Carbonyl Compounds Dr.

S Dey 2021-22
Syllabus:
GE3T: Section-B: Organic Chemistry-II (30 Lectures)
Functional group approach for the following reactions (preparations & reactions) to be
studied in context to their structures.
Carbonyl Compounds (08 Lectures)
Aldehydes and Ketones (aliphatic and aromatic): (Formaldehyde, acetaldehyde, acetone
and benzaldehyde): Preparation: from acid chlorides, from nitriles and from Grignard
reagents; general properties of aldehydes and ketones; Reactions: with HCN, ROH,
NaHSO3, NH2-G derivatives and with Tollens’ and Fehling’s reagents; iodoform test; aldol
condensation (with mechanism); Cannizzaro reaction (with mechanism),Wittig reaction,
benzoin condensation; Clemmensen reduction, Wolff-Kishner reduction and Meerwein-
Pondorff-Verley (MPV) reduction.
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Aldehydes and Ketones (aliphatic and aromatic): (Formaldehyde, acetaldehyde, acetone and
benzaldehyde):

The aldehydes and ketones (both aliphatic and aromatic) belong to the class of oxygen containing
organic compounds that have a C=O group. Therefore, they are termed as carbonyl compounds. In
carbonyl group, the carbon and oxygen are sp2 hybridized. In aldehydes, for example, the three sp2
hybrid orbitals of the carbon form three σ-bonds, namely the bonds with alkyl group (sp2–sp3
overlap), hydrogen (sp2–s overlap), and oxygen (sp2–sp2 overlap). The p orbitals each having one
electron on carbon and oxygen overlap to form a carbon–oxygen π-bond. The bond angle is 120° and
carbonyl compounds have planar structure. Aldehydes and ketones have the following general
structure:

Example:

Preparation:
From acid chlorides:
Aldehydes can be prepared from carboxylic acid halides by the following methods:

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 Carbonyl Compounds Dr. S Dey 2021-22
1. Rosenmund reduction: Acid halides on treatment with hydrogen in the presence of Pd catalyst
supported over BaSO4 get reduced to aldehydes. The catalyst is poisoned with little sulfur, which
prevents further reduction of aldehydes to alcohols. For example,

Benzoyl chloride on catalytic reduction in the presence of Pd/BaSO4 results in the formation of
benzaldehyde.

2. Reduction of acid chloride with Lithium tri-tbutoxyaluminohydride: The reagent is prepared by

treating LiAlH4 with three moles of tert-butyl alcohol. Treating the acid chloride with this reagent in
the presence of diglyme (CH3OCH2CH2OCH2CH2OCH3) as a solvent result in the reduction of acid
halide to aldehyde.

From nitriles:

Stephen reaction: The reaction of alkanenitrile with HCl in the presence of anhydrous stannous
chloride (SnCl2) yields aldimine complex as an intermediate, which on hydrolysis results in the
formation of aldehyde. The main reducing species is tetrachlorostannic acid, H2 [SnCl4], which is
formed by action of HCl and SnCl2. This is illustrated in the following reaction:

Similarly, the aromatic nitriles on reduction with stannous chloride in presence of HCl followed by
hydrolysis of aldimine complex results in the formation of aromatic aldehyde.

From Grignard reagents:

The addition of Grignard reagent to nitriles followed by hydrolysis results in the formation of
aldehydes and ketones.

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 Carbonyl Compounds Dr. S Dey 2021-22
(i) With HCN: Reaction of Grignard reagent with HCN followed by hydrolysis results in the formation
of aldehydes.

Similarly, benzenemagnesium bromide on reaction with HCN followed by hydrolysis results in the
formation of benzaldehyde.

(ii) With alkane nitriles: Reaction of Grignard reagent with alkane nitrile followed by hydrolysis
results in the formation of ketones. The preparation of aldehydes and ketones using Grignard
reagent are depicted as follows:

General properties of aldehydes and ketones:

The carbonyl compounds are polar in nature as the electronegativities of carbon and oxygen differ a
lot, and oxygen being more electronegative has a greater electron density around it compared to
carbon.

Due to polarity, the intermolecular association of carbonyl compounds occurs which makes the
boiling point of carbonyl compounds higher than the corresponding alkane of comparable mass.
However, the carbonyl compounds cannot form hydrogen bonding with each other and their boiling
points are lower compared to alcohols (of comparable mass). Methanal and ethanal are gases at
room temperature; the other members of aldehydes and ketones series are liquids. Higher
aldehydes (C20 onwards) and ketones (C30 onwards) are solid at room temperature. Methanal,
ethanal, and propanone are highly soluble in water due to their association with water through
hydrogen bonding. The higher members (C4 onwards) are either slightly soluble or completely
insoluble in water. The following table enlists the boiling points and densities of some carbonyl
compounds.

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 Carbonyl Compounds Dr. S Dey 2021-22

Reactions: with HCN, ROH, NaHSO3, NH2-G derivatives and with Tollens’ and Fehling’s reagents;
iodoform test; aldol condensation (with mechanism); Cannizzaro reaction (with mechanism),
Wittig reaction, benzoin condensation; Clemmensen reduction, Wolff-Kishner reduction and
Meerwein-Pondorff-Verley (MPV) reduction.

Questions:
Q1. How one can synthesize 2-butanone using CH3MgBr?
Q2. Which of the following compounds will take part in haloform reaction?

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