CARBONYL COMPOUNDS

CHM 121
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Carbonyl Compounds
• These compounds are an integral part of organic chemistry and their primary members are
called aldehydes, ketones, and carboxylic acids.

Compound Aldehyde Ketone Carboxylic acid Carboxylate Ester Amide

Structure

General formula RCHO RCOR' RCOOH RCOOR' RCONR'R''

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Physical Properties of Carbonyl Compounds

• The boiling point of aldehydes and ketones are higher than the boiling point of
ethers and alkanes of similar molecular mass.
• The boiling point of aldehydes and ketones are lower than the corresponding
alcohols.
• Many higher aldehydes have pleasant odour and used in perfumes or as an
artificial flavouring whereas the lower member of their homologous series have
pungent odour.
• Higher ketones have bland odour and lower have pleasant odour, such as acetone.
• Small aldehydes and ketones are soluble in water but as the chain length increase
the solubility decreases.
• The van der Waals dispersion forces get stronger as the molecules get longer.
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H-bonding in Carbonyl Group

• Because of the formation of H-bonding between the carbonyl oxygen and the hydrogen of
water molecule, the lower carbonyl compounds are soluble in water.
• But as the chain increases, it comes on the way to form hydrogen bond and the solubility
decreases.

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Van Der Waals Dipole-dipole Attraction

• Polarity in carbonyl group and the presence of dispersion forces result in an attraction between
two nearby molecules.
• This causes the boiling point of carbonyl compounds to be higher that the corresponding
alkanes.

Molecule Group Boiling point (o C)

CH3CH2CH3 Alkane -42

CH3CHO Aldehyde +21

CH3CH2OH Alcohol +78

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Carbonyl Resonance Chemistr y

• Oxygen is more electronegative than carbon, carbonyl compounds often have resonance structures
which affect their reactivity.
• This relative electronegativity draws electron density away from carbon, increasing the bond's
polarity, therefore making carbon an electrophile (i.e. slightly positive).
• Carbon can then be attacked by nucleophiles (e.g. cyanide ion) or a negatively charged part of
another molecule (e.g. the lone pair electrons of nitrogen in the ammonia molecule).
• During the reaction, the carbon-oxygen double bond is broken, and the carbonyl group may
experience addition reactions.
• The electronegative oxygen also can react with an electrophile; for example a proton in an acidic
solution or with Lewis acids to form an oxocarbenium ion.

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 Acidity of Carbonyl Compounds
• The polarity of oxygen makes the alpha hydrogens of carbonyl compounds much more acidic
(roughly 1030 times more acidic) than typical sp3 C-H bonds, such as those in methane.
• E g. the pKa values of acetaldehyde and acetone are 16.7 and 19 respectively, while the pKa
value of methane is extrapolated to be approximately 50.
• This is because a carbonyl is in tautomeric resonance with an enol.
• The deprotonation of the enol with a strong base produces an enolate, which is a powerful
nucleophile and can alkylate electrophiles such as other carbonyls.
• Amides are the most stable of the carbonyl couplings due to their high resonance stabilization
between the nitrogen-carbon and carbon-oxygen bonds.

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 Aldehyde & Ketone

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Aldehydes and Ketones

• Aldehydes and ketones 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.
• If neither is hydrogen, the compound is a ketone.

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 Occurrence of Aldehydes and Ketones

• Natural Products
• Aldehydes and ketones are widespread in nature, often combined with other functional groups.
• Some are found chiefly in plants or microorganisms others have animal origins.

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Nomenclature

• Derived from parent alkanes, defined by the longest

continuous chain that contains the functional group.
• Aldehyde, -e is replaced with -al.
• Ketone, -e becomes -one.
• The position of a substituent on an aldehyde is designated
by number.
• A ketone substituent is numbered in the manner that gives
the carbonyl carbon atom the lowest possible number.

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 Examples of Aldehydes

BUTANONE

Examples of Ketones

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Naming Aldehydes and Ketones in the same Molecule

• Aldehydes have a higher priority than ketones molecules.

• The ketone is named as an "oxo" substituent.
• A location number is given to the ketone.

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Naming Cyclic Ketones and Diketones

• In cyclic ketones the carbonyl group is assigned location

position 1.
• The rest of the ring is numbered to give substituents the
lowest possible location numbers.
• Cyclo is included to indicate that it is in a ring.
• With cycloalkanes which contain two ketones both carbonyls
need to be given a location numbers with suffix –dione is
added.

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Examples of cyclic ketones 16
Naming Carbonyls and Alkenes in the Same Molecule

• Carbonyl is given nomenclature priority .

• This means that the carbonyl is given the lowest possible location number and the appropriate
nomenclature suffix is included.
• When carbonyls are included with an alkene the following order is followed:
• Location number of the alkene with -en
• ketone –one ; aldehyde -anal ending.

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 Examples

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Common Aldehydes
a. Benzaldehyde is an
oil found in almonds
(b) cinnamaldehyde is Benzaldehyde Cinnamaldehyde
oil of cinnamon
(c) vanillin gives vanilla
its flavour
(d) cis-3-hexenal
provides an herbal
odour
(e) trans-2-cis-6-
nonadienal gives a vanilli cis-3-hexenal
n
cucumber odour.

Trans-2-cis-6-nonadienal
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 Ketones have
interesting properties:
(a)Butter flavouring
comes from 2,3-
butanedione
2,3-butanedione β-ionone
(b) β-ionone is
responsible for the
odour of violets
(c)muscone is musk
oil, an ingredient in
perfumes
(d)camphor is used in
some insect
repellents. Muscone Camphor

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• PROPERTIES

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 Polarity

• Aldehyde and ketone are polar molecules due to the high dipole moments of their carbonyl group.

• Oxygen is far more electronegative than carbon and strong tendency to pull electrons in a carbon-
oxygen bond towards itself.
• Carbon-oxygen double bond is very highly polar.
• The presence of two electron-donating R-groups in ketones makes them more polar than aldehydes.
• The dipole moments that arise from this polarity account for the higher boiling points of ketones.

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 Properties
• Aldehydes and ketones have larger molecular dipole moments than alkenes.
• (i) The resonance structures
• (ii) Relative dipole moments
*(alkyl substituents have on carbocations)
• They have higher boiling points than similar sized alkenes.
• They are hydrogen-bond acceptors (oxygen with its non-bonding electron pairs).
• aldehydes undergo autoxidation.

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• Boiling points are higher than for hydrocarbons and ethers of similar molecular
weights.
• No intermolecular H-bonding in ketones and aldehydes
• Ketones and aldehydes are good solvents for polar hydroxylic substances such as
alcohols (H- bonding).
• They are remarkably soluble in water.

aldehyde ketone
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Keto-enol Tautomerization
• Aldehyde or ketone will form an equilibrium with enols, in which the double
bond of the carbonyl group migrates to form double bond between the carbonyl
and the alpha (α) carbon.
• Equilibrium of carbonyl compounds between two forms (keto and enol).
• The presence of α-hydrogen is necessary for this equilibrium.
• Compounds not possessing it are called non-enolizable ketones.

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• Protonation of enolate into oxygen leads to enol (unstable).
• It quickly transforms (tautomerized) into a carbonyl system.
• The keto form (usually) predominates.
• It is catalyzed by acid or base (even trace amounts).
• Tautomerization always requires two steps
• (i) protonation
• (ii) deprotonation
• The order of steps depends on whether the reaction takes place
in acid or base.
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• In the presence of an acid, protonation of the oxygen group will occur,
and water will abstract an alpha (α) hydrogen.

• In the presence of a base, deprotonation of the alpha hydrogen will

occur, and a hydrogen from water will be abstracted by the carbonyl
oxygen

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 Reactivity
• Chemical reactivity of the C=O is enhances when compared with the non-
polar C=C of alkene.
• This is due to
i. The polarity of the carbonyl group
ii. Increased basicity
e. g.
• Reversible addition of water to the carbonyl is fast
• Addition of water to alkenes is immeasurably slow in the absence of a
strong acid catalyst (high EA).

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 • Aldehydes are more susceptible to nucleophilic substitution(Hydrogen atom is
small; no steric hindrance).
1a. The two alkyl/aryl groups in ketones offer steric hindrance during
substitution reactions
b. The partially positive charge on the carbonyl carbon is stabilized by
the two R groups in ketones.
2. Electronically, aldehydes have only one R group to supply electrons
toward the partially positive carbonyl carbon, while ketones have two.
(less partial positive charge on C and the weaker it will become as a nucleus).

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 Carbonly

As compared with

alkene

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 Addition of Water

Mechanism of addition of water

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 Reactions
• Most common reaction of a carbonyl group is addition of a nucleophile to form a
tetrahedral carbonyl addition compound.
• The carbonyl carbon atom is highly electrophilic due to
• a. significant partial positive charge
• b. the ability to accommodate a new bond through the conversion of the p bond to a
lone pair on oxygen of the tetrahedral carbonyl addition
• Aldehydes and ketones are much alike in many of their reactions, owing to the
presence of the carbonyl functional group in both.
• They differ greatly in one most important type of reaction: oxidation.

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Addition of HCN: Hydroxynitriles

• Nitriles of hydroxy acids; containing one hydroxyl (—OH) group and one cyano
(—C≡N).
• HCN, adds to the carbonyl group of an aldehyde or ketone to form a tetrahedral
carbonyl addition compound -cyanohydrin.
• HCN adds to acetaldehyde to form acetaldehyde cyanohydrin in 75% yield
• HCN itself is an acid, so the addition is not acid-catalyzed.
• For best results cyanide anion, C≡N(-) must be present (i.e catalytic base must be
added).
• Cyanohydrin formation is weakly exothermic, and is favoured for aldehydes, and
unhindered cyclic and methyl ketones.
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 e.g. ethanal (an aldehyde) gives 2-hydroxypropanenitrile

With acetone (a ketone) you get 2-hydroxy-2-methylpropanenitrile:

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Halogenation of Ketones
• In the presence of a base, ketones with α hydrogens react to form α haloketones

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 With Iodine

• Methyl ketones react with iodine in the presence of a base to give complete
halogenation

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 I o d o f o r m Te s t

• The generation of sodium hypoiodate in solution from the reaction of iodine

with sodium hydroxide leads to the formation of iodoform and sodium
benzoate, as shown here.

• Iodoform is a pale yellow solid, this reaction is often run as a test for methyl
ketones and is called the iodoform test.

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Oxidation
A. Oxidation Of Aldehydes

• Undergoes oxidation rapidly with common oxidizing agents to carboxylic acids

by a variety of, including chromic acid and molecular oxygen.
• Aldehydes are also oxidized to carboxylic acids by Ag(I) ion.
• One laboratory procedure is to shake a solution of the aldehyde in aqueous
ethanol or tetrahydrofuran with a slurry of Ag2O

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 Oxidation of Aldehydes and Ketones

• Aldehydes are readily oxidized to carboxylic acids. The ease of oxidation helps
identify aldehydes
• Ketones resist oxidation.

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 Tollens’ Reagent : Silvermirror Test
• Aldehydes are oxidized to carboxylic acids by Ag(I) ion

• When is added to an aldehyde, the aldehyde is oxidized to a carboxylic

anion, and Ag(I) is reduced to metallic silver (silver precipitates as a smooth,
mirror-like deposit)
• Ag(I) is rarely used at the present time for the oxidation of aldehydes
because of the cost of silver and more convenient methods exist for this
oxidation.
• Though, is still used for silvering glassware, including mirrors.
• Formaldehyde or glucose is generally used as the aldehyde to reduce Ag(I).
• Aldehydes are also oxidized to carboxylic acids by molecular oxygen and by
hydrogen peroxide.

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 Examples

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 Reduction of Aldehydes and Ketones

Aldehydes and ketones can both be reduced into alcohols.

• An aldehyde will form a primary alcohol (the carbon which is bonded to the OH is only bonded to
one other carbon).
• A ketone will form a secondary alcohol (the carbon which is bonded to the OH is bonded to two
other carbons).
• The most common reagents are: sodium borohydride with methanol, lithium-aluminum hydride
then water, or hydrogen with Pd-C.

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 C. Addition of Nitrogen Nucleophiles: Ammonia
Derivatives

• Reaction with ammonia or 1⁰ amines forms imine derivatives, Schiff bases, (C=N).
• Imines of aldehydes are relatively stable, those of ketones are unstable.
• (unless the C=N group is part of an extended system of conjugation (e.g., rhodopsin) and are
generally not isolated).
• Imines derived from aldehydes are sometimes called aldimines, from ketones are sometimes
called ketimines.
• This reaction plays an important role in the synthesis of 2 ⁰ amines
• Water is eliminated in the reaction, which is acid-catalyzed and reversible as in acetal
formation.

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 Examples

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• Enamine

• An unsaturated compound derived by the reaction of an aldehyde or ketone and a

secondary amine followed by loss of H2O.
• The name enamine is derived from -en- to indicate the presence of a carbon-
carbon double bond and -amine to indicate the presence of an amino group.
• Enamines are easily converted back to their carbonyl precursors by acid-catalyzed
hydrolysis.

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Distinguishing Tests Between Aldehydes And Ketones
• (a) Schiff’s Test:
• Aldehydes abstract sulphurous acid from Schiff’s reagent and give pink colour. The colouration
is due to the formation of complex compound. Ketones, in general, do not respond to this
reaction.
• Note: Appearance of pink, red or magenta colour indicates the presence of aldehyde group.
• (b) Fehling’s Test:
• Fehling’s solution is a complex compound of Cu2+. When the aldehyde compound is treated
with Fehling’s solution Cu2+ is reduced to Cu+ and the aldehyde is reduced to acids. During the
reaction, a red precipitate is formed.
• Aromatic aldehydes do not respond to Fehling’s test. An aqueous solution of the compound
may be used instead of an alcoholic solution. Formic acid also gives this test.

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• (c) Tollen’s Test: (Silver Mirror Test)
• This test is also called the silver mirror test. Tollens reagent consists of silver ammonia complex
in ammonia solution. Aldehydes react with Tollens reagent giving a grey-black precipitate or a
silver mirror. Always a freshly prepared Tollen’s reagent should be used. Aldehydes are oxidised
to the corresponding acids, and silver in Tollens reagent is reduced from +1 oxidation state to its
elemental form. Generally, ketones do not respond to this test.
RCHO + 2[Ag(NH3)2]OH → R-COONH4 + 3NH3 + H2O + 2Ag↓(silver mirror)

• (d) Sodium Nitroprusside Test:

• Ketone responds to this test. Ketone reacts with alkali and forms an anion which further reacts
with sodium nitroprusside and forms a coloured complex ion. Aldehydes do not respond to this
test.
CH3COCH3 + OH–→ CH3COCH2– + H2O
[Fe(CN)5NO]2- + CH3COCH2– → [Fe(CN)5NO.CH3COCH2]3-
• Note: The appearance of red colouration shows the presence of ketone.

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 Uses of Aldehydes

• Formaldehyde with 40% solution in water forms formalin which helps in the preservation of
biological specimens.
• Formaldehyde reacts with phenol to forms Bakelite used in plastics, coatings, and adhesives.
• Essential in embalming, glue preparation, tanning and manufacture of polymeric products.
• It acts as germicide, insecticide, and fungicides.
• Helps in the testing of drugs. It is also used in photography.
• Acetaldehyde is used in the production of acetic acid and pyridine derivatives
• Benzaldehyde 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

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Uses Of Ketones

• Acetone which is an excellent solvent for a number of plastics and synthetic fibres.
• In the household, acetone is used as a nail paint remover and paint thinner.
• In medicine, it is used in chemical peeling and for acne treatments.
• Methyl ethyl ketone (MEK), chemically butanone, is a common solvent. It is used in
the production of textiles, varnishes, plastics, paint remover, paraffin wax, etc.
• MEK is also used as a welding agent for plastics due to its dissolving properties.
• Cyclohexanone is another important ketone which is primarily used in the production
of nylon.

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 Nomenclature Practice questions

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