MT 633: INORGANIC AND ORGANIC CHEMISTRY
UNIT 12
ALDEHYDES AND KETONES
csmadarang 11.12.2018
Outline
1.1 Structures of Aldehydes and Ketones
1.2 Oxidation and Reduction Reactions
1.3 Synthesis of Alcohols
1.4 Acetal / Ketal Formation
1.5 Keto-Enol Tautomerism
Structure
The functional group of an aldehyde is a carbonyl
group bonded to a hydrogen atom.
• In methanal (formaldehyde), the simplest aldehyde,
the carbonyl group is bonded to two hydrogens.
• In other aldehydes, it is bonded to one hydrogen and
one carbon group.
The functional group of a ketone is a carbonyl
group bonded to two carbon groups.
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Physical Properties
• Table 17-1 Boiling Points for Six Compounds of
Comparable Molecular Weight.
• Formaldehyde, acetaldehyde, and acetone are infinitely
soluble in water.
• Aldehydes and ketones become less soluble in water as
the hydrocarbon portion of the molecule increases in
size.
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Oxidation
• Aldehydes are oxidized to carboxylic acids by a variety
of oxidizing agents, including potassium dichromate.
• Liquid aldehydes are so sensitive to oxidation by O2 in
the air that they must be protected from contact with
air during storage.
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Oxidation
• Ketones resist oxidation by most oxidizing agents,
including potassium dichromate and molecular oxygen.
• Tollens’ reagent is specific for the oxidation of
aldehydes. If done properly, silver deposits on the
walls of the container as a silver mirror.
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Reduction
• The carbonyl group of an aldehyde or ketone is
reduced to an -CHOH group by hydrogen in the
presence of a transition-metal catalyst.
• Reduction of an aldehyde gives a primary alcohol.
• Reduction a ketone gives a secondary alcohol.
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Reduction
• Reduction by NaBH4 does not affect a carbon-
carbon double bond or an aromatic ring.
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Synthesis of Alcohols
• The synthesis of alcohols involve using a Grignard
reagent
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Synthesis of Alcohols
• The synthesis below are examples AN reaction
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Addition of Alcohols
Addition of a molecule of alcohol to the carbonyl
group of an aldehyde or ketone forms a
hemiacetal (a half-acetal).
This is also an example of a nucleophilic addition
reaction
(AN)
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Addition of Alcohols
• When a hydroxyl group is part of the same molecule
that contains the carbonyl group and a five- or six-
membered ring can form, the compound exists almost
entirely in a cyclic hemiacetal form.
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Addition of Alcohols
A hemiacetal can react further with an alcohol to form
an acetal plus water.
• This reaction is acid catalyzed.
• The addition of an alcohol to a hemiacetal is a
nucleophilic addition AND elimination (ANE)
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Mechanism of Acetal Formation
Step 1: Add a proton. Adding a proton to the
carbonyl oxygen makes the carbonyl carbon a
stronger electrophile and more susceptible to
attack by a nucleophile.
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Mechanism of Acetal Formation
• Step 2: Reaction of an electrophile and a
nucleophile to form a new covalent bond.
• This step adds the first –OR group required for
acetal formation. The intermediate formed is an
oxonium ion.
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Mechanism of Acetal Formation
• Step 3: Proton transfer to another oxygen.
The proton transferred is in red.
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Mechanism of Acetal Formation
• Step 4: Break a bond to form stable molecules or
ions. In this case the stable molecule is H2O and
the stable ion is a 3°carbocation.
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Mechanism of Acetal Formation
• Step 5: Reaction of an electrophile and a
nucleophile to form a new covalent bond.
This step adds the second –OR group of the acetal
to what was the original carbonyl carbon.
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Mechanism of Acetal Formation
• Step 6: Take a proton away.
• Transfer of a proton to solvent gives the acetal
and regenerates the H+ catalyst.
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Summary
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Summary
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Summary
• Table of reactions with amines and its derivatives
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Keto-Enol Tautomerism
A carbon atom adjacent to a carbonyl group is
called an -carbon,
-carbon and a hydrogen atom bonded
to it is called an -hydrogen.
-hydrogen
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Keto-Enol Tautomerism
An aldehyde or ketone that has a hydrogen on an
-carbon is in equilibrium with a constitutional
isomer called an enol.
enol
• The name “enol” is derived from the IUPAC designation
of it as both an alkene (-en-)
en and an alcohol (-ol).
ol
• In a keto-enol equilibrium, the keto form generally
predominates.
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Keto-Enol Tautomerism
• Example 17-8: Draw structural formulas for the
two enol forms for each ketone.
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Keto-Enol Tautomerism
Example 17-8: Draw structural formulas for the two
enol forms for each ketone.
Solution:
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