ALDEHYDES AND

KETONES
 2

Learning Objectives
• This Chapter discusses carbonyl compounds and by the
end of this chapter the students will:

➢Know the structural differences between aldehydes and

ketones
➢Know how to draw aldehydes and ketones
➢ know the common and IUPAC nomenclature of
aldehydes and ketones
➢ Know the physical properties of aldehydes and ketones
➢Know how to synthesize an aldehyde or a ketone.
➢ Know the different nucleophilic attack reactions at
the carbonyl carbon.
 3

ALDEHYDES: STRUCTURE AND

NOMENCLATURE
Aldehydes and ketones are organic compounds
which incorporate a carbonyl functional group, C=O.
The carbon atom of this group has two remaining
bonds that may be occupied by hydrogen or alkyl or
aryl substituents. If at least one of these substituents
is hydrogen, the compound is an aldehyde RCHO or
RCH=O. If neither is hydrogen, the compound is
a ketone RCOR` (R and R`=alkyl or aryl).
 4

Some Common Classes Carbonyl Compounds

 5

Carbonyl Structure
• Carbon is sp2 hybridized.
• C=O bond is shorter, stronger, and more polar than
C=C bond in alkenes.

=>
 6

Common Names of Aldehydes

• In the common system, aldehydes are named from the common
names of the corresponding carboxylic acid.
• The ‘ic acid’ ending is replaced with ‘aldehyde’.
• The aldehyde group is always at the end of a chain (terminal).

Structure IUPAC name Common name Structure IUPAC Common name

HCO2H methanoic acid formic acid HCHO methanal formaldehyde
CH3CO2H ethanoic acid acetic acid CH3CHO ethanal acetaldehyde
CH3CH2CO2H propanoic acid propionic acid CH3CH2CHO propanal propionaldehyde
CH3(CH2)2CO2H butanoic acid butyric acid CH3(CH2)2CHO butanal butyraldehyde
CH3(CH2)3CO2H pentanoic acid valeric acid CH3(CH2)3CHO pentanal valeraldehyde
CH3(CH2)4CO2H hexanoic acid caproic acid CH3(CH2)4CHO hexanal caproaldehyde
 7

• Substituents locations are given using Greek letters (, , , , , .)

beginning with the carbon next to the carbonyl carbon, the -carbon.
O OH O O
CH3CHBrCH2C H CH3CHCH2CH2C H CH2C H
       
-bromobutyraldehyde -hydroxyvaleraldehyde -phenylacetaldehyde

• Aromatic aldehydes are usually designated as derivatives of the

simplest aromatic aldehyde, Benzaldehyde

O OH O O
O

H H H H

O 2N H3CO

Benzaldehyde p-Nitrobenzaldehyde o-Hydroxybenzaldehyde p-Methoxybenzaldehyde

Salicylaldehyde Anisaldehyde
 8

IUPAC Nomenclature of Aldehydes

• Select the longest continuous carbon chain that
contains the C=O group and replace the ending -e
by the suffix -al
• The CHO group is assigned the number “1” position
and takes precedence over other functional groups
that may the present such as –OH, C=C ……
• If the CHO group is bonded to a ring, name the ring
and add the suffix -carbaldehyde.
 9

O OH O O
CH3CHBrCH2C H CH3CHCH2CH2C H CH2C H

3-bromobutanal 4-hydroxypentanal 2-phenylethanal

Cl O HO O O

H3C CH H C H H3CHC=HC C H

2-Chloropropanal 3-Hydroxypropanal 2-Butenal

O O
HO CHO
C H C H

benzenecarbaldehyde 3-hydroxycyclopentanecarbaldehyde

cyclohexanecarbaldehyde
 10

Nomenclature of Ketones
❖Common name:
❑listing the alkyl substituents attached to the carbonyl group
alphabetically, followed by the word ketone. As with aldehydes,
substituents locations are given in common names using
Greek letters (, , , , , .) beginning with the -carbon.

❖IUPAC system:
• Find the longest chain containing the carbonyl group, and
change the -e ending of the parent alkane to the suffix -one.
• Number the carbon chain to give the carbonyl carbon the lower
number. Apply all of the other usual rules of nomenclature.
• Ketones are just below aldehydes in nomenclature priority.
• A ketone group is named as an ‘oxo’ substituent in an
aldehyde.
 11

O O O O
H3C C CH3 H3C C C6H5 H3C C CH=CH2 H5C6 C C6H5
Common
Dimethyl ketone Methyl phenyl ketone Methyl vinyl ketone Diphenyl ketone
Acetone Acetophenone Benzophenone
IUPAC
Propanone Phenyl ethanone 3-Buten-2-one Diphenylmethanone
OCH3
CH3   O O
O
CH3CHCCHCH3 C CH2CH2CH2
CH3CCH2CHCH3
Cl CH3   
Methyl isobutyl ketone
-Chloroethyl isopropyl ketone -Methoxypropyl phenyl ketone
(MIBK)
O
O
O OH
CHO
C2 H 5 C

C2 H 5
Cyclopentylpropanone 3-Ethyl-2-hydroxycyclohexanone 5-Oxohexanal
 12

PHYSICAL PROPERTIES OF KETONES

AND ALDEHYDE 
− +

O C
C O + -
C O
C O−
+ 

• Aldehydes and ketones are polar compounds, Because the
polarity of the carbonyl group.
• Polarization of CO group creates Dipole-dipole attractions
between the molecules of aldehydes and ketones, resulting in
higher boiling points than nonpolar alkanes and ether.
• aldehydes and ketones lower than alcohols Because Dipole-
dipole attractions , are not as strong as interactions due to
hydrogen bonding.
• The lower aldehydes and ketones are soluble. Acetone,
formaldehyde and acetaldehyde are miscible in water.
− + O + −
   
C O H H O C

capable of being mixed

 13

Preparation of Aldehydes and Ketones

• Oxidation of alcohols

CH3OH Cu / heat HCHO aldehyde

CH3CH2OH CrO3 / Pyridine CH3CHO

OH O
K2Cr2O7 / H+

• Ozonolysis of alkenes
H
i) O3
O
ii) Zn /H2O O +
 14

• Hydration of alkynes
O
H-OH/ H2SO4, HgSO4 H CH3
HC C CH3 C C H3C C CH3
H O H
Propyne Acetone
(an unstable enol)
(a stable carbonyl compound)

• Friedel Grafts acylation

O
O AlCl
+R 3 R
Cl
 15

REACTIONS OF ALDEHYDES AND

KETONES
Nucleophilic Addition Reaction to the carbon-oxygen double bond.
Nu:- tetrahedral ..
− alkoxide : O :
: O:  : O:
+ R C
C 
R C H R
3
+ sp2 Nu:- sp
E Nu

1-Reduction of carbonyl group

Addition of metal hydrides: Formation of alcohols.
 16

Reduction by hydride reagents, Lithium aluminium

hydride LiAlH4 or Sodium boron hydride NaBH4.

1) LiAlH4 / dry ether or NaBH4

2) H3O+

1) LiAlH4 / dry ether or NaBH4

2) H3O+

1) LiAlH4 / dry ether or NaBH4

2) H3O+
OH
2H2 / Pt

1) NaBH4
2) H2O OH
 17

• 2- Addition of Grignard Reagents: Formation of

alcohols
O R`
1) Dry ether
R + R`MgX R CH OH
2) H3O+
H
O OH
R``MgX 1) Dry ether
R + R C R``
2) H3O+
R` R`

Mechanism:
 18

• 3-Oxidation reaction
• A) KMnO4
R-CHO or Ar-CHO RCOOH or ArCOOH
or K2Cr2O7

• B) Iodoform reaction: The reaction occurs in any

aldehyde or ketone containing CH3CO.
ONa

R O + 3 I2 + 4 NaOH R O + CHI3 + 3 NaI

I2 / NaOH COONa + CHI3

O
 19

• 4- Addition of Hydrogen Cyanide: Formation of

cynohydrins R
R
`R O + HCN `R OH Cyanohydrine
CN

CN
CH2NH2
OH H2 / Pt
O
+ HCN OH
or LiAlH4 and H3 O+
Benzaldehyde cyanohydrine
CN COOH
O H3O+ OH
OH
+ HCN
heat

• 5-Addition of acetylide ions:

R
H3O+ R
`R O + ``R CNa `R R``
OH

OH
O H3 O+
+ CNa
 20

• 6- Addition of Ammonia and Ammonia Derivatives

2
NH3 NH hydrogen
Imine will go
with
oxygen
OH and
NH2OH N oxygen
O Oxime
Hydroxyamine will
replace
with
NH2
H2N-NH2 nitrogen
N
Hydrazine Hydrazone
 Chapter 18 21

Wittig Reaction
• Nucleophilic addition of phosphorus ylides.
• Product is alkene. C=O becomes C=C.

=>
 Chapter 18 22

Phosphorus Ylides
• Prepared from triphenylphosphine and an unhindered
alkyl halide.
• Butyllithium then abstracts a hydrogen from the carbon
attached to phosphorus.

+ _
Ph3P + CH3CH2Br Ph3P CH2CH3 Br
_
+ +
BuLi
Ph3P CH2CH3 Ph3P CHCH3
ylide =>
 Chapter 18 23

Mechanism for Wittig

• The negative C on ylide attacks the positive C of
carbonyl to form a betaine.
• Oxygen combines with phosphine to form the
phosphine oxide.

+
_ Ph3P O
+ H3C
Ph3P CHCH3 C O H C C CH3
Ph CH3 Ph
+ _ Ph3P O
Ph3P O Ph3P O
H CH3
H C C CH3 H C C CH3 C C
H3C Ph
CH3 Ph CH3 Ph =>
 Chapter 18 24

Tollens Test

• Add ammonia solution to AgNO3 solution until

precipitate dissolves.
• Aldehyde reaction forms a silver mirror.

O O
+
_ H2O _
R C H + 2 Ag(NH3)2 + 3 OH 2 Ag + R C O + 4
O
+
_ H2O _
NH3)2 + 3 OH 2 Ag + R C O + 4 NH3 + 2 H2O
=>
 25

Fehling’s test

Fehling’s reagents comprises of two solution Fehling’s solution A and solution B.

Fehling’s solution A is aqueous copper sulphate and Fehling’s solution B is
alkaline sodium potassium tartarate ( Rochelle salt). These two solution are mixed
in equal amount before test.

On heating an aldehyde or reducing sugar with Fehling’s solution give reddish

brown prepitate. Formation of red precipitate of cuprous oxide denotes the
presence of reducing sugar.
 Chapter 18 26

Clemmensen Reduction
❑ a chemical reaction described as a reduction of
ketones (or aldehydes) to alkanes using zinc
amalgam and concentrated hydrochloric acid.
O
C CH2CH2CH3
CH2CH3 Zn(Hg)
HCl, H2O Replace Oxygen
with 2 Hydrogen
O
Zn(Hg)
CH2 C CH2 CH3
H HCl, H2O

=>
 Chapter 18 27

Wolff-Kisher Reduction
• Convert carbonyl functionalities into methylene groups
• Form hydrazone, then heat with strong base like KOH
or potassium t-butoxide.
• Use a high-boiling solvent: ethylene glycol,
diethylene glycol, or DMSO.

CH2 C H CH2 C H KOH CH2 CH3

H2N NH2
heat
O NNH2

=>
 28

Difference Between Aldehyde and Ketone

 29

Alcohol
30
 31
Nomenclature of Alcohols and Phenols
• Step 1. Name the longest chain to which the
hydroxyl (—OH) group is attached. The name for
this chain is obtained by dropping the final -e from
the name of the hydrocarbon parent name and
adding the ending -ol.
• Step 2. Number the longest chain to give the lowest
possible number to the carbon bearing the hydroxyl
group.
• Step 3. Locate the position of the hydroxyl group
by the number of the C to which it is attached.
• Step 4. Locate and name any other substituents.
• Step 5. Combine the name and location for other
groups, the hydroxyl group location, and the longest
chain into the final name.
7

Examples: Naming Alcohols and Phenols

• Provide acceptable IUPAC names for the following
compounds:
OH

HO CH2 CH2 OH HO CH CH2 CH CH CH3

CH3 CH3

CH2 CH CH2 CH3 OH

OH OH OH CH CH2 CH

OH CH3

13
 32

Classification of Alcohols
Alcohols are classified as primary (1°), secondary
(2°), or tertiary (3°) according to how many carbon
groups are attached to the carbon bearing the OH
group:

R''

R C OH R C OH R C OH

R' R'
Primary Secondary Tertiary
1° 2° 3°
The number of hydrogens on the carbon bearing the
OH group does affect some chemical properties.

17
 Properties of Alcohols 33
Physical Properties of Alcohols
The physical properties of alcohol can be explained by the following points –
❑ Alcohols are colourless.
❑ They generally give a sweet smell except for glycerol and a few lower alcohols.
❑ They are flammable and produce a blue flame.
❑ They don’t produce any smoke while burning.
❑ They are generally liquid at room temperature. Although glycerol is a viscous liquid.
❑ Boiling Point of Alcohol - They generally have higher boiling points if we compare
them with other hydrocarbons. For example, ethanol shows a boiling point of 78.29℃
while hexane shows a boiling point of 69℃. This is because of the presence of
intermolecular hydrogen bonding between hydroxyl groups of alcohols. The boiling
point of alcohol increases with an increasing number of carbon atoms in organic
alcoholic compounds.
❑ Alcohols work as suitable solvents for many organic compounds as organic
compounds are insoluble in water.
❑ Alcohols are acidic in nature. They react with metals such as sodium, potassium etc. It
is due to the polarity of the bond between a hydrogen atom and the oxygen atom of
the hydroxyl group. Primary alcohols are more acidic than secondary and tertiary
alcohols.
❑ Due to the polar -OH bond in alcohols, they are more soluble in water than other
simple hydrocarbons. For example, methanol and ethanol are miscible in water.
 34

Chemical Properties of Alcohols

The chemical properties of alcohol can be explained by the following points –
•Oxidation Reaction of Alcohol – Alcohols produce aldehydes and ketones on
oxidation. The reaction is given below –

C₂H₅OH + 2O → CH₃COOH + H₂O

Ethanol Methanoic acid

•Combustion of Alcohol – On heating ethanol gives carbon dioxide and water

and burns with a blue flame. The reaction is given below –

C₂H₅OH + 3O₂ → 2CO₂ + 3H₂O

•Dehydration of Alcohol – Alcohol can be dehydrated in an acidic medium. The

removal of water molecules from a compound is called dehydration. Upon
dehydration of alcohol alkenes are produced. The reaction is given below –

C2H5OH (conc. H₂SO₄,▵)→C₂H₄ + H₂O

 35

•The reaction of Alcohol With Metal – Due to its acidic nature alcohol reacts
with metal and forms alkoxide. For example, when ethanol reacts with
sodium forms sodium ethoxide and hydrogen gas. The reaction is given
below –

2C₂H₅OH + 2Na →2C₂H₅ONa + H₂

•Formation of Halides From Alcohols – Alcohol reacts with HCl and forms
alkyl halides by removal of hydroxyl groups. The reaction is given below

ROH + HCl (Zn) → R-Cl + H₂

•Esterification – Alcohol reacts with a carboxylic acid in presence of a

catalyst and forms ester. It is called Fischer esterification. The reaction is
given below –

C₂H₅OH + C₂H₃COOH →C₄H₈O₂ + H₂O

 General methods of preparation of alcohols
1. By hydrolysis of haloalkanes :
Alcohols are produced when haloalkanes( alkyl halides ) are treated with aqueous sodium
or potassium hydroxide.

2. From aldehydes and ketones:

i. By reduction: Aldehydes and ketones on reduction with (i)H2/Ni or Pt or Pd
(ii)LiAlH4 (iii)Na/C2H5OH give corresponding alcohols.
Aldehydes give primary alcohols while ketones give secondary alcohols. 36
 37

ii. From Grignard reagent: Aldehydes and ketones (i.e carbonyl

compounds) when treated with Grignard reagent gives
addition product, which upon acidic hydrolysis give alcohols.

a. Formaldehyde gives primary alcohol. Eg.

 38

From ether (By hydrolysis): Ethers on hydrolysis in the presence of

dil.H2SO4 under high pressure gives alcohol.

By hydrolysis of esters:
Esters on hydrolysis in presence of dilute mineral acid or alkali give alcohols.
 39

Identification of primary, secondary and tertiary alcohol by oxidation method :

Alcohols are oxidized by different oxidizing agents like acidic or alkaline KMnO4,
acidified K2Cr2O7, dil. HNO3, etc. to give different products.

i. Primary alcohols are easily oxidized first to aldehyde and then to

carboxylic acids containing same number of C- atoms as in parent alcohol.
Eg.

ii. Secondary alcohols on oxidation give ketones with same number of carbon
atoms. The ketones are further oxidized only under drastic conditions ( i.e.
prolong treatment of oxidizing agent) to give carboxylic acid containing lesser
number of carbon atoms.
 40

iii. Tertiary alcohols do not contain hydrogen atom on the carbon carrying – OH
group (i.e. α- hydrogen). Thus in order to oxidize tertiary alcohol, a carbon-carbon
bond must be broken. For this reason 30 alcohol do not undergo oxidation
reaction in neutral or alkaline medium.

But if the oxidation is carried out in the acidic medium under drastic condition
tertiary alcohol oxidize to give a mixture of ketone and carboxylic acid. The
ketone thus formed further gets oxidized to carboxylic acid.
 41

What is Lucas Reagent?

The solution of concentrated hydrochloric acid with zinc chloride is called
Lucas reagent.
It is used to distinguish primary, secondary and tertiary alcohols in the
sample.
 42

Application of Alcohol
There is a long history of alcohol for myriad uses. For instance, mono-
alcohols are the most important alcohols that are used in industries. Some
of the applications of alcohol are as follows:-
1.For formaldehyde and fuel additive production, methanol is mainly
used.
2.For alcoholic beverages, fuel additives, solvent production, ethanol is
mainly used.
3.1-propanol, 1-butanol, and isobutyl alcohol are used as a solvent and
precursors to solvents.
4.C6–C11 alcohols are used for plasticizers in polyvinylchloride and many
more.
5.fatty alcohol (C12–C18) are utilized as precursors to deterg
 43

Thank You for your kind attention !

Questions