Aldehydes, Ketones and

Carboxylic Acids
ALDEHYDES AND KETONES Preparation of Aldehydes and Ketones
1.
Compounds containing formy!cgroup are called 1. From alcohols (By oxidation)
aldehydes. H (a) Primary alcohols on oxidation with CrO3 in anhydrous
HCHO CHO medium give aldehydes.
e.g. CH-CHO
Methanal Ethanal
R-CHOH CHCrO3
COOHR-CHO
(Formaldehyde) (Acetaldehyde) Benzenecarbaldehyde Primary alcohol Aldehyde
(Benzaldehyde) e.g. CrO CHsuio
2. Compounds containing oxo C=0group are called CH CH,OH .coO
Ethanol Ethanal
ketones (b) Primary alcohols on oxidation with pyridinium
chlorochromate (PCC) give aldehydes in good yield. In this
e.g. CH-C-CH CH-C-CH,CH3 reaction C=C bond remains intact.
Propanone Butan-2-one PCC
e.g. CH,CH,OH
(Acetone) CH,COOH CH-CHO
Ethanol (primary alcohol) Ethanal (aldehyde)

PCCis acomplex of chromium trioxide (CrO3), with pyridine

and HCl. It is a better reagent for oxidation of primary
CH3 alcohol to aldehyde.

Phenylethanone Diphenylmethanone (c) Secondary alcohols on oxidation with chromic anhydride

(Acetophenone) (Benzophenone) give ketones.
Ketones are of Two Types OH
(i) Simple ketones : Ketones in which both the alkyl groups R-CH-R
sec. alcohol
R-c-R
are similar.

e.g. CH-CH-CH CrO CH-C-CH,

e.g. CH-C-CH, OH Propanone
Propan-2-ol (Acetone)
Propanone Diphenylmethanone
(Acetone) (Benzophenone) (lsopropyl alcohol)
(ii) Mixed ketones : Ketones in which two alkyl groups are 2. From alcohols (By dehydrogenation)
different are called mixed ketones. (a) Vapours of primary alcohols when passed through heated
Cu tube at 573 K give aldehydes.
R-CH,OH
prim. alcohol K
RCHO
CH3 aldehyde
CH-C-CH,CH, e.g. CH,CH,OH CH-CHO
Butan-2-one Phenylethanone 573K
(Acetophenone) Ethanol Ethanal
) Secondary alcohols when passed through heated Cu tube
at 573 Kgive ketones. (ii) Propyne hydration gives propanone.
on

R-CHR Cutube
573 K R-C RR CH-CEC-H +H,0 4

OH O OH
sec. alcohol
OH
Ketone
CH -H-CH H
Cu tube H
e.g. CH-CH-CH,CH, 573 KCH-C-CHCH, Propanone
(Acetone)
Butan-2-o Butan-2-one Preparation of Aldehydes
Tertiary alcohols when passed through red hot Cu tube 1. From aromatic hydrocarbons (By oxidation)
undergo dehydration to give alkenes. () Toluene and its derivatives on oxidation with chromyl
3. From hydrocarbons chloride give a complex which on hydrolysis gives benzaldehyde.
(a) From alkenes (By ozonolysis): Alkenes when treated with CH3 CH(OCrOHCL,) CHO
ozone give alkene ozonide which on reduction with zinc dust
HO
and water gives aldehydes and ketones or both. +Cro,Cl, O
0-0 Toluene Chromium complex Benzaldehyde
R R3 (Brown)
c=c+
R Ra 0 R SR.R
(i) Toluene and its derivatives when oxidised by chromic oxide
in acetic anhydride give benzylidene diacetate which on
Zn+H,O C=0+O=c/As| hydrolysis with aqueous acid gives benzaldehyde.

Rnc=0+O=CR. CH CH(OCOCH,), CHO

This reaction is called ozonolysis. c o+Cro,CHCO)o
+ CrOs273-283 K H +2CH,cOOH
In this reaction C=C bond is converted to two >C=0.
Benzylidene Benzaldehyde
Examples diacetate
Ethene on ozonolysis gives formaldehyde. (ii) By side chain chlorination followed by hydrolysis : Toluene
HC=cH0 0 C=0 when treated with chlorine in presence of diffused sunlight
H (i) Zn +H,O gives benzal chloride which on hydrolysis gives benzaldehyde.
Methanal
But-2-ene on ozonolysis gives acetalalehyde. CH, Cyh CHC MO>1 373 H
CHO

CHaCCH CH, (i)0,

(i) Zn + H,0 CHc=0
H
Toluene Benzal chloride Benzaldehyde
H Ethanal (iv) Gattermann-Koch reaction: Benzene or its derivativewhen
2 , 3-Dimethylbut-2-ene on ozonolysis gives acetone. treated with carbon monoxide and hydrogen chloride in the
presence of anhydrous aluminium chloride gives benzaldehyde.
CH3 ()O CHc=O
uC=o
+CO+ HCI Anhyd. AlIC CHO
CH CH, (i) Zn+H,0
Propanone
Benzene Benzaldehyde
(b) From alkynes (By hydration) 2. From acid chloride (Rosenmund reduction)
Ethyne hydration with water
on
in the presence of HaSO4 Acid chloride on reduction with hydrogen
in presence of
and HgSO4 gives acetaldehyde. Lindlar's catalyst (Pd BaSO4 poisoned
+ with sulphur or

H quinoline) gives benzaldehyde.

T H-¢--H CHO
Cc-H H

Pd+ BaSO0.
Ethyne (Acetaldehyde or Ethanal)
CI+H2s or quinoliné
(Acetylene) Benzaldehyde
in the presence
ethyne on hydration
Benzoyl chloride
All the alkynes except
of HaSO4 and HgSO4 gives ketone. 3. From nitriles (Stephen's reaction)
stannous chloride in the presence
butan-2-one.
(i) Nitriles on reduction with
8 But-2-yne on hydration gives imine which on hydrolysis gives
of hydrochloric acid gives
,SO,.
CH-CC-CH,+ H,0 Hgso aldehyde. + HC1 R-CH=NH
But-2-yne H R-CEN+SnCl,
Alkane nitrile
Imine
-OH
C H - C c - C H C H - c - - C H ,
H,OR-CHO +NH
Aldehyde
H
H Butan-2-one
This reaction is called Stephen's reaction. molecular masses.
(ii) Nitriles are selectively reduced by di-isobutylaluminium
e.g. Propanal Mol. mass 58 u b.pt. 322K
hydride (DIBAL-H) to imines followed by hydrolysis to give n-Butane Mol. mass 58 u b.pt. 273 K
aldehyde. Methoxyethane Mol. mass 60 u b.pt. 281 K
CH-CH=CH-CH,CNAIHG-Bu) However, boiling points of aldehydes and ketones are lower
(ii) H,0 than those of alcohols of similar molecular masses due to
Pent-3-enenitrile Pent-3-enal
4. From Esters (By reduction) the absence of
intermolecular hydrogen bonding.
Esters on
reduction with
O
DIBAL-H gives aldehyde. e.g. Propanal Mol. mass 58 u b.pt. = 322K

Propanone Mol. mass 58 u b.pt. 329 K

CH--oc,H.DAL= CH-C-H Propan-1-ol Mol. mass 60 u b.pt. = 370 K

Ethyl acetate Ethanal Solubility of aldehydes and ketones in water

12.1.4 Preparation of Ketones The lower members of aldehydes and ketones such as
methanal (HCHO), ethanal (CH,CHO) and propanone
1. From acid chloride
(CH,COCH,) are miscible with water in all proportions
Acid chloride when reduced by dialkyl cadmium gives ketone.
because they form hydrogen bonds with water.

R-C-Cl +R^Cd>R--R+CdCl, R =-HH-0=CK

Acid chloride Ketone R
2. From nitriles (By Grignard's reagent) The solubility of aldehydes and ketones decreases rapidly
Alkyl magnesium halide adds on nitriles to give a compound on increasing the size of hydrophobic alkyl group.
which on hydrolysis gives ketone. Solubility of aldehydes and ketones in organic solvents:
Hydrolysis All aldehydes and ketones are fairly soluble in organic
CH-CN +CHMgBr>CH-C=NMgBr
solvents like benzene, ether, methanol chloroform etc.
CHs Odour: The lower aldehydes have sharp pungent odours
whereas higher aldehydes have fragrance. This is why many
CH-C-CH, naturally occurring aldehydes and ketones are used in the
Butan-2-one
perfumes and flavouring agents.
3. From benzene (By Friedel-Craft's reaction)
Benzene or its derivatives when treated with acid ch loride in Structure of the Carbonyl Group
The carbon atom of the carbonyl group is sp2
the presence of anhydrous aluminium chloride gives ketone. hybridised.
the three atoms attached to carbonyl carbon lie in the same
Al
plane. The carbon is bonded with oxygen by double bond
C-R
+R--CI Anhyd.AIC formed by p r - p r overlap. The t bond lies above and below

Ketone
the plane of molecule. Oxygen atom has two non-bonded pair
Benzene of electrons (lone pairs).
R may be alkyl or aryl.
This reaction is called Friedel-Crafts acylation reaction. e.g. bond
COCH
() +CH,cOCIAnhyd.AICl
Acetyl chloride
Benzene Acetophenone
bond

Tt bond
(ii)
Benzene Benzoyl chloride Oxygen atom is electronegative than carbon atom.
more
Benzophenone Therefore the carbon-oxygen double bond is polarised ie.
Properties of Aldehydes and Ketones electron cloud is shifted more towards oxygen atom. These
Methanal is a gas at room temperature. compounds have dipole moments, carbonyl compounds
are

Ethanal is a volatile liquid. more polar than ethers.

Other aldehydes are liquids and solids at room temperature.
Boiling points : Aldehydes and ketones are polar molecules.
There is weak molecular association in aldehydes and
ketones due to dipole-dipole interaction. This is why the |Carbonyl
compounds may be regarded as resonance hybrid o
the two given structure.
boiling points of aldehydes and ketones are higher than
correspon ding hydrocarbons and ethers of comparable -0) =)C-0o
 onolarity of carbon-oxygen bonds the carbon
mes electron deficient. It acts as an atome.g.
whereas carbonyl oxygen becomes electrophile (Lewis
acid) CN
as a nucleophile (Lewis base).
electron rich. It acts H
(i)
C-0+HCN H-C-OH
Reactivity of Carbonyl
Group Methanal H
Aldehvdes and ketones undergo
nucleophilic addition reaction. Methanal cyanohydrin
Nu (Ethane nitrile-2-ol)
Nu
R
Kin_Nu E
R,
Mechanism of nucleophilic addition reaction
R, O X, R, OE (i) CHc0
CHc=o+HCN OHsct
CH cCN
OH

Acetone Acetone cyanohydrin

carbon is electron deficient hence Carbonyl
acts as
electrophile.
Nucleophile attacks on the electrophilic carbon atom of
carbonyl group from a direction perpendicular to the the
plane of
(1) cC=0+HCN
0 +HCN OH
OH OH
the molecule. CN
Nu Benzaldehyde Benzaldehyde
Nu Nu cyanohydrin
-Slow Fast Addition of sodium hydrogensulphite (NaHSO3)
R,oH R R,I OH Sodium hydrogensulphite (NaHSO3) adds on aldehydes and
In this process ketones
hybridisation of carbon atom changes from sp? to give addition products.
to sp
and a tetrahedral alkoxide ion is
formed as intermediate. NaHSO Na +HSO
This intermediate
captures proton from the reaction medium to
give the neutral product. ONa* OH
HSO
Reactivity of Aldehydes and Ketones
Aldehydes are generally more reactive than ketones e.g. sO,H so,Nat
in
nucleophilic addition reactions. OH
Reason: There are two reasons for
Hnc-O+NaHSO H-Ç-SO,Na
higher reactivity of aldehydes
than ketones.
) Electronic factor: Reactivity of carbonyl group is due Methanal
to Methanal sodium bisulphite
clectrophilic nature of carbonyl carbon. +/ effect of two alkyl
groups in ketones reduces electrophilicity of the carbonyl carbon
nore effectively than the only one alkyl group present in QH
aldehydes. (ii) CHc=o +NaHSO
CH
CHC-SO,Na
R,
C=0 RC=0
Acetone CH
Acetone sodiumbisulphite
H Aldehyde
Ketone
Seric factor : Two alkyl substituents in ketones hinder OH
approach of nucleophile to carbonyl carbon more than the
Uny one
substituent present in aldehydes. (iii) C=0+NaHSO C H
SO,Na

1 Examples Nucleophilic Addition Reactions

of Benzaldehyde Benzaldehyde
sodiumbisulphite
ddition of hydrogen cyanide (HCN): Hydrogen
cyanide adds on
This react ldehydes and ketones to give cyanohydrins. Most of the aldehydes give product in good yield.
Occurs very slowly with pure HCN because i t is Most of the ketones give very poor yield due to steric hindrance
feebly ionised. This reaction is catalysed by a base. Base in the cyrstalline solid and highly soluble in water. These
generates cyani
and Tea:yanide ion (CN) which is a stronger nucleophile can be converted back to the original carbonyl compound by
readily adds to carbonyl ompounds. reaction with dilute mineral acids or alkali. Therefore this
Mechanism of reaction: reaction is used for the separation and purification of
OH
+HCN :CN+ H,O aldehydes.
3. Addition of Grignard reagents :Grignard reagent adds on

+CN ) CN
CN
aldehydes and ketones to give an adduct which on hydrolysis
gives alcohol.
Tetrahedral intermediate Cyanohydrin
 Ketones react with ethylene glycol in presence of dry HCl to
H,O give cyclic ketals.
o+ MeX--OMgr Hydrolysis
HO-CH HCl 0-CHH,
adduct
R Rc=0+ HO-CH +H,O
R
-C-OH + Mg(OH)X
Ethylene glycol ketal
(cyclic ketals)
R
alcohol
Role of HCI

e.g. (i) Methanal reacts with RMgX to give primary alcohol. | Dry HCl protonates the oxygen of carbonyl group and increases
H electrophilicity of carbonyl carbon which favours attack of
Hydrolysis nucleophile.
H-C=O+RMgX>R- -OMgX
H
H HOR
R-C-OH +Mg(OH)X c=o- -OH --OH
H
Primary alcohol OR
(i) Aldehydes except methanal react with RMg¥ to give
secondary alcohols. -OH + H
R
Hydrolysis Acetals and ketals on hydrolysis with aqueous mineral acids
R-C=0 +R'MgX>R--OMgX yield corresponding aldehydes and ketones respectively.
H H
R
R--OH Nucleophilic Addition-Elimination Reaction
H 1. Addition of ammonia and its derivatives
Secondary alcohol
Ammonia and its derivatives add to carbonyl group of aldchyde
(iii) Ketones react with RMgX to give tertiary alcohols.
and ketone in presence of acid catalyst followed by dehydration
R give imine derivatives (Schiff's base).
ydrolysis
pC=0+ R'MgX -R-C-OMgr
R' +H,N-Z- OHHyc=N-Z+ H,0
R-C-OH +Mg(OH)DX
R
where
ZR, Ar, OH, NH2, NHCH, NHCONH2
Tertiary alcohol Mechanism of reaction:
4. Addition of alcohols: Aldehydes react with monohydric The addition of ammonia derivatives to aldehydes and ketones
alcohol in presence of dry HCI to give hemiacetals which on is catalysed by acids. H' of acids add to the oxygen atom of
further reaction give acetals. carbonyl group which increases the positive charge on the
OR OR carbonyl carbon. As a result weak nucleophile like ammonia
R-C=O
R'OH
= R'OH- R-C-OR
R-C-OH=dry derivatives readily attack the carboxyl group.
dry HCI HCI
H H
Hemiacetal
H
Acetal
c-o+H =-¢-ÖH= OH
(alkoxy alcohol) (gem-dialkoxy
alcohol)
+

OC,H c-OH+ NH-Z CNH2_

e.g CH-Ç=0+C2H,OH dry CH-C-OH dry OH

H
Ethanol HCI
Ethanal OC Hs NH-Z H.OC=N-z

CH-C-OC,Hs OH
or
H The product formation is favoured due to rapid dehydration
1,1-Diethoxy ethane tetrahedral intermediate in weakly acidic medium.
Control of pH:
reaction occurs at an
optimum pH
value of around 3.5. RHC=0 + H,N-NHCONH,PH=3
In very weakly
acidic medium
rotonation of carbonyl
group
uill not occur. Therefore carbonyl carbon is not sufficiently
olectron deficient and weak nucleophile like ammonia derivative C=N-NHCONH,
H
Aldehyde semicarbazone
ll not be able to attack the carbon atom. Hence
reaction does Remember
not occur.
In semicarbazide the lone pair of nitrogen attached to carbonyl
In strongly acidic medium the ammonia
derivative group is involved in resonance and not available for attack
itself
undergoes protonation to form
ammonium salts. They do not onthe electrophilic centre. Hence 2nd nitrogen attacks on
have lone pair of electrons on the thecarbonyl carbon.
nitrogen atom. They are not
nucleophiles and hence reaction will not take
place. O
Examples:
Reaction with primary amine (R-NH2 or Ar-NH,)
HN-NHc-NH HN-NH=C-NH
Aldehydes or ketones react with aliphatic or aromatic primary
amine to give N-alkyl or aryl imine.
HN-NH-c=NH,
All the products i.e oxime and hydrazones are crystalline
R-C=0+R-NH, pH=3.5
R-C=N-R+H,O solids with sharp melting points. Therefore these reactions
H H are used for identification and
and ketones
characterisation of aldehydes
N-alkyl imine
(Schiff's base)
i) Reaction with
These derivatives can be decomposed by boiling with dilute
hydroxylamine (H2N-OH) : Aldehydes mineral acids to regenerate the original carbonyl compounds.
and ketones condense with
hydroxylamine (H2N-OH) to give Therefore these derivatives are used for the purification and
OXime.
separation of aldehydes and ketones.
R

H
+ H,N-OHPS -N Reduction
H
Oxime
(i) Aldehydes on reduction with hydrogen in presence of
(1i) Reaction with hydrazine metal catalyst or by sodium borohydride
(H,N-NH2): Aldehydes and (NaBH,) or lithium
ketones react with hydrazine to aluminium
hydride (LiAlH,) give primary alcohol.
give hydrazone.
H,N-NH PH=3.5 R R-CHO+H Ni orPd or Pt
0 +
C=N-NH,
H
R-CH,OH
NaBH,
Aldehyde hydrazone R-CHO AI R-CH,OH
or LiAIH,

RC 0 + H,N-NH,P c-N-NH, e8 CH-CHO H, +Metal

R NaBH, or LiAIH, CHT CH,OH
Ethanal
Ketone hydrazone Ethanol
Reaction with phenylhydrazine : Aldehydesandketones i ) Ketones on reduction with hydrogen in presence ofmetal
condense with
phenylhydrazine to give phenylhydrazone. catalyst or sodium borohydride (NaBH4) or lithium aluminium
RC=0 + H,N-NH pH-35 hydride (LiAlH,) give secondary alcohol.
H H
R
HC-N-NH R=0H,+ orNiNaBH,
or Pt or PdR-C-OH
Aldehyde phenylhydrazone Ketone or LiAIH,
aReactionwith 2,4-dinitrophenylhydrazine : Aldehydes R
Ctones condense with 2,4-dinitrophenylhydrazine to give secondary alcohol
orange red or yellow precipitate of 2,4-dinitrophenylhydrazone.
NO,
R
HC=0
H +
H.N-NH pH=3. eg. CHc=O ,or orMetal
C=0 or NaBH, C H C - O H
or LiAlH,
NO, Propanone
NO CH
Propan-2-ol
C=NNH -NO, Cii) Clemmensen reduction: Aldehydes and ketones on
H
2,4-Dinitrophenylhydrazone
reduction
wIth zinc-amalgam and concentrated hydrochloric
Condction with semicarbazide : Aldehydes and ketones
acid gives alkanes.
with semicarbazide to give semicarbazone.
 R-C=0onc HCRCH, +H,O R-CHO+2[Ag(NH,),] +30H
Alkane Aldehyde
H RCOO +2Ag+ 2H,O +4NH,
Carboxylate anion
C=0 R-CH,-R + H,O
Alkane
eg HCHO +2[Ag(NH)] +30H
Ketone Formaldchyde
HCOO+2Ag +2H,0 +4NH,
e.g. Zn-Hg
CH-(=0ane CH-CHH
HC CH Formate ion
Ethane
H
Ethanal CH-CHO+2[Ag(NH,),] +30H
Ethanal
CH,COO +2Ag +2H,0 +4NH,
CH-C-CH3 ZAnHg
Conc. HCl
CH-CH-CH Ethanoate ion

Propanone Propane CHO +2[Ag(NH,)] +30H>

(iv) Wolff-Kishner reduction: Aldehydes and ketones when
treated with hydrazine give hydrazone which on heating with Benzaldehyde
alkali in ethylene glycol gives alkanes. This reaction is called
c o o +2Ag+2H,0+ 4NH,
Wolff-Kishner reduction. Benzoate ion
This reaction is used for the test of aldehydes known as silver

H
HN.NH2R-C=N.NH2
H
KOH R-CH
Fthylene glycol Alkane
+N2
mirror test.
Gi) Oxidation with Fehling's solution : Aliphatic aldehydes
A
when heated with Fehling's reagent undergo oxidation to give
Aldehyde
corresponding carboxylate anion and produce reddish brown

C=0+HN-NH,
Ketone
C=N-NH2 precipitate.
R-CHO+2Cuf +50H->R-CO0 +Cu,O+ 3H,O
KOH

Ethylene glycol
R-CH-R Red brown
Alkane Ppt
e.g CHC=0+H,N.NH,CHC=N.NH2 e.g HCHO+2Cu+5OH HCOO +Cu,0 +3H,O
Formaldehyde Formate ion
H H
Ethanal CH-CHO+2Cu4+50H> CH,CO0 +Cu,0 +3H,0
KOH Acetaldehyde Acetate ion Red brown

Ethylene glycol
CH-CH3 Ppt.
Ethane Note : Aromatic aldehydes do not respond to Fehling's test.
This reaction is used for the test of aliphatic aldehydes known
CH-C=0+H,N-NH,CH-C=N-NH, as Fehling's reagent test.
CH3 CH Tollens reagent Ammoniacal silver nitrate solution is
Propanone
called Tollens' reagent.
KOH
Ethylene glycol
CH-CH-CH AgNO + 3NH,OH [Ag(NH;):](OH) + NHNO;
Propane a mild oxidising agent. It oxidises only aldehydes to
A It is
carboxylic acids and itself gets reduced to metallic silver
Oxidation
which forms bright silver mirror.
Aldehydes differ from ketones in their oxidation reactions.
Fehling's reagent: Fehling's reagent is a mixture oftwo
(a) Aldehydes are oxidised by even mild oxidising agents like
solutions.
Tollens' reagent and Fehling solution.
Fehling's solution A is aqueous copper sulphate solution.
(b) Aldehydes on oxidation give carboxylic acids having same
number of carbon atoms. Fehling's solution B is alkaline sodium potassium tartarate
(Rochelle salt).
Example CH(OH)COONa
i) Oxidation with Tollens reagent : An aldehyde when
warmed with freshly prepared ammoniacal silver nitrate solution CuSOaa CHOHC
CH(OH)COOK
(Tollens' reagent) is oxidised to corresponding carboxylate anion Itis a mild oxidising agent. It is weaker than Tollens' reagent.
and gives a bright silver mirror due to the formation of silver It oxidises only aliphatic aldehydes to carboxylate ions
metal. itselfgets reduced to red brown precipitate of cuprous oxide.
 Haloform Reaction

Aldehvdes and ketones having acetyl group eg 2CH-CHO 1. NaOH

CH-C- are Ethanal CH-CH-CH-CHO
oxidised
by sodium hypoha (NaOX)
(X,+OH) to
oder
halogen and alkali OH
correspon ding sodium salt
having one carbon 3-Hydroxybutanal
tom less than the carbonyl compound and
(Aldol)
O give haloform. A
NaOX
HLOCH-CH=CH-CHO
But-2-enal
R-C-ls or X, +NaOH R-C-ONa+ CHX CH
X= Cl, Br, 1)
CH-C-CH,
Propanone
L Nad CH-C-CH--CH
eg. CHC-HA HCOO Na OH
Acetaldehyde Sodium formate
+CHX,
Haloform CH
CH-C=CHCOCH
CH-C-CH,Na0X CH,COONa CHX, 4-Methylpent-3-en-2-one
Cross aldol condensation : When different
Acetone Sodium acetate ketones containing a-hydrogen atom are treated with dilute
aldehydes and
Haloform
alkali, B-hydroxyaldehydes and ketones are formed. This reaction
O is called cross aldol condensation reaction.
If both the reactants
-CHNad -COONa +CHX, contain
products.
o-hydrogen atoms then it gives a mixture of four

Acetophenone Sodium benzoate Haloform

2.g.CH CH0 + CH,CH,CHO CHCH=CH- CHO
Ethanal Propanal
i) Sodium hypoiodite (NaOl) when treated with But-2-enal
compounds +CH,CH,CH=C-CHO+CH,CH=C-CHO
containing CH,CO-group gives yellow precipitate of iodoform.
Hence this reaction is used for the detection CH
of CH,CO-group CH
in a compound. 2-Methylpent-2-enal 2-Methylbut-2-enal

OH
+CH,CH,CH=CH-CHO
Pent-2-enal
(1 Compounds containing CH-CH- group and ethanolrOniy onecarbonyl compound contains a-hydrogen then only
one product is formed.
CH,CH,OH also gives haloform reaction.
CH.CH,OH a o CHCI, + HC0ONa
Ethanol Chloroform
e.g.
-CH,+ CHO 299k
OH
Acetophenone Benzaldehyde
CH- CH- RaO> CHCI, + RCOONa
Chlorofornm
CH-CH-
1,3-Diphenylprop-2-cn-1-one
Haloform reaction does not affect acarbon-carbon double (Benzalacetophenone)
Dond present in the Mechanism of aldol condensation:
molecule.
O
NaOCI (i) HO +H-CH-C-H Slow
CHCH=CH--CH
CH,CH=CHCOONa +CHX
-H>CH=C-HJ+H,O
Some Other Reactions OH of alkali abstracts H* from acidic a-carbon atom to form
Aldol condensation carbanion which is resonance stabilised.

ldehydes and ketones having at least one

a-hydrogen atom i) a-carbanion of one molecule attacks on carbonyl carbon
'go self condensation in the presence of dilute alkali catalyst of another molecule.
to form B-hydroxya
Kyaldehydes (aldol) and B-hydroxyketones +8
(ketol). This reaction is called aldol condensation. CH-C=0+CH-CH CH-C-CH-C-
The ldols unsaturated
readily lose water molecule to give a, ß H
arbonyl compound. H
(iii) Anion abstracts H" from waterr e.g.
CH
OH -CHO +CH-C-CHOOnc. NaOH CHOH
CH-C-CH -H CH-C-CH-C-H+ OH CH
H H CH3 CH
B-Hydroxyaldehyde
-coONa +CH C-CH,OH+CH-C-COONa
(iv) Dehydration
OH CH CH
with other
Cross Cannizzaro reaction of formaldehyde
CH-C-CH-C-HH. CHC=CH-C-H formate and alcohol of other
a, B Unsaturated aldehydes always gives sodium
H H aldehyde aldehyde.
Cannizzaro reaction : Aldehydes which do not have CH,OH + HCOONa
2. CHO + HCHO >
Sodium
-hydrogen atom when treated with concentrated alkali undergo alcohol
Benzaldehyde Formaldehyde Benzyl formate
self oxidation and reduction (disproportionation) to give one Oxidation of ketones:
like
molecule of alcohol and one molecule of carboxylic acid salt. Ketonesundergo oxidation with strong oxidising agents
to give mixture
KMnO4, KCr,07, concentrated HNO3
etc. a
This reaction is called Cannizzaro reaction.
number of carbon
of carboxylic acids each containing lesser
e.g. atoms than the original ketone.

H-CHO +H-CHO H-C-OH+ HOOK

Formaldehyde
H
Potassium
formate CH-C-CH, KMnOH CH,- - OH + HCOOH
or K,Cr,O,+ H,S04 Acetic Formic
Methanol
or Conc. HNO, acid acid

rule : In case of oxidation of unsymmetrical ketones

CHOSonc. KOH,-CH,OH coONa Popoff's
the keto group stays preferentially with the smaller alkyl group.
Benzyl alcohol Sodium benzoate
Benzaldehyde
K,Cr,0,+ H,SO
Mechanism of Cannizzaro reaction : CH-C-CHCH
Butan-2-0ne
O

(i) H-C-H + ÖH H- -OH CH-C-OH +CH,COOH

Acetic acid
H

Electrophilic Substitution Reactions in the Aryl

T Hydride transter Ring
Gi H-C-H+H-¢-on Slow (R.D.S) Aldehydic and ketonic groups are electron withdrawing theretore
H they are ring deactivating and meta directing. Aromatic aldehydes
and ketones are less reactive and electrophilic substitution occurs
OH O at meta position.
In
H-C-O () Halogenation Acetophenone when treated with Br2
H-Ç-H+H-C-OH H-Ç-H +
presence of anhydrous AlCl3 gives m-bromoacetophenone
Formate 1on
side
H Halogenation in benzene ring is more difficult than the
Methanol
chain halogenation.
Cross Cannizzaro reaction
COCH COCH
Two different aldehydes having no -hydrogen when treated Anhyd. AIC
with concentrated alkali give four products, the reaction is
+Br excess Br
called cross Cannizzaro reaction. concentrateu
(ii) Nitration : Benzaldehyde when treated with
CHO+RCHO> -CH,OH +RCOO HNO3 and conc. H2SO, gives m-nitrobenzaldehyde.
Benzaldehyde Benzyl alcohol CHO Conc. HNO CHO
+RCH,OH + coo Conc. H,SO
Benzoate ion
NO
Yieeld of
srald this reaction is
poor because a
part of benzaldehyde
to benzoic acid. Denoted by R - COOH.
is oxidised
Acetophe when treated with a mixture of conc. Higher members of aliphatic carboxylic acids (C2-C18) occur
conc, HSO4 gives m-nitroacetophenone. HNO, and in natural fats as esters of glycerol, hence these are known as
COCH COCH fatty acids.
Conc. HNOg (1i) Compounds in which aryl group is attached to carboxylic
carbon are called aromatic carboxylic acids.
Conc. H,S0
NO Denoted by Ar-COOH or Ph-CoOH

Gi Sulphonation: Benzaldehyde m-Nitroacetophenone

reacts with conc. H,SO to cooH (Benzoic acid)
give m-formylbenzenesulphonic acid derivatives.
CHO CHO Preparation of Carboxylic Acids
1. From alcohols (By oxidation): Primary alcohols are
+HSO Oxidised to carboxylic acids with potassium permanganate
SO,H (KMnO,) in any medium or by potassium dichromate (KCr,0,)
m-Formylbenzenesulphonic acid and chromium trioxide (CrO3) in acidic medium.
Acetophenone reacts with conc. H2S04 to give m-carbonyl
benzenesulphonic acid derivatives. 1. alkaline KMn0
R-CH,OH R-COOH
COCH COCH primary alcohol
2. H,0 Carboxylic acid

SOA e.g. CH,CH,OH 1. KMnO, +OH

Ethanol 2. H,0
CH,COOH
Ethanoic acid
SO,H
Acetophenone m-Acetylbenzenesulphonic acid
(Acetic acid)

Uses of Aldehydes and Ketones

CH,(CH,),CH,OH CrO-H,S0, CH,(CH,),coOH
Decan-1-ol Decanoic acid
Aldehydes and ketones are used as solvents in chemical 2. From aldehydes and ketones: Aldehydes on oxidation
industry. with mild oxidising agents give carboxylic acids.
These are also used as starting materials and reagents for
the synthesis of other organic compounds. e.g. CH,CHO +2[Ag(NH)2] +3OH
Tollens' reagent
Formalin (40% solution of formaldehyde) is used to preserve
CH,COOH +2Ag + 2H,0 + 4NH
biological specimens.
Formaldehyde is also used for the synthesis of bakelite
CH,CHO+2Cuf" +50H> CHCOOH +Cu,O +3H2,0
(phenol-formaldehyde resin), urea-formaldehyde glues and Fehling's reagent Red
other polymeric products. Ketones undergo oxidation with strong oxidising agent only
Acetaldehyde (CH,CHO) is used as starting material for and give a mixture of acids each contain ing lesser number of
the manufacture of acetic acid, ethyl acetate, vinyl acetate,
carbon atoms than the corresponding ketone.
polymers and drugs. O

Benzaldehyde is used in perfumery and in dye

industries.
CH-C-CH,C0,+ H,so CH--OH +H-COOH
industrial
Acetone and methyl ethyl ketone are common Propanone Ethanoic MethanoicC
solvents. acid acid
etc. are 3. From Grignard's reagent : Alkyl magnesium halide
5utyraldehyde, vanillin, acetophenone, camphor, (Grignard's reagent) adds on carbon dioxide to give a compound
used as
flavouring agents. which on hydrolysis with mineral acid gives carboxylic acids.
This method is used for converting alkyl halide into carboxylic
CARBOXYLIC ACIDS
functional acids having one more carbon atom.
anic compounds containing carboxyl (-COOH)
group are called carboxylic acids.
-8+8 + Dry ether
e.g. HCOOH CHCOOH
Ethanoic acid
eg R-MgX+O=C=o >R--ÕMgX
Methanoic acid

CoOH H,OR--OH + Mg(OH)X

Carboxylic acid
Benzene carboxylic acid
(Benzoic acid) From nitriles (By hydrolysis) : Alkane nitriles are
4.
) Comppounds in which alkyl group is attached to caboxylic
hydrolysed under mild reaction conditions to acids in the
oare called aliphatic carboxylic acids.
 presence of H" or ÕH ion as catalyst to give amide which on H R-COOH+ ROH
RCOOR' =
complete hydrolysis gives carboxylic acids. Ester Acid Alcohol
COOH
H,O HO
R-CN R-C-NH, R-C-OH -coOCH, CH,OH
- C N H , _ H , 0

e.g.
Alkane H orOH Amide
H or OH Carboxylic acid
Ethyl benzoate Ethanol
A Benzoic acid
nitrile
(ii) Esters on basic hydrolysis give carboxylate ion which on
eg. CH-CN CH-COOH+NH acidification gives carboxylic acids.
Ethane nitrile Ethanoic acid
NaOH
CH,COOC,H, CHCOONa +CH,OH
-CN coOH Ethyl ethanoate

Benzene Benzene
HO
carbonitrile carboxylic acid CH,COOH
Ethanoic acid
5. From acid derivatives (By hydrolysis)
Physical Properties of Carboxylic Acids
(a) Amides on acidic hydrolysis give carboxylic acids.
Aliphatic carboxylic acids upto nine carbon atoms are
R-CONH, R-COOH + NH, colourless odourless liquids.
Amide Carboxylic acid The higher acids are wax like solids.
Carboxylic acids have higher boiling points than the
eg. CH-C-NH, CH--OH + NH, aldehydes, ketones and even alcohols of comparable
A
Ethanamide Ethanoic acid molecular masses. The higher boiling point is due to
O extensive bonding of carboxylic acid molecules through
H,O intermolecular hydrogen bonding. Most of the carboxylie
--NH (-c-oH +NH, acids exist as dimer in the vapour phase or in the aprotic
Benzamide
Benzoic acid solvents.
(b) Acid chlorides on hydrolysis with water give carboxylic H-0O
R-CK R
acids. 0-H-0
In vapour phase or in aprotic solvent
R-COCI R-COOH+ Cr
Acid chloride Carboxylic acid Aliphatic carboxylic acids upto four carbon atoms are
Acid chlorides are readily hydrolysed by aqueous base to give miscible in water due to the formation of intermolecular
carboxylate ions which on acidification provides corresponding hydrogen bonds with water.
carboxylic acids. H-O 0
H,0/OHR-CO0 R-COOH 0-H
R
Acid chloride Carboxylate ion Carboxylic acid C=0H H=C R
H
& CH- -CI)H,O/OH

(ii) H,O* >CH-COOH

i) H,O/ÕH Solubility decreases with increasing number of C atoms.

(ii) H,0 cooH
Benzoic acid
Higher carboxylic acids are insoluble in water due to the
Benzoyl chloride
higher hydrophobic interaction of alkyl group.
(c) Acid anhydrides on
hydrolysis with water give Aromatic acids are insoluble in water.
corresponding acids. Benzoic acid is
soluble in hot water but insoluble in cold water.
Carboxylic acids are soluble in non-polar organic solvents
e.g. (CH,CO),0 2CH,COOH like benzene, ether, alcohol, chloroform, etc.
Acetic anhydride Ethanoic acid

(CHCO),o
Benzoic anhydride
2C,H,COOH
Benzoic acid
Chemical Properties of Carboxylic Acids
Structure of carboxyl group. The carboxyl carbon is sp
hybridised. All the atoms linked to carboxyl carbon lie in the
CHCOOCOCH C,H-C0OH +CH-COOH same plane. The carboxylic carbon atom is less electrophilie
Benzoic ethanoic Benzoic Ethanoic than carbonyl carbon because of the resonance.
anhydride acid acid
(d) (i) Esters on acidic hydrolysis directly give carboxylic
acids.
R-c R-CO-H >R-C<0-H T
Acidity of carboxylic acids
acids dissoCiate in water to give Mechanism of esterification : It is a nucleophilic acyl
Cart
hydronium ion.
carboxylate ion and substitution.
(a) Protonation of carboxyl oxygen
RCOOH+ H,0>RCO0 + H,0
acidity of carboxyl group due to the
1s
The presence of positive R-C0 =R-c0HR- OH
arge on
charg oxygen which liberates
proton. The carboxylate ion 0-H OH OH
formed is resonance stabilised. (b) Nucleophilic addition of alcohol
Proton 0-R
e8.
R-C{
0-H -H,O HR-C R-OH-p--oH
OH
transfer
R-¢-ÖH

OH :OH
Tetrahedral intermediate
R-c =R-c (c) Elimination of water molecule
:0-R' 0-R
Reaction with metals: Carboxylic acids liberate hydrogen R-cLOH H,0 R-C
gas with electropositive metals.
OH OH
2R-COOH +2Na-2R-COO Nat +H, Protonated ester
(d) Protonated ester loses a proton to give ester
e.g 2CH,COOH+2Na 2CH COO Nat + H,
Acetic acid Sodium acetate O-R
i) Reaction with alkalies : Carboxylic acids react with R-C
alkalies to form salt. R- OH
-H
OR
R-COOH +NaOH>R-COONa +
H,0 Ester
(vi) Reactions with non-metal halides : Carboxylic acids
e.g CH,COOH +
NaOH>CH,COONa + H,O react with PCl3 or PCls or SOCl2 to give acid chloride.
Ethanoic acid Sodium ethanoate
(Acetic acid) (Sodium acetate) R-COOH+PC1, R-COCI+HCI+ POCI,
(ii) Reactionwith carbonates and bicarbonates: Carboxylic 3R-COOH +PCI, 3R-COCI+H,PO,
acids react with carbonates and hydrogencarbonates to give R-COOH+SOCl R-COCI+ SO, + HCI
carboxylate salt and evolve carbon dioxide gas. (vii) Reaction with ammonia : Carboxylic acid reacts with
R-COOH + NaHCO,R-COONa +H,O +CO NH, to give ammonium salt which on further heating at high
2R-COOH + Na,CO,2R-COONa + H,O +CO, temperature gives amide. e.g.
eg CHCO0H+ NaHco, CH,COONa +H,O +CO, CH-COOH + NH
Acetic acid Sodium acetate Acetic acid
his reaction gives effervescence due to the evolution of CO,
CH-COONH,>CH-CONH,
Acetamide
gas. Ammonium
his reaction is used to detect the presence of carboxylic acid acetate

group in organic compound.

react with
COOH
+NH COONH
*cOls with metals and alkalies but do not
react
Thus
caker bases like carbonates and hydrogencarbonates.
s reaction is used to distinguish between phenols and
Benzoic acid Ammonium
benzoate CONH,
carboxylic acids.
with mineral Benzamide
Dehydration: Carboxylic acids on heating
Ids such as HSO or with P,O; give corresponding anhydride.
COOH COONH Strong
COOH
+2NH, co heating
2 CH-0 o CH- -CH, +H,O Phthalic acid O
H
Ethanoic acid Ethanoic anhydride
with alcohols or
Lsterification: Carboxylic acids react concentrated
NH
phenols in the presence of mineral acid likea
HSO or HCI gas as cataly and give ester. O

H,O Phthalimide
R-coOH+ R'OH R-COOR"
(vii) Reduction : Carboxylicacids on reduction with lithium
e.g. C,H.OH2CH,cOoC,H, + H0
CH,coOH +
Ethyl ethanoate
aluminium hydride or with diborane gives primary alcohol.
Ethanoic acid Ethanol
 R-COOHLIAIHyether or B,H, i) Resonance structures show that
(ii) H,O R-CH-OOH present in aromatic acids acts as ring
carboxylic acid group
Note: Sodium directing. deactivating and meta
borohydride does not reduce carboxyl group.
Diborane does not reduce functional group like ester, nitro, Carboxylic acids
do not undergo Friedel-Crafts reactian
halo etc. because carboxyl group is
ring deacti vating and it gets bonded
(ix) Decarboxylation : (a) Sodium salts of carboxylic acids to theLewis acid catalyst required for the
reaction.
when heated with sodalime gives
hydrocarbon with less number (ii) Nitration: Aromatic carboxylic acids react with
of C atoms. of conc. HNO, and conc. H2SO4 to give
a mixture
COOH m-nitrocarboxylic
COOH
acid.
R-COOHNaO R-COONaao aR-H + Na.CO,
A
Carboxylic Sod. Alkane Conc. HNNO,
acid carboxylate Conc. H,SO
NO,
e.g. CH coOH CH,COONa m-Nitrobenzoic acid
Acetic acid iv) Halogenation : Aromatic carboxylic acids react with
NaOH +Cad>CH, halogen in presence of halogen carrier to give m-halocarboxylic
A
+Na,CO
Methane acid.
This reaction is used for
decreasing the number of carbon atoms COOH COOH
in a compound.
(b) Kolbe electrolysis: Aqueous solution
of alkali metal Br, +Br, FeBr
salts of carboxylic acids on
electrolysis gives hydrocarbons. Br
m-Bromobenzoic acid
R-COOH R-COONa Electrolysis
Variation of Acidic Strength
R-R+2cO, +2NaOH The dissociation of carboxylic acid
may be represented
CH COOH + NaOH CH,COONa + H,0 R-COO + H,0
as

R-CO0 + H,0
For the above reaction
2CHCOONa CH-CH, +2C0, +2NaOH
(x) Hell-Volhard-Zelinsky reaction: Carboxylic acids having -[RCO0 IH,O]
=

an
o-hydrogen
when treated with chlorine or bromine in the [RCOOHJ[H,O]
presence of small amount of red phosphorus gives o-halo0
carboxylic acids. or, Ke. H,O1 =XC00][H,0*
R-CH-COOH +X2
[RCOOH
R-CH-COOH where, Keq. = Equilibrium constant

Ka= Dissociation constant of acid.

=CI, Br] and
The
P-logK
e.g. CHcoOH k -CH.COOH CRed P, strength of an acid is generally indicated by its pk, value.
Acetic acid Chloroacetic acid
CI Acidic strength -
pK
C1-CH-COOH k e u C-C-COOH Forstrong acids pk1
Moderately strong pKa= 15
CI
Dichloroacetic
Cl Weak acid pk 5 15
Trichloroacetic acid Extremely weak acid pKa 15
acid

Electrophilic Substitution in Aromatic (i) Carboxylic acids are weaker than mineral acids but stronger
Carboxylic Acids than phenols and alcohols
Resonance structures of benzoic acid; Acetic acid |Hydrochloric acid Phenol
pk 4.76 0.23 10
OH O OH O OH
|Naturel Weak acid Strong acid Extremely weak |

acid
(1) Carboxylic acids are stronger acids than phenols because
conjugate base ofcarboxylic acid (carboxylate ion) is established
OCOH o¢OH OcOH by two equivalent resonance structures in which the negative
charge is at the more electronegative oxygen atom.

R-C R-C =R-C.

Coniugate base of phenol a phenox ide ion has non-equivalente.g. (i) Formic acid is stronger acid than acetic acid.
econance structure in which the negative charge is at the less H-COOH> CHCoOH
electronegative carbon atom.

:Ö Remember:
:0: O: Phenyl or vinyl group attached directly to the carboxylic acid
group increases acidity of correspondingcarboxylic acid
because ofgreater electronegativity ofsp hybridised carbon,
asinductiveeffect overweighs mesomeric (resonance) effect.
In carboxylic ion negative charge is delocalised over twoStrength of aromatic carboxylic acids
electronegative oxygen atoms whereas in phenoxide ion it is ) Electron withdrawing group attached to phenyl ring of
less effectively delocalised over one oxygen atom and less aromatic carboxylic acid increases their acidity.
electronegative carbon atom. is stronger acid than benzoic acid.
e.g. p-nitrobenzoic acid
Thus carboxylate ion is more stabilised than phenoxide so COOH COOH
carboxylic acids are more acidic than phenols.

Effect of Substituents on the Acidity of

Carboxylic Acids pk,=4.19
NO
Electron withdrawing groups (EWG) increase the acidity of pk, =3.41
carboxylic acids by stabilising the conjugate base through i) Electron releasing group attached to phenyl ring decreases
delocalisation of negative charge by inductive and/or resonance acidity.
effects. e.g p-methoxybenzoic acid is weaker acid than benzoic acid.
i) The increasing acidity order of group is COOH COOH
P h I < Br < CI< F < CN< NO2 < CF3
e.g. (a) Chloroacetic acid is stronger acid than acetic acid.
CCH-coOH>CH,coOH pk,4.19
(b) Benzoic acid is stronger acid than acetic aciId. OCH,
pk,=4.46
COOH CH-COOH
pK, = 4.19
pk,=4.76 POINTS TO BE NOTED
increases with increasing number of electron Carbonylcarbonatom is sp hybridised.
(11) Acidity
withdrawing groups. Carbonyl carbon is electrophilic (Lewis acid) and
Chloroacetic carbonyl oxygen is nucleophilic (Lewis base).
eg. Trichloroacetic acid> Dichloroacetic acid >
acid>Acetic acid.
Hydration ofethynein thepresence of H,S04 and HgSO4
CI gives acetaldehyde while all other alkynes give ketones
in this reaction
C-C-C0OH> CI-CH-C00H Aldchydes are generally more reactive than ketones in
CI Cl nucleophilic addition reaction
>Cl-CH-COOH > CH-COOH Aldehydes are easily oxidised to carboxylic acids on

increases with increasing electronegativity o

such Tollens
Acidity reaction with even mild oxidising agents as

reagent and Fehling's solution.

substituents.
CI Ketones are oxidised under vigorous condition with strong
oxidising agents and elevated temperature.
e.g F-C-COOH> Cl--Ç-COOH Aldehydes on oxidation give carboxylic acids having

F Cl same number of C-atoms whereas ketones on oxidation

Trifluoroacetic Trichloroacetic a mixture
give carboxylic acids each having less
of
acid acid number of C atoms.
distance of halogen
increases with decreasing
Cldity Fehling's test.
atom from the Aromatic aldehydes do not respond to
carboxyl grouP Haloform reaction does not affect a
carbon-carbon double
Cl CI
bond.
H,CH,CH-COOH> CH,CH-CH-COOH semicarbazide but the
3-Chloroacetic acid
There are two -NH2 groups in
2-Chloroacetic acid -CONHNH2 group will react with carboxyl group.

Phenoxide ion has more number ofresonating

> C l - C H , C H , C H - C o O H

structure.
4-Chloroacetic acid by Therefore phenol is less basic than NH.
the acidity
Electron donating groups (EDG) decrease

estabilising the conjugate bas