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Aldehydes and Ketones

Group 3:
Đỗ Thị Ý Như_19125486
Ngô Phạm Thảo Nguyên_19125485
Nguyễn Hoàng Như Thủy_19125494
Huỳnh Thị Phương Uyên_19125537

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 The application of aldehyde
MEDICAL USES:
• Formaldehyde kills most bacteria, and so a solution of formaldehyde in water is common
ly used as a disinfectant.
• Aldehyde treats the cardiovascular disease.
• Aldehyde treatment of natural tissue crates cross-links in the collagen molecules while re
taining mechanical strength and collagen structure.
 The application of aldehyde
INDUSTRIAL USES:
• Benzaldehyde is commonly employed as a commercial food flavourant (almond flavor) or in
dustrial solvent, benzaldehyde is also is also used in the synthesis of other organic compoun
ds, ranging from pharmaceuticals to plastic additives.
• It is also an important intermediate for the processing of perfume and flavoring compounds
and in the preparation of certain aniline dyes.
• Cinnamaldehyde has its most obvious application of flavoring.
• Cinnamaldehyde is used in some perfumes of natural, sweet, or fruity scents.
• Almond, apricot, butterscotch, and other aromas may partially employ the compound for the
ir pleasant smells.
 Health benefits of ketogenic diets
Ketones and the ketogenic diet have a number of health benefits.
1. The ketogenic diet has strong anti-seizure properties. Many children and adults with epilepsy, wh
ose condition cannot be treated with drugs, become seizure-free with a ketogenic diet. The effect
may be due to increased mitochondrial energy production in the brain.
2. Ketones and the ketogenic diet may be useful in the treatment of Alzheimer’s disease. A case that
was in the news not long ago was of a doctor who treated her husband’s Alzheimer’s disease with
coconut oil, which metabolizes to ketones. The treatment was quite successful.
3. The ketogenic diet may be useful for insulin resistance.
4. The ketogenic diet may help treat cancer. cells thrive on glucose, so keeping blood sugar low may
be therapeutic.
5. Finally, the ketogenic diet can be used for fat loss.
 Preparation of Aldehydes and Ketones

• 1. By Oxidation of Alcohols
• 2. From hydrocarbons
• 3. Aldehydes from esters
• 4. From nitriles
• 5. From acid chlorides
 Preparation of Aldehydes and Ketones

1. By Oxidation of Alcohols
• Oxidation of primary and
secondary alcohols leads to the
formation of aldehydes and
ketones.
• The oxidation is possible with the
help of common oxidizing agents
are KMnO4, CrO3, and Na2Cr2O7.
• Strong oxidizing agents helps in
the oxidation of the primary
alcohol to aldehyde then to a
carboxylic acid.
 Preparation of Aldehydes and Ketones

1. By Oxidation of Alcohols
We have already studied
in alcohols and phenols that 
oxidation of alcohols converts 1°
and 2° alcohols to aldehydes and
ketones respectively when any one
of the following is used :
• PCC (pyridum chlorochromate)
• Collins reagents (Chromium
trioxide-pyridine complex)
• Cu at 573 K
 Preparation of Aldehydes and Ketones

2. From hydrocarbons
• Ozonolysis of alkenes
Alkenes react with O3 in the
presence of Zn and H2O to produce
aldehydes or ketones depending
upon the structure of alkene.
 Preparation of Aldehydes and Ketones

2. From hydrocarbons
• From hydration of alkynes HgSO4, H2SO4
Alkynes follow Markovnikov’s rule in the
presence of a proper catalyst to produce
ketones. All alkynes react with water in the
presence of HgSO4 and H2SO4 to form
ketones.
• However, ethyne gives aldehyde instead
of ketones. This is an only exception ethyne
where alkyne on hydration produces
acetaldehyde. Rest all the alkyne on
hydration produces ketones.
 Preparation of Aldehydes and Ketones

3. Aldehydes from esters

 Preparation of Aldehydes and Ketones

4. From nitriles
• Nitriles are first reduced to corresponding imines with SnCl2 in the presence of
HCl, which on hydrolysis give corresponding aldehydes. Preparation of
aldehydes by this method is known as Stephen's reduction.
 Preparation of Aldehydes and Ketones

4. From nitriles
• Nitriles can alternatively be Imines contain carbon-nitrogen double bond
reduced by diisobutylaluminium and have the following structure :
hydride (DiBAL-H) to imines,
which on hydrolysis gives
corresponding aldehydes.
 Preparation of Aldehydes and Ketones

4. From nitriles
• Treatment of nitriles with Grignard's reagents followed by hydrolysis yield
ketones.

HCN reacts with Grignard's reagents to form aldehyde (not ketone).

 Preparation of Aldehydes and Ketones
5. From acid chlorides
Acid chloride is hydrogenated over catalyst Pd on BaSO4 and partially poisoned by
the addition of Sulphur or quinoline to give aldehydes.

Treatment of acid chloride with dialkylcadmium [(R)2Cd] gives ketones.

 Chemical Properties
of Aldehydes and Ketones
• Both aldehydes and ketones contain carbonyl group, therefore they undergo same
reactions like nucleophilic addition reactions, oxidation, reduction, halogenation etc.
• Aldehydes
• In aldehydes, the carbonyl group has a hydrogen atom attached to it together
with either a second hydrogen atom or, more commonly, a hydrocarbon group
which might be an alkyl group or one containing a benzene ring. 
• Ketones
• In ketones, the carbonyl group has two hydrocarbon groups attached. Again,
these can be either alkyl groups or ones containing benzene rings.
 Nucleophilic Addition Reactions
in Aldehydes and Ketones

Aldehydes are more susceptible to nucleophilic attack than ketones as described below :
• Reactivity of Aliphatic Aldehydes and Ketones
Aliphatic aldehydes are more reactive than ketones because of the following reasons :
1. Inductive effect : Alkyl groups are electron donating in nature (i.e., show +I-Effect).
Hence, the presence of alkyl groups attached to the carbonyl group increases the electron
density on the carbonyl carbon thereby decreases its reactivity towards nucleophilic
addition reactions. Therefore, the order of reactivity is :
2. Steric hinderance : The more the number and the bigger
the size of the alkyl group, the more difficult for a
nucleophile to attack due to steric hinderance (crowding).
Hence, the order of reactivity is :
 Reactivity of Aromatic Aldehydes and Ketones
• Aromatic aldehydes and ketones exhibit electron donating resonance which
increases the electron density on the carbonyl carbon.

• Because of this reason, the carbonyl carbon becomes less electrophilic, and hence
is less susceptible to nucleophilic attack.
• Aromatic aldehydes, however, are more reactive than aromatic ketones. The
reactivity of aromatic aldehydes and ketones follows the order :
 Oxidation Reaction

• Aldehydes can be easily oxidised to carboxylic acids due to the presence of a

hydrogen atom on carbonyl group which can be easily converted to OH group.
Since ketones do not have any hydrogen atom attached to the carbonyl group,
they cannot be oxidised easily, and therefore, strong oxidising agents are required
for this purpose.
 Reduction of Aldehydes and Ketones

• Aldehydes and ketones can be reduced to a variety of

compounds such as alcohols, hydrocarbons etc.
 Other Reactions of Aldehydes and Ketones

• Aldehydes and ketones undergo many other reactions that

we will discover in later chapters.
Addition of Hydrogen Cyanide to Aldehydes and Ketones

Aldehydes and ketones react with hydrogen

cyanides to give cyanohydrin.
Mechanism
• The C=O bond is polar due to the difference in
electronegativities of carbon and oxygen
atoms. The oxygen of C=O acquires a partial
negative charge while carbon acquires a partial
positive charge.
• The partial positive charge on carbon attracts
the CN− of HCN (H+CN−). Because of this
reason, the double bond breaks and a new C-
CN bond is formed.
• As a result, oxygen becomes unstable due to
excess electrons, and hence attracts H+ of
H+CN−.
 Addition of Sodium Hydrogen Sulphite to Aldehydes and Ketonen

• Aldehydes react with sodium bisulphite (sodium

hydrogen sulphite) to give addition products. Ketones,
except for methyl ketones, do not react with sodium
bisulphite due to steric hinderance (crowding).
• Mechanism
 Addition of Grignard's Reagents to
Aldehydes and Ketones
• Aldehydes and ketones react with
Grignard's reagents to form alcohols.
Addition of Alcohols to Aldehydes and
Ketones
• Aldehydes react with alcohols in the
presence of dry HCl to give hemiacetals.
Hemiacetals being unstable react with
another molecule of alcohol to
give acetals.
 Addition of Grignard's Reagents to
Aldehydes and Ketones
• The reaction of aldehydes with dihydric alcohols such as ethane-
1,2-diol yields cyclic acetals.

• Similarly, cyclic ketals are formed when ketones react with

dihydric alcohols.
 Addition of Grignard's Reagents to
Aldehydes and Ketones
• Aldehydes and ketones react with a number of ammonia derivatives
in the presence of acids to form addition products.
• Some ammonia derivatives are given below :
 NH2OH (hydroxylamine)
 NH2-NH2 (hydrazine)
 C6H5NHNH2 (phenylhydrazine)
 NH2CONH2 (Semicarbazide)
 pH of acid catalysts
• In reactions of aldehydes and ketones with ammonia
derivatives, weak acids are used as catalysts. Due to lone
pairs on oxygen, the carbonyl group reacts with weak acids.

• The above reaction yields the following product which

exhibits resonance.
 pH of acid catalysts

Due to resonance, the positive charge on carbonyl carbon increases and,

consequently, the carbon becomes more susceptible to a nucleophilic attack. The
reaction, however, is pH dependent and takes place at pH 4 to 5 only. This is due to
the following reasons :
1.When pH is very low : The ammonia derivatives being basic in nature form their
respective ammonia salts and, consequently, lose their nucleophilic nature.
2.When pH is high : At higher pH, the carbonyl group will not be sufficiently
protonated.
 Reactions of Aldehydes and Ketones
with Hydroxylamine
• Aldehydes and ketones react with hydroxylamine (NH 2OH)
to form oximes.
Reaction of Aldehydes and Ketones with Hydrazine

• Aldehydes and ketones react with hydrazine (NH2−NH2) to form hydrazones.

• Similarly, aldehydes and ketones react with phenylhydrazines (C6H5NHNH2) to

form phenylhydrazones.
 2,4-DNP Test
• Aldehydes and ketones react with 2,4-dinitrophenylhydrazine to form yellow, orange or
red ppt. This reaction is used for distinction of aldehydes and ketones from other
compounds and is known as 2,4-DNP test or Brady's test .
• Aliphatic aldehydes and ketones give yellow ppt with 2,4-dinitrophenylhydrazine.

• We get red ppt with aromatic aldehydes and ketones.

 Reactions of Aldehydes and Ketones with
semicarbazides
• Aldehydes and ketones react with semicarbazide
(NH2CONHNH2) to form semicarbazones.
 Oxidation of Aldehydes
• Aldehydes are easily oxidised to carboxylic acids containing the same number of
carbon atoms with oxidising agents like acid dichromate (K2Cr2O7/H2SO4) and
KMnO4. The oxygen of an oxidising agent is usually represented by [O].
 Oxidation of Ketones

• Ketones do not undergo oxidation easily and on vigorous

oxidation yield acids with lesser number of carbon atoms.
 Unsymmetrical ketones
• In case of unsymmetrical ketones, the C=O bond remains with the smaller chain. This rule is
known as Popoff's rule. Study the following example for better understanding :
Unsymmetrical ketones
 Symmetrical Ketones
• In case of symmetrical ketones, only one type of cleavage
occurs. A mixture of two acids is formed in this case. 
 Distinction between Aldehydes and Ketones
Weak acids like Cu2+, Ag+, bromine water have potential to oxidise aldehydes. Ketones, however, can
not be oxidised by weak acids. This difference in property between aldehydes and ketones is used to
distinguish them from each other.
Tollen's test
• When an aldehyde (aliphatic or aromatic) is warmed with ammoniated silver nitrate (Tollen's
reagent), a bright silver mirror is formed on the inner sides of the test tube due to reduction of
Tollen's reagents.

• Unsaturated aldehydes are oxidised by Tollen's reagent to unsaturated acids.

• Ketones do not react with Tollen's reagents.

 Fehling's test

• Fehling's solution contains copper (II) ions complexed with sodium potassium tartrate
(Rochelle salt). In this reaction, Cu (II) ions are reduced to Cu(I) oxide which is a red
brick ppt.

Note
• Ketones do not react with Fehling's solution.
• Aromatic aldehydes do not react with Fehling's solution either.
 Haloform reaction
• Aldehydes and ketones having methyl group attached to >C=O are oxidised by sodium
hypohalite (NaOX or X2+NaOH) to haloforms.

Iodoform test
• When sodium hypoiodide (NaOI or I2/NaOH) is used in the above haloform reaction,
yellow ppt of iodoform is formed. Due to this reason, this reaction is used for detection
of CH3CO group — or CH3CH(OH) which is discussed in distinction between alcohols.
Reduction of Aldehydes and Ketones to Alcohols

• Aldehydes and ketones are reduced to primary and secondary alcohols

respectively. Any one of the following reducing agents can be used for this
purpose.
1. H2 in the presence of Ni, Pt or Pd.
2. Lithium aluminium hydride (LiAlH4).
3. Sodium borohydride (NaBH4).
 Reduction of Aldehydes and Ketones to
Hydrocarbons
• The carbonyl group in aldehydes and ketones can be reduced to −CH2 group to form
hydrocarbons.

• Zinc amalgam (Zn-Hg) and conc. HCl are used for reduction of aldehydes and ketones to
hydrocarbons. Reduction of aldehydes and ketones by this method is known
as Clemmensen reduction.
 Reduction of Aldehydes and Ketones to
Hydrocarbons
Alternatively, the carbonyl group can be reduced to hydrocarbon using hydrazine
(NH2−NH2) followed by heating with sodium or potassium hydroxide in high
boiling solvent such as ethylene glycol. Reduction by this method is known
as Wolff-Kishner reduction.
 Cannizzaro Reaction

• Aldehydes that do not have any α-hydrogen undergo

disproportionation i.e., self oxidation-reduction, on treatment with
concentrated alkali solution.
 Electrophilic Substitution Reaction

• Aromatic aldehydes and ketones undergo electrophilic substitution reactions such as nitration,
sulphonation and halogenation. Since the aldehydic group (-CHO) and ketonic group (-COR or
-COAr) are electron-withdrawing, they are deactivating and m-directing.
 Aldol condensation
• Aldehydes and ketones having α−hydrogen atom when treated with dilute alkali,
form β-hydroxy aldehydes and β−hydroxy ketones respectively (known as aldols),
which on heating give unsaturated compounds.

α carbon : The carbon atom next to

the carbonyl group is called an α
carbon.
α hydrogen : Hydrogen atoms
attached to the α carbon are known as
α hydrogens.
 Cross aldol condensation

• When aldol condensation is carried out with two different aldehydes or ketones
having α-hydrogen, the reaction is called cross-aldol condensation. Cross-aldol
condensation can take place between :
• Two different aldehyde groups
• Two different ketone groups
• One aldehyde and one ketone groups
• The major problem in cross-aldol condensation is that a mixture of four different
products is formed which are difficult to separate.