7/27/2019 Aldehyde Ketone and Acid

Class-XII Aldehydes – Ketones – Carboxylic Acids  

ALIPHATIC PORTION
[1] Preparation of Aldehydes and Ketones 
(a) From alcohols
Primary alcohols in presence of oxidizing agents such as anhydrous CrO 3 or PCC , or by
catalytic dehydrogenation with Cu at 573 K get oxidised to aldehydes whereas secondary
alcohols results in the formation of ketones.

Cu / 573 K  Anhydrous CrO 3 / PCC

R CHO R CH 2 OH R CHO
Dehydrogenation Oxidation
Aldehyde 1o Alcohol Aldehyde

Details of dehydrogenation 2 Cu + O2 2 CuO

R CH 2 OH CuO R CHO Cu H2O

+ + +
(b) From alkenes
The alkenes on treatment with ozone followed by reductive cleavage (by Zn dust and water)
results in the formation of aldehydes whereas substituted alkenes form ketones.
R O H O O
Zn / H 2O
R CH CH2 + O3
H
C C
H
R C H + H C H
Alkene O O Aldehydes
Ozonide
R O H
O O
R CH CH2
+ O3 C C
H
Zn / H 2O
R R R C R + H C H
O O Ketone  Aldehyde

(c) From alkynes

Ethyne reacts with water in the presence of mercuric sulphate and sulphuric acid to yield
aldehyde i.e. ethanal. Other alkynes give ketones.
O H O
HgSO 4 Tautomerisation
HC CH + H OH
H2SO4 H2C CH H3C C H
Ethyne enol ( Unstable ) Ethanal
O H O
+  HgSO 4 Tautomerisation
R C CH + H OH R C CH R C CH
H2SO4 2
Ketone
3

[2] Preparation of Aldehydes only 

(a) From acid chlorides [ Rosenmund reduction ]
O O
H2
R C Cl R C H
Pd - BaSO 4
Acid chloride Aldehyde
 

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 1 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

(b) From Nitriles [ Stephen Reduction ]
The reaction of alkanenitrile with HCl in the presence of anhydrous stannous chloride
yields corresponding imine, which on hydrolysis give corresponding aldehyde.
+
SnCl 2 H3O
R C N R CH NH R CHO
HCl
imine

(c) From Acid derivatives

LiAlH 4 LiAlH 4
Acid Aldehyde 1o Alcohol
In order to prevent formation of alcohol, we use a derivative of carboxylic acid ( Acid
chloride, Ester and Nitrile ) that is more easily reduced and an derivative of aluminium
hydride ( DIBAL-H ) that is less reactive than lithium aluminium hydride.

Diisobutylaluminium hydride ( DIBAL-H ) is less reactive than LiAlH 4, because

it is much more sterically hindered and ,therefore, have difficulty in
 Al
H transferring hydride ions.
 Al H (i-Bu) 2 i.e. DIBAL-H
R C N R CHO
Nitrile H2O
O
 Al H (i-Bu) 2 i.e. DIBAL-H
R C OR1 R CHO
H2O
Ester
O
 Al H (i-Bu) 2 i.e. DIBAL-H
R C Cl R CHO
 Acid chloride H2O

[3] Preparation of Ketones only 

(a) From Acid chlorides
Treatment of acyl chlorides with dialkylcadmium, prepared by the reaction of cadmium
chloride with Grignard reagent, gives ketones.

2 R Mg X + CdCl 2 R2Cd + 2 Mg(X)Cl

O O
2 R1 C Cl + R2Cd 2 R1 C R + CdCl 2
(b) From Nitriles
Treatment of nitrile with Grignard reagent followed by hydrolysis yields a ketone.
NMgBr  O
+
R1 C N + R Mg X H3O
R1 C R R1 C R
AROMATIC PORTION
(a) From alcohols
OH O
OH +
K2Cr 2O7 / H CH C
CH 2 CHO +
K2Cr 2O7 / H

OH O
+
K2Cr 2O 7 / H C CH3
CH CH3

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 2 

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7/27/2019 Aldehyde Ketone and Acid

Class-XII Aldehydes – Ketones – Carboxylic Acids  

(b) From acyl chloride ( Rosenmund reduction )
O O

C C
H2 H
Cl
Pd - BaSO 4

Benzoyl chloride Benzaldehyde

(c) From nitriles ( stephen reaction )

O
C N
SnCl 2 CH NH
H2O C
HCl H
Imine
Benzonitrile

(d) From Methyl benzene ( Etard reaction )

O
CH3 CH ( OCrOHCl 2 )2
CS 2 + C
H3O
+ CrO 2Cl 2 H

Chromyl chloride Chromium complex

Toluene Benzaldehyde

Not Etard reaction O

CH3 CH ( OCOCH 3 )2
273 K - 283 K
+ CrO 3 + ( CH 3CO ) 2O C
H
Chromic oxide +
 Acetic anhydride H3O
Toluene Benzylidene diacetate

(e) From benzene ( Gatterman - Koch reaction )

An aldehyde group is directly introduced by treating benzene with carbon monoxide and
hydrogen chloride in the presence of aluminium chloride as a catalyst.
 AlCl 3 CHO
+ CO + HCl
+ HCl

This is an electrophilic substitution reaction ( modified Friedel-crafts reaction ), where

the most likely electrophile is acylium ion. H

CO + HCl +  AlCl 3
+C O +  AlCl 4

(f) From Toluene by side chain chlorination

CH3
CHCl 2 CHO
Cl 2
/ h H2O

373 K
Benzalchloride
(g) From Grignard reagent NMgBr  O
MgBr  C
Ether  CH3 + C
H3O CH3
+ R C N

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 3 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

Properties of Aldehydes and Ketones 
Nucleophilic Addition Reaction
Nu Nu
R1 +
Slow H
 C
C O + Nu 
O
Fast
C
OH
R2 R1 R1
R2 R2

[1] Addition of HCN in presence of a base

O OH
Base
R1 C R2 + HCN R1 C R2
CN Cyanohydrin

Base is used to generate Cyanide ion :  

HCN + OH CN + H2O
Strong Nucleophile

[2] Addition of Sodium hydrogensulphite

OSO 2Na
O OSO H
2
H+ Transfer  R1 C R2
R1 C R2 + NaHSO 3 R1 C R2
OH
ONa
Bisulphite addition product
This bisulphite addition product is formed by all aldehydes and only by methyl ketones.
The other ketones due to decrease in electrophilicity of carbonyl carbon and also because
of steric factors due to alkyl groups, do not react with sodium bisulphite.
This reaction is used to separate and purify aldehydes and
ketones, because aldehydes and ketones may be recovered from their suphite adducts by
warming them up with sodium carbonate solution.
OSO 2Na O
Na 2CO 3
R1 C R2 R1 C R2 Na 2SO3 NaHCO
+ + 3

OH

[3] Addition of Grignard Reagent  +

O O Mg Br  HO
 + H2O
R Mg Br  + C C R C OH + Mg Br  
R
Carbonyl compound
Alcohol
o
Formaldehyde results in the formation of 1 alcohol
Aldehyde ( Other than Formaldehyde ) results in the formation of 2 o alcohol
Ketones result in the formation of 3o alcohol

[4] Addition of Alcohols

Addition of alcohols ( Weak nucleophile ) to aldehydes in acidic medium first forms
hemiacetals which on addition of second molecule of alcohol results in the formation of
acetals.
Addition of alcohols to ketones to form hemiketals and ketals does not occur readily
because of the steric hindrance.
OH OR1
O R1 OH
+
H R C OR1 R C OR1
R C H + R1 OH
H Hemiacetal H  Acetal
Aldehyde
 

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 4 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

O + OH OR1
H R1 OH
R C R + R1 OH R C OR1 R C OR1
Ketone  Alcohol R
R Ketal
Hemiketal
R R
HO CH 2 O CH 2
HCl gas
C O + HO CH 2
C
dil. HCl O CH 2
R R Ethyleneglycol ketal
Acetals and ketals are hydrolysed with aqueous mineral acids to yield corresponding
aldehydes and ketones.
Nucleophilic Addition - Elimination Reaction
Addition of ammonia and its derivatives
R R
+
H
C O + H2N Z C N Z + H2O

R R

O OH xx OH
+
H H2N Z R H
+
 H+
C C C N Z
R R R +
R
R H
OH
R H
R
 H2O
C N Z C N Z

R R

R R R R
C O + H2 NH C N H C O + H2 NOH C N OH
 Ammo ni a R Imi ne R Oxime
R R Hydroxyl ami ne
R R R R

C O + H2 NR C N R C O + H2 N NH 2 C N NH2
Substituted i mine Hydrazone
R  Ami ne R Hydrazine R
R
( Schiff's base )

R R
H
C O + H
N NH C N NH
R Phenylhydrazone
Phenylhydrazine R
O2N O2 N
R R
H
C O
+ H
N NH NO 2 C N NH NO 2
R
2, 4 - dinitrophenylhydrazine R
2, 4 - dinitrophenylhydrazone
( Yellow , Orange or Red solid )

R O R O
H
C O
+ N NH C NH2 C N NH C NH2
H Semicarbazone
R Semicarbazide R  

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 5 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

Reduction Reaction
O
[1] Catalytic Reduction 
O
H2 / Pt
R C H R CH 2 OH ( Primary alcohol ) H2 / Pt
 Aldehyde LiAlH 4 / NaBH 4
OH
O

R C R H2 / Pt R HC OH ( Secondary alcohol )
LiAlH 4 / NaBH 4
Ketone R ( Secondary alcohol )

[2] Wolff - Kishner Reduction 

R R
KOH / ethylene glycol
C O + H2 N NH2 C N NH2
Heat
R CH 2 R + N2
Hydrazone  Alkane
R R
Hydrazine

[3] Clemmensen Reduction  O

Zn - Hg
R C R
Conc. HCl
R CH 2 R + H2O
Carbonyl compounds  Alkane

Oxidation Reaction
O
Mild oxidising agent Strong oxidising agent
No product R C CH3 RCOOH + HCOOH
Ketone

O
Mild oxidising agent Strong oxidising agent
RCOOH R C H RCOOH
 Aldehyde
The oxidation of ketone required cleavage of carbon - carbon bond, which can not break by

mild oxidising agents such as Tollen's reagent and Fehling's solution.

O + COOH
Tollen's reagent K2Cr 2O 7 / H
No product ( CH 2 ) 4
Fehling's solution OR +
KMnO 4 / H COOH
+
Cyclohexanone OR CrO 3 / H Hexanedioic acid ( A dipic acid )
Tollen's Test
To aqueous silver nitrate,a drop of dilute sodium hydroxide is added, forming a brown
precipitate of silver oxide. 2 AgNO 3 + 2 NaOH  Ag2O + 2 NaNO 3 + H2O

Concentrated ammonia is then added until the precipitate just dissolves

 Ag2O
+ 2 NH 3 + NaNO 3
+ H2O [ Ag ( NH 3 ) 2 ] NO 3 2 NaOH

So Tollen's reagent is ammonical silver nitrate i.e. [ Ag ( NH 3 ) 2 ] NO 3 +

Silver mirror 
RCHO + 3 OH

RCOO + 2 H 2O + 2 e
 Aldehyde + Tollen's reagent
Ketone + Tollen's reagent No silver mirror 
+
[ Ag ( NH 3 ) 2 ]
+ e X 2
 Ag + 2 NH 3

+ 
RCHO + 3 OH  + 2 [ A g ( NH 3 ) 2 ] RCOO + 2 H 2O + 4 NH 3 + 2 Ag
Silver mirror   

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 6 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

Fehling's Test
Fehling solution is a mixture of alkaline copper(II) sulphate solution and sodium poatssium
tartarate (Rochelle salt )  Aldehyde + Fehling's reagent Reddish Brow n precipitate

Ketone + Fehling's reagent No Reddish Brow n precipitate

 Aromatic aldehyde + Fehling's reagent No Reddish Brow n precipitate


+RCHO 3 OH RCOO + 2 H 2O + 2 e
2+  
2 Cu + 2 OH + 2e Cu 2O
+ H2O
2+  
RCHO + 2 Cu
+ 5 OH RCOO + 3 H 2O + Cu 2O Reddish Brow n precipitate

Hydroxyketones give positive Tollen's and Fehling test, because inhydroxyketones,the

secondary alcoholic group gets oxidised to ketonic group.
OH O 2 H 2O
+ 4 NH 3 +2 Ag
Tollen's reagent Silver mirror 
H3C CH 2 CH C CH3
Fehling's reagent
H3C CH 2 C C CH3 + 3H O Cu O
3-Hydoxypentan- 2-one O O
( hydroxyketone ) Pentane- 2, 3 - dione
2
+ 2
Reddish Brow n precipitate

O OH
Idoform Test
The reaction is used to detect the H3C C and H3C CH groups in an organic
compound. The organic compounds containing the above groups when treated with
halogen in presence of an alkali results in the formation of Chloroform,bromoform or
idoform. Idoform is a yellow solid.
O O
i.e. I 2 & NaOH
R C CH3 + NaOI
sodium hypoiodite
R C ONa + CHI 3 Idoform
( Yellow ppt. )
OH
O I2 + NaOH O
 2 HI
R CH CH3 + I2 R C CH3 R C ONa + CHI 3 Idoform
( Yellow ppt. )
This oxidation does not affect a carbon- carbon double bond, if present in the molecule.
O O
H3C CH C C CH3 + NaOI H3C CH C C ONa + CHI 3
Idoform
CH3 sodium hypoiodite CH3 ( Yellow ppt. )
The iodoform reaction is given by:
(1) Ethanol [ The only 1o alcohol ]
OH

(2) All secondary alcohols with H3C CH group. (3) Acetaldehyde [ the only aldehyde ]
O
(4) All methyl ketones [ aliphatic and aromatic ] with H3C C group.
O O

H3C C group is necessary for idoform reaction, because the C group is an

electron withdrawing group, which makes the  H of methyl group acidic in nature.
The conjugate base, after removal of H, become resonance stabilised.
O 
O O
C CH
 C CH C CH
H B 
 

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 7 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

Aldol condensation [ ALDOL = ALD ehyde + alcoh OL ]
Aldehydes and ketones having at least one H undergo a reaction in presence of dilute
alkali as catalyst to form hydroxy aldehydes or hydroxy ketones
OH
dil NaOH  H3C CH CH CHO
2 CH 3CHO H3C CH CH 2 CHO  H2O
But-2-enal
Ethanal 3 -Hydroxybutanal [ Aldol ]
O O OH H
dil NaOH 
H CH 2 C H
H3C C + H3C CH CH CHO  H2O H3C CH CH CHO

O O O
OH
Ba(OH) 2 
2 H3C C CH3 H3C CH CH 2 C CH3 H3C C CH C CH3
 H2O 4-Methylpent- 3-en- 2-one
Propanone H3C
CH3 [ Ketol ]
4-Hydroxy- 4-methylpentan- 2-one

O H
O dil NaOH OH O O

H3C C + H CH 2 C CH 3 H3C C CH C CH3
 H2O
H3C C CH C CH 3

CH 3 CH 3 CH 3

When aldol condensation is carried out between two different aldehydes or ketones, it is
called cross aldol condensation. Self
CH 3CHO H3C CH CH CHO + H3C CH2 CH C CHO condensation
1. NaOH But- 2-enal 2-Methylpent - 2-enal product
CH3
+ 2.  Mixed
CH 3CH 2CHO H3C CH C CHO
+ H3C CH2 CH CH CHO condensation
2-Methylbut- 2-enal CH3 Pent- 2-enal product

O O OH H O
dil NaOH

C + H CH2 C CH CH C
H  H2O
Benzaldehyde Acetophenone O
No  hydrogen Having  hydrogen CH CH C

Cannizzaro Reaction 1,3-diphenylprop-2-en-1-one

Aldehydes having nohydrogen,when treated with conc. alkali, undergo self oxidation
and reduction [ disproportionation / dismutation / auto oxidation-reduction ] reaction.
O

2 H C H Conc. NaOH CH 3OH + HCOONa

Methanal Methanol Sodium methanoate

O O
Conc. NaOH
2 C H CH2 OH + C ONa

Benzaldehyde Benzyl alcohol Sodium benzoate

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 8 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

Electrophilic substitution reaction.
Carbonyl groups act as deactivating and meta - directing group.
O 4  0  
Cl 2 / AlCl 3 C
 
 %   
 s  
o  l   
R O R u  t  
C Cl
i   
o  n  
 o  
O f   
 f   
o  r  
HNO 3 / H 2SO4 C
m  
a  l   
d   
e  h  
R  y  d   
R = H : aldehyde NO2 e   
i   
s   
R = alkyl : Ketone k  n  
o  w  
O
n   
H2SO4 / SO 3 a  s  
C  f   
o  r  
R
m  
a  l   
SO3H i   
n  . 

ALIPHATIC PORTION
Preparation of Carboxylic Acids 
[a] From alcohol and aldehyde
1. alkaline KMnO 4
RCH 2OH + RCOOH
o 2. H 3O
1 alcohol
1. alkaline KMnO 4
CH 3 (CH2)8CH 2OH CH 3 (CH2)8COOH
+
1-Decanol 2. H 3O Decanoic acid

O
Strong oxidising agent
R C H RCOOH
Aldehyde OR Mild oxidising agent
[b] From Grignard reagents
O
O +
H 3O
- + Dry ether  C - + RCOOH
R MgBr  + C O R
O MgBr 
Dry ice

[c] FromAcid derivatives O

H2O
R C Cl
 Acid chloride
RCOOH + HCl

O O
H2O
R C
O
C R1 RCOOH + R1COOH
 Acid anhydride

O +
+
H 3O NaOH H3O
RCOOH RCOONa + R' OH R C OR' RCOOH + R' OH
( Saponification) Ester 

+
+ O H 3O
R C N
H3 O
R C NH 2 
RCOOH + NH3

Nitrile  Amide

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 9 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

AROMATIC PORTION
CH 2 R
COOK + COOH
KMnO 4 - KOH H3O

 Benzoic acid
 Alkyl benzene
[ The entire side chain is oxidised to the carboxylic acid irrespective of length of side chain ]
CONH 2 + COOH
H3 O


+ NH3

Benzamide Benzoic acid

O O
C C H2O COOH
O CH3
+ CH 3COOH
Ethanoic acid
Benzoic ethanoic anhydride Benzoic acid
O
C C2H5 + COOH
O H3 O

Ethyl benzoate + C2H5OH

Properties of Carboxylic Acid 

[1] Acidity
Carboxylic acids dissociate in water to give resonance stabilised carboxylate anion.
O 
O O
 +
R C OH + H2O R C O R C O + H 3O

2 RCOOH + 2 Na 2 RCOONa + H2

RCOOH + NaOH RCOONa

+ H2O

RCOOH + NaHCO 3 RCOONa + H2O + CO 2 [ Test for carboxylic group ]

[ Brisk effervescence ]
2 3
SP SP
Acidity of H2C CH COOH > H3C CH 2 COOH
O O
C OH > CH C OH
2
2 3
SP SP
2 3
SP carbon is more electronegative than SP carbon,

[2] Esterification The water should remove from the mixture, because ester may undergo
O hydrolysis. O
+
H
H3C C OH + H O CH3 H3C C O CH3 + H2O

Acid Alcohol Ester

O O
+
H
H3C C OH + H O H3C C O + H2O

Ethanoic acid Phenol Phenyl ethanoate  

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 10 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

[3] Formation of Acid anhydride

O O O O
H2SO 4 / 
H3C C + C CH3 or P 2O 5 / 
H3C C C CH3 + H2O
OH H O O

Ethanoic acid Ethanoic anhydride

[4] Formation of Acid chloride

O O

H3C C OH + PCl 5 H3C C Cl + POCl 3 + HCl

O O

3 H3C C OH + PCl 3 3 H3C C Cl + H3PO 3

O O

H3C C OH + SOCl 2
H3C C Cl + SO 2 + HCl

[5] Formation of Acid amide

O O O
 + 
H3C C OH + NH3 H3C C O NH 4
 H2O
H3C C NH 2
 Ammonium ethanoate Ethanamide

COOH 
COO NH 4 CONH 2

+ NH3
 H2O
 Amm.benzoate Benzamide
O

-+ CONH
C
COOH
+ NH3 COO NH 4  2
Strong heating NH
-+  2 H 2O
COOH COO NH 4
CONH2  NH3 C

Phthalic acid  Ammonium phthalate Phthalamide O

Phthalimide
[6] Formation of Alcohol [ Reduction ]
O
LiAlH 4 / Ether [ The reaction involve hydride transfer
R CH 2 OH
R C OH + and causes reuction of carbonyl group ]
H3O
O
B 2H6 [ Diborane is better for this process, because
R C OH + it does not easily reduce ester,nitro and halo
R CH 2 OH
H3 O
groups]
Sodium borohydride does not reduce the carboxyl group.
[7] Formation of Alkane [ Decarboxylation ]
O
CaO [ NaOH & CaO in the ratio
R C ONa
+ NaO H

RH + Na 2CO 3
of 3:1 is known as sodalime ]
 Alkane
Sodium salt of carboxylic acid

Kolbe electrolysis 
Electrolysis
RCOONa R R + CO 2 + NaOH + H2

 At anode  At cathode

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 11 

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Class-XII Aldehydes – Ketones – Carboxylic Acids  

[8] Hell - Volhard - Zelinsky Reaction ( HVZ reaction )

R CH 2 COOH (i) X 2 / Red phosphorous
R HC COOH X : Cl , Br 
Having  - hydrogen (ii) H 2O X

If two  hydrogens are present, both of them may be substituted by halogen.

[9] Ring substitution reaction

Carboxylic group act as deactivating and meta directing group.
HOOC
Cl 2 / AlCl 3

HO O
C Cl
HOOC

HNO 3 / H 2SO 4

NO 2

HOOC

H2SO 4 / SO 3

SO 3H
Explanations 
Due to polarity of carbonyl group to ward oxygen,the intermolecular association of carbonyl
compounds occurs which makes the boiling point of carbonyl compounds higher than the
corresponding alkane of comparable mass.
However carbonyl compounds can not form hydrogen bonding with
each other and their boiling points are lower compared to alcohol (of comparable mass)
The lower members of aldehydes and ketones are soluble in water in all proportions,
because they associate with water molecules through hydrogen bonding.
The reaction of Grignard reagent with nitriles is considered to be the best method for the
preparation of carbonyl compounds, because, in the first stage of addition an imine is
formed as an intermediate product. The imine is then isolated and hydrolysed to give a
carbonyl compound as the final product.
Reaction of Grignard reagent with acid chloride and esters produce carbonyl
compounds,but the reaction does not stop at this stage and proceeds further with another
molecule of Grignard reagent to give corresponding alcohol as the final product.
Grignard reagent and dialkyl cadmium both are organometallic compounds, but reaction of
acid halides with
[a] Grignard reagent is not satisfactory method for the preparation of ketones.
[b] Dialkylcadmium is a satisfactory method for the preparation of ketones.
Because, in case of dialkylcadmium, due to less reactivity of cadmium, reaction with acid
chloride occurs only upto the formation of ketone. The reaction of Grignard reagent does
not stop after formation of ketone, since magnesium is more reactive metal,and proceeds
further to form tertiary alcohol.
Aryl ketones do not undergo addition of alcohol to form hemiacetals and ketals because of
O
steric factor.
C +
R R' OH H
+ No reaction

R = alkyl / aryl
 
Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 12 

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7/27/2019 Aldehyde Ketone and Acid

Class-XII Aldehydes – Ketones – Carboxylic Acids  

Aryl ketones do not give addition product with sodium bisulfite due to steric factor.
O

C R
+ NaHSO 3 No reaction

R = alkyl / aryl
The order of reactivity of aldehydes and ketones O O O
toward nucleophilic addition reaction: C C C
H H R H R R

Sterically the presence of two relatively large substituents in ketones hinder the approach
of nucleophile to carbonyl carbon than in aldehydes.
Electronically two alkyl groups in ketone reduce the electrophilicity of the carbonyl
more effectively than in aldehyde.
O
xx The right side -NH2 group is in conjugation with electron
xx
H2N NH C NH2
withdrawing carbonyl group and acquires positive charge and not
[Semicarbazide ]
in a position to act as the nucleophile, so does not involve
Involved in the formation in the formation of semicarbazone.
of semicarbazone
O OH O
HCN H3C CH3
CN HCN
No product
Cyclohexanone
cyanohydrin
CH3

2, 4, 6-trimethylcyclohexanone
In 2,4,6-trimethylcyclohexane, the three methyl groups will increase the electron density
on the carbonyl carbon atom and the nucleophile attack does not seem to be feasible.
Moreover,the two methyl substituents at the ortho position will also hinder the attack of
nucleophile CN ion on the carbonyl group.


Upon heating , formic acid loses a molecule of water and gets dehydrated to give carbon
monoxide. Therefore it does not form anhydride upon heating.
Heat
HCOOH CO + H2O

Phenoxide ion has more number of resonating structures than carboxylate ion, but
carboxylic acid is a stronger acid than phenol. Because, in carboxylate ion the negative
charge
there isisonly
dispersed on twoatom
one oxygen electronegative oxygen
to disperse the atomscharge.
negative while incase of phenoxide ion,
Benzaldehyde and other aromatic aldehydes form silver mirror with Tollen's reagent but
fail to react with fehling's solution and Benedict's solution. Due to resonance, the electron
density on the carbonyl carbon atom inbcreases, as a result the CH bond becomes
stronger. It can be oxidised to C  OH with strong oxidising agents like Tollen's reagent
( EoAg2+|Ag = +0.8 V ) but not with weaker Fehling's or Bendedict's reagent
( Eo Cu2+ |Cu = +0.34 V )

In Fehling solution , copper sulphate forms a soluble complex of Cu 2+ ions with tartarate
ion of the Rochelle's salt. The complex provides the Cu 2+ ions and also checks the
precipitation of copper hydroxide in the reaction.  

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 13 

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7/27/2019 Aldehyde Ketone and Acid

Class-XII Aldehydes – Ketones – Carboxylic Acids  

Predict the Products

OH
PCC , CH O
2Cl 2

Cyclohex- 2-en- 1-ol

? Cyclohex- 2-en- 1-one

O O

C  Anhy. AlCl 3 C
+ H5C2 Cl
CS 2 ? C2 H 5

O
( C6H5CH 2)2Cd + 2 CH 3COCl
? CH2 C
CH3
2+ O
Hg
H3C C CH C
H3C CH3
H2SO4

1. CrO 2Cl 2
?
H3C NO 2
2. H3O
+ ? OHC NO2

N OH
O +
+ HONH 2
H
? O2N

O 2N N NH NO2
O

+ H2N NH NO 2 ?
O O
+
R CH
O
CH CHO + H2N C NH NH2
H
? R CH CH CH N NH C NH2

H3C
C
CH3 + C N CH2CH3
+ CH 3CH 2NH 2 H
?
CH 2 CH3 COOK
KMnO 4
KOH , Heat ?
COCl
COOH
SOCl
Heat
2
? COCl
COOH
O
O
CH N NH C NH2
CHO
H2N C NH NH2
?
O O
+

CHO
[ Ag(NH 3)2]
? COO


Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 14 

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7/27/2019 Aldehyde Ketone and Acid

Class-XII Aldehydes – Ketones – Carboxylic Acids  

CHO OH
NaCN / HCl
COOH ? CH
CN

CH3 COOH
dil. NaOH
C6H5CHO
+ CH 3CH 2CHO
? H5 C6 CH C CHO

(i) NaBH 4 OH
CH 3COCH 2COOC 2H5
(ii) H
+ ? H3C CH CH2 COOEt

OH O
CrO 3
?
O
(i) O 3
(ii) Zn - H 2O ?
OH
CHO + CH
H 3O
+ C6H5MgBr 
? C6 H 5

CHO -
COO
-
?
+
+ [ Ag(NH 3)2] + OH

CHO O CH NHCONH 2

+ H2N C NH NH2
?
H H
H OC 2H5
C O
+ H OC 2H5 ? C
O C2H5
OC2H5

O O O
OH
dil. NaOH

+ ?
O OH
Raney Ni / H 2
?
OH
O
NaBH 4 / CH 3OH
?
CH C 6 H5 (i) O 3 O

(ii) Zn / H 2O ? + C6H5CHO

 
Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 15 

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