ALDEHYDES AND KETONES

Dr. Anthoney S. Thangiah,

M.Sc., M.Phil., Ph.D., I.A.C.T
 Nomenclature of Aldehyde
• ALDEHYDES (R-CHO):
• Aldehydes are compounds in which the carbonyl group is bonded to an organic
IUPAC system of nomenclature:

group and hydrogen atom.

• General form of aldehyde:

• Common Names are related to those of carboxylic acids.

• IUPAC Rule:
1. Select the longest chain containing the aldehyde group.
2. Name the longest chain [Alkane – e – al = Alkanal]
3. Number the chain by assigning the number 1 to the aldehyde carbon. The number 1 is not used to indicate the position of
the carbonyl carbon, since it is always located ate the end of the chain.
4. Other substituents are numbered, named, and placed as prefixes in alphabetic order.
5. When there are two aldehyde groups in a molecule, it is named as Alkanedial [Note: ‘e’ of the corresponding alkane name
is retained.
Nomenclature of Aldehyde
 Nomenclature of Ketone
• Ketones are compounds in which the carbonyl group is bonded to two organic
groups.
IUPAC system of nomenclature:

• Ketones are two types;

• Simple ketone: R-CO-R
E.g.,

• Mixed ketone: R-CO-R’

E.g.,

• Common Name:
C.Ns are obtained by naming the alkyl groups attached to the carbonyl group
and adding the word ketone. If both alkyl groups are similar, then it is named
as Dialkyl ketone. And if they are different, alphabetical order need to be
followed, i.e., Alkylalkyl ketone
 • IUPAC Rule of Ketones:
1. Select the longest chain containing the carbonyl carbon atom.
2. Name the longest chain [Alkane – e + one = Alkanone]
Nomenclature of Ketone

3. Number the chain to give the lowest number to the carbonyl carbon.
4. Other substituents are numbered, named and places as prefixes in alphabetical order.
5. When there are two carbonyl groups in a molecule, it is named as Alkanedione. Notice
that ‘e’ of the corresponding alkane name is retained.
Nomenclature of ketones
PREPARATION OF ALDEHYDES AND KETONES
PREPARATION OF ALDEHYDES AND KETONES
PREPARATION OF ALDEHYDES AND KETONES
PREPARATION OF ALDEHYDES AND KETONES
PREPARATION OF ALDEHYDES AND KETONES
PREPARATION OF ALDEHYDES AND KETONES
PREPARATION OF ALDEHYDES AND KETONES
PREPARATION OF ALDEHYDES AND KETONES
ALDEHYDES AND KETONES
PHSICAL PROPERTIES
 4. Boiling points of aldehyde and ketones:
PHSCIAL PROPERTIES OF ALDEHYDES AND KETONES

• Due to dipole-dipole attraction (intermolecular attractions) between the

partial negative on the carbonyl oxygen of one molecule and the partial
positive charge on the carbonyl carbon of another molecule, the boiling
point of aldehydes and ketones are higher than those of non-polar
alkanes.

• Boiling point of aldehyde and ketone is lower than those of alcohols, of

comparable molecular mass because alcohols can form intermolecular
hydrogen bonds.
 5. Solubility in water:
PHSCIAL PROPERTIES OF ALDEHYDES AND KETONES

 Lower members of aldehyde and ketones are soluble in water due to formation
of hydrogen bond with water. However, Solubility deceases as increases the size
of hydrocarbon portion.
 Lower and higher aldehyde and ketones are soluble in organic solvents such as
benzene, ether, CCl4
ALDEHYDES AND KETONES
CHEMICAL PROPERTIES
 Nucleophilic addition rxn of aldehyde/ketone
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

However, the addition product is same whether the reactions is acid-catalyzed or base catalyzed.
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES
Acidity of α-hydrogen
 A. ADDITION REACTION
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Addition of sodium bisulphite:

ADDITION REACTION OF ALDEHYDES AND KETONES
• Addition of Hydrogen cyanide:
Mechanism of Addition of Hydrogen cyanide
 • Addition of Grignard Reagents:
ADDITION REACTION OF ALDEHYDES AND KETONES

• Formaldehyde with G.R to give primary alcohol and other aldehyde to give secondary alcohols.
• Ketones with G.R to give tertiary alcohols.
 • Addition of Ammonia:
ADDITION REACTION OF ALDEHYDES AND KETONES

• Aldehyde (other than formaldehyde) with NH3 to form solid aldehyde ammonias.

• Formaldehyde and other ketones do not form addition compounds with ammonia, but instead to
give complex condensation products.

• HMT (hexamethylene tetramine), Urotrpine is used as a urinary antiseptic

 B. ADDITION REACTION followed by loss of water
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Addition of alcohols:

• Reaction with ammonia derivatives:

• Some ammonia derivatives (NH2-Z) react with aldehydes and ketones to form compounds
containing carbon-nitrogen double bonds, together with the elimination of H2O molecule.
Reaction with ammonia derivatives
Reaction with ammonia derivatives
 C. REACTIONS INVOLVING ALKYL GROUPS
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Aldol condensation:
• Aldehyde containing α-hydrogens undergo self addition in the presence of a base
such as dil. NaOH to form products called aldols (which contain both aldehyde
and –OH groups).
Aldol reaction
Mixed Aldol reaction
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Chlorination:
 • Reduction:
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Reduction to alcohols: Aldehyde and ketones when reacted with hydrogen in the presence of Ni
or Pt to give alcohols.
 • Reduction to alkanes:
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Reduction to pinacols:
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Oxidation of Aldehyde:
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Oxidation of ketones:
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Haloform reactions:
 • Cannizzaro reaction:
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

• Aldehydes which lack an α-hydrogen, when heated with con. NaOH, undergo a
disproportion reaction.

• Wittig reaction:
 • Reformatsky reaction: This reaction involves the treatment of an aldehyde or ketone with α-
CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

bromo ester in the presence of zinc. The product (after acid-hydrolysis) is β-hydroxy ester.
 USES OF ALDEHYDES

• Formaldehyde is found in the gaseous form. However, formaldehyde with 40%

solution in water forms formalin. Formalin helps in the preservation of
biological specimens.
• Formaldehyde reacting with phenol forms a compound Bakelite. Bakelite finds
ALDEHYDES AND KETONES

its application in plastics, coatings, and adhesives.

• The compound- formaldehyde is essential during many industrial processes
such as embalming, glue preparation, tanning and manufacture of polymeric
products.
• It acts as germicide, insecticide, and fungicides.
• Formaldehyde helps in the testing of drugs. It is also used in photography.
• Production of acetic acid and pyridine derivatives is possible from the
compound “acetaldehyde.”
• Benzaldehyde (aldehyde) is an essential component for the production of
perfumes, cosmetic products, and dyes. It is added to incorporate almond
flavour into various food products. It also acts as a bee repellant.
 USES OF KETONES
• Ketone behaves as an excellent solvent for certain types of
plastics and synthetic fibres.
• Acetone act as a paint thinner and a nail paint remover.
ALDEHYDES AND KETONES

• It also is used for medicinal purposes such as chemical peeling

procedure as well as acne treatments.
• Butanone, also known as methyl ethyl ketone, is one of the
common solvents. It is used in textile production, varnishes
production, paint remover production, paraffin wax
production, plastic production, etc.
• Another important ketone is cyclohexanone which is an
important component in nylon production.