ALDEHYDES AND KETONES

CARBONYL COMPOUNDS:

“Organic compounds containing the carbonyl functional group ( C = O) are called as

carbonyl compounds”.
 In a carbonyl group, a carbon atom is bonded to oxygen with a double bond.

( C 
O )


Classification of Carbonyl Compounds:

Carbonyl compounds are divided into two classes.
(1) Aldehydes:
“Carbonyl compounds, in which the carbonyl group is bonded to at least one hydrogen atom,
are called aldehydes.”
O
||
 Aldehydes have a general formula R  C  H
Where,
R = H atom, alkyl group or aryl group
(2) Ketones:
“Carbonyl compounds, in which the carbonyl group is bonded to two other carbon atoms are
called as ketones.”
A ketone may be represented by the general formula.
O
||
RCR
Where;
R = Alkyl group or aryl group.
Note:
“The homologous series of both aldehydes and ketones have the general formula. CnH2nO”.
Occurrence of Carbonyl Compounds:
Aldehydes and ketones are present in many naturally occurring compounds.
 Aldehyde group is present most sugars i.e., glucose.
 Aldehydes are the principal constituents of a number of essential oils used as fragrances
and flavours.
 Ketonic group is present in camphor and menthone.
Key to Chemistry [Part-II] 442 [Ch.12] Aldehydes & Ketones
NOMENCLATURE:
(1) Aldehydes:
There are two methods for naming the aldehydes.
(a) Common Names:
The common names of aldehydes are obtained from the common names of carboxylic acids
containing the same number of carbon atoms.
The ending-ic acid in the common name of the acid is replaced by the word “aldehyde”
Examples:
O O
(i) || (i) ||
H  C  OH (Formic acid) HCH (Formaldehyde)
O O
(ii) || (ii) ||
CH3  C  OH (Acetic acid) CH3  C  H (Acetaldehyde)
O O
(iii) || (iii) ||
CH3  CH2  C  OH (Propionic acid) CH3  CH2  C  H (Propionaldehyde)
O O
(iv) || (iv) ||
CH3  CH2  CH2  C  OH (Butyric acid) CH3CH2CH2 C H(Butyraldehyde)

 The aldehyde group always occur at the end of a chain.

 The positions of the other groups are indicated by Greek Letters (,,,).
Lettering starts on the carbon adjacent to the carbonyl group.
O
  
CCCCCH

IUPAC Names:
(i) The IUPAC names of aldehydes are derived from the names of alkanes having the same number
of carbon atoms.
The letter e of the corresponding alkane is replaced with al .
O O O O
|| || || ||
HCH CH3  C  H CH3  CH2  C  H CH3  CH2  CH2  C  H
Methanal Ethanal Propanal Butanal
(ii) The positions of other groups on the chain are indicated by using numbers.
 Numbering starts from the carbonyl carbon.
O
||
4
CH3  CH2 
3 2CH
 CH
1
|
Cl
2 – Chlorobutanal
[Ch.12] Aldehydes & Ketones 443 Key to Chemistry [Part-II]
 Aromatic aldehydes are not given IUPAC names.
O

C H

C6H5 C H or

Benzaldehyde
(2) Ketones:
(i) Common Names:
The common names of ketones are obtained by separately writing the names of the alkyl groups
attached to the carbonyl carbon. The word ketone is then added as a separate word.
According to nature of alkyl groups, the ketones are of two types.
(a) Symmetrical Ketones:
“If the two alkyl groups on either side of the carbonyl group are same, the ketone is called as
symmetrical ketone.”
For naming symmetrical ketones, the prefix, di-is added before the name of alkyl group.
O O
|| ||
CH3  C  CH3 CH3  CH2  C  CH2  CH3
Dimethyl ketone Diethyl ketone
(b) Unsymmetrical Ketones:
“If the two alkyl groups on either side of the carbonyl group are unlike, the ketone is called
unsymmetrical ketone.”
For naming unsymmetrical ketones, the names of both alkyl groups are written in an
alphabetical order.
O O
|| ||
CH3  C  CH2  CH3 CH3  CH2  C  CH2  CH2  CH3
Ethyl methyl ketone Ethyl-n-propyl ketone
IUPAC Names:
The IUPAC names of ketones are derived from the names of alkanes having the same number
carbon atoms.
 The letter e in the name of alkane is replaced with one.
 The position of the carbonyl group and of other groups on the chain are indicated by
numbers.
 Numbering is started from that end which is nearest to the carbonyl group.
O O O
|| || ||
CH3  C  CH3 CH3  C  CH2  CH3 CH3  CH2  C  CH2  CH2  CH3
2 – Propanone 2-Butanone (Butanone) 3-Hexanone
(Propanone)
Key to Chemistry [Part-II] 444 [Ch.12] Aldehydes & Ketones
 Aromatic ketones are not given IUPAC names.
O O
||
C6H5  C  CH3 C

(Acetophenone) Diphenyl ketone

(Methyl phenyl ketone) (Benzophenone)

PREPARATION OF ALDEHYDES

Preparation of Formaldehyde: (Formalin)

(i) Laboratory Method:
(a) From Methyl alcohol:
Formaldehyde is prepared in the laboratory by passing a mixture of methyl alcohol vapours and
air over platinised asbestos or copper or silver catalyst at 300C.
O
Pt-asbestos
||
2CH3OH + O2  2H  C  H + 2H2O
300C

Procedure:
Apparatus is set as shown in figure. Air is drawn through methyl alcohol with the help of a
suction pump. The air and vapours of methyl alcohol are then passed through heated catalyst. Methyl
alcohol is oxidized to gaseous formaldehyde which is absorbed in water. The resulting mixture is called
formalin.

Air

Platinised
asbestos
Methyl alcohol
A solution
of formalin
methanol
and
Water bath
water
To suction
pump

Preparation of Formaldehyde (formalin)

Formalin:
Formalin is a mixture of 40% formaldehyde, 8% methanol, and 52% water.
(b) From Calcium formate:
Formaldehyde can be obtained in the laboratory by the dry distillation of calcium formate.
[Ch.12] Aldehydes & Ketones 445 Key to Chemistry [Part-II]
O
O
H C O
Ca  H C H + CaCO3
H C O Methanol
O
(ii) Industrial Method:
Industrially formaldehyde is manufactured by passing a mixture of methanol vapours and air
over ironoxide-molybdenum oxide or silver catalyst at 500C.
O
FeO Mo2O3
||
2CH3OH + O2  2H  C  H + 2H2O
500C

Q# Give different methods for the preparation of acetaldehyde?

Preparation Of Acetaldehyde:

(i) Laboratory Method:

(a) From Ethyl Alcohol:

Acetaldehyde is prepared in the laboratory by the oxidation of ethyl alcohol with acidified
sodium dichromate solution.
Na2Cr2O7 + H2SO4
CH3CH2OH + [O]  CH3CHO + H2O


Procedure: C2H5OH + Na2Cr2O7 solution

Water out
A mixture of ethyl alcohol and sodium dichromate
solution is run into boiling dilute sulphuric acid. Immediately a
vigorous reaction takes place and the acetaldehyde formed in
liquid state is immediately distilled off. This prevents the
oxidation of acetaldehyde to acetic acid. Ethyl alcohol remains Dilute H2SO4
in solution until it is oxidized.
 Pure acetaldehyde is obtained by redistillation. Water in
Ice and water
(b) By dry distillation of salts: Acetaldehyde,
Acetaldehyde can also be prepared by the dry distillation Ethanol and water

of a mixture of calcium salts of formic acid and acetic acid. Preparation of Acetaldehyde

O O
O
H C O CH3 C O
Ca + Ca Heat 2CH3 C H + 2CaCO3
H C O CH3 C O (Acetaldehyde)

O O
Calcium formate Calcium acetate
Key to Chemistry [Part-II] 446 [Ch.12] Aldehydes & Ketones
(ii) Industrial methods:
(a) From Ethene:
Acetaldehyde is prepared industrially by air oxidation of ethylene using palladium
chloride catalyst with a cupric chloride promoter.
O
PdCl2 + CuCl2
||
2CH2 
 CH2 + O2  2CH3  C  H
H2O
Ethylene Acetaldehyde

Preparation of Acetone:
From Calcium acetate:
Acetone is prepared by dry distillation of calcium acetate.
O
O
CH3 C O ||
Ca Heat CH3  C  CH3 + CaCO3
CH3 C O
Acetone
O

Reactivity of Carbonyl Group:

The carbonyl group has a carbon  oxygen double bond, in which one bond is -bond and other
is -bond.
 
C
+
 O
As oxygen is more electronegative, it attracts the -electrons to itself. The attraction makes the
carbonyl group a polar group. The oxygen atom has a partial negative charge on it and is a nucleophilic
center, whereas the carbon atom has a partial positive charge and is a electrophilic center.
Nucleophilic Addition Reactions:
Aldehydes and ketones undergo addition reactions when they react with a nucleophilic
molecule. In these reactions, the negative part of the reagent combines with the electrophilic carbon of
the carbonyl group, whereas the positive part which is usually hydrogen goes to the oxygen.

H Nu C O Nu C OH

Reagent Substrate Addition Product

Types of Nucleophilic Addition Reactions
Nucleophilic addition reactions are of two types.
(a) Base-catalyzed addition reactions:
If the nucleophilic addition reaction is carried out in the presence of a base, they are called base-
catalyzed reaction.
 A base catalyzed reaction increases the nucleophilic character of the reagent.
(b) Acid-catalyzed addition reactions:
If the nucleophilic addition reaction is carried out in the presence of acid, they are called acid-
catalyzed reactions.
[Ch.12] Aldehydes & Ketones 447 Key to Chemistry [Part-II]
 An acid catalyst promotes the nucleophilic attack by increasing the positive character
(electrophilic character) of the carbonyl carbon atom.
Note:
Remember that whether the addition is base catalyzed or an acid catalyzed, the adduct (addition
product) is the same.

NUCLEOPHILIC ADDITION REACTIONS

The characteristic reactions of carbonyl compounds are nucleophilic addition reactions.

Q# Write general mechanism of base catalyzed reaction of carbonyl compound.

(a) Base-Catalyzed Addition Reactions

These reactions take place when nucleophilic molecule reacts with carbonyl compounds in
the presence of a base catalyst.
General Mechanism:
(i) Generation of a nucleophile:
The base reacts with the nucleophilic reagent and generates a strong nucleophile.
 
O
H
+
HN
uN
u
:
+H
O
H
(ii) Attack on substrate:
The nucleophile then attacks the electrophilic carbon of the carbonyl group to generate an
alkoxide ion.

 
+ 
 
N
u 

: C O N
uCO

(iii) Gain of a proton:

The anion thus produced, attacks the water molecule and abstracts a proton, regenerating the
base catalyst.

 + + 
Nu C O + H OH Nu C OH + OH

Examples:
The base catalyzed nucleophilic addition reactions of aldehydes and ketones are following.
(1) Addition of Hydrogen Cyanide:

Hydrogen cyanide adds to aldehydes and ketones to form cyanohydrins.

The reaction is carried out by adding slowly a mineral acid to an aqueous solution of sodium
cyanide. The acid generates HCN from NaCN in situ.
Key to Chemistry [Part-II] 448 [Ch.12] Aldehydes & Ketones
Examples of the Reactions:
H H OH
NaCN/HCl
C = O + HCN C
H H CN
Formaldehyde Formaldehyde cyanohydrin
CH3 CH3 OH
NaCN/HCl
C = O + HCN C
H H CN
Acetaldehyde Acetaldehyde cyanohydrin
CH3 CH3 OH
NaCN/HCl
C = O + HCN C
CH3 CH3 CN
Acetone Acetone cyanohydrin

Q# Write general mechanism of addition of HCN in carbonyl compound.

MECHANISM:
Nucleophilic attack by the negatively charged carbon of cyanide ion at the carbonyl carbon of
the aldehyde and ketone. Hydrogen cyanide itself is not very nucleophilic and does not ionize to from
cyanide to a significant extent. Thus a source of cyanide ion such as NaCN or KCN is used. The
mechanism of the reaction is as follows:
R R

N=C + C = O N=C—C—O
R R
Cyanide ion Aldehyde or Ketone Conjugate base
of Cyanohydrin
R R
N C—C—O + H—C N N C — C — OH+ C N
R R
Conjugate base of Hydrogen cyanide Cyanohydrin Cyanide ion
Cyanohydrin
The hydroxide ion liberate in the formation of cyanohydrin reacts with undissociated hydrogen
cyanide and produces more cyanide ions, which in turn react with more carbonyl compound.
Synthetic Importance:
The cyanohydrins are hydrolysed by an aqueous acid to give -hydroxy carboxylic acids that
contain one carbon atom more than the number of carbon atoms in the starting aldehydes or ketones.
OH OH
| |
CH3  CH  CN + 2H2O + H2SO4  CH3  CH  COOH + NH4HSO4
Acetaldehyde cyanohydrin 2-Hydroxypropanoic Acid
(Lactic Acid)
[Ch.12] Aldehydes & Ketones 449 Key to Chemistry [Part-II]
(2) Addition of Grignard Reagent:
Grignard Reagents add to aldehydes and ketones to form adducts, which on hydrolysis with
dilute mineral acid (HCl, H2SO4) give alcohols.

+    Ether  
C   O + R Mg X C OMgX

OH
  +  HCl
C OMgX + H O H C OH + Mg

R X
 Formaldehyde reacts with Grignard reagent to give primary alcohols.
 Acetaldehyde reacts with Grignard reagent to give secondary alcohols.
 Acetone reacts with Grignard reagent to give tertiary alcohols.

Q# Write general mechanism of addition of NaHSO3 on carbonyl compound

(3) Addition of Sodium Bisulphite:

Aldehydes and small methyl ketones react with a saturated aqueous solution of sodium
bisulphite to form a crystalline white precipitate of sodium bisulphite adduct.
Examples of the Reaction:
H H OH
C = O + NaHSO3 C
H H SO3Na
Formaldehyde Bisulphite addition product

CH3 CH3 OH
C = O + NaHSO3 C
H H SO3Na
Acetaldehyde Bisulphite addition product
CH3 CH3 OH
C = O + NaHSO3 C
CH3 CH3
SO3Na
Acetone Bisulphite addition product

Note:
 All aldehydes give this test.
 In ketones,only 2-Alkanones i.e Methyl ketones give this test.
General Mechanism:
Key to Chemistry [Part-II] 450 [Ch.12] Aldehydes & Ketones
Sodium bisulphite ionizes to form sulphite ions.
Step I:
Sodium bisulphite ionizes to form sulphite ions.
 
NaHSO3 SO2  O + H+ + Na+
Step II:
The sulphite ion act as a nucleophile, since the sulphur atom is more nucleophilic than oxygen, a
carbon  sulphur bond is formed.

O
+   
C O + SO2 ONa C
 +
SO2  ONa
Step III:
The negatively charged oxygen atom, abstracts a proton to give bisulphite addition product
( white ppt.)

O OH
+
C + H C
 +  +
SO2ONa SO2ONa
Regeneration of reactant:
 Bisulphite addition product white precipitates on heating with dilute mineral acid (HCl or
H2SO4) regenerates the parent aldehyde or ketone.
CH3 O
OH
C + HCl  CH3 C H + NaCl + H2O + SO2
H SO3Na
Bisulphite Addition Product Acetaldehyde
Importance of Reaction:
The reaction is used for the separation and purification of the carbonyl compounds from non-
carbonyl compounds such as alcohols.
Q# What is meant by condensation? Discuss the mechanism of aldol condensation reaction.
Why formaldehyde do not give aldol condensation? (Rwp 2018)
CONDENSATION REACTIONS:
“The reactions in which two molecules of the same or different compounds combine to form a
new compound with or with out the elimination of a small molecule like H2O or NH3 are called
condensation reactions”.
Aldol Condensation:
Aldehydes and ketones possessing -hydrogen atom react with a cold dilute solution of an
alkali to form addition products known as “aldols”.
The name “aldol” is given to the product because it contains both aldehyde and alcohol
functional groups.
Examples of the reaction:
[Ch.12] Aldehydes & Ketones 451 Key to Chemistry [Part-II]
(a) Reaction with Ethanal:
O O OH O
+ dil. NaOH
CH3 C +H CH2 C H CH3 CH CH2 C H + H2O

H
Ethanal 3-Hydroxybutanal (aldol)
(b) Reaction with Propanal:
O O OH O
+ dil. NaOH
CH3 CH2 C +H CH C H CH3 CH2 CH CH C H

H CH3 CH3
Propanal Propanal 3-Hydroxy-2-methylpentanal (aldol)
(c) Reaction with Propanone (Acetone):
O O OH O
+ dil. Ba(OH)2
CH3 C+H CH2 C CH3 CH3 C CH2 C CH3

CH3 CH3
Propanone Propanone 4-Hydroxy-4-methyl-2-propanone
Dehydration of aldol: (Formation of crotonaldehyde)
The aldol compound readily loses water on heating in the presence of dilute acid to form an
unsaturated carbonyl compound. A carbon-carbon double bond is formed between the -and -carbon.
OH O O
| || dil. HCl
||
CH3  CH  CH2  C  H  CH3  CH = CH  C  H + H2O

3-Hydroxybutanal Crotonaldehyde(α-βunsaturated aldehyde)
Mechanism:
Step I (Generation of Nucleophile):
The hydroxide ion removes a proton from the -carbon of one molecule of the carbonyl
compound to form a carbanion. Carbanion is resonance stable.
O O
 + 
H O+H CH2 C H CH2 C H + H2O
Hydroxide Ion Ethanal Carbanion
Step II (Attack of Nucleophile):
The carbanion acts as a nucleophile. It attacks the electrophilic carbonyl carbon atom of second
molecule to form alkoxide ion.
 
O O O O
+ 
CH3 C + CH2 C H CH3 CH CH2 C H

H
Ethanal Carbanion An alkoxide ion
Step III (Protonation of alkoxide ion):
Key to Chemistry [Part-II] 452 [Ch.12] Aldehydes & Ketones
The alkoxide ion removes a proton from water to form aldol.

O O OH O
+  
CH3 CH CH2 C H+ H OH CH3 CH CH2 C H + OH
Alkoxide Ion 3-Hydroxybutanal (aldol)

 The catalyst (OH) is regenerated.
Why formaldehyde do not give this reaction:
Those aldehyde and ketones which contain -hydrogen can give this reaction. Formaldehyde do
not have -hydrogen so it does not give this reaction.
Q# What type of aldehydes gives cannizaro’s reaction? Give mechanism.
Cannizzaro’s Reaction:
Aldehydes that have no -hydrogen atoms undergo Cannizzaro’s reaction.
It is a dispropotionation (self oxidation-reduction) reaction.
In this reaction two molecules of aldehyde react. One molecule being converted into the
corresponding alcohol (the reduced product) and the other into the acid in the salt form (the oxidized
product).
 The reaction is carried out with 50% aqueous solution of sodium hydroxide at room
temperature.
Examples:
(a) Reaction with Formaldehyde:
O O
|| ||  +
2H  C  H + NaOH  CH3OH + H  C  ONa
(Formaldehyde) (Methyl alcohol) Sodium formate
(b) Reaction with Benzaldehyde:

CHO CH2OH COONa
2 + NaOH +

Benzaldehyde Benzyl Alcohol Sodium Benzoate

Mechanism:
The NaOH ionizes to produce sodium and hydroxide ions.
NaOH Na+ + OH
Step I:
The hydroxide ion acts as a nucleophile and attacks the electrophilic carbonyl carbon to form a
complex anion.

H H O

C  O + OH
+ 
C
H H OH
Formaldehyde Anion
Step II:
Due to presence of negative charge on oxygen of the anion, it loses a hydride ion.
[Ch.12] Aldehydes & Ketones 453 Key to Chemistry [Part-II]
 O
H O

C H C OH + H
H OH Formic Acid
Step III:
The hydride ion now attacks the electrophilic carbon of the second molecule to give a
methoxide ion.
H

C 
+  
O + H H3C O
H Methoxide ion
Step IV:
The methoxide ion acts as a base and abstracts a proton from formic acid to form methanol and
formate ion.
O O
 +  
H3C O + H O C H CH3OH + H C O
Methoxide ion Formic acid Methanol Formate ion
Step V:
The formate ion then reacts with sodium hydroxide to form sodium salt of acid.
O O
|| 
||  + 
H  C  O + NaOH H  C  ONa + OH
Sodium Formate

 The OH ion again starts the reaction.
Haloform Reactions:
Only acetaldehyde and methyl ketones react with halogens in the presence of sodium hydroxide
to give haloform and sodium salt of the carboxylic acid.
The term haloform is used for the reaction because a haloform (chloroform, bromoform,
iodoform) is one of the product.
O
||
R  C  CH3 + 3X2 + 4NaOH  CHX3 + RCOONa + 3NaX + 3H2O
R = Alkyl Haloform Sod. carboxylate
aryl or hydrogen
Note:
Only those carbonyl compounds will give haloform reactions, in which a methyl group (–CH3) is
directly attached with the carbon of the carbonyl group.
Key to Chemistry [Part-II] 454 [Ch.12] Aldehydes & Ketones
O O O
|| || ||
e.g., CH3  C  H, CH3  C  CH3, CH3  C  CH2  CH3 etc.
Examples of the Reaction:
(i) With Acetaldehyde:

O
||
CH3  C H + 3I2 + 4NaOH  CHl3 + HCOONa + 3Nal + 3H2O
Acetaldehyde Iodine Iodoform Sod. formate
(Yellow ppt.)
(ii) With Acetone:

O
||
CH3  C  CH3 + 3I2 + 4NaOH  CHl3 + CH3COONa + 3Nal + 3H2O
Acetone Iodine Iodoform Sod. acetate
(Yellow ppt.)
Synthetic Importance:
From a synthetic point of view, the haloform reaction affords a convenient method for
converting a methyl ketone to a carboxylic acid containing one carbon atom less than the parent
compound.
Note:
“Primary and secondary alcohols in which β carbon is a methyl group (–CH3) give haloform
reactions”.
(iii) With Pri-alcohols:
Among primary alcohols, only ethanol gives the haloform reaction.

CH3CH2OH + 4I2 + 6NaOH  CHl3 + HCOONa + 5NaI + 5H2O
Ethanol Iodoform Sod. Formate
(iv) With Sec-alcohols:
Secondary alcohols containing the hydroxyl group on the second carbon atom ( 2-Alkanol) also
undergo this reaction.
OH
| 
R  CH  CH3 + 4I2 + 6NaOH  CHI3 + RCOONa + 5NaI + 5H2O
A secondary alcohol Iodoform Sod. carboxylate

Iodoform Test:
“The haloform reaction using iodine and aqueous solution of sodium hydroxide is called the
iodoform test”.
 It produces yellow ppt. of iodoform.
[Ch.12] Aldehydes & Ketones 455 Key to Chemistry [Part-II]
Importance:
Iodoform test is used to distinguish between following compounds.
 Methyl ketones from other ketones.
 Ethanol from methanol and other primary alcohols.
 Acetaldehyde from other aldehydes.
 In secondary alcohols 2-Alkanols from other sec. alcohols.
Acid-Catalyzed Addition Reactions:

The acid catalysed nucleophilic addition reaction will take place with a weak nucleophilic
reagent.

Q# Write general mechanism of acid catalyzed reaction of carbonyl compound.

General mechanism:
The acid catalysed nucleophilic addition reaction will take place with a weak nucleophilic
reagent.
(i) Protonation of carbonyl group:
The addition is initiated by the proton (H+) liberated by acid. The proton combines with the
carbonyl oxygen atom and thus increases the electrophilic character of carbonyl carbon.

C  C 
+  
O + H O
+
H

(ii) Generation of electrophile:

In second step the carbon-oxygen -bond shifted on oxygen, and carbon become positively
charged.

C

O
+
H C O H

(iii) Attack on a weak nucleophile:

In the last step, a weaker nucleophile can attack the electrophilic carbon to form an adduct.

+ +
H Nu C OH Nu C OH + H

 The H+ ion is regenerated and can again start the process.

Example Reactions:
The acid-catalyzed nucleophilic addition reactions of the aldehydes and ketones are following.
(i) Polymerization Reaction:
Key to Chemistry [Part-II] 456 [Ch.12] Aldehydes & Ketones
Both formaldehyde and acetaldehyde polymerize in the presence of dil. H2SO4 to give cyclic
products.

O
H2SO4 CH2 CH2
3HCHO
O O
CH2
Formoldehyde Metaformaldehyde
O
H2SO4 CH CH CH3
3CH3 CHO CH3
O O
CH
CH3
Acetaldehyde Paraldehyde
(ii) Reaction With Ammonia Derivatives:

Aldehydes and ketones react with ammonia derivatives (H2N  G) to form condensation
product ( C 
 N  G) and water.
The general reaction is as follows.

O OH H
+
+ H
C + H2N G C N G C N G + H2O

Aldehyde Ammonia Amino alcohol Condensation

or ketone derivative (unstable) product

The reaction is known as condensation reaction or addition elimination reaction because water is
lost after the addition occurs.
Examples of the Ammonia Derivatives:
Some important derivatives of ammonia are given below.

(1) Hydroxyl amine H2N  OH
 
(2) Hydrazine H2N  NH2
   
(3) Phenyl hydrazine H2N  NHC6H5 or H2NN H

O
 
||
(4) Semi carbazide H2N  NH  C  NH2
[Ch.12] Aldehydes & Ketones 457 Key to Chemistry [Part-II]
  6 5
(5) 2, 4-Dinitrophenyl hydrazine H2N  NH 1 4 NO2
2 3

NO2
Examples of the Reactions:
The reactions of the above stated ammonia derivatives with aldehydes and ketones are given
below.
(i) Reaction with Hydroxylamine:
Aldehydes and ketones react with hydroxylamine to form oximes in the presence of an acid.
H3C +
H3C
H
C O + H2NOH C N OH + H2O
H H
Ethanal Ethanaloxime
H3C +
H3C
H
C O + H2NOH C N OH + H2O
H3C H3C
Propanone Propanoneoxime
(ii) Reaction with Hydrazine:
Aldehydes and ketones react with hydrazine to form hydrazones in the presence of an acid.

H3C +
H3C
H
C O + H2NNH2 C N NH2 + H2O
H H
Acetaldehyde Acetaldehyde hydrazone

H3C H3C
+
H
C O + H2NNH2 C N NH2 + H2O
H3C H3C
Acetone Acetone hydrazone

(iii) Reaction with Phenyl hydrazine:

Aldehydes and ketones react with phenyl hydrazine to form phenyllydrazones in the presence of
an acid.
H3C +
H3C
H
C O + H2NNHC6H5 C N NHC6H5 + H2O
H H
Ethanal Ethanal phenylhydrazone
Key to Chemistry [Part-II] 458 [Ch.12] Aldehydes & Ketones
H3C +
H3C
H
C O + H2NNHC6H5 C N NHC6H5 + H2O
H3C H3C
Propanone Propanone phenylhydrazone

(iv) Reaction with 2, 4-Dinitrophenyl hydrazine:

Aldehydes and ketones react with 2,4-Dinitrophenyl hydrazine to form 2,4-Dinitrophenyl
hydrazones in the presence of an acid.
H3C H3C
+
H
C O + H2NNH NO2 C N NH NO2 + H2O
H H
NO2 NO2
Acetaldehyde 2, 4-DNPH Acetaldehyde 2, 4-DNPH
H3C H 3C
+
H
C O + H2NNH NO2 C N NH NO2 + H2O
H3C H3C
NO2 NO2
Acetone 2, 4-DNPH Acetone 2, 4-DNPH

The reaction can be used for the identification of aldehydes and ketones because
2,4-Dinitrophenylhydrazones are usually yellow or orange red crystalline solids.

Q# Write the reaction along with mechanism of the ammonia derivatives with carbonyl
compounds.

REACTION WITH AMMONIA DERIVATIVES:


Aldehydes and ketones react with ammonia derivatives (H2N —G) to form condensation

product ( C = N —G) and water.

The general reaction is as follows.

O OH H
+
+ H
C + H2N G C N G C N G + H2O

Aldehyde Ammonia Amino alcohol Condensation

or ketone derivative (unstable) product
The reaction is known as condensation reaction of addition elimination reaction because water is
lost after the addition occurs.
General Mechanism:
Step I:
Step I includes the protonation of oxygen of the carbonyl group.
[Ch.12] Aldehydes & Ketones 459 Key to Chemistry [Part-II]

C  C 
+  
O + H O
+
H

Step II:
In second step, the nucleophilic nitrogen of ammonia attack on the electrophilic positively
charged carbon.
OH N OH H
+
+ H +
C + N G C N G

H H
Step III:
In third step deprotonation takes place.
OH H OH H
+ +
C N G C N G+H

H
Step IV:
The proton (H+) attacks the oxygen of hydroxyl group.
+
OH H HOH H
+
H C N G C N G

Step V:
In the last step the water molecule is removed and a carbon-nitrogen double bond is formed. The
hydrogen of nitrogen is also released which again start the reaction.i. e recover of catalyst.
+OH2 H
+
C N G C N G + H2O + H
Product

(iii)Addition of Alcohols:
Aldehydes combine with alcohols in the presence of HCl gas to form acetals. HCl hydrogen
chloride gas acts as a catalyst.
 Both the alcohol and the HCl gas must be dry.
H3C H3C OC2H5
Dry HCl
C = O + 2C2H5OH C + H2O
H OC2H5H
Acetaldehyde 1, 1-Diethoxyethane (an acetal)
 Ketones donot react under these conditions.
Significance of Reaction:
Key to Chemistry [Part-II] 460 [Ch.12] Aldehydes & Ketones
The reaction may be used to protect the aldehyde group against alkaline oxidizing agents. To
regenerate aldehyde, the acetal is hydrolyzed in the presence of an acid.

Regeneration:
H3C OC2H5 H3C
+
H
C + H2O C = O + 2C2H5OH
H OC2H5 H

REDUCTION REACTIONS

Aldehydes and ketones can both be reduced to alcohols.

 When aldehydes are reduced, we get primary alcohols.
 When ketones are reduced, we obtain secondary alcohols.
Carbonyl compounds can be reduced by two methods.
(i) Reduction with Sodium Borohydride:
Aldehydes and ketones are reduced to alcohols with sodium borohydride NaBH4.
The reaction is carried out by adding sodium borohydride to an aqueous or alcoholic solution of
an aldehyde or ketone.

H H
| NaBH4/H2O
|
HCO  H  CH  OH
Methanal Methanol

H
| NaBH4/H2O
CH3  C 
O  CH3  CH2  OH
Ethanal Ethanol

CH3 CH3
| NaBH4 / H2O
|
CH3  C 
O  CH3  CH  OH
Propanone 2-Propanol
 Sodium borohydride can reduce the carbon-oxygen double bond but not the carbon-carbon
multiple bond.
Mechanism:
Step I:

The tetrahydridoborate (III) ion (BH4), is a source of hydride ion.
NaBH4 Na+ + H + BH3
Step II:
[Ch.12] Aldehydes & Ketones 461 Key to Chemistry [Part-II]
The hydride ion act as a nucleophile and attacks on the electrophilic carbon of the carbonyl
group to give an alkoxide ion.
 
+ 
 
H
+CO HO
C

Step III:
The alkoxide ion is protonated with water to give an alcohol.
    
H C O  OH H C OH 

Alkoxide Ion Alcohol

Note:
NaBH4 is selective in its reactions. It can only reduce carbonyl functional group in a compound.
(ii) Catalytic reduction:
Aldehydes and ketones on reduction with hydrogen in the presence of a metal catalyst like Pd,
Pt or Ni form primary and secondary alcohols respectively.
 Aldehydes on reduction form primary alcohols.
 Ketones on reduction form secondary alcohols.
Hydrogen is added across the carbonyl group.
O
|| Pd Pt or Ni
H  C  H + H2  CH3  OH
Formaldehyde Methyl alcohol
O
|| Pd Pt or Ni
CH3  C  H + H2  CH3  CH2  OH
Acetaldehyde Ethyl alcohol

O OH
|| Pd Pt or Ni
|
CH3  C  CH3 + H2  CH3  CH  CH3
Acetone iso-Propyl alcohol

OXIDATION REACTIONS
(i) Oxidation of Aldehydes:
Aldehydes are easily oxidized by oxidizing agent to carboxylic acids.
Mild Oxidizing Agents:
Tollen’s reagent, Fehling’s solution and Benedict’s solution and dil HNO3.
Strong Oxidizing Agents:
K2Cr2O7 / H2SO4 , KMnO4 / H2SO4 and concentrated. HNO3
Note:
Key to Chemistry [Part-II] 462 [Ch.12] Aldehydes & Ketones
 Aldehydes are easily oxidized by mild as well as strong oxidizing agents to carboxylic
acids.
 The hydrogen atom attached to the carbonyl group in aldehydes is oxidized to OH group.
 The carboxylic acid has the same number of the carbon as present in the parent aldehyde.
Examples:
O O
|| K2Cr2O7/H2SO4
||
CH3  C  H + [O]  CH3  C  OH
Acetaldehyde Acetic Acid
O O
|| K2Cr2O7/H2SO4
||
CH3  CH2  C  H + [O]  CH3  CH2  C  OH
Propionaldehyde Propionic acid
(ii) Oxidation of Ketones:
Ketones are also oxidized to carboxylic acids. The reaction donot take place easily because they
require breaking of strong carbon-carbon bond.
 Ketones are not oxidized by mild oxidizing agents.
 Ketones are only oxidized by strong oxidizing agents such as K2Cr2O7/H2SO4 , KMnO4 /
H2SO4 and Conc. HNO3.
 1 molecule of ketone undergo oxidative cleavage and form 2 moleules of carboxylic acid.
(a) Oxidation of Symmetrical Ketones:
In case of symmetrical ketones only one carbon atom adjacent to the carbonyl group is oxidized
and a mixture of two different carboxylic acids are produced.
O O
|| K2Cr2O7/H2SO4
||
CH3  C  CH3 + 3[O]  CH3  C  OH + HCOOH
Acetone Acetic acid Formic acid
(b) Oxidation of Unsymmetrical Ketones:
However, in case of unsymmetrical ketones, during oxidative cleavage the carbonyl group
remains with smaller carbon chain. This rule is known as Popoff’s rule.
O O O
|| K2Cr2O7/H2SO4
|| ||
CH3  C  CH2  CH3 + 3[O]  CH3  C  OH + CH3  C  OH
Butanone Acetic acid

IDENTIFICATION OF CARBONYL COMPOUNDS

Aldehydes and ketones are detected by following tests.

(1) 2, 4-DNPH Test:
Aldehydes and ketones, both form a yellow or red precipitate with 2,4-Dinitrophenyl hydrazine
solution.
(2) Sodium Bisulphite Test:
[Ch.12] Aldehydes & Ketones 463 Key to Chemistry [Part-II]
Aldehydes and small methyl ketones form a crystalline white precipitate with saturated sodium
bisulphite solution.
(3) Tollen’s Test [Silver Mirror Test]:
Preparation of Tollen’s Reagent:
Tollen’s reagent is prepared by adding NH4OH solution (drop wise) in the aqueous solution of
AgNO3, until the solution become transparent.
Reactions:
AgNO3 + 3NH4OH  [Ag (NH3)2] OH + NH4NO3 + 2H2O
Silver mirror test:
Aldehydes form silver mirror with Tollen’s reagent (Ammonical silver nitrate solution). Add
Tollen’s reagent to an aldehyde solution in a test tube and warm. A silver mirror is formed on the inside
of the test tube.
O O
|| + 
|| +
R  C  H + 2[Ag(NH3)2] + 2OH  R  C  ONH4 + 2Ag + 3NH3 + H2O
Silver Mirror
Synthetic Importance of the Reaction:
High quality mirrors are manufactured by using this principle
(4) Fehling’s Solution Test:
[Fehling’s solution is an alkaline solution containing a cupric tartrate complex ion]
To an aldehyde solution, add Fehling’s solution and boil. A brick red precipitate of cuprous
oxide (Cu2O) is formed.
 Aliphatic aldehydes form brick-red precipitate with Fehling’s solution.
 Aromatic aldehydes and Ketones donot give this test.
O O
|| || +
R  C  H + 2Cu(OH)2 + NaOH  R  C  ONa + Cu2O + 3H2O
Brick red ppt.
NOTE : Fehling solution A is Deep blue aqueous solution of copper sulphate
Fehling solution B is aqueous potassium sodium tartrate.
(5) Benedict’s Solution Test:
[Benedict’s solution is an alkaline solution containing a cupric citrate complex ion]
To an aldehyde solution, add benedict’s solution and boil. A brick red precipitate of cuprous
oxide (Cu2O) is formed.
 Aliphatic aldehydes form brick red ppt. with Benedict’s solution.
 Aromatic aldehydes and Ketones do not give this test.
O O
|| || +
R  C  H + 2Cu(OH)2 + NaOH  R  C  ONa + Cu2O + 3H2O
Brick red ppt.
Key to Chemistry [Part-II] 464 [Ch.12] Aldehydes & Ketones
(6) Sodium Nitroprusside Test: Na2[Fe (CN)5 NO]
Ketones produce a wine red or orange red colour on adding alkaline sodium nitroprusside
solution drop wise.
 Aldehydes do not give this test.

Uses of Formaldehyde: (Rwp 2018)

(i) Manufacture of resins:
It is used in the manufacture of resins like urea-formaldehyde and plastics such as bakelite.
(ii) Manufacture of dyes:
It is used in the manufacture of dyes such as indigo, para-rosaniline, etc.
(iii) Preparation of Formalin:
Its 40% aqueous solution called formalin is used as an antiseptic, disinfectant, a germicide, a
fungicide and for preserving animal specimens and sterilizing surgical instruments.
(iv) In vat dyeing:
It is used as a decolorizing agent in vat dyeing.
(v) In Silvering of Mirrors:
It is used in the silvering of mirrors.
(vi) As Antiseptic:
It is used in making medicine urotropine used as a urinary antiseptic.
(vii) Preparation of Formamint:
It is used in making formamint (formaldehyde + lactose) used as throat lozenges.
(viii) Processing of Vaccine:
It is used in the processing of anti-poliovaccine.
Uses of Acetaldehyde:
(i) Preparation of Chemicals:
It is used in the production of acetic acid, acetic anhydride, n-Butanol, Ethanol,
2-Ethyl-l-hexanol, Vinyl acetate, Paraldehyde, Ethylacetate, etc.
(ii) To make rubber accelerator:
It is used to make acetaldehyde ammonia used as a rubber accelerator.
(iii) To make poisons:
It is used to make chloral hydrate, ethanol trimer and tetramer. Chloral hydrate and ethanol
trimer are both used as hypnotic drugs whereas ethanol tetramer is used as a slug poison.
(iv) As Inhalant:
It is used as an antiseptic inhalant in nasal infections.
(v) In silvering of mirrors:
It is used in silvering of mirrors.
(vi) Preparation of drugs:
It is used to make phenolic resins and synthetic drugs.

SOLVED EXERCISE
Q.1 Fill in the blanks.
(i) Aldehydes are the first oxidation product of _________.
[Ch.12] Aldehydes & Ketones 465 Key to Chemistry [Part-II]
(ii) Ketones are the first oxidation product of _________.
(iii) Aldehydes and ketones undergo _________ addition reactions.
(iv) Formaldehyde react with _________ to give primary alcohol.
(v) Acetaldehyde react with _________ to give 2-butanol.
(vi) Aldehydes are strong _________ agents.
(vii) The oxidation of an _________always a carboxylic acid.
(viii) The reduction of a _________always gives a secondary alcohol.
(ix) Formaldehyde gives _________ test with Tollen’reagent.
(x) Acetaldehyde gives _________ precipitate with Fehling’s solution.
ANSWERS
(i) Primary Alcohols (ii) Secondary Alcohols
(iii) Nucleophilic (iv) Grignard Reagent
(v) Ethyl magnesium bromide (vi) Reducing
(vii) Aldehyde (viii) Ketone
(ix) Silver Mirror (x) Brick red
Q.2 Indicate True or False.
(i) Formaldehyde is used in the silvering of mirrors.
(ii) Ketones combine with alcohols in the presence of HCl gas to form acetals.
(iii) Acetaldehyde undergoes Cannizzaro’s reaction.
(iv) Formaldehyde is used for silvering of mirrors.
(v) Aldol condensation reaction is given by only those aldehydes and ketones which contain -
hydrogen atom.
(vi) Cannizzaro’s reaction is given by only those aldehydes containing no -hydrogen atom.
(vii) Propanal and propanone behave differently with Tollen’s reagent.
(viii) Acetone reacts with sodium bisulphite to give a yellow crystalline product.
(ix) Acetone on reduction gives a primary alcohol.
(x) 40% aqueous solution of formaldehyde is called formalin.
ANSWERS
(i) True (ii) False (iii) False (iv) True (v) True
(vi) True (vii) True (viii) False (ix) False (x) True
Q.3 Multiple Choice Questions, Encircle the correct answer.
(i) The carbon atom of a carbonyl group is.
(a) sp hybridized (b) sp2 hybridized
(c) sp3 hybridized (d) none of these
(ii) Formalin is
(a) 10% solution of formaldehyde in water
(b) 20% solution of formaldehyde in water
(c) 40% solution of formaldehyde in water
Key to Chemistry [Part-II] 466 [Ch.12] Aldehydes & Ketones
(d) 60% solution of formaldehyde in water
(iii) Which of the following will have the highest boiling point?
(a) Methanal (b) Ethanal
(c) Propanal (d) 2-Hexanone
(iv) Ketones are prepared by the oxidation of.
(a) Primary alcohol (b) Secondary alcohol
(c) Tertiary alcohol (d) None of these
(v) Acetone reacts with HCN to form a cyanohydrin. It is an example of.
(a) Electrophilic addition (b) Electrophilic substitution
(c) Nucleophilic addition (d) Nucleophilic substitution
(vi) Which of the following compounds will not give iodoform test on treatment with I 2 /
NaOH?
(a) Acetaldehyde (b) Acetone
(c) Butanone (d) 3-pentanone
(vii) Which of the following compounds will react with Tollen’s reagent.
O O
|| ||
(a) CH3  C  H (b) CH3  C  CH3
O O
|| ||
(c) CH3  C  OH (d) CH3  C  CH2  CH3
(viii) Cannizzaro’s reaction is not given by.
(a) Formaldehyde (b) Acetaldehyde
(c) Benzaldehyde (d) Trimethyl acetaldehyde
(ix) Which of the following reagents will react with both aldehydes and ketones?
(a) Grignard reagent (b) Tollen’s reagent
(c) Fehling’s reagent (d) Benedict’s reagent
ANSWERS
(i) (b) (ii) (c) (iii) (d) (iv) (b) (v) (c)
(vi) (d) (vii) (a) (viii) (b) (ix) (a)
Q.4 Give one laboratory and one industrial method for the preparation of formaldehyde.
Ans: See subjective.
Q.5 How does formaldehyde react with the following reagents?
(a) CH3MgI (b) HCN
(c) NaHSO3 (d) Conc. NaOH
(e) NaBH4,/H2O (f) Tollen’s reagent.
(g) Fehling’s reagent.
Ans: Reaction of Formaldehyde:
[Ch.12] Aldehydes & Ketones 467 Key to Chemistry [Part-II]
(a) With CH3MgI:
H OH
+ +
H
     + H3O
+
ether
C = O + CH3 Mg I CH3 C OMgI CH3 CH2 OH + Mg
H H Ethanol I
(b) With HCN:
H OH
H
+
    NaCN/HCl
H CN +C=O C
H H CN
Formaldehyde Cyanohydrin
(c) With NaHSO3:
HO
H
H
C=O+Na
H S
O3
C
+
H HS ON
3 a
B
is
ulph
it
e a
ddi
tionPr
oduct
(d)With conc. NaOH: (Cannizzaro’s reaction)
H O
+
2 C = O + NaOH CH3 OH + H C ONa
Methanol Sod. Formate
H (Reduced Product)

(e) With NaBH4 / H2O: (Reduction)

O H
N
aB
H4
HCH HO
2 HCOHor H3C  OH
H
Form al
d ehy de M eth a
nol
(f) With Tollen’s reagent: (Silver mirror test)
AgNO3 + 3NH4OH — [Ag (NH3)2] OH + NH4NO3 + 2H2O
+
HCHO + 2[Ag(NH3)2]OH  HCOONH4 + 2Ag + 3NH3 + H2O
Methanal Silver Mirror
(g) With Fehling’s reagent:
+
HCHO + 2Cu (OH)2 + NaOH  HCOONa + Cu2O + 3H2O
Brick red ppt
Q.6 Give one laboratory and one industrial method for the preparation of acetaldehyde.
Ans: See subjective.
Q.7. How does acetaldehyde react with the following reagents?
(a) C2H5MgI (b) HCN
(c) NaHSO3 (d) dilute NaOH
(e) I2/NaOH (f) NaBH4/H2O
Key to Chemistry [Part-II] 468 [Ch.12] Aldehydes & Ketones
(g) NH2OH (h) K2Cr2O7/H2SO4
Ans: Reaction of Acetaldehyde:
(a) With C2H5MgI:

CH 3 CH3 CH3 OH
+
- + - + -
CH3 CH2 Mg I + C = O Ether + H3O CH3 CH2 CH OH + Mg
CH3 CH2 C O MgI
2-Butanol
H H I
(b) With HCN:
CH 3 CH 3 OH
- + -
H C N+ C = O NaCN/HCl C

H H CN
Acetaldehyde Cyanohydrin
(c) With NaHSO3:
CH3 CH 3 OH
+ -
C=O+ NaHSO3 C
+
H H SO3Na
Sodium bisulphite addition product
(d)With dilute NaOH: ( Aldol condensation)
O O OH O

CH3 C + H CH2 C CH3 CH CH2 C H
3-Hydroxybutanal
H H
(e) With I2/NaOH: (Iodoform reaction)
O
CH3 C H + 3l2 + NaOH CHl3 + HCOO Na + 3Nal + 3H2O
Iodoform Sod.formate
(f) With NaBH4/H2O: (reduction)
O
||
NaBH4/H2O
CH3  C  H  CH3  CH2  OH
Ethanal Ethanol
(g) With NH2OH: (Hydroxylamine)
O
+

CH3 C H + NH2OH H CH3 CH = N OH + H2O

Ethanal oxime
(h) With K2Cr2O7 / H2SO4: (Oxidation)
O O
CH3 C H + [O] K2Cr2O7/H2SO4 CH3 C OH
Acetaldehydes Acetic acid
Q.8. Describe briefly the mechanism of nucleophilic addition to a carbonyl compound.
Ans: See subjective part.
[Ch.12] Aldehydes & Ketones 469 Key to Chemistry [Part-II]
Q.9. Explain with mechanism the addition of ethylmagnesium bromide to acetaldehyde. What
is the importance of this reaction.
Ans: The reaction of ethylmagnesium bromide with acetaldehyde is an example of Nucleophilic
addition reaction.
Mechanism;

H3C CH3
—   + OH

— —
  Ether + H3O
C—O

—
H3C - CH2 — C — OMgBr CH3- CH2 — CH — CH3 + Mg
— —
H3C - CH2 - MgBr +

—
—
H H OH Br

(2-Butanol)
Importance of Reaction:
The reaction is useful for the preparation of secondary alcohols from aldehydes.
Q.10. Explain with mechanism the addition of sodium bisulphite to acetone. What is the utility of
this reaction?
Ans: Addition of sodium bisulphite to acetone;
Acetone reacts with a saturated aqueous solution of sodium bisulphite to form a crystalline
white precipitate of sodium bisulphite adduct.
H3C H3C OH
C
 O + NaHSO3 C
H3C H3C SO3Na
Bisulphite addition product
Mechanism:
Step-I: Generation of Nucleophile;
Sodium bisulphite ionizes to form sulphite ions. (Nucleophile)
++
N
a
H
S
O
3 S
O
2

Step-II: Attack of Nucleophile:

The sulphite ion acts as a nucleophile and attacks the electrophilic end of acetone.

H3C—   H3C— O
—

C—
—O + SO2- ONa C
—

— H3C — SO2ONa
H3C
Step-III: Gain of Proton:
The alkoxide ion, gain a H+ ion to from bisulphite addition product

H3C— O H3C— OH
—
—

C + H+ C
—
—

— SO2ONa H3C — SO2ONa

H3C

Utility of Reaction:
Key to Chemistry [Part-II] 470 [Ch.12] Aldehydes & Ketones
(1) The reaction is used to distinguish between methyl ketones(2-Alkanones) and non-methyl
ketones.
(2) The reaction is used for the separation and purification of carbonyl compounds from non-
carbonyl compounds.
Q.11 Describe with mechanism aldol condensation reaction. Why formaldehyde does not give
this reaction?
Ans: See subjective part.
Why Formaldehyde does not give this reaction?
Aldol condensation is given by only those aldehydes and ketones which possess -hydrogen. As
O
—

Formaldehyde (H— C— H )have no -hydrogen so it does not give this reaction.

Q.12 What type of aldelydes give cannizaro’s reaction? Give its mechanism.
Ans: See subjective part.
Q13. Explain the mechanism of the reaction of phenylhydrazine with acetone?
Ans: Reaction of phenylhydrazine with acetone;
Acetone reacts with phenylhydrazine in the presence of an acid to form acetone phenyl
hydrazone. This reaction is known as condensation reaction or addition-elimination reaction
because H2O is often lost after addition occurs. The reaction is acid-catalysed.
CH3 CH3
+
C = O + H2N NHC6H5 H C = N NHC6H5+ H2O
Acetone
CH3 Propanone CH3
Propanone Phenyl hydrazone

Mechanism:
Step 1: Protonation of oxygen of the carbonyl group occurs in first setp.
H
C
3 C
H3

+ 

C O+H C
=O
H
H
C
3 C
H3

Step: 2
In the 2nd step, nucleophilic attack of nitrogen of ammonia derivative occurs on the
electropositive carbon.
CH3 H OH H
+

C OH N NHC6H5 CH3 C N NHC6H5

CH3 H CH3 H
Adduct

Step: 3
Now deprotonation of the adduct occurs.
[Ch.12] Aldehydes & Ketones 471 Key to Chemistry [Part-II]
OH H OH H
+
CH3 C N NHC6H5 CH3 C N NHC6H5+ H
CH3 H CH3
Step: 4
 In the fourth step, protonation of oxygen of hydroxyl group occurs.
+
OH H OH2 H
+
H CH3 C N NHC6H5 CH3 C N NHC6 H5
CH3 N H2O CH3
Step: 5
 Removal of water and recovery of catalyst occur.
+
OH2 H CH3
CH3 C N NHC6H5 C = N NHC6H5 + H2O + H+
CH3 CH3
Propanone phenylhydrazone

Q.14 Using ethyne as a starting material how would you get acetaldehyde, acetone and ethyl
alcohol.
Ans: Conversions:
(i) Ethyne into Acelatedehde:
OH O
H2SO4 Tantomerism
HC CH + H2O CH2 = CH CH3 C H
H2SO4
Acetaldehyde
(ii) Ethyne into Acetone:
O
HgSO4
i) HC CH + H2O CH2 = CH2 OH H3C C H
H2SO4
Vinyl alcohol Ethanal

OH OH
O
Ether
ii) CH3 C H + CH3MgBr + CH3 CH + Mg
H3O
CH3 Br
2-Propanol

CH3 O
K2Cr2O7
iii) CH3 CH OH + [O] CH3 C CH3 + H2O
H2SO4
Acetone
Key to Chemistry [Part-II] 472 [Ch.12] Aldehydes & Ketones
(ii) Ethyne into ethyl alcohol:
O
||
HgSO
HC  CH + H2O  H2C = CH  OH H3C  C  H
4

H2SO4
Vinyl alcohol ethanal
O
||
Pd PtNi
H3C  C  H + H2  H3C  CH2  OH
Ethanol
Q.15 Give the mechanism of addition of HCN to acetone.
Ans: Addition of HCN to acetone;
Acetone reacts with Hydrogen cyanide to give a addition product called Acetone Cyanohydrin.
H H3C OH
   NaCH/HCl
C O + H CN C
H H3C CN
Acetone cyanohydrin
Mechanism:
The reaction of Acetone with HCN is base catalysed. It involves following steps
Step-I: (Attack of Nucleophile)
The nucleophile attacks the electrophilic carbon of acetone.
H3C 
H3C 
O
 
C O + CN C
H3C H3C CN
alkoxide ion
Step-II: (Gain of Proton)
The alkoxide ion abstracts the proton from HCN. Cyanide ion regenerate which will react
another molecule of acetone and initiate other reaction.
 H3C
H3C O OH
  
C + H OH C + OH
H3C CN H3C CN
Q.16. How would you bring about the following conversion?
Q.16. (a) Acetone  t-butyl alcohol:
Ans:
[Ch.12] Aldehydes & Ketones 473 Key to Chemistry [Part-II]
CH3 CH3 OH
CH3
+
CH3 Mg Br + C = O Ether CH3 C O Mg+ Br H3O CH3 C OH + Mg

CH3 CH3 CH3 Br

Acetone 2 - Methyl - 2 - Propanol
(t - butylalcohol)
Q.16. (b) Propanal into 1-Propanol:
Ans:
O
||
Pd PtNi
CH3  CH2  C  H + H2  CH3  CH2  CH2  OH

Propanal 1 – Propanol

Q.16. (c) Propanone into 2-Propanol:

Ans:
O OH
|| 
Pd PtNi
CH3  C  CH3 + H2  CH3  CH  CH3

Propanone 2- Propanol
Q.16. (d) Methanal into Ethanal:
Ans:
H OH
+
 +  +  + H3O
i) Ether
CH3MgBr + C = O CH3 CH2 O Mg Br CH3 CH2 OH + Mg
H Ethanol Br
O
||
K2Cr2O7
ii) CH3  CH2  OH + [O]  H3C  C  H + H2O
H2SO4
Ethanal
Q.16. (e) Ethene into Ethanal:
Ans:
O
||
PdCl2 + CuCl2
2CH2 = CH2 + O2  2CH3  C  H
H2 O
Ethene Ethanal
Q.16. (f) Ethanal into Propanone:
Ans:
Key to Chemistry [Part-II] 474 [Ch.12] Aldehydes & Ketones
CH3 CH3 CH3 OH
 +  +  Ether +
CH3 Mg Br + C = O + H3O
CH3 CH O Mg Br CH3 CH OH + Mg

H Br
2 - Propanol
O
K2Cr2O7
CH3 CH OH + [O] CH3 C CH3 + H2O
H2SO4
Acetone
CH3 (Propanone)
Q.16. (g) Ethanal into 2-Propanol:
Ans:
CH3 CH3 CH3 OH
 +  +  Ether +
CH3 Mg Br + C = O + H3O
CH3 CH O Mg Br CH3 CH OH + Mg

H Br
2 - Propanol
Q.16. (h) Methanol into Ethanal:
Ans:
O
||
Pt asbestos
(i) CH3  OH + [O]  H  C  H + H2O
300C
Methanal
H OH
-  - + - +
+
Ether + H3O CH3 CH2 OH + Mg
CH3Mg Br + C=O CH3 CH2 O MgBr
Ethanol
(ii) H Br

O
||
K2Cr2O7
(iii) CH3 CH2 OH + [O]  CH3  C  H + H2O
H2SO4

Ethanol Ethanal
Q.16. (i) Ethyne into Ethanal:
Ans:
O
HgSO4
HC CH + H2O H2SO4
H2C = CH OH H3C C H
Vinyl alcohol Ethanal

Q.16. (j) Ethanal into Ethanol:

Ans:
[Ch.12] Aldehydes & Ketones 475 Key to Chemistry [Part-II]
O
||
Ni or Pt
CH3  C  H + H2  CH3  CH2  OH

Ethanol

Q.16. (k) Ethanol into 2-Butanone:

Ans:
O
K2Cr2O7
i) CH3 CH2 OH + [O] H3C C H
H2SO4
Acetaldehyde
CH 3 CH3
 +  + -
Ether +
CH 3 CH 2 Mg Br + C=O CH 3 CH2 CH O MgBr
H
(ii) H3O
+
CH3 OH
CH 3 CH 2 CH OH + Mg
2-Butanol
Br
OH O
 K2Cr2O7/H2SO4
||
(iii) CH3  CH2 CH  CH3 + [O]  CH3  CH2CCH3+H2O
2 - Butanone
Q.16. (l) Ethanol into Ethanoic acid:
Ans:
O
||
K2Cr2O7
(i) CH3  CH2  OH + [O]  CH3  C  H
H2SO4

Ethanol Acetaldehyde
O O
|| ||
K2Cr2O7
CH3  C  H + [O]  CH3  C  OH
H2SO4
Ethanal Ethanoic acid (Acetic acid)
Q.17. How will you distinguish between?
(i) Ethanal and Methanal:
Ans: Ethanal and Methanal can be distinguished from each other by “Iodoform test”.

Ethanal Methanal
Key to Chemistry [Part-II] 476 [Ch.12] Aldehydes & Ketones
1 Ethanal gives iodoform on reacting with 1 Methanal does not give iodoform test.
iodine in the presence of NaOH. Formation
of yellow ppt of CHl3 indicates that
aldehyde is ethanal.
O O
|| ||
H3CCH +3I2 + 4NaOH  CHI3+ 3H2O H  C H + I2 + NaOH  No reaction
HCOONa+3NaI

Q.17. (ii) Ethanal and Propanone:

Ans: Ethanal and Propanone can be distinguished by their reaction with mild oxidizing agents like
Tollen’s reagent or Fehling’s solution or Benedict’s solution.
Ethanal Propanone

1 Ethanal reacts with Tollen’s reagent and a 1 Propanone gives no reaction with Tollen’s
“Silver mirror” is produced. reagent.
O
||
CH3 CHO + 2[Ag(NH3)2]OH 
CH3CCH3 + [Ag(NH3)2]OH
CH3COONH4+3NH3+2Ag+H2O

No reaction
2 Ethanal gives brick red precipitates of Propanone does not give this reaction
cuprous oxide on reaction with Fehling’s 2 O
reagent. ||
CH3CHO + 2Cu(OH)2 + NaOH CH3CCH3 + Cu(OH)2 + NaOH
CH3COONa + Cu2O+3H2O 
brick red ppt No reaction

Reaction with sodium nitroprusside:

3 Ethanal give no reaction with 3 Propanone produces a wine red or orange
sod .Nitroprusside red colour on reaction with Na-
nitroprusside.
Q.17. (iii) Ethanal and Propanal:
Ans: Ethanal and Propanal can be distinguished by Iodoform test.
Ethanal Propanal
Ethanal gives iodoform test on Propanal gives no reaction with I2 and
1 treatment with I2 in the presence of 1 NaOH.
NaOH. Formation of yellow ppt. O
indicates the presence of Ethanal. ||
O CH3CH2CH+I2 + NaOH
|| 
CH3C–H +3I2+4NaOH No reaction

CHl3 + HCOONa+ + 3NaI+3H2O
Q.17. (iv) Acetone and Ethanol:
[Ch.12] Aldehydes & Ketones 477 Key to Chemistry [Part-II]
Ans: Acetone and Ethanol can be distinguished by their reaction with 2,4-DNPH solution.
Acetone Ethanol
Being a ketone, acetone gives a yellow or orange or Ethanol gives no reaction with 2,4 –DNPH.
red crystalline solids of 2, 4-Dinitrophenylhydrozone
on reaction with 2,4-DNPH. Noa
ct
i
on
NO
2
N
O
2
+ NO2
C = O + N2NNH H C = N NH
H2O
NO2 NO2
NO2
Acetone Acetone 2, 4-DNPH
Acetone reacts with NaHSO3 to form a white Ethanol gives no reaction with
crystalline solid of sodium bisulphite adduct. NaHSO3.
C H 3 C H 3 O H
C 
 O + N aH SO3 C CH3CH2OH + NaHSO3 No reaction
+
C H 3 C H 3
S O
N
3a

Q.17. (v) Butanone and 3-Pentanone:

Ans: Butanone and 3-Pentone can be distinguished by means of iodoform test.
Butanone 3-Pentanone

1 Being a methyl Ketone, butanone gives 1 3-Pentanone does not give reaction
yellow ppt. of CHl3 on reacting with NaOH with iodine/NaOH.
and iodine. O
O N
o
a
c
ti
o
n
C
H3C
H2CCH
+
3 3
l
2+4
Na
OH

C
H3C
H2C
OON
a+
CHl
3+3
Na
I+3
HO2

Q.17. (vi) Acetaldehyde and Benzaldehyde:

Ans: Acetaldehyde (aliphatic) and benzaldehyde (aromatic) can be distinguished by reacting them
with Fehling;s reagent.
Acetaldehyde Benzaldehyde
1 Acetaldehyde gives brick red ppt. of Cu2O 1 Benzaldehyde does not give this reaction.
on reaction with Fehling’s re-agent. C6H5CHO+Cu(OH)2+NaOHNo reaction
H3CCHO+2Cu(OH)2+NaOH 
+
H3CCOONa + Cu2O + 3H2O
Q.17 (vii) 2-Pentanone and 3-Pentanone:
Ans: 2-Pentanone and 3-Pentanone can be distinguished by iodoform test.
2-Pentanone 3-Pentanone
1 2- Pentanone being a methyl ketone gives 1 3-Pentanone does not give this reaction.
iodoform test and yellow ppt of CHl3 are O
formed. H
C
3 C
H2CC
H2C
H+
3 l
2+N
a
OH

N
or
eac
t
ion
Key to Chemistry [Part-II] 478 [Ch.12] Aldehydes & Ketones
O
H3C C CH2 CH2 CH3 + 3l2+ 4NaOH

CHl3+ CH3 CH2 CH2 COO Na + 3Nal + 3H2O

Q.18 Discuss oxidation of (a) aldehydes (b) ketones with;

(i) K2Cr2O7/H2SO4
(ii) Tollen’s reagent
(iii) Fehling’s solution
Ans: (a) Oxidation of Aldehydes:
(i) K2Cr2O7 / H2SO4:
Aldehydes are oxidized to carboxylic acids by strong oxidizing agents such as K2Cr2O7 / H2SO4.
In the process the hydrogen atom attached to the carbonyl group in aldehydes is oxidized to –OH group
Examples;
O O
—
—

—
K2Cr2O7 / H2SO4
H3C — C — H + [O] CH3—C —OH
Acetaldehyde Acetic acid
O O
—
—

—
—
K2Cr2O7 / H2SO4
CH3— CH2— C — H +[O] CH3— CH2 C — OH
Propionaldehyde Propionic acid
(ii) Tollen’s Reagent:
Tollen’s reagent (Ammonical solution of AgNO3)is a mild oxidizing agent.
Aldehydes are oxidized by Tollen’s reagent to corresponding carboxylic acids (in the salt form).
Example:
AgNO3 + 2NH4OH —— [Ag (NH3)2] OH + NH4NO3 + 2H2O
O O
—
—
—
—

R — C — H + 2 [Ag (NH)3]2OH R— C —ONH4+2Ag + 3NH3 + H2O

(iii) Fehling’s Solution:
Fehling Solution is an alkaline solution containing a cupric tartrate complex ion.
Aldehydes are oxidized by Fehling’s solution to corresponding carboxylic acids (in the salt
form).
Example;
O O
—
—

—
—

R — C — H + 2 Cu(OH)2 + NaOH R— C —ONa + Cu2O + 3H2O

(b) Oxidation of Ketones:
(i) K2Cr2O7 / H2SO4:
[Ch.12] Aldehydes & Ketones 479 Key to Chemistry [Part-II]
Ketones do not undergo oxidation easily because they require breaking of strong carbon –
carbon bond so ketones are only oxidized by strong oxidizing agents such as K2Cr2O7 / H2SO4, KMnO4
/ H2SO4 and conc. HNO3.
 In oxidation of Ketones, only the carbon atoms adjacent to the carbonyl group are oxidize.
 Oxidative cleavage of 1 molecule of ketone occur which results in formation of 2 molecules of
carboxylic acids.
Symmetrical Ketones:
In case of symmetrical ketones any one carbon atom (aliye) group adjacent to the carbonyl
group is oxidize and a mixture of two carboxylic acids is always obtained.
O O O
—
—

—
—

—
—
K2Cr2O7/ H2SO4
CH3— C — CH3 + 3[O] CH3—C —OH + H — C — OH
Acetone Acetic acid Formic acid
Unsymmetrical ketones:
During oxidation of unsymmetrical ketone, the cleavage of C-CO bond is such a way that keto
group always stays with the smaller alkyl group.
O O O
—
—

—
—

—
—
K2Cr2O7/ H2SO4
CH3— C — CH2— CH3 + 3[O] CH3—C OH + CH3 — C — OH
Butanone acetic acid
(ii) Tollen’s reagent:
Oxidation of ketones require the breaking of strong carbon – carbon bond. Hence, they are not
oxidized by mild oxidizing agents like Tollen’s reagent.
(iii) Fehling’s Solution:
Fehling’s solution (alhalic solution contain a cupric tartrate complex ion) is a mild oxidizing agent.
Ketones are not oxidized by mild oxidizing agents like Fehling’s solution.
Q.19 Discuss reduction of (a) aldehydes (b) ketones with
(i) NaBH4 / H2O (ii) H2 / Pd
Ans: (a) Reduction of Aldehydes:
Aldehydes are reduced to primary alcohols on reaction with reducing agents.
 The carbonyl group is reduced to an alcoholic group.
(i) NaBH4 / H2O:
Aldehyde are reduced to primary alcohols with sodium borohydride (NaBH4).
The reaction is carried out by adding sodium borohydride to an aqueous or alcoholic solution of
an aldehyde.
O
—

N aBH /H O
H — C — H 4 2
H 3C — O H
M
e
t
han
a
l M
e
t
han
o
l
Key to Chemistry [Part-II] 480 [Ch.12] Aldehydes & Ketones
O

—
—
NaBH4/ HO2
CH3— C — H CH3— CH2— OH
Ethanal Ethanol
(ii) H2 / Pd:
Aldehydes can also be reduced to primary alcohols with hydrogen in the presence of a metal
catalyst like Pd, Pt or Ni.
 Hydrogen is added across the carbonyl group.
O
—
—

H—C—H + H2 Pd, Pt, Ni CH3— OH

Methanal Methanol
O
—
—

CH3— C — H + H2 Pd, Pt, Ni CH3— CH2 — OH

ethanal ethanol
(b) Reduction of Ketones:
One reduction, ketones produce secondary alcohols.
(i) NaBH4 / H2O:
Ketones are reduced to secondary alcohols with sodium borohydride, NaBH4.
The reaction is carried out by adding sodium borohydride to an aqueous or alcoholic solution of
a ketone.
O OH
—
—

CH — C — CH NaBH4/ H2O —
3 3
3 3

Propanone 2-Propanol
(ii) H2 / Pd:
Ketones can also be reduced to secondary alcohols with hydrogen in the presence of a metal catalyst
like Pd, Pt or Ni.
 Hydrogen is added across the carbonyl group.
O OH
—
—

CH3— C — CH 3 + H2 Pd, Pt, Ni

3 3

Propanone 2-Propanol
Q.20 Give three uses for each of formaldehyde and acetaldehyde.
Ans: See subjective.

SHORT ANSWER QUESTIONS

Q.1: What are carbonyl compounds. Discuss its types.
Ans: Carbonyl compounds:
“Organic compounds containing the carbonyl functional group C = O are called as
carbonyl compounds”.
In a carbonyl group, a carbon atom is bonded to oxygen with double bond.
[Ch.12] Aldehydes & Ketones 481 Key to Chemistry [Part-II]
O

C C
a
rb
o
ny
lg
ro
u
p
Carbonyl compounds are of two types.
(i) Aldehydes:
In Aldehydes, the carbonyl group is bonded to at least one hydrogen atom, and, so it
occurs at the end of chain. e.g.
O
||
RCH
R = may be H, or an alkyl group.
(ii) Ketones:
In ketones, the carbonyl group is bonded to two carbon atoms, and so it occurs within a chain
e.g.
O
||
RC R
Where R =alkyl or an aryl group.
Q.2: Discuss the occurrence of carbonyl compounds.
Ans: Occurrence of carbonyl compounds;
Aldehydes and ketones are present in many naturally occurring compounds. The aldehyde
group is present in most sugars. They are the principal constituents of a number of essential oils used
as fragrances and flavours.
Ketonic group is present in camphor and menthone.
Q.3: How Acetalahyde is prepared by dry distillation of salts.
Ans: Acetalahyde can be prepared by the dry distillation of a mixture of calcium salts of formic acid
and acetic acid.
o o
H C O CH3 C O o
o Ca + o Ca 2CH3 C H + 2CaCO3
H C O CH 3 C O
Calcium formate Calcium Acetate Acetaldehyde
Q.4: How acetaldehyde can be prepared on industrial scale.
Ans: Acetaldehyde is prepared industrially by air oxidation of ethylene using palladium chloride
catalyst with a cupric chloride promoter.
o
P
d
Cl + CuCl
2 C H 2= C H 2+O 2
2 2
2CH 3 C H
H
O
2

Q.5: Discuss the reactivity of a carbonyl group.

Ans: Reactivity of a carbonyl group:
The carbonyl group has a sigma bond and a -bond(sp2 hybridized) Thus it can under go
addition reactions. Most reagent react with the carbonyl group by adding to it. As oxygen is more
electronegative, it tends to attract the - electrons towards itself. This attraction makes the carbonyl
group a polar group.
Key to Chemistry [Part-II] 482 [Ch.12] Aldehydes & Ketones
The oxygen atom has a partial negative charge on it and is nucleophilic, where as the carbon
atom has a partial positive charge and is electrophilic.
S
+ S
C O

Electrop hilic N ucle

oph
ilc
Q.6: How acetaldehyde is converted into lactic acid? (OR)
How -hydroxy acids are prepared from Acetaldehyde.
Ans: i) Reaction of ethanal with HCN;
Hydrogen cyanide adds to aldehydes and Ketones to from cyanohydrins.
CH3 CH3 OH
C = O + HCN NaCN/HCl C
H H CN
Acetaldehyde cyanohydrin
ii) hydrolysis of Acetaldehyde Cyanohydrine:
The cyano group,  C  N is then hydrolysed by an aqueous solution of an acid to form a
-hydroxy carboxylic acid.
OH OH
CH3 C CN + 2H2O + H2SO4 CH3 C COOH + NH4HSO4
H H
Lactic acid
Q.7: What is Aldol condensation reaction?
Ans: Aldol condensation;
“The reactions in which two molecules of the same or different compounds combine to
form a new compound with or without the elimination of small molecule like H2O or NH3 are called
condensation reactions”.
Aldehyde and Ketones possessing  - hydrogen atoms react in the presence of cold dilute
solution of an alkali to form addition products known as aldols.
O O OH O
+  dil NaOH
CH3 C + H CH2 C H CH3 CH CH2 C H
H (An aldol)
 The name aldol is given to the product because it contains both aldehyde and alcohol functional
groups.
Q.8: Why formaldehyde does not give aldol condensation reaction.
Ans: Aldehydes and Ketones possessing -hydrogen atoms react with a cold dilute solution of an
alkali to form addition products known as aldols. This reaction is called as aldol condensation.
O


H CH 2CH(
Et
han
al
)
 The formula of formaldehyde is
O

HC H (Eth a
n al)
As formaldehyde have no--Hydrogen, so it does not given aldol condensation reaction.
[Ch.12] Aldehydes & Ketones 483 Key to Chemistry [Part-II]
Q.9: What is Cannizzaro’s Reaction:
Ans: Cannizzaro’s Reaction:
Aldehydes that have no -hydrogen atoms when react with 50% aqueous solution of NaOH,
they undergo a self oxidation-reduction reaction. In which one molecule of aldehyde is reduced to an
alcohol and other molecules is oxidized into an acid in salt form. This reaction is called as Cannizzaro’s
reaction.
Example;
O O
2H C H + NaOH CH3 OH + H C ONa
Formaldehyde Methyl alcohol Sod. Formate
Q.10: What are Haloform reactions? Give its synthetic importance.
Ans: Haloform Reaction:
Acetaldehyde and methyl ketones react with halogen in the presence of sodium hydroxide to
give haloform and sodium salt of a carboxylic acid. This reaction is called as haloform reaction.
O
||
R  C  CH3 + 3X2 + 4NaOH  CHX3 + RCOONa + 3NaX + 3H2O
Synthetic Importance:
From a synthetic point of view, the Haloform reaction affords a convenient method for
converting a methyl ketone to a carboxylic acid containing one carbon atom less than the parent
compound.
Q.11: How can we distinguish between Butanone and 3-Pentanone.
Ans: Butanone and 3-Pentanone can be distinguished from each other by iodoform test.
Butanone 3-Pentanone

Butanone is a methyl ketone, hence it reacts with 3-Pentanone have two ethyl groups attached with
iodine in presence of NaOH to give yellow crystals the carbonyl carbon. So it does not react with I2
of iodoform. in presence of NaOH.

O O
|| ||
CH3  CH2  C  CH3+3I2 + 4NaOH  CH3  CH2  C  CH2CH3 + I2 + NaOH

CHI3 + CH3CH2COONa + 3NaI + 3H2O  No reaction

Q.12: How can we prepare metaformaldehyde from formaldehyde.

Ans: Formaldehyde, polymerizes in the presence of dil. H2SO4 to give metaformaldehyde.
O O
H2SO4 H2C CH2
3 H C H
O O
CH2
(Meta formaldehyde)
Q.13: How can we prepare paraldehyde from acetaldehyde.
Ans: Acetaldehyde, polymerizes in the presence of dil H2SO4 to give paraldehyde.
Key to Chemistry [Part-II] 484 [Ch.12] Aldehydes & Ketones

H2SO4
3CH3 CHO

Paraldehyde
Q.14: What are ammonia derivatives? How they react with carbonyl compounds?
Ans: When one hydrogen of NH3 is replaced by an atom or group of atoms, the products formed are
called as derivative of ammonia e.g, (H2N  G)
For example:

H2N  OH Hydroxylamine

H2N  NH2 Hydrazine
 compounds
Ammonia derivative (H2 N  G) react with aldehydes and ketones to form
containing the group, C
=NG
an
dwa
t
er.

General Reaction:

O + OH H
 H
:

C + H2N G C N G C= N G + H2O
Aldehyde Ammonia Amino Condensation
or Ketone Derivative Amino alcohol
(unstable) Product
Q.15: How the aldehydic group can be prevented against oxidizing agents.
Or; How acetaldehyde reacts with ethyl alcohol?
Ans: The aldehydic group can be protected against alkaline oxidizing agents by the formation of
acetals.
The aldehyde combines with alcohol in the presence of hydrogen chloride gas to form acetals.
The reaction is given as
H3C CH3 OC H
Dry HCl 2 5
C = O + 2C2H5OH C + H2O
H H OC2H5

1, 1-Diethoxyethane (an acetal)

Regeneration:
The reaction may be used to protect the aldehyde group against alkaline oxidizing agents. To regenerate
aldehyde, the acetal is hydrolyzed in the presence of an acid.

Regeneration:
H3C OC2H5 H3C
+
H
C + H2O C = O + 2C2H5OH
H OC2H5 H
[Ch.12] Aldehydes & Ketones 485 Key to Chemistry [Part-II]

Q.16: Why Ketones are not oxidized by weak oxidizing agents.

Ans: Oxidation of ketones;
Ketones do not undergo oxidation easily because they require breaking of strong carbon 
carbon bond. Hence they give no reaction with mild oxidizing agents.
O
||
Mild oxidizing agent
RCR  No reaction
They are only oxidized by strong oxidizing agents such as K2Cr2O7/H2SO4, KMnO4 / H2SO4 and
Conc. HNO3.
O O O
|| || ||
K2Cr2O7 / H2SO4
CH3  C  CH3 + 3[O]  CH3  C  OH + H  C  OH
Ethanoic acid Methanoic acid
Q.17: Discuss the chemistry of Tollen’s test.
Ans: Chemistry of Tollen’s test;
Aldehydes form silver mirror with Tollen’s reagent (Ammonical silver nitrate solution)
AgNO3 + 3NH4OH  [Ag(NH3)2] OH + NH4NO3 + 2H2O
To perform Tollen’s test, add Tollen’s reagent to an aldehyde solution in a test tube and warm.
A silver mirror is formed on the inside of the test tube.
O
||
+
R  C  H +2 [Ag(NH3)2] OH —— RCOONH4 + 2Ag + 3NH3 + H2O
Q.18: How aldehydes can be distinguished by Fehling’s solution test.
Ans: Fehling’s solution test;
Aliphatic Aldehydes form a brick-red ppt with Fehling’s solution (an alkaline solution
containing cupric tartrate complex).
To an Aldehyde solution, add Fehling’s solution and boil. A brick red precipitate of cuprous
oxide is formed. Aromatic aldehydes donot give this test.
O
||
R  C  H + 2Cu(OH)2 + NaOH  RCOONa + Cu2O + 3H2O
Brick red ppt.
Q.19: How Aldehydes can be distinguished by Benedict’s solution test?
Ans: Benedict’s solution test;
Aliphatic Aldehydes form a brick-red ppt with Benedict’s solution (an alkaline solution
containing cupric citrate complex).
To an Aldehyde, add Benedict’s solution and boil. A brick red precipitate of cuprous oxide is
formed. Aromatic aldehydes do not give this test.
Key to Chemistry [Part-II] 486 [Ch.12] Aldehydes & Ketones
O
||
R  C  H + 2Cu(OH)2 + NaOH  RCOONa + Cu2O + 3H2O
Brick Red ppt.
Q.20: What are Oximes and how they are produced.
Ans: Oximes;
Organic compounds containing >C = N – OH group are called as oximes.
Oximes can be prepared by the reaction of aldehydes and ketones with hydroxyl amine in the
presence of a mineral acid.
Examples:
H3C H + H3C
C O + H2N OH C N OH + H2O
H H
Ethanal oxime
+
H3C H H3C
C O + 2H N OH C N OH + H2O
H3C H3C
Propanone oxime
Q.21: How ketones are produced from secondary alcohols?
Ans: Preparation of ketones;
Oxidation of secondary alcohols in the presence of a strong oxidizing agent like acidified
potassium dichrmate produce ketones.
CH3 CH3
K2Cr2O7
CH OH + [O] H2SO4
C = O + H2O

CH3 CH3
2-Propanol Propanone (acetone)

Q.22: Give four important uses of formaldehyde. (Rwp 2018)

Ans: Uses of formaldehyde;
(i) Manufacture of resins:
It is used in the manufacture of resins like urea-formaldehyde and plastics such as bakelite.
(ii) Manufacture of dyes:
It is used in the manufacture of dyes such as indigo, para-rosaniline, etc.
(iii) Preparation of Formalin:
Its 40% aqueous solution called formalin is used as an antiseptic, disinfectant, a germicide, a
fungicide and for preserving animal specimens and sterilizing surgical instruments.
(iv) In vat dyeing:
[Ch.12] Aldehydes & Ketones 487 Key to Chemistry [Part-II]
It is used as a decolorizing agent in vat dyeing.
(v) In Silvering of Mirrors:
It is used in the silvering of mirrors.
Q.23: How can be we prepare acetone from acetic acid?
Ans: Acetic acid to Acetone:
2CH3COOH + 2Ca (OH)2 (CH3COO)2Ca + 2H2O
Calcium acetate
C
HCO
O O
3
He
at
C
a C
H3C CH+
3Ca
CO3
Ac
et
one
C
HCO
O
3

Q.24: Give four important uses of acetaldehyde.

Ans: Uses of Acetaldehyde:
(i) Preparation of Chemicals:
It is used in the production of acetic acid, acetic anhydride, n-Butanol, Ethanol, 2-Ethyl-l-
hexanol, vinyl acetate, paraldehyde, Ethylacetate, etc.
(ii) To make rubber accelerator:
It is used to make acetaldehyde ammonia used as a rubber accelerator.
(iii) To make poisons:
It is used to make chloral hydrate, ethanol trimer and tetramer. Chloral hydrate and ethanol
trimer are both used as hypnotic drugs whereas ethanol tetramer is used as a slug poison.
(iv) As Inhalant:
It is used as an antiseptic inhalant in nasal infections.
Q.25: Butanone on oxidation gives two molecules of acetic acid? Justify with chemical reaction.
Ans: Oxidation of butanone:
During oxidation of unsymmetrical ketone, cleavage of C-CO bond in such that the keto group
always stays with smaller alkyl group. Hence oxidation of Butanone gives two molecules of acetic acid.
O O O
|| K2Cr2O7/H2SO4 || ||
CH3 — C—CH2—CH3+3[O] ———— CH3 — C — OH + CH3 — C — OH
Butanone Acetic acid
Q.26: Ketones do not give silver mirror test but aldehyde do so. Give reasons?
Ans: Silver mirror test:
Aldehydes are powerful reducing agents and therefore they can easily oxidized by mild
oxidizing agents like Tollen’s reagent and form silver mirror with Tollen’s reagent (Ammonical silver
nitrate solution). The hydrogen atom attached to the carbonyl group in aldehydes is oxidized to OH
group.
O O
||  ||  
R — C— H + 2 [Ag(NH3)2]+ + 2OH —— R — C— O N H4 + 2Ag + 2NH3 + H2O
Silver Mirror
Key to Chemistry [Part-II] 488 [Ch.12] Aldehydes & Ketones
Ketones are difficult to oxidize because they require breaking of strong carbon-carbon bond
hence; ketones are not oxidized by mild oxidizing agents. So ketones do not give silver mirror test.
Q.27: How acid and base catalyses the reactivity of carbonyl compounds?
Ans: Carbonyl Compounds undergo Nucleophilic addition reactions


O O
H

+
—C—+H
Nu —C—

N
u
In Acid catalyze reaction, acid catalyst increases the reactivity or electrophilic character of
carbonyl carbon. Hence increase the rate of reaction.


O O
H

+ +
—C—+ H
+
— C —
greater
electrophilic
character
In base catalyze reaction, Base catalyst increases the reactivity or nucleophile by increasing its
nucleophilic character. Hence increases the speed of reaction.

+ 

H
—Nu+O
H H
O
2 +N u
gr
eat
er
N u
cl
eophi
li
c
c
har
act
er

ADDITIONAL MULTIPLE CHOICE QUESTIONS

1. In aldehydes, the functional group (CHO) will be present:

(a) In the middle of chain (b) at the start of the chain
(c) at any position in the chain (d) as a group out of the chain
2. Which functional group is present in the most of the sugars?
(a) Ketone group (b) Hydroxyl group (c) Aldehyde group (d) Carboxyl group
3. Which set out of given represents the compounds containing ketonic group?
(a) Cholesterol and progesterone (b) Camphor and Glyoxal
(c) Glucose and fructose (d) Camphor and Menthone
4. Which one of the following is not a symmetrical ketone?
(a) 3-Pentanone (b) 2-Butanone (c) 3-Heptanone (d) Acetone
5. Aldehydes are colourless organic liquids except:
(a) Acetaldehyde (b) Formaldehyde (c) Propionaldehyde (d) Butyraldehyde
6. Which type of reaction converts alcohols into aldehydes and Ketones?
(a) Dehydration (b) Oxidation (c) Reduction (d) Dehydrogenation
7. What is %age of methyl alcohol in formalin?
(a) 8% (b) 12% (c) 6% (d) 10%
[Ch.12] Aldehydes & Ketones 489 Key to Chemistry [Part-II]
8. On dry distillation of calcium salt of acetic acid alone, which one of the following compound
is most likely to be formed?
(a) Formaldehyde (b) Acetone (c) Acetaldehyde (d) Methane
9. The nucleophilic addition reactions of carbonyl group are catalysed by:
(a) Bases only (b) acids only (c) both acids or bases (d) salts
10. Which one of the following compound form as a intermediate during hydrolysis of nitriles?
(a) acid halide (b) acid amide (c) carboxylic acid (d) acid imide
11. Which of the following primary alcohol will give iodoform test with I2/NaOH:
(a) Ethanol (b) Methanol (c) 1-Propanol (d) 2-Propanol
12. During aldol condensation, the base used acts as,
(a) A promoter (b) A reactant
(c) A catalyst (d) A promoter as well as a catalyst
13. In aldol condensation how many molecules of carbonyl compound take part in reaction to
form an aldol?
(a) Three (b) Four (c) one (d) Two
14. The aldol product on heating undergoes which process?
(a) Decomposition (b) Oxidation (c) Dehydration (d) Rearrangement
15. The carbanion forms during aldol condensation acts as:
(a) An electrophile (b) A nucleophile (c) An acid (d) None of these
16. The carbanion forms in aldol condensation reacts with second molecule of carbonyl
compound and forms:
(a) A carbanion (b) A carbonium ion (c) An alkoxide ion (d) Aldol
17. Which one of the following compound does not give aldol condensation?
(a) Benzaldehyde (b) Acetophenone (c) Ethyl phenyl ketone (d) dichloro ethanal
18. Which one of the following does not give cannizzaro’s reaction?
(a) Methanal (b) Trifloro ethanal (c) Propionaldehyde (d) Formaldehyde
19. The Cannizzaro’s reaction takes place in the presence of:
(a) An acid (b) A base (c) An acid or base (d) none of these
20. Which one of the following secondary alcohols does not give iodoform test?
(a) 2-Propanol (b) 2-Butanol (c) 2-Pentanol (d) 3-Hexanol
21. Which Haloform test does not occur?
(a) Bromform test (b) chloroform (c) flouroform test (d) iodoform test
22. The formation of metaformaldehyde from formaldehyde in the presence of H2SO4 is:
(a) Condensation reaction (b) Polymerization reaction
(c) Elimination reaction (d) None of these
23. Aldehydes are:
(a) Weak oxidizing agents (b) Strong reducing agent
(c) Mild reducing agents (d) Strong oxidizing agents
24. Which of the following tests are given by only aldehydes?
Key to Chemistry [Part-II] 490 [Ch.12] Aldehydes & Ketones
(a) Fehling solution test (b) Silver mirror test
(c) Benedict test (d) All of them
25. Which of the following reagent can be used to protect the aldehydes group against alkaline
oxidizing agents?
(a) Ethanol (b) NH2–OH (c) NH2 – NH – C6H5 (d) Ethanal
26. Acetone on oxidation forms:
(a) CH3COOH+CH3COOH (b) HCOOH + HCOOH
(c) CH3COOH + HCOOH (d) CH3CH2COOH+CO2+H2O
27. Which one of the following is used as a slug poison?
(a) Chloral hydrate (b) Ethanol trimer (c) Ethanol tetramer (d) None of these
28. Which is used as hypnotic drugs?
(a) Urea-formaldehyde (b) Ethanol trimer (c) Chloral hydrate (d) Both B and C
29. Formamint is used as:
(a) Respiratory antiseptic in lungs infection. (b) An antiseptic in halent in nasal infections.
(c) Throat lozenges. (d) None of these
30. In Benedict’s solution test an alkaline solution is used which contain a:
(a) Cupric oleate complex ion (b) Cupric acetate complex ion
(c) Cupric citrate complex ion (d) Cupric palmatate complex ion
31. In which of the following class of organic compounds the position of functional group is not
mentioned while writing the IUPAC name
(a) Alcohol (b) Ketone (c) Alkyl halide (d) Aldehyde
32. IUPAC names are not given to:
(a) Aromatic aldehydes (b) Aromatic ketones (c) Both (a) and (b) (d) None
33. Ketones are prepared by:
(a) Oxidation of secondary alcohols (b) Hydration of propyne
(c) Dry distillation of calcium acetate (d) All of the above
PdCl2 CuCl2
34. In the reaction 2CH2 = CH2 + O2  we get:
H2 O
(a) Acetaldehyde (b) Butyraldehyde (c) Ethyl alcohol (d) Acetone + CO
35. Which compound do not react with NaHSO3?
(a) Methanal (b) Ethanal (c) Acetone (d) 3-Pentanone
36. Ketones are less reactive than aldehydes because
(a) Ketones have more bulky hindrance
(b) Both alkyl groups in ketones are electron donation
(c) Both alkyl groups decrease the polarity of carbonyl group (d) All of these
37. In cannizzaro’s reaction, alkoxide ion acts as a:
(a) Nucleophile (b) Base (c) Electrophile (d) Acid
38. Formula of semi-carbazide is:
[Ch.12] Aldehydes & Ketones 491 Key to Chemistry [Part-II]
(a) CH3NHCONH2 (b) NH2NHCONH2 (c) NH2NHCONHNH2 (d) CH3NHCONHCH3
39. 2, 4-Dinitrophenyl hydrazone has colour,
(a) Yellow (b) Purple (c) Pink (d) Colourless
40. Acetals on acid hydrolysis, give:
(a) Aldehydes (b) Ketones (c) Both (a) and (b) (d) None
41. Butanone on oxidation with K2Cr2O7 + H2SO4 gives:
(a) Acetic acid (b) Butanoic acid
(c) Propanoic acid and Methanoic acid (d) 2-Butanol
42. When alkaline sodium nitroprusside solution is added to ketones, they give colour:
(a) Orange red (b) Purple (c) Pink (d) Yellow
43. Ketones donot show all of the following reactions except
(a) Cannizzaro’s reaction (b) Reducing Fehling solution
(c) Polymerization reaction (d) Aldol condensation
44. Cuprous oxide has colour:
(a) Brick red (b) Wine red (c) Orange red (d) Purple
45. A compound “X” react with acidified potassium dichromate and form “Y” . This Y product
give no reaction with Fehling solution but give 2,4-DNPH test. The product “Y” is
(a) primary alcohol (b) sec.alcohol (c) Aldehyde (d) Ketone
46. Mild oxidizing agent among the following is:
(a) K2Cr2O7 (acidified) (b) KMnO4 (alkaline)
(c) Ammonical AgNO3 (d) All of the above
47. Which one of the following is not a derivative of NH3?
(a) Aniline (b) Hydrazine (c) Picric acid (d) Phenyl hydrazine
48. Among methanal ,Propanone and Ethanal , the correct reactivity order is
(a) Methanal> Propanone> Ethanal (b) Ethanal> Propanone> Methanal
(c) Methanal> Ethanal> Propanone (d) Propanone> Methanal> Ethanal
49. Hybridization of C-atom in HCN is:
(a) sp3 (b) sp2 (c) sp (d) dsp2
50. Cyanohydrin are formed from carbonyl group by mechanism:
(a) Free radical (b) Nucleophilic substitution
(c) Nucleophilic addition (d) Electrophilic addition
51. Which catalyst is used in the following reaction?
O
||
2CH2 = CH2 + O2  2CH3  C  H
(a) PdCl2 + CuCl2 (b) PtCl2 + CuCl2 (c) PdCl2 + Cu2Cl2 (d) PdCl2 + CoCl2
52. CnH2nO is the general formula of:
(a) Aldehydes (b) Ketones (c) Both (a) and (b) (d) None
53. 2-Pentanol and 3-Pentanol can be distinguished by:
(a) Haloform test (b) Lucas test (c) Silver mirror test (d) 2, 4-DNPH test
54. Acetaldehyde is used in production of:
(a) 2-Ethyl-1-hexanol (b) Vinyl acetate (c) Ethyl acetate (d) All of the above
Key to Chemistry [Part-II] 492 [Ch.12] Aldehydes & Ketones
55. NaBH4 is a source of:
(a) H (b) H+ (c) H (d) H2
56. When sodium bisulphite reacts with aldehydes, the precipitates formed have colour:
(a) Wine red (b) Brick red (c) White (d) Yellow
57. The cyano group is hydrolyzed by an aqueous acid into:
(a) Carboxylic acid (b) Alcohol (c) Amide (d) Alkane
58. Which of the following is resistant to oxidation?
(a) Methanol (b) Ethanol (c) Acetaldehyde (d) Acetone
59. Consider the reaction:
2HCHO + NaOH  CH3OH + HCOONa
The type of above reaction is:
(a) Addition reaction (b) Disproportionation reaction
(c) Elimination reaction (d) Free radical reaction
60. Which of the following is strongest reducing agent?
(a) C3H8 (b) CH2O (c) C3H7OH (d) CH3COCH3
61. In which of the following compounds, carbon number is decreased during oxidation?
(a) Aldehyde (b) Ketone (c) Alcohol (d) Ether
Answers:
(1) b (2) c (3) d (4) b (5) b

(6) b (7) a (8) b (9) c (10) b

(11) a (12) c (13) d (14) c (15) b

(16) c (17) a (18) c (19) b (20) d

(21) c (22) b (23) b (24) d (25) a

(26) c (27) c (28) d (29) c (30) c

(31) d (32) c (33) d (34) a (35) d

(36) d (37) b (38) b (39) a (40) a

(41) c (42) a (43) d (44) a (45) d

(46) c (47) c (48) c (49) c (50) c

(51) a (52) c (53) a (54) d (55) c

(56) c (57) a (58) d (59) b (60) b

(61) b

PAST PAPERS

SHORT ANSWER QUESTIONS

1. What type of aldehyde give aldol condensation? Give example. 2008)
2. How does formaldehyde react with the reagents? (2008)
(a) H3MgI (b) CN
3. Which are those weak oxidizing agents which can oxidize aldehydes but Not ketones? (2009)
[Ch.12] Aldehydes & Ketones 493 Key to Chemistry [Part-II]
4. What is benedict’s solution test? Also give its reaction with acetaldehyde? (2009, 2016)
5. Write the mechanism of addition of HCN to acetone, (2010)
6. How will you prepare dehyde crotonal from acetaldehyde. (2010)
7. Define nucleophilic addition reaction with an example. (2011)
8. What is the use of iodoform test to distinguish between acetaldehyde and Formaldehyde? (2012)
9. How does acetaldehyde react with the given reagents: (2012)
(i) dilute NaOH (ii) NH2OH
10. Justify that cannizzaro’s reaction is a self-redox reaction. (2013)
11. Define nucleophilic addition reaction with an example. (2013)
12. What is iodoform test? Illustrate with an example. (2013)
13. Give Fehling’s solution test with an example. (2013)
14. Why aldehydes are more reactive than ketones? (2014)
15. What is sodium nitroprusside test? (2014)
16. Give preparation of acetal. (2014)
17. Iodoform test can be used to distinguish between methyl alcohol and ethyl Alcohol. Justify it. (2014)
18. What is halo form reaction? (2015)
19. Give four uses of acetal dehyde? (2015)
20. How formaldehyde is prepared on industrial scale? (2016)
21. Which products are formed by the catalytic reduction of aldehydes? Give one example. (2016)
22. Justify that aldehydes with no α-hydrogen give cannizzaro reaction. (2017 Gr.I)
23. Why Tollen’s test is called as Silver Mirror test? (2017 Gr.I)
24. Give mechanism of addition of HCN to acetaldehyde. (2017 Gr.II)
25. How will you distinguish between acetaldehyde and benzaldehyde? (2017 Gr.II)
26. How is formaldehyde prepared in laboratory? Give its chemical reaction. (2018)
27. Write four uses of formaldehyde. (2019)
28. How acid and base catalyses the reactivity of carboxyl compound?

LONG ANSWER QUESTONS

1. Describe cannizzaro’s reaction with mechanism? (2008, 2009, 2011, 2012, 15, 18)
2. Describe briefly the mechanism of nucleophilic addition to a carbonyl compound. (2010)
3. What is aldol condensation? Write down its mechanism using a catalyst. (2013,2 017 Gr.I)
4. Explain the mechanism of reaction of phenyl hydrazine with acetone. (2016)
5. Explain the mechanism of Aldol condensation reaction in detail. (2019, Gr.I 2017)
6. Describe laboratory method of preparation of formaldehyde with diagram. (Group II, 2017)
7. Define cannizzaro’s reaction with an example, also give its mechanism. (2018)
8. Describe the mechanism of aldol condensation reaction? Why does formaldehyde Not give this
reaction? (2019)

