms which, though they form the same bonds,have different relative positions in space.

(b) Insert the following formulae. in pairs, into the 9Ppropriateboxes as examples of different types of isomerism. Addtheir names ..CH3OCH3 CH3CH2OHCH2==CHOH CH3CHO

Br Br©JBr ©Br

CH3NHC3H7 (C2HsJ2NHCH3CH2CH2CH20H (CH3)2CHCH20H

OHH ' C2Hs....C .•..•..

ICH3

(c) In each box labelled 'properties' insert one of thefollowing:Similar, but with some important differences.Very different.Identical except for optical rotation.


Finally, we consider the methods of distinguishing between pairs of isomers.Apart from optical isomers, most pairs of isomers can be distinguished byboth physical and chemical methods.

71

Distinguishing isomersObjective. When you have completed this section you should be able to:

(41J distinguish between pairs of isomers by physical and/or chemicalmethods.

Find out how pairs of structural isomers and geometrical isomers can 0be distinguished by physical and chemical methods. In particular, m,look for a chemical method of distinguishing between the geometric .~isomers of butenedioic acid, commonly known as maleic acid andfumaric acid. Then do the next exercise.

( a JExercise 69 Describe one physica.l test which would enable you to 0distinguish between A

(i) the structural isomers pentane and2,2-dimethyl-propane,

(ii) the geometric isomers of butenedioic acid,C02HCH=CHC02H (maleic acid and fumaric acid),

(iii) the optical isomers of butan-2-ol.(bJ Explain how the geometric isomers of butenedioic acid can

be distinguished by chemical testing.(Answers on page 103 )

To consolidate your understanding of isomerism you should attemptthe following Teacher-marked Exercise.


Describe the different types of isomerism which occurin carbon compounds. Illustrate your answer byreference to isomers of each of the following:C4H10' C3H7Cl, C4Hs and CH3CH(OH)COOH.State what differences (if any) in chemical behaviour and inphysical properties you would expect the various isomers ofeach formula to show.A hydrocarbon, CSH10' reacts with sulphuric acid and theproduct is hydrolysed to give an alcohol, CSH120. Thisalcohol can be separated into two enantiomeric forms (opticalisomers). Suggest one possible structure for the hydrocarbon.

We complete this Unit by asking you to identify, by experiment, some organicsubstances which you have studied. This is both useful revision of organicreactions and preparation for a practical examination.

If it is available, view the second part of the ILPAC video-programme [QJJIdentifying unknown substancesJ before you do the practical test. 0This will help you not only with the practical technique but also

00with the interpretation of observations.

72

END-OF-UNIT PRACTICAL TESTThis experiment is intended primarily for students preparing for anA-level practical examination in which one of the questions couldrequire the identification of an unknown compound by means ofspecified tests. If your teacher wants you to do this test, askwhether you may use practical textbooks and your own notes during thetest (we have assumed that you may).

The question which follows is taken from three A-level practicalexamination papers. Since you should preferably work underexamination conditions, all the apparatus and chemicals should beprovided for you so we have not included a requirements list. However, takenote of the hazard warning.

Hazard warningConcentrated hydrochloric acid, phosphorus pentachloride, unknowncompound H and solutions of silver nitrate, sodium chlorate(I)(sodium hypochlorite) and sodium hydroxide are all corrosive.Phenylamine (aniline) and 2,4-dinitrophenylhydrazine are toxic byskin absorption. Therefore you MUST:WEAR SAFETY SPECTACLES AND GLOVES THROUGHOUT.Phosphorus pentachloride and compounds G and H produce harmfulvapours. Therefore you MUST:PERFORM EXPERIMENTS WITH THESE COMPOUNDS AT A FUME CUPBOARD.KEEP TOPS ON BOTTLES AS MUCH AS POSSIBLE.Compounds G and H are flammable. Therefore you MUST:KEEP THESE COMPOUNDS AWAY FROM FLAMES.

You are provided with three organic com-pounds, labelled F, G and H. Each compoundcontains the elements carbon, hydrogen andoxygen only. Carry out the followingexperiments. Record your observations andinferences in (a larger copy of) the tableprovided. Comment on the types of chemicalreaction occurring and, where possible, deducethe functional groups present in these compounds.Then answer the questions which follow.( 1 ) Comment on the structural features of F.(2) Comment on the structural features of G.( 3) What functional group is present in H?

Give your reasoning.

73

Results Table 7

EXPERIMENT

(a) To 2 cm3 of the solution of F add 2,4-dinitrophenylhydrazine reagent.

(b) Prepare a sample of Tollens' reagentas follows: to 5 cm3 of aqueoussilver nitrate in a test-tube add1-2 drops of aqueous sodium hydro-xide. Then add dilute aqueousammonia until only a trace ofprecipitate remains. Now add 5drops of the solution of F and placethe tube in hot water. (Pour thecontents of the tube down the sinkon completion of the test.)

(c) Add a little of the solution of Fto some sodium hydrogencarbonate.

(d) To 1 cm3 of the solution of F add3 cm3 of aqueous potassium iodideand then 10 cm3 of sodiumchlorate(I) (sodium hypochlorite)solution.

(e) Place ONE drop of G on an invertedcrucible lid and ignite G fromabove.

(f) To 1-2 cm3 of G add 2,4-dinitro-phenylhydrazine reagent.

(g) Prepare a sample of Tollens' reagentas in (b). Add 5 drops of G, shakethe mixture and place the tube inhot water. (N.B. Pour the contentsof the tube down the sink on comple-tion of the test.)

(h) To 0.5 cm3 of G add 2 cm3 of 6 Msodium hydroxide. Warm the mixtureand stir well for 5 minutes. Thenadd sufficient water to dissolve anyresidue which has formed. Separatea portion of the aqueous layer andadd a little concentrated hydro-chloric acid to it. Cool.

(i) Test to see if H is miscible with(i) cold water,

(ii) hot water.

(j) (i) To about 2 cm3 Df H in a drybeaker add a little anhydroussodium carbonate.

(ii) Now add about 5 cm3 of hotwater to the mixture from test(j),(i).

(k) (This reaction should be performedin a fume cupboard.) Place 2 or3 cm3 of H in a dry beaker. Add alittle phosphorus pentachloride(CARE!).

(1) Place 24cm3 of glacial ethanoic acidand 2 cm3 of H in a boiling tUbe andadd 2 cm3 of phenylamine (aniline).Heat cautiously until the mixturebegins to boil. Remove from theflame and allow to stand for 2minutes. Now pour the mixture intoabout 125 cm3 of cold water withstirring and allow to stand.

OB~=RVATIONS INFERENCES

A SUGGESTION FOR REVISIONYou have now completed your study of the main functional groups in organicchemistry and you have completed charts which summarise their reactions andpreparations. You may find it helpful as part of your revision to combinethese into a single master-chart which shows the inter-relationships of thefunctional groups.

The construction of such a chart will consolidate what you have learned andprovide a quicK reference to help you solve problems in synthetic pathways.

END-OF-UNIT CHECKLISTYou have now come to the end of this Unit. Read carefully through thefollowing summary of objectives and checK that you have adequate notes.

(1) write the structural formulae and names of aldehydes and Ketones;(2) describe the shapes of some simple aldehydes and Ketones;(3) & (4) write equations for the reactions of aldehydes and Ketones which

illustrate their similarities;(5) & (6) describe the mechanisms of nucleophilic addition and of

condensation reactions of carbonyl compounds;(8) compare and contrast the reactions of aldehydes and Ketones with

oxidizing agents and with alKalis;(9) recognise the structural grouping that a carbonyl compound must have

in order to undergo the triiodomethane (iodoform] reaction;(10) describe simple chemical tests which you could use to distinguish

carbonyl compounds;(7) describe how the reaction with 2,4-dinitrophenylhydrazine is used to

identify carbonyl compounds;(11) to (13) explain the steps involved in preparing a solid derivative of

a compound, purifying it by recrystallization, and measuringits melting-point;

(14) write equations for the preparations of aldehydes and Ketones givingspecific reaction conditions;

(15) describe some of the uses of carbonyl compounds;(16) write the structural formulae and names of carboxylic acids;(17) & (19) write equations for the reactions of carboxylic acids giving

reaction conditions;(18) & (20) compare the reactions of carboxylic acids, hydroxy compounds

and carbonyl compounds, and describe simple distinguishingtests;

(21) account for the acidity of carboxylic acids;(22) write equations for the reactions in which carboxylic acids are

produced, giving specific reaction conditions;(23) describe some of the uses of carboxylic acids;

(24) perform specified tests on a given salt of a carboxylic acid aDdfrom your observations make inferences about its identity;

(25) write the structural formulae and names of carboxylic acid derivatives;(26) & (27) write equations for the reactions of carboxylic acid

derivatives with nucleophilic reagents, and describe amechanism;

(28) & (29) write equations for the reduction of carboxylic acidderivatives, the Hofmann degradation reaction and thedehydration of amides;

(30) compare the reactivity of acyl halides and alkyl halides and relate thedifferences to their structure;

(31) & (32) .describe how the presence of the carbonyl group modifies theproperties of the adjacent --NH2 group in an amide and explainwhy amides are weaker bases than amines;

(33) describe some simple chemical tests to distinguish between carboxylicacid derivatives and compounds containing similar groups;

(34) write equations for the preparation of carboxylic acid derivatives~giving specific reaction conditions;

(35) & (36) recognise optical isomers by their structural formulae, andexplain the meanings of the terms, asymmetric, enantiomer andchiral molecules;

(37) explain how two optical isomers can be distinguished by their effecton polarized light;

(38) & (39) explain the meaning of the term racemic form (racemate), anddescribe a chemical method for the resolution of a racemicmixture;

(40) describe the different types of isomerism which occur in carboncompounds;

(41) distinguish between pairs of isomers by physical and/or chemical methods.

Check that you have adequate notes before going on to the End-of-Unit Test.

END-Of-UNIT TESTTo find out how well you have learned the material in this Unit, try ~.the test which follows. Read the notes below before starting.

~\\\1. You should spend about 2 hours on this test.2. You will need a small piece of graph paper.3. Hand your answers to your teacher for marking.

76

1. The name of the compound (CH3)2CHCHO is

END-OF-UNIT TEST

A butanalB propanal

C 1-methylpropanalo 2-methylethanal

E 2-methylpropanal

~(1J

Questions 2 - 5 concern the preparation of a crystalline organic compound, X.5 g of phenol (C6HsOH) were dissolved in about 90 cm3 of dilutel aqueoussodium hydroxide in a stoppered glass bottle. In a fume cupboard, 9 cm3 ofbenzoyl chloride (C6HsCOCI; density 1.2 g cm-3) were cautiously added to thebottle which was then stoppered and shaken for about 15 minutes. The solidsample of X was filtered off, washed with water and recrystallized fromethanol.The white crystals of X obtained were found to melt below 100 DC and to havea relative molecular mass of 198 (C6HsOH = 94, C6HsCOCI 140.5).

2. The formula of the white, crystalline compound X isA

@-O-@C 0

@-g-o-@ E 0@-g-@-OH

B 0 0@-o-@-<o@-g-@ Cl ( 1 )

3. The most likely reason for carrying out the preparation in a fumecupboard is thatA phenol is causticB sodium hydroxide is corrosiveC benzoyl chloride is highly flammableo phenol hydrolyses to give an irritant vapourE benzoyl chloride vapour is an eye irritant ( 1 )

4. Recrystallization was carried out from ethanol rather than waterbecauseA X is rapidly hydrolysed by waterB the boiling point of water is above the melting point of XC X forms hydrogen bonds with watero X is more soluble in ethanol than in waterE water would also dissolve the sodium hydroxide used in the

preparation

77

( 1 )

One mole of X is formed from one mole of phenol and one mole ofbenzoyl chloride. The maximum yield, in grams, of X in thepreparation would be

5.

A

B

5 + (9 x 1.2)198

140.5 x 9 x 1.2

C

D

19894 x 5

198 9140.5 x U ( 1 J

In Questions 6 to 10 inclusive, one, or more than one, of the suggestedanswers may be correct. You should answer as follows:A if only 1, 2 and 3 are correctB if only 1 and 3 are correctC if only 2 and 4 are correctD if only 4 is correctE if some other response, or combination, is correct.

stronger acids than ethanoic acid (CH3C02H) include6.

1 methanoic acid (HC02H)2 benzoic acid (C6HsC02HJ

3 bromoethanoic acid (CH2BrC02HJ4 carbonic acid (H2C03J ( 1 )

7. Which of the following statements about chloroethanoyl chloride(CH2ClCOCl) is (are) true?1 It can be reduced by lithium aluminium hydride (lithium tetra-

hydridoaluminate(IIIJ J in dry ether to form a hydroxy-compound.2 It will react readily with water to give an organic compound

containing no chlorine.3 On boiling with aqueous sodium hydroxide, it will give the

sodium salt of a hydroxy-acid.4 It will react with ammonia solution to form an addition product. (1)

In which pair(s) of reagents will each member of the pair reactseparately with ethanoic acid (CH3C02H)?

8.

1 H2S04; NaoH2 NH3; PC13

3 H2S04; PC13

4 NH3; C12 ( 1 )

Propanone (CH3CoCH3J and propanal (CH3CH2CHo) would be OBSERVED toDIFFER in their reactions with

Ethanoyl chloride (CH3COClJ is formed when ethanoic acid(CH3C02H) reacts with

9.

10.

1 2,4-dinitrophenylhydrazine2 ammoniacal silver nitrate

1 phosphorus penta chloride2 hydrogen chloride

3 phosphorus pentachloride4 iodine and aqueous potassium

hydroxide (iodoform testJ

3 thionyl chloride (SoC12J4 chlorine

78

( 1 )

( 1 J

11. (a) Write the structural formula of each of the followingderivatives of ethanoic acid:

(i) ethanoic anhydride~(ii) ethyl ethanoatel

(iii) ethanoyl chloridel(iv) ethanamide. (4 )

(bJ Write equations for the hydrolysis of each derivativementioned in (a). Name the products and state the reactionconditions. (8 )

(c) Write the derivatives in order of ease of hydrolysis~ puttingthe easiest first. (1)

The following are some reactions of benzaldehyde.formulae for A~ B1 C and D.

Draw structural

B

acidified•KMn04 solnr'8YCHO

0'PCls

12.

concentratedNaOH(aq)

!+

(4)

13. Write short explanatory notes on the following items of information:(a J structural formula of acid pK a

CH3CH2CH2CO2H 4.82CH3CH2CHClC02H 2.84CH3CHClCH2C02H 4.06CH2ClCH2CH2C02H 4.52 (4 )

(b) Benzenecarboxylic (benzoic) acid is a stronger acid than ethanoic(acetic) acid in aqueous solution. (3)

(c) Ammonia is a weaker base than ethylamine but a stronger basethan ethanamide. (4)

(d) The formula of ethanoic acid contains the carbonyl group~ butethanoic acid does not show the reactions characteristic ofthis groupl such as addition and condensation. (3)

79

( 14)

14. Deduce the structures of the compounds A to G below~ giving thereason for selecting each structure.C7H6O LiAlH4 C7HaO•A B

I NaOH C~4H~202air C

+C7H602 SOC12 C7HsOCl•D

~ENH3

NaOH C~3H~~NO~ G

C7H7NO @'NH2

F ·0Describe chemical tests which can be used to distinguish betweenthe members of each pair of compounds listed. Describe theexperiment you would perform and what you would observe.

(c) C6HsC02C2Hs and CH3C02C2Hs(d) C2HsOH and C2HsCHO

and

and

COCH3

©(b)

15.

CHO ( 12)

Suggest synthetic pathways suitable for bringing about thefollowing conversions. State~ where appropriate~ any reagentsto be used and give the names of any intermediate compounds.

16.

(a) CH3C02H ~ CH2(NH2JC02H(bJ C2HsC02H ~ C2HsNH2

(c) CH3CHBrCH3 ~ CH3COCH3

(d) C6HsC02CH3 ~ C6H6 ( 16)

17. The flow chart shows the reactions of some propane derivativesand Fig. 24 illustrates the infra-red spectra of propane andsome of the same derivatives.

p

zwarm concentratedsodium hydroxide Q

C3 H60

Iexcess acidifiedsodium dichromate(VIJ

R

80

887456wavelength/ JAm

Q)

ucIt)::::

"E(Jlc~Q)

OJIt)

CQ)

uQ;0.2

Q)

ucIt)::::

"E(Jlc~Q)

C>It)

CQ)

uQ;0.2 3

Fig. 24.

(a) Compound Q gives a positive result with Fehling's solution.(i) Describe how tests with Fehling's solution are carried out

and describe the appearance of a positive result.(ii] What is the functional group in Q?

(iii) Draw a diagram of the structural formula of Q.(b) Compound P is readily converted to Q in a single stage.

(il Draw a diagram of the structural formula of P.(iil Give the name(s) of the reagent(s) needed to convert

p to Q.(iii) What experimental conditions would you use?

(c] Compound R is weakly acidic.

(4 )

(4)

(i) Draw a diagram of the structural formula of R.(ii) What is the formula of the product of the reaction of R

with phosphorus pentachloride? (2)Cd) Ci) Suggestl as far as possiblel which bonds may be

responsible for the peaks in the infra-red absorptionspectra in Fig. 24 at about 3 ~ml 3.5 ~ml 5.9 ~m and6.6 - 7.2 ~m.

(ii] Sketchl on graph paperl the infra-red absorption spectrumyou would predict for compound R. (5)

(e] What type of reaction occurs in the change of Q to Z? (1)

81

18. (a) (i) There are three structural isomers which have themolecular formula C4H~OH. Draw their structuralformulae.

(iiJ Which one of these isomers would be optically active?Explain your choice. (5)

(b) Explain briefly why compound A exhibits geometrical isomerismbut compound B does not.

HOOCCH == CHCOOHA

HOOCCH2CH2COOHB

( 2)

( 3)

19 . The following is a description of an experiment in which ethylbenzoate is hydrolysed.5 cm3 (0.03 mol) of ethyl benzoate are mixed with 30 cm3 of 2 Msodium hydroxide solution and heated under reflux for about fifteenminutes, until all the oily drops have disappeared. The flask isthen fitted for fractional distillation and the mixture distilleduntil the boiling point reaches 78°C to give a distillate A. Thecontents of the flask are allowed to cool and then slowly acidifiedwith concentrated hydrochloric acid, when a precipitate B separates.This precipitate is purified by recrystallization from water.

(a) Write the equation for the reaction between ethyl benzoateand sodium hydroxide solution. (1)

(bJ Sketch the apparatus required for heating the mixture underreflux. (2)

(cJ During the distillation~ where would you place the bulb ofthe thermometer and why? (1)

(d) (i) What is the liquid A?(ii) Give one CHEMICAL test, and its result, which would

support your answer to (iJ.(e) (iJ What is the white precipitate B?

(ii) Write the equation for its formation.(f) (i) Describe how you would separate and recrystallize the

precipitate B. Indicate the apparatus you would use.(iiJ State how you would check that your recrystallized

specimen was pure.

(2 )

( 5 J

(Total 120 marks)

82

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102

ISOMers havedi fferent carbon

skeletons.

Isomers have thesame carbon

skeleton but witha functional group

(or groups) atdifferentpositions.

Isomers havedifferentfunctional

groups.

I ISOMERISMI

Isomers have thesame functionalgroup but it is

attached to two ormore different

carbon skeletons.

I TAUTOMERISMI

Isomers (of anytype) are inequilibrium

with each other.

Isomers have atomswhich, though they

form the samebonJs, have

different relativeposi tions in space.

I somers havemolecules withno plane of

symmetry. Thestructures are

non -superimposablemirror images.

Examples Examples Examples Examples Examples Examples Examples

co(D

CH. CH2 CH2 CH2 oHbutan-1-ol

CH.CHCH2oHICH.

2-methyl-propan-1-ol

Br

1. Z-dibromobenzene

Br

oL;J.-l Br

1,3-dibromobenzene

CH.oCH.methoxymethane

CH.CH2oHethanol

CH.NHC.H7

Iv-methyl propylamine

(C2Ho laNHdiethylamine

CH2=CHoHethenol

(vinyl alcohol)

H

CH3C~O

ethfJnal

Ho2C'C=C/Co2H

H' 'Hcis-butenedioic

acid

Ho2C,C=C/

H' 'Co2Htl"ans-butenedioic

acid

TH•

W_C

"~H C2Ho

oHH~~/C2Ho

ICH.

(+) and (-)butan-2-Ql

OJ(J]'r!U>-<OJX

W

Properties

Similar, but witt",some importantdifferences.

Properties

Similar. but withsome importantdifferences.

Properties

Very different.

Pro pert ies

Similar, but withsome importantdifferences.

Properties

Similar, but withsome importantdifferences.

Properties

Identical exceptfor optical

rotation.

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More functional groups: unit O3 - STEM Learning

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