DISTINGUISHING TESTS

ALDEHYDES ARE EASILY OXIDISED TO CARBOXYLIC ACIDS . THE REASON OF THEIR

EASY OXIDATION IS PRESENCE OF H- ATOM ON CARBONYL GROUP , WHICH CAN BE
EASILY CONVERTED TO –OH GROUPWITHOUT INVOLVING CLEAVAGE OF ANY OTHER
BOND. SO, THEY ARE NOT ONLY OXIDISED BY STRONG OXIDIZING AGENTS LIKE
KMNO4, K2CR2O7 AND HNO3 BUT ALSO BY WEAK OXIDISING AGENTS LIKE BROMINE
WATER, TOLLEN REAGENT AND FEHLING REAGENT
Chemistry of Tollen Reagent Test-The Tollens test, also known as the silver mirror test,
is a chemical test that differentiates between aldehydes and ketones. It utilizes Tollens reagent, an
ammoniacal solution of silver nitrate, which oxidizes aldehydes to carboxylic acids and
simultaneously reduces silver ions to metallic silver. This reduction of silver ions results in the
formation of a silver mirror on the inner surface of the test tube.

• Tollen reagent isprepared by adding silver nitrate (AgNO3) to an aqueous solution of

ammonium hydroxide (NH4OH).
• The reaction produces a complex ion, [Ag(NH3)2]+, which is the active component in
the test.

• Aldehydes (RCHO) are readily oxidized by Tollens reagent to form carboxylic acids
(RCOOH).
• Simultaneously, silver ions (Ag+) in the reagent are reduced to metallic silver (Ag).
Chemistry of Fehling Test-
• Fehling's solution is composed of two solutions: Fehling's A (copper sulfate) and
Fehling's B (alkaline sodium potassium tartrate).
• When equal volumes of A and B are mixed, a deep blue solution is formed.
• The tartrate ions in Fehling's B act as a chelating agent, forming a complex with
copper(II) ions.
• When an aldehyde (or reducing sugar) is added to this solution and heated, the
aldehyde is oxidized to a carboxylic acid, and the copper(II) ions are reduced to
copper(I) oxide, which precipitates as a reddish-brown solid.
Etard Reaction- prepration of benzaldehyde-The Étard reaction is a
chemical reaction that involves the direct oxidation of an aromatic or
heterocyclic bound methyl group to an aldehyde using chromyl chloride.
Preparation of aldehydes-1. From Nitriles and Esters using DIBAL-H – Nitriles are
selectively reduced by DIBAL-H (di -isobutylaluminium hydride) to imine followed by
hydrolysis to aldehydes.
Similarly esters can also be reduced to aldehydes with DIBAL-H
2. By chromic oxide(CrO2) -Benzaldehyde can be prepared from toluene using
chromic oxide (CrO3) in acetic anhydride. This oxidation reaction converts the methyl
group of toluene into a carbonyl group, forming benzaldehyde. The acetic anhydride helps
to control the reaction, preventing the further oxidation of benzaldehyde to benzoic acid.

■ Benzaldehyde can be prepared from toluene using chromium trioxide (CrO3) and acetic
anhydride in a process known as the Etard reaction. Toluene reacts with CrO3 in acetic
anhydride to form benzylidene diacetate, which is then hydrolyzed to yield
benzaldehyde.
By side chain chlorination followed by hydrolysis- Side chain
chlorination of Toluene gives benzal chloride which on
hydrolysis gives benzaldehyde

■ H2O
■ C6H5CH3 + Cl2 -------------→ C6H5CHCl2---------→ C6H5CHO
Prepration of ketones- a)From acyl chloride-Ketones can be prepared from acyl
chlorides using dialkyl cadmium or by reacting with a palladium-catalyzed boronic acid. Dialkyl
cadmium reacts selectively with acyl chlorides to form ketones without further reaction with the
product.
Prepration of ketones from nitriles-Ketones can be prepared from nitriles by
first reacting the nitrile with a Grignard reagent, which forms an imine
intermediate. This imine intermediate is then hydrolyzed (usually with aqueous
acid) to yield the desired ketone.
Chemicals reactions of aldehydes and ketones- Nucleophilic addition
reactions-Aldehydes and ketones undergo nucleophilic addition reactions
because of the polar nature of the carbonyl group (C=O), where the carbon
atom is partially positive and the oxygen atom is partially negative. These
reactions involve a nucleophile (a molecule or ion with a negative charge or
lone pair of electrons) attacking the partially positive carbonyl carbon.
1)CYANOHYDRINS- a cyanohydrin is a compound where a cyano (CN) group
and a hydroxyl (OH) group are attached to the same carbon atom. They are
formed by the nucleophilic addition of hydrogen cyanide (HCN) to a
carbonyl compound (aldehyde or ketone).
2) SEMICARBAZONE-Semicarbazones are compounds formed when an
aldehyde or ketone reacts with semicarbazide, a derivative of urea. This
reaction is a type of condensation reaction where a water molecule is
eliminated, and a carbon-nitrogen double bond is formed.
3) HEMIACETAL-Hemiacetals are functional groups formed when an
aldehyde or ketone reacts with one molecule of alcohol, resulting in a
carbon atom bonded to one alkoxy group (OR) and one hydroxyl group
(OH).
4) ACETAL-An aldehyde reacts with two molecules of alcohol to form an
acetal. This reaction typically proceeds through a hemiacetal intermediate, where
the first alcohol molecule adds to the carbonyl carbon, and then a second alcohol
molecule attacks the hemiacetal to form the acetal. The reaction is acid-catalyzed
and involves the elimination of a water molecule.
5) KETAL- A ketal is a functional group formed from a ketone by replacing
the carbonyl group (C=O) with two alkoxy groups (O-R). It is formed when a
ketone reacts with dihydroxy alcohol.
6)2,4- DNP derivative -A 2,4-dinitrophenylhydrazine (2,4-DNP)
derivative is formed when 2,4-dinitrophenylhydrazine (2,4-DNPH) reacts
with a carbonyl compound, like an aldehyde or ketone. This reaction
produces a 2,4-dinitrophenylhydrazone, which is a substituted hydrazine.
8) OXIME- Oximes are organic compounds belonging to the imine family,
characterized by a carbon-nitrogen double bond with a hydroxyl group attached to
the nitrogen. They are formed by the reaction of carbonyl compounds (aldehydes
or ketones) with hydroxylamine. Oximes can be either aldoximes (derived from
aldehydes) or ketoximes (derived from ketones).
CARBOXYLIC ACIDS- PREPRATION- a) From alkyl benzene-
alkylbenzene can be converted to a carboxylic acid through oxidation, specifically
using strong oxidizing agents like potassium permanganate (KMnO4) or chromic
acid in presence of KOH.The side chain on the benzene ring is completely oxidized,
yielding an aromatic carboxylic acid.
b) From nitriles and amides-Carboxylic acids can be prepared from nitriles and
amides through hydrolysis reactions. Both nitriles and amides undergo hydrolysis
in the presence of acid or base to produce carboxylic acids. The reaction is a two-
step process, with nitriles first hydrolyzing to amides before being further
hydrolyzed to carboxylic acids.
ACIDIC CHARACTER OF CARBOXYLIC ACIDS- ( Cleavage of –O-/-
H-
■ The acidic character of carboxylic acids stems from the ability of the -
COOH group to dissociate, releasing a proton (H+) and forming a
carboxylate ion (RCOO-). This dissociation is facilitated by the resonance
stabilization of the carboxylate anion, where the negative charge is
delocalized over both oxygen atoms, making the resulting anion more
stable.
■ The hydrogen atom in the -COOH group is acidic because it can be easily
removed as a proton (H+).
■ When a carboxylic acid dissociates, it forms a carboxylate ion (RCOO-)
and a hydronium ion (H3O+).
■ The carboxylate ion has a negative charge that is delocalized over both
oxygen atoms due to resonance. This delocalization stabilizes the anion
and makes it more stable, contributing to the acidity of carboxylic acids.
■ The presence of electron-withdrawing substituents near the carboxyl
group can further increase the acidity by stabilizing the carboxylate
anion and making it easier to form.
Reactions of carboxylic acids showing acidic behaviour

■ React with active metals to release hydrogen gas

■ 2CH3COOH + 2Na --------→ 2CH3COONa + H2
■ Reacts with alkalies to form salt and water
■ CH3COOH + NaOH ---------→ CH3COONa+ H2O
■ React with NaHCO3 to release CO2
■ CH3COOH+ NaHCO3------→ CH3COONa + CO2 + H2O
 Reactions involving cleavage of C-------/ -----OH bond
■ 1. Formation of acetic anhydride
■ H+ , heat/P2O5, heat
2CH₃COOH ------------------------------------> (CH₃CO)₂O + H₂O.
2. Esterification- CH3COOH+ C2H5OH ----------→ CH3COOC2H5 + H20
3. Reaction with PCl5, PCl3 and SOCl2
3CH3COOH + PCl3 → 3CH3COCl + H3PO3.

CH3COOH + PCl5 ---→ CH3COCl + POCl3 + H2O

CH3COOH + SOCl2 ------→ CH3COCl+ SO2 + H2O

Reaction with NH3- On reaction of carboxylic acids with NH3, it
gives ammonium salt which on heating gives amide

■ CH3COOH + NH3 ----→ CH3COONH4 ----HEAT----→ CH3CONH2

■ ammonium acetate acetamide
■ C6H5COOH + NH3 -----→ C6H5COONH4 -----HEAT------→ C6H5CONH2
■ ammonium benzoate benzamide
Reactions involving –COOH group ---

■ Reduction --- CH3COOH --------------LiAlH4 / ether or B2H6-----→ CH3CH2OH

■ Decarboxylation– CH3COOH + NaOH---------CaO, HEAT -------→ CH4 + Na2CO3

Electrophilic substitution of benzoic acid-Benzoic acid undergoes
electrophilic substitution reactions, but primarily at the meta position due
to the electron-withdrawing nature of the carboxyl group (-COOH). This
group deactivates the benzene ring, making it less reactive than benzene
itself, and directing the electrophile to the meta position.
NOTE: Benzoic acid does not undergo Friedel-Crafts reactions primarily
because the carboxylic acid group (-COOH) is an electron-withdrawing substituent
that deactivates the benzene ring. This deactivation makes the aromatic ring less
reactive towards electrophiles, which are required for Friedel-Crafts alkylation or
acylation. The catalyst (AlCl3) can interact with the -COOH group, further hindering
the reaction.