Aldehydes, Ketones &

Carboxylic Acids
General
• Aldehydes, Ketones and Carboxylic acids are widespread in plant and
animal kingdom.
• They are responsible for fragrance and flavour

• Used as solvents in paints, resins, perfumes, plastics, fabrics

Some common aldehydes
Some common Ketones
Structure
Preparation
Aldehydes
From alcohols (oxidation)
From alcohols (catalytic dehydrogenation)
From Alkenes (Ozonolysis)
From Alkenes (Ozonolysis)
 From Alkynes (Hydration)

Keto-enol tautomerism

Keto-enol tautomerism

It follows Morkownikoff’s rule. Dil. H2SO4 in 1 % HgSO4 is used

From acid chlorides (Rosenmund’s
Reduction)

• Pd is Catalyst
• BaSO4 is catalytic poison, it reduces the activity of palladium, and
stops the reaction at aldehyde stage, preventing further reduction to
alcohol
From acid chlorides (Dimethyl Cadmium Reaction)
Dry distillation of Calcium Salts
From calcium salt of carboxylic acids
Symmetric compounds
From calcium salt of carboxylic acids
Symmetric compounds
From calcium salt of carboxylic acids
Unsymmetric compounds
From nitriles (Grignard’s reagent)
From nitriles (Stephen reaction)
From Esters
Physical Properties: Boiling Point

• Methanal = gas, Ethanal = volatile liquid. Other

aldehydes and ketones are liquid or solid at RT
• Hydrocarbons < Aldehydes, Ketones < Alcohols
(Vander walls < dipole-dipole < hydrogen bonding)
Physical Property: Solubility
• The lower members of aldehydes and ketones are miscible in water
• Due to formation of hydrogen bond with water
• Solubility decreases with increase in alkyl chain.
• All aldehydes and ketones are fairly soluble in organic solvents.
Chemical Properties

• Aldehydes are more reactive than ketones in nucleophilic addition

reactions due to two factors:
• Electronic Factor or Inductive Effect: This which effect in ketones is
more due to presence of more electron releasing groups stabilizes the
positively charged carbon in ketones.
• Steric Factor: This effect is again more in ketones than those of
aldehydes, therefore the order of reactivity will
Nucleophilic addition reactions
with mechanism
(ammonia and its derivatives, HCN, NaHSO3 and Grignard’s reagent).
Reaction with Ammonia & its derivatives
With Acetaldehyde
Reaction with Ammonia & its derivatives

Used as an antibiotic to treat

urinary tract infections

Structure of hexamethylenetetramine
Reaction with Hydroxylamine

Produce Oximes
Reaction with Hydrazine

Produce hydrazone
Reaction with Phenyl hydrazine

Produce hydrazone
Reaction with 2,4-dinitrophenyl hydrazine
Reaction with semicarbazide

semicarbazide
 Reaction with Sodium bisulphite

When R is up to 3 Carbon chain the reaction works, beyond that

the reaction do not proceed, probably due to steric effect. Other
ketones included aromatic ketones fail to react.

The bisulphide compounds can be decomposed back to parent

carbonyl compound by heating them with mineral acids (used in
purification)
 Reaction with HCN

In actual practice HCN required in the reaction is produced insitu with sodium cyanide and mineral acid.
Reaction with Grignard Reagent
• (done in alcohol lesson)
Oxidation Reactions
• (done in alcohol lesson)
Iodoform Reaction
• (done in alcohol lesson)
Reduction: Clemmensen
Reduction: Wolff-Kishner
Reduction: Red P & HI
Aldol Condensation
• Aldehydes or Ketones with at least one α hydrogen atom undergo this
• Dilute solutions of bases like NaOH, Ba(OH)2, K2CO3, etc, are used
• It is as self condensation reaction.
• The products are β- hydroxy aldehydes or β-hydroxy ketones.
• As β- hydroxy aldehydes contain both aldehyde and alcohol groups they
are commonly called as aldols
Aldol Condensation: Mechanism
OH- catalyses by
proton abstraction,
producing water

OH- regenerated by
reacting with water
Cross Aldol Condensation

Mixture of products obtained in this case

When one aldehyde

don’t have α H, then
single product is
obtained
 Cannizzaro Reaction
The disproportionation of aldehydes lacking α-hydrogens (for example, HCHO,
C6H5-CHO, R3C-CHO etc.,) in presence of a strong base to form salt of an acid
and a corresponding primary alcohol is known as Cannizzaro reaction. Here,
one molecule is oxidized and the other is reduced.
Cannizzaro Reaction: Mechanism
Step: 1

Step: 2

Step: 3
Cross-Cannizzaro Reaction (not in syllabus)
• It is the formaldehye molecule that undergoes oxidation
Common tests for aldehydes and ketones
• Only aldehydes restore pink colour of Schif's reagent.
• Aldehydes reduce Tollen's reagent to silver mirror and give red brown
ppt. with Fehling's solution.
• Ketones do not respond to these tests.
Special tests
Formaldehyde
• Schryver's Test : 1 mL of 1%
phenyl hydrazine hydrochloride
and 1 mL of 5% potassium
ferricyanide solution is added to
formalin. It is acidified by adding
1 mL of conc. HCI. Appearance
of rosy red colour confirms
formaldehyde.
Acetaldehyde
• Acetaldehyde gives yellow
precipitate of iodoform on
heating with l, and NaOH
solution.
• With freshly prepared sodium
nitroprusside and excess of dil.
NaOH, it produces deep red
colour.
Uses of Aldehydes and Ketones
• Aldehydes and ketones are responsible for many flavours and odours
such as vanllin (vanilla flavour), cinnamaldehyde (cinnamon flavour),
benzaldehyde (almond flavour). They are used as solvents and
starting materials for the synthesis of other products. Formalin (40%
aqueous solution of formaldehyde) is used as preservative for
biological specimens: and to prepare bakelite.
• Acetaldehyde is used as starting material for acetic acid, esters,
polymers and drugs. Benzaldehyde is used in perfumery and in dye
industries.
Aromatic aldehyde
(Benzaldehyde)
Lab preparation from toluene by oxidation
with chromyl chloride.
• Alkyl benzenes can also be oxidised to benzaldehyde with a solution
of chromyl chloride (CrO2Cl2) in CCl4 or CS2. A brown complex is
formed which is decomposed by water to give corresponding
aldehyde. It is called Etard reaction.
Physical properties: state and stability.
• It is a colourless oily liquid and has smell of bitter almonds.
• It is sparingly soluble in water
Chemical Properties Aromatic
Aldehyde (Benzaldehyde)
Oxidation and reduction.
Nucleophilic addition reaction (hydrogen
cyanide).
• However, the reactivity is low as compared to that of aliphatic
aldehydes.
Nucleophilic addition reaction (sodium
bisulphite)
• However, the reactivity is low as compared to that of aliphatic
aldehydes.
Reactions with ammonia and its derivatives
(hydroxyl amine, hydrazine and phenyl hydrazine).
Reactions with ammonia and its derivatives
(hydroxyl amine, hydrazine and phenyl hydrazine).
Reaction with phosphorus pentachloride.
Cannizzaro reaction.
• Unlike aliphatic aldehydes, benzaldehyde undergoes Cannizzaro’s
reaction.
Benzoin condensation.
• Benzaldehyde when heated with an alcoholic solution of potassium cyanide
undergoes self condensation to form benzoin, known as benzoin condensation.
Perkin’s reaction.
• Benzaldehyde on heating with acetic anhydride in presence of sodium
acetate first forms condensation product which upon hydrolysis gives
the corresponding a,ß-unsaturated acid.
Electrophilic substitution - halogenation,
nitration and sulphonation.
Test: distinction between aromatic and
aliphatic aldehydes.
• Aliphatic aldehydes reduce Fehling solution to give red precipitate of
Cu2O but aromatic aldehydes do not respond to this reagent.
• Aliphatic aldehydes containing CH3CO group give iodoform test but
aromatic aldehydes never give iodoform test.
Uses of benzaldehyde
• Used in perfumery.
• In the manufacture of dyes, benzoic acid.
• as a flavouring agent for food, beverages, etc.
• in the manufacture of triphenylmethane dyes like malachite green
• as a starting material for the preparation of cinnamaldehyde,
cinnamic acid, benzoyl chloride, etc.
Carboxylic Acids
Classification of mono and di carboxylic
acids with examples.
mono di
NOMENCLATURE
Preparation of aliphatic and
aromatic carboxylic acid:
From alcohols, aldehydes
From alcohols, aldehydes
From nitriles
From Grignard’s reagent
Physical properties: state, boiling point and
solubility
Aliphatic carboxylic acids up to nine carbon atoms are colourless liquids at
room temperature with unpleasant smel. The higher acids are wax like solids
with no odour.
Carboxylic acids have higher boiling points than aldehydes, ketones and
alcohols of comparable molecular masses. This is due to their association as
they can form intermolecular hydrogen bond. This also increases their
solubility in water.
The solubility decreases with increase in the number of carbon atoms.
Benzoic acid is nearly insoluble in cold water but also soluble in hot water,
benzene, ethe, alcohol, chloroform etc.
Carboxylic acids exist as dimer in the vapours phase or in the aprotic solvents.
Chemical properties:
• Carboxylic acids are weaker acids than mineral acids but stronger than
alcohols and phenols.

• The carboxylate ions are stable due to resonance.

Acidic character: (aliphatic, aromatic carboxylic acids with the
effect of substituents on the acidic character – to be dealt with in
detail)
• Electron withdrawing substituents disperse negative charge on the carboxylate
ion and stabilize it and thus increase acidity but the electron releasing
substituents intensify the negative charge of the carboxylate ion, destabilise it
and thus decrease the acidity.
• On the basis of above facts, the common acids have been arranged in the
following order of acidic strength based on their pK, values :
• The phenyl and vinyl groups attached directly to the carboxylic group increases
the acidity of the carboxylic acids. Since +I effect of –C6H5 group is smaller than
+ I effect of alkyl group, C6H5COOH is stronger acid than CH3COOH.
Acidic character: (aliphatic, aromatic carboxylic acids with the
effect of substituents on the acidic character – to be dealt with in
detail)
• The electron withdrawing groups like –Cl, -NO2, etc., increase the acidic strength of
benzoic acid whereas electron releasing groups like –CH3,-OH, -OCH3, and-NH2,
decrease the acidic strength of benzoic acid.
• In both the above cases, the substituent at the ortho and para position has more
influence than the meta isomer.
Acidic character: (aliphatic, aromatic carboxylic acids with the
effect of substituents on the acidic character – to be dealt with in
detail)
• Again the ortho isomer of every substituted benzoic acid is the
strongest acid among the three isomers, no matter whether the
substituent is electron releasing or electron withdrawing.
Reaction with active metals, alkalies,
carbonates and bicarbonates,
• Carboxylic acids react with active metals such as Na, K, Mg, Ca, Zn, etc.,
to form corresponding salts with the liberation of hydrogen. All these
reactions are due to H-atom of the carboxyl group.
Reaction with active metals, alkalies,
carbonates and bicarbonates,
• Carboxylic acids react with alkalis, neutralise them and form salts.
Reaction with active metals, alkalies,
carbonates and bicarbonates,
• Carboxylic acids decompose carbonates and bicarbonates evolving
carbon dioxide gas with effervescence.
 Formation of acid derivatives. (Esters)

• It is a reversible reaction, but the equilibrium may be shifted towards right by

using excess of alcohol or by removing water continuously from the site by a
suitable method.
• Conc. Sulfuric acid or dry HCl can be used
• The reactivity of alcohol towards esterification increases:
3º OH < 2º OH < 1º OH < methanol (stearic effect)
• Similarly, reactivity of carboxylic acid increases as:
R3COOH < R2CHCOOH < RCH2COOH < CH3COOH < HCOOH (stearic effect)
 Formation of acid derivatives. (Anhdrides)

• The reaction proceeds in the presence of a strong dehydrating agent like

Conc. Sulfuric acid or Phosphorous pentoxide
Formation of acid derivatives. (Acid
Chlorides)
Formation of acid derivatives. (Amides)
Decarboxylation (chemical and Kolbe’s
electrolytic reaction)
• Sodium salts of carboxylic acid on heating with sodalime (3:1 NaOH
and CaO) give alkane.
Decarboxylation (chemical and Kolbe’s
electrolytic reaction)
• Decarboxylation of carboxylic acids can also be carried out by the electrolysis of concentrated
aqueous solution of their sodium or potassium salts. The process is known as Kolbe's electrolysis.
HVZ reactions
• Carboxylic acids (except formic acid which does not contain any alkyl
group) react with chlorine or bromine in the presence of a small
amount of phosphorus to give a-halogenated carboxylic acids.
Halogenation takes place mainly at a-position and continues till all the
α-halogen atoms are replaced by chlorine or bromine atoms. The
reaction is called Hell-Volhard-Zelinsky (HVZ) reaction.
Substitution of benzene ring (meta directive effect of
carboxylic acid group) nitration and sulphonation.
Carboxyl group is an electron-withdrawing group and therefore acts as a meta-
directing group. Therefore, in aromatic carboxylic acids, the electrophilic
substitution takes place at meta position. Further; the carboxyl group is a
deactivating group. Therefore, the electrophilic substitution reactions take place
only under drastic conditions.
Tests for acids: formic acid
Tests for acids: acetic acid and benzoic acid.
• Acetic acid gives wine red colour with neutral ferric chloride solution.
• Acetic acid on heating with ethanol in presence of conc. H,SO4 gives
pleasant fruity smell due to the formation of ester.
• Benzoic acid gives buff coloured precipitate with neutral FeCl3
solution.
• Benzoic acid gives sweet smelling ester on warming with ethanol and
little conc. H2SO4.
Uses of formic acid, acetic acid and benzoic
acid
• Formic Acid: As a reducing agent, as an antiseptic, as a preservative.
In medicine as a remedy for gout, In dyeing textiles.
• Acetic Acid: It is used as vinegar (5-8% aqueous solution of acetic
acid), As a solvent for resins, In the preparation of acetyl chloride,
acetic anhydride etc.
• Benzoic Acid: It is used as food preservative in the form of sodium
benzoate, In the perfumery, In medicine as urinary antiseptic and for
treatment of skin diseases like eczema.