Topic 4.5 COMPOUNDS CONTAINING THE CARBONYL GROUP Aldehyde !"d #e$o"e C!%&o'ylic Acid !"d $hei% S!

l$ E $e% Acyl Chlo%ide !"d Acid A"hyd%ide

ALDEHYDES AND KETONES 1. Introduction

Aldehydes and ketones are collectively known as carbonyls and represented by the general formula CnH2nO. They have the following functional group:
O C

n aldehydes one of the groups attached to the carbon is a hydrogen atom and the other is a hydrogen atom or an alkyl groups. n ketones both of the groups attached to the carbon are alkyl groups: H
O
CH3

H C H

H C H

O C H

O H C H

C H

C H

ethanal H H C H H C H O C

methanal H C H H H H C H H C H

butanal O C H C H pentan!2!one H C H H

butanone

2.

Redox reactions

The redo" reactions involving carbonyls have been discussed at A# level and are summari$ed by the following diagram:
primary alcohols [O] [R] secondary alcohols [O] [R] tertiary alcohols X

aldehydes [O] carboxylic acids

ketones X

a) oxidation reactions Carbonyls are formed by the o"idation of alcohols. %artial o"idation of a primary alcohol results in the formation of an alde !de. O"idation of a secondary alcohol results in the formation of a "etone. %rimary alcohols& secondary alcohols and aldehydes are o"idi$ed using potassium dichromate '(2Cr2O)* in sulphuric acid 'H2#O+*. ,entle warming is necessary to start the reaction. -hen making an aldehyde& care must be taken to prevent further o"idation to the carbo"ylic acid. This is achieved by using distillation apparatus so that the aldehyde can be distilled off as soon as it is formed. The orange Cr2O)2! is reduced to the green Cr./.

#implified e0uations for these o"idation reactions can be written using the symbol 1O2 as the o"idant: %rimary alcohol aldehyde 3!CH2OH / 1O2 3!CHO / H2O #econdary alcohol ketone 34!CH'OH*!32 / 1O2 34!CO!32 / H2O Aldehyde carbo"ylic acid 3!CHO / 1O2 3!COOH The most important difference in the reactions of aldehydes and ketones is the fact that aldehydes can be readily o"idi$ed to carbo"ylic acids but ketones are not readily o"idi$ed. This is used as the basis for two important distinguishing tests between aldehydes and ketones. Ammoniacal silver nitrate& 1Ag'5H.*22/& is known as Tollen#s rea$ent. t is a mild o"idising agent: 1Ag'5H.*22/'a0* / e Ag's* / 25H.'a0* t can be reduced by aldehydes& o"idising them to carbo"ylic acids: 3!CHO / H2O 3COOH / 2H/'a0* / 2e The overall e0uation for the reaction is: R%&HO ' 2(A$)NH*)2+' ' H2O R&OOH ' 2A$ ' ,NH* ' 2H' Thus aldehydes give a grey precipitate or 6silver mirror6 if boiled with ammoniacal silver nitrate. This is a standard test for an aldehyde& since ketones cannot be o"idised in this way. -e lin$.s solution is an alkaline solution containing Cu2/ ions. t is a mild o"idi$ing agent: 2Cu2/ / 2e / 2OH! Cu2O / H2O t is also reduced by aldehydes& and the overall e0uation for the reaction is: R%&HO ' ,OH% ' 2&u2' R%&OOH ' &u2O ' 2H2O The blue Cu2/ is reduced to the brick!red precipitate Cu2O on gentle warming. This is another standard test for an aldehyde.

/)

reduction reactions

Aldehydes and ketones can be reduced to primary and secondary alcohols respectively using the reducing agent sodium tetrahydroborate ' *& 5a7H+. #implified e0uations for these reduction reactions can be written using the symbol 1H2 as the reductant: Aldehyde primary alcohol 3!CHO / 21H2 3!CH2OH (etone #econdary alcohol 34!CO!32 / 21H2 34!CH'OH*!32 Carbo"ylic acids cannot be reduced using 5a7H+ but can be reduced to primary alcohols using the stronger reducing agent 8iAlH+. *. Nucleo0 ilic addition

Carbonyls are unsaturated and can thus undergo addition reactions. The C9O bond is polar so the carbon is a positive centre. Thus carbonyls can react with nucleophiles:
O + C

Nu: Carbonyls therefore tend to undergo nucleophilic addition.

1ec anis2 o3 nucleo0 ilic addition4 Exa20le 14 addition o3 H&N to 2a"e !drox!nitriles N5 H&N is a 6er! 0oisonous $as. It is not sa3e to carr! out t is reaction in t e la/orator!. H&N is not stored7 /ut 2ade in situ /! 2ixin$ K&N and H&l. K&N is also 6er! 0oisonous /ut it is sa3er to store as it is a solid.

Hydrogen cyanide& HC5& is a nucleophile. t reacts with carbonyls as follows: 34!CO!32 / HC5 34!C'C5*'OH*!32
OH

R!

+ R

HCN

R!

C
CN

HC5 is a very to"ic gas& so is generated in situ: (C5's* / HCl'a0* HC5'g* / (Cl'a0* The mechanism consists of three steps: #tep 4: the HC5 is a weak acid and dissociates: HC5 H/ / C5! The C5! behaves as a nucleophile. #tep 2: The nucleophile attacks the carbonyl:
O +

R!
:CN-

#tep .: The O atom picks up the H/ ion:

H

OR
C CN

""

R!

:g propanal / HC5 2!hydo"ybutanenitrile

+
H

CN

CH3CH

+
C

""O
CH3CH
C H CN

H+
CH3CH

OH
C H CN

:CN-

Exa20le 24 reduction /! Na5H, to 2a"e alco ols The reduction of aldehydes and ketones as described above is another e"ample of a nucleophilic addition reaction. 34!CO!32 / 21H2 34!CH'OH*!32
O

OH

R!

+ R

[H]

R!

5a7H+ contains hydrogen in a negative o"idation state& which can therefore behave as a nucleophile. #tep 4: the H! ion attacks the ;/ carbon atom:

+ O

OC

R! H:

R!

#tep 2: the O! pulls a H atom off a water molecule

H
OH

OR
C

""

H
H

O R

OH

R!

R!

eg propanone / 21H2 propan!2!ol

CH3 CH3

O +
CH3

OC
CH3

""

O
CH3

OH
C

OH

H:

CH3

,.

Su22ar! o3 reactions o3 alde !des and "etones 1ec anis2 n>a

T!0e o3 reaction 4. oxidation 'aldehydes only*: aldehyde carbo"ylic acid reagents: potassium dichromate '(2Cr2O)* in sulphuric acid 'H2#O+* conditions: warm under reflu" e0uation: 3!CHO / 1O2 3!COOH observation: orange to green to distinguish between aldehydes and ketones: either: add <ehling=s solution and heat observation: blue solution to brick red precipitate e0uation: 3!CHO / +OH! / 2Cu2/ 3!COOH / Cu2O / 2H2O or: add Tollen=s reagent and heat observation: colourless solution to silver mirror e0uation: 3!CHO / 21Ag'5H.*22/ / H2O 3COOH / 2Ag / +5H. / 2H/ 2. reduction: carbonyl alcohol reagents: 5a7H+'a0* conditions: room temperature e0uation: 34!CO!32 / 21H2 34!CH'OH*!32 .. addition o3 H&N: carbonyl hydro"ynitrile reagents: (C5 and HCl'a0* conditions: room temperature e0uation: 34!CO!32 / HC5 34!C'C5*'OH*!32

5ucleophilic addition 're0uired*

5ucleophilic addition 're0uired*

&AR5O8YLI& A&IDS AND &AR5O8YLATE SALTS Carbo"ylic acids have the general formula C2H2nO2 and contain the following functional group:
O C

OH :g methanoic acid
O H C
H C H C OH
H H H

ethanoic acid
H O
H H C

butanoic acid
H C H C C OH O

OH

They can form hydrogen bonds with water& so most carbo"ylic acids with relatively short chains are highly soluble in water. They are often less soluble in non!polar solvents. a) Reactions o3 car/ox!lic acids 9it /ases

Carbo"ylic acids are weak acids? they dissociate partially in water to form carbo"ylate 'or alkanoate* salts. 3!COOH'a0* / H2O'l* 99 3COO!'a0* / H.O/'a0* The ability of carbo"ylic acids to behave as acids is due to the relatively high stability of the 3!COO! anion. These anions are known as carbo"ylate or alkanoate ions and have the following structure:
O

The ion has a delocalised system which accounts for its relatively high stability. Ne6ert eless t ese acids are 9ea" acids and 9ill onl! dissociate 0artiall! in 9ater.

n the presence of stronger bases such as carbonate ions or hydro"ide ions& the acid will dissociate completely: i* 9it sodiu2 !droxide

&ar/ox!lic acids react 9it sodiu2 !droxide to 0roduce t e sodiu2 salt and 9ater: 3!COOH'a0* / 5aOH'a0* 3!COO!5a/'a0* / H2O'l* :g ethanoic acid / sodium hydro"ide sodium ethanoate / water
H H C H C OH O
H

O C

+ +####Na###OH

C H

+######H O
-#####+ O##Na

ii)

9it sodiu2 car/onate

&ar/ox!lic acids react 9it sodiu2 car/onate to 0roduce t e sodiu2 salt7 car/on dioxide and 9ater: 23!COOH'a0* / 5a2CO.'a0* 23!COO!5a/'a0* / CO2'g* / H2O'l* eg 2C2H@COOH'a0* / 5a2CO.'a0* 2 C2H@COO!5a/'a0* / CO2'g* / H2O'l* Thus when carbo"ylic acids are treated with sodium carbonate& a colourless gas is evolved which turns limewater milky. This is the standard test for a carbo"ylic acid. /) Reaction o3 car/ox!late salts 9it acids

#ince these salts are the salts of weak acids& they have basic properties. Aost have a pH of between B and C: 3!COO!'a0* / H2O'l* 99 3!COOH'a0* / OH!'a0* They react completely with strong acids to form the original carbo"ylic acid: 3!COO!'a0* / H/'a0* 3!COOH'a0* :g CH.COO!5a/'a0* / HCl'a0* CH.COOH'a0* / 5aCl'l* sodium ethanoate ethanoic acid

&ar/ox!late salts can readil! /e con6erted into car/ox!lic acids /! addition o3 a stron$ acid suc as !droc loric acid.

c)

Reaction o3 car/ox!lic acids 9it alco ols

f a carbo"ylic acid and an alcohol are heated under reflu" with concentrated H2#O+& a condensation reaction takes place and an ester is formed: Carbo"ylic acid / alcohol 99 ester / H2O 34!COOH / 32OH 99 34!COO32 / H2O This reaction is known as esteri3ication. :sterifcation is an e"ample of condensation? a reaction in which two or more organic molecules Doin together to form a single large molecule& and in so doing give off a small molecule such as HCl or H2O. :g ethanoic#acid#+#ethanol
H H C H C OH O

ethyl#ethanoate#+#$ater
O

CH3

CH

OH

CH3

C O

+#########H O
CH CH3

methanoic#acid#+#propan- -ol##################methylethyl#methanoate#+#$ater
OH
O H C OH H
O

CH3

CH3

C O CH

CH3

+#########H O

CH3

propanoic#acid#+#methanol##################methyl#propanoate#+#$ater
H H C H H C H C OH
H

C H

OH

CH3

CH

C O

+###H O
CH3

The H2#O+ acts as a catalyst. The alcohol behaves as a nucleophile& and the lone pair on the O attacks the positive centre on the carbo"ylic acid:
O

R!

C OH

O H

This reaction is reversible and reaches an e0uilibrium. The e0uilibrium constant for the reaction has a value of appro"imately +& indicating that about )EF of the reactants are converted into products at e0uilibrium. d) Su22ar! o3 reactions o3 car/ox!lic acids and t eir salts 1ec anis2 n>a

T!0e o3 reaction 4. acid%/ase a* car/ox!lic acids 9it sodiu2 !droxide reagent: 5aOH conditions: room temperature e0uation: 3!COOH'a0* / 5aOH'a0* 3!COO!5a/'a0* / H2O'l* b* car/ox!lic acids 9it sodiu2 car/onate reagent: 5a2CO. conditions: room temperature e0uation: 23!COOH'a0* / 5a2CO.'a0* 23!COO!5a/'a0* / CO2'g* / H2O'l* observations: colourless gas evolved which turns limewater milky c* car/ox!late salts 9it acids reagent: HCl'a0* conditions: room temperature e0uation: 3!COO!'a0* / H/'a0* 3!COOH'a0* 2. esteri3ication reagents: any alcohol& concentrated sulphuric acid catalyst conditions: heat and reflu" e0uation: 34!COOH / 32OH 99 34!COO32 / H2O

5ucleophilic addition> :limination 'not re0uired*

ESTERS :sters are made when carbo"ylic acids and alcohols are heated together under reflu" in the presence of a strong acid catalyst as described above. They have the same general formula 'CHO* as carbo"ylic acids and contain the following functional group:
O C O

R
O

:g
O H C O H C H H
O

C O CH

CH3

CH

C O

CH3

CH

CH3

CH3

methyl methanoate a)

ethyl propanoate

methylethyl methanoate

:ro0erties and uses o3 esters

:sters have pleasant& often sweet smells. They are widely used as 3ood 3la6ourin$s for this reason 'eg ethyl methanoate gives raspberry flavour and ethyl butanoate gives pear flavour*. This sweet smell can also be used to test for the presence of carbo"ylic acids and alcohols? a carbo"ylic acid will give a sweet smell if heated with ethanol and a strong acid& and an alcohol will give a sweet smell if heated with ethanoic acid and a strong acid. :sters are also used as 0lastici;ers. They can be added to polymers to make them less rigid and more fle"ible. %lasticiser molecules weaken the intermolecular forces between the polymer chains. :sters are also used as sol6ents for organic compounds such as nail varnish. The ester evaporates easily& leaving the solute behind.

/)

H!drol!sis o3 esters

i* acid !drol!sis #ince the esterification reaction is reversible& it follows that if an ester is heated under reflu" with concentrated H2#O+& a carbo"ylic acid and an alcohol will be formed in a reversible reaction: 34!COO32 / H2O 99 34!COOH / 32OH :g ethyl ethanoate / H2O 99 ethanoic acid / ethanol
H
O

O C OH

CH3

C O

+#####H O
CH CH3

C H

CH3

CH

OH

:g methyl propanoate / H2O 99 propanoic acid / methanol

O

CH3

CH

C O

+#####H O
CH3

CH3

CH

C OH

CH3

OH

:g propyl methanoate / H2O 99 methanoic acid / propan!4!ol

O

C O

CH

CH

CH3

+#####H O

C O

+
H

CH3

CH

CH

OH

This reaction is known as ester hydrolysis. t does not go to completion but reaches e0uilibrium with only appro"imately .EF of the ester hydrolysed. t does not therefore give a very good yield of the carbo"ylic acid or the alcohol.

ii* al"aline !drol!sis )sa0oni3ication) f an ester is heated under reflu" with a strong alkali such as 5aOH& a carbo"ylate salt and an alcohol are formed: 34!COO32 / 5aOH 99 34!COO!5a/ / 32OH :g ethyl ethanoate / 5aOH'a0* sodium ethanoate / ethanol
H
O

O C
O Na

CH3

C O

+#####NaOH
CH CH3

C H

- +

CH3

CH

OH

:g methyl propanoate / 5aOH'a0* sodium propanoate / methanol

O

CH3

CH

C O

+#####NaOH
CH3

CH3

CH

+ O- Na

CH3

OH

:g propyl methanoate / 5aOH'a0* sodium methanoate / propan!4!ol

O

C O

CH

CH

CH3

+#####NaOH

O Na

- +

CH3

CH

CH

OH

This reaction is known as alkaline hydrolysis. t is also known as sa0oni3ication. t is not readily reversible& so results in a better yield of the alcohol and carbo"ylate than the acid hydrolysis of the same ester. The 5aOH in this reaction is not a catalyst? it is a reactant. The e0uilibrium can thus be moved further to the right by using the 5aOH in e"cess. #aponification is thus a more efficient way of hydrolysing an ester than acid hydrolysis& since it results in a much better yield. After the mi"ture is cooled& the carbo"ylate salt can be readily converted to the carbo"ylic acid by acidifying the mi"ture. 3!COO!'a0* / H/'a0* 3!COOH'a0* This means that even if you want a carbo"ylic acid as your final product& it is better to hydrolyse the ester in alkaline conditions first and then acidify the mi"ture afterwards.

c)

naturall! occurrin$ 3ats and oils

5aturally occurring fats and oils are in fact esters. They have the general formula: H
O

H H H

C C C H

C O

R!

C O

R3

3 9 C4.H2)& C4@H.4& C4)H.@ & or C4CH.C

They contain three ester groups. These esters are hydrolysed in the acidic conditions of the stomach and can be broken down into the constituent acid and alcohol. They can also be hydrolysed artificially in alkaline conditions. i) acid !drol!sis o3 3ats Guring digestion& some fats are broken down into the constituent parts. The reaction is catalysed by an en$yme called lipase and the acidic conditions of the stomach:
H
O O

H
R!

H H H

C C C H

C O

HO OH OH OH

R!

C C C H

+
O

C O

3H O

H H

HO

+
O

R3

HO

R3

The products of this hydrolysis are propan!4&2&.Htri!ol 'more commonly known as $l!cerol* and three long!chain carbo"ylic acids 'generally known as 3att! acids*. #o the hydrolysis of a fat or oil molecule in the stomach produces glycerol and three fatty acid molecules. The formula for a typical fatty acid molecule would be C4)H.@COOH. <l!cerol is used /! t e /od! to 2a"e $lucose 3or res0iration 'which is why fats are good energy sources* and 3att! acids are used to 2a"e cell 2e2/ranes 'which is why fats are essential for healthy tissue growth*.

ii) al"aline !drol!sis o3 3ats )sa0oni3ication) <ats and oils are hydrolysed commercially in alkaline conditions. The products are glycerol and the salts of the fatty acids:
H
O O

H
R!

H H H

C C C H

C O

+ Na###O
OH OH OH

C C C H

+
O

R!

C O

+ 3NaOH

H H

+ Na###O

+
+ Na###O -

R3

O C

R3

The salts of the long!chain fatty acids are known as soa0s. T e! are extre2el! use3ul as t e! el0 oil and 9ater 2ix to$et er. <l!cerol is a useful by!product of this reaction as it can be used to make 0 ar2aceuticals and cos2etics. #o the alkaline hydrolysis of fats and oils produces soap& which usually has the formula C4)H.@COO!5a/. ,lycerol is also formed as a useful by!product. #oap molecules have a polar end& which is the carbo"ylate end& which attracts water and other hydrophilic groups. They also have a non!polar end& which is the long!chain hydrocarbon end& which attracts oils and other hydrophobic groups. The same molecule is thus attracted to a0ueous species and oily species& thus enabling them to mi". This means that oil will come off skin 'or cooking utensils* into water which contains soap.
hydrophobic#end#%attracts#&ats#and#oils' O C ONa+

hydrophilic#end#%attracts#$ater( #ionic#and#polar#)roups'

iii) 2a"in$ /iodiesel 7iodiesel is a mi"ture of methyl esters of long chain fatty acids. t is made by hydrolysing naturally occurring fats or oils 'as described above* to make fatty acids. The fatty acids can then be mi"ed with methanol in the presence of a suitable catalyst to make a methyl ester. This is an esterification reaction. :g C4)H.@COOH / CH.OH 99 C4)H.@COOCH. / H2O 7iodiesel is a renewable fuel because it is made from vegetable oil& which can be produced 0uickly by growing crops such as rape. d) su22ar! o3 reactions o3 esters 1ec anis2 n>a

T!0e o3 reaction !drol!sis a* acid !drol!sis reagent: concentrated H2#O+ conditions: heat under reflu" e0uation: 34!COO32 / H2O 99 34!COOH / 32OH b* al"aline !drol!sis )sa0oni3ication) reagent: 5aOH'a0* conditions: heat under reflu" e0uation: 34!COO32 / 5aOH 99 34!COO!5a/ / 32OH

A&YL &HLORIDES AND A&ID ANHYDRIDES Carbo"lyic acids will react with bases and with alcohols& but are generally unreactive otherwise. Although the ;/ve C atom can attract nucleophiles& the stability of the HCOOH group means that these reactions do not take place readily. 5ucleophilic attack at the C atom will take place if the carbo"ylic acid is first converted into a more reactive derivative. Two such derivatives are ac!l c lorides and acid an !drides. a) structure o3 ac!l c lorides and acid an !drides
O C Cl

Acyl chlorides contain the following functional group:

:g
H
H

O
H C H

O
H C H

C Cl

C
H

C Cl

ethanoyl chloride

propanoyl chloride

The carbon atom is attached to two electronegative atoms and so is very ;/ve. t attracts nucleophiles readily:
-

+
C

O Cl

Nu :

Acid anhydrides contain the following functional group:

O C O C O

:g
O
CH3 CH3

O
H

C O C O

C O C O

CH3
CH3

CH CH

C O C O

CH3

ethanoic anhydride

methanoic ethanoic anhydride

propanoic anhydride

Again& the carbon atom is attached to two electronegative atoms& is very ;/ve and attracts nucleophiles readily: -

+ C Nu:
C

O
O O

Acyl chlorides and acid anhydrides both react readily with nucleophiles.

/)

2ec anis24 nucleo0 ilic addition%eli2ination

Acyl chlorides react by a mechanism called nucleophilic addition!elimination. -hen an acyl chloride is attacked by a nucleophile& addition occurs and the IHbond is broken: R
Cl

OC Nu+ Cl

R "" Nu

+
C

However& the C!Cl bond then breaks and the IHbond is reformed. The e"tra H on the nucleophile is also lost: O O: R C Nu+ H The chloride ion& or another nucleophile may combine with the free proton. Acyl chlorides and acid anhydrides react with water& ammonia& alcohols and primary amines by this mechanism. This reaction is also known as ac!lation. Cl R C Nu + Cl + + H

c)

ac!lation reactions o3 ac!l c lorides

i* 9it 9ater Acyl chlorides react with water violently. -hite fumes of HCl can be clearly seen: 3!COCl / H2O 3!COOH / HCl The organic product is a carbo"ylic acid. The mechanism is nucleophilic addition!elimination: O: + O Cl R C R C R Cl + O "" O H H H H

O C O + H HCl

e"ample:
H

O
H C H

O C OH

C Cl

HO

C H

HCl

ii* 9it a22onia Acyl chlorides also react with ammonia violently. -hite fumes of HCl can be clearly seen: 3!COCl / 5H. 3!CO5H2 / HCl n e"cess ammonia& the left!over 5H. and the HCl may react: 3!COCl / 25H. 3!CO5H2 / 5H+Cl The organic product is an amide. The mechanism is nucleophilic addition!elimination: R O: C N H + H H Cl R C N

R "" N H

O Cl

O + HCl H

H H

e"ample:
H H C H

O
C
H

C Cl

NH3

C H

C H

NH

HCl

or in e"cess ammonia:
H H C H

O
C
H

C Cl

NH3

C H

C H

NH

NH*Cl

iii* 9it alco ols Acyl chlorides react violently with alcohols. -hite fumes of HCl can be seen: 34!COCl / 32!OH 34!COO32 / HCl The organic product is an ester. The mechanism is nucleophilic addition!elimination: O : O + R! C Cl R C
Cl
!

O R! C O + HCl R

"" O R

+ O H

e"ample:
H H C H C O
O

+
Cl

CH3

CH

OH

CH3

C O

+
CH CH3

HCl

iv* 9it 0ri2ar! a2ines Acyl chlorides react vigorously with primary amines. -hite fumes of HCl can be seen: 34!COCl / 32!5H2 34!CO5H32 / HCl n e"cess amine& the left!over amine can react with the HCl: 34!COCl / 232!5H2 34!CO5H32 / 32!5H.Cl The organic product is an 5!substituted amide. The mechanism is nucleophilic addition!elimination:

R! R H

+
C

O Cl

O: O C + N H H Cl R! C N + HCl R

"" N R H

e"ample:
H

O
H C H

C Cl

O
CH3 CH NH CH3

C
N
H

H C H

H C H H

HCl

or& in e"cess amine:

H

O
H C H

C Cl

CH3

CH

NH

CH3

C
N
H

H C H

H C H H

+ CH

CH

NH3Cl

d)

ac!lation reactions o3 acid an !drides

Acid anhydrides react in the same way as acyl chlorides. They react with water& ammonia& alcohols and primary amines. The mechanism is also nucleophilic addition! elimination. The reactions are much slower than the acyl chloride reactions& and do not produce the to"ic gas HCl but produce a carbo"ylic acid instead. Commercially& acid anhydrides are therefore used preferentially to acyl chlorides in acylation reactions? t e reactions are easier to control and t e! do not 0roduce a toxic $as. i* 9it 9ater Acid anhydrides react with water slowly when the mi"ture is warmed. Two carbo"ylic molecules are produced. 34!COOCO!32 / H2O 34!COOH / 32!COOH :"ample:
O
H

O C OH

C O C O

CH3

HO

C H

OH

ii* 9it a22onia Acid anhydrides react with ammonia slowly when the mi"ture is warmed. An amide and a carbo"ylic acid are produced. 34!COOCO!32 / 5H. 34!CO5H2 / 32!COOH :"ample:
O
CH3 CH3

H O C

C O C O

O C OH

NH3

C H

NH

C H

iii* 9it alco ols Acid anhydrides react with alcohols on gentle heating to produce esters. A carbo"ylic acid is also produced. 34!COOCO!32 / 3.!OH 34!COO!3. / 32!COOH :"ample:
O
CH3 CH3

H H C H C

O H O C H H

O C OH

C O C O

C H

OH

C H

iv* 9it 0ri2ar! a2ines Acid anhydrides react with primary amines on gentle heating to produce 5!substituted amides. A carbo"ylic acid is also produced. 34!COOCO!32 / 3.!5H2 34!CO5H!3. / 32!COOH :"ample:
O
CH3 CH3

H
O
CH3

O C OH

C O C O

CH3

CH

N H

C
N
H

H C H

H C H H

C H

e)

0re0aration o3 as0irin

Aspirin is an ester with the following formula: O C O OH O C H C H t is made be reacting the !OH group on 2!hydro"yben$oic acid with either ethanoic acid& ethanoyl chloride or ethanoic anhydride. The reaction with ethanoic acid needs strongly acidic conditions& heat and reflu" and only goes to e0uilibrium. The reaction with ethanoyl chloride is violent& difficult to control and produces the to"ic gas hydrogen chloride. The reaction with ethanoic anhydride is reasonably fast when heated gently and does not produce to"ic by!products. t is therefore the chosen method for the preparation of aspirin.
O C O H OH
O

OH C O

O C

H C H H

CH3 CH3

C O C O

O C OH

C H

3)

su22ar! o3 reactions o3 ac!l c lorides and acid an !drides

1ec anis2 5ucleophilic addition! elimination 're0uired*

T!0e o3 reaction 1. ac!lation usin$ ac!l c lorides a* 9it 9ater 'to make carbo"ylic acids* conditions: room temperature e0uation: 3!COCl / H2O 3!COOH / HCl observation: white misty fumes b* 9it a22onia 'to make amides* conditions: room temperature e0uation: 3!COCl / 25H. 3!CO5H2 / 5H+Cl observation: white misty fumes c* 9it alco ols 'to make esters* conditions: room temperature e0uation: 34!COCl / 32!OH 34!COO32 / HCl observation: white misty fumes d* 9it 0ri2ar! a2ines 'to make 5!substituted amides* conditions: room temperature e0uation: 34!COCl / 232!5H2 34!CO5H32 / 32!5H.Cl observation: white misty fumes 2. ac!lation usin$ acid an !drides a* 9it 9ater 'to make carbo"ylic acids* conditions: room temperature e0uation: 34!COOCO!32 / H2O 34!COOH / 32!COOH observation: no visible change b* 9it a22onia 'to make amides* conditions: room temperature e0uation: 34!COOCO!32 / 5H. 34!CO5H2 / 32!COOH observation: no visible change c* 9it alco ols 'to make esters* conditions: room temperature e0uation: 34!COOCO!32 / 3.!OH 34!COO!3. / 32!COOH observation: no visible change d* 9it 0ri2ar! a2ines 'to make 5!substituted amides* conditions: room temperature e0uation: 34!COOCO!32 / 3.!5H2 34!CO5H!3. / 32!COOH observation: no visible change

5ucleophilic addition! elimination 'not re0uired*